WO2009035131A1 - Procédé servant à produire une membrane de polyélectrolyte, membrane de polyélectrolyte, assemblage membrane-électrode et pile à combustible - Google Patents

Procédé servant à produire une membrane de polyélectrolyte, membrane de polyélectrolyte, assemblage membrane-électrode et pile à combustible Download PDF

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WO2009035131A1
WO2009035131A1 PCT/JP2008/066805 JP2008066805W WO2009035131A1 WO 2009035131 A1 WO2009035131 A1 WO 2009035131A1 JP 2008066805 W JP2008066805 W JP 2008066805W WO 2009035131 A1 WO2009035131 A1 WO 2009035131A1
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group
polymer electrolyte
electrolyte membrane
block
carbon atoms
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PCT/JP2008/066805
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English (en)
Japanese (ja)
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Hirohiko Hasegawa
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Sumitomo Chemical Company, Limited
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H01M8/109—After-treatment of the membrane other than by polymerisation thermal other than drying, e.g. sintering
    • 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
    • C08J5/2287—After-treatment
    • 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
    • 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
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • 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
    • H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
    • 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
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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 method for producing a polymer electrolyte membrane, a polymer electrolyte membrane obtained by the production method, a membrane-one-electrode assembly and a fuel cell using the polymer electrolyte membrane. More specifically, a method for producing a polymer electrolyte membrane suitable for a direct methanol fuel cell, a polymer electrolyte membrane obtained by the production method, a membrane-electrode assembly using the polymer electrolyte membrane, and It relates to fuel cells.
  • Background art a method for producing a polymer electrolyte membrane suitable for a direct methanol fuel cell, a polymer electrolyte membrane obtained by the production method, a membrane-electrode assembly using the polymer electrolyte membrane, and It relates to fuel cells.
  • polymer electrolyte fuel cells have attracted attention as energy devices for housing and automobile power.
  • direct methanol fuel cells using methanol as fuel are attracting attention as power sources for personal computers and portable devices because of their small size.
  • a fuel cell is composed of basic minimum units called cells.
  • Each unit cell is composed of an electrolyte membrane, a catalyst layer provided on both sides of the electrolyte membrane, and a gas diffusion layer provided outside the catalyst layer.
  • Each unit cell is separated and stacked by a separator provided outside the gas diffusion layer to constitute one fuel cell.
  • the catalyst layer provided on both sides of the electrolyte membrane, or the catalyst layer and the gas diffusion layer constitute an electrode part of the unit cell, and fuel (hydrogen molecule, methanol aqueous solution, etc.) is supplied to one electrode part (anode)
  • fuel hydrogen molecule, methanol aqueous solution, etc.
  • an acid-rich reaction occurs in the catalyst layer, and hydrogen ions and electrons are released.
  • Hydrogen ions enter the electrolyte membrane and move in the direction of the other electrode part (force sword) in the electrolyte membrane.
  • the electrons reach the external circuit through the anode, and reach the catalyst layer on the power sword side through the external circuit.
  • the electrode in the unit cell of the fuel cell as described above may indicate only the catalyst layer, or may indicate a joined body of the catalyst layer and the gas diffusion layer.
  • MEA MembraneElectrodeAssembly
  • the membrane-electrode assembly means a catalyst layer or an assembly in which an electrolyte membrane is sandwiched between a catalyst layer and a gas diffusion layer. That is, the membrane-electrode assembly is an assembly in which at least a catalyst layer is formed on both surfaces of the electrolyte membrane.
  • a fuel cell has a principle of directly extracting electric power and heat from a fuel (hydrogen or methanol aqueous solution) and oxygen (air) by an electrochemical reaction, while an electrolyte serving as a passage for hydrogen ions (protons). It is classified into multiple types according to the type.
  • the polymer electrolyte fuel cell is mainly composed of a perfluoroalkane polymer electrolyte membrane represented by “Nafion J (a registered trademark of DuPont)” (fluorine resin ion exchange).
  • Nafion J a registered trademark of DuPont
  • fluorine resin ion exchange fluorine resin ion exchange
  • a methanol aqueous solution is used as the fuel, and direct methanol fuel cells (DMFC: Dielectric Me thanol Fuel 1 Ce 1 1) are handled because the fuel is liquid. It is easy to use and requires no auxiliary equipment such as a humidifier, so it can be downsized and is attracting attention as a battery source for portable equipment such as personal computers and mobile phones.
  • DMFC Dielectric Me thanol Fuel 1 Ce 1 1
  • a direct methanol fuel cell supplies an aqueous methanol solution as fuel to the anode (fuel electrode). Therefore, the anode (fuel electrode) and the power sword (empty Polymer electrolyte membrane (proton conductive membrane) between the gas electrode and the electrode ⁇ Phenomena in which methanol passes through the polymer electrolyte membrane and moves into a force sword when the barrier property to methanol (methanol paraffinity) is low Occurs.
  • This phenomenon is called methanol crossover (MCO), and if a phenomenon occurs, power generation performance deteriorates or methanol leaks from the power sword, causing damage to the battery itself. Such a problem may occur.
  • MCO methanol crossover
  • the perfluoroalkane polymer electrolyte membranes used in conventional solid polymer fuel cells have low methanol barrier properties and are susceptible to methanol crossover. If the fuel cell configuration is directly applied to a methanol fuel cell, sufficient power generation performance cannot be obtained.
  • the present invention provides a method for producing a polymer electrolyte membrane capable of achieving both high methanol barrier properties and proton conductivity, a polymer electrolyte membrane obtained by the production method, and the polymer electrolyte.
  • a membrane-one electrode assembly and a fuel cell using a membrane are provided.
  • the present invention provides the following inventions.
  • the hydrocarbon block-type polymer electrolyte used in the production method of the present invention is also simply referred to as a polymer electrolyte.
  • the polymer electrolyte membrane obtained in the production method of the present invention is a hydrocarbon block type polymer electrolyte membrane obtained from a hydrocarbon block type polymer electrolyte. It is called a membrane.
  • a block copolymer comprising the hydrocarbon-based block-type polyelectrolyte power, a block having a cation exchange group, and a block having substantially no ion exchange group.
  • the block having a cation exchange group has the following general formula (1)
  • Ar 11 represents a divalent aromatic group
  • the divalent aromatic group is a C 1-20 alkyl group which may have a substituent
  • An optionally substituted alkoxy group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, and an optionally substituted carbon number 6 May have at least one selected from the group consisting of an aryloxy group of ⁇ 20, and an acyl group of 2 to 20 carbon atoms which may have a substituent.
  • X 11 is a direct bond
  • a group represented by 1-O a group represented by 1S-
  • d is an integer of 5 or more.
  • each R 1 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms.
  • X 12 is a direct bond, a group represented by 1O—, a group represented by 1S—, a carbo Represents a dil group or a sulfonyl group, J 1 represents a cation exchange group, and p and q are 1 or 2
  • d is an integer greater than or equal to 5.
  • Ar 22 represents a divalent aromatic group, and the divalent aromatic group is a carbon number:! -20 alkyl group, a carbon number 1-20 alkoxy group, a carbon number It may have at least one selected from the group consisting of an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms, and X 22 is directly A bond, a group represented by 1 O—, a group represented by 1 S—, a carbonyl group or a sulfole group, and e is an integer of 5 or more.
  • Ar 2 , Ar 3 , Ar 4 and Ar 5 independently represent a divalent aromatic group, and the divalent aromatic group is an alkyl group having 1 to 20 carbon atoms. And at least one selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or an acyl group having 2 to 20 carbon atoms.
  • X and X ′ each independently represent a direct bond or a divalent group
  • the table A, b and c each independently represent 0 or 1, and n represents an integer of 5 or more.
  • a membrane-one-electrode assembly comprising the polymer electrolyte membrane according to [10] and a catalyst layer provided on both surfaces of the polymer electrolyte membrane.
  • a polymer electrolyte solution containing a hydrocarbon block type polymer electrolyte and a solvent is formed into a membrane to obtain a solvent-containing block type polymer electrolyte membrane (membrane) Process).
  • the solvent-containing block type polymer electrolyte membrane is heated (heat treatment step) to obtain a polymer electrolyte membrane for a fuel cell.
  • the following is a method for forming a hydrocarbon block polymer electrolyte, a method for forming a polymer electrolyte solution containing the polymer electrolyte and a solvent, a method for heat-treating a filmed solvent-containing block-type polymer electrolyte membrane, and heat treatment
  • the polymer electrolyte membrane obtained by the above, and the membrane-electrode assembly and fuel cell obtained using this polymer electrolyte membrane will be described.
  • hydrocarbon block type polymer electrolyte (simply a polymer)
  • electrolyte refers to a block copolymer having a cation exchange group and 50% or more of the total number of atoms composed of carbon and hydrogen.
  • “Plock-type polymer electrolyte” refers to an electrolyte composed of a copolymer in which two or more types of Plock forces having different chemical properties are bonded directly or through a linking group.
  • the copolymer constituting the polymer electrolyte is substantially free of an ion exchange group and a block having a cation exchange group as two or more types of chemically different properties.
  • a block copolymer having a block is preferable.
  • the block copolymer has a block having a cation exchange group and a block having substantially no ion exchange group, the effect of the present invention is remarkably exhibited.
  • the polymer electrolyte preferably contains an aromatic block copolymer from the viewpoint of heat resistance and ease of recycling.
  • the aromatic block copolymer means a block copolymer having an aromatic ring in the main chain of the polymer chain and having a cation exchange group in the side chain and Z or the main chain of the polymer chain.
  • a solvent-soluble one is usually used. It is preferable that it is soluble in a solvent because it can be easily formed into a film by a known solution casting method.
  • the cation exchange group of these aromatic block copolymers may be directly substituted on the aromatic ring constituting the main chain of the polymer, and is linked to the aromatic ring constituting the main chain. It may be linked through a group or a combination thereof.
  • the polymer electrolyte is preferably one in which at least 10% or more of the cation exchange group is in a proton type.
  • the cation exchange group is preferably a sulfonic acid group, a phosphonic acid group, or a sulfonyl imide group. Among these, a sulfonic acid group in which the cation exchange group is a strong acid group is more preferable.
  • the polymer electrolyte may have one of these, or may have two or more of these.
  • the polymer electrolyte is preferably one that forms a Mikuguchi phase separation structure when filmed.
  • a polymer electrolyte that forms such a Mikuguchi phase separation structure is used, the effects of the present invention Appears prominently.
  • “microphase separation structure” means that when polymer electrolyte is made into a membrane, different polymer segments are bonded by chemical bonds, resulting in microscopic phase separation on the order of molecular chain size. Refers to the structure formed by For example, when observed with a transmission electron microscope (TEM), a fine phase (microdomain) having a high density of a block having a cation exchange group and a density of a block having substantially no ion exchange group are present.
  • TEM transmission electron microscope
  • the identity period is several nm to several OO nm.
  • the identity period is 5 ⁇ ⁇ ! ⁇ 100 nm is preferred.
  • block copolymer examples include “a block copolymer having a sulfonated aromatic polymer block” described in JP-A-2001-250567, JP-A-2003-31232, “Polyetherketone, polyethersulfone has a main chain structure and a block having a sulfonic acid group” described in JP-A-2004-359925, JP-A-2005-232439, JP-A-2003-113136, etc. "Plock copolymer”.
  • the block having a cation exchange group is preferably a block including a structure in which a plurality of structural units represented by the following general formula (1) are linked, cation exchange groups is preferably at 0.5 or more on average, and more preferably an average of 1. is 0 or more Re, 0
  • Ar 11 represents a divalent aromatic group
  • the divalent aromatic group represents a C 1-20 alkyl group which may have a substituent, or a substituent.
  • Group, extension, setting The divalent aromatic group may have at least one selected from the group consisting of an acyl group having 2 to 20 carbon atoms which may have a substituent.
  • a cation exchange group is directly bonded to the aromatic ring
  • X 11 represents a direct bond, a group represented by 1 O—, a group represented by 1 S—, a carbo group or a sulfonyl group
  • d is An integer greater than or equal to 5.
  • alkyl group having 1 to 20 carbon atoms that may have the substituent include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and an isoptyl group.
  • N-pentyl group 2,2-dimethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, 2-methylpentyl group, 2-ethylhexyl group, nor group, decyl group, Alkyl groups having 1 to 20 carbon atoms such as dodecyl group, hexadecyl group, adamantyl group, and icosyl group, and these groups include fluorine atom, hydroxyl group, nitryl group, amino group, methoxy group, ethoxy group An isopropyloxy group, a phenyl group, a naphthyl group, a phenoxy group, a naphthyloxy group, and the like, and an alkyl group having 1 to 20 carbon atoms in total.
  • alkoxy group having 1 to 20 carbon atoms which may have the substituent include, for example, a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, a sec group.
  • aryl group having 6 to 20 carbon atoms which may have the above substituent include aryl groups such as phenyl group, naphthyl group, anthracenyl group, biphenyl group, and the like. These groups are substituted with fluorine atoms, hydroxyl groups, nitrile groups, amino groups, methoxy groups, ethoxy groups, isopropyloxy groups, phenol groups, naphthyl groups, phenoxy groups, naphthyloxy groups, etc.
  • Aryl groups with 6 to 20 carbon atoms are listed.
  • aryloxy group having 6 to 20 carbon atoms which may have a substituent include, for example, aryloxy groups such as phenoxy group, naphthyloxy group, anthraceroxy group, biphenyloxy group, and the like, and these groups Is substituted with fluorine atom, hydroxyl group, nitrile group, amino group, methoxy group, ethoxy group, isopropyloxy group, phenyl group, naphthyl group, phenoxy group, naphthyloxy group, etc., and the total carbon number is 6 ⁇ 2 And 0 aryloxy group.
  • aryloxy groups such as phenoxy group, naphthyloxy group, anthraceroxy group, biphenyloxy group, and the like, and these groups Is substituted with fluorine atom, hydroxyl group, nitrile group, amino group, methoxy group, ethoxy group, isopropyloxy group, phenyl group, naphth
  • acyl group having 2 to 20 carbon atoms which may have the substituent include, for example, an acetyl group, a propiol group, a butyryl group, an isoptylyl group, a benzoyl group, 1 a naphthoyl group, and a 2-naphthoyl group.
  • Examples include an acyl group substituted with a phenoxy group, a naphthyloxy group, or the like, and having a total carbon number of 20 or less.
  • d is an integer of 5 or more that represents the degree of polymerization of the block, 5 to: 100 is preferable, more preferably 10 to 100, and particularly preferably 20 to 5 0 0.
  • a value of d of 5 or more is preferred because the proton conductivity is sufficient as a polymer electrolyte for fuel cells.
  • the value of d is 1 00 0 0 or less, it is preferable because the production of the block is easier.
  • the block having a cation exchange group is more preferably a block represented by the following general formula (2) or (3).
  • each R 1 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 2 carbon atoms.
  • X 12 is a direct bond, a group represented by ____, a group represented by S-, a carbo group or a sulfol group.
  • J 1 represents a cation exchange group
  • p and q are 1 or 2
  • d is an integer of 5 or more.
  • R 1 represents a substituent as described above.
  • a phenylene group or a naphthalenedyl group has substantially no substituent other than a cation exchange group, and is preferably a hydrogen atom. More preferred.
  • the cation exchange group represented by a sulfonic acid group can be represented by the following formulas (2 a-1) to (2 a-3 0).
  • Examples thereof include a block in which d structural units selected from the group consisting of the structural units shown are connected.
  • d is the number of definitions equivalent to d in the above general formula (2), that is, an integer of 5 or more.
  • cation exchange groups represented by sulfonic acid groups are represented by the following (3b-1) to (3b-28).
  • d is the same number of definitions as d in general formula (2), that is, an integer of 5 or more.
  • the block represented by the general formula (2) or (3) can be manufactured based on, for example, a manufacturing method described in JP-A-2004-90002. Furthermore, as the block having the cation exchange group, a structural unit constituting the block represented by the general formula (2) or a structural unit constituting the block represented by the general formula (3), Each of the blocks may be a block formed by connecting d pieces, and it constitutes a structural unit constituting the block represented by the general formula (2) and a block represented by the general formula (3). It may be a block consisting of d structural units connected together. Next, the block having substantially no ion exchange group will be described.
  • substantially free of ion exchange groups means that most of the repeating units mainly constituting this block do not have ion exchange groups. Specifically, the average number of ion-exchange groups per structural unit constituting this block is 0.1 or less, preferably 0.05 or less, and ions are contained in the structural unit. More preferably, no exchange groups are included.
  • the block having substantially no ion exchange group is preferably a block represented by the following general formula (4).
  • Ar 22 represents a divalent aromatic group, and the divalent aromatic group includes an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, It may have at least one selected from the group consisting of an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms,
  • X 22 represents a direct bond, a group represented by 1 O—, a group represented by 1 S—, a carbo group or a sulfo group, and e is an integer of 5 or more.
  • alkyl group the alkoxy group, the aryl group, the aryl group, and the opacyl group, which are the substituents of the aromatic group Ar 22 of the general formula (4), are as described above. It is equivalent to general formula (1).
  • E is an integer of 5 or more representing the degree of polymerization of the block, preferably 5 to 1000, more preferably 10 to 1000, and still more preferably 20 to 500.
  • a value of e of 5 or more is preferable because a polymer electrolyte membrane having excellent membrane strength can be obtained.
  • the value of e is 1000 or less, it is preferable because the production of the block is easier.
  • the block having substantially no ion-exchange group is more preferably a block represented by the following general formula (5).
  • Ar 2 , Ar 3 , Ar 4 , and Ar 5 independently represent a divalent aromatic group, and the divalent aromatic group has 1 to 20 carbon atoms. At least one selected from the group consisting of an alkyl group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 2 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an acyl group having 2 to 20 carbon atoms.
  • X and X ′ each independently represent a direct bond or a divalent group
  • Y and Y ′ each independently represent a group represented by 1— or 1 S—.
  • A, b, c each independently represents 0 or 1 and n represents an integer of 5 or more.
  • n is an integer of 5 or more representing the degree of polymerization related to the block, preferably 5 to 1,000, more preferably 10 to 1000, and still more preferably 20 to 500.
  • a value of n of 5 or more is preferable because a polymer electrolyte membrane having excellent membrane strength can be obtained.
  • the value of n is 1000 or less, it is preferable because the production of the block is easier.
  • examples of suitable block copolymers include the copolymers (6-1) to (6-18) having the combination constitution shown in the following (Table 1).
  • (2a-1), (2a-4), (2a-19) and (2a-25) described in the column of the block having a cation exchange group are (5), (5-2), (5-9), ((5)) indicates the structural unit that constitutes the block having a cation exchange group, and is described in the column of the block having substantially no ion exchange group.
  • 5-10) represent structural units constituting a block substantially free of the ion exchange group.
  • the block copolymers are preferably those represented by the following general formulas (7-1) and (7-2).
  • the ion exchange capacity of the block copolymer is 0.5 by adjusting the abundance ratio of the block having a cationic group and the block having substantially no ion group. It is preferable to be in the range of ⁇ 4. Ome qZg, more preferably in the range of 0.8 to 3.5 me qZg.
  • the ion exchange capacity can be determined by a titration method.
  • the above-mentioned block type polyelectrolyte can obtain the optimum molecular weight range as appropriate depending on its structure, etc., but generally expressed in terms of polystyrene-reduced number average molecular weight by GPC (gel permeation chromatography) method, 1000-1000000 is preferred.
  • the lower limit of the number average molecular weight is more preferably 5000, further preferably 10000, while the upper limit is more preferably 500000, further preferably 300000.
  • the film strength tends to be further improved.
  • the average molecular weight is 1000000 or less, the solubility of the polymer electrolyte in a solvent is improved, and the solution viscosity of the resulting solution is lowered. Therefore, film formation by the solution casting method becomes easy.
  • the cation exchange group of the block type polymer electrolyte is a proton type.
  • the thermal decomposition initiation temperature of the block-type molecular electrolyte Accordingly, the heat treatment temperature in the heat treatment described later can be lowered.
  • the proportion of the proton type cation exchange group is preferably 10% or more. More preferably, it is 50% or more, and further preferably 80% or more.
  • Solvent-containing block-type polymer electrolyte membranes can be obtained by membrane-forming a polymer electrolyte solution obtained by dissolving the polymer electrolyte in a suitable solvent (hereinafter also simply referred to as a solution). Process).
  • the method for forming the polymer electrolyte solution into a film is not particularly limited, and a known method such as a spin coating method or a solution casting method can be used, but a solution casting method is preferable.
  • the solution casting method for producing a solvent-containing block type polymer electrolyte membrane on the support material by applying the solution on a support substrate and reducing the amount of solvent is easy to operate.
  • a solution obtained by dissolving the above polymer electrolyte in an appropriate solvent is applied to a porous membrane support, and the polymer electrolyte is retained on the porous membrane support. Then, by reducing the amount of the solvent in the solution, a membrane forming method is also possible in which a composite membrane comprising the porous membrane-like support and the polymer electrolyte held on the membrane-like support is obtained. .
  • a polymer electrolyte membrane may be produced by using this composite membrane as a solvent-containing block type polymer electrolyte membrane.
  • porous membrane support examples include polyimide, polysulfone, polyamide, polytetrafluoroethylene (PTFE), and ethylene-tetrafluoroethylene copolymer (ETFE).
  • PTFE polytetrafluoroethylene
  • ETFE ethylene-tetrafluoroethylene copolymer
  • PET Polyethylene terephthalate
  • PTFE polytetrafluoroethylene
  • the solvent is not particularly limited as long as it can dissolve the polyelectrolyte and can be removed thereafter.
  • DM F N, N-dimethylformamide
  • DMA c N, N-dimethylacetamide
  • NMP N-methyl-2-pyrrolidone
  • DM SO dimethyl sulfoxide
  • Aprotic polar solvents such as dichloromethane, chlorohonolem, chlorinated solvents such as 1,2-dichloroethane, black benzene and dichlorobenzene, alcohols such as methanol, ethanol and propanol, ethylene glycol
  • alkylene glycol monoalkyl ethers such as monomethylenoatenole, ethylene glycolenomonoethylenoleate, propyleneglycolenomonomethyle / leinetenole, and
  • N, N-dimethylformamide hereinafter referred to as “DMF”
  • DMA c N, N-dimethylacetamide
  • DMC N-methyl-2-pyrrolidone
  • NMP N-methyl sulfoxide
  • DMSO dimethyl sulfoxide
  • DMF, DMAc, NMP, DMSO, etc. are preferable because the solubility of the block type polymer electrolyte is high.
  • the support substrate used in the solution casting method is not particularly limited as long as the solvent-containing block type polymer electrolyte membrane obtained after strong film formation can be peeled off without swelling or dissolving by the solution.
  • glass, stainless steel, stainless steel belt, polyethylene terephthalate (PET) film, polytetrafluoroethylene (PTFE) film, etc. are preferably used.
  • PET polyethylene terephthalate
  • PTFE polytetrafluoroethylene
  • the surface of the base material may be subjected to a mold release process, a mirror surface process, an embossing process, or an erasing process as necessary.
  • the concentration of the block type polyelectrolyte in the solution used in the solution casting method is usually 5 to 40% by weight, preferably 5 to 30% by weight, although it depends on the molecular weight of the block type polyelectrolyte itself used. .
  • concentration of the block-type polymer electrolyte is 5% by weight or more, a polymer electrolyte membrane having a practical film thickness is easy to process, and when the concentration is 40% by weight or less, the solution viscosity of the resulting solution is lowered. Therefore, it becomes easy to obtain a film having a smooth surface.
  • heating may be performed in order to reduce the amount of solvent and cure the coating film. In this case, the temperature range of the heating is the heat of the block type polymer electrolyte. It is preferable that the temperature is not higher than the decomposition start temperature. (Heat treatment process for solvent-containing block type polymer electrolyte membrane)
  • the solvent-containing block type polymer electrolyte membrane is heat-treated to obtain a desired polymer electrolyte membrane.
  • the solvent-containing block-type polymer electrolyte membrane is heated at a temperature higher than the thermal decomposition start temperature of the block-type polymer electrolyte constituting the solvent-containing block-type polymer electrolyte membrane.
  • Heat treatment is preferably performed at a temperature 10 to 100 ° C higher than the thermal decomposition start temperature, and heat treatment is performed at a temperature 20 ° C to 80 ° C higher than the thermal decomposition start temperature. Is more preferable.
  • the thermal decomposition starting temperature of the block-type polymer electrolyte can be measured by TGNODTA.
  • the block-type polymer electrolyte When heat at a predetermined temperature higher than the thermal decomposition start temperature of the block-type polymer electrolyte is applied to the solvent-containing block-type polymer electrolyte membrane, the block-type polymer electrolyte in a state where the solvent remains at that temperature The degree of thermal decomposition of can be reduced. That is, even if the polymer electrolyte is heated at a temperature at which thermal decomposition starts, if the solvent remains, it may be possible to increase the molecular weight of the polymer electrolyte before the polymer electrolyte decomposes. is there.
  • the molecular weight of the block type polymer electrolyte constituting the polymer electrolyte membrane after the heat treatment is increased as compared with that before the heat treatment.
  • the degree of increase in the molecular weight of the polymer electrolyte is preferably such that the number average molecular weight after the heat treatment is 1.05 times or more, and 1.10 times or more as compared to the number average molecular weight before the heat treatment. More preferably.
  • the heating time in this heat treatment largely depends on the kind of the solvent-containing block type polymer electrolyte membrane and the heat treatment temperature, but constitutes the solvent-containing block type polymer electrolyte membrane.
  • it is preferably from 1 minute to 5 hours, more preferably from 5 minutes to 3 hours.
  • the control of the heating temperature and the heating time within the above range and the amount of residual solvent in the polymer electrolyte membrane after the heat treatment are set. It is important to maintain the amount of residual solvent in the polymer electrolyte membrane after the heat treatment to be 1% by weight or more.
  • residual solvent amount means the amount of the solvent remaining in the polymer electrolyte membrane after the heat treatment.
  • solvent refers to the solvent used in the casting film formation.
  • after heat treatment means a time range within 6 hours from the end of the heat treatment step.
  • the amount of residual solvent in the polymer electrolyte membrane is 1 in a certain time within a time range of 6 hours or less immediately after the end of the heat treatment step. weight. More than / o.
  • This residual solvent amount can be determined by a gas chromatography method.
  • a solvent-containing block type polymer electrolyte membrane obtained by forming the solution into a membrane is used as a block type high polymer electrolyte membrane constituting the solvent-containing block type polymer electrolyte membrane.
  • Treating at a temperature higher than the thermal decomposition start temperature of the molecular electrolyte, and maintaining the amount of solvent in the solvent-containing polymer electrolyte membrane so that the amount of residual solvent after the heat treatment is 1% by weight or more As a result, it is possible to reduce the thermal decomposition degree of the block-type polymer electrolyte in a state where the solvent remains.
  • the molecular weight of the polymer electrolyte can be increased before the polymer electrolyte decomposes. It may become.
  • the molecular weight of the block-type polymer electrolyte constituting the polymer electrolyte membrane after the heat treatment is increased in the range in which the polymer electrolyte is soluble in the solvent as compared with that before the heat treatment.
  • the obtained polymer electrolyte membrane has been increased in molecular weight (densified) while maintaining flexibility.
  • the polymer electrolyte membrane obtained by the production method of the present invention has a solid polymer fuel cell that has high proton conductivity and hardly permeates methanol, and has excellent handling properties. Especially direct methanol This is considered to be suitable for a fuel cell.
  • the amount of the residual solvent is less than 1% by weight, the flexibility and handling properties of the polymer electrolyte membrane are insufficient. The reason why such an effect is manifested is not necessarily clear, but the present inventor estimates as follows. That is, in the block-type hydrocarbon polymer electrolyte, the block having a cation exchange group has a relatively dense collection of cation exchange groups, and the accumulated cation exchange groups react with each other. It is estimated that good methanol pariasis is developed.
  • the film-forming step (solution casting method) is performed in a temperature region below the thermal decomposition start temperature of the polymer electrolyte, and then the above-described heat treatment is continuously performed.
  • the film-forming step in a temperature range below the thermal decomposition start temperature in advance, it is possible to prevent the appearance failure of the polymer electrolyte membrane due to rapid volatilization of the solvent, and the like. Maintenance of the residual solvent amount is also facilitated.
  • the heat treatment for increasing the molecular weight of the subsequent film is performed at a high temperature exceeding the thermal decomposition start temperature of the block type polymer electrolyte by the solvent component remaining by such control, the heat treatment is not performed.
  • the obtained polymer electrolyte membrane is highly flexible, hardly cracks, and has excellent handling properties.
  • a polymer electrolyte membrane can be produced by the method for producing a polymer electrolyte membrane of the present invention.
  • the thickness of the polymer electrolyte membrane of the present invention is not particularly limited, but is 5 to 200 m. preferable. When it is 5 ⁇ or more, a membrane strength that can be practically used can be obtained, and when it is 200 ⁇ m or less, membrane resistance can be reduced, that is, power generation performance can be improved. More preferably, it is 8 to 100 ⁇ , and even more preferably 15 to 80.
  • the polymer electrolyte membrane of the present invention can be suitably applied to a fuel cell.
  • the direct methanol fuel cell can be preferably applied.
  • the membrane-electrode assembly (MEA) of the present invention and the fuel cell of the present invention will be described.
  • the membrane-electrode assembly of the present invention can be produced by forming at least a catalyst layer on both surfaces of the obtained polymer electrolyte membrane.
  • the catalyst layer contains a catalyst material.
  • the catalyst substance is not particularly limited as long as it can activate an acid reduction reaction between methanol and oxygen, and a known substance can be used.
  • the catalyst substance include noble metals such as platinum and platinum-ruthenium alloys, and complex electrode catalysts (for example, “Fuel Cell and Polymer” edited by the Society of Polymer Science, Fuel Cell Materials Research Group, 1 2 pages, Kyoritsu Shuppan, 2 2005 1 January 10th issue)).
  • platinum or platinum-ruthenium alloy fine particles is used as the catalyst for the catalyst layer (first catalyst layer) on the fuel electrode (anode) side, and the catalyst layer (second catalyst layer) on the air electrode (force sword) side.
  • Platinum fine particles is used as the catalyst.
  • a conductive material carrying the catalyst substance on the surface as the catalyst substance because hydrogen ions and electrons can be easily transported in the catalyst layer.
  • the conductive material include known materials such as conductive carbon materials such as car pump racks and carbon nanotubes, and ceramic materials such as titanium oxide.
  • the catalyst layer preferably contains a polymer electrolyte.
  • the polymer electrolyte has ion conductivity and a binder that binds the catalyst substance.
  • examples include conventionally known Nafion (trade name), aliphatic polymer electrolyte, and aromatic polymer electrolyte made by DuPont.
  • the catalyst layer may contain a water repellent material such as PTFE for the purpose of enhancing the water repellency of the catalyst layer, and calcium carbonate for the purpose of enhancing the gas diffusibility of the catalyst layer.
  • the membrane-one electrode assembly preferably has a gas diffusion layer outside the catalyst layer in order to diffuse the fuel efficiently and uniformly.
  • the gas diffusion layer is not particularly limited as long as it has conductivity, but is preferably a porous carbon nonwoven fabric or carbon paper because it is inexpensive and easy to handle.
  • the other base material is not particularly limited as long as it does not swell or dissolve when the catalyst layer is formed.
  • the gas diffusion layer, glass, stainless steel material, stainless steel belt, polyethylene terephthalate (PET ) Film etc. are preferably used.
  • Other substrate surfaces may be subjected to a mold release treatment, a mirror finish treatment, an embossing treatment, a matting treatment, or the like as necessary.
  • the heating temperature is not particularly limited as long as the resulting polymer electrolyte membrane is not denatured, but is preferably 30 ° C. or higher and 30 ° C. or lower. Such temperature range As a result, the bondability between the catalyst layer and the polymer electrolyte membrane is improved, and the resulting polymer electrolyte membrane is not altered. 50 ° C or more and 250 ° C or less is more preferable.
  • the pressure is preferably 5 kgf / cm 2 or more and 300 kgf Zcm 2 or less. In such a pressure region, the obtained polymer electrolyte membrane is not deformed. 3 O kgf Zcni 2 or more and 2 OO kgf Zcm 2 or less are more preferable. In this way, a membrane-electrode assembly comprising the polymer electrolyte membrane of the present invention and the catalyst layers provided on both surfaces of the polymer electrolyte membrane is obtained. When this membrane-electrode assembly is used in a direct methanol fuel cell (DMFC), the resulting DMFC is excellent in power generation performance and markedly suppresses battery damage due to methanol crossover.
  • DMFC direct methanol fuel cell
  • the force described by taking the case where the membrane-electrode assembly of the present invention is applied to a direct methanol fuel cell (D MFC) as an example.
  • D MFC direct methanol fuel cell
  • it can be suitably used for a fuel cell using hydrogen as a raw material.
  • examples of the present invention will be described. However, the examples shown below are suitable examples for explaining the present invention, and do not limit the present invention at all.
  • the number average molecular weight in terms of polystyrene was determined by gel permeation chromatography (GPC) under the following conditions.
  • the heat-treated polymer electrolyte membrane was placed at room temperature and atmospheric pressure, dissolved in a sample solution (dimethylformamide) within 6 hours, and measured by gas chromatography using a GC device. . The obtained measured values were analyzed based on the following analysis method, and the amount of residual solvent remaining in the polymer electrolyte membrane was calculated.
  • the resistance value was measured, then, the polymer electrolyte membrane was removed, the resistance value was measured again, and the membrane resistance was calculated from the difference between the two.
  • lmo 1 / L dilute sulfuric acid was used as a solution to be brought into contact with both sides of the polymer electrolyte membrane. The proton conductivity was calculated from the film thickness and resistance value when immersed in dilute sulfuric acid.
  • the polymer electrolyte membrane sample obtained in each example was immersed in a 10 wt ° / o methanol water solution for 2 hours, and then this sample polymer electrolyte membrane was formed into an H-shaped diaphragm consisting of cell A and cell B. Hold in the center of the cell, put 10 wt% methanol aqueous solution into cell A and pure water into cell B, and leave at 23 ° C for the initial state and for a certain time t (sec) from the initial state.
  • the methanol concentration in cell B was analyzed, and the methanol permeability coefficient D (cm 2 / sec) was determined by the following equation.
  • V Volume of liquid in cell B (cm 3 )
  • Polymer electrolyte membrane suitable for direct methanol fuel cell is proton conductivity ( ⁇ ) PT / JP2008 / 066805
  • D methanol permeability coefficient
  • the obtained polymer electrolyte membrane was dried at 110 ° C. with a halogen moisture content meter (Mettler Toledo Co., Ltd., trade name “ ⁇ R73”) to determine the absolute dry weight.
  • This polymer electrolyte membrane was immersed in 5 mL of a 0.1 mo 1ZL aqueous solution of sodium hydroxide and then 50 mL of ion exchanged water was added and left for 2 hours. Thereafter, the solution in which the polymer electrolyte membrane was immersed was titrated by gradually adding 0.1 mol 1 ZL of hydrochloric acid to determine the neutralization point.
  • the ion exchange capacity was determined from the absolute dry weight and the amount of 0.1 lmo 1 / L hydrochloric acid required for the neutralization point.
  • the salt exchange rate Y (%) was determined by the following formula (B).
  • the thermal decomposition starting temperature was measured using TG / DTA (Seiko Instruments Inc., SSC-5 200). Increase the temperature from 30 ° C to 110 ° C at 50 ° C / min, hold at 110 ° C for 30 minutes, then increase the temperature from 110 ° C to 300 ° C in 5 ° 0 minutes, reducing weight The temperature at which is started was defined as the thermal decomposition start temperature.
  • reaction mass [A] and the reaction mass [B] were mixed while diluted with DMSO: 68 ml, and this mixture was reacted at 145 ° C for 33 hours 30 minutes. After allowing to cool, the reaction mixture was dropped into a large amount of 2 m o 1 Z L hydrochloric acid aqueous solution, and the resulting precipitate was collected by filtration, and washed and filtered repeatedly with water until the washing solution became neutral. Next, the filtrate was treated twice with a large excess of hot water for 1 hour, then dried under reduced pressure, and the target polymer electrolyte represented by the following general formula (8) (block copolymer A) 33. 3 3 g
  • the number average molecular weight of this block copolymer A is 79000, and the thermal decomposition onset temperature is 210 ° C.
  • the path temperature was raised to 190 ° C, and toluene was distilled off by heating to azeotropically dehydrate water in the system. After toluene was distilled off, the reaction was carried out at the same temperature for 9 hours and 30 minutes. After allowing to cool, the reaction mixture was dropped into a large amount of 2mo 1ZL hydrochloric acid aqueous solution, and the resulting precipitate was collected by filtration, and washed and filtered repeatedly with water until the washing solution became neutral. Next, the filtrate was treated twice with a large excess of hot water for 1 hour, then dried under reduced pressure, and the desired polymer electrolyte represented by the following general formula (9) (random copolymer A) 1 8. 99 g was obtained.
  • general formula (9) random copolymer A
  • the random copolymer A had a number average molecular weight of 43,000 and a thermal decomposition starting temperature of 215 ° C. (Production Example 3)
  • the block copolymer B had a number average molecular weight of 115,000 and a thermal decomposition initiation temperature of 200 ° C.
  • the block copolymer A (thermal decomposition start temperature 210 ° C) obtained in Production Example 1 was dissolved in NMP so as to be 20% by weight to obtain a solution, and then the solution was applied onto a glass substrate. Dried at normal pressure at ° C (filming process).
  • a polymer electrolyte membrane was obtained by the same method as in Example 1 except that the temperature of nitrogen open was 2400 ° C. The amount of residual solvent in the obtained polymer electrolyte membrane was 4% by weight. (Example 3)
  • the block copolymer B obtained in Production Example 3 (pyrolysis start temperature 20 ° C.) was dissolved in NMP to 20% by weight to obtain a solution, and then the solution was applied onto a glass substrate. Then, it was dried at 80 ° C. under normal pressure (film forming process).
  • the temperature of the nitrogen oven is 200.
  • a polymer electrolyte membrane was obtained by the same method as in Example 1 except that C was used. The amount of residual solvent in the obtained polymer electrolyte membrane was 10% by weight. (Comparative Example 2)
  • the block copolymer A obtained in Production Example 1 was dissolved in NMP so as to be 20% by weight to obtain a solution, and the solution was applied on a glass substrate and dried at 80 ° C. under normal pressure. (Membrane process). It was then heated for 30 minutes in a nitrogen oven at 2700C. The amount of residual solvent in the obtained polymer electrolyte membrane was 0% by weight.
  • the block copolymer A obtained in Production Example 1 is dissolved in NMP so as to be 20% by weight. After the solution was obtained, the solution was applied onto a glass substrate and dried at 80 ° C. under normal pressure (film formation step). The obtained polymer electrolyte membrane was washed with running water for 2 hours to remove substantially all of the remaining solvent and dried at room temperature.
  • Random copolymer A obtained in Production Example 2 (pyrolysis start temperature 2 15 ° C) was dissolved in NMP so as to be 25% by weight, and a solution was obtained. Then, the solution was applied onto a glass substrate. Then, it was dried at 80 ° C. under normal pressure (film forming process).
  • Random copolymer A obtained in Production Example 2 (pyrolysis start temperature 2 15 ° C) was dissolved in NMP so as to be 25% by weight, and a solution was obtained. Then, the solution was applied onto a glass substrate. Then, it was dried at 80 ° C. under normal pressure (film forming process). Next, heating was performed for 1 hour in nitrogen open at 200 ° C. (heat treatment step). The amount of residual solvent in the obtained polymer electrolyte membrane was 11% by weight.
  • a polymer electrolyte membrane was obtained in the same manner as in Example 3 except that the temperature of the nitrogen oven was 200 ° C. The amount of residual solvent in the obtained polymer electrolyte membrane was 16% by weight. In Comparative Example 3, the obtained film was fragile and could not be used for post-treatment.
  • each polymer electrolyte membrane was immersed in hydrochloric acid of lnio 1ZL for 3 hours, and the cation exchange group was substantially added. It was converted to a Proton type and washed with running water for 3 hours. The number average molecular weight, proton conductivity ( ⁇ ), and methanol permeability coefficient (D) of the obtained polymer electrolyte membrane were measured based on each of the measurement methods described above.
  • the examples and comparative examples are examples examined by considering the case where a polymer electrolyte membrane is mainly used for a direct methanol fuel cell.
  • Preferred characteristics of polymer electrolytes for direct methanol fuel cells include high proton conductivity ( ⁇ ) and low methanol permeability coefficient (D), that is, low characteristic coefficient (D / ⁇ ). It is.
  • Examples 1 and 2 and Comparative Example 1 both use block copolymer ⁇ ⁇ ⁇ ⁇ as the electrolyte material. Then, with respect to the thermal decomposition starting temperature 2 10 ° C, in Comparative Example 1, heat treatment (film formation) was performed at 200 ° C which is lower than the thermal decomposition starting temperature. In Examples 1 and 2, the thermal decomposition was performed. Heat treatment (film formation) at 230 ° C and 240, which are higher than the starting temperature. As a result, characteristic coefficient, in Comparative Example 1 8. 5 X 1 0- 6, 7. 1 X 1 0- 6 In Example 1, Example 2, 6. 2 X 1 0 one 6, and the electrolyte material The characteristic coefficient is smaller when heat treatment is performed at a temperature higher than the thermal decomposition start temperature.
  • Comparative Examples 4 and 5 both use random copolymers as the electrolyte material.
  • heat treatment film formation was performed at 240 ° C, which is higher than the thermal decomposition start temperature.
  • Heat treatment film formation at 200 ° C.
  • characteristic coefficient in Comparative Example 4 2.
  • Comparative Example 2 and Comparative Example 3 the same electrolyte material (Plock Copolymer A) as in Examples 1 and 2 and Comparative Example 1 was used. Unlike 1, the amount of residual solvent after heat treatment is less than 0.1% by weight. Results remaining Solvent amount became 0.1 less than 1 wt%, has become Comparative Example 2, characteristic coefficient ⁇ ) ⁇ poor (2. 5 X 1 0- 5) , film in Comparative Example 3 becomes brittle, Handling is poor. Examples 3 and 6 both use the block copolymer B as the electrolyte material.
  • a method for producing a polymer electrolyte membrane for a fuel cell that is inexpensive and can achieve both methanol barrier properties and proton conductivity at a high level, and a high yield obtained by the method.
  • a molecular electrolyte membrane, a membrane-one electrode assembly using the polymer electrolyte membrane, and a fuel cell can be provided.
  • the direct methanol fuel cell using the polymer electrolyte membrane of the present invention has high power generation characteristics and low methanol crossover, and the reduction in fuel consumption is reduced based on such characteristics. It can use suitably for the use of. Industrial applicability
  • the production method of the present invention it is possible to obtain a polymer electrolyte membrane that is inexpensive and has both high methanol pariasis and proton conductivity.
  • the direct methanol fuel cell using the polymer electrolyte membrane of the present invention has high power generation characteristics and low methanol crossover, and the reduction in fuel consumption is reduced based on such characteristics. Can be suitably used.

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Abstract

Cette invention concerne un procédé servant à produire une membrane de polyélectrolyte, comprenant une étape de formation de membrane consistant à former une membrane à partir d'une solution de polyélectrolyte contenant un polyélectrolyte de type polyélectrolyte à blocs d'hydrocarbures et un solvant pour produire une membrane de polyélectrolyte de type polyélectrolyte à blocs contenant du solvant et une étape de traitement thermique consistant à chauffer la membrane de polyélectrolyte de type polyélectrolyte à blocs contenant du solvant pour former une membrane de polyélectrolyte. Le procédé est caractérisé en ce que la température du traitement thermique est une température supérieure à la température de début de décomposition thermique du polyélectrolyte de type polyélectrolyte à blocs d'hydrocarbures et en ce que la quantité résiduelle du solvant dans la membrane de polyélectrolyte après le traitement thermique est amenée à une valeur supérieure ou égale à 1 % en poids.
PCT/JP2008/066805 2007-09-11 2008-09-10 Procédé servant à produire une membrane de polyélectrolyte, membrane de polyélectrolyte, assemblage membrane-électrode et pile à combustible WO2009035131A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102329423A (zh) * 2010-07-13 2012-01-25 现代自动车株式会社 具有阳离子交换基的聚(芳醚)共聚物、其制备方法和其应用
CN107074754A (zh) * 2014-12-19 2017-08-18 株式会社Lg化学 新型化合物和使用该化合物的聚合物电解质膜

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002008440A (ja) * 2000-06-20 2002-01-11 Jsr Corp プロトン伝導膜
JP2005171025A (ja) * 2003-12-09 2005-06-30 Jsr Corp プロトン伝導膜の製造方法
JP2005243492A (ja) * 2004-02-27 2005-09-08 Toyobo Co Ltd イオン伝導膜
JP2007126645A (ja) * 2005-10-04 2007-05-24 Sumitomo Chemical Co Ltd イオン交換性基を有する重合体およびその用途
JP2007305571A (ja) * 2006-04-13 2007-11-22 Sumitomo Chemical Co Ltd 高分子電解質膜の製造方法、高分子電解質膜及び直接メタノール型燃料電池

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5168758B2 (ja) * 2005-03-11 2013-03-27 東洋紡株式会社 イオン交換膜の製造方法
JP2006253002A (ja) * 2005-03-11 2006-09-21 Toyobo Co Ltd イオン交換膜の製造方法
JP5000109B2 (ja) * 2005-07-13 2012-08-15 日本曹達株式会社 電極作製用結着剤、電極及びポリマー電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002008440A (ja) * 2000-06-20 2002-01-11 Jsr Corp プロトン伝導膜
JP2005171025A (ja) * 2003-12-09 2005-06-30 Jsr Corp プロトン伝導膜の製造方法
JP2005243492A (ja) * 2004-02-27 2005-09-08 Toyobo Co Ltd イオン伝導膜
JP2007126645A (ja) * 2005-10-04 2007-05-24 Sumitomo Chemical Co Ltd イオン交換性基を有する重合体およびその用途
JP2007305571A (ja) * 2006-04-13 2007-11-22 Sumitomo Chemical Co Ltd 高分子電解質膜の製造方法、高分子電解質膜及び直接メタノール型燃料電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102329423A (zh) * 2010-07-13 2012-01-25 现代自动车株式会社 具有阳离子交换基的聚(芳醚)共聚物、其制备方法和其应用
CN107074754A (zh) * 2014-12-19 2017-08-18 株式会社Lg化学 新型化合物和使用该化合物的聚合物电解质膜

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