JP5384335B2 - イオン伝導性メンブラン - Google Patents
イオン伝導性メンブラン Download PDFInfo
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- JP5384335B2 JP5384335B2 JP2009514903A JP2009514903A JP5384335B2 JP 5384335 B2 JP5384335 B2 JP 5384335B2 JP 2009514903 A JP2009514903 A JP 2009514903A JP 2009514903 A JP2009514903 A JP 2009514903A JP 5384335 B2 JP5384335 B2 JP 5384335B2
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- 239000012528 membrane Substances 0.000 title claims description 88
- 229920000642 polymer Polymers 0.000 claims description 47
- 150000002678 macrocyclic compounds Chemical class 0.000 claims description 34
- 239000010411 electrocatalyst Substances 0.000 claims description 19
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 9
- 229920001940 conductive polymer Polymers 0.000 claims description 8
- 229920006260 polyaryletherketone Polymers 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000012779 reinforcing material Substances 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 description 23
- 239000000835 fiber Substances 0.000 description 17
- 239000000446 fuel Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000976 ink Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HMPXSWYLSSRSQF-UHFFFAOYSA-J ac1l4snl Chemical compound [Na+].[Na+].[Na+].[Na+].[Cu+2].C12=CC(S(=O)(=O)[O-])=CC=C2C(N=C2[N-]C(C3=CC=C(C=C32)S([O-])(=O)=O)=N2)=NC1=NC([C]1C=CC(=CC1=1)S([O-])(=O)=O)=NC=1N=C1[C]3C=CC(S([O-])(=O)=O)=CC3=C2[N-]1 HMPXSWYLSSRSQF-UHFFFAOYSA-J 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 150000004032 porphyrins Chemical class 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052752 metalloid Inorganic materials 0.000 description 3
- 150000002738 metalloids Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- GZEFZLXJPGMRSP-UHFFFAOYSA-N 37,38,39,40-tetrazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1(37),2,4,6,8,10,12(39),13,15,17,19,21,23,25,27,29,31,33,35-nonadecaene Chemical compound c1ccc2c3cc4[nH]c(cc5nc(cc6[nH]c(cc(n3)c2c1)c1ccccc61)c1ccccc51)c1ccccc41 GZEFZLXJPGMRSP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229920003935 Flemion® Polymers 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011067 equilibration Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012458 free base Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 1
- 229920003934 Aciplex® Polymers 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 0 C1C23*4=CC=C*2c(cccc2)c2*3=CC=CC1c1c4cccc1 Chemical compound C1C23*4=CC=C*2c(cccc2)c2*3=CC=CC1c1c4cccc1 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910009369 Zn Mg Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
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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
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- 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
-
- 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
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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
- H01M8/02—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
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
-
- 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
- H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
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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
- H01M8/1041—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
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- 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
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- Y02E60/50—Fuel cells
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Description
銅(II)フタロシアニン-テトラスルホン酸四ナトリウム塩(0.0348 g、0.0354 mmol、Na+ FW 984.26、H+ FW 896.26)を脱イオン水(0.188 g)中に飽和させた。酸形態にあり、下記の反復単位を有するスルホン化ポリアリールエーテルケトン重合体のビーズ(0.3 g、0.284 mmol)をこの混合物に加え、続いてN-メチル-2-ピロリドン(2.512 g)を加え、乾燥窒素下で透明な粘性溶液が得られるまで攪拌した。
銅(II)フタロシアニン-テトラスルホン酸四ナトリウム塩(0.0657 g、0.0668 mmol)及び酸形態にあるスルホン化ポリアリールエーテルケトン重合体ビーズ(例1に示す反復形態)(0.285 g、0.27 mmol)の混合物を98%硫酸(A.R.等級)(3 ml)中、60℃で一晩攪拌した。得られた透明で粘性の青色溶液を冷却し、脱イオン水中で凝固させた。凝固が完了した時、ビーズを粗いガラスシンター上に濾別し、脱イオン水(100 mL)中、室温で30分間攪拌し、次いで濾過した。この工程を、洗浄液の導電率が10μs未満になるまで数回繰り返した。得られたビーズを空気流中、75℃で、最後に真空下、75℃で一定重量になるまで乾燥させた。酸形態にある重合体の青色ビーズ(0.33 g)をN-メチル-2-ピロリドン(3.1 g)に加え、透明な粘性溶液が得られるまで、窒素下で攪拌した。この溶液を、綿のパッドを付けたCelite 521 (Aldrich)を通して、圧縮空気の下で濾過した。メンブランをガラス板上に、Gardner Knife (ガラス表面の上300μmの高さに設定)を使用してキャスティングし、50℃で乾燥させて大部分の溶剤を除去し、次いで105℃、真空下で、一定重量に乾燥させた。得られた青色の重合体フィルムは、大気中の水蒸気で数時間平衡化させた後、板から容易に引き離すことができた。メンブランの厚さ(約28μm)は6地点で測定し、それらの値を平均した。
メンブランを例2と同様に、銅(II)フタロシアニン-テトラスルホン酸四ナトリウム塩のモル比を2倍高くして製造した(重合体とフタロシアニンのモル比2:1)。組み合わせたメンブランの等価重量は420であった。
例1のメンブランを試験し、フタロシアニンがメンブラン中に保持されているか、否かを確認した。メンブランを1 M硫酸中に90℃で数時間浸漬し、次いで水中で1時間煮沸した。この処理の前後に、メンブランの乾燥質量を測定したが、2つの結果は、実験誤差の範囲内で等しかった(0.0210 g及び0.0218 g)。メンブランは、その強い青色を維持し、硫酸も水も青く染まらなかった。フタロシアニンはメンブラン中に保持されていることが結論付けられた。
現状技術水準のガス拡散槽及び触媒層を使用して2個のMEAを形成した。第一MEA(例MEA)中のメンブランは、例2により製造したメンブランであった。第二MEA(比較例MEA)中のメンブランは、そのメンブランが銅フタロシアニンを含まない以外は、例2により製造したスルホン化ポリアリールエーテルケトン重合体メンブランであった。これら2個のMEAを燃料電池で、燃料電池の温度を80℃から110℃に増加させる温度上昇実験で試験した(H2/空気、210 kPa、80℃露点)。図1は、温度をある時間にわたって増加させた時に電池電圧がどのように変化するかを示す。実験の大部分を通して、例MEAに対する電池電圧は、比較MEAに対する電池電圧よりも高い。
Claims (10)
- 前記化学式中、Mが、Cu、Fe、Co、Ni、Zn、Mg、Rh、Ru、Pd又はPtである、請求項1に記載のイオン伝導性メンブラン。
- 前記Mが、Cuである、請求項2に記載のイオン伝導性メンブラン。
- 前記イオン伝導性重合体成分と前記大環状化合物の重量比が50:1〜1:2である、請求項1〜3のいずれか一項に記載のイオン伝導性メンブラン。
- 前記イオン伝導性重合体成分が、過フッ化スルホン酸重合体、スルホン化ポリアリールエーテルケトン重合体、又はスルホン化ポリアリールエーテルスルホン重合体である、請求項1〜4のいずれか一項に記載のイオン伝導性メンブラン。
- 前記イオン伝導性メンブランが、補強材料をさらに含んでなる、請求項1〜5のいずれか一項に記載のイオン伝導性メンブラン。
- 請求項1〜6のいずれか一項に記載のイオン伝導性メンブラン及び前記メンブラン上の電気触媒層を備えてなる、触媒被覆されたメンブラン。
- 請求項1〜7のいずれか一項に記載のイオン伝導性メンブランを備えてなる、メンブラン電極アセンブリー。
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WO2010092175A1 (en) * | 2009-02-16 | 2010-08-19 | Hyet Holding B.V. | High differential pressure electrochemical cell comprising a specific membrane |
US8409765B2 (en) | 2009-08-31 | 2013-04-02 | GM Global Technology Operations LLC | Co(II)tetramethoxyphenylporphyrin additive to PFSA PEMS for improved fuel cell durability |
CN102612781B (zh) | 2009-11-10 | 2015-11-25 | 戴姆勒股份公司 | 用于燃料电池的具有经改善的添加剂的复合质子传导性电解质 |
US9101886B2 (en) | 2009-11-10 | 2015-08-11 | Daimler Ag | Composite proton conducting membrane with low degradation and membrane electrode assembly for fuel cells |
US20110111321A1 (en) * | 2009-11-10 | 2011-05-12 | Daimler Ag | Composite proton conducting membrane with low degradation and membrane electrode assembly for fuel cells |
CN102002167A (zh) * | 2010-10-30 | 2011-04-06 | 华南理工大学 | 应用于直接醇类燃料电池的质子交换膜及其制备方法 |
KR20120063163A (ko) | 2010-12-07 | 2012-06-15 | 삼성전자주식회사 | 리튬 공기 전지 |
US8758955B2 (en) | 2011-04-07 | 2014-06-24 | Daimler Ag | Additives to mitigate catalyst layer degradation in fuel cells |
US10566640B2 (en) | 2015-07-24 | 2020-02-18 | Daimler Ag | Composite proton conducting electrolyte with improved additives for fuel cells |
JP7366892B2 (ja) * | 2017-11-09 | 2023-10-23 | ザ ボード オブ トラスティーズ オブ ザ レランド スタンフォード ジュニア ユニバーシティー | 陽子交換膜燃料電池のための触媒担体上の超薄型電気化学触媒 |
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US4973391A (en) * | 1988-08-30 | 1990-11-27 | Osaka Gas Company, Ltd. | Composite polymers of polyaniline with metal phthalocyanine and polyaniline with organic sulfonic acid and nafion |
US5731105A (en) * | 1993-09-07 | 1998-03-24 | E.C.R. - Electro-Chemical Research Ltd. | Battery electrochemical cell with a non-liquid electrolyte |
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CA2655251A1 (en) | 2007-12-21 |
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EP2030273A1 (en) | 2009-03-04 |
WO2007144633A1 (en) | 2007-12-21 |
DE602007009679D1 (de) | 2010-11-18 |
EP2030273B1 (en) | 2010-10-06 |
GB0611736D0 (en) | 2006-07-26 |
KR101329494B1 (ko) | 2013-11-14 |
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