JPH02297865A - Manufacture of gas dispersion type complex electrode - Google Patents
Manufacture of gas dispersion type complex electrodeInfo
- Publication number
- JPH02297865A JPH02297865A JP1343365A JP34336589A JPH02297865A JP H02297865 A JPH02297865 A JP H02297865A JP 1343365 A JP1343365 A JP 1343365A JP 34336589 A JP34336589 A JP 34336589A JP H02297865 A JPH02297865 A JP H02297865A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- base material
- gas
- resin
- electrolytic polymerization
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000006185 dispersion Substances 0.000 title abstract description 6
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 24
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 8
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 238000009792 diffusion process Methods 0.000 claims description 16
- 125000002524 organometallic group Chemical group 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 230000035699 permeability Effects 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 17
- 229920000642 polymer Polymers 0.000 abstract description 5
- 150000004696 coordination complex Chemical class 0.000 abstract description 4
- 239000004020 conductor Substances 0.000 abstract description 3
- 230000000149 penetrating effect Effects 0.000 abstract 1
- 230000035515 penetration Effects 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000002585 base Substances 0.000 description 21
- 239000007789 gas Substances 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- -1 polytetrafluoroethylene Polymers 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzenecarbonitrile Natural products N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- NLSSXFUOMMOQSZ-UHFFFAOYSA-N [Co].C(=O)N(C)C Chemical compound [Co].C(=O)N(C)C NLSSXFUOMMOQSZ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- KPRZOPQOBJRYSW-UHFFFAOYSA-N o-hydroxybenzylamine Natural products NCC1=CC=CC=C1O KPRZOPQOBJRYSW-UHFFFAOYSA-N 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920001291 polyvinyl halide Polymers 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LYTMVABTDYMBQK-UHFFFAOYSA-N 2-benzothiophene Chemical compound C1=CC=CC2=CSC=C21 LYTMVABTDYMBQK-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000013522 chelant 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
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- IYPQZXRHDNGZEB-UHFFFAOYSA-N cobalt sodium Chemical compound [Na].[Co] IYPQZXRHDNGZEB-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 125000003630 glycyl group Chemical class [H]N([H])C([H])([H])C(*)=O 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical compound N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 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
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Inert Electrodes (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の目的〕
（産業上の利用分野）
本発明は、燃料電池、金属／空気電池、炭酸ガスの電解
還元電極、ガスセンサ、湿度センサなどに用いられるガ
ス拡散型複合電極の製造方法に関する。[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention relates to a gas diffusion type composite used in fuel cells, metal/air batteries, carbon dioxide electrolytic reduction electrodes, gas sensors, humidity sensors, etc. The present invention relates to a method for manufacturing an electrode.
（従来の技術）
燃料電池、金属／空気電池、炭酸ガスの電解還元電極、
ガスセンサ、湿度センサなどに用いられるガス拡散型複
合電極の多孔構造の本体としては、従来。(Prior technology) Fuel cells, metal/air batteries, carbon dioxide electrolytic reduction electrodes,
Conventionally, the porous structure body of gas diffusion type composite electrodes used in gas sensors, humidity sensors, etc.
ガス酸化還元過電圧の低いニッケルタングステン酸。Nickel tungstic acid with low gas redox overpotential.
パラジウムやコバルトで被覆された炭化タングステン、
ペロブスカイト型構造の酸化物、ニッケル、銀。Tungsten carbide coated with palladium or cobalt,
Oxides with perovskite structure, nickel, silver.
白金、パラジウムなどを触媒として用い、これらの触媒
を活性炭粉末などの導電性粉末に担持させた粉末、およ
び成膜性が比較的低いポリテトラフルオロエチレンなど
の結着剤からなるものを、さらに、金属多孔体、カーボ
ン多孔体、カーボン繊維不織布などの導電性基材と一体
化させたものが用いられている。しかしながら、触媒、
導電性粉末および結着剤からなるこのような組成物は、
多量の導電性粉末を含み、しかも成膜性の低い結着剤を
用いているため。Using platinum, palladium, etc. as a catalyst, these catalysts are supported on conductive powder such as activated carbon powder, and a binder such as polytetrafluoroethylene, which has relatively low film-forming properties, is further used. Those integrated with a conductive base material such as a metal porous body, a carbon porous body, and a carbon fiber nonwoven fabric are used. However, the catalyst
Such a composition consisting of a conductive powder and a binder is
This is because it contains a large amount of conductive powder and uses a binder with low film-forming properties.
きわめて脆く、亀裂が発生しやすく、電橋寿命が短くな
るという欠点とともに、触媒の欠損を生じるという欠点
があった。また、このような組成物では。It is extremely brittle, prone to cracking, shortens the life of the bridge, and causes catalyst loss. Also in such compositions.
成形加工性にとぼしいため薄膜化が困難であるとともに
、細孔径の制御が困難なため、電極として用いたときに
、電解液の液もれを生じやすいという欠点があった。It has poor moldability, making it difficult to form a thin film, and it is also difficult to control the pore diameter, so when used as an electrode, the electrolyte tends to leak.
（発明が解決しようとする課題）
本発明者は、導電性粉末を使わず、電解重合可能な芳香
族化合物および（または）複素環化合物を電解重合して
形成させた導電性の重合体を用いることによって、従来
のガス拡散型複合電極の上記の種々の欠点を改良できる
ことを見出し２本発明にいたったもので９本発明は、電
極寿命が長い、触媒の欠損のないガス拡散型複合電極の
製造方法を提供するものである。(Problems to be Solved by the Invention) The present inventor uses a conductive polymer formed by electrolytically polymerizing an aromatic compound and/or a heterocyclic compound that can be electrolytically polymerized, without using a conductive powder. It was discovered that the above-mentioned drawbacks of conventional gas diffusion type composite electrodes can be improved by this method, which led to the present invention.9 The present invention is to provide a gas diffusion type composite electrode with a long electrode life and no catalyst defects. A manufacturing method is provided.
（課題を解決するための手段）
本発明は、有機金属錯体および樹脂からなるガス透過性
を有する樹脂部材と導電性基材とからなる複合材の上記
導電性基材上で、電解重合可能な芳香族化合物および（
または）複素環化合物を電解重合し。(Means for Solving the Problems) The present invention provides a composite material comprising a gas-permeable resin member made of an organometallic complex and a resin, and a conductive base material, which can be electrolytically polymerized on the conductive base material. Aromatic compounds and (
or) Electrolytic polymerization of heterocyclic compounds.
必要に応じて上記導電性基材を除去することを特徴とす
るガス拡散型複合電極の製造方法である。This method of manufacturing a gas diffusion type composite electrode is characterized in that the conductive base material is removed if necessary.
本発明において用いられる樹脂としては、ポリテトラ°
フルオロエチレンなどのふっ素糸樹脂、シリコーン樹脂
、ポリサルホンなどのいおう系樹脂、ビニル系樹脂、オ
レフィン系樹脂、フェノール系樹脂などの樹脂をあげる
ことができる。The resin used in the present invention is polytetra
Examples include resins such as fluorine thread resins such as fluoroethylene, silicone resins, sulfur resins such as polysulfone, vinyl resins, olefin resins, and phenol resins.
本発明においてガス拡散型複合電極の触媒として用いら
れる有機金属錯体としては、フタロシアニン。In the present invention, the organometallic complex used as a catalyst for the gas diffusion type composite electrode is phthalocyanine.
ナフタロシアニン、ポルフィリン、フエナトポルフィリ
ン、ビスシクロペンタジェニル、カルボニル。Naphthalocyanine, porphyrin, phenatoporphyrin, biscyclopentagenyl, carbonyl.
ヒドリド、カルベン、カルビン、アセチルアセトン錯塩
、サリチルアミンキレート サリチルアルデヒド錯塩、
エチレンジアミン四節酸塩、グリシンキｌ／−ト、フェ
ロセンなど、あるいはこれらに、ハロゲン原子、ニトロ
基、スルホン基、スルホン酸塩基。hydride, carbene, carbine, acetylacetone complex salt, salicylamine chelate salicylaldehyde complex salt,
Ethylenediamine tetranosate, glycine salt, ferrocene, etc., or a halogen atom, a nitro group, a sulfonic group, a sulfonic acid group.
アルキル基、アリル基、水酸基、カルボキシル基などの
原子または置換基が導入された誘導体の、白金。Platinum is a derivative into which atoms or substituents such as alkyl groups, allyl groups, hydroxyl groups, and carboxyl groups are introduced.
鉄、コバルトニッケル、ｍ、パラジウム、モリブデンな
どの金属の錯体である。It is a complex of metals such as iron, cobalt nickel, m, palladium, and molybdenum.
また、触媒の有効利用率を向上させるためには。Also, in order to improve the effective utilization rate of the catalyst.
これらの有機金属錯体のうち、用いる樹脂部材と同一・
の溶媒に可溶性のものを用いることが望ましく。Among these organometallic complexes, the same or
It is desirable to use one that is soluble in the solvent.
例えば、有機金属錯体、溶媒、樹脂の組み合わせとして
は、アセチルアセトン錯塩では、アセトン溶媒。For example, as a combination of an organometallic complex, a solvent, and a resin, for an acetylacetone complex salt, an acetone solvent is used.
ポリビニルハロゲン化合物および（または）ポリスチレ
ン樹脂の組み合わせ、サリチルアミンキレートでは、ジ
メチルホルムアミドおよび（または）ピリジン溶媒、ポ
リビニルアルコールおよび（または）ポリアセチレンお
よび（または）ポリビニルハロゲン化物樹脂の組み合わ
せ、サリチルアルデヒド錯塩では、クロロホルム溶媒、
ポリビニルアセテートおよび（または）ポリビニルスル
ホキシド樹脂の組み合わせ、フェロセンでは、ベンゼン
溶媒、ポリビニルアセテートおよび（または）ポリスチ
レン樹脂の組み合わせ、ポルフィリン、フタロシアニン
などのスルホン酸塩誘導体、カルボキシル誘導体では、
ジメチルホルムアミドまたはジメチルスルホキシド溶媒
、ポリビニルアルコールおよび（または）ポリビニルハ
ロゲン化物および（または）ポリアクロニトリルブタジ
ェンスチレンおよび（または）ポリアクリロニトリルお
よび（または）ポリアセチレン樹脂等を挙げることがで
きるが、これらに限定されるものではない。Combinations of polyvinyl halogen compounds and/or polystyrene resins, dimethylformamide and/or pyridine solvents for salicylamine chelates, combinations of polyvinyl alcohol and/or polyacetylene and/or polyvinyl halide resins, chloroform for salicylaldehyde complexes solvent,
Combinations of polyvinyl acetate and (or) polyvinyl sulfoxide resins, for ferrocene, benzene solvents, combinations of polyvinyl acetate and (or) polystyrene resins, sulfonate derivatives such as porphyrins, phthalocyanines, and carboxyl derivatives.
Examples include, but are not limited to, dimethylformamide or dimethyl sulfoxide solvents, polyvinyl alcohol and/or polyvinyl halides and/or polyacronitrile butadiene styrene and/or polyacrylonitrile and/or polyacetylene resins. It's not something you can do.
上記有機金属錯体と樹脂とからなる樹脂部材は。A resin member made of the above-mentioned organometallic complex and resin.
本発明にかかわるガス拡散型複合電極において利用され
るガスを透過する性質を有するものでなければならない
。例えば、ガスが酸素である場合に、樹脂部材の酸素透
過係数は、ｌＸｌ０一番’ （ｃｏ＋’（ＳＴＰ）ｃ
ｍ−ｃｓ＋−”ｓ−暴（ｃｍＨｇ） −’ ）以上、好
ましくはｌＸｌ０−”（ｃｓ＋’（ＳＴＰ）ｃｍ−ｃ＋
ｓ−” ｓ−’（ｃｍＨｇ）−’１以上である。It must have the property of permeating the gas used in the gas diffusion type composite electrode according to the present invention. For example, when the gas is oxygen, the oxygen permeability coefficient of the resin member is lXl0'(co+'(STP)c
m−cs+−”s−(cmHg)−′) or higher, preferably lXl0−”(cs+′(STP)cm−c+
s-"s-'(cmHg)-' is 1 or more.
本発明において電解重合の電極として用いられる導電性
基材としては、白金、ニッケル、 ！Ｍ、 Ｓ！、金。In the present invention, the conductive base material used as an electrode for electrolytic polymerization includes platinum, nickel, ! M, S! ,Money.
パラジウムなどの金属材料、およびグラジ−カーボンな
どの炭素質材料からなるものの他、インジウムトリオキ
シドなどを蒸着させた透明電極（ＩＴＯガラスなど）を
用いることができる。導電性基材の形状としては、特に
限定はなく、線状、板状、棒状。In addition to those made of metal materials such as palladium and carbonaceous materials such as grady carbon, transparent electrodes (such as ITO glass) on which indium trioxide or the like is vapor-deposited can be used. The shape of the conductive base material is not particularly limited, and may be linear, plate-like, or rod-like.
球状、メツシュ状、ペーパー状、クロス状などのものを
用いることができる。A spherical, mesh-like, paper-like, cross-like shape, etc. can be used.
本発明において複合材は上記樹脂部材と導電性基材とか
らなる。複合材は、■上記有機金属錯体および樹脂を、
テトラヒドロフランなどのエーテル系溶媒、ジアミノジ
フェニルメタンなどのアミン系溶媒。In the present invention, the composite material consists of the above resin member and a conductive base material. The composite material consists of ■the above organometallic complex and resin,
Ether solvents such as tetrahydrofuran, amine solvents such as diaminodiphenylmethane.
アセトン、メチルエチルケトンなどのケトン系溶媒。Ketone solvents such as acetone and methyl ethyl ketone.
フェノール、トルエン、キシレンなどの芳香族系溶媒、
シクロヘキセンなどの脂肪族化合物系溶媒など適切な有
機溶媒に溶解（溶融溶解を含む）または分散させた塗布
剤を、上記導電性基材上に塗布し、乾燥させる。■上記
有機金属錯体および樹脂の混合物を押出成形、射出成形
、加圧成形など適切な方法により成形し、得られた成形
物と上記導電性基材とを。Aromatic solvents such as phenol, toluene, xylene,
A coating agent dissolved (including melting) or dispersed in a suitable organic solvent such as an aliphatic compound solvent such as cyclohexene is applied onto the conductive substrate and dried. (2) Molding the mixture of the above-mentioned organometallic complex and resin by an appropriate method such as extrusion molding, injection molding, or pressure molding, and combining the obtained molded product with the above-mentioned conductive base material.
熱圧着するか導電性接着剤を用いて接着する。■上記有
機金属錯体および樹脂の混合物を、上記導電性基材上に
粉体塗装または押出しコーティングする。Adhere by heat compression or conductive adhesive. (2) The mixture of the organometallic complex and resin is powder coated or extrusion coated onto the conductive substrate.
■上記有機金属錯体および樹脂の混合物を押出成形。■Extrusion molding of the mixture of the above organometallic complex and resin.
射出成形、加圧成形など適切な方法により成形し。Molded using appropriate methods such as injection molding and pressure molding.
得られた成形物上に、蒸着により導電性基材を設ける。A conductive base material is provided on the obtained molded article by vapor deposition.
などの方法により作ることができる。得られるガス拡散
型複合電極の性能の面からは、これらの方法のなかでも
、特に５■上上記機金属錯体および樹脂を適切な有機溶
媒に溶解（溶融溶解を含む）または分散、さらに好まし
くは溶解（溶融溶解を含む）させた塗布剤を、上記導電
性基材上に塗布し、乾燥させる方法により複合材を作る
ことが好ましい。It can be made by methods such as From the viewpoint of the performance of the resulting gas diffusion type composite electrode, among these methods, particularly 5. above, dissolving (including melting) or dispersing the above-mentioned metal complex and resin in an appropriate organic solvent, more preferably It is preferable to make a composite material by applying a dissolved (including melting) coating agent onto the conductive substrate and drying it.
このようにして得られた複合材の導電性基材上で。On the conductive substrate of the composite thus obtained.
電解重合可能な芳香族化合物および（または）複素環化
合物が電解重合される。電解重合可能な芳香族化合物ま
たは複素環化合物としては、アズレン、ピレン、トリフ
ェニレン、アニリン、ビロール、チオフェン、３−メチ
ルチオフェン、フラン、ピペラジン。Electropolymerizable aromatic and/or heterocyclic compounds are electropolymerized. Examples of electropolymerizable aromatic compounds or heterocyclic compounds include azulene, pyrene, triphenylene, aniline, virol, thiophene, 3-methylthiophene, furan, and piperazine.
イソチアナ°フテンなどをあげることができる。Examples include isothiana phthene.
これら電解重合可能な芳香族化合物および（または）複
素環化合物１通電させるための電解質、および有機溶媒
からなる溶液中に、上記複合材を対向電極とともに入れ
２通電させることにより、複合材の導電性基材上で、す
なわち、導電性基材の樹脂部材で覆われた部分の上、樹
脂部材中で、また、導電性基村上に樹脂部材で覆われて
いない部分がある場合には、この樹脂部材で覆われてい
ない部分の上で。By placing the composite material together with a counter electrode in a solution consisting of an electrolyte for energizing these electrolytically polymerizable aromatic compounds and/or heterocyclic compounds, and an organic solvent and energizing them, the conductivity of the composite material can be improved. On the base material, that is, on the part of the conductive base material covered with the resin member, in the resin member, or on the conductive base layer, if there is a part not covered with the resin member, this resin On parts not covered by parts.
それぞれ電解重合がおこり１重合体が堆積（生長）する
。電解重合は、少なくとも、導電性基材の樹脂部材で覆
われた部分の上、樹脂部材中だけでおこればよく、電解
重合による重合体の形成効率の面から。Electrolytic polymerization occurs in each case, and one polymer is deposited (grown). Electrolytic polymerization only needs to be carried out on at least the portion of the conductive base material covered with the resin member, from the viewpoint of the efficiency of forming a polymer by electrolytic polymerization.
導電性基材上の樹脂部材で覆われていない部分を剥離可
能なまたは不可能な絶縁材料で覆ってから、電解重合を
行なうことが好ましい。It is preferable to perform electrolytic polymerization after covering the portions of the conductive substrate that are not covered with the resin member with an insulating material that may or may not be peeled.
上記電解質を構成するカチオンとしては、アルカリ金属
イオン、アルカリ土類金属イオン、第４フルキルアンモ
ニウムイオン、第４アルキルホスホニウムイオン、第４
アルキルアルセニウムイオン、第４スルホニウムイオン
、あるいはこれらの置換体などがあり、アニオンとして
は、スルホン酸イオン、硝酸イオン、過塩素酸イオン、
カルボン酸イオン、テトラフルオロはう酸イオン、ヘキ
サフルオロりん酸イオン、あるいはこれらの置換体があ
る。これらのカチオンおよびアニオンから構成される電
解質のうち、有機溶媒への溶解性などの面から、特に、
テトラブチルアンモニウムバークロレート、テトラエチ
ルアンモニウムバークロレート、テトラブチルアンモニ
ウムテトラフルオロはう酸塩、テトラフルオロはう酸ナ
トリウムなどを用いることが好ましい。電解重合の際に
用いられる有機溶媒としては、アセトニトリル、ベンジ
ルニトリル、ベンゾニトリルナトのニトリル類、ジメチ
ルホルムアミド、ジメチルアセトアミド、Ｎ−メチルア
セトアミドなどのアミド類２エチレンジアミン、ヘキサ
メチルホスホルアミド。The cations constituting the electrolyte include alkali metal ions, alkaline earth metal ions, quaternary flukylammonium ions, quaternary alkylphosphonium ions, quaternary
There are alkyl arsenium ions, quaternary sulfonium ions, and substituted products thereof, and anions include sulfonate ions, nitrate ions, perchlorate ions,
These include carboxylate ions, tetrafluorophosphate ions, hexafluorophosphate ions, or substituted products thereof. Among these electrolytes composed of cations and anions, in terms of solubility in organic solvents, in particular,
It is preferable to use tetrabutylammonium verchlorate, tetraethylammonium verchlorate, tetrabutylammonium tetrafluorobolate, sodium tetrafluorobolate, and the like. Examples of organic solvents used during electrolytic polymerization include acetonitrile, benzylnitrile, benzonitrile natriles, amides such as dimethylformamide, dimethylacetamide, and N-methylacetamide, diethylenediamine, and hexamethylphosphoramide.
ピリジンなどのアミン類、テトラヒドロフラン、ジオキ
サン、 １．２−ジメトキシエタンなどのエーテル類。Amines such as pyridine, ethers such as tetrahydrofuran, dioxane, and 1,2-dimethoxyethane.
酢酸、無水酢酸などのカルボン酸類、メタノール。Carboxylic acids such as acetic acid and acetic anhydride, methanol.
エタノールなどのアルコール類、ジメチルスルホキシド
、スルホラン、ジメチルスルホンなどのいおう化合物、
プロピレンカーボネート、ニトロメタン。Alcohols such as ethanol, sulfur compounds such as dimethyl sulfoxide, sulfolane, dimethyl sulfone,
Propylene carbonate, nitromethane.
塩化メチレン、アセトンなどを用いることができる。Methylene chloride, acetone, etc. can be used.
電離係数を考慮するなら、これらの有機溶媒のうちでも
、特に、メタノール、エタノール、アセトニトリル２
ジメチルホルムアミド、ジメチルスルホキシド、テトラ
ヒドロフラン、プロピレンカーボネート。Considering the ionization coefficient, among these organic solvents, methanol, ethanol, acetonitrile 2
Dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, propylene carbonate.
ニトロメタンなどを用いることが好ましい。It is preferable to use nitromethane or the like.
電解重合時の通電量は３通常、０．１〜１００Ｃ／ｃｍ
”であるが１通電量を１〜１０Ｃ／ｃｍ２に設定するな
ら、電解重合によって堆積（生長）する重合体の表面を
平滑とすることができ、導電性の高いガス拡散型複合電
極を得ることができる。このようにして電解重合を行な
い、必要に応じて上記導電性基材が除去され、ガス拡散
型複合電極が得られる。The amount of current applied during electrolytic polymerization is usually 0.1 to 100 C/cm.
However, if the amount of current applied per unit is set to 1 to 10 C/cm2, the surface of the polymer deposited (grown) by electrolytic polymerization can be made smooth, and a highly conductive gas diffusion type composite electrode can be obtained. Electrolytic polymerization is carried out in this manner, and the conductive base material is removed if necessary, to obtain a gas diffusion type composite electrode.
導電性基材を除去しない場合には、用いる導電性基材を
、軽量のものとする。薄膜のものとする。あるいは成形
性の良好なものとすることによって、それぞれ１．得ら
れるガス拡散型複合電極の軽量化、薄膜化、あるいは易
成形性化が可能である。また、導電性基材を除去するこ
とによって、さらに軽量化・薄膜化をはかることができ
るとともに、成形などの加工をより容易に行なうことが
できる。When the conductive base material is not removed, the conductive base material used is lightweight. It shall be a thin film. Or, by making it good in moldability, each of the following 1. The resulting gas diffusion type composite electrode can be made lighter, thinner, or easier to form. Furthermore, by removing the conductive base material, it is possible to further reduce the weight and thickness of the film, and it is also possible to perform processing such as molding more easily.
（作用）
本発明において導電性基材は電解重合時の電極として作
用する。(Function) In the present invention, the conductive substrate acts as an electrode during electrolytic polymerization.
本発明により得られたガス拡散型複合電極において、有
機金属錯体は触媒として作用し、電解重合によって堆積
（生長）した重合体は電極本体における導電体として作
用する。また、導電性基材を除去しない場合には、導電
性基材もまた電極本体における導電体として作用する。In the gas diffusion type composite electrode obtained by the present invention, the organometallic complex acts as a catalyst, and the polymer deposited (grown) by electrolytic polymerization acts as a conductor in the electrode body. In addition, if the conductive base material is not removed, the conductive base material also acts as a conductor in the electrode body.
（実施例） 以下、実施例により本発明をより詳細に説明する。(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
なお２例中１部とは重量部を表わす。Note that in the two examples, 1 part represents part by weight.
実施例１゜
ポリサルホン５０部およびジメチルホルムアミド２００
部からなる溶液２５０部にコバルトフタロシアニン２５
部を分散させて得られた分散液をＩＴＯガラス上に塗布
し、１２０℃で２時間乾燥し、複合材を得た。得られた
複合材を電極として用い、対向電極として白金板を用い
て、アセトニトリル１００部、ピロール０．７部および
テトラブチルアンモニウムバークロレート３．５部から
なる電解質含有溶液中で１通電量が３Ｃ／Ｃｍｚに達す
るまで電解重合を行ない、つぎにＩＴＯガラスを剥離さ
せ、アセトニトリルで十分洗浄し、８０℃で５時間乾燥
し、厚さ２０μｍの薄膜状の電極を得た。得られた電極
中には、ポリピロールが３重量％含まれていた。Example 1 50 parts of polysulfone and 200 parts of dimethylformamide
250 parts of a solution consisting of 25 parts of cobalt phthalocyanine
The resulting dispersion was applied onto ITO glass and dried at 120° C. for 2 hours to obtain a composite material. Using the obtained composite material as an electrode and a platinum plate as a counter electrode, the amount of current applied per 3C in an electrolyte-containing solution consisting of 100 parts of acetonitrile, 0.7 parts of pyrrole, and 3.5 parts of tetrabutylammonium verchlorate. Electrolytic polymerization was performed until /Cmz was reached, and then the ITO glass was peeled off, thoroughly washed with acetonitrile, and dried at 80° C. for 5 hours to obtain a thin film electrode with a thickness of 20 μm. The obtained electrode contained 3% by weight of polypyrrole.
このようにして得られた電極を用い、電解液として水酸
化カリウム１規定水溶液を、対向電極として白金板をそ
れぞれ用い、酸素ガス圧を１ ａｔｍ＋ 酸素ガス供
給速度をｌ ＯＯｍｊ！／分、設定電流密度を０゜１ｍ
Ａ／ａｍ”として酸素半電池を組み立て、電極電位を測
定したところ、電極電位は一〇、 ３９ Ｖであった。Using the electrode thus obtained, using a 1N aqueous solution of potassium hydroxide as the electrolyte and a platinum plate as the counter electrode, the oxygen gas pressure was set to 1 atm+ and the oxygen gas supply rate was set to l OOmj! /min, set current density to 0゜1m
When an oxygen half cell was assembled and the electrode potential was measured, the electrode potential was 10.39 V.
測定開始後１ｏｏｏ時間以上経過しても、電極電位に変
化はなく、電解液の液もれも生じなかった。なお、この
際、参照電極としてはＨｇ ／ Ｈｇ Ｏ電極を用いた
。Even after more than 100 hours had passed after the start of the measurement, there was no change in the electrode potential and no leakage of the electrolyte solution occurred. Note that at this time, a Hg/HgO electrode was used as a reference electrode.
比較例１゜
ポリサルホン５０部およびジメチルホルムアミド２００
部からなる溶液２５０部に、コバルトフタロシアニン２
５部およびカーボンブランク２．２５部を分散させて得
られた分散液を、乾燥膜厚２０μｍとなるようにＩＴＯ
ガラス上に塗布し、１２０℃で２時間乾燥した後、ＩＴ
Ｏガラスを剥離させ、薄膜状の電極を得た。得られた電
極を用い、実施例１と同様にして、酸素半電池を組み立
てようとしたが、電極電位は−１，０Ｖ以下であり、酸
素半電池としての実用性はないことがわかった。Comparative Example 1 50 parts of polysulfone and 200 parts of dimethylformamide
Cobalt phthalocyanine 250 parts
A dispersion obtained by dispersing 5 parts of carbon blank and 2.25 parts of carbon blank was mixed with ITO to give a dry film thickness of 20 μm.
After coating on glass and drying at 120°C for 2 hours, IT
The O glass was peeled off to obtain a thin film electrode. An attempt was made to assemble an oxygen half cell using the obtained electrode in the same manner as in Example 1, but the electrode potential was -1.0 V or less, and it was found that it was not practical as an oxygen half cell.
比較例２゜
ポリサルホン５０部およびジメチルホルムアミド２００
部からなる溶液２５０部に、コバルトフタロシアニン２
５部およびカーボンブラック５０部を分散させて得られ
た分散液を、乾燥膜厚２０μｍとなるようにＩＴＯガラ
ス上に塗布し、１２０℃で２時間乾燥した後、ＩＴＯガ
ラスを剥離させ、薄膜状の電極を得た。得られた電極を
用い、実施例１と同様にして、酸素半電池を組み立て、
電極電位を測定したところ、電極電位は一〇、 ３９
Ｖであったが、測定開始後１００時間で電解液の液もれ
が生じ、電極電位も−１，Ｏｖとなった。Comparative Example 2 50 parts of polysulfone and 200 parts of dimethylformamide
Cobalt phthalocyanine 250 parts
A dispersion obtained by dispersing 5 parts of carbon black and 50 parts of carbon black was applied onto ITO glass to a dry film thickness of 20 μm, and after drying at 120°C for 2 hours, the ITO glass was peeled off to form a thin film. electrodes were obtained. Using the obtained electrode, assemble an oxygen half cell in the same manner as in Example 1,
When the electrode potential was measured, the electrode potential was 10.39
However, 100 hours after the start of the measurement, leakage of the electrolytic solution occurred, and the electrode potential also became -1.Ov.
実施例２゜
カーボンペーパーに、実施例１において用いた分散液を
含浸させ、１２０℃で５時間乾燥させ、得られた含浸乾
燥物を一方の電極とし、対向電極として白金板を用い、
実施例１と同様に電解重合し、厚さ４００μｍの電極を
得た。得られた電極を用い、実施例１と同様にして、酸
素半電池を組み立て、電極電位を測定したところ、電極
電位は一〇、 ３９ Ｖであり、測定開始後３０００時
間以上経過しても、電極電位に変化はなく、電解液の液
もれも生じなかった。Example 2 Carbon paper was impregnated with the dispersion used in Example 1 and dried at 120°C for 5 hours, the resulting impregnated dry product was used as one electrode, and a platinum plate was used as the counter electrode,
Electrolytic polymerization was carried out in the same manner as in Example 1 to obtain an electrode with a thickness of 400 μm. Using the obtained electrode, an oxygen half cell was assembled in the same manner as in Example 1, and the electrode potential was measured. The electrode potential was 10.39 V, and even after more than 3000 hours had passed since the start of the measurement, There was no change in the electrode potential, and no electrolyte leakage occurred.
実施例３゜ ポリアクリろニトリルブタジェンメチレフ１０部。Example 3゜ 10 parts of polyacrylonitrile butadiene methyleph.
ジメチルホルムアミド９０部からなる溶液１００部に、
コバルトフタロシアニントリスルホン酸ナトリウム５部
を溶解させて得られた混合溶液をＩＴＯガラス上に塗布
し、１００℃で２時間乾燥し、複合材を得た。得られた
複合材を電極どして用い、対向電極として白金板を用い
て、実施例１と同様にして酸素半電池を組み立て電極電
位を測定したところ、電極電位は−０，２４Ｖに向上し
た。In 100 parts of a solution consisting of 90 parts of dimethylformamide,
A mixed solution obtained by dissolving 5 parts of sodium cobalt phthalocyanine trisulfonate was applied onto ITO glass and dried at 100° C. for 2 hours to obtain a composite material. Using the obtained composite material as an electrode and a platinum plate as a counter electrode, an oxygen half cell was assembled in the same manner as in Example 1, and the electrode potential was measured, and the electrode potential was improved to -0.24V. .
いガス拡散型複合電極が得られるようになった。 It is now possible to obtain a gas diffusion type composite electrode.
また１本発明において、導電性基材を除去しない場合に
は、用いる導電性基材を、軽量のものとする。Furthermore, in the present invention, when the conductive base material is not removed, the conductive base material used is lightweight.
薄膜のものとする。あるいは成形性の良好なものとする
ことによって、それぞれ、得られるガス拡散型複合電橋
の軽量化、薄膜化、あるいは易成形性化が可能である。It shall be a thin film. Alternatively, by providing good moldability, the resulting gas diffusion type composite electrical bridge can be made lighter, thinner, or easier to mold.
また、導電性基材を除去することによって、さらに軽量
化・薄膜化をはかることができるとともに、成形などの
加工もより容易に行なうことができる。Furthermore, by removing the conductive base material, it is possible to further reduce the weight and thickness of the film, and it is also possible to perform processing such as molding more easily.
Claims (1)
る樹脂部材と導電性基材とからなる複合材の上記導電性
基材上で、電解重合可能な芳香族化合物および（または
）複素環化合物を電解重合し、必要に応じて上記導電性
基材を除去することを特徴とするガス拡散型複合電極の
製造方法。 ２、有機金属錯体および樹脂からなるガス透過性を有す
る樹脂部材が同一溶媒に可溶性であることを特徴とする
請求項１記載のガス拡散型複合電極の製造方法。[Scope of Claims] 1. An electrolytically polymerizable aromatic compound and ( or) A method for producing a gas diffusion type composite electrode, which comprises electrolytically polymerizing a heterocyclic compound and removing the conductive base material as required. 2. The method for manufacturing a gas diffusion type composite electrode according to claim 1, wherein the resin member having gas permeability made of the organometallic complex and the resin is soluble in the same solvent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP741289 | 1989-01-13 | ||
| JP1-7412 | 1989-01-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02297865A true JPH02297865A (en) | 1990-12-10 |
| JPH0766816B2 JPH0766816B2 (en) | 1995-07-19 |
Family
ID=11665150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1343365A Expired - Lifetime JPH0766816B2 (en) | 1989-01-13 | 1989-12-29 | Method for manufacturing gas diffusion type composite electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0766816B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006521469A (en) * | 2003-03-28 | 2006-09-21 | アルケマ | Method for forming a metal oxide film on a conductive substrate, the resulting active cathode and its use in the electrolysis of aqueous alkali metal chloride solutions |
| JP2006344525A (en) * | 2005-06-09 | 2006-12-21 | Toyota Motor Corp | Gas diffuser, its manufacturing method and fuel cell |
| JP2008509520A (en) * | 2004-08-05 | 2008-03-27 | ゼネラル・モーターズ・コーポレーション | Increasing the hydrophilicity of carbon fiber paper by electropolymerization. |
| JP2018052068A (en) * | 2016-09-30 | 2018-04-05 | 三菱ケミカル株式会社 | Laminate film and manufacturing method therefor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS624898A (en) * | 1985-07-01 | 1987-01-10 | Agency Of Ind Science & Technol | Production of electrically conductive polymer film containing particle |
-
1989
- 1989-12-29 JP JP1343365A patent/JPH0766816B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS624898A (en) * | 1985-07-01 | 1987-01-10 | Agency Of Ind Science & Technol | Production of electrically conductive polymer film containing particle |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006521469A (en) * | 2003-03-28 | 2006-09-21 | アルケマ | Method for forming a metal oxide film on a conductive substrate, the resulting active cathode and its use in the electrolysis of aqueous alkali metal chloride solutions |
| JP2008509520A (en) * | 2004-08-05 | 2008-03-27 | ゼネラル・モーターズ・コーポレーション | Increasing the hydrophilicity of carbon fiber paper by electropolymerization. |
| JP2006344525A (en) * | 2005-06-09 | 2006-12-21 | Toyota Motor Corp | Gas diffuser, its manufacturing method and fuel cell |
| JP2018052068A (en) * | 2016-09-30 | 2018-04-05 | 三菱ケミカル株式会社 | Laminate film and manufacturing method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0766816B2 (en) | 1995-07-19 |
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