WO2014129971A1 - Électrolyte polymère composite conducteur à ion unique en polyamide - Google Patents

Électrolyte polymère composite conducteur à ion unique en polyamide Download PDF

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WO2014129971A1
WO2014129971A1 PCT/SG2014/000068 SG2014000068W WO2014129971A1 WO 2014129971 A1 WO2014129971 A1 WO 2014129971A1 SG 2014000068 W SG2014000068 W SG 2014000068W WO 2014129971 A1 WO2014129971 A1 WO 2014129971A1
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optionally substituted
alkyl
ion conducting
conducting polymer
polymer electrolyte
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Hansong Cheng
Yubao SUN
Rupesh ROHAN
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National University of Singapore
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National University of Singapore
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
    • 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
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • lithium salts such as LiPF 6 , LiC10 4 , TFSI, FSI, and LiBOB are dissolved in non-aqueous polar solvent such as PC, EC, DEC, MEC and DMC and used as electrolytes.
  • non-aqueous polar solvent such as PC, EC, DEC, MEC and DMC
  • both cations and anions contribute to the overall current.
  • the anode loses electrons and releases lithium ions. Electrons and lithium ions then move to the cathode.
  • the counter ions in the electrolyte move in the opposite direction accumulating near the anode.
  • lithium single-ion electrolytes have been proposed as an alternative to lithium salts.
  • lithium single-ion electrolytes are mostly in a liquid form, which poses serious concerns about battery thermal stability and safety. Lithium single-ion electrolytes can also suffer from low ionic conductivity which rarely exceed 10 "4 S/cm.
  • the present invention provides solid polymer electrolytes with enhanced ionic conductivity.
  • the polyamide single-ion conducting polymer electrolytes of the present invention enable facile ionization and high mobility of the lithium atoms through the delocalization of negative charges on the N atoms arising from the strong electron withdrawing capability of the bis(sulfonyl) groups.
  • FIG. 1 is a synthetic scheme for the synthesis of a polyamide single-ion conducting polymer.
  • FIG. 2 is a photograph of a composite film comprising the polyamide single-ion conducting polymer electrolyte, Compound (2), and polyvinylidene difluoride (PVDF) made by solution cast method.
  • PVDF polyvinylidene difluoride
  • FIG. 3 shows the infrared absorbance spectra of 2,4-diaminobenzene sulfonic acid, 4,4'-((hydrosulfonylamino)sulfonyl)dibenzoic acid and of the polyamide single-ion conducting polymer electrolyte, Compound (2). (See example 2)
  • FIG. 4 is a thermogravimetry curve of the polyamide single-ion conducting polymer electrolyte, Compound (2).
  • FIG. 5 is a gel permeation chromatography (GPC) profile of the polyamide single-ion conducting polymer, Compound (2), showing the molecular distribution of the polymer electrolyte.
  • GPC gel permeation chromatography
  • FIG. 6 shows an ionic conductivity plot of a composite film comprising the polyamide single-ion conducting polymer electrolyte, Compound (2), and
  • FIG. 7 shows the electrochemical stability of a composite film comprising the polyamide single-ion conducting polymer electrolyte, Compound (2) and polyvinylidene difluoride (PVDF) measured using linear sweep voltammetry (LSV).
  • FIG. 8 is a scanning electron micrograph of the polyamide single-ion conducting polymer electrolyte, Compound (2).
  • FIG. 9 is nuclear resonance spectrum of the polyamide single-ion conducting polymer electrolyte, Compound (2).
  • Alkyl as used alone or as part of a larger moiety as in “alkyl amino” or “haloalkyl” means a saturated aliphatic branched or straight-chain monovalent hydrocarbon radical, typically C1-C8, preferably C1-C4.
  • (C1-C4) alkyl means a radical having from 1- 4 carbon atoms in a linear or branched arrangement.
  • (C1-C4) alkyl includes methyl, ethyl, propyl, sec-butyl, tert-butyl, and butyl.
  • Alkoxy refers to the group -O-R where R is “alkyl”, “cycloalkyl”,
  • alkenyl or "alkynyl”.
  • alkoxyalkyl means alkyl substituted with one or more alkmy ⁇ groups ⁇ Examples of -alkox-y-grou-ps include methoxy ethoxy7prop )xy, butoxy and the like.
  • (C1-C4) alkoxy refers to the group -O-R where R is a radical having from 1 -4 carbons in a linear or branched arrangement.
  • aromatic ring refers to an aromatic carbocyclic group of from 6 to 18 carbon atoms having a single ring or multiple condensed rings.
  • (C6-C10) aryl means an aromatic ring having between 6-10 carbons.
  • aryl also includes aromatic carbocycle(s) fused to cycloalkyl or heterocycloalkyl groups.
  • Suitable aryl groups include, but are not limited to, phenyl, tolyl, anthacenyl, fluorenyl, indenyl, azulenyl, and naphthyl, benzo[i/][l,3]dioxole, phenanthrenyl, as well as benzo-fused carbocyclic moieties such as 5,6,7,8-tetrahydronaphthyl and the like.
  • An aryl group can be unsubstituted or substituted with one or more substituents, e.g.
  • substituents as described herein for alkyl groups including without limitation alkyl or alkyl substituted with one or more halo
  • the aryl group is a monocyclic ring, wherein the ring comprises 6 carbon atoms.
  • Halogen and "halo” are interchangeably used herein and each refers to fluorine, chlorine, bromine, or iodine.
  • haloalkyl means alkyl, cycloalkyl, or alkoxy, as the case may be, substituted with one or more halogen atoms.
  • Acyl or “Ac” refers to R"-C(0)-, where R" is H, alkyl, substituted alkyl, heteroalkyl, substituted heteroalkyl, alkenyl, substituted alkenyl, aryl, alkylaryl, or substituted alkylaryl.
  • (C1-C4) acyl refers to R"-C(0)-, where R" is a radical having from 1 -4 carbons in a linear or branched arrangement.
  • Amino means -NH 2 ;
  • alkylamine and “dialkylamine” mean -NHR and - NR 2 , respectively, wherein R is an alkyl group.
  • Cycloalkylamine and
  • dicycloalkylamine mean -NHR and -NR 2 , respectively, wherein R is a cycloalkyl group.
  • (C1-C4) alkyl amine refers to an amine group, -NHR, where R is a radical having from 1-4 carbons in a linear or branched arrangement.
  • (C1-C4) dialkyl amine refers to an amine group, -NR 2 , where each R is a radical having from 1 -4 carbons in a linear or branched arrangement.
  • alkali metal is defined as a metal found within the Group (I) element of the periodic table.
  • the alkali metals of the invention include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr).
  • the present invention relates to a polyamide single-ion conducting polymer electrolyte of the following Structural Formula (I):
  • each M is independently H or an alkali metal
  • each Ri is independently H, halogen, an optionally substituted (C1-C4) alkyl, an optionally substituted (C1-C4) alkoxy, an optionally substituted (C1-C4) alkyl amino, an optionally substituted (C1-C4) dialkyl amino, an optionally substituted (Cl- C4) acyl, or an optionally substituted (C1-C4)NR3C(0), wherein the optional substituents are each independently H, halogen, (C1-C4) alkyl, (C1-C4) alkoxy, (Cl- C4) halo alkyl, (C1-C4) haloalkyl alkoxy (C1-C4) alkyl amino, or (C1-C4) acyl;
  • each R 2 is independently H, halogen, an optionally substituted (C1-C4) alkyl, an optionally substituted (C1-C4) alkoxy, an optionally substituted (C1-C4) alkyl amino, an optionally substituted (C1-C4) dialkyl amino, an optionally substituted (Cl- C4) acyl, or an optionally substituted (C1-C4)NR 3 C(0), wherein the optional substituents are each independently H, halogen, (C1-C4) alkyl, (C1-C4) alkoxy, (Cl- C4) halo alkyl, (C1-C4) haloalkyl alkoxy (C1-C4) alkyl amino, or (C1-C4) acyl;
  • R 3 , Rt and R 5 are each independently H or an optionally substituted (C1-C4) alkyl
  • each mi and m 2 is independently an integer from 1 to 4.
  • n is an integer from 1-100.
  • M in Structural Formula (I) can be an alkali metal.
  • Alkali metals can include, for example, Li, Na, K, Cs, Rb, and Fr.
  • M in a preferred polyamide single- ion conducting polymer electrolyte having the structure shown in Structural Formula (I) M is lithium.
  • M is hydrogen.
  • M is sodium.
  • M is potassium.
  • the polyamide single-ion conducting polymer electrolyte having the structure shown in Structural Formula (I) can have R ⁇ and R 2 groups that are the same or different.
  • R] may be hydrogen and R 2 may be alkyl or Ri and R 2 may both be hydrogen.
  • Ri and R 2 are hydrogen.
  • Ri is hydrogen and R 2 is fluoride.
  • Ri is fluoride and R 2 is hydrogen.
  • Rv and R 2 are fluorine.
  • R l5 R 2 , R 4 , R 5 , and M are hydrogen.
  • Rj, R 2 , R 4 and R 5 are hydrogen and M is lithium.
  • Rt is hydrogen, R 2 is fluoride, R and R 5 are hydrogen, M is lithium, and mi and m 2 are each 1.
  • R 1 is fluoride, R 2 is hydrogen, R 4 and R 5 are hydrogen, M is lithium, and mi and m 2 are each 1
  • the present invention relates to a polyamide single-ion con
  • each M is independently H or an alkali metal; and n is selected to provide a polymer with a weight average molecular weight in the range of about 10,000 to about 300,000.
  • a conductive polymer is a polymer that possesses conducting properties as opposed to possessing insulating electron-transport properties.
  • the term "polymer” refers to a macromolecule made of repeating monomer units.
  • copolymer is defined as a polymer of at least two chemically distinct monomers.
  • the copolymers of the invention include, but are not limited to, alternating copolymers, statistical copolymers, block copolymers, random copolymer, and graft copolymers.
  • the polymers and copolymers of the invention also include, but are not, limited to, dendrimers and hyperbranched polymers and copolymers.
  • the polyamide single-ion conducting polymer electrolyte is a polymer comprising at least one monomer. In another embodiment, the polyamide single-ion conducting polymer electrolyte is a copolymer comprising one or more monomers.
  • Ion transference number is defined to describe the current contribution of various ions in the electrolyte. Typically, the lithium transference number in lithium ion batteries is around 0.3. Increasing this value is a good way to solve the problem of cell polarization, especially at a high charge/discharge rate.
  • the polyamide single-ion conducting polymer electrolyte of the invention can have an ion transference number between about 0.2 to about 0.95. Preferably the polymer electrolyte has an ion transference number between about 0.3 to about 0.95; more preferably between about 0.5 to about 0.95.
  • the polyamide single-ion conducting polymer electrolyte of the invention demonstrates high ionic conductivity.
  • the polymer electrolyte of the invention can have an ionic conductivity between about 10 " S/cm to about 10 " S/cm.
  • Preferably the polymer electrolyte has an ionic conductivity between about 10 " S/cm to about 10 "
  • the polyamide single-ion conducting polymer electrolyte has an ionic conductivity of 3.4 x
  • the polyamide single-ion conducting polymer electrolyte of the present invention can have a molecular weight between about 5,000 to about 500,000.
  • the polyamide polymer electrolyte has a molecular weight between about 8,000 to about 400,000; more preferably between about 10,000 to about 300,000.
  • the present invention also relates to a method for synthesizing a polyamide single-ion conducting polymer electrolyte comprising: a) heating a mixture of a bis(4- carbonyl benzene sulphonyl) imide and a dibenzenesulfonic acid to form a single-ion conducting polymer; and b) combining the single-ion conducting polymer with an alkali metal base to form the single-ion conducting polymer electrolyte of Structural Formula (la):
  • each Ri is independently H, halogen, an optionally substituted (C1-C4) alkyl, an optionally substituted (C1-C4) alkoxy, an optionally substituted (C1-C4) alkyl amino, an optionally substituted (C1-C4) dialkyl amino, an optionally substituted (Cl- C4) acyl, or an optionally substituted (C1-C4)NR 3 C(0), wherein the optional substituents are each independently H, halogen, (C1-C4) alkyl, (C1-C4) alkoxy, (Cl- C4) halo alkyl, (C1-C4) haloalkyl alkoxy (C1-C4) alkyl amino, or (C1-C4) acyl;
  • each R 2 is independently H, halogen, an optionally substituted (C1-C4) alkyl, an optionally substituted (C1-C4) alkoxy, an optionally substituted (C1-C4) alkyl amino, an optionally substituted (C1-C4) dialkyl amino, an optionally substituted (Cl- C4) acyl, or an optionally substituted (C1-C4)NR 3 C(0), wherein the optional substituents are each independently H, halogen, (C1-C4) alkyl, (C1-C4) alkoxy, (Cl- C4) halo alkyl, (C1-C4) haloalkyl alkoxy (C1-C4) alkyl amino, or (C1-C4) acyl;
  • R 3 , R4 and R5 are each independently H or an optionally substituted (CI -C4) alkyl
  • each mi and m 2 is independently an integer from 1 to 4.
  • n is an integer from 1-100.
  • FIG. 1 shows a synthetic scheme according to the invention for synthesizing a polyamide single-ion conducting polymer electrolyte.
  • the synthesis includes two main steps: a) polymerization of the bis(4-carbonyl benzene sulphonyl) imide and the dibenzenesulfonic acid; and b) metal cation exchange.
  • Incorporation of anionic groups (e.g., nitrogen and S0 2 " ) within the polymeric backbone allows immobilization of the anionic groups thereby preventing accumulation of anions and polarization inside the cell.
  • anionic groups e.g., nitrogen and S0 2 "
  • the bis(4-carbonyl benzene sulphonyl) imide has a Structural Formula ( ⁇ ):
  • each Ri is independently H, halogen, an optionally substituted (C1-C4) alkyl, an optionally substituted (C1-C4) alkoxy, an optionally substituted (C1-C4) alkyl amino, an optionally substituted (C 1 -C4) dialkyl amino, an optionally substituted (C 1 - C4) acyl, or an optionally substituted (C1-C4)NR 3 C(0), wherein the optional substituents are each independently H, halogen, (C1-C4) alkyl, (C1-C4) alkoxy, (Cl- C4) halo alkyl, (C1-C4) haloalkyl alkoxy (C1-C4) alkyl amino, or (C1-C4) acyl;
  • each R 2 is independently H, halogen, an optionally substituted (C1-C4) alkyl, an optionally substituted (C1-C4) alkoxy, an optionally substituted (C1-C4) alkyl amino, an optionally substituted (C1-C4) dialkyl amino, an optionally substituted (Cl- C4) acyl, or an optionally substituted (C1-C4)NR 3 C(0), wherein the optional substituents are each independently H, halogen, (C1-C4) alkyl, (C1-C4) alkoxy, (Cl- C4) halo alkyl, (C1-C4) haloalkyl alkoxy (C1-C4) alkyl amino, or (C1-C4) acyl;
  • each mi and m 2 is independently an integer from 1 to 4.
  • the bis(4-carbonyl benzene sulphonyl) imide is a compound of Structural Formula (II) wherein Ri and R 2 are hydrogen.
  • the bis(4-carbonyl benzene sulphonyl) imide is a compound of Structural Formula (II) wherein Ri is hydrogen and R 2 are fluorine.
  • the bis(4-carbonyl benzene sulphonyl) imide is a compound of Structural Formula (II) wherein Ri is fluorine and R 2 are hydrogen.
  • dibenzenesulfonic acids that can be used to synthesize the polyamide single-ion conducting polymer electrolytes of the present invention.
  • the dibenzenesulfonic acid has a Structural Formula (III):
  • each R4 and R 5 are each independently H or an optionally substituted (C 1- C4) alkyl. In one embodiment, R4 and R 5 are H. In another embodiment, the dibenzenesulfonic acid is 2,4-diaminobenzenesulfonic acid. In yet another embodiment the dibenzenesulfonic acid is 3,5-diaminobenzenesulfonic acid. In yet another embodiment, the dibenzenesulfonic acid is 2,6-diaminobenzenesulfonic acid.
  • the molar ratio used in the polymerization step can be between about 1 : 1 to about 10:1 of the bis(4-carbonyl benzene sulphonyl) imide to the dibenzenesulfonic acid; preferably 1 :1 to about 8:1; more preferably 1 :1 to about 5:1.
  • the polymerization of the bis(4-carbonyl benzene sulphonyl) imide and the dibenzenesulfonic acid is conducted at an elevated temperature, preferably between about 50 °C to about 300 °C, more preferably between about 70 °C to about 150 °C, and most preferably between about 80 °C to about 120°C.
  • Metal cation exchange can be carried out with an alkali metal base.
  • the choice of alkali metal base will depend on the identity of the alkali metal on the polyamide single-ion conducting polymer electrolyte.
  • the alkali metal base used in the methods of the present invention can include, but is not limited to, lithium hydroxide (LiOH), sodium hydroxide (NaOH), and potassium hydroxide (KOH).
  • the metal cation exchange can be carried out in the presence of a polar or non- polar solvent.
  • the metal base is aqueous lithium hydroxide.
  • the metal base is aqueous sodium hydroxide.
  • the metal base is aqueous potassium hydroxide.
  • the present invention relates to a method for manufacturing a polyamide single-ion conducting composite film, comprising: a) dissolving a polyamide single-ion conducting polymer electrolyte and second polymer in a solvent to form a solution mixture; and b) evaporating the solvent at a temperature between about 50 °C to about 150 °C to form the polyamide single-ion conducting polymer electrolyte conducting composite film.
  • the second polymer that can be used to make the composite film can be an electrochemically stable polymer or a copolymer of low or high molecular weight.
  • the second polymer can have a low or a high transition glass transition temperature.
  • the monomers that can be used to synthesize the second polymers or copolymers of the present invention include, but are not limited to, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 1,1- chlorofluoroethylene, ethylene oxide, 11-aminoundecanoic acid, and thiourea, or a combination thereof.
  • the second polymer used to make the composite film can be a copolymer comprising two or more monomers.
  • the second polymer is polyvinylidene fluoride (PVDF).
  • the second polymer is a high molecular weight polymer.
  • the second polymer has a low glass transition temperature (Tg).
  • non-polar solvents refers to solvents with a dielectric constant of less than 15 and can include, but are not limited to, aliphatic solvents, aromatic solvents, and other aprotic solvents.
  • non-polar solvents include, but are not limited to, pentane, hexanes, heptane, hexadecane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran, diethylether, ethyl acetate, and methylene chloride.
  • Polar solvents refer to solvents with a dielectric constant of more than 15 and include, but are not limited to, aprotic and protic solvents.
  • polar solvents include, but are not limited to, acetone, dimethylformamide, N-methyl-2-pyrrolidinone, acetonitrile, propylene carbonate, acetic acid, formic acid, methanol, ethanol, n-propanol, isopropanol, n-butanol, nitromethane, and water.
  • the solvent is ⁇ , ⁇ -dimethylformamide.
  • the solvent is N-methyl-2-pyrrolidinone.
  • the solvent is water.
  • FIG. 2 is a photograph of a composite film comprising Compound (2) and PVDF made by a solution cast method.
  • Both A and B display a broad peak between 3100 and 2900 cm “1 , which is attributed to the O-H stretching vibration. After polymerization, this peak disappears as expected in C.
  • the broad peak observed in curve C can be attributed to the infrared absorption of water molecules. The increased exposure of lithium cations in the polymer electrolyte, make it very sensitive to moisture and other absorbates.
  • FIG. 5 shows the gel permeation chromatography (GPC) profile of a Compound (2) showing the molecular distribution of the polymer electrolyte.
  • GPC gel permeation chromatography
  • Electrochemical test results can be seen in FIGs. 6 and 7 for the composite film comprising Compound (2) and PVDF.
  • the results show that the Compound(l)/ PVDF composite film has an ion conductivity of 7.2 mS/cm.
  • FIG. 6 shows that a remarkable oxidation current is observed to start at 4.8V and increases substantially after 6V.
  • FIG. 9 is the nuclear resonance( ⁇ -NMR) spectrum of Compound (2).
  • the 1 H-NMR shows that there thirteen hydrogen atoms in each polymer unit.
  • the two peaks at 10.06 ppm and 8.93 ppm correlate to the two hydrogen atoms from the amide groups.
  • the large peaks between 8.2 ppm and 7.5 ppm are merged and can be attributed to the hydrogen atoms on the benzene rings.
  • the 'H-N!VIR peak at 1 1.52 ppm correlates to the hydrogen atom from the sulfonic acid group.
  • the polyamide single-ion conducting polymer electrolytes are useful in a variety of contexts.
  • the specific industrial applications include energy storage and conversion devices, such as solid- state batteries (e.g., lithium ion battery, sodium ion battery), fuel cells and supercapacitors.
  • solid- state batteries e.g., lithium ion battery, sodium ion battery
  • fuel cells e.g., fuel cells and supercapacitors.
  • the present invention relates to a battery comprising a polyamide single-ion conducting polymer electrolyte.
  • Solid state batteries made with the polyamide single-ion conducting polymer electrolytes of the present invention can comprise a positive electrode or anode, a negative electrode or cathode, and the polyamide single-ion conducting polymer electrolyte.
  • the battery comprises a polyamide single-ion conducting polymer electrolyte, a positive electrode, and a negative electrode.
  • the anode and the cathode can be made from a variety of materials.
  • the materials that can be used for the cathode include, but are not limited to, LiMn 2 0 4 , LiFeP 4 , LiCo0 2 , LiNi0 2 , LiNi 0.8 Co 0.2 O 2 , LiNi 1/3 Co 1/3 Mni /3 0 2 , Li 2 FeSi0 4 , LiFeS0 4 F, LiFeB0 3 , and LiMn t 5 Ni 0 5 O 4 .
  • the materials that can be used for the anode include, but are not limited to, carbon-based materials, silicon, Sn0 2 , CoO, Ti0 2 , Li 4 Ti 5 0 12 , V 2 0 5 , Mn0 2 , NiO, Fe 2 0 3 , and Co 3 0 4 .
  • Example 1 Synthesis of the Polyamide Single- Ion Conducting Polymer
  • DMSO-d6) ⁇ ppm 11.52 (s.lH), 10.60 (s.lH), 8.93 (s,2H), 8.20-7.50 (m,l 1H); 13 C NMR: (75MHz; DMSO-d6): ⁇ ppm 163.24, 131.11, 127.64, 127.60, 127.43, 127.26, 126.84, 126.81, 126.69, 126.60, 126.13, 126.08.
  • the gel permeation chromatography profile shows the average molecular weight for Compound (2) is about 30,000 with a polydispersity of 1.18 (FIG. 5).
  • Example 3 Synthesis of the polyvinylidine difluoride/ Polyamide Single-Ion Conducting Polymer Electrolyte Composite Film (3)
  • PVDF Polyvinylidene difluoride
  • Compound (2) (about 1 :2 of PVDF to Compound (2)) were dissolved in N-dimethyl-2-pyrrolidone (NMP) and the resulting mixture was placed in a glass culture dish. Heating of the mixture in the culture dish to 90 °C for 12 to 24 hours to slowly remove the solvent provided the PVDF/polyamide single-ion conducting polymer electrolyte composite film (3).
  • NMP N-dimethyl-2-pyrrolidone

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Abstract

La présente invention concerne des compositions et des procédés de synthèse d'électrolytes polymères conducteurs à ion unique en polyamide et des films composites électrolytiques polymères conducteurs à ion unique en polyamide. Dans des modes de réalisation supplémentaires, l'invention concerne également l'utilisation d'électrolytes polymères conducteurs à ion unique en polyamide et des films composites électrolytiques polymères conducteurs à ion unique en polyamide dans des piles au lithium-ion.
PCT/SG2014/000068 2013-02-25 2014-02-20 Électrolyte polymère composite conducteur à ion unique en polyamide Ceased WO2014129971A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105789531A (zh) * 2014-12-25 2016-07-20 杭州聚力氢能科技有限公司 阻挡隔膜、其制备方法及包括其的二次电池
CN107317049A (zh) * 2017-05-08 2017-11-03 浙江大学 一种单离子导电聚合物电解质及其制备方法和用途
CN108878777A (zh) * 2017-05-11 2018-11-23 杭州聚力氢能科技有限公司 一种单离子传导聚合物锂硫电池
EP3716388A3 (fr) * 2019-03-08 2020-12-09 Robert Bosch GmbH Polyamides, polyurées et polyphosphoramides en tant qu'anolytes pour batteries au lithium
US11552328B2 (en) * 2019-01-18 2023-01-10 Sila Nanotechnologies, Inc. Lithium battery cell including cathode having metal fluoride core-shell particle

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US20020160272A1 (en) * 2001-02-23 2002-10-31 Kabushiki Kaisha Toyota Chuo Process for producing a modified electrolyte and the modified electrolyte
US20030157388A1 (en) * 1999-07-19 2003-08-21 Koichiro Hinokuma Ionic conductor, process for production thereof, and electrochemical device
US20050209421A1 (en) * 2004-01-22 2005-09-22 Asahi Kasei Kabushiki Kaisha Vinyl monomer with superacid ester group and polymer of the same
WO2009132241A2 (fr) * 2008-04-24 2009-10-29 3M Innovative Properties Company Matériaux conducteurs de protons

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Publication number Priority date Publication date Assignee Title
US20030157388A1 (en) * 1999-07-19 2003-08-21 Koichiro Hinokuma Ionic conductor, process for production thereof, and electrochemical device
US20020160272A1 (en) * 2001-02-23 2002-10-31 Kabushiki Kaisha Toyota Chuo Process for producing a modified electrolyte and the modified electrolyte
US20050209421A1 (en) * 2004-01-22 2005-09-22 Asahi Kasei Kabushiki Kaisha Vinyl monomer with superacid ester group and polymer of the same
WO2009132241A2 (fr) * 2008-04-24 2009-10-29 3M Innovative Properties Company Matériaux conducteurs de protons

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105789531A (zh) * 2014-12-25 2016-07-20 杭州聚力氢能科技有限公司 阻挡隔膜、其制备方法及包括其的二次电池
CN105789531B (zh) * 2014-12-25 2019-03-15 杭州聚力氢能科技有限公司 阻挡隔膜、其制备方法及包括其的二次电池
CN107317049A (zh) * 2017-05-08 2017-11-03 浙江大学 一种单离子导电聚合物电解质及其制备方法和用途
CN107317049B (zh) * 2017-05-08 2019-07-09 浙江大学 一种单离子导电聚合物电解质及其制备方法和用途
CN108878777A (zh) * 2017-05-11 2018-11-23 杭州聚力氢能科技有限公司 一种单离子传导聚合物锂硫电池
CN108878777B (zh) * 2017-05-11 2020-10-30 杭州聚力氢能科技有限公司 一种单离子传导聚合物锂硫电池
US11552328B2 (en) * 2019-01-18 2023-01-10 Sila Nanotechnologies, Inc. Lithium battery cell including cathode having metal fluoride core-shell particle
EP3716388A3 (fr) * 2019-03-08 2020-12-09 Robert Bosch GmbH Polyamides, polyurées et polyphosphoramides en tant qu'anolytes pour batteries au lithium

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