WO2014157389A1 - Composition de membrane électrolytique, membrane électrolytique polymère solide, procédé permettant de produire ladite membrane électrolytique, ensemble membrane-électrode, pile à combustible de type polymère, ainsi que cellule d'électrolyse de l'eau et appareil d'électrolyse de l'eau - Google Patents

Composition de membrane électrolytique, membrane électrolytique polymère solide, procédé permettant de produire ladite membrane électrolytique, ensemble membrane-électrode, pile à combustible de type polymère, ainsi que cellule d'électrolyse de l'eau et appareil d'électrolyse de l'eau Download PDF

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WO2014157389A1
WO2014157389A1 PCT/JP2014/058640 JP2014058640W WO2014157389A1 WO 2014157389 A1 WO2014157389 A1 WO 2014157389A1 JP 2014058640 W JP2014058640 W JP 2014058640W WO 2014157389 A1 WO2014157389 A1 WO 2014157389A1
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polymer
electrolyte membrane
group
composition
independently
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Japanese (ja)
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法寛 山本
宣彰 若林
敏明 門田
翔平 藤下
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Jsr株式会社
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Publication of WO2014157389A1 publication Critical patent/WO2014157389A1/fr

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    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/12—Polythioether-ethers
    • C—CHEMISTRY; METALLURGY
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    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
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    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
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    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
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    • C08G75/0204—Polyarylenethioethers
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    • C08G75/0213—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur
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    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/025—Preparatory processes
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • 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]
    • 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
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/126—Copolymers block
    • C—CHEMISTRY; METALLURGY
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/145—Side-chains containing sulfur
    • C08G2261/1452—Side-chains containing sulfur containing sulfonyl or sulfonate-groups
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/312—Non-condensed aromatic systems, e.g. benzene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
    • C08G2261/3444—Polyethersulfones
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • C08G2261/516—Charge transport ion-conductive
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • 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
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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
    • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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

  • the present invention relates to an electrolyte membrane composition, a solid polymer electrolyte membrane, a method for producing the electrolyte membrane, a membrane-electrode assembly, a solid polymer fuel cell, a water electrolysis cell, and a water electrolysis apparatus.
  • a fuel cell is a power generator that directly takes out electricity by electrochemically reacting hydrogen gas obtained by reforming various hydrocarbon fuels (natural gas, methane, etc.) and oxygen gas in the air. It is attracting attention as a pollution-free power generator that can directly convert chemical energy into electrical energy with high efficiency.
  • Such a fuel cell is composed of a pair of electrode films (anode electrode and cathode electrode) carrying a catalyst and a proton conductive solid polymer electrolyte membrane sandwiched between the electrode films. Hydrogen ions and electrons are generated at the anode electrode, and the hydrogen ions pass through the solid polymer electrolyte membrane and react with oxygen at the cathode electrode to generate water.
  • solid polymer electrolyte membrane examples include Nafion (registered trademark, manufactured by DuPont), Aciplex (registered trademark, manufactured by Asahi Kasei Kogyo Co., Ltd.), and Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.).
  • fluorocarbon polymer electrolyte membranes having sulfonic acid groups mainly aromatic rings such as polyaromatic hydrocarbons, polyether ether ketones, polyphenylene sulfides, polyimides or polybenzazoles
  • a polymer electrolyte membrane having a chain skeleton and having a sulfonic acid group is used.
  • a polymer electrolyte membrane comprising an ion exchange membrane made of a polymer compound having a sulfonic acid group and a polyphenylene sulfide resin (Patent Document 1), a polymer electrolyte and a high platinum affinity
  • Patent Document 2 a polymer electrolyte membrane containing a compound
  • Patent Document 3 a polymer electrolyte membrane containing a polymer electrolyte and a specific sulfur-containing heterocyclic aromatic compound
  • the polymer electrolyte membrane described in Patent Document 1 may be inferior in film forming property because the polyphenylene sulfide resin has poor solubility in an organic solvent. Further, in the polymer electrolyte membranes described in Patent Documents 2 and 3, the durability of the electrolyte membrane is reduced due to elution from the electrolyte membrane of a compound having a high platinum affinity or a sulfur-containing heterocyclic aromatic compound, and the battery. There was room for improvement due to concerns about the decline in power generation performance.
  • An object of the present invention is to provide a composition capable of easily obtaining a polymer electrolyte membrane that is excellent in durability and can suppress a decrease in power generation performance and water electrolysis performance over time.
  • the present inventors have intensively studied to solve the above problems, and as a result, a polymer having an arylene sulfide skeleton and a polymer soluble in an organic solvent together with a polymer having an ion exchange group.
  • the electrolyte membrane composition containing the present invention the inventors have found that the above object can be achieved, and have completed the present invention.
  • the configuration of the present invention is as follows.
  • An electrolyte membrane composition comprising a polymer (A) having an ion exchange group and a polymer (B) having an arylene sulfide skeleton and soluble in an organic solvent.
  • R 1 and R 2 are each independently an alkyl group having 1 to 5 carbon atoms, an alkylsulfanyl group having 1 to 5 carbon atoms, a cyano group or a halogen atom, and a and b are each Independently, it is an integer of 0 to 3.
  • X 1 and X 2 are each independently a direct bond, —S—, —NH—, —SO— or —SO 2 —, but at least one of X 1 and X 2 is —S—.
  • R 3 represents an alkyl group having 1 to 5 carbon atoms, an alkylsulfanyl group having 1 to 5 carbon atoms, a cyano group, or a halogen atom, and c represents an integer of 0 to 4.
  • R 1, R 2, X 1, X 2, a and b are each independently, R 1 in the formula (1), R 2, X 1, X 2, a and b Is synonymous with ]
  • R 3 and c are each independently synonymous with R 3 and c in the formula (2).
  • D is independently a direct bond, —CO—, —SO 2 —, —SO—, —CONH—, —COO—, — (CF 2 ) 1 — (l is 1 to 10 -C (CF 3 ) 2 -,-(CH 2 ) l- (l is an integer of 1 to 10), -C (CR ' 3 ) 2- (R' is independently A cyclohexylidene group, a fluorenylidene group, —O— or —S—, and A and E are each independently a direct bond, —O— or —S—.
  • R 4 to R 11 are each independently a hydrogen atom, a fluorine atom, an alkyl group, an allyl group, an aryl group, a halogenated alkyl group in which some or all of the hydrogen atoms are halogenated, a nitro group, or a cyano group.
  • r is an integer of 0-4.
  • the structural unit represented by Formula (7) is not the structural unit represented by Formula (2).
  • electrolyte membrane composition according to any one of [1] to [7], further comprising at least one metal component selected from the group consisting of metal-containing compounds and metal ions.
  • a platinum surface having a surface area of 0.785 mm 2 is immersed in an aqueous solution obtained by immersing the electrolyte membrane (volume 0.036 cm 3 ) in 50 mL of 1N sulfuric acid aqueous solution at 80 ° C. for 100 hours and then removing the electrolyte membrane.
  • the poisoning rate of platinum is 20% or less when immersed in 20 cycles of cyclic voltammetry at a sweep rate of 0.01 V / s and a sweep potential range of 0.05 to 0.4 V. 9].
  • the solid polymer electrolyte membrane according to [9].
  • a membrane-electrode assembly in which a gas diffusion layer, a catalyst layer, the solid polymer electrolyte membrane according to any one of [9] to [11], a catalyst layer, and a gas diffusion layer are laminated in this order.
  • a polymer electrolyte fuel cell having the membrane-electrode assembly according to [13].
  • a water electrolysis cell in which a catalyst layer, the solid polymer electrolyte membrane according to any one of [9] to [11], and a catalyst layer are laminated in this order.
  • a water electrolysis apparatus having the water electrolysis cell according to [15].
  • the present invention it is possible to easily obtain a polymer electrolyte membrane that is excellent in durability and can suppress a decrease in power generation performance and water electrolysis performance over time.
  • composition for electrolyte membrane of this invention contains the polymer (A) which has an ion exchange group, and the polymer (B) which has an arylene sulfide skeleton and is soluble in an organic solvent. According to such a composition, it is possible to easily obtain a polymer electrolyte membrane that is excellent in durability and that can suppress a decrease in power generation performance and water electrolysis performance over time.
  • composition for an electrolyte membrane of the present invention is preferably a liquid composition from the viewpoint of ease of production of a solid polymer electrolyte membrane (hereinafter also simply referred to as “electrolyte membrane”).
  • the polymer (A) having an ion exchange group is not particularly limited as long as it is a polymer having an ion exchange group, and may be one used for a conventional solid polymer electrolyte membrane.
  • As an ion exchange group a well-known thing can be used, although it does not specifically limit, A phosphonic acid group, a sulfonic acid group, etc. are mentioned. Among these, by using a polymer having a sulfonic acid group, an electrolyte membrane excellent in power generation performance and water electrolysis performance can be obtained.
  • the said polymer (A) may be used individually by 1 type, and may use 2 or more types together.
  • Examples of such a polymer (A) include polyacetal, polyethylene, polypropylene, acrylic resin, polystyrene, polystyrene-graft-ethylenetetrafluoroethylene copolymer, polystyrene-graft-polytetrafluoroethylene, and aliphatic polycarbonate.
  • Polymers in which sulfonic acid groups are introduced into aliphatic polymers aliphatic polymers having sulfonic acid groups
  • polyesters polysulfones, polyphenylene ethers, polyether imides, aromatic polycarbonates, polyether ether ketones, poly Ether ketone, polyether ketone ketone, polyether ether sulfone, polyether sulfone, polycarbonate, polyphenylene sulfide, aromatic polyamide, aromatic polyamideimide, aromatic polyimide ,
  • a polymer in which a sulfonic acid group is introduced into an aromatic polymer having an aromatic ring in part or all of the main chain thereof such as polybenzoxazole, polybenzothiazole, polybenzimidazole, etc.
  • polymer (A) a known polymer can be used, and is not limited to, but is not limited to a total fluorocarbon polymer having a sulfonic acid group commercially available under a trade name such as Nafion, Aciplex or Flemion, JP 2012-067216, JP 2010-238374, JP 2010-174179, JP 2010-135282, JP 2004-137444, JP 2004-345997, JP 2004. -346163, International Publication No. 2011/155528, Japanese Patent Application Laid-Open No. 2007-177197, International Publication No. 2007/043274, and the like.
  • the polymer (A) is a polymer comprising a hydrophilic segment (A1) serving as a structural unit having a proton conductive group and a hydrophobic segment (B1) serving as a hydrophobic structural unit. It is preferable.
  • the polymer (A) may be a block polymer or a random polymer, but an electrolyte membrane that is more excellent in power generation, water electrolysis performance, and dimensional stability during a wet and dry cycle is obtained. From the viewpoint of being obtained, a block copolymer of the hydrophilic segment (A1) and the hydrophobic segment (A2) is preferable.
  • the hydrophilic segment (A1) is not particularly limited as long as it has a proton conductive group and exhibits hydrophilicity.
  • the hydrophilic segment (A1) has an aromatic ring in the main chain and a proton conductive group such as a sulfonic acid group. From the point that an electrolyte membrane having high continuity of the hydrophilic segment and high proton conductivity can be obtained (hereinafter referred to as “structural unit”). (9) ”) is preferable, and a segment composed of the structural unit (9) is more preferable.
  • the hydrophilic segment (A1) may consist of only one type of structural unit or may contain two or more types of structural units.
  • Ar 11 , Ar 12 and Ar 13 are each independently a halogen atom, a nitrile group, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated carbon atom having 1 to 20 carbon atoms.
  • R 18 and R 19 each independently represents a hydrogen atom or a protecting group. However, at least one of all R 18 and R 19 contained in the structural unit (9) is a hydrogen atom.
  • x 1 independently represents an integer of 0 to 6
  • x 2 represents an integer of 1 to 7
  • a represents 0 or 1
  • b represents an integer of 0 to 20.
  • the protecting group refers to an ion, atom or atomic group used for the purpose of temporarily protecting a reactive group (—SO 3 — or —SO 3 ⁇ ).
  • a reactive group —SO 3 — or —SO 3 ⁇
  • Specific examples include an alkali metal atom, an aliphatic hydrocarbon group, an alicyclic group, an oxygen-containing heterocyclic group, and a nitrogen-containing cation.
  • the hydrophilic segment (A1) includes, in addition to the structural unit (9) having a sulfonic acid group, as a structural unit having a proton conductive group other than the sulfonic acid group, for example, a structural unit having a phosphonic acid group, Aromatic structural units having a nitrogen-containing heterocyclic ring described in Kaikai 2011-089036 and International Publication No. 2007/010731 may be included.
  • hydrophobic segment (A2) is not particularly limited as long as it is a hydrophobic segment.
  • the hydrophilic segment (A2) may consist of only one type of structural unit or may contain two or more types of structural units.
  • the hydrophobic segment (A2) is preferably a hydrophobic segment having an aromatic ring in the main chain and not containing a proton conductive group such as a sulfonic acid group, and an electrolyte membrane that is more excellent in suppressing hot water swelling.
  • a structural unit represented by the following formula (10) hereinafter also referred to as “structural unit (10)”
  • a structural unit represented by the following formula (11) hereinafter referred to as “structural unit (11)”.
  • a segment containing at least one structural unit selected from the group consisting of structural units represented by the following formula (12) hereinafter also referred to as “structural unit (12)”.
  • it is a segment composed of at least one structural unit selected from the group consisting of the structural unit (10) and the structural unit (11).
  • the polymer (A) contains any one of the structural units (10) to (12), in particular, the structural unit (10) or (11), the hydrophobicity of the polymer is remarkably improved. Therefore, it is possible to obtain an electrolyte membrane having excellent hot water resistance while having proton conductivity similar to the conventional one. Moreover, when segment (A2) contains a nitrile group, an electrolyte membrane having high toughness and mechanical strength can be produced.
  • the hydrophobic segment (A2) includes the polymer (10) obtained by increasing the rigidity of the segment (A2) and increasing the aromatic ring density.
  • the hot water resistance, radical resistance to peroxide, gas barrier properties, mechanical strength, dimensional stability, etc. of the electrolyte membrane can be improved.
  • the hydrophobic segment (A2) may include one type of structural unit (10), or may include two or more types of structural units (10).
  • At least one substitutable carbon atom constituting the aromatic ring may be replaced with a nitrogen atom, and R 21 is independently a halogen atom, a hydroxy group, a nitro group, a nitrile group or R 22 —.
  • L- (L is a direct bond, —O—, —S—, —CO—, —SO 2 —, —CONH—, —COO—, —CF 2 —, —CH 2 —, —C (CF 3 ) 2 -or -C (CH 3 ) 2- ;
  • R 22 represents an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, a halogenated aryl group or a nitrogen-containing heterocyclic ring, and at least one of these groups one of the hydrogen atoms, further hydroxy group, a nitro group, may be substituted with at least one group selected from nitrile group and a group consisting of R 22 -L-.
  • the plurality of L may be the same or different, and a plurality of R 22 (provided that The structure of the portion excluding the structural difference caused by the substitution may be the same or different.
  • c 1 and c 2 independently represent an integer of 0 or 1 or more, d represents an integer of 1 or more, and e independently represents an integer of 0 to (2c 1 + 2c 2 +4).
  • the hydrophobic segment (A2) contains the structural unit (11) because radical resistance to peroxide and the like is improved, and an electrolyte membrane excellent in power generation / water electrolysis durability can be obtained. Further, when the hydrophobic segment (A2) contains the structural unit (11), an appropriate flexibility (flexibility) can be imparted to the segment (A2), and the electrolyte membrane containing the resulting polymer Toughness can be improved.
  • the hydrophobic segment (A2) may include one type of structural unit (11), or may include two or more types of structural units (11).
  • At least one substitutable carbon atom constituting the aromatic ring may be replaced with a nitrogen atom, and R 31 is independently a halogen atom, a hydroxy group, a nitro group, a nitrile group or R 22 —.
  • f represents 0 or an integer of 1 or more
  • g represents an integer of 0 to (2f + 4).
  • the structural unit represented by Formula (11) is a structural unit other than the structural unit represented by Formula (10).
  • the hydrophobic segment (A2) contains the structural unit (12), the segment (A2) can be imparted with appropriate flexibility (flexibility), and the toughness of the electrolyte membrane containing the resulting polymer Can be improved.
  • the hydrophobic segment (A2) may include one type of structural unit (12) or may include two or more types of structural units (12).
  • G and J are each independently a direct bond, —O—, —S—, —CO—, —SO 2 —, —SO—, —CONH—, —COO—, — (CF 2 I ⁇ (i is an integer of 1 to 10), — (CH 2 ) j — (j is an integer of 1 to 10), —CR ′ 2 — (R ′ is an aliphatic hydrocarbon group, aromatic A hydrocarbon group or a halogenated hydrocarbon group.), A cyclohexylidene group or a fluorenylidene group, Q independently represents an oxygen atom or a sulfur atom, and R 1 to R 16 each independently represents a hydrogen atom.
  • R 22-L-(L and R 22 are independently the same as L and R 22 in formula (10).) indicates, R 1 ⁇
  • a plurality of groups of R 16 may be bonded to form a ring structure.
  • s and t each independently represent an integer of 0 to 4, and r represents 0 or an integer of 1 or more.
  • the polymer (A) can be synthesized by a conventionally known method, and is not particularly limited.
  • the compound serving as the structural unit is reacted in the presence of a catalyst or a solvent.
  • it can be synthesized by introducing a proton conductive group by a method such as conversion of a sulfonic acid ester group or the like to a sulfonic acid group, or sulfonation using a sulfonating agent.
  • the polystyrene equivalent weight average molecular weight (Mw) of the polymer (A) by gel permeation chromatography (GPC) is preferably 10,000 to 1,000,000, more preferably 20,000 to 800,000, and even more preferably 50,000 to 300,000.
  • the ion exchange capacity of the polymer (A) is preferably 0.5 to 3.5 meq / g, more preferably 0.5 to 3.0 meq / g, still more preferably 0.8 to 2.8 meq / g. is there.
  • An ion exchange capacity of 0.5 meq / g or more is preferable because an electrolyte membrane having high proton conductivity and high power generation performance and water electrolysis performance can be obtained.
  • it is 3.5 meq / g or less, an electrolyte membrane having sufficiently high water resistance can be obtained, which is preferable.
  • the ion exchange capacity can be measured, for example, by the method described in the examples below.
  • the ion exchange capacity can be adjusted, for example, by changing the type of each structural unit, the use ratio, the combination, and the amount of ion exchange groups introduced. Therefore, it can be adjusted by changing the charge amount ratio and type of the precursor (monomer / oligomer) that induces the structural unit during polymerization.
  • the proportion of the structural unit containing an ion exchange group when the proportion of the structural unit containing an ion exchange group is increased in the polymer, the ion exchange capacity of the obtained electrolyte membrane is increased and the proton conductivity is increased, but the water resistance tends to be reduced.
  • the proportion of the structural unit is reduced, the ion exchange capacity of the obtained electrolyte membrane is reduced and the water resistance is increased, but the proton conductivity tends to be lowered.
  • the polymer (B) is a polymer having an arylene sulfide skeleton and soluble in an organic solvent.
  • a polymer (B) By using such a polymer (B), it is possible to obtain a composition for an electrolyte membrane in which the polymer (B) is uniformly dispersed, and to the outside of the electrolyte membrane during battery operation or water electrolysis device operation. The elution of the polymer and the deterioration of the electrolyte membrane are suppressed, and an electrolyte membrane excellent in durability can be easily obtained.
  • the said polymer (B) may be used individually by 1 type, and may use 2 or more types together.
  • a catalyst layer is provided on an electrode of a polymer electrolyte fuel cell, and platinum, ruthenium, or the like is used as a catalyst contained in the catalyst layer.
  • platinum, ruthenium, or the like is used as a catalyst contained in the catalyst layer.
  • These catalysts are important because they promote the chemical reaction that is the source of the extracted electrical energy.
  • a part of the catalyst in the catalyst layer is deposited in the electrolyte membrane. It is believed that the electrolyte membrane is deteriorated by the catalyst, and this is a factor that lowers the long-term stability of the polymer electrolyte fuel cell.
  • platinum, ruthenium, iridium, iron, etc. are used as the catalyst contained in the catalyst layer.
  • a part of the catalyst in the catalyst layer is deposited in the electrolyte membrane during the operation of the water electrolysis device, and this deposited catalyst causes deterioration of the electrolyte membrane, and the long-term stability of the water electrolysis device. Is considered to be a factor that reduces In particular, the deposited platinum and iron may cause significant deterioration of the electrolyte membrane.
  • the present inventors inactivate a catalyst such as platinum in the vicinity of the interface between the electrolyte membrane and the electrode, while being located away from the interface between the electrolyte membrane and the electrode, Catalysts such as platinum, which are thought to have little impact on the battery, are not deactivated, so that the polymer electrolyte fuel cell has a good balance between power generation performance and long-term stability, and water electrolysis performance and long-term stability. We thought that an excellent water electrolysis apparatus with good balance could be obtained.
  • the present inventors have used an electrolyte membrane containing the polymer (B) together with the polymer (A) having an ion exchange group, so that the solid state excellent in balance between power generation performance and long-term stability can be obtained. It has been found that a molecular fuel cell and a water electrolysis device excellent in balance between water electrolysis performance and long-term stability can be obtained.
  • the electrolyte membrane containing the polymer (B) has a specific poisoning rate of platinum. It becomes as follows. This means that the elution amount of the polymer (B) from the electrolyte membrane is below a certain range. This inactivates platinum in the vicinity of the interface between the electrolyte membrane and the electrode, while deactivating platinum, which is located far from the interface between the electrolyte membrane and the electrode and has little effect on the deterioration of the electrolyte membrane. It is not considered to be converted.
  • composition for electrolyte membrane of the present invention contains the polymer (B), a polymer electrolyte fuel cell excellent in balance between power generation performance and long-term stability, and water electrolysis performance and long-term stability. It is possible to obtain a water electrolysis apparatus excellent in balance.
  • the polymer (B) has an arylene sulfide skeleton.
  • the polymer (B) has an arylene sulfide skeleton, so that the polymer (B) has excellent compatibility with the polymer (A), and the elution to the outside of the electrolyte membrane during battery power generation or water electrolysis is suppressed.
  • the arylene sulfide skeleton refers to a structural unit in which a sulfide bond (—S—) is bonded to a monocyclic or polycyclic aromatic hydrocarbon group, for example, a heavy unit having a thianthrene structure.
  • the polymer is also referred to as a polymer having an arylene sulfide skeleton because it has a portion in which a sulfide bond is bonded to a benzene ring.
  • the sulfide bond portion is easily coordinated to platinum. For this reason, it is thought that this sulfide bond part contributes to inactivation of platinum.
  • the polymer (B) becomes a polymer having excellent compatibility with the polymer (A), and becomes a polymer in which elution to the outside of the electrolyte membrane during battery power generation or water decomposition is suppressed.
  • at least one of the structural units represented by the following formula (1) or (2) (hereinafter also referred to as “structural unit (1)” and “structural unit (2)”) is included.
  • R 1 and R 2 are each independently an alkyl group having 1 to 5 carbon atoms, an alkylsulfanyl group having 1 to 5 carbon atoms, a cyano group, or a halogen atom, and a and b are each Independently, it is an integer of 0 to 3.
  • X 1 and X 2 are each independently a direct bond, —S—, —NH—, —SO— or —SO 2 —, but at least one of X 1 and X 2 is —S—.
  • R 1 and R 2 are preferably a cyano group or a halogen atom from the viewpoint of improving the solubility in a polar solvent.
  • Said a and b are preferably 0 or 1, more preferably 0.
  • At least one of X 1 and X 2 is —S—, and the other is preferably a single bond or —S— from the viewpoint of becoming a polymer having a high sulfur content, and is an organic solvent. From the viewpoints of obtaining a polymer excellent in solubility in water and obtaining an electrolyte membrane that can sufficiently inactivate platinum in the vicinity of the interface between the electrolyte membrane and the electrode even if the amount of the polymer (B) added is small. More preferably, it is —S—.
  • R 3 is an alkyl group having 1 to 5 carbon atoms, an alkylsulfanyl group having 1 to 5 carbon atoms, a cyano group or a halogen atom, and c is an integer of 0 to 4.
  • R 3 is preferably a cyano group, a chlorine atom, a bromine atom, or an iodine atom from the viewpoint of improving the solubility in a polar solvent.
  • the c is preferably 0 or 1, more preferably 0.
  • the polymer (B) can obtain a composition for an electrolyte membrane in which the polymer (B) is uniformly dispersed, and is a solid polymer fuel excellent in balance in power generation performance, water electrolysis performance, long-term stability, etc. It is preferable that at least one of the structural units represented by the following formulas (3) to (5) is included from the viewpoint that a battery or a water electrolysis device can be obtained.
  • R 1, R 2, X 1, X 2, a and b are each independently, R 1 in the formula (1), R 2, X 1, X 2, a and b Is synonymous with ]
  • R 3 and c are each independently synonymous with R 3 and c in the formula (2).
  • the polymer (B) contains the structural unit (2), a polymer having better solubility in an organic solvent is obtained, and an electrolyte membrane composition in which the polymer (B) is uniformly dispersed is obtained.
  • the structural unit represented by the formulas (4) and (5) it is preferable that the structural unit represented by the formula (5) is included in the structural units represented by the formula (5). It is more preferable that the structural unit and the structural unit represented by the following formula (2 ′) are included.
  • R 3 and c are independently the same meanings as R 3 and c in the formula (2).
  • the polymer (B) As the polymer (B), a polymer excellent in compatibility with the polymer (A) or an organic solvent can be obtained, and a composition for an electrolyte membrane in which the polymer (B) is uniformly dispersed can be obtained. It is preferable to have a structural unit represented by the following formula (6) from the viewpoint of obtaining a polymer electrolyte fuel cell and a water electrolysis device that are excellent in performance, water electrolysis performance, long-term stability and the like. .
  • R 1, R 2, X 1, X 2, a and b are each independently, R 1 in the formula (1), R 2, X 1, X 2, a and b X 3 is —O— or —S—. ]
  • the polymer (B) has at least one group selected from the group consisting of a polar group, a group containing a fluorine atom and a fluorenylidene group, so that a polymer excellent in solubility in a polar solvent can be obtained. From the point of view, it is preferable.
  • These groups are not particularly limited as long as they are contained in the polymer (B), but may be contained in any one of the groups represented by the above or the following formulas (1) to (8). preferable.
  • Examples of the polar group include a cyano group, a hydroxy group, and a carboxy group.
  • Examples of the group containing a fluorine atom include —CF 3 , —C (CF 3 ) 2 — and the like.
  • the polymer (B) preferably has a structural unit represented by the following formula (7) from the viewpoint of obtaining a polymer excellent in solubility in an organic solvent, and the structural unit (1) and In addition to the structural unit (2), it is more preferable to further have a structural unit represented by the following formula (7).
  • D is independently a direct bond, —CO—, —SO 2 —, —SO—, —CONH—, —COO—, — (CF 2 ) 1 — (l is 1 to 10 -C (CF 3 ) 2 -,-(CH 2 ) l- (l is an integer of 1 to 10), -C (CR ' 3 ) 2- (R' is independently A cyclohexylidene group, a fluorenylidene group, —O— or —S—, and A and E are each independently a direct bond, —O— or —S—.
  • R 4 to R 11 are each independently a hydrogen atom, a fluorine atom, an alkyl group, an allyl group, an aryl group, a halogenated alkyl group in which some or all of the hydrogen atoms are halogenated, a nitro group, or a cyano group.
  • r is an integer of 0-4.
  • the structural unit represented by Formula (7) is not the structural unit (2).
  • the hydrocarbon group for R ′ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and 1 to 5 carbon atoms.
  • the linear or branched alkyl group is more preferable.
  • Preferable specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group. And n-heptyl group.
  • Examples of the cyclic hydrocarbon group for R ′ include an alicyclic hydrocarbon group and an aromatic hydrocarbon group.
  • the alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms, specifically, a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; And cycloalkenyl groups such as cyclobutenyl group, cyclopentenyl group, and cyclohexenyl group.
  • the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, and specific examples include a phenyl group, a biphenyl group, and a naphthyl group.
  • the alkyl group in R 4 to R 11 is preferably a group exemplified as a preferred example of the hydrocarbon group in R ′.
  • the halogenated alkyl group for R 4 to R 11 is preferably a group obtained by halogenating some or all of the alkyl groups.
  • the aryl group in R 4 to R 11 is preferably a group listed as a preferred example of the aromatic hydrocarbon group.
  • D is preferably —S—, —O—, —C (CF 3 ) 2 — or a fluorenylidene group from the viewpoint of obtaining a polymer having excellent solubility in a polar solvent.
  • a and E are preferably —O— or —S— from the viewpoint of improving the solubility of the polymer (B).
  • R 4 to R 11 are each a hydrogen atom, a fluorine atom, a halogenated alkyl group in which some or all of the hydrogen atoms are halogenated from the viewpoint of obtaining a polymer excellent in solubility in a polar solvent, A nitro group or a cyano group is preferred.
  • the polymer (B) includes the structural unit (1)
  • the polymer (B) has a structural unit represented by the following formula (8), which is superior in solubility in an organic solvent and has a high sulfur content. Is preferable from the viewpoint of obtaining
  • R 1, R 2, X 1, X 2, a and b are each independently, R 1 in the formula (1), R 2, X 1, X 2, a and b in the above formula, D, E, R 4 ⁇ R 11 and r are as defined above D in the formula (7), E, R 4 ⁇ R 11 and r, a 'is -O- or -S- It is. ]
  • the method for synthesizing the polymer (B) is not particularly limited, and can be synthesized by a conventionally known method. For example, a method for polymerizing a monomer having an arylene sulfide skeleton, a sulfide bond when synthesizing a polymer, and the like. And a method of polymerizing so that the resulting polymer has an arylene sulfide skeleton.
  • the polymer (B) includes, for example, a dihydroxy compound containing a dihalide containing the structural unit (1) and a structural unit represented by the formula (7) (where A and E are direct bonds). Can be obtained by polymerizing by heating in an appropriate organic solvent in the presence of an alkali metal compound such as potassium carbonate, and the structural unit represented by the formula (7) (where A and E are The dihalogen compound containing a direct bond) and an alkali metal sulfide salt such as sodium sulfide are heated and polymerized in a suitable organic solvent. Specific examples include the methods shown in Synthesis Examples 3 to 7 below.
  • the amount of the dihalide containing the structural unit (1) and the monomer that can become the post-polymerization structural unit (2) are the solubility in an organic solvent and the deterioration of the electrolyte membrane. From the viewpoint of the balance with the inhibitory effect, it is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, based on 100 mol% of all monomers used for the synthesis of the polymer (B).
  • the number average molecular weight of the polymer (B) is preferably 1000 or more, more preferably 1100 or more, and further preferably 1200 or more. Further, the upper limit of the number average molecular weight of the polymer (B) is preferably 10,000 or less, more preferably 9000 or less, and further preferably 8000 or less. When the number average molecular weight of the polymer (B) is less than 1000, the amount of the polymer (B) eluted out of the electrolyte membrane during battery power generation or water decomposition may be excessively increased.
  • the molecular weight of the said polymer (B) can be measured by the method as described in a following example.
  • the polymer (B) preferably has a sulfur atom content constituting a sulfide bond in the polymer of 2.0 mmol / g or more. More preferably, it is 2.5 mmol / g or more, More preferably, it is 2.7 mmol / g or more. When the content of sulfur atoms constituting the sulfide bond in the polymer (B) is less than 2.0 mmol / g, the effect of suppressing deterioration of the electrolyte membrane during battery power generation or water decomposition may not be sufficient.
  • the polymer (B) preferably has a sulfur atom content constituting a sulfide bond in the polymer of 10.0 mmol / g or less. Content of the sulfur atom which comprises the sulfide bond in such a polymer (B) can be quantified by a Raman spectroscopy, for example.
  • the polymer (B) is a polymer soluble in an organic solvent.
  • the “polymer soluble in an organic solvent” is preferably a polymer that is soluble in 10 g or more in 1 L of an organic solvent, and more preferably a polymer that is soluble in 20 g or more.
  • the organic solvent is not particularly limited, but for example, aprotic systems such as NMP, N, N-dimethylformamide, ⁇ -butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, dimethylurea, dimethylimidazolidinone, and acetonitrile.
  • aprotic systems such as NMP, N, N-dimethylformamide, ⁇ -butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, dimethylurea, dimethylimidazolidinone, and acetonitrile.
  • Polar solvents chlorinated solvents such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, alcohols such as methanol, ethanol, propanol, iso-propyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol Alkylene glycol monoalkyl ethers such as monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, acetone, methyl ethyl Tons, ketones such as cyclohexanone, tetrahydrofuran, ethers 1,3-dioxane and the like.
  • chlorinated solvents such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene
  • alcohols such as methanol, ethanol, propanol, iso-propyl alcohol, sec-butyl
  • the said polymer (B) is a polymer which does not have crystallinity from the point that the polymer excellent in the solubility to an organic solvent is obtained. Whether or not the polymer has crystallinity can be determined, for example, by the presence or absence of a melting peak in DSC measurement.
  • the melting point of the polymer (B) measured by Yanagimoto Seisakusho, precision melting point measuring device is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and still more preferably 120. °C or more.
  • the melting point of the polymer (B) is less than 80 ° C., the polymer (B) is likely to move in the electrolyte membrane while the battery or water electrolysis apparatus is operating at a high temperature, and is easily eluted out of the electrolyte membrane. Therefore, durability of the electrolyte membrane, power generation performance, and water electrolysis performance tend to decrease.
  • the polymer (B) has a mass ratio of the polymer (A) to the polymer (B) of 99.99: 0.01 to 70:30, preferably 99.95: 0.05 to 75. : 25, more preferably 99.9: 0.1 to 80:20, particularly preferably 99.5: 0.5 to 85:15 in an amount of 99.5: 0.5 to 85:15. .
  • a mass ratio of the polymer (A) to the polymer (B) of 99.99: 0.01 to 70:30, preferably 99.95: 0.05 to 75. : 25, more preferably 99.9: 0.1 to 80:20, particularly preferably 99.5: 0.5 to 85:15 in an amount of 99.5: 0.5 to 85:15.
  • the electrolyte membrane composition of the present invention may further contain at least one metal component selected from the group consisting of a metal-containing compound and a metal ion in addition to the polymer (A) and the polymer (B).
  • a component having hydrogen peroxide decomposability is preferable. Specifically, hydrogen peroxide that can be generated during battery power generation or water decomposition is converted into water by using a redox reaction or a disproportionation reaction. A component having capacity is more preferred.
  • the metal component examples include tin (Sn), aluminum (Al), manganese (Mn), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), and nickel (Ni). , Palladium (Pd), silver (Ag), cerium (Ce), vanadium (V), neodymium (Nd), praseodymium (Pr), samarium (Sm), cobalt (Co), gadolinium (Gd), terbium (Tb) And metal-containing compounds such as dysprosium (Dy), holmium (Ho) and erbium (Er), or metal ions thereof.
  • Dy dysprosium
  • Ho holmium
  • Er erbium
  • oxides of these metals are preferable.
  • a tin oxide and a tin ion are preferable, and the electrolyte membrane excellent in durability is obtained by using the composition containing these.
  • the compounding amount of the metal component is not particularly limited, but is preferably 0.01 to 30% by weight, more preferably 0.1 to 25% by weight with respect to 100% by weight of the electrolyte membrane composition of the present invention. More preferably, it is 1 to 20% by weight.
  • the electrolyte membrane composition according to the present invention preferably further contains a solvent.
  • a liquid composition can be obtained because the composition for electrolyte membrane of this invention contains the said solvent.
  • the solvent which can melt
  • the said organic solvent etc. are mentioned. These solvents can be used alone or in combination of two or more.
  • NMP is preferable from the viewpoint of the solubility of the polymer (A) and the polymer (B) and the viscosity of the composition.
  • the composition of the mixture is preferably 25 to 95% by mass, more preferably 25 to 90% by mass of the aprotic polar solvent. %, And the other solvent is preferably 5 to 75% by mass, more preferably 10 to 75% by mass (provided that the total is 100% by mass).
  • the blending amount of the other solvent is within the above range, the effect of reducing the viscosity of the resulting composition is excellent.
  • NMP is preferable as the aprotic polar solvent
  • methanol or methyl ethyl ketone is effective as the other solvent in reducing the viscosity of the composition in a wide composition range.
  • the content of the polymer (A) in the liquid composition is preferably 1 to 40% by mass, more preferably 3 to 25% by mass, although it depends on the molecular weight of the polymer.
  • the content of the polymer (A) is less than 1% by mass, the obtained electrolyte membrane tends to cause poor appearance and tends to generate pinholes.
  • the content of the polymer (A) exceeds 40% by mass, the viscosity of the composition may be too high to form a film from the composition, and the obtained electrolyte film may have surface smoothness. May be lacking.
  • the viscosity of the liquid composition is preferably 2,000 to 100,000 mPa ⁇ s, more preferably 3,000 to 50, although it depends on the molecular weight and concentration of the polymers (A) and (B). 1,000 mPa ⁇ s.
  • the viscosity of the liquid composition is within the above range, it is preferable because the composition has excellent retention during film formation, the thickness can be easily adjusted, and the film can be easily formed by a casting method.
  • the liquid composition can be prepared by mixing the polymer (A) and the polymer (B) in the solvent. Specifically, a method of simultaneously dissolving or dispersing the polymers (A) and (B) in the solvent, and after dissolving or dispersing the polymer (A) in the solvent, the polymer (B) Examples thereof include a method of preparing by mixing with this, or a method of dissolving or dispersing the polymer (A) after dissolving the polymer (B) in the solvent.
  • inorganic acids such as sulfuric acid and phosphoric acid; phosphate glass; tungstic acid; phosphoric acid Salt hydrate; ⁇ -alumina proton substitution product; inorganic proton conductor particles such as proton-introduced oxide; organic acid containing carboxylic acid; organic acid containing sulfonic acid; organic acid containing phosphonic acid; May be.
  • the electrolyte membrane of the present invention is not particularly limited as long as it is a membrane obtained from the electrolyte membrane composition, but is preferably a membrane obtained from the liquid composition.
  • the electrolyte membrane of the present invention can be suitably used as an electrolyte membrane for a polymer electrolyte fuel cell and as an electrolyte membrane for water electrolysis, and particularly preferably used as an electrolyte membrane for a polymer electrolyte fuel cell. it can.
  • the electrolyte membrane of the present invention contains the polymer (A) and the polymer (B), it is difficult to deteriorate during battery power generation, has excellent power generation performance and durability, and when an electrode containing platinum is used, The platinum poisoning rate due to the eluate that can be eluted from the electrolyte membrane is low. Similarly, it is hardly deteriorated during water electrolysis, is excellent in water electrolysis performance and durability, and when an electrode containing platinum is used, the poisoning rate of platinum due to an eluate that can be eluted from the electrolyte membrane is low.
  • the electrolyte membrane of the present invention (volume 0.036 cm 3 ) was immersed in 50 mL of 1N sulfuric acid aqueous solution at 80 ° C. for 100 hours, and then the platinum membrane having a surface area of 0.785 mm 2 was added to the aqueous solution obtained by removing the electrolyte membrane.
  • the lower limit of the platinum poisoning rate may be 0%.
  • the platinum poisoning rate is in the above range
  • the platinum in the vicinity of the interface between the electrolyte membrane and the electrode is inactivated and located at a location away from the interface between the electrolyte membrane and the electrode.
  • the polymer (B) is preferably present at least within 30% of the thickness of the membrane from the surface of the membrane. Since the polymer (B) usually has low proton conductivity, in order to obtain an electrolyte membrane having high power generation performance and high water electrolysis performance, the content of the polymer (B) contained in the electrolyte membrane is reduced as much as possible. It is considered that it is desired to improve the durability of the electrolyte membrane. In particular, as described above, the polymer (B) only needs to be able to inactivate platinum in the vicinity of the interface between the electrolyte membrane and the electrode. Electrolyte membrane excellent in balance between power generation performance, water electrolysis performance and long-term stability even when the content of the polymer (B) contained in the electrolyte membrane is small because it is located within 30% of the surface of Can be obtained.
  • the polymer (B) is preferably unevenly distributed in the vicinity of the surface of the membrane, and may be present only at a position within 30% from the surface of the electrolyte membrane with respect to the thickness of the membrane. More preferred.
  • the electrolyte membrane has a concentration gradient such that the concentration of the polymer (B) gradually increases as it approaches the surface of the membrane. It may be.
  • the electrolyte membrane of the present invention may be a single layer film or a multilayered film.
  • the thickness of each layer is arbitrary. For example, one layer may be thick and the other layer may be thin.
  • the electrolyte membrane of the present invention contains the polymer (B) on one side or both surfaces in contact with the electrode when the membrane-electrode assembly is produced,
  • the electrolyte membrane which does not contain a polymer (B) in the part other than that may be sufficient.
  • the electrode is preferably a cathode electrode.
  • the electrolyte membrane according to the present invention includes, for example, a step of applying the electrolyte membrane composition onto a substrate by a known method such as die coating, spray coating, knife coating, roll coating, spin coating, or gravure coating. Can be manufactured.
  • the electrolyte membrane of the present invention can be obtained by applying the electrolyte membrane composition onto a substrate, drying the applied composition, and peeling the resulting film from the substrate, if necessary. it can. Since the composition for electrolyte membrane of this invention contains a polymer (A) and a polymer (B), an electrolyte membrane can be easily manufactured with the said well-known method.
  • the substrate is not particularly limited as long as it is a substrate used when a normal solution is applied, and examples thereof include a substrate made of resin, metal, glass, and preferably a polyethylene terephthalate (PET) film. And a base made of a thermoplastic resin.
  • a substrate made of resin, metal, glass, and preferably a polyethylene terephthalate (PET) film.
  • PET polyethylene terephthalate
  • a base made of a thermoplastic resin.
  • the drying is preferably performed by holding at a temperature of 50 to 150 ° C. for 0.1 to 10 hours. Note that the drying may be performed in one step, or may be performed in two or more steps, that is, pre-drying after preliminary drying. Moreover, you may perform the said drying in inert gas atmosphere, such as nitrogen atmosphere, or under reduced pressure as needed.
  • inert gas atmosphere such as nitrogen atmosphere
  • the preliminary drying can be performed by holding at 30 to 100 ° C., more preferably 50 to 100 ° C., preferably 10 to 180 minutes, more preferably 15 to 60 minutes. Further, the main drying can be carried out preferably by holding at a temperature not lower than the preliminary drying temperature, more preferably at a temperature of 50 to 150 ° C., and preferably for 0.1 to 10 hours.
  • the organic solvent in the dried film can be replaced with water, and the residual organic solvent in the obtained electrolyte film The amount can be reduced.
  • the amount of residual organic solvent in the electrolyte membrane thus obtained is preferably 5% by mass or less.
  • the amount of the remaining organic solvent in the obtained film can be 1% by mass or less.
  • the amount of water used is 50 parts by weight or more with respect to 1 part by weight of the dried film, the temperature of the water during immersion is 10 to 60 ° C., and the immersion time is 10 minutes to 10 hours. It is.
  • the dried membrane After the dried membrane is immersed in water as described above, it is further dried at 30 to 100 ° C., preferably 50 to 80 ° C. for 10 to 180 minutes, preferably 15 to 60 minutes, and then 50 to 150 ° C.
  • the composition (I) is applied onto a substrate by a known method, and after drying or as necessary, a layer is formed, and then the layer is formed.
  • coating composition (II) on top and drying and forming a layer is mentioned.
  • another composition may be applied on the obtained layer and dried.
  • the composition (I) is applied onto a substrate by a known method and, if necessary, pre-dried, a film previously formed from the composition (II) or the like is placed thereon and subjected to hot pressing or the like.
  • a laminated film can also be obtained.
  • compositions (I), the composition (II), and other compositions that can be further used are not particularly limited as long as they can form a layer and do not impair the effects of the present invention.
  • the composition containing (A) or the composition for electrolyte membrane of the present invention is preferred.
  • at least one composition is the electrolyte membrane composition of the present invention.
  • composition (I), composition (II), and other compositions that can be further used differ in the composition (formulation component and / or amount) of the composition forming the adjacent layers.
  • formulation component and / or amount of the composition forming the adjacent layers.
  • composition of the composition forming the non-adjacent layers may be the same or different.
  • the composition for an electrolyte membrane of the present invention is used as the composition (I), and the polymer (B) includes the polymer (A) as the composition (II).
  • the polymer (B) is easily produced at least at a position within 30% of the thickness of the membrane from the membrane surface or an unevenly distributed electrolyte membrane. be able to.
  • a reinforced solid polymer electrolyte membrane can also be produced by using a porous substrate or a sheet-like fibrous material.
  • the method for producing the reinforced solid polymer electrolyte membrane include a method of impregnating the liquid composition into a porous substrate or a sheet-like fibrous material, and a method for impregnating the electrolyte membrane composition of the present invention with a porous substrate.
  • the porous substrate preferably has a large number of pores or voids penetrating in the thickness direction.
  • organic porous substrates made of various resins, metal oxides such as glass and alumina And inorganic porous base materials composed of metal and the metal itself.
  • the porous substrate may have a large number of through holes penetrating in a direction substantially parallel to the thickness direction.
  • Examples of such a porous substrate include, for example, JP 2008-119662, JP 2007-154153, JP 8-20660, JP 8-20660, JP 2006-120368.
  • JP 2008-119662 JP 2007-154153
  • JP 8-20660 JP 8-20660
  • JP 2006-120368 JP 2008-119662
  • JP 2007-154153 JP 8-20660
  • JP 8-20660 JP 8-20660
  • JP 2006-120368 Japanese Patent Laid-Open No. 2004-171994
  • Japanese Patent Laid-Open No. 2009-64777 can be used.
  • an organic porous substrate is preferable.
  • the porous substrate include polyolefins such as polytetrafluoroethylene, high molecular weight polyethylene, cross-linked polyethylene, polyethylene and polypropylene, polyimide, polyacrylotolyl, polyamideimide, polyetherimide, and polyether.
  • a base material composed of one or more selected from the group consisting of sulfone and glass is preferred.
  • the polyolefin is preferably high molecular weight polyethylene, cross-linked polyethylene, polyethylene or the like.
  • porous base materials examples include stretched porous polytetrafluoroethylene GORE-SELECT (manufactured by Japan Gore-Tex) and high molecular weight polyethylene porous base materials (manufactured by Lydall, SOLUPOR (registered trademark)). Is mentioned.
  • the porous base material is preferably a base material made of polyolefin such as polytetrafluoroethylene, high molecular weight polyethylene, cross-linked polyethylene, polyethylene and the like because it contacts the polymer (A). If necessary, the polyolefin substrate may be hydrophilized.
  • polyolefin such as polytetrafluoroethylene, high molecular weight polyethylene, cross-linked polyethylene, polyethylene and the like because it contacts the polymer (A). If necessary, the polyolefin substrate may be hydrophilized.
  • the hydrophilization treatment is a treatment that modifies the polyolefin constituting the porous using an alkali metal solution, and this treatment modifies the surface of the porous substrate and imparts hydrophilicity. Since the denatured portion may be browned, the browned portion may be removed by oxidative decomposition with hydrogen peroxide, sodium hypochlorite, ozone, or the like. Such hydrophilic treatment is sometimes referred to as chemical etching.
  • the alkali metal solution include a solution obtained by dissolving methyl lithium, a metal sodium-naphthalene complex, a metal sodium-anthracene complex, and the like in an organic solvent such as tetrahydrofuran, a metal sodium-liquid ammonia solution, and the like.
  • the porosity and thickness of the porous substrate are not particularly limited as long as the effects of the present invention are not impaired.
  • a sheet-like fibrous substance a nonwoven fabric, a woven fabric, a knitted fabric, etc. are mentioned.
  • the fibers constituting the woven fabric include, but are not limited to, polyethylene fibers, fluoropolymer reinforced fibers, polyimide fibers, polyphenylene sulfide sulfone fibers, polysulfone fibers, and glass fibers.
  • fibers constituting the nonwoven fabric examples include polyamide resins, polyvinyl alcohol resins, polyvinylidene chloride resins, polyvinyl chloride resins, polyester resins, polyacrylonitrile resins, polyolefin resins (for example, polyethylene resins, Polypropylene resin), polystyrene resin (for example, crystalline polystyrene, amorphous polystyrene), aromatic polyamide resin or polyurethane resin, or glass, carbon, potassium titanate, silicon carbide, silicon nitride Further, fibers composed of inorganic components such as zinc oxide, aluminum borate, and wollastonite can be used.
  • inorganic components such as zinc oxide, aluminum borate, and wollastonite
  • the thickness of the sheet-like fibrous substance is not particularly limited as long as the effects of the present invention are not impaired.
  • the electrolyte membrane of the present invention has a dry film thickness of preferably 5 to 200 ⁇ m, more preferably 10 to 150 ⁇ m. Even when the electrolyte membrane of the present invention is a laminated membrane or a reinforced solid polymer electrolyte membrane, the thickness of the laminated membrane is preferably within this range.
  • the membrane-electrode assembly according to the present invention is a membrane-electrode assembly in which a gas diffusion layer, a catalyst layer, an electrolyte membrane of the present invention, a catalyst layer, and a gas diffusion layer are laminated in this order.
  • a catalyst layer for the cathode electrode is provided on one surface of the electrolyte membrane of the present invention
  • a catalyst layer for the anode electrode is provided on the other surface
  • each of the catalyst layers for the cathode electrode and the anode electrode is further provided.
  • a gas diffusion layer is provided on each of the cathode electrode side and the anode electrode side in contact with the side opposite to the electrolyte membrane.
  • Known gas diffusion layers and catalyst layers can be used without particular limitation.
  • the gas diffusion layer examples include a porous substrate or a laminated structure of a porous substrate and a microporous layer.
  • the gas diffusion layer is composed of a laminated structure of a porous base material and a microporous layer, the microporous layer is preferably in contact with the catalyst layer.
  • the gas diffusion layer preferably contains a fluoropolymer in order to impart water repellency.
  • the catalyst layer is composed of a catalyst, an ion exchange resin, or the like.
  • the catalyst include metal catalysts such as platinum, palladium, gold, ruthenium, iridium, cobalt and iron, and noble metal catalysts such as platinum, palladium, gold, ruthenium and iridium are preferably used.
  • the metal catalyst may contain two or more elements such as an alloy or a mixture. As such a metal catalyst, a catalyst supported on carbon particles having a high specific surface area can be used.
  • the ion exchange resin serves as a binder component for binding the catalyst, and efficiently supplies ions generated by a reaction on the catalyst to the electrolyte membrane at the anode electrode, and is supplied from the electrolyte membrane at the cathode electrode.
  • a substance that efficiently supplies ions to the catalyst is preferable.
  • the ion exchange resin is preferably a polymer having a proton exchange group in order to improve proton conductivity in the catalyst layer.
  • Proton exchange groups contained in such polymers include sulfonic acid groups, carboxylic acid groups, and phosphoric acid groups, but are not particularly limited.
  • the ion exchange resin known ones can be used without particular limitation, and examples thereof include Nafion
  • the polymer (A) may be used as an ion exchange resin, and further a fluorine having a proton exchange group. It may be a polymer containing atoms, another polymer obtained from ethylene or styrene, a copolymer or a blend thereof.
  • the catalyst layer may further contain additives such as carbon fiber and a resin not having an ion exchange group, if necessary.
  • This additive is preferably a component having high water repellency, and examples thereof include a fluorine-containing copolymer, a silane coupling agent, a silicone resin, a wax, and polyphosphazene. It is a coalescence.
  • the polymer electrolyte fuel cell according to the present invention has the membrane-electrode assembly. Therefore, the polymer electrolyte hydrogen fuel cell according to the present invention is particularly excellent in durability, suppresses a decrease in power generation performance with time, and enables stable power generation over a long period of time.
  • the polymer electrolyte fuel cell according to the present invention includes at least one electricity generating unit including a separator and located on both outer sides of at least one membrane-electrode assembly and its gas diffusion layer;
  • a polymer electrolyte fuel cell comprising: a fuel supply unit for supplying electricity to the electricity generation unit; and an oxidant supply unit for supplying oxidant to the electricity generation unit, wherein the membrane-electrode assembly is as described above preferable.
  • separator those used in ordinary solid polymer fuel cells can be used. Specifically, a carbon type separator, a metal type separator, or the like can be used.
  • the polymer electrolyte fuel cell of the present invention may be a single cell or a stack cell in which a plurality of single cells are connected in series.
  • a known method can be used as the stacking method. Specifically, it may be planar stacking in which single cells are arranged in a plane, or bipolar in which single cells are stacked via separators each having a fuel or oxidant flow path formed on the back surface of the separator. Stacking may be used.
  • the water electrolysis cell according to the present invention includes a laminate in which the catalyst layer, the electrolyte membrane of the present invention, and the catalyst layer are laminated in this order.
  • the catalyst layer known ones can be used without particular limitation, and specific examples include the same layers as the catalyst layer described in the membrane-electrode assembly.
  • the water electrolysis apparatus according to the present invention has the water electrolysis cell.
  • a sample film is prepared from the polymers obtained in Synthesis Examples 1 and 2 below, and the sample film is immersed in deionized water to completely remove the acid remaining in the film.
  • a hydrochloric acid aqueous solution was prepared by immersing in 2 mL of 2N saline per 1 mg to exchange ions. This hydrochloric acid aqueous solution was neutralized with a standard aqueous solution of 0.001N sodium hydroxide using phenolphthalein as an indicator. The membrane after ion exchange was washed with deionized water and vacuum dried at 110 ° C. for 2 hours, and the dry weight of the membrane was measured.
  • Ion exchange capacity titration amount of sodium hydroxide (mmol) / dry weight of membrane (g)
  • the molecular weight was measured using the following two methods depending on the polymer to be measured.
  • the polymer to be measured is dissolved in an N-methyl-2-pyrrolidone buffer solution (hereinafter referred to as “NMP buffer solution”), the NMP buffer solution is used as an eluent, and TOSOH HLC-8220 (manufactured by Tosoh Corporation) is used as an apparatus.
  • NMP buffer solution N-methyl-2-pyrrolidone buffer solution
  • TOSOH HLC-8220 manufactured by Tosoh Corporation
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of polystyrene were determined by gel permeation chromatography (GPC) using TSKgel ⁇ -M (manufactured by Tosoh Corporation) as a column.
  • the NMP buffer solution was prepared at a ratio of NMP (3 L) / phosphoric acid (3.3 mL) / lithium bromide (7.83
  • the polymer to be measured was dissolved in tetrahydrofuran (THF), THF was used as an eluent, TOSOH HLC-8220 (manufactured by Tosoh Corporation) was used as an apparatus, and TSKgel ⁇ -M (manufactured by Tosoh Corporation) was used as a column.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • the addition system solution was added to the obtained reaction system under nitrogen. After heating the system to 60 ° C. with stirring, 15.39 g (235.43 mmol) of zinc and 2.05 g (3.14 mmol) of bis (triphenylphosphine) nickel dichloride were added to further promote the polymerization, and 80 ° C. For 3 hours. An exotherm and an increase in viscosity were observed with the reaction.
  • the obtained solution was diluted with 273 mL of DMAc, and filtered using Celite as a filter aid. To the filtrate, 29.82 g (343.33 mmol) of lithium bromide was added and reacted at 100 ° C. for 7 hours. After the reaction, the reaction solution was cooled to room temperature and poured into 3.2 L of water to be solidified. The solidified product was washed and filtered four times while stirring with acetone. The washed product was washed and filtered seven times while stirring with 1N sulfuric acid. Further, the washed product was washed and filtered with deionized water until the pH of the washing solution became 5 or more. The obtained washed product was dried at 75 ° C. for 24 hours to obtain 25.18 g of a polymer having a target ion exchange group.
  • the number average molecular weight (Mn) of the molecular weight in terms of polystyrene measured by GPC (solvent: NMP buffer solution) of the polymer having an ion exchange group was 53,000, and the weight average molecular weight (Mw) was 120,000.
  • the ion exchange capacity of this polymer was 2.30 meq / g.
  • the separated organic layer was washed successively with 740 mL of water, 740 mL of a 10 wt% aqueous potassium carbonate solution and 740 mL of saturated brine, and then the solvent was distilled off under reduced pressure.
  • the residue was purified by silica gel column chromatography (chloroform solvent). Subsequently, the solvent was distilled off from the obtained eluate under reduced pressure. Thereafter, the residue was dissolved in 970 mL of hexane at 65 ° C. and then cooled to room temperature. The precipitated solid was separated by filtration. The separated solid was dried to obtain 99.4 g of a white solid of 2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl) represented by the following formula in a yield of 82.1%.
  • the nickel-containing solution was poured into the obtained liquid, and a polymerization reaction was performed at 70 ° C. for 4 hours.
  • the reaction mixture was added to 60 mL of methanol, and then 60 mL of a 6 mol / L hydrochloric acid aqueous solution was added to the resulting mixture and stirred for 1 hour.
  • the precipitated solid was separated by filtration and dried to obtain 1.62 g of a grayish white polymerization intermediate.
  • 1.62 g of the obtained polymerization intermediate was added to a mixed solution of 1.13 g (13.0 mmol) of lithium bromide and 56 mL of NMP, and reacted at 120 ° C. for 24 hours.
  • the reaction mixture was poured into 560 mL of 6 mol / L hydrochloric acid aqueous solution and stirred for 1 hour.
  • the precipitated solid was separated by filtration.
  • the separated solid was dried to obtain 0.42 g of an off-white polymer having a target sulfonic acid group.
  • the number average molecular weight (Mn) of the molecular weight in terms of polystyrene measured by GPC (solvent: NMP buffer solution) of the polymer having a sulfonic acid group was 75000, and the weight average molecular weight (Mw) was 173,000.
  • the ion exchange capacity of this polymer was 1.95 meq / g.
  • the obtained polymer having an ion exchange group was a polymer having the following structural unit (hereinafter also referred to as “polymer (A2)”).
  • n and n are each independently a value calculated from the charged amount of the raw material forming each structural unit.
  • the resulting reaction solution was allowed to cool and then poured into 110 mL of a methanol / 4 wt% sulfuric acid solution (5/1 (volume ratio)).
  • the precipitated product was filtered, and the filtrate was placed in 110 mL of water and stirred at 55 ° C. for 1 hour.
  • the liquid after stirring was filtered, and the residue was again stirred in 110 mL of water at 55 ° C. for 1 hour.
  • the liquid after stirring was filtered, and the filtrate was put into 110 mL of methanol and stirred at 55 ° C. for 1 hour, and then filtered.
  • the filtrate was again put into 110 mL of methanol and stirred and filtered at 55 ° C. for 1 hour. .
  • the filtrate was air-dried and then vacuum-dried at 80 ° C. to obtain 9.91 g of the desired polymer.
  • the resulting reaction solution was allowed to cool and then poured into 90 mL of a methanol / 4 wt% sulfuric acid solution (5/1 (volume ratio)).
  • the precipitated product was filtered, and the filtrate was placed in 90 mL of water and stirred at 55 ° C. for 1 hour.
  • the liquid after stirring was filtered, and the residue was again stirred in 90 mL of water at 55 ° C. for 1 hour.
  • the liquid after stirring was filtered, and the filtrate was put into 90 mL of methanol and stirred at 55 ° C. for 1 hour, and then filtered.
  • the filtrate was again put into 90 mL of methanol and stirred at 55 ° C. for 1 hour and filtered. .
  • the filtrate was air-dried and then vacuum-dried at 80 ° C. to obtain 9.91 g of the desired polymer.
  • the solution dissolved in 85 ml was cast coated on a PET film with a die coater, pre-dried at 80 ° C. for 40 minutes, and then dried at 120 ° C. for 40 minutes.
  • the dried PET film with a coating film is immersed in a large amount of distilled water overnight to remove residual NMP in the coating film, and then air-dried.
  • the polymer (A1) and the polymer (B1) have a mass ratio (heavy weight)
  • the electrolyte membrane 1 was obtained that was contained in a combination (A1) / polymer (B1)) 97/3 and had a thickness of 40 ⁇ m.
  • Platinum poisoning test A platinum disk electrode with a surface area of 0.785 mm 2 is immersed in a 1N sulfuric acid aqueous solution degassed with N 2 gas, a sweep rate of 0.01 V / s, and a sweep potential range of 0.05 to 1.5 V. The platinum voltammetry was performed by repeating the sweep until the cyclic voltammogram became constant, and a platinum disk electrode having a clean surface was obtained. In addition, the amount of electricity of the hydrogen desorption wave of the last measured cyclic voltammogram was the amount of electricity measured when the electrode surface was clean.
  • the electrolyte membrane 1 (thickness 40 ⁇ m, area 9 cm 2 , that is, volume 0.036 cm 3 ) peeled from the PET film is placed in a container containing 50 mL of 1N sulfuric acid aqueous solution, and the container is sealed and sealed at 80 ° C. for 100 hours.
  • the heated aqueous solution was collected as a test solution.
  • a platinum disk electrode surface having a clean surface was immersed in a test solution deaerated with N 2 gas, and cyclic voltammetry was measured for 20 cycles at a sweep rate of 0.01 V / s and a sweep potential range of 0.05 to 0.4 V. .
  • Platinum poisoning rate (%) [(quantity of electricity measured when electrode surface is clean) ⁇ (quantity of electricity measured when electrode surface is poisoned)] ⁇ 100 / (clean electrode surface) Measured quantity of electricity)
  • a platinum wire was used as the counter electrode for cyclic voltammetry, and a reversible hydrogen electrode was used as the reference electrode. Further, during cyclic voltammetry, N 2 gas was kept flowing to prevent air from entering the portion above the electrolyte in the electrochemical cell. The measurement was performed at room temperature. The results are shown in Table 1.
  • Example 2 In Example 1, a polymer (A1) and a polymer (B2) were obtained in the same manner as in Example 1 except that the polymer (B2) obtained in Synthesis Example 4 was used instead of the polymer (B1). Was obtained at a mass ratio of 97/3, and an electrolyte membrane 2 having a thickness of 40 ⁇ m was obtained. Using this electrolyte membrane, the same platinum poisoning test as in Example 1 was performed. The results are shown in Table 1.
  • Example 4 In Example 3, the polymer (A1) and the polymer (B4) were obtained in the same manner as in Example 3 except that the polymer (B4) obtained in Synthesis Example 6 was used instead of the polymer (B3). Was obtained at a mass ratio of 97/3, and an electrolyte membrane 4 having a thickness of 40 ⁇ m was obtained. Using this electrolyte membrane, the same platinum poisoning test as in Example 1 was performed. The results are shown in Table 1.
  • EPS-12A 12 wt% SnO 2 aqueous dispersion, manufactured by Yamanaka Sangyo Co., Ltd.
  • a mixed solvent of NMP / methyl ethyl ketone / methanol 60/20/20 (mass ratio).
  • the same procedure as in Example 1 was performed except that 15 g of the polymer (A1) obtained in Synthesis Example 1 and 0.47 g of the polymer (B1) obtained in Synthesis Example 3 were dissolved in the solution.
  • an electrolyte membrane 5 was obtained.
  • the electrolyte membrane 5 includes a polymer (A1), a polymer (B1), and SnO 2 (metal component) at a mass ratio (polymer (A1) / polymer (B1) / metal component) 94/3/3.
  • the film thickness was 40 ⁇ m.
  • Example 6 In Example 3, the polymer (A1) and the polymer (B5) were used in the same manner as in Example 3 except that the polymer (B5) obtained in Synthesis Example 7 was used instead of the polymer (B3). Was obtained at a mass ratio of 97/3, and an electrolyte membrane 6 having a film thickness of 40 ⁇ m was obtained. Using this electrolyte membrane, the same platinum poisoning test as in Example 1 was performed. The results are shown in Table 1.
  • Example 7 In Example 1, the polymer (A2) and the polymer (B1) were obtained in the same manner as in Example 1 except that the polymer (A2) obtained in Synthesis Example 2 was used instead of the polymer (A1). Was obtained at a mass ratio of 97/3, and an electrolyte membrane 7 having a thickness of 40 ⁇ m was obtained. Using this electrolyte membrane, the same platinum poisoning test as in Example 1 was performed. The results are shown in Table 1.
  • Example 8 In Example 1, 71.4 ml of Nafion D2020 (manufactured by DuPont, polymer concentration 21% dispersion, ion exchange capacity 1.08 meq / g) was used instead of the polymer (A1), NMP was added, and water was added. In addition, Nafion and polymer (B1) were contained at a mass ratio of 97/3 in the same manner as in Example 1 except that the total amount of NMP was changed to 85 ml by distilling off 1-propanol and replacing the solvent. An electrolyte membrane 8 having a thickness of 40 ⁇ m was obtained. Using this electrolyte membrane, the same platinum poisoning test as in Example 1 was performed. The results are shown in Table 1.
  • Example 1 In Example 1, polymer (A1) and thianthrene were in a mass ratio of 97/3 in the same manner as in Example 1 except that thianthrene (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of polymer (B1). An electrolyte membrane having a thickness of 40 ⁇ m was obtained. Using this electrolyte membrane, the same platinum poisoning test as in Example 1 was performed. The results are shown in Table 1.
  • Example 2 an electrolyte membrane having a thickness of 40 ⁇ m was obtained in the same manner as in Example 1 except that the polymer (B1) was not used. Using this electrolyte membrane, the same platinum poisoning test as in Example 1 was performed. The results are shown in Table 1.
  • the electrolyte membranes obtained in Examples 1 to 8 and Comparative Example 2 have a low platinum poisoning rate even at high temperatures, and there is little concern about performance degradation due to a decrease in catalytic activity during battery power generation or water decomposition. It was a membrane.
  • the electrolyte membrane obtained in Comparative Example 1 has a high platinum poisoning rate, and is a membrane in which the power generation performance and the water resolution are liable to be lowered due to a decrease in catalytic activity.
  • cathode electrode paste 80 g of zirconia balls (YTZ balls) having a diameter of 5 mm are placed in a 200 ml plastic bottle, and platinum-supported carbon particles (“TEC10E50E” manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., Pt: 45.6% by mass) 1.25 g, distilled 3.64 g of water, 11.91 g of n-propyl alcohol and Nafion D2020 (4.40 g) were added, and the mixture was stirred for 60 minutes with a paint shaker, and then the zirconia balls were removed to obtain a cathode electrode paste.
  • platinum-supported carbon particles (“TEC10E50E” manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., Pt: 45.6% by mass) 1.25 g, distilled 3.64 g of water, 11.91 g of n-propyl alcohol and Nafion D2020 (4.40 g) were added, and the mixture was stirred for 60 minutes with a
  • Example 9 [Production of electrodes] Using the mask having an opening of 5 cm ⁇ 5 cm on one side (the side opposite to the PET film) of the electrolyte membrane 1 with the PET film obtained in Example 1, the anode electrode paste was applied with a doctor blade, and the PET film Then, the cathode electrode paste was applied with a doctor blade using a mask having an opening of 5 cm ⁇ 5 cm on the peeled surface. This was dried at 120 ° C. for 60 minutes to obtain a laminate in which catalyst layers were formed on both surfaces of the electrolyte membrane. The catalyst coating amount of each catalyst layer was 0.50 mg / cm 2 .
  • GDL24BC manufactured by SGL CARBON was used as the gas diffusion layer.
  • the electrolyte membrane having the catalyst layer formed on both sides was sandwiched between two gas diffusion layers and hot-pressed at 160 ° C. for 20 minutes under a pressure of 60 kg / cm 2 to prepare a membrane-electrode assembly.
  • a separator also serving as a gas flow path is laminated on the gas diffusion layer of the obtained membrane-electrode assembly, and is sandwiched between two titanium current collectors.
  • Two evaluation fuel cells were prepared.
  • Example 10 evaluation was performed in the same manner as in Example 9 except that instead of the electrolyte membrane 1 with PET film obtained in Example 1, the electrolyte membrane 2 with PET film obtained in Example 2 was used. A fuel cell was prepared, and an OCV durability test and an output voltage measurement before and after the OCV durability test were performed using the fuel cell. The results are shown in Table 2.
  • Example 11 evaluation was performed in the same manner as in Example 9 except that instead of the electrolyte membrane 1 with PET film obtained in Example 1, the electrolyte membrane 3 with PET film obtained in Example 3 was used. A fuel cell was prepared, and an OCV durability test and an output voltage measurement before and after the OCV durability test were performed using the fuel cell. The results are shown in Table 2.
  • Example 12 evaluation was performed in the same manner as in Example 9 except that instead of the electrolyte membrane 1 with PET film obtained in Example 1, the electrolyte membrane 4 with PET film obtained in Example 4 was used. A fuel cell was prepared, and an OCV durability test and an output voltage measurement before and after the OCV durability test were performed using the fuel cell. The results are shown in Table 2.
  • Example 13 evaluation was performed in the same manner as in Example 9 except that instead of the electrolyte membrane 1 with PET film obtained in Example 1, the electrolyte membrane 5 with PET film obtained in Example 5 was used. A fuel cell was prepared, and an OCV durability test and an output voltage measurement before and after the OCV durability test were performed using the fuel cell. The results are shown in Table 2.
  • Example 14 In Example 9, instead of the electrolyte membrane 1 with PET film obtained in Example 1, the evaluation was performed in the same manner as in Example 9 except that the electrolyte membrane 6 with PET film obtained in Example 6 was used. A fuel cell was prepared, and an OCV durability test and an output voltage measurement before and after the OCV durability test were performed using the fuel cell. The results are shown in Table 2.
  • Example 15 In Example 9, instead of the electrolyte membrane 1 with PET film obtained in Example 1, the evaluation was performed in the same manner as in Example 9 except that the electrolyte membrane 7 with PET film obtained in Example 7 was used. A fuel cell was prepared, and an OCV durability test and an output voltage measurement before and after the OCV durability test were performed using the fuel cell. The results are shown in Table 2.
  • Example 16 In Example 9, instead of the electrolyte membrane 1 with PET film obtained in Example 1, the evaluation was performed in the same manner as in Example 9 except that the electrolyte membrane 8 with PET film obtained in Example 8 was used. A fuel cell was prepared, and an OCV durability test and an output voltage measurement before and after the OCV durability test were performed using the fuel cell. The results are shown in Table 2.
  • a layered product (electrolyte membrane 9, 40 ⁇ m) in which the layer (F1) and the layer (F2) having a thickness of 39 ⁇ m and consisting only of the polymer (A1) were laminated in this order was obtained.
  • the mass ratio (polymer (A1) / polymer (B1)) of the polymer (A1) and the polymer (B1) in the entire electrolyte membrane 9 was 99.72 / 0.28.
  • Example 9 instead of the electrolyte membrane 1 with PET film obtained in Example 1, the electrolyte membrane 9 with PET film was used, and the cathode electrode paste was layered on the surface (F1) and the anode electrode paste was layered.
  • F2 A fuel cell for evaluation was prepared in the same manner as in Example 9 except that it was applied to the surface, and an OCV durability test and an output voltage measurement before and after the OCV durability test were performed using the fuel cell. The results are shown in Table 2.
  • a laminate (electrolyte film 10, thickness 40 ⁇ m) in which a layer (F4) having a thickness of 38 ⁇ m and a layer (F3) made of only (F3), the polymer (A1), and the layer (F3) was obtained in this order was obtained.
  • the mass ratio (polymer (A1) / polymer (B1)) of the polymer (A1) and the polymer (B1) in the entire electrolyte membrane 8 was 99.5 / 0.5.
  • Example 9 instead of the electrolyte membrane 1 with PET film obtained in Example 1, an evaluation fuel cell was prepared in the same manner as in Example 9 except that the electrolyte membrane 10 with PET film was used. Using the fuel cell, an OCV durability test and an output voltage measurement before and after the OCV durability test were performed. The results are shown in Table 2.
  • the solution dissolved in 85 ml was cast coated on a PET film with a die coater.
  • a high molecular weight polyethylene porous substrate manufactured by Lydall, SOLUPOR (registered trademark), 3P07A; specific gravity 3.0 g / m 2 , air permeability 1.4 s / 50 ml, porosity 83 %, Thickness 20 ⁇ m).
  • the solution was cast again from the side of the porous substrate not in contact with the coating solution, and both surfaces of the porous substrate were impregnated with the solution.
  • drying was performed at 120 ° C. for 40 minutes to obtain a laminate in which a coating film was formed on both surfaces of the substrate.
  • the laminated body after drying is immersed in a large amount of distilled water overnight, the remaining NMP in the coating film is removed, and then air-dried to be reinforced with a porous substrate made of high molecular weight polyethylene, and the polymer (A1) and An electrolyte membrane 11 having a thickness of 20 ⁇ m was obtained, in which the mass ratio of polymer (B1) to polymer (A1) / polymer (B1) was 97/3.
  • Example 9 an evaluation fuel cell was prepared in the same manner as in Example 9 except that the electrolyte membrane 11 was used instead of the electrolyte membrane 1 with the PET film obtained in Example 1.
  • the OCV durability test and the output voltage measurement before and after the OCV durability test were performed. The results are shown in Table 2.
  • Comparative Example 5 Fuel for evaluation in the same manner as in Example 9 except that the electrolyte membrane with PET film obtained in Comparative Example 1 was used instead of the electrolyte membrane with PET film obtained in Example 1 in Example 9. A battery was created. The fuel cell was used to measure the OCV durability test and the output voltage before and after the OCV durability test. The initial voltage could not be measured due to platinum catalyst poisoning. could not.

Abstract

La présente invention se rapporte à une composition de membrane électrolytique, à une membrane électrolytique polymère solide, à un procédé permettant de produire ladite membrane électrolytique, à un ensemble membrane-électrode, à une pile à combustible de type polymère, à une cellule d'électrolyse de l'eau et à un appareil d'électrolyse de l'eau. Cette composition de membrane électrolytique comprend un polymère (A) qui comporte un groupe d'échange d'ions, et un polymère (B) qui comporte un squelette de sulfure d'arylène et est soluble dans un solvant organique.
PCT/JP2014/058640 2013-03-28 2014-03-26 Composition de membrane électrolytique, membrane électrolytique polymère solide, procédé permettant de produire ladite membrane électrolytique, ensemble membrane-électrode, pile à combustible de type polymère, ainsi que cellule d'électrolyse de l'eau et appareil d'électrolyse de l'eau WO2014157389A1 (fr)

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EP3322018A4 (fr) * 2016-05-04 2018-07-18 LG Chem, Ltd. Procédé de production de membrane d'électrolyte polymère, membrane d'électrolyte polymère produite au moyen de celui-ci, ensemble d'électrodes à membrane comprenant ladite membrane d'électrolyte polymère, et pile à combustible comprenant ledit ensemble d'électrodes à membrane
CN109923242A (zh) * 2016-11-04 2019-06-21 株式会社日本多宁 固体高分子膜电极
JP7455605B2 (ja) 2019-03-29 2024-03-26 現代自動車株式会社 燃料電池用酸化防止剤及びこれを含む燃料電池
JP7473153B2 (ja) 2020-01-23 2024-04-23 国立研究開発法人物質・材料研究機構 水素製造装置、及び、水素製造方法

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US10790528B2 (en) 2016-05-04 2020-09-29 Lg Chem, Ltd. Polymer electrolyte membrane production method, polymer electrolyte membrane produced using same, membrane electrode assembly comprising said polymer electrolyte membrane, and fuel cell comprising said membrane electrode assembly
EP3322018A4 (fr) * 2016-05-04 2018-07-18 LG Chem, Ltd. Procédé de production de membrane d'électrolyte polymère, membrane d'électrolyte polymère produite au moyen de celui-ci, ensemble d'électrodes à membrane comprenant ladite membrane d'électrolyte polymère, et pile à combustible comprenant ledit ensemble d'électrodes à membrane
WO2018012812A1 (fr) * 2016-07-15 2018-01-18 주식회사 엘지화학 Polymère à base de sulfure, film le comprenant et son procédé de fabrication
CN107849251A (zh) * 2016-07-15 2018-03-27 株式会社Lg化学 硫化物类聚合物、包含该聚合物的薄膜以及该薄膜的制备方法
CN107849251B (zh) * 2016-07-15 2020-03-10 株式会社Lg化学 硫化物类聚合物、包含该聚合物的薄膜以及该薄膜的制备方法
US10428182B2 (en) 2016-07-15 2019-10-01 Lg Chem, Ltd. Sulfide-based polymer, film comprising same and method for preparing same
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CN109923242A (zh) * 2016-11-04 2019-06-21 株式会社日本多宁 固体高分子膜电极
CN109923242B (zh) * 2016-11-04 2021-10-29 株式会社日本多宁 固体高分子膜电极
JP2018110108A (ja) * 2016-12-12 2018-07-12 東レ株式会社 高分子電解質組成物、それを用いた高分子電解質膜、触媒層付電解質膜、膜電極複合体、固体高分子形燃料電池、固体高分子形水電解式水素発生装置および電気化学式水素圧縮装置、ならびに高分子電解質組成物の製造方法
JP7059608B2 (ja) 2016-12-12 2022-04-26 東レ株式会社 高分子電解質組成物、それを用いた高分子電解質膜、触媒層付電解質膜、膜電極複合体、固体高分子形燃料電池、固体高分子形水電解式水素発生装置および電気化学式水素圧縮装置、ならびに高分子電解質組成物の製造方法
JP7455605B2 (ja) 2019-03-29 2024-03-26 現代自動車株式会社 燃料電池用酸化防止剤及びこれを含む燃料電池
JP7473153B2 (ja) 2020-01-23 2024-04-23 国立研究開発法人物質・材料研究機構 水素製造装置、及び、水素製造方法

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