CA2527871A1 - Polymer electrolyte membrane having high durability and method for producing the same - Google Patents

Polymer electrolyte membrane having high durability and method for producing the same Download PDF

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CA2527871A1
CA2527871A1 CA002527871A CA2527871A CA2527871A1 CA 2527871 A1 CA2527871 A1 CA 2527871A1 CA 002527871 A CA002527871 A CA 002527871A CA 2527871 A CA2527871 A CA 2527871A CA 2527871 A1 CA2527871 A1 CA 2527871A1
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polymer electrolyte
electrolyte membrane
polymer
membrane
weight
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CA2527871C (en
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Naoto Miyake
Masanobu Wakizoe
Eiji Honda
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Asahi Kasei Chemicals Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/18—Polybenzimidazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2275—Heterogeneous membranes
    • C08J5/2281—Heterogeneous membranes fluorine containing heterogeneous membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C08K5/3447—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • 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
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements

Abstract

A polymer electrolyte membrane composed of (a) a fluorine polymer electrolyt e having an ion-exchange group and (b) a basic polymer is characterized in tha t at least a part of the component (a) and at least a part of the component (b ) are chemically bonded with each other if desired. A method for producing suc h a polymer electrolyte membrane is also disclosed. A membrane electrode assembly wherein the polymer electrolyte membrane is tightly held between an anode and a cathode and a solid polymer fuel cell using such a membrane electrode assembly are further disclosed.

Claims (42)

1. A polymer electrolyte membrane comprising:

(a) 50.000 to 99.999 % by weight, based on the to-tal weight of components (a) and (b), of a fluorinated polymer electrolyte having an ion exchange group, and (b) 0.001 to 50.000 % by weight, based on the total weight of components (a) and (b), of a basic polymer, wherein, optionally, at least a part of component (a) and at least a part of component (b) are chemically bonded to each other, said polymer electrolyte membrane exhibiting a sea/islands structure when a cross-section of said mem-brane which is taken in a thicknesswise direction of the membrane is examined with respect to a 15 µm x 15 µm area thereof by a transmission electron microscope.
2. The polymer electrolyte membrane according to claim 1, wherein the amount of said basic polymer (b) is from 0.01 to 10.000 % by weight, based on the total weight of components (a) and (b).
3. The polymer electrolyte membrane according to claim 2, wherein the amount of said basic polymer (b) is from 0.100 to 5.000 % by weight, based on the total weight of components (a) and (b).
4. The polymer electrolyte membrane according to any one of claims 1 to 3, wherein said basic polymer (b) is a nitrogen-containing aromatic basic polymer.
5. The polymer electrolyte membrane according to any one of claims 1 to 4, which has an ion exchange capac-ity of from 1.0 to 1.5 milliequivalents per gram of said membrane.
6. The polymer electrolyte membrane according to any one of claims 1 to 5, wherein said fluorinated polymer electrolyte (a) is represented by the following for-mula:

[CF2CF2]a- [CF2-CF(-O- (CF2-CF(CF3))b-O- (CF2) f-X4)] g wherein 0 <= a < 1, 0 < g <= 1, a + g = 1, 1 <= b <=3, 1 <= f <= 8, and X4 represents -COOH, -SO3H, -PO3H2 or - PO3H.
7. The polymer electrolyte membrane according to any one of claims 1 to 5, wherein said fluorinated polymer electrolyte (a) is represented by the following for-mula:

[CF2CF2] a- [CF2-CF (-O- (CF2) f-X4)] g wherein 0 <= a < 1, 0 < g <= 1, a + g = 1, 1 <= f <= 8, and X4 represents -COOH, -SO3H, -PO3H2 or - PO3H.
8. The polymer electrolyte membrane according to claim 4, wherein said nitrogen-containing aromatic ba-sic polymer is poly[2,2'-(m-phenylene)-5,5'-bibenz-imidazole].
9. The polymer electrolyte membrane according to any one of claims 1 to 8, which has a thickness of from 2 to 150 µm.
10. The polymer electrolyte membrane according to any one of claims 1 to 9, which exhibits a haze value of 25 % or less as measured in accordance with JIS K 7136, when it has a thickness of 50 µm.
11. The polymer electrolyte membrane according to any one of claims 1 to 10, which has a thickness other than 50 µm and exhibits a calculated haze value (H50) of 25 % or less, wherein said calculated haze value (H50) is defined as a haze value calculated on the assumption that the polymer electrolyte membrane has a thickness of 50 µm, said calculated haze value (H50) being obtained by the following formula:

wherein t represents the thickness (µm) of the polymer electrolyte membrane, and H t represents the haze value of the polymer electrolyte mem-brane, as measured in accordance with JIS K
7136.
12. The polymer electrolyte membrane according to any one of claims 1 to 11, wherein the ratio of the island particles in said sea/islands structure is from 0.1 to 70 %, in terms of the percentage of the total area of the island particles in said 15 µm x 15 µm area of the cross-section of said membrane.
13. The polymer electrolyte membrane according to any one of claims 1 to 12, wherein the density of the is-land particles in said sea/islands structure is from 0.1 to 100 island particles/µm2 in said 15 µm x 15 µm area of the cross-section of said membrane.
14. The polymer electrolyte membrane according to any one of claims 1 to 13, which has at least one rein-forcement selected from the group consisting of a rein-forcement contained in said membrane and a reinforce-ment secured to a surface of said membrane.
15. The polymer electrolyte membrane according to any one of claims 1 to 14, wherein at least a part of com-ponent (a) and at least a part of component (b) are chemically bonded to each other.
16. A polymer electrolyte membrane comprising:

(a) 50.000 to 99.999 % by weight, based on the to-tal weight of components (a) and (b), of a fluorinated polymer electrolyte having an ion exchange group, and (b) 0.001 to 50.000 % by weight, based on the total weight of components (a) and (b), of a basic polymer, wherein, optionally, at least a part of component (a) and at least a part of component (b) are chemically bonded to each other, wherein:

when said polymer electrolyte membrane has a thickness of 50 µm, said membrane exhibits a haze value of 25 % or less as measured in accordance with JIS K
7136, and when said polymer electrolyte membrane has a thickness other than 50 µm, said membrane exhibits a calculated haze value (H50) of 25 % or less, wherein said calculated haze value (H50) is defined as a haze value calculated on the assumption that the polymer electrolyte membrane has a thickness of 50 µm, said calculated haze value (H50) being obtained by the following formula:

wherein t represents the thickness (µm) of the polymer electrolyte membrane, and H t represents the haze value of the polymer electrolyte mem-brane, as measured in accordance with JIS K
7136.
17. The polymer electrolyte membrane according to claim 16, wherein the amount of said basic polymer (b) is from 0.01 to 10.000 % by weight, based on the total weight of components (a) and (b).
18. The polymer electrolyte membrane according to claim 17, wherein the amount of said basic polymer (b) is from 0.100 to 5.000 % by weight, based on the total weight of components (a) and (b).
19. The polymer electrolyte membrane according to any one of claims 16 to 18, wherein said basic polymer (b) is a nitrogen-containing aromatic basic polymer.
20. The polymer electrolyte membrane according to any one of claims 16 to 19, which exhibits a sea/islands structure when a cross-section of said membrane which is taken in a thicknesswise direction of the membrane is examined with respect to a 15 µm x 15 µm area thereof by a transmission electron microscope.
21. The polymer electrolyte membrane according to any one of claims 16 to 20, which has an ion exchange ca-pacity of from 1.0 to 1.5 milliequivalents per gram of said membrane.
22. The polymer electrolyte membrane according to any one of claims 16 to 21, wherein said fluorinated poly-mer electrolyte (a) is represented by the following formula:

[CF2CF2]a- [CF2-CF (-O-(CF2-CF (CF3)) b-O- (CF2) f-X4)]g wherein 0 <= a < 1, 0 < g <= 1, a + g = 1, 1 <= b <= 3, 1 <= f <= g, and X4 represents -COOH, -SO3H, -PO3H2 or -PO3H.
23. The polymer electrolyte membrane according to any one of claims 16 to 21, wherein said fluorinated poly-mer electrolyte (a) is represented by the following formula:

[CF2CF2]a- [CF2-CF(-O-(CF2)f-X4)]g wherein 0 <= a < 1, 0 < g <= 1, a + g = 1, 1 <= f <= 8, and X4 represents -COOH, -SO3H, -PO3H2 or -PO3H.
24. The polymer electrolyte membrane according to claim 19, wherein said nitrogen-containing aromatic ba-sic polymer is poly[2,2'-(m-phenylene)-5,5'-bibenz-imidazole].
25. The polymer electrolyte membrane according to any one of claims 16 to 24, which has a thickness of from 2 to 150 µm.
26. The polymer electrolyte membrane according to claim 20, wherein the ratio of the island particles in said sea/islands structure is from 0.1 to 70 %, in terms of the percentage of the total area of the island particles in said 15 µm ×15 µm area of the cross -section of said membrane.
27. The polymer electrolyte membrane according to claim 20 or 26, wherein the density of the island par-ticles in said sea/islands structure is from 0.1 to 100 island particles/µm2 in said 15 µm × 15 µm area of the cross-section of said membrane.
28. The polymer electrolyte membrane according to any one of claims 16 to 27, which has at least one rein-forcement selected from the group consisting of a rein-forcement contained in said membrane and a reinforce-ment secured to a surface of said membrane.
29. The polymer electrolyte membrane according to any one of claims 16 to 28, wherein at least a part of com-ponent (a) and at least a part of component (b) are chemically bonded to each other.
30. A method for producing a polymer electrolyte mem-brave, comprising:

providing a casting liquid in which a liquid me-dium comprising a protic solvent is mixed with a poly-mer mixture of:

(a) 50.000 to 99.999 % by weight, based on the to-tal weight of components (a) and (b), of a fluorinated polymer electrolyte having an ion exchange group, and (b) 0.001 to 50.000 % by weight, based on the total weight of components (a) and (b), of a basic polymer, casting said casting liquid onto a substrate to thereby form a liquid coating on said substrate, and removing said liquid medium from said liquid coat-ing to thereby form a solid polymer electrolyte mem-brave.
31. The method according to claim 30, wherein said liq-uid medium further comprises an aprotic solvent, and the amount of said protic solvent is 0.5 to 99.5 % by weight, and the amount of said aprotic solvent is 99.5 to 0.5 %
by weight, each based on the total weight of said protic solvent and said aprotic solvent.
32. The method according to claim 30 or 31, wherein the concentration of said liquid medium in said casting liq-uid is 75.000 to 98.990 % by weight, based on the weight of the casting liquid.
33. The method according to claim 31, wherein said casting liquid is prepared by a process comprising the steps of:
(1) dissolving the basic polymer (b) and the fluorinated polymer electrolyte (a) individually in an aprotic solvent to thereby obtain preliminary solutions A and B respectively, and mixing the obtained prelimi-nary solutions A and B together, followed by stirring, thereby obtaining a mixture of preliminary solutions A
and B;
(2) dissolving the fluorinated polymer electrolyte (a) in a protic solvent, to thereby obtain a preliminary solution C; and (3) mixing said mixture of preliminary solutions A
and B with said preliminary solution C, followed by stirring, thereby obtaining a casting liquid, said steps (1) and (2) being performed in either order or simultaneously.
34. The method according to any one of claims 30 to 33, which further comprises subjecting the formed polymer electrolyte membrane to heat treatment.
35. The method according to any one of claims 30 to 34, wherein said protic solvent is water.
36. A polymer electrolyte membrane obtained by the method of any one of claims 30 to 35.
37. A membrane/electrode assembly comprising the poly-mer electrolyte membrane of any one of claims 1 to 15, which is securely sandwiched between an anode and a cathode, wherein said anode comprises an anodic cata-lyst layer and is proton-conductive, and said cathode comprises a cathodic catalyst layer and is proton -conductive.
38. A membrane/electrode assembly comprising the poly-mer electrolyte membrane of any one of claims 16 to 29, which is securely sandwiched between an anode and a cathode, wherein said anode comprises an anodic cata-lyst layer and is proton-conductive, and said cathode comprises a cathodic catalyst layer and is proton -conductive.
39. A membrane/electrode assembly comprising the poly-mer electrolyte membrane of claim 36, which is securely sandwiched between an anode and a cathode, wherein said anode comprises an anodic catalyst layer and is proton -conductive, and said cathode comprises a cathodic catalyst layer and is proton-conductive.
40. A polymer electrolyte fuel cell comprising the membrane/electrode assembly of claim 37, wherein said anode and said cathode are connected to each other through an electron conductive material which is posi-tinned in the outside of said polymer electrolyte mem-brane.
41. A polymer electrolyte fuel cell comprising the membrane/electrode assembly of claim 38, wherein said anode and said cathode are connected to each other through an electron conductive material which is posi-tinned in the outside of said polymer electrolyte mem-brane.
42. A polymer electrolyte fuel cell comprising the membrane/electrode assembly of claim 39, wherein said anode and said cathode are connected to each other through an electron conductive material which is posi-tioned in the outside of said polymer electrolyte mem-brane.
CA2527871A 2003-06-27 2004-06-23 Polymer electrolyte membrane having high durability and method for producing the same Active CA2527871C (en)

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JP2003184226 2003-06-27
JP2003-184226 2003-06-27
JP2003-326230 2003-09-18
JP2003326230 2003-09-18
PCT/JP2004/009220 WO2005000949A1 (en) 2003-06-27 2004-06-23 Polymer electrolyte membrane with high durability and method for producing same

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CA2527871A1 true CA2527871A1 (en) 2005-01-06
CA2527871C CA2527871C (en) 2010-08-17

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JP (1) JP3983259B2 (en)
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DE (2) DE112004001057B4 (en)
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JP5008272B2 (en) * 2004-04-30 2012-08-22 旭化成イーマテリアルズ株式会社 Composite proton exchange membrane
US20060051648A1 (en) * 2004-09-06 2006-03-09 Fusaki Fujibayashi Solid polymer electrolyte membrane, method for producing the same, and fuel cell including the solid poymer electrolyte membrane
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