TW202118904A - Porous substrate with catalyst supported thereon for water electrolysis, electrode for water electrolysis, gas diffusion layer, stack cell for water electrolysis, and cell module for water electrolysis - Google Patents
Porous substrate with catalyst supported thereon for water electrolysis, electrode for water electrolysis, gas diffusion layer, stack cell for water electrolysis, and cell module for water electrolysis Download PDFInfo
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- TW202118904A TW202118904A TW109134169A TW109134169A TW202118904A TW 202118904 A TW202118904 A TW 202118904A TW 109134169 A TW109134169 A TW 109134169A TW 109134169 A TW109134169 A TW 109134169A TW 202118904 A TW202118904 A TW 202118904A
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- water electrolysis
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- 239000003054 catalyst Substances 0.000 title claims abstract description 332
- 239000000758 substrate Substances 0.000 title claims abstract description 217
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 192
- 238000009792 diffusion process Methods 0.000 title claims abstract description 26
- 239000000835 fiber Substances 0.000 claims abstract description 52
- 239000011148 porous material Substances 0.000 claims abstract description 24
- 229920000831 ionic polymer Polymers 0.000 claims description 95
- 239000011159 matrix material Substances 0.000 claims description 89
- 239000012528 membrane Substances 0.000 claims description 75
- 239000005518 polymer electrolyte Substances 0.000 claims description 48
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 35
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 24
- 238000010304 firing Methods 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- 239000012685 metal catalyst precursor Substances 0.000 claims description 14
- 238000011049 filling Methods 0.000 claims description 12
- 239000011800 void material Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052741 iridium Inorganic materials 0.000 claims description 9
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- 229920001940 conductive polymer Polymers 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000554 ionomer Polymers 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 31
- 238000000576 coating method Methods 0.000 description 29
- 239000011248 coating agent Substances 0.000 description 26
- 239000007788 liquid Substances 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- -1 sulfuric acid ions Chemical class 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
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- 238000001354 calcination Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
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- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 2
- FFQCZYROKVPTGV-UHFFFAOYSA-M Cl[Ir+3] Chemical compound Cl[Ir+3] FFQCZYROKVPTGV-UHFFFAOYSA-M 0.000 description 2
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 229910033181 TiB2 Inorganic materials 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
- JUFNXAFOTZCFOK-UHFFFAOYSA-M platinum(4+);chloride Chemical compound [Pt+3]Cl JUFNXAFOTZCFOK-UHFFFAOYSA-M 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical group FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910001029 Hf alloy Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- WHWMXYJYULKLCO-UHFFFAOYSA-N [Ir+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Ir+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WHWMXYJYULKLCO-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- FGEKTVAHFDQHBU-UHFFFAOYSA-N dioxoruthenium;hydrate Chemical compound O.O=[Ru]=O FGEKTVAHFDQHBU-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- IUJMNDNTFMJNEL-UHFFFAOYSA-K iridium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ir+3] IUJMNDNTFMJNEL-UHFFFAOYSA-K 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
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- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
-
- B01J35/58—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
Description
本發明係關於水電解用的擔持有觸媒之多孔質基體以及水電解用電極，更詳細而言，係關於使用高分子電解質膜(PEM：Polymer Electrolyte Membrane)來進行水電解時所使用，且於觸媒的擔持型態以及接觸該觸媒之離子聚合物與其存在型態(填充型態)具有特徵之水電解用的擔持有觸媒之多孔質基體、水電解用電極、氣體擴散層、水電解用堆疊單元及水電解用單元模組。 The present invention relates to a porous substrate supporting a catalyst for water electrolysis and an electrode for water electrolysis. More specifically, it relates to the use of a polymer electrolyte membrane (PEM: Polymer Electrolyte Membrane) for water electrolysis. In addition, the porous substrate for supporting the catalyst, the electrode for water electrolysis, and the gas for water electrolysis are characterized by the supporting type of the catalyst and the ionic polymer contacting the catalyst and its existence type (filling type). Diffusion layer, stacked unit for water electrolysis, and unit module for water electrolysis.
使用在燃料電池或「氫產生裝置用的水電解單元」之膜電極接合體(membrane electrode assembly(MEA))係具有：形成有觸媒層之電極、以及由陽極與陰極所夾持之高分子電解質膜(PEM膜)。 The membrane electrode assembly (MEA) used in fuel cells or "water electrolysis cells for hydrogen generators" has: an electrode formed with a catalyst layer, and a polymer sandwiched between the anode and the cathode Electrolyte membrane (PEM membrane).
此外，於歷來的膜電極接合體(MEA)中，其一例如圖1(b)、圖2(b)及圖2(c)所示，觸媒係形成層而存在，亦即作為觸媒層而存在於膜電極接合體(MEA)中。此外，氣體擴散層接觸該觸媒層以擷取所產生之氣體。 In addition, in the conventional membrane electrode assembly (MEA), for example, as shown in Figure 1 (b), Figure 2 (b) and Figure 2 (c), the catalyst system forms a layer and exists, that is, as a catalyst The layer is present in the membrane electrode assembly (MEA). In addition, the gas diffusion layer contacts the catalyst layer to capture the generated gas.
專利文獻1所記載之發明係關於電極觸媒層所含有之硫酸離子的量為規定值以下時判定為良品之膜電極接合體(MEA)的製造方法，於專利文獻1中揭示一種於高分子電解質膜的面上形成有電極觸媒層之膜電極接合體及其製造方法。
The invention described in
關於此製造方法中的製造步驟係記載如下。準備電解質膜並準備電極觸媒層，使用所準備之電解質膜及電極觸媒層來製作觸媒層形成膜，然後準備氣體擴散層，並使用所製作之觸媒層形成膜及所準備之氣體擴散層來製作膜電極接合體(MEA)。 The manufacturing steps in this manufacturing method are described below. Prepare the electrolyte membrane and prepare the electrode catalyst layer, use the prepared electrolyte membrane and electrode catalyst layer to make the catalyst layer forming membrane, then prepare the gas diffusion layer, and use the produced catalyst layer to form the membrane and the prepared gas The diffusion layer is used to produce a membrane electrode assembly (MEA).
然而，專利文獻1之膜電極接合體(MEA)除了燃料電池用者之外，該膜電極接合體(MEA)所具有之電極觸媒層是將含有離子聚合物與觸媒之印墨連續地塗佈於基材或電解質膜的面上並使之乾燥而製作(藉此降低硫酸離子的量)。
However, the membrane electrode assembly (MEA) of
於專利文獻2中揭示一種「堆積有觸媒層之擴散介質」未被加熱模壓於膜上之具有耐久性之膜電極組裝體的製作方法。於此專利文獻2中，係將觸媒層堆積於擴散介質層上，接著將離子聚合物層設置在該觸媒層的表面來製作燃料電池用的膜電極組裝體(MEA)。
然而，專利文獻2之膜電極組裝體(MEA)除了燃料電池用者之外，該觸媒是以觸媒層的形式形成於擴散介質上，離子聚合物亦藉由噴霧而設置在該觸媒層上的全面。此外，關於該膜電極組裝體(MEA)所具有之觸媒層的製造方
法，係將觸媒層以漿液的型態連續地轉製或塗佈於擴散介質層上而形成，一旦將觸媒被覆於轉印基板後，藉由加熱模壓將此轉印於膜。
However, in the membrane electrode assembly (MEA) of
近年來伴隨著氫之需求的擴大，係要求優異之水的電分解技術，惟於先前技術中仍有所不足，對於水電解單元的性能或耐久性等仍要求更優異的技術。 In recent years, as the demand for hydrogen has expanded, it is an electrolysis technology that requires excellent water. However, there are still shortcomings in the prior art, and more excellent technology is still required for the performance or durability of the water electrolysis unit.
[先前技術文獻] [Prior Technical Literature]
[專利文獻] [Patent Literature]
[專利文獻1] 日本特許第6128099號公報 [Patent Document 1] Japanese Patent No. 6128099
[專利文獻2] 日本特許第4738350號公報 [Patent Document 2] Japanese Patent No. 4738350
本發明係鑑於上述情況而完成者，該課題在於提供一種水電解用單元(包含水電解用單一單元、水電解用堆疊單元等)的水電解性能或其耐久性優異，且具有與歷來不同的嶄新構成(型態)之擔持有觸媒之多孔質基體。 The present invention was made in view of the above circumstances. The subject is to provide a unit for water electrolysis (including a single unit for water electrolysis, a stacked unit for water electrolysis, etc.) that has excellent water electrolysis performance or durability, and has a difference from the past. The new structure (type) of the porous matrix that holds the catalyst.
換言之，係在於提供一種水電解性能或其耐久性優異之水電解用電極以及該水電解用電極所使用之擔持有觸媒之多孔質基體。 In other words, it is to provide an electrode for water electrolysis with excellent water electrolysis performance or durability, and a porous substrate supporting a catalyst used in the electrode for water electrolysis.
本發明者們為了解決上述課題而進行精心探討，結果發現到脫離所謂「觸媒層」的概念且不是在(多孔質)基體上設置觸媒層之樣態或型態者，水電解性能及其耐久性優異。 The inventors of the present invention conducted intensive studies to solve the above-mentioned problems. As a result, they found that the water electrolysis performance and the type of the catalyst layer are not provided on the (porous) substrate without the concept of the so-called "catalyst layer". Its durability is excellent.
發現到若是將觸媒擔持於構成多孔質基體之孔或是形成多孔質基體之纖維，則水電解性能或其耐久性優異。 It has been found that if the catalyst is supported in the pores constituting the porous matrix or the fibers forming the porous matrix, the water electrolysis performance or durability is excellent.
此外，並發現到若是如上述般擔持觸媒並藉由所得到之擔持有觸媒之多孔質基體來夾持高分子電解質膜(PEM：Polymer Electrolyte Membrane)，則不易引起由氣舉(Gas Lift)所造成之觸媒的脫離，而變得不易產生性能劣化。 In addition, it has been found that if the catalyst is supported and the polymer electrolyte membrane (PEM: Polymer Electrolyte Membrane) is sandwiched by the obtained porous matrix supporting the catalyst as described above, it is not easy to cause gas lift ( Gas Lift) caused by the separation of the catalyst, it becomes less likely to cause performance degradation.
再者，更發現到藉由從接觸高分子電解質膜之電極面、亦即擔持有觸媒之多孔質基體的表面涵蓋至內部以特定的樣態(狀態)來填充離子聚合物，可得到單元電壓(電解電壓)經降低，且水電解性能及其耐久性優異之水電解用的擔持有觸媒之多孔質基體，因而完成本發明。 Furthermore, it has been discovered that by filling the ionic polymer in a specific state (state) from the electrode surface contacting the polymer electrolyte membrane, that is, the surface of the porous matrix holding the catalyst to the inside, it is possible to obtain The cell voltage (electrolysis voltage) is reduced, and the porous substrate for the water electrolysis with excellent water electrolysis performance and durability, which supports the catalyst, has completed the present invention.
亦即，本發明係提供一種擔持有觸媒之多孔質基體，其係具有下列構造：於水電解用單一單元中以夾持高分子電解質膜(PEM)之方式存在，並接觸該高分子電解質膜(PEM)而構成陰極或陽極，且亦發揮氣體擴散層的機能之構造， That is, the present invention provides a porous substrate that holds a catalyst, which has the following structure: it exists in a single unit for water electrolysis by sandwiching a polymer electrolyte membrane (PEM) and contacts the polymer Electrolyte membrane (PEM) constitutes a cathode or anode, and also functions as a gas diffusion layer,
該觸媒被擔持於該多孔質基體所具有之孔的側面或是形成該多孔質基體之纖維的側面，且以從該多孔質基體本身的表面涵蓋至內部之方式存在，並且 The catalyst is supported on the side surface of the pores of the porous matrix or the side surface of the fiber forming the porous matrix, and exists in a manner of covering from the surface of the porous matrix itself to the inside, and
離子聚合物接觸該觸媒，且以從該多孔質基體的表面朝向內部在該多孔質基體的厚度方向具有濃度梯度之狀態被填充。 The ionic polymer contacts the catalyst and is filled with a concentration gradient in the thickness direction of the porous substrate from the surface of the porous substrate toward the inside.
此外，本發明係提供經由下列步驟而得到之上述擔持有觸媒之多孔質基體：使金屬觸媒或金屬觸媒前驅物附著於焙燒前的多孔質基體所具有之孔的側面或是形成焙燒前的多孔質基體之纖維的側面並進行焙燒之步驟。 In addition, the present invention provides the porous substrate supporting the catalyst obtained by the following steps: attaching a metal catalyst or a metal catalyst precursor to the side surface of the pores of the porous substrate before firing or forming The side faces of the fibers of the porous matrix before firing are then fired.
此外，本發明係提供上述擔持有觸媒之多孔質基體，其中上述觸媒的膜厚或粒徑係小於「由上述孔及/或『上述纖維之間的間隙』所形成之空隙」的平均口徑長。 In addition, the present invention provides the above-mentioned porous substrate supporting the catalyst, wherein the film thickness or particle size of the above-mentioned catalyst is smaller than the "void formed by the above-mentioned pores and/or "the gap between the above-mentioned fibers"". The average caliber is long.
換言之，係提供上述擔持有觸媒之多孔質基體，其中在以膜來擔持上述觸媒時之該膜厚或是以粒子來擔持上述觸媒時之該粒徑係小於「『上述孔』及/或『上述纖維之間的間隙』之空隙」的大小。 In other words, the porous substrate for supporting the catalyst is provided, wherein the thickness of the film when the catalyst is supported by a film or the particle size when the catalyst is supported by particles is less than "" The size of the "hole" and/or "the gap between the above-mentioned fibers".
此外，本發明係提供上述擔持有觸媒之多孔質基體，其中上述多孔質基體的材質為鈦(Ti)或鈦(Ti)合金或是碳(C)。 In addition, the present invention provides the above-mentioned porous substrate supporting the catalyst, wherein the material of the above-mentioned porous substrate is titanium (Ti) or titanium (Ti) alloy or carbon (C).
此外，本發明係提供一種水電解用電極，其係上述擔持有觸媒之多孔質基體。 In addition, the present invention provides an electrode for water electrolysis, which is the above-mentioned porous substrate supporting a catalyst.
此外，本發明係提供一種氣體擴散層，其係上述擔持有觸媒之多孔質基體。 In addition, the present invention provides a gas diffusion layer, which is the porous substrate supporting the catalyst.
此外，本發明係提供一種水電解用單一單元，其係具有：藉由上述擔持有觸媒之多孔質基體夾持高分子電解質膜(PEM)而成之構造。 In addition, the present invention provides a single unit for water electrolysis, which has a structure in which a polymer electrolyte membrane (PEM) is sandwiched by the porous substrate supporting the catalyst.
此外，本發明係提供一種水電解用堆疊單元，其係在以藉由擔持有觸媒之多孔質基體夾持高分子電解質膜(PEM)之構造作為1個水電解用單一單元時，係積層2個以上之上述水電解用單一單元而成者。 In addition, the present invention provides a stacked unit for water electrolysis. When a structure in which a polymer electrolyte membrane (PEM) is sandwiched by a porous matrix supporting a catalyst is used as a single unit for water electrolysis, It is formed by stacking two or more single cells for water electrolysis.
此外，本發明係提供一種水電解用單元模組，其係二維或三維地排列配置上述水電解用堆疊單元而成者。 In addition, the present invention provides a unit module for water electrolysis in which the above-mentioned stacked units for water electrolysis are arranged two-dimensionally or three-dimensionally.
根據本發明，可提供一種解決前述問題點與上述課題，例如，由於具有單元電壓維持一定的(低)值且穩定等之優異的水電解性能，並且觸媒的擔 持呈堅固且接觸良好等，所以可提供一種耐久性優異之水電解用電極。此外，可提供一種使用該水電解用電極之水電解用單一單元或水電解用堆疊單元。 According to the present invention, it is possible to provide a solution to the aforementioned problems and the aforementioned problems, for example, due to the excellent water electrolysis performance of maintaining a constant (low) value and stability of the cell voltage, and the support of the catalyst It is strong and has good contact, so it can provide an electrode for water electrolysis with excellent durability. In addition, a single unit for water electrolysis or a stacked unit for water electrolysis using the electrode for water electrolysis can be provided.
具體而言，以特定的樣態或型態將觸媒擔持於多孔質基體，可使觸媒與該多孔質基體達到一體化。具體而言，藉由觸媒粒子或觸媒膜將該觸媒擔持於「構成多孔質碳基體之孔或纖維的表面」，藉此，與以觸媒層的形式堆積於(多孔質)基體的上表面(或下表面)之樣態相比，可具有更優異的水電解性能及其耐久性。 Specifically, by supporting the catalyst on the porous substrate in a specific shape or pattern, the catalyst can be integrated with the porous substrate. Specifically, the catalyst is supported on "the surface of the pores or fibers constituting the porous carbon matrix" by catalyst particles or a catalyst film, thereby accumulating in the form of a catalyst layer (porous) Compared with the shape of the upper surface (or lower surface) of the substrate, it can have more excellent water electrolysis performance and durability.
具體而言，例如在歷來以層的型態將觸媒堆積於基體上之方法中，該觸媒層會有因為氣舉而從基體中潛在性剝離之虞，但根據本發明，可提供一種防止觸媒從多孔質基體剝離或是觸媒從構成該多孔質基體之材料剝離之水電解用的擔持有觸媒之多孔質基體或水電解用電極。 Specifically, for example, in the conventional method of depositing a catalyst on a substrate in the form of a layer, the catalyst layer may potentially peel off from the substrate due to gas lift. However, according to the present invention, a method can be provided. A porous substrate or electrode for water electrolysis for water electrolysis that prevents the catalyst from peeling from the porous substrate or the catalyst is peeled from the material constituting the porous substrate.
此外，可提供一種使用該擔持有觸媒之多孔質基體(水電解用電極)之水電解用單一單元或水電解用堆疊單元。 In addition, a single unit for water electrolysis or a stacked unit for water electrolysis using the porous substrate (electrode for water electrolysis) supporting the catalyst can be provided.
再者，藉由使離子聚合物以在厚度方向具有濃度梯度之方式存在(或填充)於擔持有觸媒之多孔質基體，則可帶來單位電壓(施加電壓)的穩定低值，此外，可提供一種更不易產生由氣舉所造成之觸媒的剝離或觸媒的脫離之水電解用電極。 Furthermore, by allowing the ionic polymer to have a concentration gradient in the thickness direction (or filling) in the porous matrix supporting the catalyst, a stable low value of the unit voltage (applied voltage) can be brought about. In addition, , It can provide an electrode for water electrolysis that is less likely to cause the separation of the catalyst or the separation of the catalyst caused by gas lift.
此種「觸媒(膜或粒子)的脫離」尤其是可藉由前述「特定型態下之觸媒往多孔質基體的擔持」與上述「特定型態下之離子聚合物層的存在」的相乘性作用而有效地防止及抑制。 This kind of "catalyst (film or particle) detachment" can especially be achieved by the aforementioned "support of the catalyst in a specific type to the porous matrix" and the aforementioned "existence of an ionic polymer layer in a specific type" The synergistic effect of the anti-corrosion system can effectively prevent and suppress.
將本發明之擔持有觸媒之多孔質基體用作為水電解用電極，並依序具有水電解用陰極、高分子電解質膜(PEM)、水電解用陽極之水電解單一單元， 可在低電解電壓下進行水電解，且不會產生觸媒膜或觸媒粒子的剝離或脫離，所以耐久性極高。 The porous substrate supporting the catalyst of the present invention is used as an electrode for water electrolysis, and a single unit of water electrolysis having a cathode for water electrolysis, a polymer electrolyte membrane (PEM), and an anode for water electrolysis in sequence, Water electrolysis can be performed at a low electrolysis voltage without peeling or detachment of the catalyst film or catalyst particles, so the durability is extremely high.
此外，即使單位電壓(施加電壓)低，該單一單元亦會運作，所以積層2個以上之「使用該擔持有觸媒之多孔質基體的水電解用單一單元」而成之水電解用堆疊單元，即使施加電壓低亦會運作。亦即，在積層2個以上的水電解用單一單元之情形下，更可達到該「低電壓運作」的效果，並且能夠以更少的電力獲得更多的氫(及氧)。 In addition, even if the unit voltage (applied voltage) is low, the single cell will operate. Therefore, a stack of two or more "single cells for water electrolysis using the porous substrate supporting the catalyst" is stacked for water electrolysis. The unit will operate even if the applied voltage is low. That is, in the case of stacking two or more single cells for water electrolysis, the effect of "low voltage operation" can be achieved, and more hydrogen (and oxygen) can be obtained with less electricity.
1:水電解用單一單元 1: Single unit for water electrolysis
2:水電解用電極 2: Electrode for water electrolysis
3:擔持有觸媒之多孔質基體 3: Porous matrix that holds the catalyst
3c:金屬觸媒、金屬氧化物觸媒、觸媒 3c: Metal catalyst, metal oxide catalyst, catalyst
3p:多孔質基體 3p: porous matrix
3q:形成多孔質基體之纖維、纖維 3q: Fibers and fibers forming a porous matrix
4:離子聚合物 4: ionic polymer
5:高分子電解質膜(PEM) 5: Polymer electrolyte membrane (PEM)
6:供電體 6: Power supply
7:樹脂槽體 7: Resin tank
8:雙極板 8: Bipolar plate
9:水電解用堆疊單元 9: Stacking unit for water electrolysis
10:水電解用單元模組 10: Unit module for water electrolysis
圖1為具有水電解用單一單元之水電解用單元的概略展開立體圖。(a)為使用本發明之擔持有觸媒之多孔質基體(水電解用電極、氣體擴散層)的概略展開立體圖，(b)為歷來之水電解用單元的概略展開立體圖。 Fig. 1 is a schematic exploded perspective view of a unit for water electrolysis having a single unit for water electrolysis. (a) is a schematic development perspective view of a porous substrate (electrode for water electrolysis, gas diffusion layer) using the catalyst of the present invention, and (b) is a schematic development perspective view of a conventional unit for water electrolysis.
圖2為顯示觸媒的存在型態之水電解用單一單元的概略剖面圖。(a)為顯示本發明之擔持有觸媒之多孔質基體中之「觸媒往多孔質基體之擔持型態」的概略剖面圖，(b)及(c)為顯示歷來之觸媒的存在型態的概略剖面圖。 Fig. 2 is a schematic cross-sectional view of a single unit for water electrolysis showing the presence of a catalyst. (a) is a schematic cross-sectional view showing the "supporting state of the catalyst to the porous substrate" in the porous substrate holding the catalyst of the present invention, (b) and (c) are showing the historical catalyst A schematic cross-sectional view of the existence pattern of.
圖3為本發明之擔持有觸媒之多孔質基體的概略擴大剖面圖。 Fig. 3 is a schematic enlarged cross-sectional view of the porous substrate supporting the catalyst of the present invention.
圖4為顯示於本發明之擔持有觸媒之多孔質基體中，離子聚合物與接觸觸媒，且以從多孔質基體的表面朝向內部具有濃度梯度之狀態被填充的擴大剖面圖。(a)為對應於圖3的概略擴大剖面圖，(b)為顯示實際之擔持有觸媒之多孔質基體的剖面的SEM照片。 4 is an enlarged cross-sectional view showing that the ionic polymer and the contact catalyst are filled with a concentration gradient from the surface of the porous substrate toward the inside in the porous substrate supporting the catalyst of the present invention. (a) is a schematic enlarged cross-sectional view corresponding to FIG. 3, and (b) is an SEM photograph showing a cross-section of the actual porous substrate supporting the catalyst.
圖5為本發明之擔持有觸媒之多孔質基體(可為水電解用電極亦可為氣體擴散層)夾持高分子電解質膜(PEM)而成之本發明之水電解用單一單元的概略擴大剖面圖。 Figure 5 is a porous substrate (which can be an electrode for water electrolysis or a gas diffusion layer) of the present invention that holds a catalyst for sandwiching a polymer electrolyte membrane (PEM) of the single unit for water electrolysis of the present invention The cross-sectional view is roughly enlarged.
圖6為顯示以從水電解用電極(擔持有觸媒之多孔質基體)的表面朝向內部在厚度方向具有濃度梯度之狀態填充離子聚合物之樣態的一例之概略擴大剖面圖。(a)為以從接觸高分子電解質膜(PEM)與供電體之側的表面(亦即從兩面)朝向內部具有濃度梯度之狀態填充離子聚合物之樣態，(b)為以從接觸高分子電解質膜(PEM)之側的表面朝向內部具有濃度梯度之狀態填充離子聚合物之樣態。 Fig. 6 is a schematic enlarged cross-sectional view showing an example of a state in which an ion polymer is filled with a concentration gradient in the thickness direction from the surface of the electrode for water electrolysis (the porous substrate supporting the catalyst) toward the inside. (a) is a state in which ionic polymer is filled with a concentration gradient from the surface (that is, from both sides) on the side contacting the polymer electrolyte membrane (PEM) and the power supply body toward the inside, and (b) is the state in which the contact is high The surface on the side of the molecular electrolyte membrane (PEM) is filled with an ionic polymer in a state with a concentration gradient toward the inside.
圖7為積層2個本發明之水電解用單一單元而成之本發明之水電解用堆疊單元的概略展開立體圖。 Fig. 7 is a schematic exploded perspective view of the stacked unit for water electrolysis of the present invention in which two single units for water electrolysis of the present invention are stacked.
圖8為本發明之水電解用堆疊單元的概略圖。(a)為連接有配線與配管之堆疊單元的立體圖，(b)為顯示陰極側的「氫出口」與陽極側的「水入口」與「水出口兼氧出口」之概略剖面圖，(c)為省略配線與配管之堆疊單元的立體圖。 Fig. 8 is a schematic view of the stack unit for water electrolysis of the present invention. (a) is a perspective view of the stack unit connected with wiring and piping, (b) is a schematic cross-sectional view showing the "hydrogen outlet" on the cathode side and the "water inlet" and "water outlet and oxygen outlet" on the anode side, (c ) Is a perspective view of the stacking unit without wiring and piping.
圖9為三維地排列配置本發明之水電解用堆疊單元而成之水電解用單元模組的概略立體圖。 Fig. 9 is a schematic perspective view of a unit module for water electrolysis in which the stacked units for water electrolysis of the present invention are arranged three-dimensionally.
以下係說明本發明，惟本發明並不限定於下列的具體型態，在技術性思想的範圍內可任意地變形。 The following is an explanation of the present invention, but the present invention is not limited to the following specific forms, and can be arbitrarily modified within the scope of technical ideas.
<擔持有觸媒之多孔質基體> <Porous substrate holding catalyst>
本發明之擔持有觸媒之多孔質基體為具有下列構造之擔持有觸媒之多孔質基體：於水電解用單一單元中以夾持高分子電解質膜(PEM(Polymer Electrolyte Membrane))之方式存在，並接觸該高分子電解質膜(PEM)而構成陰極或陽極，且亦發揮氣體擴散層的機能之構造， The porous substrate supporting the catalyst of the present invention is a porous substrate supporting the catalyst having the following structure: a polymer electrolyte membrane (PEM (Polymer Electrolyte Membrane)), and contact the polymer electrolyte membrane (PEM) to form a cathode or anode, and also play the function of a gas diffusion layer.
該觸媒被擔持於該多孔質基體所具有之孔的側面或是形成該多孔質基體之纖維的側面，且以從該多孔質基體本身的表面涵蓋至內部之方式存在，並且 The catalyst is supported on the side surface of the pores of the porous matrix or the side surface of the fiber forming the porous matrix, and exists in a manner of covering from the surface of the porous matrix itself to the inside, and
離子聚合物接觸該觸媒，且以從該多孔質基體的表面朝向內部在該多孔質基體的厚度方向具有濃度梯度之狀態被填充。 The ionic polymer contacts the catalyst and is filled with a concentration gradient in the thickness direction of the porous substrate from the surface of the porous substrate toward the inside.
本發明之擔持有觸媒之多孔質基體係使用在「水電解用單一單元」或「積層2個以上的該水電解用單一單元而成之水電解用堆疊單元」(以下有時將兩者統稱為「水電解用單元」)。 The porous base system supporting the catalyst of the present invention is used in "single unit for water electrolysis" or "stacked unit for water electrolysis formed by stacking two or more single units for water electrolysis" (hereinafter sometimes two These are collectively referred to as "units for water electrolysis").
如圖1(a)、圖2(a)、圖5等所記載，本發明之擔持有觸媒之多孔質基體3在水電解用單一單元1中，係以夾持高分子電解質膜(PEM)5之方式存在，並接觸該高分子電解質膜(PEM)5來構成水電解用電極2(陰極或陽極)。
As shown in Fig. 1(a), Fig. 2(a), Fig. 5, etc., the
於本發明中，水電解用單一單元1的陰極或陽極必須是由本發明之擔持有觸媒之多孔質基體3所構成，較佳係陰極與陽極皆由本發明之擔持有觸媒之多孔質基體3所構成。
In the present invention, the cathode or anode of the
惟陰極與陽極中之實際的觸媒3c、多孔質基體3p等的種類或型態，甚至其製造方法等，於陰極與陽極中可根據各自的極性而相異。
However, the type or type of the
本發明之擔持有觸媒之多孔質基體3係具有發揮水電解用電極2的機能，且亦發揮氣體擴散層的機能之構造。因此，本發明之擔持有觸媒之多孔質基體3亦為氣體擴散層。
The
如圖3、圖4(a)、(b)及圖5的剖面圖所示，本發明之擔持有觸媒之多孔質基體3係於可進行氣體的擴散之多孔質擔持體上擔持有觸媒。亦即，於擔持有觸媒
之多孔質基體3的觸媒附近所產生之氣體係由於該擔持有觸媒之多孔質基體本身亦發揮氣體擴散層的機能，所以使氣體移動(擴散)而擷取至外部。
As shown in the cross-sectional views of Figures 3, 4(a), (b) and Figure 5, the
《多孔質基體》 "Porous Matrix"
於本發明中所謂「多孔質」，意指(具有)可擔持觸媒至內部為止之構造(的性質)，並不限定於僅在平面(上表面)上形成開孔之型態，而是有藉由化學性或物理性蝕刻、濺鍍等形成糙面化之狀態；多孔狀態；成為有空間狀態等之型態；纖維狀者之聚集體；編物、織物、不織布的狀態等之全部者。上述「孔」或「纖維狀者構成聚集體所形成之空隙」亦可在厚度方向形成不規則的空隙。此外，「多孔質」亦可稱為具有透氣性之狀態或性質。 In the present invention, the term "porous" means (has) a structure (property) capable of supporting the catalyst to the inside, and is not limited to the type where openings are formed only on the plane (upper surface), and It is a state that is roughened by chemical or physical etching, sputtering, etc.; a porous state; a form that has a space state, etc.; a fibrous aggregate; a state of knitted fabric, fabric, non-woven fabric, etc. By. The above-mentioned "pores" or "voids formed by the fibrous ones constituting aggregates" may also form irregular voids in the thickness direction. In addition, "porous" can also be referred to as a state or property with air permeability.
圖3為賦予離子聚合物4前的概略剖面圖，左圖為賦予觸媒前，右圖為賦予觸媒後，惟本發明之多孔質基體3p只要是具有不僅於外部，亦可擔持觸媒至內部為止之空間即可，可為具有所謂貫穿孔者(惟並非排除獨立孔的存在者)，亦可為編織纖維者或是不織布等。例如，不織布等之纖維的聚集體亦於該纖維間的間隙存在有孔，所以於本發明中廣義而言係稱為「多孔質基體」。
Fig. 3 is a schematic cross-sectional view before the
如圖3至圖5所示，由於本發明之特徵在於觸媒(觸媒粒子或觸媒膜)以從多孔質基體3p本身的表面涵蓋至內部之方式存在，且其特徵在於離子聚合物4以從多孔質基體3p本身的表面涵蓋至內部之方式存在，所以本發明之多孔質基體3p必須具有觸媒或離子聚合物4可進入至(可賦予至)其內部為止之空隙。
As shown in Figures 3 to 5, the present invention is characterized in that the catalyst (catalyst particles or catalyst film) is present in a manner that covers the surface of the
本發明之多孔質基體3p的材質只要是具有導電性即可，並無特別限定，較佳係具有電子傳導性、不易腐蝕(氧化等)、不易受到各種化學反應或
電化學反應、強度高等之性質者，具體而言，較佳為鈦族金屬、鈦族金屬的合金、鈦族金屬的化合物或是碳(C)。
The material of the
在此所謂「鈦族金屬」，意指鈦、鋯或鉿。亦即，鈦族的基體可列舉出：鈦基體、鋯基體、鉿基體、鈦合金基體、鋯合金基體或鉿合金基體。 The so-called "titanium group metal" here means titanium, zirconium or hafnium. That is, the matrix of the titanium group includes a titanium matrix, a zirconium matrix, a hafnium matrix, a titanium alloy matrix, a zirconium alloy matrix, or a hafnium alloy matrix.
此外，「鈦族金屬的化合物」例如可列舉出：氮化鈦(鈦氮化物(TiN))、碳化鈦(鈦碳化物(TiC))、二硼化鈦(鈦二硼化物(TiB2))等。 In addition, "compounds of titanium group metals" include, for example, titanium nitride (titanium nitride (TiN)), titanium carbide (titanium carbide (TiC)), and titanium diboride (titanium diboride (TiB 2 ) )Wait.
從單元電壓低且較佳地防止觸媒粒子從電極基材中脫離者來看，鈦族的金屬或合金尤佳為鈦或鈦合金，特佳為鈦。 From the viewpoint of low cell voltage and better prevention of catalyst particles from detaching from the electrode substrate, the metal or alloy of the titanium group is particularly preferably titanium or a titanium alloy, and particularly preferably titanium.
此外，碳(C)較佳係具有石墨結構(石墨烯結構)。 In addition, carbon (C) preferably has a graphite structure (graphene structure).
本發明之多孔質基體3p特佳為鈦纖維或鈦合金纖維的聚集體，或是碳纖維的聚集體。
The
《觸媒》 "catalyst"
於本發明中，觸媒係如前述般以從多孔質基體3p本身的表面涵蓋至內部之方式存在，具體而言，該觸媒被擔持於該多孔質基體3p所具有之孔的側面或是形成該多孔質基體3p之纖維3q的側面，且以從該多孔質基體3p本身的表面涵蓋至內部之方式存在(圖3至圖5)。
In the present invention, the catalyst is present so as to cover from the surface of the
圖5為本發明之擔持有觸媒之多孔質基體3的概略剖面圖，碳纖維、鈦纖維等之纖維3q係構成多孔質基體3p，不僅該多孔質基體3p本身的表面之纖維3q的表面，觸媒粒子亦被擔持至該多孔質基體3p本身的內部之纖維3q的表面為止。
Fig. 5 is a schematic cross-sectional view of the
上述所謂「多孔質基體本身的表面」為相對於「多孔質基體本身的內部」之用語，因此，上述「多孔質基體本身的表面」並非意指多孔質基體3p所具有之孔的側面或是構成多孔質基體3p之材料(纖維等)的表面。
The above-mentioned "surface of the porous substrate itself" is a term relative to the "inside of the porous substrate itself." Therefore, the above-mentioned "surface of the porous substrate itself" does not mean the side surface of the pores of the
於本發明中，上述觸媒較佳係並非僅堆積於多孔質基體3p本身的表面作為觸媒層，而是被擔持於上述多孔質基體3p所具有之孔的側面或是形成上述多孔質基體3p之纖維3q的側面，且以從上述多孔質基體3p本身的表面涵蓋至內部之方式存在(圖3至圖5)。
In the present invention, it is preferable that the catalyst is not only deposited on the surface of the
於觸媒以觸媒層的型態，換言之，觸媒以層的型態如圖2(b)所示般僅存在(形成或堆積)於高分子電解質膜(PEM)5的表面，或是如圖2(c)所示般僅存在(形成或堆積)於多孔質基體3p本身的表面時，觸媒與多孔質基體3p之接觸面積變小，此外，觸媒與高分子電解質膜(PEM)5之接觸面積變小，因此無法得到前述本發明之優異效果。
The catalyst is in the form of a catalyst layer, in other words, the catalyst is only present (formed or accumulated) on the surface of the polymer electrolyte membrane (PEM) 5 as shown in Figure 2(b), or As shown in Figure 2(c), when only (formed or deposited) on the surface of the
本發明之擔持有觸媒之多孔質基體3較佳係具有下列構成，亦即藉由使金屬觸媒或金屬觸媒前驅物附著於焙燒前的多孔質基體3p所具有之孔的側面或是形成焙燒前的多孔質基體3p之纖維3q的側面並進行焙燒之步驟而得到之構成。
The
於本發明之上述較佳樣態中，觸媒以何種型態及組成形成於多孔質基體3p或是觸媒粒子以何種型態來擔持等，不論是直接具體指定或是以參數等來具體指定者，皆無法達成或不切實際。因此，上述較佳構成(樣態)僅能藉由該製造方法來具體指定。
In the above-mentioned preferred aspect of the present invention, the type and composition of the catalyst formed on the
具體而言，本發明之觸媒較佳係將溶解或微分散有「金屬觸媒或金屬觸媒前驅物」之塗佈液予以塗佈於多孔質基體3p，接著將此進行焙燒而藉此形成並得到。
Specifically, the catalyst of the present invention is preferably to apply a coating solution in which "metal catalyst or metal catalyst precursor" is dissolved or finely dispersed on the
亦即，本發明之觸媒特佳係藉由塗佈液的塗佈及乾燥，使「金屬觸媒或金屬觸媒前驅物」附著於多孔質基體3p之孔的側面或纖維3q的側面，接著進行焙燒而得到。
That is, the catalyst of the present invention is particularly preferred to attach the "metal catalyst or metal catalyst precursor" to the side surface of the hole of the
在此，塗佈的方法並無特別限定，可列舉出：經噴霧器之噴霧塗佈、浸漬塗佈、筆刷塗佈、刷毛塗刷塗佈、經網版印刷之塗佈等。塗佈後可視需要依循常用方法進行乾燥以餾除塗佈溶劑。 Here, the coating method is not particularly limited, and examples include spray coating via a sprayer, dip coating, brush coating, brush coating, and screen printing coating. After coating, it can be dried according to common methods as needed to distill off the coating solvent.
於附著後所進行之「焙燒」，廣泛而言意指一般的熱處理。焙燒溫度係取決於觸媒(前驅物)的種類，並無特別限定，較佳為160℃以上800℃以下，尤佳為230℃以上750℃以下，特佳為300℃以上700℃以下。 The "baking" performed after the attachment means a general heat treatment in a broad sense. The firing temperature depends on the type of catalyst (precursor) and is not particularly limited. It is preferably 160°C or higher and 800°C or lower, particularly preferably 230°C or higher and 750°C or lower, and particularly preferably 300°C or higher and 700°C or lower.
焙燒時間(熱處理時間)只要是可達到觸媒效果即可，並無特別限定，較佳為10分鐘以上8小時以下，尤佳為30分鐘以上5小時以下，特佳為1小時以上3小時以下。 The roasting time (heat treatment time) is not particularly limited as long as it can achieve the catalytic effect. It is preferably 10 minutes or more and 8 hours or less, particularly preferably 30 minutes or more and 5 hours or less, and particularly preferably 1 hour or more and 3 hours or less .
焙燒時間為上述下限以上時，可得到與上述焙燒溫度為前述下限以上時為相同之效果，焙燒時間為上述上限以下時，可得到與上述焙燒溫度為前述上限以下時為相同之效果，可較佳地擔持觸媒。 When the calcination time is above the above lower limit, the same effect as when the above calcination temperature is above the above lower limit can be obtained. When the calcination time is below the above upper limit, the same effect can be obtained as when the above calcination temperature is below the above upper limit. Support the catalyst well.
如圖2(b)所示，在觸媒存在於高分子電解質膜(PEM)5上之型態的情形下欲藉由焙燒來擔持觸媒時，由於高分子電解質膜(PEM)5的耐熱性差，所以於上述焙燒溫度下會熔解或變質。因此於圖2(b)所示之型態的情形下，無法藉由焙燒來生成觸媒。 As shown in Figure 2 (b), when the catalyst is present on the polymer electrolyte membrane (PEM) 5, when the catalyst is to be supported by firing, due to the polymer electrolyte membrane (PEM) 5 It has poor heat resistance, so it melts or deteriorates at the above-mentioned firing temperature. Therefore, in the case of the type shown in Figure 2(b), the catalyst cannot be generated by firing.
根據本發明，由於可使金屬觸媒或金屬觸媒前驅物附著於(一般而言具有耐熱性較強的傾向之)多孔質基體3p並進行焙燒而得到(擔持於此之)觸媒，所以與僅進行塗佈及乾燥並進行焙燒之情形相比，往多孔質基體3p之密著性增高，可利用優異樣態及組成的觸媒，並且可使用之觸媒的範圍更寬廣。
According to the present invention, since a metal catalyst or a metal catalyst precursor can be attached to the
於本發明中，有時會因為焙燒而使構成多孔質基體3p的孔之部分的體積產生變化，使孔變大，或是構成多孔質基體3p之纖維3q的粗度變細。反而在引起此現象時，使觸媒容易被擔持於「多孔質基體所具有之孔的側面或是形成該多孔質基體之纖維3q的側面」，於觸媒為粒子之情形下，尺寸上可變得更充裕而使觸媒容易以從多孔質基體3p本身的表面涵蓋至內部之方式緩慢地(均一地)存在(擔持)。
In the present invention, the volume of the pores constituting the
再者，後述離子聚合物4有時容易以從多孔質基體3p的表面朝向內部在該多孔質基體3p的厚度方向具有濃度梯度之狀態被填充。
In addition, the
本發明之擔持有觸媒之多孔質基體3較佳係使金屬觸媒或金屬觸媒前驅物附著於多孔質基體3p並進行焙燒而得到，該金屬觸媒或金屬觸媒前驅物中的金屬只要是焙燒此而成之觸媒粒子或觸媒膜發揮觸媒的作用即可，並無特別限定。當中從觸媒效果高之點來看，較佳為選自由鉑(Pt)、釕(Ru)、銥(Ir)、鈀(Pd)、鉭(Ta)及鎳(Ni)所組成之群組中的金屬。上述金屬可為1種或併用2種以上。此外，亦可與上述以外的金屬併用。
The
換言之，本發明之觸媒較佳為選自由鉑(Pt)、釕(Ru)、銥(Ir)、鈀(Pd)、鉭(Ta)及鎳(Ni)所組成之群組中之1種以上的金屬或含金屬之化合物。 In other words, the catalyst of the present invention is preferably one selected from the group consisting of platinum (Pt), ruthenium (Ru), iridium (Ir), palladium (Pd), tantalum (Ta) and nickel (Ni) The above metals or metal-containing compounds.
屬於觸媒的原料之金屬觸媒/金屬觸媒前驅物中的金屬化合物並不限定於下列所示者，具體而言例如可列舉出：氯鉑(IV)酸n水合物、氯鉑(IV) 酸銨、二硝基二氨鉑(II)、二氯化鉑(II)、四氯化鉑(IV)、二氯化四氨鉑(II)n水合物、氫氧化四氨鉑(II)、六羥基鉑(IV)酸等含鉑化合物；氯化釕(III)水合物、硝酸釕(III)、氧化釕(IV)水合物等含釕化合物；氯銥(IV)酸n水合物、氯化銥(III)n水合物、氯化銥(III)無水物、硝酸銥(IV)、氯銥(IV)酸銨、氫氧化六氨銥(III)等含銥化合物；氯化鈀(II)、硝酸鈀(II)、二硝基二氨鈀(II)、乙酸鈀(II)、二氯化四氨鈀(II)等含鈀化合物；氯化鎳(II)無水物、氯化鎳(II)六水合物、硝酸鎳(II)六水合物等含鎳化合物；五氯化鉭、烷氧化鉭等。 The metal compound in the metal catalyst/metal catalyst precursor that is the raw material of the catalyst is not limited to those shown below. Specifically, for example, chloroplatin (IV) acid n hydrate, chloroplatin (IV) ) Ammonium acid, dinitrodiammine platinum (II), platinum dichloride (II), platinum tetrachloride (IV), tetraammine platinum (II) n hydrate, tetraammine platinum (II) , Hexahydroxyplatinum(IV) acid and other platinum-containing compounds; ruthenium(III) chloride hydrate, ruthenium(III) nitrate, ruthenium(IV) oxide hydrate and other ruthenium-containing compounds; chloroiridium(IV) acid n-hydrate, Iridium(III) chloride n hydrate, iridium(III) chloride anhydrate, iridium(IV) nitrate, ammonium chloride(IV) ammonium, hexaamine iridium(III) hydroxide and other iridium-containing compounds; Palladium chloride( II), palladium nitrate (II), dinitrodiamine palladium (II), palladium acetate (II), tetraammonium palladium (II) and other palladium compounds; nickel chloride (II) anhydrous, chlorinated Nickel-containing compounds such as nickel (II) hexahydrate and nickel nitrate (II) hexahydrate; tantalum pentachloride, tantalum alkoxide, etc.
金屬觸媒前驅物並無特別限定，具體而言例如可列舉出醇配位於上述金屬化合物者等。特佳係將上述金屬化合物溶解於醇溶劑等以調製金屬觸媒前驅物，然後將含有該金屬觸媒前驅物之塗佈液塗佈於多孔質基體3p並使之乾燥，然後進行焙燒以轉換為觸媒並擔持而調製出擔持有觸媒之多孔質基體3。
The metal catalyst precursor is not particularly limited. Specifically, for example, an alcohol coordinated to the above-mentioned metal compound can be mentioned. It is particularly preferred to dissolve the above-mentioned metal compound in an alcohol solvent to prepare a metal catalyst precursor, and then apply a coating solution containing the metal catalyst precursor to the
在藉由塗佈使金屬觸媒或金屬觸媒前驅物往多孔質基體3p附著之情形下，「使用於該塗佈之塗佈液的溶劑(分散介質)」及/或上述「配位於金屬化合物之醇」較佳可列舉出：甲醇、乙醇、丙醇、異丙醇、丁醇、戊醇、己醇、環己醇等。
In the case of attaching a metal catalyst or a metal catalyst precursor to the
在藉由塗佈來進行往多孔質碳基體之附著的情形下，塗佈液的塗佈方法並無限定，惟較佳方法可列舉出：刷毛塗刷法、噴霧法、噴霧塗佈法、浸漬法等。 In the case of adhesion to the porous carbon substrate by coating, the coating method of the coating liquid is not limited, but preferred methods include: brushing method, spray method, spray coating method, Impregnation method, etc.
此外，例如圖3、圖4所示，觸媒可以膜的型態擔持於孔的側面或是纖維3q的側面，或是例如圖5所示，可以粒子的狀態擔持於孔的側面或是纖維3q的側面。
In addition, for example, as shown in Figures 3 and 4, the catalyst can be supported on the side of the hole or the side of the
通常，銥(Ir)、鉭(Ta)等是以膜的形式擔持於孔或是纖維3q的側面等，鉑(Pt)等是以粒子的形式擔持於孔或是纖維3q的側面等。
Generally, iridium (Ir), tantalum (Ta), etc. are supported on the side of the hole or
觸媒粒子的平均粒徑因觸媒種類的不同而不同，並無特別限定，以數量平均粒徑計較佳為300μm以下，尤佳為200μm以下，特佳為100μm以下。本發明之該數量平均粒徑係可藉由掃描式電子顯微鏡(SEM：Scanning Electron Microscope)來觀察焙燒後所得到之擔持有觸媒之多孔質的剖面，隨機選擇20個觸媒粒子並得到該直徑的加算平均值，然後以如此得到之直徑的加算平均值來定義。 The average particle size of the catalyst particles differs depending on the type of the catalyst and is not particularly limited. The number average particle size is preferably 300 μm or less, particularly preferably 200 μm or less, and particularly preferably 100 μm or less. The number-average particle size of the present invention can be observed by scanning electron microscope (SEM: Scanning Electron Microscope) to observe the cross section of the porous material holding the catalyst obtained after firing, and 20 catalyst particles are randomly selected and obtained The average value of the diameter is then defined by the average value of the diameter thus obtained.
觸媒粒子的平均粒徑過大時，觸媒效果降低，有時使單元電壓上升或是從電極基材中脫離。 When the average particle size of the catalyst particles is too large, the catalyst effect is reduced, which may increase the cell voltage or detach from the electrode substrate.
再者，除此之外，於本發明之情形時，如後述般尤其是觸媒粒子難以進入至多孔質基體3p的內部，有時難以擔持在多孔質基體3p的內部。
Furthermore, in addition to this, in the case of the present invention, as described later, in particular, it is difficult for the catalyst particles to enter the inside of the
另一方面，平均粒徑過小時，有時會從多孔質基體3p之孔的側面或是纖維3q的側面潛入至微觀的深部等。惟若可藉由使複數個微小粒子相鄰接及鍵結來增大觸媒表面積，則不一定需位於上述粒徑範圍。
On the other hand, if the average particle size is too small, it may infiltrate from the side surface of the pores of the
所謂「單元電壓」，意指為了進行水的電分解而施加於水電解單元的陰極與陽極之間之電解電壓。 The so-called "cell voltage" refers to the electrolysis voltage applied between the cathode and anode of a water electrolysis cell for the electrolysis of water.
在觸媒以膜的型態被擔持於多孔質基體3p之孔的側面或是纖維3q的側面之情形下，該膜的平均膜厚因觸媒種類的不同而不同，並無特別限定，惟較佳為50μm以下，尤佳為40μm以下，特佳為30μm以下。該平均膜厚可藉由掃描式電子顯微鏡(SEM)來觀察焙燒後所得到之擔持有觸媒之多孔質的剖面而得到，然後以如此得到者來定義。
In the case where the catalyst is supported on the side surface of the pores of the
《離子聚合物》 "Ionic Polymer"
本發明之擔持有觸媒之多孔質基體3較佳係於鄰接於高分子電解質膜(PEM)5之側存在有離子聚合物4。
The
在此，「離子聚合物」亦稱為陽離子交換聚合物、於側鏈具有強酸基之聚合物、質子傳導性聚合物、離子傳導性聚合物等，所謂「離子聚合物」，意指具有上述化學結構或物性之聚合物。 Here, "ionic polymer" is also referred to as a cation exchange polymer, a polymer having a strong acid group in the side chain, a proton conductive polymer, an ion conductive polymer, etc. The so-called "ionic polymer" means having the above Polymers of chemical structure or physical properties.
例如，碳纖維、鈦纖維等的聚集體之多孔質基體3p的上表面原先並不平坦(圖2(a)、圖3至圖5)，所以與高分子電解質膜(PEM)5之接觸有時會不足，因此，觸媒與高分子電解質膜(PEM)之接觸有時亦不足。
For example, the upper surface of the
此外，於本發明中，由於觸媒亦存在於多孔質基體3p的內部，再者亦有大量的觸媒存在於多孔質基體3p的內部，若無離子聚合物4，則觸媒與高分子電解質膜(PEM)之接觸會變得更不足。
In addition, in the present invention, since the catalyst also exists inside the
根據本發明，在如圖2(a)、圖3至圖6所示之樣態中，由於存在離子聚合物4，所以存在於多孔質基體3p本身的內部以及多孔質基體3p與高分子電解質膜(PEM)之間的空隙被埋填，使此等之間的接觸達到良好，並且離子聚合物4與觸媒之接觸以及高分子電解質膜(PEM)5與觸媒之接觸達到良好。
According to the present invention, in the configuration shown in Fig. 2(a) and Figs. 3 to 6, due to the presence of the
於本發明之擔持有觸媒之多孔質基體中，離子聚合物4係接觸所擔持之觸媒，且以從該多孔質基體3p的表面朝向內部在該多孔質基體3p的厚度方向具有濃度梯度之狀態被填充(參考圖2(a)、圖4至圖6)。
In the porous substrate supporting the catalyst of the present invention, the
離子聚合物的濃度高之方向為擔持有觸媒之多孔質基體之與高分子電解質膜(PEM)5接觸的一側(圖6(b))，除此之外，較佳亦於該相反側，亦即與供電體6
接觸之一側的濃度亦高，且以從該表面朝向內部在該多孔質基體3p的厚度方向具有濃度梯度之狀態被填充(圖6(a))。
The direction in which the concentration of the ionic polymer is high is the side of the porous matrix supporting the catalyst that is in contact with the polymer electrolyte membrane (PEM) 5 (Figure 6(b)). In addition, it is also preferable to The opposite side, that is, with the
從接觸的必要性來看，以離子聚合物4來包圍觸媒膜或觸媒粒子者於本發明中為重要。再者，該離子聚合物4係以在多孔質基體3p的厚度方向具有濃度梯度之狀態被填充。
In view of the necessity of contact, it is important in the present invention to surround the catalyst film or the catalyst particles with the
如圖6(b)所示，於(擔持有觸媒之)多孔質基體3p的深部(亦即，與高分子電解質膜(PEM)5接觸之一側為相反側)的附近，離子聚合物4可不存在或較少，再者，從穿透性之點來看，較佳係具有不存在離子聚合物4之部分或較少之部分。
As shown in Fig. 6(b), near the deep part of the
此外，如圖6(a)所示，於(擔持有觸媒之)多孔質基體3p的深部(亦即遠離與PEM5及供電體6之接觸面的部分)的附近，離子聚合物4可不存在或較少，再者，從穿透性之點來看，較佳係具有不存在離子聚合物4之部分或較少之部分。
In addition, as shown in FIG. 6(a), in the vicinity of the deep portion (that is, the portion away from the contact surface with the PEM5 and the power supply body 6) of the
如前述般，為了調製觸媒而進行焙燒，惟在構成多孔質基體3p之纖維3q變細之情形等，係變得更不易接觸，例如圖5所示，於離子聚合物4接觸觸媒3c且以從多孔質基體3p的表面朝向內部具有濃度梯度之狀態存在時，擔持有觸媒之多孔質基體(的觸媒3c)與高分子電解質膜(PEM)5之接觸變得極為良好。
As mentioned above, firing is performed to prepare the catalyst, but when the
亦即，該離子聚合物4係具有將「氫離子(質子)往陰極側」傳導之機能，並藉由存在於擔持有觸媒之多孔質基體3之鄰接於高分子電解質膜(PEM)5的一側，可大幅地降低將質子從高分子電解質膜(PEM)5往觸媒表面傳導時的電阻。
That is, the
因此，藉由使該離子聚合物4朝向擔持有觸媒之多孔質基體3的內部填充，可將在「無法與高分子電解質膜(PEM)直接接觸之『供電體及/或樹脂槽體側的觸媒』」中所產生之質子往陰極側傳導，而提高觸媒的利用效率。
Therefore, by filling the
其結果為，在以本發明之上述樣態來填充離子聚合物4並以電流值為一定之條件下進行運轉時，即使單元電壓(電解電壓)低，亦使水電解單元運作，並且抑制由所產生之氣體所造成之觸媒粒子的脫離。
As a result, when the
該離子聚合物4的存在量係伴隨著擔持有觸媒之多孔質基體3的厚度或空隙度，以及水電解用單元的使用條件，例如每單位時間的產生氫量而變化，並無特別限定，惟伴隨著水電解而產生氣體且需將該氣體擷取至外部，所以微觀上較佳係不藉由離子聚合物4較厚地被覆觸媒表面全部，而是使觸媒表面就微觀上部分地暴露出，宏觀上較佳係不藉由離子聚合物4來填充擔持有觸媒之多孔質基體3所具有之空隙全部，而是以在該擔持有觸媒之多孔質基體3的厚度方向具有濃度梯度之狀態被填充，並排出所產生的氣體。
The amount of the
由於需從供電體6及/或樹脂槽體7側擷取所產生的氣體，為了更有效率地擷取氣體，較佳係於「高分子電解質膜(PEM)」與「供電體6及/或樹脂槽體7」之間使離子聚合物4的存在量具有斜率。
Since it is necessary to extract the generated gas from the side of the
因此，雖無特別限定，惟於該擔持有觸媒之多孔質基體3所具有之空隙體積中，藉由離子聚合物4來填充該空隙之體積的比率(以下有時稱為「填充率」)較佳為10體積%以上90體積%以下，尤佳為20體積%以上80體積%以下，特佳為30體積%以上70體積%以下。
Therefore, although not particularly limited, in the void volume of the
亦即，本發明亦為：於上述擔持有觸媒之多孔質基體3的空隙內注入上述離子聚合物4，並且於該擔持有觸媒之多孔質基體3所具有之空隙體積
中，藉由該離子聚合物4來填充空隙之比率為10體積%以上90體積%以下之上述擔持有觸媒之多孔質基體3。
That is, the present invention is also: the
該離子聚合物4的上述效果不論是對於水電解用陰極或水電解用陽極的任一電極，皆可較佳地達成(參考圖5)。
The above-mentioned effects of the
離子聚合物4的填充例如可將離子聚合物分散液或離子聚合物溶液塗佈於擔持有觸媒之多孔質基體3p來形成。
The filling of the
本發明亦為：在將上述觸媒擔持於上述多孔質基體3p後，塗佈該離子聚合物4的溶液並使之乾燥，以從該多孔質基體3p的表面朝向內部具有濃度梯度之方式填充上述離子聚合物4而得到之上述擔持有觸媒之多孔質基體3。
The present invention is also: after the catalyst is supported on the
可從與高分子電解質膜(PEM)5接觸之一側來塗佈，而得到如圖6(b)般之具有濃度梯度之擔持有觸媒之多孔質基體3，或是進一步在此之後，亦從與供電體6接觸之一側來塗佈，而得到如圖6(a)般之於兩側具有濃度梯度之擔持有觸媒之多孔質基體3。
It can be coated from the side in contact with the polymer electrolyte membrane (PEM) 5 to obtain a catalyst-supporting
於本發明之較佳樣態中，離子聚合物4以何種質量及型態填充於多孔質基體3p，或是以何種樣態接觸觸媒等，不論是直接具體指定或是以參數等來具體指定，皆無法達成或幾乎不切實際。因此，上述較佳樣態(構成)僅能藉由該製造方法來具體指定。
In a preferred aspect of the present invention, the quality and type of the
塗佈方法可列舉出：刷毛塗刷法、噴霧法、噴霧塗佈法等。 Examples of the coating method include a brushing method, a spray method, and a spray coating method.
在塗佈離子聚合物分散液(離子聚合物溶液)後，於60℃左右使溶劑(分散介質)揮發，較佳於120℃以上250℃以下，特佳於140℃以上200℃以下，且較佳以1分鐘以上1小時以下，特佳以3分鐘以上30分鐘以下進行熱處理。 After coating the ionic polymer dispersion (ionic polymer solution), volatilize the solvent (dispersion medium) at about 60°C, preferably above 120°C and below 250°C, particularly preferably above 140°C and below 200°C, and more The heat treatment is preferably carried out in 1 minute or more and 1 hour or less, and particularly preferably in 3 minutes or more and 30 minutes or less.
《離子聚合物的化學結構》 "Chemical Structure of Ionomers"
上述離子聚合物4只要是具有離子傳導性，尤其是質子傳導性，且可在水電解用單一單元1中使用即可，並無特別限定。亦即，所謂本發明之「離子聚合物」，意指質子傳導性聚合物。
The above-mentioned
該離子聚合物4並無特別限定，可為於分子內具有氟原子之氟系離子聚合物4，或是於分子內不具有氟原子之非氟系離子聚合物4。
The
雖無特別限定，惟當中較佳為氟系離子聚合物，尤佳為具有聚氟乙烯骨架作為主鏈，且於末端具有磺酸基作為側鏈之具有全氟乙烯醚骨架之離子傳導性聚合物(質子傳導性聚合物)。 Although not particularly limited, fluorine-based ionic polymers are preferred, and ion-conducting polymers having a perfluorovinyl ether skeleton having a polyvinyl fluoride skeleton as the main chain and a sulfonic acid group as a side chain at the end are particularly preferable.物(Proton Conductive Polymer).
雖無特別限定，惟本發明中所使用之尤佳的離子聚合物4的例子係顯示如下。
Although not particularly limited, examples of particularly preferred
該式(1)中，m為自然數。 In this formula (1), m is a natural number.
該式(2)中，p為自然數。 In this formula (2), p is a natural number.
該式(3)中，n為自然數。 In this formula (3), n is a natural number.
以式(1)所表示之離子聚合物是由：作為主鏈的聚四氟乙烯(PTFE：Polytetrafluoroethylene)骨架、以及於末端具有磺酸基之全氟醚懸垂側鏈所構成之聚合物。由於側鏈相對較長，故亦稱為長側鏈(LSC：long-side-chain)離子聚合物。 The ionic polymer represented by formula (1) is a polymer composed of a polytetrafluoroethylene (PTFE: Polytetrafluoroethylene) skeleton as the main chain and a perfluoroether pendant side chain having a sulfonic acid group at the end. Because the side chain is relatively long, it is also called long-side-chain (LSC: long-side-chain) ionic polymer.
以式(1)所表示之離子聚合物的等效質量(EW：equivalent weight)(供給1莫耳的質子所需之聚合物的質量)並無限定，特佳為900g/mol至1200g/mol。式(1)之m的較佳範圍為可從該等效質量來計算之範圍。 The equivalent weight (EW: equivalent weight) of the ionic polymer represented by formula (1) (the weight of the polymer required to supply 1 mol of proton) is not limited, and is particularly preferably 900g/mol to 1200g/mol . The preferable range of m in formula (1) is a range that can be calculated from the equivalent mass.
以式(1)所表示之長側鏈(LSC)離子聚合物並無限定，可較佳地使用市售品，可列舉出Du Pont公司製的Nafion(註冊商標)等。 The long side chain (LSC) ionic polymer represented by the formula (1) is not limited, and commercially available products can be preferably used, and examples include Nafion (registered trademark) manufactured by Du Pont Co., Ltd. and the like.
以式(1)所表示之長側鏈(LSC)離子聚合物之較佳為Nafion(註冊商標)(EW=1100g/mol、式(1)的m=6.6)等。 The long side chain (LSC) ionic polymer represented by the formula (1) is preferably Nafion (registered trademark) (EW=1100 g/mol, m=6.6 in the formula (1)) and the like.
以式(2)或式(3)所表示之離子聚合物是由：作為主鏈的聚四氟乙烯(PTFE)骨架、以及於末端具有磺酸基之全氟懸垂側鏈所構成之聚合物。由於側鏈相對較短，故亦稱為短側鏈(SSC：short-side-chain)離子聚合物。 The ionic polymer represented by formula (2) or formula (3) is a polymer composed of a polytetrafluoroethylene (PTFE) skeleton as the main chain and a perfluoro pendant side chain with a sulfonic acid group at the end . Because the side chain is relatively short, it is also called short-side-chain (SSC: short-side-chain) ionic polymer.
以式(2)或式(3)所表示之離子聚合物的等效質量(EW)並無限定，特佳為700g/mol至950g/mol。式(2)之p的較佳範圍與式(3)之n的較佳範圍為可從該等效質量來計算之範圍。 The equivalent mass (EW) of the ionic polymer represented by formula (2) or formula (3) is not limited, and is particularly preferably 700 g/mol to 950 g/mol. The preferable range of p in formula (2) and the preferable range of n in formula (3) are ranges that can be calculated from the equivalent mass.
以式(2)或式(3)所表示之短側鏈(SSC)離子聚合物並無限定，可較佳地使用市售品，例如可列舉出3M Corporation公司製的3M離子聚合物等。 The short side chain (SSC) ionic polymer represented by formula (2) or formula (3) is not limited, and commercially available products can be preferably used. For example, 3M ionic polymer manufactured by 3M Corporation can be cited.
〈「觸媒的膜厚或粒徑」與「多孔質基體的空隙」之關係〉 "The relationship between "the film thickness or particle size of the catalyst" and "the voids of the porous matrix">
本發明之擔持有觸媒之多孔質基體3中，擔持於多孔質基體3p之觸媒的膜厚或粒徑較佳係小於「由孔及/或纖維之間的間隙所形成之空隙」的平均口徑長。於較大之情形下，觸媒有時難以較佳地擔持於構成多孔質基體3p之材料。
In the
此外，上述空隙雖是藉由焙燒等而擔持觸媒後之多孔質基體3p所具有的空隙，惟藉由焙燒等而擔持觸媒前之多孔質基體3p所具有的空隙，較佳亦大於擔持所得到之觸媒的大小(膜厚或粒徑)。於較小之情形下，溶解或微分散於觸媒塗佈液中之「金屬觸媒或金屬觸媒前驅物」有時難以進入至該多孔質內部，其結果有時無法使觸媒以從多孔質基體3p本身的表面涵蓋至內部之方式存在。
In addition, although the above-mentioned voids are voids of the
此外，本發明之擔持有觸媒之多孔質基體中，排除離子聚合物4之擔持有觸媒之多孔質基體3之以下述定義式(1)所表示的空隙率較佳為3體積%以上80體積%以下。
In addition, in the porous matrix supporting the catalyst of the present invention, the
空隙率(體積%)=100×[擔持有觸媒之多孔質基體之空隙的體積]/[擔持有觸媒之多孔質基體的體積] (1) Porosity (volume %)=100×[volume of the void of the porous substrate holding the catalyst]/[volume of the porous substrate holding the catalyst] (1)
由於所謂「擔持有觸媒之多孔質基體」意指已擔持有觸媒者，所以在藉由焙燒來進行觸媒的擔持之情形下，上述「空隙率」的「空隙」意指焙燒後之多孔質基體3p的空隙。
Since the so-called "porous matrix supporting the catalyst" means the one that already holds the catalyst, when the catalyst is supported by firing, the "void" of the above-mentioned "void ratio" means The voids of the
由於觸媒粒子(觸媒膜)的體積與上述空隙的體積相比非常小，所以「多孔質基體的空隙」幾乎與「擔持有觸媒之多孔質基體的空隙」相等。 Since the volume of the catalyst particles (catalyst film) is very small compared to the volume of the above-mentioned voids, the "voids of the porous substrate" are almost equal to the "voids of the porous substrate holding the catalyst".
上述定義式(1)的分子可測定擔持有觸媒之多孔質基體3的重量與體積，並使用材質(Ti、C等)的真比重來計算，且由於分母亦容易測定，所以上述空隙率可如此地求取並以如此地求取者來定義。
The molecule of the above definition formula (1) can be used to measure the weight and volume of the
該空隙率較佳係在賦予(填充)離子聚合物4之前測定。
The void ratio is preferably measured before the
該空隙率尤佳為5體積%以上70體積%以下，特佳為10體積%以上60體積%以下。 The void ratio is particularly preferably from 5 vol% to 70 vol%, and particularly preferably from 10 vol% to 60 vol%.
空隙率過小時，難以擔持觸媒，有時無法擔持至多孔質基體3p的內部。此外，離子聚合物溶液/分散液難以流入至多孔質基體3p的內部，有時無法將離子聚合物4填充至多孔質基體3p的內部，或是無法以在多孔質基體3p的厚度方向具有濃度梯度之狀態被填充等。此外，氣體的擴散性變差，作為氣體擴散層的機能有時會惡化。
If the porosity is too small, it is difficult to support the catalyst, and sometimes it cannot be supported to the inside of the
另一方面，空隙率過大時，擔持有觸媒之多孔質基體3的強度有時會降低，或是導電度有時會降低。
On the other hand, when the porosity is too large, the strength of the
本發明之擔持有觸媒之多孔質基體3中，「『以從多孔質基體本身的表面涵蓋至內部之方式存在之觸媒』接觸上述離子聚合物之微觀面積」的總和，較佳為「擔持有觸媒之多孔質基體3之接觸上述高分子電解質膜(PEM)5之面的宏觀面積」之2倍以上。將上述倍率稱為「接觸面積倍率」。
In the
上述微觀面積係藉由掃描式電子顯微鏡(SEM)來觀察填充離子聚合物後之擔持有觸媒之多孔質基體3的剖面，並從當中之觸媒的剖面可算出(計算)觸媒的表面積，未填充離子聚合物4之擔持有觸媒之多孔質基體3的內部之觸媒的表面(積)係被排除在該微觀面積之外。
The above-mentioned microscopic area is observed by scanning electron microscope (SEM) to observe the cross section of the
上述宏觀面積例如在擔持有觸媒之多孔質基體3為長方形之情形下，可將其縱長與橫長相乘而求取。
The above-mentioned macroscopic area can be obtained by multiplying the vertical length and the horizontal length, for example, when the
上述「接觸面積倍率」係將上述微觀面積除以上述宏觀面積來求取，所以可以如此求取之值來定義。 The above-mentioned "contact area magnification" is obtained by dividing the above-mentioned microscopic area by the above-mentioned macroscopic area, so it can be defined by the value obtained in this way.
該接觸面積倍率尤佳為3倍以上，更佳為4倍以上300倍以下，特佳為5倍以上100倍以下。 The contact area magnification is particularly preferably 3 times or more, more preferably 4 times or more and 300 times or less, and particularly preferably 5 times or more and 100 times or less.
該接觸面積倍率過小時，有時無法得到前述各種「離子聚合物4的(填充)效果」，過大時，有時難以製造擔持有觸媒之多孔質基體3。
If the contact area ratio is too small, the aforementioned various "(filling) effects of the
〈水電解用電極〉 <Electrode for Water Electrolysis>
如前述般，本發明亦為一種水電解用電極2，其特徵係本發明之上述擔持有觸媒之多孔質基體3。
As described above, the present invention is also an
此外，如前述般，本發明亦為一種氣體擴散層，其特徵係本發明之上述擔持有觸媒之多孔質基體3。
In addition, as described above, the present invention is also a gas diffusion layer, which is characterized by the
亦即如前述般，從本發明之擔持有觸媒之多孔質基體3所具有的型態與機能來看，本發明之擔持有觸媒之多孔質基體3亦可發揮水電解用電極2的機能來使用，此外，本發明之擔持有觸媒之多孔質基體3亦可發揮氣體擴散層的機能來使用。
That is, as described above, in view of the type and function of the
〈水電解用單一單元〉 〈Single unit for water electrolysis〉
本發明亦為一種水電解用單一單元1，其特徵係具有藉由本發明之上述擔持有觸媒之多孔質基體3夾持高分子電解質膜(PEM)5而成之構造。
The present invention is also a
如圖1(a)中顯示其一例般，本發明之水電解用單一單元1係具有藉由本發明之擔持有觸媒之多孔質基體3夾持高分子電解質膜(PEM)5而成之構造，且進一步具體而言以墊片、供電體6、樹脂槽體7等來夾持此而成。此外，本發明之水電解用單一單元1係藉由上述構造體來夾持圖5般的擔持有觸媒之多孔質基體3(水電解用電極)而成。
As shown in Figure 1(a) as an example, the
該供電體6、該樹脂槽體7等之構造體並無特別限定，可使用一般所知者。
The structure of the
圖7顯示連結了2個本發明之水電解用單一單元之水電解用堆疊單元9，其右側與左側分別為水電解用單一單元1。
Fig. 7 shows a
本發明之水電解用單一單元1的發明除了上述者或圖示者之外，並不排除其他層或其他構件/構造體等之使用(併用)。
The invention of the
〈水電解用堆疊單元〉 <Stacking unit for water electrolysis>
本發明亦為一種水電解用堆疊單元9，其係在以藉由擔持有觸媒之多孔質基體3夾持高分子電解質膜(PEM)5之構造作為1個水電解用單一單元1時，係積層2個以上之上述水電解用單一單元1而成。
The present invention is also a
圖7顯示本發明之水電解用堆疊單元9的概略。如圖7所示，本發明之水電解用堆疊單元9係藉由上述本發明之水電解用單一單元1夾持雙極板8而構成。
Fig. 7 shows the outline of the
本發明之水電解用堆疊單元9係積層2個以上之本發明之水電解用單一單元而成，較佳係積層3個以上10個以下而成，特佳係積層4個以上6個以下而成。
The
積層個數過少時，水電解效率(氫產生效率)有時會惡化，另一方面，積層個數過多時，水電解所需之電壓有時會增大等。 When the number of layers is too small, the water electrolysis efficiency (hydrogen generation efficiency) may deteriorate. On the other hand, when the number of layers is too large, the voltage required for water electrolysis may increase.
如前述般，使用了本發明之擔持有觸媒之多孔質基體3的水電解用單一單元1的特徵在於單元電壓小，故即使串聯複數個水電解用單一單元1，亦可壓低水電解用堆疊單元9之陰極與陽極間的電解電壓。
As mentioned above, the
本發明之水電解用堆疊單元9的發明除了上述者或圖示者之外，並不排除其他層或其他構件/構造體等之使用(併用)。
The invention of the
圖8(a)、(b)為顯示於本發明之水電解用堆疊單元9上更設置有陰極配線、陽極配線、水入口、水出口、氫排出配管(氫出口)、氧排出配管(氧出口)等之概念圖。水出口與氧排出配管(氧出口)可為同一者(共用)。
8(a) and (b) show that the
〈水電解用單元模組〉 〈Unit module for water electrolysis〉
本發明亦為一種水電解用單元模組10，其特徵係二維或三維地排列配置上述水電解用堆疊單元9而成。
The present invention is also a
圖9為顯示三維地排列配置本發明之水電解用堆疊單元9而成之水電解用單元模組10的概略立體圖。
FIG. 9 is a schematic perspective view showing the
藉由構成為水電解用單元模組10的型態，可有效率地電解多量的水而得到多量的氫或氧。
By being configured as the
此外，如圖9所示，亦可裝設設置板，並僅抽出一部分的水電解用堆疊單元9來進行更換或維護或是停止通電(設定停電期間)，而能夠提高運轉的效率。
In addition, as shown in FIG. 9, a setting board may be installed, and only a part of the
本發明之水電解用單元模組10的發明除了上述者或圖示者之外，並不排除添加於此等之其他構件等之使用(併用)。
The invention of the
[實施例] [Example]
以下係列舉實施例及比較例等來更具體地說明本發明，惟本發明在不脫離其主旨下，並不限定於此等實施例。 The following series of examples and comparative examples will illustrate the present invention more specifically, but the present invention is not limited to these examples without departing from the spirit thereof.
以下在無特別言明時，與比或%相關之值為質量比或質量%。 Below, unless otherwise stated, the value related to ratio or% is mass ratio or mass %.
實施例1 Example 1
〈擔持有觸媒之多孔質基體、水電解用電極的製造〉 <Manufacturing of porous substrates that hold catalysts and electrodes for water electrolysis>
使用噴霧器，將含有氯銥(IV)酸六水合物作為金屬觸媒(金屬前驅物)之醇系的塗佈液，以不會產生不均之方式塗佈於使纖維徑50μm的鈦纖維如平板般地聚集體化之多孔質基體3p來作為觸媒。
Using a sprayer, apply an alcohol-based coating solution containing chloroiridium (IV) acid hexahydrate as a metal catalyst (metal precursor) to a titanium fiber with a fiber diameter of 50μm in a manner that does not cause unevenness. The
此時已確認到塗佈液從多孔質基體3p本身的表面滲入至內部之模樣。
At this time, it was confirmed that the coating liquid penetrated into the inside from the surface of the
接著為了使塗佈液的溶劑揮發，係於70℃將多孔質基體加熱30分鐘以進行乾燥。為了提升金屬觸媒3c與多孔質基體之材質的面(纖維的側面)之密著性，係以較上述乾燥時的溫度更高之溫度的600℃加熱2小時以進行熱處理。
Next, in order to volatilize the solvent of the coating liquid, the porous substrate was heated at 70°C for 30 minutes to dry it. In order to improve the adhesion between the
藉由掃描式電子顯微鏡(SEM)來觀察所得到之「離子聚合物填充前的擔持有觸媒之多孔質基體」，係如圖2至圖4所示，銥觸媒被擔持於形成多孔質基體3p之鈦纖維的側面，並且以從該多孔質基體3p本身的表面涵蓋至內部被覆鈦纖維之方式，以外套狀而存在。該觸媒的膜厚為0.3μm至10μm。
Observed by scanning electron microscope (SEM) the "porous matrix supporting the catalyst before ionic polymer filling", as shown in Figures 2 to 4, the iridium catalyst is supported in the formation The side surface of the titanium fiber of the
使用噴霧器，從與PEM接觸之一側將離子聚合物(Du Pont公司製的Nafion(註冊商標))的分散液塗佈於上述擔持有金屬觸媒3c之多孔質基體3p。
Using a sprayer, a dispersion liquid of an ionic polymer (Nafion (registered trademark) manufactured by Du Pont) was applied to the
此時已確認到此分散液從擔持有觸媒之多孔質基體3的表面滲入至內部之模樣。
At this time, it was confirmed that the dispersion liquid penetrated into the inside from the surface of the
接著為了使離子聚合物分散液的分散介質揮發，係於100℃將擔持有觸媒之多孔質基體3加熱30分鐘以進行乾燥。
Next, in order to volatilize the dispersion medium of the ionic polymer dispersion, the
藉由掃描式電子顯微鏡(SEM)來觀察所得到之「離子聚合物填充後的擔持有觸媒之多孔質基體」，係如圖4、圖5所示，可確認到離子聚合物4接觸屬於觸媒的銥，且以從多孔質基體3p的表面朝向內部在厚度方向具有濃度梯度之狀態被填充(尤其參考圖4(b)、圖6(b))。
Observed by scanning electron microscope (SEM), the obtained "porous matrix supporting catalyst after ionomer filling" is shown in Figures 4 and 5. It can be confirmed that the
所得到之「離子聚合物填充後的擔持有觸媒之多孔質基體」的空隙率為40體積%，接觸面積率為10倍，「由構成多孔質基體之纖維之間的間隙所形成之空隙」的平均口徑長為25μm至50μm。 The porosity of the obtained "porous matrix supporting the catalyst filled with ionic polymer" has a porosity of 40% by volume and a contact area ratio of 10 times. "It is formed by the gaps between the fibers constituting the porous matrix. The average aperture length of the voids is 25 μm to 50 μm.
實施例2 Example 2
於實施例1中，除了使用由碳纖維所構成之多孔質基體3p來取代由鈦纖維所構成之多孔質基體3p之外，其他與實施例1相同而得到擔持有觸媒之多孔質基體3(水電解用電極2)。
In Example 1, except that a
途中已確認到觸媒的塗佈液從多孔質基體3p本身的表面滲入至內部之模樣。
On the way, it was confirmed that the coating liquid of the catalyst penetrated into the inside from the surface of the
此外，途中已確認到離子聚合物分散液從擔持有觸媒之多孔質基體3的表面滲入至內部之模樣。
In addition, it was confirmed that the ionic polymer dispersion liquid penetrated into the inside from the surface of the
藉由掃描式電子顯微鏡(SEM)來觀察所得到之擔持有觸媒之多孔質基體3，可得知銥觸媒被擔持於形成多孔質基體3p之碳纖維的側面，並且以從該多孔質基體3p本身的表面涵蓋至內部之方式存在。
Observing the obtained
此外，可確認到離子聚合物4接觸觸媒，且以從多孔質基體3p的表面朝向內部在厚度方向具有濃度梯度之狀態被填充(尤其參考圖4(b)、圖6(b))。
In addition, it was confirmed that the
實施例3 Example 3
於實施例1中，除了使用鉑觸媒來取代銥觸媒之外，其他與實施例1相同而得到擔持有觸媒之多孔質基體3(水電解用電極2)。
In Example 1, except that a platinum catalyst was used instead of the iridium catalyst, the porous substrate 3 (
途中已確認到觸媒的塗佈液從多孔質基體3p本身的表面滲入至內部之模樣。
On the way, it was confirmed that the coating liquid of the catalyst penetrated into the inside from the surface of the
此外，途中已確認到離子聚合物分散液從擔持有觸媒之多孔質基體3的表面滲入至內部之模樣。
In addition, it was confirmed that the ionic polymer dispersion liquid penetrated into the inside from the surface of the
藉由掃描式電子顯微鏡(SEM)來觀察所得到之擔持有觸媒之多孔質基體3，可得知鉑觸媒被擔持於形成多孔質基體3p之鈦纖維的側面，並且以從該多孔質基體3p本身的表面涵蓋至內部之方式存在。
Observing the obtained
此外，可確認到離子聚合物4接觸觸媒，且以從多孔質基體3p的表面朝向內部在厚度方向具有濃度梯度之狀態被填充(尤其是圖5、圖6(b))。
In addition, it was confirmed that the
比較例1 Comparative example 1
於實施例1中，除了使用由空隙率為1體積%的鈦纖維所構成之基體作為(多孔質)基體之外，其他與實施例1相同而得到水電解用電極2(觸媒層形成基體)。
In Example 1, except that a matrix composed of titanium fibers with a porosity of 1% by volume was used as a (porous) matrix, the same as in Example 1 was used to obtain an
用作為(多孔質)基體之由空隙率為1體積%的鈦纖維所構成之基體，由於該孔(空隙)較金屬觸媒粒子小，所以觸媒的塗佈液難以從多孔質基體3p本身的表面滲入至內部。
As a (porous) substrate, a substrate composed of titanium fibers with a porosity of 1% by volume. Since the pores (voids) are smaller than metal catalyst particles, it is difficult for the catalyst coating liquid to escape from the
藉由掃描式電子顯微鏡(SEM)來觀察所得到之水電解用電極2，可得知觸媒並不存在於多孔質基體3p本身的內部，而是在(多孔質)基體上形成觸媒層。亦即成為「多孔質基體\金屬觸媒層\離子聚合物層」之層構成。
Observing the obtained
比較例2 Comparative example 2
於實施例1中，除了不填充離子聚合物4，亦即不塗佈離子聚合物4的分散液之外，其他與實施例1相同而得到擔持有觸媒之多孔質基體3。
In Example 1, except that the
藉由掃描式電子顯微鏡(SEM)來觀察所得到之擔持有觸媒之多孔質基體3，可得知雖然觸媒存在至多孔質基體3p本身的內部，但由於未填充離子聚合物4，所以觸媒呈孤立。
Observing the obtained
比較例3 Comparative example 3
使用歷來的膜電極接合體(MEA)作為水電解用電極。 A conventional membrane electrode assembly (MEA) was used as an electrode for water electrolysis.
所使用之膜電極接合體(MEA)分別於PEM的單面上塗佈碳粒子與「成為觸媒之鉑粒子」，於另一單面上塗佈「成為觸媒之氧化銥粒子」後，進行乾燥以固定。 The membrane electrode assembly (MEA) used is coated with carbon particles and "catalyst platinum particles" on one side of the PEM, and "catalyst iridium oxide particles" are coated on the other side. Dry to fix.
評估例1 Evaluation example 1
〈水電解用單一單元的組裝〉 <Assembly of a single unit for water electrolysis>
以圖1(a)所示之構成來組裝水電解用單一單元1。
The
具體而言，將高分子電解質膜(PEM)配置在中央，並於該兩外側配置上述實施例中所得到之「具有金屬觸媒3c與離子聚合物4之擔持有觸媒之多孔質基體3(水電解用電極2)」或比較例中所得到之水電解用電極。
Specifically, a polymer electrolyte membrane (PEM) is placed in the center, and the porous matrix that has a
再者，於該兩側配置供電體6且更於該兩外側配置樹脂槽體7後，藉由螺栓來鎖固該兩端以夾入各構成物，而組裝水電解用單一單元1。
Furthermore, after disposing the
〈依據水電解試驗所進行之初期性能評估〉 <Initial performance evaluation based on water electrolysis test>
藉由泵使溫度20℃的純水循環於上述實施例及比較例中所得到之水電解用單一單元1，將電解用的純水供給至該水電解用單元的陽極側，並使用直流電源來記錄既定的電流密度下之水電解時的單元電壓之值。
The pure water at a temperature of 20°C was circulated in the
100A/dm2的電流密度下之初期單元電壓(V)係如下列表1所示。 The initial cell voltage (V) at a current density of 100A/dm 2 is shown in Table 1 below.
〈依據水電解試驗所進行之水電解用單一單元的耐久性評估〉 <Durability evaluation of a single unit for water electrolysis based on the water electrolysis test>
與上述初期性能評估相同，使純水循環並供給至水電解用單一單元1，使用直流電源以使電流密度成為100A/dm2之方式來設定電流值，連續地進行電解並記錄單元電壓。
As in the initial performance evaluation described above, pure water was circulated and supplied to the
經過500小時後的單元電壓[V]係如下列表2所示。 The cell voltage [V] after 500 hours is shown in Table 2 below.
評估例2 Evaluation example 2
〈水電解用堆疊單元的組裝〉 <Assembly of stack unit for water electrolysis>
以圖7所示之構成來堆疊水電解用單一單元1以組裝水電解用堆疊單元9。
The
具體而言，以「擔持有觸媒之多孔質基體(陽極)/高分子電解質膜(PEM)/擔持有觸媒之多孔質基體(陰極)」作為1個水電解用單一單元1，並隔著雙極板8來重疊(堆疊)5個該單一單元彼此，而構成1個水電解用堆疊單元9。於圖7中係重疊2個單一單元，於評估例2中則重疊5個。
Specifically, "Porous substrate supporting catalyst (anode)/Polymer electrolyte membrane (PEM)/Porous substrate supporting catalyst (cathode)" is used as a
〈水電解用堆疊單元的初期性能評估〉 〈Initial performance evaluation of stacking unit for water electrolysis〉
藉由泵使溫度20℃的純水循環於如上述般地重疊5個「前述實施例及比較例中所得到之水電解用單一單元」後之水電解用堆疊單元9，將電解用的純水供給至水電解用單元的陽極側(參考圖8)，並使用直流電源來記錄既定的電流密度下之水電解時的堆疊單元電壓之值。
The pure water at a temperature of 20°C was circulated by a pump in the
100A/dm2的電流密度下之初期堆疊單元電壓係如下列表3所示。 The initial stack cell voltage at a current density of 100A/dm 2 is shown in Table 3 below.
〈水電解用堆疊單元的耐久性評估〉 <Durability Evaluation of Stacked Units for Water Electrolysis>
使用如評估例2般地重疊實施例1中所得到之擔持有觸媒之多孔質基體3(水電解用電極2)所得到的水電解用堆疊單元9，於電流值呈一定的條件下連續地進行水的電解，並記錄堆疊單元電壓的變化。
Using the
經過500小時後的堆疊單元電壓與初期的堆疊單元電壓相比雖稍微地上升，但為單一單元之對應於表2的等級，故無特別問題。 The stack cell voltage after 500 hours has risen slightly compared to the initial stack cell voltage, but the single cell corresponds to the level in Table 2, so there is no particular problem.
水電解用單一單元的初期性能評估(初期單元電壓) Initial performance evaluation of a single cell for water electrolysis (initial cell voltage)
[表1]
水電解用單一單元的耐久性評估(經過500小時後之單元電壓) Durability evaluation of a single cell for water electrolysis (cell voltage after 500 hours)
[表2]
水電解用堆疊單元9的初期性能評估(初期堆疊單元電壓)
Initial performance evaluation of
[表3]
從表1至表3中，可得知使用本發明之擔持有觸媒之多孔質基體3之水電解用電極2、水電解用單一單元1及水電解用堆疊單元9，於水電解的開始時，單元電壓(必要施加電壓)為穩定低值。
From Tables 1 to 3, it can be seen that the
此外，於耐久試驗後亦可維持該值。 In addition, this value can be maintained after the endurance test.
另一方面，比較例之水電解用電極2、水電解用單一單元1及水電解用堆疊單元9於水電解的開始時，單元電壓(必要施加電壓)高，於耐久試驗後亦為高值。
On the other hand, the
即使是使用實施例2、3中所得到之擔持有觸媒之多孔質基體3，亦與實施例1相同，單元電壓為穩定低值。亦即，初期單元電壓、經過500小時後的單元電壓、初期堆疊單元電壓以及經過500小時後的堆疊單元電壓，係與實施例1之表1至表3的結果幾乎相同，其電壓較低。
Even if the
[產業上之可應用性] [Industrial Applicability]
本發明之擔持有觸媒之多孔質基體3係具有作為水電解用電極或氣體擴散層的優異特性，使用其之水電解單一單元或積層該單一單元之水電解用堆疊單元9的單元電壓低，防止觸媒從電極基材中脫離且製造性和耐久性優異，所以被廣泛地利用在需用到氫或氧之所有領域。
The
2:水電解用電極 2: Electrode for water electrolysis
3:擔持有觸媒之多孔質基體 3: Porous matrix that holds the catalyst
3c:金屬觸媒或金屬氧化物觸媒 3c: Metal catalyst or metal oxide catalyst
3q:形成多孔質基體之纖維 3q: Fiber forming a porous matrix
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