JP4955209B2 - 固体高分子型燃料電池用膜−電極構造体及び固体高分子型燃料電池 - Google Patents
固体高分子型燃料電池用膜−電極構造体及び固体高分子型燃料電池 Download PDFInfo
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- JP4955209B2 JP4955209B2 JP2004370433A JP2004370433A JP4955209B2 JP 4955209 B2 JP4955209 B2 JP 4955209B2 JP 2004370433 A JP2004370433 A JP 2004370433A JP 2004370433 A JP2004370433 A JP 2004370433A JP 4955209 B2 JP4955209 B2 JP 4955209B2
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- polymer electrolyte
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- membrane
- solid polymer
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 113
- 239000000446 fuel Substances 0.000 title claims abstract description 32
- 239000012528 membrane Substances 0.000 claims abstract description 97
- 239000007787 solid Substances 0.000 claims abstract description 90
- 229920000412 polyarylene Polymers 0.000 claims abstract description 81
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 130
- -1 sulfonate ester Chemical class 0.000 claims description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 9
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 100
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 96
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 89
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 72
- 239000000243 solution Substances 0.000 description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 59
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 50
- 229910052757 nitrogen Inorganic materials 0.000 description 49
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 42
- 239000000047 product Substances 0.000 description 38
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 36
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 36
- 239000002904 solvent Substances 0.000 description 35
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 33
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 32
- 238000003756 stirring Methods 0.000 description 31
- 239000007789 gas Substances 0.000 description 27
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 25
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 23
- 238000005227 gel permeation chromatography Methods 0.000 description 22
- 239000011572 manganese Substances 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 20
- 238000012916 structural analysis Methods 0.000 description 20
- 125000000542 sulfonic acid group Chemical group 0.000 description 20
- 239000004793 Polystyrene Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 18
- 238000009792 diffusion process Methods 0.000 description 18
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- 238000010992 reflux Methods 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 229910052697 platinum Inorganic materials 0.000 description 16
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 13
- 239000011701 zinc Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- 235000009518 sodium iodide Nutrition 0.000 description 12
- 238000012546 transfer Methods 0.000 description 12
- 229910001260 Pt alloy Inorganic materials 0.000 description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 150000002430 hydrocarbons Chemical group 0.000 description 11
- ZBRJXVVKPBZPAN-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Ni+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZBRJXVVKPBZPAN-UHFFFAOYSA-L 0.000 description 11
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 10
- 238000010790 dilution Methods 0.000 description 10
- 239000012895 dilution Substances 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000006467 substitution reaction Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000003446 ligand Substances 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000001226 reprecipitation Methods 0.000 description 8
- 125000002130 sulfonic acid ester group Chemical group 0.000 description 8
- 229910052723 transition metal Inorganic materials 0.000 description 8
- 229930185605 Bisphenol Natural products 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000013557 residual solvent Substances 0.000 description 7
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 239000002798 polar solvent Substances 0.000 description 6
- 229920001940 conductive polymer Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 229920000265 Polyparaphenylene Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000005074 adamantylmethyl group Chemical group 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 2
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 2
- ICYDRUIZSPKQOH-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)decyl]phenol Chemical compound C=1C=C(O)C=CC=1C(CCCCCCCCC)C1=CC=C(O)C=C1 ICYDRUIZSPKQOH-UHFFFAOYSA-N 0.000 description 2
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- NSWRSAFGHPRHGG-UHFFFAOYSA-L dichloronickel;2-pyridin-2-ylpyridine Chemical compound Cl[Ni]Cl.N1=CC=CC=C1C1=CC=CC=N1 NSWRSAFGHPRHGG-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 2
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Classifications
-
- 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
Landscapes
- Polyethers (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Conductive Materials (AREA)
- Fuel Cell (AREA)
Description
(化学式(2)〜(7)において、nは1以上の整数である)
(Yは2価の電子吸引基であり、Zは2価の電子供与基または直接接合であり、Arは−SO 3 R b で表される置換基を備える芳香族基であり、R a 、R b は炭素原子数1〜20の炭化水素基であり、jは0〜4の整数であり、kは0〜10の整数であり、lは0〜10の整数である)
(化学式(2)〜(7)において、nは1以上の整数である)
〔スルホン化ポリアリーレンのイオン交換容量〕
まず、本実施例で得られたスルホン化ポリアリーレンの水洗水がpH4〜6になるまで洗浄して、残存している遊離の酸を充分に除去して乾燥した後、所定量を秤量してTHF/水の混合溶剤に溶解した。次に、フェノールフタレインを指示薬としてNaOHの標準液にて滴定し、中和点からイオン交換容量を求めた。
〔固体高分子電解質膜のプロトン伝導度〕
まず、本実施例で得られた固体高分子電解質膜を5mm幅に裁断し、短冊状の試料とした。次に、前記試料の表面に、白金線(直径0.5mm)を押し当て、恒温恒湿装置中に試料を保持し、85℃、相対湿度90%の条件下、白金線間の交流インピーダンス測定することにより交流抵抗を求めた。抵抗測定装置として、ソーラートロン(Solartron)社製SI1260インピーダンスアナライザ(商品名)を用い、恒温恒湿装置にはエスペック社製小型環境試験機SH−241(商品名)を使用した。白金線を5mm間隔に5本押し当てて、線間距離を5〜20mmに変化させて交流抵抗を測定した。次に、線間距離と抵抗の勾配とから次式により固体高分子電解質膜の比抵抗を算出し、比抵抗の逆数から交流インピーダンスを算出し、このインピーダンスからプロトン伝導度を算出した。
〔固体高分子電解質膜の熱変形温度〕
まず、本実施例で得られた固体高分子電解質膜を、5mm×30mmに裁断し、短冊状の試料とした。次に、動的粘弾性測定器(レオメトリック・サイエンティフィック・エフ・イー株式会社製RSAII(商品名))を用いて、前記試料の熱変形温度を測定した。
〔膜−電極構造体の接着性〕
まず、本実施例で得られた膜−電極構造体(電極転写膜)を結露サイクル試験機(エスペック社製DCTH−200(商品名))に投入して、85℃、相対湿度95%の条件に加熱した後、−20℃に冷却する冷熱サイクル処理を20回行った。次に、前記冷熱サイクル処理を行った膜−電極構造体を1.0cm×5.0cmに裁断し、短冊状の試料とした。次に、前記試料の一方の面を両面粘着テープでアルミニウム板に貼り付け、他方の面に粘着テープを貼り付け、該粘着テープを反転する方向に50mm/分の速度で引っ張り、前記膜−電極構造体の固体高分子電解質膜から電極を剥離させた。前記電極の剥離は、豊光エンジニアリング社製SPG加重測定機(商品名:HPC.A50.500)を用いて行った。次に、前記電極が剥離された固体高分子電解質膜の表面の画像を、エプソン株式会社製スキャナGT−8200UF(商品名)を用いて取り込み、二値化することにより、電極が残存した面積を算出した。次に、次式により前記固体高分子電解質膜の表面の全面積に対する電極が残存した面積の割合を電極接着率とした。
〔比較例1〕
本比較例では、まず、攪拌機、温度計、Dean-stark管、窒素導入管、冷却管を取り付けた1リットルの三口フラスコに、2,2−ビス(4−ヒドロキシフェニル)−1,1,1,3,3,3−ヘキサフルオロプロパン(ビスフェノールAF)50.4g(150ミリモル)、4,4’−ジクロロベンゾフェノン40.2g(160ミリモル)、炭酸カリウム27.0g(200ミリモル)、スルホラン300ミリリットル、トルエン150ミリリットルを秤り取った。これを窒素雰囲気下で撹拌し、オイルバスを用いて130℃で反応させた。反応によって生成する水をトルエンと共沸させ、Dean-stark管により系外に除去しながら反応させると、約3時間で水の生成がほとんど認められなくなった。その後、反応温度を130℃から徐々に上げて200℃とし、その間に大部分のトルエンを系外に除去した。200℃で10時間撹拌を続けた後、4,4’−ジクロロベンゾフェノン16.1g(64ミリモル)を加え、さらに5時間反応させた。
〔比較例2〕
本比較例では、まず、攪拌機、温度計、Dean-stark管、窒素導入管、冷却管を取り付けた1リットルの三口フラスコに、メチレンビスフェノール20.2g(100ミリモル)、2,6−ジクロロベンゾニトリル18.9g(110ミリモル)、炭酸カリウム20.0g(145ミリモル)、を秤り取った。窒素置換後、スルホラン300ミリリットル、トルエン150ミリリットルを加えて撹拌した。その後、オイルバスを用いて150℃で反応液を加熱還流させた。反応によって生成する水はDean-stark管により系外に除去した。前記加熱還流を3時間続けた後、水の生成がほとんど認められなくなったところで、トルエンをDean-stark管により系外に除去した。その後、反応温度を徐々に上げて200℃とし、5時間撹拌を続けた後、2,6−ジクロロベンゾニトリル5.16g(30ミリモル)を加え、さらに8時間反応させた。
〔比較例3〕
本比較例では、まず、攪拌機、温度計、Dean-stark管、窒素導入管、冷却管を取り付けた1リットルの三口フラスコに、ビフェノール18.6g(100ミリモル)、4,4’−ジクロロベンゾフェノン27.6g(110ミリモル)、炭酸カリウム20.0g(145ミリモル)、を秤り取った。窒素置換後、スルホラン300ミリリットル、トルエン150ミリリットルを加えて撹拌した。その後、オイルバスを用いて150℃で反応液を加熱還流させた。反応によって生成する水はDean-stark管により系外に除去した。前記加熱還流を3時間続けた後、水の生成がほとんど認められなくなったところで、トルエンをDean-stark管により系外に除去した。その後、反応温度を徐々に上げて200℃とし、5時間撹拌を続けた後、4,4’−ジクロロベンゾフェノン7.53g(30ミリモル)を加え、さらに8時間反応させた。
Claims (2)
- 固体高分子電解質膜を、触媒を含む1対の電極で挟持した固体高分子型燃料電池用膜−電極構造体において、
前記固体高分子電解質膜は、下記一般式(1)で表される第1の繰り返し単位と、下記化学式(2)〜(8)で表される群から選択されるいずれか1種の第2の繰り返し単位とを備えるポリアリーレン系共重合体を加水分解してスルホン酸エステルをスルホン酸基に変換してなる、ポリアリーレン系共重合体のスルホン化物からなることを特徴とする固体高分子型燃料電池用膜−電極構造体。
(Yは2価の電子吸引基であり、Zは2価の電子供与基または直接接合であり、Arは−SO3Rbで表される置換基を備える芳香族基であり、Ra、Rbは炭素原子数1〜20の炭化水素基であり、jは0〜4の整数であり、kは0〜10の整数であり、lは0〜10の整数である)
(化学式(2)〜(7)において、nは1以上の整数である) - 下記一般式(1)で表される第1の繰り返し単位と、下記化学式(2)〜(8)で表される群から選択されるいずれか1種の第2の繰り返し単位とを備えるポリアリーレン系共重合体を加水分解してスルホン酸エステルをスルホン酸基に変換してなる、ポリアリーレン系共重合体のスルホン化物からなる固体高分子電解質膜を、触媒を含む1対の電極で挟持した固体高分子型燃料電池用膜−電極構造体を備えることを特徴とする固体高分子型燃料電池。
(Yは2価の電子吸引基であり、Zは2価の電子供与基または直接接合であり、Arは−SO3Rbで表される置換基を備える芳香族基であり、Ra、Rbは炭素原子数1〜20の炭化水素基であり、jは0〜4の整数であり、kは0〜10の整数であり、lは0〜10の整数である)
(化学式(2)〜(7)において、nは1以上の整数である)
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