JP2008130460A - 固体高分子電解質膜及び固体高分子型燃料電池用膜電極接合体 - Google Patents
固体高分子電解質膜及び固体高分子型燃料電池用膜電極接合体 Download PDFInfo
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- JP2008130460A JP2008130460A JP2006316308A JP2006316308A JP2008130460A JP 2008130460 A JP2008130460 A JP 2008130460A JP 2006316308 A JP2006316308 A JP 2006316308A JP 2006316308 A JP2006316308 A JP 2006316308A JP 2008130460 A JP2008130460 A JP 2008130460A
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- polymer electrolyte
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- cerium
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- 239000012528 membrane Substances 0.000 title claims abstract description 132
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 79
- 239000000446 fuel Substances 0.000 title claims abstract description 30
- -1 cerium ions Chemical class 0.000 claims abstract description 63
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 51
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 38
- 239000007787 solid Substances 0.000 claims description 48
- 229920000642 polymer Polymers 0.000 claims description 33
- 239000003792 electrolyte Substances 0.000 claims description 30
- 150000003983 crown ethers Chemical class 0.000 claims description 21
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003456 ion exchange resin Substances 0.000 claims description 10
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 10
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 9
- 239000004020 conductor Substances 0.000 claims description 8
- 238000009792 diffusion process Methods 0.000 claims description 7
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 238000010248 power generation Methods 0.000 abstract description 13
- 230000005611 electricity Effects 0.000 abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 25
- 239000007788 liquid Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000005342 ion exchange Methods 0.000 description 12
- 239000003014 ion exchange membrane Substances 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000000703 Cerium Chemical class 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- KHSBAWXKALEJFR-UHFFFAOYSA-H cerium(3+);tricarbonate;hydrate Chemical compound O.[Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O KHSBAWXKALEJFR-UHFFFAOYSA-H 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 2
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 description 1
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- FZIZEIAMIREUTN-UHFFFAOYSA-N azane;cerium(3+) Chemical compound N.[Ce+3] FZIZEIAMIREUTN-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000002739 cryptand Substances 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- QBEGYEWDTSUVHH-UHFFFAOYSA-P diazanium;cerium(3+);pentanitrate Chemical compound [NH4+].[NH4+].[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBEGYEWDTSUVHH-UHFFFAOYSA-P 0.000 description 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 230000005499 meniscus Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920005649 polyetherethersulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920012287 polyphenylene sulfone Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1039—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
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/881—Electrolytic membranes
-
- 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
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- Chemical & Material Sciences (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
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- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
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Abstract
【解決手段】セリウムイオンと抱接化合物を形成できる有機化合物(X)とセリウムイオンとを含有するか、又は、セリウムイオンを抱接した有機化合物(X)からなる抱接化合物(Y)を含有する、スルホン酸基を有する高分子電解質からなる固体高分子電解質膜。並びに、該固体高分子電解質膜の層とその両面に設けられた触媒層とを有する、燃料電池用の膜電極接合体。
【選択図】なし
Description
(a)セリウムイオン、及び、セリウムイオンと抱接化合物を形成できる有機化合物(X)
(b)セリウムイオンを抱接した前記有機化合物(X)からなる抱接化合物(Y)
(c)セリウムイオン及び前記有機化合物(X)の少なくとも一方、及び、前記抱接化合物(Y)
上記固体高分子電解質膜の層、及び、該固体高分子電解質膜の両面に設けられ、かつ触媒と導電物質とイオン交換樹脂とを含む触媒層を有する、燃料電池用膜電極接合体。
(1)スルホン酸基を有する高分子電解質膜を、セリウムイオンを含む溶液中に浸漬してスルホン酸基をセリウムイオンにイオン交換した後、有機化合物(X)を含む溶液に浸漬して、膜中に有機化合物(X)を含ませる。
(2)スルホン酸基を有する高分子電解質の分散液中に可溶性セリウム化合物を添加してスルホン酸基をセリウムイオンにイオン交換した後、該分散液に有機化合物(X)を含む溶液又は固体を添加し、得られた液を用いて塗工により製膜する方法。
(3)溶媒中でセリウム塩と有機化合物(X)を反応させて抱接化合物(Y)を形成し、次に抱接化合物(Y)を溶媒に溶解した溶液にスルホン酸基を有する高分子電解質膜を浸漬してスルホン酸基を抱接化合物(Y)にイオン交換して、抱接化合物(Y)を膜中に含ませる方法。
(4)溶媒中でセリウム塩と有機化合物(X)を反応させて抱接化合物(Y)を形成し、次に抱接化合物(Y)又はその溶液をスルホン酸基を有する高分子電解質の分散液中に添加し、得られた液を用いて塗工により製膜する。
PTFE:ポリテトラフルオロエチレン。
ETFE:エチレン・テトラフルオロエチレンコポリマー。
スルホン酸基を有するパーフルオロカーボン重合体(イオン交換容量1.1ミリ当量/g乾燥樹脂)300gとエタノール420gと水280gとを2Lオートクレーブに仕込み、密閉し、ダブルヘリカル翼にて105℃で6時間混合撹拌して均一な液(以下、溶液Aという)を得た。溶液Aの固形分濃度は30質量%であった。
例1と同様に作成した均一な透明の液状組成物Cを用い、炭酸セリウム水和物のセリウムと等モルのクラウンエーテルとして、アルドリッチ社製15−クラウン−5の0.73gを前記の均一な透明の液状組成物Cに添加し、室温で24時間撹拌して均一な透明の液状組成物Fを得た。次に例1と同様にして、セリウム及び15−クラウン−5の合算の質量は、膜に対して3.9%となることがわかった。
固体高分子電解質膜として、スルホン酸基を有するパーフルオロカーボン重合体からなる厚さ50μmのイオン交換膜(イオン交換容量1.1ミリ当量/g乾燥樹脂)であって、大きさ5cm×5cm(面積25cm2)を使用した。この膜全体の重さを乾燥窒素中で16時間放置した後、乾燥窒素中で測定したところ、0.251gであった。この膜のスルホン酸基の量は以下の式により求められる。
0.251×1.1(1.1ミリ当量/g乾燥樹脂)=0.276(ミリ当量)。
300mlガラス製丸底フラスコに、溶液Aを100gを用い、これにアルドリッチ社製18−クラウン−6の0.87gを仕込み、PTFE製半月板翼にて、室温で24時間撹拌して、均一な透明の液状組成物Fを得た。次に、この組成物Fを100μmのETFEシート(商品名:アフレックス100N、旭硝子社製)上に、ダイコータにてキャスト塗工し、80℃で10分予備乾燥した後、120℃、10分乾燥し、さらに150℃、30分のアニールを施し、膜厚50μmの固体高分子電解質膜を得た。
次に、この膜を用い、例1と同様の手法でこの膜に電極層を接合して膜電極接合体を作成し、例1と同様の評価を行った。結果を表1〜4に示す。
固体高分子電解質膜として、例3で用いたものと同じイオン交換膜を何も処理せずに用い、次に、この膜を用いて例1と同様にして膜電極接合体を得た。この膜電極接合体について例1と同様の評価を行ったところ、表1〜4に示す結果のとおりとなった。
Claims (9)
- 下記(a)〜下記(c)のいずれかを含む、スルホン酸基を有する高分子電解質からなる固体高分子電解質膜。
(a)セリウムイオン、及び、セリウムイオンと抱接化合物を形成できる有機化合物(X)
(b)セリウムイオンを抱接した前記有機化合物(X)からなる抱接化合物(Y)
(c)セリウムイオン及び前記有機化合物(X)の少なくとも一方、及び、前記抱接化合物(Y) - 前記有機化合物(X)がクラウンエーテル類である、請求項1記載の固体高分子電解質膜。
- 前記クラウンエーテル類が、15−クラウン−5、18−クラウン−6及びそれら構造を分子内に有する有機化合物からなる群から選ばれた少なくとも一種のクラウンエーテル類である、請求項2記載の固体高分子電解質膜。
- 前記固体高分子電解質膜が、セリウムイオンと有機化合物(X)(ただし、抱接化合物(Y)は両者の混合物とみなす)を合計量として0.5〜80質量%含む、請求項1〜3のいずれかに記載の固体高分子電解質膜。
- 前記固体高分子電解質膜が、セリウムイオン1モルに対し有機化合物(X)を0.2〜1.2モルの割合で含む(ただし、抱接化合物(Y)は両者の混合物とみなす)、請求項1〜4のいずれかに記載の固体高分子電解質膜。
- 前記高分子電解質が、スルホン酸基含有パーフルオロカーボン重合体である、請求項1〜5のいずれかに記載の固体高分子電解質膜。
- 前記スルホン酸基含有パーフルオロカーボン重合体が、−(OCF2CFX)m−Op−(CF2)n−SO3Hで表されるスルホン酸基含有側鎖(mは0〜3の整数を示し、nは1〜12の整数を示し、pは0又は1を示し、Xはフッ素原子又はトリフルオロメチル基を示す。)を有するパーフルオロカーボン重合体である、請求項6に記載の固体高分子電解質膜。
- 請求項1〜7のいずれかに記載の固体高分子電解質膜の層、及び、該固体高分子電解質膜の両面に設けられ、かつ触媒と導電物質とイオン交換樹脂とを含む触媒層を有する、燃料電池用膜電極接合体。
- 両触媒層の外側にそれぞれガス拡散層をさらに有する、請求項8に記載の燃料電池用膜電極接合体。
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