WO2012152357A1 - Électrode pour batteries lithium-ion - Google Patents

Électrode pour batteries lithium-ion Download PDF

Info

Publication number
WO2012152357A1
WO2012152357A1 PCT/EP2012/001444 EP2012001444W WO2012152357A1 WO 2012152357 A1 WO2012152357 A1 WO 2012152357A1 EP 2012001444 W EP2012001444 W EP 2012001444W WO 2012152357 A1 WO2012152357 A1 WO 2012152357A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
substrate
separator
electrode
ceramic particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2012/001444
Other languages
German (de)
English (en)
Inventor
Tim Schaefer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Li Tec Battery GmbH
Original Assignee
Li Tec Battery GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Li Tec Battery GmbH filed Critical Li Tec Battery GmbH
Priority to JP2014508698A priority Critical patent/JP2014519143A/ja
Priority to KR1020137031647A priority patent/KR20140024011A/ko
Priority to CN201280022076.3A priority patent/CN103503200A/zh
Priority to EP12712076.4A priority patent/EP2705558A1/fr
Publication of WO2012152357A1 publication Critical patent/WO2012152357A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/12—Electroforming by electrophoresis
    • C25D1/14—Electroforming by electrophoresis of inorganic material
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/02—Electrophoretic coating characterised by the process with inorganic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
    • C25D13/16—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0457—Electrochemical coating; Electrochemical impregnation from dispersions or suspensions; Electrophoresis
    • 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
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method of manufacturing an electrode for lithium ion batteries.
  • the invention further relates to an electrode produced by the method and to a lithium-ion battery having this electrode.
  • Electrodes for lithium ion batteries can be made by coating suitable conductive substrates with active materials.
  • Active materials are materials or substances which can donate or absorb lithium ions or which can intercalate lithium.
  • Suitable substrates are, for example, aluminum or copper (foils).
  • Coating processes are, for example, extrusion or calendering processes.
  • the substrate is extruded and / or calendered together with the applied active material, which is usually in the form of a suspension.
  • the electrode is obtained.
  • the active materials used for the transport of the lithium ions or the lithium can be present on the nanoscale. Due to the comparatively large surface area of the nanoparticles, mass transport by the active material is facilitated, thereby increasing the conductivity.
  • An object of the present invention is to provide an electrode for a lithium ion battery having a further improved conductivity.
  • a first aspect of the invention relates to a method of manufacturing an electrode for a lithium ion battery comprising the step (ii): (ii) electrophoretic deposition of ceramic particles
  • Electrode in the following means both a positive and a negative electrode of the lithium-ion battery.
  • positive electrode in the following means the electrode which, when the battery is connected to a consumer, for example to a
  • Electric motor capable of picking up electrons. It then represents the cathode.
  • negative electrode in the following means the electrode which, in use, is capable of giving off electrons. It then represents the anode.
  • lithium ion battery and “lithium ion secondary battery” are used interchangeably.
  • the terms also include the terms “Lithium battery”, “lithium ion battery” and “lithium ion line”.
  • a lithium-ion battery generally consists of a serial or series connection of individual lithium-ion cells. This means that the term “lithium-ion battery” is used as a generic term for the terms used in the prior art.
  • electrophoretic refers hereinafter to the migration of electrically charged particles in the electric field by a serving as a carrier material.
  • the term "electrophoretic deposition” means that the ceramic particles migrate to a substrate by electrophoresis and are deposited on this substrate, whereby in electrophoresis the electric field is generated by applying a voltage difference between two spaced-apart electrodes the electrically charged particles migrate.
  • JP 2002042791 discloses the production of a double layer of separator and electrode.
  • ceramic material which may form a separator, is deposited from a suspension containing the ceramic material by electrophoresis on an electrode immersed in this suspension.
  • an electrode is formed with the separator applied thereon.
  • step (ii) it excludes the formation of a separator.
  • ceramic particles means inorganic material or inorganic compounds in particle form. It is preferable to use particles which, under the working conditions of the lithium-ion battery, are used Due to their chemical nature, lithium ions or lithium can be taken up and released again. In the prior art, such material is also referred to as "active material" for the electrode In the method according to the invention ceramic particles can be used as active material, as they are usually used for cathodes.
  • particles that are a lithium transition metal with olivine structure are used.
  • lithium manganate, lithium cobaltate, lithium nickelate, or mixtures of two or more of these oxides or mixed oxides may be used.
  • these oxides have a spinel structure.
  • the ceramic particles are used in the suspension as nanoparticles.
  • the nanoparticles can take any shape, that is, they can be coarse-spherical or elongated.
  • the particles have a particle size measured as D95 value of less than 15 ⁇ .
  • the particle size is less than 10 ⁇ .
  • the particles have a particle size measured as D95 value between 0.005 ⁇ to 10 ⁇ , or a particle size measured as D95 value of less than 10 ⁇ m, the D50 value being 4 ⁇ m 2 ⁇ m and the D10 value being less than 1.5 ⁇ m.
  • the particles contain carbon to increase the conductivity.
  • Such particles can be prepared by known processes, for example by coating with carbon compounds such as acrylic acid or ethylene glycol. It is then pyrolyzed, for example at a temperature of 2500 ° C.
  • Suitable ceramic particles for the negative electrode preferably have lithium metal oxides such as lithium titanium oxide.
  • Further suitable materials are graphite, synthetic graphite, carbon black, mesocarbon, doped carbon, fullerenes, niobium pentoxide, tin alloys, titanium dioxide, tin dioxide, and / or silicon, or mixtures of two or more of these substances.
  • the term “suspension” is used interchangeably below with the terms “emulsion”, “dispersion”, “colloid” or "slurry”.
  • the suspension is an aqueous suspension.
  • organic solvents are preferably ethanol, isopropanol, acetone or dimethylformamide, or mixtures of these solvents.
  • the suspension may also contain binders. These can help the adhesion of the particles on the substrate. Suitable binders are known in the art.
  • polymeric binders may be used, preferably polyvinylidene fluoride, polyethylene oxide, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylate, Ethylene (propylene-diene monomer) copolymer (EPDM) and blends and copolymers thereof.
  • the suspension may also contain acids or bases for adjusting the pH, dispersing aids, polyelectrolytes and surfactants.
  • suspension stability and electrophoretic mobility i. the rate of migration of the ceramic particles in the electric field can be adjusted.
  • the suspension can be prepared by the conventional methods in ceramic technology, for example by mixing the components used, preferably by mixing or by stirring the components. The mixing can also be supported by sonication.
  • the term “substrate” refers to the material on which the ceramic particles are deposited electrophoretically,
  • the substrate comprises a ceramic material, in particular a ceramic material, which is suitable for a separator.
  • the substrate is a metal. Suitable metals are preferably aluminum or copper.
  • the substrate can also consist of carbon or have carbon.
  • the substrate of step (ii) may be in sheet form.
  • the substrate may be in the form of wires or fibers.
  • Wires may also be in the form of nanowires and carbon nanotubes.
  • the metals are in the form of sheets, ie in sheet form, used or in the form of wires.
  • the carbon and / or the ceramic material is used in the form of fibers.
  • the substrate is used as one of the electrodes in the electrophoretic method.
  • the substrate can be switched electrically in such a way that negatively charged or positively charged ceramic particles can be deposited or deposited thereon.
  • step (ii) After depositing the ceramic particles on the substrate according to step (ii), it can be dried, for example by heating.
  • the substrate, which is then coated with the ceramic particles, can then be used as an electrode in a lithium-ion battery.
  • the voltage applied between the electrodes in the electrophoretic method and / or the composition of the suspension used is selected such that water is electrolyzed simultaneously in step (ii).
  • step (ii) water is electrolysed in step (ii) at the same time.
  • the voltage applied in the electrophoresis is increased until the electrolysis of the water occurs. This can i.A. be well recognized by the incoming gas bubble development.
  • the electrolysis can be facilitated by adding acid to the suspension.
  • a suitable acid is preferably acetic acid.
  • the gas bubble formation occurring during the electrolysis can be used specifically for the formation of pores in the layer of ceramic particles deposited on the substrate. The basics of this principle of the generation of pores are described in DE 10 2008 012 586 A1.
  • Lithium ion batteries commonly used and produced by conventional methods electrodes can be improved.
  • pattern in the sense of the invention means spatial structures on the surface of the substrate.
  • a net-like pattern may be created by applying a mesh to the substrate.
  • net-like patterns or other patterns may be applied by applying metal wires or polymer fibers to the substrate
  • Substrate are generated.
  • a nanowire may be applied to the substrate.
  • nanowire in the sense of the invention means an elongate piece of metal, semimetal or a compound semiconductor with a
  • the nanowire has carbon nanotubes or consists of carbon nanotubes.
  • Methods for producing nanowires are known. They can be applied to the substrate by known methods such as spin coating or doctoring.
  • patterns may be formed on the surface of the substrate by methods known in photolithography.
  • Embodiments may be electron beam and ion lithography or laser lithography.
  • the deposited particles which are in the form of a layer on the substrate, and the substrate are removed from the mold.
  • the method is also characterized in that it comprises the step (iii): (iii) demolding of deposited particles and substrate.
  • step (iii) may be particularly desirable when producing a particularly porous active material which, due to its porosity and the associated large surface to facilitate the access of lithium ions and thus increase the conductivity further.
  • a substrate is used which is in the form of intertwined wires or in fiber form.
  • a composite of a layer of the ceramic particles in which the wires or fibers are embedded can be obtained.
  • the composite of ceramic particles and substrate is heated until the substrate is decomposed and the decomposition products are at least partially or completely removed from the composite.
  • the resulting ceramic now has a plurality of pores or channels, preferably in addition to the locations at which the substrate was located.
  • Carbon fibers are particularly suitable for this embodiment. They can be used in the form of fabrics or mats. By selecting the fiber thickness, additional pores or channels of defined diameter can be introduced into the ceramic in addition to the pores introduced via the electrolysis of the water.
  • fibers of organic polymers can be used.
  • a substrate which has "carbon” means, in particular, “organic polymers", ie carbon atoms. Materials.
  • polyester or polyolefin fibers are used.
  • demolding according to step (iii) can be initiated by chemical action.
  • chemical action in the context of the invention means that the substrate is reacted with a reactant until it is partially or completely removed from the composite.
  • metal substrates preferably metal wires
  • the substrate can be released from the composite.
  • pores or channels are also formed.
  • the invention relates to an electrode for lithium-ion battery, wherein the electrode can be produced by the method according to the invention.
  • the invention relates to a lithium-ion battery having an electrode produced by the method according to the invention; or having the electrode according to the invention.
  • one electrode in the sense of the invention means no numerical restriction, but rather means that the battery can have a plurality of electrodes, preferably two electrodes.
  • the battery has a separator.
  • separator means a material that separates the negative and positive electrodes of the lithium ion battery from each other, and the separator used for the battery must be permeable to lithium ions for ion transport of the lithium ions between the positive and the negative On the other hand, the separator must be insulating for electrons, in one embodiment the separator comprises a nonwoven web
  • Polymer fibers which are electrically non-conductive are produced in particular by spinning processes with subsequent solidification.
  • An embodiment of the lithium ion battery is characterized in that it comprises a separator comprising a nonwoven web of nonwoven polymer fibers coated on one or both sides with an inorganic material.
  • nonwoven is used synonymously with terms such as “nonwoven fabrics”, “knits” or “felt”. Instead of the term “unwoven” the term “not woven” is used.
  • the polymer fibers are selected from the group of polymers consisting of polyacrylonitrile, polyolefin, polyester, polyimide, polyether imide, polysulfone, polyamide, polyether.
  • Suitable polyolefins are, for example, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride.
  • Preferred polyesters are polyethylene terephthalates.
  • the nonwoven contained in the separator is preferably coated on one or both sides with an ion-conducting inorganic material.
  • coating in the context of the invention also means that the ion-conducting inorganic material may be located not only on one side or both sides of the nonwoven fabric but also inside the nonwoven fabric.
  • the ionically conductive inorganic material is ion conducting in a temperature range of -40 ° C to 200 ° C, i. ionic for lithium ions.
  • the material used for the coating is at least one compound from the group of oxides, phosphates, sulfates, titanates, silicates, aluminosilicates at least one of zirconium, aluminum, silicon or lithium.
  • the ion-conducting material comprises or consists of alumina or zirconia or alumina and zirconia.
  • a separator is used in the battery according to the invention, which consists of an at least partially permeable carrier, which is not or only poorly electron-conducting.
  • This support is coated on at least one side with an inorganic material.
  • an organic material is used, which is designed as a non-woven fleece.
  • the organic material is in the form of polymer fibers, preferably polymer fibers of polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the nonwoven fabric is coated with an inorganic ion-conducting material which is preferably ion-conducting in a temperature range of -40 ° C to 200 ° C.
  • the inorganic ion-conducting material preferably has at least one compound from the group of the oxides, phosphates, sulfates, titanates, silicates, aluminosilicates with at least one of the elements zirconium, aluminum, lithium, particularly preferably zirconium oxide.
  • the inorganic ion-conducting material preferably has particles with a maximum diameter of less than 100 nm.
  • Such a separator is marketed in Germany, for example, under the trade name "Separion ®" by the company Evonik AG.
  • Method for producing such separators are known from the prior art, for example from EP 1017476 B1, WO 2004/021477 and WO 2004 / 021,499th.
  • shut-down temperature which is typically around 120 ° C.
  • break-down temperature the temperature at which the pore structure of the separator collapses at this temperature All the pores are closed, so that no more ions can be transported, the dangerous reaction, which can lead to an explosion, comes to a standstill, but if the cell continues to be warmed up due to external circumstances, then at approx so-called “break-down temperature” exceeded. From this temperature it comes in conventional separators to melt the separator, which contracts. In many places in the battery cell, there is now a direct contact between the two electrodes and thus to a large internal short circuit.
  • the separator used in the battery according to the invention comprising a non-woven of non-woven polymer fibers and the inorganic coating, it can only come to shut-down (shutdown), if by the high Temperature melts the polymer structure of the carrier material and penetrates into the pores of the inorganic material and thereby closes. On the other hand, there is no such break-down (collapse) as the inorganic particles ensure that complete melting of the separator can not occur. This ensures that there are no operating states in which a large-area short-circuit can occur.
  • separators can be produced that can meet the requirements for separators in high-performance batteries, especially lithium high-performance batteries.
  • the separators used for the invention also have the advantage that partially adhere to the inorganic surfaces of the separator material, the anions of the conducting salt, resulting in an improvement of the dissociation and thus to a better ion conductivity in the high current range.
  • the separator used for the battery according to the invention comprising a flexible nonwoven with a porous inorganic coating on and in this nonwoven, wherein the material of the nonwoven is selected from nonwoven, non-electrically conductive polymer fibers, is also characterized in that the nonwoven a thickness of less than 30 [im, a porosity of more than 50%, preferably from 50 to 97% and a
  • pore radius distribution in which at least 50% of the pores have a pore radius of 75 to 150 ⁇ .
  • the separator particularly preferably has a nonwoven which has a thickness of 5 to 30 ⁇ m, preferably a thickness of 10 to 20 ⁇ m. Also particularly important is a homogeneous distribution of pore radii in the web as indicated above. An even more homogeneous pore radius distribution in the nonwoven, in combination with optimally matched oxide particles of a certain size, leads to an optimized porosity of the separator.
  • the thickness of the substrate has a great influence on the properties of the separator, since on the one hand the flexibility but also the sheet resistance of the electrolyte-impregnated separator depends on the thickness of the substrate. Due to the small thickness, a particularly low electrical resistance of the separator is achieved in the application with an electrolyte.
  • the separator itself has a very high electrical resistance, since it itself must have insulating properties. In addition, thinner separators allow increased packing density in a battery pack so that one can store a larger amount of energy in the same volume.
  • the web has a porosity of 60 to 90%, more preferably from 70 to 90%.
  • the porosity is defined as the volume of the web (100%) minus the volume of the fibers of the web, ie the proportion of the volume of the web that is not filled by material.
  • the volume of the fleece can be calculated from the dimensions of the fleece.
  • the volume of the fibers results from the measured weight of the fleece considered and the density of the polymer fibers.
  • the large porosity of the substrate also allows a higher porosity of the separator, which is why a higher uptake of electrolytes with the separator can be achieved.
  • non-electrically conductive fibers of polymers as defined above which are preferably selected from polyacrylonitrile (PAN), polyesters such as polyethylene terephthalate (PET) and as polymer fibers for the nonwoven fabric or polyolefin (PO), such as polypropylene (PP) or polyethylene (PE), or mixtures of such polyolefins.
  • PAN polyacrylonitrile
  • PET polyethylene terephthalate
  • PO polyolefin
  • PP polypropylene
  • PE polyethylene
  • the polymer fibers of the nonwovens preferably have a diameter of from 0.1 to 10 ⁇ m, more preferably from 1 to 4 ⁇ m.
  • Particularly preferred flexible nonwovens have a basis weight of less than 20 g / m 2 , preferably from 5 to 10 g / m 2 .
  • the nonwoven is flexible and has a thickness of less than 30 pm.
  • the separator has a porous, electrically insulating, ceramic coating on and in the fleece.
  • the porous inorganic coating on and in the nonwoven preferably has oxide particles of the elements Li, Al, Si and / or Zr with an average particle size of 0.5 to 7 ⁇ m, preferably 1 to 5 ⁇ m and very particularly preferably 1 , 5 to 3 pm up.
  • the separator has a porous inorganic coating on and in the nonwoven, which has aluminum oxide particles.
  • these have an average particle size of 0.5 to 7 pm, preferably from 1 to 5 pm and most preferably from 1, 5 to 3 pm.
  • the alumina particles are bonded to an oxide of the elements Zr or Si.
  • the separator preferably has a porosity of from 30 to 80%, preferably from 40 to 75% and particularly preferably from 45 to 70%.
  • the porosity refers to the achievable, ie open pores.
  • the porosity can be determined by the known method of mercury porosimetry or can be calculated from the volume and density of the feedstock used, if it is assumed that only open pores are present.
  • the separators used for the battery according to the invention are also distinguished by the fact that they can have a tensile strength of at least 1 N / cm, preferably of at least 3 N / cm and very particularly preferably of 3 to 10 N / cm.
  • the separators can be
  • the high tensile strength and the good bendability of the separator have the advantage that changes in the geometries of the electrodes occurring during the charging and discharging of a battery can be through the separator without being damaged.
  • the flexibility also has the advantage that commercially standardized winding cells can be produced with this separator. In these cells, the electrode / separator layers are spirally wound together in a standardized size and contacted.
  • the separator it is possible to design the separator to have the shape of a concave or convex sponge or pad, or the shape of wires or a felt. This embodiment is well suited to compensate for volume changes in the battery. Corresponding preparation methods are known to the person skilled in the art.
  • the polymer fleece used in the separator has a further polymer.
  • this polymer is disposed between the separator and the negative electrode and / or the separator and the positive electrode, preferably in the form of a polymer layer.
  • the separator is coated with this polymer on one or both sides.
  • Said polymer may be in the form of a porous membrane, i. as a film, or in the form of a nonwoven, preferably in the form of a nonwoven fabric of non-woven polymer fibers.
  • polymers are preferably selected from the group consisting of polyester, polyolefin, polyacrylonitrile, polycarbonate, polysulfone,
  • Polyethersulfone polyvinylidene fluoride, polystyrene, polyetherimide.
  • the further polymer is a polyolefin.
  • Preferred polyolefins are polyethylene and polypropylene.
  • the separator is preferably coated with one or more layers of the further polymer, preferably of the polyolefin, which is preferably also present as a nonwoven, that is to say as nonwoven polymer fibers.
  • a non-woven of polyethylene terephthalate is used, which with one or more layers of the further polymer,
  • the polyolefin which is preferably also present as a non-woven, so as non-woven polymer fibers coated.
  • separator of the above-described type of separation which is coated with one or more layers of the further polymer, preferably of the polyolefin, which is preferably likewise present as a nonwoven, that is to say as nonwoven polymer fibers.
  • the coating with the further polymer can be achieved by gluing, lamination, by a chemical reaction, by welding or by a mechanical connection.
  • Such polymer composites and processes for their preparation are known from EP 1 852 926.
  • the fiber diameters of the polyethylene terephthalate fleece are preferably larger than the fiber diameters of the further polymer fleece, preferably the polyolefin fleece, with which the separator is coated on one or both sides.
  • the nonwoven made of polyethylene terephthalate then has a higher pore diameter than the nonwoven, which is made of the other polymer.
  • the nonwovens usable in the separator are made of nanofibers of the polymers used, whereby nonwovens are formed which have a high porosity with formation of small pore diameters. This can further reduce the risk of short-circuit reactions.
  • a polyolefin in addition to the polyethylene terephthalate ensures increased safety of the electrochemical cell, since undesirable or excessive heating of the cell, the pores of the polyolefin contract and the charge transport through the separator is reduced or terminated. Should the temperature of the electrochemical cell increase to such an extent that the polyolefin begins to melt, the polyethylene terephthalate effectively counteracts the melting together of the separator and thus an uncontrolled destruction of the electrochemical cell.
  • the lithium ion battery has a nonaqueous electrolyte.
  • electrolyte in the sense of the invention preferably means a liquid and a conducting salt
  • the electrolyte is a solvent for the conducting salt
  • the electrolyte is then preferably in the form of an electrolyte solution Suitable electrolytes are known from the prior art Suitable solvents are preferably Suitable solvents are preferably solvents such as ethylene carbonate, propylene carbonate,
  • ionic liquids may also be used as the solvent.
  • Ionic liquids are known in the art. They contain only ions. Examples of usable cations which can be alkylated in particular are imidazolium, pyridinium, pyrrolidinium, guanidinium, uronium, thiuronium, piperidinium, morpholinium, sulfonium, ammonium and phosphonium cations. Examples of useful anions are Halide, tetrafluoroborate, trifluoroacetate, triflate, hexafluorophosphate, phosphinate and tosylate anions.
  • ionic liquids which may be mentioned are: N-methyl-N-propyl piperidinium bis (trifluoromethylsulfonyl) imide, N-methyl-N-butylpyrrolidinium bis (trifluoromethylsulfonyl) imide, N-butyl-N-trimethyl ammonium bis (trifluoromethylsulfonyl) imide, triethylsulfonium bis (trifluoromethylsulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) -ammonium bis (trifluoromethylsulfonyl) -imide. Two or more of the above liquids can be used.
  • Preferred conductive salts are lithium salts which have inert anions and which are non-toxic. Suitable lithium salts are preferably lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium bis (trifluoromethylsulfonylimide), lithium trifluoromethanesulfonate, lithium tris (trifluoromethylsulfonyl) methide, lithium tetrafluoroborate, lithium perchlorate, lithium tetrachloroaluminate, lithium bisoxalatoborate, lithium difluorooxalatoborate and / or lithium chloride; and mixtures of one or more of these salts.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Molecular Biology (AREA)
  • Health & Medical Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une électrode pour une batterie lithium-ion comprenant l'étape (ii) : (ii) déposition par électrophorèse de particules céramiques d'une suspension aqueuse, qui comporte les particules céramiques, sur un support.
PCT/EP2012/001444 2011-05-06 2012-03-30 Électrode pour batteries lithium-ion Ceased WO2012152357A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2014508698A JP2014519143A (ja) 2011-05-06 2012-03-30 リチウムイオン電池用電極
KR1020137031647A KR20140024011A (ko) 2011-05-06 2012-03-30 리튬 이온 배터리용 전극
CN201280022076.3A CN103503200A (zh) 2011-05-06 2012-03-30 用于锂离子电池的电极
EP12712076.4A EP2705558A1 (fr) 2011-05-06 2012-03-30 Électrode pour batteries lithium-ion

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011100724A DE102011100724A1 (de) 2011-05-06 2011-05-06 Elektrode für Lithiumionen-Batterien
DE102011100724.9 2011-05-06

Publications (1)

Publication Number Publication Date
WO2012152357A1 true WO2012152357A1 (fr) 2012-11-15

Family

ID=45929496

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/001444 Ceased WO2012152357A1 (fr) 2011-05-06 2012-03-30 Électrode pour batteries lithium-ion

Country Status (6)

Country Link
EP (1) EP2705558A1 (fr)
JP (1) JP2014519143A (fr)
KR (1) KR20140024011A (fr)
CN (1) CN103503200A (fr)
DE (1) DE102011100724A1 (fr)
WO (1) WO2012152357A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9666852B2 (en) 2014-10-02 2017-05-30 Ford Global Technologies, Llc Composite separator with aligned particles
CN112567075A (zh) * 2018-07-03 2021-03-26 3D电池有限公司 作为浆料和epd浴稳定剂的抗絮凝剂及其用途

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014221194A1 (de) * 2014-10-20 2016-04-21 Bayerische Motoren Werke Aktiengesellschaft Dotiertes Zinndioxid als Elektrodenmaterial einer Batterie
US9923189B2 (en) * 2016-02-02 2018-03-20 GM Global Technology Operations LLC Electrophoretic deposition of an electrode for a lithium-based battery
JP7032180B2 (ja) * 2018-03-07 2022-03-08 トヨタ自動車株式会社 電池およびその製造方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002042791A (ja) 2000-07-28 2002-02-08 Denso Corp セパレータ付き電池用電極の製造方法
WO2004021477A1 (fr) 2002-08-27 2004-03-11 Creavis Gesellschaft Für Technologie Und Innovation Mbh Separateur de batterie conducteur d'ions pour des batteries au lithium, son procede de production et son utilisation
WO2004021499A2 (fr) 2002-08-24 2004-03-11 Creavis Gesellschaft Für Technologie Und Innovation Mbh Separateur electrique, son procede de production et son utilisation dans des piles haute puissance au lithium
EP1017476B1 (fr) 1998-06-03 2006-10-18 Degussa AG Materiau composite conducteur d'ions permeable aux substances, procede permettant de le produire et son utilisation
EP1852926A1 (fr) 2006-05-05 2007-11-07 Carl Freudenberg KG Séparateur destiné à l'agencement dans des batteries et batterie
EP2000557A1 (fr) * 2007-06-04 2008-12-10 United Technologies Corporation Barrière contre l'érosion pour revêtements de barrière thermique
DE102008012586A1 (de) 2008-03-05 2009-09-10 Technische Universität Bergakademie Freiberg Elektrophoretisches Verfahren zur Herstellung keramischer Strukturen mit regelmäßig angeordneten gerichteten Porenkanälen
US20100203391A1 (en) * 2009-02-09 2010-08-12 Applied Materials, Inc. Mesoporous carbon material for energy storage
US7828619B1 (en) * 2005-08-05 2010-11-09 Mytitek, Inc. Method for preparing a nanostructured composite electrode through electrophoretic deposition and a product prepared thereby

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1017476B1 (fr) 1998-06-03 2006-10-18 Degussa AG Materiau composite conducteur d'ions permeable aux substances, procede permettant de le produire et son utilisation
JP2002042791A (ja) 2000-07-28 2002-02-08 Denso Corp セパレータ付き電池用電極の製造方法
WO2004021499A2 (fr) 2002-08-24 2004-03-11 Creavis Gesellschaft Für Technologie Und Innovation Mbh Separateur electrique, son procede de production et son utilisation dans des piles haute puissance au lithium
WO2004021477A1 (fr) 2002-08-27 2004-03-11 Creavis Gesellschaft Für Technologie Und Innovation Mbh Separateur de batterie conducteur d'ions pour des batteries au lithium, son procede de production et son utilisation
US7828619B1 (en) * 2005-08-05 2010-11-09 Mytitek, Inc. Method for preparing a nanostructured composite electrode through electrophoretic deposition and a product prepared thereby
EP1852926A1 (fr) 2006-05-05 2007-11-07 Carl Freudenberg KG Séparateur destiné à l'agencement dans des batteries et batterie
EP2000557A1 (fr) * 2007-06-04 2008-12-10 United Technologies Corporation Barrière contre l'érosion pour revêtements de barrière thermique
DE102008012586A1 (de) 2008-03-05 2009-09-10 Technische Universität Bergakademie Freiberg Elektrophoretisches Verfahren zur Herstellung keramischer Strukturen mit regelmäßig angeordneten gerichteten Porenkanälen
US20100203391A1 (en) * 2009-02-09 2010-08-12 Applied Materials, Inc. Mesoporous carbon material for energy storage

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9666852B2 (en) 2014-10-02 2017-05-30 Ford Global Technologies, Llc Composite separator with aligned particles
CN112567075A (zh) * 2018-07-03 2021-03-26 3D电池有限公司 作为浆料和epd浴稳定剂的抗絮凝剂及其用途

Also Published As

Publication number Publication date
CN103503200A (zh) 2014-01-08
KR20140024011A (ko) 2014-02-27
JP2014519143A (ja) 2014-08-07
DE102011100724A1 (de) 2012-11-08
EP2705558A1 (fr) 2014-03-12

Similar Documents

Publication Publication Date Title
EP2564461B1 (fr) Batterie lithium-soufre
WO2013017217A1 (fr) Batterie lithium-ion
EP1535357B1 (fr) Separateur utilise dans des batteries haute energie et son procede de production
EP1532701B1 (fr) Separateur de batterie conducteur d'ions pour des batteries au lithium, son procede de production et son utilisation
DE102011109137A1 (de) Lithiumionen-Batterie
WO2013135353A1 (fr) Séparateur contenant du graphène pour batteries lithium-ion
EP2697844A1 (fr) Batterie lithium-ion à tension élevée
DE102012023294A1 (de) Separator für eine Lithium-lonen-Batterie sowie Lithium-lonen-Batterie enthaltend den Separator
DE102015112067A1 (de) Durch spinnen hergestellte batterien
DE102005042215A1 (de) Separator mit verbesserter Handhabbarkeit
EP2583335A1 (fr) Batterie aux ions lithium comprenant des matières d'électrode amorphes
DE112012000882T5 (de) Elektrochemisches Element
WO2010092059A1 (fr) Electrodes planes à densités de puissance et d'énergie optimisées pour accumulateur d'énergie électrochimique
WO2012152357A1 (fr) Électrode pour batteries lithium-ion
WO2013135351A1 (fr) Graphène dans des batteries lithium-ion
DE102010020992A1 (de) Additiv für Elektrolyte in wiederaufladbaren Lithiumionen-Batterien
EP2514019B1 (fr) Batterie lithium-ion
WO2013020661A1 (fr) Accumulateur au lithium-ion et procédé de fabrication d'un accumulateur au lithium-ion
WO2010121696A1 (fr) Accumulateur électrochimique au titanate de lithium
DE102013018235A1 (de) Elektrochemische Zelle
DE112017004317T5 (de) Laminierter Elektrodenkörper und ein elektrisches Speicherelement
DE102013011273A1 (de) Separator für eine Lithium-lonen-Batterie, sowie Lithium-lonen-Batterie enthaltend den Separator
WO2011009620A1 (fr) Batterie au lithium-ion
DE102014221279A1 (de) Kompositelektrode und diese umfassende Lithiumionenbatterie sowie Verwendung der Lithiumionenbatterie in einem Kraftfahrzeug
EP2732493A2 (fr) Batterie de structure poreuse

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12712076

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014508698

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2012712076

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20137031647

Country of ref document: KR

Kind code of ref document: A