JPWO2016063922A1 - 燃料電池用電極触媒層及びその製造方法、膜電極接合体並びに固体高分子形燃料電池 - Google Patents
燃料電池用電極触媒層及びその製造方法、膜電極接合体並びに固体高分子形燃料電池 Download PDFInfo
- Publication number
- JPWO2016063922A1 JPWO2016063922A1 JP2016555263A JP2016555263A JPWO2016063922A1 JP WO2016063922 A1 JPWO2016063922 A1 JP WO2016063922A1 JP 2016555263 A JP2016555263 A JP 2016555263A JP 2016555263 A JP2016555263 A JP 2016555263A JP WO2016063922 A1 JPWO2016063922 A1 JP WO2016063922A1
- Authority
- JP
- Japan
- Prior art keywords
- catalyst layer
- fuel cell
- catalyst
- supported
- granulated product
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 179
- 239000000446 fuel Substances 0.000 title claims abstract description 59
- 239000012528 membrane Substances 0.000 title claims description 36
- 229920000642 polymer Polymers 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000007787 solid Substances 0.000 title claims description 12
- 238000000034 method Methods 0.000 claims abstract description 75
- 239000002245 particle Substances 0.000 claims abstract description 60
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 57
- 239000011148 porous material Substances 0.000 claims abstract description 43
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 22
- 238000009826 distribution Methods 0.000 claims abstract description 21
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 14
- 210000004027 cell Anatomy 0.000 claims description 59
- 238000010304 firing Methods 0.000 claims description 35
- 239000002243 precursor Substances 0.000 claims description 33
- 239000005518 polymer electrolyte Substances 0.000 claims description 30
- 238000005469 granulation Methods 0.000 claims description 24
- 230000003179 granulation Effects 0.000 claims description 24
- 239000008187 granular material Substances 0.000 claims description 19
- 229910052715 tantalum Inorganic materials 0.000 claims description 13
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 12
- 238000002459 porosimetry Methods 0.000 claims description 6
- 239000010411 electrocatalyst Substances 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 210000000170 cell membrane Anatomy 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 73
- 239000000047 product Substances 0.000 description 48
- 229910052697 platinum Inorganic materials 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000000976 ink Substances 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 238000009792 diffusion process Methods 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000084 colloidal system Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229920000557 Nafion® Polymers 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000003411 electrode reaction Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229920001940 conductive polymer Polymers 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 125000006850 spacer group Chemical group 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000002737 fuel gas Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000010248 power generation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000000366 colloid method Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000005660 hydrophilic surface Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910003437 indium oxide Inorganic materials 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
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- DPUUHRCXEPJVAT-UHFFFAOYSA-N [Ta].[Sb] Chemical compound [Ta].[Sb] DPUUHRCXEPJVAT-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 239000010953 base metal Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 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
- 239000012698 colloidal precursor Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- UYXRCZUOJAYSQR-UHFFFAOYSA-N nitric acid;platinum Chemical compound [Pt].O[N+]([O-])=O UYXRCZUOJAYSQR-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940068107 nitrogen 100 % Drugs 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical class [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920005649 polyetherethersulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 150000003481 tantalum Chemical class 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
-
- 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
- B01J37/02—Impregnation, coating or precipitation
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
- H01M4/8626—Porous electrodes characterised by the form
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/881—Electrolytic membranes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6486—Tantalum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0211—Impregnation using a colloidal suspension
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Fuel Cell (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
Description
前記多孔質構造の細孔径分布を水銀圧入法で測定したとき、0.005μm以上0.1μm以下の範囲にピークが観測されるとともに、0.1μm超1μm以下の範囲にもピークが観察され、
0.005μm以上0.1μm以下の範囲のピーク強度をP1とし、0.1μm超1μm以下の範囲のピーク強度をP2としたとき、P2/P1の値が0.2以上10以下である燃料電池用電極触媒層を提供するものである。ここでいうピーク強度とはピークの高さのことである。
前記造粒物を焼成して前記前駆体を無機酸化物に変化させ、
焼成後の前記造粒物に触媒を担持させて、触媒担持造粒物を得、
前記触媒担持造粒物を含むインクの塗布によって燃料電池用電極触媒層を形成する、燃料電池用電極触媒層の製造方法を提供するものである。
前記造粒物に触媒を担持させて、触媒担持造粒物を得、
前記触媒担持造粒物を含むインクの塗布によって燃料電池用電極触媒層を形成する、燃料電池用電極触媒層の製造方法を提供するものである。
<水銀圧入法による細孔径分布の測定方法>
例えば株式会社島津製作所社製のAutoPore IV Model9520を用いて測定する。詳細にはJIS R 1655に従って、例えば粉状の測定サンプルをサンプルセルに投入し、0から60000psi(4137kPa)まで連続的に圧力を加えてサンプルの細孔に圧入された水銀の量を静電容量から見積もり、細孔径と細孔容積の関係を得る。
(1)カソード用の電極触媒層の形成
(イ)無機酸化物の前駆体粒子の製造工程
148gのNa2SnO3を1630gの純水に溶解させて、スズ含有水溶液を調製した。この操作とは別に、5.1gのTaCl5を140mLのエタノールに溶解したタンタル含有溶液を調製し、このタンタル含有溶液を硝酸水溶液(116gの硝酸を1394gの純水に溶解)と混合した。混合後の液に、前記のスズ含有水溶液を添加し混合撹拌した。撹拌を1時間継続した後に撹拌を停止し、12時間静置した。これによって、タンタルを含有するスズ酸化物の前駆体が生成・沈殿した。液を濾過し、固形物を水洗した後、60℃で乾燥させた。乾燥後の前駆体を、大気雰囲気下に450℃で5時間焼成した。
焼成後の前駆体粒子を、メノウ乳鉢で粗砕して平均粒径を100μm以下になるようにし、次いでイットリウム安定化ジルコニア製のボールを使用してボールミルで粉砕した。ボールミルによる粉砕においては、焼成後の前駆体粒子40gを、純水700mL及びエタノール40gと混合してスラリーとなし、このスラリーを粉砕に用いた。粉砕後、スラリーとボールとを分離し、分離されたスラリーを用いて噴霧乾燥法による造粒を行い造粒物を得た。造粒条件は、入口温度:220℃、出口温度60℃、噴霧圧力:0.15−0.2MPa、送液速度:8.3mL/分、スラリー濃度:10g/250mLとした。
得られた造粒物を大気雰囲気下に、680℃、5時間の条件で焼成を行った。これによって、前記前駆体から、タンタル含有スズ酸化物を生成させた。このときのタンタル含有スズ酸化物造粒物は、平均粒子径が2.68μmの略球状であり、体積抵抗率は57.3MPa圧力下で5.23×103Ω・cmであった。体積抵抗率は圧粉抵抗測定システム(三菱化学アナリテックMCP−PD41)と抵抗測定器(三菱化学アナリテックMCP−T610)を用いて測定した。
工程(ハ)で得られたタンタル含有スズ酸化物造粒物に白金を担持させた。担持は、特開2006−79904号公報の実施例に記載の方法に従った。具体的には次のとおりである。まず塩化白金酸を用いて、白金1gを含有する白金コロイド溶液を調製した。これに還元剤として亜硫酸水素ナトリウムを加え、純水で希釈後5%水酸化ナトリウム水溶液を加えてpHを5にした。更にコロイド凝集防止のため過酸化水素水を滴下した。液性は5%水酸化ナトリウム水溶液を用いてpH5を維持した。これにより得たコロイド溶液に造粒物を分散し白金コロイドを吸着させた後、濾過・洗浄・乾燥し白金担持造粒物を得た。その後4体積%H2/N2の弱還元雰囲気下で2時間にわたり熱処理を行った。白金の担持量は分析の結果7.5%であった。なお担持量は質量基準で〔白金/(白金+造粒物)〕×100と定義する。
白金を担持した造粒物1.24gを容器に入れ、更に純水、エタノール及びイソプロパノールを35:45:20の質量比(混合液として1.61g)で順に加えた。このようにして得られたインクを、超音波で3分間にわたり分散した。次いで、直径10mmのイットリウム安定化ジルコニア製ボールを容器内に入れ、遊星ボールミル(シンキーARE310)で800rpmで20分間撹拌した。更にインクに5%ナフィオン(登録商標)(274704−100ML、Aldrich社製)を加え、超音波分散と遊星ボールミルにより前記と同様な撹拌を行った。ナフィオンの添加量は、ナフィオン/造粒物の質量比が0.074となるような量とした。このようにして得られたインクを、ポリ四フッ化エチレンのシート上にバーコーターを用いて塗工し、塗膜を60℃で乾燥させた。
田中貴金属社製の白金担持カーボンブラック(TEC10E50E)1.00gを容器に入れ、更に純水、エタノール及びイソプロパノールを45:35:20の質量比(混合液として12.8g)で順に加えた。このようにして得られたインクを、超音波で3分間にわたり分散した。次いで、直径10mmのイットリウム安定化ジルコニア製ボールを容器内に入れ、遊星ボールミル(シンキーARE310)によって800rpmで20分間撹拌した。更にインクに5%ナフィオン(登録商標)(274704−100ML、Aldrich社製)を加え、超音波分散と遊星ボールミルにより前記と同様な撹拌を引き続き行った。ナフィオンの添加量は、ナフィオン/白金担持カーボンブラックの質量比が0.70となるような量とした。このようにして得られたインクを、ポリ四フッ化エチレンのシート上にバーコーターを用いて塗工し、塗膜を60℃で乾燥させた。
得られたカソード用及びアノード用電極触媒層付ポリ四フッ化エチレンのシートを54mm四方の正方形状に切り出し、ナフィオン(登録商標)(NRE−212、Du−Pont社製)の電解質膜と重ね合わせ、140℃、25kgf/cm2の条件下に2分間大気中で熱プレスし、転写を行った。このようにして、ナフィオンからなる固体高分子電解質膜の各面にカソード及びアノード触媒層を形成した。得られたカソード触媒層の厚み方向断面における走査電子顕微鏡像を図4に示す。また、得られたカソード触媒層の細孔径分布は、カソード用電極触媒層付ポリ四フッ化エチレンのシートを用いて、上述した<水銀圧入法による細孔径分布の測定方法>に記載の方法で測定した。その結果を表1及び図5に示す。電極触媒層における白金の量は、カソード触媒層では0.088mg−Pt/cm2でアノード触媒層では0.080mg−Pt/cm2であった。
前記(3)で得られたCCM及びJARI標準セルを用いて燃料電池を組み立てた。ガス拡散層としてSIGRACET(登録商標)25BCH(SGL社製)を用いた。また、ガスケットとして、Si/PEN/Si(180μm)を用いた。
実施例1において、(ロ)の造粒工程を行わなかった。これ以外は実施例1と同様にして燃料電池を得た。このときのタンタル含有スズ酸化物の体積抵抗率は57.3MPa圧力下において5.33×102Ω・cmであった。これに白金を担持したものの白金担持量は分析の結果7.4%であった。電極触媒層における白金の量は、カソード触媒層では0.078mg−Pt/cm2で アノード触媒層では0.067mg−Pt/cm2であった。燃料電池におけるカソード触媒層の細孔径分布を、上述の方法で測定した。その結果を表1及び図6に示す。
実施例1においてカソードにも白金担持カーボンブラック(TEC10E50E)を用いた。これ以外は実施例1と同様にして燃料電池を組み立てた。電極触媒層における白金の量はカソード触媒層では0.071mg−Pt/cm2で アノード触媒層では0.070mg−Pt/cm2であった。
実施例1及び比較例1で得られた燃料電池について、発電特性を評価した。燃料電池のアノード及びカソードに、80℃に加熱し、100%RHに加湿した窒素を流通させて安定化した後、加湿した水素をアノードに供給するとともに、加湿した空気をカソードに供給した。加湿の程度は30%RH、53%RH及び100%RHとした。この条件下で発電特性(電流−電圧特性)を測定した。そして測定結果からIRフリーでの最大出力、すなわち燃料電池セルの内部抵抗による電圧低下を差し引くことで補正した出力を算出した。その結果を表1に示す。
実施例1において、本製造方法の(ロ)前駆体粒子の造粒物の製造工程及び(ハ)造粒物の焼成工程の各工程において、送液速度、スラリー濃度、焼成温度条件を変えて、担体であるタンタル含有酸化スズの平均粒子径及び体積抵抗率を、以下の表2に示す値とした。また、MEAにおけるカソード触媒層及びアノード触媒層の白金担持量を、以下の表2に示す値とした。これら以外は実施例1と同様にして燃料電池を得た。
実施例2ないし6で得られた燃料電池について、実施例1と同様にして水銀圧入法で第1ピーク及び第2ピークを測定した。また、実施例1と同様にして100%RH下での発電特性(電流−電圧特性)を測定した。そして測定結果からIRフリーでの最大出力を差し引くことで補正した出力を算出した。更に、電流密度0.02A/cm2でのセル電圧を測定した。これらの結果を以下の表3に示す。同表には、先に述べた実施例1、比較例1及び参考例の結果も併せて記載されている。
Claims (11)
- 触媒が無機酸化物粒子の担体に担持されており、多孔質構造を有する燃料電池用電極触媒層であって、
前記多孔質構造の細孔径分布を水銀圧入法で測定したとき、0.005μm以上0.1μm以下の範囲にピークが観測されるとともに、0.1μm超1μm以下の範囲にもピークが観察され、
0.005μm以上0.1μm以下の範囲のピーク強度をP1とし、0.1μm超1μm以下の範囲のピーク強度をP2としたとき、P2/P1の値が0.2以上10以下である燃料電池用電極触媒層。 - 前記無機酸化物がスズ酸化物である請求項1に記載の燃料電池用電極触媒層。
- スズ酸化物に、ニオブ、タンタル、アンチモン及びタングステンのうち1種以上の元素が含まれている請求項2に記載の燃料電池用電極触媒層。
- スズ酸化物に、フッ素が含まれている請求項2に記載の燃料電池用電極触媒層。
- ノニオン性ポリマーを非含有である請求項1ないし4のいずれか一項に記載の燃料電池用電極触媒層。
- 請求項1ないし5のいずれか一項に記載の燃料電池用電極触媒層が、固体高分子電解質膜の少なくとも一面に形成されてなる燃料電池用膜電極接合体。
- 請求項6に記載の膜電極接合体を有し、前記電極触媒層をカソード触媒層として用いた固体高分子形燃料電池。
- 無機酸化物の前駆体粒子を造粒して造粒物となし、
前記造粒物を焼成して前記前駆体を無機酸化物に変化させ、
焼成後の前記造粒物に触媒を担持させて、触媒担持造粒物を得、
前記触媒担持造粒物を含むインクの塗布によって燃料電池用電極触媒層を形成する、燃料電池用電極触媒層の製造方法。 - 無機酸化物の粒子を造粒して造粒物となし、
前記造粒物に触媒を担持させて、触媒担持造粒物を得、
前記触媒担持造粒物を含むインクの塗布によって燃料電池用電極触媒層を形成する、燃料電池用電極触媒層の製造方法。 - 0.05μm以上10μm以下の平均粒子径を有する前記触媒担持造粒物を形成し、これを用いて前記触媒層を形成する請求項8又は9に記載の製造方法。
- 噴霧乾燥法によって造粒を行う請求項8ないし10のいずれか一項に記載の製造方法。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014217617 | 2014-10-24 | ||
JP2014217617 | 2014-10-24 | ||
JP2015133068 | 2015-07-01 | ||
JP2015133068 | 2015-07-01 | ||
PCT/JP2015/079739 WO2016063922A1 (ja) | 2014-10-24 | 2015-10-21 | 燃料電池用電極触媒層及びその製造方法、膜電極接合体並びに固体高分子形燃料電池 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPWO2016063922A1 true JPWO2016063922A1 (ja) | 2017-08-03 |
JP6632987B2 JP6632987B2 (ja) | 2020-01-22 |
Family
ID=55760953
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2016555263A Active JP6632987B2 (ja) | 2014-10-24 | 2015-10-21 | 燃料電池用電極触媒層、膜電極接合体及び固体高分子形燃料電池 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10629935B2 (ja) |
EP (1) | EP3211697B1 (ja) |
JP (1) | JP6632987B2 (ja) |
KR (1) | KR102039332B1 (ja) |
CN (1) | CN106663819B (ja) |
WO (1) | WO2016063922A1 (ja) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6748080B2 (ja) * | 2015-08-04 | 2020-08-26 | 三井金属鉱業株式会社 | 酸化スズ、燃料電池用電極触媒、膜電極接合体及び固体高分子形燃料電池 |
US10886540B2 (en) * | 2015-12-14 | 2021-01-05 | Indiana University Research And Technology Corporation | Systems and methods of graphene supported catalysts |
KR101901223B1 (ko) * | 2017-11-07 | 2018-09-21 | 광주과학기술원 | 자동차용 연료전지를 위한 다기능성 비백금 담지 촉매 및 그 제조 방법 |
CN111902982A (zh) * | 2018-03-30 | 2020-11-06 | 凸版印刷株式会社 | 膜电极接合体及固体高分子型燃料电池 |
CN111868980B (zh) * | 2018-07-25 | 2024-05-24 | 松下知识产权经营株式会社 | 燃料电池的阴极催化剂层及燃料电池 |
KR102610519B1 (ko) * | 2018-08-09 | 2023-12-07 | 미쓰이금속광업주식회사 | 연료 전지용 전극 촉매층 및 그것을 사용한 고체 고분자형 연료 전지 |
KR102592198B1 (ko) | 2020-05-28 | 2023-10-19 | 코오롱인더스트리 주식회사 | 연료전지용 혼합 촉매, 그 제조방법, 그것을 이용한 전극 형성방법, 및 그것을 포함하는 막-전극 어셈블리 |
CA3203817A1 (en) * | 2020-12-29 | 2022-07-07 | Rajesh Bashyam | Dry fuel cell electrodes and methods of manufacture |
WO2023120094A1 (ja) * | 2021-12-21 | 2023-06-29 | 株式会社キャタラー | 触媒貴金属担持導電性酸化物粒子の製造方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004079244A (ja) * | 2002-08-12 | 2004-03-11 | Toshiba Corp | 燃料電池用触媒及び燃料電池 |
JP2005174835A (ja) * | 2003-12-12 | 2005-06-30 | Nissan Motor Co Ltd | 電極 |
JP2008034300A (ja) * | 2006-07-31 | 2008-02-14 | Toshiba Corp | 燃料電池用電極、膜電極複合体および燃料電池、ならびにそれらの製造法 |
JP2009059575A (ja) * | 2007-08-31 | 2009-03-19 | Toshiba Corp | 燃料電池用アノードおよびそれを用いた燃料電池 |
JP2009146760A (ja) * | 2007-12-14 | 2009-07-02 | Nissan Motor Co Ltd | 燃料電池用電極触媒層及び燃料電池用電極触媒層の製造方法 |
WO2014136908A1 (ja) * | 2013-03-06 | 2014-09-12 | 三井金属鉱業株式会社 | 燃料電池電極材料用タンタル含有酸化スズ |
WO2015151714A1 (ja) * | 2014-03-31 | 2015-10-08 | 三井金属鉱業株式会社 | 膜電極接合体及びそれを用いた固体高分子形燃料電池 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19611510A1 (de) | 1996-03-23 | 1997-09-25 | Degussa | Gasdiffusionselektrode für Membranbrennstoffzellen und Verfahren zu ihrer Herstellung |
EP2172999B1 (en) | 2007-06-29 | 2015-04-22 | Toppan Printing Co., Ltd. | Membrane electrode assembly and solid polymer electrolyte fuel cell |
US8968967B2 (en) * | 2008-09-17 | 2015-03-03 | Ballard Power Systems Inc. | Fuel cell catalyst support with fluoride-doped metal oxides/phosphates and method of manufacturing same |
CN103011125B (zh) * | 2012-12-04 | 2014-05-21 | 西北师范大学 | 一种介孔碳材料的制备及作为贵金属催化剂载体的应用 |
-
2015
- 2015-10-21 EP EP15852815.8A patent/EP3211697B1/en active Active
- 2015-10-21 WO PCT/JP2015/079739 patent/WO2016063922A1/ja active Application Filing
- 2015-10-21 US US15/505,679 patent/US10629935B2/en active Active
- 2015-10-21 KR KR1020177003472A patent/KR102039332B1/ko active IP Right Grant
- 2015-10-21 JP JP2016555263A patent/JP6632987B2/ja active Active
- 2015-10-21 CN CN201580045126.3A patent/CN106663819B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004079244A (ja) * | 2002-08-12 | 2004-03-11 | Toshiba Corp | 燃料電池用触媒及び燃料電池 |
JP2005174835A (ja) * | 2003-12-12 | 2005-06-30 | Nissan Motor Co Ltd | 電極 |
JP2008034300A (ja) * | 2006-07-31 | 2008-02-14 | Toshiba Corp | 燃料電池用電極、膜電極複合体および燃料電池、ならびにそれらの製造法 |
JP2009059575A (ja) * | 2007-08-31 | 2009-03-19 | Toshiba Corp | 燃料電池用アノードおよびそれを用いた燃料電池 |
JP2009146760A (ja) * | 2007-12-14 | 2009-07-02 | Nissan Motor Co Ltd | 燃料電池用電極触媒層及び燃料電池用電極触媒層の製造方法 |
WO2014136908A1 (ja) * | 2013-03-06 | 2014-09-12 | 三井金属鉱業株式会社 | 燃料電池電極材料用タンタル含有酸化スズ |
WO2015151714A1 (ja) * | 2014-03-31 | 2015-10-08 | 三井金属鉱業株式会社 | 膜電極接合体及びそれを用いた固体高分子形燃料電池 |
Also Published As
Publication number | Publication date |
---|---|
EP3211697A4 (en) | 2018-05-02 |
CN106663819B (zh) | 2020-03-03 |
EP3211697B1 (en) | 2020-01-29 |
EP3211697A1 (en) | 2017-08-30 |
JP6632987B2 (ja) | 2020-01-22 |
CN106663819A (zh) | 2017-05-10 |
KR20170030584A (ko) | 2017-03-17 |
KR102039332B1 (ko) | 2019-11-01 |
US10629935B2 (en) | 2020-04-21 |
WO2016063922A1 (ja) | 2016-04-28 |
US20170279143A1 (en) | 2017-09-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6632987B2 (ja) | 燃料電池用電極触媒層、膜電極接合体及び固体高分子形燃料電池 | |
JP5332429B2 (ja) | 電極触媒 | |
KR101229400B1 (ko) | 직접 메탄올형 연료 전지용 백금/루테늄 촉매 | |
JP2019517110A (ja) | 触媒 | |
US11931724B2 (en) | Catalyst, method for producing same, electrode comprising same, membrane-electrode assembly comprising same, and fuel cell comprising same | |
JP6173569B2 (ja) | 膜電極接合体及びそれを用いた固体高分子形燃料電池 | |
JP2019505376A (ja) | 触媒 | |
EP3903935B1 (en) | Catalyst, method for producing same, electrode comprising same, membrane-electrode assembly comprising same, and fuel cell comprising same | |
JP7145508B2 (ja) | 電気化学デバイスの膜触媒層接合体、膜電極接合体、電気化学デバイス、電気化学デバイスの膜触媒層接合体の製造方法 | |
CN115298862A (zh) | 电化学电池用电极催化剂层、电化学电池用膜电极接合体及电化学电池 | |
CN111788728B (zh) | 燃料电池用电极催化剂和使用它的燃料电池 | |
KR102610519B1 (ko) | 연료 전지용 전극 촉매층 및 그것을 사용한 고체 고분자형 연료 전지 | |
JP7310855B2 (ja) | 触媒層 | |
US20160104895A1 (en) | Templated non-carbon metal oxide catalyst support |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180808 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190709 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190724 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20191203 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20191211 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6632987 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |