JP7471794B2 - Polyelectrolytes - Google Patents
Polyelectrolytes Download PDFInfo
- Publication number
- JP7471794B2 JP7471794B2 JP2019186341A JP2019186341A JP7471794B2 JP 7471794 B2 JP7471794 B2 JP 7471794B2 JP 2019186341 A JP2019186341 A JP 2019186341A JP 2019186341 A JP2019186341 A JP 2019186341A JP 7471794 B2 JP7471794 B2 JP 7471794B2
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- Prior art keywords
- polymer electrolyte
- electrode catalyst
- catalyst layer
- mass
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920000867 polyelectrolyte Polymers 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims description 149
- 239000005518 polymer electrolyte Substances 0.000 claims description 109
- FTNJQNQLEGKTGD-UHFFFAOYSA-N 1,3-benzodioxole Chemical compound C1=CC=C2OCOC2=C1 FTNJQNQLEGKTGD-UHFFFAOYSA-N 0.000 claims description 43
- 229910052760 oxygen Inorganic materials 0.000 claims description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 42
- 239000001301 oxygen Substances 0.000 claims description 42
- 239000000446 fuel Substances 0.000 claims description 41
- 229910052731 fluorine Inorganic materials 0.000 claims description 39
- 239000012528 membrane Substances 0.000 claims description 38
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 32
- 125000001153 fluoro group Chemical group F* 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- 125000000962 organic group Chemical group 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229940124530 sulfonamide Drugs 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 86
- 229920000642 polymer Polymers 0.000 description 43
- 125000004432 carbon atom Chemical group C* 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 150000002430 hydrocarbons Chemical group 0.000 description 28
- 239000002245 particle Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 27
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 24
- 239000007787 solid Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 239000000126 substance Substances 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000010248 power generation Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 12
- 238000010526 radical polymerization reaction Methods 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 230000035699 permeability Effects 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 10
- 125000000542 sulfonic acid group Chemical group 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 238000005336 cracking Methods 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 150000005528 benzodioxoles Chemical class 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 239000011246 composite particle Substances 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 230000002940 repellent Effects 0.000 description 7
- 239000005871 repellent Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- UIOFUWFRIANQPC-JKIFEVAISA-N Floxacillin Chemical compound N([C@@H]1C(N2[C@H](C(C)(C)S[C@@H]21)C(O)=O)=O)C(=O)C1=C(C)ON=C1C1=C(F)C=CC=C1Cl UIOFUWFRIANQPC-JKIFEVAISA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- LUSZGTFNYDARNI-UHFFFAOYSA-N Sesamol Natural products OC1=CC=C2OCOC2=C1 LUSZGTFNYDARNI-UHFFFAOYSA-N 0.000 description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- -1 perfluoro ring Chemical group 0.000 description 6
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- YBMDPYAEZDJWNY-UHFFFAOYSA-N 1,2,3,3,4,4,5,5-octafluorocyclopentene Chemical compound FC1=C(F)C(F)(F)C(F)(F)C1(F)F YBMDPYAEZDJWNY-UHFFFAOYSA-N 0.000 description 4
- YSYRISKCBOPJRG-UHFFFAOYSA-N 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole Chemical compound FC1=C(F)OC(C(F)(F)F)(C(F)(F)F)O1 YSYRISKCBOPJRG-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000006259 organic additive Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 3
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 3
- UOYPNWSDSPYOSN-UHFFFAOYSA-N hexahelicene Chemical compound C1=CC=CC2=C(C=3C(=CC=C4C=CC=5C(C=34)=CC=CC=5)C=C3)C3=CC=C21 UOYPNWSDSPYOSN-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- ZILSBZLQGRBMOR-UHFFFAOYSA-N 1,3-benzodioxol-5-ylmethanamine Chemical compound NCC1=CC=C2OCOC2=C1 ZILSBZLQGRBMOR-UHFFFAOYSA-N 0.000 description 2
- ABADUMLIAZCWJD-UHFFFAOYSA-N 1,3-dioxole Chemical group C1OC=CO1 ABADUMLIAZCWJD-UHFFFAOYSA-N 0.000 description 2
- LVJZCPNIJXVIAT-UHFFFAOYSA-N 1-ethenyl-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(C=C)C(F)=C1F LVJZCPNIJXVIAT-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- HYHHGFFTWSYNMV-UHFFFAOYSA-N 5-bromobenzene-1,3-diol Chemical compound OC1=CC(O)=CC(Br)=C1 HYHHGFFTWSYNMV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910003202 NH4 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- ODPUKHWKHYKMRK-UHFFFAOYSA-N cerium;nitric acid Chemical compound [Ce].O[N+]([O-])=O ODPUKHWKHYKMRK-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- WXEHBUMAEPOYKP-UHFFFAOYSA-N methyl ethyl thioether Natural products CCSC WXEHBUMAEPOYKP-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 125000000565 sulfonamide group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 2
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- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
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- 235000004416 zinc carbonate Nutrition 0.000 description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- BLBNEWYCYZMDEK-UHFFFAOYSA-N $l^{1}-indiganyloxyindium Chemical compound [In]O[In] BLBNEWYCYZMDEK-UHFFFAOYSA-N 0.000 description 1
- RIQRGMUSBYGDBL-UHFFFAOYSA-N 1,1,1,2,2,3,4,5,5,5-decafluoropentane Chemical compound FC(F)(F)C(F)C(F)C(F)(F)C(F)(F)F RIQRGMUSBYGDBL-UHFFFAOYSA-N 0.000 description 1
- XSLYISNQTJHKMP-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-2-iodoethoxy)ethanesulfonyl fluoride Chemical compound FC(F)(I)C(F)(F)OC(F)(F)C(F)(F)S(F)(=O)=O XSLYISNQTJHKMP-UHFFFAOYSA-N 0.000 description 1
- VQUGQIYAVYQSAB-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-2-(1,2,2-trifluoroethenoxy)ethanesulfonyl fluoride Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)S(F)(=O)=O VQUGQIYAVYQSAB-UHFFFAOYSA-N 0.000 description 1
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 1
- FTNJQNQLEGKTGD-ZFJHNFROSA-N 1,3-benzodioxole Chemical group C1O[13C]=2[13CH]=[13CH][13CH]=[13CH][13C]=2O1 FTNJQNQLEGKTGD-ZFJHNFROSA-N 0.000 description 1
- WCXXISMIJBRDQK-UHFFFAOYSA-N 1-methylsulfanylbutane Chemical compound CCCCSC WCXXISMIJBRDQK-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HFNSTEOEZJBXIF-UHFFFAOYSA-N 2,2,4,5-tetrafluoro-1,3-dioxole Chemical compound FC1=C(F)OC(F)(F)O1 HFNSTEOEZJBXIF-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- ZERULLAPCVRMCO-UHFFFAOYSA-N Dipropyl sulfide Chemical compound CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 229920000292 Polyquinoline Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- LUFPJJNWMYZRQE-UHFFFAOYSA-N benzylsulfanylmethylbenzene Chemical compound C=1C=CC=CC=1CSCC1=CC=CC=C1 LUFPJJNWMYZRQE-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 150000004294 cyclic thioethers Chemical class 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- AEHWKBXBXYNPCX-UHFFFAOYSA-N ethylsulfanylbenzene Chemical compound CCSC1=CC=CC=C1 AEHWKBXBXYNPCX-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 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 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- CZDSWLXAULJYPZ-UHFFFAOYSA-J molybdenum(4+);dicarbonate Chemical compound [Mo+4].[O-]C([O-])=O.[O-]C([O-])=O CZDSWLXAULJYPZ-UHFFFAOYSA-J 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-OUBTZVSYSA-N potassium-40 Chemical compound [40K] ZLMJMSJWJFRBEC-OUBTZVSYSA-N 0.000 description 1
- NDCDGGJGNYRKMV-UHFFFAOYSA-M potassium;1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-2-iodoethoxy)ethanesulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)OC(F)(F)C(F)(F)I NDCDGGJGNYRKMV-UHFFFAOYSA-M 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- FOZHTJJTSSSURD-UHFFFAOYSA-J titanium(4+);dicarbonate Chemical compound [Ti+4].[O-]C([O-])=O.[O-]C([O-])=O FOZHTJJTSSSURD-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 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
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Conductive Materials (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Description
本発明は、高分子電解質、上記高分子電解質を含む電極触媒インク、上記高分子電解質を含む電極触媒層、上記電極触媒層を備える膜電極接合体、上記膜電極接合体を備える燃料電池に関する。 The present invention relates to a polymer electrolyte, an electrode catalyst ink containing the polymer electrolyte, an electrode catalyst layer containing the polymer electrolyte, a membrane electrode assembly including the electrode catalyst layer, and a fuel cell including the membrane electrode assembly.
固体高分子形燃料電池は近年、家庭用燃料電池システムや燃料電池自動車に搭載、市販され、地球温暖化防止の観点から、今後も成長が期待される。
この固体高分子型燃料電池には、パーフルオロカーボンスルホン酸のような電解質膜とその両面に白金担持カーボンとバインダー樹脂(アイオノマー)からなる電極触媒層が密着した膜電極接合体(MEA)が設けられている。
このMEAの片方の電極触媒層に加湿した水素ガスを、もう一方の電極触媒層に加湿した酸素ガスを流通させると、水素ガス側(以下、アノード)の電極触媒上でプロトンが生成し、電解質膜を通して酸素ガス側(以下、カソード)に移動する。反対にカソードの電極触媒上では酸素が還元され、別回路から流れてきた電子と、アノードから流れてきたプロトンと反応し水が生成する。
In recent years, polymer electrolyte fuel cells have been installed in home fuel cell systems and fuel cell vehicles and are commercially available, and their use is expected to continue to grow from the perspective of preventing global warming.
This solid polymer electrolyte fuel cell is provided with a membrane electrode assembly (MEA) in which an electrolyte membrane such as perfluorocarbon sulfonic acid is attached to both sides of the electrolyte membrane, and electrode catalyst layers made of platinum-loaded carbon and a binder resin (ionomer) are bonded to both sides of the electrolyte membrane.
When humidified hydrogen gas flows through one electrode catalyst layer of this MEA, and humidified oxygen gas flows through the other electrode catalyst layer, protons are generated on the electrode catalyst on the hydrogen gas side (hereafter, anode) and move through the electrolyte membrane to the oxygen gas side (hereafter, cathode). Conversely, oxygen is reduced on the electrode catalyst of the cathode, and water is generated by reacting with electrons flowing from a separate circuit and protons flowing from the anode.
固体高分子形燃料電池では、特に、カソードの電極触媒上での酸素還元反応を如何に効率よく起こすかが課題となる。
一方、今後、固体高分子形燃料電池システムの更なる市場成長のためには、システムを構成する各種部材のコスト低減が必要であるが、特に、コスト比率の高い白金触媒の使用量を削減することが必要である。
従来の固体高分子形燃料電池システムではカソードに多くの白金触媒を使用することで性能を担保していたが、白金触媒の使用量を削減すると、発電に寄与する触媒表面積の低下から発電性能が低くなる問題が生じる。
そこで、少ない触媒表面により多くの酸素を供給する為にアイオノマーの酸素透過性を向上させて、電極中に酸素を行き渡らせる試みがなされてきた。
In a polymer electrolyte fuel cell, a particular issue is how to efficiently cause the oxygen reduction reaction on the electrode catalyst of the cathode.
Meanwhile, in order to ensure further market growth for polymer electrolyte fuel cell systems in the future, it is necessary to reduce the costs of the various components that make up the systems, and in particular, it is necessary to reduce the amount of platinum catalyst used, which has a high cost ratio.
In conventional solid polymer fuel cell systems, performance was ensured by using a large amount of platinum catalyst in the cathode, but reducing the amount of platinum catalyst used results in a problem of reduced power generation performance due to a decrease in the catalyst surface area that contributes to power generation.
Therefore, in order to supply more oxygen to a small catalyst surface, attempts have been made to improve the oxygen permeability of the ionomer and distribute oxygen throughout the electrode.
特許文献1、2には、酸素透過性が高く、カソード側触媒層高分子電解質として好適な高分子電解質として、ラジカル重合により主鎖に脂肪族環構造を有するポリマーを与える含フッ素モノマーに基づく繰り返し単位と、フッ素系スルホン酸含有モノマーに基づく繰り返し単位とを含む共重合体並びに当該共重合体を含有するガス拡散電極が記載されている。 Patent Documents 1 and 2 describe a copolymer containing repeating units based on a fluorine-containing monomer that gives a polymer having an aliphatic ring structure in the main chain by radical polymerization and repeating units based on a fluorine-based sulfonic acid-containing monomer, as a polymer electrolyte with high oxygen permeability and suitable as a polymer electrolyte for a cathode-side catalyst layer, and a gas diffusion electrode containing the copolymer.
特許文献3には、嵩高い環構造を有することで低密度化し、酸素透過性を促進する高分子電解質として、2位にパーフルオロ環構造を有するパーフルオロ(1,3-ジオキソール)とスルホン酸を有するパーフルオロビニルエーテルの共重合体が記載されている。 Patent Document 3 describes a copolymer of perfluoro(1,3-dioxole) having a perfluoro ring structure at the 2-position and perfluorovinyl ether having sulfonic acid as a polymer electrolyte that has a bulky ring structure, thereby reducing density and promoting oxygen permeability.
特許文献4には、プロトン伝導性と酸素透過性を両立する高分子電解質として、主鎖又は側鎖に、パーフルオロ脂肪族とスルホンイミドを有する電解質が記載されている。 Patent Document 4 describes an electrolyte having a perfluoroaliphatic and sulfonimide in the main chain or side chain as a polymer electrolyte that has both proton conductivity and oxygen permeability.
しかしながら、上記特許文献1~4に開示されている高分子電解質は、嵩高い環構造の影響で、配合量を多くすると酸素透過性は上昇するものの、電極触媒層を形成させると表面に亀裂を生じ、発電性能が低下する、電池での耐久性が低下する、という問題が生じた。 However, the polymer electrolytes disclosed in Patent Documents 1 to 4 above have a bulky ring structure, and although increasing the amount of the polymer electrolyte increases the oxygen permeability, when an electrode catalyst layer is formed, cracks appear on the surface, reducing the power generation performance and the durability of the battery.
本発明は、上記現状に鑑み、電極触媒層のひび割れを抑制し、電池での発電性能、耐久性が良好な高分子電解質を提供することを目的とする。 In view of the above-mentioned current situation, the present invention aims to provide a polymer electrolyte that suppresses cracking of the electrode catalyst layer and has good power generation performance and durability in a battery.
本発明者らは、上記の課題を解決するために鋭意検討した結果、ベンゾジオキソール誘導体骨格を含む高分子電解質が、電極触媒層の表面に亀裂を生じることなく、電池での発電性能、耐久性が高くなることを見出し、本発明を完成するに至った。 As a result of intensive research to solve the above problems, the inventors discovered that a polymer electrolyte containing a benzodioxole derivative skeleton improves the power generation performance and durability of a battery without causing cracks on the surface of the electrode catalyst layer, and thus completed the present invention.
すなわち、本発明は以下のとおりである。
[1]
下記式(1)で表される構造を含むベンゾジオキソール誘導体骨格を側鎖に有するベンゾジオキソール構造単位を含み、
高分子電解質100mol%中の上記ベンゾジオキソール構造単位の割合が12~100mol%であり、
80℃30%RH条件でPt厚膜法により測定した酸素溶解度が、7.0mol/m3以上であり、
当量重量EWが100~2000g/eqである、高分子電解質。
[2]
上記式(1)中、Xが、下記式(2)又は下記式(3)で表される構造を含む、[1]に記載の高分子電解質。
[3]
[1]または[2]に記載の高分子電解質と、触媒とを含むことを特徴とする、電極触媒インク。
[4]
[1]または[2]に記載の高分子電解質と、触媒とを含むことを特徴とする、電極触媒層。
[5]
[4]に記載の電極触媒層と電解質膜とを備えることを特徴とする、膜電極接合体。
[6]
[5]に記載の膜電極接合体を備えることを特徴とする、燃料電池。
That is, the present invention is as follows.
[1]
The compound includes a benzodioxole structural unit having a benzodioxole derivative skeleton in a side chain, the skeleton including the structure represented by the following formula (1):
The ratio of the benzodioxole structural unit in 100 mol % of the polymer electrolyte is 12 to 100 mol %,
The oxygen solubility measured by the Pt thick film method under the condition of 80°C and 30% RH is 7.0 mol/m3 or more ,
A polymer electrolyte having an equivalent weight EW of 100 to 2000 g/eq.
[2]
The polymer electrolyte according to [1], wherein in the above formula (1), X includes a structure represented by the following formula (2) or the following formula (3):
[3]
An electrode catalyst ink comprising the polymer electrolyte according to [1] or [2] and a catalyst.
[4]
An electrode catalyst layer comprising the polymer electrolyte according to [1] or [2] and a catalyst .
[5]
A membrane electrode assembly comprising the electrode catalyst layer according to [4] and an electrolyte membrane.
[6]
A fuel cell comprising the membrane electrode assembly according to [5].
本発明の高分子電解質は、電極触媒層のひび割れを抑制し、発電性能、耐久性が良好な高分子電解質を提供することができる。 The polymer electrolyte of the present invention can suppress cracking of the electrode catalyst layer and provide a polymer electrolyte with good power generation performance and durability.
以下、本発明を具体的に説明する。
[高分子電解質]
本実施形態の高分子電解質は、ベンゾジオキソール誘導体骨格を含むことで、高酸素透過性を発現するだけでなく、上記高分子電解質を含む電極触媒層の表面にひび割れがなく、燃料電池の運転において、高性能、高化学耐久性を発現する。
The present invention will be specifically described below.
[Polymer electrolyte]
The polymer electrolyte of the present embodiment contains a benzodioxole derivative skeleton, and therefore not only exhibits high oxygen permeability, but also has no cracks on the surface of the electrode catalyst layer containing the polymer electrolyte, and exhibits high performance and high chemical durability during operation of the fuel cell.
上記ベンゾジオキソール誘導体骨格としては、下記式(1)で表される構造を含む骨格が挙げられ、下記式(1)で表される構造である骨格が好ましい。
式(1)において、Xは、それぞれ独立にエーテル結合を含む構造又はスルホンアミド結合を含む構造を表し、Yは、それぞれ独立に水素原子、フッ素原子、又は有機基を表し、a及びbは整数を表し、a+b=4、a≧1である。上記有機基としては、例えば、部分的又は完全にフッ素化されていてもよい炭素数1~10の炭化水素基等が挙げられる。Xは他の構造との連結基であってよく、Yはベンゼン環の末端置換基であってよい。
The benzodioxole derivative skeleton includes a skeleton containing a structure represented by the following formula (1), and the skeleton having a structure represented by the following formula (1) is preferable.
In formula (1), X's each independently represent a structure containing an ether bond or a structure containing a sulfonamide bond, Y's each independently represent a hydrogen atom, a fluorine atom, or an organic group, a and b represent integers, a+b=4, a≧1. Examples of the organic group include hydrocarbon groups having 1 to 10 carbon atoms which may be partially or completely fluorinated. X may be a linking group to another structure, and Y may be a terminal substituent of a benzene ring.
上記Xとしては、電極触媒層のひび割れを一層抑制し、酸素透過性を一層向上させる観点から、下記式(2)又は下記式(3)で表される構造を含むことが好ましく、下記式(2)又は下記式(3)で表される構造であることがより好ましい。
ここで、ベンゾジオキソール誘導体とは、ベンゾジオキソール骨格の少なくとも1つの水素原子が、ヒドロキシル基、チオール基、アミノ基、カルボキシル基、置換されていてもよい炭素数1~10の炭化水素基、エーテル結合又はスルホンアミド結合を含む構造、芳香族環等の置換基で置換された構造をいう。ベンゾジオキソール誘導体とは、例えば、上記式(1)で表される1、3ベンゾジオキソール骨格のジオキソール環の2個の水素原子、ベンゼン環の4個の水素原子の1つ以上が上記置換基で置換された構造が挙げられる。なお、上記式(1)で表される構造が、ベンゾジオキソール誘導体にa個のX、b個のY、R1及びR2が結合した構造である場合、式(1)において、1個のXを除き、R1、R2、a個のX、b個のYは存在しなくてもよく、例えば、a+b等は適宜変更してよい。 Here, the benzodioxole derivative refers to a structure in which at least one hydrogen atom of the benzodioxole skeleton is substituted with a substituent such as a hydroxyl group, a thiol group, an amino group, a carboxyl group, a hydrocarbon group having 1 to 10 carbon atoms which may be substituted, a structure containing an ether bond or a sulfonamide bond, or an aromatic ring. The benzodioxole derivative may be, for example, a structure in which two hydrogen atoms of the dioxole ring of the 1,3-benzodioxole skeleton represented by the above formula (1) and one or more of the four hydrogen atoms of the benzene ring are substituted with the above substituents. Note that when the structure represented by the above formula ( 1 ) is a structure in which a number of Xs, b number of Ys, R 1 and R 2 are bonded to the benzodioxole derivative, in formula (1), R 1 , R 2 , a number of Xs, and b number of Ys may not be present except for one X, and for example, a+b, etc. may be appropriately changed.
上記高分子電解質は、少なくともベンゾジオキソール誘導体骨格を含む構造単位(繰り返し単位)(本明細書において、「ベンゾジオキソール構造単位」と称する場合がある)を含む単独重合体又は共重合体であることが好ましい。上記高分子電解質に含まれる上記ベンゾジオキソール構造単位は、一種であってもよいし複数種であってもよいが、生産性の観点から、一種であることが好ましい。
上記高分子電解質は、ベンゾジオキソール構造単位以外に、他の構造単位を有していてもよい。上記他の構造単位は、一種であってもよいし複数種であってもよい。
The polymer electrolyte is preferably a homopolymer or copolymer containing at least a structural unit (repeating unit) containing a benzodioxole derivative skeleton (sometimes referred to as a "benzodioxole structural unit" in this specification). The benzodioxole structural unit contained in the polymer electrolyte may be of one type or of multiple types, but is preferably of one type from the viewpoint of productivity.
The polymer electrolyte may have other structural units in addition to the benzodioxole structural unit. The other structural units may be of one type or of multiple types.
(ベンゾジオキソール構造単位)
上記ベンゾジオキソール構造単位としては、上記ベンゾジオキソール誘導体骨格を主鎖に有する構造単位(本明細書において、「構造単位A」と称する場合がある)、上記ベンゾジオキソール誘導体骨格を側鎖に有する構造単位(本明細書において、「構造単位B」と称する場合がある)、上記ベンゾジオキソール誘導体骨格を主鎖及び側鎖に有する構造単位、等が挙げられる。
(Benzodioxole structural unit)
Examples of the benzodioxole structural unit include a structural unit having the benzodioxole derivative skeleton in its main chain (sometimes referred to as "structural unit A" in this specification), a structural unit having the benzodioxole derivative skeleton in its side chain (sometimes referred to as "structural unit B" in this specification), a structural unit having the benzodioxole derivative skeleton in its main chain and side chain, and the like.
-構造単位A-
上記構造単位Aは、主鎖にベンゾジオキソール誘導体骨格を1個有していてもよいし、複数個有していてもよい。
--Structural unit A--
The structural unit A may have one or more benzodioxole derivative skeletons in the main chain.
上記構造単位Aとしては、例えば、下記式(4)の構造等が挙げられる。
上記式(4)中、側鎖R6、R7、R8、R9としては、それぞれ独立に水素原子、フッ素原子、プロトン伝導性基を末端に有する側鎖、部分的又は完全にフッ素化されていてもよい炭素数1~10個の炭化水素基、エーテル結合、これらの組み合わせ、等が挙げられる。上記炭化水素基は構造中にエーテル性酸素原子を含んでも良い。プロトン伝導性基としては、スルホン酸基、カルボン酸基、リン酸基、スルホンアミド基等が挙げられ、後述の式(37)~(40)で表される構造等が挙げられる。
Examples of the structural unit A include a structure represented by the following formula (4).
In the above formula (4), the side chains R 6 , R 7 , R 8 , and R 9 each independently represent a hydrogen atom, a fluorine atom, a side chain having a proton-conducting group at its end, a hydrocarbon group having 1 to 10 carbon atoms which may be partially or completely fluorinated, an ether bond, or a combination thereof. The above-mentioned hydrocarbon group may contain an ether oxygen atom in the structure. Examples of the proton-conducting group include a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, and a sulfonamide group, and examples of the structures represented by the formulas (37) to (40) described below are given.
-構造単位B-
上記構造単位Bは、主鎖と側鎖末端との間にベンゾジオキソール誘導体骨格を有していてもよいし、側鎖末端にベンゾジオキソール誘導体骨格を有していてもよい。中でも、合成の容易性から、側鎖末端にベンゾジオキソール誘導体骨格を有することが好ましく、ジオキソール環が側鎖末端側に配置されることがより好ましい。
--Structural unit B--
The structural unit B may have a benzodioxole derivative skeleton between the main chain and the side chain terminal, or may have a benzodioxole derivative skeleton at the side chain terminal. Among them, from the viewpoint of ease of synthesis, it is preferable that the benzodioxole derivative skeleton is at the side chain terminal, and it is more preferable that the dioxole ring is located on the side chain terminal side.
上記構造単位Bにおいて、主鎖と側鎖末端のベンゾジオキソール誘導体骨格とは、エーテル結合、上記式(3)で表される構造、スルホニル基、チオエーテル基、ケトン基、エステル基、イミド基、芳香族環、部分的又は完全にフッ素化されていてもよい炭素数1~10の炭化水素基、又はこれらの組み合わせ等を介して結合されていてよい。 In the structural unit B, the main chain and the benzodioxole derivative skeleton at the end of the side chain may be bonded via an ether bond, the structure represented by the above formula (3), a sulfonyl group, a thioether group, a ketone group, an ester group, an imide group, an aromatic ring, a hydrocarbon group having 1 to 10 carbon atoms which may be partially or completely fluorinated, or a combination thereof.
上記構造単位Bの主鎖としては、特に限定されないが、例えば、下記式(21)で表される構造の主鎖
(式(21)中、nは構造単位の繰り返し数を表す。X1~X3は、それぞれ独立に、水素原子、フッ素原子、塩素原子を表す。Aはベンゾジオキソール誘導体骨格を有する側鎖を表す。);下記式(23)で表される主鎖
(式(23)中、nは構造単位の繰り返し数を表す。Arは、ベンゼン、ナフタレン、アントラセン、フルオレン、ヘリセン、ピレン等の芳香環を表す。Aは、ベンゾジオキソール誘導体骨格を有する側鎖を表す。Rxは、水素原子、フッ素原子、塩素原子、部分的又は完全にフッ素化されていてもよい炭素数1~10の炭化水素基、プロトン伝導性基などが挙げられる。上記炭化水素基は構造中にエーテル性酸素原子を含んでも良い。プロトン伝導性基としては、例えば、-(CF2)2O(CF2)2SO3H、-OCF2CF2SO3H、-OCF2CFH-OCF2CF2SO3H、-OCF2CFH-OCF2CF(CF3)-OCF2CF2SO3H、-OCF2CFH-OCF2CF(CF2OCF2CF2SO3H)-OCF2CF2SO3H等が挙げられる。);下記式(24)で表される主鎖
(式(24)中、nは構造単位の繰り返し数を表す。Arは、ベンゼン、ナフタレン、アントラセン、フルオレン、ヘリセン、ピレン等の芳香環を表す。Aは、ベンゾジオキソール誘導体骨格を有する側鎖を表す。Rxは、水素原子、フッ素原子、塩素原子、部分的又は完全にフッ素化されていてもよい炭素数1~10の炭化水素基、プロトン伝導性基などが挙げられる。上記炭化水素基は構造中にエーテル性酸素原子を含んでも良い。プロトン伝導性基としては、例えば、-(CF2)2O(CF2)2SO3H、-OCF2CF2SO3H、-OCF2CFH-OCF2CF2SO3H、-OCF2CFH-OCF2CF(CF3)-OCF2CF2SO3H、-OCF2CFH-OCF2CF(CF2OCF2CF2SO3H)-OCF2CF2SO3H等)が挙げられる。);等が挙げられる。
The main chain of the structural unit B is not particularly limited, but may be, for example, a main chain having a structure represented by the following formula (21):
(In formula (21), n represents the number of repeating structural units. X 1 to X 3 each independently represent a hydrogen atom, a fluorine atom or a chlorine atom. A represents a side chain having a benzodioxole derivative skeleton.) A main chain represented by the following formula (23):
In formula (23), n represents the number of repeating structural units. Ar represents an aromatic ring such as benzene, naphthalene, anthracene, fluorene, helicene, or pyrene. A represents a side chain having a benzodioxole derivative skeleton. Rx represents a hydrogen atom, a fluorine atom, a chlorine atom, a hydrocarbon group having 1 to 10 carbon atoms which may be partially or completely fluorinated, a proton conductive group, or the like. The hydrocarbon group may contain an etheric oxygen atom in the structure. Examples of the proton conductive group include -( CF2 ) 2O ( CF2 ) 2SO3H , -OCF2CF2SO3H , -OCF2CFH - OCF2CF2SO3H , -OCF2CFH - OCF2CF ( CF3 ) -OCF2CF2SO3H , -OCF2 CFH-OCF 2 CF(CF 2 OCF 2 CF 2 SO 3 H)-OCF 2 CF 2 SO 3 H, etc.; a main chain represented by the following formula (24):
In formula (24), n represents the number of repetitions of the structural unit. Ar represents an aromatic ring such as benzene, naphthalene, anthracene, fluorene, helicene, or pyrene. A represents a side chain having a benzodioxole derivative skeleton. Rx represents a hydrogen atom, a fluorine atom, a chlorine atom, a hydrocarbon group having 1 to 10 carbon atoms which may be partially or completely fluorinated, a proton conductive group, or the like. The hydrocarbon group may contain an etheric oxygen atom in the structure. Examples of the proton conductive group include -( CF2 ) 2O ( CF2 ) 2SO3H , -OCF2CF2SO3H , -OCF2CFH - OCF2CF2SO3H , -OCF2CFH - OCF2CF ( CF3 ) -OCF2CF2SO3H , -OCF2 CFH-OCF 2 CF(CF 2 OCF 2 CF 2 SO 3 H)-OCF 2 CF 2 SO 3 H, etc.
上記主鎖としては、-(CF2-CFA)-、-(CH2-CHA)-等のエチレン系主鎖;ポリエーテルケトン(PEK)、ポリエーテルエーテルケトン(PEEK)、ポリエーテルスルホン(PES)、ポリフェニレンエーテル(PPE)等の主鎖にエーテル結合を有する主鎖;式(23)又は(24)で表される主鎖等が好ましい。 Preferred examples of the main chain include ethylene-based main chains such as -( CF2 -CFA)- and -( CH2 -CHA)-; main chains having an ether bond in the main chain, such as polyether ketone (PEK), polyether ether ketone (PEEK), polyether sulfone (PES), and polyphenylene ether (PPE); and main chains represented by formula (23) or (24).
上記構造単位Bとしては、合成の容易性と、電極触媒層のひび割れを一層抑制し、酸素透過性を一層向上させる観点から、下記式(25)~(30)で表される構造が好ましい。
式(27)において、R7は、下記式(31)の構造を表し、R8は、それぞれ独立に水素原子、フッ素原子、又は有機基を表す。上記有機基としては、例えば、部分的又は完全にフッ素化されていてもよい炭素数1~10の炭化水素基等が挙げられる。R9は、エーテル結合及びプロトン交換基を含む炭素数1以上のフッ素化炭化水素基を表し、フッ素化炭化水素基の炭素数が2以上である場合は炭素-炭素原子間にエーテル結合が挿入されていてもよい。上記R9としては、例えば、-(CF2)2O(CF2)2SO3H、-OCF2CF2SO3H、-OCF2CFH-OCF2CF2SO3H、-OCF2CFH-OCF2CF(CF3)-OCF2CF2SO3H、-OCF2CFH-OCF2CF(CF2OCF2CF2SO3H)-OCF2CF2SO3H等が挙げられる。
c~gは整数を表し、c+d=5、c+e≧1、e+f+g=5、g≧1である。
式(29)、(30)において、R1、R2はそれぞれ独立に水素原子、フッ素原子、又は有機基を表す。R3、R4、R5は、それぞれ独立に水素原子、フッ素原子、又は有機基を表す。上記有機基としては、例えば、部分的又は完全にフッ素化されていてもよい炭素数1~10の炭化水素基、エーテル結合、芳香族環等が挙げられる。lは、1から10のいずれかの整数を表す。qは0~2の整数であり、rは0~12の整数である。ただし、q及びrは同時に0にならない。R10、R11はそれぞれ独立にフッ素原子、又は下記式(31)の構造を表す。
式(31)において、R1、R2は、それぞれ独立に水素原子、フッ素原子、又は有機基を表す。上記有機基としては、例えば、部分的又は完全にフッ素化されていてもよい炭素数1~10の炭化水素基、エーテル結合、芳香族環等が挙げられる。
As the structural unit B, from the viewpoints of ease of synthesis, further suppression of cracking of the electrode catalyst layer, and further improvement of oxygen permeability, structures represented by the following formulae (25) to (30) are preferred.
In formula (27), R 7 represents a structure of formula (31) below, and R 8 each independently represents a hydrogen atom, a fluorine atom, or an organic group. Examples of the organic group include a hydrocarbon group having 1 to 10 carbon atoms which may be partially or completely fluorinated. R 9 represents a fluorinated hydrocarbon group having 1 or more carbon atoms which contains an ether bond and a proton exchange group, and when the fluorinated hydrocarbon group has 2 or more carbon atoms, an ether bond may be inserted between the carbon atoms. Examples of R9 include -( CF2 ) 2O ( CF2 ) 2SO3H , -OCF2CF2SO3H , -OCF2CFH - OCF2CF2SO3H , -OCF2CFH - OCF2CF ( CF3 ) -OCF2CF2SO3H , -OCF2CFH - OCF2CF ( CF2OCF2CF2SO3H ) -OCF2CF2SO3H , and the like .
c to g represent integers, where c+d=5, c+e≧1, e+f+g=5, and g≧1.
In formulae (29) and (30), R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom, or an organic group. R 3 , R 4 , and R 5 each independently represent a hydrogen atom, a fluorine atom, or an organic group. Examples of the organic group include a hydrocarbon group having 1 to 10 carbon atoms, which may be partially or completely fluorinated, an ether bond, and an aromatic ring. l represents an integer from 1 to 10. q is an integer from 0 to 2, and r is an integer from 0 to 12. However, q and r are not 0 at the same time. R 10 and R 11 each independently represent a fluorine atom, or a structure of the following formula (31).
In formula (31), R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom, or an organic group, such as a hydrocarbon group having 1 to 10 carbon atoms which may be partially or completely fluorinated, an ether bond, or an aromatic ring.
(他の構造単位)
上記他の構造単位としては、上記ベンゾジオキソール構造単位と同じ主鎖を有し、側鎖にベンゾジオキソール誘導体骨格を有さない構造単位としてもよい。上記他の構造単位は、例えば、上記ベンゾジオキソール構造単位と同じ主鎖を有し、側鎖を有さない構造単位と、上記ベンゾジオキソール構造単位と同じ主鎖を有し、プロトン伝導性を促す側鎖を有する構造単位とであってもよい。
例えば、上記他の構造単位としては、テトラフルオロエチレンに由来する構造単位(-CF2-CF2-)を含んでいてもよい。
(Other structural units)
The other structural unit may be a structural unit having the same main chain as the benzodioxole structural unit and not having a benzodioxole derivative skeleton in the side chain. The other structural unit may be, for example, a structural unit having the same main chain as the benzodioxole structural unit and not having a side chain, or a structural unit having the same main chain as the benzodioxole structural unit and having a side chain that promotes proton conductivity.
For example, the other structural units may include a structural unit (--CF 2 -CF 2 -) derived from tetrafluoroethylene.
上記高分子電解質は、プロトン伝導性を促す側鎖を有してもよい。
プロトン伝導性を促す側鎖としては、下記式(37)~下記式(40)で表わされる構造であることが好ましい。
(式(37)中、Xは、F、Cl、又は置換されていてもよい炭素数1~3のフッ素化炭化水素基を表す。kは0~2の整数、nは0~8の整数を表す。n個のXは、同一でも異なっていてもよい。Yは、F又はClを表す。mは1~6の整数を表す。m個のYは、同一でも異なっていてもよい。Zは、H、アルカリ金属、又はアルカリ土類金属表す。)
上記式(37)において、特に、kが0又は2、nが0、mが2、YがF、ZがHであることが好ましい。
(式(38)中、Xは、F、Cl、又は置換されていてもよい炭素数1~3のフッ素化炭化水素基を表す。kは0~2の整数、nは0~8の整数を表す。n個のXは、同一でも異なっていてもよい。Yは、F又はClを表す。mは1~6の整数を表す。m個のYは、同一でも異なっていてもよい。Zは、NR1R2を表す。R1及びR2は、それぞれ独立に、置換されていてもよい炭素数1~10のアルキル基、水素原子、-SO2-R3を表す。ここでR3は、炭素数1~10の炭化水素基を表す。R1、R2の一方が置換されても良いアルキル基又は水素であるとき、R2は、-SO2-R3である。)
上記式(38)において、特に、kが0又は2、nが0、mが2であることが好ましい。
(式(39)中、Rfは、それぞれ独立にエーテル結合性酸素原子を含む炭素数1~10のフッ素化炭化水素基、単結合を表す。Xは、H、アルカリ金属、又はアルカリ土類金属を表す。)
(式(40)中、Rfは、それぞれ独立にエーテル結合性酸素原子を含む炭素数1~10のフッ素化炭化水素基、単結合を表す。Xは、NR1R2を表す。R1及びR2は、それぞれ独立に、置換されていてもよい炭素数1~10のアルキル基又は水素原子、-SO2-R3を表す。ここでR3は、炭素数1~10の炭化水素基を表す。R1、R2の一方が置換されても良いアルキル基又は水素原子であるとき、R2は、-SO2-R3である。)
The polymer electrolyte may have side chains that promote proton conductivity.
The side chain that promotes proton conductivity is preferably one having a structure represented by the following formula (37) to formula (40).
(In formula (37), X represents F, Cl, or a fluorinated hydrocarbon group having 1 to 3 carbon atoms which may be substituted. k represents an integer of 0 to 2, and n represents an integer of 0 to 8. The n number of Xs may be the same or different. Y represents F or Cl. m represents an integer of 1 to 6. The m number of Ys may be the same or different. Z represents H, an alkali metal, or an alkaline earth metal.)
In the above formula (37), it is particularly preferable that k is 0 or 2, n is 0, m is 2, Y is F, and Z is H.
(In formula (38), X represents F, Cl, or an optionally substituted fluorinated hydrocarbon group having 1 to 3 carbon atoms. k represents an integer of 0 to 2, and n represents an integer of 0 to 8. The n Xs may be the same or different. Y represents F or Cl. m represents an integer of 1 to 6. The m Ys may be the same or different. Z represents NR 1 R 2. R 1 and R 2 each independently represent an optionally substituted alkyl group having 1 to 10 carbon atoms, a hydrogen atom, or -SO 2 -R 3. Here, R 3 represents a hydrocarbon group having 1 to 10 carbon atoms. When one of R 1 and R 2 is an optionally substituted alkyl group or hydrogen, R 2 is -SO 2 -R 3. )
In the above formula (38), it is particularly preferable that k is 0 or 2, n is 0, and m is 2.
(In formula (39), Rf's each independently represent a fluorinated hydrocarbon group having 1 to 10 carbon atoms containing an ether-bonded oxygen atom or a single bond. X represents H, an alkali metal, or an alkaline earth metal.)
(In formula (40), Rf's each independently represent a fluorinated hydrocarbon group having 1 to 10 carbon atoms containing an ether-bonding oxygen atom or a single bond. X represents NR 1 R 2. R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms which may be substituted, a hydrogen atom, or -SO 2 -R 3. Here, R 3 represents a hydrocarbon group having 1 to 10 carbon atoms. When one of R 1 and R 2 is an alkyl group which may be substituted or a hydrogen atom, R 2 is -SO 2 -R 3. )
上記他の構造単位としては、下記式(41)で表される構造を有する側鎖(D)を有する構造単位を含んでいてもよく、-(CF2-CFA)-のAに上記側鎖(D)が直接結合した構造単位としてよい。上記側鎖(D)を有する構造単位を導入することで、高分子電解質溶液を調製する際に、溶媒への溶解性を調整しやすくなる。
(式(41)中、Rfは、炭素数1~10のフッ素化炭化水素基を表す。上記フッ素化炭化水素基は構造中にエーテル性酸素原子を含んでも良い。)
上記側鎖(D)としては、-O-CF3、-O-C2F5、-O-C3F7、-O-C2F4-O-C2F5、-O-(CF2CF(CF3))-O-C3F7、が挙げられる。
The other structural unit may include a structural unit having a side chain (D) having a structure represented by the following formula (41), and may be a structural unit in which the side chain (D) is directly bonded to A in -( CF2 -CFA)-. By introducing the structural unit having the side chain (D), it becomes easier to adjust the solubility in a solvent when preparing a polymer electrolyte solution.
(In formula (41), Rf represents a fluorinated hydrocarbon group having 1 to 10 carbon atoms. The fluorinated hydrocarbon group may contain an etheric oxygen atom in the structure.)
Examples of the side chain (D) include -O -CF3, -O-C2F5, -O-C3F7 , -O - C2F4 - O - C2F5 , and -O-( CF2CF ( CF3 ))-O- C3F7 .
上記他の構造単位における主鎖としては、上述の構造単位Bにおける主鎖と同様のものが挙げられる。 The main chain in the other structural units may be the same as the main chain in structural unit B described above.
上記高分子電解質中に、プロトン伝導性基が含まれていることが好ましい。プロトン伝導性基としては、スルホン酸基、カルボン酸基、リン酸基、スルホンアミド基等が挙げられる。プロトン伝導性の観点から、強酸であるスルホン酸基が好ましい。
上記高分子電解質は、上記プロトン伝導性基を有する構造単位を含むことが好ましい。上記プロトン伝導性基を有する構造単位としては、上記ベンゾジオキソール構造単位であってもよいし、他の構造単位であってもよい。
The polymer electrolyte preferably contains a proton-conducting group. Examples of the proton-conducting group include a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, and a sulfonamide group. From the viewpoint of proton conductivity, a sulfonic acid group, which is a strong acid, is preferable.
The polymer electrolyte preferably contains a structural unit having the proton-conducting group. The structural unit having the proton-conducting group may be the benzodioxole structural unit or another structural unit.
上記高分子電解質は、化学耐久性と疎水性の観点から、含フッ素高分子電解質であることが好ましい。 From the viewpoints of chemical durability and hydrophobicity, the above polymer electrolyte is preferably a fluorine-containing polymer electrolyte.
上記高分子電解質としては、電極触媒層のひび割れを一層抑制でき、発電性能、耐久性が一層良好な電池が得られる観点から、上記式(25)、上記式(26)、及び上記式(27)からなる群から選ばれる少なくとも1種の構造単位からなる重合体;下記式(7)で表される化合物
;下記式(8)で表される化合物
(式(7)、(8)中、R1、R2はそれぞれ独立に水素原子、フッ素原子、又は有機基を表す。R3、R4、R5はそれぞれ独立に水素原子、フッ素原子、又は有機基を表す。上記有機基としては、例えば、部分的又は完全にフッ素化されていてもよい炭素数1~10の炭化水素基、エーテル結合、芳香族環等が挙げられる。lは、1から10のいずれかの整数を表す。qは0~2の整数であり、rは0~12の整数である。ただし、q及びrは同時に0にならない。R10、R11はそれぞれ独立にフッ素原子、又は上記式(31)の構造を表す。);が好ましい。
As the polymer electrolyte, from the viewpoint of further suppressing cracking of the electrode catalyst layer and obtaining a battery having better power generation performance and durability, a polymer comprising at least one structural unit selected from the group consisting of the above formula (25), the above formula (26), and the above formula (27); a compound represented by the following formula (7):
A compound represented by the following formula (8):
(In formulas (7) and (8), R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom, or an organic group. R 3 , R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, or an organic group. Examples of the organic group include a hydrocarbon group having 1 to 10 carbon atoms which may be partially or completely fluorinated, an ether bond, an aromatic ring, and the like. l represents an integer of 1 to 10. q is an integer of 0 to 2, and r is an integer of 0 to 12, with the proviso that q and r are not 0 at the same time. R 10 and R 11 each independently represent a fluorine atom, or a structure of the above formula (31).) is preferable.
(構造単位の含有割合)
上記高分子電解質100mol%中の上記ベンゾジオキソール構造単位の合計割合は、電極触媒層のひび割れを一層抑制でき、発電性能、耐久性が一層良好な電池が得られる観点から、5~600mol%であることが好ましく、より好ましくは10~500mol%である。
上記高分子電解質100mol%中の上記構造単位Aの合計割合は、電極触媒層のひび割れを一層抑制でき、発電性能、耐久性が一層良好な電池が得られる観点から、1~100mol%であることが好ましく、より好ましくは5~90mol%である。
上記高分子電解質100mol%中の上記構造単位Bの合計割合は、電極触媒層のひび割れを一層抑制でき、発電性能、耐久性が一層良好な電池が得られる観点から、1~100mol%であることが好ましく、より好ましくは5~90mol%である。
高分子電解質中の構造単位のモル割合は、後述の実施例に記載の方法により測定することができる。
(Ratio of structural units)
The total proportion of the benzodioxole structural units in 100 mol % of the polymer electrolyte is preferably 5 to 600 mol %, more preferably 10 to 500 mol %, from the viewpoint of further suppressing cracking of the electrode catalyst layer and obtaining a battery with better power generation performance and durability.
The total proportion of the structural unit A in 100 mol % of the polymer electrolyte is preferably 1 to 100 mol %, and more preferably 5 to 90 mol %, from the viewpoint of further suppressing cracking of the electrode catalyst layer and obtaining a battery having better power generation performance and durability.
The total proportion of the structural unit B in 100 mol % of the polymer electrolyte is preferably 1 to 100 mol %, and more preferably 5 to 90 mol %, from the viewpoint of further suppressing cracking of the electrode catalyst layer and obtaining a battery having better power generation performance and durability.
The molar ratio of the structural units in the polymer electrolyte can be measured by the method described in the Examples below.
(特性)
上記高分子電解質は、当量重量EW(プロトン交換基1当量あたりの高分子電解質の乾燥質量グラム数)が100~2000g/eqであることが好ましい。即ち、上記EWの範囲内となるように共重合比やプロトン性伝導基導入率を制御することが好ましい。EWの上限は、好ましくは1000g/eqであり、より好ましくは900g/eqである。EWの下限は、好ましくは300g/eqであり、より好ましくは500g/eqである。EWが上記の範囲内にあることにより、加工性に一層優れ、電極触媒層の伝導度が低くなりすぎず、熱水への溶解性も小さい。上記EWは、後述の実施例に記載の方法により、算出することができる。
(Characteristic)
The polymer electrolyte preferably has an equivalent weight EW (the number of grams of dry mass of the polymer electrolyte per equivalent of proton exchange group) of 100 to 2000 g/eq. That is, it is preferable to control the copolymerization ratio and the proton conductive group introduction rate so as to be within the above EW range. The upper limit of the EW is preferably 1000 g/eq, more preferably 900 g/eq. The lower limit of the EW is preferably 300 g/eq, more preferably 500 g/eq. By having the EW within the above range, the processability is further excellent, the conductivity of the electrode catalyst layer is not too low, and the solubility in hot water is also small. The EW can be calculated by the method described in the Examples below.
上記高分子電解質は、加工性、電気伝導度及び機械的強度がより一層優れることから、数平均分子量が、1万~200万であることが好ましく、より好ましくは3万~100万である。数平均分子量が比較的低く機械的強度に劣る場合は、特願2016-171717の参考例1に記載のあるようなMIが比較的低い、すなわち高分子量のポリマーと混合しても良い。
上記数平均分子量は、GPC(ゲルパーミェーションクロマトグラフ)法により測定される値であり、例えば、以下に示す方法により、標準ポリスチレンを基準として数平均分子量を算出することができる。
TOSOH社製 HLC-8020を用い、カラムはポリスチレンゲル製MIXカラム(東ソーGMHシリーズ、30cmサイズ)を3本、40℃、NMP(5mmol/L LiBr含有)溶剤、流速0.7mL/分で行うことができる。サンプル濃度は、0.1重量%で打ち込み量は500μLで行うことができる。数平均分子量がポリスチレン換算値で10万~80万程度のものが更に好ましく、13万~70万程度のものが更により好ましく、16万~60万程度のものが特に好ましい。
The polymer electrolyte preferably has a number average molecular weight of 10,000 to 2,000,000, and more preferably 30,000 to 1,000,000, in order to provide even better processability, electrical conductivity, and mechanical strength. When the number average molecular weight is relatively low and the mechanical strength is poor, the polymer may be mixed with a polymer having a relatively low MI, i.e., a high molecular weight polymer, as described in Reference Example 1 of Japanese Patent Application No. 2016-171717.
The number average molecular weight is a value measured by GPC (gel permeation chromatography). For example, the number average molecular weight can be calculated using standard polystyrene as the standard by the method described below.
The column is a Tosoh HLC-8020, and three polystyrene gel MIX columns (Tosoh GMH series, 30 cm size) are used, and the temperature is 40° C., NMP (containing 5 mmol/L LiBr) is used as the solvent, and the flow rate is 0.7 mL/min. The sample concentration is 0.1 wt %, and the injection amount is 500 μL. The number average molecular weight is more preferably about 100,000 to 800,000, more preferably about 130,000 to 700,000, and particularly preferably about 160,000 to 600,000, in terms of polystyrene.
GPCにより分子量が測定できないポリマーについては、メルトフローレート(MFR)により測定しても良い。
上記高分子電解質のMFRは、0.1~1000g/10分であることが好ましく、0.5g/10分以上であることがより好ましく、1.0g/10分以上であることが更に好ましく、200g/10分以下であることがより好ましく、100g/10分以下であることが更に好ましい。
上記MFRは、ASTM規格D1238に従って270℃、荷重2.16kgの条件下で、MELT INDEXER TYPE C-5059D(商品名、東洋精機社製)を用いて測定することができる。
For polymers whose molecular weight cannot be measured by GPC, it may be measured by melt flow rate (MFR).
The MFR of the polymer electrolyte is preferably 0.1 to 1000 g/10 min, more preferably 0.5 g/10 min or more, and even more preferably 1.0 g/10 min or more, more preferably 200 g/10 min or less, and even more preferably 100 g/10 min or less.
The MFR can be measured according to ASTM standard D1238 under conditions of 270° C. and a load of 2.16 kg using a MELT INDEXER TYPE C-5059D (product name, manufactured by Toyo Seiki Seisakusho Co., Ltd.).
(製造方法)
上記高分子電解質は、所定の構造単位を形成できるモノマーを重合して得てもよいし、重合後の重合体に所定の側鎖を導入してもよい。
上記高分子電解質は、例えば、重縮合、ラジカル重合、アニオン重合等の従来公知の方法にて合成することができ、中でも、重縮合又はラジカル重合が好ましく用いられる。
上記高分子電解質粒子が水に分散又は溶解したエマルションの形態で、上記高分子電解質が得られる。
(Production method)
The polymer electrolyte may be obtained by polymerizing a monomer capable of forming a predetermined structural unit, or by introducing a predetermined side chain into a polymer after polymerization.
The polymer electrolyte can be synthesized by a conventional method such as polycondensation, radical polymerization, or anionic polymerization, and among these, polycondensation or radical polymerization is preferably used.
The polymer electrolyte is obtained in the form of an emulsion in which the polymer electrolyte particles are dispersed or dissolved in water.
上記ラジカル重合は、界面活性剤の存在下に行ってもよい。界面活性剤としては、公知の含フッ素アニオン界面活性剤が好ましい。 The radical polymerization may be carried out in the presence of a surfactant. The surfactant is preferably a known fluorine-containing anionic surfactant.
上記ラジカル重合は、重合開始剤を添加して行うことが好ましい。上記重合開始剤としては、重合温度でラジカルを発生しうるものであれば特に限定されず、公知の油溶性及び/又は水溶性の重合開始剤を使用することができる。また、レドックス開始剤を使用してもよい。上記重合開始剤の濃度は、目的とする重合体の分子量、反応速度によって適宜決定される。
上記重合開始剤としては、過硫酸アンモニウム、過硫酸カリウム等の過硫酸塩、ジコハク酸パーオキシド、ジグルタル酸パーオキシド、tert-ブチルヒドロパーオキシド等の有機過酸化物が挙げられる。上記レドックス開始剤としては、過硫酸塩又は有機過酸化物と、亜硫酸ナトリウム等の亜硫酸塩、亜硫酸水素ナトリウム等の重亜硫酸塩、臭素酸塩、ジイミン、シュウ酸等の還元剤とを組み合わせたものが挙げられる。
The radical polymerization is preferably carried out by adding a polymerization initiator. The polymerization initiator is not particularly limited as long as it can generate radicals at the polymerization temperature, and a known oil-soluble and/or water-soluble polymerization initiator can be used. A redox initiator may also be used. The concentration of the polymerization initiator is appropriately determined depending on the molecular weight and reaction rate of the target polymer.
Examples of the polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, and organic peroxides such as disuccinic acid peroxide, diglutaric acid peroxide, and tert-butyl hydroperoxide. Examples of the redox initiator include a combination of a persulfate or an organic peroxide with a reducing agent such as a sulfite such as sodium sulfite, a bisulfite such as sodium hydrogensulfite, a bromate, a diimine, or oxalic acid.
ラジカル重合は、0.05~5.0MPaの圧力下で行うことができる。好ましい圧力の範囲は0.1~1.5MPaである。また、ラジカル重合は、5~100℃の温度で行うことができる。好ましい温度の範囲は10~90℃である。ラジカル重合では、また、目的に応じて、公知の安定剤、連鎖移動剤等を添加してもよい。 Radical polymerization can be carried out under a pressure of 0.05 to 5.0 MPa. The preferred pressure range is 0.1 to 1.5 MPa. Radical polymerization can be carried out at a temperature of 5 to 100°C. The preferred temperature range is 10 to 90°C. In radical polymerization, known stabilizers, chain transfer agents, etc. may also be added depending on the purpose.
上記式(25)の高分子電解質の合成方法としては、特に限定されないが、例えば、オクタフルオロシクロペンテンを、水酸基を2つ以上有するモノマーと重縮合させた後、水酸基を有するベンゾジオキソール誘導体(例えば、セサモール等)と反応させ、アリル位のフッ素原子を置換することで合成できる。 The method for synthesizing the polymer electrolyte of the above formula (25) is not particularly limited, but for example, it can be synthesized by polycondensing octafluorocyclopentene with a monomer having two or more hydroxyl groups, and then reacting it with a benzodioxole derivative having a hydroxyl group (e.g., sesamol, etc.) to substitute the fluorine atom at the allylic position.
上記式(26)の高分子電解質の合成方法としては、特に限定されないが、例えば、まずオクタフルオロシクロペンテンを、水酸基を有するベンゾジオキソール誘導体(例えば、セサモール等)と反応させ、式(10)のようなモノマーを合成する。その後、このモノマーと、水酸基を2つ以上有するモノマーを重縮合させることで合成できる。スルホン酸基の導入方法としては、特に限定されないが、例えば、脱ハロゲンカップリング等で導入可能である。
上記式(27)の高分子電解質の合成方法としては、特に限定されないが、例えば、ペンタフルオロスチレンモノマーをラジカル重合した後に、水酸基を有するベンゾジオキソール誘導体(例えば、セサモール等)を芳香族求核置換反応によって導入できる。スルホン酸基の導入方法は、特に限定されないが、例えば、得られたポリマーを水酸化カリウムや水酸化ナトリウムで処理し、芳香環に水酸基を導入した後に、二重結合を有するスルホン酸誘導体(例えば、CF2=CF-OCF2CF2SO3X、CF2=CF-OCF2CF(CF3)-OCF2CF2SO3X、CF2=CF-OCF2CF(CF2OCF2CF2SO3X)-OCF2CF2SO3X、Xは水素やアルカリ金属、アルカリ土類金属、4級アンモニウム塩である)を付加させることで導入できる。 The method for synthesizing the polymer electrolyte of the above formula (27) is not particularly limited. For example, after radical polymerization of a pentafluorostyrene monomer, a benzodioxole derivative having a hydroxyl group (e.g., sesamol, etc.) can be introduced by an aromatic nucleophilic substitution reaction. The method for introducing sulfonic acid groups is not particularly limited, but for example, the obtained polymer can be treated with potassium hydroxide or sodium hydroxide to introduce hydroxyl groups into the aromatic rings, and then a sulfonic acid derivative having a double bond (for example, CF 2 ═CF-OCF 2 CF 2 SO 3 X, CF 2 ═CF-OCF 2 CF(CF 3 )-OCF 2 CF 2 SO 3 X, CF 2 ═CF-OCF 2 CF(CF 2 OCF 2 CF 2 SO 3 X)-OCF 2 CF 2 SO 3 X, where X is hydrogen, an alkali metal, an alkaline earth metal, or a quaternary ammonium salt) can be added to introduce the sulfonic acid groups.
上記式(29)、(30)の高分子電解質の合成方法としては、特に限定されないが、例えば、ラジカル重合で合成する方法や、式(11)のポリマーに対してアミノ基を有するベンゾジオキソール誘導体(例えば、ピペロニルアミン等)を反応させ、その後加水分解処理することで合成できる。
上記高分子電解質は、80℃30%RH条件でPt厚膜法により測定した酸素溶解度が7.0mol/m3以上であることが、電池性能の観点から好ましい。触媒表面を覆う高分子電解質の薄膜は数nm程度であり、そこでの酸素透過性はバルクでの挙動とは異なる。すなわち、バルクでは酸素拡散性が律速となるが、薄膜では酸素溶解性が律速となる。上記酸素溶解度は、後述の実施例に記載の方法により、算出することができる。 From the viewpoint of cell performance, it is preferable that the above-mentioned polymer electrolyte has an oxygen solubility of 7.0 mol/ m3 or more measured by the Pt thick film method under conditions of 80°C and 30% RH. The thin film of the polymer electrolyte covering the catalyst surface is about several nm thick, and the oxygen permeability therein differs from the behavior in the bulk. That is, oxygen diffusivity is the rate-limiting factor in the bulk, but oxygen solubility is the rate-limiting factor in the thin film. The above-mentioned oxygen solubility can be calculated by the method described in the Examples below.
(高分子電解質溶液)
本実施形態の高分子電解質溶液は、上記高分子電解質と水及び/又は有機溶媒とを含むことが好ましい。上記高分子電解質溶液は、燃料電池の電極触媒層(例えば、カソード用電極触媒層)を形成する原料として好適に用いることができる。上記高分子電解質溶液は、燃料電池の電極触媒層形成用高分子電解質溶液であることが好ましい。
(Polyelectrolyte solution)
The polymer electrolyte solution of the present embodiment preferably contains the above-mentioned polymer electrolyte and water and/or an organic solvent. The above-mentioned polymer electrolyte solution can be suitably used as a raw material for forming an electrode catalyst layer of a fuel cell (e.g., an electrode catalyst layer for a cathode). The above-mentioned polymer electrolyte solution is preferably a polymer electrolyte solution for forming an electrode catalyst layer of a fuel cell.
上記高分子電解質溶液中の上記高分子電解質の質量割合は、2~50質量%であることが好ましく、5質量%以上であることがより好ましく、10質量%以上であることが更に好ましく、40質量%以下であることがより好ましく、30質量%以下であることが更に好ましく、25質量%以下であることが特に好ましい。 The mass proportion of the polymer electrolyte in the polymer electrolyte solution is preferably 2 to 50% by mass, more preferably 5% by mass or more, even more preferably 10% by mass or more, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less.
上記有機溶媒としては、メタノール、エタノール、n-プロパノール、イソプロピルアルコール、ブタノール、グリセリン等のプロトン性有機溶媒;N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン、アセトニトリル、酢酸エチル等の非プロトン性溶媒;トリフルオロエタノール、バートレルXF、ノベック7100、ノベック7300等のフッ素系溶媒;等が挙げられる。これらは1種を単独で、又は2種以上を併用することができる。 Examples of the organic solvent include protic organic solvents such as methanol, ethanol, n-propanol, isopropyl alcohol, butanol, and glycerin; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, and ethyl acetate; and fluorine-based solvents such as trifluoroethanol, Vertrel XF, Novec 7100, and Novec 7300. These can be used alone or in combination of two or more.
上記高分子電解質溶液は、有機系添加剤を含んでもよい。また、上記高分子電解質溶液は、無機系添加剤を含んでもよい。 The polymer electrolyte solution may contain an organic additive. The polymer electrolyte solution may also contain an inorganic additive.
上記有機系添加剤としては、例えば、3級炭素に結合した水素、炭素-ハロゲン結合等を構造中に有する化合物等の原子がラジカルにより引き抜かれやすい化合物が挙げられる。具体的には、ポリアニリンのような官能基で一部置換された芳香族化合物、ポリベンゾイミダゾール、ポリベンゾオキサゾール、ポリベンゾチアゾール、ポリベンゾオキサジアゾール、フェニル化ポリキノキサリン、フェニル化ポリキノリン等の不飽和の複素環化合物を挙げることができる。
また、チオエーテル化合物も挙げられる。例えば、ジメチルチオエーテル、ジエチルチオエーテル、ジプロピルチオエーテル、メチルエチルチオエーテル、メチルブチルチオエーテルのようなジアルキルチオエーテル;テトラヒドロチオフェン、テトラヒドロアピランのような環状チオエーテル;メチルフェニルスルフィド、エチルフェニルスルフィド、ジフェニルスルフィド、ジベンジルスルフィドのような芳香族チオエーテル;等が挙げられる。
Examples of the organic additives include compounds whose atoms are easily extracted by radicals, such as compounds having hydrogen bonded to a tertiary carbon or a carbon-halogen bond in the structure. Specific examples include aromatic compounds partially substituted with functional groups, such as polyaniline, and unsaturated heterocyclic compounds, such as polybenzimidazole, polybenzoxazole, polybenzothiazole, polybenzoxadiazole, phenylated polyquinoxaline, and phenylated polyquinoline.
In addition, thioether compounds may also be used, for example, dialkyl thioethers such as dimethyl thioether, diethyl thioether, dipropyl thioether, methyl ethyl thioether, and methyl butyl thioether, cyclic thioethers such as tetrahydrothiophene and tetrahydroapyran, and aromatic thioethers such as methyl phenyl sulfide, ethyl phenyl sulfide, diphenyl sulfide, and dibenzyl sulfide.
上記高分子電解質溶液中の上記有機系添加剤の質量割合は、0.1質量%以上が好ましく、1質量%以上がより好ましく、3質量%以上がさらに好ましい。上記有機系添加剤を0.1質量%以上含有することで、燃料電池運転での化学耐久性を向上させることが可能となる。 The mass ratio of the organic additive in the polymer electrolyte solution is preferably 0.1 mass% or more, more preferably 1 mass% or more, and even more preferably 3 mass% or more. By containing 0.1 mass% or more of the organic additive, it is possible to improve chemical durability during fuel cell operation.
上記無機系添加剤としては、例えば、金属酸化物、金属炭酸塩、金属硝酸塩等が挙げられる。上記無機添加剤は、一種を単独で用いても良いし、2種以上の混合物を用いても良い。
上記金属酸化物としては、例えば、ジルコニア(ZrO2)、チタニア(TiO2)、シリカ(SiO2)、アルミナ(Al2O3)、酸化鉄(Fe2O3、FeO、Fe3O4)、酸化銅(CuO、Cu2O)、酸化亜鉛(ZnO)、酸化イットリウム(Y2O3)、酸化ニオブ(Nb2O5)、酸化モリブデン(MoO3)、酸化インジウム(In2O3、In2O)、酸化スズ(SnO2)、酸化タンタル(Ta2O5)、酸化タングステン(WO3、W2O5)、酸化鉛(PbO、PbO2)、酸化ビスマス(Bi2O3)、酸化セリウム(CeO2、Ce2O3)、酸化アンチモン(Sb2O3、Sb2O5)、酸化ゲルマニウム(GeO2、GeO)、酸化ランタン(La2O3)、酸化ルテニウム(RuO2)、酸化マンガン(MnO)等が挙げられる。これら金属酸化物は、単独で用いても、混合物を用いてもよいし、例えば、スズ添加酸化インジウム(ITO)、アンチモン添加酸化スズ(ATO)、酸化アルミニウム亜鉛(ZnO・Al2O3)、等に挙げられる複合酸化物を挙げることができる。
上記金属炭酸塩としては、例えば、炭酸ジルコニウム(Zr(CO3)2)、炭酸チタニウム(Ti(CO3)2)、炭酸鉄(FeCO3)、炭酸銅(Cu2CO3)、炭酸亜鉛(ZnCO3)、炭酸モリブデン、炭酸セリウム(CeCO3)、炭酸ニッケル(NiCO3)、炭酸コバルト(CoCO3)、炭酸マンガン(MnCO3)、等が挙げられる。
上記金属硝酸塩としては、例えば、硝酸ジルコニウム(Zr(NO3)4)、硝酸鉄(Fe(NO3)3)、硝酸銅(Cu(NO3)2)、硝酸チタン(Ti(NO3)4)、硝酸セリウム(Ce(NO3)3)、硝酸ニッケル(Ni(NO3)2)、硝酸コバルト(Co(NO3)2)、硝酸マンガン(Mn(NO3)2)、等が挙げられる。
中でも、親水性向上の観点からシリカ(SiO2)が好ましく、化学耐久性向上の観点から酸化セリウム(CeO2、Ce2O3)、酸化マンガン(MnO)、炭酸セリウム(CeCO3)、炭酸マンガン(MnCO3)、硝酸セリウム(Ce(NO3)3)、硝酸マンガン(Mn(NO3)2)、硝酸チタン(Ti(NO3)4)が好ましい。
Examples of the inorganic additives include metal oxides, metal carbonates, metal nitrates, etc. The inorganic additives may be used alone or in combination of two or more.
Examples of the metal oxide include zirconia ( ZrO2 ), titania ( TiO2 ), silica ( SiO2 ), alumina ( Al2O3 ) , iron oxide ( Fe2O3 , FeO, Fe3O4 ), copper oxide (CuO, Cu2O ), zinc oxide ( ZnO), yttrium oxide (Y2O3 ) , niobium oxide ( Nb2O5 ), molybdenum oxide ( MoO3 ), indium oxide ( In2O3 , In2O ), tin oxide ( SnO2 ) , tantalum oxide ( Ta2O5 ), tungsten oxide ( WO3 , W2O5 ), lead oxide (PbO, PbO2 ), bismuth oxide ( Bi2O3 ), cerium oxide ( CeO2 , Ce2O3 ) . ), antimony oxide (Sb2O3 , Sb2O5 ) , germanium oxide ( GeO2 , GeO), lanthanum oxide ( La2O3 ) , ruthenium oxide ( RuO2 ), manganese oxide (MnO), etc. These metal oxides may be used alone or in combination, and examples of the metal oxides include composite oxides such as tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), aluminum zinc oxide ( ZnO.Al2O3 ), etc.
Examples of the metal carbonates include zirconium carbonate (Zr( CO3 ) 2 ), titanium carbonate (Ti( CO3 ) 2 ), iron carbonate ( FeCO3 ), copper carbonate ( Cu2CO3 ), zinc carbonate ( ZnCO3 ), molybdenum carbonate, cerium carbonate ( CeCO3 ), nickel carbonate ( NiCO3 ), cobalt carbonate (CoCO3 ) , manganese carbonate ( MnCO3 ), and the like.
Examples of the metal nitrates include zirconium nitrate (Zr( NO3 ) 4 ), iron nitrate (Fe( NO3 ) 3 ), copper nitrate (Cu( NO3 ) 2 ), titanium nitrate (Ti( NO3 ) 4 ), cerium nitrate (Ce( NO3 ) 3 ), nickel nitrate (Ni( NO3 ) 2 ), cobalt nitrate (Co( NO3 ) 2 ), manganese nitrate (Mn( NO3 ) 2 ), and the like.
Among these, silica ( SiO2 ) is preferred from the viewpoint of improving hydrophilicity, and cerium oxide ( CeO2 , Ce2O3 ), manganese oxide ( MnO ), cerium carbonate (CeCO3), manganese carbonate ( MnCO3 ), cerium nitrate (Ce( NO3 ) 3 ), manganese nitrate (Mn( NO3 ) 2 ), and titanium nitrate (Ti( NO3 ) 4 ) are preferred from the viewpoint of improving chemical durability.
無機系添加剤の形態としては、粒子状や繊維状といったものを用いても構わないが、特に非定形であることが望ましい。ここでいう非定形とは、光学顕微鏡や電子顕微鏡で観察しても、粒子状や繊維状の金属酸化物が観察されないことをいう。特に、走査型電子顕微鏡(SEM)を用いて電極触媒層を数10万倍までに拡大して観察しても、粒子状や繊維状の金属酸化物は観察されない。また、透過型電子顕微鏡(TEM)を用いて電極触媒層を数10万倍~数100万倍に拡大して観察しても、明確に粒子状や繊維状の金属酸化物は観察することができない。このように現状の顕微鏡技術の範囲内では、金属酸化物の粒子状や繊維状を確認することができないことを指す。 The inorganic additive may be in the form of particles or fibers, but it is particularly desirable that the additive be amorphous. In this case, "amorphous" means that no particulate or fibrous metal oxide is observed when observed with an optical microscope or electron microscope. In particular, no particulate or fibrous metal oxide is observed when the electrode catalyst layer is magnified to several hundred thousand times using a scanning electron microscope (SEM). Furthermore, no particulate or fibrous metal oxide can be clearly observed when the electrode catalyst layer is magnified to several hundred thousand times to several million times using a transmission electron microscope (TEM). In this way, it means that the particulate or fibrous metal oxide cannot be confirmed within the scope of current microscopy technology.
上記高分子電解質溶液中の上記無機系添加剤の質量割合は、0.01~100質量%であることが好ましく、より好ましくは0.01~45質量%、更に好ましくは0.01~25質量%、特に好ましくは0.5~6.0質量%である。上記無機系添加剤を0.01質量%以上含有することで、燃料電池運転での化学耐久性を向上させることが可能となる。 The mass ratio of the inorganic additive in the polymer electrolyte solution is preferably 0.01 to 100 mass%, more preferably 0.01 to 45 mass%, even more preferably 0.01 to 25 mass%, and particularly preferably 0.5 to 6.0 mass%. By including 0.01 mass% or more of the inorganic additive, it is possible to improve chemical durability during fuel cell operation.
上記高分子電解質溶液は、所望の固形分濃度にするために、濃縮することが可能である。濃縮の方法としては特に限定されない。例えば、加熱し、溶媒を蒸発させる方法や、減圧濃縮する方法等がある。その結果得られる高分子電解質溶液の固形分率は、取り扱い性及び生産性を考慮して、最終的な高分子電解質溶液の固形分率は0.5~50質量%が好ましい。 The polymer electrolyte solution can be concentrated to a desired solids concentration. There are no particular limitations on the concentration method. For example, there is a method of heating to evaporate the solvent, or a method of concentrating under reduced pressure. The solids content of the resulting polymer electrolyte solution is preferably 0.5 to 50% by mass, taking into account ease of handling and productivity.
上記高分子電解質溶液は、粗大粒子成分を除去する観点から、濾過されることがより好ましい。濾過方法は、特に限定されず、従来行われている一般的な方法が適用できる。例えば、通常使用されている定格濾過精度を有する濾材を加工したフィルターを用いて、加圧濾過する方法が代表的に挙げられる。フィルターについては、90%捕集粒子径が粒子の平均粒子径の10~100倍の濾材を使用することが好ましい。この濾材は濾紙でもよいし、金属焼結フィルターのような濾材でもよい。特に濾紙の場合は、90%捕集粒子径が粒子の平均粒子径の10~50倍であることが好ましい。金属焼結フィルターの場合は、90%捕集粒子径が粒子の平均粒子径の50~100倍であることが好ましい。当該90%捕集粒子径を平均粒径の10倍以上に設定することは、送液するときに必要な圧力が高くなりすぎることを抑制したり、フィルターが短期間で閉塞したりすることを抑制し得る。一方、平均粒子径の100倍以下に設定することは、フィルムで異物の原因となるような粒子の凝集物や樹脂の未溶解物を良好に除去する観点から好ましい。 It is more preferable that the polymer electrolyte solution is filtered from the viewpoint of removing coarse particle components. The filtration method is not particularly limited, and a conventional method can be applied. For example, a method of pressure filtration using a filter processed from a filter material having a commonly used rated filtration accuracy is exemplified. It is preferable to use a filter material whose 90% collection particle size is 10 to 100 times the average particle size of the particles. This filter material may be filter paper or a filter material such as a sintered metal filter. In particular, in the case of filter paper, it is preferable that the 90% collection particle size is 10 to 50 times the average particle size of the particles. In the case of a sintered metal filter, it is preferable that the 90% collection particle size is 50 to 100 times the average particle size of the particles. Setting the 90% collection particle size to 10 times or more the average particle size can prevent the pressure required for liquid delivery from becoming too high or the filter from clogging in a short period of time. On the other hand, setting it to 100 times or less the average particle size is preferable from the viewpoint of effectively removing particle aggregates and undissolved resin that may cause foreign matter in the film.
上記高分子電解質溶液は、1種類以上の上記ベンゾジオキソール誘導体骨格を含む高分子電解質以外にも、ベンゾジオキソール誘導体骨格を持たない他の高分子電解質を含んでいてもよい。
ベンゾジオキソール誘導体骨格を持たない他の高分子電解質としては、特に限定されず、既知の高分子電解質を使うことができる。例えば、下記式(12)又は(13)で表わされる繰り返し単位を有す重合体が挙げられる。
(式(12)中、Y31は、F、Cl、又は炭素数1~3のパーフルオロアルキル基を表す。kは0~2の整数、nは0~8の整数を表し、n個のY31は、同一でも異なっていてもよい。Y32は、F又はClを表す。mは2~6の整数を表す。m個のY32は、同一でも異なっていてもよい。Z31は、H、アルカリ金属、アルカリ土類金属、又はNR4を表す。Rは、それぞれ独立に、アルキル基又はHを表わす。)
(式(13)中、Y33は、F、Cl、又は炭素数1~3のパーフルオロアルキル基を表す。oは0~1の整数を表す。Q31は、エーテル結合を有していてもよい炭素数1~6のパーフルオロアルキレン基であり、Q32は、単結合又はエーテル結合を有していてもよい炭素数1~6のパーフルオロアルキレン基である。R31は、エーテル結合を有していてもよいパーフルオロアルキル基である。Xは、O、N、又はCであって、XがOの場合はaは0であり、XがNの場合はaは1であり、XがCの場合はaは2である。Z32は、H、アルカリ金属、アルカリ土類金属、又はNR32
4を表す。R32は、それぞれ独立に、アルキル基又はHを表わす。)
上記繰り返し単位(12)について、Y31はF又はCF3であることが好ましい。kは0であることが好ましい。nは0又は1であることが好ましい。Y32はFであることが好ましい。mは2であることが好ましい。Z31はH、Na、K、又はNH4であることが好ましい。
上記繰り返し単位(12)は、上述したものの中でも特に、-CF2-CF(-O-CF2-CF2-SO3H)-、又は-CF2-CF(-O-CF2-CF(CF3)-O-CF2-CF2-SO3H)-が好ましい。
上記繰り返し単位(13)について、Y33はFであることが好ましい。oは0であることが好ましい。Q31は、-CF2-CF2-又は-CF2-O-CF2-CF2-であることが好ましい。Q32は、-O-CF2-CF2-であることが好ましい。R31は、-CF3又は-CF2-CF3であることが好ましい。XはOであることが好ましい。Z32は、H、Na、K、又はNH4であることが好ましい。
上記繰り返し単位(13)は、上述したものの中でも特に、-CF2-CF(-O-CF2-CF(-CF2-O-CF2-CF2-SO3H)(-O-CF2-CF2-SO3H)-が好ましい。
The polymer electrolyte solution may contain, in addition to one or more types of polymer electrolytes containing a benzodioxole derivative skeleton, other polymer electrolytes not having a benzodioxole derivative skeleton.
The other polymer electrolyte not having a benzodioxole derivative skeleton is not particularly limited, and any known polymer electrolyte can be used, for example, a polymer having a repeating unit represented by the following formula (12) or (13).
(In formula (12), Y 31 represents F, Cl, or a perfluoroalkyl group having 1 to 3 carbon atoms. k represents an integer of 0 to 2, n represents an integer of 0 to 8, and the n Y 31s may be the same or different. Y 32 represents F or Cl. m represents an integer of 2 to 6. The m Y 32s may be the same or different. Z 31 represents H, an alkali metal, an alkaline earth metal, or NR 4. Each R independently represents an alkyl group or H.)
(In formula (13), Y 33 represents F, Cl, or a perfluoroalkyl group having 1 to 3 carbon atoms. o represents an integer of 0 to 1. Q 31 represents a perfluoroalkylene group having 1 to 6 carbon atoms which may have an ether bond, and Q 32 represents a perfluoroalkylene group having 1 to 6 carbon atoms which may have a single bond or an ether bond. R 31 represents a perfluoroalkyl group which may have an ether bond. X represents O, N, or C, and when X is O, a is 0, when X is N, a is 1, and when X is C, a is 2. Z 32 represents H, an alkali metal, an alkaline earth metal, or NR 32 4. Each of R 32 independently represents an alkyl group or H.)
In the above repeating unit (12), Y31 is preferably F or CF3 . k is preferably 0. n is preferably 0 or 1. Y32 is preferably F. m is preferably 2. Z31 is preferably H, Na, K, or NH4 .
Of the repeating units mentioned above, the repeating unit (12) is preferably --CF 2 --CF(--O--CF 2 --CF 2 --SO 3 H)-- or --CF 2 --CF(--O--CF 2 --CF(CF 3 )--O--CF 2 --CF 2 --SO 3 H)--.
In the above repeating unit (13), Y 33 is preferably F. o is preferably 0. Q 31 is preferably -CF2 - CF2- or -CF2 -O- CF2 - CF2- . Q 32 is preferably -O- CF2 - CF2- . R 31 is preferably -CF3 or -CF2 - CF3 . X is preferably O. Z 32 is preferably H, Na, K, or NH4 .
Of the repeating units mentioned above, the repeating unit (13) is preferably --CF 2 --CF(--O--CF 2 --CF(--CF 2 --O--CF 2 --CF 2 --SO 3 H)(--O--CF 2 --CF 2 --SO 3 H)--.
(電極触媒インク)
上記高分子電解質は、電極触媒インクを形成する原料として好適に用いることができる。上記電極触媒インクは、上記高分子電解質と触媒とを含むことが好ましく、さらに水及び/又は有機溶媒を含んでいてもよい。上記電極触媒インクは、燃料電池の電極触媒層(例えば、カソード用電極触媒層)を形成する原料として好適に用いることができる。上記電極触媒インクは、燃料電池の電極触媒層形成用電極触媒インクであることが好ましい。
(Electrocatalytic ink)
The polymer electrolyte can be suitably used as a raw material for forming an electrode catalyst ink. The electrode catalyst ink preferably contains the polymer electrolyte and a catalyst, and may further contain water and/or an organic solvent. The electrode catalyst ink can be suitably used as a raw material for forming an electrode catalyst layer (e.g., an electrode catalyst layer for a cathode) of a fuel cell. The electrode catalyst ink is preferably an electrode catalyst ink for forming an electrode catalyst layer of a fuel cell.
上記触媒としては、電極触媒層において活性を有し得るものであれば特に限定されず、上記電極触媒層が用いられる燃料電池の使用目的に応じて適宜選択される。上記触媒は、触媒金属であることが好ましい。
上記触媒としては、水素の酸化反応及び酸素の還元反応を促進する金属であることが好ましく、白金、金、銀、パラジウム、イリジウム、ロジウム、ルテニウム、鉄、コバルト、ニッケル、クロム、タングステン、マンガン、バナジウム、及びこれらの合金からなる群より選択される少なくとも一種の金属であることがより好ましい。中でも、白金が好ましい。
The catalyst is not particularly limited as long as it can have activity in the electrode catalyst layer, and is appropriately selected depending on the intended use of the fuel cell in which the electrode catalyst layer is used. The catalyst is preferably a catalytic metal.
The catalyst is preferably a metal that promotes the oxidation reaction of hydrogen and the reduction reaction of oxygen, and more preferably at least one metal selected from the group consisting of platinum, gold, silver, palladium, iridium, rhodium, ruthenium, iron, cobalt, nickel, chromium, tungsten, manganese, vanadium, and alloys thereof. Of these, platinum is preferred.
触媒金属の粒子径は限定されないが、10~1000オングストロームが好ましく、より好ましくは10~500オングストローム、最も好ましくは15~100オングストロームである。 The particle size of the catalyst metal is not limited, but is preferably 10 to 1000 angstroms, more preferably 10 to 500 angstroms, and most preferably 15 to 100 angstroms.
上記電極触媒インク中の上記高分子電解質の含有量は、上記電極触媒インクに対して、5~30質量%であることが好ましく、8質量%以上であることがより好ましく、10質量%以上であることが更に好ましく、20質量%以下であることがより好ましく、15質量%以下であることが更に好ましい。
上記電極触媒インク中の上記触媒の含有量は、上記高分子電解質に対して、50~200質量%であることが好ましく、80質量%以上であることがより好ましく、100質量%以上であることが更に好ましく、150質量%以下であることがより好ましく、130質量%以下であることが更に好ましい。
The content of the polymer electrolyte in the electrode catalyst ink is preferably 5 to 30% by mass, more preferably 8% by mass or more, even more preferably 10% by mass or more, more preferably 20% by mass or less, and even more preferably 15% by mass or less, relative to the electrode catalyst ink.
The content of the catalyst in the electrode catalyst ink is preferably 50 to 200% by mass, more preferably 80% by mass or more, and even more preferably 100% by mass or more, more preferably 150% by mass or less, and even more preferably 130% by mass or less, relative to the polymer electrolyte.
上記電極触媒インクは、更に、導電剤を含むことが好ましい。上記触媒及び上記導電剤は、上記触媒の粒子を担持した導電剤からなる複合粒子(例えば、Pt担持カーボン等)であることも好ましい形態の一つである。この場合、上記高分子電解質は、バインダーとしても機能する。 It is preferable that the electrode catalyst ink further contains a conductive agent. In one preferred embodiment, the catalyst and the conductive agent are composite particles (e.g., Pt-supported carbon, etc.) made of a conductive agent carrying particles of the catalyst. In this case, the polymer electrolyte also functions as a binder.
導電剤としては、導電性を有する粒子(導電性粒子)であれば限定されないが、例えば、ファーネスブラック、チャンネルブラック、アセチレンブラック等のカーボンブラック、活性炭、黒鉛及び各種金属(触媒金属を除く)からなる群より選択される少なくとも1種の導電性粒子であることが好ましい。これら導電剤の粒子径としては、好ましくは10オングストローム~10μm、より好ましくは50オングストローム~1μm、最も好ましくは100~5000オングストロームである。 The conductive agent is not limited as long as it is a particle having electrical conductivity (conductive particle), but it is preferable that it is at least one type of conductive particle selected from the group consisting of carbon black such as furnace black, channel black, and acetylene black, activated carbon, graphite, and various metals (excluding catalytic metals). The particle diameter of these conductive agents is preferably 10 angstroms to 10 μm, more preferably 50 angstroms to 1 μm, and most preferably 100 to 5000 angstroms.
上記複合粒子としては、導電性粒子に対する触媒粒子の含有量が、好ましくは1~99質量%、より好ましくは10~90質量%、最も好ましくは30~70質量%である。具体的には、田中貴金属工業(株)製TEC10E40E、TEC10E50E、TEC10E50HT等のPt触媒担持カーボンが好適な例として挙げられる。 The composite particles preferably have a catalyst particle content relative to the conductive particles of 1 to 99% by mass, more preferably 10 to 90% by mass, and most preferably 30 to 70% by mass. Specific examples of suitable catalyst particles include Pt catalyst-supported carbon such as TEC10E40E, TEC10E50E, and TEC10E50HT manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.
複合粒子の含有量は、上記高分子電解質に対して、1.0~3.0質量%であることが好ましく、より好ましくは1.4~2.9質量%、更に好ましくは1.7~2.9質量%、特に好ましくは1.7~2.3質量%である。 The content of the composite particles is preferably 1.0 to 3.0% by mass, more preferably 1.4 to 2.9% by mass, even more preferably 1.7 to 2.9% by mass, and particularly preferably 1.7 to 2.3% by mass, relative to the polymer electrolyte.
上記電極触媒インクは、更に、撥水剤を含んでもよい。
上記電極触媒インクは、撥水性の向上のため、更にポリテトラフルオロエチレン(以下、PTFE)、テトラフルオロエチレンとパーフルオロ(2,2-ジメチル-1,3-ジオキソール)の共重合体を含有してもよい。この場合、撥水剤の形状としては特に限定されないが、定形性のものであればよく、粒子状、繊維状であることが好ましく、これらが単独で使用されても混合して使用されていてもよい。
The electrode catalyst ink may further contain a water repellent agent.
The electrode catalyst ink may further contain polytetrafluoroethylene (hereinafter, PTFE) or a copolymer of tetrafluoroethylene and perfluoro(2,2-dimethyl-1,3-dioxole) to improve water repellency. In this case, the shape of the water repellent is not particularly limited as long as it has a fixed shape, and is preferably particulate or fibrous, and these may be used alone or in combination.
上記撥水剤の含有量は、上記高分子電解質に対して、0.01~30.0質量%であることが好ましく、より好ましくは1.0~25.0質量%、更に好ましくは2.0~20.0質量%、特に好ましくは5.0~10.0質量%である。 The content of the water repellent agent is preferably 0.01 to 30.0% by mass, more preferably 1.0 to 25.0% by mass, even more preferably 2.0 to 20.0% by mass, and particularly preferably 5.0 to 10.0% by mass, relative to the polymer electrolyte.
(電極触媒層)
本実施形態の電極触媒層としては、上記高分子電解質を含む電極触媒層であることが好ましい。上記電極触媒層は、上記電極触媒インクを含むことが好ましく、上記電極触媒インクからなることがより好ましい。上記電極触媒層は、安価に製造することができる上、酸素透過性が高い。上記電極触媒層は、カソード用電極触媒層として用いることができ、燃料電池用として好適に用いることができる。
(Electrode catalyst layer)
The electrode catalyst layer of this embodiment is preferably an electrode catalyst layer containing the above polymer electrolyte. The electrode catalyst layer preferably contains the above electrode catalyst ink, and more preferably is made of the above electrode catalyst ink. The electrode catalyst layer can be produced at low cost and has high oxygen permeability. The electrode catalyst layer can be used as a cathode electrode catalyst layer, and is suitable for use in fuel cells.
上記電極触媒層は、上記高分子電解質及び上記触媒からなることが好ましい。上記電極触媒層は、電極面積に対する上記高分子電解質の担持量が、好ましくは0.001~10mg/cm2、より好ましくは0.01~5mg/cm2、更に好ましくは0.1~1mg/cm2である。 The electrode catalyst layer preferably comprises the polymer electrolyte and the catalyst, and the amount of the polymer electrolyte supported in the electrode catalyst layer relative to the electrode area is preferably 0.001 to 10 mg/cm 2 , more preferably 0.01 to 5 mg/cm 2 , and even more preferably 0.1 to 1 mg/cm 2 .
上記電極触媒層は、高分子電解質、触媒及び導電剤からなるものであることが好ましい。上記電極触媒層は、高分子電解質と、触媒の粒子及びこれを担持した導電剤からなる複合粒子(例えば、Pt担持カーボン等)と、からなるものであることも好ましい形態の一つである。この場合、上記高分子電解質は、バインダーとしても機能する。 The electrode catalyst layer is preferably made of a polymer electrolyte, a catalyst, and a conductive agent. In one preferred embodiment, the electrode catalyst layer is made of a polymer electrolyte and composite particles (e.g., Pt-supported carbon, etc.) made of catalyst particles and a conductive agent supporting the catalyst. In this case, the polymer electrolyte also functions as a binder.
上記導電剤としては、上述のものが挙げられ、上述と同様のものが好ましい。
上記複合粒子としては、導電性粒子に対して触媒粒子が、好ましくは1~99質量%、より好ましくは10~90質量%、最も好ましくは30~70質量%である。具体的には、田中貴金属工業(株)製TEC10E40E等のPt触媒担持カーボンが好適な例として挙げられる。
The conductive agent may be any of those mentioned above, and is preferably the same as those mentioned above.
In the composite particles, the catalyst particles are preferably 1 to 99% by mass, more preferably 10 to 90% by mass, and most preferably 30 to 70% by mass relative to the conductive particles. Specifically, a suitable example is Pt catalyst-supported carbon such as TEC10E40E manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.
上記複合粒子の含有率は、電極触媒層の全質量に対し、20~95質量%であることが好ましく、より好ましくは40~90質量%、更に好ましくは50~85質量%、特に好ましくは60~80質量%である。電極触媒層が燃料電池の電極触媒層として用いられる場合、電極面積に対する触媒金属の担持量としては、電極触媒層を形成した状態で、好ましくは0.001~10mg/cm2、より好ましくは0.01~5mg/cm2、更に好ましくは0.1~1mg/cm2、更により好ましくは0.2~0.5mg/cm2である。 The content of the composite particles is preferably 20 to 95 mass%, more preferably 40 to 90 mass%, even more preferably 50 to 85 mass%, and particularly preferably 60 to 80 mass%, relative to the total mass of the electrode catalyst layer. When the electrode catalyst layer is used as an electrode catalyst layer for a fuel cell, the amount of catalyst metal supported relative to the electrode area is preferably 0.001 to 10 mg/ cm2 , more preferably 0.01 to 5 mg/ cm2 , even more preferably 0.1 to 1 mg/ cm2 , and even more preferably 0.2 to 0.5 mg/ cm2 , after the electrode catalyst layer is formed.
上記電極触媒層の厚みとしては、好ましくは0.01~200μm、より好ましくは0.1~100μm、最も好ましくは1~50μmである。 The thickness of the electrode catalyst layer is preferably 0.01 to 200 μm, more preferably 0.1 to 100 μm, and most preferably 1 to 50 μm.
上記電極触媒層は、必要に応じて撥水剤を含んでもよい。
上記撥水剤としては、上述のものが挙げられ、上述と同様のものが好ましい。
電極触媒層が撥水剤を含有する場合、PTFE並びにテトラフルオロエチレンとパーフルオロ(2,2-ジメチル-1,3-ジオキソール)の共重合体の含有率としては、電極触媒層の全質量に対し、好ましくは0.001~20質量%、より好ましくは0.01~10質量%、最も好ましくは0.1~5質量%である。
The electrode catalyst layer may contain a water repellent agent as necessary.
The water repellent agent may be any of those mentioned above, and is preferably the same as those mentioned above.
When the electrode catalyst layer contains a water repellent, the content of PTFE and a copolymer of tetrafluoroethylene and perfluoro(2,2-dimethyl-1,3-dioxole) is preferably 0.001 to 20 mass%, more preferably 0.01 to 10 mass%, and most preferably 0.1 to 5 mass%, relative to the total mass of the electrode catalyst layer.
上記電極触媒層は、親水性向上及び化学耐久性向上のため、無機系添加剤を配合しても良い。
無機系添加剤としては、上述のものが挙げられ、上述と同様のものが好ましい。
上記無機系添加剤の含有率としては、電極触媒層の全質量に対し、好ましくは0.001~20質量%、より好ましくは0.01~10質量%、最も好ましくは0.1~5質量%である。
The electrode catalyst layer may contain an inorganic additive in order to improve hydrophilicity and chemical durability.
Examples of the inorganic additives include those mentioned above, and the same ones as those mentioned above are preferable.
The content of the inorganic additive is preferably 0.001 to 20 mass %, more preferably 0.01 to 10 mass %, and most preferably 0.1 to 5 mass %, relative to the total mass of the electrode catalyst layer.
上記電極触媒層の空隙率としては特に限定されないが、好ましくは10~90体積%、より好ましくは20~80体積%、最も好ましくは30~60体積%である。 The porosity of the electrode catalyst layer is not particularly limited, but is preferably 10 to 90% by volume, more preferably 20 to 80% by volume, and most preferably 30 to 60% by volume.
上記電極触媒層の製造方法は、得られた高分子電解質溶液に上記触媒を分散させて上記電極触媒インクを調製する工程と、電極触媒インクを基材に塗布する工程と、基材に塗布した電極触媒インクを乾燥させて電極触媒層を得る工程と、を含む。 The method for producing the electrode catalyst layer includes the steps of dispersing the catalyst in the obtained polymer electrolyte solution to prepare the electrode catalyst ink, applying the electrode catalyst ink to a substrate, and drying the electrode catalyst ink applied to the substrate to obtain an electrode catalyst layer.
得られた高分子電解質溶液に上記触媒を分散させて電極触媒インクを調製する工程は、得られたエマルジョン又は高分子電解質溶液に、触媒の粒子及びこれを担持した導電剤からなる複合粒子を分散させた電極触媒インクを調製するものであることが好ましい。 The step of preparing an electrode catalyst ink by dispersing the catalyst in the obtained polymer electrolyte solution preferably involves preparing an electrode catalyst ink by dispersing composite particles of catalyst particles and a conductive agent carrying the catalyst in the obtained emulsion or polymer electrolyte solution.
上記電極触媒インクの塗布は、スクリーン印刷法、スプレー法等の一般的に知られている各種方法を用いることが可能である。 The electrode catalyst ink can be applied using a variety of commonly known methods, such as screen printing and spraying.
(膜電極接合体)
本実施形態の膜電極接合体(membrane/electrode assembly)(以下、「MEA」ともいう。)は、上記電極触媒層を備えることが好ましい。本実施形態の膜電極接合体は、上記電極触媒層を備えるため、電池特性並びに機械的強度に優れ、安定性に優れる。上記膜電極接合体は、燃料電池用として好適に用いることができる。
(Membrane Electrode Assembly)
The membrane/electrode assembly (hereinafter also referred to as "MEA") of this embodiment preferably includes the above-mentioned electrode catalyst layer. Since the membrane/electrode assembly of this embodiment includes the above-mentioned electrode catalyst layer, it has excellent battery characteristics, mechanical strength, and stability. The membrane/electrode assembly can be suitably used for fuel cells.
電解質膜の両面にアノードとカソードの2種類の電極触媒層が接合したユニットは、膜電極接合体(以下「MEA」ともいう。)と呼ばれる。電極触媒層のさらに外側に一対のガス拡散層を対向するように接合したものについても、MEAと呼ばれる場合がある。電極触媒層はプロトン伝導性を有することが必要となる。 A unit in which two types of electrode catalyst layers, an anode and a cathode, are bonded to both sides of an electrolyte membrane is called a membrane electrode assembly (hereinafter also referred to as "MEA"). An assembly in which a pair of gas diffusion layers are bonded to the outer sides of the electrode catalyst layers so that they face each other may also be called an MEA. The electrode catalyst layers are required to have proton conductivity.
アノードとしての電極触媒層は、燃料(例えば水素)を酸化して容易にプロトンを生じさせる触媒を包含し、カソードとしての電極触媒層は、プロトン及び電子と酸化剤(例えば酸素や空気)を反応させて水を生成させる触媒を包含する。アノードとカソードのいずれについても、触媒としては上述した触媒金属を好適に用いることができる。 The electrode catalyst layer serving as the anode contains a catalyst that easily produces protons by oxidizing fuel (e.g., hydrogen), and the electrode catalyst layer serving as the cathode contains a catalyst that reacts protons and electrons with an oxidant (e.g., oxygen or air) to produce water. For both the anode and the cathode, the above-mentioned catalytic metals can be suitably used as the catalyst.
ガス拡散層としては、市販のカーボンクロス、カーボンペーパー、カーボンフェルト等を用いることができる。これらのガス拡散層にはポリテトラフルオロエチレン等により撥水処理されていることが好ましい。
具体例として、炭素繊維トレカ(東レ社製)、パイロフィル(三菱ケミカル社製)、SIGRACET GDL(MFCテクノロジー社製)等が挙げられる。
The gas diffusion layer may be made of commercially available carbon cloth, carbon paper, carbon felt, etc. These gas diffusion layers are preferably treated with polytetrafluoroethylene or the like to make them water repellent.
Specific examples include carbon fiber Torayca (manufactured by Toray Industries, Inc.), Pyrofil (manufactured by Mitsubishi Chemical Corporation), and SIGRACET GDL (manufactured by MFC Technologies, Inc.).
MEAは、例えば、電極触媒層の間に電解質膜を挟みこみ、熱プレスにより接合することにより作製することができる。より具体的には、上記高分子電解質をアルコールと水の混合溶液に分散又は溶解したものに、触媒として市販の白金担持カーボン(例えば、田中貴金属(株)製TEC10E40E)を分散させてペースト状にする。これを2枚のPTFEシートのそれぞれの片面に一定量塗布して乾燥させて電極触媒層を形成する。次に、各PTFEシートの塗布面を向かい合わせにして、その間に電解質膜を挟み込み、100~200℃で熱プレスにより転写接合してから、PTFEシートを取り除くことにより、MEAを得ることができる。当業者にはMEAの作製方法は周知である。MEAの作製方法は、例えば、JOURNAL OF APPLIED ELECTROCHEMISTRY,22(1992)p.1-7に詳しく記載されている。 The MEA can be produced, for example, by sandwiching an electrolyte membrane between electrode catalyst layers and bonding them by heat pressing. More specifically, the polymer electrolyte is dispersed or dissolved in a mixed solution of alcohol and water, and a commercially available platinum-supported carbon (for example, TEC10E40E manufactured by Tanaka Kikinzoku Co., Ltd.) is dispersed as a catalyst in the resulting mixture to form a paste. A certain amount of this is applied to one side of each of two PTFE sheets and dried to form an electrode catalyst layer. Next, the coated surfaces of the PTFE sheets are placed face to face, an electrolyte membrane is sandwiched between them, and the sheets are transferred and bonded by heat pressing at 100 to 200°C, and then the PTFE sheets are removed to obtain an MEA. The method of producing an MEA is well known to those skilled in the art. The method of producing an MEA is described in detail, for example, in JOURNAL OF APPLIED ELECTROCHEMISTRY, 22 (1992), pp. 1-7.
上記MEA(一対のガス拡散電極が対向した構造のMEAを含む。)は、更にバイポーラプレートやバッキングプレート等の一般的な燃料電池に用いられる構成成分と組み合わされて、燃料電池が構成される。 The above-mentioned MEA (including an MEA with a pair of gas diffusion electrodes facing each other) is further combined with components used in general fuel cells, such as bipolar plates and backing plates, to form a fuel cell.
(燃料電池)
本実施形態の燃料電池は、上記膜電極接合体を備えることが好ましい。上記燃料電池は、固体高分子形燃料電池であることが好ましい。上記燃料電池は、上記膜電極接合体を有するものであれば特に限定されず、通常、燃料電池を構成するガス等の構成成分を含むものであってよい。上記燃料電池は、上記電極触媒層を有する膜電極接合体を備えるものであるため、電池特性並びに機械的強度に優れ、安定性に優れる。
(Fuel cell)
The fuel cell of this embodiment preferably includes the membrane electrode assembly. The fuel cell is preferably a polymer electrolyte fuel cell. The fuel cell is not particularly limited as long as it includes the membrane electrode assembly, and may generally include components such as gas that constitute a fuel cell. Since the fuel cell includes the membrane electrode assembly having the electrode catalyst layer, it has excellent cell characteristics and mechanical strength, and is excellent in stability.
バイポーラプレートとは、その表面に燃料や酸化剤等のガスを流すための溝を形成させたグラファイトと樹脂との複合材料、又は金属製のプレート等を意味する。バイポーラプレートは、電子を外部負荷回路へ伝達する機能の他、燃料や酸化剤を電極触媒近傍に供給する流路としての機能を持っている。こうしたバイポーラプレートの間にMEAを挿入して複数積み重ねることにより、燃料電池が製造される。 A bipolar plate is a composite material of graphite and resin, or a metal plate, with grooves on its surface for the flow of gases such as fuel and oxidant. In addition to transmitting electrons to an external load circuit, bipolar plates also function as flow paths that supply fuel and oxidant to the vicinity of the electrode catalyst. A fuel cell is manufactured by stacking multiple bipolar plates by inserting an MEA between them.
次に本発明を、実施例をあげて説明するが、本発明はかかる実施例のみに限定されるものではない。 The present invention will now be described with reference to examples, but the present invention is not limited to these examples.
(イオン交換容量)
イオン交換基の対イオンがプロトンの状態となっている高分子電解質膜、およそ2~20cm2を、25℃、飽和NaCl水溶液30mlに浸漬し、攪拌しながら30分間放置した。次いで、飽和NaCl水溶液中のプロトンを、フェノールフタレインを指示薬として0.01N水酸化ナトリウム水溶液として中和滴定した。中和後に得られた、イオン交換基の対イオンがナトリウムイオンの状態となっている高分子電解質膜を、純水ですすぎ、更に真空乾燥して秤量した。中和に要した水酸化ナトリウムの物質量をM(mmol)、イオン交換基の対イオンがナトリウムイオンの高分子電解質膜の重量をW(mg)とし、下記式により当量重量EW(g/eq)を求めた。
EW=(W/M)-22
(Ion exchange capacity)
A polymer electrolyte membrane with a size of approximately 2 to 20 cm2 in which the counter ions of the ion exchange groups are in the state of protons was immersed in 30 ml of a saturated NaCl aqueous solution at 25°C and left for 30 minutes while stirring. Next, the protons in the saturated NaCl aqueous solution were neutralized by titration with a 0.01N aqueous sodium hydroxide solution using phenolphthalein as an indicator. The polymer electrolyte membrane obtained after neutralization in which the counter ions of the ion exchange groups are in the state of sodium ions was rinsed with pure water, further vacuum dried, and weighed. The amount of sodium hydroxide required for neutralization was M (mmol), and the weight of the polymer electrolyte membrane in which the counter ions of the ion exchange groups are sodium ions was W (mg), and the equivalent weight EW (g/eq) was calculated by the following formula.
EW = (W/M) - 22
(酸素溶解度)
高分子電解質の膜の酸素溶解度を、クロノアンペロメトリー法を用いて測定した。ガラス封入した100μmφの白金微小電極を厚さ200μm程度のサンプルに押し当てて、温度、湿度を調整した。窒素又は酸素雰囲気下にて、電位を1100mV(vs.SHE)に保持した後、400mVにステップして電流値を測定した。窒素及び酸素雰囲気下で観測された電流値の差分を印加時間の-1/2乗に対してプロットし、直線性が得られた範囲において下記式を用いて酸素溶解度を算出した。
I=4πFrDc[1+r/(πDt)1/2+0.2732exp{-0.3911r/(Dt)1/2}]
ただし、Iは電流値(A)、Fはファラデー定数(96500C/mol)、rは電極半径(cm)、Dは酸素拡散係数(cm2/s)、cは酸素溶解度(mol/m3)、tは時間(s)である。
本検討では評価温度80℃、湿度30%での酸素溶解度を示した。
(Oxygen Solubility)
The oxygen solubility of the polymer electrolyte membrane was measured using the chronoamperometry method. A glass-encapsulated platinum microelectrode with a diameter of 100 μm was pressed against a sample with a thickness of about 200 μm to adjust the temperature and humidity. After the potential was held at 1100 mV (vs. SHE) under a nitrogen or oxygen atmosphere, the potential was stepped to 400 mV to measure the current value. The difference in the current values observed under the nitrogen and oxygen atmospheres was plotted against the power of −1/2 of the applied time, and the oxygen solubility was calculated using the following formula within the range where linearity was obtained.
I = 4πFrDc [1 + r/(πDt) 1/2 + 0.2732 exp {-0.3911r/(Dt) 1/2 }]
In the above, I is the current value (A), F is the Faraday constant (96,500 C/mol), r is the electrode radius (cm), D is the oxygen diffusion coefficient (cm 2 /s), c is the oxygen solubility (mol/m 3 ), and t is time (s).
In this study, the oxygen solubility was evaluated at a temperature of 80° C. and a humidity of 30%.
(SEM観察)
ダイコーターで作製した触媒層の表面を、走査型電子顕微鏡(製品名:VE8800、キーエンス社製)を用い、倍率50倍、加速電圧1kVの条件で観察した。観察の結果、触媒層表面にひび割れがなかった場合を「A」(良好)、ひび割れが見られた場合を「B」(不良)と表記した。
(SEM Observation)
The surface of the catalyst layer prepared by the die coater was observed using a scanning electron microscope (product name: VE8800, manufactured by Keyence Corporation) at a magnification of 50 times and an acceleration voltage of 1 kV. As a result of the observation, the catalyst layer surface was marked with "A" (good) when no cracks were observed, and marked with "B" (poor) when cracks were observed.
(燃料電池評価)
高温低加湿条件下におけるMEAの性能を評価するため、以下のような手順で発電試験を実施した。
(1)電極触媒インクの調製
固形分濃度15質量%の高分子電解質溶液、電極触媒(TEC10E40E、田中貴金属工業(株)製、白金担持量36.7wt%)を白金/パーフルオロスルホン酸ポリマーが1/1.15(質量)となるように配合し、次いで、固形分(電極触媒とパーフルオロスルホン酸ポリマーの和)が11wt%となるようにエタノールを加え、ホモジナイザー(アズワン社製)により回転数が3000rpmで10分間、撹拌することで電極触媒インクを得た。
(2)電極触媒層の作製
ダイコーター(製品名:理化ダイ、伊藤忠ファインテクノ社製)を用い、膜厚100μmのテフロン(登録商標)基材(製品名:ナフロンテープ、ニチアス社製)上に上記電極触媒インクを、白金量が0.2mg/cm2となる様に塗布し、160℃、5分の条件で乾燥・固化させることで電極触媒層を得た。
(3)MEAの作製
プレス機(製品名:SFA-37、神藤金属工業社製)を用い、電解質膜(製品名:NafionHP、ケマーズ社製)の両面に、アノード側に高分子電解質としてNafionDE2020CSを用いた電極触媒層を、カソード側に本実施形態の高分子電解質を用いた電極触媒層を、温度160℃、圧力13MPaの条件で熱プレスすることで、MEAを得た。
(4)燃料電池単セルの作製
上記MEAの両極にガス拡散層(製品名:GDL35BC、MFCテクノロジー社製)を重ね、次いでガスケット、バイポーラプレート、バッキングプレートを重ねることで燃料電池単セルを得た。
(5)発電試験
上記燃料電池単セルを評価装置(東陽テクニカ社製燃料電池評価システム890CL)にセットして、発電試験を実施した。
発電の試験条件は、高加湿条件が、セル温度65℃、アノード及びカソードの加湿ボトル60℃に設定し、低加湿条件が、セル温度90℃、アノード及びカソードの加湿ボトル61℃に設定し、アノード側に水素ガス、カソード側に空気ガスを、それぞれ900ml/minの条件で供給した。また、アノード側とカソード側の両方を無加圧(大気圧)とした。
上記高加湿条件において、電流密度0.2A/cm2において電圧値が0.830V以上であれば「A」(優れる)、0.820V超0.830V未満であれば「B」(普通)、0.820V以下であれば「C」(劣る)、電流密度0.8A/cm2において電圧値が0.685V以上であれば「A」(優れる)、0.675V超0.685V未満であれば「B」(普通)、0.675V以下であれば「C」(劣る)として表記した。
また、上記低加湿条件において、電流密度0.2A/cm2において電圧値が0.750V以上であれば「A」(優れる)、0.720V超0.750V未満であれば「B」(普通)、0.720V以下であれば「C」(劣る)、電流密度0.8A/cm2において電圧値が0.550V以上であれば「A」(優れる)、0.440V超0.550V未満であれば「B」(普通)、0.440V以下であれば「C」(劣る)として表記した。
(Fuel cell evaluation)
In order to evaluate the performance of the MEA under high temperature and low humidity conditions, a power generation test was carried out according to the following procedure.
(1) Preparation of electrode catalyst ink A polymer electrolyte solution with a solid content concentration of 15% by mass and an electrode catalyst (TEC10E40E, manufactured by Tanaka Kikinzoku Kogyo K.K., platinum loading 36.7 wt%) were mixed so that the platinum/perfluorosulfonic acid polymer was 1/1.15 (by mass), and then ethanol was added so that the solid content (sum of the electrode catalyst and perfluorosulfonic acid polymer) was 11 wt%, and the mixture was stirred with a homogenizer (manufactured by AS ONE CORPORATION) at a rotation speed of 3000 rpm for 10 minutes to obtain an electrode catalyst ink.
(2) Preparation of electrode catalyst layer Using a die coater (product name: Rika Die, manufactured by Itochu Fine Techno Co., Ltd.), the above electrode catalyst ink was applied to a Teflon (registered trademark) substrate (product name: Naflon Tape, manufactured by Nichias Corporation) with a thickness of 100 μm so that the amount of platinum was 0.2 mg/ cm2 , and the coating was dried and solidified under conditions of 160° C. and 5 minutes to obtain an electrode catalyst layer.
(3) Preparation of MEA Using a press (product name: SFA-37, manufactured by Shinto Metal Industries Co., Ltd.), an electrode catalyst layer using NafionDE2020CS as a polymer electrolyte on the anode side and an electrode catalyst layer using the polymer electrolyte of this embodiment on the cathode side were hot-pressed on both sides of an electrolyte membrane (product name: NafionHP, manufactured by Chemours) at a temperature of 160° C. and a pressure of 13 MPa to obtain an MEA.
(4) Preparation of a Single Fuel Cell A gas diffusion layer (product name: GDL35BC, manufactured by MFC Technologies) was laminated on both electrodes of the MEA, and then a gasket, a bipolar plate, and a backing plate were laminated to obtain a single fuel cell.
(5) Power Generation Test The above single fuel cell was set in an evaluation device (Fuel Cell Evaluation System 890CL manufactured by Toyo Corporation) and a power generation test was carried out.
The power generation test conditions were as follows: high humidity condition: cell temperature 65° C., anode and cathode humidification bottles 60° C., low humidity condition: cell temperature 90° C., anode and cathode humidification bottles 61° C., hydrogen gas was supplied to the anode side and air gas was supplied to the cathode side at 900 ml/min. Both the anode side and the cathode side were unpressurized (atmospheric pressure).
Under the above-mentioned high humidity conditions, if the voltage value was 0.830 V or more at a current density of 0.2 A/ cm2 , it was indicated as "A" (excellent), if it was more than 0.820 V and less than 0.830 V, it was indicated as "B" (average), if it was 0.820 V or less, it was indicated as "C" (poor), if the voltage value was 0.685 V or more at a current density of 0.8 A/ cm2, it was indicated as "A" (excellent), if it was more than 0.675 V and less than 0.685 V, it was indicated as "B" (average), and if it was 0.675 V or less, it was indicated as "C" (poor).
In addition, under the above-mentioned low humidification conditions, if the voltage value was 0.750 V or more at a current density of 0.2 A/ cm2 , it was indicated as "A" (excellent), if it was more than 0.720 V and less than 0.750 V, it was indicated as "B" (average), if it was 0.720 V or less, it was indicated as "C" (poor), if the voltage value was 0.550 V or more at a current density of 0.8 A/ cm2 , it was indicated as "A" (excellent), if it was more than 0.440 V and less than 0.550 V, it was indicated as "B" (average), and if it was 0.440 V or less, it was indicated as "C" (poor).
(化学耐久性)
上記燃料電池単セルを評価装置(東陽テクニカ製燃料電池評価システム890CL)にセットして、セル温度90℃、加湿ボトル61℃(相対湿度30%RH)、アノード側に水素ガス、カソード側に空気ガスを、それぞれ300cc/minの条件で流通させることでOCV試験を実施した。
上記OCV試験の終点を判定するために、カソード側にマイクロガスクロマトグラフ(製品名:CP-4900、GLサイエンス社製)を接続し、アノード側より透過するH2ガスの濃度を測定した。上記H2ガスの濃度が1000ppmを越えた時点を終点とした。上記終点が200時間以上を「A」(良好)、200時間未満を「B」(不良)と表記した。
(Chemical durability)
The above single fuel cell was set in an evaluation device (Toyo Technica Fuel Cell Evaluation System 890CL) and an OCV test was performed under the following conditions: cell temperature 90°C, humidification bottle 61°C (relative humidity 30% RH), hydrogen gas on the anode side, and air gas on the cathode side, each at 300 cc/min.
To determine the end point of the OCV test, a micro gas chromatograph (product name: CP-4900, manufactured by GL Sciences) was connected to the cathode side, and the concentration of H2 gas permeating from the anode side was measured. The end point was determined to be the time when the concentration of H2 gas exceeded 1000 ppm. The end point was indicated as "A" (good) for 200 hours or more, and "B" (bad) for less than 200 hours.
(構造単位の割合)
ベンゾジオキソール構造単位の導入率は、上記高分子電解質のH-NMR並びにF-NMR解析を行い、EW測定でのプロトン伝導基導入量と併せることで算出した。
(Proportion of structural units)
The introduction rate of the benzodioxole structural unit was calculated by subjecting the polymer electrolyte to H-NMR and F-NMR analysis, and combining the results with the amount of proton-conductive groups introduced by EW measurement.
(実施例1)
300ml三つ口フラスコに、5-ブロモレソルシノール4.2g(22mmol)、脱水N,N-ジメチルアセトアミド50ml、トリエチルアミン4.9g(49mmol)を入れ、窒素置換してキャップをした後、常温で撹拌混合した。オクタフルオロシクロペンテン4.7g(22mmol)を入れ、室温で30分攪拌後、50℃で30分攪拌、80℃で30分攪拌し、100℃で24時間撹拌混合した。反応終了後、放冷し、反応液をイオン交換水500mL中に投入し、ガラスフィルターで減圧ろ過後、イオン交換水で十分に洗浄し、60℃で12時間減圧乾燥した。得られたポリマーA1は薄茶色固体で、収量6.0g(収率77%)であった。19F-NMR(d-DMSO)では、-113~-121ppmに積分比4、-133~-137ppmに積分比2のブロードなピークが各々見られた。
次に、ベンゾジオキソール誘導体の導入反応を下記の通り実施した。
300ml三つ口フラスコに、上記A1 5.0g、脱水N,N-ジメチルアセトアミド50ml、セサモール5.7g(42mmol)、炭酸カリウム5.7g(42mmol)を入れ、窒素置換してキャップをした。その後、100℃で24時間撹拌混合した。反応終了後、放冷し、反応液をイオン交換水500mL中に投入し、ガラスフィルターで減圧ろ過後、イオン交換水で十分に洗浄し、60℃で12時間減圧乾燥した。得られたポリマーA2は薄茶色固体で、収量5.0g(収率61%)であった。19F-NMR(d-DMSO)では-113~-121ppmに積分比2、-133~-137ppmに積分比2のブロードなピークが各々見られた。
次にスルホン酸基の導入反応を下記の通り実施した。
300mL三つ口フラスコに、上記A2 4.0g、直径100nmの銅粉3.0g、ジメチルスルホキシド20mLを入れ、窒素置換してキャップをした後、120℃で2時間撹拌混合した。次に、Macromolecules,2009年,Vol.42,p.9302-9306を参考に、1,1,2,2-テトラフルオロ-2-(1,1,2,2-テトラフルオロ-2-ヨードエトキシ)エタンスルホニルフルオライドを加水分解して得られた1,1,2,2-テトラフルオロ-2-(1,1,2,2-テトラフルオロ-2-ヨードエトキシ)エタンスルホン酸カリウム6.0g(13mmol)をジメチルスルホキシド20mlに溶解し、上記反応液に滴下し、120℃で6時間撹拌混合した。反応終了後、放冷し、反応液をセライトろ過し銅粉を除去した。その後、ろ液を5N塩酸500mLに滴下し、遠心分離を行った後、減圧ろ過することで沈殿物を回収した。これをさらに3回繰り返した。その後、イオン交換水によって、上澄み液のpHが中性になるまで洗浄を行った。得られた固体を50℃12時間減圧乾燥した。得られたポリマーA3は黒色固体で、収量2.8g(収率52%)であった(式(14))。ポリマーA3のベンゾジオキソール構造単位のモル割合は100mol%であった。
得られた固形分濃度10質量%のポリマー溶液を80℃にて減圧濃縮して、固形分濃度15質量%のポリマー溶液AS1(高分子電解質溶液)を作製した。
上記AS1を用いて上述の方法によりキャスト製膜して、厚み200μmの膜AM1を作製した。AM1のEW及び酸素溶解度を表1に示す。またAS1を含む電極触媒層のひび割れ有無、電池性能及び化学耐久性の結果を表2に示す。
AM1は高い酸素溶解度を示す。またAS1を含む電極触媒層にはひび割れがなく、電池性能及び化学耐久性が比較例の材料よりも高いことが分かる。
Example 1
In a 300 ml three-neck flask, 4.2 g (22 mmol) of 5-bromoresorcinol, 50 ml of dehydrated N,N-dimethylacetamide, and 4.9 g (49 mmol) of triethylamine were placed, replaced with nitrogen, and then capped, followed by stirring and mixing at room temperature. 4.7 g (22 mmol) of octafluorocyclopentene was placed, and the mixture was stirred at room temperature for 30 minutes, then stirred at 50°C for 30 minutes, then stirred at 80°C for 30 minutes, and then stirred and mixed at 100°C for 24 hours. After the reaction was completed, the mixture was allowed to cool, and the reaction solution was poured into 500 mL of ion-exchanged water, filtered under reduced pressure with a glass filter, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60°C for 12 hours. The obtained polymer A1 was a light brown solid, and the yield was 6.0 g (yield 77%). In 19 F-NMR (d-DMSO), broad peaks with an integral ratio of 4 were observed at -113 to -121 ppm, and broad peaks with an integral ratio of 2 were observed at -133 to -137 ppm.
Next, the introduction reaction of a benzodioxole derivative was carried out as follows.
In a 300 ml three-neck flask, 5.0 g of the above A1, 50 ml of dehydrated N,N-dimethylacetamide, 5.7 g (42 mmol), and 5.7 g (42 mmol) of potassium carbonate were placed, substituted with nitrogen, and capped. Then, the mixture was stirred and mixed at 100° C. for 24 hours. After the reaction was completed, the mixture was allowed to cool, and the reaction solution was poured into 500 mL of ion-exchanged water, filtered under reduced pressure with a glass filter, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60° C. for 12 hours. The obtained polymer A2 was a light brown solid, and the yield was 5.0 g (yield 61%). In 19 F-NMR (d-DMSO), broad peaks with an integral ratio of 2 were observed at -113 to -121 ppm and at -133 to -137 ppm.
Next, a reaction for introducing a sulfonic acid group was carried out as follows.
In a 300 mL three-neck flask, 4.0 g of the above A2, 3.0 g of copper powder having a diameter of 100 nm, and 20 mL of dimethyl sulfoxide were placed, replaced with nitrogen, and then capped, and mixed by stirring at 120 ° C. for 2 hours. Next, referring to Macromolecules, 2009, Vol. 42, p. 9302-9306, 6.0 g (13 mmol) of potassium 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-2-iodoethoxy)ethanesulfonate obtained by hydrolysis of 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-2-iodoethoxy)ethanesulfonyl fluoride was dissolved in 20 ml of dimethyl sulfoxide, dropped into the reaction solution, and mixed by stirring at 120 ° C. for 6 hours. After the reaction was completed, the flask was cooled, and the reaction solution was filtered through Celite to remove the copper powder. The filtrate was then dropped into 500 mL of 5N hydrochloric acid, centrifuged, and filtered under reduced pressure to recover the precipitate. This was repeated three more times. The supernatant was then washed with ion-exchanged water until the pH of the supernatant became neutral. The solid obtained was dried under reduced pressure at 50° C. for 12 hours. The polymer A3 obtained was a black solid, with a yield of 2.8 g (52% yield) (formula (14)). The molar ratio of the benzodioxole structural unit in polymer A3 was 100 mol%.
The obtained polymer solution having a solid content concentration of 10% by mass was concentrated under reduced pressure at 80° C. to prepare a polymer solution AS1 (polymer electrolyte solution) having a solid content concentration of 15% by mass.
The AS1 was used to produce a 200 μm-thick membrane AM1 by the above-mentioned method. The EW and oxygen solubility of AM1 are shown in Table 1. Table 2 also shows the results of the presence or absence of cracks in the electrode catalyst layer containing AS1, as well as the cell performance and chemical durability.
AM1 exhibits high oxygen solubility, and the electrode catalyst layer containing AS1 is crack-free and has higher cell performance and chemical durability than the comparative materials.
(実施例2)
300ml三つ口フラスコに、セサモール13g(94mmol)、脱水N,N-ジメチルアセトアミド50ml、トリエチルアミン11g(105mmol)を入れ、窒素置換してキャップをした後、常温で撹拌混合した。オクタフルオロシクロペンテン10g(47mmol)を入れ、室温で2時間攪拌後、80℃で6時間撹拌混合した。反応終了後、放冷し、反応液にイオン交換水200mLと酢酸エチル200mlを加え、有機層を硫酸ナトリウムで乾燥させた後、ガラスフィルターで減圧ろ過後、溶媒をエバポレーターで除去した。その後、カラムクロマトグラフィーで精製し、式(10)のR1、R2が水素原子である化合物B1を薄茶色固体で、収量16g(収率78%)で得た。19F-NMR(CDCl3)では、-116ppmに積分比4、-132ppmに積分比2のピークが各々見られた。
次に、300ml三つ口フラスコに、上記B1 9.9g(22mmol)、5-ブロモレソルシノール4.2g(22mmol)、脱水N,N-ジメチルアセトアミド50ml、トリエチルアミン4.9g(49mmol)を入れ、窒素置換してキャップをした。その後、100℃で24時間撹拌混合した。反応終了後、放冷し、反応液をイオン交換水500mL中に投入し、ガラスフィルターで減圧ろ過後、イオン交換水で十分に洗浄し、60℃で12時間減圧乾燥した。得られたポリマーB2は薄茶色固体で、収量8.8g(収率67%)であった。19F-NMR(d-DMSO)では、-113~-121ppmに積分比2、-133~-137ppmに積分比2のブロードなピークが各々見られた。
ポリマーB2(6.0g)を用いる以外は実施例1と同様にスルホン酸基の導入反応を行い、ポリマーB3を得た(式(15))。ポリマーB3のベンゾジオキソール構造単位のモル割合は100mol%であった。
BM1は高い酸素溶解度を示す。またBS1を含む電極触媒層にはひび割れがなく、電池性能及び化学耐久性が比較例の材料よりも高いことが分かる。
Example 2
In a 300 ml three-neck flask, 13 g (94 mmol) of sesamol, 50 ml of dehydrated N,N-dimethylacetamide, and 11 g (105 mmol) of triethylamine were placed, replaced with nitrogen, and then capped, followed by stirring and mixing at room temperature. 10 g (47 mmol) of octafluorocyclopentene was placed, stirred at room temperature for 2 hours, and then stirred and mixed at 80°C for 6 hours. After the reaction was completed, the reaction solution was allowed to cool, and 200 mL of ion-exchanged water and 200 mL of ethyl acetate were added to the reaction solution. The organic layer was dried with sodium sulfate, filtered under reduced pressure with a glass filter, and the solvent was removed with an evaporator. The mixture was then purified by column chromatography to obtain Compound B1, in which R 1 and R 2 in formula (10) are hydrogen atoms, as a light brown solid in a yield of 16 g (78%). In 19 F-NMR (CDCl 3 ), peaks with an integral ratio of 4 at -116 ppm and an integral ratio of 2 at -132 ppm were observed, respectively.
Next, 9.9 g (22 mmol) of the above B1, 4.2 g (22 mmol) of 5-bromoresorcinol, 50 ml of dehydrated N,N-dimethylacetamide, and 4.9 g (49 mmol) of triethylamine were placed in a 300 ml three-neck flask, substituted with nitrogen, and capped. Then, the flask was stirred and mixed at 100° C. for 24 hours. After the reaction was completed, the flask was cooled, and the reaction solution was poured into 500 mL of ion-exchanged water, filtered under reduced pressure with a glass filter, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60° C. for 12 hours. The obtained polymer B2 was a light brown solid, and the yield was 8.8 g (yield 67%). In 19 F-NMR (d-DMSO), broad peaks with an integral ratio of 2 were observed at -113 to -121 ppm and at -133 to -137 ppm.
The introduction reaction of sulfonic acid groups was carried out in the same manner as in Example 1, except that polymer B2 (6.0 g) was used, to obtain polymer B3 (formula (15)). The molar proportion of benzodioxole structural units in polymer B3 was 100 mol %.
BM1 exhibits high oxygen solubility, and the electrode catalyst layer containing BS1 is crack-free and has higher cell performance and chemical durability than the comparative materials.
(実施例3)
100ml三つ口フラスコに、アゾビスイソブチロニトリル0.795g(4.8mmol)、2,3,4,5,6-ペンタフルオロスチレン10g(52mmol)、トルエン20gを入れ、窒素置換してキャップをした後、60℃で8時間撹拌混合した。反応終了後、放冷し、反応液を200mlのメタノールに滴下し、減圧濾過、乾燥することで白色固体としてポリペンタフルオロスチレンC1 4.9g(収率49%)を得た。19F-NMR(CDCl3)では、-140~-147ppmに積分比2、-153~-157ppmに積分比1、-159~-164ppmに積分比2のブロードなピークが各々見られた。
次に、200ml三つ口フラスコに、上記ポリマーC1 4g、脱水N,N-ジメチルアセトアミド40g、セサモール1.6g(12mmol)、炭酸カリウム1.6g(12mmol)を入れ、窒素置換してキャップをした。その後、90℃で6時間撹拌混合した。反応終了後、放冷し、反応液を200mlのメタノールに滴下し、減圧濾過、乾燥することで白色固体として、ポリペンタフルオロスチレンのパラ位にセサモールを導入したポリマーC2 3.0g(収率58%)を得た。19F-NMR(CDCl3)では、-140~-147ppmに積分比2、-153~-157ppmに積分比0.5、-159~-164ppmに積分比2のブロードなピークが各々見られた。NMRより、ベンゾジオキソール構造単位の導入量は50mol%であった。
次に、200ml3つ口フラスコに、上記ポリマーC2 2.6g、18-クラウン6-エーテル8.2g(31mmol)、水2g(111mmol)、水酸化カリウム1.7g(31mmol)、ジエチレングリコールジメチルエーテル40gを入れ、窒素置換してキャップをした後、90℃で6時間撹拌混合した。反応液を空冷した後、上澄みを除去してから37質量部の濃塩酸3.8g、エタノール40gを添加し、60℃で1時間撹拌混合した。反応終了後、放冷し、反応液を200mlの水に滴下し、減圧濾過、水洗、乾燥することで淡褐色の固体としてポリペンタフルオロスチレンのパラ位に水酸基を導入したポリマーC3 2.3g(収率89%)を得た。19F-NMR(CDCl3)では、-140~-149ppmに積分比2、-163~-167ppmに積分比2のブロードなピークが各々見られ、パラ位に対応する-153~-157ppmにピークがないことを確認した。
更に、200ml三つ口フラスコに、上記ポリマーC3 2g、水素化ナトリウム0.48g(65%、13mmol)、1,2-ジメトキシエタン40gを加え、窒素置換してキャップをした後、50℃で1時間撹拌混合した。反応液を空冷した後、CF2=CF-OCF2CF2SO3Na 3.7g(12mmol)を加え、90℃で6時間撹拌混合した。反応終了後、真空乾燥により溶媒を除去し、残固体を60mlのジエチルエーテルで5回洗浄し、0.5Mの塩化水素のメタノール溶液を60ml加え、1時間撹拌混合した後濾過、水洗、真空乾燥することで、スルホン酸基を導入した式(16)のポリマーC4 1.8g(収率58%)を得た。固体19F-NMRでは、-70~-100ppmに積分比4、-110~-120ppmに積分比2、-130~-170ppmに積分比9のブロードなピークが各々見られた。NMRとEWより、スルホン酸基の導入量は50mol%であった。ポリマーC4のベンゾジオキソール構造単位のモル割合は50mol%であった。
CM1は高い酸素溶解度を示す。またCS1を含む電極触媒層にはひび割れがなく、電池性能及び化学耐久性が比較例の材料よりも高いことが分かる。
Example 3
A 100 ml three-neck flask was charged with 0.795 g (4.8 mmol) of azobisisobutyronitrile, 10 g (52 mmol) of 2,3,4,5,6-pentafluorostyrene, and 20 g of toluene, and the flask was replaced with nitrogen, capped, and mixed with stirring at 60° C. for 8 hours. After the reaction was completed, the flask was allowed to cool, and the reaction liquid was dropped into 200 ml of methanol, filtered under reduced pressure, and dried to obtain 4.9 g (49% yield) of polypentafluorostyrene C1 as a white solid. In 19 F-NMR (CDCl 3 ), broad peaks with an integral ratio of 2 were observed at -140 to -147 ppm, an integral ratio of 1 at -153 to -157 ppm, and an integral ratio of 2 at -159 to -164 ppm.
Next, 4 g of the above polymer C1, 40 g of dehydrated N,N-dimethylacetamide, 1.6 g (12 mmol) of sesamol, and 1.6 g (12 mmol) of potassium carbonate were placed in a 200 ml three-neck flask, and the flask was capped after nitrogen replacement. The flask was then stirred and mixed at 90° C. for 6 hours. After the reaction was completed, the flask was cooled, and the reaction liquid was dropped into 200 ml of methanol, filtered under reduced pressure, and dried to obtain 3.0 g (yield 58%) of polymer C2, in which sesamol was introduced at the para position of polypentafluorostyrene, as a white solid. In 19 F-NMR (CDCl 3 ), broad peaks with an integral ratio of 2 were observed at -140 to -147 ppm, an integral ratio of 0.5 at -153 to -157 ppm, and an integral ratio of 2 at -159 to -164 ppm. From NMR, the amount of benzodioxole structural units introduced was 50 mol%.
Next, 2.6 g of the above polymer C2, 8.2 g (31 mmol) of 18-crown 6-ether, 2 g (111 mmol) of water, 1.7 g (31 mmol) of potassium hydroxide, and 40 g of diethylene glycol dimethyl ether were placed in a 200 ml three-neck flask, and after replacing with nitrogen and capping, the flask was stirred and mixed at 90 ° C. for 6 hours. After cooling the reaction solution in air, the supernatant was removed, and 3.8 g of concentrated hydrochloric acid (37 parts by mass) and 40 g of ethanol were added, and the mixture was stirred and mixed at 60 ° C. for 1 hour. After the reaction was completed, the reaction solution was allowed to cool, dropped into 200 ml of water, filtered under reduced pressure, washed with water, and dried to obtain 2.3 g (yield 89%) of polymer C3 in which a hydroxyl group was introduced at the para position of polypentafluorostyrene as a light brown solid. In 19 F-NMR (CDCl 3 ), broad peaks with an integral ratio of 2 were observed at -140 to -149 ppm and at -163 to -167 ppm, respectively, but it was confirmed that there was no peak at -153 to -157 ppm corresponding to the para position.
Further, 2 g of the above polymer C3, 0.48 g (65%, 13 mmol) of sodium hydride, and 40 g of 1,2-dimethoxyethane were added to a 200 ml three-neck flask, and the flask was replaced with nitrogen, capped, and then stirred and mixed at 50° C. for 1 hour. The reaction liquid was air-cooled, and then 3.7 g (12 mmol) of CF 2 ═CF-OCF 2 CF 2 SO 3 Na was added, and the mixture was stirred and mixed at 90° C. for 6 hours. After the reaction was completed, the solvent was removed by vacuum drying, and the remaining solid was washed five times with 60 ml of diethyl ether, and 60 ml of a 0.5 M solution of hydrogen chloride in methanol was added, and the mixture was stirred and mixed for 1 hour, followed by filtration, washing with water, and vacuum drying to obtain 1.8 g (yield 58%) of polymer C4 of formula (16) into which a sulfonic acid group had been introduced. In the solid-state 19F -NMR, broad peaks with integral ratios of 4 at -70 to -100 ppm, 2 at -110 to -120 ppm, and 9 at -130 to -170 ppm were observed. From NMR and EW, the amount of sulfonic acid groups introduced was 50 mol%. The molar ratio of benzodioxole structural units in polymer C4 was 50 mol%.
CM1 exhibits high oxygen solubility, and the electrode catalyst layer containing CS1 is crack-free and has higher cell performance and chemical durability than the comparative materials.
(実施例4)
100mLオートクレーブ用のガラス内筒に、ラジカル重合法で取得した、テトラフルオロエチレンとCF2=CFOCF2CF2SO2Fとの共重合体(3.5g)、及び3M社製ノベックTM7300(70g)を投入し、160℃で2時間窒素下で撹拌することで、溶解させた。冷却後に溶液を取り出し、固形分重量を200℃1時間で測定したところ、5.0重量%の溶液(D1)であった。別の100mLオートクレーブ用のガラス内筒に、N,N-ジイソプロピルエチルアミン(2.8g、21mmol)とピペロニルアミン(2.6g、17mmol)を加え、均一に混合した。さらに同ガラス内筒に、上記溶液D1(40g)とノベックTM7300(40g)加え、130℃で6時間窒素下で撹拌することで、反応させた。冷却後、反応液をエタノール400ccにゆっくりと注ぎ、沈殿物をろ別回収し、エタノールで濃黄色着色成分が除去されるまで洗浄した。得られた濃黄色固体を乾燥させ、ポリマー前駆体D2を得た。上記ポリマー前駆体D2を、水酸化カリウム(15質量%)を溶解した水溶液中に70℃で10時間接触させ、70℃水中に5時間浸漬後、70℃の2N塩酸水溶液に1時間浸漬させる処理を4回繰り返した後、イオン交換水で水洗し、乾燥させて、ポリマーD3(2.0g)を得た(式(17))。ポリマーD3のベンゾジオキソール構造単位のモル割合は12mol%であった。
DM1は高い酸素溶解度を示す。またDS1を含む電極触媒層にはひび割れがなく、電池性能及び化学耐久性が比較例の材料よりも高いことが分かる。
Example 4
Into a glass cylinder for a 100 mL autoclave, a copolymer (3.5 g) of tetrafluoroethylene and CF 2 ═CFOCF 2 CF 2 SO 2 F obtained by radical polymerization and Novec ™ 7300 (70 g) manufactured by 3M were charged and dissolved by stirring under nitrogen at 160° C. for 2 hours. After cooling, the solution was taken out and the solid content weight was measured at 200° C. for 1 hour, which was 5.0 wt % of the solution (D1). Into another glass cylinder for a 100 mL autoclave, N,N-diisopropylethylamine (2.8 g, 21 mmol) and piperonylamine (2.6 g, 17 mmol) were added and mixed uniformly. Further, the above solution D1 (40 g) and Novec ™ 7300 (40 g) were added to the same glass cylinder and reacted by stirring under nitrogen at 130° C. for 6 hours. After cooling, the reaction solution was slowly poured into 400 cc of ethanol, and the precipitate was collected by filtration and washed with ethanol until the deep yellow coloring component was removed. The obtained deep yellow solid was dried to obtain polymer precursor D2. The above polymer precursor D2 was contacted with an aqueous solution of potassium hydroxide (15 mass%) dissolved therein at 70° C. for 10 hours, immersed in 70° C. water for 5 hours, and then immersed in 2N hydrochloric acid aqueous solution at 70° C. for 1 hour, and the process was repeated four times, followed by washing with ion-exchanged water and drying to obtain polymer D3 (2.0 g) (formula (17)). The molar ratio of the benzodioxole structural unit of polymer D3 was 12 mol%.
DM1 exhibits high oxygen solubility, and the electrode catalyst layer containing DS1 is crack-free and has higher cell performance and chemical durability than the comparative materials.
(比較例1)
市販のナフィオン溶液(Nafion DE2020CS、SIGMA-ALDRICH社製)を用いて、実施例1と同様にして、厚さ200μmのキャスト膜を製膜し、EW、酸素溶解度を測定した。結果を表1に示す。
また上記ナフィオン溶液を用い実施例1と同様に電極触媒層を作製し、ひび割れ有無、電池性能及び化学耐久性試験を行った。結果を表2に示す。
Nafion DE2020CSは、酸素溶解度が低い。また電極触媒層にひび割れが生じており、電池性能及び化学耐久性が低くなる。
(Comparative Example 1)
A cast membrane having a thickness of 200 μm was formed using a commercially available Nafion solution (Nafion DE2020CS, manufactured by SIGMA-ALDRICH) in the same manner as in Example 1, and the EW and oxygen solubility were measured. The results are shown in Table 1.
Furthermore, an electrode catalyst layer was prepared using the above Nafion solution in the same manner as in Example 1, and tests were carried out to check for cracks, as well as cell performance and chemical durability. The results are shown in Table 2.
Nafion DE2020CS has low oxygen solubility and cracks in the electrode catalyst layer, which reduces the cell performance and chemical durability.
(比較例2)
ラジカル重合法で得られた、パーフルオロ(2,2-ジメチル-1,3-ジオキソール)とCF2=CFOCF2CF(CF3)OCF2CF2SO2Fとの共重合体(69.8mol%/30.2mol%)をポリマー前駆体として用い、実施例4と同様の方法で、加水分解処理によりパーフルオロ(2,2-ジメチル-1,3-ジオキソール)/CF2=CFOCF2CF(CF3)OCF2CF2SO3Hからなる高分子電解質を得た。実施例1と同様の方法で、パーフルオロスルホン酸樹脂溶液-1、及び厚さ200μmのキャスト膜を作製した。キャスト膜のEW及び酸素溶解度を表1に示す。
また上記パーフルオロスルホン酸樹脂溶液-1を用いて実施例1と同様に電極触媒層を作製し、ひび割れ有無、電池性能及び化学耐久性試験を行った。結果を表2に示す。
パーフルオロスルホン酸樹脂溶液-1を用いたキャスト膜は、酸素溶解度は高いものの、電極触媒層にひび割れが生じており、電池性能及び化学耐久性が低くなる。
(Comparative Example 2)
A copolymer (69.8 mol%/30.2 mol%) of perfluoro(2,2-dimethyl-1,3-dioxole) and CF2 = CFOCF2CF ( CF3 ) OCF2CF2SO2F obtained by radical polymerization was used as a polymer precursor, and a polymer electrolyte consisting of perfluoro( 2,2 -dimethyl-1,3-dioxole)/ CF2 = CFOCF2CF ( CF3 ) OCF2CF2SO3H was obtained by hydrolysis treatment in the same manner as in Example 4. Perfluorosulfonic acid resin solution-1 and a cast membrane having a thickness of 200 μm were prepared in the same manner as in Example 1. The EW and oxygen solubility of the cast membrane are shown in Table 1.
Moreover, an electrode catalyst layer was prepared using the above perfluorosulfonic acid resin solution-1 in the same manner as in Example 1, and tests were carried out to check for the presence or absence of cracks, as well as the cell performance and chemical durability. The results are shown in Table 2.
The cast membrane using the perfluorosulfonic acid resin solution-1 has a high oxygen solubility, but cracks occur in the electrode catalyst layer, resulting in poor cell performance and chemical durability.
Claims (6)
高分子電解質100mol%中の前記ベンゾジオキソール構造単位の割合が12~100mol%であり、
80℃30%RH条件でPt厚膜法により測定した酸素溶解度が、7.0mol/m3以上であり、
当量重量EWが100~2000g/eqである、高分子電解質。
The ratio of the benzodioxole structural unit in 100 mol % of the polymer electrolyte is 12 to 100 mol %,
The oxygen solubility measured by the Pt thick film method under the condition of 80°C and 30% RH is 7.0 mol/m3 or more ,
A polymer electrolyte having an equivalent weight EW of 100 to 2000 g/eq.
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