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WO2010067743A1 - Membrane électrolytique multicouches, ensemble électrode-membrane et pile à combustible - Google Patents

Membrane électrolytique multicouches, ensemble électrode-membrane et pile à combustible Download PDF

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Publication number
WO2010067743A1
WO2010067743A1 PCT/JP2009/070308 JP2009070308W WO2010067743A1 WO 2010067743 A1 WO2010067743 A1 WO 2010067743A1 JP 2009070308 W JP2009070308 W JP 2009070308W WO 2010067743 A1 WO2010067743 A1 WO 2010067743A1
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Prior art keywords
electrolyte
polymer
block
polymer block
group
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English (en)
Japanese (ja)
Inventor
友裕 小野
武史 仲野
竹友 山下
敬次 久保
望 須郷
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to JP2010542085A priority Critical patent/JPWO2010067743A1/ja
Publication of WO2010067743A1 publication Critical patent/WO2010067743A1/fr
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Classifications

    • 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
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
    • 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
    • H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
    • 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
    • H01M8/1093—After-treatment of the membrane other than by polymerisation mechanical, e.g. pressing, puncturing
    • 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 an electrolyte laminated film, a membrane-electrode assembly comprising the electrolyte laminated film, and a polymer electrolyte fuel cell.
  • PEFCs polymer electrolyte fuel cells
  • a polymer electrolyte fuel cell is generally configured as follows. First, a catalyst layer containing carbon powder carrying a white metal catalyst and an ion conductive binder made of a polymer electrolyte is formed on both sides of a polymer electrolyte membrane having proton conductivity. A gas diffusion layer, which is a porous material through which fuel gas and oxidant gas are passed, is formed outside each catalyst layer. Carbon paper, carbon cloth, or the like is used as the gas diffusion layer. A structure in which a catalyst layer and a gas diffusion layer are integrated is called a gas diffusion electrode.
  • a structure in which a pair of gas diffusion electrodes is bonded to an electrolyte membrane so that the catalyst layer faces the electrolyte membrane is a membrane-electrode assembly ( MEA; Membrane Electrode Assembly).
  • MEA Membrane Electrode Assembly
  • separators having conductivity and airtightness are disposed on both sides of the membrane-electrode assembly.
  • a gas flow path for supplying fuel gas or oxidant gas (for example, air) to the electrode surface is formed in the contact portion of the membrane-electrode assembly and the separator or in the separator. Electric power is generated by supplying fuel gas to one electrode (fuel electrode) and supplying an oxidant gas containing oxygen such as air to the other electrode (oxygen electrode).
  • the fuel is ionized to produce protons and electrons
  • the protons pass through the electrolyte membrane
  • the electrons travel through an external electric circuit formed by connecting both electrodes, and are sent to the oxygen electrode
  • Water is produced by the reaction.
  • the chemical energy of the fuel can be directly converted into electric energy and taken out.
  • Nafion registered trademark of Nafion, DuPont
  • Nafion which is a perfluorocarbon sulfonic acid polymer
  • Nafion is excellent in ionic conductivity under low humidity, so it is possible to obtain good output in the initial stage.However, since the dimensional change between dry and wet is large, the performance deteriorates during long-term power generation tests. It tends to be easy.
  • an electrolyte membrane in which a film subjected to simultaneous biaxial stretching near the ⁇ dispersion temperature and a film subjected to a heat treatment process are laminated (Patent Document 1).
  • Patent Document 1 a film subjected to simultaneous biaxial stretching near the ⁇ dispersion temperature and a film subjected to a heat treatment process are laminated.
  • Nafion is a fluorine-based polymer, environmental considerations are necessary during synthesis and disposal, and it is expensive. Therefore, development of new electrolyte membrane is desired
  • PEEK polyether ether ketone
  • Patent Document 2 which is a heat-resistant aromatic polymer
  • Patent Document 3 an electrolyte membrane in which an ion conductive block copolymer suitable as an electrolyte membrane for a fuel cell using methanol as a fuel is cross-linked with a polyvalent amine or a radical has been studied.
  • Patent Document 4 an electrolyte membrane is also proposed in which a polymer membrane having a low ion exchange capacity (preferably less than 0.7 meq / g) and a polymer membrane having a high ion exchange capacity (preferably 0.7 meq / g or more) are laminated ( Patent Document 4).
  • this electrolyte membrane is excellent in dimensional stability and methanol barrier property, a configuration excellent in proton conductivity and power generation characteristics under low humidity is not disclosed. As described above, in the solid oxide fuel cell using hydrogen fuel, the current power generation characteristics under low humidity cannot be obtained while keeping the dimensional stability low.
  • the object of the present invention is to combine high dimensional stability and high proton conductivity (low resistance) under low humidity, and when used in a polymer electrolyte fuel cell using hydrogen as a fuel, high output even under low humidity.
  • an electrolyte membrane that is capable of obtaining characteristics and also has durability and good bondability with an electrode, and a membrane-electrode assembly and a polymer electrolyte fuel cell using the electrolyte membrane. It is in.
  • the inventors of the present invention are electrolyte laminated films obtained by laminating at least two polymer electrolyte membranes as constituent electrolyte membranes, and at least one of the polymer electrolyte membranes.
  • One has an ion exchange capacity higher than 1.60 meq / g, and at least one of the polymer electrolyte membranes has an ion exchange capacity of 0.70 to 1.60 meq / g, and at least one of the constituent electrolyte membranes Provided as an electrolyte membrane an electrolyte laminate film comprising a block copolymer (I) comprising a polymer block (A) having an ion conductive group and a flexible polymer block (B) as constituent components
  • a block copolymer (I) comprising a polymer block (A) having an ion conductive group and a flexible polymer block (B) as constituent components
  • the present invention is an electrolyte laminate film in which at least two polymer electrolyte membranes are laminated as a constituent electrolyte membrane, and at least one of the polymer electrolyte membranes has an ion exchange capacity higher than 1.60 meq / g. Furthermore, at least one of the polymer electrolyte membranes has an ion exchange capacity of 0.70 to 1.60 meq / g, and at least one of the constituent electrolyte membranes has a polymer block (A) And a block copolymer (I) containing a flexible polymer block (B) as a constituent component.
  • the present invention is an electrolyte laminate film in which at least two polymer electrolyte membranes are laminated as a constituent electrolyte membrane, and at least one of the polymer electrolyte membranes has an ion exchange capacity higher than 1.60 meq / g. Furthermore, at least one of the polymer electrolyte membranes has an ion exchange capacity of 0.70 to 1.60 me
  • At least two of the constituent electrolyte films are preferably electrolyte films containing the block copolymer (I).
  • at least one of the constituent electrolyte films containing the block copolymer (I) has an ion exchange capacity higher than 1.60 meq / g, and further contains the block copolymer (I). It is preferable that at least one of the constituent electrolyte membranes has an ion exchange capacity of 0.70 to 1.60 meq / g.
  • the electrolyte laminate film is formed by laminating at least three polymer electrolyte membranes as constituent electrolyte membranes, and two constituent electrolyte membranes constituting the outermost layer of the electrolyte laminate membrane are ions higher than 1.60 meq / g.
  • An electrolyte laminated film that is a polymer electrolyte film having an exchange capacity is preferable.
  • the polymer block (A) is preferably a polymer block having an aromatic vinyl compound unit as a main repeating unit.
  • the ratio of the aromatic vinyl-type compound unit which occupies for a polymer block (A) is 50 mass% or more.
  • the polymer block (A) has substantially no ion conductive group and has a constraining block (A1) that functions as a constraining phase and an ion conductive block (A2) having an ion conductive group. It is preferable that it consists of.
  • the constraining block (A1) is a polymer block having an aromatic vinyl compound unit represented by the general formula (a) as a main repeating unit.
  • the ion conductive block (A2) is preferably a polymer block having an aromatic vinyl compound unit represented by the following general formula (b) as a main repeating unit.
  • the polymer block (B) has an alkene unit having 2 to 8 carbon atoms, a cycloalkene unit having 5 to 8 carbon atoms, a vinylcycloalkene unit having 7 to 10 carbon atoms, and a 4 to 8 carbon atom number.
  • a polymer block comprising at least one repeating unit selected from the group consisting of a conjugated alkadiene unit and a conjugated cycloalkadiene unit having 5 to 8 carbon atoms is preferred.
  • the mass ratio of the polymer block (A1) to the polymer block (A2) is preferably 85:15 to 20:80.
  • the mass ratio of the polymer block (A) to the polymer block (B) is preferably 95: 5 to 5:95.
  • the ion conductive group is preferably a group represented by —SO 3 M or —PO 3 HM (wherein M represents a hydrogen atom, an ammonium ion, or an alkali metal ion). .
  • the present invention also relates to a membrane-electrode assembly comprising the electrolyte laminate film.
  • the present invention also relates to a polymer electrolyte fuel cell comprising the membrane-electrode assembly.
  • the polymer block (A) and the polymer block (B) in the block copolymer (I) contained in at least one constituent electrolyte membrane cause microphase separation, and the polymer block (A) and polymer block (B) have a property to gather together, and since polymer block (A) has an ion conductive group, an ion channel is formed by the gathering of polymer blocks (A). It becomes a passage for ions such as protons.
  • the presence of the polymer block (B) makes the block copolymer (I) elastic and flexible as a whole, and formability (assembly) in the production of membrane-electrode assemblies and solid polymer fuel cells.
  • the flexible polymer block (B) is composed of an alkene unit or a conjugated alkadiene unit.
  • microphase separation means phase separation in a microscopic sense, and more specifically means phase separation in which the formed domain size is less than or equal to the wavelength of visible light (3800 to 7800 mm). It shall be.
  • the electrolyte laminated membrane of the present invention has high dimensional stability and high proton conductivity (low resistance) under low humidity, and the membrane-electrode assembly comprising the electrolyte laminated membrane as an electrolyte membrane uses hydrogen as a fuel.
  • the membrane-electrode assembly comprising the electrolyte laminated membrane as an electrolyte membrane uses hydrogen as a fuel.
  • the block copolymer (I) contained in at least one of the polymer electrolyte membranes which are constituent electrolyte membranes of the electrolyte laminated membrane of the present invention is at least 50 of the polymer electrolyte membrane containing the block copolymer (I) in order to sufficiently exhibit its characteristics. It is preferably contained in a ratio of ⁇ 100% by mass, more preferably 70% by mass or more, and even more preferably 90% by mass or more.
  • a polymer having an aromatic vinyl compound unit as a main repeating unit a polymer having a conjugated alkadiene as a main repeating unit, a hydrogenated product thereof, an alkene as a main repeating unit
  • Polymer having (meth) acrylic acid ester as the main repeating unit polymer having vinyl ester as the main repeating unit, polymer having vinyl ether as the main repeating unit, polyether ketone, polysulfide, polyphosphazene, polyphenylene , Polybenzimidazole, polyethersulfone, polyphenylene oxide, polycarbonate, polyamide, polyimide, polyurea, polysulfone, polysulfonate, polybenzoxazole, polybenzothiazole, polyphenylquinoxaline, polysiloxane
  • Other polymer materials such as phosphorus and polytriazine, softeners, stabilizers, light stabilizers, antistatic agents, mold release
  • the block copolymer (I) comprises an ion conductive group-containing polymer block (A) and a flexible polymer block (B) as constituent components.
  • the polymer block (A) an aromatic vinyl compound is used.
  • the aromatic ring in the aromatic vinyl compound is preferably a carbocyclic aromatic ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a pyrene ring.
  • Specific examples of these aromatic vinyl compounds include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-isopropylstyrene when ⁇ -carbon is tertiary carbon.
  • the hydrogen atom bonded to the ⁇ -carbon atom is an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group, n- Substituted with a butyl group, isobutyl group, sec-butyl group or tert-butyl group), a halogenated alkyl group having 1 to 4 carbon atoms (chloromethyl group, 2-chloroethyl group, 3-chloroethyl group, etc.) or a phenyl group
  • aromatic vinyl compounds such as ⁇ -methylstyrene, ⁇ -methyl-4-methylstyrene, ⁇ -methyl-4-ethylstyrene, ⁇ -methyl-4-t-butylstyrene.
  • 1,1-diphenylethylene and the like can be used alone or in combination of two or more.
  • styrene, ⁇ -methylstyrene, 4-methylstyrene, 4-ethylstyrene, ⁇ -methyl-4-methylstyrene, ⁇ -methyl-2-methylstyrene Is preferred.
  • the form in the case of copolymerizing two or more of these may be random copolymerization, block copolymerization, graft copolymerization or tapered copolymerization.
  • the polymer block (A) may contain one or more other monomer units as long as the effects of the present invention are not impaired.
  • examples of such other monomers include conjugated alkadienes having 4 to 8 carbon atoms (1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, 2,4-hexadiene, 2,3- Dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-heptadiene, 1,4-heptadiene, 3,5-heptadiene, etc.), alkenes having 2 to 8 carbon atoms (ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 1-heptene, 2-heptene, 1-octene, 2-octene, etc.), (meth) acrylic acid ester (Methyl (meth) acryl
  • the polymer block (A) is a repeating unit mainly composed of an aromatic vinyl compound unit
  • microphase separation from the polymer block (B) is more likely to occur, and as a result, ion conductivity can be increased.
  • the aromatic vinyl compound unit preferably occupies 50% by mass or more of the polymer block (A) in order to impart sufficient ion conductivity to the finally obtained polymer electrolyte laminate film, It is more preferable to occupy 70% by mass or more, and even more preferable to occupy 90% by mass or more.
  • each polymer block (A) can be appropriately selected depending on the properties of the electrolyte laminated film, required performance, other polymer components, and the like.
  • the mechanical properties of the electrolyte laminate film tend to be high.
  • the molecular weight is too large, it becomes difficult to form and form the block copolymer (I). In this case, it is difficult to form an ion channel, and thus there is a tendency that ion conductivity is not exhibited, and mechanical characteristics tend to be low. Therefore, it is important to appropriately select a molecular weight according to required performance.
  • the molecular weight of each polymer block (A) in the state where the ion conductive group is not introduced is usually selected from the range of 1,000 to 1,000,000 as the number average molecular weight in terms of polystyrene. Preferably, it is selected from the range of 2,000 to 250,000, more preferably selected from the range of 3,000 to 100,000.
  • the polymer block (A) may be crosslinked by a known method within a range not impairing the effects of the present invention. By introducing cross-linking, the ion channel phase formed by the polymer block (A) is less likely to swell, and the change in mechanical properties (such as tensile properties) between drying and wetting tends to be further reduced.
  • the ion conductive group that can be used in the present invention is not particularly limited, and a normal polar functional group having ion conductivity can be used, and those having a high affinity with anions and / or cations, particularly functional groups.
  • Those which are easily dissociated as ions are preferred, and examples thereof include sulfonic acid groups, phosphonic acid groups, carboxylic acid groups, quaternary ammonium salts, and quaternary salts of pyridine.
  • a salt obtained by exchanging a protonic functional group or a proton of the protonic functional group with another ion is excellent in proton conductivity, and examples thereof include a sulfonic acid group, a phosphonic acid group, a carboxylic acid group, and salts thereof. From the viewpoints of ion conductivity, ease of introduction, cost, etc., sulfonic acid groups and phosphonic acid groups and their salts are preferably used. The ion exchange capacity can be adjusted by appropriately selecting the type and concentration of the ion conductive group. *
  • the polymer block (A) may be composed of a constraining block (A1) having substantially no ion conductive group and an ion conductive block (A2) having an ion conductive group.
  • the polymer block (A1) and the polymer block (A2) have a property of causing microphase separation, and the polymer blocks (A1) and the polymer blocks (A2) are aggregated. Since the polymer block (A1) needs to exhibit a restraining function in an atmosphere where power is generated, the polymer block has a glass transition point or softening point of 40 ° C. or higher when it becomes a homopolymer.
  • the constraint block is preferably 70 ° C. or higher, more preferably 80 ° C. or higher.
  • the polymer block (A2) has an ion conductive group, an ion channel is formed by the assembly of the polymer blocks (A2) and becomes a passage for protons.
  • the monomer unit constituting the constraining block (A1) and the ion conductive block (A2) can be selected from monomer units that can constitute the polymer block (A).
  • the ratio between the constraining block (A1) and the ion conductive block (A2) is not particularly limited, but the ratio of the monomer units before introducing the ion conductive group is 85:15 to 0: 100. Is preferable, and is preferably 85:15 to 20:80, more preferably 80:20 to 20:80, from the viewpoint that the characteristics of each block can be sufficiently obtained.
  • (I) has a low molecular weight (for example, 50,000 or less), that is, 75:25 to 25:75 in that the characteristics of each block can be sufficiently obtained even in a configuration excellent in moldability, film forming property and the like. Is most preferred.
  • Constraint block (A1) having substantially no ion conductive group is represented by the following general formula (a)
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 2 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, at least one of which is a carbon atom
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 2 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, at least one of which is a carbon atom
  • R 2 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, at least one of which is a carbon atom
  • the alkyl group having 1 to 4 carbon atoms represented by R 1 may be linear or branched, and is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl. Group, isobutyl group, tert-butyl group and the like.
  • the alkyl group having 1 to 8 carbon atoms represented by R 2 to R 4 may be independently linear or branched, and is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl.
  • aromatic vinyl compound unit represented by the general formula (a) include p-methylstyrene unit, 4-tert-butylstyrene unit, p-methyl- ⁇ -methylstyrene unit, 4-tert -Butyl- ⁇ -methylstyrene units and the like may be mentioned, and these may be used alone or in combination of two or more.
  • the form in the case of polymerizing (copolymerizing) two or more of these may be random copolymerization, block copolymerization, graft copolymerization, or tapered copolymerization.
  • the polymer block (A1) may contain one or more other monomer units in addition to the aromatic vinyl compound unit as long as the function as a constraining phase is not hindered.
  • Examples of such a monomer that gives other monomer units include conjugated alkadienes having 4 to 8 carbon atoms, alkenes having 2 to 8 carbon atoms, (meth) acrylic acid esters, vinyl esters, vinyl ethers, and the like. Specific examples thereof are the same as in the description of the polymer block (A) described above.
  • the copolymerization form of the aromatic vinyl compound and the other monomer needs to be random copolymerization.
  • the above-mentioned aromatic vinyl compound unit preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and 90% by mass of the polymer block (A1). It is even more preferable to occupy% or more.
  • the molecular weight of each polymer block (A1) is appropriately selected depending on the properties of the polymer electrolyte constituting the polymer electrolyte membrane in the present invention, the required performance, other polymer components, and the like.
  • the mechanical properties of the polymer electrolyte tend to be high.
  • the molecular weight is too large, it is difficult to form and form the block copolymer (I), and when the molecular weight is small, the mechanical properties tend to be low. Therefore, it is important to appropriately select the molecular weight according to the required performance.
  • the molecular weight is usually selected from the range of 800 to 500,000, more preferably from 2000 to 150,000, and more preferably from 3000 to 50,000, as the number average molecular weight in terms of polystyrene. Even more preferably, it is selected from a range.
  • the ion conductive block (A2) having an ion conductive group is represented by the following general formula (b)
  • An aromatic vinyl-based compound unit represented by the formula (A) represents an optionally substituted aryl group having 6 to 14 carbon atoms) as a main repeating unit.
  • Examples of the aryl group having 6 to 14 carbon atoms represented by Ar 1 in the general formula (b) include a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, an indenyl group, a biphenylyl group, and a pyrenyl group. And a naphthyl group is preferable, and a phenyl group is more preferable.
  • the optional 1 to 3 substituents that can be directly bonded to the aromatic ring of the aryl group are each independently a linear or branched alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group).
  • the alkyl group having 1 to 4 carbon atoms represented by R 5 in the general formula (b) may be linear or branched, and is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group. , Isobutyl group, tert-butyl group and the like.
  • Examples of the aryl group having 6 to 14 carbon atoms which may have 1 to 3 substituents in R 5 include a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, an indenyl group, a biphenylyl group, and a pyrenyl group.
  • the optional 1 to 3 substituents that can be directly bonded to the aromatic ring of the aryl group are each independently a linear or branched alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, Group, propyl group, isopropyl group, butyl group, sec-butyl group, isobutyl group, tert-butyl group, etc.).
  • aromatic vinyl compound giving the aromatic vinyl compound unit represented by the general formula (b) include styrene, vinyl naphthalene, vinyl anthracene, vinyl phenanthrene, vinyl biphenyl, ⁇ -methyl styrene, 1-methyl. Examples include 1-naphthylethylene and 1-methyl-1-biphenylylethylene, and styrene and ⁇ -methylstyrene are particularly preferable.
  • the aromatic vinyl compound that gives the aromatic vinyl compound unit represented by the general formula (b) may be used alone or in combination of two or more. The form in the case of copolymerizing two or more types may be random copolymerization, block copolymerization, graft copolymerization, or tapered copolymerization.
  • the polymer block (A2) may contain one or more other monomer units in addition to the aromatic vinyl compound unit within a range not impairing the effects of the present invention.
  • Examples of such a monomer that gives other monomer units include conjugated alkadienes having 4 to 8 carbon atoms, alkenes having 2 to 8 carbon atoms, (meth) acrylic acid esters, vinyl esters, vinyl ethers, and the like. Specific examples thereof are the same as in the description of the polymer block (A) described above.
  • the copolymerization form of the aromatic vinyl compound and the other monomer needs to be random copolymerization.
  • the proportion of the aromatic vinyl compound unit contained in the polymer block (A2) is preferably 50 mol% or more, more preferably 60 mol% or more from the viewpoint of imparting sufficient ion conductivity, It is still more preferable that it is 80 mol% or more.
  • each polymer block (A2) in the state where the ion conductive group is not introduced is appropriately selected depending on the properties of the polymer electrolyte, required performance, other polymer components, etc., but the number average in terms of polystyrene
  • the molecular weight is usually preferably selected from the range of 500 to 500,000, more preferably selected from the range of 1000 to 100,000, and more preferably selected from the range of 2000 to 50,000. Even more preferred.
  • the polymer block (A2) may be crosslinked by a known method within a range not impairing the effects of the present invention. By introducing cross-linking, changes in dimensions and mechanical properties (tensile properties) between drying and wetting tend to be further reduced.
  • the block copolymer (I) used in the polymer electrolyte laminate film of the present invention comprises a flexible polymer block (B) as a constituent component in addition to the polymer block (A).
  • the polymer block (B) forms a flexible phase.
  • the polymer block (A) and the polymer block (B) undergo a microphase separation, and the polymer block (A) and the polymer block (B) have a property of gathering together, and the polymer block (A ) Has an ion conductive group, so that an ion channel is formed by the assembly of the polymer blocks (A) and becomes a passage for protons.
  • the block copolymer (I) becomes elastic and flexible as a whole, and formability (assembleability) in the production of membrane-electrode assemblies and polymer electrolyte fuel cells. , Bondability, tightenability, etc.) are improved.
  • the flexible polymer block (B) here is a so-called rubber-like polymer block having a glass transition point or softening point of 50 ° C. or lower, preferably 20 ° C. or lower, more preferably 10 ° C. or lower.
  • Monomers that can constitute the repeating unit constituting the flexible polymer block (B) include alkenes having 2 to 8 carbon atoms, cycloalkenes having 5 to 8 carbon atoms, and vinylcycloalkenes having 7 to 10 carbon atoms.
  • Conjugated alkadienes having 4 to 8 carbon atoms and conjugated cycloalkadienes having 5 to 8 carbon atoms vinylcycloalkenes having 7 to 10 carbon atoms in which one of the carbon-carbon double bonds is hydrogenated, carbon-carbon double bonds
  • the form in the case of copolymerizing two or more types may be random copolymerization, block copolymerization, graft copolymerization, or tapered copolymerization.
  • the monomer to be used for (co) polymerization has two carbon-carbon double bonds, any of them may be used for the polymerization, and in the case of conjugated alkadiene, it is a 1,2-bond. 1,4-bonds may be used, and the ratio of 1,2-bonds to 1,4-bonds is not particularly limited as long as the glass transition point or softening point is 50 ° C. or lower.
  • the repeating unit constituting the polymer block (B) has a carbon-carbon double bond as in the case of a vinylcycloalkene unit, a conjugated alkadiene unit or a conjugated cycloalkadiene unit
  • the present invention From the standpoint of improving the power generation performance and heat resistance deterioration of the membrane-electrode assembly using the polymer electrolyte laminate film, it is preferable that 30 mol% or more of such carbon-carbon double bonds are hydrogenated. More preferably, 50 mol% or more is hydrogenated, and more preferably 80 mol% or more is hydrogenated.
  • the hydrogenation rate of the carbon-carbon double bond can be calculated by a commonly used method, for example, iodine value measurement method, 1 H-NMR measurement or the like.
  • the polymer block (B) has 2 to 2 carbon atoms from the viewpoint of giving the resulting block copolymer (I) elasticity and, in turn, good moldability in the production of a membrane-electrode assembly and a polymer electrolyte fuel cell.
  • the block is an alkene unit having 2 to 8 carbon atoms, a conjugated alkadiene unit having 4 to 8 carbon atoms, and a conjugate having 4 to 8 carbon atoms in which some or all of the carbon-carbon double bonds are hydrogenated.
  • the polymer block is composed of at least one repeating unit selected from alkadiene units, and includes an alkene unit having 2 to 6 carbon atoms, a conjugated alkadiene unit having 4 to 8 carbon atoms, and a carbon-carbon double bond. It is even more preferred that the polymer block is composed of at least one repeating unit selected from conjugated alkadiene units having 4 to 8 carbon atoms partially or wholly hydrogenated.
  • the most preferable alkene unit is an isobutene unit
  • the most preferable conjugated alkadiene unit is a 1,3-butadiene unit and / or an isoprene unit.
  • alkene having 2 to 8 carbon atoms examples include ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 1-heptene, 2-heptene, 1 -Octene, 2-octene and the like.
  • cycloalkene having 5 to 8 carbon atoms examples include cyclopentene, cyclohexene, cycloheptene and cyclooctene.
  • Examples of the vinylcycloalkene having 7 to 10 carbon atoms include vinylcyclopentene, vinylcyclohexene
  • Examples of the conjugated alkadiene having 4 to 8 carbon atoms include 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, 2,4-hexadiene, and the like.
  • 3-Dimethyl-1,3-butadiene, 2-ethyl-1 Examples include 3-butadiene, 1,3-heptadiene, 1,4-heptadiene, 3,5-heptadiene
  • examples of the conjugated cycloalkadiene having 5 to 8 carbon atoms include cyclopentadiene and 1,3-cyclohexadiene. It is done.
  • the polymer block (B) may contain other monomers as long as the purpose of the polymer block (B) to give elasticity to the block copolymer (I) is not impaired.
  • it may contain aromatic vinyl compounds such as styrene and vinyl naphthalene; halogen-containing vinyl compounds such as vinyl chloride.
  • the copolymerization form of the monomer and other monomer needs to be random copolymerization.
  • the amount of such other monomer used is preferably less than 50% by weight, more preferably less than 30% by weight, based on the total of the above monomers and other monomers. It is still more preferable that it is less than mass%.
  • the structure of the block copolymer (I) having the polymer block (A) and the polymer block (B) as constituent components is not particularly limited, but it is desirable that there are a plurality of polymer blocks (A). It is desirable that at least one end of (B) is not a terminal of the block copolymer (I).
  • Examples include an ABA type triblock copolymer, an ABBA type triblock copolymer and an AB type diblock copolymer, an ABBA type AB block copolymer.
  • Block copolymers (I) may be used alone or in combination of two or more.
  • the mass ratio of the polymer block (A) to the polymer block (B) is preferably 95: 5 to 5:95, more preferably 90:10 to 10:90, and 65:35 to 10 : 90 is even more preferable.
  • this mass ratio is 95: 5 to 5:95, it is advantageous for the ion channel formed by the polymer block (A) to become a cylindrical or continuous phase by microphase separation, which is practically sufficient. Excellent ionic conductivity is exhibited, and the ratio of the polymer block (B) that is hydrophobic is appropriate, and excellent water resistance is exhibited.
  • the structure of the block copolymer is not particularly limited. Examples include A2-B-A2-type triblock copolymer, A2-B-A1-A2 tetrablock copolymer, B-A2-B-A1 tetrablock copolymer, A2-B-A1-B tetra Block copolymer, A1-B-A1-A2 tetrablock copolymer, A2-B-A2-A1 tetrablock copolymer, A2-A1-B-A1-A2 pentablock copolymer, A1-A2- B-A2-A1 pentablock copolymer, A2-A1-B-A2-A1 pentablock copolymer, A1-B-A2-B-A1 pentablock copolymer, A2-B-A1 pentablock copolymer, A2-B-A2-B-A1 pentablock copolymer, A2-B-A1 pentablock copolymer, A
  • the block copolymer (I) used in the present invention includes those partially containing graft bonds.
  • Examples of the block copolymer partially containing a graft bond include those in which a part of the constituting polymer block is grafted to the main part (for example, main chain) of the block copolymer.
  • the number average molecular weight of the block copolymer (I) used in the present invention is not particularly limited, but is generally 10,000 to 1,000 as the number average molecular weight in terms of polystyrene in a state where no ion conductive group is introduced. 15,000 is preferred, 15,000 to 700,000 is more preferred, and 20,000 to 500,000 is even more preferred.
  • the block copolymer (I) constituting the polymer electrolyte laminate film of the present invention needs to have an ion conductive group in the polymer block (A).
  • ions in the present invention when referring to ionic conductivity include protons.
  • the ion conductive group is not particularly limited as long as the membrane-electrode assembly produced using the polymer electrolyte laminate film can exhibit sufficient ionic conductivity, and among them, —SO 3 M or A sulfonic acid group, a phosphonic acid group or a salt thereof represented by —PO 3 HM (wherein M represents a hydrogen atom, an ammonium ion or an alkali metal ion) is preferably used.
  • a carboxyl group or a salt thereof can also be used.
  • the introduction position of the ion conductive group is the polymer block (A) because it is particularly effective for improving the radical resistance of the entire block copolymer.
  • the introduction position of the ion conductive group into the polymer block (A) is not particularly limited, but when the polymer block (A) contains an aromatic ring in the repeating unit, the viewpoint of facilitating ion channel formation. Therefore, it is preferably introduced into the aromatic ring.
  • the amount of ion-conducting group introduced is appropriately selected depending on the required performance of the resulting block copolymer (I), etc., but has sufficient ion conductivity to be used as an electrolyte membrane for a polymer electrolyte fuel cell.
  • the ion exchange capacity of the block copolymer (I) is 0.70 meq / g or more, and 0.80 meq / g or more. It is more preferable.
  • the upper limit of the ion exchange capacity of the block copolymer (I) is 4.0 meq / g or less because if the ion exchange capacity becomes too large, the hydrophilicity tends to increase and the water resistance becomes insufficient. preferable.
  • the production method of the block copolymer (I) used in the present invention is not particularly limited, and a known method can be used, but after producing a block copolymer having no ion conductive group, A method of bonding an ion conductive group is preferable.
  • the production method of the polymer block (A) or (B) can be a radical polymerization method, an anionic polymerization method, a cationic polymerization method, although it is appropriately selected from coordination polymerization method and the like, radical polymerization method, anionic polymerization method and cationic polymerization method are preferably selected from the viewpoint of industrial ease.
  • the so-called living polymerization method is preferable from the viewpoint of molecular weight, molecular weight distribution, polymer structure, ease of bonding between the polymer block (B) and the polymer block (A) made of flexible components, and specifically living A radical polymerization method, a living anion polymerization method, and a living cation polymerization method are preferred.
  • a production method of a block copolymer comprising a polymer block (A) composed of poly ( ⁇ -methylstyrene) and a polymer block (B) composed of a conjugated alkadiene
  • a living anionic polymerization method from the viewpoint of industrial ease, molecular weight, molecular weight distribution, ease of bonding between the polymer block (A) and the polymer block (B), and the following specific examples
  • a typical synthesis example is shown.
  • the production method include a polymer block (A1) mainly composed of an aromatic vinyl compound such as 4-tert-butylstyrene, a polymer block (A2) composed of styrene or ⁇ -methylstyrene, and a conjugated alkadiene.
  • a method for producing a block copolymer or graft copolymer having a polymer block (B) comprising the above as a constituent component will be described.
  • the living anion polymerization method is preferable from the viewpoint of industrial ease, molecular weight, molecular weight distribution, ease of bonding of the polymer blocks (A1), (B) and (A2), and the following specific synthesis examples Is shown.
  • Aromatic vinyl compounds such as 4-tert-butylstyrene are polymerized at a temperature of 10 to 100 ° C. using an anionic polymerization initiator in a cyclohexane solvent, and then conjugated alkadiene and styrene are sequentially polymerized.
  • Aromatic compounds such as 4-tert-butylstyrene using an anionic polymerization initiator in a cyclohexane solvent at a temperature of 10 to 100 ° C.
  • aromatic vinyl compounds such as 4-tert-butylstyrene, conjugated alkadienes, 4-tert-butylstyrene, etc.
  • A1-B-A1 type block copolymer is prepared by sequential polymerization of aromatic vinyl compounds and an anionic polymerization initiator system (anionic polymerization initiator / N, N, N ′, N′-tetramethylethylenediamine) is added.
  • the block copolymer thus produced is subjected to a hydrogenation reaction of a double bond of a conjugated alkadiene unit having 4 to 8 carbon atoms constituting the polymer block (B).
  • a hydrogenation reaction a solution of a block copolymer obtained by anionic polymerization or the like is charged into a pressure vessel, and a hydrogenation reaction is performed in a hydrogen atmosphere using a Ziegler type hydrogenation catalyst such as a Ni / Al type. The method of performing can be illustrated.
  • a method for bonding an ion conductive group to the obtained block copolymer will be described.
  • a method for introducing a sulfonic acid group into the obtained block copolymer will be described.
  • Sulfonation can be performed by a known sulfonation method.
  • an organic solvent solution or suspension of a block copolymer is prepared, a sulfonating agent is added and mixed, a method of adding a gaseous sulfonating agent directly to the block copolymer, etc. Is exemplified.
  • Sulfonating agents used include sulfuric acid, a mixture of sulfuric acid and aliphatic acid anhydride, chlorosulfonic acid, a mixture of chlorosulfonic acid and trimethylsilyl chloride, sulfur trioxide, a mixture of sulfur trioxide and triethyl phosphate.
  • aromatic organic sulfonic acids represented by 2,4,6-trimethylbenzenesulfonic acid.
  • organic solvent to be used include halogenated hydrocarbons such as methylene chloride, linear aliphatic hydrocarbons such as hexane, cyclic aliphatic hydrocarbons such as cyclohexane, and the like. You may use it, selecting suitably from several combinations.
  • a method for removing the sulfonated product as a solid from the reaction solution containing the sulfonated product of the block copolymer a method of pouring the reaction solution into water and precipitating the sulfonated product, and then distilling off the solvent at atmospheric pressure, Stopper water is gradually added and suspended in the reaction solution, and the sulfonated product is precipitated, and then the solvent is distilled off at atmospheric pressure. From the viewpoint of increasing the washing efficiency, a method of gradually adding and suspending the stopper water in the reaction solution to precipitate the sulfonated product is suitably used.
  • Phosphonation can be performed by a known phosphonation method. Specifically, for example, an organic solvent solution or suspension of a block copolymer is prepared, and the copolymer is reacted with chloromethyl ether or the like in the presence of anhydrous aluminum chloride to introduce a halomethyl group into the aromatic ring. Thereafter, there may be mentioned a method in which phosphorus trichloride and anhydrous aluminum chloride are added and reacted, followed by a hydrolysis reaction to introduce a phosphonic acid group.
  • a method may be exemplified in which phosphorus trichloride and anhydrous aluminum chloride are added to the copolymer and reacted to introduce a phosphinic acid group into the aromatic ring, and then the phosphinic acid group is oxidized with nitric acid to form a phosphonic acid group.
  • the degree of sulfonation or phosphonation is, as already mentioned, until the ion exchange capacity of the block copolymer is 0.70 meq / g or more, especially 0.80 meq / g or more, but 4.0 meq / g or less. It is desirable to be sulfonated or phosphonated so that Thereby, practical ion conduction performance is obtained.
  • the ion exchange capacity of the sulfonated or phosphonated block copolymer, or the sulfonation rate or phosphonation rate in the aromatic vinyl compound in the block copolymer is determined by acid value titration, infrared spectroscopic measurement, nuclear It can be calculated using analytical means such as magnetic resonance spectrum ( 1 H-NMR spectrum) measurement.
  • the electrolyte laminate film of the present invention has at least two electrolyte membranes having different ion exchange capacities so that the electrolyte laminate membrane has both high dimensional stability and high proton conductivity (low resistance) under low humidity. Is important to. That is, when there are two constituent electrolyte membranes, they have different ion exchange capacities, and when there are three or more constituent electrolyte membranes, at least two of them have different ion exchange capacities.
  • the electrolyte laminate membrane of the present invention In order for the electrolyte laminate membrane of the present invention to exhibit sufficient ion conductivity for use as an electrolyte laminate membrane for a polymer electrolyte fuel cell, at least one ion exchange of the polymer electrolyte membrane which is a constituent electrolyte membrane
  • the capacity needs to be higher than 1.60 meq / g, and preferably 1.70 meq / g or more.
  • the upper limit of the ion exchange capacity is preferably 4.0 meq / g or less because if the ion exchange capacity becomes too large, the hydrophilicity tends to increase and the water resistance becomes insufficient.
  • At least one ion exchange capacity of the polymer electrolyte membrane which is a constituent electrolyte membrane is in a range of 0.70 to 1.60 meq / g, It is preferably 0.80 to 1.50 meq / g. If the ion exchange capacity becomes too small, proton conductivity tends to decrease under low humidity.
  • the electrolyte laminate film of the present invention As the electrolyte membrane constituting the electrolyte laminate film of the present invention, it is important to reduce the resistance between the electrolyte membrane and the electrode in order to bring out high power generation characteristics under low humidity. From this point of view, the electrolyte laminate film of the present invention is formed by laminating at least three polymer electrolyte membranes as constituent electrolyte membranes, and the two constituent electrolyte membranes constituting the outermost layer of the electrolyte laminate membrane are both 1.60 meq. A polymer electrolyte membrane having an ion exchange capacity higher than / g is preferred.
  • the electrolyte laminate film of the present invention when used as an electrolyte laminate film for a polymer electrolyte fuel cell, in order to have sufficient ion conductivity and high dimensional stability under low humidity,
  • the difference between the ion exchange capacity of the electrolyte membrane having the larger capacity and the ion exchange capacity of the electrolyte membrane having the smaller capacity is preferably 0.05 meq / g or more, more preferably 0.10 meq / g or more. Is more preferably 0.15 meq / g or more.
  • the ion exchange capacity as a whole of the electrolyte laminated film of the present invention is preferably in the range of 1.0 to 3.0 meq / g in order to have sufficient ion conductivity and high dimensional stability. More preferably, it is within the range of 0.2 to 2.7 meq / g, and even more preferably within the range of 1.3 to 2.5 meq / g.
  • the degree of sulfonation or phosphonation in the block copolymer (I) is such that, in the case of an electrolyte membrane having a large ion exchange capacity, the ion exchange capacity is higher than 1.60 meq / g. In the case of an electrolyte membrane having a small ion exchange capacity, it is preferable to sulfonate or phosphonate to 1.70 meq / g or more and 4.0 meq / g or less.
  • the ion exchange capacity of a sulfonated or phosphonated copolymer or an electrolyte membrane containing the copolymer, the sulfonation rate or phosphonation rate of the copolymer is determined by acid value titration method, infrared spectroscopic measurement, nuclear magnetic resonance It can be calculated using analytical means such as spectrum ( 1 H-NMR spectrum) measurement.
  • At least two of the electrolyte membranes constituting the electrolyte laminate film of the present invention contain the block copolymer (I), and at least one of the block copolymer (I) -containing electrolyte membranes is from 1.60 meq / g.
  • Sufficient ions under low humidity have a high ion exchange capacity and at least one of the block copolymer (I) -containing electrolyte membranes has an ion exchange capacity in the range of 0.70 to 1.60 meq / g. From the viewpoint of combining conductivity and high dimensional stability, it is preferable.
  • the ion conductive group may be introduced in the form of a salt neutralized with a suitable metal ion (for example, alkali metal ion) or counter ion (for example, ammonium ion).
  • a suitable metal ion for example, alkali metal ion
  • counter ion for example, ammonium ion
  • a block copolymer having a sulfonic acid group in a salt form can be obtained by ion exchange by an appropriate method.
  • the electrolyte laminate film of the present invention may have a film containing at least one other ion-conducting group-containing polymer in addition to the film containing the block copolymer (I) as the constituent electrolyte film.
  • ion conductive group-containing polymers include ionomers such as polystyrene sulfonic acid, poly (trifluorostyrene) sulfonic acid, polyvinyl sulfonic acid, polyvinyl carboxylic acid, and polyvinyl phosphonic acid; polytetrafluoroethylene, tetrafluoro Perfluorocarbon polymers such as ethylene / ethylene copolymer, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, polyvinylidene fluoride, sulfonic acid group, phosphonic acid group and
  • Polysulfone, polyethersulfone and polyetherketone as used herein are generic names for polymers having a sulfone bond, an ether bond or a ketone bond in the molecular chain.
  • Polyetherketoneketone, polyetheretherketone, polyketone Includes ether ketone sulfone.
  • the other ion conductive group-containing polymer may be an ion exchange resin further containing at least one of a sulfonic acid group, a phosphonic acid group, and a carboxyl group.
  • the electrolyte laminate film of the present invention is various additives such as softeners, stabilizers, light stabilizers, antistatic agents, mold release agents, flame retardants, foaming agents, pigments, Dyes, brighteners, carbon fibers, inorganic fillers and the like may be contained alone or in combination of two or more.
  • softener examples include petroleum softeners such as paraffinic, naphthenic or aromatic process oils, paraffin, vegetable oil softeners, plasticizers, and the like.
  • Stabilizers include phenol-based stabilizers, sulfur-based stabilizers, phosphorus-based stabilizers, and the like.
  • the content of the block copolymer (I) in the electrolyte laminated film of the present invention is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass. The above is even more preferable.
  • the electrolyte laminated membrane of the present invention preferably has a thickness of about 5 to 500 ⁇ m from the viewpoint of performance, membrane strength, handling properties, etc. required as an electrolyte membrane for a polymer electrolyte fuel cell.
  • a thickness of about 5 to 500 ⁇ m from the viewpoint of performance, membrane strength, handling properties, etc. required as an electrolyte membrane for a polymer electrolyte fuel cell.
  • the film thickness is more preferably 11 to 300 ⁇ m, still more preferably 15 to 80 ⁇ m.
  • the thickness of the individual membranes in the electrolyte laminated membrane of the present invention is not particularly limited, but the polymer electrolyte membrane having a higher ion exchange capacity, that is, a polymer electrolyte membrane having a higher ion exchange capacity than 1.60 meq / g
  • the thickness is preferably 2 to 20 ⁇ m, more preferably 4 to 15 ⁇ m, and the polymer electrolyte membrane having a lower ion exchange capacity, that is, the ion exchange capacity is 0.70 to 1.60 meq / g.
  • the thickness of one layer of the polymer electrolyte membrane is preferably 3 to 40 ⁇ m, and more preferably 7 to 35 ⁇ m.
  • the ratio of the total film thickness of the polymer electrolyte membrane having a higher ion exchange capacity and the total film thickness of the polymer electrolyte film having a lower ion exchange capacity in the electrolyte laminated film of the present invention is not particularly limited,
  • the total film thickness of the polymer electrolyte membrane having a higher ion exchange capacity) / (total film thickness of the polymer electrolyte membrane having a lower ion exchange capacity) is preferably 0.2 to 8.8, preferably 0.3 to 3.6 is more preferable.
  • any method can be adopted as long as it is a normal method for such preparation.
  • the constituent material of the electrolyte laminated film of the present invention (block copolymer (I), the above-mentioned other ion-conducting group-containing polymer, the above-mentioned additive, etc.) is mixed with a suitable solvent, and 5% by mass.
  • Stroke method a method of forming a film using a known method such as hot press molding, roll molding, extrusion molding, etc. can be used, but from the viewpoint of easily preparing an electrolyte membrane having good strength and flexibility, A solution coating method is preferably used.
  • another layer may be formed on the electrolyte film layer obtained by the above film forming method by any one of the above film forming methods. .
  • the solvent used at this time is not particularly limited as long as it can prepare a solution having a viscosity that allows solution coating without destroying the structure of the block copolymer (I).
  • halogenated hydrocarbons such as methylene chloride, aromatic hydrocarbons such as toluene, xylene, and benzene, linear aliphatic hydrocarbons such as hexane and heptane, and cyclic aliphatic carbonization such as cyclohexane.
  • ethers such as hydrogen and tetrahydrofuran
  • alcohols such as methanol, ethanol, propanol, isopropanol, butanol and isobutyl alcohol, or mixed solvents thereof.
  • a mixed solvent of tetrahydrofuran and methanol is preferable, and a mixed solvent of toluene and isobutyl alcohol and a mixed solvent of toluene and isopropyl alcohol are particularly preferable.
  • the solvent removal conditions in the solution coating method are arbitrarily selected as long as the conditions are such that the ion conductive groups such as sulfonic acid groups of the block copolymer (I) can be removed and the solvent can be completely removed. Is possible.
  • a plurality of temperatures may be arbitrarily combined, or a combination of ventilation and vacuum may be arbitrarily combined. Specifically, a method of removing the solvent by hot air drying at about 60 to 100 ° C. over 4 minutes, a method of removing the solvent in 2 to 4 minutes by hot air drying at about 100 to 140 ° C., After preliminarily drying at about 25 ° C. for about 1 to 3 hours and then drying with hot air drying at about 100 ° C.
  • Examples include a method of drying for about 1 to 12 hours by vacuum drying under an atmosphere of about 40 ° C. From the viewpoint of easy preparation of an electrolyte membrane having good strength and flexibility, a method of removing the solvent over 4 minutes or more by hot air drying at about 60 to 100 ° C., or about 1 to 3 hours at about 25 ° C. After drying, it is dried by hot air drying at about 100 ° C. over several minutes, or after preliminary drying at about 25 ° C. for about 1 to 3 hours, and then vacuum drying in an atmosphere at about 25 to 40 ° C. For example, a method of drying for about 1 to 12 hours is preferably used.
  • a membrane-electrode assembly using the electrolyte laminated film of the present invention will be described.
  • a known method can be applied.
  • a catalyst paste containing an ion conductive binder is applied on the gas diffusion layer by a printing method or a spray method and dried.
  • a solution or suspension containing an ion conductive binder is applied to both surfaces of the electrolyte laminated film and / or the catalyst layer surface of a pair of gas diffusion electrodes, and the electrolyte laminated film and the catalyst layer surface are bonded together.
  • the solution or suspension may be applied to either the electrolyte membrane or the catalyst layer surface, or may be applied to both.
  • the catalyst paste is applied to a base film made of polytetrafluoroethylene (PTFE) and dried to form a catalyst layer, and then a pair of base films on the base film is formed.
  • PTFE polytetrafluoroethylene
  • the catalyst layer is transferred to both sides of the electrolyte laminate film by thermocompression bonding, and the base film is peeled to obtain a joined body of the electrolyte laminate film and the catalyst layer, and the gas diffusion layer is crimped to each catalyst layer by hot pressing.
  • an ion conductive group may be in a salt state with a metal such as Na, and a treatment for returning to a proton type by acid treatment after bonding may be performed.
  • Examples of the ion-conductive binder constituting the membrane-electrode assembly include existing perfluorosulfones such as “Nafion” (registered trademark, manufactured by DuPont) and “Gore-select” (registered trademark, manufactured by Gore).
  • An ion conductive binder made of an acid polymer, an ion conductive binder made of sulfonated polyethersulfone or sulfonated polyetherketone, an ion conductive binder made of polybenzimidazole impregnated with phosphoric acid or sulfuric acid can be used. .
  • an ion conductive binder from the block copolymer (I) which comprises the electrolyte laminated film of this invention.
  • an ion conductive binder formed of the same material as the constituent electrolyte film on the surface in close contact with the gas diffusion electrode it is preferable to use an ion conductive binder formed of the same material as the constituent electrolyte film on the surface in close contact with the gas diffusion electrode.
  • the constituent material of the catalyst layer of the membrane-electrode assembly is not particularly limited as the conductive material / catalyst support, and examples thereof include carbon materials.
  • the carbon material include carbon black such as furnace black, channel black, and acetylene black, activated carbon, graphite, and the like. These may be used alone or in combination of two or more.
  • the catalyst metal may be any metal that promotes the oxidation reaction of fuel such as hydrogen and methanol and the reduction reaction of oxygen, such as platinum, gold, silver, palladium, iridium, rhodium, ruthenium, iron, Cobalt, nickel, chromium, tungsten, manganese, palladium, etc., or alloys thereof, for example, platinum-ruthenium alloy can be mentioned.
  • the particle size of the metal serving as a catalyst is usually 10 to 300 angstroms.
  • the catalyst layer may contain a water repellent as necessary.
  • the water repellent include various thermoplastic resins such as polytetrafluoroethylene, polyvinylidene fluoride, styrene butadiene copolymer, and polyether ether ketone.
  • the gas diffusion layer of the membrane-electrode assembly is made of a material having conductivity and gas permeability, and examples of such a material include porous materials made of carbon fibers such as carbon paper and carbon cloth. Moreover, in order to improve water repellency, this material may be subjected to water repellency treatment.
  • the membrane-electrode assembly of the present invention uses a pure hydrogen type using hydrogen as a fuel gas, a methanol reforming type using hydrogen obtained by reforming methanol, and hydrogen obtained by reforming natural gas. Natural gas reforming type, gasoline reforming type using hydrogen obtained by reforming gasoline, direct methanol type using methanol directly, etc. is there.
  • the electrolyte laminate film, membrane-electrode assembly, and polymer electrolyte fuel cell of the present invention are economical, environmentally friendly, and have both high dimensional stability and high ionic conductivity under low humidity. Can exhibit high output characteristics and can also exhibit excellent durability.
  • the number average molecular weight (GPC measurement, polystyrene conversion) of the obtained mSBmS was 78000, the 1,4-bond content determined from 1 H-NMR measurement was 55%, and the content of ⁇ -methylstyrene unit was 28.0. It was mass%.
  • mSEBmS poly ⁇ -methylstyrene-b-hydrogenated polybutadiene-b-poly ⁇ -methylstyrene type triblock copolymer
  • tBSSIStBS poly (4-tert-butylstyrene) -b-polystyrene- b-polyisoprene-b-polystyrene-b-poly ( 4-tert-butylstyrene)
  • tBSSIStBS number average molecular weight (GPC measurement, polystyrene conversion) of the obtained tBSSIStBS was 86050, which was obtained from 1 H-NMR measurement.
  • -Bonding amount was 94.0%
  • styrene unit content was 32.9% by mass
  • 4-tert-butylstyrene unit content was 29.8% by mass.
  • tBSSEPStBS poly (4-tert-butylstyrene) -b-polystyrene-b-hydrogenated polyisoprene-b-polystyrene-b-poly (4-tert-butylstyrene)
  • tBSSISt BS Poly (4-tert-butylstyrene) (tBSSISt BS) was synthesized.
  • the number average molecular weight (GPC measurement, polystyrene conversion) of the obtained tBSSIStBS is 103600, the 1,4-bond content determined from 1 H-NMR measurement is 94.0%, and the content of styrene units is 17.0 mass.
  • tBSSEPStBS poly (4-tert-butylstyrene) -b-polystyrene-b-hydrogenated polyisoprene-b-polystyrene-b-poly (4-tert-butylstyrene)
  • Poly (4-tert-butylstyrene) -b-polystyrene by sequentially adding 80.4 ml of isoprene, 28.1 ml of styrene, and 16.6 ml of 4-tert-butylstyrene, followed by polymerization at 60 ° C.
  • tBSSIStBS polybisulfonate-butylstyrene
  • the number average molecular weight (GPC measurement, polystyrene conversion) of the obtained tBSSIStBS was 38910, the 1,4-bond content determined from 1 H-NMR measurement was 94.0%, and the content of styrene units was 37.5 mass. %, 4-tert-butylstyrene unit content was 22.0% by mass.
  • a hydrogenation reaction was performed at 70 ° C. for 8 hours in a hydrogen atmosphere using a Ni / Al Ziegler hydrogenation catalyst.
  • tBSSEPStBS poly (4-tert-butylstyrene) -b-polystyrene-b-hydrogenated polyisoprene-b-polystyrene-b-poly (4-tert-butylstyrene)
  • the number average molecular weight (GPC measurement, polystyrene conversion) of the obtained tBSSIStBS is 113960
  • the 1,4-bond content determined from 1 H-NMR measurement is 93.8%
  • the content of styrene units is 24.2 mass. %
  • 4-tert-butylstyrene unit content was 27.6% by mass.
  • tBSSEPStBS poly (4-tert-butylstyrene) -b-polystyrene-b-hydrogenated polyisoprene-b-polystyrene-b-poly (4-tert-butylstyrene)
  • Poly (4-tert-butylstyrene) -b-polystyrene by sequentially adding 81.6 ml of isoprene, 8.0 ml of styrene, and 28.3 ml of 4-tert-butylstyrene, followed by polymerization at 60 ° C.
  • tBSSIStBS polyisoprene-b-polystyrene-b-poly (4 -Tert-butylstyrene)
  • the number average molecular weight (GPC measurement, polystyrene conversion) of the obtained tBSSIStBS is 109570
  • the 1,4-bond content determined from 1 H-NMR measurement is 93.8%
  • the content of styrene units is 10.9 mass. %
  • 4-tert-butylstyrene unit content was 42.8% by mass.
  • tBSSEPStBS poly (4-tert-butylstyrene) -b-polystyrene-b-hydrogenated polyisoprene-b-polystyrene-b-poly (4-tert-butylstyrene)
  • Production Example 1 (1) Synthesis of sulfonated mSEBmS 70 g of the block copolymer (mSEBmS) obtained in Reference Example 1 was vacuum-dried in a glass reaction vessel equipped with a stirrer for 1 hour and then purged with nitrogen, and then 563 ml of methylene chloride. And dissolved by stirring at room temperature. After dissolution, a sulfonation reagent obtained by reacting 162 ml of acetic anhydride and 122 ml of sulfuric acid at 0 ° C. in 385.0 ml of methylene chloride was gradually added dropwise over 5 minutes. After stirring at room temperature for 72 hours, 30 ml of distilled water as a stopper was added.
  • the sulfonation rate of the benzene ring of the ⁇ -methylstyrene unit of the obtained sulfonated mSEBmS was 99.9 mol% from 1 H-NMR analysis, and the ion exchange capacity was 1.91 meq / g.
  • the sulfonation rate of the benzene ring of the ⁇ -methylstyrene unit of the obtained sulfonated mSEBmS was 72.0 mol% from 1 H-NMR analysis, and the ion exchange capacity of the sulfonated mSEBmS was 1.44 meq / g.
  • the sulfonation rate of the benzene ring of the ⁇ -methylstyrene unit of the obtained sulfonated mSEBmS was 22.5 mol% from 1 H-NMR analysis, and the ion exchange capacity of the sulfonated mSEBmS was 0.49 meq / g.
  • the sulfonation rate of the benzene ring of the styrene unit in the obtained sulfonated tBSSEPStBS was 100 mol% from 1 H-NMR analysis, and the ion exchange capacity of the sulfonated tBSSEPStBS was 2.50 meq / g.
  • the sulfonation rate of the benzene ring of the styrene unit in the obtained sulfonated tBSSEPStBS was 99 mol% from 1 H-NMR analysis, and the ion exchange capacity was 1.47 meq / g.
  • the sulfonation rate of the benzene ring of the styrene unit in the obtained sulfonated tBSSEPStBS was 99.6 mol% from 1 H-NMR analysis, and the ion exchange capacity of the sulfonated tBSSEPStBS was 2.80 meq / g.
  • the sulfonation rate of the benzene ring of the styrene unit in the obtained sulfonated tBSSEPStBS was 97 mol% from 1 H-NMR analysis, and the ion exchange capacity of the sulfonated tBSSEPStBS was 1.89 meq / g.
  • the sulfonation rate of the benzene ring of the styrene unit in the obtained sulfonated tBSSEPStBS was 51.3 mol% from 1 H-NMR analysis, and the ion exchange capacity of the sulfonated tBSSEPStBS was 0.52 meq / g.
  • Example 1 (1) Preparation of electrolyte laminated film A 16% by mass toluene / isopropyl alcohol (mass ratio 5/5) solution of the sulfonated tBSSEPStBS (ion exchange capacity 2.50 meq / g) obtained in Production Example 4 was prepared and separated. The first layer is formed by coating the PET film [Toyobo Ester Film K1504] manufactured by Toyobo Co., Ltd. with a thickness of about 75 ⁇ m and drying in a hot air dryer at 100 ° C. for 4 minutes. A film (A) having a thickness of 8 ⁇ m was obtained.
  • PET film [Toyobo Ester Film K1504] manufactured by Toyobo Co., Ltd. with a thickness of about 75 ⁇ m and drying in a hot air dryer at 100 ° C. for 4 minutes.
  • a film (A) having a thickness of 8 ⁇ m was obtained.
  • a Pt-Ru alloy catalyst-supported carbon is mixed with a 10% by weight aqueous dispersion of Nafion so that the mass ratio of the Pt-Ru alloy catalyst-supported carbon and Nafion is 1: 1, and the paste is uniformly dispersed.
  • This paste was uniformly applied to one side of the carbon paper.
  • the electrode for anode was produced by drying at 130 ° C. for 30 minutes. Further, a 10% by mass solution of Nafion is added to and mixed with Pt catalyst-carrying carbon so that the mass ratio of Pt catalyst-carrying carbon and Nafion is 1: 0.75 to prepare a uniformly dispersed paste.
  • a cathode electrode was prepared in the same manner as the anode side.
  • the electrolyte laminate film prepared in (1) is sandwiched between the two types of electrodes so that the membrane and the catalyst face each other, and the outside is sandwiched between two heat-resistant films and two stainless steel plates in order, and hot pressing is performed.
  • a membrane-electrode assembly was produced by (130 ° C., 20 kg / cm 2, 8 min). Next, the membrane-electrode assembly produced is sandwiched between two conductive separators that also serve as gas supply channels, and the outside is sandwiched between two current collector plates and two clamping plates.
  • An evaluation cell for a molecular fuel cell was produced.
  • Example 2 (1) Preparation of electrolyte laminated membrane A 7% by mass toluene / isobutyl alcohol (mass ratio 6/4) solution of the sulfonated mSEBmS (ion exchange capacity 1.91 meq / g) obtained in Production Example 1 was prepared and separated. The first layer is formed by coating the PET film [Toyobo Co., Ltd. “Toyobo Ester Film K1504”] with a thickness of about 150 ⁇ m and drying with a hot air dryer at 100 ° C. for 4 minutes. A film (A) having a thickness of 6 ⁇ m was obtained.
  • PET film Toyobo Co., Ltd. “Toyobo Ester Film K1504”
  • Example 3 (1) Preparation of electrolyte laminated film A 14% by mass toluene / isobutyl alcohol (mass ratio 75/25) solution of the sulfonated tBSSEPStBS (ion exchange capacity 1.47 meq / g) obtained in Production Example 5 was prepared and separated.
  • Form-treated PET film [Toyobo Co., Ltd. “Toyobo Ester Film K1504”] is coated with a thickness of about 100 ⁇ m and dried in a hot air dryer at 100 ° C. for 4 minutes to form the first layer. A film (A) having a thickness of 8 ⁇ m was obtained.
  • Comparative Example 1 (1) Production of electrolyte membrane for polymer electrolyte fuel cell 18% by mass toluene / isopropyl alcohol (mass ratio 5/5) solution of sulfonated tBSSEPStBS (ion exchange capacity 2.50 meq / g) obtained in Production Example 4 A 30 ⁇ m thick film was obtained by coating with a thickness of about 350 ⁇ m on a PET film [Toyobo “Toyobo Ester Film K1504” manufactured by Toyobo Co., Ltd.] and drying at 100 ° C. for 4 minutes. It was. (2) Production of single cell for polymer electrolyte fuel cell An evaluation cell for polymer electrolyte fuel cell was produced under the same conditions as in Example 1- (2) except that the obtained membrane was used. .
  • Comparative Example 2 (1) Preparation of electrolyte membrane A 17% by mass toluene / isobutyl alcohol (mass ratio 75/25) solution of the sulfonated tBSSEPStBS (ion exchange capacity 1.47 meq / g) obtained in Production Example 5 was prepared and released. A coated PET film [“Toyobo Ester Film K1504” manufactured by Toyobo Co., Ltd.] is coated with a thickness of about 300 ⁇ m and dried in a hot air dryer at 100 ° C. for 4 minutes to obtain a film having a thickness of 30 ⁇ m. It was. (2) Production of single cell for polymer electrolyte fuel cell An evaluation cell for polymer electrolyte fuel cell was produced under the same conditions as in Example 1- (2) except that the obtained membrane was used. .
  • Comparative Example 3 (1) Production of electrolyte membrane A 6% by mass toluene / isobutyl alcohol (mass ratio 6/4) solution of the sulfonated mSEBmS (ion exchange capacity 1.91 meq / g) obtained in Production Example 1 was prepared and released. A treated PET film [“Toyobo Ester Film K1504” manufactured by Toyobo Co., Ltd.] is coated with a thickness of about 250 ⁇ m and dried in a hot air dryer at 100 ° C. for 4 minutes to obtain a film having a thickness of 11 ⁇ m. It was. On the obtained film, a film having a thickness of 29 ⁇ m was obtained by applying it twice in the same manner. (2) Production of single cell for polymer electrolyte fuel cell An evaluation cell for polymer electrolyte fuel cell was produced under the same conditions as in Example 1- (2) except that the obtained membrane was used. .
  • Comparative Example 4 (1) Preparation of electrolyte membrane A 14% by mass toluene / isobutyl alcohol (mass ratio 7/3) solution of the sulfonated mSEBmS (ion exchange capacity 1.44 meq / g) obtained in Production Example 2 was prepared and released. A coated PET film [“Toyobo Ester Film K1504” manufactured by Toyobo Co., Ltd.] is coated at a thickness of about 275 ⁇ m and dried in a hot air dryer at 100 ° C. for 4 minutes to obtain a film having a thickness of 29 ⁇ m. It was. (2) Production of single cell for polymer electrolyte fuel cell An evaluation cell for polymer electrolyte fuel cell was produced under the same conditions as in Example 1- (2) except that the obtained membrane was used. .
  • Comparative Example 5 (1) Production of electrolyte laminated film A 12.5 mass% toluene / isobutyl alcohol (mass ratio 7/3) solution of the sulfonated tBSSEPStBS (ion exchange capacity 2.80 meq / g) obtained in Production Example 6 was prepared. The first layer was formed by coating with a thickness of about 75 ⁇ m on a PET film [Toyobo Co., Ltd. “Toyobo Ester Film K1504”] having been subjected to a release treatment, and dried at 100 ° C. for 4 minutes to form a first layer having a thickness of 7 ⁇ m. The electrolyte membrane (A) was obtained.
  • Comparative Example 7 (1) Preparation of electrolyte laminated membrane A 7% by mass toluene / isobutyl alcohol (mass ratio 6/4) solution of the sulfonated mSEBmS (ion exchange capacity 1.91 meq / g) obtained in Production Example 1 was prepared and separated. The first layer is formed by coating the PET film [Toyobo Co., Ltd. “Toyobo Ester Film K1504”] with a thickness of about 150 ⁇ m and drying with a hot air dryer at 100 ° C. for 4 minutes. An electrolyte membrane (A) having a thickness of 6 ⁇ m was obtained.
  • the air supply conditions were oxygen equivalent stoichiometric 2.0 and humidification 30% R.V. H and the cell temperature was 80 ° C.
  • a power generation test was carried out after sufficiently flowing 30% humidified gas, and the current density was 0.4 A / cm 2 The voltage value of was evaluated.
  • Example 1 and Comparative Examples 1 and 2 As can be seen from the comparison between Example 1 and Comparative Examples 1 and 2 and the comparison between Example 2 and Comparative Examples 3 and 4, the laminated films of Examples 1 and 2 were kept relative to each other while the linear expansion coefficient was suppressed. It was confirmed that excellent power generation performance was exhibited even at a humidity of 30%. Further, as can be seen from Comparative Example 5, the electrolyte laminated film composed of the electrolyte membrane having an ion exchange capacity larger than 1.6 shows excellent power generation performance even under a relative humidity of 30%, but the linear expansion coefficient. Becomes higher.
  • Comparative Example 6 in the electrolyte laminated film composed of the electrolyte membrane having an ion exchange capacity larger than 1.6 and the electrolyte membrane having an ion exchange capacity smaller than 0.7, although the linear expansion coefficient is suppressed, It was difficult to conduct a power generation test at a relative humidity of 30%.
  • Comparative Example 7 in the electrolyte laminated film including the electrolyte membrane having an ion exchange capacity smaller than 0.7, the linear expansion coefficient is suppressed, but it is difficult to perform the power generation test under a relative humidity of 30%. there were.
  • Example 3 when the electrolyte membrane having a high ion exchange capacity is arranged on the side in contact with the electrode, the electrolyte membrane having a low ion exchange capacity is arranged on the side in contact with the electrode. Compared with the case where it was made to show, the power generation performance was excellent.
  • the polymer electrolyte laminate film of the present invention can obtain high output characteristics even under low humidity in addition to high dimensional stability.
  • excellent bondability with the electrode is excellent, it can be said that the durability of the membrane-electrode assembly and the polymer electrolyte fuel cell using the same is also excellent.

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Abstract

L'invention concerne une membrane électrolytique mettant en oeuvre à la fois des propriétés de stabilité dimensionnelle élevée et de conductivité protonique élevée (faible résistance) dans des conditions de basses températures; permettant d'obtenir des propriétés de sortie élevées, lorsqu'elle est utilisée dans une pile à combustible à polymère solide mettant en oeuvre de l'hydrogène comme combustible, même dans des conditions de températures basses; et mettant également en oeuvre des propriétés de durée de vie et de bonne connexion avec une électrode. L'invention concerne aussi un ensemble électrode-membrane et une pile à combustible à polymère solide utilisant ladite membrane électrolytique. La membrane électrolytique multicouches est obtenue par superposition de plusieurs membranes électrolytiques polymères, au moins l'une desdites membranes électrolytiques possédant une capacité d'échange d'ions supérieure à 1,60meq/g, au moins l'une desdites membranes électrolytiques possédant une capacité d'échange d'ions comprise entre 0,70 et 1,60meq/g, et au moins l'une des membranes électrolytiques susmentionnées possédant un copolymère à blocs (I) dont les composants structurels sont une séquence polymère (A) comprenant un groupe conducteur d'ions; et une séquence polymère flexible (B). L'invention concerne aussi un ensemble électrode-membrane et une pile à combustible à polymère solide utilisant ladite membrane électrolytique.
PCT/JP2009/070308 2008-12-12 2009-12-03 Membrane électrolytique multicouches, ensemble électrode-membrane et pile à combustible Ceased WO2010067743A1 (fr)

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CN111875759A (zh) * 2019-05-03 2020-11-03 克拉通聚合物研究有限公司 嵌段共聚物及其用途
US11401410B2 (en) 2019-05-03 2022-08-02 Kraton Polymers Llc Block copolymer compositions, prepregs, and laminates made therefrom

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