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WO2011125735A1 - Membrane composite électrolytique polymère solide et son procédé de fabrication - Google Patents

Membrane composite électrolytique polymère solide et son procédé de fabrication Download PDF

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Publication number
WO2011125735A1
WO2011125735A1 PCT/JP2011/058004 JP2011058004W WO2011125735A1 WO 2011125735 A1 WO2011125735 A1 WO 2011125735A1 JP 2011058004 W JP2011058004 W JP 2011058004W WO 2011125735 A1 WO2011125735 A1 WO 2011125735A1
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Prior art keywords
polymer
polymer electrolyte
porous substrate
sulfonic acid
solid polymer
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Japanese (ja)
Inventor
淳司 川井
樋上　誠
康広 坂倉
大月　敏敬
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JSR Corp
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JSR Corp
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    • 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
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
    • 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
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • 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]
    • 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
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • 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
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • 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
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a novel solid polymer electrolyte composite membrane and a method for producing the same.
  • a fuel cell is a power generator that takes out electricity directly by electrochemically reacting hydrogen obtained by reforming hydrogen gas and various hydrocarbon fuels (natural gas, methane, etc.) and oxygen in the air. It is attracting attention as a pollution-free power generation system that can directly convert the chemical energy of fuel into electrical energy with high efficiency.
  • Such a fuel cell is composed of a pair of electrode membranes (anode electrode and cathode electrode) carrying a catalyst and a proton conductive solid polymer electrolyte membrane (hereinafter also referred to as a proton conductive membrane) sandwiched between the electrode membranes. Composed.
  • the catalyst of the anode electrode is divided into hydrogen ions and electrons. The hydrogen ions pass through the solid polymer electrolyte membrane and react with oxygen at the air electrode (cathode electrode) to become water.
  • Solid polymer electrolyte membranes 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 membrane with sulfonic acid group, aromatic hydrocarbon polymer system, polyether ether ketone system, polyphenylene sulfide system, polyimide system, polybenzazole system aromatic ring as main chain skeleton And an aromatic hydrocarbon polymer electrolyte membrane having a sulfonic acid group has been proposed.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2004-345997
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2004-346163
  • Patent Document 3 proposes a polyarylene polymer having a sulfonic acid group.
  • the present inventors have intensively studied to solve the above problems, and as a result, in the solid polymer electrolyte composite membrane comprising a polymer electrolyte membrane and a porous substrate, the polymer electrolyte
  • the membrane contains a polymer having a sulfonic acid group and a fluorine-containing polymer, and the pores of the porous substrate are filled with the polymer having a sulfonic acid group and the fluorine-containing polymer, thereby maintaining proton conductivity.
  • the inventors have found that the durability of the wet and dry cycle can be improved, and have completed the present invention.
  • a solid polymer electrolyte composite membrane comprising a polymer [A] having a sulfonic acid group, a fluoropolymer [B] and a porous substrate [C], wherein the porous substrate [C]
  • the solid polymer electrolyte composite membrane is filled with a polymer [A] having a sulfonic acid group and a fluorine-containing polymer [B].
  • One or more polymer electrolyte membranes are laminated on at least one surface of the porous substrate [C] filled with the polymer [A] having a sulfonic acid group in the pores and the fluoropolymer [B].
  • the solid polymer electrolyte composite membrane according to [1].
  • the fluorine-containing polymer [B] is selected from vinylidene fluoride polymers, tetrafluoroethylene-propylene copolymers, fluorine-containing olefin / vinyl ether copolymers, and fluorine-containing olefin / vinyl ester copolymers.
  • the above [1] to [3], wherein the weight ratio of the polymer [A] having a sulfonic acid group in the proton conducting membrane to the fluoropolymer [B] is 99: 1 to 50:50 ]
  • the solid polymer electrolyte composite membrane in any one of.
  • porous substrate is at least one selected from polyimide, polytetrafluoroethylene, polyolefin, polyacrylonitrile, polyamideimide, polyetherimide, and polyethersulfone. 4].
  • the solid polymer electrolyte composite membrane according to any one of 4).
  • [6] A step of applying a liquid composition containing the polymer [A] having the sulfonic acid group and the fluoropolymer [B] onto a non-porous substrate to form a film, And a step of bringing the porous substrate [C] into contact with the film on the obtained non-porous substrate, the solid content according to any one of the above [1] to [5] A method for producing a molecular electrolyte composite membrane.
  • the above [1] to [5] comprising a step of applying a liquid composition containing the polymer [A] having the sulfonic acid group and the fluoropolymer [B] to the porous substrate [C].
  • a method for producing the solid polymer electrolyte composite membrane according to any one of the above [8] The solid polymer electrolyte composite membrane according to any one of [1] to [5], and a catalyst layer and a gas diffusion layer in contact with both sides of the solid polymer electrolyte composite membrane A membrane-electrode assembly. [9] A polymer electrolyte fuel cell having the membrane-electrode assembly according to [8].
  • the solid polymer electrolyte composite membrane of the present invention is a solid polymer electrolyte composite membrane comprising a polymer [A] having a sulfonic acid group and a porous substrate [C], wherein the porous substrate [
  • a configuration filled with the polymer [A] having a sulfonic acid group and the fluorine-containing polymer [B] in the pores of C] it can be used as a proton conductive membrane having excellent durability. Therefore, the polymer electrolyte fuel cell including the membrane electrode assembly having the solid polymer electrolyte composite membrane of the present invention is excellent in durability and can stably generate power over a long period of time.
  • the solid polymer electrolyte composite membrane of the present invention is a solid polymer electrolyte composite membrane comprising a polymer [A] having a sulfonic acid group, a fluoropolymer [B] and a porous substrate [C], The pores of the porous substrate [C] are filled with a polymer [A] having a sulfonic acid group and a fluorine-containing polymer [B].
  • a solid polymer electrolyte composite membrane having excellent durability while maintaining proton conductivity can be obtained because the deformation of the porous substrate is suppressed during the production of the solid polymer electrolyte composite membrane.
  • Filling is a concept that includes the polymer [A] in which all regions in the pores are not filled with the sulfonic acid group [A] and the fluorine-containing polymer [B] and some voids are generated. is there.
  • the solid polymer electrolyte composite membrane of the present invention is provided on one or both sides of the porous substrate [C] filled with the polymer [A] having a sulfonic acid group in the pores and the fluorine-containing polymer [B].
  • a laminate structure in which one or more polymer electrolyte membranes are further provided may be employed.
  • the polymer electrolyte membrane preferably contains a polymer [A] having a sulfonic acid group, and may further contain a fluorine-containing polymer.
  • the fluorine-containing polymer contained in the polymer electrolyte membrane may be the same as or different from the fluorine-containing polymer filled in the pores of the porous substrate.
  • [A] Polymer having a sulfonic acid group The polymer having a sulfonic acid group is not particularly limited as long as it has been used in a conventional solid polymer electrolyte membrane and has a sulfonic acid group.
  • sulfonic acid to aliphatic hydrocarbon polymers such as polyacetal, polyethylene, polypropylene, acrylic resin, polystyrene, polystyrene-graft-ethylenetetrafluoroethylene copolymer, polystyrene-graft-polytetrafluoroethylene, aliphatic polycarbonate, etc.
  • Group-introduced polymer aliphatic hydrocarbon polymer having sulfonic acid group
  • polyester polysulfone, polyphenylene ether, polyetherimide, aromatic polycarbonate, polyetheretherketone, polyetherketone, polyetherketoneketone , Polyether ether sulfone, polyether sulfone, polycarbonate, polyphenylene sulfide, aromatic polyamide, aromatic polyamideimide, aromatic polyimide, polyben Polymers in which sulfonic acid groups are introduced into aromatic hydrocarbon polymers having an aromatic ring in the main chain such as oxazole, polybenzothiazole, polybenzimidazole, etc. (aromatic hydrocarbon polymers having sulfonic acid groups) are also available It is possible to use.
  • a perfluorinated carbon-based polymer having a sulfonic acid group (which may contain an etheric oxygen atom) can also be used.
  • the perfluorinated carbon-based polymer is not particularly limited, but a perfluorovinyl compound represented by CF 2 ⁇ CF— (OCF 2 CFX) m —O p — (CF 2 ) n —SO 3 H (m is 0 And n represents an integer of 1 to 12, p represents 0 or 1, and X represents a fluorine atom or a trifluoromethyl group.) And a polymerization based on tetrafluoroethylene A copolymer containing units.
  • a polymer in which the polymer terminal is fluorinated by fluorination after polymerization may be used.
  • Examples of the total fluorocarbon polymer having a sulfonic acid group include Nafion (registered trademark, manufactured by DuPont), Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.), Aciplex (manufactured by Asahi Kasei Kogyo Co., Ltd.), etc. Is commercially available.
  • a perfluoroalkyl sulfonic acid polymer combined with polytetrafluoroethylene or a partially fluorinated sulfonated polymer such as polytetrafluoroethylene graft sulfonated polystyrene can also be used.
  • GORE-SELECT manufactured by Japan Gore-Tex
  • a stretched porous polytetrafluoroethylene is impregnated with a polymer having a sulfonic acid group can also be used.
  • an aromatic hydrocarbon polymer having a sulfonic acid group it is preferable to use an aromatic hydrocarbon polymer having a sulfonic acid group.
  • aromatic hydrocarbon polymers having a sulfonic acid group examples include those described in Japanese Patent Application Laid-Open Nos. 2008-247857, 2007-210919, and 2007-91788 by the present applicant. Are illustrated.
  • the aromatic hydrocarbon polymer having a sulfonic acid group used in the present invention includes a structural unit having a sulfonic acid group and a structural unit having an aromatic structure.
  • Ar 11 , Ar 12 , and Ar 13 are each independently at least one selected from the group consisting of a benzene ring, a condensed aromatic ring, and a nitrogen-containing heteroaromatic ring, which may be substituted with a fluorine atom.
  • a divalent group having a structure is shown.
  • Y represents —CO—, —SO 2 —, —SO—, —CONH—, —COO—, — (CF 2 ) u — (u is an integer of 1 to 10), —C (CF 3 ) 2 -Or indicates direct binding.
  • Z is —O—, —S—, a direct bond, —CO—, —SO 2 —, —SO—, — (CH 2 ) l — (l is an integer of 1 to 10), or —C ( CH 3 ) 2 —.
  • R 11 represents a direct bond, —O (CH 2 ) p —, —O (CF 2 ) p —, — (CH 2 ) p — or — (CF 2 ) p — (p is 1 to 12) Indicates an integer).
  • R 12 and R 13 each independently represent a hydrogen atom, an alkali metal atom, an aliphatic hydrocarbon group, an alicyclic group, or a heterocyclic group containing oxygen. However, at least one of all R 12 and R 13 included in the above formula is a hydrogen atom.
  • x 1 is an integer from 0 to 4.
  • x 2 is an integer of 1 to 5.
  • a is an integer of 0 to 1.
  • b represents an integer of 0 to 3.
  • the structural unit having a sulfonic acid group is preferably one represented by the following formula (1-1).
  • Y is —CO—, —SO 2 —, —SO—, —CONH—, —COO—, — (CF 2 ) 1 — (l is an integer of 1 to 10).
  • Z is a direct bond, or — (CH 2 ) 1 — (l is an integer of 1 to 10), C (CH 3 ) 2 —, —O—, —S—, —CO—, —SO 2 — represents at least one structure selected from the group consisting of —SO 3 H or —O (CH 2) p SO 3 H or -O (CF 2) .p showing an aromatic group having a p SO 3 substituents represented by H is an integer of 1 ⁇ 12, m is an integer from 0 to 10 N represents an integer of 0 to 10, and k represents an integer of 1 to 4.)
  • Specific examples of the structural unit having a sulfonic acid group include the following
  • the aromatic hydrocarbon copolymer has an effect of obtaining good durability by having such a structural unit having a sulfonic acid group together with a structural unit having a heterocyclic structure containing nitrogen. Can do.
  • the aromatic hydrocarbon copolymer has a structural unit having an aromatic structure.
  • the structural unit having an aromatic structure is represented by the following formula (2).
  • Ar 21 , Ar 22 , Ar 23 and Ar 24 each independently represent a divalent group having a benzene ring, condensed aromatic ring or nitrogen-containing heteroaromatic ring structure.
  • some or all of the hydrogen atoms may be fluorine-substituted, nitro group, nitrile groups, or some or all of the hydrogen atoms may be halogen-substituted. It may be substituted with at least one atom or group selected from the group consisting of an alkyl group, an allyl group or an aryl group.
  • those not having a substituent displayed on one side mean connection with the adjacent structural unit.
  • a and D are each independently a direct bond or —CO—, —COO—, —CONH—, —SO 2 —, —SO—, — (CF 2 ) 1 — (l is an integer of 1 to 10 A), — (CH 2 ) l — (l is an integer of 1 to 10), —CR ′ 2 — (R ′ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group and a halogenated hydrocarbon group) ), Cyclohexylidene group, fluorenylidene group, —O— or S— B is an oxygen atom or a sulfur atom, s and t each independently represent an integer of 0 to 4, and r represents 0 or an integer of 1 or more.
  • the structural unit having an aromatic structure is preferably one represented by the following formula (2-1).
  • a and D are independently a direct bond or —CO—, —SO 2 —, —SO—, —CONH—, —COO—, — (CF 2 ) l — (l is -C (CF 3 ) 2 -,-(CH 2 ) l- (l is an integer of 1 to 10), -C (CR ' 2 ) 2- (R' is an integer of 1 to 10)
  • Each of R 1 to R 16 may be the same as or different from each other, and may be a hydrogen atom, a fluorine atom, an alkyl group, a halogenated alkyl group partially or wholly halogenated, an allyl group, an aryl group, a nitro group, S and t are at least one atom or group selected from the group consisting of nitrile groups. Represents an integer of ⁇ 4, r is 0 or an integer of 1 or more.) Specific examples of such structural units include the following.
  • Ar 10 represents a divalent group having at least one structure selected from the group consisting of a benzene ring, a condensed aromatic ring, and a nitrogen-containing heteroaromatic ring.
  • Ar 10 is a part of or all of the hydrogen atoms from a fluorine atom, a nitro group, a nitrile group, or an alkyl group, an allyl group or an aryl group in which part or all of the hydrogen atoms may be substituted with fluorine. It may be substituted with at least one atom or group selected from the group consisting of
  • V is not particularly limited as long as it is an electron-withdrawing group, but is preferably selected from the group consisting of —O—, —S—, direct bond, —CO—, —SO 2 — or — or —SO—. It shows at least one selected structure.
  • R s is a direct bond or any divalent organic group that is not particularly limited.
  • the divalent organic group may be any hydrocarbon group having 1 to 20 carbon atoms, and specific examples include an alkylene group such as a methylene group and an ethylene group, and an aromatic ring such as a phenylene group.
  • R s may be a group represented by —W—Ar 9 —.
  • Ar 9 represents a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic group
  • W represents Each independently represents at least one structure selected from the group consisting of a direct bond, —O—, —S—, —CO—, —SO 2 — or — or —SO—.
  • E represents an integer of 0 to 4
  • f represents an integer of 1 to 5.
  • R h represents a nitrogen-containing heterocyclic group, and examples thereof include 5- and 6-membered ring structures containing nitrogen. Further, the number of nitrogen atoms in the heterocycle is not particularly limited as long as it is 1 or more, and the heterocycle may contain oxygen or sulfur in addition to nitrogen.
  • nitrogen-containing heterocyclic group constituting R h examples include pyrrole, thiazole, isothiazole, oxazole, isoxazole, pyridine, imidazole, imidazoline, pyrazole, 1,3,5-triazine, pyrimidine, pyritazine, and pyrazine.
  • nitrogen-containing heterocyclic groups may have a substituent.
  • substituents include alkyl groups such as a methyl group, an ethyl group, and a propyl group, and aryl groups such as a phenyl group, a toluyl group, and a naphthyl group. Group, cyano group, fluorine atom and the like.
  • the structure having a nitrogen-containing heterocyclic group preferably has a structure represented by the following formula (3-1) in the aromatic hydrocarbon copolymer.
  • V, e, f, R s and R h are the same as in the case of the formula (3).
  • those not having a substituent displayed on one side mean connection with the adjacent structural unit.
  • V is preferably —CO— or —SO 2 —.
  • —CO— When —CO— is combined with a pyridine ring, it tends to have a thermally stable structure due to the stabilization effect by conjugation.
  • —SO 2 — lowers the electron density and further suppresses the basicity of nitrogen, whereby proton conductivity in a low humidity region can be particularly increased.
  • the aromatic ring of the main chain and the electron-withdrawing group V are preferably bonded directly from the viewpoint of stability, but an arbitrary divalent group (that is, R s ) is interposed as long as the effect of the present invention is not impaired. You may do it.
  • the intervening structure is not particularly limited as long as it is a divalent organic group having 1 to 20 carbon atoms.
  • A, B, D, V, Y, Z, Ar, Ar 11 , Ar 12 , Ar 13 , Ar 21 to Ar 24 , R 11 to R 13 , R s , R h , a, b, s, t, r, x 1 and x 2 have the same meanings as in the above formulas (1) to (3), respectively.
  • the number of moles of the structural unit represented by the formula (1) possessed by 1 mole of the aromatic hydrocarbon copolymer used in the present invention is (x), and the number of moles of the structural unit represented by the formula (3) is ( y)
  • the value of (x) / ⁇ (x) + (y) + (z) ⁇ ⁇ 100 is preferably 0. 0.05 to 100, more preferably 0.5 to 99.9, and particularly preferably 1 to 90.
  • (y) may be 0.
  • the value of (y) / ⁇ (x) + (y) + (z) ⁇ ⁇ 100 is preferably 0.05 to 99.95. More preferably, it is 0.1 to 99, and particularly preferably 0.5 to 90.
  • the aromatic hydrocarbon polymer having the sulfonic acid group is preferable because it is excellent in suppression of swelling and area change under hot water conditions and is excellent in cross-linking resistance under high temperature conditions.
  • the ratio (y) / (x) of the structural unit represented by the formula (3) and the structural unit represented by the formula (1) is 0.01 to 20, preferably 0.1 to 15, more preferably Is 0.5-10.
  • the ratio of the structural unit represented by the formula (3) to the structural unit represented by the formula (1) is in the above range, the copolymer swells in hot water without decreasing the proton conductivity. Can be suppressed, and heat resistance can be improved.
  • the value of (z) / ⁇ (x) + (y) + (z) ⁇ ⁇ 100 is preferably 0 to 99.5, more preferably 0.01 to 99, and particularly preferably 0. 1 to 98.
  • the molecular weight of the aromatic hydrocarbon polymer having a sulfonic acid group used in the present invention is preferably a polystyrene-converted weight average molecular weight by gel permeation chromatography (GPC), preferably 10,000 to 1,000,000, more preferably 2 It is 10,000 to 800,000, more preferably 50,000 to 300,000.
  • GPC gel permeation chromatography
  • the ion exchange capacity of the aromatic hydrocarbon polymer having a sulfonic acid group is 0.5 to 3.5 meq / g, preferably 0.5 to 3.0 meq / g, more preferably 0.8 to 2.8 meq / g. g is desirable.
  • An ion exchange capacity of 0.5 meq / g or more is preferable because a polymer electrolyte having high proton conductivity and high power generation performance can be obtained.
  • it is 3.5 meq / g or less, it is preferable because sufficiently high water resistance can be provided.
  • the above-mentioned ion exchange capacity can be adjusted by changing the type, usage ratio, and combination of each structural unit. 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 aromatic hydrocarbon polymer having a sulfonic acid group used in the present invention contains, for example, a sulfonic acid ester that becomes a structural unit having a sulfonic acid group by a method described in JP-A-2004-137444. It can be synthesized by copolymerizing a monomer that becomes a structural unit having a nitrogen aromatic ring structure, a monomer that becomes a structural unit having an aromatic structure, or an oligomer, and converting a sulfonic acid ester group into a sulfonic acid group. .
  • Fluoropolymer In the present invention, a solvent-soluble fluoropolymer is preferably used. Such a fluorine-containing polymer is characterized by excellent heat resistance, chemical resistance, mechanical properties, wear resistance and the like, and low gas permeability.
  • the fluoropolymer can be uniformly dispersed in the pores of the solid polymer electrolyte membrane or the porous substrate.
  • a solvent-soluble fluorine-containing polymer is not particularly limited, and examples thereof include vinylidene fluoride homo (co) polymers, fluoroolefin / hydrocarbon olefin copolymers, and fluoroacrylate copolymers. , Fluoroepoxy compounds and the like can be used.
  • the vinylidene fluoride homo (co) polymer is not particularly limited, but for example, polyvinylidene fluoride, vinylidene fluoride and hexafluoropropylene Examples thereof include a copolymer, a copolymer of vinylidene fluoride and tetrafluoroethylene, and a terpolymer of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene.
  • the at least one other monomer copolymerizable with vinylidene fluoride for example, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, hexafluoropropylene, trifluoropropylene, tetrafluoropropylene
  • examples thereof include fluorine-containing monomers such as pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, perfluoro (alkyl vinyl ether) and vinyl fluoride, and non-fluorine monomers such as ethylene, propylene and alkyl vinyl ether.
  • Such polyvinylidene fluoride homo (co) polymers are particularly excellent in high-temperature mechanical properties such as high impact strength and high heat distortion temperature over a wide temperature range, and almost all processing methods can be applied. Since it has characteristics, it is preferable when used in an atmosphere other than a strong oxidizing atmosphere.
  • the fluoroolefin used in the present invention is vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene, tetrafluoroethylene, 1,1-dichloro-2,2-difluoroethylene.
  • Typical examples of the hydrocarbon-based olefin copolymer copolymerizable with the fluoroolefin include carboxylic acid vinyl esters, hydroxyalkyl vinyl ethers or alkyl vinyl ethers.
  • carboxylic acid esters include acetic acid.
  • Linear or branched aliphatic carboxylic acid vinyl esters such as vinyl, vinyl propionate, vinyl butyrate, vinyl bivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl versatate, vinyl laurate or vinyl stearate
  • a vinyl ester of an alicyclic carboxylic acid such as cyclohexanecarboxylic acid vinyl ester; or an aromatic vinyl ester such as vinyl benzoate, vinyl p-tert-butylbenzoate or vinyl salicylate.
  • hydroxyalkyl vinyl ethers include hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether and the like
  • specific examples of the above alkyl vinyl ether include methyl vinyl ether, ethyl vinyl ether, n-propyl. Examples thereof include vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether and tert-butyl vinyl ether.
  • hydrocarbon-based olefin copolymers copolymerizable with fluoroolefins include ⁇ -olefins such as ethylene, propylene or butene; vinyl halides such as vinyl chloride or vinylidene chloride, excluding fluoroolefins ( Vinylidenes); aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-tert-butylstyrene, o-methylstyrene or p-methylstyrene; (ethylenically unsaturated) double bonds such as maleic acid or fumaric acid Mono- or diesters of other basic acids containing; nitrogen-containing vinyl compounds such as (meth) acrylonitrile, (meth) acrylamide, N-methylolated (meth) acrylamide or N-butoxymethyl (meth) acrylamide; or (anhydrous) maleic acid Or (anhydrous) ita (Ethylenically uns
  • the hydrocarbon-based olefin used for such copolymerization is selected from the viewpoint of solubility of the copolymer in a solvent or curing characteristics.
  • the fluoroolefin / hydrocarbon olefin copolymer is not particularly limited.
  • an alternating copolymer of tetrafluoroethylene and propylene an alternating copolymer of tetrafluoroethylene and propylene, or vinylidene fluoride.
  • the molecular weight of the fluorine-containing polymer [B] used in the present invention is preferably 5,000 to 10,000,000 in terms of polystyrene-equivalent weight average molecular weight by gel permeation chromatography (GPC), preferably 30,000 to More preferably, it is 1,000,000, and even more preferably 50,000 to 800,000.
  • the molecular weight of the fluorine-containing polymer [B] is preferably within the above range from the viewpoint of filling the pores of the porous substrate with the fluorine-containing polymer, and while maintaining proton conductivity, the solid polymer electrolyte composite membrane It is preferable at the point which can improve toughness more.
  • the weight ratio of the polymer [A] having a sulfonic acid group and the fluoropolymer [B] in the solid polymer electrolyte composite membrane used in the present invention is 99.5: 0.5 to 50:50, The ratio is preferably 99: 1 to 80:20, more preferably 98: 2 to 90:10. The If the weight ratio of the polymer having a sulfonic acid group and the fluorine-containing polymer is within the above range, the solid polymer electrolyte composite having good proton conductivity, toughness, heat resistance, chemical resistance, mechanical properties, and wear resistance A membrane is obtained.
  • porous substrate In the present invention, a porous substrate is used together with the polymer [A] having a sulfonic acid group and the fluorine-containing polymer [B].
  • the porous substrate is not particularly limited as long as it has a large number of pores or voids penetrating in the thickness direction.
  • organic porous substrates made of various resins, glass, alumina Inorganic porous base materials composed of metal oxides and metals themselves.
  • the porous substrate may have a large number of through holes penetrating in a direction substantially parallel to the thickness direction.
  • JP 2008-119662 A, JP 2007-154153 A, JP 8-20660 A, JP 8-20660 A, JP 2006-120368 A, What was disclosed by Unexamined-Japanese-Patent No. 2004-171994 can be used.
  • an organic porous substrate is preferable, and specifically, polyimide, polytetrafluoroethylene, polyolefin, polyacrylonitrile, polyamideimide, polyetherimide, polyethersulfone. What consists of 1 or more types chosen from the group which consists of is preferable.
  • polyolefin high molecular weight polyethylene, cross-linked polyethylene, polyethylene, polypropylene and the like are desirable.
  • the porous substrate is preferably composed of polytetrafluoroethylene or high molecular weight polyethylene, and more preferably subjected to hydrophilic treatment.
  • high molecular weight polyethylene so-called ultrahigh molecular weight polyethylene having an average molecular weight of 1 ⁇ 10 6 to 7 ⁇ 10 6 is preferable from the viewpoint of mechanical strength.
  • Hydrophilic treatment can be performed by any method.
  • an alkali metal solution is used to modify the polytetrafluoroethylene that constitutes the porous structure, and this treatment modifies the porous membrane surface and imparts hydrophilicity.
  • Such hydrophilic treatment is sometimes referred to as chemical etching.
  • alkali metal solution examples include an organic solvent solution such as tetrahydrofuran, such as methyl lithium, a metal sodium-naphthalene complex, and a metal sodium-anthracene complex, and a solution of metal sodium-liquid ammonia.
  • organic solvent solution such as tetrahydrofuran, such as methyl lithium, a metal sodium-naphthalene complex, and a metal sodium-anthracene complex
  • metal sodium-liquid ammonia examples of the alkali metal solution.
  • hydrophilizing high molecular weight polyethylene it can be hydrophilized by oxygen plasma treatment or the like.
  • the porous base material made of polytetrafluoroethylene or high molecular weight polyethylene thus hydrophilized has high water retention and also has a sulfonic acid group-containing heavy sulfonate group used in the present invention. Since the affinity with the polymer [A] is also high, the polymer [A] having a sulfonic acid group can be filled efficiently.
  • the average pore diameter of the porous base material is 0.005 to 5 ⁇ m, preferably 0.01 to 3 ⁇ m, more preferably 0.1 to 1 ⁇ m, and the porosity is 40 to 95%.
  • the content is preferably 60 to 90%, more preferably 70 to 90%. If it has such characteristics, it is possible to fill the polymer [A] having an appropriate sulfonic acid group, and to increase the strength, durability and heat resistance of the solid polymer electrolyte composite membrane. It becomes possible.
  • the air permeability is preferably 0.1 s / 100 ml or more, more preferably 0.3 s / 100 ml or more, and further preferably 0.5 s / 100 ml or more.
  • the air permeability is preferably 100 s / 100 ml or less, more preferably 50 s / 100 ml or less, and further preferably 20 s / 100 ml or less from the viewpoint of proton conductivity.
  • the average pore diameter is measured by a bubble point method (ASTM F316-03, JIS K 3832).
  • the air permeability (sec / 100 cc) is measured by the Gurley tester method (JIS P8117).
  • the porosity (%) is represented by (1 ⁇ density 2 / density 1) ⁇ 100.
  • the density 1 refers to the material constituting the porous substrate (for example, polytetrafluoroethylene in the case of a porous substrate made of polytetrafluoroethylene, high molecular weight polyethylene in the case of a porous substrate made of high molecular weight polyethylene).
  • the density 2 is the density of the entire porous substrate including the voids of the porous substrate.
  • the thickness of the porous substrate is desirably 1 to 150 ⁇ m, preferably 5 to 100 ⁇ m, and more preferably 10 to 50 ⁇ m. Within this range, the strength, durability and heat resistance of the solid polymer electrolyte composite membrane can be increased.
  • the porous substrate may be a laminate of two or more types having different pore diameters.
  • the solid polymer electrolyte composite membrane according to the present invention may contain a metal compound or a metal ion in addition to the above components.
  • metal compounds or metal ions include aluminum (Al), manganese (Mn), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W) iron, iron (Fe), Ruthenium (Ru), nickel (Ni), tin (Sn), palladium (Pd), platinum (Pt), silver (Ag), cerium (Ce), vanadium (V), neodymium (Nd), praseodymium (Pr), Examples thereof include metal compounds such as samarium (Sm), cobalt (Co), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), and erbium (Er), or metal ions thereof.
  • the solid polymer electrolyte composite membrane according to the present invention is produced using a liquid composition containing the polymer [A] having a sulfonic acid group and the fluoropolymer [B] and a porous substrate [C]. Can do.
  • the polymer formed on the non-porous substrate and the thickness of the porous substrate [C] are appropriately adjusted, whereby the polymer [A] having the sulfonic acid group in the pores and the fluorine-containing material
  • a laminated structure in which one or more polymer electrolyte membranes are provided on at least one surface of the porous substrate [C] filled with the polymer [B] can be obtained.
  • a liquid composition containing the polymer [A] having the sulfonic acid group and the fluorine-containing polymer [B] is applied to the porous substrate [C], and the sulfonic acid group is added.
  • Examples thereof include a method (second embodiment) for obtaining a porous substrate [C] in which pores are filled with a polymer and a fluorine-containing polymer.
  • the inside of the pores is the polymer [A] having the sulfonic acid group and the fluorine-containing polymer [B].
  • a laminated structure in which one or more polymer electrolyte membranes are provided on at least one surface of the filled porous substrate [C] can be obtained.
  • the above embodiments can be used in combination. Specifically, after performing the first embodiment, the method of performing the second embodiment, and the method of performing the first embodiment after performing the second embodiment, after performing the first embodiment The method of performing the second embodiment is preferably used.
  • the composition containing a fluoropolymer [B] when performing combining a 1st aspect and a 2nd aspect, what is necessary is just to use the said liquid composition containing a fluoropolymer [B] when forming at least 1 layer.
  • the fluorine-containing polymer [B] when the fluorine-containing polymer [B] is contained in a film that has already been formed, the composition containing a polymer having a sulfonic acid group that is subjected to coating or hot pressing for laminating includes a fluorine-containing polymer. The polymer may not be contained.
  • a liquid composition containing the fluorine-containing polymer according to the present invention may be used as a composition to be applied or hot pressed for lamination.
  • a composition containing a polymer having no fluorinated polymer [B] and having a sulfonic acid group is applied to form a multilayer structure, or hot-pressed into a film made of the composition. Before or after, it may be immersed in a solution containing a fluorine-containing polymer.
  • the non-porous substrate is not particularly limited as long as it is a substrate used in an ordinary solution casting method, and for example, a substrate made of plastic, metal, etc. is used, preferably A base material made of a thermoplastic resin such as a polyethylene terephthalate (PET) film is used.
  • a substrate used in an ordinary solution casting method for example, a substrate made of plastic, metal, etc. is used, preferably A base material made of a thermoplastic resin such as a polyethylene terephthalate (PET) film is used.
  • PET polyethylene terephthalate
  • the liquid composition preferably contains a solvent in addition to the polymer having a sulfonic acid group and the fluoropolymer.
  • the solvent may be any solvent that dissolves or swells the polymer having a sulfonic acid group.
  • the composition of the mixture is 95 to 25% by mass of the aprotic polar solvent, preferably 90 to 25% by mass,
  • the solvent is 5 to 75% by mass, preferably 10 to 75% by mass (however, the total is 100% by mass).
  • the amount of the other solvent is within the above range, the effect of lowering the solution viscosity is excellent.
  • N-methyl-2-pyrrolidone is preferred as the aprotic polar solvent, and methanol having an effect of lowering the solution viscosity in a wide composition range is preferred as the other solvent. .
  • the liquid composition according to the present invention may be one in which both the polymer having a sulfonic acid group and the fluorine-containing polymer are dissolved, or at least one of them is dispersed without being dissolved. Although it may be a mixture with a dispersion, it is preferable that both the polymer having a sulfonic acid group and the fluoropolymer are dissolved.
  • the concentration of the polymer having a sulfonic acid group in the liquid composition is preferably 5 to 40% by mass, more preferably 7 to 25% by mass, although it depends on the molecular weight. If it is less than 5% by mass, it is difficult to form a thick film, and pinholes are easily generated. On the other hand, if it exceeds 40% by mass, the solution viscosity is too high to form a film, and surface smoothness may be lacking.
  • the concentration of the fluorine-containing polymer in the liquid composition is preferably 0.05 to 40% by mass, more preferably 0.5 to 10% by mass.
  • the solution viscosity depends on the molecular weight of the polymer having a sulfonic acid group, the polymer concentration, and the concentration of the additive, but is preferably 2,000 to 100,000 mPa ⁇ s, more preferably 3,000 to 50,000 mPa ⁇ s. If the viscosity is low, the retention of the solution during film formation is poor, and it may flow from the substrate. On the other hand, if the viscosity is too high, film formation by the casting method may be difficult.
  • the liquid composition according to the present invention can be prepared by mixing a polymer having a sulfonic acid group and a fluorine-containing polymer in the solvent. Specifically, after the polymer having a sulfonic acid group is dissolved or dispersed in the solvent, the fluorine-containing polymer is mixed with the polymer, or the fluorine-containing polymer is dissolved or dissolved in the solvent. A method of dissolving or dispersing a polymer having a sulfonic acid group after the dispersion is exemplified.
  • a known method can be employed, and examples thereof include spray coating, knife coating, roll coating, spin coating, and gravure coating.
  • this method it is possible to apply different polymer solutions to one side and the other side of the porous substrate, and the thickness of the polymer layer may be adjusted by adjusting the coating amount.
  • one polymer layer may be thick and the other thin.
  • the organic solvent in the undried film can be replaced with water, and the amount of residual solvent in the obtained solid polymer electrolyte membrane Can be reduced.
  • the undried film may be preliminarily dried before the undried film is immersed in water.
  • the preliminary drying is carried out by holding the undried film at a temperature of preferably 50 to 150 ° C. for 0.1 to 10 hours.
  • a liquid composition containing a polymer having a sulfonic acid group may be further applied to form a solid polymer electrolyte membrane in a multilayer structure.
  • the amount of residual solvent in the film thus obtained is preferably 5% by mass or less.
  • the amount of residual solvent in the obtained film can be set to 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 undried film
  • the temperature of the water during immersion is 10 to 60 ° C.
  • the immersion time is 10 minutes to 10 hours. is there.
  • the film After immersing the undried film in water as described above, the film is preferably dried at 30-100 ° C., more preferably 50-80 ° C., preferably 10-180 minutes, more preferably 15-60 minutes, and then The film can be obtained by vacuum drying at 50 to 150 ° C., preferably under reduced pressure of 500 mmHg to 0.1 mmHg for 0.5 to 24 hours.
  • the dry film thickness of the solid polymer electrolyte membrane obtained by the method of the present invention is preferably 10 to 100 ⁇ m, more preferably 20 to 80 ⁇ m.
  • the membrane-electrode assembly is a membrane-electrode assembly comprising the solid polymer electrolyte membrane, a catalyst layer, and a gas diffusion layer.
  • a catalyst layer for the cathode electrode is provided on one side of the solid polymer electrolyte membrane
  • a catalyst layer for the anode electrode is provided on the other side, and each of the catalyst layers on the cathode side and the anode side is further provided.
  • Gas diffusion layers are provided on the cathode side and the anode side, respectively, in contact with the side opposite to the solid polymer electrolyte membrane.
  • gas diffusion layer and the catalyst layer known ones can be used without particular limitation.
  • the gas diffusion layer is composed of 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 substrate and a microporous layer
  • the microporous layer is provided in contact with the catalyst layer.
  • the gas diffusion layers on the cathode side and the anode side preferably contain a fluoropolymer in order to impart water repellency.
  • the catalyst layer is composed of a catalyst and an ion exchange resin electrolyte.
  • a noble metal catalyst such as platinum, palladium, gold, ruthenium or iridium is preferably used.
  • the noble metal catalyst may contain two or more elements such as an alloy or a mixture.
  • a catalyst supported on carbon particles having a high specific surface area can be preferably used.
  • the ion exchange resin electrolyte functions as a binder component for binding the carbon carrying the catalyst, and at the anode electrode, efficiently supplies ions generated by the reaction on the catalyst to the solid polymer electrolyte membrane. Then, ions supplied from the solid polymer electrolyte membrane are efficiently supplied to the catalyst.
  • a polymer having a proton exchange group is preferable 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.
  • such a polymer having a proton exchange group is also selected without any particular limitation, but a polymer having a proton exchange group composed of a fluoroalkyl ether side chain and a fluoroalkyl main chain, a sulfonic acid group
  • An aromatic hydrocarbon polymer having the same is preferably used.
  • an aromatic hydrocarbon polymer having a sulfonic acid group constituting the solid polymer electrolyte membrane may be used as an ion-exchange resin, and a polymer containing a fluorine atom having a proton exchange group or ethylene Or other polymers obtained from styrene or the like, copolymers or blends thereof.
  • an ion exchange resin electrolyte a known one can be used without particular limitation, and for example, Nafion (DuPont, registered trademark), an aromatic hydrocarbon polymer having a sulfonic acid group or the like can be used without any particular limitation. .
  • the catalyst layer used in the present invention may further include a resin having no carbon fiber or ion exchange group.
  • resins are preferably resins with high water repellency.
  • fluorine-containing copolymers, silane coupling agents, silicone resins, waxes, polyphosphazenes and the like can be mentioned, and fluorine-containing copolymers are preferred.
  • the polymer electrolyte fuel cell according to the present invention is characterized by including the membrane-electrode assembly. Specifically, at least one electricity generating part including at least one membrane-electrode assembly and separators located on both sides thereof; a fuel supply part for supplying fuel to the electricity generating part; and an oxidant for the electricity A fuel cell including an oxidant supply unit for supplying to a generation unit, wherein the membrane-electrode assembly is as described above.
  • separator used in the fuel cell of the present invention those used in ordinary fuel cells can be used. Specifically, carbon type or metal type can be used.
  • a known member can be used without any particular limitation.
  • the battery of the present invention can be used as a single cell or as a stack in which a plurality of single cells are connected in series.
  • a stacking method a known method can be used. Specifically, planar stacking in which single cells are arranged in a plane and bipolar stacking in which single cells are stacked via separators each having a fuel or oxidant flow path formed on the back surface of the separator can be used. .
  • the flask was placed in an oil bath and heated to reflux 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 200 ° C. for 3 hours.
  • 12.3 g (0.072 mol) of 2,6-dichlorobenzonitrile was added and reacted for another 5 hours.
  • the resulting reaction solution was allowed to cool and then diluted by adding 100 ml of toluene.
  • the precipitate of the inorganic compound produced as a by-product was removed by filtration, and the filtrate was put into 2 L of methanol.
  • the precipitated product was separated by filtration, collected, dried, and dissolved in 250 ml of tetrahydrofuran. This was reprecipitated in 2 L of methanol to obtain 107 g of the objective compound.
  • the number average molecular weight in terms of polystyrene determined by GPC (solvent: tetrahydrofuran) of the obtained target compound was 7,300.
  • the obtained compound was an oligomer represented by the following structural formula.
  • the reaction system was heated with stirring (finally heated to 82 ° 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 175 mL of DMAc, stirred for 30 minutes, and filtered using Celite as a filter aid. Lithium bromide (24.4 g, 281 mmol) was added to the filtrate in 1/3 portions at 1-hour intervals through a 1-L three-neck equipped with a stirrer, and the internal temperature was 120 ° C. for 5 hours. Reacted below. After the reaction, the mixture was cooled to room temperature, poured into 4 L of acetone and solidified.
  • the coagulum was collected by filtration, air-dried, pulverized with a mixer, and washed with 1500 mL of 1N sulfuric acid while stirring. After filtration, the product is washed with ion-exchanged water until the pH of the washing solution becomes 5 or higher, and then dried at 80 ° C. overnight, and 38.0 g of a polymer having a sulfonic acid group into which a target basic unit has been introduced.
  • the ion exchange capacity of this polymer was 2.33 meq / g.
  • the obtained polymer having a sulfonic acid group is a compound (polymer A) represented by the following structural formula.
  • the separated organic layer was washed successively with 740 mL of water, 740 mL of 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). The solvent was distilled off from the resulting eluate under reduced pressure.
  • 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 structural formula in a yield of 82.1%.
  • the reaction mixture was added to 60 mL of methanol, and then 60 mL of 6 mol / L hydrochloric acid was added and stirred for 1 hour.
  • the precipitated solid was separated by filtration and dried to obtain 1.62 g of an off-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 N-methyl-2-pyrrolidone (NMP) and reacted at 120 ° C. for 24 hours. .
  • the reaction mixture was poured into 560 mL of 6 mol / L hydrochloric acid 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 ion exchange capacity of this polymer was 1.95 meq / g.
  • the obtained polymer having a sulfonic acid group is a compound (polymer B) represented by the following structural formula.
  • NMP N-methyl-2-pyrrolidone
  • a high molecular weight polyethylene porous substrate (manufactured by Lydall, SOLUPOR (registered trademark), 3P07A; air permeability of 1.4 s / 50 ml, porosity of 83%, thickness of 20 ⁇ m) is contacted on the coating solution. I let you. Further, the solution was cast again from above the porous substrate, and the coating solution was impregnated from both sides of the porous substrate. Next, after preliminary drying at 80 ° C. for 40 minutes, drying was performed at 120 ° C. for 40 minutes.
  • the anode electrode paste is applied with a doctor blade using a mask having an opening of 5 cm ⁇ 5 cm on one side of the polymer electrolyte membrane, and the surface not coated with the electrode paste has an opening of 5 cm ⁇ 5 cm.
  • the cathode electrode paste was applied with a doctor blade using a mask. This was dried at 120 ° C. for 60 minutes. The amount of catalyst applied to each electrode catalyst layer was 0.50 mg / cm 2 .
  • GDL24BC manufactured by SGL CARBON was used as the gas diffusion layer.
  • Electrode membrane having the electrode catalyst layer formed on both sides is sandwiched between two gas diffusion layers and hot press molded under a pressure of 60 kg / cm 2 and at 130 ° C. for 20 minutes to produce a membrane-electrode assembly. did.
  • a separator also serving as a gas flow path is laminated on both sides of the obtained electrode-membrane assembly, sandwiched between two current collectors made of titanium, and a heater is further disposed on the outside thereof to evaluate an effective area of 25 cm 2 .
  • a fuel cell was prepared.
  • the obtained solid polymer electrolyte composite membrane is processed into a strip-shaped membrane sample having a width of 5 mm, a platinum wire (diameter 0.5 mm) is pressed against the surface of the sample, the sample is held in a constant temperature and humidity device, and platinum
  • the AC resistance was obtained from the AC impedance measurement between the lines. That is, the impedance at AC 10 kHz was measured in an environment of 75 ° C. and relative humidity 70%.
  • a chemical impedance measurement system manufactured by NF Circuit Design Block Co., Ltd. was used as the resistance measurement device, and JW241 manufactured by Yamato Scientific Co., Ltd. was used as the constant temperature and humidity device.
  • NMP N-methyl-2-pyrrolidone
  • a polytetrafluoroethylene porous substrate manufactured by Donaldson Japan, Tetlatex, TX1316; air permeability of about 5.3 s / 100 ml, pore size of 0.07 ⁇ m, porosity of about 85% , 18 ⁇ m thick. Further, the solution was cast again from above the porous substrate, and the coating solution was impregnated from both sides of the porous substrate. Next, after preliminary drying at 80 ° C. for 40 minutes, drying was performed at 120 ° C. for 40 minutes.
  • NMP N-methyl-2-pyrrolidone
  • 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. Further, the solution was cast again from above the porous substrate, and the coating solution was impregnated from both sides of the porous substrate. Next, after preliminary drying at 80 ° C. for 40 minutes, drying was performed at 120 ° C. for 40 minutes.
  • NMP N-methyl-2-pyrrolidone
  • a high molecular weight polyethylene porous substrate (manufactured by Lydall, SOLUPOR (registered trademark), 3P07A; air permeability of 1.4 s / 50 ml, porosity of 83%, thickness of 20 ⁇ m) is contacted on the coating solution. I let you. Further, the solution was cast again from above the porous substrate, and the coating solution was impregnated from both sides of the porous substrate. Next, after preliminary drying at 80 ° C. for 40 minutes, drying was performed at 120 ° C. for 40 minutes.

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Abstract

L'invention concerne une membrane composite électrolytique polymère solide convenant tout particulièrement à une pile à combustible du type à polymère solide du fait de sa durabilité et de sa capacité à produire de l'énergie électrique de façon stable et prolongée. L'invention concerne également un ensemble membrane/électrodes et une pile à combustible du type à polymère solide l'utilisant. La membrane composite électrolytique polymère solide comprend un polymère [A] à groupes acide sulfonique et un substrat poreux [C]. Les pores du substrat poreux [C] sont remplis du polymère [A] à groupes acide sulfonique et d'un polymère contenant du fluor [B]. L'invention concerne en outre un ensemble membrane/électrodes comprenant la membrane composite électrolytique polymère solide et une couche catalytique et une couche de diffusion venant au contact des deux côtés de la membrane composite électrolytique polymère solide. L'invention concerna aussi une pile à combustible du type à polymère solide comprenant l'ensemble membrane/électrodes.
PCT/JP2011/058004 2010-03-31 2011-03-30 Membrane composite électrolytique polymère solide et son procédé de fabrication Ceased WO2011125735A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101579001B1 (ko) * 2013-04-29 2015-12-18 주식회사 엘지화학 고분자 전해질막, 고분자 전해질막을 포함하는 막전극 접합체 및 막 전극 접합체를 포함하는 연료전지
CN115672039A (zh) * 2022-10-25 2023-02-03 东华大学 一种ptfe微孔膜/二维纳米纤网复合膜及其制备和应用

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