WO2019126532A1 - Battery electrode with solid polymer electrolyte and aqueous soluble binder - Google Patents

Battery electrode with solid polymer electrolyte and aqueous soluble binder Download PDF

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Publication number
WO2019126532A1
WO2019126532A1 PCT/US2018/066849 US2018066849W WO2019126532A1 WO 2019126532 A1 WO2019126532 A1 WO 2019126532A1 US 2018066849 W US2018066849 W US 2018066849W WO 2019126532 A1 WO2019126532 A1 WO 2019126532A1
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Prior art keywords
polymer
battery
solid
lithium
electrolyte
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PCT/US2018/066849
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French (fr)
Inventor
Michael A. Zimmerman
Randolph Leising
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Ionic Materials Inc
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Ionic Materials Inc
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Priority to KR1020207021176A priority Critical patent/KR20200118800A/en
Priority to SG11202005853SA priority patent/SG11202005853SA/en
Priority to EP18892463.3A priority patent/EP3729551A4/en
Priority to US16/956,246 priority patent/US20210119213A1/en
Priority to JP2020534262A priority patent/JP2021507471A/en
Priority to CN201880089863.7A priority patent/CN112154564A/en
Publication of WO2019126532A1 publication Critical patent/WO2019126532A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • binders typically require binders to both maintain electrode integrity and to ensure adherence with corresponding current collector surfaces.
  • the binders are used in electrode forming processes with appropriate solvents.
  • Non-aqueous solvents are used with binders such as Polyvinylidene fluoride also known as polyvinylidene difluoride.
  • Aqueous binders including water are less toxic, but water can damage electrolytes by, for example, disassociating electrolyte salts from the solute.
  • prior art use of aqueous binders generally requires processes that isolate the aqueous solution from the electrolyte and/or additional process steps for addition of supplementary electrolyte after the aqueous solution is driven or removed from the electrode.
  • the invention features an electrode useful in an electrochemical cell.
  • the electrode includes an electrochemically active material; an electrically conductive material; a solid ionically conductive polymer electrolyte; and a binder; wherein the binder is dispersed in an aqueous solution.
  • the binder is soluble in an aqueous solution.
  • the binder is partially soluble in an aqueous solution.
  • the electrode further includes a lithium.
  • the electrochemically active material includes a graphite.
  • the electrochemically active material is in an amount having a range of 70-90 wt. % of the electrode.
  • the electrode further includes an electrically conductive current collector which is in electrical communication with the electrically conductive material.
  • the electrode further includes a second binder which is soluble in an aqueous solution.
  • the solid ionically conductive polymer electrolyte is in an amount having a range of 52-15 wt.% of the electrode.
  • the solid ionically conductive polymer electrolyte has an ionic conductivity of at least lxl O 4 S/cm.
  • the solid ionically conductive polymer electrolyte has a crystallinity of at least 30%.
  • the solid ionically conductive polymer electrolyte has a cathodic transference number greater than 0.4 and less than 1.0.
  • the solid ionically conductive polymer electrolyte is in a glassy state.
  • the electrochemically active material, the electrically conductive material, the solid ionically conductive polymer electrolyte and the binder include a plurality of dispersed, intermixed particulates.
  • the electrode further includes an electrically conductive current collector; and the electrode is adhered to the electrically conductive current collector.
  • the electrochemically active material, the electrically conductive material, the solid ionically conductive polymer electrolyte and the binder include a plurality of dispersed, intermixed particulates forming a mixture; and the mixture is adhered to the electrically conductive current collector by an aqueous slurry.
  • the invention features a method of making a battery structure.
  • the method includes the steps of selecting an electrically conductive current collector and an electrode; wherein the electrode comprises an electrochemically active material, an electrically conductive material, a solid ionically conductive polymer electrolyte, and a binder; mixing the electrochemically active material, the electrically conductive material, the solid ionically conductive polymer electrolyte, and the binder in an aqueous solution to create a slurry; positioning the slurry adjacent the electrically conductive current collector; and drying the slurry; wherein the electrode adheres to the electrically conductive current collector.
  • FIG. 1 is a schematic of an electrochemical cell according to an exemplary embodiment of the invention
  • FIG. 2 is a discharge curve for the electrochemical cell described in Example 1 ;
  • FIG. 3 is a plot of a cycle test for the electrochemical cell described in Example 1 during Lithium intercalation and deintercalation;
  • FIG. 4 is a discharge curve for the comparative electrochemical cell described in Example
  • FIG. 5 is a plot of a cycle test for the electrochemical cell described in Example 2.
  • an electrochemical cell 10 is shown in representative cross- section.
  • the electrochemical cell has a first electrode 20 attached to a first electrically conductive current collector 30.
  • the electrochemical cell also includes a second electrode 50 which is similarly attached to a second electrically conductive current collector 60.
  • An electrolyte layer 40 is interposed between the first and second electrodes.
  • the electrolyte layer 40 acts as a dielectric separator and enables ionic conduction between the electrodes.
  • Each of the current collectors 30 and 60 includes a respective tab 25 and 65 extending from each respective current collector 30 and 60 so that at least a portion of the tab can extend from the cell enclosure (not shown). Each tab 25 and 65 thus can act as an electrical lead, either positive and negative for the cell.
  • the first 20 and second electrodes 50 each contain an electrochemically active material that forms an electrochemical couple which produces electrons when the cell in under load.
  • an electrochemical cell and its electrodes can vary depending on the electrochemical couple, in an aspect, the invention features an electrode having a basic or typically design known to those of ordinary skill in the art.
  • the electrode components typically include an electrolyte, an electrically conductive material and a binder. Liquid electrolytes or non-solid electrolytes such as, for a non-limiting example, gels, or electrolytes having a non-solid state are typically used in the prior art as the ionically conductive media in electrochemical cells.
  • the invention features an electrochemical cell which includes a solid, ionically conductive, polymer electrolyte.
  • the solid ionically conductive polymer electrolyte can function as an analyte and as a catholyte.
  • the solid, ionically conductive polymer electrolyte can include a plurality of particulates. These particulates can be arranged in an array having a shape of a film, such as, for a non-limiting example, a planar film.
  • the solid ionically conductive polymer electrolyte can be interposed between the electrodes to enable ionic conductivity between the electrodes while also providing the dielectric barrier necessary for the electrochemical cell.
  • the particulates of the solid ionically conductive polymer electrolyte can be dispersed throughout the electrode whether the particulates function as an analyte and/or as a catholyte.
  • the particulates can be interspersed with and encapsulate the particles of the electrochemically active material, the binder, and the electrically conductive material.
  • the electrolyte includes at least one salt for the required ionic conductivity for the cell.
  • the salt contains at least an anion and a cation.
  • the invention features a lithium battery, wherein the diffusivity and ionic conductivity of the cation is preferably greater than that of the anion.
  • the present invention includes a lithium metal battery enabled to operate efficiently at a high voltage by a solid ionically conductive polymer material.
  • depolarizers refers to a synonym for an electrochemically active substance(s), i.e., a substance(s) which changes its oxidation state or partakes in a formation or breaking of chemical bonds, in a charge-transfer step of an electrochemical reaction and an electrochemically active material.
  • electrochemically active substance(s) i.e., a substance(s) which changes its oxidation state or partakes in a formation or breaking of chemical bonds, in a charge-transfer step of an electrochemical reaction and an electrochemically active material.
  • co-depolarizers co-depolarizers.
  • thermoplastic(s) refers to a characteristic of a plastic material or polymer, wherein the plastic material or polymer becomes reversibly pliable or moldable above a specific temperature, the specific temperature being typically around or at the melting temperature of the plastic material or polymer, and wherein the plastic material or polymer reversibly solidifies upon cooling below the melting temperature.
  • solid electrolyte(s) and/or“solid phase electrolytes” refer to solvent free polymers and/or ceramic compounds including crystalline, semi-crystalline and/or amorphous compounds and/or compounds in a glassy state.
  • the terms“solid electrolyte(s)” and/or“solid phase electrolyte(s)” do not refer to or include gelled or wet polymer(s), solvent(s) and/or other material(s) which depend upon a liquid, liquid phase, and/or liquid phase material for ionic conductivity.
  • solid(s) and/or“solid phase(s) and/or solid phase material and/or material is a solid phase” can be used interchangeably and refer to the ability to maintain indefinitely a particular shape, wherein the“solid” is distinguishable and different from a liquid or a liquid phase or a liquid phase material or a material in a liquid phase.
  • the atomic structure of the“solid(s)” can be crystalline or amorphous.
  • The“solid(s)” can be mixed with or include components in composite structures.
  • a“solid” ionically conductive or conducting material enables ionic conductivity through the“solid” material and not through any solvent, gel, liquid, liquid phase or liquid phase material, unless it is otherwise described.
  • polymer(s) refers to an organic compound which includes carbon-based macromolecules. Each macromolecule can have one or more types of repeating units, also known as monomers and/or monomer residues, as understood by those persons of ordinary skill in the art.
  • a “polymer(s)” is characterized as lightweight, ductile, usually or typically electrically non- conductive, and melts at a relatively low temperature.
  • a polymer(s) can be made into products by injection, blowing and other molding processes, extrusion, pressing, stamping, three-dimensional printing, machining and other plastic or polymer forming processes known to those of ordinary skill in the art.
  • a polymer(s) typically has a glassy state at a temperature below the glass transition temperature or Tg of the polymer(s).
  • the glass transition temperature is a function of polymer chain flexibility. At temperatures above the glass transition temperature, there is enough vibrational and/or thermal energy in the system of the polymer(s) to create sufficient free -volume to permit sequences of segments of the polymer macromolecule to move together as a unit. However, when in the glassy state, a polymer has no segmental motion of the polymer.
  • ceramic(s) which is distinguishable from the term“polymer(s)”, refers to an inorganic, non- metallic material; ceramics typically include compounds which consist of metals covalently bonded to oxygen, nitrogen or carbon. A“ceramic(s)” is characterized as brittle, strong and non-conducting.
  • glass transition temperature which is observed, determined or estimated in some but not all polymers, is a temperature or temperature range which falls between the temperature of a supercooled liquid state and the temperature of a glassy state as a polymer material is cooled.
  • the thermodynamic measurements of the glass transition are done by measuring a physical property of the polymer, e.g. volume, enthalpy or entropy and other derivative properties as a function of temperature.
  • the glass transition temperature is observed on such a plot as a break in the selected property (volume of enthalpy) or from a change in slope (heat capacity or thermal expansion coefficient) at the transition temperature.
  • a polymer(s) can include a crystalline, a semi-crystalline and/or an amorphous phase.
  • the term“percentage crystallinity” of a polymer(s) refers to the percentage or amount of the crystalline phase of the polymer relative the total amount of the polymer including both the amorphous and crystalline phases of the polymer. Crystallinity percentage can be calculated via x-ray diffraction of the polymer and analysis of the relative areas of the amorphous and crystalline phases of the polymer.
  • the term“polymer film” generally refers to a thin portion of polymer.
  • the term“polymer film” should be understood to equal a portion of polymer which is equal to or less than 300 micrometers in thickness.
  • Ionic conductivity differs from electrical conductivity. Ionic conductivity depends on ionic diffusivity, and the properties of ionic conductivity are related by the Nemst-Einstein equation. Ionic conductivity and ionic diffusivity are both measures of ionic mobility. An ion is considered mobile in a material if the diffusivity of the ion in the material is positive, that is, greater than zero, and/or the movement of the ion contributes to a positive ionic conductivity.
  • Ionic mobility measurements are generally taken at room temperature, that is, around 2l°C, unless otherwise stated. Ionic mobility is affected by temperature. Thus, it can be difficult to detect ionic mobility at low temperatures. Equipment detection limits can be a factor in determining relatively low ionic mobility.
  • An ion can be considered mobile in a material when a measurement of the diffusivity of the ion is at least 1 x 10 14 m 2 /s and preferably is at leastl x l0 13 m 2 /s.
  • solid polymer ionically conductive and/or conducting material(s) refers to a solid material that includes a polymer and conducts ions as will be further described.
  • An aspect of the invention includes a method of synthesizing a solid ionically conductive polymer material from at least three distinct components: a base polymer, a dopant and an ionic compound.
  • the components and method of synthesis are chosen or selected for the particular application of the material.
  • the selection of the base polymer, dopant and ionic compound may also vary based on the desired performance of the material.
  • the desired components and method of synthesis may be determined by optimization of a desired physical characteristic (e.g. ionic conductivity).
  • the method of synthesis can also vary depending on the particular components and the desired form of the end material (e.g. film, particulate, etc.). However, the method includes the basic steps of mixing at least two of the components initially, adding the third component in an optional second mixing step, and heating the components/reactants to synthesis the solid ionically conductive polymer material in a heating step.
  • the resulting mixture can be optionally formed into a film of desired size. If the dopant was not present in the mixture produced in the first step, then it can be subsequently added to the mixture while heat and optionally pressure (positive pressure or vacuum) are applied. All three components can be present and mixed and heated to complete the synthesis of the solid ionically conductive polymer material in a single step.
  • this heating step can be done when in a separate step from any mixing or can completed while mixing is being done.
  • the heating step can be performed regardless of the form of the mixture (e.g. film, particulate, etc.)
  • all three components are mixed and then extruded into a film. The film is heated to complete the synthesis.
  • An aspect of the method of synthesis includes a step of mixing the base polymer, ionic compound and dopant together followed by a step of heating the mixture.
  • the heating step can be performed in the presence of the dopant where the dopant can be in the gas phase.
  • the mixing step can be performed in an extruder, blender, mill or other equipment typical of plastic processing.
  • the heating step can last several hours (e.g. twenty-four (24) hours) and the color change is a reliable indication that synthesis is complete or partially complete. Additional heating past synthesis (color change) does not appear to negatively affect the material.
  • the base polymer and ionic compound can be first mixed.
  • the dopant is then mixed with the polymer-ionic compound mixture and heated.
  • the heating can be applied to the mixture during the mixture step or the heating can be applied to the mixture subsequent to the mixing step.
  • the base polymer and the dopant are first mixed, and then heated.
  • This heating step can be applied after the mixing or during the mixing.
  • the heating step produces a color change indicating the formation of charge transfer complexes and reaction between the dopant and the base polymer.
  • the ionic compound is then mixed with the reacted polymer dopant material to complete the formation of the solid ionically conductive polymer material.
  • Typical methods of adding the dopant are known to those skilled in the art and can include vapor doping of film containing the base polymer and ionic compound and other doping methods known to those skilled in the art.
  • vapor doping of film containing the base polymer and ionic compound Upon doping the solid polymer material becomes ionically conductive. It is believed that the doping acts to activate the ionic components of the solid polymer material, so they are diffusing ions.
  • non-reactive components can be added to the above described mixtures during the initial mixing steps, secondary mixing steps or mixing steps subsequent to heating.
  • Such other components include but are not limited to depolarizers or electrochemically active materials such as anode or cathode active materials, electrically conductive materials such as carbons, rheological agents such as binders or extrusion aids (e.g. ethylene propylene diene monomer "EPDM”), catalysts and other components useful to achieve the desired physical properties of the mixture.
  • Polymers that are useful as reactants in the synthesis of the solid ionically conductive polymer material are electron donors or polymers which can be oxidized by electron acceptors.
  • Semi-crystalline polymers with a crystallinity index greater than 30%, and greater than 50% are suitable reactant polymers.
  • Totally crystalline polymer materials such as liquid crystal polymers (“LCPs") are also useful as reactant polymers. LCPs are totally crystalline and therefore their crystallinity index is hereby defined as 100%.
  • Undoped conjugated polymers and polymers such as polyphenylene sulfide (“PPS”) are also suitable polymer reactants.
  • Polymers are typically not electrically conductive.
  • virgin PPS has an electrical conductivity of 10 20 S/cm.
  • Non-electrically conductive polymers are suitable reactant polymers.
  • Non limiting examples of the polymers used in this aspect of the invention can be selected from the group including PPS, Poly (p-phenylene oxide) (“PPO”), LCPs, Polyether ether ketone (“PEEK”), Polyphthalamide (“PPA”), Polypyrrole, Polyaniline, and Polysulfone.
  • PPS Poly (p-phenylene oxide)
  • PEEK Polyether ether ketone
  • PPA Polyphthalamide
  • Polypyrrole Polyaniline
  • Polysulfone Co-polymers including monomers or monomer residues of the listed polymers and mixtures of these polymers may also be used.
  • copolymers of p-hydroxybenzoic acid can be appropriate liquid crystal polymer base polymers.
  • TABLE 1 details non-limiting examples of reactant polymers useful in the synthesis of the solid ionically conductive polymer material along with monomer or monomer residue structures and some physical property information.
  • TABLE 1 includes non-limiting examples where polymers can take multiple forms which can affect their physical properties.
  • Dopants that are useful as reactants in the synthesis of the solid ionically conductive polymer material are electron acceptors or oxidants. It is believed that the dopant(s) release ions for ionic transport and mobility. It is believed that the dopant release of ions creates site(s) analogous to charge transfer complex(es) or site(s) within the polymer which allow or permit ionic conductivity.
  • Non- limiting examples of dopants which can be used in the present invention include quinones such as: 2,3-dicyano-5,6-dichlorodicyanoquinone (CTCnN O ) also known as “DDQ”, and tetrachloro-l,4-benzoquinone (CeCi t Ch), also known as chloranil, tetracyanoethylene (CeN t ) also known as TCNE, sulfur tri oxide (“SO3”), ozone (tri oxygen or O3), oxygen (O2, including air), transition metal oxides including manganese dioxide (“MnCh”), or any suitable electron acceptor, etc. and combinations thereof.
  • CTCnN O 2,3-dicyano-5,6-dichlorodicyanoquinone
  • DDQ tetrachloro-l,4-benzoquinone
  • CeCi t Ch tetracyanoethylene
  • SO3 sulfur tri oxide
  • O3 ozone
  • Dopants that are temperature stable at the temperatures of the synthesis heating step are useful or preferred, and quinones and other dopants which are both temperature stable and strong oxidizers quinones are very useful and even more preferred.
  • TABLE 2 provides a non-limiting listing of dopants, along with their chemical formulas and structures.
  • Ionic compounds that are useful as reactants in the synthesis of the solid ionically conductive polymer material are compounds that release desired lithium ions during the synthesis of the solid ionically conductive polymer material.
  • the ionic compound is distinct from the dopant in that both an ionic compound and a dopant are required.
  • Non- limiting examples include Li 2 0, LiOH, LiNCb, LiTFSI (LiC 2 F 6 N0 4 S 2 or lithium bis-trifluoromethanesulfonimide), LiFSI (F 2 LiN0 4 S 2 or Lithium bis(fluorosulfonyl)imide), LiBOB (Lithium bis(oxalato)borate or CLBLiOs), lithium triflate (LiCFiOiS or lithium trifluoromethane sulfonate), Li PLT, (lithium hexafluorophosphate), LiBF4 (lithium tetrafluoroborate), LiAsFe (lithium hexafluoroarsenate) and other lithium salts and combinations thereof.
  • Li 2 0, LiOH, LiNCb LiTFSI (LiC 2 F 6 N0 4 S 2 or lithium bis-trifluoromethanesulfonimide), LiFSI (F 2 LiN0 4 S 2 or Lithium bis(flu
  • Hydrated forms (e.g. monohydride) of these compounds can be used to simplify handling of the compounds.
  • Inorganic oxides, chlorides and hydroxide are suitable ionic compounds in that they dissociate during synthesis to create at least one anionic and/or cationic diffusing ion. Any such ionic compound that dissociates to create at least one anionic and/or cationic diffusing ion would similarly be suitable.
  • Multiple ionic compounds can also be useful that result in multiple anionic and/or cationic diffusing ions can be preferred. The particular ionic compound included in the synthesis depends on the utility desired for the material.
  • a lithium hydroxide or a lithium oxide convertible to a lithium and hydroxide ion can be appropriate.
  • a lithium containing compound that releases both a lithium cathode and a diffusing anion can be used in the the synthesis method.
  • a non-limiting group of such lithium ionic compounds includes those used as lithium salts in organic solvents.
  • the purity of the materials can be relevant for the prevention of unintended side reactions and for the maximization of the effectiveness of the synthesis reaction to produce a highly conductive material.
  • Substantially pure reactants with generally high purities of the dopant, the base polymer and the ionic compound are useful, and purities greater than 98% are more useful with even higher purities, e.g. LiOH: 99.6%, DDQ: >98%, and Chloranil: >99% also useful.
  • useful anode materials include typical anode intercalation materials comprising: lithium titanium oxide (LTO), Silicon (Si), germanium (Ge), and tin (Sn) anodes doped and undoped; and other elements, such as antimony (Sb), lead (Pb), Cobalt (Co), Iron (Fe), Titanium (Ti), Nickel (Ni), magnesium (Mg), aluminum (Al), gallium (Ga), Germanium (Ge), phosphorus (P), arsenic (As), bismuth (Bi), and zinc (Zn) doped and undoped; oxides, nitrides, phosphides, and hydrides of the foregoing; and carbons (C) including nanostructured carbon, graphite, graphene and other materials including carbon, and mixtures thereof.
  • LTO lithium titanium oxide
  • Si Silicon
  • Ge germanium
  • Sn tin
  • other elements such as antimony (Sb), lead (Pb), Cobalt (Co), Iron (Fe),
  • anode intercalation material can be mixed with and dispersed within the solid ionically conductive polymer material such that the solid ionically conductive polymer material can act to ionically conduct the lithium ions to and from the intercalation material during both intercalation and deintercalation (or lithiation/ de-lithiation).
  • the cathode current collector 60 and/or the anode current collector 30 can include aluminum, copper, or other electrically conducting film onto which the corresponding cathode 50 or anode 20 can be located or positioned.
  • either the cathode current collector 60 and/or the anode current collector 30 can have a planar form.
  • Typical electrochemically active cathode compounds which can be used in the present invention include but are not limited to: NCA - Lithium Nickel Cobalt Aluminum Oxide (LiNiCoA10 2 ); NCM (NMC) - Lithium Nickel Cobalt Manganese Oxide (LiNiCoMn0 2 ); LFP - Lithium Iron Phosphate (LiFePO t ); LMO - Lithium Manganese Oxide (LiMmCL); LCo - Lithium Cobalt Oxide (L1C0O2); lithium oxides or phosphates that contain nickel, cobalt or manganese, and LiTiS2, LiNi02, and other layered materials, other spinels, other olivines and tavorites, and combinations thereof.
  • the electrochemically active cathode compounds can be an intercalation material or a cathode material that reacts with the lithium in a solid state redox reaction.
  • Such conversion cathode materials can include: metal halides including but not limited to metal fluorides such as FeF 2 , B1F 3 , CuF 2 , and N1F 2 , and metal chlorides including but not limited to FeCh, Fed 2, C0CI2, N1CI2, Cud 2, and AgCl; Sulfur (S); Selenium (Se); Tellerium (Te); Iodine (I); Oxygen (O); and related materials such as but not limited to pyrite (FeS2) and LLS.
  • metal fluorides such as FeF 2 , B1F 3 , CuF 2 , and N1F 2
  • metal chlorides including but not limited to FeCh, Fed 2, C0CI2, N1CI2, Cud 2, and AgCl
  • Sulfur (S) Selenium (Se); Tellerium (
  • the solid polymer electrolyte is stable at high voltages (exceeding 5.0V relative to the anode electrochemically active material).
  • an aspect of the invention involves the increase of the energy density by enabling as high a voltage battery as possible.
  • High voltage cathode compounds are preferred in this aspect.
  • Certain NCM or NMC material can provide such high voltages with high concentrations of the nickel atom.
  • NCMs that have an atomic percentage of nickel which is greater than that of cobalt or manganese, such as NCM523, NCM712, NCM721, NCM811, NCM532, NCM622 and NCM523, and other variations are useful to provide a higher voltage relative the anode electrochemically active material.
  • An electrically conductive material is necessary to establish electrical communication between electrochemically active particles and with the associated current collector for the support of electrical conduction within and to and from the electrode.
  • Such electrically conductive material typically contains particulate carbon and various graphites and carbons which are useful for this purpose such as. carbon black, a natural graphite, a synthetic graphite, a graphene, other electrically conductive materials comprising carbon, a conductive polymer, a metal particle, and a combination of at least two of the preceding components.
  • Binders act to maintain electrode integrity and adhesion to the current collector. Like the electrically conductive material and the electrolyte, the binders are not electrochemically active.
  • Binders which are soluble in aqueous solution are substantially soluble in water-based solvents, and can include Carboxymethyl cellulose or“CMC”, and styrene-butadiene rubber or“SBR”, similar aqueous soluble binders and mixtures thereof.
  • PTFE Polytetrafluoroethylene
  • EPDM Ethylene propylene diene monomer
  • PDA poly-polystyrene
  • Additional natural binders which can be dispersed or are soluble in an aqueous solution include: Amylose, Caseine, Cyclodextrines (carbonyl-beta), Cellulose (natural), Starches, alginate, chitosan, gums (e.g., gellan, guar, xanthan, karaya, tara, tragacanth, and arabic), agar-agar, pectine, and carrageenan.
  • binders can be dispersed in an aqueous solution such that the binder particulates are distributed for coherence of the electrode and/or for maintenance of electrical conductivity between the electrode and a respective electrode lead.
  • binders which are soluble in an aqueous solution can be used in the present invention.
  • the invention features binders which can be crosslinked if desired, e.g. PAA with CMC, and the crosslinked binder mixture can include tertiary and other additional binders to provide desired mechanical benefits.
  • the invention features binders which are soluble and are well dispersed in the water-based solvent, and/or binders which are partially soluble or otherwise dispersed.
  • Electrochemically active material needs to be in ionic communication with the solid polymer electrolyte, and in electrical communication with the electrically conductive material.
  • the invention features a plurality of particles of each electrode component intermixed and dispersed such that the particles are intimately mixed.
  • the binder must be added to the mixture.
  • a non-aqueous soluble binder such as PVDF can be added in solution in a mixing step.
  • Non-aqueous binders may not be compatible with certain electrode ingredients or components, as further discussed below, however. Such non-aqueous binders can result in poor electrical communication between an electrode and a current collector. If an aqueous binder is substituted for the non-aqueous binder in such applications, the aqueous solution can degrade the electrolyte.
  • the electrolyte is added after the aqueous solution is driven off in a drying or heating step.
  • Prior art solid electrolytes can be incompatible with aqueous binders, however.
  • Prior art solid electrolytes cannot be added after a drying step, as the electrode is cast and additional mixing would render an incoherent electrode.
  • Inclusion of prior art solid electrolytes such as PEO-salt complexes in the electrode mixture prior to drying can result in electrolyte degradation during exposure to the aqueous solution.
  • the salt contained within the electrolyte can react with water resulting in unreactive or lower performing reactants.
  • the solid polymer electrolyte of the present invention can be used with an aqueous soluble binder without experiencing any performance degradation, while producing a coherent electrode with excellent electrical communication with the associated current collection. Additional details will be described in the following Examples.
  • An electrochemical cell with a lithium ion graphite intercalation active material was constructed generally according to the electrochemical cell description provided above in association with FIG. 1. Details of the components and their weight percentages is provided in
  • Carbon black included LiTX50 from Cabot.
  • Natural Graphite intercalation material included SPGPT803 from Targray.
  • the binder consisted of Polyvinylidene fluoride or PVDF along with a non-aqueous slurry of N-Methyl-2-pyrrolidone or“NMP” solvent. The resulting slurry was adhered to a copper foil current collector and a coin cell was constructed. The cell was cycled and voltage over time was graphed. FIG. 2 shows the resulting discharge curve over many cycles.
  • FIG. 3 Graphite capacity per cycle was calculated during Lithium intercalation and deintercalation, as shown in FIG. 3.
  • FIGs. 2 and 3 demonstrate a significant capacity fade resulting in poor performance after approximately ten cycles.
  • An electrochemical cell with a lithium ion graphite intercalation active material was constructed generally according to the electrochemical cell description provided above in association with FIG. 1. Details of the components and their weight percentages is provided in TABLE 3. Carbon black included LiTX50 from Cabot. Natural Graphite intercalation material included SPGPT803 from Targray.
  • the binder consisted of a mixture of Carboxymethyl cellulose or CMC and styrene-butadiene rubber or SBR in a ratio of 60/40 wt.%, along with an aqueous slurry. Apart from the binder and associated solution, the electrochemical cell was constructed following the same procedure as in Comparative Example 1. The resulting slurry was adhered to a copper foil current collector and a coin cell was constructed.
  • FIG. 4 shows the resulting discharge curve over many cycles. Graphite capacity per cycle was calculated during Lithium intercalation and deintercalation, as shown in FIG. 5. FIGs. 4 and 5 demonstrate repeatable cycling with little to no capacity loss over numerous cycles. TABLE 3
  • FIG. 2, and FIG. 3 show graphical representation data from cycling of the cells described in
  • Example 1 the voltage per time is depicted with the voltage peaks of each cycle taking place with decreasing frequency after about the first four cycles.
  • the decreasing area under each cycle also indicates decreasing capacity which is confirmed in FIG. 3, and which depicts the capacity of the cell during charge (intercalation), and discharge (deintercalation).
  • the capacity measured in mAh/g of active anode material is graphically depicted per cycle. Again, the anode loses significant capacity in every cycle.
  • anodes are losing adhesion with the anode current collector, which increases resistance. This resistance lowers the voltage and the associated capacity.
  • the adhesion loss is analogous to a hose being gradually clamped closed every cycle, with less and less fluid being able to flow because of the reduced flow area.
  • the anode electrode made with the non- aqueous slurry and non-aqueous soluble binder does not provide adequate adhesion.
  • Example 2 the goal was to improve the current collector adhesion, and thus prevent the current restriction that occurred with the Example 1 (Comparative) cells.
  • the cells from Example 2 were initially kept for 16 hours and the OCV was very stable over this time. The cells were then cycled at a C/7 charge-discharge.
  • the Example 2 cell first cycle efficiency was 76.2%, and the intercalation (graphite) averaged about 364-374 mAh/g.
  • FIG. 5 shows the capacity of the cell during charge (intercalation), and discharge (deintercalation) over the first ten cycles. No capacity fade is shown, and a 99.6% cycle efficiency is demonstrated.
  • the solid ionically conductive polymer electrolyte prevents water from degrading the electrolyte.
  • the combination of the aqueous binder and the solid ionically conductive polymer electrolyte provides superior electrode performance while enabling the elimination of a costly electrode manufacturing step.
  • FIG. 3 Battery manufacture
  • Lithium foil Oxygen atom Lithium insertion
  • FIG. 10 U.S. Patent Nov. 14, 2017 Sheet 8 of 14 LS 9,819,053 131
  • FIG. 11 U.S. Patent Nov. 14, 2017 Sheet 9 of 14 LS 9,819,053 131
  • FIG. 20 U.S. Patent Nov. 14, 2017 Sheet 14 oM 4 LS 9,819,053 131
  • the weight of the novel battery is substant ially less than a battery of conventional construction s ] n i ⁇ -i i INIT RT ;c ; A R DINK , F i mi IR A I I Y having similar pow er capacity
  • the SFONSORHD RHSKARCH OR DFVFTOPMFNT ⁇ weight of the novel battery can be less than half the weight of a conventional battery.
  • flic electrolyte material is a solid ionieally conductive polymer which has preferably a semi-crystalline or crystal ⁇
  • I itliimn ion (and other) batteries generally employ a This w ill allow for new battery formats
  • liquid electrolyte which is hazardous to humans and to the
  • the electrolyte environment and which can he subject to (ire or explosion
  • An electrode material is in the fonn of an ionic polymer film.
  • I iquid electrolyte batteries are hermetically sealed in a steel
  • L new innovation is the charge collector or terminal is applied over each electrode poach cell which has been used in lightweight batteries but surface A light w eight protective polymer covering can he these have not seen widespread acceptance applied over the terminals to complete the lilm based
  • the batteries sa iler lyte is in the form o f an ionic polymer monof ilament from a limited number of recharges since the chemical (hollow ) rileclrode materials and charge collectors are read ion williin the baiters reaches completion and limits the its directly applied (eo-exlruded) to each surface ol ' llie elec rc-chargeabilily because of corrosion and dendrite forma trolyte and a terminal is applied at each electrode surf ace A tion
  • the liquid electrolyte also limits the maximum energy light w eight protective polymer covering can be applied density
  • the electrolyte starts to break down at about 4 2 over the terminals to complete the structure T his form of volts.
  • a solid tures which have not been deployed due to the limitations of electrolyte can be molded in a desired shape.
  • Anode and the liquid electrolyte lithium ion batteries w ith liquid cathode electrode materials are disposed on respective oppo electrolytes su ffer from safely problems w ith respect to I s site surfaces ol ’ llie electrolyte to fonn a cell unit Hleclrical flammabil ity o f the liquid electrolyte term inals are provided on the anode and cathode electrodes
  • a l ithium ion battery is m VIKWS OF ’ TI IF DRAWINGS provided which has a solid polymer electrolyte The solid
  • electrolyte enables a lighter weight and much safer archi fi l e foregoing summary as well as the following descrip tecture by eliminating the need for heavy and bulky metal tion of the invention, is better understood when read in hermetic packaging and protection circuitry
  • novel solid conjunction with the appended draw ings For the purpose o f polymer battery can be of smaller size, lighter weight and w illustrating the invention, exemplary construct ions are higher energy density than liquid electrolyte balleries of the show n in the draw ings, file invention is not limited, how same capacity, file solid polymer ballery also belief its from ever. to the specific methods and instrumentalities disclosed less complex manu facturing processes, lower cosl and herein
  • FIG 1 show s show a schematic of a conventional lithium flammable
  • the novel battery will also provide cell voltages ion battery according to the prior art
  • FIG. 2 shows reactions tit electrodes in a conventional into variou shapes by extrusion (and co-extrusion), molding lithium ion battery according to the prior art.
  • FIG .1 exemplarily illustrates a method of the invention provided for the battery Particular shapes can be made to lit including steps for manu facturing a sol id stale battery using into differently shaped enclosures in devices or equipment tit an extruded polymer
  • FIG. 4 exemplarily illustrates the extrusion process require a separator as with liquid electrolyte batteries. according to the invention i;s 9.8 9.05 A B
  • 1- lCT 5 exemplarily illustrates a schematic representation ture limits the kinds of applications PfO can be used in. o f an embodiment according to the invention even with necessary safely precautions for thermal runaway
  • MC I 6 shows a schematic of a solid polymer battery with The flammability of PfO
  • L1G 7 shows a dynamic scanning calorimetry plot show- s volatile nature and high operating temperature.
  • a ill the a lass transition temperature and melting temperature battery utilizing PfO as an electrolyte requires a hermetic of polyethylene oxide according to prior art. package around it to prevent thermal runaway ' i bis adds an riC l S shows the relationship o f ionic conduct ivity versus expensive thermal management system adds sa fely risk to temperature of traditional amorphous polyethylene oxide the end user which can prevent end user adoption and according to the prior art : : creates a rigid bulky structure which the battery manage ment system has to be designed around
  • MC I 11 exemplarily illustrates a dynamic scanning calo is sti ff thick and costly to integrate into an end application rimeter ciin o f a se icrystallinc polymer Moreover although PfO has been in existence for over 20 h lth 1 exemplarily illustrates formulations which were years it is still not commercially produced
  • Liquid electrolytes embody many of the same problems as h lth 13 exemplarily illustrates a chemical diagram of I:: PHO as used in the prior art: high cost safety concerns cost 2.3-dicyano-5.6-ilichlorodieyanoqiiinone (P1 IQ) and manu facturability challenges poor mechanical proper
  • IdC h 14 exemplarily illustrates possihle mechanisms of ties and of ten a cause of performance degradation
  • the solid conduction o f the solid electrolyte polymer according to the polymer approach of the present invention solves the prob invention.
  • lems associated with liquid electrolytes and addresses the h lth 15 exemplarily illustrates a plot of the conductivity Is limitations of PfO material.
  • the invention oilers three key advantages in its polymer tion in comparison with a liquid electrolyte and a polyeth performance characteristics: (1 ) It has an expansive tem ylene oxide lithium salt compound perature range.
  • (1 ) It has an expansive tem ylene oxide lithium salt compound perature range.
  • h id 17 exemplarily shows a I JI l J4 flammabil ity lest non-flammable
  • the polymer self-extinguishes passing the conducted on a polymer according to the invent ton IJI -V0 f lammability l est
  • the ability to operate at room h lth 18 exemplarily shows a plot of volts versus current temperature and the non-llnmmable characteristics demon of an ionically conductive polymer according to the inven strate a transformative safety improvement that eliminates tion versus lithium metal.
  • Mt h H exemplarily illustrates a schematic o f extruded cost bulk manufacturing Rather than spraying the polymer ionically conductive electrolyte and electrode components onto electrodes the polymer material can he extruded into a according to the invention.
  • thi ll lilm via a roll-to-roll process an industry standard for hlth 20 exemplarily illustrates the solid stale battery plastics manu facturers.
  • electrode and electrolyte 4:: coated w ith the electrode and charge collector materials to are bonded together build a battery "from the inside out” [ ’ his enables thin hit ! 21 exemplarily illustrates a final solid slate battery 11 ex i b 1 e form factors without the need for hermetic packag according to the invention having a new and flexible form. ing. resulting in easy integration into vehicle and storage applications at low cost.
  • INV] 1N ⁇ N based on a transformative material that creates a new ionic conduction mechanism that provides a higher density of file inventor has developed a non-flammable solid poly sites for ionic transport and allows higher voltages to run mer electrolyte which is conductive at room temperature and through the electrolyte w ith no risk of thermal runaway or can he used in any battery ⁇ application
  • the three primary limitat ions w ith PI 10 are its m voltages through an electrolyte that is conductive mechani temperature limitations safety issues in commercial appli cally robust chemical and moisture resistant and nonflam cations. and its manufacturability mable not only at room temperature but over a ide range
  • Pf.O according to the prior art is conductive only above electrodes without costly thermal and safely mechanisms the material’s glass transition temperature (typical ly>50 ;> employed by the industry today
  • the film is facturing conditions tit batch scale
  • the polymer electrolyte created a doping procedure can be used using an electron allows the development of new high throughput low-cost acceptor
  • the dopant can be“pre-mixed” with manufacturing lines for solid electrolyte production and can the initial ingredients and extruded without post processing be integrated into a variety of product lines including 7 flic purpose of the electron acceptor is two-fold: release lithium and zinc battery manufacture
  • the poly ions for transport mobility and to create polar high density mer electrolyte is not limited to use in batteries but can be sites within the polymer to allow for ionic conductivity used in any device or composition that includes an electro Note: there is a clear distinction between electrical conduc lyte material for example the polymer electrolyte material tivity and ionic conductivity
  • Typical materials that can be used for the polymer include separation of ions in eleetrochromic devices electrochemi
  • liquid crystal polymers and polyphenylene sullide (ITS) or cal sensors and fuel cell membranes are liquid crystal polymers and polyphenylene sullide (ITS) or cal sensors and fuel cell membranes
  • MC I .1 shows a method of manufacturing a solid state any semicrystahine polymer w ith a crystallinity index battery using an extruded polymer according to the inven greater than 30%. or other typical oxygen acceptors f 1G 11 tion file material is compounded into pellets and then exemplarily illustrates a dynamic scantling calorimeter extruded through a die to make dims of variable thicknesses curve of a semicrystalline polymer fable 1 of TIG 12
  • the electrodes can be applied to the film using several illustrates exemplary formulations which were investigated techniques such as sputtering or conventional casting in a f lectron acceptors can be supplied in a vapor doping s lu rry. process. They can also be pre-mixed with the other ingre-
  • MG 4 shows a method of manufacturing of an ionic terminals
  • Typical electron acceptors suitable for use include polymer f ilm according to the invention which involves but are not l imited to: 2 3-dicyuno-5 6-dichlorndicyatmqui- heating the f ilm to a temperature around 2')v’ C anti then none (DDQ) (CTCl -N -O,) as exemplarily illustrated in TIG casting the him onto a chill roll which freezes the plastic.
  • DDQ diichlorndicyatmqui- heating the f ilm to a temperature around 2')v’ C anti then none (DDQ) (CTCl -N -O,) as exemplarily illustrated in TIG casting the him onto a chill roll which freezes the plastic.
  • 13 Tetracyanoelhylene P GNK) (C K , ) and sulfur trioxide
  • the film can be very thin in the range of 10 microns thick (SO, )
  • TIG 15 In sition temperature TIG. 6 shows a schematic of a solid
  • TIG 15 the conduct ivity of ionically conductive polymer polymer battery with polyethylene oxide according to the
  • G 7 is a dynamic scanning calo, . according to the invention (L ) is compared with that o f rimetry (DSC ) plot showing the glass transition temperature trifluoro methane sulfonate l’l 'lO (I I) and the liquid electro (T ) and the melting temperature of Ph O lyte C ' elgard/(T;C ' :TC ' /I iT T6)(0).
  • the conductivity of the file mechanism for ion transport involves "motion" of the ionic polymer according to the invention tracks the conduc amorphous chains above the T .
  • the cost fK i S is a plot which shows the relationship of ionic 4s "ductile f ailure" mode indicates that the material can he very conductivity versus temperature of traditional amorphous robust
  • fliO polymer (fliO) according to the prior art.
  • f lG 8 shows that f lammability of the polymer was tested using a LMJ4 traditional amorphous polymer (TTO) does not have mean Hume test for a polymer to be rated L f‘J4-V0. it must ingful conductivity at room temperature "sel f-extinguish” within 10 seconds and ’ not drip"
  • TTO LMJ4 traditional amorphous polymer
  • the invent ion uses a "crystalline or semi-crystalline poly w resistance high temperature behavior and good mechanical mer ” .
  • FIG. 9 which typically is properties it s necessary that the polymer material not be above a crystallinity value of 30%. and has a glass transition subject to chemical reaction or attack by lithium metal or temperature above 2(X) l; and a melting temperature above other active species of the electrode materials
  • the tradi 2 iff C Added to this are compounds containing appropriate tional lest for attack by polymers by lithium is done by the ions which are in stable form which can be modified after t;:: use of cyclic voltammetry This is a test where the polymer creation of the film.
  • f lG I ll show s the molecular structure is sandwiched between a lithium metal anode and blocking of the crystalline polymer.
  • Lite molecular weight of the stainless steel electrode L voltage is applied and it is swept monomeric unit of the polymer is 10b 1 6 g/mol from a low value (-2 volts) up to a high value greater than
  • Typical compounds for ion sources include but are not 4 volts
  • the current oulpul is measured to determine i f there limited to I i -O I iOI I and ZnO
  • Other examples are TiO, ti t is any significant reaction happening with Ihe polymer/ AW),. and the like Additionally other additives may be lithium metal.
  • I ligli output currents would indicate a chemi included to further enhance conductivity or current density.
  • cal reaction which is not desirable TIG 18 shows the result i;s 9.819.053 B 1
  • L sci lid. ionicully conducting material having an ionic stale battery file invention allows for a new generation of conductivity greater than 1 c KG 4 S/cm at room temperature batteries having the follow ing properties: and formed f rom a polymer an electron acceptor and at
  • polymer is polyphenylene sulfide and and the compound is
  • MGS. 19 21 and 21 show several elements of the solid is 23-dichloro-i 6-dicyano- 1 4-hcnzoquinonc stale battery which are. respectively: L) extruded electro-
  • FIG. 3 A A first figure.
  • FIG. 15 Patent Application Publication Jan. 5, 2017 Sheet 18 of 20 US 2017/0005356 L1
  • the present invent inn generally relates to polymer
  • Gel electrolytes are obtained by incorporating large goals requiring tradeoifs which limit the viability of end amount of liquid sol ent(s)/liquid plasticizer into a polymer applications such as grid-level storage and mobile power. matrix capable of forming a gel w ith the polymer host The demand for transformational batteries has reached the structure The liquid solvent remains trapped within the level of national interest driving a massive ellbrl to deliver matrix of the polymer and forms a liquid conductive path saf e electrochemical energy storage with higher energy way through the otherwise non-conduclive solid polymer density and lower cost. Gel electrolytes can tiller high ambient conductivities but
  • Composite polymer electrolytes are prepared sim These challenges make solid-slate electrolytes enormously ply by dispersing a small fraction of niicro/nanosixe inor attractive for battery development.
  • Solid electrolytes can ganic (ceramic /organic filler particles into the conventional provide substantial benefits such as non-leakage o f the polymer host The polymer acts as a first phase while f iller electrolyte more flexible geometry higher energy density material are di persed in a second phase As a consequence electrodes and improved saf ely. of dispersal the ionic conductivity mechanical stability and
  • 1‘olyelectrolyles include charged groups which are example.
  • Toyota Japan has announced development work covalently bonded to the polymer backbone which allow using a new “crystalline superionic crystal” which is a opposite charged ions to be very mobile.
  • the charged group glassy ceramic I i , C i eP ⁇ S ⁇ However this material only is flexible via segmental motion which is required for has high conductivity above 140‘ C and ceramics su ffer cationic diflusivily
  • the material is formed from at leasl one ionic is raised higher in the viscoelastic stale
  • the segmental compound, wherein the ionic compound comprises each motions are thought to promote ion motion hy both disrupt cationic and anionic diffusing ion:
  • the material is a thermoplastic
  • the material ' s ealionie diffusing ion comprises which the ion may diffuse file fact that polymer segmental lithium:
  • SUMMARY Oh fl lh IN VI INTI ON material is greater than 0.5 and less than 1 0:
  • ion is greater than 3 moles of cation per liter oi material ;
  • tive. polymer material is provided that comprises a crystal
  • the material’s ealionie diffusing ion comprise linity greater than 10%: a melting temperature: a glassy
  • the valence oi the diflusing ealionie ion is greater material may further comprise a plurality of charge transfer
  • Hie material includes greater than one diffusing
  • trans fer complex is positioned on a monomer [0041 ]
  • the material's diffusing anion is a hydroxyl ion:
  • the material's diffusing anion is monovalent : conductive, polymer material i provided liavinu,; a plurality [0043]
  • the material's diffusing anion and the diihtsing o f monomers: a plurality o f charge transf er complexes, cation are monovalent:
  • each charge transfer complex is positioned on a [0044]
  • the material s at least one cationic and anionic monomer
  • the material may have a crystallinity greater than diihtsing ion have a dilfusivity.
  • the anionic di fiu- 30% a glassy state which exists at temperatures below the sivity is greater than the cationic di ffusivily:
  • the material's al least one anionic diffusing ion has may include one or more of the following: a diffusivily than 1.0x 10 mVs:
  • the charge trans fer complex is formed by the [1)048]
  • the material ' s at leasl one anionic diffusing ion reaction of a polymer and an electron acceptor: and at least one ealionie di ihtsing ion has a dt flusivily
  • the material has a glassy state and at least one greater than 1 0x 10 m Vs:
  • the material has at least three dillusing ions: bone of the monomer:
  • the material includes more than one anionic di f [0050]
  • the material further includes a helcroatom incor fusing ion; porated in the ring structure or positioned on the backbone
  • Th e material comprises a single cationic dt flusmg backbone of the monomer adjacent the ring structure: ion. wherein the diffusivily of the cationic diffusin ion is [0053]
  • the material's heleroatom is sul fur greater than l .Ox l O - - in- s at room temperature: [1)054] fi l e material is pi-conjugated:
  • flic maternal comprises a single anionic diffusing [0055]
  • the material s tit leasl anionic diffusing ion per ion wherein the di lfusivity o f the anionic diffusing ion is monomer, and wherein at least one monomer comprises a greater than 1 0x 10 nrVS at room temperature; lithium ion:
  • the material wherein at least one cationic diffus comprises a plurality o f monomers ing ion comprises an alkali metal, an alkaline earlli metal, a wherein the molecular weigh! of llie monomer is grealer transition metal, or a post transition metal: than 100 grams mole:
  • flic material includes at least one anionic diffusing [0057]
  • the material is hydrophilic:
  • the material includes at least one cationic di flits i ng [0059]
  • the material has an ionic conductivity grealer than ion per monomer: 1 x 10 " S/cm at room temperature:
  • L further aspeel is a method of making a solid 1 x 1 0-' S/cm ill -40" ionically conductive polymer material comprising the tep
  • Th c material's cat ionic diiliising ion comprises oh mixing a polymer comprised o f a plurality ol monomers lithium and wherein the dillusivity oP ⁇ Ii ⁇ iiih ion is greater and a compound comprising ions to create a iirst mixture: llian 1.0x 10 nr/s al room temperature: doping the first mixture with an electron acceptor to create
  • the material in non -Hummable a second mixture: and healing the second mixture
  • L f urther aspect is a method of making a solid second material wherein the second material is selected from ionically conductive polymer material comprising the steps a group comprising a eleetroeheniieally active material an of: mixing a polymer comprised of a plurality of monomers electrically conductive material a rheological modifying and an electron acceptor to create a lirsl mixture; heating the material and a stabilizing material: first mixture to create an intermediate material comprising
  • the material is in the shape of a f ilm: charge transfer complexes: mixing the intermediate material
  • the base polymer comprises a plurality of mono and anionic diiliising ion via oxidation by the electron mers. and wherein the molar ratio of monomer to electron acceptor: acceptor is equal to or greater than 1 : 1 :
  • he base polymer has a glass transition tempera a base polymer electron acceptor and an ionic compound:
  • base polymer is a conjugated poly
  • polymer is greater than K0 l; ( ' .:
  • the ateriuTs base polymer is PPS or a liquid
  • fi l e weight ratio of the base polymer and the ionic crystal polymer: compound in the mixing step is less than 5 : 1 :
  • fhe material’s ionic compound reactant is an [0091] Positive pressure is appl ied to the mixture in the oxide chloride hydroxide or a salt: heating step;
  • a solid ionically conducting macro- [0096] An additional mixing step of mixing the solid molecule and a material including the macromolecule is ionically conductive polymer material with a second male- provided which is comprised of: rial:
  • a cationic and anionic ddfusing ion wherein both [0099] further aspects include: An electrnchemically the cationic and anionic diffusing ions arc incorporated into active material composite comprising the material of previ the structure of the macromolecule: ous aspects and an eleetroeheniieally active material:
  • a battery comprising the material of previous mer material when a cationic or anionic diffuse along the aspects:
  • a fuel cell comprising the material oi previous
  • this aspect may include on or more of the
  • the material has an ionic conductivity greater than [ 1 1]
  • An electrolyte comprising the material of previous aspects:
  • T h material s al least one cationic diiliising ion
  • a process for conducting ions comprising the male- comprises an alkali metal an alkal ine earth metal a transi rial of previous aspects: and
  • Lh aspect is a method of making a solid ionically rial of previous aspects:
  • conductive polymer material comprising the steps of: mix [01 07]
  • liquid at room temperature L S 2017 000535 z ⁇ 1 Jan. 5, 2017
  • I in id f Ki. 1 is a plot of a cycle lest of I ithiuni Ion cells ments of the disclosure the following explanations of spe using I CO cathodes containing the solid ionically conduc cif ic terms are provided:
  • L depolarizer is a synonym of electrocbemically
  • [OU ti] I K r 4 is a DSC plot described in Hxnmple 10: tion and elcctmchcmicahy active material
  • I C r 5 is a plot o f the measured conduct ivity trode has more than one eleclroactive substances they can be relative temperature as described in Comparative hxample referred to as codepolari/ers.
  • FIG. 7 is a plot of the measured conductivity for [0117] Solid electrolytes include solvent free polymers samples of the material described in hxample 14: and ceramic compounds (crystall ine and glasses )
  • 10121 1 BIG 9 is a NMR dithusiviiy plot for a omparative' and different from a material in a liquid phase.
  • the atomic structure of solids can be either crystalline or amorphous material described in Hxample 1 7:
  • Solids can be mixed with or be components in composite
  • FIG 1 1 is a NMR spectra of the material described
  • [ 125] 1 ' 1( 1 1 1 is a NMR spectra of the electron acceptor ionic conductivity are deiined as not being solid electrolytes described in hxample 18 in that they rely on a liquid phase for their ionic conduct ivity
  • FIG 14, ⁇ is a NMR spectra of the material
  • a polymer is typically organic and comprised o f described in Hxample 18
  • FIG I S Ls a NMR spectra of the material described
  • Polymers can be made into in Hxample 1 products by injection blow and other molding processes
  • Flti l b is a graphic depiction of a battery using the extrusion pressing stamping three dimensional printing material as described in Hxample HJ. machining and other plastic processes. Polymers typically
  • U 1 21 Fit; 1 is a discharge curve for the battery as volu e to permit sequences of segments of the polymer described in hxample 22 macromolecule to move together as a unit.
  • U 1 21 Fit; 1 is a discharge curve for the battery as volu e to permit sequences of segments of the polymer described in hxample 22 macromolecule to move together as a unit.
  • o f a polymer there is no segmental motion of the
  • litis heating step can be done when in a transition are done by measuring a physical properly oi the separate step from any mixing or can completed while polymer e g volu e enthalpy or entropy and other deriva mixing is being done
  • the heat ing step can be performed tive properties as a function oi temperature
  • the glass regardless oi lbe form of the mixture (e g film particulate transit ion temperature is observed on such a plot as a break etc )
  • ail three compo in the selected properly (volume of enthalpy) or from a nents are mixed and then extruded into a film l lie him is change in slope (heal capacity or thermal expansion coef heated to complete the synthesis
  • An aspect of the method of synthesis is mixing the the relative areas of the amorphous and crystalline phases.
  • base polymer ionic compound and dopant together and [014.1] L polymer film is generally described as a thin heating the mixture in a second step
  • the dopant can he portion of polymer but should be understood as equal to or in the gas phase the healing step can he performed in the less than 300 micrometers thick presence of the dopant
  • the mixing step can be performed in
  • the ionic conductivity is an extruder blender mill or other equipment typical of different from electrical conductivity.
  • Ionic conductivity plastic processing The heating step can last several hours depends on ionic diflu ivily and the properties are related by (e g twenty-four (24) hours) and the color change is a the Nernsl-T.instein equation Ionic conductivity and ionic reliable indication that synthesis is complete or partially diffusivily arc both measures of ionic mobility. An ionic is complete Additional heating past syslhesis does not appear mobile in a material if its diffusivily in the material is to negatively affect flic material.
  • the healing can be applied to flic mixture during the difficult to detect at low temperatures Hquipmenl detection second mixture step or subsequent to the mixing step limits can be a f actor in determining small mobility amounts [1) 152]
  • the base Mobil ity can be understood as diffusivily of an ion at least polymer and the dopant are first mixed and then healed 1 x 1 0 1 m Vs and preferably at least I xl O ’ m 7s which
  • This healing step can b applied a f ter the mixing or during both communicate ai l ion is mobile in a material and produces a color change indicating the formation of the
  • lid polymer kmicully conducting material is a charge transfer complexes and the read ion between the sol id that comprises a polymer and that conducts ions as will dopant and the base polymer
  • the ionic compound is then he further described mixed to the reacted polymer dopant material to complete
  • An aspect of the present invention includes a the formation o f the solid ionically conduct ing polymer method f synthesizing a solid ionically conductive polymer material
  • Typical methods of adding llie dopant are known to a dopant and an ionic compound fi l e components and th e skilled in the art and can include vapor doping of a iilm method oi ynthesis are chosen for the particular application containing the polymer and ionic compound and other o f the material
  • the selection oi the polymer dopant and doping methods know n to those skilled in the art
  • Upon ionic compound may also vary based on llie desired perfor doping the solid polymer material becomes ionically con mance of llie materi l. Tor example the desired components ductive.
  • llial lie do ing acts to activate the and method oi ynthesis may he determined by optimization ionic components oi lbe solid polymer materia] so they are o f a desired physical characteristic (c g ionic conductivity) diffusing ions
  • 1 lie method of synthesis can also vary depending above described mixtures during the initial mixing steps on tlie particular components and the desired form of the end secondary mixing steps or mixing steps subsequent to lietil material (e.g. film particulate etc )
  • the method ing include but are not limited to includes the basic steps o f mixing at least two o f the depolarizers or cleclrocbemically active materials such as components initially adding the third component in an anode or cathode active materials electrically conduct ive optional second mixing slop and lien ling the components materials such as carbons rheological agents such as binders reactants to synthesis the solid ionically conducting polymer or extrusion aids (e g ethylene propylene diene monomer material in a heat ing step
  • the "KPDM”) catalysts and other components useful to achieve resulting mixture can be opt ionally formed into a film oi the desired physical properties of the mixture desired size I f the dopant was
  • U 1561 Polymers are typically not electrically conductive 1’olysul (one Co-polymers including monomers o f the listed hor example virgin PPS has electrical conductivity of HG- polymers and mixtures of these polymers may also be used
  • S cm - l hon-electrically conduct ive polymers are suitable for example copolymers of p-hydroxyben/oic acid can be reactant polymers appropriate liquid crystal polymer base polymers fable 11 157
  • polymers useful as reactants can details non-limiting examples o f reactant polymers useful in possess an aromatic or heterocyclic component in the back the present invention along with monomer structure and bone of each repealing monomer group and a heteroalom some physical properly information which should be con either incorporated il l the heterocyclic ring or positioned sidered also non-limiting as polymers can take multiple along the backbone in a position adjacent the aromat ic ring forms which can aifect their physical properties
  • Dopants are those that are temperature
  • the base polymer has a melting
  • polymer include liquid crystal polymers and polyphenylene compound and a dopant arc required.
  • sullidc also known as ITS. or semi-crystalline polymer with examples include I LO. LiOl l. ZnO. 1KT. Al NaOl I.
  • the dopant is an electron acceptor bis(fluorosulfonyl)imidc).
  • Lithium bis(oxalato)borate Lithium bis(oxalato)borate (Lil S such us. DDQ. TCNL. ehloranil and sulfur trioxide (803) (( ’ Tl,) , "I ii SOB”) and other lithium salts and combinations file electron acceptor can be“pre-mixed" w ith all other thereof Hydrated forms (e.g.
  • lnonohydride of these com ingredients and extruded without post-processing or alter pounds can he used lo simplify handling of the compounds natively a doping procedure such as vapor doping can he
  • Inorganic oxides chlorides and hydroxide are suitable ionic used to add the electron acceptor to the composition after compounds in thal they dissociate during synthesis to create other components are mixed such as in an extruder and at least one anionic and cationic diffusing ion Any such formed into a Him
  • ionic compound thal dissociates lo create al least one anionic [01 65]
  • Typical compounds including an ion source or and cationic dillusing ion would similarly be suitable Mul "ionic compounds’ for use in this aspect o f the invention tiple ionic compounds can also be usef ul thal result in include but are not limited lo. Li ,0. LiOl l. ZnO. Tit),. multiple anionic and cationic di ffusing ions can be preferred L1 O ,. 1 i f LSI.
  • the ionic compounds contain appro depends on the utility desired for the material Lor example priate ions in stable form which are modified lo release the in an application where it ould be desired lo have a lithium ions during synthesis o f the solid ionieally conducting cation a lithium hydroxide or a lithium oxide convertible to polymer material.
  • BPS and ehloranil pnw er are mixed in a 4 2: 1 non-limiting group of such lithium ionic compounds molar ratio (base polymer monomer to d pant ratio greater includes those used as lithium salts in organic solvents. than 1 : 1 )
  • the mixture is then heated in arg n or air at a high
  • reaction mixture is then strated.
  • ionic compounds including alkaline metals alkaline regromid to a small average particle si/e between 1 -40 earth metals transition metals and post transition metals in micrometers J iTLSI is then mixed with the react ion mix a form that can produce both the desired cat ionic and anionic ture to create the synthesized solid ionieally conducting diffusing species are appropriate as synthesis reactant ionic polymer material.
  • Lithium cobalt oxide (I iCoCLii”! CO”) cathodes maximize the effectiveness of the synthesis reaction to were prepared containing the synthesized material from produce a highly conductive material.
  • Substantially pure Lxample 1 The cathodes used a high loading of 70% 1 CO reactants with generally high purities o f the dopant base by eight which is mixed w ith the solid ionieally conductive polymer and the ionic compound are preferred and purities polymer material and an electrically conducting carbon i;S 2017/0005356 L 1 Jan. 5, 2017
  • Culls were prepared using lithium metal amides, pern us oxygen, air. transition metal oxides, ineluding MnO ,. or any polypropylene separator and a standard I d-ton liquid elec suitable electron acceptor etc
  • trolyte composed of I iPKi salt and carbonate-based sol [0177]
  • the cells were assembled in a dry glovebox and cycle source is a salt, a hydroxide, an oxide or other material tested. containing hydroxyl ions or convertible to such materials,
  • TBS polymer and I iOI I monohydrale were added to a higher charge voltage of 4 5V, which ut ilizes a higher together in the proportion of 67% to 33% (by wl ). respec percentage o f lithium f rom the cathode, and resulted in the tively. and mixed using jet milling Additional alkaline high capacity of >140 niAli/g The slight drop in capacity battery cathode components were additionally mixed: ith cycle number observed for the 4.5V charge tests is MnO,. Bi,0.
  • a zinc-manganese dioxide alkaline cell was cre
  • the base polymer of this aspect o the invention has a glass ated using the cathode of T.xample 4 and a commercial transit ion temperature above 80‘ ‘ C , and pref erably above non-woven separator (NKK). /n foil anode, and 6M I iOI I 120 l: and more preferably above 150 1 ’ Ch. and most solution as an electrolyte.
  • C. file base polymer has a melting [1) 181 ]
  • the cell was discharged under constant current temperature of above 25(G C . and preferably above 2 0 1' conditions of 0 5 tu ⁇ /cm2 using a Rio-I ogic VST 15 test and more preferably above 30(T C system
  • the specific capacity o f MnQ2 was found to be 303
  • the solid ionically conducting poly aspect o f the invention are DDQ cbloranil TCNT, SO,.
  • mer material is used in a metal air battery and comprises a Oxygen (including Air).
  • Oxygen including Air
  • MnO, and other etal oxides etc base polymer a compound comprising an ion source and a
  • 1721 fhe compound including an ion source of the solid, dopant, fhe polymer can be selected from the group BBS. ionically conducting polymer material having mobility for l.C ' B. Bolypyrrole. Tolyaniline. and
  • hydroxyd ions includes a salt a hydro ide, an o ide or other [0184] Polysulfone and Other Base Polymers material containing hydroxyl ions or convertible to such [0185]
  • the dopant may be an electron acceptor or com materials, including hut not limited to I iOI I, NaOI L KOI I, pound containing functional electron acceptor groups I TO. l .iNO etc capable of initialing an oxidizing read ion w ith the polymer
  • Typical dopants are DDQ. chloranil. TCNT. S03. ozone,
  • the ionic compound comprising ion source can be in a form of salt hydroxide I iOI I monohydrate in the proportion of 67% to 33% (by oxide or other material containing hydroxyl ions or convert wt ), respectively and mixed using jet nulling DDQ dopant ible to such materials, including, but not limited to.
  • I iOI I. was added via vapor doping to the resulting mixture in the Na(2>I I. KOI I. Ti20. I iN03. etc.
  • this aspect of the invention related to manufac tive polymer material w ith a variety of carbons Specifi ture of a solid ionically conducting polymer material cally: TIMCAL SLPTR C45 Conductive Carbon Black MnO, composite cathode
  • the base polymer can be a semi- (('45 ) Timcal SlT ifi (synthet ic graphite), A5303 carbon cryslalline having a crystall inity index greater than 30% or black from Ashbury anil natural vein graphite nano 99 from a f ully crystalline polymer and can be selected f rom a group Ashbury (K 9 ) Carbon content was varied f rom 15 to 25% which consists of a conjugated polymer or a polymer which wl %.
  • the dopant is an electron acceptor or the coin lop facing the cathode Cells w ere discharge at room oxidant
  • dopants are DDQ. cltlo- temperature using a MTI coin cell tester at a 0.5 mA constant ranil. letracyanoelhylene also known as TCNT, SO ; , ozone. current. L S 2017/0005356 L 1 Jan. 5, 2017
  • the medal (or other ductive polymer material can vary based on the reactants cation) oxides yield ihe metal (or other cation) cation and used flic specific ion mobility and anionic and cationic hydroxyl ions diffusing ions are derived from the material synthesis: i;S 2017/0005356 L 1 Jan. 5, 2017
  • Hxample 1 was conducted to determine the water content o f the material After storage of the material in a dry atmo
  • thermogravimetric analysts was con
  • the base polymer glass transition from 3 0 Ml’a to 4 Gl’a fi l e synthesized material remains a temperature Tg is between 80- 100” C , however, in the DSC thermoplast ic, and can be reformed using plastic processing plot no Tg inflection appears and it is believed that upon techniques
  • the materia] o f Hxample 3 was healed in excess synthesis, the solid ionically conductive polymer material of its melting point and then allowed to cool The material loses its viscoelastic slate which was evident in the PI’S base w as then reformed into a iiltn.
  • the material is show n to polymer and the gla sy stale extends below the temperature both have a high modulus and to be thermoplastic L S 2017/0005356 L 1 Jan. 5, 2017
  • ionically conductive material has a hi dilfusivily of 5.7x temperature dependence of the conductivity for the solid
  • mult iple ions which can diffuse and be mobile and to polymer electrolyte material i not occurring as the material
  • polymer material has a similar level of ionic conductivity [1)225] file ditfusivity of the Ol ff ion was 4.1 c KG ' nr/s at room temperature Thus the solid ionically conductive relative to liquid electrolytes.
  • polymer material has a very high di fhision rale for a solid
  • sol id ionically conductive polymer material is greater than
  • I iPON has a cation di ffusiv tty D o f 1 0 meaning that the I i ions carry all the electric current ( I i ) of 0 54x 10 17 niff s at 100" C [ ' his di flits ivily is about
  • Anion mobility results in electrode polarization eifects eighty limes smaller than the dilfusivity of the material of which can limit battery performance.
  • a solid ionically conductive polymer material having a [1)241] Referring to l lti. 13 which displays the 'C spec crystallinity greater than 30%: a glassy stale: and both at trum MAS KMR spectrum of electron acceptor compound least one cat ionic and anionic di flusing ion wherein at least taken on a 500 Ml lz instrument by direct polarization with one (in tins aspect both diffusing ions) di ffusing ton is proposed spectral assignments o f the electron acceptor mobile in the glassy stale. DDQ Because there is no hydrogen in this molecule the
  • Llxample 19 electrolyte The material can be in a particulate slurry film
  • the centration in llie material from hxample can be accom material can he interposed between electrodes or between an lished by inserting the material into an interior coaxial lube electrode and a current collector positioned encapsulating a and having it surrounded by an external ref erence solut ion of current collector or electrode or positioned anywhere where a shi ft reagent complex such as lithium Dysprosium poly ionic conductivity is required.
  • TIG 16 all phosphate (Dy). Referring to TICi. 15.
  • the quantif ication oi lithium in the sample In the measured film shaped electrodes and the interposed separator or elec sample the lithium cation concentration was found to be trolyte can be independent structure or be a ffixed to each about three moles per liter of materia] (
  • FIG when used w ith other battery components such as eleclro- 18 shows the resulting discharge curve over many cycles chemically active materials including intercalation materi [0252]
  • the charge-discharge curves show almost no polar als. electrically conductive additives rheological agent and ization. and the elite iency is at least 99% This result other additives In addit ion at high voltages above 4 0
  • An anode comprises lithium metal 10 l ixa tuple 22
  • I iS battery is constructed which includes lithium intercalation material is chosen the solid ionically conduc etal anode and a sul fur cathode made in the construction tive polymer material is intermixed therew ith
  • Material from hxample 1 is used in comprises both a cathode collector (not shown) and an making the battery.
  • the solid polymor Toting’ s modulus which is the ratio of stress to strain
  • the material can transport lithium ions while blocking the poly- range of Young’s modulus f or the electrolyte made f rom the sul f ide ion f rom reaching the anode
  • the sol id polymer solid polymer material is 5 0 MPa-4 0 C iPa and it can he material limits the solubility oi ’ sulfur particles and transport engineered to be higher by utilizing additives such as glass of sullidos. thereby enabling more ol ' lhe sulfur to participate liber or carbon fiber if required.
  • sol id electrolyte must remain stable over a fhis improved capacity relat ive a battery comprising a w ide temperature range w ithout curling or puckering laying standard cathode containing only sulfur and carbon is shown completely lint.
  • the ionic transport properties of in f Ki. 19. was the solid electrolyte of the present invention vary with taken at room temperature file solid polymer material does temperature the structural integrity remains stable even not enable“indiscriminate di lfusion” typical o f liquid elec when exposed to extreme heat as will be more fully trolytes and some typical polymer electrolytes hnl instead described below
  • the solid ionically conducting polymer mate the material during synthesis
  • sulhdes cannot diffuse rial meets the requires of a separator and solid polymer and are instead non-ionically conductive mu eh like any electrolyte as it performs each of the above listed require other ion other than the dillusing anion(s) and cation(s) ments
  • the solid polymer electrolyte possesses
  • the material can act as an ion separation memhrane in a Young’s modulus greater than 3 0 MPa. thickness less than that it can be engineered to enable ion mobility for only 50 micrometers isotropic ionic conductivity dilfusivity of selected ions. multiple ions at temperatures as low as -45 1; C.. stability
  • solid ionically conducting poly materials and electrically conductive additives at high volt mer material acts as a solid electrolyte As a solid electrolyte ages thermoplastic and moklable
  • L separator is a ion permeable membrane plaeed [1)264] file solid polymer material was tested for flamma between a battery ⁇ ’ anode and cathode dhe main fnnet ion of bility according to the parameters o f the 1 JI 94-VO flam a separator is to keep the two electrodes apart to prevent mability Test
  • the sol id polymer material was found to he electrical short circuits while also allowing the transport of virtually non-llammahle self-extinguishing in two sec ionic charge carriers that are needed to close the circuit onds By UI 4-V0 standards in order to be considered during the passage of current in an electrochemical cell This nonllammable. the material needs to self-extinguish in less separation and ionic transport operations arc required in all than ten seconds
  • the thickness o f a solid 1 L solid ionically conductive polymer material having: electrolyte can he measured using the ⁇ 41 1 om-K3 method a crystall inity greater than 30%; a melting temperature; by the Technical Association of lhe 1‘ulp and Paper Industry a glassy slate;
  • each monomer anionic dilhising ion is greater than 1 Ox 10 1 ' ni VS at room comprises an aromatic or heterocyclic ring structure posi tempera tu re. tioned in the backbone of the monomer
  • ion comprises lithium 49 The material of claim 1 wherein the ionic conduc
  • cationic and anionic diffusing ion have a diffusivity.
  • the material of claim 1 having an ionic conductivity the cationic diffusivity is greater than the anionic diffusivity. greater than 1 x 10 S/cm at room temperature
  • lithium is greater than 3 moles of lithium per liter of 5.3 fhe material of claim 1. where the cationic diffusing material. ion comprises lithium and wherein the diffusivity of lithium
  • cationic and anionic diffusing ion have a diffusivity. wherein a plurality of monomers wherein each monomer com the anionic diffusivity is greater than the cationic diffusivity. prises an aromatic or heterocyclic ring structure: i;s 2017 0005356 L 1 Jan. 5, 20 17
  • file material of claim 59 wherein the material has an PI‘5 or a liquid crystal polymer.
  • One or more embodiments relate to electrodes including a solid polymer electrolyte, manufacturing methods thereof, and lithium batteries containing the same
  • Lithium secondary batteries provide an energy density by generating a discharge voltage below around 4 0 Volts.
  • the typical electrolytes used in these batteries can decompose and limit the life of the battery.
  • the electrolytes that have been developed so far do not afford such a high state of charge, and electrolyte stability at satisfactory levels
  • Typical electrolytes used in lithium secondary batteries also limit the temperature range of useful performance of such batteries L solid ionically conductive polymer material with high conductivity over a wide range of temperatures, including room temperature and below has been demonstrated to provide high performance over a wide temperature range.
  • the current state-of-the-art lithium ion electrode fabrication process involves several steps: mixing, slurry coating, drying, calendaring and electrode finishing. Some of these steps can be eliminated by using an extruded electrode method, incorporating the solid polymer electrolyte into the Lithium battery electrode
  • a battery comprising: an anode having a first electrochemical! ⁇ active material; a cathode having both a second electrochemically active material and a first electrolyte; a second electrolyte interposed between the anode and the cathode, wherein at least one of the first electrolyte and second electrolyte comprises a solid polymer electrolyte; wherein the solid polymer electrolyte comprises both at least one cationic and anionic diffusing ion, wherein at least one cationic diffusing ions comprises lithium
  • the battery the solid polymer electrolyte further comprises: a crystallinity greater than 0%; a melting temperature; a glassy state; and wherein at least one diffusing ion is mobile in the glassy state
  • Further aspects of the battery can include one or more of the following:
  • the battery wherein the solid polymer electrolyte comprises a plurality of monomers, and wherein each charge transfer complex is positioned on a monomer
  • the battery wherein the electronic conductivity of the solid polymer electrolyte is less than 1 x 10 s S/cm at room temperature.
  • the battery wherein the solid polymer electrolyte comprises: a plurality of monomers; a plurality of charge transfer complexes, wherein each charge transfer complex is positioned on a monomer; wherein the electronic conductivity of the solid polymer electrolyte is less than 1 x 10 K S/cm at room temperature
  • the solid polymer electrolyte further comprises both a cationic and anionic diffusing ion, whereby at least one diffusing ion is mobile in a glassy state of the solid polymer electrolyte, and wherein the crystallinity of the solid polymer electrolyte is greater than 30%
  • the battery wherein the melting temperature of the solid polymer electrolyte is greater than 250°C
  • the battery wherein the solid polymer electrolyte is non-flammable wherein the solid polymer electrolyte is non-flammable.
  • the battery wherein the Young’s modulus of the solid polymer electrolyte is equal to or ureater than 3 0 MPa
  • the battery wherein the ionic conductivity of the solid polymer electrolyte is greater than 1 0 x 10 ° S/cm at room temperature
  • the solid polymer electrolyte comprises a single cationic diffusing ion, wherein the single anionic diffusing ion comprises lithium, and wherein the diffusivity of the eationie diffusing ion is greater than 1 0 x 10 L m7s at room temperature
  • the battery wherein the solid polymer electrolyte comprises a single anionic diffusing ion, and wherein the diffusivity of the anionic diffusing ion is greater than 1.0 x 10 12 nr/s at room temperature.
  • the battery wherein one of the at least cationic diffusing ion, has a diffusivity greater than l O x l O ⁇ nTVs
  • one of the at least one anionic diffusing ion has a diffusivity greater than l O x l O ⁇ nf/s
  • the battery wherein one of both the at least one anionic diffusing ion and at least one cationic diffusing ion has a diffusivity greater than l O x 10 12 nr/s
  • the battery wherein the solid polymer electrolyte has an ionic conductivity greater than 1 x 10 4 S/cm at room temperature.
  • the wherein the solid polymer electrolyte has an ionic conductivity greater than 1 x 10’ S/em at 80“C
  • the battery wherein the solid polymer electrolyte has an ionie conductivity greater than 1 x 10 ' S/em at -40“C
  • each at least one cationic and anionic diffusing ion have a diffusivity, wherein the cationic diffusivity i s greater than the anionic diffusivity
  • the battery wherein the cationic transference number of the solid polymer electrolyte is greater than 0 5 and less than 1 0
  • the battery wherein at least one anionic diffusing ion comprises fluorine or boron
  • the battery wherein the solid polymer electrolyte comprises a plurality of monomers and wherein there is at least one cationic diffusing ion per monomer.
  • the battery wherein there is at least one mole of the lithium per liter of solid polymer electrolyte
  • the battery wherein the solid polymer electrolyte comprises a plurality of monomers, wherein each monomer comprises an aromatic or heterocyclic ring structure positioned in the backbone of the monomer.
  • the battery wherein the solid polymer electrolyte further includes a heteroatom incorporated in the ring structure or positioned on the backbone adjacent the ring structure.
  • heteroatom is selected from the group consisting of sulfur, oxygen or nitrogen
  • the battery wherein the solid polymer electrolyte comprises a plurality of monomers, wherein the molecular weight of each monomer is greater than 100 grams/mole.
  • the battery wherein the charge transfer complex is formed by the reaction of a polymer, electron acceptor, and an ionic compound, wherein each cationic and anionic diffusing ion is a reaction product of the ionic compound
  • the battery wherein the solid polymer electrolyte is formed from at least one ionic compound, wherein the ionic compound comprises each at least one cationic and anionic diffusing ion
  • the battery wherein the charge transfer complex is formed by the reaction of a polymer and an electron acceptor.
  • the battery wherein the base poly er is a conjugated polymer.
  • the battery wherein the base polymer is PPS or a liquid crystal polymer
  • both the first and seeond electrolyte comprise the solid polymer electrolyte, wherein the electronic conductivity of the second electrolyte is less than 1 x 10 w S/cm at room temperature
  • the battery wherein both the first and seeond electrolyte comprise the solid polymer electrolyte
  • the battery wherein the anode comprises a third electrolyte, and wherein the third electrolyte comprises the solid polymer electrolyte.
  • the battery wherein the second electrolyte comprises the solid polymer electrolyte and is formed into a film, wherein the thickness of the film is between 200 and 15 micrometers
  • the battery wherein the second electrochcmically active material comprises an intercalation material
  • the battery wherein the second electro chemically active material comprises a lithium oxide comprising nickel, cobalt or manganese, or a combination of two or all three of these elements
  • the battery wherein the second electrochemically active material has an electrochemical potential greater than 4 2 volts relative lithium metal
  • the battery wherein the cathode has an electrode potential greater than 4 2 volts relative lithium metal
  • the battery wherein the electrically conductive material comprises carbon.
  • the battery wherein the cathode comprises 70-90 percent by weight of the second electrochemically active material
  • the battery wherein the cathode comprises 4- 1 5 percent by weight of the solid polymer electrolyte
  • the battery wherein the cathode comprises 2- 10 percent by weight of an electrically conductive material
  • the battery wherein the cathode is formed from a slurry.
  • the battery wherein the second electro chemically active material comprises a lithium oxide or a lithium phosphate that contain nickel, cobalt or manganese
  • the second electro chemically active material comprises a lithium intercalation material
  • the lithium intercalation material comprises lithium
  • the battery wherein the lithium intercalation material comprises Lithium Nickel Cobalt Aluminum Oxide; Lithium Nickel Cobalt Manganese Oxide; Lithium Iron Phosphate; Lithium Manganese Oxide; Lithium cobalt phosphate or lithium manganese nickel oxide, Lithium Cobalt Oxide, LiTiS 2 , LiNiO?, or combinations thereof
  • the battery wherein the second electrochcmically active material comprises an clcctrochemically active cathode compound that reacts with lithium in a solid state redox reaction
  • the battery' wherein the electrochcmically active cathode material comprises a metal halide; Sulfur; Selenium; Tellurium; Iodine; FeS; or l,i;-
  • the battery wherein the lithium intercalation material comprises Lithium Nickel Cobalt Manganese Oxide, wherein the atomic concentration of nickel in the Lithium Nickel Cobalt Manganese Oxide is greater than the atomic concentration of cobalt or manganese
  • the battery wherein the cathode is about 15 to 1 15 micrometers in thickness
  • the battery' wherein the first electrochcmically active material comprises an intercalation material.
  • the battery wherein the anode further comprises the solid polymer electrolyte, wherein the first electrochemically active material is mixed with the solid polymer electrolyte.
  • the battery wherein the first electrochcmically active material comprises lithium metal
  • the battery' wherein the lithium metal in the anode 20 micrometers or less in thickness
  • the battery further comprising an anode current collector in ionic communication with the anode, wherein lithium deposits on the anode current collector when the battery is charged
  • the battery wherein the density of the lithium deposited on the anode current collector is greater than 0 4 g/cc
  • the battery further comprising an anode current collector in ionic communication with the anode, wherein the electrolyte is positioned adjacent the anode current collector
  • the battery wherein the first clcctrochemically active material comprises Silicon, Tin, antimony, lead, Cobalt, Iron, Titanium, Nickel, magnesium, aluminum, gallium, Germanium, phosphorus, arsenic, bismuth, zinc, carbon and mixtures thereof
  • the battery wherein the second electrochemically active material comprises an intercalation material, wherein the first electrochemically active material comprises lithium metal
  • the battery wherein the charged voltage of the battery' is greater than 4 1 volts
  • the battery wherein the charged voltage of the battery' is greater than 4 5 volts
  • the battery wherein the charged voltage of the battery' is greater than 5 0 volts
  • the battery wherein the lithium is cycled between the anode and cathode for greater than 150 cycles
  • the battery further comprising an anode current collector, wherein lithium is plated onto the anode current collector when the battery is charged, wherein the density of the lithium plated onto the anode current collector is greater than 0 4 g/cc
  • the battery wherein the lithium cycling efficiency is greater than 99° o
  • the battery wherein the second electrolyte comprises the solid polymer electrolyte and is formed into a film, and wherein the anode eom prises a third electrolyte, and wherein the third electrolyte comprises the solid polymer electrolyte, whereby the second electrolyte is attached to the anode
  • a method of manufacturing a battery comprising the steps of: mixing a polymer with an electron acceptor to create a first mixture; heating the first mixture to form a reaction product comprising a plurality charge transfer complexes; mixing at least one ionic compound comprising lithium with the reaction product to form a solid ionically conductive polymer material.
  • the method further comprising including mixing an intercalation material w ith the solid ionically conductive polymer material to form a cathode
  • the method wherein the cathode forming step further includes mixing an electrically conductive material with the intercalation material and the solid ionically conductive polymer material.
  • cathode forming step further comprising a calendaring step wherein the density of the cathode is increased
  • the method wherein the polymer is PPS, a conjugated polymer or a liquid crystal polymer.
  • the ionic compound is a salt, hydroxide, oxide or other material containing lithium.
  • the ionic compound comprises lithium oxide, lithium hydroxide, lithium nitrate, lithium bis-trifluoromethanesulfonimide, Lithium bis(fluorosulfonyl)imide, Lithium bis(oxalato)borate, lithium trifluorom ethane sulfonate), lithium hexafluorophosphate, lithium tetrafluorob orate, or lithium h e x a P u oro arse n ate. and combinations thereof
  • cathode is positioned adjacent an electrically conducting cathode current collector to form a cathode assembly
  • the method further comprising an electrically conducting anode current collector and an enclosure, and further comprising an assembly step wherein the solid polymer electrolyte is positioned between the anode current collector and the cathode assembly to form a battery assembly, and the battery assembly is placed within the enclosure
  • the battery further comprises a anode and a cathode, wherein the solid ionically conductive polymer material is formed into a film to form a solid polymer electroly te, further comprising attaching the film to the anode, the cathode or both the anode and the cathode
  • FIG. 1 is a representation of a battery cross section
  • FIG 2 is a plot of a capacity voltage (CV) curve of a battery deseribed in
  • Example 2 which is cycled at two different voltages
  • FIG 3 is cycle plot of a battery described in Example 4.
  • FIG 4 is cycle plot of a battery described in Example 4.
  • FIG. 5 is cyclic voltammetry plot of a battery described in F.x ample 5;
  • FIG. 6 is cyclic voltammetry plot of a comparative battery described in Example 6;
  • FIG. 7 is a representation of a test fixture cross section described in Ex ample 7;
  • FIG. 8 is cycle plot of a battery described in Fx ample 7;
  • FIG 9 is electrochemical impedance spectroscopy (FIS) plot of a battery described in Example 8.
  • FIG 10 is a voltage relative time plot of a battery described in Example 9
  • the present invention includes a lithium metal battery enabled to operate efficiently at a high voltage by a solid ionically conductive polymer material
  • a depolarizer is a synonym of electrochemically active substance, i.e., a substance which changes its oxidation state, or partakes in a formation or breaking of chemical bonds, in a charge-transfer step of an electrochemical reaction and electrochemically active material.
  • electrochemically active substance i.e., a substance which changes its oxidation state, or partakes in a formation or breaking of chemical bonds, in a charge-transfer step of an electrochemical reaction and electrochemically active material.
  • electrochemically active substance i.e., a substance which changes its oxidation state, or partakes in a formation or breaking of chemical bonds
  • Solid electrolytes include solvent free polymers, and ceramic compounds (crystalline and glasses).
  • A“Solid” is characterized by the ability to keep its shape over an indefinitely long period, and is distinguished and different from a material in a liquid phase
  • the atomic structure of solids can be cither crystalline or amorphous Solids can be mixed with or be components in composite structures
  • a solid material requires that that material be ionically conductive through the solid and not through any solvent, gel or liquid phase, unless it is otherwise described
  • gelled (or wet) polymers and other materials dependent on liquids for ionic conductivity are defined as not being solid electrolytes in that they rely on a liquid phase for their ionic conductivity.
  • a polymer is typically organic and comprised of carbon based macromolecules, each of which have one or more type of repeating units or monomers
  • Polymers arc light weight, ductile, usually non -conductive and melt at relatively low temperatures
  • Polymers can be made into products by injection, blow and other molding processes, extrusion, pressing, stamping, three dimensional printing, machining and other plastic processes
  • Polymers typically have a glassy state at temperatures below the glass transition temperature Tg. This glass temperature is a function of chain flexibility, and occurs when there is enough vibrational (thermal) energy in the system to create sufficient free-volume to permit sequences of segments of the polymer macromolecule to move together as a unit However, in the glassy state of a polymer, there is no segmental motion of the polymer
  • Polymers arc distinguished from ceramics which are defined as inorganic, non- metal lie materials, typically compounds consisting of metals covalently bonded to oxygen, nitrogen or carbon, brittle, strong and non-conducting
  • the glass transition which occurs in some polymers, is a midpoint temperature between the supercooled liquid state and a glassy state as a polymer material is cooled.
  • the thermodynamic measurements of the glass transition are done by measuring a physical property of the polymer, e.g volume, enthalpy or entropy and other derivative properties as a function of temperature
  • the glass transition temperature is observed on such a plot as a break in the selected property (volume of enthalpy) or from a ehange in slope (heat capacity or thermal expansion coefficient) at the transition temperature
  • the polymer molecular mobility slows down until the polymer reaches its glassy state.
  • polymer cry stallinity is the amount of this crystalline phase relative the amount of the polymer and is represented as a percentage Crystallinity percentage can be calculated via x-ray diffraction of the polymer by analysis of the relative areas of the amorphous and crystalline phases
  • L polymer film is generally described as a thin portion of polymer, but should be understood as equal to or less than 300 micrometers thick
  • Ionic conductivity depends on ionic diffusi vity, and the properties are related by the Nemst-F.in stein equation tonic conductivity and ionic diffusi vity are both measures of ionic mobility
  • An ionic is mobile in a material if its diffusi vity in the material is positive (greater than zero), or it contributes to a positive conductivity All such ionic mobility measurements are taken at room temperature (around 2 l“C), unless otherwise stated
  • Equipment detection limits can be a factor in determining small mobility amounts
  • Mobility can be understood as diffusivity of an ion at least 1 x 10 14 m 2 /s and preferably at least 1 xl 0 1 m 2 /s, which both communicate an ion is mobile in a material.
  • a solid polymer ionically conducting material is a solid that comprises a polymer and that conducts ions as will be further described
  • An aspect includes a method of synthesizing a solid ionically conductive polymer material from at least three distinct components: a polymer, a dopant and an ionic compound
  • the components and method of synthesis are chosen for the particular application of the material
  • the selection of the polymer, dopant and ionic compound may also vary based on the desired performance of the material Tor example, the desired components and method of synthesis may be determined by optimization of a desired physical characteristic (e g ionic conductivity)
  • the method of synthesis can also vary depending on the particular components and the desired form of the end material (e g film, parti eu late, ete ) However, the method includes the basic steps of mixing at least two of the components initially, adding the third component in an optional second mixing step, and heating the components/ react ants to synthesis the solid ionically conducting polymer material in a heating step
  • the resulting mixture can be optionally formed into a film of desired si/e If the dopant was not present in the mixture produced in the first step, then it can be subsequently added to the mixture while heat and optionally pressure (positive pressure or vacuum) arc applied All three components ean be present and mixed and heated to complete the synthesis of the solid ionically conductive polymer material in a single step
  • this heating step can be done when in a separate step from any mixing or can completed while mixing is being done
  • the heating step can be performed regardless of the form of the mixture (e g. film, particulate, etc.)
  • the synthesis method includes the basic steps
  • An aspect of the method of synthesis is mixing the base polymer, ionic compound and dopant together and heating the mixture in a second step As the dopant can be in the gas phase, the heating step can be performed in the presence of the dopant.
  • the 13 step can be performed in an extruder, blender, mill or other equipment typical of plastic processing.
  • the heating step can last several hours (e.g. twenty-four (24) hours) and the color change is a reliable indication that synthesis is complete or partially complete. Additional heating past synthesis (color change) does not appear to negatively affect the material
  • the base polymer and ionie compound ean be first mixed
  • the dopant is then mixed with the polymer-ionic compound mixture and heated
  • the heating can be applied to the mixture during the second mixture step or subsequent to the mixing step
  • the base polymer and the dopant are first mixed, and then heated.
  • This heating step can be applied after the mixing or during, and produces a color change indicating the formation of the charge transfer complexes and the reaction between the dopant and the base polymer
  • the ionic compound is then mixed to the reacted polymer dopant material to complete the formation of the solid ionically conducting polymer material
  • Typical methods of adding the dopant are known to those skilled in the art and ean include vapor doping of film containing the base polymer and ionic compound and other doping methods known to those skilled in the art. Upon doping the solid polymer material becomes ionically conductive, and it is believed that he doping acts to activate the ionic components of the solid polymer material so they are diffusing ions.
  • non-rcactive components ean be added to the above described mixtures during the initial mixing steps, secondary mixing steps or mixing steps subsequent to heating
  • Such other components include but arc not limited to depolarizers or clcctrochemically active materials such as anode or cathode active materials, electrically conductive materials such as carbons, rheological agents such as binders or extrusion aids (e g. ethylene propylene diene monomer“UPDVt”), catalysts and other components useful to achieve the desired phy sical properties of the mixture.
  • Polymers are typically not electrically conductive.
  • virgin PPS has electrical conductivity of 10’° S cm 1
  • Non-clcctrically conductive polymers arc suitable reactant polymers
  • polymers useful as reactants can possess an aromatic or heterocyclic component in the backbone of each repeating monomer group, and a hetcroatom either incorporated in the heterocyclic ring or positioned along the backbone in a position adjacent the aromatic ring
  • the heteroatom can be located directly on the backbone or bonded to a carbon atom which is positioned directly on the backbone.
  • Non-limiting examples of the polymers used in this aspect of the invention can be selected from the group including PPS, Poly(p-phcnylenc oxide)(‘PPO’), LCPs, Polyether ether ketone (‘PHUK.’), Polyphthalamide (‘RRL’), Polypyrrole, Polyaniline, and Polysulfone.
  • PPS Poly(p-phcnylenc oxide)(‘PPO’)
  • LCPs Polyether ether ketone
  • PRRL Polyphthalamide
  • Polypyrrole Polyaniline
  • Polysulfone Co-polymers including monomers of the listed polymers and mixtures of these polymers may also be used.
  • copolymers of p-hydroxybenzoic acid can be appropriate liquid crystal polymer base polymers
  • Table 1 details non-limiting examples of reactant polymers useful in the synthesis of the solid ionically conductive polymer material along with monomer structure and some physical property information which should be considered also non-limiting as polymers can take multiple forms which can affect their physical properties
  • Dopants that are useful as reactants in the synthesis of the solid ionically conductive polymer aterial are electron acceptors or oxidants. It is believed that the dopant acts to release ions for ionic transport and mobility, and it is believed to create a site analogous to a charge transfer complex or site within the polymer to allow for ionic 5 conductivity
  • Non-limiting examples of useful dopants arc qui nones such as: 2,3-dicyano- 5,6-dichlorodicyanoquinone (CsCbNTO?) also known as ‘DDQ’, and tetrachloro-1,4- benzoquinonc (C f ,Cl O;-), also known as chloranil, tetracyanoethylenc (C f ,N ) also known as TCNIty sulfur trioxide (“SO;’), ozone (trioxygen or CL), oxygen (O;-, including air), transition metal oxides including manganese dioxide (“MnCL”)
  • tonic compounds that are useful as reactants in the synthesis of the solid ionically conductive polymer material are compounds that release desired lithium ions during the synthesis of the solid ionically conductive polymer material
  • the ionic compound is 0 distinct from the dopant in that both an ionic compound and a dopant arc required
  • I.f-O Li Oil
  • LiNCL Liclear Organic Chemical Vaporous Chemical Vapor
  • I.iTFSI lithium bis- trifluoromethanesulfonimide
  • Li LSI Lithium bis(nuorosulfbnyl)imide
  • Lithium bis(oxalato)borate LiBftbCL “Li BOB”
  • lithium Inflate LiCFiChS lithium trifluorom ethane sulfonate
  • LiPF6 lithium hexafluorophosphate
  • LiBF4 lithium tetrafluoroborate
  • LiAsF6 lithium hexafluoroarscnatc
  • Hydrated forms e g monohydride
  • Inorganic oxides, chlorides and hydroxide suitable ionic compounds in that they dissociate during synthesis to create at least one anionic and cationic diffusing ion Any such ionic
  • the purity of the materials is potentially important so as to prevent any unintended side reactions and to maximize the effectiveness of the synthesis reaction to produce a highly conductive material
  • Substanti lly pure reactants with generally high purities of the dopant, base polymer and the ionic compound are useful, and purities greater than 98% arc more useful with even higher purities, e g LiOH: 99 6%, DDQ: >98%», and Chloranih >99% also useful
  • the battery 10 of an aspect in a cross sectional view includes both a cathode 20 and an anode 30 l he cathode is positioned adjacent or is attached to a cathode current collector 40 which can act to conduct electrons to the cathode l he anode 30 is similarly positioned adjacent or is attached to an anode
  • 1 8 current collector 50 which also acts to conduct electrons from the anode to an external load.
  • the solid polymer electrolyte 60 Interposed between the anode 50 and the cathode 20 is the solid polymer electrolyte 60 which acts both as a dielectric layer preventing electrical conduction and internal shorts between the anode and cathode while ionically conducting ions between the anode and cathode
  • the described battery components arc similar to typical battery components however the solid polymer electrolyte and its combination with each battery component is further described in aspects of the lithium cell
  • the anode current collector 50 is electrically conducting and positioned adjacent the solid polymer electrolyte film 60 Interposed between the anode current collector and the solid polymer electrolyte is an anode which can comprise any of the multiple typical lithium intercalation materials or lithium metal Upon charge the solid polymer electrolyte acts to conduct lithium metal to the anode, and to the lithium intercalation material in an aspect, or to the anode current collector if lithium metal is used In the aspect of a lithium metal anode excess lithium can be added to the cell and is maintained at the anode collector and can act as a deposition surface upon cell charging
  • useful anode materials include typical anode intercalation materials comprising: lithium titanium oxide (LTO), Silicon (Si), germanium (Ge), and tin (Sn) anodes doped and undoped; and other elements, such as antimony (Sb), lead (Pb), Cobalt (Co), Iron (he).
  • LTO lithium titanium oxide
  • Si Silicon
  • Ge germanium
  • Sn tin
  • other elements such as antimony (Sb), lead (Pb), Cobalt (Co), Iron (he).
  • anode intercalation material can be mixed with and dispersed within the solid ionically conducting polymer material such that the solid ionically conducting polymer material can act to ionically conduct the lithium ions to and from the intercalation material during both intercalation and deintcrcalation (or lithiation/dclithiation)
  • the lithium can be added with the cathode material, added to the anode as lithium foil, dispersed in the solid ionically conducting polymer material, or added to both battery components
  • the solid polymer electrolyte acts to transport the lithium metal to and from the anode and therefore must be positioned within the battery so it is enabled to do so
  • the solid polymer electrolyte can be positioned as a film layer in a planar or jellyroll battery construction, a convolute positioned around the anode current collector, or any other shape which enables the solid polymer electrolyte to perform its lithium ion conduction
  • the thickness of the solid polymer electrolyte can be in a desired range of uniform thicknesses such as 200 to 25 micrometers or thinner
  • a rheological or extrusion aid can be added such as LPDM (ethylene propylene diene monomer) in amounts necessary to affect the desired extrusion properties
  • the cathode current collector 40 is also a typical aluminum or other electrically conducting film onto which the cathode 20 can be located or positioned.
  • Typical clcctrochemically active cathode compounds which can be used include but are not limited to: NCA - Lithium Nickel Cobalt Aluminum Oxide (LiNiCoA10 2 ); NCM (NIMC) - Lithium Nickel Cobalt Manganese Oxide (LiNiCoMnO;-), LLP - Lithium Iron Phosphate (LibePCf), LMO - Lithium Manganese Oxide (LiMn ; -0 ); LCO - Lithium Cobalt Oxide (LiCoCL); lithium oxides tor phosphates that contain nickel, cobalt or manganese, and LiTiS2, LiN ⁇ i02, and other layered materials, other spinels, other olivines and tavorites, and combinations thereof.
  • NCA Lithium Nickel Cobalt Aluminum Oxide
  • NIMC NCM
  • LLP Lithium Iron Phosphate
  • LMO Lithium Manganese Oxide
  • the electrochemically active cathode compounds can be an intercalation material or a cathode material that reacts with the lithium in a solid state redox reaction
  • conversion cathode materials include: metal halides including but not limited to metal fluorides such as bebb, Bibb, Cub?, and Nlibb, and metal chlorides including but not limited to beCL, bed;-, CoCf-, NiCf-, Cud;-, and AgCl; Sulfur (S); Selenium (Se); Tellerium (Tc); Iodine (I); Oxygen (O), and related materials such as but not limited to pyrite (beS ?
  • an aspect is to increase the energy density by enabling as high a voltage battery as possible, therefore high voltage cathode compounds are preferred in this aspect.
  • Certain NCM or NIMC material can provide such high voltages with high concentrations of the nickel atom
  • NCMs that have an atomic percentage of nickel which is greater than that of cobalt or manganese such as NCM- ⁇ NCM ⁇ NCM ⁇ ⁇ .
  • PPS and chloranil powder are mixed in a 4 2: 1 molar ratio (base polymer monomer to dopant ratio greater than 1 : 1 ).
  • the mixture is then heated in argon or air at a temperature up to 350°C for about twenty-four (24) hours at atmospheric pressure A color change is observed confirming the creation of charge transfer complexes in the polymer- dopant reaction mixture
  • the reaction mixture is then reground to a small average particle size between 1 -40 micrometers
  • LiTFSl powder 12 wt % of total mixture
  • the solid, ionically conducting polymer material which is used as a solid polymer electrolyte in this aspect is referred to as a solid polymer electrolyte when thus used.
  • the solid polymer electrolyte can be used in multiple locations in a battery, including in an electrode, or as a standalone dielectric, non-electrochemically active electrolyte interposed between electrodes.
  • the solid polymer electrolyte can be the same material in all battery application, and in the aspect of a lithium battery if the ionic mobility of lithium is maximized, this property and attribute of the solid polymer electrolyte allows the solid polymer electrolyte to function well in an anode, cathode and as a standalone dielectric, non-clcctrochcmically active electrolyte interposed between anode and cathode electrodes.
  • the solid polymer electrolyte can vary so as to accommodate different properties that may be desired in an application
  • an electronically conductive material could be added to the solid polymer electrolyte or integrated into the solid polymer electrolyte during its synthesis thus increasing the electrical conductivity of the solid polymer electrolyte and making it suitable for use in an electrode and reducing and or eliminating the need for additional electrical conductive additives in such an electrode lf so used, such a formulation would not be appropriate for use as a standalone dielectric, non-electrochemically active
  • solid polymer electrolyte in an anode, cathode and as a standalone dielectric, non-el ectrochenii call y active electrolyte interposed between anode and cathode electrodes enables a battery designer to take advantage of the thermoplastic nature of the solid polymer electrolyte
  • the standalone dielectric, non-elcctrochcmically active electrolyte can be thermoformed onto the anode or cathode by being heated and fixed thereto, such as in a lamination process, or by being co-extruded and thus formed together with the electrode
  • all three battery components include the solid polymer electrolyte and are thermoformed together or coextruded to form a battery
  • Flee ironic conductivity of the synthesized material is measured using potentio static method between blocking electrodes, and was determined to be 6 5 x 10 S/cm or less than 1 x 10 w S/em
  • the conductivity of the material is calculated via the ernst- Hinstein equation, using the measured diffusion measurements, it was determined the associated calculated conductivity to be much greater than the measured conductivity. The difference was on average at least an order of magnitude (or l Ox). Therefore, it is believed that conductivity can be improved by improving ion dissociation, and the calculated conductivities can be considered within the range of conductivity
  • the cation transference number can be estimated via equation ( 1) from the diffusion coefficient data as: t- - D-/(D+ + D-) ( 1 )
  • the 1 1 is dependent on anion diffusion as lithium cation diffusion is high. As the cation diffusion is greater than the corresponding anion diffusion the cation transference number is always above 0 5, and as the anion is mobile the cation transference number must also be less than TO It is believed that a survey of lithium salts as ionic compounds would produce this range of cation transference numbers greater than 0 5 and less than TO As a comparative example, some ceramics have been reported to have high diffusion numbers, however such ceramics only transport a single ion, therefore the cation transference number reduces to 1 .0 as the D- is zero
  • Lithium cobalt oxide (LiCoO;-)(“LCO”) cathodes were prepared containing the synthesized material from Fxample 1 .
  • the cathodes used a loading of 70% LCO by weight which is mixed with the solid ionically conductive polymer material and an electrically conducting carbon.
  • Cells were prepared using lithium metal anodes, porous polypropylene separator and a standard Li-ion liquid electrolyte composed of LiPF f , salt and carbonate-based solvents The cells were assembled in a dry glovebox and cycle tested
  • the capacity in terms of the weight in grams of LCO used in these cells is displayed in FIG. 2. It can be seen that the capacity was stable when charged to 4.3 V, and consistent with the target of 0 5 equivalents of Li removed from the cathode during charging The cell was also cycled to a higher charge voltage of 4.5V, which utilizes a higher percentage of lithium from the cathode, and resulted in the high capacity of > 140 mAh/g The slight drop in capacity with cycle number observed for the 4 5 V charge tests
  • the performance of the ECO cathode containing the material of the present invention is favorably comparable to a slurry coated ECO cathode.
  • Example 1 Additional solid ionically conductive polymer materials are listing in Table , along with the material synthesized and described in Example 1 (PPS-Chloranil-LiTESl), which were prepared using the synthesis method of Example 1, along with their reactants and associated ionic conductivity (EIS method) at room temperature.
  • the solid ionically conductive polymer materials are measured and it is determined that the solid ionically conductive polymer materials: the electronic area specific resistance is greater than I xl Cd Ohm-cnr; can be molded to thicknesses from 200 micrometers down to 20 micrometers; possesses significant ionic mobility to very low temperatures, e g -40°C, and have ionic conductivities at room temperature greater than 1 0E-05 S/cm, 1 0E-04 S/cm, and l OE-03 S/em, and these ionic conductivities include lithium as one of the mobile ions being conducted through the solid ionically conductive polymer material
  • anodes were prepared with materials such as graphite (meso-carbon micro beads), silicon, tin, and lithium titanatc (LifTEOu, LTO) These materials were chosen for evaluation since they arc currently cither being used in
  • Li-ion cells Commercially available Li-ion cells, or are actively being researched for application to Li- ion anodes.
  • solid poly er electrolyte material was added to the active anode material and an anode was prepared These anodes were then tested by cycling versus a lithium metal anode with polypropylene separator and standard liquid electrolyte.
  • FIG 3 displays a cycle test of a Tin anode combined with the solid polymer electrolyte
  • the Li/Sn and solid polymer electrolyte coin cell is discharged at a constant current of 0 5 m/V and charged at a constant current of 0 2 mA
  • FIG 4 displays a cycle test of a Graphite anode combined with the solid polymer electrolyte.
  • the Li /Graphite and solid polymer electrolyte coin cell is discharged at a constant current of 0.5 mA, and charged at a constant current of 0.2 mA.
  • the solid polymer electrolyte w as found to be compatible with the anode materials and demonstrates the utility of the solid polymer electrolyte in preparing both cathodes and anodes for lithium ion cells Furthermore, the solid polymer electrolyte has been shown to be stable either as a stand-alone ionically conductive electrolyte and separator, or in combination with standard Li-ion separator and liquid electrolyte This flexibility in cell design provides an advantage to battery manufacturers where the battery chemistry, design and overall cell performance can be tailored to meet specific device requirements.
  • the Li/SPF./Ti coin cell was then placed on cyclic voltammetry (CV) test, where the voltage of the cell is varied at a constant scan rate (in this case, 2 niV/sec) between set voltage limits of -0.5V and 5 5V
  • the current is measured for the cell and plotted as a function of the voltage, as displayed in TIG. 5, which displays cyclic voltammetry of the Li/SPH/Ti cell, at a scan rate of 2 mV/sec, cycled between the voltage limits of -0 5 V and 5 5 V
  • This test is useful to simulate the use of the SPH in a high voltage cell in which the charged battery voltage extends upwards greater than 4 2 V and up to at least 5 5 V
  • Li-Ion batteries are limited in voltage range by the liquid electrolytes used in these systems Li-ion electrolytes typically containing carbonate- based solvents, for example: propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, etc , limit the positive voltage of the battery Typically, batteries of this nature can only be charged to 4 3 V, because the liquid electrolyte starts to oxidize and decompose above this potential The use of the solid polymer electrolyte in lithium-based batteries enables charging to a higher voltage, which in turn will increase the amount of energy stored in the battery and lead to longer battery run-time.
  • Charging to a higher voltage will also enable the use of higher voltage cathodes, such as lithium cobalt phosphate, NCV1 and other new ' cathode materials for lithium ion cells that have electrochemical potentials relative lithium metal greater than 4 3V
  • higher voltage cathodes such as lithium cobalt phosphate, NCV1 and other new ' cathode materials for lithium ion cells that have electrochemical potentials relative lithium metal greater than 4 3V
  • the research on these new high voltage cathodes has been hindered by a lack of stable electrolytes at voltages greater than 4 3 V
  • the solid polymer electrolyte solves this problem by providing a lithium ion conductive electrolyte which is stable at high voltages
  • FIG. 8 shows a plot of the voltage V relative time of a cell with > 420 charge- discharge cycles, using a current density of 0 5 mA/cnr and tested at room temperature.
  • the current is held constant and the voltage is measured, as can be seen on the y-axis of FIG 8
  • the voltage displayed by the cell during the constant current test depends on the polarization of the cell, which is related to the overall resistance of the cell (i e the higher the resistance of the cell, the larger the change in voltage, or higher polarization)
  • the overall resistance of the cell is due to the bulk resistance of the solid polymer electrolyte plus the interfacial resistance of the polymer electrolyte in contact with the lithium metal surfaces.
  • the FIG 8 plot shows that the polarization of the cell is relatively constant for the entire test.
  • FIG 8 plot voltage is above 1 0 V as the cell is put in series with a NiMH cell during testing.
  • eells were constructed using lithium metal anodes (20 mierometers or less in thickness), solid polymer electrolyte and lithium cobalt oxide cathodes containing the solid polymer electrolyte
  • the lithium cobalt oxide, LiCoO (‘LCO’) is used since this is a high voltage cathode material with a charged voltage over 4 V.
  • lithium metal anodes increases the energy density of the battery, since lithium metal has much higher capacity than a lithiated graphite electrode that is typically used in a Li-ion battery
  • the theoretical capacity of lithiated graphite is 072 niAh/g, while lithium metal has a capacity of 0860 mAh/g more than ten times the capacity of graphite anodes
  • FIG 9 shows electrochemical impedance spectroscopy (LIS) of the bipolar Li/S PH/Li Battery- L1G 9 shows the L1S initially, the LIS after 1 month of storage, after 2 months of storage, and after 3 months of storage.
  • LIS electrochemical impedance spectroscopy
  • the capacity of the LiCoO;- used in these cells was 124 mAh/g, which corresponds to the target 0.5 equivalents of Li removed from the cathode during charging.
  • the cycling efficiency for lithium was found to be over 99%, which matches or exceeds that found for liquid electrolyte systems Cycling efficiency is calculated by counting coulombs over a single cycle and comparing the charge and discharge cycles to calculate the efficiency ((charge out/ charge into battery-) times 100) Overall, these results demonstrate the function of the solid polymer electrolyte as an electrolyte for high voltage lithium-based battery systems
  • the density of the lithium deposited onto the anode current collector during battery- charging was measured and determined to be greater than 0.4 g/cc
  • Li/ solid polymer electrolyte /LCO cells were tested on open circuit storage This test utilized fully charged Li/SPL solid polymer electrolyte LCO cells, as described in Lxamplc 8, and stored the cells for a two-week period at room
  • the cells displayed good voltage stability, as displayed in FIG 10. Following the 2 weeks of open circuit storage, the cells were fully discharged and the discharge capacity was compared to the cell performance prior to storage. Both cells displayed 84 to 853 ⁇ 4 of pre-storage discharge (greater than 80%), demonstrating low self- discharge during the two- week storage, and further demonstrating the stability of the high voltage Li/ SPL /LCO battery system
  • the cell comprised a lithium metal anode
  • the solid polymer electrolyte was interposed between the anode and a slurry cathode
  • the slurry cathode also comprised the solid polymer electrolyte and the cathode is manufactured u ing a stepwise process
  • the process initially includes a polyvinylidene difluoride (PVDF) binder in a solvent such as A-Mcthyl -2-pyrrol idone ( MP) or Dimethylacetamide (DMA) Electrically conductive carbon and graphite and the solid polymer electrolyte arc then added in a first mixing step in which the carbon and solid polymer electrolyte remain stable and insoluble in the binder solvent This first mixture is then mixed in a second mixing step with a electrochemically active cath
  • the high density cathode is about 15 to 1 15 micrometers in thickness, and has a cathode coating density in the range of 1 . 2 to 3 6 g/cc.
  • the high density cathode is then added to the described secondary lithium cell and displays significant performance Specifically, the lithium cell displays voltage stability above 5 0V to at least 5.5V (greater than 4 1 V and 4 5 V); the lithium metal can be cycled through the solid polymer electrolyte a rates greater than 0.5 m.A/cm 2 , 1 0 m A/cm 2 and to at least 1 5 mA/cm 2 at room temperature, while also being able to cycle lithium in excess of an areal capacity of 3 0 mAh/cm’ for greater than 10 cycles, and greater than 18 0 mAh/em’; being cycled for greater than 150 cycles at 1 0 m. ⁇ err. and 0 25 mAh cm.
  • an anode comprising a first electrochcmically active material
  • first electrolyte and second electrolyte comprises a solid polymer electrolyte
  • the solid polymer electroly te has a glassy state, and comprises both at least one cationic and anionic diffusing ion, wherein at least one cationic di ffusing ions comprises lithium and wherein at least one diffusing ion is mobile in the glassy state 2
  • the solid polymer electrolyte comprises:
  • the glassy state extends in a range of temperatures of the solid polymer electrolyte from a melting temperature of the solid polymer electrolyte to a temperature lower than the melting temperature.
  • each charge transfer complex is positioned on a monomer
  • the electronic conductivity of the solid polymer electrolyte is less than 1 x 10 s S/cm at room temperature.

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Abstract

The invention features an electrode useful in an electrochemical cell. The electrode includes an electrochemically active material; an electrically conductive material; a solid ionically conductive polymer electrolyte; and a binder; wherein the binder is dispersed in an aqueous solution. The invention also features a method of making the battery including the electrode.

Description

TITLE OF THE INVENTION
BATTERY ELECTRODE WITH SOLID POLYMER ELECTROLYTE AND AQUEOUS
SOLUBLE BINDER
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR
DEVELOPMENT
Not Applicable.
BACKGROUND OF THE INVENTION
Methods of making battery electrodes, particularly lithium-ion batteries, typically require binders to both maintain electrode integrity and to ensure adherence with corresponding current collector surfaces. The binders are used in electrode forming processes with appropriate solvents. Non-aqueous solvents are used with binders such as Polyvinylidene fluoride also known as polyvinylidene difluoride. Aqueous binders including water are less toxic, but water can damage electrolytes by, for example, disassociating electrolyte salts from the solute. Thus, prior art use of aqueous binders generally requires processes that isolate the aqueous solution from the electrolyte and/or additional process steps for addition of supplementary electrolyte after the aqueous solution is driven or removed from the electrode.
BRIEF SUMMARY OF THE INVENTION
It has been surprisingly found that the solid ionically conductive polymer electrolyte described US Application 13/861,170 granted as US9,8 l9,053 and US Application 15/148,085 can enable the use of aqueous soluble binders without the previously required step of adding electrolytes. US Application 13/861, 170 granted as US9,8l9,053 and US Application 15/148,085 are incorporated herein in their entireties except for any definitions, subject matter disclaimers or disavowals, and except to the extent that the incorporated material is inconsistent with the express disclosure herein, in which case the language in this disclosure controls. The granted patent US9,8l9,053 and US Application 15/148,085 are included in this specification as respective Attachment A and Attachment B prior to the claim listing in this application. In one aspect, the invention features an electrode useful in an electrochemical cell. The electrode includes an electrochemically active material; an electrically conductive material; a solid ionically conductive polymer electrolyte; and a binder; wherein the binder is dispersed in an aqueous solution.
Further aspects of the invention including the electrode useful in an electrochemical cell can include one or more of the following embodiments:
In an embodiment, the binder is soluble in an aqueous solution.
In another embodiment, the binder is partially soluble in an aqueous solution.
In yet another embodiment, the electrode further includes a lithium.
In an embodiment, the electrochemically active material includes a graphite.
In another embodiment, the electrochemically active material is in an amount having a range of 70-90 wt. % of the electrode.
In yet another embodiment, the electrode further includes an electrically conductive current collector which is in electrical communication with the electrically conductive material.
In an embodiment, the electrode further includes a second binder which is soluble in an aqueous solution.
In another embodiment, the solid ionically conductive polymer electrolyte is in an amount having a range of 52-15 wt.% of the electrode.
In yet another embodiment, the solid ionically conductive polymer electrolyte has an ionic conductivity of at least lxl O 4 S/cm.
In an embodiment, the solid ionically conductive polymer electrolyte has a crystallinity of at least 30%.
In another embodiment, the solid ionically conductive polymer electrolyte has a cathodic transference number greater than 0.4 and less than 1.0.
In yet another embodiment, the solid ionically conductive polymer electrolyte is in a glassy state.
In an embodiment, the electrochemically active material, the electrically conductive material, the solid ionically conductive polymer electrolyte and the binder include a plurality of dispersed, intermixed particulates.
In yet another embodiment, the electrode further includes an electrically conductive current collector; and the electrode is adhered to the electrically conductive current collector.
In an alternative embodiment, the electrochemically active material, the electrically conductive material, the solid ionically conductive polymer electrolyte and the binder include a plurality of dispersed, intermixed particulates forming a mixture; and the mixture is adhered to the electrically conductive current collector by an aqueous slurry.
In another aspect, the invention features a method of making a battery structure. The method includes the steps of selecting an electrically conductive current collector and an electrode; wherein the electrode comprises an electrochemically active material, an electrically conductive material, a solid ionically conductive polymer electrolyte, and a binder; mixing the electrochemically active material, the electrically conductive material, the solid ionically conductive polymer electrolyte, and the binder in an aqueous solution to create a slurry; positioning the slurry adjacent the electrically conductive current collector; and drying the slurry; wherein the electrode adheres to the electrically conductive current collector.
These and other aspects, features, advantages, and objects will be further understood and appreciated by those skilled in the art by reference to the following specification including Attachments A, B and C, claims and appended drawings. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
In the drawings:
FIG. 1 is a schematic of an electrochemical cell according to an exemplary embodiment of the invention;
FIG. 2 is a discharge curve for the electrochemical cell described in Example 1 ;
FIG. 3 is a plot of a cycle test for the electrochemical cell described in Example 1 during Lithium intercalation and deintercalation;
FIG. 4 is a discharge curve for the comparative electrochemical cell described in Example
2; and
FIG. 5 is a plot of a cycle test for the electrochemical cell described in Example 2.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1, an electrochemical cell 10 is shown in representative cross- section. The electrochemical cell has a first electrode 20 attached to a first electrically conductive current collector 30. The electrochemical cell also includes a second electrode 50 which is similarly attached to a second electrically conductive current collector 60. An electrolyte layer 40 is interposed between the first and second electrodes. The electrolyte layer 40 acts as a dielectric separator and enables ionic conduction between the electrodes. Each of the current collectors 30 and 60 includes a respective tab 25 and 65 extending from each respective current collector 30 and 60 so that at least a portion of the tab can extend from the cell enclosure (not shown). Each tab 25 and 65 thus can act as an electrical lead, either positive and negative for the cell.
Additional information on the design of electrochemical cells and their associated electrodes is included in the following examples and description and in PCT Application US2016/035628, which is incorporated herein by reference in its entirety except for any definitions, subject matter disclaimers or disavowals, and except to the extent that the incorporated material is inconsistent with the express disclosure herein, in which case the language in this disclosure controls. A copy of PCT Application US2016/035628 is also included as Attachment C in the present specification.
The first 20 and second electrodes 50 each contain an electrochemically active material that forms an electrochemical couple which produces electrons when the cell in under load. Although the construction of an electrochemical cell and its electrodes can vary depending on the electrochemical couple, in an aspect, the invention features an electrode having a basic or typically design known to those of ordinary skill in the art. In addition to the electrochemically active material, the electrode components typically include an electrolyte, an electrically conductive material and a binder. Liquid electrolytes or non-solid electrolytes such as, for a non-limiting example, gels, or electrolytes having a non-solid state are typically used in the prior art as the ionically conductive media in electrochemical cells. In an aspect, the invention features an electrochemical cell which includes a solid, ionically conductive, polymer electrolyte. The solid ionically conductive polymer electrolyte can function as an analyte and as a catholyte.
In one non-limiting exemplary embodiment the solid, ionically conductive polymer electrolyte can include a plurality of particulates. These particulates can be arranged in an array having a shape of a film, such as, for a non-limiting example, a planar film. The solid ionically conductive polymer electrolyte can be interposed between the electrodes to enable ionic conductivity between the electrodes while also providing the dielectric barrier necessary for the electrochemical cell. The particulates of the solid ionically conductive polymer electrolyte can be dispersed throughout the electrode whether the particulates function as an analyte and/or as a catholyte. The particulates can be interspersed with and encapsulate the particles of the electrochemically active material, the binder, and the electrically conductive material. The electrolyte includes at least one salt for the required ionic conductivity for the cell. The salt contains at least an anion and a cation. In one non-limiting exemplary embodiment, the invention features a lithium battery, wherein the diffusivity and ionic conductivity of the cation is preferably greater than that of the anion. The present invention includes a lithium metal battery enabled to operate efficiently at a high voltage by a solid ionically conductive polymer material.
The following explanations of terms are provided to better detail the descriptions of aspects, embodiments and objects of the invention. Unless explained or defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs. In order to facilitate review of the various aspects and/or embodiments of the disclosure, the following explanations of specific terms are provided:
The term“depolarizers)” refers to a synonym for an electrochemically active substance(s), i.e., a substance(s) which changes its oxidation state or partakes in a formation or breaking of chemical bonds, in a charge-transfer step of an electrochemical reaction and an electrochemically active material. When an electrode has more than one of the electroactive substances, they can be referred to as co-depolarizers.
The term“thermoplastic(s)” refers to a characteristic of a plastic material or polymer, wherein the plastic material or polymer becomes reversibly pliable or moldable above a specific temperature, the specific temperature being typically around or at the melting temperature of the plastic material or polymer, and wherein the plastic material or polymer reversibly solidifies upon cooling below the melting temperature.
The terms “solid electrolyte(s)” and/or“solid phase electrolytes” refer to solvent free polymers and/or ceramic compounds including crystalline, semi-crystalline and/or amorphous compounds and/or compounds in a glassy state. For purposes of this application including its claims, the terms“solid electrolyte(s)” and/or“solid phase electrolyte(s)” do not refer to or include gelled or wet polymer(s), solvent(s) and/or other material(s) which depend upon a liquid, liquid phase, and/or liquid phase material for ionic conductivity.
The terms "solid(s)" and/or“solid phase(s) and/or solid phase material and/or material is a solid phase” can be used interchangeably and refer to the ability to maintain indefinitely a particular shape, wherein the“solid” is distinguishable and different from a liquid or a liquid phase or a liquid phase material or a material in a liquid phase. The atomic structure of the“solid(s)” can be crystalline or amorphous. The“solid(s)” can be mixed with or include components in composite structures. For purposes of this application including its claims, a“solid” ionically conductive or conducting material enables ionic conductivity through the“solid” material and not through any solvent, gel, liquid, liquid phase or liquid phase material, unless it is otherwise described.
The term “polymer(s)” refers to an organic compound which includes carbon-based macromolecules. Each macromolecule can have one or more types of repeating units, also known as monomers and/or monomer residues, as understood by those persons of ordinary skill in the art. A “polymer(s)” is characterized as lightweight, ductile, usually or typically electrically non- conductive, and melts at a relatively low temperature. A polymer(s) can be made into products by injection, blowing and other molding processes, extrusion, pressing, stamping, three-dimensional printing, machining and other plastic or polymer forming processes known to those of ordinary skill in the art. A polymer(s) typically has a glassy state at a temperature below the glass transition temperature or Tg of the polymer(s). The glass transition temperature is a function of polymer chain flexibility. At temperatures above the glass transition temperature, there is enough vibrational and/or thermal energy in the system of the polymer(s) to create sufficient free -volume to permit sequences of segments of the polymer macromolecule to move together as a unit. However, when in the glassy state, a polymer has no segmental motion of the polymer.
The term“ceramic(s)”, which is distinguishable from the term“polymer(s)”, refers to an inorganic, non- metallic material; ceramics typically include compounds which consist of metals covalently bonded to oxygen, nitrogen or carbon. A“ceramic(s)” is characterized as brittle, strong and non-conducting.
The term“glass transition temperature”, which is observed, determined or estimated in some but not all polymers, is a temperature or temperature range which falls between the temperature of a supercooled liquid state and the temperature of a glassy state as a polymer material is cooled. The thermodynamic measurements of the glass transition are done by measuring a physical property of the polymer, e.g. volume, enthalpy or entropy and other derivative properties as a function of temperature. The glass transition temperature is observed on such a plot as a break in the selected property (volume of enthalpy) or from a change in slope (heat capacity or thermal expansion coefficient) at the transition temperature. Upon cooling a polymer from above the Tg to below the Tg, the polymer molecular mobility slows down until the polymer reaches its glassy state.
A polymer(s) can include a crystalline, a semi-crystalline and/or an amorphous phase. The term“percentage crystallinity” of a polymer(s) refers to the percentage or amount of the crystalline phase of the polymer relative the total amount of the polymer including both the amorphous and crystalline phases of the polymer. Crystallinity percentage can be calculated via x-ray diffraction of the polymer and analysis of the relative areas of the amorphous and crystalline phases of the polymer.
The term“polymer film” generally refers to a thin portion of polymer. For the purposes of the present application, the term“polymer film” should be understood to equal a portion of polymer which is equal to or less than 300 micrometers in thickness. Ionic conductivity differs from electrical conductivity. Ionic conductivity depends on ionic diffusivity, and the properties of ionic conductivity are related by the Nemst-Einstein equation. Ionic conductivity and ionic diffusivity are both measures of ionic mobility. An ion is considered mobile in a material if the diffusivity of the ion in the material is positive, that is, greater than zero, and/or the movement of the ion contributes to a positive ionic conductivity. Ionic mobility measurements are generally taken at room temperature, that is, around 2l°C, unless otherwise stated. Ionic mobility is affected by temperature. Thus, it can be difficult to detect ionic mobility at low temperatures. Equipment detection limits can be a factor in determining relatively low ionic mobility. An ion can be considered mobile in a material when a measurement of the diffusivity of the ion is at least 1 x 10 14 m2/s and preferably is at leastl x l0 13 m2/s.
The term“solid polymer ionically conductive and/or conducting material(s)” refers to a solid material that includes a polymer and conducts ions as will be further described.
An aspect of the invention includes a method of synthesizing a solid ionically conductive polymer material from at least three distinct components: a base polymer, a dopant and an ionic compound. The components and method of synthesis are chosen or selected for the particular application of the material. The selection of the base polymer, dopant and ionic compound may also vary based on the desired performance of the material. For example, the desired components and method of synthesis may be determined by optimization of a desired physical characteristic (e.g. ionic conductivity).
The method of synthesis can also vary depending on the particular components and the desired form of the end material (e.g. film, particulate, etc.). However, the method includes the basic steps of mixing at least two of the components initially, adding the third component in an optional second mixing step, and heating the components/reactants to synthesis the solid ionically conductive polymer material in a heating step. In one aspect of the invention, the resulting mixture can be optionally formed into a film of desired size. If the dopant was not present in the mixture produced in the first step, then it can be subsequently added to the mixture while heat and optionally pressure (positive pressure or vacuum) are applied. All three components can be present and mixed and heated to complete the synthesis of the solid ionically conductive polymer material in a single step. However, this heating step can be done when in a separate step from any mixing or can completed while mixing is being done. The heating step can be performed regardless of the form of the mixture (e.g. film, particulate, etc.) In an aspect of the synthesis method, all three components are mixed and then extruded into a film. The film is heated to complete the synthesis.
When the solid ionically conductive polymer material is synthesized, a color change occurs which can be visually observed as the reactants color is a relatively light color, and the solid ionically conductive polymer material is a relatively dark or black color. It is believed that this color change occurs as charge transfer complexes are formed and can occur gradually or quickly depending on the synthesis method.
An aspect of the method of synthesis includes a step of mixing the base polymer, ionic compound and dopant together followed by a step of heating the mixture. The heating step can be performed in the presence of the dopant where the dopant can be in the gas phase. The mixing step can be performed in an extruder, blender, mill or other equipment typical of plastic processing. The heating step can last several hours (e.g. twenty-four (24) hours) and the color change is a reliable indication that synthesis is complete or partially complete. Additional heating past synthesis (color change) does not appear to negatively affect the material.
In an aspect of the synthesis method, the base polymer and ionic compound can be first mixed. The dopant is then mixed with the polymer-ionic compound mixture and heated. The heating can be applied to the mixture during the mixture step or the heating can be applied to the mixture subsequent to the mixing step.
In another aspect of the synthesis method, the base polymer and the dopant are first mixed, and then heated. This heating step can be applied after the mixing or during the mixing. The heating step produces a color change indicating the formation of charge transfer complexes and reaction between the dopant and the base polymer. The ionic compound is then mixed with the reacted polymer dopant material to complete the formation of the solid ionically conductive polymer material.
Typical methods of adding the dopant are known to those skilled in the art and can include vapor doping of film containing the base polymer and ionic compound and other doping methods known to those skilled in the art. Upon doping the solid polymer material becomes ionically conductive. It is believed that the doping acts to activate the ionic components of the solid polymer material, so they are diffusing ions.
Other non-reactive components can be added to the above described mixtures during the initial mixing steps, secondary mixing steps or mixing steps subsequent to heating. Such other components include but are not limited to depolarizers or electrochemically active materials such as anode or cathode active materials, electrically conductive materials such as carbons, rheological agents such as binders or extrusion aids (e.g. ethylene propylene diene monomer "EPDM"), catalysts and other components useful to achieve the desired physical properties of the mixture.
Polymers that are useful as reactants in the synthesis of the solid ionically conductive polymer material are electron donors or polymers which can be oxidized by electron acceptors. Semi-crystalline polymers with a crystallinity index greater than 30%, and greater than 50% are suitable reactant polymers. Totally crystalline polymer materials such as liquid crystal polymers ("LCPs") are also useful as reactant polymers. LCPs are totally crystalline and therefore their crystallinity index is hereby defined as 100%. Undoped conjugated polymers and polymers such as polyphenylene sulfide ("PPS") are also suitable polymer reactants.
Polymers are typically not electrically conductive. For example, virgin PPS has an electrical conductivity of 10 20 S/cm. Non-electrically conductive polymers are suitable reactant polymers.
In an aspect, polymers useful as reactants can possess an aromatic or heterocyclic component in the backbone of each repeating monomer group, otherwise known as a monomer residue, and a heteroatom either incorporated in the heterocyclic ring or positioned along the backbone in a position adjacent the aromatic ring. The heteroatom can be located directly on the backbone or bonded to a carbon atom which is positioned directly on the backbone. In both cases where the heteroatom is located on the backbone or bonded to a carbon atom positioned on the backbone, the backbone atom is positioned on the backbone adjacent to an aromatic ring. Non limiting examples of the polymers used in this aspect of the invention can be selected from the group including PPS, Poly (p-phenylene oxide) ("PPO"), LCPs, Polyether ether ketone ("PEEK"), Polyphthalamide ("PPA"), Polypyrrole, Polyaniline, and Polysulfone. Co-polymers including monomers or monomer residues of the listed polymers and mixtures of these polymers may also be used. For example, copolymers of p-hydroxybenzoic acid can be appropriate liquid crystal polymer base polymers.
TABLE 1 details non-limiting examples of reactant polymers useful in the synthesis of the solid ionically conductive polymer material along with monomer or monomer residue structures and some physical property information. TABLE 1 includes non-limiting examples where polymers can take multiple forms which can affect their physical properties.
TABLE 1
Figure imgf000012_0001
Dopants that are useful as reactants in the synthesis of the solid ionically conductive polymer material are electron acceptors or oxidants. It is believed that the dopant(s) release ions for ionic transport and mobility. It is believed that the dopant release of ions creates site(s) analogous to charge transfer complex(es) or site(s) within the polymer which allow or permit ionic conductivity. Non- limiting examples of dopants which can be used in the present invention include quinones such as: 2,3-dicyano-5,6-dichlorodicyanoquinone (CTCnN O ) also known as "DDQ", and tetrachloro-l,4-benzoquinone (CeCi tCh), also known as chloranil, tetracyanoethylene (CeN t) also known as TCNE, sulfur tri oxide ("SO3"), ozone (tri oxygen or O3), oxygen (O2, including air), transition metal oxides including manganese dioxide ("MnCh"), or any suitable electron acceptor, etc. and combinations thereof. Dopants that are temperature stable at the temperatures of the synthesis heating step are useful or preferred, and quinones and other dopants which are both temperature stable and strong oxidizers quinones are very useful and even more preferred. TABLE 2 provides a non-limiting listing of dopants, along with their chemical formulas and structures.
TABLE 2
Figure imgf000013_0001
Ionic compounds that are useful as reactants in the synthesis of the solid ionically conductive polymer material are compounds that release desired lithium ions during the synthesis of the solid ionically conductive polymer material. The ionic compound is distinct from the dopant in that both an ionic compound and a dopant are required. Non- limiting examples include Li20, LiOH, LiNCb, LiTFSI (LiC2F6N04S2 or lithium bis-trifluoromethanesulfonimide), LiFSI (F2LiN04S2 or Lithium bis(fluorosulfonyl)imide), LiBOB (Lithium bis(oxalato)borate or CLBLiOs), lithium triflate (LiCFiOiS or lithium trifluoromethane sulfonate), Li PLT, (lithium hexafluorophosphate), LiBF4 (lithium tetrafluoroborate), LiAsFe (lithium hexafluoroarsenate) and other lithium salts and combinations thereof. Hydrated forms (e.g. monohydride) of these compounds can be used to simplify handling of the compounds. Inorganic oxides, chlorides and hydroxide are suitable ionic compounds in that they dissociate during synthesis to create at least one anionic and/or cationic diffusing ion. Any such ionic compound that dissociates to create at least one anionic and/or cationic diffusing ion would similarly be suitable. Multiple ionic compounds can also be useful that result in multiple anionic and/or cationic diffusing ions can be preferred. The particular ionic compound included in the synthesis depends on the utility desired for the material. For example, in an aspect where it can be desired to have a lithium cation, a lithium hydroxide or a lithium oxide convertible to a lithium and hydroxide ion can be appropriate. A lithium containing compound that releases both a lithium cathode and a diffusing anion can be used in the the synthesis method. A non-limiting group of such lithium ionic compounds includes those used as lithium salts in organic solvents.
The purity of the materials can be relevant for the prevention of unintended side reactions and for the maximization of the effectiveness of the synthesis reaction to produce a highly conductive material. Substantially pure reactants with generally high purities of the dopant, the base polymer and the ionic compound are useful, and purities greater than 98% are more useful with even higher purities, e.g. LiOH: 99.6%, DDQ: >98%, and Chloranil: >99% also useful.
In the aspect of the invention when an anode intercalation material is used as the anode electrochemically active material, useful anode materials include typical anode intercalation materials comprising: lithium titanium oxide (LTO), Silicon (Si), germanium (Ge), and tin (Sn) anodes doped and undoped; and other elements, such as antimony (Sb), lead (Pb), Cobalt (Co), Iron (Fe), Titanium (Ti), Nickel (Ni), magnesium (Mg), aluminum (Al), gallium (Ga), Germanium (Ge), phosphorus (P), arsenic (As), bismuth (Bi), and zinc (Zn) doped and undoped; oxides, nitrides, phosphides, and hydrides of the foregoing; and carbons (C) including nanostructured carbon, graphite, graphene and other materials including carbon, and mixtures thereof. In this aspect the anode intercalation material can be mixed with and dispersed within the solid ionically conductive polymer material such that the solid ionically conductive polymer material can act to ionically conduct the lithium ions to and from the intercalation material during both intercalation and deintercalation (or lithiation/ de-lithiation).
Referring again to FIG. 1, the cathode current collector 60 and/or the anode current collector 30 can include aluminum, copper, or other electrically conducting film onto which the corresponding cathode 50 or anode 20 can be located or positioned. In alternative embodiments, either the cathode current collector 60 and/or the anode current collector 30 can have a planar form.
Typical electrochemically active cathode compounds which can be used in the present invention include but are not limited to: NCA - Lithium Nickel Cobalt Aluminum Oxide (LiNiCoA102); NCM (NMC) - Lithium Nickel Cobalt Manganese Oxide (LiNiCoMn02); LFP - Lithium Iron Phosphate (LiFePO t); LMO - Lithium Manganese Oxide (LiMmCL); LCo - Lithium Cobalt Oxide (L1C0O2); lithium oxides or phosphates that contain nickel, cobalt or manganese, and LiTiS2, LiNi02, and other layered materials, other spinels, other olivines and tavorites, and combinations thereof.
In an aspect of the invention, the electrochemically active cathode compounds can be an intercalation material or a cathode material that reacts with the lithium in a solid state redox reaction. Such conversion cathode materials can include: metal halides including but not limited to metal fluorides such as FeF2, B1F3, CuF2, and N1F2, and metal chlorides including but not limited to FeCh, Fed 2, C0CI2, N1CI2, Cud 2, and AgCl; Sulfur (S); Selenium (Se); Tellerium (Te); Iodine (I); Oxygen (O); and related materials such as but not limited to pyrite (FeS2) and LLS.
The solid polymer electrolyte is stable at high voltages (exceeding 5.0V relative to the anode electrochemically active material). Thus, an aspect of the invention involves the increase of the energy density by enabling as high a voltage battery as possible. High voltage cathode compounds are preferred in this aspect. Certain NCM or NMC material can provide such high voltages with high concentrations of the nickel atom. In an aspect, NCMs that have an atomic percentage of nickel which is greater than that of cobalt or manganese, such as NCM523, NCM712, NCM721, NCM811, NCM532, NCM622 and NCM523, and other variations are useful to provide a higher voltage relative the anode electrochemically active material.
An electrically conductive material is necessary to establish electrical communication between electrochemically active particles and with the associated current collector for the support of electrical conduction within and to and from the electrode. Such electrically conductive material typically contains particulate carbon and various graphites and carbons which are useful for this purpose such as. carbon black, a natural graphite, a synthetic graphite, a graphene, other electrically conductive materials comprising carbon, a conductive polymer, a metal particle, and a combination of at least two of the preceding components. Binders act to maintain electrode integrity and adhesion to the current collector. Like the electrically conductive material and the electrolyte, the binders are not electrochemically active. Thus, the less binder added, the more electrochemically active material can be added - thus increasing the energy density and cell capacity. Binders which are soluble in aqueous solution are substantially soluble in water-based solvents, and can include Carboxymethyl cellulose or“CMC”, and styrene-butadiene rubber or“SBR”, similar aqueous soluble binders and mixtures thereof.
In addition to SBR and CMC, other binders which can be dispersed or are soluble in an aqueous solution include: Polytetrafluoroethylene (PTFE), Ethylene propylene diene monomer (EPDM) rubber and other rubbers, poly-polystyrene sulfonate (PEDOT-PSS), Polyacrylic acid (PAA), Poly(methyl acrylate) (PMA) , Poly(vinyl alcohol) (PVA) , Poly(vinyl acetate) (PVAc), Polyacrylonitrile (PAN), Polyisoprene (PIpr), Polyaniline (PANi), Polyethylene (PE), Polyimide (PI), Polystyrene (PS), Polyurethane, Polyvinyl butyral (PVB), Polyvinyl pyrrolidone (PVP) and modifications and combinations thereof. Additional natural binders which can be dispersed or are soluble in an aqueous solution include: Amylose, Caseine, Cyclodextrines (carbonyl-beta), Cellulose (natural), Starches, alginate, chitosan, gums (e.g., gellan, guar, xanthan, karaya, tara, tragacanth, and arabic), agar-agar, pectine, and carrageenan.
In an aspect of the invention, chemical and/or physical modifications to these natural binders can be made. Combinations of one or more of the natural and/or modified binders can be used. The binders can be dispersed in an aqueous solution such that the binder particulates are distributed for coherence of the electrode and/or for maintenance of electrical conductivity between the electrode and a respective electrode lead. Further, binders which are soluble in an aqueous solution can be used in the present invention. In an aspect, the invention features binders which can be crosslinked if desired, e.g. PAA with CMC, and the crosslinked binder mixture can include tertiary and other additional binders to provide desired mechanical benefits. In other aspects, the invention features binders which are soluble and are well dispersed in the water-based solvent, and/or binders which are partially soluble or otherwise dispersed.
Processes for manufacturing electrochemical cells also vary depending upon the construction of the cell, the electrochemical couple, the other components or ingredients of the cell, and the cell size. The electrochemically active material needs to be in ionic communication with the solid polymer electrolyte, and in electrical communication with the electrically conductive material.
In an aspect, the invention features a plurality of particles of each electrode component intermixed and dispersed such that the particles are intimately mixed. The binder must be added to the mixture. Typically, a non-aqueous soluble binder such as PVDF can be added in solution in a mixing step. Non-aqueous binders may not be compatible with certain electrode ingredients or components, as further discussed below, however. Such non-aqueous binders can result in poor electrical communication between an electrode and a current collector. If an aqueous binder is substituted for the non-aqueous binder in such applications, the aqueous solution can degrade the electrolyte. Therefore, in such applications, the electrolyte is added after the aqueous solution is driven off in a drying or heating step. Prior art solid electrolytes can be incompatible with aqueous binders, however. Prior art solid electrolytes cannot be added after a drying step, as the electrode is cast and additional mixing would render an incoherent electrode. Inclusion of prior art solid electrolytes such as PEO-salt complexes in the electrode mixture prior to drying can result in electrolyte degradation during exposure to the aqueous solution. Specifically, the salt contained within the electrolyte can react with water resulting in unreactive or lower performing reactants.
In an aspect, it has been surprisingly found that the solid polymer electrolyte of the present invention can be used with an aqueous soluble binder without experiencing any performance degradation, while producing a coherent electrode with excellent electrical communication with the associated current collection. Additional details will be described in the following Examples.
Example 1 (Comparative Electrochemical Cell Example)
An electrochemical cell with a lithium ion graphite intercalation active material was constructed generally according to the electrochemical cell description provided above in association with FIG. 1. Details of the components and their weight percentages is provided in
TABLE 3. Carbon black included LiTX50 from Cabot. Natural Graphite intercalation material included SPGPT803 from Targray. The binder consisted of Polyvinylidene fluoride or PVDF along with a non-aqueous slurry of N-Methyl-2-pyrrolidone or“NMP” solvent. The resulting slurry was adhered to a copper foil current collector and a coin cell was constructed. The cell was cycled and voltage over time was graphed. FIG. 2 shows the resulting discharge curve over many cycles.
Graphite capacity per cycle was calculated during Lithium intercalation and deintercalation, as shown in FIG. 3. FIGs. 2 and 3 demonstrate a significant capacity fade resulting in poor performance after approximately ten cycles. Example 2
An electrochemical cell with a lithium ion graphite intercalation active material was constructed generally according to the electrochemical cell description provided above in association with FIG. 1. Details of the components and their weight percentages is provided in TABLE 3. Carbon black included LiTX50 from Cabot. Natural Graphite intercalation material included SPGPT803 from Targray. The binder consisted of a mixture of Carboxymethyl cellulose or CMC and styrene-butadiene rubber or SBR in a ratio of 60/40 wt.%, along with an aqueous slurry. Apart from the binder and associated solution, the electrochemical cell was constructed following the same procedure as in Comparative Example 1. The resulting slurry was adhered to a copper foil current collector and a coin cell was constructed. FIG. 4 shows the resulting discharge curve over many cycles. Graphite capacity per cycle was calculated during Lithium intercalation and deintercalation, as shown in FIG. 5. FIGs. 4 and 5 demonstrate repeatable cycling with little to no capacity loss over numerous cycles. TABLE 3
Figure imgf000018_0001
FIG. 2, and FIG. 3 show graphical representation data from cycling of the cells described in
Example 1. In FIG. 2, the voltage per time is depicted with the voltage peaks of each cycle taking place with decreasing frequency after about the first four cycles. The decreasing area under each cycle also indicates decreasing capacity which is confirmed in FIG. 3, and which depicts the capacity of the cell during charge (intercalation), and discharge (deintercalation). Specifically, the capacity measured in mAh/g of active anode material is graphically depicted per cycle. Again, the anode loses significant capacity in every cycle.
It is believed that the anodes are losing adhesion with the anode current collector, which increases resistance. This resistance lowers the voltage and the associated capacity. The adhesion loss is analogous to a hose being gradually clamped closed every cycle, with less and less fluid being able to flow because of the reduced flow area. The anode electrode made with the non- aqueous slurry and non-aqueous soluble binder does not provide adequate adhesion.
In Example 2, the goal was to improve the current collector adhesion, and thus prevent the current restriction that occurred with the Example 1 (Comparative) cells. The cells from Example 2 were initially kept for 16 hours and the OCV was very stable over this time. The cells were then cycled at a C/7 charge-discharge. Referring to FIG. 4, the Example 2 cell first cycle efficiency was 76.2%, and the intercalation (graphite) averaged about 364-374 mAh/g. FIG. 5 shows the capacity of the cell during charge (intercalation), and discharge (deintercalation) over the first ten cycles. No capacity fade is shown, and a 99.6% cycle efficiency is demonstrated.
It is believed that the solid ionically conductive polymer electrolyte prevents water from degrading the electrolyte. Thus, the combination of the aqueous binder and the solid ionically conductive polymer electrolyte provides superior electrode performance while enabling the elimination of a costly electrode manufacturing step.
Figure imgf000020_0001
Figure imgf000021_0001
U.S. Patent Nov. 14, 2017 Sheet 1 of 14 LS 9,819,053 B1
Figure imgf000022_0001
U.S. Patent Nov. 14, 2017 Sheet 2 of 14 LS 9,819,053 B1
Figure imgf000023_0001
electrolyte
Li MZBy
Li+ Reactions at Electrodes
FIG. 2 c in o
Ionic Materials Battery Cell Constriction
Figure imgf000024_0001
4- Layers with one Insulation Layer
Figure imgf000024_0002
kage into mult
Figure imgf000024_0003
form factors
Figure imgf000024_0004
Figure imgf000024_0005
r
Figure imgf000024_0007
C/5 n
O H
Cell Unit Wrapped to Size, Ready for Packaging be m
FIG. 3 Battery manufacture
Figure imgf000024_0006
U.S. Patent Nov.14, 2017 Sheet 4 of 14 LS 9,819,053131
FIG.4
Film Thickness as low
as H 0.0003" have been
achieved
Figure imgf000025_0003
Extrusion Process
Figure imgf000025_0001
Current Collector
FIG.5
Figure imgf000025_0002
urrent o ector U.S. Patent Nov. 14, 2017 Sheet 5 of 14 LS 9,819,053 131
Figure imgf000026_0001
Polymer <H>
electrolyte
/ Li+ ion \ Li+ insertion \
V carrier / host structure/
Figure imgf000026_0002
Figure imgf000026_0003
Figure imgf000026_0004
O Oxygen atom
• Carbon atom
Li Polyethylene oxide MzBy
Lithium foil Oxygen atom Lithium insertion
or
Figure imgf000026_0005
electrode lithium alloy (Electron donor)
Carbon atom
Figure imgf000026_0006
(CH2)—
Schematic of solid polymer battery with PEO
FIG. 6
PRIOR ART U.S. Patent Nov. 14, 2017 Sheet 6 of 14 LS 9,819,053 B1
Dynamic scanning calorimetry (CDS) of
polyethelyne oxide (PEO)-shows glass
transition temperature and melting Melt
temperature. temperature
Figure imgf000027_0001
Temperature/ °C
DSC of PEO showing Tg and Tr
FIG. 7
PRIOR ART U.S. Patent Nov. 14, 2017 Sheet 7 of 14 LS 9,819,053 131
Figure imgf000028_0002
Ionic Conductivity vs. temperature of traditional amorphous PEO polymer
FIG. 8
PRIOR ART
Figure imgf000028_0003
on themselves like this is called a lamella.
Amorphous and Crystalline Polymers
FIG. 9
Figure imgf000028_0001
CIC6H4CI + Na,S ®1 /n [CsH4S]n + 2 NaCI
FIG. 10 U.S. Patent Nov. 14, 2017 Sheet 8 of 14 LS 9,819,053 131
Figure imgf000029_0001
3
Temperature (X)
Dynamic Scanning Calorimetry Curve Of Semicrystalline Polymer
FIG. 11 U.S. Patent Nov. 14, 2017 Sheet 9 of 14 LS 9,819,053 131
Figure imgf000030_0003
Table 1
FIG. 12 Exemplary formulations investigated
FIG. 13
Figure imgf000030_0001
2,3-dicyano-5 6-dichlorodicyanoquinone
Figure imgf000030_0002
Neutral Chain Poiaron Solitons Soiiton Band
FIG. 14 U.S. Patent Nov.14, 2017 Sheet 10 of ! 4 LS 9,819,053131
Figure imgf000031_0001
((iuo/s)‘AijAi npuoo) Bo~] U.S. Patent Nov. 14, 2017 Sheet P oM4 LS 9,819,053 131
Figure imgf000032_0001
U.S. Patent Nov.14,2017 Sheet 12 oM4 LS 9,819,053131
Figure imgf000033_0001
U.S. Patent Nov. 14, 2017 Sheet 13 oM 4 LS 9,819,053 131
1 00
E o
<
0 00
c
3 -too
Figure imgf000034_0004
0 1 2 3 4 5 6 7
Volts (Li/Li+)
Cyclic Voltammetry of lonica!ly Conductive Polymer versus Lithium Metal
FIG. 18
— Ionic Solid Polymer Film Electrolyte Matrix
Containing Active Anode Material
Figure imgf000034_0002
Ionic Solid Polymer
Ionic Solid Polymer Film
Film Electrolyte Electrolyte Matrix
Figure imgf000034_0001
Containing Active Ionic Polymer
Cathode Material Bonding Layer
lonically conductive electrolyte and electrode components
FIG. 19
Charge Carrier Foil
A d
(e g Copper)
Figure imgf000034_0003
Charge Carrier Foil athode Electrolyte Film Layer
(e.g Aluminum)
Solid State Battery-Electrode and electrolyte bonded together
FIG. 20 U.S. Patent Nov. 14, 2017 Sheet 14 oM 4 LS 9,819,053 131
Figure imgf000035_0001
Flexible form of battery
FIG, 21
i;s 9.819.053 B 1
1 2
soi. in i l i t: I KOIL 1 1-: HIGH HM-IRGY between the electrolyte and electrodes, nor does the novel
BLTTGHU battery require a vent The weight of the novel battery is substant ially less than a battery of conventional construction s ] n i\-i i INIT RT ;c ; A R DINK , F i mi IR A I I Y having similar pow er capacity In some embodiments the SFONSORHD RHSKARCH OR DFVFTOPMFNT ^ weight of the novel battery can be less than half the weight of a conventional battery.
(Not applicable) flic electrolyte material is a solid ionieally conductive polymer which has preferably a semi-crystalline or crystal¬
BACKGROUND OF TI IK I YFNTION line structure which provides a high density o f sites for ionic transport The polymer st me lure can he folded hack on itsel f
I itliimn ion (and other) batteries generally employ a This w ill allow for new battery formats
liquid electrolyte which is hazardous to humans and to the
According to one aspect of the invention, the electrolyte environment and which can he subject to (ire or explosion
is in the fonn of an ionic polymer film. An electrode material
I iquid electrolyte batteries are hermetically sealed in a steel
is directly ap lied to each surface of the electrolyte and a f oil or other strong packaging material which adds to the weight A
and balk of the packaged baiters. L new innovation is the charge collector or terminal is applied over each electrode poach cell which has been used in lightweight batteries but surface A light w eight protective polymer covering can he these have not seen widespread acceptance applied over the terminals to complete the lilm based
Conventional liquid electrolyte also sailers from the structure This thin film batten is ilexible and can be rolled build-up of a solid interlace layer at the electrode electrolyte or folded into intended shapes to suit installation require interface which causes eventual failure of the battery Con ments
ventional lithium ion batteries can also exhibit slow charge According to another aspect of the invent ion the electro limes on the order of hours In addition the batteries sa iler lyte is in the form o f an ionic polymer monof ilament from a limited number of recharges since the chemical (hollow ) rileclrode materials and charge collectors are read ion williin the baiters reaches completion and limits the its directly applied (eo-exlruded) to each surface ol' llie elec rc-chargeabilily because of corrosion and dendrite forma trolyte and a terminal is applied at each electrode surf ace A tion The liquid electrolyte also limits the maximum energy light w eight protective polymer covering can be applied density The electrolyte starts to break down at about 4 2 over the terminals to complete the structure T his form of volts. New industry requirements lor battery power are often battery is thin, ilexible. and can be coiled into intended 4.8 volts and higher which cannot be achieved by present shapes to suit installation requirements, including very small liquid electrolyte lithium ion cells There have been devel applications
opments in both spinel structures and layered oxide struc According to another aspect of the invention, a solid tures which have not been deployed due to the limitations of electrolyte can be molded in a desired shape. Anode and the liquid electrolyte Also, lithium ion batteries w ith liquid cathode electrode materials are disposed on respective oppo electrolytes su ffer from safely problems w ith respect to I s site surfaces ol’llie electrolyte to fonn a cell unit Hleclrical flammabil ity o f the liquid electrolyte term inals are provided on the anode and cathode electrodes
In a conventional lithium ion battery having a liquid of each cell unit f or interconnection with other cell units to electrolyte there is also a need for a separator in the liquid provide a multi cell ballery or for connection to a utilization electrolyte file separator is a porous structure which allows device.
for tons to llow through it and blocks electrons f ro passing 4:: In yet other aspects of lhe invent ion methods f or making through it The liquid electrolyte battery usually requires a such hatleries are disclosed
vent to relieve pressure in the housing, and in addition, such In all o f lhe above aspects of lhe invent ion, the electrode conventional batteries usually include safety circuitry to materials (cathode and anode) can be combined w ith a fonn minimize potentially dangerous over-currents and over-tem of the novel electrolyte material to further facilitate ionic peratures 1'K rS 1 and 2 show schematics and general 4t movement between the two electrodes This is analogous to reactions in such conventional lithium ion batteries a conventional liquid electrolyte soaked into each electrode material in a conventional lithium-ion battery .
BRU IT SUMMARY Of fi ll ; INVHNTION
HR IFF DKSCRIPTION OF TI 1F. SKVKRAI
In accordance with the invent ion a l ithium ion battery is m VIKWS OF’ TI IF DRAWINGS provided which has a solid polymer electrolyte The solid
electrolyte enables a lighter weight and much safer archi file foregoing summary as well as the following descrip tecture by eliminating the need for heavy and bulky metal tion of the invention, is better understood when read in hermetic packaging and protection circuitry The novel solid conjunction with the appended draw ings For the purpose o f polymer battery can be of smaller size, lighter weight and w illustrating the invention, exemplary construct ions are higher energy density than liquid electrolyte balleries of the show n in the draw ings, file invention is not limited, how same capacity, file solid polymer ballery also belief its from ever. to the specific methods and instrumentalities disclosed less complex manu facturing processes, lower cosl and herein
reduced safety hazard as the electrolyte material is non FIG 1 show s show a schematic of a conventional lithium flammable The novel battery will also provide cell voltages ion battery according to the prior art
greater than 4.2 volts. 1 lie solid electrolyte can be formed FIG. 2 shows reactions tit electrodes in a conventional into variou shapes by extrusion (and co-extrusion), molding lithium ion battery according to the prior art.
and other techniques such that di fferent form i actors can be FIG .1 exemplarily illustrates a method of the invention provided for the battery Particular shapes can be made to lit including steps for manu facturing a sol id stale battery using into differently shaped enclosures in devices or equipment tit an extruded polymer
being pow ered. In addition, the novel battery does nol FIG. 4 exemplarily illustrates the extrusion process require a separator as with liquid electrolyte batteries. according to the invention i;s 9.8 9.05 A B
3 4
1- lCT 5 exemplarily illustrates a schematic representation ture limits the kinds of applications PfO can be used in. o f an embodiment according to the invention even with necessary safely precautions for thermal runaway
MC I 6 shows a schematic of a solid polymer battery with The flammability of PfO
polyethylene oxide according to the prior art Pf Os according to the prior art are flammable due to their
L1G 7 shows a dynamic scanning calorimetry plot show- s volatile nature and high operating temperature. Currently a ill” the a lass transition temperature and melting temperature battery utilizing PfO as an electrolyte requires a hermetic of polyethylene oxide according to prior art. package around it to prevent thermal runaway 'i bis adds an riC l S shows the relationship o f ionic conduct ivity versus expensive thermal management system adds sa fely risk to temperature of traditional amorphous polyethylene oxide the end user which can prevent end user adoption and according to the prior art : :: creates a rigid bulky structure which the battery manage ment system has to be designed around
h ltT !) shows a schematic illustration of amorphous and
Manufacturability of Pf O Ratleries
crystalline polymers Commercial Pf O manufacturers currently spray the poly h lth 10 exeinplarily shows a resulting formula for the mer onto the electrodes during manufacturing This batcli- crystalline polymer of the present invention : s scale process is inefficient and creates an end product that
MC I 11 exemplarily illustrates a dynamic scanning calo is sti ff thick and costly to integrate into an end application rimeter ciin o f a se icrystallinc polymer Moreover although PfO has been in existence for over 20 h lth 1 exemplarily illustrates formulations which were years it is still not commercially produced
investigated for use w ith the invention Liquid electrolytes embody many of the same problems as h lth 13 exemplarily illustrates a chemical diagram of I:: PHO as used in the prior art: high cost safety concerns cost 2.3-dicyano-5.6-ilichlorodieyanoqiiinone (P1 IQ) and manu facturability challenges poor mechanical proper
IdC h 14 exemplarily illustrates possihle mechanisms of ties and of ten a cause of performance degradation The solid conduction o f the solid electrolyte polymer according to the polymer approach of the present invention solves the prob invention. lems associated with liquid electrolytes and addresses the h lth 15 exemplarily illustrates a plot of the conductivity Is limitations of PfO material.
o f the tonically conductive polymer according to the inven The invention oilers three key advantages in its polymer tion in comparison with a liquid electrolyte and a polyeth performance characteristics: (1 ) It has an expansive tem ylene oxide lithium salt compound perature range. In lab-scale testing the crystalline polymer h lth 16 exeinphirily illustrates the mechanical properties design has shown high ionic conductivity both at room of the ionicully conducting film according to the invention. v: temperature and over a wide temperature range (2) It is h id 17 exemplarily shows a I JI lJ4 flammabil ity lest non-flammable The polymer self-extinguishes passing the conducted on a polymer according to the invent ton IJI -V0 f lammability l est The ability to operate at room h lth 18 exemplarily shows a plot of volts versus current temperature and the non-llnmmable characteristics demon of an ionically conductive polymer according to the inven strate a transformative safety improvement that eliminates tion versus lithium metal. I t expensive thermal management systems (3 ) It o ffers low-
Mt h H) exemplarily illustrates a schematic o f extruded cost bulk manufacturing Rather than spraying the polymer ionically conductive electrolyte and electrode components onto electrodes the polymer material can he extruded into a according to the invention. thill lilm via a roll-to-roll process an industry standard for hlth 20 exemplarily illustrates the solid stale battery plastics manu facturers. After the film is extruded it can be according to the invention where electrode and electrolyte 4:: coated w ith the electrode and charge collector materials to are bonded together build a battery "from the inside out” [’his enables thin hit ! 21 exemplarily illustrates a final solid slate battery 11 ex i b 1 e form factors without the need for hermetic packag according to the invention having a new and flexible form. ing. resulting in easy integration into vehicle and storage applications at low cost.
DLTAII I dl Ill SCRIP PO Of TI IK 4t The solid polymer electrolyte o f the present invention is
INV] 1NΊΊ N based on a transformative material that creates a new ionic conduction mechanism that provides a higher density of file inventor has developed a non-flammable solid poly sites for ionic transport and allows higher voltages to run mer electrolyte which is conductive at room temperature and through the electrolyte w ith no risk of thermal runaway or can he used in any battery· application The material s novel s:: damage to ion transport sites from hlhialion litis charac conductivity mechanism improves energy density by terist ic enables a durable electrolyte for higher voltage 10-fold and reduces battery costs by up to 50%. cathode and anode materials in thin-lilm applications result
Lxislhig solid stale polymers used for ionic conductivity ing in higher energy densities for batteries in vehicle and are based on alkali metals blended with polyethylene o ide stationary storage applications The ability to run high (I’l ()) The three primary limitat ions w ith PI 10 are its m voltages through an electrolyte that is conductive mechani temperature limitations safety issues in commercial appli cally robust chemical and moisture resistant and nonflam cations. and its manufacturability mable not only at room temperature but over a ide range
The Limited Temperature Range of PhlO of temperatures ill allow integration of high performance
Pf.O according to the prior art is conductive only above electrodes without costly thermal and safely mechanisms the material’s glass transition temperature (typical ly>50;> employed by the industry today
C.): below that temperature it is in a glassy state and lacks Halleries prepared using the polymer electrolyte of the con uctivity. Above that temperature PfO exists in a visco present invention are characterized by a 10-fold energy elastic stale through which ions can conduct via chain density improvement over current commercially available mobility Accordingly the current blends o f PfO w ith other electrolytes as w ell as a performance range of -4( C to materials used in laboratory· and commercial appl ications all tit 150;> C w ith minima] conductivity degradation The poly require high temperatures (>50l; (’ ) to achieve the slate mer electrolyte can be extruded by a process that produces necessary for the polymer to be reactive. This high tempera- working polymers at a thickness of 6 microns hich enables i;s 9.819.053 B 1
5 6
these traits in a ihin-lilin formal under commercial manu such as carbon nanolubes or the like Alter the film is facturing conditions tit batch scale The polymer electrolyte created a doping procedure can be used using an electron allows the development of new high throughput low-cost acceptor Alternatively the dopant can be“pre-mixed” with manufacturing lines for solid electrolyte production and can the initial ingredients and extruded without post processing be integrated into a variety of product lines including 7 flic purpose of the electron acceptor is two-fold: release lithium and zinc battery manufacture In addition the poly ions for transport mobility and to create polar high density mer electrolyte is not limited to use in batteries but can be sites within the polymer to allow for ionic conductivity used in any device or composition that includes an electro Note: there is a clear distinction between electrical conduc lyte material for example the polymer electrolyte material tivity and ionic conductivity
can be u ed in chemical separation processes uch as for the Typical materials that can be used for the polymer include separation of ions in eleetrochromic devices electrochemi
liquid crystal polymers and polyphenylene sullide (ITS) or cal sensors and fuel cell membranes
MC I .1 shows a method of manufacturing a solid state any semicrystahine polymer w ith a crystallinity index battery using an extruded polymer according to the inven greater than 30%. or other typical oxygen acceptors f 1G 11 tion file material is compounded into pellets and then exemplarily illustrates a dynamic scantling calorimeter extruded through a die to make dims of variable thicknesses curve of a semicrystalline polymer fable 1 of TIG 12 The electrodes can be applied to the film using several illustrates exemplary formulations which were investigated techniques such as sputtering or conventional casting in a f lectron acceptors can be supplied in a vapor doping s lu rry. process. They can also be pre-mixed with the other ingre-
MG 4 shows a method of manufacturing of an ionic dients Typical electron acceptors suitable for use include polymer f ilm according to the invention which involves but are not l imited to: 2 3-dicyuno-5 6-dichlorndicyatmqui- heating the f ilm to a temperature around 2')v’ C anti then none (DDQ) (CTCl -N -O,) as exemplarily illustrated in TIG casting the him onto a chill roll which freezes the plastic. 13 Tetracyanoelhylene P GNK) (C K , ) and sulfur trioxide The film can be very thin in the range of 10 microns thick (SO, ) L preferred dopant is Dl KJ. and doping is preferably or less f lG 5 show s a schematic representation of the A performed in the presence of heal and vacuum architecture of an embodiment according to the invention TIG 14 shows possible mechanisms of conduction of the
Previous attempts to fabricate polymer electrolytes were solid electrolyte polymer according to the invent ion Charge based on a specific ionically conductive material whose carrier complexes are set up in the polymer as a result of the mechanism was discovered in 1 lJ7 The material is poly doping process
ethylene oxide iTT.O) and the ionic conduct ion mechanism l ixlruded films have been made in thickness ranges from is based on the "chain mobility’ concept which requires the
0 0003'' thick to 0 0051' Surface conductivity measurements polymer to be at a temperature higher than the glass tran
have been made and the results are reported in TIG 15 In sition temperature TIG. 6 shows a schematic of a solid
TIG 15 the conduct ivity of ionically conductive polymer polymer battery with polyethylene oxide according to the
prior art Included in G 7 is a dynamic scanning calo, . according to the invention (L ) is compared with that o f rimetry (DSC ) plot showing the glass transition temperature trifluoro methane sulfonate l’l 'lO (I I) and the liquid electro (T ) and the melting temperature of Ph O lyte C'elgard/(T;C':TC'/I iT T6)(0). The conductivity of the file mechanism for ion transport involves "motion" of the ionic polymer according to the invention tracks the conduc amorphous chains above the T . Above this temperature the tivity of the liquid electrolyte and f ar surpasses that o f polymer is very "s If” and its mechanical properties are very 4:: triiluoromethnne sulfonate I'TO at the lower te eratures low for application in lithium ion batteries tradit ional TIG 16 shows the mechanical properties of the ionically lithium ion salts are used as additives such as TiPlT . TiBlh . conductive lilm of llie invention which were evaluated using or l iC’l 04 Lithium salts are a source of issues in conven I STM ITG-TM-f SO lest Methods Manuals 4 18.3. In the tional hi ion batteries such as corrosion reliability and high tensile strength versus elongation curve of TIG 16 the cost fK i S is a plot which shows the relationship of ionic 4s "ductile f ailure" mode indicates that the material can he very conductivity versus temperature of traditional amorphous robust
polymer (fliO) according to the prior art. f lG 8 shows that f lammability of the polymer was tested using a LMJ4 traditional amorphous polymer (TTO) does not have mean Hume test for a polymer to be rated L f‘J4-V0. it must ingful conductivity at room temperature "sel f-extinguish” within 10 seconds and ’not drip" The
The solid polymer electrolyte according to the invention s:: electrolyte was tested for this property and it was determined has the following characteristics: ionic conduction mecha that it sel f-extinguished with 2 seconds did not drip and nism at room temperature wide temperature range ion therefore easily passed the V-0 rating TIG 17 show s "hopping" from a high density of atomic sites and a new pictures of the result.
means o f supplying ions (l ithium or otherwise) In addition to the properties of ionic conductivity flame
The invent ion uses a "crystalline or semi-crystalline poly w resistance high temperature behavior and good mechanical mer”. exemplurily illustrated in f lG 9. which typically is properties it s necessary that the polymer material not be above a crystallinity value of 30%. and has a glass transition subject to chemical reaction or attack by lithium metal or temperature above 2(X)l; and a melting temperature above other active species of the electrode materials The tradi 2 iff C Added to this are compounds containing appropriate tional lest for attack by polymers by lithium is done by the ions which are in stable form which can be modified after t;:: use of cyclic voltammetry This is a test where the polymer creation of the film. f lG I ll show s the molecular structure is sandwiched between a lithium metal anode and blocking of the crystalline polymer. Lite molecular weight of the stainless steel electrode L voltage is applied and it is swept monomeric unit of the polymer is 10b 1 6 g/mol from a low value (-2 volts) up to a high value greater than
Typical compounds for ion sources include but are not 4 volts The current oulpul is measured to determine i f there limited to I i -O I iOI I and ZnO Other examples are TiO, ti t is any significant reaction happening with Ihe polymer/ AW),. and the like Additionally other additives may be lithium metal. I ligli output currents would indicate a chemi included to further enhance conductivity or current density. cal reaction which is not desirable TIG 18 shows the result i;s 9.819.053 B 1
7 8
of this study and indicates that this ionically conductive lyle: B) extruded anodes and cathodes: and C) linal solid polymer is stable to at least 6 volts The results showed good slate battery allowing for new form factors and ilexibtlity high voltage stability While the present invention has been described in con
The solid polymer electrolyte according to the invention junction w ith preferred embodiments one of ordinary skill is able to achieve the follow ing properties: L) high ionic alter reading the foregoing specilieation. will be able lo eifect various changes substitutions oi equivalents and conductivity at room temperature and through a wide tem other alterations lo that set forth herein It is therefore perature range (at least - 101’ C lo +601’ ( ' ): I S) non intended that the protection granted by 1.etters Patent hereon flammabil ity: C ) exlrudnbilily into thin f ilms allow ing for be limited only by the deiinitions contained in the appended reel-reel processing and a new way oi manufacturing: P) claims and equivalents thereof
compatibility with Lithium metal and other active materials What is claimed is:
this invention will allow for the fabrication of a true solid 1. L sci lid. ionicully conducting material having an ionic stale battery file invention allows for a new generation of conductivity greater than 1 c KG4 S/cm at room temperature batteries having the follow ing properties: and formed f rom a polymer an electron acceptor and at
No sa fely issues: least one compound comprising an ion source wherein the
Now form factors: polymer is polyphenylene sulfide and and the compound is
Large increases in energy density: and LiOl l
large improvements in cost of energy storage 2. Lite material of claim 1. wherein the electron acceptor
MGS. 19 21 and 21 show several elements of the solid is 23-dichloro-i 6-dicyano- 1 4-hcnzoquinonc stale battery which are. respectively: L) extruded electro-
Figure imgf000040_0001
Patent Application Publication Jan. 5, 2017 Sheet 1 of 20 US 2017/0005356 L1
Figure imgf000041_0001
(B/M\/W) Ajpedeo ¾00!1 Patent Application Publication Jan. 5, 2017 Sheet 2 of 20 US 2017/0005356 L1
Figure imgf000042_0001
L/I°L Patent Application Publication Jan. 5, 2017 Sheet 3 of 20 US 2017/0005356 L1
Figure imgf000043_0002
FIG. 3 A
Figure imgf000043_0001
Figure imgf000043_0003
FIG. 3C
Figure imgf000044_0003
-50 -20 10 40 70 100 130 160 190 220 250 280 310 340 370 400
Temperature (°C)
FIG . 4
Figure imgf000044_0001
Figure imgf000044_0002
Patent Application Publication Jan. 5, 2017 Sheet 5 of 20 US 2017/0005356 L1
Figure imgf000045_0001
((UJO S)‘^i!A! npuoQ) 6o~| Patent Application Publication Jan. 5, 2017 Sheet 6 of 20 US 2017/0005356 L1
Figure imgf000046_0001
Patent Application Publication Jan. 5, 2017 Sheet 7 of 20 US 2017/0005356 L1
Figure imgf000047_0001
[(LUO/S)‘Ai!A!pnpuoQ] Bh Patent Application Publication Jan. 5, 2017 Sheet 8 of 20 US 2017/0005356 L1
Figure imgf000048_0001
Patent Application Publication Jan. 5, 2017 Sheet 9 of 20 US 2017/0005356 L1
Figure imgf000049_0001
Os
S: Patent Application Publication Jan. 5, 2017 Sheet 10 of 20 US 2017/0005356 L1
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000051_0002
Figure imgf000051_0003
Figure imgf000051_0004
Figure imgf000051_0006
Figure imgf000051_0007
Figure imgf000051_0008
Figure imgf000051_0005
1H chemical shift (ppm)
FIG, 11
Figure imgf000051_0009
Figure imgf000052_0001
134.7 ppm
Figure imgf000052_0002
Figure imgf000052_0004
Figure imgf000052_0003
Figure imgf000052_0005
Figure imgf000053_0001
Electron acceptor Proposed
MAS13 C NMR assignment:
Varian 500
Figure imgf000053_0002
Figure imgf000053_0003
pp
Figure imgf000053_0004
Figure imgf000053_0005
Figure imgf000053_0006
Figure imgf000053_0011
Figure imgf000053_0007
240 230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80
Figure imgf000053_0008
13 C chemical shift (ppm)
FfG.13
Figure imgf000053_0009
Figure imgf000053_0010
Patent Application Publication Jan. 5, 2017 Sheet 14 of 20 US 2017/0005356 L1
G FI.
Figure imgf000054_0001
Patent Application Publication Jan. 5, 2017 Sheet 15 of 20 US 2017/0005356 L1
Figure imgf000055_0001
Patent Application Publication Jan. 5, 2017 Sheet 16 of 20 US 2017/0005356 L1
Figure imgf000056_0001
b ϋ chemical shift (ppm)
FIG . 15
Figure imgf000057_0001
Patent Application Publication Jan. 5, 2017 Sheet 18 of 20 US 2017/0005356 L1
Figure imgf000058_0001
(A) oBei|OA ||OQ Patent Application Publication Jan. 5, 2017 Sheet 19 of 20 US 2017/0005356 L1
Figure imgf000059_0001
(L) QBBIIOL
Figure imgf000060_0001
L S 2017/0005356 L 1 Jan. 5, 2017
1
SOLID ION K ALIA CONDUCTING nism. but chain entanglements and partial crystallinity can POI .YYIF.R MAI L RIAL give the electrolyte some bulk properties o f a solid How ever segmental motion is essential for PTO to be ionically
FII iLD Ob TUT INVENTION conductive.
[1)01)7] 1‘laslici/ed polymer-salt complex are prepared by
[1)001 ] The present invent inn generally relates to polymer
adding liquid plasticizers into 1‘HO in such a way that a chemistry and particularly to solid polymer electrolytes and compromise between solid polymer and liquid electrolyte their methods of synthesis. exists The magnitude of ambient conductivity gets substan tially enhanced because segmental motion is increased but
RACKGROI JKD OF TPT I YTNTION
at the cost of deterioration in the mechanical integrity of the
| 00021 I he history of halleries has been one of slow film as well as increased corrosive reactivity of polymer progress and incremental improvements Rallery perfor electrolyte towards the metal electrode
mance cost and safety have historically been con Hiding [000S] Gel electrolytes are obtained by incorporating large goals requiring tradeoifs which limit the viability of end amount of liquid sol ent(s)/liquid plasticizer into a polymer applications such as grid-level storage and mobile power. matrix capable of forming a gel w ith the polymer host The demand for transformational batteries has reached the structure The liquid solvent remains trapped within the level of national interest driving a massive ellbrl to deliver matrix of the polymer and forms a liquid conductive path saf e electrochemical energy storage with higher energy way through the otherwise non-conduclive solid polymer density and lower cost. Gel electrolytes can tiller high ambient conductivities but
1000 1 Alessandro Volta invented the first true battery stiller from similar disadvantages as mentioned for the which became to be known as the ‘Voltaic pile”. This plast icized polymer electrolytes
consisted ol pairs of zinc and copper discs piled on top of [0000] Rubbery electrolytes are actually‘polymer-in-salt’ each other separated by a layer ofcloth or care board soaked systems in contrast to‘salt-in-polymer’ in which a large in brine as an electrolyte This discovery though not prac amount of salt is mixed with a small amount of polymer tical. gave rise to the understanding of electrochemical cells namely poly (ethylene oxide) (I’l lO). poly (propylene oxide) and the role of the electrolyte (PRO) etc The glass transition temperature o f these mate
[1)0(14] Since Volta inventors have created improvements rials can be low to maintain the rubbery or viscoelastic stale in liquid electrolytes which are based on a porous separator at room temperature which in turn provides high conduc filled w ith a concentrated solution of salt alkali or acid in tivity by enhancement of segmental motion However the waler or an organic solvent These liquid electrolytes are eomplexed/dissolved salts can have a tendency to crystal typically corrosive and/or combustible and in many cases lize hence hampering their uses in pract ical electrochemi thermodynamically unstable with the electrode materials cal devices
resulting in performance limitations and safely hazards [1)010] Composite polymer electrolytes are prepared sim These challenges make solid-slate electrolytes enormously ply by dispersing a small fraction of niicro/nanosixe inor attractive for battery development. Solid electrolytes can ganic (ceramic /organic filler particles into the conventional provide substantial benefits such as non-leakage o f the polymer host The polymer acts as a first phase while f iller electrolyte more flexible geometry higher energy density material are di persed in a second phase As a consequence electrodes and improved saf ely. of dispersal the ionic conductivity mechanical stability and
11)0051 Ceramics and glasses were the lirst solid materials the inlerfacial activity can be enhanced The ionic conduc to be discovered and developed to have ionic conductivity. tivity is attributed to the decrease in the level of polymer Additional materials followed but all of these materials all crystallinity in the presence of the fillers and the corre have the characteristic that sulftciently high ionic conduc sponding increase in segmental mot ion
tivity is only available at very high temperatures f or [1)011 ] 1‘olyelectrolyles include charged groups which are example. Toyota Japan has announced development work covalently bonded to the polymer backbone which allow using a new “crystalline superionic crystal” which is a opposite charged ions to be very mobile. The charged group glassy ceramic I i , C i eP^S ^ However this material only is flexible via segmental motion which is required for has high conductivity above 140‘ C and ceramics su ffer cationic diflusivily
from the usual problems of manufacturability and brittle [1)012] Other polymer electrolytes include Rod-Coil block ness. file manufacturing challenges with ceramics would be polyimides (NASA research) and various polymer/liquid particularly prohibitive for the incorporation of the material blends (ionic liquid, P Df -l IhRs). Unfortunately low con into battery electrodes ductivity at room temperature excludes all of these know n
[00(16] Init ial interest in polymer electrolytes was sparked polymer electrolytes f rom practical applications because o f in 1975 by fro lessor 1‘eler V. Wright’s discovery that their need for segmental motion to enable ionic conductivity complexes of polyethylene oxide (Tl fO) can conduct metal Since typical polymer electrolyte ionic conductivity relies ions Shortly after that. 1‘rofessor Michel Arniand recog on segmental motion above the material’s glass transition nized the potential use o f TTO-lilhmm salt complexes for temperature ( Tj all attempts to make a useful sol id polymer battery applications The combinat ion of PTO and lithium electrolyte have been focused on suppressing the crystalline salts has been in development for a number of years An phase and/or reduction of the temperature where the glassy example of this material is a l’(l iO)„ I ilJTTl complex f or slate transitions to a state (i e viscoelastic or rubbery) where the past thirty years there have been numerous attempts to segmental motion is enabled
improve the conductivity of Polyelhene Oxide ( 151 O ) - [0013] In polymer-salt complexes where both crystalline (P I, P !,())„ In these PT.O based materials cation and amorphous phases exist ion transport occurs in the mobility is governed by polymer segmental motion. This amorphous phase The Vugel-Tamman-bulcher (VfT) equa segmental motion of PI T) is effectively a liquid- like mecha tion describes the behavior of diffusion of ions through L S 2017/0005356 L 1 Jan. 5, 2017
2 polymers. 1 he \ I T equation is based on the assumption llial [1)030] Hie charge transfer complex of the material is ions arc transported by the semi random motion of short formed hy the reaction of a polymer electron acceptor, and polymer segments The onset of such segmental motion an ionic compound wherein each cat ionic and anionic occurs as the temperature is raised above the glass transition diffusing ion is a reaction produel of the ionic compound: temperature. Tg. and becomes more rapid as the temperature [1)0.3 1] The material is formed from at leasl one ionic is raised higher in the viscoelastic stale The segmental compound, wherein the ionic compound comprises each motions are thought to promote ion motion hy both disrupt cationic and anionic diffusing ion:
ing the solvation of the ion relative multiple coordination [0032] The material is a thermoplastic;
sites on the polymer and providing space or free volume into [1)0.33] The material's ealionie diffusing ion comprises which the ion may diffuse file fact that polymer segmental lithium:
motion is necessary for ion transport has typically required [0034] The material's at least one cat ionic and anionic that such complexes focus on amorphous materials with low diihtsing ion have a diffusivily, wherein the cationic di fiu- glass transition temperatures sivity is greater than the anionic iffusivily:
[1)0.35] The material's cationic transference number of the
SUMMARY Oh fl lh IN VI INTI ON material is greater than 0.5 and less than 1 0:
[D03(i] The material' s concentration of cationic diffusing
| l)l) 14| According to one aspect, a solid, ionically conduc
ion is greater than 3 moles of cation per liter oi material ; tive. polymer material is provided that comprises a crystal
[1)0.37] The material’s ealionie diffusing ion comprise linity greater than 10%: a melting temperature: a glassy
state: and both at least one cationic and anionic diffusing ion, lithium:
[1)0.38] The material's diffusing cation is nionovalenl: wherein each dillusing ion is mobile in the glassy slate The
[0039] The valence oi the diflusing ealionie ion is greater material may further comprise a plurality of charge transfer
than one:
complexes and
[0040] Hie material includes greater than one diffusing
[0015] a plurality o f monomers, wherein each charge anion per monomer:
trans fer complex is positioned on a monomer [0041 ] The material's diffusing anion is a hydroxyl ion:
| 0016 | I li an aspe t. a sulicl. seinicn s lllme. uinic lly [0042] The material's diffusing anion is monovalent : conductive, polymer material i provided liavinu,; a plurality [0043] The material's diffusing anion and the diihtsing o f monomers: a plurality o f charge transf er complexes, cation are monovalent:
wherein each charge transfer complex is positioned on a [0044] The material’s at least one cationic and anionic monomer The material may have a crystallinity greater than diihtsing ion have a dilfusivity. wherein the anionic di fiu- 30%: a glassy state which exists at temperatures below the sivity is greater than the cationic di ffusivily:
material melting temperature; and both a cationic and [0045] file material's cationic transference number of the anionic di ihtsing ion whereby each dilfusing ion is mobile material is equal to or less llian 0.5. and greater than zero: in the glassy state [1)046] The material's at leasl ealionie diffusing ion. lias a
[ 017] According hi further aspects of the solid, ionically diffusivily greater than 1 0x10 - J mr/S:
conductive, polymer mute rial, the aspects of the material [0047] The material's al least one anionic diffusing ion has may include one or more of the following: a diffusivily than 1.0x 10 mVs:
[0018] The charge trans fer complex is formed by the [1)048] The material's at leasl one anionic diffusing ion reaction of a polymer and an electron acceptor: and at least one ealionie di ihtsing ion has a dt flusivily
[1)019] The material has a glassy state and at least one greater than 1 0x 10 m Vs:
cationic and at least one anionic diffusing ion. wherein each [0049] T.ach monomer oi the material comprises an aro diffusing ion is mobile in the glassy slate; matic or heterocyclic ring structure positioned in the back
[ 020] The material has at least three dillusing ions: bone of the monomer:
[0021 ] The material includes more than one anionic di f [0050] The material further includes a helcroatom incor fusing ion; porated in the ring structure or positioned on the backbone
| l)l)22| flic melting temperature of the material is greater adjacent the ring structure:
than 250;> ('.: [0051] The material's included heleroatom is selected
11)02 1 fhe ionic conductivity of th material is greater from the group consisting of sulfur, oxygen or nitrogen: than l Ox l O-' S/ctn at room temperature: [0052] The material’s heleroatom is positioned on the
[1)024] Th e material comprises a single cationic dt flusmg backbone of the monomer adjacent the ring structure: ion. wherein the diffusivily of the cationic diffusin ion is [0053] The material's heleroatom is sul fur greater than l .Ox l O- - in- s at room temperature: [1)054] file material is pi-conjugated:
11)0251 flic maternal comprises a single anionic diffusing [0055] The material’s tit leasl anionic diffusing ion per ion wherein the di lfusivity o f the anionic diffusing ion is monomer, and wherein at least one monomer comprises a greater than 1 0x 10 nrVS at room temperature; lithium ion:
[0026] The material wherein at least one cationic diffus [0056] The material comprises a plurality o f monomers ing ion comprises an alkali metal, an alkaline earlli metal, a wherein the molecular weigh! of llie monomer is grealer transition metal, or a post transition metal: than 100 grams mole:
11)0271 flic material includes at least one anionic diffusing [0057] The material is hydrophilic:
ion per monomer; [0058] The ionic conductivity o f lhc material is isotropic:
[ 028] The material includes at least one cationic di flits i ng [0059] The material has an ionic conductivity grealer than ion per monomer: 1 x 10 " S/cm at room temperature:
| l)l)29| fhe material includes at least one mole of the [0060] The material lias an ionic conductivity grealer than cationic diffusing ion per liter material: 1x 10-' S/cm at K01’ C : L S 2017/0005356 L 1 Jan. 5, 2017
101)61 1 P malarial has an ionic conductivity greater llian [1)086] L further aspeel is a method of making a solid 1 x 1 0-' S/cm ill -40" ionically conductive polymer material comprising the tep
[0062] Th c material's cat ionic diiliising ion comprises oh mixing a polymer comprised o f a plurality ol monomers lithium and wherein the dillusivity oPίΐIiίiiih ion is greater and a compound comprising ions to create a iirst mixture: llian 1.0x 10 nr/s al room temperature: doping the first mixture with an electron acceptor to create
[006.1] The material in non -Hummable: a second mixture: and healing the second mixture
[0064] The material is not reactive when mixed with a [0087] L f urther aspect is a method of making a solid second material wherein the second material is selected from ionically conductive polymer material comprising the steps a group comprising a eleetroeheniieally active material an of: mixing a polymer comprised of a plurality of monomers electrically conductive material a rheological modifying and an electron acceptor to create a lirsl mixture; heating the material and a stabilizing material: first mixture to create an intermediate material comprising
[0065] The material is in the shape of a f ilm: charge transfer complexes: mixing the intermediate material
| 066| fhe Young’s modulus of the material is equal to or with a compound comprising ions to create the sol id ioni greater than 1 0 Ml‘a: cally conductive polymer material
| 0067| Th maleriL l be omes ionically conductive alter [1)088] f urther aspects of the methods of making u solid being doped by an electron acceptor: ionically conductive polymer material may include one of
[0008] The material becomes ionically conductive al ter more o f the following:
being doped by an electron acceptor in llie presence of an [0089] An anneal ing step wherein in the annealing step ionic compound that either contains both the cationic and the cry stal Unity of the base polymer is increased:
anionic dill'u sing ion or is convertible into both the cationic [0090] The base polymer comprises a plurality of mono and anionic diiliising ion via oxidation by the electron mers. and wherein the molar ratio of monomer to electron acceptor: acceptor is equal to or greater than 1 : 1 :
| 0069 | f li material is formed from the reaction product of
[1)091 ] [’he base polymer has a glass transition tempera a base polymer electron acceptor and an ionic compound:
ture and wherein the glass transition temperature of the base [ 070] Th e material’s base polymer is a conjugated poly
polymer is greater than K0l; ('.:
mer:
[0071 ] The ateriuTs base polymer is PPS or a liquid [0092] file weight ratio of the base polymer and the ionic crystal polymer: compound in the mixing step is less than 5 : 1 :
10072| fhe material’s ionic compound reactant is an [0091] Positive pressure is appl ied to the mixture in the oxide chloride hydroxide or a salt: heating step;
[007.1] Th e millormPs charge transfer complex is formed [0094] In the heating step the mixture undergoes a color b the reaction of an electron acceptor and a polymer: and change:
11)0741 fhe material's reactant electron acceptor is a ui- [0095] i the heating step charge transfer complexes are lione or oxygen. formed:
[ 075] In an aspect a solid ionically conducting macro- [0096] An additional mixing step of mixing the solid molecule and a material including the macromolecule is ionically conductive polymer material with a second male- provided which is comprised of: rial:
100761 a plurality of monomers. wherein each monomer [0097] An extruding step wherein the solid ionically comprises an aromatic or heterocyclic ring structure: conductive polymer material is extruded: and
[0077] a h eteroalom either incorporated in the ring struc [0098] An ion conducting step wherein the solid ionically ture or positioned adjacent the ring structure: conductive polymer material transports al least one ion
[0078] a cationic and anionic ddfusing ion wherein both [0099] further aspects include: An electrnchemically the cationic and anionic diffusing ions arc incorporated into active material composite comprising the material of previ the structure of the macromolecule: ous aspects and an eleetroeheniieally active material:
[0079] wherein both the cationic and anionic can dillu e [0100] An electrode comprising the material of previous along the macr molecule: aspects:
[0080] wherein there is no segmental motion in the poly [01 01 ] A battery comprising the material of previous mer material when a cationic or anionic diffuse along the aspects:
macromolec ule.
[01 02] A fuel cell comprising the material oi previous
[0081 ] 1 Tirther this aspect may include on or more of the
aspects:
following:
[0082] The material has an ionic conductivity greater than [ 1 1] An electrolyte comprising the material of previous aspects:
1 x 10 1 S/cni:
11)0811 fhe molecular weight of each monomer is greater [01 04] An apparatus fur conducting ions comprising the than 1 00 grams per mole: material o f of previous aspects:
[0084] T h material’s al least one cationic diiliising ion [01 05] A process for conducting ions comprising the male- comprises an alkali metal an alkal ine earth metal a transi rial of previous aspects: and
tion metal or a post transition metal [ 1 6] A process lor separating ions comprising the mate
11)085| Lh aspect is a method of making a solid ionically rial of previous aspects:
conductive polymer material comprising the steps of: mix [01 07] In a furt er aspect a new ionic conduction mecha ing a base polymer comprised of a plural ity ol monomers an nism which enables ionic conduction in both the crystalline electron acceptor and a ionic compound to create a f irst phase and the amorphous glassy stale of a polymer which mixture: heating the first mixture to create the solid ioni- enables a solid polymer material with the conductivity of a eally conductive polymer material. liquid at room temperature: L S 2017 000535 z\ 1 Jan. 5, 2017
4
101 OKI And allows th creation of composite anodes and both (a) L.S. patent application Ser. No. 14/559.430. tiled cathodes containing the polymer and elcctrochcmictdly Dee 1 2014 which claims priority from I J S Provisional act ive compounds [dr increased capacity and cycle life: Patent Appl icat ion No : 61 A 1 1 04T f iled Dec 3 201 3 ; and
| ()1 (1 | hnables the use of abundant and Ion oust active (b) from L.S. patent application Ser No. 13/86 1.170. hied materials: and Apr. 1 1. 2013. which claims priority from ITS Provisional
[1)1 10] Allows for a new battery manufacture methods Patent Application No : 61 /622 705 f iled Apr 1 1 201 2 the u in low cost high volume extrusion and other plastic disclosures of which are incorporated hy reference herein in processing techniques their entirety
101 11 1 These and other aspects. features advantages and [0114] The following explanat ions of terms are provided objects will be further understood and appreciated by those to belter detail the descriptions of aspects embodiments and skilled in the art by reference to the following specification objects that will be set forth in this section Lilies s explained claims and appended drawings or defined otherwise all technical and scienti f ic terms used herein have the same meaning as commonly understood to
BRU T DHSCRIPTION Oh 1 1 lli DRAWINGS one of ordinary skill in the art to which this disclosure 11) 1 121 In the draw ings: belongs. In order to facilitate review of the various embodi
I in id | f Ki. 1 is a plot of a cycle lest of I ithiuni Ion cells ments of the disclosure the following explanations of spe using I CO cathodes containing the solid ionically conduc cif ic terms are provided:
tive polymer material ; [0115] L depolarizer is a synonym of electrocbemically
[1)1 14] ] 1 ( r 2 is a plot of a discharge cnn c f or h xample active substance i e a substance which changes its oxida
| l)1 15| IΊίt. 3L. 3B and 3C arc x-ray Llilhraction plots tion slate or partakes in a formation or breaking of chemical described in Hxample 9: bonds in a charge-transfer step of an electrochemical reac
[OU ti] I K r 4 is a DSC plot described in Hxnmple 10: tion and elcctmchcmicahy active material When an elec [01 17] 1 I C r 5 is a plot o f the measured conduct ivity trode has more than one eleclroactive substances they can be relative temperature as described in Comparative hxample referred to as codepolari/ers.
13 : [1) 116] Thermoplastic is a characteristic of plastic mate
| l)1 18| f Ki. 6 is a plot of the measured conductivity rial or polymer to become pliable or moldable above a relative temperature as described in Comparative T sample speci fic temperature often around or at its melting tempera
13 : ture and to solidi fy upon cooling
11)1 1 | FIG. 7 is a plot of the measured conductivity for [0117] Solid electrolytes include solvent free polymers samples of the material described in hxample 14: and ceramic compounds (crystall ine and glasses )
| U 1201 Fit; 8 is a plot of the measured diffusivity relative
temperature lor samples of the materia] described in [0118] L "Solid’ is characterized hy the ability to keep its Hxample 16: shape over an indefinitely long period and is distinguished
10121 1 BIG 9 is a NMR dithusiviiy plot for a omparative' and different from a material in a liquid phase. The atomic structure of solids can be either crystalline or amorphous material described in Hxample 1 7:
Solids can be mixed with or be components in composite
| U 1221 f lti I t) is a NMR spectra of base polymer reactant
structures However for purposes of this application and its described in hxample 18
claims a solid material requires that that material be io i-
[1)123] FIG 1 1 is a NMR spectra of the material described
eally conductive through the solid and not through any in Hxample 1 . solvent gel or l iquid phase unless it is otherwise described
11)1241 Fit; 12 is a NMR spectra of the material described For purposes of this applicat ion and its claims gelled (or in Hxample I S. w et) polymers and oilier materials dependent on liquids for
[ 125] 1 '1( 1 1 1 is a NMR spectra of the electron acceptor ionic conductivity are deiined as not being solid electrolytes described in hxample 18 in that they rely on a liquid phase for their ionic conduct ivity
[1)126] FIG 14, \ is a NMR spectra of the material
[0119] A polymer is typically organic and comprised o f described in Hxample 18
carbon based macromolecules each o f which have one or
| l)127| Fit; 141 J is a NMR spectra of the material
more type o f repealing units or monomers Polymers are described in Hxample 18
light-weight ductile usually non-eonduelive and melt at
[0128] FIG I S Ls a NMR spectra of the material described
relatively low temperatures. Polymers can be made into in Hxample 1 products by injection blow and other molding processes
| l)129| Flti l b is a graphic depiction of a battery using the extrusion pressing stamping three dimensional printing material as described in Hxample HJ. machining and other plastic processes. Polymers typically
[I)11l)[ 1 I ( ί 17 is t discharge curve of three batteries as have a glassy stale at temperatures below the glass transition described in hxample 20 temperature Tg This glass temperature is a function o chain
[01 11 ] 1 I ( ί I S is a discharge curve for the batters as flexibility and occurs when there is enough vibrational described in Hxample 21 (thermal) energy in the system to create suilicient free-
| U 1 21 Fit; 1 !) is a discharge curve for the battery as volu e to permit sequences of segments of the polymer described in hxample 22 macromolecule to move together as a unit. However in the glassy state o f a polymer there is no segmental motion of the
DFTMI HD Dl SCRIP PON OF TI IF polymer
PRHFKRRHD HM1JODIMKNTS
[0140] Polymers are distinguished from ceramics which
[1)111] Th e present patent application clai priority from are def ined as inorganic non-tnetallic materials; typically L.S. Provisional Patent Application No : 62/ 158.841. filed compounds consisting of metals covalently bonded to oxy May 8. 2015 : and is a cnntinualion-In-Parl application of gen. nitrogen or carbon brittle strong and noil-conducting L S 2017/0005356 L 1 Jan. 5, 2017
I U 141 1 Tin; " lass transition. which occurs in sunn: poly pressure or vacuum) are applied All three components can m rs is n midpoint temperature between the supercooled be present and mixed and heated to complete the synthesis liquid stale and a glassy stale as a polymer material is oi lbe solid ionically conduct ive polymer material in a single cook'd The ihornuidynamic measuremenl of llie "lass step. However litis heating step can be done when in a transition are done by measuring a physical properly oi the separate step from any mixing or can completed while polymer e g volu e enthalpy or entropy and other deriva mixing is being done The heat ing step can be performed tive properties as a function oi temperature The glass regardless oi lbe form of the mixture (e g film particulate transit ion temperature is observed on such a plot as a break etc ) In an aspect of the synthesis method ail three compo in the selected properly (volume of enthalpy) or from a nents are mixed and then extruded into a film l lie him is change in slope (heal capacity or thermal expansion coef heated to complete the synthesis
f icient ) at llie transit ion temperature Upon cooling a poly [0149] When the solid ionically conducting polymer mate mer f rom above the Tg to below the Tg the polymer rial is synthesized a color change occurs which can he molecular mobility slows down until the polymer reaches its visually observed as the reactants color is a relatively light glassy stale. color and the solid ionically conducting polymer material is
| U 142 | As a polymer can com ri e both amorphous and a relatively dark or black color. It is believed that this color crystalline phase polymer crystallinity i the iimminl G this change occurs as charge transfer complexes are being crystalline phase relative the amount o f the polymer and is formed and can occur gradually or quickly depending on the represented as percentage C’rystallinity percentage can be synthesis method.
calculated via x-ray diffraction of th polymer by analysis of [1) 150] An aspect of the method of synthesis is mixing the the relative areas of the amorphous and crystalline phases. base polymer ionic compound and dopant together and [014.1] L polymer film is generally described as a thin heating the mixture in a second step As the dopant can he portion of polymer but should be understood as equal to or in the gas phase the healing step can he performed in the less than 300 micrometers thick presence of the dopant The mixing step can be performed in
| U 1441 It is important to not that the ionic conductivity is an extruder blender mill or other equipment typical of different from electrical conductivity. Ionic conductivity plastic processing The heating step can last several hours depends on ionic diflu ivily and the properties are related by (e g twenty-four (24) hours) and the color change is a the Nernsl-T.instein equation Ionic conductivity and ionic reliable indication that synthesis is complete or partially diffusivily arc both measures of ionic mobility. An ionic is complete Additional heating past syslhesis does not appear mobile in a material if its diffusivily in the material is to negatively affect flic material.
positive (greater than zero) or it contributes to a positive [1) 1 1] In an aspect of the syndic’s is method the base conductivity All such ionic mobility measurements arc polymer and ionic compound can be f irst mixed ['he dopant taken at room temperature (around 21 !> C i unless otherwise i then mi ed with the polymer- ionic co pound mi ture and staled. As ionic mobility is affected by temperature it can be heated. The healing can be applied to flic mixture during the difficult to detect at low temperatures Hquipmenl detection second mixture step or subsequent to the mixing step limits can be a f actor in determining small mobility amounts [1) 152] In another aspect of llic synthesis method the base Mobil ity can be understood as diffusivily of an ion at least polymer and the dopant are first mixed and then healed 1 x 1 0 1 m Vs and preferably at least I xl O ’ m 7s which This healing step can b applied a f ter the mixing or during both communicate ail ion is mobile in a material and produces a color change indicating the formation of the
| l)145| A so lid polymer kmicully conducting material is a charge transfer complexes and the read ion between the sol id that comprises a polymer and that conducts ions as will dopant and the base polymer The ionic compound is then he further described mixed to the reacted polymer dopant material to complete
[0146] An aspect of the present invention includes a the formation o f the solid ionically conduct ing polymer method f synthesizing a solid ionically conductive polymer material
material from at least three distinct components; a polymer [1) 15.4] Typical methods of adding llie dopant are known to a dopant and an ionic compound file components and th e skilled in the art and can include vapor doping of a iilm method oi ynthesis are chosen for the particular application containing the polymer and ionic compound and other o f the material The selection oi the polymer dopant and doping methods know n to those skilled in the art Upon ionic compound may also vary based on llie desired perfor doping the solid polymer material becomes ionically con mance of llie materi l. Tor example the desired components ductive. and it is believed llial lie do ing acts to activate the and method oi ynthesis may he determined by optimization ionic components oi lbe solid polymer materia] so they are o f a desired physical characteristic (c g ionic conductivity) diffusing ions
[0147] Synthesis: [0154] Other non-reaclive components can be added to the
11)141$ | 1 lie method of synthesis can also vary depending above described mixtures during the initial mixing steps on tlie particular components and the desired form of the end secondary mixing steps or mixing steps subsequent to lietil material (e.g. film particulate etc ) However the method ing Such other components include but are not limited to includes the basic steps o f mixing at least two o f the depolarizers or cleclrocbemically active materials such as components initially adding the third component in an anode or cathode active materials electrically conduct ive optional second mixing slop and lien ling the components materials such as carbons rheological agents such as binders reactants to synthesis the solid ionically conducting polymer or extrusion aids (e g ethylene propylene diene monomer material in a heat ing step In one aspect of the invention the "KPDM”) catalysts and other components useful to achieve resulting mixture can be opt ionally formed into a film oi the desired physical properties of the mixture desired size I f the dopant was not present in the mixture [01 5] Polymers that are useful as reactants in the synthe produced in the first step then it can be subsequently added sis of the solid ionically conductive polymer material arc to the mixture while heal and optionally pressure (positive electron donors or polymers which can be oxidized by L S 2017/0005356 L 1 Jan. 5, 2017
6 cluutRui a c ptors S mi- rys illin polvmuR w ith a crys flic heleroatoni can be located directly on the backbone or tallinity ind x reater than 30% and greater than 50% are bonded to a carbon atom which is posit ioned directly on the suitable reactant polymers Totally crystalline polymer backbone In both cases where the heteroatom is located on materials such as liquid crystal polymers ("I CPs”) are also the backbone or bonded to a carbon atom positioned on the useful as reactant polymers LC’Ps are totally crystalline and backbone the backbone atom is po itioned on the backbone therefore their crystallinity index is hereby defined as 100% adjacent to an aromat ic ring Kon-limit tng examples of the ndoped conjugated polymers and polymers such as poly polymers used in Ibis aspect of the invention can be selected phenylene sulf ide TPPS”) are also suitable polymer reac from the group including 1‘1’S. Polyfp-phenylene oxide) tants. GI'RO"). l .CTs. 1‘oly ether ether’ ketone’ (‘Tkff ’).
I’olypbthalamide (“PPV’) Polypyrrole Polyaniline and
| U 1561 Polymers are typically not electrically conductive 1’olysul (one Co-polymers including monomers o f the listed hor example virgin PPS has electrical conductivity of HG- polymers and mixtures of these polymers may also be used S cm - l hon-electrically conduct ive polymers are suitable for example copolymers of p-hydroxyben/oic acid can be reactant polymers appropriate liquid crystal polymer base polymers fable 11 157 In an aspect polymers useful as reactants can details non-limiting examples o f reactant polymers useful in possess an aromatic or heterocyclic component in the back the present invention along with monomer structure and bone of each repealing monomer group and a heteroalom some physical properly information which should be con either incorporated ill the heterocyclic ring or positioned sidered also non-limiting as polymers can take multiple along the backbone in a position adjacent the aromat ic ring forms which can aifect their physical properties
Figure imgf000066_0001
US 2017/0005356 L1 Jan.5,2017
7
Figure imgf000067_0001
n
Figure imgf000067_0003
oethylene ((fN4) also known as T( Mi. sulfur trioxide
( SO,”). o/one (trioxygen or O,). oxygen (() . including ( r O
air) transition metal oxides including manganese dioxide rvr: i
(“MnO,*’) or any suitable electron acceptor etc and com
binations thereof Dopants are those that are temperature
stable at the temperatures of the synthesis heating step are
useful and quinones and other dopants which are both
temperature stable and strong oxidizers quinones are most
Figure imgf000067_0002
useful Table 2 provides a non-limiting listing of dopants
along with their chemical diagrams i;S 2017/0005356 L 1 Jan. 5, 2017
8
Figure imgf000068_0001
above 1 20" C and more preferably above 150" C and most preferably above 200" C The base polymer has a melting
| ()159| i lni compounds that arc useful us reactants in the temperature of above 250" and preferably above 280" synthesis of the solid ionieally conductive polymer material and more preferably above 320l; G. The molecular weight of are compounds that release desired ions during the synthesis the monomeric unit of the hase polymer o f the invention is o f the solid ionieally conductive polymer material The tonic in the 100-200 g /mol range and can be greater than 200 gm/mol Typical materials that can he used for the base compound is distinct from the dopant in thal both an ionic
polymer include liquid crystal polymers and polyphenylene compound and a dopant arc required. Non-limiting
sullidc also known as ITS. or semi-crystalline polymer with examples include I LO. LiOl l. ZnO. 1KT. Al NaOl I.
a crystallinity index greater than 30% and preferably greater KOI I I iNO. Nu ;0~ MgO CaCl ,. MgCl, Aid. I iTLSI
than 50%
(lithium bis-lrifluoronielhancsul fbmmidci I iLSI (Lithium
[01 4] In this aspect the dopant is an electron acceptor bis(fluorosulfonyl)imidc). Lithium bis(oxalato)borate (Lil S such us. DDQ. TCNL. ehloranil and sulfur trioxide (803) ((’Tl,) , "I ii SOB") and other lithium salts and combinations file electron acceptor can be“pre-mixed" w ith all other thereof Hydrated forms (e.g. lnonohydride) of these com ingredients and extruded without post-processing or alter pounds can he used lo simplify handling of the compounds natively a doping procedure such as vapor doping can he Inorganic oxides chlorides and hydroxide are suitable ionic used to add the electron acceptor to the composition after compounds in thal they dissociate during synthesis to create other components are mixed such as in an extruder and at least one anionic and cationic diffusing ion Any such formed into a Him
ionic compound thal dissociates lo create al least one anionic [01 65] Typical compounds including an ion source or and cationic dillusing ion would similarly be suitable Mul "ionic compounds’ for use in this aspect o f the invention tiple ionic compounds can also be usef ul thal result in include but are not limited lo. Li ,0. LiOl l. ZnO. Tit),. multiple anionic and cationic di ffusing ions can be preferred L1 O ,. 1 i f LSI. and other lithium ionic compounds and The particular ionic compound included in the synthesis combinations thereof The ionic compounds contain appro depends on the utility desired for the material Lor example priate ions in stable form which are modified lo release the in an application where it ould be desired lo have a lithium ions during synthesis o f the solid ionieally conducting cation a lithium hydroxide or a lithium oxide convertible to polymer material.
a l ithium and hydroxide ion would he appropriate As would
he any l ithium containing compound that releases both a I 'xaniplc 1
lithium cathode and a di ffusing anion during synthesis L [1) 166] BPS and ehloranil pnw er are mixed in a 4 2: 1 non-limiting group of such lithium ionic compounds molar ratio (base polymer monomer to d pant ratio greater includes those used as lithium salts in organic solvents. than 1 : 1 ) The mixture is then heated in arg n or air at a high Similarly an aluminum or other speciiic ionic compound temperature | up to 350° C | for twenty-four (241 hours at reacts to release the specific desired ion and a dilfusing anion atmospheric pressure. A color change is observed eoniinn- during synthesis in those systems where an aluminum or ing the creation of charge transfer complexes in the polymer- other speci fic cation is desired As will be further demon dopant reaction mixture The reaction mixture is then strated. ionic compounds including alkaline metals alkaline regromid to a small average particle si/e between 1 -40 earth metals transition metals and post transition metals in micrometers J iTLSI is then mixed with the react ion mix a form that can produce both the desired cat ionic and anionic ture to create the synthesized solid ionieally conducting diffusing species are appropriate as synthesis reactant ionic polymer material.
compounds.
Lxample 2
[0160] Th c purity of the materials is potentially important
so as lo prevent any unintended side reactions and to [01 67] Lithium cobalt oxide (I iCoCLii"! CO”) cathodes maximize the effectiveness of the synthesis reaction to were prepared containing the synthesized material from produce a highly conductive material. Substantially pure Lxample 1 The cathodes used a high loading of 70% 1 CO reactants with generally high purities o f the dopant base by eight which is mixed w ith the solid ionieally conductive polymer and the ionic compound are preferred and purities polymer material and an electrically conducting carbon i;S 2017/0005356 L 1 Jan. 5, 2017
9
Culls were prepared using lithium metal amides, pern us oxygen, air. transition metal oxides, ineluding MnO ,. or any polypropylene separator and a standard I d-ton liquid elec suitable electron acceptor etc
trolyte composed of I iPKi salt and carbonate-based sol [0177] In this aspect, the compound including the ion vents. The cells were assembled in a dry glovebox and cycle source is a salt, a hydroxide, an oxide or other material tested. containing hydroxyl ions or convertible to such materials,
[Dl (i8] l b e capacity in terms of the weight in grams of including but not limited to, I iOI I, NaOI L KOH I i20 I CO used in these cells is displayed in h it I 1 It cart he seen I iN03. etc
that the capacity was stable when charged to 4 3 V and
consistent w ith the target of 0 5 equivalents of I i removed Txample 4
from the cathode during charging, flic cell was also cycled [0178] TBS polymer and I iOI I monohydrale were added to a higher charge voltage of 4 5V, which ut ilizes a higher together in the proportion of 67% to 33% (by wl ). respec percentage o f lithium f rom the cathode, and resulted in the tively. and mixed using jet milling Additional alkaline high capacity of >140 niAli/g The slight drop in capacity battery cathode components were additionally mixed: ith cycle number observed for the 4.5V charge tests is MnO,. Bi,0. and conductive carbon MnO, content varied consistent w ith decomposition (i e non-stable) of the liquid from 50 to 80 wl %. Bi,Q, ranged from 0 to 30 wl. %. carbon electrolyte at this high voltage Overall, the perf ormance of black amount was 3-25 wt % and polymer ! iOl 1 content the I CO cathode containing the material of the present was 10-30 wl %
invention is favorably comparable to a slurry coaled l .CO [0179] The mixture was healed to synthesize an alkaline cathode battery cathode comprising the sol id ionically conducting
11)16 1 Alkaline Batteries polymer material which is useful in a typical zinc-manga
[1)170] T he base polymer o f the solid ionically conducting nese dioxide alkaline battery.
polymer material having mobil ity for hydroxyl ions is
preferably a crystalline or semi-crystalline polymer which T.xample 5
typically has a crystallinity value above 30% and up to and
including 100% and preferably between 50% and 100% [0180] A zinc-manganese dioxide alkaline cell was cre The base polymer of this aspect o the invention has a glass ated using the cathode of T.xample 4 and a commercial transit ion temperature above 80‘‘ C , and pref erably above non-woven separator (NKK). /n foil anode, and 6M I iOI I 120l: and more preferably above 1501’ Ch. and most solution as an electrolyte.
preferably above 200l; C. file base polymer has a melting [1) 181 ] The cell was discharged under constant current temperature of above 25(G C . and preferably above 2 01' conditions of 0 5 tu \/cm2 using a Rio-I ogic VST 15 test and more preferably above 30(T C system The specific capacity o f MnQ2 was found to be 303
11) 171 1 fhe dopant of the solid, ionically conducting poly niAli g or close to theoretical 1 e- discharge mer material having mobility for hydroxyl ions is an elec [1) 182] Metal Air Battery
tron acceptor or oxidant Typical dopants for use in this [0183] In this aspect, the solid ionically conducting poly aspect o f the invention are DDQ cbloranil TCNT, SO,. mer material is used in a metal air battery and comprises a Oxygen (including Air). MnO, and other etal oxides etc base polymer a compound comprising an ion source and a
11) 1721 fhe compound including an ion source of the solid, dopant, fhe polymer can be selected from the group BBS. ionically conducting polymer material having mobility for l.C'B. Bolypyrrole. Tolyaniline. and
hydroxyd ions includes a salt a hydro ide, an o ide or other [0184] Polysulfone and Other Base Polymers material containing hydroxyl ions or convertible to such [0185] The dopant may be an electron acceptor or com materials, including hut not limited to I iOI I, NaOI L KOI I, pound containing functional electron acceptor groups I TO. l .iNO etc capable of initialing an oxidizing read ion w ith the polymer
Typical dopants are DDQ. chloranil. TCNT. S03. ozone,
Txample 3 and transition metal oxides, including Mn02 The material
11)1731 l’l’S polymer was mixed with the ionic compound comprising ion source can be in a form of salt hydroxide I iOI I monohydrate in the proportion of 67% to 33% (by oxide or other material containing hydroxyl ions or convert wt ), respectively and mixed using jet nulling DDQ dopant ible to such materials, including, but not limited to. I iOI I. was added via vapor doping to the resulting mixture in the Na(2>I I. KOI I. Ti20. I iN03. etc.
amount of 1 mole of DDQ per 4.2 moles of TBS monomer.
The mixture was heat treated at 1 90-200;1 C for 30 minutes T.xample 6
under moderate pressure (500-1000 PS I ) [018(i] The material synthesized in Txample 3 was used to
[0174] C'o tnp ilc MnO- O thod prepare air elect miles by m ixing the solid ionically conduc
| U175| Ill this aspect of the invention related to manufac tive polymer material w ith a variety of carbons Specifi ture of a solid ionically conducting polymer material cally: TIMCAL SLPTR C45 Conductive Carbon Black MnO, composite cathode the base polymer can be a semi- (('45 ) Timcal SlT ifi (synthet ic graphite), A5303 carbon cryslalline having a crystall inity index greater than 30% or black from Ashbury anil natural vein graphite nano 99 from a f ully crystalline polymer and can be selected f rom a group Ashbury (K 9 ) Carbon content was varied f rom 15 to 25% which consists of a conjugated polymer or a polymer which wl %.
can easily be oxidized ith a seleeted dopant. Non-limiting [0187] Cathodes were punched to ill a 2032 coin cell. Zinc examples of the base polymers used in this aspect o f the foil was used as the anode Non-woven separator was soaked invent ion include PBS, BBO, PT.TK, BBA etc with aqueous 40% KOI ! solution Two boles w ere drilled in
[1)176] In Ibis aspect, the dopant is an electron acceptor or the coin lop facing the cathode Cells w ere discharge at room oxidant Non-limiting examples of dopants are DDQ. cltlo- temperature using a MTI coin cell tester at a 0.5 mA constant ranil. letracyanoelhylene also known as TCNT, SO ; , ozone. current. L S 2017/0005356 L 1 Jan. 5, 2017
10
I ui »s| c 'atliode parameters and te t results are summa [1) 195] Ability to conduct a plurality of ions in addition to rized in the [’able 2 Discharge curves arc shown at I K i 2 the l ithium cation opens new a ppl teal ions for the material o[’he cells with the air cathode of this example using the the present invention Sodium- and potassium-based energy material til’ the present invention demonstrate typical dis storage systems are viewed as alternative to I i-ion. driven charge behavior lor Zn-air cells w ithout any traditional primarily by low cost and relative abundance of the raw catalyst (transition metal based) added to the mixture In materials Calcium magnesium and aluminum conductivity addition to conducting hydroxyl ions from the air cathode to is necessary for multivalent intercalat ion systems poten the anode the material acts to catalyze the formation oi the tially capable of increasing energy density beyond capabili hydroxyl ions from the oxygen present at the cathode ties of I i-ion batteries There is also a possibility to utilize surface As demonstrated by this example, the material of such materials to create power sources w ith metal anodes, the present invention possesses catalytic functionality more stable sa ler and less costly than lithium
ΊLHI 3 T.xample K
C eric r C h l i m i t : Wl ig a rc OCV i V;. niA li [0 l 9(i] Additional solid Ϊ on tea I ly conduct ive polymer i ( i so: : :>j o o v M ar s t e ssv s tes materials are listing in’fable 5 which were prepared using e vjy v; ;s :i iitv s " e-v l oans -vvnj the synthesis method of l ixample l . along with their reac tants and associated ionic conductivity (HIS method).
4 suis j s·- i: an a n /yt i a : ss t say
m
Figure imgf000070_0002
er | . l an an on c compoun n va ous propor
tions. l DlD was used a dopant Molar ratio of polymer
monomer to dopant was 4 2: 1 is listed in Table 4 Mixtures [0197] Additional solid ionically conduct ive polymer were heat treated at 1 90-200 C for 20 minutes under materials are listing in Table 6 which were prepared using moderate pressure (500- 1000 psi ) the synthesis method of l ixample 3. along with their reac
11)192| Samples were sandwiched between stainless sled tants and associated ionic conductivity (HIS method). electrodes and placed in test fixture AC impedance was
Figure imgf000070_0001
[1)194] Any ionic compound that can he disassociated by [0198] The I C Ps listed in the Tabic 6 w ere sourced from the dopant can be used as long as the dissociated ions are Solvay under the Xydar tradename, and arc TCI1 grades with desirable in the applicable electrochemical application the different melling temperatures
material is used in. The union and cationic derived from the [0199] Physical properties of the solid ionically conduct ionic compound are thus ionically conducted by the mate ing polymer material:
rial ['he ionic compound include oxides, chlorides, hydrox [0200] ['he physical properties of the solid ionically con ides and other sails In this example the medal (or other ductive polymer material can vary based on the reactants cation) oxides yield ihe metal (or other cation) cation and used flic specific ion mobility and anionic and cationic hydroxyl ions diffusing ions are derived from the material synthesis: i;S 2017/0005356 L 1 Jan. 5, 2017
1 1 however oilier physical properties app ar to hoΊ be signiii- range below the material melting temperature It is believed canlly altered relative the retictant polymer that the dip in the plot at 1 30” C is an artifact of the ionic compound
Hxample 9 [1)21)9] Ionic Conductivity
1 210 Ionic conductivity of the solid ionically conductive
[1)201 ] Crystall inity polymer material of the present invent ion arc measured and
[1)202] The reactants PI’S, DDQ and I iOI I from hxample compared relat ive conventional electrolytes The material o f 3 wa used to compare the relative physical properties of the the present invention was f ound to be ionically conductive reactant polymer and the synthesized solid ionioally con at ambient conditions while in the glassy slate, whereas the ductive polymer material reactant polymer was ionically insulalive As the material is
[1)20.3] In a first step, the PI’S reactant and the I iOH in the glassy stale, there cannot be any associated segmental monohydride were mixed and analyzed via x-ray diffraction motion, theref ore the di ff usion of the lithium cation and the (“XRD”). In f lit. 3 A. tlie XRD oi’lliis amorphous polymer anion must be enabled via a different ion conduction mecha mixture shows peaks between 30 and 34 degrees that nism in which segmental motion is not required.
correspond to the I iOI I monohydride. Other ise that XR1J [1)211 ] Specilically. films of lhe solid ionically conducting shows that the polymer is amorphous and lackin any polymer materials ol the present invention as described in significant crystallinity Hxample 1 are extruded in thickness ranging upwards from
[1)204] The m ixture is extruded and draw n into a iiltn The .0003 inches (7.6 micrometers) The ionic surface conduc healing of the PPS polymer via an extruder in this step tivity of the films is measured using a standard test of anneals (heating and holding at an appropriate temperature AC-Hleclrocheniical Impedance Spectroscopy (HIS) known helow the melting point followed hy slow cool ing) the to those o f ordinary skill in the art Samples of the solid amorphous PPS material while extruding the material into a ionically conducting polymer material film are sandw iched f ilm thus creating or increasing crystallinity In PIC i 315, betw een stainless steel blocking electrodes and placed ill a there is show n significant crystalline polymer peaks that also test lixlure A(’-impedance was recorded in the range from can be used to quantify the cry tallinity of the PPS material 800 KI Iz to 1 00 I I/ using a Hio-I ogic VSP test system to at about 60% The peaks of the I iOI I monohydride remain determine the material ionic conductivity In-plane and [0205] Th e f ilm mixture is then vapor doped with the through plane ionic conductivity was measured by using the DDQ dopant to create the solid ionically conductive poly Bio-l .ogic by placing the material film in an appropriate j ig mer material of the present invention and the corresponding Through plane conductivity was measured at b. l x lO-4 5/cm. XRD is shown in TICi. 3C L color change is observed and in-plane conductivity was measured at 3 5x 1 0-- S/cm during doping as the material turns black a fter being doped These measurements were similar enough to consider the[’his color change indicates that the ionic charge trans fer material isotropic relative ionic conductivity complexes are being f ormed, the polymer and dopant reac [1)212] Material from Hxample 1 was used to make a lilm tants have reacted in the presence of the ionic compound, of about 150 micrometers in thickness Hlectronic conduc and the material has been activated to become ionically tivity was directly measured via a polenlioslattc experiment conductive The polymer peaks remain and indicate that the The f ilm was place between two stainless steel blocking degree o f crystall inity of the material remains at about 60% electrodes, and a 0.25 V voltage was held across the elec and therefore unchanged. However, the I .iOI I monohydride trodes Current was measured at 180 nanoAmps yielding an peaks have disappeared and tire not replaced by any oilier electrical conductivity of 2.3x 10’ ohm cm- at room tem peaks. The conclusion draw n is that the ionic compound has perature This electrical conductivity (area specific resis disassociated into its component cation and anions and these tance) is low and below 1 0x 10 1 S/cm at room temperature ions are now part of the material structure which is su fficient for an electrolyte.
[1)21.3] Thermogrnvinietric analysis of the material from
[0206] C 1 lass Transition and Melting Point Temperature
Hxample 1 was conducted to determine the water content o f the material After storage of the material in a dry atmo
I 'lxample 10 sphere glove box, the thermogravimetric analysts was con
[1)207] Although there are many techniques for determi ducted and showed the material contains <5 ppm water nation of the melting temperature and Tg in a bulk or thin Certain sails (e.g. I iOI I as an ionic compound) used as film polymer sample, differential scanning calorimetry reactants for the solid ionically conductive polymer material ("DSC” and described in ASTM 07426 (2013 )) provides a attract al mo spheric wafer and thus can render the material rapid test method f or determining changes in specific heat hydrophilic.
capacity in a polymer material The glass transition tem
perature is manifested as a step change in specific heal Hxample 12
capacity [1)214] The modulus of the synthesized material of
| l)208| Referring to TICi 4. there is shown a DSC plot for Hxample 3 was tested The range of Young's modulus for the the synthesized material from Hxample 1 The melting point electrolyte made from this specif ic solid polymer materia] is o f the material [ PPfs-C hloranil-I iTHSI are derived via DSC 3 3-4 0 GPa However lire range of Young’s modulus for the and determined to not be different from the reactant polymer materials listed in this application is much larger and spans ITS: fin around 3(X)1; C’. The base polymer glass transition from 3 0 Ml’a to 4 Gl’a file synthesized material remains a temperature Tg is between 80- 100” C , however, in the DSC thermoplast ic, and can be reformed using plastic processing plot no Tg inflection appears and it is believed that upon techniques The materia] o f Hxample 3 was healed in excess synthesis, the solid ionically conductive polymer material of its melting point and then allowed to cool The material loses its viscoelastic slate which was evident in the PI’S base w as then reformed into a iiltn. Thus the material is show n to polymer and the gla sy stale extends below the temperature both have a high modulus and to be thermoplastic L S 2017/0005356 L 1 Jan. 5, 2017
12
(’omparalive Txample 13 lithium NMR method flic TGST-NMR measurements were made using a Varian-S Direct Drive 300 (7 1 T) spectrom
| l)215| The results of lhe ionic conductivity measurements
eter Magic angle spinning technique was used to average as reported in Txample 1 are illustrated in TIGS 5 and 6.
out chemical shift anisotropy and dipolar interaction. Pulsed [’he conduct ivily oi solid ionically conduct ive polymer
gradient spin stimulated echo pulse sequence was used for material film according to the invention (L ) is compared
the scl f-di fusion (dilfusivily ) measurements dlie measure with that oflrifluorumethnne sulfonate RTO (I I) and a liquid
ments of the sel f -diffusion coelbc tents for the cation and eleelrolyte made up of a I i salt solute and an ethylene
anion in each material sa ple were made using 111 and I i carbonate propylene carbonate“TCt PC” combination sol
nuclei respectively Hie NMR-determined self-dilfusiun vent using a Cclgard separator (Of
coefficient is a measure of random thermally induced trans
[1)216] Referring to IdC f 5 the measured conductivity of
lational motion akin to Brow nian motion where there is no the solid polymer ionically conductive material as a function
external directional driving force How ever self-diffusion is of temperature is displayed Also show are measured ionic
closely related to ionic mobility and ionic conductivity via conductivity o f both a l iquid electrolyte 1 if : 1 with I iPf’6
the Nerst Tinstein equation and hence is an important salt with a Celgard separator and a TTO-I iTTSI electrolyte
parameter to measure when characterizing battery electro flic conductivity of the solid ionically conductive polymer
lytes When one has both ionic conductivity and diffusion material at room temperature is about 2 5 orders of magni
data it is possible to ascertain the presence of ion pairing or tude higher compared to 1‘TO-TiTTSI electrolytes and com
higher aggregation effects that limit the performance of the parable to the conductivity of a conventional licptkl electro
electrolyte. These tests concluded that the solid polymer lyte/ separator system measured in similar condit ions The
ionically conductive material has a hi dilfusivily of 5.7x temperature dependence of the conductivity for the solid
10 1 1 m /s at room temperature making it higher than ionically conductive polymer material does not display a
PKO/I i'ff SI at 90;> C and at least an order o f magnitude sharp increase above its glass transition temperature asso
higher than I i , tf el 1 , S , (measured at high temperatures) ciated with chain mobility as described by Vogel -Ί am niatt- file solid ionically conductive polymer material can thus act hulcher behavior act ivated by temperature Therefore seg
as a new solid eleelrolyte with the unique ability to conduct mental movement as the ion-conduction mechanism in the
mult iple ions which can diffuse and be mobile and to polymer electrolyte material i not occurring as the material
provide sufficiently high ionic conductivity for batteries and displays signif icant ionic conductivity while in its glassy
other applications at room temperature.
state furthermore this demonstrates that the inventive
polymer material has a similar level of ionic conductivity [1)225] file ditfusivity of the Ol ff ion was 4.1 c KG ' nr/s at room temperature Thus the solid ionically conductive relative to liquid electrolytes.
polymer material has a very high di fhision rale for a solid
11)217| In hICi. 6. the ionic conductivity of the solid
ionically conductive polymer material is compared to both Ol I conductor The corresponding cation transference num the conventional liquid electrolyte comparative example ber (deiined in equation ( 1 ) below) is 0.58 . which is also lithium phosphorous oxynitride“TllON" and relative DOT significantly high and different from prior art solid electro targets for conductivity and temperature lytes
[0218] Referring to TIG 5B the ionic conductivity of the
Txample 1 6
sol id ionically conductive polymer material is greater than
1 x 1 0 1, 1 S/cm at room temperature (about 2G' (V) about [0226] Di lfusivily measurements were conducted on the l x l O”1 S/cm at about -301’ C. (and greater than 1 x 10 material created in Txample 1 | lTS-DD^-I iTTSI | Self S/cm. and greater than 1 x 10 S/cm at about H0l; G diffusion was measured using the technique set forward in
Txample 1 5 The material cat ion di f!usivily D ( I i ) o f
I !xample 1 4 0 23x 1 0 m /s at room temperature and the anion di flu-
[1)219] fh e ionic conductivity can be optimized by adjust sivity D ( ' l l ) o f Was 45x 10 " m Vs at room temperature ments to the material formulation TIG 7 shows improve [1)227] In order to determine the degree of ion association ments and optimization of ionic conductivity that have which would decrease the conductiv ity of the material the resulted from adj ustments to the polymer material formula conductivity o f the material is calculated via the ernsl- tion c g changes in base polymer dopant or ionic com Tinstein equation using the measured diffusion measure pound ments it was determined the associated calculated conduc
[0220] Dibits ivily tivity to be much greater than the measured conductivity
11)221 1 In addition to ionic conductivity dilfusivily is an file difference was on average at least an order of magnitude important intrinsic quality of any electrolyte and ionically (or l Ox) Theref ore it is believed that conductivity can he conductive material improved by improving ion dissociation and the calculated conductiv ities can be considered within the range of con
T.xample 1 5 ductivity
[1)228] The cation transference number can be estimated
[1)222] Di flits ivily measurements w ere conducted on the via equation ( 1 ) f rom the di ffusion coefficient data as: material created in Txample 3
11)2231 fundamental N VR techniques was used to unam
biguously identify l i+ as a free Row ing ion in the solid where 1 )+ and 1 )- refer to the diffusion coefficients of the I i ionically conductive polymer material NMR is element cation and T SI anion res ectively from the above data specific (c g I I I i C ] ' P and Co) and sensitive to small one obtains a t+ value of about 0 7 in the solid ionically changes in local structure conductive polymer materia] as compared t+ o f about 0 2 in
| l)224| Specifically the dilfusivily of lithium and hydroxyl the corresponding RTO electrolyte (liquid carbonate elec ions was evaluated by a pulsed gradient spin echo If Pt IS! l”) trolytes also have t+ values of about 0.2). This property of i;s 2017 0005356 L 1 Jan. 3, 2017
13 high cation transference number has impurU il implications Hxample 15 and 1 6. and a dilfusivity curve is set forward in Ui battery performanc Ideally one would prefer a t+ value PO 9 It was determined I iPON has a cation di ffusiv tty D o f 1 0 meaning that the I i ions carry all the electric current ( I i ) of 0 54x 10 17 niff s at 100" C ['his di flits ivily is about Anion mobility results in electrode polarization eifects eighty limes smaller than the dilfusivity of the material of which can limit battery performance. In materials where the present invention at ambient temperature (21 11 C'.). both ions can be mobile t+ values of 0 5 or greater are [0234] Chemical Structure of the Material highly sought though very rarely achieved The calculated [0235] experiments are conducted to determine inf orma trans ference number of 0 7 is not bel ieved to have been tion about the chemical structure oi the solid ionically observed in any liquid or 1’BO based electrolyte. Although conducting polymer material.
ion association may affect the calculation electrochemical [0236] Hxample l b
results confirm the trans ference number range o f between [0237] in this Hxample. the material synthesized in 0 65 and 0 75 Lxampic 3 is studied along with its reactant components
[1)229] It is believed thin the t+ is dependent on anion i’l'S and DDQ and I i Oi l monohydride
diffusion as lithium eatuui diffusion is high. As the cation [0238] The reactant or base polymer BPS is f irst analyzed diffusion is greater than the corresponding anion diffusion and referring to FIG 10 a proton ( l i) NMR spectrum of the cation transf erence number is always above 0 5 und as Li’S is characterized by a single peak centered at 6.8 ppm. the union is mobile the eat inn trans ference number must ulso relative to a letramelhylsilane (“TMS”) spectroscopic stan he less than 1 0 It is believed that u survey o f lithium suits dard 'ibis is a clear indication of aromatic hydrogen as as ionic compounds would produce this range of cation expected from the street lire of the polymer file proton solid transference numbers greater than 0 5 and less than 1 0 As slate MAS NMR spectrum of PI’S polymer was taken oil a a comparat ive example some ceramics have been reported 300 MHz instrument Asterisks denote spinning sidebands to have high di ffusion numbers however such ceramics only and the inset shows expanded resolution
transport a single ion. therefore the cation transference [0239] Referring to LK f 11 the I I NMR speclmm of the number reduces to 1 0 as the D- is zero solid ionically conductive polymer material (top) with
11)2 01 Although flic transference numbers tire being cal spectral deconvolution into Oi l-type protons (middle) and culated from NMR derived di fiusivily measurement alter aromatic protons (bottom) The spectrum confirms aromatic nat ive means o f calculating transference can he achieved by hydrogen and hydroxides The proton solid state MAS KMR direct methods such as the Bruce and Vincent method Hie spectrum o f material is taken on a 500 MHz instrument Bruce and Vincent methods was used to calculate the Asterisks denote spinning sidebands inset shows expanded transference number of the solid ionically conductive poly resolution. Spectral deconvolution into OTb and base poly mer material and good correlat ion was found relative the mer protons is shown in the inset as addit ional experimental NMR derived easurement spectrum Because KMR spectroscopy is quantitative (as
11)221 1 Referring to f Ki. 8 show a result of diffusion long as care was taken not to saturate the signal ) direct mea urements the solid ionically conductive polymer mate integration of the spectral peaks gives the proportion of rial over a large temperature' range and compared to 1‘l fO nuclei ill a particular phase Hie results of this integration containing I iTFSI as the ion source The most important shows that the material possesses greater than one mobile conclusions are: (i) at temperatures where both compounds OH ion per repeat group aromatic and contains about two can be measured the l i diffusion is nearly two orders of LiOl l molecules per polymer repeal unit (monomer) which magnitude higher in the solid polymer ionically conductive is a very high ion concentration The narrow Oi l signal material than in the RTO I iff] SI polymer electrolyte: (i ij the shows high mobility of the OH ion.
diffusion coefficients in solid polymer ionically conductive [0240] Additional structural inf ormation can he obtained material arc measurenble dow n to at least— 45 C a very by Carbon- 13 solid state MAS KMR which is enabled by low temperature for I i diffusion to be measured in any solid the—1% natural abundance of 1 Cross polarizat ion (CP) material speciiically the lithium ion ditfusivity is greater is utilized whereby nearby protons are resonated simulta than 1 x 1 fT ruffs lit is superior ionic conductivity perfor neously with the ‘C nuclei in such a way as to transfer mance o f the solid ionically conductive polymer material at nuclear magnetizat ion onto the “rare" spins to enhance low temperatures surpasses that of typical liquid battery detection sensit ivity In FIG 12 the Pi’S polymer spectrum electrolytes. It is also noteworthy that the NMR spectra is depicted under both direet polarization where all the temperature dependence suggests that ion motion is carbons participate in the signal (bottom) and Cl’ (lop) decoupled from the polymer in that it does not rely on where only those directly bonded to hydrogen participate polymer segmental motion and instead enables significant The di fference spectrum (middle) thus corresponds to car ionic diffusion ill its gla sy slate Thus there is demonstrated bon ho tided to sulf ur
a solid ionically conductive polymer material having a [1)241] Referring to l lti. 13 which displays the 'C spec crystallinity greater than 30%: a glassy stale: and both at trum MAS KMR spectrum of electron acceptor compound least one cat ionic and anionic di flusing ion wherein at least taken on a 500 Ml lz instrument by direct polarization with one (in tins aspect both diffusing ions) di ffusing ton is proposed spectral assignments o f the electron acceptor mobile in the glassy stale. DDQ Because there is no hydrogen in this molecule the
| 0232| (’omparalive Hxample 1 / spectrum was acquired under direct detection. Because of
1023.11 The cation dilfusivity of I il’ON is taken from very long spin-lattice relaxation limes (likely in excess of 1 “Structural C'haracteri/alion and I i dynamics in new I d ,1’S^ minute) the signal to noise ratio is rather low Assignments ceram ic ion conductor by solid-state and pulscd-iieid gra for the various peaks are indicated in FIG 13 The appear dient KMR” Mallory· ( iovel Steve Greenhanm Chengdu ance of six distinct peaks as opposed to the expected four Liang and iiaynri Saj u. Chemistry of Metals (2014) An (corresponding to four chemically incquivalenl carbons) experimental method is used similar to that set forward in suggests the possible presence of isomers. i;S 2017/0005356 L 1 Jan. 5, 2017
14
| l)242| The solid slattr MAS NMR spectrum of the electroeheniically active material or intercalation material sol id ionically conducting polymer material taken tin a 500 Again the solid ionically conductive polymer material is Mi l/ instrument by direct polarizat ion is shown in FIG mixed therewith along with an electrically conductive mate 14L. indicating a shill in the main peak (dominated by the rial. A film of the solid ionically conductive polymer mate aromatic carbon) in going from the PI’S to the ionically rial is used as a separalor/eleclrolyte 40 and interposed conducting material The CP spectrum in the middle of the between the anode anti cathode
inset suggests that the PP polymer is strongly interacting [0248] hxample 20
with the OI I groups of the I iOI I 1 ixpanded scale spectra of [0249] The solid ionically conductive polymer material both the material and DDQ electron acceptor are compared demonstrates compatibility with a w ide variety of current in Tlti. 14H. show ing that there has been a chemical reaction lithium ion chemistries. Referring to TICi. 17 performance of in the material that obscures the original spectral signatures baltenes constructed according to TICi. 16 and labeled o f the reactants according to the associated cathode eleclrochemically active
11)2411 This NMR analysis clearly shows that the three material Specifically batteries were constructed with distinct reactants have reacted to form the solid ionically hihel’O,. LiMigO, and 1 K'oO, cathodes. and lithium metal conductive polymer material of llie present invention. L new anodes. The batteries constructed with material of the pres material has been formed which is not merely a mixture of ent invention which was mixed with electrocliemically its constituents There is a reaction between the three com active material in the cathode used as an electrolyte to ponents and the solid polymer ionically conductive material conduct lithium ions to and from the anode and cathode and is the reaction product. In particular there is a shift in the demonstrates appropriate discharge performance 1‘C’ NMR peak between the base polymer and the synthe [1)250] Hy using the solid polymer material as an electro sized material Purlhermore the eflecl of simultaneous irra lyte in all battery structures or ill one of the structures diation of the 1 1 1 resonance of the hydrogen associated with (anode cathode separator and electrolyte) new levels o f Ol 1 and 1 '(’ resonance shows that the ions have been performance can be achieved without the use of any liquid incorporated into the structure so all three distinct compo electrolyte file material can be intermixed w ith an electro - nents have reacted and are part of the new synthesized chemically active material or an intercalation material in at material least one o f the electrodes Ions necessary in the electro chemical reaction of the battery are conducted through the
Llxample 19 electrolyte The material can be in a particulate slurry film
| l)244| Quanliiication of the cation (e.g. lithium ion) con or other form as befits the use ill a battery As a film the centration in llie material from hxample can be accom material can he interposed between electrodes or between an lished by inserting the material into an interior coaxial lube electrode and a current collector positioned encapsulating a and having it surrounded by an external ref erence solut ion of current collector or electrode or positioned anywhere where a shi ft reagent complex such as lithium Dysprosium poly ionic conductivity is required. As described in TIG 16 all phosphate (Dy). Referring to TICi. 15. a shift in hi cation three major components of a battery can be made using the resonance is induced by the paramagnetic Dy which allows solid polymer material. In the aspect shown in LKi. 16. the the quantif ication oi lithium in the sample In the measured film shaped electrodes and the interposed separator or elec sample the lithium cation concentration was found to be trolyte can be independent structure or be a ffixed to each about three moles per liter of materia] (| I i |--3 mole/1) This other by thermal welding or other means of integrating large concentration of cation enables the solid ionically thermoplastic Hints
conductive material to possess very high ionic conductivity
at room temperature and over a w ide temperature range l ixa tuple 2 1
[0245] Material Stability [1)251] A cathode was manufactured w ith I CO encapsu
[1)246] I iquid electrolytes and other polymer electrolytes lated by material from hxample 1 The cathode was paired can sulfer from lithium stability issues Their interaction with a lithium metal anode and a f ilm of the material was with lithium results in a reaction between the lithium and the interposed between the anode and cathode as described in electrolyte winch is disadvantageous for battery hie An the construction of MG 16. The assembled battery was then electrolyte also needs to be compatible and nun-reactive charged and discharged through a plural ity o f cycles FIG when used w ith other battery components such as eleclro- 18 shows the resulting discharge curve over many cycles chemically active materials including intercalation materi [0252] The charge-discharge curves show almost no polar als. electrically conductive additives rheological agent and ization. and the elite iency is at least 99% This result other additives In addit ion at high voltages above 4 0
demonstrates the polymer’s functionality as the ionic trans Volts typical electrolytes can simply decompose which port medium within the cathode and also its ability to serve again results in poor battery life Lithium '‘stability" is thus as the electrolyte in a solid state battery Also important is a requirement for a polymer electrolyte Spec ideally, the the voltage stability of the electrolyte while operating over polymer electrolyte is non-reaclive and does not decompose
four (4.0) Volts to 4 3V and to 5.0V. stability with lithium while transport ing l ithium etal at voltages above 4 0V
metal and stability transporting lithium at rates in excess of 4 5V and 5 0V
100 inAh/g (specifically at least: 133 5 tuAh/g l ithium)
11)247| Referring to TICi. 16. a thin Him battery construc
tion 11) is displayed. An anode comprises lithium metal 10 l ixa tuple 22
with an associated current collector (not shown) or an anode
intercalation material typical of lithium ion batteries I f an [0253] A I iS battery is constructed which includes lithium intercalation material is chosen the solid ionically conduc etal anode and a sul fur cathode made in the construction tive polymer material is intermixed therew ith A cathode 30 described in FIG. 16. Material from hxample 1 is used in comprises both a cathode collector (not shown) and an making the battery. Traditionally lithium- ulfur systems L S 2017/0005356 L 1 Jan. 5, 2017
15 have stru gled to o eiwme low c cle life iuse by the battery assembly or bending or other abuse of lhe battery dissolulion of sul fur reuclinri chemieul intermediaries in the Mechanical strength is typically defined in terms of the liquid electrolyte typical of such butteries tensile strength in both the machine (winding) direct ion and
| 0254| 1 lit; solid polymor material acts Ui enable a l i S the Iransverse direction in terms of tear resistance and system by limiting this dissolulion of reaction intermediates puncture strength. These parameters are delined in lerms of by capturing them in a solid system. The solid polymor Toting’ s modulus which is the ratio of stress to strain The material can transport lithium ions while blocking the poly- range of Young’s modulus f or the electrolyte made f rom the sul f ide ion f rom reaching the anode The sol id polymer solid polymer material is 5 0 MPa-4 0 C iPa and it can he material limits the solubility oi’ sulfur particles and transport engineered to be higher by utilizing additives such as glass of sullidos. thereby enabling more ol' lhe sulfur to participate liber or carbon fiber if required.
in the reaction and improving the capacity of the cathode [0262] The sol id electrolyte must remain stable over a fhis improved capacity relat ive a battery comprising a w ide temperature range w ithout curling or puckering laying standard cathode containing only sulfur and carbon is shown completely lint. Although the ionic transport properties of in f Ki. 19. Again it is important to note that this data was the solid electrolyte of the present invention vary with taken at room temperature file solid polymer material does temperature the structural integrity remains stable even not enable“indiscriminate di lfusion” typical o f liquid elec when exposed to extreme heat as will be more fully trolytes and some typical polymer electrolytes hnl instead described below
only enables dilfusion of the ions that are incorporated into [1)263] Thus the solid ionically conducting polymer mate the material during synthesis Thus sulhdes cannot diffuse rial meets the requires of a separator and solid polymer and are instead non-ionically conductive mu eh like any electrolyte as it performs each of the above listed require other ion other than the dillusing anion(s) and cation(s) ments Specifically the solid polymer electrolyte possesses Thus the material can act as an ion separation memhrane in a Young’s modulus greater than 3 0 MPa. thickness less than that it can be engineered to enable ion mobility for only 50 micrometers isotropic ionic conductivity dilfusivity of selected ions. multiple ions at temperatures as low as -451; C.. stability
| D255| Solid Lolvmer Lleclrolyte (non-reaclive) with lithium metal electrochemically act ive
[0256] As described the solid ionically conducting poly materials and electrically conductive additives at high volt mer material acts as a solid electrolyte As a solid electrolyte ages thermoplastic and moklable
it obviates the need for a separator but many of the same
separator properties are required of a solid electrolyte. Kxample 23
| 0257 | L separator is a ion permeable membrane plaeed [1)264] file solid polymer material was tested for flamma between a battery·’ anode and cathode dhe main fnnet ion of bility according to the parameters o f the 1 JI 94-VO flam a separator is to keep the two electrodes apart to prevent mability Test The sol id polymer material was found to he electrical short circuits while also allowing the transport of virtually non-llammahle self-extinguishing in two sec ionic charge carriers that are needed to close the circuit onds By UI 4-V0 standards in order to be considered during the passage of current in an electrochemical cell This nonllammable. the material needs to self-extinguish in less separation and ionic transport operations arc required in all than ten seconds
batteries [0265] While the invention has been described in detail
11)258| L solid electrolyte must also be chemically stable herein in accordance w ith certain preferred embodiments against the electrode materials under the strongly reactive thereof many modifications and changes therein may be environments when the battery is repeatedly fully charged affected by those skilled in the art w ithout departing from the and discharged The separator should not degrade during spirit of the invention Accordingly it is our intent to he normal and abnormal uses of the battery Of particular limited only by the scope of lhe appending claims and not by importance is voltage stability over the range of voltage way of the details and instrumentalities describing the encountered during charge and discharge embodiments shown herein.
11)259| L solid electrolyte must be thin to facilitate the [1)266] It is to be understood that variations and modifi battery’s energy and power densities However the solid cations can he made on the aforement ioned structure ithout electrolyte must operate as a separator and cannot be too thin departing from the concepts of the present invention and so as to compromise mechanical strength and safety Thick further it is to be understood that such concepts are intended ness should be uniform to support many charging cycles. to be covered by the following claims unless these claims by About 25 4 um-( 1 0 mil ) and less than 40 micrometers is their language expressly slate otherwise
generally the standard width The thickness o f a solid 1 L solid ionically conductive polymer material having: electrolyte can he measured using the Ί 41 1 om-K3 method a crystall inity greater than 30%; a melting temperature; by the Technical Association of lhe 1‘ulp and Paper Industry a glassy slate;
and has been extruded in thicknesses from 5- 1 50 microm and both at least one cationic and anionic diffusing ion. eters wherein at least one di ffusing ion is mobile in the glassy
[0260] Polymer separators typically increase the resis slate
tance of the electrolyte by a factor of four to five and 2. The material of claim 1. further comprising a plurality deviations from uniform permeability produce uneven cur of charge transfer complexes.
rent density distribution which causes the formation of 3. file material of claim 2. wherein the material comprises dendrites Both issues can be eliminated with the use of solid a plurality of monomers and wherein each charge transfer electrolyte that yields uni formity of and possesses isotropic complex is positioned on a monomer
ion conductivity. 4- 10 (canceled)
10261 1 The solid electrolyte must be strong enough to 11 file material of claim 1. hav ing at leasl three dillusing withstand the tension of any winding operation during ions. i;s 2017 0005356 L 1 Jan. 5, 2017
16
12. Tin; material of claim 1 . having more limn line anionic 36 file material of claim 1. wherein the cationic trans diffusing inn ference number of the material is equal to or less than 0 5
13 The material o f claim 1 wherein Ihc melting tem and greater than zero
perature el' the material is greater than 2501’ C. 37 flic material of claim 1. wherein one of the at least
14. The material tif daim 1. wherein the ionic conduc cationic diffusing ion. has a diffusivity greater than 1.0x 10 tivity of the material is greater than 1 0x 1 IP' S/cin at room m nr/s
temperature 38 The material o [ claim 1 wherein one o [ the at least one
15 The material of claim 1 wherein the material com anionic di ffusing ion has a di ihisivity greater than 1 0x 10 1 ' prises a single cationic dill’ll sing ion. wherein the diihisivity in 7s
ol’llie cationic dilhising ion is greater than I .Oc HG nr/s at 39 file material of claim 1. wherein one of both the at room temperature least one anionic diffusing ion and at least one cationic l (i The material of 1 wherein the material comprises a dilhising ion has a di ffusivity greater than l Oxl fT mr/s single anionic di ffusing ion wherein the di fliisivity of the 41) The material of claim 3 wherein each monomer anionic dilhising ion is greater than 1 Ox 10 1 ' ni VS at room comprises an aromatic or heterocyclic ring structure posi tempera tu re. tioned in the backbone of the monomer
17. The material of claim 1. wherein at least one cationic 41 Ihe material of claim 40. wherein the material further diff using ion comprises an alkal i metal an alkaline earth includes a heteroalom incorporated in the ring structure or metal a transit ion metal or a post transition metal posit ioned on the backbone adjacent the ring structure
IS. The material of claim 3. wherein there is at least one 42 file material of claim .3.3. wherein the heteroatom is anionic dilhising ion per monomer selected from the group consisting of sulfur oxygen or
1 i) . The material of claim 3. wherein there is at least one nitrogen
cat ionic dilhising ion per monomer 43 The material of claim 34 wherein the heteroatom is
20 The material oi claim 1 wherein there is at least one posit ioned on the backbone o f the monomer adjacent the mole oh the cationic diffusin ion per liter material. ring structure.
21. The material of claim 2. wherein the charge transfer 44 file material of claim .35. wherein the heteroatom is complex is formed by llie reaction of a polymer electron sulfu r
acceptor and an ionic compound wherein each cationic and 45 The material of claim 1 wherein the material is anionic di ffusing ion is a reaction product of the ionic pi-conjugated
compound 46 file material of claims 33. wherein there is at least one
22. The material of claim 1. wherein the material is anionic diffusing ion per monomer and wherein at least one formed from at least one ionic compound wherein the ionic monomer comprises a lithium ion
compound comprises each cationic and anionic di flusing 47 The material o f claim 1 wherein the polymer com ion prises a plurality of monomers wherein the molecular
23. file material of claim 1. wherein the material is a weight of the monomer is greater than 100 granis/niole. thermoplastic 48 1 he material of claims claim 1 or 5. wherein the
24. i he material of claim 1. wherein the cationic diffusing material is hydrophilic
ion comprises lithium 49 The material of claim 1 wherein the ionic conduc
25 The material o f claim 1 wherein each at least one tivity o f the material is isotropic
cationic and anionic diffusing ion have a diffusivity. wherein 51) The material of claim 1 having an ionic conductivity the cationic diffusivity is greater than the anionic diffusivity. greater than 1 x 10 S/cm at room temperature
26. file material of claim 1. wherein the cationic trans 51 file material of claim 1. having an ionic conductivity ference number of the material is greater than 0 5 and less greater than 1 x 10 ’ S cm at SO1’ C
than 1 0 52 The material of claim 1 having an ionic conductivity
27 The material o f claim 17 wherein the concentration of greater than 1 10’ S/cm at -TO1’ C
lithium is greater than 3 moles of lithium per liter of 5.3 fhe material of claim 1. where the cationic diffusing material. ion comprises lithium and wherein the diffusivity of lithium
28 'Ihe material of claim 19 wherein the cationic di f ion is greater than 1.0x 10 nr/s at room temperature fusing ion comprise lithium 54 The material of claim 1 wherein the material in
29 The material o f claim 1 wherein the dilhising cation non-tin mmablc
is monovalent 55 The material of claim 1 wherein the material remains
30. file material of claim 1. wherein the valence of the is noil-reactive when mixed w ilh a second material wherein diffusing cation is greater than one the second material is selected from a group comprising a
31 The material o f claim 3 wherein the material includes clectrochetnically act ive material an electrically conduct ive greater than one dilhising anion per monomer material a rheological modifying material and a stabilizing 32 The material of chum 1 wherein the di ffusing anion material
is a hydroxyl ion 56 file material of claim 1. wherein the material is in the
33. file material of claim 1. wherein diffusing anion is shape of a lilin
nionova lent. 57 file material of claim 1. herein the Young's modulus 34 The material of claim 1 wherein both the di lhising of the material is equal to or greater than 3 0 MPa anion and the diffusing cation are monovalent 58 L solid ionically conducting macromolecnle com 35 The material o f claim 1 wherein each at least one prised of:
cationic and anionic diffusing ion have a diffusivity. wherein a plurality of monomers wherein each monomer com the anionic diffusivity is greater than the cationic diffusivity. prises an aromatic or heterocyclic ring structure: i;s 2017 0005356 L 1 Jan. 5, 20 17
1 7 a heleroatom cither incorporated in tilt; ring r.tructure or 64 file material of claim 1. w herein the material becomes posit ioned adjacent the ring structure; ionically conductive alter being doped by an electron accep
:i cationic and anionic diffusin ton wherein both the tor in the presence o f an ionic compound that either contains cationic and anionic diffusing ions arc incorporated into both the cationic and anionic diffusing ion or is convertible the structure of the niacroinolecule; into both the cationic and anionic diffusing ion via oxidation by the electron acceptor
wherein both the cationic and anionic diffusing ions can
65 The material of claim 1 wherein the material is diffuse along the macromolecule:
formed from the reaction product of a base polymer electron wherein there is no segmental motion in the polymer acceptor and an ionic compound
material when the cationic or anionic di ffusing tons 66 'fhe material of claim 57 wherein the base polymer is diffuse along ihe niacroinolecule. a conjugated polymer
50. A material comprising the niacroinolecule of claim 58. 67 fhe material of claim 57. wherein the base polymer is
60. file material of claim 59. wherein the material has an PI‘5 or a liquid crystal polymer.
ionic conductivity greater than I x l O- S/cm 68 'fhe materia] of claim 57 wherein the ionic compound
61 fhe material of claim 59 wherein the molecular is an oxide chloride hydroxide or a salt
weight o f each monomer is greater than 100 grams per mole 69 fhe material of claim 2. wherein the charge transfer
62. The material ofclaim 59. wherein at least one cationic complex is formed by the reaction of an electron acceptor diifii ing ion comprises an alkali metal an alkaline earth and a polymer.
metal a transition metal or a post transition metal. 71) The material of claim 57 wherein the electron accep
65 The material o fclaim 1 wherein the material becomes tor is a quinonc or oxygen
ionically conductive after being doped by an electron accep 71 -92 (canceled)
tor
ATTACHMENT C
Figure imgf000078_0001
Figure imgf000079_0001
iiu, RW, SA, sc, sn, si;, SG, SK, SI, SM, ST, SV, SY, the earlier application /Rule 417 (ill)/
p 1, TJ, TM. TN, TR, TT, TZ, UA, UG. US. UZ, VC, ai inventorship (Hale 417/ivJ/
\ V ZA, ZM, Z\V
Published:
(84) Designated States /unless otherwise indicated for every
kind of regional protection uvaitabh): AR1PO (RW, (ill, — with international search report /Art 71/3/)
. \I. KIL I.R, I. , MW, MZ, NL, RW, SIX SI , ST, SZ, before the aspiration of the time limit lor tmentlinp. the TZ, UG, ZM, ZW), l!urasian (AM, LZ, I5Y, KG, KZ, RU, claims and to he republished at the ttnent of receipt of Tl. I'M), l!umpcan (AL. AT, l«;, IK* Gil, C'Y, C'Z. DH, amendments (Rule 131 i..
DK. I I t;.S, · I PR, till, GK, HR, IIU, IT, IS, IT, LT,
I L, I.V, MC, MK, MT, KI., NO, PI., PT, KO, RS, SH,
SI, SK, SM, TR), OLRI (HI', HJ, Cl', CCJ, Cl, CM, GA,
\ Gy, GW, KM, ML, MR, 'si SN, II) TG)
LITHIUM METAL BATTERY WITH SOLID POLYMER ELECTROLYTE
Figure imgf000080_0001
One or more embodiments relate to electrodes including a solid polymer electrolyte, manufacturing methods thereof, and lithium batteries containing the same
DESCR1PT1QN OF THE RELATED TECHNOLOGY
Lithium secondary batteries, provide an energy density by generating a discharge voltage below around 4 0 Volts. However, at higher voltages the typical electrolytes used in these batteries can decompose and limit the life of the battery. The electrolytes that have been developed so far do not afford such a high state of charge, and electrolyte stability at satisfactory levels
Typical electrolytes used in lithium secondary batteries also limit the temperature range of useful performance of such batteries L solid ionically conductive polymer material with high conductivity over a wide range of temperatures, including room temperature and below has been demonstrated to provide high performance over a wide temperature range.
The current state-of-the-art lithium ion electrode fabrication process involves several steps: mixing, slurry coating, drying, calendaring and electrode finishing. Some of these steps can be eliminated by using an extruded electrode method, incorporating the solid polymer electrolyte into the Lithium battery electrode
The present embodiments overcome the above problems as well as provide additional advantages
Figure imgf000080_0002
According to an aspect, a battery comprising: an anode having a first electrochemical!} active material; a cathode having both a second electrochemically active material and a first electrolyte; a second electrolyte interposed between the anode and the cathode, wherein at least one of the first electrolyte and second electrolyte comprises a solid polymer electrolyte; wherein the solid polymer electrolyte comprises both at least one cationic and anionic diffusing ion, wherein at least one cationic diffusing ions comprises lithium In the aspect, the battery the solid polymer electrolyte further comprises: a crystallinity greater than 0%; a melting temperature; a glassy state; and wherein at least one diffusing ion is mobile in the glassy state
Further aspects of the battery can include one or more of the following:
The battery wherein the solid polymer electrolyte further eomprises a plurality of eharge transfer complexes
The battery wherein the solid polymer electrolyte comprises a plurality of monomers, and wherein each charge transfer complex is positioned on a monomer
The battery wherein the electronic conductivity of the solid polymer electrolyte is less than 1 x 10 s S/cm at room temperature.
The battery wherein the solid polymer electrolyte comprises: a plurality of monomers; a plurality of charge transfer complexes, wherein each charge transfer complex is positioned on a monomer; wherein the electronic conductivity of the solid polymer electrolyte is less than 1 x 10 K S/cm at room temperature
T he battery wherein the crystallinity of the solid polymer electrolyte is greater than
30%
The battery wherein the solid polymer electrolyte has a glassy state which exists at temperatures below the melting temperature of the solid polymer electrolyte
The battery wherein the solid polymer electrolyte further comprises both a cationic and anionic diffusing ion, whereby at least one diffusing ion is mobile in a glassy state of the solid polymer electrolyte, and wherein the crystallinity of the solid polymer electrolyte is greater than 30%
The battery wherein the melting temperature of the solid polymer electrolyte is greater than 250°C
The battery wherein the solid polymer electrolyte is a thermoplastic
The battery wherein the ionic conductivity of the solid polymer electrolyte is isotropic
The battery wherein the solid polymer electrolyte is non-flammable.
The battery wherein the Young’s modulus of the solid polymer electrolyte is equal to or ureater than 3 0 MPa
2 The battery wherein the solid polymer electrolyte has a glassy state, and at least one cationic and at least one anionic diffusing ion, wherein each diffusing ion is mobile in the glassy state.
The battery wherein the ionic conductivity of the solid polymer electrolyte is greater than 1 0 x 10 ° S/cm at room temperature
The battery wherein the solid polymer electrolyte comprises a single cationic diffusing ion, wherein the single anionic diffusing ion comprises lithium, and wherein the diffusivity of the eationie diffusing ion is greater than 1 0 x 10 L m7s at room temperature
The battery wherein the solid polymer electrolyte comprises a single anionic diffusing ion, and wherein the diffusivity of the anionic diffusing ion is greater than 1.0 x 10 12 nr/s at room temperature.
The battery wherein one of the at least cationic diffusing ion, has a diffusivity greater than l O x l O ^ nTVs
The battery wherein one of the at least one anionic diffusing ion has a diffusivity greater than l O x l O ^ nf/s
The battery wherein one of both the at least one anionic diffusing ion and at least one cationic diffusing ion has a diffusivity greater than l O x 10 12 nr/s
The battery wherein the solid polymer electrolyte has an ionic conductivity greater than 1 x 10 4 S/cm at room temperature.
The wherein the solid polymer electrolyte has an ionic conductivity greater than 1 x 10’ S/em at 80“C
The battery wherein the solid polymer electrolyte has an ionie conductivity greater than 1 x 10 ' S/em at -40“C
The battery wherein the concentration of lithium is greater than 3 moles of lithium per liter of solid polymer electroly te
The battery wherein each at least one cationic and anionic diffusing ion have a diffusivity, wherein the cationic diffusivity i s greater than the anionic diffusivity
The battery wherein the cationic transference number of the solid polymer electrolyte is greater than 0 5 and less than 1 0
The battery wherein at least one diffusing anion is monovalent
The battery wherein at least one anionic diffusing ion comprises fluorine or boron
3 The battery wherein the solid polymer electrolyte comprises a plurality of monomers and wherein there is at least one anionic diffusing ion per monomer
The battery wherein the solid polymer electrolyte comprises a plurality of monomers and wherein there is at least one cationic diffusing ion per monomer.
The battery wherein there is at least one mole of the lithium per liter of solid polymer electrolyte
The battery wherein the solid polymer electrolyte comprises a plurality of monomers, wherein each monomer comprises an aromatic or heterocyclic ring structure positioned in the backbone of the monomer.
The battery wherein the solid polymer electrolyte further includes a heteroatom incorporated in the ring structure or positioned on the backbone adjacent the ring structure.
The battery wherein the heteroatom is selected from the group consisting of sulfur, oxygen or nitrogen
The battery wherein the hctcroatom is positioned on the backbone of the monomer adj cent the ring structure
The battery wherein the heteroatom is sulfur
The battery wherein the solid polymer electrolyte is pi-conjugated
The battery wherein the solid polymer electrolyte comprises a plurality of monomers, wherein the molecular weight of each monomer is greater than 100 grams/mole.
The battery wherein the charge transfer complex is formed by the reaction of a polymer, electron acceptor, and an ionic compound, wherein each cationic and anionic diffusing ion is a reaction product of the ionic compound
The battery wherein the solid polymer electrolyte is formed from at least one ionic compound, wherein the ionic compound comprises each at least one cationic and anionic diffusing ion
The battery wherein the charge transfer complex is formed by the reaction of a polymer and an electron acceptor.
The battery wherein the solid polymer electrolyte becomes ionically conductive after being doped by an electron acceptor in the presence of an ionic compound that either contains both a cationic and anionic diffusing ion or is convertible into both the cationic and anionic diffusing ion via reaction with the electron acceptor
4 The battery wherein the solid polymer electrolyte is formed from the reaction product of a base polymer electron acceptor and an ionic compound
The battery wherein the base poly er is a conjugated polymer.
The battery wherein the base polymer is PPS or a liquid crystal polymer
The battery wherein both the first and seeond electrolyte comprise the solid polymer electrolyte, wherein the electronic conductivity of the second electrolyte is less than 1 x 10 w S/cm at room temperature
The battery wherein both the first and seeond electrolyte comprise the solid polymer electrolyte
The battery wherein the anode comprises a third electrolyte, and wherein the third electrolyte comprises the solid polymer electrolyte.
The battery wherein the second electrolyte comprises the solid polymer electrolyte and is formed into a film, wherein the thickness of the film is between 200 and 15 micrometers
The battery wherein the second electrochcmically active material comprises an intercalation material
The battery wherein the second electro chemically active material comprises a lithium oxide comprising nickel, cobalt or manganese, or a combination of two or all three of these elements
The battery wherein the second electrochemically active material has an electrochemical potential greater than 4 2 volts relative lithium metal
The battery wherein the cathode has an electrode potential greater than 4 2 volts relative lithium metal
The battery wherein the second electrochcmically active material is intermixed with an electrically conductive material and the solid polymer electrolyte.
The battery wherein the electrically conductive material comprises carbon.
The battery wherein the cathode comprises 70-90 percent by weight of the second electrochemically active material
The battery wherein the cathode comprises 4- 1 5 percent by weight of the solid polymer electrolyte
The battery wherein the cathode comprises 2- 10 percent by weight of an electrically conductive material
5 The battery wherein the electrically conductive material comprises carbon.
The battery wherein the cathode is formed from a slurry.
The battery wherein the cathode is positioned on a cathode collector
The battery wherein the second electro chemically active material comprises a lithium oxide or a lithium phosphate that contain nickel, cobalt or manganese
The batters wherein the second electro chemically active material comprises a lithium intercalation material, wherein the lithium intercalation material comprises lithium
The battery wherein the lithium intercalation material comprises Lithium Nickel Cobalt Aluminum Oxide; Lithium Nickel Cobalt Manganese Oxide; Lithium Iron Phosphate; Lithium Manganese Oxide; Lithium cobalt phosphate or lithium manganese nickel oxide, Lithium Cobalt Oxide, LiTiS2 , LiNiO?, or combinations thereof
The battery wherein the second electrochcmically active material comprises an clcctrochemically active cathode compound that reacts with lithium in a solid state redox reaction
The battery' wherein the electrochcmically active cathode material comprises a metal halide; Sulfur; Selenium; Tellurium; Iodine; FeS; or l,i;-
The battery wherein the lithium intercalation material comprises Lithium Nickel Cobalt Manganese Oxide, wherein the atomic concentration of nickel in the Lithium Nickel Cobalt Manganese Oxide is greater than the atomic concentration of cobalt or manganese
The battery wherein the cathode is about 15 to 1 15 micrometers in thickness
The battery wherein the cathode coating density in the range of 1 2 to 3 6 g/cc
The battery' wherein the first electrochcmically active material comprises an intercalation material.
The battery wherein the anode further comprises the solid polymer electrolyte, wherein the first electrochemically active material is mixed with the solid polymer electrolyte.
The battery wherein the first electrochcmically active material comprises lithium metal
The battery' wherein the lithium metal in the anode 20 micrometers or less in thickness
6 The battery further comprising an anode current collector in ionic communication with the anode, wherein lithium deposits on the anode current collector when the battery is charged
The battery wherein the density of the lithium deposited on the anode current collector is greater than 0 4 g/cc
The battery further comprising an anode current collector in ionic communication with the anode, wherein the electrolyte is positioned adjacent the anode current collector
The battery wherein the first clcctrochemically active material comprises Silicon, Tin, antimony, lead, Cobalt, Iron, Titanium, Nickel, magnesium, aluminum, gallium, Germanium, phosphorus, arsenic, bismuth, zinc, carbon and mixtures thereof
The battery wherein the second electrochemically active material comprises an intercalation material, wherein the first electrochemically active material comprises lithium metal
The battery wherein the charged voltage of the battery' is greater than 4 1 volts The battery wherein the charged voltage of the battery' is greater than 4 5 volts
The battery wherein the charged voltage of the battery' is greater than 5 0 volts
The battery wherein lithium is cycled between the anode and cathode at a rate greater than 0.5 m.A/cmr at room temperature
The battery wherein lithium is cycled between the anode and cathode at a rate greater than 1 .0 m.A/cmr at room temperature
The battery wherein the lithium is cycled between the anode and cathode for greater than 150 cycles
The battery' wherein lithium is cycled between the anode and cathode at a rate greater than 3 0 mAh/cm' at room temperature for greater than ten cycles
The battery wherein lithium is cycled between the anode and cathode at a rate greater than 1 8 0 mAh/cnr.
The battery wherein lithium is cycled between the anode and cathode at a rate greater than 0.25 m Ah/cnr at room temperature for greater than 150 cycles
The battery further comprising an anode current collector, wherein lithium is plated onto the anode current collector when the battery is charged, wherein the density of the lithium plated onto the anode current collector is greater than 0 4 g/cc
The battery wherein the lithium cycling efficiency is greater than 99° o
7 The battery wherein the second electrolyte comprises the solid polymer electrolyte and is formed into a film, and wherein the first electrolyte comprises the solid polymer electrolyte, whereby the second electrolyte is attached to the cathode
The battery wherein the second electrolyte comprises the solid polymer electrolyte and is formed into a film, and wherein the anode eom prises a third electrolyte, and wherein the third electrolyte comprises the solid polymer electrolyte, whereby the second electrolyte is attached to the anode
In an aspect, a method of manufacturing a battery comprising the steps of: mixing a polymer with an electron acceptor to create a first mixture; heating the first mixture to form a reaction product comprising a plurality charge transfer complexes; mixing at least one ionic compound comprising lithium with the reaction product to form a solid ionically conductive polymer material.
Further aspects of the method of manufacturing a battery can include one or more of the following:
The method further comprising including mixing an intercalation material w ith the solid ionically conductive polymer material to form a cathode
The method wherein the cathode forming step further includes mixing an electrically conductive material with the intercalation material and the solid ionically conductive polymer material.
The method wherein the cathode forming step further comprising a calendaring step wherein the density of the cathode is increased
The method wherein the solid ionically conductive polymer material is formed into a film to form a solid polymer electrolyte
The method wherein the dopant is a quinonc
The method wherein the polymer is PPS, a conjugated polymer or a liquid crystal polymer.
The method wherein the ionic compound is a salt, hydroxide, oxide or other material containing lithium.
8 The method wherein the ionic compound comprises lithium oxide, lithium hydroxide, lithium nitrate, lithium bis-trifluoromethanesulfonimide, Lithium bis(fluorosulfonyl)imide, Lithium bis(oxalato)borate, lithium trifluorom ethane sulfonate), lithium hexafluorophosphate, lithium tetrafluorob orate, or lithium h e x a P u oro arse n ate. and combinations thereof
The method wherein in the heating step the first mixture is heated to a temperature between 250 and 450 deg C
The method wherein the cathode is positioned adjacent an electrically conducting cathode current collector to form a cathode assembly
The method wherein the solid ionically conductive polymer material is formed into a film to form a solid polymer electrolyte.
The method further comprising an electrically conducting anode current collector and an enclosure, and further comprising an assembly step wherein the solid polymer electrolyte is positioned between the anode current collector and the cathode assembly to form a battery assembly, and the battery assembly is placed within the enclosure
The method wherein the battery further comprises a anode and a cathode, wherein the solid ionically conductive polymer material is formed into a film to form a solid polymer electroly te, further comprising attaching the film to the anode, the cathode or both the anode and the cathode
The method wherein in the attaching step the film is coextruded with either the anode, cathode or both the anode and the cathode
These and other features, advantages, and objects of the present invention will be further understood and appreciated by those skilled in the art by reference to the following specification, claims, and appended drawings
BRIEF DESCRIPTION OG THF. DRAWINGS
In the drawings:
FIG. 1 is a representation of a battery cross section;
FIG 2 is a plot of a capacity voltage (CV) curve of a battery deseribed in
Example 2, which is cycled at two different voltages,
FIG 3 is cycle plot of a battery described in Example 4;
FIG 4 is cycle plot of a battery described in Example 4;
9 FIG. 5 is cyclic voltammetry plot of a battery described in F.x ample 5;
FIG. 6 is cyclic voltammetry plot of a comparative battery described in Example 6;
FIG. 7 is a representation of a test fixture cross section described in Ex ample 7;
FIG. 8 is cycle plot of a battery described in Fx ample 7;
FIG 9 is electrochemical impedance spectroscopy (FIS) plot of a battery described in Example 8, and
FIG 10 is a voltage relative time plot of a battery described in Example 9
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
This application claims the benefit of U.S Provisional Patent Application
No 62/ 170, 963 filed June 4, 2015; hereby incorporated by reference; and also incorporates by reference U. S Provisional Patent Application No 62/ 158,841 filed May 8, 2015, U S Patent Application 14/559,430 filed December 3, 2014; U S Provisional Patent Application No 61/91 1 ,049 filed December 3, 2013, U Patent Application No 13/861 , 170 filed April 1 1, 2013, and U Provisional Patent Application No 61/622,705 filed April 1 1 , 2012
The present invention includes a lithium metal battery enabled to operate efficiently at a high voltage by a solid ionically conductive polymer material
The following explanations of terms are provided to better detail the descriptions of aspects, embodiments and objects that will be set forth in this section Unless explained or defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs In order to facilitate review of the various embodiments of the disclosure, the following explanations of specific terms are provided:
A depolarizer is a synonym of electrochemically active substance, i.e., a substance which changes its oxidation state, or partakes in a formation or breaking of chemical bonds, in a charge-transfer step of an electrochemical reaction and electrochemically active material. When an electrode has more than one electroactive substances they can be referred to as eodcpolarizcrs
Thermoplastic is a characteristic of a plastic material or polymer to become pliable or moldable above a specific temperature often around or at its melting temperature and to solidify upon cooling
10 Solid electrolytes include solvent free polymers, and ceramic compounds (crystalline and glasses).
A“Solid” is characterized by the ability to keep its shape over an indefinitely long period, and is distinguished and different from a material in a liquid phase The atomic structure of solids can be cither crystalline or amorphous Solids can be mixed with or be components in composite structures However, for purposes of this application and its claims, a solid material requires that that material be ionically conductive through the solid and not through any solvent, gel or liquid phase, unless it is otherwise described Tor purposes of this application and its claims, gelled (or wet) polymers and other materials dependent on liquids for ionic conductivity are defined as not being solid electrolytes in that they rely on a liquid phase for their ionic conductivity.
A polymer is typically organic and comprised of carbon based macromolecules, each of which have one or more type of repeating units or monomers Polymers arc light weight, ductile, usually non -conductive and melt at relatively low temperatures Polymers can be made into products by injection, blow and other molding processes, extrusion, pressing, stamping, three dimensional printing, machining and other plastic processes Polymers typically have a glassy state at temperatures below the glass transition temperature Tg. This glass temperature is a function of chain flexibility, and occurs when there is enough vibrational (thermal) energy in the system to create sufficient free-volume to permit sequences of segments of the polymer macromolecule to move together as a unit However, in the glassy state of a polymer, there is no segmental motion of the polymer
Polymers arc distinguished from ceramics which are defined as inorganic, non- metal lie materials, typically compounds consisting of metals covalently bonded to oxygen, nitrogen or carbon, brittle, strong and non-conducting
1 1 The glass transition, which occurs in some polymers, is a midpoint temperature between the supercooled liquid state and a glassy state as a polymer material is cooled. The thermodynamic measurements of the glass transition are done by measuring a physical property of the polymer, e.g volume, enthalpy or entropy and other derivative properties as a function of temperature The glass transition temperature is observed on such a plot as a break in the selected property (volume of enthalpy) or from a ehange in slope (heat capacity or thermal expansion coefficient) at the transition temperature Upon cooling a polymer from above the Tg to below the Tg, the polymer molecular mobility slows down until the polymer reaches its glassy state.
As a polymer can comprise both amorphous and crystalline phase, polymer cry stallinity is the amount of this crystalline phase relative the amount of the polymer and is represented as a percentage Crystallinity percentage can be calculated via x-ray diffraction of the polymer by analysis of the relative areas of the amorphous and crystalline phases
L polymer film is generally described as a thin portion of polymer, but should be understood as equal to or less than 300 micrometers thick
It is important to note that the ionic conductivity is different from electrical conductivity Ionic conductivity depends on ionic diffusi vity, and the properties are related by the Nemst-F.in stein equation tonic conductivity and ionic diffusi vity are both measures of ionic mobility An ionic is mobile in a material if its diffusi vity in the material is positive (greater than zero), or it contributes to a positive conductivity All such ionic mobility measurements are taken at room temperature (around 2 l“C), unless otherwise stated As ionic mobility is affected by temperature, it can be difficult to detect at low temperatures Equipment detection limits can be a factor in determining small mobility amounts Mobility can be understood as diffusivity of an ion at least 1 x 10 14 m2/s and preferably at least 1 xl 0 1 m2/s, which both communicate an ion is mobile in a material.
A solid polymer ionically conducting material is a solid that comprises a polymer and that conducts ions as will be further described
12 An aspect includes a method of synthesizing a solid ionically conductive polymer material from at least three distinct components: a polymer, a dopant and an ionic compound The components and method of synthesis are chosen for the particular application of the material The selection of the polymer, dopant and ionic compound may also vary based on the desired performance of the material Tor example, the desired components and method of synthesis may be determined by optimization of a desired physical characteristic (e g ionic conductivity)
Synthesis:
The method of synthesis can also vary depending on the particular components and the desired form of the end material (e g film, parti eu late, ete ) However, the method includes the basic steps of mixing at least two of the components initially, adding the third component in an optional second mixing step, and heating the components/ react ants to synthesis the solid ionically conducting polymer material in a heating step In one aspect of the invention, the resulting mixture can be optionally formed into a film of desired si/e If the dopant was not present in the mixture produced in the first step, then it can be subsequently added to the mixture while heat and optionally pressure (positive pressure or vacuum) arc applied All three components ean be present and mixed and heated to complete the synthesis of the solid ionically conductive polymer material in a single step However, this heating step can be done when in a separate step from any mixing or can completed while mixing is being done The heating step can be performed regardless of the form of the mixture (e g. film, particulate, etc.) In an aspect of the synthesis method, all three components are mixed and then extruded into a film. The film is heated to complete the synthesis
When the solid ionically conducting polymer material is synthesized, a color change occurs which ean be visually observed as the reactants color is a relatively light color, and the solid ionically conducting polymer material is a relatively dark or black color It is believed that this color change occurs as charge transfer complexes are being formed, and can occur gradually or quickly depending on the synthesis method.
An aspect of the method of synthesis is mixing the base polymer, ionic compound and dopant together and heating the mixture in a second step As the dopant can be in the gas phase, the heating step can be performed in the presence of the dopant The mixing
13 step can be performed in an extruder, blender, mill or other equipment typical of plastic processing. The heating step can last several hours (e.g. twenty-four (24) hours) and the color change is a reliable indication that synthesis is complete or partially complete. Additional heating past synthesis (color change) does not appear to negatively affect the material
In an aspect of the synthesis method, the base polymer and ionie compound ean be first mixed The dopant is then mixed with the polymer-ionic compound mixture and heated The heating can be applied to the mixture during the second mixture step or subsequent to the mixing step
In another aspect of the synthesis method, the base polymer and the dopant are first mixed, and then heated. This heating step can be applied after the mixing or during, and produces a color change indicating the formation of the charge transfer complexes and the reaction between the dopant and the base polymer The ionic compound is then mixed to the reacted polymer dopant material to complete the formation of the solid ionically conducting polymer material
Typical methods of adding the dopant are known to those skilled in the art and ean include vapor doping of film containing the base polymer and ionic compound and other doping methods known to those skilled in the art. Upon doping the solid polymer material becomes ionically conductive, and it is believed that he doping acts to activate the ionic components of the solid polymer material so they are diffusing ions.
Other non-rcactive components ean be added to the above described mixtures during the initial mixing steps, secondary mixing steps or mixing steps subsequent to heating Such other components include but arc not limited to depolarizers or clcctrochemically active materials such as anode or cathode active materials, electrically conductive materials such as carbons, rheological agents such as binders or extrusion aids (e g. ethylene propylene diene monomer“UPDVt”), catalysts and other components useful to achieve the desired phy sical properties of the mixture.
Polymers that are useful as reactants in the synthesis of the solid ionically conductive polymer material arc electron donors or polymers which ean be oxidized by electron acceptors Semi-crystalline polymers with a crystallinity index greater than 30%, and greater than 50% arc suitable reactant polymers Totally crystalline polymer materials such as liquid crystal polymers (“LCPs’) arc also useful as reactant polymers LCPs are
14 totally crystalline and therefore their crystallinity index is hereby defined as 100% Undoped conjugated polymers and polymers such as polyphenylene sulfide (“PPS”) are also suitable polymer reactants.
Polymers are typically not electrically conductive. For example, virgin PPS has electrical conductivity of 10’° S cm 1 Non-clcctrically conductive polymers arc suitable reactant polymers
In an aspect, polymers useful as reactants can possess an aromatic or heterocyclic component in the backbone of each repeating monomer group, and a hetcroatom either incorporated in the heterocyclic ring or positioned along the backbone in a position adjacent the aromatic ring The heteroatom can be located directly on the backbone or bonded to a carbon atom which is positioned directly on the backbone. In both cases where the heteroatom is located on the backbone or bonded to a carbon atom positioned on the backbone, the backbone atom is positioned on the backbone adjacent to an aromatic ring Non-limiting examples of the polymers used in this aspect of the invention can be selected from the group including PPS, Poly(p-phcnylenc oxide)(‘PPO’), LCPs, Polyether ether ketone (‘PHUK.’), Polyphthalamide (‘RRL’), Polypyrrole, Polyaniline, and Polysulfone. Co-polymers including monomers of the listed polymers and mixtures of these polymers may also be used. For example, copolymers of p-hydroxybenzoic acid can be appropriate liquid crystal polymer base polymers
Table 1 details non-limiting examples of reactant polymers useful in the synthesis of the solid ionically conductive polymer material along with monomer structure and some physical property information which should be considered also non-limiting as polymers can take multiple forms which can affect their physical properties
\ 5 TABI.I71
Figure imgf000095_0001
16 Dopants that are useful as reactants in the synthesis of the solid ionically conductive polymer aterial are electron acceptors or oxidants. It is believed that the dopant acts to release ions for ionic transport and mobility, and it is believed to create a site analogous to a charge transfer complex or site within the polymer to allow for ionic 5 conductivity Non-limiting examples of useful dopants arc qui nones such as: 2,3-dicyano- 5,6-dichlorodicyanoquinone (CsCbNTO?) also known as ‘DDQ’, and tetrachloro-1,4- benzoquinonc (Cf,Cl O;-), also known as chloranil, tetracyanoethylenc (Cf,N ) also known as TCNIty sulfur trioxide (“SO;’), ozone (trioxygen or CL), oxygen (O;-, including air), transition metal oxides including manganese dioxide (“MnCL”), or any suitable electron 10 acceptor, etc. and combinations thereof Dopants that are temperature stable at the temperatures of the synthesis heating step are useful, and qui nones and other dopants which are both temperature stable and strong oxidi/ers qui nones are very useful Table 2 provides a non-limiting listing of dopants, along with their chemical diagrams
\ 5 TABLE 2
Figure imgf000096_0001
tonic compounds that are useful as reactants in the synthesis of the solid ionically conductive polymer material are compounds that release desired lithium ions during the synthesis of the solid ionically conductive polymer material The ionic compound is 0 distinct from the dopant in that both an ionic compound and a dopant arc required Non-
1 7 limiting examples include I.f-O, Li Oil, LiNCL, I.iTFSI (lithium bis- trifluoromethanesulfonimide), Li LSI (Lithium bis(nuorosulfbnyl)imide), Lithium bis(oxalato)borate (LiBftbCL “Li BOB”), lithium Inflate LiCFiChS (lithium trifluorom ethane sulfonate), LiPF6 (lithium hexafluorophosphate), LiBF4 (lithium tetrafluoroborate), LiAsF6 (lithium hexafluoroarscnatc) and other lithium salts and combinations thereof Hydrated forms (e g monohydride) of these compounds can be used to simplify handling of the compounds Inorganic oxides, chlorides and hydroxide arc suitable ionic compounds in that they dissociate during synthesis to create at least one anionic and cationic diffusing ion Any such ionic compound that dissociates to create at least one anionic and cationic diffusing ion would similarly be suitable Multiple ionic compounds can also be useful that result in multiple anionic and cationic diffusing ions can be preferred The particular ionic compound included in the synthesis depends on the utility desired for the material For example, in an aspect where it would be desired to have a lithium cation, a lithium hydroxide, or a lithium oxide convertible to a lithium and hydroxide ion would be appropriate As would be any lithium containing compound that releases both a lithium cathode and a diffusing anion during synthesis A non-limiting group of such lithium ionic compounds includes those used as lithium salts in organic solvents.
The purity of the materials is potentially important so as to prevent any unintended side reactions and to maximize the effectiveness of the synthesis reaction to produce a highly conductive material Substanti lly pure reactants with generally high purities of the dopant, base polymer and the ionic compound are useful, and purities greater than 98% arc more useful with even higher purities, e g LiOH: 99 6%, DDQ: >98%», and Chloranih >99% also useful
To further describe the utility of the solid ionically conductive polymer material and the versatility of the above described method of the synthesis of the solid ionically conductive polymer material, use of the solid ionically conductive polymer material in certain aspects of lithium metal electrochemical applications are described:
Referring to FIG 1 there is shown the battery 10 of an aspect in a cross sectional view The battery includes both a cathode 20 and an anode 30 l he cathode is positioned adjacent or is attached to a cathode current collector 40 which can act to conduct electrons to the cathode l he anode 30 is similarly positioned adjacent or is attached to an anode
1 8 current collector 50 which also acts to conduct electrons from the anode to an external load. Interposed between the anode 50 and the cathode 20 is the solid polymer electrolyte 60 which acts both as a dielectric layer preventing electrical conduction and internal shorts between the anode and cathode while ionically conducting ions between the anode and cathode
The described battery components arc similar to typical battery components however the solid polymer electrolyte and its combination with each battery component is further described in aspects of the lithium cell
The anode current collector 50 is electrically conducting and positioned adjacent the solid polymer electrolyte film 60 Interposed between the anode current collector and the solid polymer electrolyte is an anode which can comprise any of the multiple typical lithium intercalation materials or lithium metal Upon charge the solid polymer electrolyte acts to conduct lithium metal to the anode, and to the lithium intercalation material in an aspect, or to the anode current collector if lithium metal is used In the aspect of a lithium metal anode excess lithium can be added to the cell and is maintained at the anode collector and can act as a deposition surface upon cell charging
In the aspect when an anode intercalation material is used as the anode electrochemical!} active material, useful anode materials include typical anode intercalation materials comprising: lithium titanium oxide (LTO), Silicon (Si), germanium (Ge), and tin (Sn) anodes doped and undoped; and other elements, such as antimony (Sb), lead (Pb), Cobalt (Co), Iron (he). Titanium ( hi), Nickel (Ni), magnesium (Mg), aluminum (L1), gallium (Ga), Germanium (Gc), phosphorus (P), arsenic (As), bismuth (Bi), and zinc (Zn) doped and undoped; oxides, nitrides, phosphides, and hydrides of the foregoing, and carbons (C) including nano structured carbon, graphite, graphene and other materials including carbon, and mixtures thereof. In this aspect the anode intercalation material can be mixed with and dispersed within the solid ionically conducting polymer material such that the solid ionically conducting polymer material can act to ionically conduct the lithium ions to and from the intercalation material during both intercalation and deintcrcalation (or lithiation/dclithiation)
In the aspect when lithium metal is used, the lithium can be added with the cathode material, added to the anode as lithium foil, dispersed in the solid ionically conducting polymer material, or added to both battery components
1 The solid polymer electrolyte acts to transport the lithium metal to and from the anode and therefore must be positioned within the battery so it is enabled to do so Thus the solid polymer electrolyte can be positioned as a film layer in a planar or jellyroll battery construction, a convolute positioned around the anode current collector, or any other shape which enables the solid polymer electrolyte to perform its lithium ion conduction The thickness of the solid polymer electrolyte can be in a desired range of uniform thicknesses such as 200 to 25 micrometers or thinner To aid in extrusion of the solid polymer electrolyte, a rheological or extrusion aid can be added such as LPDM (ethylene propylene diene monomer) in amounts necessary to affect the desired extrusion properties
The cathode current collector 40 is also a typical aluminum or other electrically conducting film onto which the cathode 20 can be located or positioned.
Typical clcctrochemically active cathode compounds which can be used include but are not limited to: NCA - Lithium Nickel Cobalt Aluminum Oxide (LiNiCoA102); NCM (NIMC) - Lithium Nickel Cobalt Manganese Oxide (LiNiCoMnO;-), LLP - Lithium Iron Phosphate (LibePCf), LMO - Lithium Manganese Oxide (LiMn;-0 ); LCO - Lithium Cobalt Oxide (LiCoCL); lithium oxides tor phosphates that contain nickel, cobalt or manganese, and LiTiS2, LiN~i02, and other layered materials, other spinels, other olivines and tavorites, and combinations thereof. In an aspect, the electrochemically active cathode compounds can be an intercalation material or a cathode material that reacts with the lithium in a solid state redox reaction Such conversion cathode materials include: metal halides including but not limited to metal fluorides such as bebb, Bibb, Cub?, and Nlibb, and metal chlorides including but not limited to beCL, bed;-, CoCf-, NiCf-, Cud;-, and AgCl; Sulfur (S); Selenium (Se); Tellerium (Tc); Iodine (I); Oxygen (O), and related materials such as but not limited to pyrite (beS?) and LLS As the solid polymer electrolyte is stable at high voltages (exceeding 5 0V relative the anode electrochemically active material), an aspect is to increase the energy density by enabling as high a voltage battery as possible, therefore high voltage cathode compounds are preferred in this aspect. Certain NCM or NIMC material can provide such high voltages with high concentrations of the nickel atom In an aspect, NCMs that have an atomic percentage of nickel which is greater than that of cobalt or manganese, such as NCM- · NCM · NCM · · . NCMK i i , NC\L; .
20 and NCM i ; , are useful to provide a higher voltage relative the anode electrochemical!} active material
EXAMPLES
The battery article and its components arc described here, and ways to make and use them arc illustrated in the following examples
Example 1
PPS and chloranil powder are mixed in a 4 2: 1 molar ratio (base polymer monomer to dopant ratio greater than 1 : 1 ). The mixture is then heated in argon or air at a temperature up to 350°C for about twenty-four (24) hours at atmospheric pressure A color change is observed confirming the creation of charge transfer complexes in the polymer- dopant reaction mixture The reaction mixture is then reground to a small average particle size between 1 -40 micrometers LiTFSl powder ( 12 wt % of total mixture) is then mixed with the reaction mixture to create the synthesized solid, ionically conducting polymer material The solid, ionically conducting polymer material which is used as a solid polymer electrolyte in this aspect is referred to as a solid polymer electrolyte when thus used.
The solid polymer electrolyte can be used in multiple locations in a battery, including in an electrode, or as a standalone dielectric, non-electrochemically active electrolyte interposed between electrodes. When so used, the solid polymer electrolyte can be the same material in all battery application, and in the aspect of a lithium battery if the ionic mobility of lithium is maximized, this property and attribute of the solid polymer electrolyte allows the solid polymer electrolyte to function well in an anode, cathode and as a standalone dielectric, non-clcctrochcmically active electrolyte interposed between anode and cathode electrodes. However, in an aspect, the solid polymer electrolyte can vary so as to accommodate different properties that may be desired in an application In a non-limiting example, an electronically conductive material could be added to the solid polymer electrolyte or integrated into the solid polymer electrolyte during its synthesis thus increasing the electrical conductivity of the solid polymer electrolyte and making it suitable for use in an electrode and reducing and or eliminating the need for additional electrical conductive additives in such an electrode lf so used, such a formulation would not be appropriate for use as a standalone dielectric, non-electrochemically active
2 1 electrolyte interposed between anode and cathode electrodes as it is electrically conductive and would act to short the battery
Further, use of the solid polymer electrolyte in an anode, cathode and as a standalone dielectric, non-el ectrochenii call y active electrolyte interposed between anode and cathode electrodes enables a battery designer to take advantage of the thermoplastic nature of the solid polymer electrolyte The standalone dielectric, non-elcctrochcmically active electrolyte can be thermoformed onto the anode or cathode by being heated and fixed thereto, such as in a lamination process, or by being co-extruded and thus formed together with the electrode In an aspect all three battery components include the solid polymer electrolyte and are thermoformed together or coextruded to form a battery
Flee ironic conductivity of the synthesized material is measured using potentio static method between blocking electrodes, and was determined to be 6 5 x 10 S/cm or less than 1 x 10 w S/em
Diffusivity measurements were conducted on the synthesized material PGSH- NMR measurements were made using a Varian-S Direct Drive 300 (7 1 T) spectrometer Magic angle spinning technique was used to average out chemical shift anisotropy and dipolar interaction Pulsed gradient spin stimulated echo pulse sequence was used for the self-diffusion (diffusivity) measurements The measurements of the self-diffusion coefficients for the cation and anion in each material sample were made using’ll and Li nuclei, respectively The material cation diffusivity D ( Fi) of 0.23 xI O 9 nr/s at room temperature, and the anion diffusivity D (lH) of was 0 45 x 10 9 m7s at room temperature
In order to determine the degree of ion association which would decrease the conductivity of the material, the conductivity of the material is calculated via the ernst- Hinstein equation, using the measured diffusion measurements, it was determined the associated calculated conductivity to be much greater than the measured conductivity. The difference was on average at least an order of magnitude (or l Ox). Therefore, it is believed that conductivity can be improved by improving ion dissociation, and the calculated conductivities can be considered within the range of conductivity
The cation transference number can be estimated via equation ( 1) from the diffusion coefficient data as: t- - D-/(D+ + D-) ( 1 )
22 where D - and D- refer to the diffusion coefficients of the Li cation and TFSI anion, respectively From the above data, one obtains a L value of about 0.7 in the solid ionically conductive polymer material This property of high cation transference number has important implications to battery performance. Ideally one would prefer a t value of 1 0, meaning that the Li ions ca all the electric current Anion mobility results in electrode polarization effects which can limit battery' performance The calculated transference number of 0 7 is not believed to have been observed in any liquid or PHO based electrolyte Although ion association may affect the calculation, electrochemical results confirm the transference number range of between 0 65 and 0.75
It is believed that the 1 1 is dependent on anion diffusion as lithium cation diffusion is high. As the cation diffusion is greater than the corresponding anion diffusion the cation transference number is always above 0 5, and as the anion is mobile the cation transference number must also be less than TO It is believed that a survey of lithium salts as ionic compounds would produce this range of cation transference numbers greater than 0 5 and less than TO As a comparative example, some ceramics have been reported to have high diffusion numbers, however such ceramics only transport a single ion, therefore the cation transference number reduces to 1 .0 as the D- is zero
Hxamplc 2
Lithium cobalt oxide (LiCoO;-)(“LCO”) cathodes were prepared containing the synthesized material from Fxample 1 . The cathodes used a loading of 70% LCO by weight which is mixed with the solid ionically conductive polymer material and an electrically conducting carbon. Cells were prepared using lithium metal anodes, porous polypropylene separator and a standard Li-ion liquid electrolyte composed of LiPFf, salt and carbonate-based solvents The cells were assembled in a dry glovebox and cycle tested
The capacity in terms of the weight in grams of LCO used in these cells is displayed in FIG. 2. It can be seen that the capacity was stable when charged to 4.3 V, and consistent with the target of 0 5 equivalents of Li removed from the cathode during charging The cell was also cycled to a higher charge voltage of 4.5V, which utilizes a higher percentage of lithium from the cathode, and resulted in the high capacity of > 140 mAh/g The slight drop in capacity with cycle number observed for the 4 5 V charge tests
23 is consistent with decomposition (i.e non-stable) of the liquid electrolyte at this higher voltage. Overall, the performance of the ECO cathode containing the material of the present invention is favorably comparable to a slurry coated ECO cathode.
Example 3
Additional solid ionically conductive polymer materials are listing in Table , along with the material synthesized and described in Example 1 (PPS-Chloranil-LiTESl), which were prepared using the synthesis method of Example 1, along with their reactants and associated ionic conductivity (EIS method) at room temperature.
Table 3:
Figure imgf000103_0001
Various physical properties of the solid ionically conductive polymer materials are measured and it is determined that the solid ionically conductive polymer materials: the electronic area specific resistance is greater than I xl Cd Ohm-cnr; can be molded to thicknesses from 200 micrometers down to 20 micrometers; possesses significant ionic mobility to very low temperatures, e g -40°C, and have ionic conductivities at room temperature greater than 1 0E-05 S/cm, 1 0E-04 S/cm, and l OE-03 S/em, and these ionic conductivities include lithium as one of the mobile ions being conducted through the solid ionically conductive polymer material
Example 4
To demonstrate the ability of the solid polymer electrolyte to be combined with a lithium ion electrochemically active material, anodes were prepared with materials such as graphite (meso-carbon micro beads), silicon, tin, and lithium titanatc (LifTEOu, LTO) These materials were chosen for evaluation since they arc currently cither being used in
24 commercially available Li-ion cells, or are actively being researched for application to Li- ion anodes. In each case, solid poly er electrolyte material was added to the active anode material and an anode was prepared These anodes were then tested by cycling versus a lithium metal anode with polypropylene separator and standard liquid electrolyte. Results of this testing arc presented in FlGs 3 and 4 FIG 3 displays a cycle test of a Tin anode combined with the solid polymer electrolyte The Li/Sn and solid polymer electrolyte coin cell is discharged at a constant current of 0 5 m/V and charged at a constant current of 0 2 mA FIG 4 displays a cycle test of a Graphite anode combined with the solid polymer electrolyte. The Li /Graphite and solid polymer electrolyte coin cell is discharged at a constant current of 0.5 mA, and charged at a constant current of 0.2 mA.
In each case, the solid polymer electrolyte w'as found to be compatible with the anode materials and demonstrates the utility of the solid polymer electrolyte in preparing both cathodes and anodes for lithium ion cells Furthermore, the solid polymer electrolyte has been shown to be stable either as a stand-alone ionically conductive electrolyte and separator, or in combination with standard Li-ion separator and liquid electrolyte This flexibility in cell design provides an advantage to battery manufacturers where the battery chemistry, design and overall cell performance can be tailored to meet specific device requirements. F.xample 5
To demonstrate the solid polymer electrolyte is stable at and can enable high voltage batteries, coin cells were constructed using lithium metal anodes The solid polymer electrolyte is cut into a disk to completely cover a lithium metal disk, and a titanium metal disk is used as a blocking electrode The coin cell of this Li/ solid polymer electrolyte (“SPT”) /Ti construction was prepared in an Argon-filled glovebox with very low' w'ater content, to prevent the reaction of the lithium electrode with moisture
25 The Li/SPF./Ti coin cell was then placed on cyclic voltammetry (CV) test, where the voltage of the cell is varied at a constant scan rate (in this case, 2 niV/sec) between set voltage limits of -0.5V and 5 5V The current is measured for the cell and plotted as a function of the voltage, as displayed in TIG. 5, which displays cyclic voltammetry of the Li/SPH/Ti cell, at a scan rate of 2 mV/sec, cycled between the voltage limits of -0 5 V and 5 5 V This test is useful to simulate the use of the SPH in a high voltage cell in which the charged battery voltage extends upwards greater than 4 2 V and up to at least 5 5 V
As can be seen in the cyclic voltammetry curve in TIG 5, there arc strong anodic and cathodic waves, near 0 V, which are attributed to the plating and stripping of lithium metal Below 0 V, the negative current indicates that lithium metal is plating onto the stainless steel disk. Slightly above 0 V, the positive current is due to the stripping-off of lithium metal from the stainless steel disk These waves are very important in that they demonstrate the ability of the solid polymer electrolyte to transfer lithium ions through the electrolyte, which is necessary for the operation of any lithium anode secondary battery Just as important as the Li plating and stripping waves, is the absence of other waves in the CV curve This test demonstrates that the polymer electrolyte is stable within this voltage window (up to or exceeding 5.5 V) and would be similarly stable in a battery where the charged or operating voltage extends to 5.5V or greater.
Typical lithium ion (“Li-Ion”) batteries are limited in voltage range by the liquid electrolytes used in these systems Li-ion electrolytes typically containing carbonate- based solvents, for example: propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, etc , limit the positive voltage of the battery Typically, batteries of this nature can only be charged to 4 3 V, because the liquid electrolyte starts to oxidize and decompose above this potential The use of the solid polymer electrolyte in lithium-based batteries enables charging to a higher voltage, which in turn will increase the amount of energy stored in the battery and lead to longer battery run-time. Charging to a higher voltage will also enable the use of higher voltage cathodes, such as lithium cobalt phosphate, NCV1 and other new' cathode materials for lithium ion cells that have electrochemical potentials relative lithium metal greater than 4 3V The research on these new high voltage cathodes has been hindered by a lack of stable electrolytes at voltages greater than 4 3 V The solid polymer electrolyte solves this problem by providing a lithium ion conductive electrolyte which is stable at high voltages
26 Comparative F.xample 6.
As a comparison to the cyclic voltammetry displayed in FIG 5, a Current- Voltage (“CV”) curve was measured for a Li/Stainless Steel cell containing liquid electrolyte (F.C- DMC-DHC and VC with LiPFf, salt) and a polypropylene separator (from Cel ard) The curve is displayed in L1G 6
As can be seen in the CV curve for the liquid electrolyte comparison example, a cathodic peak appears on the positive scan (as indicated by the arrow) which is attributed to the decomposition of the liquid electrolyte at a voltage above 4 V This comparison shows that the liquid electrolyte is prone to decomposition, while the polymer electrolyte is stable at high voltage and does not decompose, as illustrated in F.xample 5
Example 7
Referring to F1G 7, there is shown a test battery with the solid polymer electrolyte interposed between two strips of lithium metal The Li/ solid polymer electrolyte /Li cells were constructed in an inert atmosphere and lithium was transferred by applying constant current to the cell for a period of time (in this example, the period of time was 1 h). The current was then reversed and the lithium was transferred in the opposite direction FIG. 8 shows a plot of the voltage V relative time of a cell with > 420 charge- discharge cycles, using a current density of 0 5 mA/cnr and tested at room temperature. In this example, the current is held constant and the voltage is measured, as can be seen on the y-axis of FIG 8 The voltage displayed by the cell during the constant current test depends on the polarization of the cell, which is related to the overall resistance of the cell (i e the higher the resistance of the cell, the larger the change in voltage, or higher polarization) The overall resistance of the cell is due to the bulk resistance of the solid polymer electrolyte plus the interfacial resistance of the polymer electrolyte in contact with the lithium metal surfaces. The FIG 8 plot shows that the polarization of the cell is relatively constant for the entire test. The results of this test further demonstrates the stability of the polymer electrolyte, where 1565 microns of lithium were transferred over the entire test, and the lithium metal electrodes were only about 85 microns in thickness to begin These results demonstrate that the solid polymer electrolyte has the capability to transfer large amounts
27 of lithium with high stability. FIG 8 plot voltage is above 1 0 V as the cell is put in series with a NiMH cell during testing.
F.xample 8
To demonstrate the utility of the solid polymer electrolyte in high voltage batteries, eells were constructed using lithium metal anodes (20 mierometers or less in thickness), solid polymer electrolyte and lithium cobalt oxide cathodes containing the solid polymer electrolyte The lithium cobalt oxide, LiCoO (‘LCO’), is used since this is a high voltage cathode material with a charged voltage over 4 V. The use of lithium metal anodes increases the energy density of the battery, since lithium metal has much higher capacity than a lithiated graphite electrode that is typically used in a Li-ion battery The theoretical capacity of lithiated graphite is 072 niAh/g, while lithium metal has a capacity of 0860 mAh/g more than ten times the capacity of graphite anodes Coin cells of the Li/SPH/LCO configuration were cycle tested and demonstrated good performance, as displayed in FIG 9, which shows electrochemical impedance spectroscopy (LIS) of the bipolar Li/S PH/Li Battery- L1G 9 shows the L1S initially, the LIS after 1 month of storage, after 2 months of storage, and after 3 months of storage.
The capacity of the LiCoO;- used in these cells was 124 mAh/g, which corresponds to the target 0.5 equivalents of Li removed from the cathode during charging. The cycling efficiency for lithium was found to be over 99%, which matches or exceeds that found for liquid electrolyte systems Cycling efficiency is calculated by counting coulombs over a single cycle and comparing the charge and discharge cycles to calculate the efficiency ((charge out/ charge into battery-) times 100) Overall, these results demonstrate the function of the solid polymer electrolyte as an electrolyte for high voltage lithium-based battery systems
The density of the lithium deposited onto the anode current collector during battery- charging was measured and determined to be greater than 0.4 g/cc
Lxamplc 9
The stability of the Li/ solid polymer electrolyte /LCO cells were tested on open circuit storage This test utilized fully charged Li/SPL solid polymer electrolyte LCO cells, as described in Lxamplc 8, and stored the cells for a two-week period at room
28 temperature. The cells displayed good voltage stability, as displayed in FIG 10. Following the 2 weeks of open circuit storage, the cells were fully discharged and the discharge capacity was compared to the cell performance prior to storage. Both cells displayed 84 to 85¾ of pre-storage discharge (greater than 80%), demonstrating low self- discharge during the two- week storage, and further demonstrating the stability of the high voltage Li/ SPL /LCO battery system
Example 10
The solid polymer electrolyte of Example 3, specifically PP S/Chlorani 1/Li TF SI- LiFSI-LiBOB, was used to make a secondary lithium cell The cell comprised a lithium metal anode, the solid polymer electrolyte was interposed between the anode and a slurry cathode The slurry cathode also comprised the solid polymer electrolyte and the cathode is manufactured u ing a stepwise process The process initially includes a polyvinylidene difluoride (PVDF) binder in a solvent such as A-Mcthyl -2-pyrrol idone ( MP) or Dimethylacetamide (DMA) Electrically conductive carbon and graphite and the solid polymer electrolyte arc then added in a first mixing step in which the carbon and solid polymer electrolyte remain stable and insoluble in the binder solvent This first mixture is then mixed in a second mixing step with a electrochemically active cathode material such as Lithium cobalt oxide (LiCoCLX“LCO”) to create a slurry mix which is then coated onto a cathode collector After a drying step in which the binder solvent is driven out of the cathode, the cathode is calendared to create a high density cathode
fable 4 details composition ranges for each of the cathode components included in the described slurry cathode process Table 4
Figure imgf000108_0001
The high density cathode is about 15 to 1 15 micrometers in thickness, and has a cathode coating density in the range of 1 . 2 to 3 6 g/cc.
29 The high density cathode is then added to the described secondary lithium cell and displays significant performance Specifically, the lithium cell displays voltage stability above 5 0V to at least 5.5V (greater than 4 1 V and 4 5 V); the lithium metal can be cycled through the solid polymer electrolyte a rates greater than 0.5 m.A/cm2, 1 0 m A/cm 2 and to at least 1 5 mA/cm2 at room temperature, while also being able to cycle lithium in excess of an areal capacity of 3 0 mAh/cm’ for greater than 10 cycles, and greater than 18 0 mAh/em’; being cycled for greater than 150 cycles at 1 0 m.\ err. and 0 25 mAh cm. having greater than 80% depth of discharge of the lithium anode (i e fraction of the lithium metal present that is cycled, and over 70% depth of discharge for at least 10 cycles at 0.5 mA/cnr and 3 mAh/cm2; and produces plated lithium on the anode current collector greater than 0.4 g/cc (greater than 0 4 g/cc) thus maintaining battery volume with little to no swelling.
While the invention has been described in detail herein in accordance with certain aspects thereof, many modifications and changes therein may be affected by those skilled in the art without departing from the spirit of the invention Accordingly, it is our intent to be limited only by the scope of the appending claims and not by wav of the details and instrumentalities describing the embodiments shown herein
It is to be understood that variations and modifications can be made on the aforementioned structure without departing from the concepts of the present invention, and further it is to be understood that such concepts are intended to be covered by the following claims unless these claims by their language expressly state otherwise
30 Cl, AIMS
What is claimed i s:
1 A battery comprising:
an anode comprising a first electrochcmically active material;
a eathode eom prising both a second electrochcmically active material and a first electrolyte;
a second electrolyte interposed between the anode and the eathode;
wherein at least one of the first electrolyte and second electrolyte comprises a solid polymer electrolyte;
wherein the solid polymer electroly te has a glassy state, and comprises both at least one cationic and anionic diffusing ion, wherein at least one cationic di ffusing ions comprises lithium and wherein at least one diffusing ion is mobile in the glassy state 2 The battery of claim 1 , wherein the solid polymer electrolyte comprises:
a crystallinity greater than 30%;
wherein the glassy state extends in a range of temperatures of the solid polymer electrolyte from a melting temperature of the solid polymer electrolyte to a temperature lower than the melting temperature.
3 The battery of claim 2, w hercin the solid polymer electrolyte further comprises a plurality of charge transfer complexes
4 The battery of claim 3, w hercin the solid polymer electrolyte comprises a plurality of monomers, and wherein each charge transfer complex is positioned on a monomer.
5 The battery of claims 1 or 4, wherein the electronic conductivity of the solid polymer electrolyte i s less than 1 x 10 R S/cm at room temperature. 6 The battery of claim 1 , wherein the solid polymer electrolyte comprises:
a plurality of monomers. a plurality of charge transfer complexes, wherein each charge transfer complex is positioned on a monomer;
wherein the electronic conductivity of the solid polymer electrolyte is less than 1 x 10 s S/cm at room temperature.
7 The battery of claim 6, wherein the crystallinity of the solid polymer electrolyte is greater than 30° ::
8 The battery of claim 6, wherein the solid polymer electrolyte has a glassy state which exists at temperatures below the melting temperature of the solid polymer electrolyte.
9 The battery of claim 6, wherein the solid polymer electrolyte further comprises both a cationic and anionic diffusing ion, whereby at least one diffusing ion is mobile in a glassy state of the solid polymer electrolyte, and wherein the crystallinity of the solid polymer electrolyte is greater than 30 %
10. The battery of claim 1 , wherein the melting temperature of the solid polymer electrolyte is greater than 250°C.
1 1 The battery of claim 1, wherein the solid polymer electrolyte is a thermoplastic
12 The battery of claim 13, wherein the ionic conductivity of the solid polymer electrolyte is isotropic
13. The battery of claim 1 , wherein the solid polymer electrolyte is non-Hamm able.
14. The battery of claim 1 , wherein the Young’s modulus of the solid polymer electrolyte is equal to or greater than 3 0 MPa
32 15. The battery of claim 6, wherein the solid polymer electrolyte has a glassy state, and at least one cationic and at least one anionic diffusing ion, wherein each diffusing ion is mobile in the glassy state. 16 The battery of claim 1, wherein the ionic conductivity of the solid polymer electrolyte is greater than 1 0 x 10 S/cm at room temperature
17 The battery of claim 1, wherein the solid polymer electrolyte comprises a single cationic diffusing ion, wherein the single anionic diffusing ion comprises lithium, and wherein the diffusivity of the cationic diffusing ion is greater than 1 .0 x 10 12 nr/s at room temperature.
18 The battery of claim 1, wherein the solid polymer electrolyte comprises a single anionic diffusing ion, and wherein the diffusivity of the anionic diffusing ion is greater than l O x 10 u m7s at room temperature
19. The battery of claim 2, wherein one of the at least cationic diffusing ion, has a diffusivity greater than 1 0 x 10 12 nr/s 20. The battery of claim 2, wherein one of the at least one anionic diffusing ion has a diffusivity greater than l O x 10 l 2 m Vs
21 The battery of claim 2, wherein one of both the at least one anionic diffusing ion and at least one cationic diffusing ion has a diffusivity greater than l O x 10 u m'Vs
22. The battery of claim 1 , wherein the solid polymer electrolyte has an ionic conductivity greater than 1 x 10 4 S/cm at room temperature.
23 The battery of claim 1, wherein the solid polymer clectroKte has an ionic conductivity greater than 1 x 10’ S/cm at 80“C
3 24. The battery of claim 1 , wherein the solid polymer electrolyte has an ionic conductivity greater than 1 x 10 " S/cm at -40°C.
25. The battery of claim 1 , wherein the concentration of lithium is greater than 3 moles of lithium per liter of solid polymer electrolyte
26 The battery of elaims 2, wherein each at least one eationie and anionie diffusing ion have a diffusivity, wherein the cationic diffusivity is greater than the anionic diffusivity.
27. The battery of claim 1 , wherein the cationic transference number of the solid polymer electrolyte is greater than 0.5 and less than 1 0
28 The battery of claim 2, wherein at least one diffusing anion is monovalent
29 The battery of claim 2, wherein at least one anionie diffusing ion comprises fluorine or boron
30. The battery of claim 2, wherein the solid polymer electrolyte comprises a plurality of monomers and wherein there is at least one anionic diffusing ion per monomer
3 1 T he battery of claim 2, wherein the solid polymer eleetrolyte comprises a plurality of monomers and wherein there is at least one eationie diffusing ion per monomer 32. The battery of claim 1 , wherein there is at least one mole of the lithium per liter of solid polymer electrolyte.
33. The battery of claim 1 , wherein the solid polymer electrolyte comprises a plurality of monomers, wherein each monomer comprises an aromatic or heterocyclic ring structure positioned in the backbone of the monomer
34
Ill 34. The battery of claim 8, wherein the solid poly er electrolyte further includes a heteroatom incorporated in the ring structure or positioned on the backbone adjacent the ring structure. 35 The battery of claim 39, wherein the hetero tom is selected from the group consisting of sulfur, oxygen or nitrogen
36 The battery of claim 40, wherein the heteroatom is positioned on the backbone of the monomer adjacent the ring structure.
37. The battery of claim 41 , wherein the heteroatom is sulfur
38 The battery of claim 1, wherein the solid polymer electrolyte is pi -conjugated 39 The battery of claim 1 , wherein the solid polymer electrolyte comprises a plurality of monomers, wherein the molecular weight of each monomer is greater than 100 gram s/mole.
40. The battery of claim 6, wherein the charge transfer complex is formed by the reaction of a polymer, electron acceptor, and an ionic compound, wherein each cationic and anionic diffusing ion is a reaction product of the ionic compound
41 The battery of claim 2, wherein the solid polymer electrolyte is formed from at least one ionic compound, wherein the ionic compound comprises each at least one cationic and anionic diffusing ion.
42. The battery of claims 3 or 6, wherein the charge transfer complex is formed by the reaction of a polymer and an electron acceptor.
5 43. The battery of claim 1 , wherein the solid polymer electrolyte becomes ionically conductive after being doped by an electron acceptor in the presence of an ionic compound that either contains both a cationic and anionic diffusing ion or is convertible into both the cationic and anionic diffusing ion via reaction with the electron acceptor.
44 The battery of claim 1 , wherein the solid polymer electrolyte is formed from the reaction product of a base polymer, electron acceptor and an ionic compound
45. The battery of claim 42, wherein the base polymer is a conjugated polymer
46. The battery of claim 42, wherein the base polymer is PPS or a liquid crystal polymer.
47 Th battery of claim 1 , wherein both the first and seeond electrolyte comprise the solid polymer electrolyte, wherein the electronic conductivity of the second electrolyte is less than 1 x 10 w S/cm at room temperature
48. The battery of claim 1 , wherein both the first and second electrolyte comprise the solid polymer electrolyte.
49 The battery of claim 1, wherein the anode comprises a third electrolyte, and wherein the third electrolyte comprises the solid polymer electrolyte
50 The battery of claim 1, wherein the second electrolyte comprises the solid polymer electrolyte and is formed into a film, wherein the thickness of the film is between 200 and
15 micrometers.
51 . The battery of claim 2, wherein the second electrochemically active material comprises an intercalation material
52 The battery of claim 2, wherein the second electrochemically active material comprises a lithium oxide comprising nickel, cobalt or manganese
36 53. The battery of claim 2, wherein the second electrochemical!} active material has an electrochemical potential greater than 4 2 volts relative lithium metal. 54. The battery of claim 2, wherein the cathode has an electrode potential greater than
4 2 volts relative lithium metal
55. The battery of claim 1 , wherein the second electrochemical!} active material is intermixed with an electrically conductive material and the solid polymer electrolyte
56 The battery of claim 53, wherein the electrically conductive material comprises carbon
57 The battery of claim 1 , wherein the cathode comprises 70-90 percent by weight of the second electrochemically active material
58. The battery of claim 1 , wherein the cathode comprises 4-1 5 percent by weight of the solid polymer electrolyte 59. The battery of claim 1 , wherein the cathode comprises 2-10 percent by weight of an electrically conductive material
60 The battery of claim 57, wherein the electrically conductive material comprises carbon
61 The battery of claim 1, wherein the cathode is formed from a slurry
62 The battery of claim 1, wherein the cathode is positioned on a cathode collector 63. The battery of claim 1 , wherein the second electrochemically active material comprises a lithium oxide or a lithium phosphate that contain nickel, cobalt or manganese
37 64. The battery of claim 1 , wherein the second electrocheniically active material comprises a lithium intercalation material, wherein the lithium intercalation material comprises lithium. 65 The battery of claim 64, wherein the lithium intercalation material comprises
Lithium Nickel Cobalt Aluminum Oxide; Lithium Nickel Cobalt Manganese Oxide, Lithium lron Phosphate; Lithium Manganese Oxide, Lithium cobalt phosphate or lithium manganese nickel oxide. Lithium Cobalt Oxide, LiTi , LiNiO , or combinations thereof 66. The battery of claim 1 , wherein the second electrocheniically active material comprises an electrocheniically active cathode compound that reacts with lithium in a solid state redox reaction.
67 The battery of claim 66, wherein the electrocheniically active cathode material comprises a metal halide. Sulfur, Selenium, Tellurium; Iodine, Fe or LL
68. The battery of claim 65, wherein the lithium intercalation material comprises Lithium Nickel Cobalt Manganese Oxide, wherein the atomic concentration of nickel in the L thium Nickel Cobalt Manganese Oxide is greater than the atomic concentration of cobalt or manganese
69 The battery of claim 1 , wherein the first clcctrochemically active material comprises an intercalation material 70. The battery of claim 69, wherein the anode further comprises the solid polymer electrolyte, wherein the first electrocheniically active material is mixed with the solid polymer electrolyte
71 The battery of claim 1 , wherein the first clcctrochemically active material comprises lithium metal
38 72. The battery of claim 1 , further comprising an anode current collector in ionic communication with the anode, wherein lithium deposits on the anode current collector when the battery is charged. 73 The battery of claim 72, wherein the density of the lithium deposited on the anode current collector is vreater than 0 4 g/cc
74 Th batters of claim 1 , further comprising an anode current collector in ionic communication with the anode, wherein the electrolyte is positioned adjacent the anode current collector.
75. The battery of claim 69, wherein the first electrochemicallv active material comprises Silicon, Tin, antimony, lead. Cobalt, lron. Titanium, Nickel, magnesium, aluminum, gallium, Germanium, phosphorus, arsenic, bismuth, zinc, carbon and mixtures thereof
76. The battery of claim 1 , wherein the second electrochemicallv active material comprises an intercalation material, wherein the first electrochemicallv active material comprises lithium metal.
77 The battery of claim 76, wherein the charged voltage of the battery is greater than 4 1 volts
78 The battery of claim 76, wherein the charged voltage of the battery is greater than 4 5 volts.
79. The battery of claim 76, wherein the charged voltage of the battery is greater than 5 0 volts. 80 The battery of claim 1, wherein lithium is cycled between the anode and cathode at a rate greater than 0 5 mA/cirf at room temperature
39 81 . The battery of claim 1 , wherein lithium is cycled between the anode and cathode at a rate greater than 1 .0 m A/cnr at room temperature
82. The battery of claim 72, wherein the lithium is cycled between the anode and cathode for greater than 150 cycles
S3 The battery of claim 1, wherein lithium is cycled between the anode and cathode at a rate greater than 3 0 mAh/cm' at room temperature for greater than ten cycles 84. The battery of claim 1 , wherein lithium is cycled between the anode and cathode at a rate greater than 1 8 0 mAh/cnr.
85 The battery of claim 1, wherein lithium is cycled between the anode and cathode at a rate greater than 0 25 mAh/cm’ at room temperature for greater than 150 cycles
86 The batten. of claim 1 , further comprising an anode current collector, wherein lithium is plated onto the anode current collector when the battery is charged, wherein the density of the lithium plated onto the anode current collector is greater than 0 4 g/cc. 87. The battery of claim 1 , wherein the lithium cycling efficiency is greater than 99 b
88 The battery of claim 1, wherein the second electrolyte comprises the solid polymer electrolyte and is formed into a film, and wherein the first electrolyte comprises the solid polymer electrolyte, whereby the second electrolyte is attached to the cathode
89. The battery of claim 1 , wherein the second electrolyte comprises the solid polymer electrolyte and is formed into a film, and wherein the anode comprises a third electrolyte, and wherein the third electrolyte comprises the solid polymer electrolyte, whereby the second electrolyte is attached to the anode
90 A method of manufacturing a batten. comprising the steps of:
mixing a polymer with an electron acceptor to create a first mixture.
40 heating the first mixture to form a reaction product comprising a plurality charge transfer complexes;
mixing at least one ionic compound comprising lithium with the reaction product to form a solid ionically conductive polymer material.
91 The method of claim 90, further comprising including mixing an intercalation material with the solid ionically conductive polymer material to form a cathode
92. The method of claim 91 , wherein the cathode forming step further includes mixing an electrically conductive material with the intercalation material and the solid ionically conductive polymer material.
92. The method of claim 92, wherein the cathode forming step further comprising a calendaring step wherein the density of the cathode is increased
94 The method of claim 90, wherein the solid ionically conductive polymer material is formed into a film to form a solid polymer electrolyte
95 The method of claim 90, wherein the dopant is a quinone
96. The method of claim 90, wherein the polymer is PPS, a conjugated polymer or a liquid crystal polymer
97. The method of claim 90, wherein the ionic compound is a salt, hydroxide, oxide or other material containing lithium
98 The method of claim 90, wherein the ionic compound comprises lithium oxide, lithium hydroxide, lithium nitrate, lithium bis-trif uoromcthancsulfonimidc. Lithium bis(fluorosulfonyl)imide, Lithium bis(oxalato)borate, lithium trifluorom ethane sulfonate), lithium hexafluorophosphate, lithium tetrafluoroborate, or lithium hexafluoroarsenate, and combinations thereof
4 1 99. The method of claim 90, wherein in the heating step the first mixture is heated to a temperature between 250 and 450 deg. C.
100 The method of claim 91 , wherein the cathode is positioned adjacent an electrically conducting cathode current collector to form a cathode assembly
101 The method of claim 100, wherein the solid ionically conductive polymer material is formed into a film to form a solid polymer electrolyte 102 The method of claim 101 , further comprising an electrically conducting anode current collector and an enclosure, and further comprising an assembly step wherein the solid polymer electrolyte is positioned between the anode current collector and the cathode assembly to form a batten assembly, and the battery assembly is placed within the cnclosu re
103 The method of claim 90, wherein the battery further comprises a anode and a cathode, wherein the solid ionically conductive polymer material is formed into a film to form a solid polymer electrolyte, further comprising attaching the film to the anode, the cathode or both the anode and the cathode
104 The method of claim 103, wherein in the attaching step the film is coextruded with either the anode, cathode or both the anode and the cathode.
42 1/8
Figure imgf000122_0001
/7<7. 1 2/8
Figure imgf000123_0001
3/8
Figure imgf000124_0001
4/8
Figure imgf000125_0001
Figure imgf000126_0001
vw<|>
Figure imgf000127_0001
(A) a6ei|OA 7/8
Figure imgf000128_0001
8/8
Figure imgf000129_0001

Claims

CLAIMS What is claimed is:
1. An electrode useful in an electrochemical cell comprising:
an electrochemically active material;
an electrically conductive material;
a solid ionically conductive polymer electrolyte; and
a binder;
wherein the binder is dispersed in an aqueous solution.
2. The electrode of claim 1, wherein the binder is soluble in an aqueous solution.
3. The electrode of claim 1, wherein the binder is partially soluble in an aqueous solution.
4. The electrode of claim 1 further comprising a lithium.
5. The electrode of claim 1, wherein the electrochemically active material comprises a graphite.
6. The electrode of claim 1, wherein the electrochemically active material is in an amount having a range of 70-90 wt. % of the electrode.
7. The electrode of claim 1 further comprising an electrically conductive current collector which is in electrical communication with the electrically conductive material.
8. The electrode of claim 1 further comprising a second binder which is soluble in an aqueous solution.
9. The electrode of claim 1 , wherein the solid ionically conductive polymer electrolyte is in an amount having a range of 52- 15 wt.% of the electrode.
10. The electrode of claim 1, wherein the solid ionically conductive polymer electrolyte has an ionic conductivity of at least lxlO-4 S/cm.
11. The electrode of claim 1, wherein the solid ionically conductive polymer electrolyte has a crystallinity of at least 30%.
12. The electrode of claim 1, wherein the solid ionically conductive polymer electrolyte has a cathodic transference number greater than 0.4 and less than 1.0.
13. The electrode of claim 1, wherein the solid ionically conductive polymer electrolyte is in a glassy state.
14. The electrode of claim 1, wherein the electrochemically active material, the electrically conductive material, the solid ionically conductive polymer electrolyte and the binder comprise a plurality of dispersed, intermixed particulates.
15. The electrode of claim 1,
wherein the electrode further comprises an electrically conductive current collector; and wherein the electrode is adhered to the electrically conductive current collector.
16. The electrode of claim 15,
wherein the electrochemically active material, the electrically conductive material, the solid ionically conductive polymer electrolyte and the binder comprise a plurality of dispersed, intermixed particulates forming a mixture; and
wherein the mixture is adhered to the electrically conductive current collector by an aqueous slurry.
17. A method of making a battery structure comprising the following steps:
selecting an electrically conductive current collector and an electrode;
wherein the electrode is comprised of an electrochemically active material,
an electrically conductive material, a solid ionically conductive polymer electrolyte, and a binder;
mixing the electrochemically active material, the electrically conductive material, the solid ionically conductive polymer electrolyte, and the binder in an aqueous solution to create a slurry; positioning the slurry adjacent to the electrically conductive current collector; and drying the slurry;
wherein the electrode adheres to the electrically conductive current collector.
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EP3729551A1 (en) 2020-10-28
KR20200118800A (en) 2020-10-16

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