JP2003036859A - Solid polymer type fuel cell and its fabrication method - Google Patents
Solid polymer type fuel cell and its fabrication methodInfo
- Publication number
- JP2003036859A JP2003036859A JP2001223435A JP2001223435A JP2003036859A JP 2003036859 A JP2003036859 A JP 2003036859A JP 2001223435 A JP2001223435 A JP 2001223435A JP 2001223435 A JP2001223435 A JP 2001223435A JP 2003036859 A JP2003036859 A JP 2003036859A
- Authority
- JP
- Japan
- Prior art keywords
- anode
- platinum
- carbon
- fuel cell
- catalyst
- 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.)
- Withdrawn
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 229920000642 polymer Polymers 0.000 title claims abstract description 14
- 239000007787 solid Substances 0.000 title claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 162
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 142
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 127
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 102
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 71
- 239000002923 metal particle Substances 0.000 claims abstract description 54
- 229910001260 Pt alloy Inorganic materials 0.000 claims abstract description 26
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 21
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 21
- 239000005518 polymer electrolyte Substances 0.000 claims description 59
- 239000003014 ion exchange membrane Substances 0.000 claims description 36
- 238000009792 diffusion process Methods 0.000 claims description 33
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 29
- 229910052707 ruthenium Inorganic materials 0.000 claims description 29
- 239000006229 carbon black Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 8
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 238000002050 diffraction method Methods 0.000 claims 1
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 32
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 22
- 239000001257 hydrogen Substances 0.000 abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 15
- 238000002441 X-ray diffraction Methods 0.000 abstract description 3
- 239000002574 poison Substances 0.000 abstract description 2
- 231100000614 poison Toxicity 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 60
- 239000010410 layer Substances 0.000 description 47
- 239000002245 particle Substances 0.000 description 22
- 208000005374 Poisoning Diseases 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 20
- 238000005087 graphitization Methods 0.000 description 20
- 231100000572 poisoning Toxicity 0.000 description 20
- 230000000607 poisoning effect Effects 0.000 description 20
- 239000012528 membrane Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 150000002431 hydrogen Chemical class 0.000 description 12
- 239000003575 carbonaceous material Substances 0.000 description 11
- 238000000634 powder X-ray diffraction Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000010718 Oxidation Activity Effects 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000003411 electrode reaction Methods 0.000 description 8
- 239000002737 fuel gas Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000010248 power generation Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000002407 reforming Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 150000001721 carbon Chemical class 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000010411 electrocatalyst Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 150000003057 platinum Chemical class 0.000 description 6
- 238000004088 simulation Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000429 assembly Methods 0.000 description 4
- 230000000712 assembly Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229920003935 Flemion® Polymers 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical class [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- -1 perfluorovinyl compound Chemical class 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 208000001408 Carbon monoxide poisoning Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、固体高分子型燃料
電池及びその製造方法に関する。TECHNICAL FIELD The present invention relates to a polymer electrolyte fuel cell and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】燃料電池は、原料となるガスの化学エネ
ルギを電気エネルギに直接変換する電池である。特に、
水素・酸素燃料電池は、その反応生成物が原理的に水の
みであり、地球環境への影響のほとんどないクリーンな
発電システムとして注目されている。その中でも、イオ
ン交換膜からなる高分子電解質膜を有する固体高分子型
燃料電池は、小型軽量化が容易であり、常温でも作動で
き、高出力密度が得られることから、近年のエネルギ、
地球環境問題への社会的要請の高まりとともに、電気自
動車等の移動車両や、小型コジェネレーションシステム
等の定置型電源等としての実用化が期待されている。2. Description of the Related Art A fuel cell is a cell that directly converts the chemical energy of a raw material gas into electrical energy. In particular,
The hydrogen / oxygen fuel cell is attracting attention as a clean power generation system that has almost no effect on the global environment because its reaction product is only water in principle. Among them, a polymer electrolyte fuel cell having a polymer electrolyte membrane made of an ion exchange membrane is easy to be small and lightweight, can operate even at room temperature, and can obtain a high output density.
With the increasing social demand for global environmental problems, it is expected to be put to practical use as mobile vehicles such as electric vehicles and stationary power sources such as small cogeneration systems.
【０００３】固体高分子型燃料電池としては、スルホン
酸基を有するパーフルオロカーボン重合体からなるイオ
ン交換膜を使用したタイプのものが基本特性に優れてい
る。そして、イオン交換膜の両面にガス拡散電極からな
るアノード及びカソードを配置し、燃料である水素をア
ノードに供給し、酸化剤となる酸素又は空気をカソード
に供給することにより発電を行う。As the polymer electrolyte fuel cell, a type using an ion exchange membrane made of a perfluorocarbon polymer having a sulfonic acid group has excellent basic characteristics. Then, an anode and a cathode composed of gas diffusion electrodes are arranged on both sides of the ion exchange membrane, hydrogen as a fuel is supplied to the anode, and oxygen or air serving as an oxidant is supplied to the cathode to generate electricity.
【０００４】固体高分子型燃料電池のアノード及びカソ
ードとして使用するガス拡散電極は、通常、電極触媒と
イオン交換樹脂とを含む触媒層と、ガス拡散層とを有し
ている。触媒層の電極触媒としては、通常、白金又は白
金合金触媒が比表面積の大きい導電性のカーボンブラッ
ク等に担持されたものを使用する。そして、ガス拡散電
極の触媒層における反応は、電解質、触媒及びガス（例
えば、水素又は酸素）が同時に存在する三相界面でのみ
進行するため、イオン交換樹脂で電極触媒を被覆し、三
相界面を増大させることにより電池の性能の向上が図ら
れている。A gas diffusion electrode used as an anode and a cathode of a polymer electrolyte fuel cell usually has a catalyst layer containing an electrode catalyst and an ion exchange resin, and a gas diffusion layer. As the electrode catalyst of the catalyst layer, one in which a platinum or platinum alloy catalyst is supported on conductive carbon black or the like having a large specific surface area is usually used. Then, since the reaction in the catalyst layer of the gas diffusion electrode proceeds only at the three-phase interface where the electrolyte, the catalyst and the gas (for example, hydrogen or oxygen) are present at the same time, the electrode catalyst is coated with the ion-exchange resin to form the three-phase interface. The battery performance is improved by increasing
【０００５】従来より、固体高分子型燃料電池のアノー
ドに供給する燃料ガスとしては、メタンやメタノール、
ガソリン等を改質装置を用いて水蒸気改質し、得られる
水素リッチな改質ガスを使用することが検討されてい
る。例えば、燃料としてメタノールを使用する場合、例
えば、２５０〜３００℃の温度条件のもとでＣｕ−Ｚｎ
系などの触媒を使用して改質反応を行う。Conventionally, methane, methanol, or the like has been used as the fuel gas supplied to the anode of the polymer electrolyte fuel cell.
It has been studied to use hydrogen-rich reformed gas obtained by steam reforming gasoline or the like using a reformer. For example, when methanol is used as fuel, Cu-Zn is used under the temperature condition of 250 to 300 ° C.
The reforming reaction is carried out using a catalyst such as a system.
【０００６】この改質反応としては、例えば、以下に示
す化学式（１）及び（２）で表現される反応が段階的に
進行する。すなわち、メタノールを水蒸気と反応させて
水素と一酸化炭素とを含有する改質ガスに転化させ、更
に、このガス中の一酸化炭素を水蒸気とシフト反応させ
ることにより、水素ガスを主成分とする改質ガスを得
る。
CH3OH→２H2＋CO ΔＨ＝＋90kJ/mol…（１）
CO＋H2O→H2＋CO2 ΔＨ＝−40kJ/mol…（２）As the reforming reaction, for example, the reactions represented by the following chemical formulas (1) and (2) proceed stepwise. That is, methanol is reacted with steam to convert it into a reformed gas containing hydrogen and carbon monoxide, and further carbon monoxide in this gas is subjected to a shift reaction with steam to make hydrogen gas a main component. Obtain reformed gas. CH 3 OH → 2H 2 + CO ΔH = + 90kJ / mol… (1) CO + H 2 O → H 2 + CO 2 ΔH = −40kJ / mol… (2)
【０００７】しかし、このシフト反応を行っても、得ら
れる改質ガス中には、通常１％程度の一酸化炭素が含ま
れ、これがアノードに使用される白金系の電極触媒に対
する触媒毒として作用する。However, even if this shift reaction is carried out, the obtained reformed gas usually contains about 1% carbon monoxide, which acts as a catalyst poison for the platinum-based electrode catalyst used for the anode. To do.
【０００８】特に、１００℃以下の低温作動を特徴とす
る固体高分子型燃料電池においては、一酸化炭素による
電極触媒の被毒の影響が顕著であり、改質ガス中の一酸
化炭素の濃度が僅かであっても電池特性を大きく低下さ
せることが知られている。In particular, in a polymer electrolyte fuel cell characterized by low temperature operation of 100 ° C. or lower, the poisoning of the electrode catalyst by carbon monoxide is remarkable, and the concentration of carbon monoxide in the reformed gas is remarkable. It is known that the battery characteristics are greatly deteriorated even when the amount is small.
【０００９】このような改質ガス中に含まれる一酸化炭
素による電極触媒の被毒の影響を回避する方法の一つと
しては、改質ガス中の一酸化炭素を触媒を用いて選択的
に酸化する方法がある。One of the methods for avoiding the effect of poisoning of the electrode catalyst by carbon monoxide contained in the reformed gas is to selectively use carbon monoxide in the reformed gas by using a catalyst. There is a method of oxidation.
【００１０】例えば、従来より、改質装置に改質反応
部、シフト反応部及び一酸化炭素選択酸化用の触媒を有
する選択酸化部を設けて、改質ガス中に含まれる一酸化
炭素の酸化反応を選択的に進行させるようにこれらを連
携制御する方法がある。また、特開平９−１２９２４３
号公報には、一酸化炭素選択酸化触媒を燃料電池のアノ
ードのガス拡散層（燃料ガス拡散層）に組み込むこと
で、一酸化炭素による電極触媒の被毒を防ぎ、しかも、
発電システム全体の小型化を図った電池が提案されてい
る。更に、S.Gottesfeld and J.Pafford, J.Electroche
m. soc., 135(1988)2654には、アノード白金触媒表面に
吸着するＣＯを酸化除去するために燃料ガス中に空気あ
るいは酸素ガスを直接導入する方法が提案されている。For example, conventionally, a reforming apparatus is provided with a reforming reaction section, a shift reaction section and a selective oxidation section having a catalyst for selective oxidation of carbon monoxide to oxidize carbon monoxide contained in the reformed gas. There is a method of cooperatively controlling these so as to selectively proceed the reaction. Also, JP-A-9-129243
In the publication, by incorporating a carbon monoxide selective oxidation catalyst into a gas diffusion layer (fuel gas diffusion layer) of an anode of a fuel cell, poisoning of an electrode catalyst by carbon monoxide is prevented, and moreover,
A battery has been proposed in which the entire power generation system is downsized. Furthermore, S. Gottesfeld and J. Pafford, J. Electroche
m. soc., 135 (1988) 2654, a method of directly introducing air or oxygen gas into a fuel gas in order to oxidize and remove CO adsorbed on the anode platinum catalyst surface is proposed.
【００１１】しかしながら、上記の何れの方法において
も、定常運転時における燃料ガス中の水素ガスの酸化
（燃焼）を十分に抑制することができず、燃料電池全体
で利用することができる水素ガスの量が減少して、燃料
電池全体の発電効率の低下を招くことになっていた。更
に、空気や酸素ガスの流量制御機構を設けることが必要
となり発電システム全体として軽量コンパクト化するこ
とが困難となっていた。However, in any of the above methods, the oxidation (combustion) of hydrogen gas in the fuel gas during steady operation cannot be sufficiently suppressed, and the hydrogen gas that can be used in the entire fuel cell is The decrease in the amount has led to a decrease in the power generation efficiency of the entire fuel cell. Further, it is necessary to provide a flow rate control mechanism for air and oxygen gas, which makes it difficult to reduce the weight and size of the entire power generation system.
【００１２】そのため、上記の検討の他に一酸化炭素に
対する被毒耐性に優れた電極触媒をアノードに使用する
方法も検討されている。このような触媒が使用可能にな
れば、改質ガス中の一酸化炭素濃度を十分に低減せずに
使用でき、先に述べた改質ガス中の水素の無駄な消費を
低減できることや燃料電池を含む発電システム全体をコ
ンパクト化できること、システムコストを低減できるこ
と等のメリットがある。Therefore, in addition to the above investigation, a method of using an electrode catalyst having excellent poisoning resistance to carbon monoxide for the anode has also been studied. If such a catalyst becomes available, it will be possible to use it without sufficiently reducing the carbon monoxide concentration in the reformed gas, and it will be possible to reduce the above-mentioned wasteful consumption of hydrogen in the reformed gas and the fuel cell. It has the merits that the entire power generation system including can be made compact and the system cost can be reduced.
【００１３】従来より、このような触媒の中でも、白金
とルテニウムが担体上に複合的に担持された触媒（以
下、「白金−ルテニウム系触媒」という）は、特に優れ
た一酸化炭素に対する被毒耐性を有するとされている。
この触媒が優れた被毒耐性を有する理由の一つとして
は、水分子との結合によってルテニウム上に生じた−Ｏ
Ｈ基が白金上に吸着した一酸化炭素を酸化除去している
ことが考えられている。Conventionally, among such catalysts, a catalyst in which platinum and ruthenium are compositely supported on a carrier (hereinafter referred to as "platinum-ruthenium catalyst") is particularly excellent in poisoning of carbon monoxide. It is said to have resistance.
One of the reasons why this catalyst has excellent resistance to poisoning is that —O generated on ruthenium due to binding with water molecules.
It is considered that the H group oxidizes and removes carbon monoxide adsorbed on platinum.
【００１４】[0014]
【発明が解決しようとする課題】しかしながら、上記従
来のアノードの触媒層に白金−ルテニウム系触媒を使用
した固体高分子型燃料電池においては、電極触媒に白金
に加えてルテニウムを添加することにより一酸化炭素に
対する被毒耐性は向上させることができるが、水素酸化
活性は逆に低下させることになり、燃料電池の出力特性
を低下させる原因となっていた。However, in a polymer electrolyte fuel cell in which a platinum-ruthenium-based catalyst is used in the above-mentioned conventional catalyst layer of the anode, the ruthenium is added to the electrode catalyst in addition to platinum. Although the poisoning resistance to carbon oxide can be improved, the hydrogen oxidation activity is decreased, which causes the output characteristics of the fuel cell to be deteriorated.
【００１５】上記の水素酸化活性の低下を改善するため
に、例えば、特開平１０−２７００５７号公報には、ア
ノードの触媒層をそれぞれ白金−ルテニウム触媒を含む
２つの層から構成し、ガス拡散層側に配置される触媒層
のルテニウム含有量を、高分子電解質膜（イオン交換
膜）側に配置される触媒層のルテニウム含有量よりも多
くした固体高分子型燃料電池が提案されている。しかし
ながら、この方法の場合、一酸化炭素に対する被毒耐性
を確保するために使用するルテニウムの量が多くなり、
コストが高くなってしまうという問題があった。In order to improve the above-mentioned decrease in hydrogen oxidation activity, for example, in Japanese Unexamined Patent Publication No. 10-270057, a catalyst layer of an anode is composed of two layers each containing a platinum-ruthenium catalyst, and a gas diffusion layer is provided. There has been proposed a polymer electrolyte fuel cell in which the ruthenium content of the catalyst layer arranged on the side is higher than the ruthenium content of the catalyst layer arranged on the side of the polymer electrolyte membrane (ion exchange membrane). However, in the case of this method, the amount of ruthenium used to secure poisoning resistance to carbon monoxide increases,
There was a problem that the cost would be high.
【００１６】すなわち、白金に対してルテニウム等の白
金以外の金属の使用量を低減させた電極触媒を使用した
場合、或いは、白金以外の金属を全く使用しない白金の
みを担体に担持した電極触媒を使用した場合であっても
一酸化炭素に対する優れた被毒耐性を発揮しうるアノー
ドを備えた発電効率の高い軽量かつコンパクトな固体高
分子型燃料電池は、これまでに実現されていなかった。That is, when an electrode catalyst in which the amount of a metal other than platinum such as ruthenium is reduced with respect to platinum is used, or when an electrode catalyst in which only a platinum other than platinum is supported on a carrier is used. A lightweight and compact polymer electrolyte fuel cell with high power generation efficiency, which has an anode capable of exhibiting excellent poisoning resistance to carbon monoxide even when used, has not been realized so far.
【００１７】本発明は、上記従来技術の有する課題に鑑
みてなされたものであり、一酸化炭素に対する優れた被
毒耐性と優れた水素酸化活性とを兼ね備えたアノードを
有し、高い出力電圧を長期にわたって安定して得ること
ができる軽量かつコンパクトな固体高分子型燃料電池及
びその製造方法を提供することを目的とする。The present invention has been made in view of the above problems of the prior art, and has an anode having both excellent poisoning resistance to carbon monoxide and excellent hydrogen oxidation activity, and has a high output voltage. An object of the present invention is to provide a lightweight and compact polymer electrolyte fuel cell that can be stably obtained over a long period of time, and a method for manufacturing the same.
【００１８】[0018]
【課題を解決するための手段】本発明者らは、上記目的
を達成するべく鋭意研究を重ねた結果、白金又は白金合
金からなる金属粒子と、該金属粒子の担体となるカーボ
ン担体とから構成された電極触媒において、カーボン担
体の黒鉛化度を制御することにより、電極触媒の優れた
水素酸化活性を確保しつつ一酸化炭素に対する優れた被
毒耐性を得ることが可能となることを見出し、本発明に
到達した。Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that metal particles composed of platinum or a platinum alloy and carbon carriers serving as carriers for the metal particles are used. In the electrocatalyst thus obtained, by controlling the graphitization degree of the carbon carrier, it is possible to obtain an excellent poisoning resistance to carbon monoxide while securing an excellent hydrogen oxidation activity of the electrode catalyst, The present invention has been reached.
【００１９】すなわち、本発明は、アノードと、カソー
ドと、アノードとカソードとの間に配置されたイオン交
換膜とを有する固体高分子型燃料電池であって、アノー
ドが、電極触媒とイオン交換樹脂とを含む触媒層を有す
るガス拡散電極であり、電極触媒が、白金又は白金合金
からなる金属粒子と、該金属粒子の担体となるカーボン
担体とから構成されており、カーボン担体は、Ｘ線回折
法により求められる格子面［００２］の平均格子面間隔
ｄ002が０．３４０〜０．３６２ｎｍであり、結晶子の
大きさＬｃ002が０．６〜４ｎｍであり、かつ、比表面
積が２６０〜８００ｍ2／ｇであること、を特徴とする
固体高分子型燃料電池を提供する。That is, the present invention is a polymer electrolyte fuel cell having an anode, a cathode, and an ion exchange membrane arranged between the anode and the cathode, wherein the anode is an electrode catalyst and an ion exchange resin. A gas diffusion electrode having a catalyst layer containing, wherein the electrode catalyst is composed of metal particles composed of platinum or a platinum alloy, and a carbon carrier serving as a carrier for the metal particles. The average lattice spacing d 002 of the lattice plane [002] obtained by the method is 0.340 to 0.362 nm, the crystallite size Lc 002 is 0.6 to 4 nm, and the specific surface area is 260 to 260. Provided is a polymer electrolyte fuel cell, which is 800 m 2 / g.
【００２０】このように、アノードに使用する電極触媒
の担体として、上述の平均格子面間隔ｄ002、結晶子の
大きさＬｃ002及び比表面積の条件を同時に満たす黒鉛
化度の高いカーボン担体を使用することにより、アノー
ドにおいて十分な水素酸化活性を確保しつつ、一酸化炭
素による電極触媒の被毒を十分に防止することが可能と
なる。そのため、本発明の固体高分子型燃料電池は、高
い出力特性を有するとともに長期にわたって安定した出
力を保持できる。また、アノードに供給する改質ガス中
の一酸化炭素濃度を従来の電池に求められていた水準ま
で十分に本発明の固体高分子型燃料電池は容易に軽量化
及びコンパクト化を図ることができる。そのため、固体
高分子型燃料電池を含む発電システム全体の軽量化及び
コンパクト化も容易に図ることができる。As described above, as the carrier of the electrocatalyst used for the anode, a carbon carrier having a high degree of graphitization which simultaneously satisfies the above-mentioned average lattice spacing d 002 , crystallite size Lc 002 and specific surface area is used. By doing so, it becomes possible to sufficiently prevent the poisoning of the electrode catalyst by carbon monoxide while ensuring a sufficient hydrogen oxidation activity in the anode. Therefore, the polymer electrolyte fuel cell of the present invention has high output characteristics and can maintain stable output over a long period of time. Further, the carbon monoxide concentration in the reformed gas supplied to the anode can be sufficiently brought to the level required for the conventional cell, and the polymer electrolyte fuel cell of the present invention can easily be made lightweight and compact. . Therefore, it is possible to easily reduce the weight and size of the entire power generation system including the polymer electrolyte fuel cell.
【００２１】本発明の固体高分子型燃料電池のアノード
に使用する電極触媒が高い一酸化炭素に対する被毒耐性
を示す理由は明確ではないが、カーボン担体の黒鉛化が
十分に進行していてカーボン担体中の炭素の電子状態密
度が高いため、このカーボン担体上に担持される白金又
は白金合金からなる金属粒子の電子状態が変化し、一酸
化炭素に対する優れた被毒耐性を示すものと推定され
る。Although the reason why the electrocatalyst used in the anode of the polymer electrolyte fuel cell of the present invention exhibits high resistance to poisoning with respect to carbon monoxide is not clear, the graphitization of the carbon support is sufficiently progressing. Since the electron state density of carbon in the carrier is high, the electronic state of the metal particles made of platinum or platinum alloy supported on the carbon carrier changes, and it is presumed that it exhibits excellent poisoning resistance to carbon monoxide. It
【００２２】ここで、本発明において、カーボン担体の
「格子面［００２］の平均格子面間隔ｄ002」（以下、
「ｄ002」という）とは、カーボン担体を構成する炭素
の黒鉛構造に基づく六角網面の面間隔であり、六角網面
の垂直方向であるＣ軸方向の格子定数Ｃの１／２層間距
離の平均値を表す。また、「結晶子の大きさＬｃ002」
（以下、「Ｌｃ002」という）とは、上記のＣ軸方向の
六角網面の積層厚さを示す。そして、ｄ002及びＬｃ002
は何れもＸ線回折法により得られるカーボン担体のＸ線
回折パターンから算出される値である。Here, in the present invention, the “average lattice plane spacing d 002 of the lattice plane [002]” of the carbon support (hereinafter,
"D 002 ") is the interplanar spacing of hexagonal mesh planes based on the graphite structure of carbon constituting the carbon support, and is the 1/2 interlayer distance of the lattice constant C in the C-axis direction which is the direction perpendicular to the hexagonal mesh planes. Represents the average value of. In addition, “crystallite size Lc 002 ”
(Hereinafter, referred to as “Lc 002 ”) indicates the laminated thickness of the hexagonal mesh plane in the C-axis direction. And d 002 and Lc 002
Are all values calculated from the X-ray diffraction pattern of the carbon support obtained by the X-ray diffraction method.
【００２３】ｄ002とＬｃ002は、構造が明確な黒鉛を基
準として測定される値であり、本発明において使用する
カーボン担体等のカーボン材料の黒鉛化度の目安となる
値である。完全な黒鉛結晶では、ｄ002は０．３３４５
ｎｍであり、ｄ002がこの値に近いカーボン材料ほど黒
鉛化度が高い。D 002 and Lc 002 are values measured on the basis of graphite having a clear structure, and are values that serve as a measure of the degree of graphitization of the carbon material such as the carbon support used in the present invention. For perfect graphite crystals, d 002 is 0.3345
and the carbon material having d 002 closer to this value has a higher degree of graphitization.
【００２４】本発明において、カーボン担体のｄ002は
０．３４０〜０．３６２ｎｍである。ｄ002が０．３４
０ｎｍ未満であると、カーボン担体の黒鉛化度が高すぎ
て比表面積が減少するため、カーボン担体上に担持され
る金属粒子の分散性が低下したり、金属粒子の表面積が
減少したりして、水素酸化活性が低下する。In the present invention, the carbon carrier has d 002 of 0.340 to 0.362 nm. d 002 is 0.34
If it is less than 0 nm, the graphitization degree of the carbon support is too high and the specific surface area is reduced, so that the dispersibility of the metal particles supported on the carbon support is reduced or the surface area of the metal particles is reduced. , The hydrogen oxidation activity decreases.
【００２５】一方、ｄ002が０．３６２ｎｍを超える
と、黒鉛化度が低すぎてアノードにおける一酸化炭素に
対する十分な被毒耐性を得ることができなくなる。その
結果、固体高分子型燃料電池を長期間にわたって使用し
た場合に、作動開始時に得られた電池出力が大きく低下
するという問題を招く。なお、上述した同様の観点か
ら、ｄ002は、０．３４５〜０．３５３ｎｍであること
がより好ましい。On the other hand, when d 002 exceeds 0.362 nm, the degree of graphitization is too low to obtain sufficient poisoning resistance to carbon monoxide in the anode. As a result, when the polymer electrolyte fuel cell is used for a long period of time, there arises a problem that the cell output obtained at the start of operation is greatly reduced. From the same viewpoint as described above, d 002 is more preferably 0.345 to 0.353 nm.
【００２６】また、本発明において、カーボン担体のＬ
ｃ002が０．６ｎｍ未満となると、黒鉛化度が低すぎて
充分な一酸化炭素に対する被毒耐性が得られない。一
方、カーボン担体のＬｃ002が４ｎｍを超えると、カー
ボン担体の黒鉛化度が高すぎて比表面積が大きく減少す
るため、カーボン担体上に担持される金属粒子の分散性
が低下する。なお、上述した同様の観点から、Ｌｃ002
は１〜２ｎｍであることがより好ましい。Further, in the present invention, L of the carbon support is used.
If c 002 is less than 0.6 nm, the degree of graphitization is too low to obtain sufficient resistance to carbon monoxide poisoning. On the other hand, when Lc 002 of the carbon support exceeds 4 nm, the degree of graphitization of the carbon support is too high and the specific surface area is greatly reduced, so that the dispersibility of the metal particles supported on the carbon support is lowered. From the same viewpoint as described above, Lc 002
Is more preferably 1 to 2 nm.
【００２７】また、本発明において、カーボン担体の比
表面積は２６０〜８００ｍ2／ｇである。この比表面積
の条件を満たすカーボン担体であれば、金属粒子がカー
ボン担体上に分散性よく担持される。また、この場合、
電極触媒はスルホン酸基を有するパーフルオロカーボン
重合体などの強酸性ポリマーに被覆された条件の下で
も、カーボン担体上に担持された金属粒子の粒子成長が
抑制されるため、長期にわたって安定した電極反応活性
を得ることができる。In the present invention, the carbon support has a specific surface area of 260 to 800 m 2 / g. If the carbon support satisfies the condition of the specific surface area, the metal particles are supported on the carbon support with good dispersibility. Also in this case,
Even under the condition that the electrode catalyst is coated with a strongly acidic polymer such as a perfluorocarbon polymer having a sulfonic acid group, particle growth of the metal particles supported on the carbon carrier is suppressed, resulting in a stable electrode reaction over a long period of time. The activity can be obtained.
【００２８】ここで、カーボン担体の比表面積が２６０
ｍ2／ｇ未満であると、高担持率で担持しようとする
と、金属粒子の分散性が悪くなる。一方、カーボン担体
の比表面積が８００ｍ2／ｇを超えると、黒鉛化度が低
く、耐酸化性が悪くなる。また、イオン交換樹脂による
充分な被覆が行えなくなり、水素の酸化反応に使用され
ない金属粒子の量が多くなる。なお、上述した同様の観
点から、カーボン担体の比表面積は３００〜５００ｍ2
／ｇであることがより好ましい。Here, the specific surface area of the carbon carrier is 260
If it is less than m 2 / g, the dispersibility of the metal particles will deteriorate when attempting to carry it at a high carrying rate. On the other hand, when the specific surface area of the carbon support exceeds 800 m 2 / g, the degree of graphitization is low and the oxidation resistance is poor. In addition, sufficient coverage with the ion exchange resin cannot be achieved, and the amount of metal particles not used in the hydrogen oxidation reaction increases. From the same viewpoint as described above, the carbon support has a specific surface area of 300 to 500 m 2.
/ G is more preferable.
【００２９】なお、本発明において、白金又は白金合金
からなる金属粒子の比表面積を求める場合に使用する該
金属粒子の表面積は、金属表面へのＣＯガスの吸着量を
用いる一酸化炭素吸着法に基づいて算出されるＣＯ−Ｍ
ＳＡ（Ｍｅｔａｌ Ｓｕｒｆａｃｅ Ａｒｅａ）、又
は、電気化学的分析方法に基づいて算出されるＥＣ（Ｅ
ｌｅｃｔｒｏ Ｃｈｅｍｉｃａｌ）−ＭＳＡとして求め
られる値を示す。In the present invention, the surface area of the metal particles used when determining the specific surface area of the metal particles made of platinum or a platinum alloy is determined by the carbon monoxide adsorption method using the adsorption amount of CO gas on the metal surface. CO-M calculated based on
SA (Metal Surface Area) or EC (E calculated based on an electrochemical analysis method)
(electro Chemical) -indicates a value determined as MSA.
【００３０】また、本発明は、アノードとカソードとア
ノードとカソードとの間に配置されたイオン交換膜とを
有しており、アノードが電極触媒とイオン交換樹脂とを
含む触媒層を有しており、かつ、電極触媒が白金又は白
金合金からなる金属粒子とカーボン担体とから構成され
た固体高分子型燃料電池の製造方法であって、比表面積
が３００ｍ2／ｇ以上であるカーボンブラック又は活性
炭を１０００〜２２００℃の温度条件のもとで加熱処理
することによりカーボン担体を調製し、次いで、得られ
たカーボン担体に金属粒子を担持させることにより電極
触媒を調製する工程を含むこと、を特徴とする固体高分
子型燃料電池の製造方法を提供する。The present invention also has an anode, a cathode, and an ion exchange membrane disposed between the anode and the cathode, and the anode has a catalyst layer containing an electrode catalyst and an ion exchange resin. And a carbon black or activated carbon having a specific surface area of 300 m 2 / g or more, which is a method for producing a polymer electrolyte fuel cell in which an electrode catalyst is composed of metal particles made of platinum or a platinum alloy and a carbon carrier. To prepare a carbon carrier by heat treatment under a temperature condition of 1000 to 2200 ° C., and then to prepare an electrode catalyst by supporting metal particles on the obtained carbon carrier. A method for manufacturing a polymer electrolyte fuel cell is provided.
【００３１】上述のように本発明の製造方法では、カー
ボン担体は、比表面積３００ｍ2／ｇ以上のカーボンブ
ラック又は比表面積３００ｍ2／ｇ以上の活性炭を１０
００〜２２００℃で加熱処理することにより得る。通
常、ファーネスブラックなどのカーボンブラックや活性
炭はｄ002が０．３５５〜０．３８５ｎｍであり、Ｌｃ0
02が０．１〜０．３ｎｍであり、比表面積が１００〜２
５００ｍ2／ｇであるが、上述の温度条件を満たす加熱
処理により、その黒鉛化度を高められるとともにその比
表面積を低下させられ、先に述べたｄ002、Ｌｃ002及び
比表面積の条件を同時に満たす黒鉛化度の高いカーボン
担体を得ることができる。[0031] In the production method of the present invention as described above, the carbon support has a specific surface area 300 meters 2 / g or more carbon black or a specific surface area of 300 meters 2 / g or more activated carbon 10
Obtained by heat treatment at 00 to 2200 ° C. Generally, carbon black such as furnace black and activated carbon have d 002 of 0.355 to 0.385 nm, and Lc 0
02 is 0.1 to 0.3 nm, and the specific surface area is 100 to 2
Is a 500 meters 2 / g, the temperature satisfying the heat treatment described above, with enhanced its degree of graphitization is to reduce its specific surface area, above-mentioned d 002, Lc 002 and specific surface area conditions simultaneously It is possible to obtain a carbon support which has a high degree of graphitization.
【００３２】このようにカーボン担体を構成する炭素の
黒鉛化度が高まることにより、六角網面の端部（エッ
ジ）に存在する表面官能基（例えば、カルボキシル基、
フェノール性水酸基等の酸性官能基や、カルボニル基等
の中性官能基等）が相対的に減少し、その結果、カーボ
ン担体は撥水性を確保できるようになる。また、この場
合には、固体高分子型燃料電池の発電状態において、強
酸性のスルホン酸基を有するパーフルオロカーボン重合
体に対する安定性を十分に確保することができる。By increasing the degree of graphitization of carbon constituting the carbon support in this way, surface functional groups (eg, carboxyl groups, etc.) present at the edges of the hexagonal net surface are formed.
Acidic functional groups such as phenolic hydroxyl groups and neutral functional groups such as carbonyl groups are relatively reduced, and as a result, the carbon carrier can secure water repellency. Further, in this case, in the power generation state of the polymer electrolyte fuel cell, it is possible to sufficiently secure the stability to the perfluorocarbon polymer having a strongly acidic sulfonic acid group.
【００３３】そして、このカーボン担体に白金又は白金
合金からなる金属粒子を担持させて調製される電極触媒
は、優れた水素酸化活性と一酸化炭素に対する優れた被
毒耐性を示し、長期に渡って安定した電極反応活性を得
ることができる。The electrode catalyst prepared by supporting the metal particles of platinum or a platinum alloy on the carbon carrier shows excellent hydrogen oxidation activity and excellent poisoning resistance to carbon monoxide, and has a long life. Stable electrode reaction activity can be obtained.
【００３４】ここで、本発明の製造方法において、カー
ボンブラック又は活性炭としては比表面積が３００ｍ2
／ｇ以上のものを使用する。比表面積が３００ｍ2／ｇ
未満であると、加熱処理により得られるカーボン担体の
比表面積が小さくなりすぎて分散性よく金属粒子を担持
できなくなる。例えば、カーボンブラックの一種とし
て、原料としてアセチレンを用いて製造するアセチレン
ブラックと呼ばれる黒鉛化度の高い炭素材料もあるが、
アセチレンブラックは一般に比表面積が３０〜２００ｍ
2／ｇと小さいため、金属粒子を分散性よく担持できな
い。In the production method of the present invention, the carbon black or activated carbon has a specific surface area of 300 m 2.
/ G or more is used. Specific surface area of 300m 2 / g
When it is less than the above range, the specific surface area of the carbon support obtained by the heat treatment becomes too small and the metal particles cannot be supported with good dispersibility. For example, as a kind of carbon black, there is also a carbon material with a high degree of graphitization called acetylene black produced using acetylene as a raw material,
Acetylene black generally has a specific surface area of 30 to 200 m.
Since it is as small as 2 / g, metal particles cannot be supported with good dispersibility.
【００３５】なお、上記と同様の観点から、カーボンブ
ラック又は活性炭の比表面積は、５００ｍ2／ｇ以上で
あることがより好ましい。また、カーボンブラック又は
活性炭の比表面積が大きすぎる場合、加熱処理を行って
も黒鉛化が充分に進行せず、電極触媒としたときの電極
反応活性を高められなかったり、撥水性を高められない
おそれがある。そのため、カーボンブラック又は活性炭
の比表面積は２５００ｍ2／ｇ以下であることが好まし
い。From the same viewpoint as above, the specific surface area of carbon black or activated carbon is more preferably 500 m 2 / g or more. Further, if the specific surface area of carbon black or activated carbon is too large, graphitization does not proceed sufficiently even if heat treatment is performed, and the electrode reaction activity when used as an electrode catalyst cannot be increased or the water repellency cannot be increased. There is a risk. Therefore, the specific surface area of carbon black or activated carbon is preferably 2500 m 2 / g or less.
【００３６】また、本発明の製造方法において、上述の
比表面積の条件を有するカーボンブラック又は活性炭を
加熱処理するときの温度が１０００℃未満であると、黒
鉛化が進行せず、高い一酸化炭素に対する被毒耐性を有
する電極触媒を得られない。一方、加熱処理するときの
温度が２２００℃を超えると、カーボン担体の黒鉛化度
が高くなりすぎるとともに比表面積が極度に減少するた
め、カーボン担体上における金属粒子の分散性が低下す
ることがある。In the production method of the present invention, if the temperature at which the carbon black or activated carbon having the above-mentioned specific surface area condition is heat-treated is less than 1000 ° C., graphitization does not proceed and high carbon monoxide is produced. It is not possible to obtain an electrode catalyst having poisoning resistance to. On the other hand, when the temperature during the heat treatment exceeds 2200 ° C., the graphitization degree of the carbon support becomes too high and the specific surface area extremely decreases, so that the dispersibility of the metal particles on the carbon support may decrease. .
【００３７】なお、上記と同様の観点から、本発明にお
いて、上記の比表面積の条件を有するカーボンブラック
又は活性炭を加熱処理するときの温度は、１２００〜２
０００℃であることがより好ましい。From the same viewpoint as above, in the present invention, the temperature at which the carbon black or activated carbon having the above-mentioned specific surface area condition is heat treated is 1200 to 2
More preferably, it is 000 ° C.
【００３８】[0038]
【発明の実施の形態】以下、本発明の固体高分子型燃料
電池及びその製造方法の好適な実施形態について詳細に
説明する。BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the polymer electrolyte fuel cell and the method for producing the same according to the present invention will be described in detail below.
【００３９】本発明の固体高分子型燃料電池は、アノー
ドと、カソードと、アノードとカソードとの間に配置さ
れたイオン交換膜を備える。The polymer electrolyte fuel cell of the present invention comprises an anode, a cathode and an ion exchange membrane arranged between the anode and the cathode.
【００４０】アノードは電極触媒とイオン交換樹脂とを
含む触媒層を有するガス拡散電極である。電極触媒は、
白金又は白金合金からなる金属粒子と、該金属粒子の担
体となるカーボン担体とから構成されている。そして、
電極触媒を構成するカーボン担体は、先に述べた
ｄ002、Ｌｃ002及び比表面積の条件を満たす高い黒鉛化
度を有している。The anode is a gas diffusion electrode having a catalyst layer containing an electrode catalyst and an ion exchange resin. The electrode catalyst is
It is composed of metal particles composed of platinum or a platinum alloy, and a carbon carrier serving as a carrier for the metal particles. And
The carbon carrier constituting the electrode catalyst has a high degree of graphitization that satisfies the conditions of d 002 , Lc 002 and the specific surface area described above.
【００４１】また、高い電極反応活性を得る観点から、
アノードの電極触媒には充分な量の金属粒子が担持され
ていることが必要である。そのため、電極触媒における
金属粒子の担持量が、電極触媒の全質量に対して１０〜
６５質量％であることが好ましく、３０〜６０質量％で
あることがより好ましい。From the viewpoint of obtaining high electrode reaction activity,
It is necessary that the electrocatalyst of the anode carry a sufficient amount of metal particles. Therefore, the supported amount of metal particles in the electrode catalyst is 10 to the total mass of the electrode catalyst.
The content is preferably 65% by mass, more preferably 30 to 60% by mass.
【００４２】更に、一酸化炭素に対する優れた被毒耐性
を得る観点から、アノードの電極触媒を構成する金属粒
子の平均粒子径は１〜２０ｎｍであることが好ましく、
２〜５ｎｍであることがより好ましい。特に、金属粒子
の平均粒子径が２〜５ｎｍである場合には、金属粒子の
表面積を大きく確保できるため優れた水素酸化反応活性
を得ることが容易となる。Further, from the viewpoint of obtaining excellent poisoning resistance to carbon monoxide, the average particle size of the metal particles constituting the electrode catalyst of the anode is preferably 1 to 20 nm,
It is more preferably 2 to 5 nm. In particular, when the average particle diameter of the metal particles is 2 to 5 nm, a large surface area of the metal particles can be secured, so that it becomes easy to obtain excellent hydrogen oxidation reaction activity.
【００４３】また、アノードの電極触媒において、カー
ボン担体に担持される金属粒子である白金又は白金合金
のうち、白金は固体高分子型燃料電池におけるアノード
での水素酸化反応に対して高い活性を有する。また、白
金合金を使用すると電極触媒としてのより高い安定性や
より高い電極反応活性を更に付与することができる。In the anode electrocatalyst, of the metal particles platinum or platinum alloy supported on the carbon carrier, platinum has high activity for hydrogen oxidation reaction at the anode in the polymer electrolyte fuel cell. . Further, when a platinum alloy is used, higher stability as an electrode catalyst and higher electrode reaction activity can be further imparted.
【００４４】ここで、アノードに用いる電極触媒を構成
する金属粒子として白金合金を使用する場合、白金合金
は、ルテニウム、ロジウム、パラジウム、オスミウム、
イリジウム、コバルト、ニッケル、クロム、金、鉄、モ
リブデン及びスズからなる群から選択される少なくとも
１種の金属と白金との合金であることが好ましい。When a platinum alloy is used as the metal particles constituting the electrode catalyst used for the anode, the platinum alloy is ruthenium, rhodium, palladium, osmium,
An alloy of platinum with at least one metal selected from the group consisting of iridium, cobalt, nickel, chromium, gold, iron, molybdenum and tin is preferable.
【００４５】なお、本発明において、「白金合金」と
は、上述の白金と合金化される金属の少なくとも１種と
白金との合金であり、該合金の組織には、金属間化合
物、固溶体、共融混合物或いはこれらが共存するものが
含有されていてもよい。In the present invention, the "platinum alloy" is an alloy of platinum with at least one of the above-mentioned metals alloyed with platinum, and the texture of the alloy includes intermetallic compounds, solid solutions, A eutectic mixture or those in which these coexist may be contained.
【００４６】更に、電極触媒の金属粒子として白金合金
を使用する場合、その組成は合金化する金属の種類にも
よるが、金属粒子中において白金が３０〜９０原子％、
合金化する金属が１０〜７０原子％であることが好まし
い。When a platinum alloy is used as the metal particles of the electrode catalyst, its composition depends on the kind of metal to be alloyed, but platinum in the metal particles is 30 to 90 atom%,
The metal to be alloyed is preferably 10 to 70 atom%.
【００４７】本発明におけるアノードの触媒層に含有さ
れるイオン交換樹脂は、スルホン酸基を有するパーフル
オロカーボン重合体からなることが好ましい。特に、下
記式（Ａ）で表されるパーフルオロビニル化合物に基づ
く重合単位（式中、ｍは０〜３の整数、ｎは１〜１２の
整数、ｐは０又は１であり、Ｘはフッ素原子又はトリフ
ルオロメチル基である）と、テトラフルオロエチレン
（ＣＦ2＝ＣＦ2）に基づく重合単位とからなる共重合体
が好ましい。The ion exchange resin contained in the catalyst layer of the anode in the present invention is preferably made of a perfluorocarbon polymer having a sulfonic acid group. In particular, polymerized units based on a perfluorovinyl compound represented by the following formula (A) (in the formula, m is an integer of 0 to 3, n is an integer of 1 to 12, p is 0 or 1, and X is fluorine). Atoms or trifluoromethyl groups) and polymer units based on tetrafluoroethylene (CF 2 ═CF 2 ) are preferred.
【化１】 [Chemical 1]
【００４８】なお、本明細書において、「パーフルオロ
カーボン重合体」とは、炭素原子とフッ素原子のみから
なる重合体だけではなく、炭素原子と結合する水素原子
が全てフッ素原子と置換されていればエーテル結合性の
酸素原子等を含有するものも含むものとする。In the present specification, the "perfluorocarbon polymer" is not limited to a polymer consisting of carbon atoms and fluorine atoms only, but all hydrogen atoms bonded to carbon atoms are replaced with fluorine atoms. Those containing an ether-bonding oxygen atom and the like are also included.
【００４９】また、アノードにおいて、電極内における
反応サイト（三相界面）を十分に確保して高い電極反応
活性を得る観点から、電極触媒はイオン交換樹脂に被覆
されていることが好ましい。触媒層に含有される電極触
媒に対するイオン交換樹脂の被覆量は、電池の性能を大
きく作用する。この観点から、アノードの触媒層中のイ
オン交換樹脂の含有量は、電極触媒の全質量に対して２
０〜６０質量％であることが好ましい。アノードの触媒
層中のイオン交換樹脂の含有量が２０％よりも小さい
と、十分な水素酸化活性が得られなくなるおそれがあ
る。一方、触媒層中のイオン交換樹脂の含有量が６０％
よりも多くなると、ＣＯによる被毒が起こりやすくなり
電池性能が低下するおそれがある。In the anode, the electrode catalyst is preferably coated with an ion exchange resin from the viewpoint of sufficiently securing reaction sites (three-phase interface) in the electrode and obtaining high electrode reaction activity. The coating amount of the ion exchange resin with respect to the electrode catalyst contained in the catalyst layer greatly affects the performance of the battery. From this viewpoint, the content of the ion exchange resin in the catalyst layer of the anode is 2 with respect to the total mass of the electrode catalyst.
It is preferably from 0 to 60 mass%. When the content of the ion exchange resin in the catalyst layer of the anode is less than 20%, sufficient hydrogen oxidation activity may not be obtained. On the other hand, the content of ion exchange resin in the catalyst layer is 60%
If it is more than the above range, poisoning by CO is likely to occur and the battery performance may be deteriorated.
【００５０】更に、アノードの触媒層中には、撥水化剤
が含まれていてもよく、撥水化剤は特に限定されず、公
知のものを使用してよい。Further, a water repellent agent may be contained in the catalyst layer of the anode, and the water repellent agent is not particularly limited, and known ones may be used.
【００５１】なお、電極内におけるガス拡散性を十分に
確保して高い電極反応活性を得る観点から、アノード
は、触媒層のイオン交換膜に接触していない側の面にガ
ス拡散層を更に配置した構成とすることが好ましい。こ
のようなガス拡散層の構成材料は特に限定されないが、
例えば、電子伝導性を有する多孔質体（例えば、カーボ
ンクロスやカーボンペーパー）を用いてもよい。From the viewpoint of ensuring sufficient gas diffusibility in the electrode and obtaining high electrode reaction activity, the anode further has a gas diffusion layer on the surface of the catalyst layer that is not in contact with the ion exchange membrane. It is preferable to adopt the above configuration. The constituent material of such a gas diffusion layer is not particularly limited,
For example, a porous body having electron conductivity (for example, carbon cloth or carbon paper) may be used.
【００５２】また、本発明において、カソードの構成は
特に限定されないが、アノードと同様に、触媒層の他に
ガス拡散層を有していることが好ましい。更に、カソー
ドに使用する電極触媒は特に限定されず、例えば、アノ
ードに用いた電極触媒を使用してもよい。固体高分子型
燃料電池では、出力を確保するために大電流を流すこと
が想定されており、この条件下では、カソードにおいて
酸素の還元反応によって多量の水が生成するため、特
に、カソードの撥水性を十分に確保することが重要とな
る。この観点から、アノードに用いた電極触媒を用いる
場合、電極触媒を構成するカーボン担体は黒鉛化度が高
いので高い撥水性を有しており、カソードにおける生成
水の外部への排除を効率よく行うことが可能となる。そ
のため、長期にわたって安定した電池出力特性が得られ
る。In the present invention, the structure of the cathode is not particularly limited, but it is preferable that the cathode has a gas diffusion layer in addition to the catalyst layer, like the anode. Further, the electrode catalyst used for the cathode is not particularly limited, and for example, the electrode catalyst used for the anode may be used. In a polymer electrolyte fuel cell, it is assumed that a large current is passed in order to secure the output. Under this condition, a large amount of water is generated by the reduction reaction of oxygen at the cathode. It is important to ensure sufficient water content. From this point of view, when the electrode catalyst used for the anode is used, the carbon carrier constituting the electrode catalyst has a high degree of graphitization and thus has high water repellency, and the generated water at the cathode is efficiently removed to the outside. It becomes possible. Therefore, stable battery output characteristics can be obtained over a long period of time.
【００５３】また、カソードの電極触媒において、カー
ボン担体に担持される金属粒子は特に限定されない。例
えば、アノードと同様に白金又は白金合金からなる金属
粒子を用いてもよい。白金又は白金合金のうち、白金は
固体高分子型燃料電池におけるカソードでの酸素還元反
応に対して高い活性を有する。また、白金合金を使用す
ると電極触媒としてより高い安定性やより高い電極反応
活性を更に付与することができる。Further, in the cathode electrode catalyst, the metal particles supported on the carbon carrier are not particularly limited. For example, like the anode, metal particles made of platinum or a platinum alloy may be used. Of platinum and platinum alloys, platinum has high activity for oxygen reduction reaction at the cathode in a polymer electrolyte fuel cell. In addition, when a platinum alloy is used, higher stability as an electrode catalyst and higher electrode reaction activity can be further imparted.
【００５４】また、本発明において、カソードの触媒層
に含まれるイオン交換樹脂も特に限定されるものではな
く、例えば、上述したアノードの触媒層に含まれるイオ
ン交換樹脂と同様の樹脂を使用してもよい。In the present invention, the ion exchange resin contained in the cathode catalyst layer is not particularly limited, and for example, the same resin as the ion exchange resin contained in the anode catalyst layer described above is used. Good.
【００５５】更に、本発明において、イオン交換膜を構
成するイオン交換樹脂は特に限定されないが、アノード
の触媒層に含有されるイオン交換樹脂と同様にスルホン
酸基を有するパーフルオロカーボン重合体からなること
が好ましい。このようなイオン交換膜としては、例え
ば、ナフィオン（デュポン社製、商品名）、フレミオン
（旭硝子社製、商品名）等が挙げられる。Further, in the present invention, the ion exchange resin constituting the ion exchange membrane is not particularly limited, but is made of a perfluorocarbon polymer having a sulfonic acid group like the ion exchange resin contained in the catalyst layer of the anode. Is preferred. Examples of such an ion exchange membrane include Nafion (manufactured by DuPont, trade name) and Flemion (manufactured by Asahi Glass Co., Ltd.).
【００５６】また、本発明の固体高分子型燃料電池は、
イオン交換膜とその両面に配置されるアノード及びカソ
ードが接合されて一体化されたいわゆる膜・電極接合体
であることが好ましい。The polymer electrolyte fuel cell of the present invention is
A so-called membrane-electrode assembly in which an ion exchange membrane and an anode and a cathode arranged on both surfaces thereof are joined and integrated is preferable.
【００５７】次に、本発明の固体高分子型燃料電池の製
造方法について説明する。本発明の固体高分子型燃料電
池の製造方法は、先に述べたように、比表面積が３００
ｍ2／ｇ以上であるカーボンブラック又は活性炭を１０
００〜２２００℃の温度条件のもとで加熱処理すること
によりカーボン担体を調製し、次いで、得られたカーボ
ン担体に金属粒子を担持させることにより電極触媒を調
製する工程を含む方法であればよく、他の製造手順は特
に限定されない。Next, a method for manufacturing the polymer electrolyte fuel cell of the present invention will be described. As described above, the method for producing a polymer electrolyte fuel cell of the present invention has a specific surface area of 300.
m 2 / g or more carbon black or activated carbon 10
Any method may be used as long as it includes a step of preparing a carbon carrier by heat treatment under a temperature condition of 00 to 2200 ° C., and then preparing an electrode catalyst by supporting metal particles on the obtained carbon carrier. The other manufacturing procedure is not particularly limited.
【００５８】この電極触媒を調製する工程において使用
する上述の比表面積の条件を満たすカーボンブラックと
しては、チャンネルブラック、ファーネスブラック、サ
ーマルブラック等があげられる。また、上述の比表面積
の条件を満たす活性炭としては、種々の炭素原子を含む
材料を炭化、賦活処理したものが使用できる。なお、
「カーボンブラック」とは、炭化水素の液体や気体の熱
分解によって製造されるものである。また、「活性炭」
とは、原料として植物系の木材、のこくず、ヤシ殻、パ
ルプ廃液などと鉱物系の石炭、石油コークス、石油ピッ
チなどを使用し、これを炭化し、更に水蒸気賦活、薬品
賦活などを行って製造されるものである。Examples of carbon black used in the step of preparing this electrode catalyst which satisfies the above-mentioned specific surface area include channel black, furnace black and thermal black. Further, as the activated carbon satisfying the above-mentioned specific surface area, those obtained by carbonizing and activating a material containing various carbon atoms can be used. In addition,
"Carbon black" is produced by thermal decomposition of a liquid or gas of hydrocarbon. Also, "activated carbon"
Is used as raw materials, such as plant-based wood, sawdust, coconut shells, pulp waste liquor and mineral-based coal, petroleum coke, petroleum pitch, etc., which are carbonized, and steam activation and chemical activation are performed. It is manufactured by
【００５９】また、電極触媒を調製する工程において、
加熱処理後に得られるカーボン担体に金属粒子を担持す
る場合、例えば、以下の手順により行うことができる。
すなわち、先ず、白金からなる金属粒子を担持させる場
合には、例えば、白金の塩（例えば、塩化第一白金酸
等）の水溶液、又は、白金の塩を水／アルコール混合溶
媒に溶解した溶液に、カーボン担体を分散させる。一
方、白金合金からなる金属粒子を担持させる場合には、
上述した白金の塩の溶液に対して更に白金と合金化させ
る金属の化合物を溶解又は分散させる。ここで、白金と
合金化させる金属の化合物としては、塩化物、臭化物等
のハロゲン化物、メトキシド、エトキシド等のアルコキ
シド、酸化物、硝酸塩、硫化物等を用いることが好まし
い。In the step of preparing the electrode catalyst,
When carrying the metal particles on the carbon support obtained after the heat treatment, for example, the following procedure can be performed.
That is, first, in the case of supporting metal particles made of platinum, for example, an aqueous solution of a platinum salt (for example, chloroplatinic acid chloride) or a solution of the platinum salt dissolved in a water / alcohol mixed solvent is used. , Disperse the carbon support. On the other hand, when supporting metal particles made of platinum alloy,
Further, a compound of a metal which is alloyed with platinum is dissolved or dispersed in the above-mentioned platinum salt solution. Here, as the compound of the metal to be alloyed with platinum, it is preferable to use a halide such as chloride and bromide, an alkoxide such as methoxide and ethoxide, an oxide, a nitrate, and a sulfide.
【００６０】次に、上述の溶液を加熱撹拌することによ
り、白金の塩を用いた場合には、白金の塩又はその反応
生成物をカーボン担体上に析出させる。また、白金合金
を用いた場合には、白金の塩若しくはその反応生成物、
及び／又は、白金と合金化させる金属の化合物若しくは
その反応生成物をカーボン担体上に析出させる。なお、
このとき上述の溶液のｐＨを必要に応じて調節してアル
カリ性とし、白金及び必要に応じて添加された白金と合
金化させる金属を、例えば水酸化物としてカーボン担体
上に析出させてもよい。Next, when a platinum salt is used, the platinum salt or its reaction product is deposited on the carbon support by heating and stirring the above solution. When a platinum alloy is used, platinum salt or its reaction product,
And / or a compound of a metal to be alloyed with platinum or a reaction product thereof is deposited on a carbon support. In addition,
At this time, the pH of the above-mentioned solution may be adjusted as necessary to make it alkaline, and a metal to be alloyed with platinum and optionally added platinum may be deposited on the carbon support as, for example, a hydroxide.
【００６１】次に、ろ過、洗浄、乾燥を適宜行う。次
に、水素ガス等により還元処理を施した後、ヘリウム、
アルゴン、窒素等の不活性ガス雰囲気下で、熱処理する
ことにより電極触媒を得ることができる。この熱処理の
温度条件としては、カーボン担体上に析出した金属の化
合物の粒子径と分散状態にもよるが、４５０〜９００℃
であることが好ましい。Next, filtration, washing and drying are appropriately performed. Next, after reducing with hydrogen gas or the like, helium,
An electrode catalyst can be obtained by heat treatment in an atmosphere of an inert gas such as argon or nitrogen. The temperature condition of this heat treatment depends on the particle size and dispersion state of the metal compound deposited on the carbon support, but it is 450 to 900 ° C.
Is preferred.
【００６２】また、本発明において、アノード又はカソ
ードとなるガス拡散電極とイオン交換膜とを一体化させ
た膜・電極接合体を製造する方法は特に限定されない
が、例えば、１）イオン交換膜上にガス拡散電極を直接
形成する方法、２）カーボンペーパー、カーボンクロス
等のガス拡散層となる基材上に触媒層を形成してガス拡
散電極とし、これとイオン交換膜と接合する方法、３）
平板上にガス拡散電極を形成し，これをイオン交換膜に
転写する方法等の種々の方法が採用できる。In the present invention, the method for producing the membrane / electrode assembly in which the gas diffusion electrode serving as the anode or the cathode and the ion exchange membrane are integrated is not particularly limited. For example, 1) on the ion exchange membrane 2) A method for directly forming a gas diffusion electrode on a substrate, 2) A method for forming a catalyst layer on a base material such as carbon paper or carbon cloth, which serves as a gas diffusion layer, to form a gas diffusion electrode, and bonding this to an ion exchange membrane, 3 )
Various methods such as a method of forming a gas diffusion electrode on a flat plate and transferring it to an ion exchange membrane can be adopted.
【００６３】更に、本発明において、アノード或いはカ
ソードとなるガス拡散電極の形成方法は特に限定されな
いが、電極触媒（アノードの場合には上述の電極触媒を
調製する工程において調製したものを使用する）、イオ
ン交換樹脂、撥水剤及び必要に応じて造孔剤、増粘剤、
希釈溶媒等を含む液を、イオン交換膜上又はカーボンペ
ーパー等の導電性多孔体上に噴霧、塗布、濾過等により
形成させる既知の手法が好ましい。また、ガス拡散電極
をイオン交換膜とは別個にカーボンペーパー等の導電性
多孔体上に形成した場合には、ガス拡散電極とイオン交
換膜とは、ホットプレス法、接着法（特開平７−２２０
７４１号公報参照）等により接合することが好ましい。Further, in the present invention, the method for forming the gas diffusion electrode serving as the anode or the cathode is not particularly limited, but an electrode catalyst (in the case of an anode, the one prepared in the above step of preparing the electrode catalyst is used). , Ion exchange resin, water repellent and, if necessary, pore former, thickener,
A known method in which a liquid containing a diluting solvent or the like is formed by spraying, coating, filtering or the like on the ion exchange membrane or the conductive porous body such as carbon paper is preferable. Further, when the gas diffusion electrode is formed on a conductive porous body such as carbon paper separately from the ion exchange membrane, the gas diffusion electrode and the ion exchange membrane are formed by a hot pressing method or an adhesion method (Japanese Patent Laid-Open No. 7- 220
No. 741)) and the like.
【００６４】[0064]
【実施例】以下、実施例及び比較例を挙げて本発明の固
体高分子型燃料電池及びその製造方法の内容を更に詳し
く説明するが、本発明はこれらの実施例に限定されるも
のではない。The contents of the polymer electrolyte fuel cell and the method for producing the same according to the present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. .
【００６５】（実施例１）先ず、以下の手順によりアノ
ードの触媒層に含有させる電極触媒を調製した。カーボ
ンブラック（比表面積：７５０ｍ2／ｇ、ｄ002：０．３
７１ｎｍ、Ｌｃ00 2：０．５ｎｍ）を、高周波誘導炉を
使用して、アルゴン雰囲気中、１２００℃の温度で５時
間加熱処理した。得られた炭素材料（カーボン担体）を
粉末Ｘ線回折法により解析したところ、ｄ002は０．３
５６ｎｍ、Ｌｃ002は１．０ｎｍであった。また、窒素
吸着法（ＢＥＴ法）によりその比表面積を測定したとこ
ろ７００ｍ2／ｇであった。Example 1 First, an electrode catalyst to be contained in the catalyst layer of the anode was prepared by the following procedure. Carbon black (specific surface area: 750 m 2 / g, d 002 : 0.3
71 nm, Lc 00 2 : 0.5 nm) was heat-treated for 5 hours at a temperature of 1200 ° C. in an argon atmosphere using a high frequency induction furnace. When the obtained carbon material (carbon carrier) was analyzed by a powder X-ray diffraction method, d 002 was 0.3.
56 nm and Lc 002 were 1.0 nm. The specific surface area was 700 m 2 / g as measured by the nitrogen adsorption method (BET method).
【００６６】次に、得られた炭素材料をイオン交換水中
に分散させ、５質量％の塩化第一白金酸（Ｈ2ＰｔＣ
ｌ6）水溶液と３５質量％ホルマリンを加えて−１０℃
に冷却して撹拌した。これに４０質量％水酸化ナトリウ
ム水溶液を滴下し、１時間還流した後、ろ過洗浄し、カ
ーボン担体上に白金が担持された電極触媒（白金の質
量：カーボン担体の質量＝４０：６０）を調製した。こ
の電極触媒を粉末Ｘ線回折法で測定したところ、カーボ
ン担体に担持された白金粒子の平均粒子径は約２．０ｎ
ｍであった。Next, the obtained carbon material is dispersed in ion-exchanged water, and 5 mass% of chloroplatinic acid (H 2 PtC) is added.
l 6 ) Add an aqueous solution and 35% by mass formalin to -10 ° C
It was cooled to and stirred. A 40 mass% sodium hydroxide aqueous solution was added dropwise to this, and the mixture was refluxed for 1 hour and then filtered and washed to prepare an electrode catalyst in which platinum was supported on a carbon carrier (mass of platinum: mass of carbon carrier = 40:60). did. When this electrode catalyst was measured by a powder X-ray diffraction method, the average particle size of the platinum particles supported on the carbon carrier was about 2.0 n.
It was m.
【００６７】次に、上記のアノードの触媒層に含有させ
る電極触媒を、ＣＦ2＝ＣＦ2に基づく繰返し単位と、Ｃ
Ｆ2＝ＣＦ−ＯＣＦ2ＣＦ（ＣＦ3）ＣＦ2ＣＦ2ＳＯ3Ｈに
基づく繰返し単位とからなる共重合体（イオン交換容
量：１．１ミリ当量／ｇ乾燥樹脂）の６％エタノール溶
液中に混合し、分散させた後、イオン交換水を添加し、
撹拌してアノードの触媒層形成用のインク（以下、イン
ク１という）を調製した。次にこのインク１をカーボン
クロス（厚さ：４００μｍ）上に塗工し、次いで、乾燥
させた。そして、電極の単位面積当たりの金属粒子の含
有量が０．４ｍｇ／ｃｍ2であるアノード用のガス拡散
電極を作製した。Next, the electrocatalyst contained in the above-mentioned anode catalyst layer was mixed with a repeating unit based on CF 2 = CF 2 and C
F 2 = CF-OCF 2 CF (CF 3 ) CF 2 CF 2 SO 3 H in a 6% ethanol solution of a copolymer (repeating unit based on ion exchange capacity: 1.1 meq / g dry resin) After mixing and dispersing, add ion-exchanged water,
An ink for forming a catalyst layer of the anode (hereinafter referred to as ink 1) was prepared by stirring. Next, this ink 1 was applied onto carbon cloth (thickness: 400 μm), and then dried. Then, a gas diffusion electrode for an anode having a content of metal particles per unit area of the electrode of 0.4 mg / cm 2 was produced.
【００６８】次に、上記のインク１を用いてアノードの
作成手順と同様の手順により、電極の単位面積当たりの
金属粒子の含有量が０．４ｍｇ／ｃｍ2であるカソード
用のガス拡散電極を作製した。また、イオン交換膜とし
ては、膜厚が５０μｍのスルホン酸基を有するパーフル
オロカーボン重合体からなるイオン交換膜（商品名：フ
レミオン，旭硝子社製）を準備した。Next, a gas diffusion electrode for a cathode having a metal particle content of 0.4 mg / cm 2 per unit area of the electrode was prepared by the same procedure as the anode preparation procedure using Ink 1 described above. It was made. As the ion exchange membrane, an ion exchange membrane (trade name: Flemion, manufactured by Asahi Glass Co., Ltd.) made of a perfluorocarbon polymer having a sulfonic acid group and having a thickness of 50 μm was prepared.
【００６９】次に、アノードの触媒層とカソードの触媒
層との間にイオン交換膜が配置される状態でアノードと
カソードとの間にイオン交換膜を接触させてホットプレ
スし、膜・電極接合体（有効電極面積；２５ｃｍ2）を
作製した。Next, in a state where the ion exchange membrane is arranged between the catalyst layer of the anode and the catalyst layer of the cathode, the ion exchange membrane is brought into contact with the anode and the cathode and hot-pressed to bond the membrane and the electrode. A body (effective electrode area; 25 cm 2 ) was prepared.
【００７０】（実施例２）以下の手順により調製した電
極触媒をアノードの触媒層の電極触媒として使用したこ
と以外は、実施例１と同様にしてアノード用のガス拡散
電極を作製し、実施例１と同様にして膜・電極接合体を
作製した。(Example 2) A gas diffusion electrode for an anode was prepared in the same manner as in Example 1 except that the electrode catalyst prepared by the following procedure was used as the electrode catalyst of the catalyst layer of the anode. A membrane / electrode assembly was prepared in the same manner as in 1.
【００７１】すなわち、先ず、実施例１において調製し
た白金をカーボン担体に担持させた電極触媒５ｇをイオ
ン交換水２５０ｍｌ中に分散させた。次に、この分散液
に塩化ルテニウムを添加し、加熱撹拌を行い、塩化ルテ
ニウムを含浸させた。なお、このときの塩化ルテニウム
は、この塩中のルテニウムの質量（金属状態に換算した
場合の質量）が１．２ｇとなるようにその質量を調節し
て添加した。その後、この液にエタノールを５０ｍｌ加
えて加熱撹拌を３時間行った。That is, first, 5 g of the electrode catalyst prepared by loading platinum on a carbon carrier prepared in Example 1 was dispersed in 250 ml of ion-exchanged water. Next, ruthenium chloride was added to this dispersion, and the mixture was heated and stirred to impregnate ruthenium chloride. The ruthenium chloride at this time was added by adjusting its mass so that the mass of ruthenium in this salt (mass in terms of metal state) would be 1.2 g. Then, 50 ml of ethanol was added to this liquid, and the mixture was heated and stirred for 3 hours.
【００７２】加熱撹拌終了後、ろ過、乾燥した後、白金
とルテニウムの合金化処理を水素ガス中で行い、白金と
ルテニウムの原子比率が白金：ルテニウム＝１：１の合
金状態で担持された電極触媒（白金とルテニウムとを合
わせた質量：カーボンの質量＝５０：５０）を調製し
た。After completion of heating and stirring, filtration and drying are performed, and then an alloying treatment of platinum and ruthenium is performed in hydrogen gas, and an electrode is supported in an alloy state in which the atomic ratio of platinum and ruthenium is platinum: ruthenium = 1: 1. A catalyst (mass of platinum and ruthenium combined: mass of carbon = 50: 50) was prepared.
【００７３】（実施例３）以下の手順によりアノードの
触媒層に含有させる電極触媒を調製し、電極の単位面積
当たりの金属粒子の含有量が０．４ｍｇ／ｃｍ2である
アノード用のガス拡散電極を作製したこと以外は、実施
例１と同様にして固体高分子型燃料電池（膜・電極接合
体）を作製した。なお、イオン交換膜及びカソードは、
実施例１と同様のものを使用した。Example 3 An electrode catalyst to be contained in the catalyst layer of the anode was prepared according to the following procedure, and the gas diffusion for the anode in which the content of the metal particles per unit area of the electrode was 0.4 mg / cm 2. A polymer electrolyte fuel cell (membrane / electrode assembly) was produced in the same manner as in Example 1 except that the electrode was produced. The ion exchange membrane and the cathode are
The same one as in Example 1 was used.
【００７４】カーボンブラックの熱処理条件を１４００
℃で３時間とした以外は実施例１と同様に熱処理して、
ｄ002が０．３５１ｎｍ、Ｌｃ002が１．３ｎｍ、比表面
積が４００ｍ2／ｇの炭素材料を得た。The heat treatment condition of carbon black is 1400.
Heat treatment was performed in the same manner as in Example 1 except that the temperature was 3 hours,
A carbon material having d 002 of 0.351 nm, Lc 002 of 1.3 nm and a specific surface area of 400 m 2 / g was obtained.
【００７５】次に、この炭素材料を担体として用いた以
外は実施例１と同様にしてカーボン担体に白金が担持さ
れた触媒を調製した。この触媒を粉末Ｘ線回折法で測定
したところ、カーボン担体に担持された白金粒子の平均
粒子径は約２．０ｎｍであった。次に、この白金が担持
された触媒を使用して実施例２と同様にして白金とルテ
ニウムが合金状態で担持された電極触媒（白金とルテニ
ウムとを合わせた質量：カーボンの質量＝５０：５０）
を調製した。Next, a catalyst in which platinum was supported on a carbon carrier was prepared in the same manner as in Example 1 except that this carbon material was used as a carrier. When this catalyst was measured by a powder X-ray diffraction method, the average particle size of the platinum particles supported on the carbon carrier was about 2.0 nm. Next, using this platinum-supported catalyst, an electrode catalyst in which platinum and ruthenium were supported in an alloy state (mass of platinum and ruthenium combined: mass of carbon = 50: 50) was carried out in the same manner as in Example 2. )
Was prepared.
【００７６】（実施例４）以下の手順によりアノードの
触媒層に含有させる電極触媒を調製し、電極の単位面積
当たりの金属粒子の含有量が０．４ｍｇ／ｃｍ2である
アノード用のガス拡散電極を作製したこと以外は、実施
例１と同様にして固体高分子型燃料電池（膜・電極接合
体）を作製した。なお、イオン交換膜及びカソードは、
実施例１と同様のものを使用した。Example 4 An electrode catalyst to be contained in the catalyst layer of the anode was prepared by the following procedure, and the gas diffusion for the anode in which the content of metal particles per unit area of the electrode was 0.4 mg / cm 2. A polymer electrolyte fuel cell (membrane / electrode assembly) was produced in the same manner as in Example 1 except that the electrode was produced. The ion exchange membrane and the cathode are
The same one as in Example 1 was used.
【００７７】すなわち、実施例１で用いたものと同様の
カーボンブラックを使用し、このカーボンブラックの熱
処理条件を１１００℃で５時間とし、更に、抵抗加熱炉
を用いた以外は実施例１と同様にしてカーボン担体を得
た。得られたカーボン担体を実施例１と同様に評価した
ところ、ｄ002は０．３６１ｎｍ、Ｌｃ002は０．８ｎ
ｍ、比表面積は７２０ｍ2／ｇであった。That is, the same carbon black as that used in Example 1 was used, the heat treatment condition of this carbon black was 1100 ° C. for 5 hours, and the resistance heating furnace was used. To obtain a carbon support. When the obtained carbon support was evaluated in the same manner as in Example 1, d 002 was 0.361 nm and Lc 002 was 0.8 n.
m, the specific surface area was 720 m 2 / g.
【００７８】次に、このカーボン担体を担体として用い
た以外は実施例１と同様にしてカーボン担体に白金が担
持された触媒を調製した。この触媒を粉末Ｘ線回折法で
測定したところ、白金粒子の平均粒子径は約１．９ｎｍ
であった。次に、この白金が担持された触媒を使用して
実施例２と同様にして白金とルテニウムが合金状態で担
持された電極触媒（白金とルテニウムとを合わせた質
量：カーボンの質量＝５０：５０）を調製した。Next, a catalyst in which platinum was supported on a carbon carrier was prepared in the same manner as in Example 1 except that this carbon carrier was used as a carrier. When this catalyst was measured by a powder X-ray diffraction method, the average particle size of platinum particles was about 1.9 nm.
Met. Next, using this platinum-supported catalyst, an electrode catalyst in which platinum and ruthenium were supported in an alloy state (mass of platinum and ruthenium combined: mass of carbon = 50: 50) was carried out in the same manner as in Example 2. ) Was prepared.
【００７９】（比較例１）以下の手順によりアノードの
触媒層に含有させる電極触媒を調製し、電極の単位面積
当たりの金属粒子の含有量が０．４ｍｇ／ｃｍ2である
アノード用のガス拡散電極を作製したこと以外は、実施
例１と同様にして固体高分子型燃料電池（膜・電極接合
体）を作製した。なお、イオン交換膜及びカソードは、
実施例１と同様のものを使用した。Comparative Example 1 An electrode catalyst to be contained in the catalyst layer of the anode was prepared by the following procedure, and the gas diffusion for the anode in which the content of metal particles per unit area of the electrode was 0.4 mg / cm 2. A polymer electrolyte fuel cell (membrane / electrode assembly) was produced in the same manner as in Example 1 except that the electrode was produced. The ion exchange membrane and the cathode are
The same one as in Example 1 was used.
【００８０】すなわち、実施例１で用いたものと同様の
カーボンブラック使用し、このカーボンブラックの熱処
理条件を１９００℃で５時間とした以外は実施例１と同
様にしてカーボン担体を得た。得られたカーボン担体を
実施例１と同様に評価したところ、ｄ002は０．３４１
ｎｍ、Ｌｃ002は３．５ｎｍ、比表面積は２１０ｍ2／ｇ
であった。That is, a carbon support was obtained in the same manner as in Example 1 except that the same carbon black as that used in Example 1 was used and the heat treatment condition of this carbon black was 1900 ° C. for 5 hours. When the obtained carbon support was evaluated in the same manner as in Example 1, d 002 was 0.341.
nm, Lc 002 is 3.5 nm, specific surface area is 210 m 2 / g
Met.
【００８１】次に、このカーボン担体を担体として用い
た以外は実施例１と同様にしてカーボン担体に白金が担
持された触媒を調製した。この触媒を粉末Ｘ線回折法で
測定したところ、白金粒子の平均粒子径は約２．１ｎｍ
であった。次に、この白金が担持された触媒を使用して
実施例２と同様にして白金とルテニウムが合金状態で担
持された電極触媒（白金とルテニウムとを合わせた質
量：カーボンの質量＝５０：５０）を調製した。Then, a catalyst in which platinum was supported on a carbon carrier was prepared in the same manner as in Example 1 except that this carbon carrier was used as a carrier. When this catalyst was measured by a powder X-ray diffraction method, the average particle size of platinum particles was about 2.1 nm.
Met. Next, using this platinum-supported catalyst, an electrode catalyst in which platinum and ruthenium were supported in an alloy state (mass of platinum and ruthenium combined: mass of carbon = 50: 50) was carried out in the same manner as in Example 2. ) Was prepared.
【００８２】（比較例２）以下の手順によりアノードの
触媒層に含有させる電極触媒を調製し、電極の単位面積
当たりの金属粒子の含有量が０．４ｍｇ／ｃｍ2である
アノード用のガス拡散電極を作製したこと以外は、実施
例１と同様にして固体高分子型燃料電池（膜・電極接合
体）を作製した。なお、イオン交換膜及びカソードは、
実施例１と同様のものを使用した。Comparative Example 2 An electrode catalyst to be contained in the catalyst layer of the anode was prepared by the following procedure, and the gas diffusion for the anode in which the content of metal particles per unit area of the electrode was 0.4 mg / cm 2. A polymer electrolyte fuel cell (membrane / electrode assembly) was produced in the same manner as in Example 1 except that the electrode was produced. The ion exchange membrane and the cathode are
The same one as in Example 1 was used.
【００８３】すなわち、実施例１で用いたものと同様の
カーボンブラックを熱処理せずにそのまま担体として使
用した以外は実施例１と同様にして電極触媒を調製し
た。この電極触媒を粉末Ｘ線回折法で測定したところ、
白金粒子の平均粒子径は約２．０ｎｍであった。That is, an electrode catalyst was prepared in the same manner as in Example 1 except that the same carbon black as that used in Example 1 was used as a carrier as it was without heat treatment. When this electrode catalyst was measured by a powder X-ray diffraction method,
The average particle size of the platinum particles was about 2.0 nm.
【００８４】（比較例３）以下の手順によりアノードの
触媒層に含有させる電極触媒を調製し、電極の単位面積
当たりの金属粒子の含有量が０．４ｍｇ／ｃｍ2である
アノード用のガス拡散電極を作製したこと以外は、実施
例１と同様にして固体高分子型燃料電池（膜・電極接合
体）を作製した。なお、イオン交換膜及びカソードは、
実施例１と同様のものを使用した。(Comparative Example 3) An electrode catalyst to be contained in the catalyst layer of the anode was prepared by the following procedure, and gas diffusion for the anode in which the content of metal particles per unit area of the electrode was 0.4 mg / cm 2. A polymer electrolyte fuel cell (membrane / electrode assembly) was produced in the same manner as in Example 1 except that the electrode was produced. The ion exchange membrane and the cathode are
The same one as in Example 1 was used.
【００８５】すなわち、比較例２で調製した白金が担持
された触媒を使用して、実施例２と同様にして白金とル
テニウムが合金状態で担持された電極触媒（白金とルテ
ニウムとを合わせた質量：カーボンの質量＝５０：５
０）を調製した。That is, the platinum-supported catalyst prepared in Comparative Example 2 was used in the same manner as in Example 2 to carry out the platinum-ruthenium alloy-supported electrode catalyst (the mass of platinum and ruthenium combined). : Carbon mass = 50: 5
0) was prepared.
【００８６】（比較例４）以下の手順によりアノードの
触媒層に含有させる電極触媒を調製し、電極の単位面積
当たりの金属粒子の含有量が０．４ｍｇ／ｃｍ2である
アノード用のガス拡散電極を作製したこと以外は、実施
例１と同様にして固体高分子型燃料電池（膜・電極接合
体）を作製した。なお、イオン交換膜及びカソードは、
実施例１と同様のものを使用した。(Comparative Example 4) An electrode catalyst to be contained in the catalyst layer of the anode was prepared by the following procedure, and the gas diffusion for the anode in which the content of metal particles per unit area of the electrode was 0.4 mg / cm 2. A polymer electrolyte fuel cell (membrane / electrode assembly) was produced in the same manner as in Example 1 except that the electrode was produced. The ion exchange membrane and the cathode are
The same one as in Example 1 was used.
【００８７】すなわち、カーボンブラック（比表面積：
２５０ｍ2／ｇ、ｄ002：０．３５７ｎｍ、Ｌｃ002：
１．５ｎｍ）を高周波誘導炉を使用して、アルゴンガス
雰囲気中、２０００℃の温度で５時間加熱処理した。得
られた炭素材料（カーボン担体）を実施例１と同様に評
価したところ、ｄ002は０．３４４ｎｍ、Ｌｃ002は６．
０ｎｍ、比表面積は１００ｍ2／ｇであった。That is, carbon black (specific surface area:
250 m 2 / g, d 002 : 0.357 nm, Lc 002 :
(1.5 nm) was heat-treated at a temperature of 2000 ° C. for 5 hours in an argon gas atmosphere using a high frequency induction furnace. When the obtained carbon material (carbon carrier) was evaluated in the same manner as in Example 1, d 002 was 0.344 nm and Lc 002 was 6.
The surface area was 0 nm and the specific surface area was 100 m 2 / g.
【００８８】そして、このカーボン担体を用いた以外は
実施例１と同様にして白金がカーボン担体に担持された
触媒を調製した。この触媒を粉末Ｘ線回折法で測定した
ところ、白金粒子の平均粒子径は約２．２ｎｍであっ
た。次に、この白金が担持された触媒を使用して実施例
２と同様にして白金とルテニウムが合金状態で担持され
た電極触媒（白金とルテニウムとを合わせた質量：カー
ボンの質量＝５０：５０）を調製した。なお、イオン交
換膜及びカソードは、実施例１と同様のものを使用し
た。Then, a catalyst in which platinum was supported on a carbon carrier was prepared in the same manner as in Example 1 except that this carbon carrier was used. When this catalyst was measured by powder X-ray diffractometry, the average particle size of platinum particles was about 2.2 nm. Next, using this platinum-supported catalyst, an electrode catalyst in which platinum and ruthenium were supported in an alloy state (mass of platinum and ruthenium combined: mass of carbon = 50: 50) was carried out in the same manner as in Example 2. ) Was prepared. The same ion exchange membrane and cathode as in Example 1 were used.
【００８９】（比較例５）以下の手順によりアノードの
触媒層に含有させる電極触媒を調製し、電極の単位面積
当たりの金属粒子の含有量が０．４ｍｇ／ｃｍ2である
アノード用のガス拡散電極を作製したこと以外は、実施
例１と同様にして固体高分子型燃料電池（膜・電極接合
体）を作製した。なお、イオン交換膜及びカソードは、
実施例１と同様のものを使用した。Comparative Example 5 An electrode catalyst to be contained in the catalyst layer of the anode was prepared by the following procedure, and the gas diffusion for the anode in which the content of metal particles per unit area of the electrode was 0.4 mg / cm 2. A polymer electrolyte fuel cell (membrane / electrode assembly) was produced in the same manner as in Example 1 except that the electrode was produced. The ion exchange membrane and the cathode are
The same one as in Example 1 was used.
【００９０】すなわち、カーボンブラック（比表面積：
７５０ｍ2／ｇ、ｄ002：０．３７１ｎｍ、Ｌｃ002：
０．５ｎｍ）を抵抗加熱炉を使用して、８００℃の温度
で５時間加熱処理した。得られた炭素材料（カーボン担
体）を実施例１と同様に評価したところ、ｄ002は０．
３６９ｎｍ、Ｌｃ002は０．４５ｎｍ、比表面積は７４
０ｍ2／ｇであった。That is, carbon black (specific surface area:
750 m 2 / g, d 002 : 0.371 nm, Lc 002 :
0.5 nm) was heat-treated at a temperature of 800 ° C. for 5 hours using a resistance heating furnace. When the obtained carbon material (carbon support) was evaluated in the same manner as in Example 1, d 002 was 0.
369 nm, Lc 002 0.45 nm, specific surface area 74
It was 0 m 2 / g.
【００９１】そして、このカーボン担体を用いた以外は
実施例１と同様にして白金がカーボン担体に担持された
触媒を調製した。この触媒を粉末Ｘ線回折法で測定した
ところ、白金粒子の平均粒子径は約２．０ｎｍであっ
た。次に、この白金が担持された触媒を使用して実施例
２と同様にして白金とルテニウムが合金状態で担持され
た電極触媒（白金とルテニウムとを合わせた質量：カー
ボンの質量＝５０：５０）を調製した。Then, a catalyst in which platinum was supported on a carbon carrier was prepared in the same manner as in Example 1 except that this carbon carrier was used. When this catalyst was measured by a powder X-ray diffraction method, the average particle size of platinum particles was about 2.0 nm. Next, using this platinum-supported catalyst, an electrode catalyst in which platinum and ruthenium were supported in an alloy state (mass of platinum and ruthenium combined: mass of carbon = 50: 50) was carried out in the same manner as in Example 2. ) Was prepared.
【００９２】（比較例６）以下の手順によりアノードの
触媒層に含有させる電極触媒を調製し、電極の単位面積
当たりの金属粒子の含有量が０．４ｍｇ／ｃｍ2である
アノード用のガス拡散電極を作製したこと以外は、実施
例１と同様にして固体高分子型燃料電池（膜・電極接合
体）を作製した。なお、イオン交換膜及びカソードは、
実施例１と同様のものを使用した。Comparative Example 6 An electrode catalyst to be contained in the catalyst layer of the anode was prepared by the following procedure, and the gas diffusion for the anode in which the content of metal particles per unit area of the electrode was 0.4 mg / cm 2. A polymer electrolyte fuel cell (membrane / electrode assembly) was produced in the same manner as in Example 1 except that the electrode was produced. The ion exchange membrane and the cathode are
The same one as in Example 1 was used.
【００９３】すなわち、カーボンブラック（比表面積：
７５０ｍ2／ｇ、ｄ002：０．３７１ｎｍ、Ｌｃ002：
０．５ｎｍ）を高周波誘導炉を使用して、２３００℃で
３時間加熱処理した。得られた炭素材料（カーボン担
体）を実施例１と同様に評価したところ、ｄ002は０．
３３９ｎｍ、Ｌｃ002は１．５ｎｍ、比表面積は２１０
ｍ2／ｇであった。That is, carbon black (specific surface area:
750 m 2 / g, d 002 : 0.371 nm, Lc 002 :
0.5 nm) was heat-treated at 2300 ° C. for 3 hours using a high frequency induction furnace. When the obtained carbon material (carbon support) was evaluated in the same manner as in Example 1, d 002 was 0.
339 nm, Lc 002 1.5 nm, specific surface area 210
It was m 2 / g.
【００９４】そして、このカーボン担体を用いた以外は
実施例１と同様にして白金がカーボン担体に担持された
触媒を調製した。この触媒を粉末Ｘ線回折法で測定した
ところ、白金粒子の平均粒子径は約２．３ｎｍであっ
た。次に、この白金が担持された触媒を使用して実施例
２と同様にして白金とルテニウムが合金状態で担持され
た電極触媒（白金とルテニウムとを合わせた質量：カー
ボンの質量＝５０：５０）を調製した。なお、イオン交
換膜及びカソードは、実施例１と同様のものを使用し
た。Then, a catalyst in which platinum was supported on a carbon carrier was prepared in the same manner as in Example 1 except that this carbon carrier was used. When this catalyst was measured by a powder X-ray diffraction method, the average particle size of platinum particles was about 2.3 nm. Next, using this platinum-supported catalyst, an electrode catalyst in which platinum and ruthenium were supported in an alloy state (mass of platinum and ruthenium combined: mass of carbon = 50: 50) was carried out in the same manner as in Example 2. ) Was prepared. The same ion exchange membrane and cathode as in Example 1 were used.
【００９５】（比較例７）以下の手順によりアノードの
触媒層に含有させる電極触媒を調製し、電極の単位面積
当たりの金属粒子の含有量が０．４ｍｇ／ｃｍ2である
アノード用のガス拡散電極を作製したこと以外は、実施
例１と同様にして固体高分子型燃料電池（膜・電極接合
体）を作製した。なお、イオン交換膜及びカソードは、
実施例１と同様のものを使用した。Comparative Example 7 An electrode catalyst to be contained in the catalyst layer of the anode was prepared by the following procedure, and the gas diffusion for the anode in which the content of metal particles per unit area of the electrode was 0.4 mg / cm 2. A polymer electrolyte fuel cell (membrane / electrode assembly) was produced in the same manner as in Example 1 except that the electrode was produced. The ion exchange membrane and the cathode are
The same one as in Example 1 was used.
【００９６】すなわち、カーボンブラック（比表面積：
２５０ｍ2／ｇ、ｄ002：０．３５７ｎｍ、Ｌｃ002：
１．５ｎｍ）を高周波誘導炉を使用し、アルゴンガス雰
囲気下中、１５００℃の温度で３時間加熱処理した。得
られた炭素材料（カーボン担体）を実施例１と同様に評
価したところ、ｄ002は０．３４５ｎｍ、Ｌｃ002は３．
５ｎｍ、比表面積は１１０ｍ2／ｇであった。That is, carbon black (specific surface area:
250 m 2 / g, d 002 : 0.357 nm, Lc 002 :
(1.5 nm) was heat-treated for 3 hours at a temperature of 1500 ° C. in an argon gas atmosphere using a high frequency induction furnace. When the obtained carbon material (carbon support) was evaluated in the same manner as in Example 1, d 002 was 0.345 nm and Lc 002 was 3.
The surface area was 5 nm and the specific surface area was 110 m 2 / g.
【００９７】そして、このカーボン担体を用いた以外は
実施例１と同様にして白金がカーボン担体に担持された
触媒を調製した。この触媒を粉末Ｘ線回折法で測定した
ところ、白金粒子の平均粒子径は約２．８ｎｍであっ
た。次に、この白金が担持された触媒を使用して例２と
同様にして白金とルテニウムが合金状態で担持された電
極触媒（白金とルテニウムとを合わせた質量：カーボン
の質量＝５０：５０）を調製した。Then, a catalyst in which platinum was supported on a carbon carrier was prepared in the same manner as in Example 1 except that this carbon carrier was used. When this catalyst was measured by a powder X-ray diffraction method, the average particle size of platinum particles was about 2.8 nm. Next, using this platinum-supported catalyst, an electrode catalyst in which platinum and ruthenium were supported in an alloy state in the same manner as in Example 2 (mass of platinum and ruthenium combined: mass of carbon = 50: 50) Was prepared.
【００９８】[電池特性試験]上記の実施例１〜実施例
４、比較例１〜比較例７の各膜・電極接合体にガスの流
路が形成されたセパレータを装着して測定セルとし、電
子負荷と直流電源（高砂製作所社製，ＦＫ４００Ｌ及び
ＥＸ７５０Ｌ）を用いて測定セルの電流電圧特性試験を
行った。[Battery Characteristic Test] A separator having a gas channel formed therein was attached to each of the membrane / electrode assemblies of Examples 1 to 4 and Comparative Examples 1 to 7 to form a measurement cell. A current-voltage characteristic test of the measurement cell was performed using an electronic load and a DC power supply (FK400L and EX750L manufactured by Takasago Seisakusho Co., Ltd.).
【００９９】アノードに供給する燃料ガスとして、改質
模擬ガス（全圧：０．１５ＭＰａ，ガスの組成：Ｈ2７
５％，ＣＯ2２５％，ＣＯ２０ｐｐｍ）を使用し、カソ
ードに供給する酸化剤ガスとして空気（全圧：０．１５
ＭＰａ）を使用した。測定条件は、測定セルの作動温
度：８０℃、アノード側の水素ガス加湿器の温度；８０
℃、カソード側の空気加湿器の温度；８０℃とした。[0099] As the fuel gas supplied to the anode, reformed model gas (total pressure: 0.15 MPa, the composition of the gas: H 2 7
5%, CO 2 25%, CO 20 ppm) was used, and air (total pressure: 0.15) was used as the oxidant gas supplied to the cathode.
MPa) was used. The measurement conditions are: operating temperature of the measuring cell: 80 ° C., temperature of the hydrogen gas humidifier on the anode side; 80
The temperature of the air humidifier on the cathode side was 80 ° C.
【０１００】先ず、電流密度：０．８Ａ／ｃｍ2にて８
時間定電流駆動の通電を行った後、電流密度を０．３Ａ
／ｃｍ2に保持した場合における各測定セルの端子間電
圧（オーム損込みの電圧）の値の経時変化を測定した。
なお、測定時間は、電流密度を０．３Ａ／ｃｍ2に切り
替えた時点を測定開始時とし、初期（測定開始直後）、
５００時間後、１０００時間後における端子間電圧を測
定した。First, 8 at current density: 0.8 A / cm 2 .
After energizing for constant time current drive, current density is 0.3A
The time-dependent change in the value of the voltage between terminals (voltage of ohmic loss) of each measurement cell when held at / cm 2 was measured.
In addition, the measurement time is the time when the current density was switched to 0.3 A / cm 2 as the measurement start time, and the initial period (immediately after the measurement start)
The voltage between terminals was measured after 500 hours and 1000 hours.
【０１０１】また、表１に各測定セルのアノードの触媒
層に含有された電極触媒の特徴を示す。更に、表２に各
測定セルの電流電圧特性試験の結果を示す。Table 1 shows the characteristics of the electrode catalyst contained in the catalyst layer of the anode of each measurement cell. Further, Table 2 shows the result of the current-voltage characteristic test of each measuring cell.
【０１０２】また、実施例１、実施例２、比較例２及び
比較例３の各膜・電極接合体については、アノードに供
給する燃料ガスとして純水素（全圧：０．１５ＭＰａ）
を用いた以外は上述と同様の電池特性試験を行った。Further, in each of the membrane-electrode assemblies of Example 1, Example 2, Comparative Example 2 and Comparative Example 3, pure hydrogen (total pressure: 0.15 MPa) was used as the fuel gas supplied to the anode.
The same battery characteristic test as described above was performed except that the above was used.
【０１０３】その結果として、図１に、実施例１と比較
例２の膜・電極接合体について、燃料ガスとして純水素
を用いた場合と、改質模擬ガスを用いた場合の電流密度
−電池電圧特性曲線を示す。また、図２に、実施例２と
比較例３の膜・電極接合体について、燃料ガスとして純
水素を用いた場合と、改質模擬ガスを用いた場合の電流
密度−電池電圧特性曲線を示す。As a result, FIG. 1 shows the current densities of the membrane-electrode assemblies of Example 1 and Comparative Example 2 when pure hydrogen was used as the fuel gas and when the reforming simulation gas was used. A voltage characteristic curve is shown. Further, FIG. 2 shows current density-battery voltage characteristic curves of the membrane-electrode assemblies of Example 2 and Comparative Example 3 when pure hydrogen was used as the fuel gas and when the reforming simulation gas was used. .
【０１０４】[0104]
【表１】 [Table 1]
【０１０５】[0105]
【表２】 [Table 2]
【０１０６】[0106]
【発明の効果】本発明では、黒鉛化度の高められたカー
ボン担体を有する電極触媒を用いて、一酸化炭素に対す
る優れた被毒耐性と優れた水素酸化活性とを兼ね備えた
アノードを構成することができる。そのため、このアノ
ードを備えることにより、高い出力電圧を長期にわたっ
て安定して得ることができる軽量かつコンパクトな固体
高分子型燃料電池を構成することができる。EFFECTS OF THE INVENTION In the present invention, an anode having both excellent poisoning resistance to carbon monoxide and excellent hydrogen oxidation activity is constructed by using an electrode catalyst having a carbon support having an increased degree of graphitization. You can Therefore, by including this anode, it is possible to configure a lightweight and compact polymer electrolyte fuel cell that can stably obtain a high output voltage for a long period of time.
【図１】 本発明の固体高分子型燃料電池（実施例１）
と従来の固体高分子型燃料電池（比較例２）との電流密
度−電池電圧（端子間電圧）特性曲線を示すグラフであ
る。FIG. 1 is a polymer electrolyte fuel cell of the present invention (Example 1).
5 is a graph showing a current density-cell voltage (terminal voltage) characteristic curve of a conventional solid polymer electrolyte fuel cell (Comparative Example 2).
【図２】 本発明の固体高分子型燃料電池（実施例２）
と従来の固体高分子型燃料電池（比較例３）との電流密
度−電池電圧（端子間電圧）特性曲線を示すグラフであ
る。FIG. 2 is a polymer electrolyte fuel cell of the present invention (Example 2).
5 is a graph showing a current density-cell voltage (terminal voltage) characteristic curve of a conventional polymer electrolyte fuel cell (Comparative Example 3).
【符号の説明】
Ｃ１…アノードに水素ガスを供給した場合の実施例１の
固体高分子型燃料電池の電流密度−電池電圧特性曲線、
Ｃ２…アノードに水素ガスを供給した場合の比較例２の
固体高分子型燃料電池の電流密度−電池電圧特性曲線、
Ｃ３…アノードに改質模擬ガスを供給した場合の実施例
１の固体高分子型燃料電池の電流密度−電池電圧特性曲
線、Ｃ４…アノードに改質模擬ガスを供給した場合の比
較例２の固体高分子型燃料電池の電流密度−電池電圧特
性曲線、Ｃ５…アノードに水素ガスを供給した場合の実
施例２の固体高分子型燃料電池の電流密度−電池電圧特
性曲線、Ｃ６…アノードに水素ガスを供給した場合の比
較例３の固体高分子型燃料電池の電流密度−電池電圧特
性曲線、Ｃ７…アノードに改質模擬ガスを供給した場合
の実施例２の固体高分子型燃料電池の電流密度−電池電
圧特性曲線、Ｃ８…アノードに改質模擬ガスを供給した
場合の比較例３の固体高分子型燃料電池の電流密度−電
池電圧特性曲線。[Explanation of Codes] C1 ... Current density-cell voltage characteristic curve of the polymer electrolyte fuel cell of Example 1 when hydrogen gas is supplied to the anode,
C2 ... Current density-cell voltage characteristic curve of the polymer electrolyte fuel cell of Comparative Example 2 when hydrogen gas was supplied to the anode,
C3 ... Current density-cell voltage characteristic curve of polymer electrolyte fuel cell of Example 1 when reforming simulation gas was supplied to the anode, C4 ... Solid of comparative example 2 when reforming simulation gas was supplied to the anode Current density-cell voltage characteristic curve of polymer electrolyte fuel cell, C5 ... Current density-cell voltage characteristic curve of polymer electrolyte fuel cell of Example 2 when hydrogen gas is supplied to anode, C6 ... Hydrogen gas on anode Current density-cell voltage characteristic curve of the polymer electrolyte fuel cell of Comparative Example 3 when C is supplied, C7 ... Current density of the polymer electrolyte fuel cell of Example 2 when reforming simulation gas is supplied to the anode -Cell voltage characteristic curve, C8 ... Current density of the polymer electrolyte fuel cell of Comparative Example 3 when reforming simulation gas was supplied to the anode-Cell voltage characteristic curve.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 35/02 Ｂ０１Ｊ 35/02 Ｈ 37/02 １０１ 37/02 １０１Ｅ 37/08 37/08 37/18 37/18 Ｈ０１Ｍ 4/86 Ｈ０１Ｍ 4/86 Ｂ 4/88 4/88 Ｃ 4/92 4/92 8/02 8/02 Ｅ 8/10 8/10 Ｆターム(参考） 4G069 AA03 AA08 BA08A BA08B BB02A BB02B BC22A BC33A BC58A BC59A BC66A BC67A BC68A BC70A BC70B BC71A BC72A BC73A BC74A BC75A BC75B CC32 DA06 EA02X EA02Y EA08 EB18X EB18Y EB19 EC03X EC03Y EC04X EC04Y EC25 FA01 FA02 FA03 FB08 FB23 FB29 FB44 FC07 FC08 5H018 AA06 AS02 BB01 BB03 BB06 BB08 BB12 BB13 BB17 EE03 EE07 EE08 EE19 HH00 HH02 HH08 5H026 AA06 BB01 BB02 BB03 BB04 BB08 BB10 CX05 EE19 HH00 HH02 HH08 Front page continuation (51) Int.Cl. 7 Identification code FI theme code (reference) B01J 35/02 B01J 35/02 H 37/02 101 37/02 101E 37/08 37/08 37/18 37/18 H01M 4/86 H01M 4/86 B 4/88 4/88 C 4/92 4/92 8/02 8/02 E 8/10 8/10 F Term (reference) 4G069 AA03 AA08 BA08A BA08B BB02A BB02B BC22A BC33A BC58A BC59A BC66A BC67A BC68A BC70A BC70B BC71A BC72A BC73A BC74A BC75A BC75B CC32 DA06 EA02X EA02Y EA08 EB18X EB18Y EB19 EC03X EC03Y EC04X EC04Y EC25 FA01 FA02 FA03 FB08 FB23 FB29 FB44 FC07 FC08 5H018 AA06 AS02 BB01 BB03 BB06 BB08 BB12 BB13 BB17 EE03 EE07 EE08 EE19 HH00 HH02 HH08 5H026 AA06 BB01 BB02 BB03 BB04 BB08 BB10 CX05 EE19 HH00 HH02 HH08
Claims (5)
と前記カソードとの間に配置されたイオン交換膜とを有
する固体高分子型燃料電池であって、 前記アノードが、電極触媒とイオン交換樹脂とを含む触
媒層を有するガス拡散電極であり、 前記電極触媒が、白金又は白金合金からなる金属粒子
と、該金属粒子の担体となるカーボン担体とから構成さ
れており、 前記カーボン担体は、Ｘ線回折法により求められる格子
面［００２］の平均格子面間隔ｄ002が０．３４０〜
０．３６２ｎｍであり、結晶子の大きさＬｃ002が０．
６〜４ｎｍであり、かつ、比表面積が２６０〜８００ｍ
2／ｇであること、を特徴とする固体高分子型燃料電
池。1. A polymer electrolyte fuel cell having an anode, a cathode, and an ion exchange membrane disposed between the anode and the cathode, the anode comprising an electrode catalyst and an ion exchange resin. A gas diffusion electrode having a catalyst layer containing, wherein the electrode catalyst is composed of metal particles made of platinum or a platinum alloy, and a carbon carrier serving as a carrier for the metal particles, wherein the carbon carrier is an X-ray. The average lattice spacing d 002 of the lattice plane [002] obtained by the diffraction method is 0.340 to
The crystallite size Lc 002 is 0.32 nm.
6 to 4 nm and specific surface area of 260 to 800 m
The polymer electrolyte fuel cell is characterized in that it is 2 / g.
ム、パラジウム、オスミウム、イリジウム、コバルト、
ニッケル、クロム、金、鉄、モリブデン及びスズからな
る群から選択される少なくとも１種の金属と白金との合
金であることを特徴とする請求項１に記載の固体高分子
型燃料電池。2. The platinum alloy is ruthenium, rhodium, palladium, osmium, iridium, cobalt,
The polymer electrolyte fuel cell according to claim 1, which is an alloy of platinum and at least one metal selected from the group consisting of nickel, chromium, gold, iron, molybdenum, and tin.
持量が、前記電極触媒の全質量に対して１０〜６５質量
％であることを特徴とする請求項１又は２に記載の固体
高分子型燃料電池。3. The solid polymer type according to claim 1, wherein the amount of the metal particles supported on the electrode catalyst is 10 to 65% by mass with respect to the total mass of the electrode catalyst. Fuel cell.
れるイオン交換樹脂がスルホン酸基を有するパーフルオ
ロカーボン重合体からなることを特徴とする請求項１〜
３の何れかに記載の固体高分子型燃料電池。4. The ion exchange resin contained in the ion exchange membrane and the catalyst layer is made of a perfluorocarbon polymer having a sulfonic acid group.
3. The polymer electrolyte fuel cell according to any one of 3 above.
記カソードとの間に配置されたイオン交換膜とを有して
おり、前記アノードが電極触媒とイオン交換樹脂とを含
む触媒層を有しており、かつ、前記電極触媒が白金又は
白金合金からなる金属粒子とカーボン担体とから構成さ
れた固体高分子型燃料電池の製造方法であって、 比表面積が３００ｍ2／ｇ以上であるカーボンブラック
又は活性炭を１０００〜２２００℃の温度条件のもとで
加熱処理することにより前記カーボン担体を調製し、次
いで、得られた前記カーボン担体に前記金属粒子を担持
させることにより前記電極触媒を調製する工程を含むこ
と、を特徴とする固体高分子型燃料電池の製造方法。5. An anode and a cathode, and an ion-exchange membrane disposed between the anode and the cathode, the anode having a catalyst layer containing an electrode catalyst and an ion-exchange resin. A method for producing a polymer electrolyte fuel cell in which the electrode catalyst is composed of metal particles made of platinum or a platinum alloy and a carbon carrier, wherein carbon black or activated carbon has a specific surface area of 300 m 2 / g or more. To prepare the carbon carrier by heat treatment under a temperature condition of 1000 to 2200 ° C., and then to prepare the electrode catalyst by supporting the metal particles on the obtained carbon carrier. And a method for manufacturing a polymer electrolyte fuel cell.
Priority Applications (1)
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|---|---|---|---|
| JP2001223435A JP2003036859A (en) | 2001-07-24 | 2001-07-24 | Solid polymer type fuel cell and its fabrication method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001223435A JP2003036859A (en) | 2001-07-24 | 2001-07-24 | Solid polymer type fuel cell and its fabrication method |
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| Publication Number | Publication Date |
|---|---|
| JP2003036859A true JP2003036859A (en) | 2003-02-07 |
Family
ID=19056774
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001223435A Withdrawn JP2003036859A (en) | 2001-07-24 | 2001-07-24 | Solid polymer type fuel cell and its fabrication method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003036859A (en) |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1069914A (en) * | 1996-08-26 | 1998-03-10 | N E Chemcat Corp | Carbon carrier platinum skeleton alloy electrode catalyst having vacancy type lattice defect |
| JP2000012043A (en) * | 1998-04-23 | 2000-01-14 | Ne Chemcat Corp | Electrode catalyst for solid high-polymer electrolyte- type fuel cell, and electrode, electrolyte film/electrode junction body and solid high-polymer electrolyte-type fuel cell using the catalyst |
| JP2000268828A (en) * | 1999-03-18 | 2000-09-29 | Asahi Glass Co Ltd | Solid highpolymer type fuel cell |
-
2001
- 2001-07-24 JP JP2001223435A patent/JP2003036859A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1069914A (en) * | 1996-08-26 | 1998-03-10 | N E Chemcat Corp | Carbon carrier platinum skeleton alloy electrode catalyst having vacancy type lattice defect |
| JP2000012043A (en) * | 1998-04-23 | 2000-01-14 | Ne Chemcat Corp | Electrode catalyst for solid high-polymer electrolyte- type fuel cell, and electrode, electrolyte film/electrode junction body and solid high-polymer electrolyte-type fuel cell using the catalyst |
| JP2000268828A (en) * | 1999-03-18 | 2000-09-29 | Asahi Glass Co Ltd | Solid highpolymer type fuel cell |
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