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WO2013161405A1 - Composition pour membranes d'électrolyte, membrane d'électrolyte polymère solide, procédé de production de membrane d'électrolyte polymère solide, système membrane-électrode, pile à combustible à polymère solide, cellule d'électrolyse d'eau et système d'électrolyse d'eau - Google Patents

Composition pour membranes d'électrolyte, membrane d'électrolyte polymère solide, procédé de production de membrane d'électrolyte polymère solide, système membrane-électrode, pile à combustible à polymère solide, cellule d'électrolyse d'eau et système d'électrolyse d'eau Download PDF

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WO2013161405A1
WO2013161405A1 PCT/JP2013/056648 JP2013056648W WO2013161405A1 WO 2013161405 A1 WO2013161405 A1 WO 2013161405A1 JP 2013056648 W JP2013056648 W JP 2013056648W WO 2013161405 A1 WO2013161405 A1 WO 2013161405A1
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electrolyte membrane
compound
composition
group
solid polymer
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Japanese (ja)
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淳司 川井
宣彰 若林
法寛 山本
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Jsr株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C08L65/02—Polyphenylenes
    • 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
    • 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
    • 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]
    • 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
    • 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
    • C08G2261/14—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
    • 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
    • C08G2261/34—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
    • 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
    • C08G2261/35—Macromonomers, i.e. comprising more than 10 repeat units
    • C08G2261/354—Macromonomers, i.e. comprising more than 10 repeat units containing hetero atoms
    • 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
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/412—Yamamoto reactions
    • 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
    • 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
    • C08G2261/90—Applications
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • 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.
  • the solid polymer electrolyte membrane is commercially available under the trade names 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 with sulfonic acid groups; aromatic backbones such as polyaromatic hydrocarbons, polyether ether ketones, polyphenylene sulfides, polyimides or polybenzazoles And a polymer electrolyte membrane having a sulfonic acid group; and the like have been proposed.
  • Patent Document 1 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 2 a polymer electrolyte and a high platinum affinity
  • Patent Document 2 a polymer electrolyte membrane containing a compound
  • the polymer electrolyte membrane described in Patent Document 1 has room for improvement in durability because the polyphenylene sulfide resin is dispersed in islands. Further, in the polymer electrolyte membrane described in Patent Document 2, there is a concern that the durability of the electrolyte membrane may be reduced and the power generation performance of the battery may be reduced due to the elution of a compound having a high platinum affinity from the electrolyte membrane. There was room for improvement.
  • An object of the present invention is to provide a composition for an electrolyte membrane that can provide a polymer electrolyte membrane that is excellent in durability and that suppresses a decrease in power generation performance and water electrolysis performance over time.
  • the present inventors have a specific structure together with a polymer having an ion exchange group, and the number average molecular weight is 500 or more, And according to the composition for electrolyte membrane containing a compound soluble in an organic solvent, it discovered that the said objective could be achieved and came to complete this invention.
  • the configuration of the present invention is as follows.
  • a polymer (A) having an ion exchange group and
  • ring A and ring B each independently represent a group having a cyclic structure
  • R I and R II each independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a carbon number of 1 to 12
  • L represents a direct bond
  • aI and aII are each independently 0 to 6 Indicates an integer.
  • electrolyte membrane composition according to any one of [1] to [4], further comprising at least one metal component selected from the group consisting of a metal-containing compound and a metal ion.
  • a membrane-electrode assembly in which a gas diffusion layer, a catalyst layer, the solid polymer electrolyte membrane according to any one of [6] to [9], 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 [12].
  • a water electrolysis cell comprising a catalyst layer, the solid polymer electrolyte membrane according to any one of [6] to [9], and a laminate in which the catalyst layers are laminated in this order.
  • a water electrolysis apparatus having the water electrolysis cell according to [14].
  • the present invention it is possible to obtain a polymer electrolyte membrane that is excellent in durability and in which a decrease in power generation performance and water electrolysis performance over time is suppressed.
  • composition for an electrolyte membrane of the present invention comprises a polymer (A) having an ion exchange group, a compound (B1) having a specific structure, a number average molecular weight of 500 or more and soluble in an organic solvent. including. According to such a composition, it is possible to obtain a polymer electrolyte membrane that is excellent in durability and in which a decrease in power generation performance and water electrolysis performance over time is suppressed.
  • 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 Unexamined Patent Application Publication No. 2007-177197, International Publication No. 2007/043274, and the like.
  • 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.
  • the ion exchange capacity can be measured, for example, by the method described in the examples below.
  • the ion exchange capacity can be adjusted by changing the type, use ratio, combination, and the like of each structural unit. Therefore, it can be adjusted by changing the charge amount ratio, type, etc. of the precursor (monomer / oligomer) that induces the structural unit during the polymerization.
  • 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 compound (B1) has a group (B ′) represented by the following formula (B ′), has a number average molecular weight of 500 or more, and is soluble in an organic solvent. Such a compound (B1) 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 considered that the catalyst that has been deteriorated causes deterioration of the electrolyte membrane, which causes the long-term stability of the polymer electrolyte fuel cell to decrease.
  • a catalyst layer is provided on the electrode of the water electrolysis apparatus, and platinum, ruthenium, iridium, iron, or the like is used as a catalyst contained in the catalyst layer.
  • platinum, ruthenium, iridium, iron, or the like is used as a catalyst contained in the catalyst layer.
  • Some of these catalysts are deposited in the electrolyte membrane during the operation of the water electrolysis apparatus, and the deposited catalyst causes deterioration of the electrolyte membrane and becomes a factor that reduces the long-term stability of the water electrolysis apparatus. It is believed that 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 compound (B1) together with the polymer (A) having an ion-exchange group, thereby improving the power of the solid state and the long-term stability. 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 compound (B1) is made of platinum.
  • the poisoning rate falls below a specific value. This means that the elution amount of the compound (B1) from the electrolyte membrane is below a certain range. This can inactivate platinum in the vicinity of the interface between the electrolyte membrane and the electrode, while inactivating platinum that is located away from the interface between the electrolyte membrane and the electrode and has little effect on the deterioration of the electrolyte membrane. It is thought not to activate.
  • composition for an electrolyte membrane of the present invention contains the compound (B1), the polymer electrolyte fuel cell excellent in balance between power generation performance and long-term stability, and water electrolysis performance and long-term stability. A water electrolysis apparatus excellent in balance can be obtained.
  • the compound (B1) contains a sulfide bond in the molecule. This 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 compound (B1) preferably has a sulfur atom content constituting a sulfide bond in the compound of 2.0 mmol / g or more. More preferably, it is 2.3 mmol / g or more, More preferably, it is 2.5 mmol / g or more. If the content of the sulfur atom constituting the sulfide bond in the compound (B1) is less than 2.0 mmol / g, the effect of suppressing deterioration of the electrolyte membrane during operation of the battery or the water electrolysis device may not be sufficient. Moreover, it is preferable that content of the sulfur atom which comprises the sulfide bond in this compound (B1) in this compound is 5.0 mmol / g or less. The content of the sulfur atom constituting the sulfide bond in such a compound can be quantified by, for example, Raman spectroscopy.
  • the compound (B1) contains at least one cyclic structure in the molecule.
  • the compound (B1) contains a cyclic structure, particularly an aromatic ring, the compound (B1) has excellent compatibility with the polymer (A), and elution to the outside of the electrolyte membrane during operation of the battery or the water electrolysis apparatus is suppressed.
  • the number of cyclic structures contained in the compound (B1) is not particularly limited as long as it is 1 or more, and can be appropriately selected from the relationship with the molecular weight of the following compound (B1).
  • the compound (B1) is a compound having a group (B ′) represented by the following formula (B ′).
  • ring A and ring B each independently represent a group having a cyclic structure
  • R I and R II each independently represent a hydrogen atom, a halogen atom, a hydroxy group, or a carbon number of 1 to 12
  • L represents a direct bond, an oxygen atom or a sulfur atom
  • aI and aII each independently represent an integer of 0 to 6.
  • R I ′ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, preferably a linear or branched alkyl group having 1 to 8 carbon atoms, A branched alkyl group is more preferred.
  • Preferred examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , N-hexyl group and n-heptyl group.
  • aryl group examples include an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a phenyl group, a biphenyl group, a naphthyl group, and the like are preferable.
  • ring A and ring B examples include a benzene ring, a naphthalene ring, and a cyclohexane ring, and a benzene ring is preferable.
  • R I and R II are each independently preferably a hydroxy group and an alkyl group having 1 to 5 carbon atoms from the viewpoint of the solubility of the compound (B1) in an organic solvent, and the hydroxy group, methyl group, A tert-butyl group is more preferred.
  • L is preferably an oxygen atom.
  • AI and aII are each independently preferably an integer of 0 to 4, more preferably an integer of 1 to 4.
  • the group (B ′) preferably has a molecular weight of 300 or more, more preferably 300 to 1,000.
  • the molecular weight of the group (B ′) can be calculated by, for example, NMR structural analysis.
  • the compound (B1) is preferably a compound represented by the following formula (B2).
  • the compound represented by the following formula (B2) is used as the compound (B1), elution of the compound to the outside of the electrolyte membrane during operation of the battery or the water electrolysis apparatus and deterioration of the electrolyte membrane are suppressed, and durability is improved. There is a tendency to obtain an excellent electrolyte membrane.
  • ring A, ring B, R I , R II , L, aI and aII are each independently ring A, ring B, R I , R II in the formula (B ′), It is synonymous with L, aI and aII, and preferable ring A, ring B, R I , R II , L, aI and aII are the same.
  • M preferably represents a carbon atom, a phosphorus atom, a nitrogen atom, a silicon atom, a boron atom or a hydrocarbon group, and mB represents a valence of M.
  • the hydrocarbon group in M is preferably a hydrocarbon group having 1 to 5 carbon atoms or a benzene ring.
  • the benzene ring refers to, for example, a phenyl group when M is monovalent and a phenylene group when M is divalent.
  • the M is preferably a phosphorus atom.
  • a catalyst such as platinum that can be contained in a catalyst layer provided on an electrode tends to be difficult to deposit in the electrolyte membrane.
  • the compound represented by said Formula (B2) is preferable, and the elution of this compound and the deterioration of an electrolyte membrane are suppressed outside a battery and a water electrolysis apparatus operation
  • Tris [2-tert-butyl-5-methyl-4-thio-5′-tert-butyl-4′-hydroxy-2′-methylphenyl] from the viewpoint of obtaining an electrolyte membrane having excellent durability. More preferred is phenyl phosphite.
  • the compound (B1) a compound (synthetic product) produced by a known method may be used, or a commercially available product may be used.
  • a commercial item containing the said compound (B1) HOSTANOX OSP 1 (made by Clariant) etc. are mentioned.
  • the synthetic product is not particularly limited.
  • a compound having a sulfide bond and at least one cyclic structure in the molecule such as thiobis-tert-butylmethylbenzene, a carbon atom such as phosphorus trichloride, phosphorus
  • a compound obtained by reacting a halide having an atom, nitrogen atom, silicon atom, boron atom or hydrocarbon group is preferred.
  • the synthetic product includes a compound having a sulfide bond and at least one cyclic structure in the molecule, such as thiobis-tert-butylmethylphenol, and at least one hydroxy group or thiol group, and phosphorus trichloride.
  • the compound (B1) has a number average molecular weight of 500 or more, preferably 800 or more, more preferably 1000 or more. Moreover, the upper limit of the number average molecular weight of the compound (B1) is preferably 100,000 or less, more preferably 50000 or less, and still more preferably 10,000 or less. When the number average molecular weight of the compound (B1) is less than 500, the amount of the compound (B1) eluted out of the electrolyte membrane during operation of the battery or the water electrolysis device may be excessively increased. In addition, when the number average molecular weight of the compound (B1) exceeds 100,000, the solubility of the compound (B1) in an organic solvent described later decreases, or the compatibility (dispersibility) of the polymer (A) decreases. There is a case.
  • the number average molecular weight of the compound (B1) is calculated from the obtained result when structural analysis such as NMR is possible with a low molecular weight compound, and the molecular weight is large like an oligomer or a polymer, and the molecular weight is unambiguous. Can be measured and calculated by GPC.
  • compound (B1) is dissolved in N-methyl-2-pyrrolidone (NMP), NMP is used as an eluent, and TOSOH HLC-8220 (manufactured by Tosoh Corp.)
  • NMP N-methyl-2-pyrrolidone
  • TOSOH HLC-8220 manufactured by Tosoh Corp.
  • Mn number average molecular weight in terms of polystyrene can be determined by gel permeation chromatography (GPC) using TSKgel ⁇ -M (manufactured by Tosoh Corporation) as a column.
  • the compound (B1) is a compound that is soluble in an organic solvent.
  • the “compound soluble in an organic solvent” is preferably a compound that is soluble in 100 g or more in 1 L of the organic solvent, and more preferably a compound that is soluble in 200 g or more. Since the compound (B1) is soluble in an organic solvent, it is possible to produce an electrolyte membrane by a simple production method, which is preferable because the compatibility (dispersibility) with the polymer (A) is good. .
  • 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 melting point of the compound (B1) measured by Yanagimoto Seisakusho, precision melting point measuring device is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 120 ° C. That's it.
  • the melting point of the compound (B1) is less than 80 ° C., the compound (B1) is likely to move in the electrolyte membrane and easily elute out of the electrolyte membrane while the battery or the water electrolysis apparatus is operating at a high temperature. The durability of the electrolyte membrane and the power generation performance and water electrolysis performance tend to decrease.
  • the compound (B1) has a mass ratio of the polymer (A) to the compound (B1) of 99.99: 0.01 to 70:30, preferably 99.95: 0.05 to 75:25. More preferably, it is added to the electrolyte membrane composition of the present invention in an amount of 99.9: 0.1 to 80:20, particularly preferably 99.7: 0.3 to 85:15. When the polymer (A) and the compound (B1) are contained within such a range, an electrolyte membrane exhibiting good durability and proton conductivity can be obtained.
  • 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 compound (B1).
  • a component having hydrogen peroxide decomposability is preferable. Specifically, hydrogen peroxide that can be generated during operation of a battery or a water electrolysis apparatus 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 0.3 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 viewpoints of the solubility of the polymer (A) and the compound (B1) and the composition viscosity.
  • 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 have poor appearance and tends to cause 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 resulting electrolyte membrane may have surface smoothness. May be lacking.
  • the viscosity of the liquid composition depends on the molecular weight and concentration of the polymer (A), the concentration of the compound (B1), etc., but is preferably 2,000 to 100,000 mPa ⁇ s, more preferably 3,000 to 50,000 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 compound (B1) in the solvent. Specifically, after the polymer (A) is dissolved or dispersed in the solvent, the compound (B1) is mixed with the compound (B1), or the compound (B1) is dissolved in the solvent. A method for dissolving or dispersing the polymer (A) is mentioned later.
  • inorganic acids such as sulfuric acid and phosphoric acid; phosphate glass; tungstic acid; ⁇ -alumina proton-substituted 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 (1) A membrane obtained from the electrolyte membrane composition, or (2) The polymer (A) and a compound (B) having a group having a sulfide bond and at least one cyclic structure in the molecule, a number average molecular weight of 500 or more, and soluble in an organic solvent
  • the electrolyte membrane (volume 0.036 cm 3 ) is immersed in 50 mL of 1N sulfuric acid aqueous solution at 80 ° C. for 100 hours, and then the electrolyte membrane is removed to remove the electrolyte membrane.
  • the platinum poisoning rate when immersed on a 1 mm platinum surface during 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 is 15% or less. It is a film.
  • 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. Can do.
  • the electrolyte membrane of the present invention is not easily deteriorated during battery power generation, has excellent power generation 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 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.
  • a film obtained from the liquid composition is preferable.
  • the electrolyte membrane composition is preferably a membrane obtained from the composition (B) containing the compound (B) instead of the compound (B1). More preferably, the composition is an electrolyte membrane obtained from the liquid composition.
  • the electrolyte membrane of the present invention (volume 0.036 cm 3 ) was swabbed into a 1 mm diameter platinum surface in an aqueous solution obtained by immersing it 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 when immersed for 20 cycles of cyclic voltammetry at a speed of 0.01 V / s and a sweep potential range of 0.05 to 0.4 V is preferably 15% or less, more preferably What becomes 12% or less is desirable.
  • 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 compound (B) and the compound (B1) are present at least within 30% of the thickness of the membrane from the surface of the electrolyte membrane. Since the compound (B) and the compound (B1) usually have low proton conductivity, in order to obtain an electrolyte membrane having high power generation performance and high water electrolysis performance, the compound (B) and the compound (B1) contained in the electrolyte membrane are used. ) Content as low as possible to improve the durability of the electrolyte membrane.
  • the compound (B) and the compound (B1) have at least the thickness of the electrolyte membrane.
  • the power generation performance, water electrolysis performance and long-term stability can be achieved even if the content of the compound (B) and the compound (B1) contained in the electrolyte membrane is small by being present within 30% of the surface of the membrane.
  • an electrolyte membrane excellent in balance can be obtained.
  • the electrolyte membrane of the present invention it is preferable that the compound (B) and the compound (B1) are unevenly distributed near the surface of the membrane, and from the surface of the electrolyte membrane with respect to the thickness of the membrane. More preferably, it is present only at a position within 30%.
  • the concentrations of the compound (B) and the compound (B1) are gradually increased as the surface of the membrane is approached.
  • an electrolyte membrane having a concentration gradient may be used.
  • 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 has a compound (B) and a compound (B1) on the surface of one surface or both surfaces in contact with the electrode when a membrane-electrode assembly is produced.
  • the electrolyte membrane may contain the compound (B) and the compound (B1) in the other part.
  • the compound (B) and the compound (B1) are contained only in the vicinity of one surface, and the other parts do not contain the compound (B) and the compound (B1).
  • the surface containing the compound (B) and the compound (B1) is preferably the cathode side.
  • the electrolyte membrane according to the present invention is obtained by applying the composition for an electrolyte membrane or the composition (B) onto a substrate by a known method such as die coating, spray coating, knife coating, roll coating, spin coating, or gravure coating. It can manufacture by including the process of apply
  • the substrate is not particularly limited as long as it is a substrate used when a normal solution is applied.
  • the substrate include plastic and metal substrates, and preferably a heat treatment such as a polyethylene terephthalate (PET) film.
  • PET polyethylene terephthalate
  • Examples include a substrate made of a plastic resin.
  • the drying is preferably performed by holding at a temperature of 50 to 150 ° C. for 0.1 to 10 hours.
  • the drying may be performed in one step, or may be performed in two or more steps, that is, after the preliminary drying in advance and then the main drying.
  • you may perform the said drying in inert gas atmosphere, such as nitrogen atmosphere, or under reduced pressure as needed.
  • 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 film after the preliminary drying or the main drying is replaced with water.
  • the amount of residual organic solvent in the obtained electrolyte membrane 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 film after preliminary drying or main drying
  • the temperature of water at the time of immersion is 10 to 60 ° C.
  • the immersion time is 10 minutes to 10 hours.
  • the film 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 It is desirable to obtain an electrolyte membrane by vacuum drying at 150 ° C. and preferably under reduced pressure of 500 mmHg to 0.1 mmHg for 0.5 to 24 hours.
  • 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 the polymer (A), the composition for an electrolyte membrane of the present invention, or the composition (B) is preferable.
  • at least one composition is the electrolyte membrane composition of the present invention or the composition (B). It is preferable.
  • 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 electrolyte membrane of the present invention or the composition (B) is used as the composition (I), and the polymer (A) is used as the composition (II).
  • the compound (B) or the compound (B1) is used, so that the compound (B) or the compound (B1) is at least within 30% from the surface of the film to the thickness of the film. It is possible to easily obtain an electrolyte membrane that exists or is unevenly distributed.
  • 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 a reinforced solid polymer electrolyte membrane include a method of impregnating the liquid composition into a porous substrate or a sheet-like fibrous material, the composition for an electrolyte membrane of the present invention, or the composition.
  • a method of applying (B) to a porous substrate or a sheet-like fibrous material, and after forming a membrane from the composition for an electrolyte membrane of the present invention or the composition (B) in advance examples thereof include a method in which a film obtained on a sheet-like fibrous material is stacked and hot pressed.
  • 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, specifically, polyolefins such as polytetrafluoroethylene, high molecular weight polyethylene, cross-linked polyethylene, polyethylene, and polypropylene, polyimide, polyacrylotolyl, polyamideimide, A substrate composed of one or more selected from the group consisting of polyetherimide, polyethersulfone, and glass is preferred.
  • the polyolefin is preferably high molecular weight polyethylene, cross-linked polyethylene, polyethylene or the like.
  • porous substrate Commercially available products of the porous substrate include GORE-SELECT (manufactured by Japan Gore-Tex), which is stretched porous polytetrafluoroethylene, and a porous substrate made of high molecular weight polyethylene (manufactured by Lydall, SOLUPOR (registered trademark)). Can be mentioned.
  • GORE-SELECT manufactured by Japan Gore-Tex
  • Lydall stretched porous polytetrafluoroethylene
  • SOLUPOR registered trademark
  • 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 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 Those composed of inorganic components such as zinc oxide, aluminum borate and wollastonite can be used.
  • 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, these thicknesses are 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 preferably 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.
  • an ion exchange resin known ones can be used without particular limitation, and examples thereof include Nafion, and the polymer (A) may be used as an ion exchange resin and further has a proton exchange group.
  • 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; It is preferable that the polymer electrolyte fuel cell includes a fuel supply unit that supplies an electricity generation unit; and an oxidant supply unit that supplies an oxidant to the electricity generation unit.
  • 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 membrane was prepared from the polymer obtained below, and the sample membrane was immersed in deionized water to completely remove the acid remaining in the membrane, and then immersed in saline to ionize By exchanging, an aqueous hydrochloric acid solution was prepared. This hydrochloric acid aqueous solution was neutralized and titrated with a standard aqueous solution of sodium hydroxide using phenolphthalein as an indicator. The sample membrane after ion exchange was washed with deionized water and vacuum dried to measure the dry weight of the membrane.
  • Ion exchange capacity titration amount of sodium hydroxide (mmol) / dry weight of membrane (g)
  • a polymer having a sulfonic acid group is dissolved in an NMP buffer solution.
  • NMP buffer solution Using the NMP buffer solution as an eluent, TOSOH HLC-8220 (manufactured by Tosoh Corp.) is used as an apparatus, and TSKgel ⁇ -M (manufactured by Tosoh Corp.) is used as a column.
  • 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 The NMP buffer solution was prepared at a ratio of NMP (3 L) / phosphoric acid (3.3 mL) / lithium bromide (7.83 g).
  • the reaction solution was heated to reflux in an oil bath at 150 ° C.
  • water produced by the reaction was azeotroped with toluene and reacted while being removed out of the system with a Dean-Stark tube, almost no water was observed in about 3 hours.
  • the reaction was continued at 190 ° C. for 3 hours.
  • 12.3 g (0.072 mol) of 2,6-dichlorobenzonitrile was added, and the reaction was further continued for 5 hours.
  • the resulting reaction solution was allowed to cool and then poured into 2401 mL of a methanol / 4 wt% sulfuric acid solution (5/1 (volume ratio)).
  • the precipitated product was filtered and the filtrate was placed in 2401 mL of water and stirred at 55 ° C. for 1 hour.
  • the liquid after stirring was filtered, and the residue was again stirred in 2401 mL of water at 55 ° C. for 1 hour.
  • the liquid after stirring was filtered, and the filtrate was put in 2401 mL of methanol, stirred at 55 ° C. for 1 hour, filtered, and the filtrate was again put in 2401 mL of methanol, stirred at 55 ° C. for 1 hour, and filtered. .
  • the filtrate was air-dried and then vacuum-dried at 80 ° C. to obtain 125 g of the desired compound.
  • the number average molecular weight (Mn) in terms of polystyrene determined by GPC (solvent: tetrahydrofuran) of the obtained target compound was 7,000.
  • the obtained compound was an oligomer represented by the following formula.
  • the obtained mixture was heated with stirring (finally heated to 79 ° C.) and reacted for 3 hours. An increase in viscosity in the system was observed during the reaction.
  • the polymerization reaction solution was diluted with 200 mL of DMAc, stirred for 30 minutes, and filtered using Celite as a filter aid. This filtrate was put into a 1 L three-necked flask equipped with a stirrer, and 37.8 g (435 mmol) of lithium bromide was added thereto, and reacted at an internal temperature of 120 ° C. for 7 hours under a nitrogen atmosphere. After the reaction, the mixture was cooled to room temperature, and the cooled liquid was poured into 5.0 L of water and solidified.
  • the coagulated product was put in acetone, the obtained liquid was filtered, and the filtrate was washed.
  • the washed product was added to 6500 g of a 1N aqueous sulfuric acid solution, and washed with stirring.
  • the washed liquid was filtered, and the residue was washed with ion exchange water. This washing was performed until the pH of the liquid after washing reached 5 or higher.
  • the object to be cleaned was dried at 80 ° C. overnight to obtain 36.0 g of a polymer having a target sulfonic acid group.
  • the polystyrene-converted molecular weight of the polymer having a sulfonic acid group measured by GPC (solvent: NMP) was 50,000 for Mn and 112,000 for Mw.
  • the ion exchange capacity of this polymer was 2.38 meq / g.
  • the obtained polymer having a sulfonic acid group was a compound having the following structural unit (polymer (i)).
  • p to s are each independently a value calculated from the charged amount of the raw material forming each structural unit.
  • the polymer (i) and HOSTANOX OSP 1 have a mass ratio (polymer ( i) / HOSTANOX OSP 1)
  • a PET film with an electrolyte membrane 1 contained in 97/3 and having a film thickness of 40 ⁇ m was obtained.
  • the HOSTANOX OSP 1 used here is composed mainly of tris [2-tert-butyl-5-methyl-4-thio-5′-tert-butyl-4′-hydroxy-2′-methylphenyl] phenylphosphine. It is a phyto (number average molecular weight 1104), and the content of sulfur atoms constituting the sulfide bond is 2.7 mmol / g. Further, the melting point of HOSTANOX OSP 1 is 106 to 124 ° C., and the melting point of the main component is 155 ° C.
  • 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 (%) [(amount of electricity measured when electrode surface is clean) ⁇ (amount of electricity measured when electrode surface is poisoned)] ⁇ 100 / (electrode surface is clean) 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.
  • a PET film with an electrolyte membrane 2 was obtained in the same manner as in Example 1 except that 16 g of the polymer (i) obtained in Synthesis Example 1 and HOSTANOX OSP 1 (0.5 g) were used. It was.
  • the electrolyte membrane 2 contains the polymer (i), HOSTANOX OSP 1, and SnO 2 (metal component) in a mass ratio (polymer (i) / HOSTANOX OSP 1 / metal component) 94/3/3. Was 40 ⁇ m. Using this electrolyte membrane 2, the same platinum poisoning test as in Example 1 was conducted. The results are shown in Table 1.
  • Example 1 In Example 1, except that HOSTANOX OSP 1 was used instead of Sumilizer TP-D (pentaerythrityl tetrakis (3-laurylthiopropionate), manufactured by Sumitomo Chemical Co., Ltd.), An electrolyte membrane having a polymer (i) and a pulverizer TP-D at a mass ratio of 97/3 and 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. Note that, the Sumilizer TP-D has a melting point of 46 ° C., a number average molecular weight of 1162, and the content of sulfur atoms constituting the sulfide bond is 3.4 mmol / g.
  • Sumilizer TP-D has a melting point of 46 ° C., a number average molecular weight of 1162, and the content of sulfur atoms constituting the sulfide
  • Example 2 The polymer (Example 1) was prepared in the same manner as in Example 1 except that Sumilizer TPL-R (Dilauryl 3,3′-thiodipropionate, manufactured by Sumitomo Chemical Co., Ltd.) was used instead of HOSTANOX OSP 1. An electrolyte membrane containing i) and the sumiser TPL-R at a mass ratio of 97/3 and 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.
  • Sumilizer TPL-R Diilauryl 3,3′-thiodipropionate, manufactured by Sumitomo Chemical Co., Ltd.
  • the Smizer TPL-R has a melting point of 39 to 42 ° C., a number average molecular weight of 515, and the content of sulfur atoms constituting the sulfide bond is 1.9 mmol / g.
  • Example 3 In Example 1, in the same manner as in Example 1 except that phenothiazine (2,3: 5,6-dibenzo-1,4-thiazine, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of HOSTANOX OSP 1, An electrolyte membrane containing polymer (i) and phenothiazine at a mass ratio of 97/3 and 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. Phenothiazine has a melting point of 182 to 185 ° C., a number average molecular weight of 199, and the content of sulfur atoms constituting the sulfide bond is 5.0 mmol / g.
  • Example 4 An electrolyte membrane having a film thickness of 40 ⁇ m was obtained in the same manner as in Example 1 except that HOSTANOX OSP 1 was not used in Example 1. Using this electrolyte membrane, the same platinum poisoning test as in Example 1 was performed. The results are shown in Table 1.
  • 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 1.25 g of platinum-supported carbon particles (“TEC10E50E” manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., Pt: 45.6% by mass) are 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 to obtain a cathode electrode paste.
  • TEC10E50E platinum-supported carbon particles
  • Example 3 [Production of electrodes] After applying the anode electrode paste with a doctor blade on the surface of the electrolyte membrane 1 with PET film obtained in Example 1 (on the side opposite to the PET film side) using a mask having a 5 cm ⁇ 5 cm opening, The PET film was peeled off. Further, the cathode electrode paste was applied with a doctor blade using a mask having an opening of 5 cm ⁇ 5 cm on the surface of the electrolyte membrane 1 opposite to the side on which the anode electrode paste was applied. 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 4 In Example 3, a fuel cell was prepared in the same manner as in Example 3 except that instead of the electrolyte membrane 1 obtained in Example 1, the electrolyte membrane 2 obtained in Example 2 was used. Were used to measure the OCV durability test and the output voltage before and after the OCV durability test. The results are shown in Tables 2 and 3.
  • the polymer (i) and HOSTANOX OSP 1 are contained in a mass ratio (polymer (i) / HOSTANOX OSP 1) 90/10 on the PET film (F1). ) And a layer (F2) having a thickness of 39 ⁇ m and consisting only of the polymer (i) were obtained in this order.
  • a material obtained by removing the PET film from the laminate was used as the electrolyte membrane 5 (thickness 40 ⁇ m).
  • the mass ratio (polymer (i) / HOSTANOX OSP 1) of polymer (i) and HOSTANOX OSP 1 in the entire electrolyte membrane 5 was 99.75 / 0.25.
  • Example 3 instead of the electrolyte membrane 1 obtained in Example 1, the electrolyte membrane 5 was used, except that the cathode electrode paste was applied to the surface of the layer (F1) and the anode electrode paste was applied to the surface of the layer (F2).
  • the cathode electrode paste was applied to the surface of the layer (F1)
  • the anode electrode paste was applied to the surface of the layer (F2).
  • Ratio was dissolved in 95 ml of the mixed solvent and cast-coated with a die coater so that the film thickness after drying was 1 ⁇ m, pre-dried at 80 ° C. for 40 minutes, and then heated at 120 ° C. for 40 minutes. Dried for minutes.
  • the dried PET film with a coating film was immersed in a large amount of distilled water overnight to remove the remaining NMP in the coating film.
  • a polymer (i) and HOSTANOX OSP 1 are contained in a mass ratio (polymer (i) / HOSTANOX OSP 1) 90/10 on the PET film (F3) having a thickness of 1 ⁇ m.
  • a layered product comprising only the polymer (i) and having a layer (F4) having a thickness of 38 ⁇ m and a layer (F3) laminated in this order was obtained.
  • an electrolyte membrane 6 (thickness 40 ⁇ m) was used after removing the PET film from this laminate.
  • the mass ratio (polymer (i) / HOSTANOX OSP 1) of polymer (i) and HOSTANOX OSP 1 in the entire electrolyte membrane 6 was 99.5 / 0.5.
  • Example 3 a fuel cell was prepared in the same manner as in Example 3 except that the electrolyte membrane 6 was used instead of the electrolyte membrane 1 obtained in Example 1, and the OCV durability was obtained using the fuel cell. The test and the output voltage measurement before and after the OCV durability test were performed. The results are shown in Tables 2 and 3.
  • 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 dried laminate is soaked 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 (i) and An electrolyte membrane 7 having a thickness of 20 ⁇ m was obtained, in which the mass ratio of HOSTANOX OSP 1 (polymer (i) / HOSTANOX OSP 1) was 97/3.
  • Example 3 a fuel cell was prepared in the same manner as in Example 3 except that the electrolyte membrane 7 was used instead of the electrolyte membrane 1 obtained in Example 1, and the OCV durability was obtained using the fuel cell. The test and the output voltage measurement before and after the OCV durability test were performed. The results are shown in Tables 2 and 3.
  • Example 5 In Example 3, a fuel cell was prepared in the same manner as in Example 3 except that the electrolyte membrane obtained in Comparative Example 4 was used instead of the electrolyte membrane 1 obtained in Example 1, and the fuel cell was used. The OCV durability test and the output voltage measurement before and after the OCV durability test were performed. The results are shown in Tables 2 and 3.
  • Example 3 a fuel cell was prepared in the same manner as in Example 3 except that the electrolyte membrane obtained in Comparative Examples 1 to 3 was used instead of the electrolyte membrane 1 obtained in Example 1. 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.

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Abstract

L'invention concerne une composition pour membranes d'électrolyte, contenant un polymère (A) possédant un groupe d'échange d'ions et un composé (B1) soluble dans un solvant organique et comprenant un groupe (B') de la formule (B') et un poids moléculaire moyen de 500 ou plus. (Dans la formule, chaque anneau A et chaque anneau B représente indépendamment un groupe ayant une structure cyclique, chacun de RI et RII représente indépendamment un atome d'hydrogène, un atome halogène, un groupe hydroxy, un groupe alkyle ayant de 1 à 12 atomes de carbone, un groupe alkylthio ayant de 1 à 12 atomes de carbone, ou un groupe aryle ayant de 1 à 12 atomes de carbone ; L représente une liaison directe, un atome d'oxygène ou un atome de soufre, et chacun de aI et aII représente indépendamment un entier de 0 à 6.)
PCT/JP2013/056648 2012-04-26 2013-03-11 Composition pour membranes d'électrolyte, membrane d'électrolyte polymère solide, procédé de production de membrane d'électrolyte polymère solide, système membrane-électrode, pile à combustible à polymère solide, cellule d'électrolyse d'eau et système d'électrolyse d'eau WO2013161405A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018159121A (ja) * 2017-03-23 2018-10-11 株式会社東芝 積層電解質膜、膜電極複合体、水電解用セル、スタックおよび水電解装置
JP2019083123A (ja) * 2017-10-30 2019-05-30 株式会社豊田中央研究所 膜−電極−ガス拡散層接合体

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003183526A (ja) * 2001-12-25 2003-07-03 Jsr Corp ポリアリーレン系重合体組成物およびプロトン伝導膜
JP2004134269A (ja) * 2002-10-11 2004-04-30 Toyota Motor Corp 高耐久性高分子電解質、同組成物、および燃料電池
JP2009227979A (ja) * 2008-02-29 2009-10-08 Sumitomo Chemical Co Ltd 高分子電解質組成物
JP2009544786A (ja) * 2006-07-25 2009-12-17 クラリアント ファイナンス （ビーブイアイ） リミティド 溶融加工によるそれらの製造中ポリエチレン製品の改良加工条件

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JP5279294B2 (ja) * 2007-02-21 2013-09-04 旭化成イーマテリアルズ株式会社 高耐久性を有する高分子電解質組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003183526A (ja) * 2001-12-25 2003-07-03 Jsr Corp ポリアリーレン系重合体組成物およびプロトン伝導膜
JP2004134269A (ja) * 2002-10-11 2004-04-30 Toyota Motor Corp 高耐久性高分子電解質、同組成物、および燃料電池
JP2009544786A (ja) * 2006-07-25 2009-12-17 クラリアント ファイナンス （ビーブイアイ） リミティド 溶融加工によるそれらの製造中ポリエチレン製品の改良加工条件
JP2009227979A (ja) * 2008-02-29 2009-10-08 Sumitomo Chemical Co Ltd 高分子電解質組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018159121A (ja) * 2017-03-23 2018-10-11 株式会社東芝 積層電解質膜、膜電極複合体、水電解用セル、スタックおよび水電解装置
JP2019083123A (ja) * 2017-10-30 2019-05-30 株式会社豊田中央研究所 膜−電極−ガス拡散層接合体

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