WO2010064556A1 - 炭素触媒及びその製造方法、これを用いた電極及び電池 - Google Patents
炭素触媒及びその製造方法、これを用いた電極及び電池 Download PDFInfo
- Publication number
- WO2010064556A1 WO2010064556A1 PCT/JP2009/069778 JP2009069778W WO2010064556A1 WO 2010064556 A1 WO2010064556 A1 WO 2010064556A1 JP 2009069778 W JP2009069778 W JP 2009069778W WO 2010064556 A1 WO2010064556 A1 WO 2010064556A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon
- catalyst
- carbon catalyst
- thermoplastic resin
- metal
- Prior art date
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 253
- 239000003054 catalyst Substances 0.000 title claims abstract description 241
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 197
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 96
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 78
- 229910052751 metal Inorganic materials 0.000 claims abstract description 57
- 239000002184 metal Substances 0.000 claims abstract description 57
- 239000002994 raw material Substances 0.000 claims abstract description 56
- 238000003763 carbonization Methods 0.000 claims abstract description 40
- 230000000694 effects Effects 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims description 70
- 238000009826 distribution Methods 0.000 claims description 34
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 18
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 16
- 238000010000 carbonizing Methods 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- -1 polybismaleimide Polymers 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004962 Polyamide-imide Substances 0.000 claims description 3
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 3
- 229920002312 polyamide-imide Polymers 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 239000000088 plastic resin Substances 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 44
- 239000003273 ketjen black Substances 0.000 description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 34
- 239000001301 oxygen Substances 0.000 description 34
- 229910052760 oxygen Inorganic materials 0.000 description 34
- 239000000203 mixture Substances 0.000 description 21
- 238000006722 reduction reaction Methods 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 230000010757 Reduction Activity Effects 0.000 description 13
- 229920001187 thermosetting polymer Polymers 0.000 description 13
- 239000010419 fine particle Substances 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000010453 quartz Substances 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 229910003460 diamond Inorganic materials 0.000 description 9
- 239000010432 diamond Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- 229910052737 gold Inorganic materials 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- 150000004698 iron complex Chemical class 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 229920001169 thermoplastic Polymers 0.000 description 6
- 239000004416 thermosoftening plastic Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 4
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 4
- 229960003540 oxyquinoline Drugs 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000005518 polymer electrolyte Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 235000002597 Solanum melongena Nutrition 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000004700 cobalt complex Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000333 X-ray scattering Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 description 2
- WHJXGGISJBFSJJ-UHFFFAOYSA-N iron;pyridine Chemical compound [Fe].C1=CC=NC=C1 WHJXGGISJBFSJJ-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 241000234282 Allium Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- CGJVXRAYTNZWDW-UHFFFAOYSA-N benzene coronene Chemical compound C1=CC2=CC=C3C=CC4=CC=C5C=CC6=CC=C1C1=C6C5=C4C3=C21.C2=CC=CC=C2 CGJVXRAYTNZWDW-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000002078 nanoshell Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a carbon catalyst and a method for producing the same, and an electrode and a battery using the carbon catalyst, and more particularly, to a carbon catalyst that can replace a noble metal catalyst such as platinum or palladium.
- the polymer electrolyte fuel cell can be operated in a low temperature region, has high energy conversion efficiency, has a short start-up time, and can be made compact and lightweight. For this reason, PEFC is expected to be applied to power sources for electric vehicles, portable power sources, and home cogeneration systems.
- the present invention has been made in view of the above problems, and an object thereof is to provide a carbon catalyst having excellent activity, a production method thereof, an electrode and a battery using the carbon catalyst.
- a carbon catalyst according to an embodiment of the present invention for solving the above-described problems has a conductive carbon material and a carbon structure that covers a surface of the conductive carbon material. According to the present invention, a carbon catalyst having excellent activity can be provided.
- the ratio of 1 to 5 nm may be 50% or more. In the crystallite size La distribution, the ratio of less than 1 nm may be 40% or less.
- the carbon structure may be a carbon structure formed by heating and carbonizing a raw material containing a thermoplastic resin, a metal, and a conductive carbon material. In this way, a carbon catalyst having excellent activity can be provided more reliably.
- An electrode according to an embodiment of the present invention for solving the above problems is characterized in that any one of the above carbon catalysts is supported.
- ADVANTAGE OF THE INVENTION According to this invention, the outstanding electrode by which the carbon catalyst which has the outstanding activity was carry
- a battery according to an embodiment of the present invention for solving the above-described problems has the above-described electrode.
- ADVANTAGE OF THE INVENTION According to this invention, the outstanding battery which has the electrode by which the carbon catalyst which has the outstanding activity was carry
- a method for producing a carbon catalyst according to an embodiment of the present invention for solving the above-described problem is obtained by heating a raw material containing a thermoplastic resin, a metal, and a conductive carbon material, thereby melting the thermoplastic resin. The surface of the conductive carbon material is covered, and the thermoplastic resin is carbonized on the surface of the conductive carbon material to obtain a carbon catalyst.
- ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the carbon catalyst which has the outstanding activity can be provided.
- the thermoplastic resin may be a polymer ligand capable of coordinating to the metal, and the raw material may contain a complex formed by coordinating the thermoplastic resin to the metal. . In this way, the metal can be effectively dispersed on the surface of the conductive carbon material.
- the thermoplastic resin may contain one or more nitrogen atoms as coordination atoms in the molecule. In this way, the metal and nitrogen can be effectively dispersed on the surface of the conductive carbon material.
- the thermoplastic resin is one or two selected from the group consisting of polyvinylpyridine, salen polymer, polypyrrole, polyvinylpyrrole, 3-methylpolypyrrole, polyvinylcarbazole, polyamide, polyaniline, polybismaleimide, and polyamideimide. It is good also as containing the above.
- the conductive carbon material may be carbon black.
- the metal may be a transition metal. If it carries out like this, the carbon catalyst which has the outstanding activity can be manufactured effectively.
- the method for producing the carbon catalyst includes a step of subjecting the carbon catalyst obtained by carbonization to a treatment for removing the metal, and subjecting the carbon catalyst to which the treatment has been performed to a heat treatment. And a step of improving the activity.
- the heat treatment may be performed by heating the carbon catalyst at a temperature in the range of 300 to 1500 ° C. In this way, a more active carbon catalyst can be produced.
- a carbon catalyst according to an embodiment of the present invention for solving the above-described problems is characterized by being manufactured by any one of the methods described above. According to the present invention, a carbon catalyst having excellent activity can be provided.
- FIG. 1 is an explanatory diagram showing main steps included in an example of a carbon catalyst production method according to the present embodiment (hereinafter referred to as “the present production method”). As shown in FIG. 1, this manufacturing method includes raw material preparation process S1 and carbonization process S2.
- thermoplastic resin is not particularly limited as long as it is meltable by heating in the carbonization step S ⁇ b> 2 to be described later and exhibits fluidity and can be carbonized. That is, for example, among general-purpose plastics such as polymethacrylic acid, engineering plastics such as polyamide, super engineering plastics such as polysulfone and polyimide, or other thermoplastic resins such as ionomer resins, the decomposition point (thermal decomposition temperature) is higher than the melting point. Higher ones can be used. These thermoplastic resins can be used individually by 1 type or in combination of 2 or more types.
- thermoplastic resin those having a large difference between the melting point and the decomposition point can be preferably used. That is, for example, a thermoplastic resin having a decomposition point higher than the melting point by 50 ° C. or more can be preferably used. The more the melting point and the decomposition point are separated, the more the thermoplastic resin can be surely melted in the carbonization step S2 and the carbonization can be performed.
- thermoplastic resin can be a polymer ligand capable of coordinating with the metal contained in the raw material. That is, in this case, a thermoplastic resin having one or a plurality of coordination atoms in the molecule and having a thermoplastic property in a coordinated state with a metal is used.
- thermoplastic resin containing one or more selected from the group consisting of a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom in the molecule is used as a coordination atom.
- a thermoplastic resin containing one or more selected from the group consisting of an amino group, a phosphino group, a carboxyl group, and a thiol group in the molecule is used. it can.
- thermoplastic resin which is a ligand when using the thermoplastic resin which is a ligand, a raw material will contain the complex formed when the said thermoplastic resin coordinated to the metal. Therefore, the thermoplastic resin and the metal can be efficiently and integrally dispersed in the raw material.
- thermoplastic resin which is a polymer ligand
- those containing one or more nitrogen atoms as coordination atoms in the molecule can be preferably used.
- thermoplastic resin the metal, and the nitrogen atom can be efficiently and integrally dispersed in the raw material.
- nitrogen atom contained in a thermoplastic resin brings about the effect of nitrogen dope in the carbon catalyst manufactured by this manufacturing method, and can improve the activity of the said carbon catalyst.
- thermoplastic resin containing one or more nitrogen atoms in the molecule can be preferably used.
- a thermoplastic resin containing one or more nitrogen atoms in the molecule can be preferably used.
- PAN polyacrylonitrile
- the thermoplastic resin and the nitrogen atom can be integrally and efficiently dispersed in the raw material.
- thermoplastic resin those in which the molecules are not cross-linked can be preferably used.
- the thermoplastic resin can be efficiently melted and fluidized by heating in the carbonization step S2.
- shape of the mixture of the thermoplastic resin and the metal or the shape of the metal complex of the thermoplastic resin is not particularly limited as long as the activity of the carbon catalyst produced by the production method is not impaired, for example, a sheet shape, a fiber shape, a block shape Can be in the form of particles.
- the metal is not particularly limited as long as it does not inhibit the activity of the carbon catalyst produced by this production method. That is, as the metal, for example, a transition metal can be preferably used, and a metal belonging to Group 4 to Group 4 of the periodic table can be particularly preferably used.
- metals can be used singly or in combination of two or more.
- one or more selected from the group consisting of cobalt, iron, nickel, manganese, zinc, and copper can be preferably used, and cobalt and iron can be particularly preferably used.
- metal a simple substance of the metal or a compound of the metal can be used.
- metal compound for example, metal salts, metal hydroxides, metal oxides, metal nitrides, metal sulfides, metal carbonides, metal complexes can be preferably used, and metal chlorides, metal oxides, metal complexes can be used. Can be used particularly preferably.
- the conductive carbon material is not particularly limited as long as it is a conductive carbon material. That is, for example, a carbon material having conductivity and having no catalytic activity by itself can be used.
- the shape of the conductive carbon material is not particularly limited, and for example, a particulate material or a fibrous material can be used.
- the average particle size of the fine particles is preferably in the range of 3 to 100 nm.
- the BET specific surface area of the fine particles is preferably in the range of 100 to 2000 m 2 / g.
- the conductive carbon material for example, one or more selected from the group consisting of carbon black, carbon nanotube, carbon nanofiber, graphite, activated carbon, glassy carbon, carbon fiber, and fullerene is preferable.
- carbon black for example, ketjen black, Vulcan, Toka black, Denka black can be used.
- a raw material can be prepared by mixing such a thermoplastic resin, a metal, and a conductive carbon material. That is, the raw material can be, for example, a mixed powder of a thermoplastic resin metal complex and conductive carbon material fine particles.
- the method for mixing the raw materials is not particularly limited. That is, for example, mixing methods such as powder mixing, solvent mixing, supercritical fluid mixing, and electrolytic polymerization coating can be used alone or in combination of two or more.
- the blending ratio of the thermoplastic resin and the conductive carbon material in the raw material can be appropriately set as long as an active carbon catalyst can be produced. That is, for example, the proportion of the conductive carbon material contained in the raw material is preferably in the range of 1 to 85% by mass, and more preferably in the range of 5 to 50% by mass. When the content of the conductive carbon material is less than 1% by mass, sufficient conductivity may not be imparted to the carbon catalyst produced by this production method. Moreover, when content of an electroconductive carbon material exceeds 85 mass%, the activity of the carbon catalyst manufactured by this manufacturing method may fall on the contrary.
- the raw material can also contain a thermosetting resin.
- a raw material will contain the thermoplastic composition containing a thermoplastic resin and a thermosetting resin, for example.
- the thermosetting resin is not particularly limited as long as it can be carbonized by heating in the carbonization step S2.
- thermosetting resin for example, one or more selected from the group consisting of a phenol resin, a melamine resin, an epoxy resin, and a furan resin can be preferably used.
- the surface of the conductive carbon material is coated with the molten thermoplastic resin by heating the raw material prepared as described above, and the thermoplastic resin is coated on the surface of the conductive carbon material. Is carbonized to obtain a carbon catalyst.
- the raw material is heated at a temperature at which the thermoplastic resin contained in the raw material is melted and the thermoplastic resin is not thermally decomposed (that is, a temperature not lower than the melting point of the thermoplastic resin and lower than the decomposition point). To do.
- This heating can melt the thermoplastic resin in the raw material and allow the thermoplastic resin to flow along the surface of the conductive carbon material. That is, the molten thermoplastic resin can be spread so as to cover the surface of the conductive carbon material.
- the proportion of the portion of the surface of the conductive carbon material that is covered with the thermoplastic resin increases. That is, the area where the thermoplastic resin covers the conductive carbon material can be increased.
- thermoplastic resin can be widely dispersed and held on the surface of the conductive carbon material.
- the raw material is held at a predetermined temperature (carbonization temperature) at which the thermoplastic resin contained in the raw material can be carbonized.
- a predetermined temperature carbonization temperature
- the thermoplastic resin can be carbonized while covering the surface of the conductive carbon material.
- a thin film-like carbon structure along the surface can be formed on the surface of the conductive carbon material. That is, the surface of the conductive carbon material can be effectively covered with the carbon structure.
- the carbonization temperature is not particularly limited and can be appropriately set according to conditions such as the melting point and decomposition point of the thermoplastic resin. That is, the carbonization temperature can be, for example, in the range of 300 to 1500 ° C., preferably in the range of 500 to 1200 ° C., and more preferably in the range of 600 to 1200 ° C. And particularly preferably within the range of 700 to 1200 ° C.
- the rate of temperature rise can be in the range of 0.5 to 300 ° C./min.
- the time for holding the raw material at the above-mentioned carbonization temperature can be, for example, within a range of 5 to 180 minutes, and preferably within a range of 20 to 120 minutes. If the holding time is less than 5 minutes, the resin may not be uniformly carbonized. On the other hand, if the holding time exceeds 180 minutes, the catalytic activity may be significantly reduced due to the disappearance of the edge surface of the carbon network surface. Further, the carbonization treatment is preferably performed under a flow of an inert gas such as nitrogen.
- the raw material contains a thermoplastic resin that forms a complex with a metal
- the raw material is heated at a temperature at which the complex does not melt and decompose, and the surface of the conductive carbon material is covered with the complex.
- the complex is carbonized on the surface by holding the complex at a carbonization temperature for a predetermined time.
- the raw material contains a thermosetting resin
- the raw material is heated at a temperature at which the thermoplastic composition containing the thermosetting resin and the thermoplastic resin melts and does not decompose,
- the surface of the conductive carbon material is coated with the thermoplastic composition, and the thermoplastic composition is carbonized on the surface by holding the thermoplastic composition at a carbonization temperature for a predetermined time.
- a carbon catalyst having a conductive carbon material and a carbon structure that covers the surface of the conductive carbon material can be obtained.
- this carbon structure includes a carbon network surface constituted by a hexagonal network surface of carbon extending in a two-dimensional manner. It is considered that defective portions such as edge portions and bent portions of the carbon network surface serve as active points of the carbon catalyst.
- the carbon structure can be a structure in which a plurality of carbon network surfaces are stacked.
- a conductive carbon material is used to increase the conductivity of the carbon catalyst, and a thermoplastic resin is used as a carbon raw material for forming a carbon structure. Can be mentioned.
- the inventors of the present invention have so far developed a carbon layer of a thermosetting resin in the presence of a metal so as to be laminated and developed in the shape of an onion around the fine particles of the metal. It has been found that a carbon catalyst having a structure (nanoshell structure) can be produced. In this carbon catalyst, it is considered that the edge portion of the carbon network surface included in the turbulent layer structure and the bent portion of the carbon network surface serve as active points, and the catalytic activity of the carbon material itself is extracted.
- the present inventors considered using a conductive carbon material in order to improve the conductivity of the carbon catalyst.
- thermosetting resin when used as the carbon raw material, the carbon structure formed by carbonization of the thermosetting resin cannot be sufficiently brought into contact with the conductive carbon material. That is, for example, when carbonizing a raw material obtained by mixing a thermosetting resin and fine particles of a conductive carbon material such as carbon black, the thermosetting resin is separated from the fine particles. Carbonized as it is.
- thermoplastic resin is used as a carbon raw material. Therefore, as described above, the thermoplastic resin layer that covers the surface of the conductive carbon material can be formed by melting the thermoplastic resin in the process of carbonization. And carbon structure along the surface of the said conductive carbon material can be formed by carbonizing the thermoplastic resin layer which coat
- the conductive carbon material and the active site of the carbon structure can be sufficiently brought into contact over a wide range of the surface of the conductive carbon material. Therefore, this carbon catalyst can exhibit high catalytic activity based on the synergistic effect of the activity of the carbon structure and the conductivity of the conductive carbon material.
- thermoplastic resin is widely dispersed on the surface of the conductive carbon material. Then, by carbonizing the thermoplastic resin widely dispersed on the surface of the conductive carbon material on the surface, a carbon structure widely dispersed on the surface can be formed. Therefore, it is possible to produce a carbon catalyst in which the active points of the carbon structure are widely and uniformly dispersed by effectively using the surface of the conductive carbon material.
- the metal when the thermoplastic resin forms a complex with a metal, the metal can be widely dispersed on the surface of the conductive carbon material in the process of carbonization. Therefore, the effect of the metal effective for forming the carbon structure can be exhibited over a wide range and uniformly on the surface of the conductive carbon material.
- the thermoplastic resin contains a nitrogen atom as a coordination atom in the molecule
- the nitrogen atom can be introduced by being widely dispersed in the carbon structure. Therefore, the effect of nitrogen doping can be exhibited over a wide range and uniformly on the surface of the conductive carbon material.
- the volume of the thermoplastic resin shrinks as the carbonization progresses. For this reason, a thin film-like carbon structure along the surface is formed on the surface of the conductive carbon material, and the structure of the conductive carbon material is maintained. Therefore, according to this manufacturing method, it can be set as the carbon catalyst which utilized the original characteristic of the electroconductive carbon material.
- this manufacturing method can further include a metal removal step of performing a treatment for removing the metal on the carbon catalyst obtained in the carbonization step S2.
- a metal removal treatment By this metal removal treatment, the metal contained in the carbon catalyst can be removed or the content of the metal can be reduced.
- the method for removing the metal is not particularly limited. That is, for example, an acid cleaning process or an electrolytic process can be used. When washing with an acid, a boiled acid can be used. As the acid, for example, hydrochloric acid can be preferably used.
- the production method may further include a heat treatment step for improving the activity of the carbon catalyst by performing a heat treatment on the carbon catalyst that has been subjected to the metal removal treatment.
- heat treatment is performed to heat the carbon catalyst after the metal removal treatment.
- the heat treatment is performed by holding the carbon catalyst at a predetermined temperature (heat treatment temperature).
- the heat treatment temperature can be, for example, a temperature within the range of 300 to 1500 ° C., preferably 400 ° C. or higher, more preferably 600 ° C. or higher, and particularly preferably 700 ° C. or higher.
- the heat treatment temperature is preferably 1200 ° C. or less, and more preferably 1000 ° C. or less.
- the range of the heat treatment temperature can be a range obtained by arbitrarily combining these lower limit value and upper limit value. That is, the heat treatment temperature can be, for example, in the range of 400 ° C. to 1200 ° C., preferably in the range of 600 ° C. to 1200 ° C., and more preferably in the range of 700 to 1200 ° C. Particularly preferably, it can be in the range of 700 to 1000 ° C.
- the time for holding the carbon catalyst at these heat treatment temperatures can be, for example, in the range of 10 minutes to 5 hours, and preferably in the range of 30 minutes to 2 hours.
- the rate of temperature increase in the heat treatment can be, for example, in the range of 0.5 to 1000 ° C./min.
- the heat treatment is preferably performed at a temperature lower than the heating temperature generally employed in so-called graphitization treatment. That is, the heat treatment can be performed, for example, by heating the carbon catalyst at a heat treatment temperature equal to or lower than the temperature at which the raw material is heated in the carbonization step S2 or at a heat treatment temperature lower than the temperature.
- the heating temperature in the carbonization treatment is in the range of 600 ° C. to 1200 ° C. or in the range of 700 ° C. to 1200 ° C.
- the heating temperature is within the range.
- the heat treatment can be performed at the following heat treatment temperature or a heat treatment temperature lower than the heating temperature.
- Such a heat treatment can effectively form, for example, structural defects serving as active points on the surface of the carbon catalyst.
- this heat treatment can remove, for example, an inactive metal component slightly remaining in the carbon catalyst after the metal removal treatment. Therefore, a more active carbon catalyst in which the active sites are effectively exposed can be obtained.
- the present production method can also include a step of introducing (doping) nitrogen atoms or boron atoms into the carbon catalyst.
- the method for introducing nitrogen atoms or boron atoms into the carbon catalyst is not particularly limited. That is, when doping nitrogen atoms, for example, a vapor phase doping method such as an ammoxidation method or a CVD method, a liquid phase doping method, or a gas phase-liquid phase doping method can be used.
- a carbon catalyst and a nitrogen source such as ammonia, melamine, and acetonitrile are mixed, and the mixture is subjected to an inert gas such as nitrogen, argon, and helium and an air atmosphere.
- Nitrogen atoms can be introduced to the surface of the carbon catalyst by holding at a temperature in the range of 550 to 1200 ° C. for a time in the range of 5 to 180 minutes or by heat treatment in NOx gas. .
- the nitrogen atom can be introduced into, for example, a hexagonal network structure having a carbon structure to form a pyrrole-type, graphene-substituted type, pyridine-type, pyridone-type, or oxidized-type structure.
- the carbon catalyst according to the present embodiment (hereinafter referred to as “the present catalyst”) is a carbon catalyst produced by imparting catalytic activity to the carbon material itself, and is efficiently produced by the production method as described above. Can do.
- the present catalyst is a carbon catalyst having a conductive carbon material and a carbon structure covering the surface of the conductive carbon material.
- This carbon structure is, for example, a carbon structure formed by heating and carbonizing a raw material containing a thermoplastic resin, a metal, and a conductive carbon material as described above. And this carbon structure is comprised including the carbon network surface in which defect parts, such as an edge part and a bending part, were formed as an active point.
- the carbon structure can be formed in a film shape along the surface of the conductive carbon material.
- the conductive carbon material is a fine particle such as carbon black
- the carbon structure is formed so as to cover the surface of the fine particle.
- the present catalyst comprises a conductive carbon material part as a carrier (base material), and a carbon structure part (carbonized layer) including active sites formed on the surface of the conductive carbon material.
- the present catalyst can be configured to include a conductive carbon material that maintains the original carbon structure. That is, as described above, in the carbonization process of the present manufacturing method, the thermoplastic resin covering the surface of the conductive carbon material is carbonized while reducing its volume.
- the present catalyst can be a carbon catalyst utilizing the original characteristics of the conductive carbon material.
- the carbon structure of the present catalyst can be composed of, for example, 1 to 5 layers of carbon network surface laminated on the surface of the conductive carbon material.
- This carbon structure can be composed of 1 to 4 layers of carbon network, 1 to 3 layers of carbon network, or 1 to 2 layers of carbon network.
- the number of carbon network surfaces stacked in the carbon structure is calculated from, for example, the crystallite size Lc in the direction in which the carbon network surfaces are stacked (c-axis direction) obtained based on the measurement result of X-ray diffraction. be able to.
- the appearance of the present catalyst is similar to the appearance of the conductive carbon material itself in which the carbon structure is not formed.
- the carbon structure coats the conductive carbon material, the nano-level active site of the carbon structure and the conductive carbon material may form an interface in good contact. it can. Therefore, even if the conductive carbon material itself does not have catalytic activity, the present catalyst has a synergistic effect between the carbon structure and the conductive carbon material, compared with the case where the conductive carbon material is not included. High activity.
- the present catalyst has, for example, oxygen reduction activity as catalytic activity. That is, the present catalyst can effectively catalyze an oxygen reduction reaction in a fuel cell electrode, for example.
- the oxygen reduction activity can be evaluated by, for example, the oxygen reduction start potential. That is, the oxygen reduction onset potential of the catalyst, when evaluated as a voltage reduction current flow of -10 ⁇ A / cm 2, for example, 0.7 V vs. NHE (vs. normal hydrogen electrode) than, 1.2V vs Within the range below NHE. Further, the oxygen reduction start potential can be set to, for example, 0.75 V or more, preferably 0.76 V or more, and more preferably 0.77 V or more.
- the oxygen reduction start potential is determined based on, for example, data indicating the relationship between the voltage and current obtained by sweeping the potential using a rotating ring disk electrode device having a working electrode coated with the catalyst. can do.
- the catalytic activity of the present catalyst can be evaluated by, for example, the number of electrons involved in the reaction in the oxygen reduction reaction. This number of electrons involved in the reaction is calculated as the number of electrons involved in the reduction reaction per molecule of oxygen in the oxygen reduction reaction catalyzed by the present catalyst.
- the number of electrons participating in the oxygen reduction reaction can be in the range of 3.5 to 4, preferably 3.6 or more, and more preferably 3.8. This can be done.
- the present catalyst can have a characteristic distribution with respect to the crystallite size La of the carbon network surface constituting the carbon structure.
- the crystallite size La indicates the spread of the carbon network surface in the a-axis direction.
- the ratio of 1 to 5 nm can be 50% or more.
- the ratio of less than 1 nm can be 40% or less.
- the ratio of 1 to 5 nm can be preferably 60% or more.
- the ratio of less than 1 nm can be preferably 30% or less, and more preferably 20% or less.
- the ratio of 1 to 5 nm and the ratio of less than 1 nm in the crystallite size La distribution can be any combination of the above ranges.
- the ratio of 2 to 5 nm can be 20% or more, and preferably 30% or more. Can do. Furthermore, in this case, the ratio of less than 2 nm can be 60% or less.
- the ratio of 2 to 5 nm and the ratio of less than 2 nm in the crystallite size La distribution can be any combination of the above ranges.
- the ratio of 2 to 5 nm can be made 80% or more. Furthermore, in this case, the ratio of less than 2 nm can be 15% or less, preferably 10% or less, and more preferably 5% or less.
- the ratio of 2 to 5 nm and the ratio of less than 2 nm in the crystallite size La distribution can be any combination of the above ranges.
- the ratio of 3 to 5 nm can be 50% or more, preferably 60% or more, and more preferably 70% or more. Furthermore, in this case, the ratio of less than 3 nm can be 50% or less, preferably 40% or less, more preferably 30% or less, and particularly preferably 20% or less. can do.
- the ratio of 3 to 5 nm and the ratio of less than 3 nm in the crystallite size La distribution can be any combination of the above ranges.
- the ratio exceeding 5 nm can be 60% or less, preferably 40% or less, and more preferably 20% or less.
- the ratio of 5 nm or less and the ratio exceeding 5 nm in the crystallite size La distribution can be any combination of the above ranges.
- the distribution of the crystallite size La can be obtained by the Diamond method based on the measurement result by X-ray diffraction, for example.
- the Diamond method is a method proposed by Diamond in 1956 to evaluate the average size and distribution of carbon network surfaces in samples with relatively small network sizes such as coal and pitch (for example, , R. Diamond, Ph. D. Dissertation, University of Cambridge, England, 1956, R. Diamond, Acta. Cryst. 10 (1957) 359-363., R. Diamond, Acta. Cryst. 11 (1958) 129- 138., R. Diamond, Phil. Trans. Roy. Soc. London A252 (1960) 193-223).
- the electrode according to the present embodiment (hereinafter referred to as “main electrode”) is an electrode on which the present catalyst as described above is supported. That is, the present electrode can be configured to have a predetermined electrode base material and the present catalyst supported on the electrode base material.
- the electrode can be, for example, a fuel cell electrode, and more specifically, for example, a polymer electrolyte fuel cell (PEFC) electrode. That is, in this case, the present catalyst can be a fuel cell electrode catalyst, preferably a PEFC electrode catalyst, and particularly preferably a PEFC cathode electrode catalyst.
- PEFC polymer electrolyte fuel cell
- the battery according to the present embodiment (hereinafter referred to as “the present battery”) is a battery having the above-described main electrode. That is, as described above, this battery can be, for example, a fuel cell, and preferably a PEFC.
- the battery when the battery is PEFC, the battery includes a polymer electrolyte membrane, cathode electrodes (positive electrode and air electrode) formed on one side and the other side of the polymer electrolyte membrane, and An anode electrode (negative electrode, fuel electrode) is integrated with a membrane / electrode assembly (MEA), and the present catalyst can be supported on the cathode electrode.
- a polymer electrolyte membrane when the battery is PEFC, the battery includes a polymer electrolyte membrane, cathode electrodes (positive electrode and air electrode) formed on one side and the other side of the polymer electrolyte membrane, and An anode electrode (negative electrode, fuel electrode) is integrated with a membrane / electrode assembly (MEA), and the present catalyst can be supported on the cathode electrode.
- MEA membrane / electrode assembly
- Example 1 1.5 g of vinylpyridine was dissolved in 20 mL of dimethylformamide, and then polymerized at 70 ° C. for 5 days to obtain polyvinylpyridine. To this polyvinyl pyridine, 0.65 g of iron chloride hexahydrate was added and stirred at room temperature for 24 hours to obtain a polyvinyl pyridine iron complex.
- Ketjen black (EC600JD, Lion Co., Ltd.) is added to this complex and mixed using a mortar to contain a polyvinylpyridine iron complex and ketjen black, and a raw material containing 50% by weight of the ketjen black. Obtained.
- each of the raw materials prepared as described above was placed in a quartz tube, and the quartz tube was placed in an ellipsoidal reflection type infrared gold image furnace and purged with nitrogen for 20 minutes.
- composition thus obtained was set in a planetary ball mill (P-7, Fritsch Japan Co., Ltd.) with a 1.5 mm diameter silicon nitride ball, and the composition was pulverized at a rotation speed of 800 rpm for 60 minutes. The pulverized composition was taken out, and the carbon catalyst fine particles that passed through a sieve having an opening of 105 ⁇ m were collected.
- the carbon catalyst obtained as described above was subjected to pickling treatment for removing the metal. That is, 37% HCl was added to the carbon catalyst, stirred for 2 hours, and allowed to stand to decant the supernatant. This operation was performed three times. Furthermore, after performing suction filtration, washing with distilled water was performed, followed by boiling. In this way, two types of carbon catalysts (PVP / Fe / KB catalyst and PVP / Co / KB catalyst) subjected to metal removal treatment were obtained.
- the PVP / Fe / KB catalyst obtained as described above was subjected to heat treatment. That is, the PVP / Fe / KB catalyst was placed in a quartz tube, and the quartz tube was placed in an ellipsoidal reflection type infrared gold image furnace.
- Example 2 10 g of 8-quinolinol (oxin), 10 g of formaldehyde, and 1 g of oxalic acid dihydrate were put into a 100 mL eggplant flask and refluxed at 100 ° C. overnight. Then 5.5 mL of 1M HCl was added and refluxed overnight as well. The obtained solid was subjected to suction filtration, washed 3 times with distilled water, and vacuum dried overnight to obtain a polymer (Q polymer).
- ketjen black E600JD, Lion Co., Ltd.
- Each of the two types of raw materials thus prepared was heated to 1000 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere using an infrared image furnace, and carbonized by holding at 1000 ° C. for 1 hour. .
- the obtained composition was ground in a mortar, and fine particles having a particle size of 106 ⁇ m or less that passed through a sieve having an opening of 106 ⁇ m were collected as a carbon catalyst.
- the carbon catalyst obtained as described above was subjected to a pickling treatment for removing cobalt. That is, 37% HCl was added to the carbon catalyst, stirred for 2 hours, and allowed to stand to decant the supernatant. This operation was performed three times. Further, the carbon catalyst was suction filtered, washed with distilled water, and then boiled. In this way, two types of carbon catalysts (Q / Co / KB catalyst, Q-Ph / Co / KB catalyst) subjected to metal removal treatment were obtained.
- Example 3 To 300 mL of acetone, 3.275 g of phenol resin (Gunei Chemical Industry Co., Ltd.) was added and dissolved by irradiation with ultrasonic waves. Furthermore, 1.0 g of cobalt phthalocyanine complex (Tokyo Chemical Industry Co., Ltd.) was added, and the solvent was removed at 40 ° C. using a rotary evaporator while irradiating ultrasonic waves. Thereafter, the remaining composition was vacuum-dried at a temperature of 80 ° C. for 24 hours to synthesize a cobalt phthalocyanine complex containing a phenol resin.
- phenol resin Ltd.
- cobalt phthalocyanine complex Tokyo Chemical Industry Co., Ltd.
- the cobalt phthalocyanine complex thus prepared was put into a quartz tube, and the quartz tube was purged with nitrogen gas for 20 minutes in an ellipsoidal reflection type infrared gold image furnace. Then, heating was started, and the temperature of the gold image furnace was increased from room temperature to 800 ° C. at a temperature increase rate of 10 ° C./min. Thereafter, the quartz tube was held at 800 ° C. for 1 hour. A carbon catalyst was obtained by such carbonization treatment.
- the carbon catalyst was thus subjected to pickling treatment for removing cobalt. That is, 37% HCl was added to the carbon catalyst, stirred for 2 hours, and allowed to stand to decant the supernatant. This operation was performed three times. Further, the carbon catalyst was suction filtered, washed with distilled water, and then boiled. In this way, a carbon catalyst (Pc / Co catalyst) subjected to metal removal treatment was obtained.
- the Pc / Co catalyst was put in a quartz tube, and the quartz tube was put in an ellipsoidal reflection type infrared gold image furnace. Then, in the infrared gold image furnace, the quartz tube was held at 400 ° C., 700 ° C. or 1000 ° C. for 1 hour in a nitrogen atmosphere. In this way, three types of carbon catalysts (Pc / Co (H400) catalyst, Pc / Co (H700) catalyst, Pc / Co (H1000) catalyst) subjected to heat treatment at three different temperatures were obtained.
- Example 4 The oxygen reduction activity was evaluated for each of the five types of carbon catalysts obtained in Example 1, the two types of carbon catalysts obtained in Example 2, and the four types of carbon catalysts obtained in Example 3. That is, first, 5 mg of a powdered carbon catalyst was weighed, and 50 ⁇ L of a binder solution (Nafion (registered trademark), DuPont), 150 ⁇ L of water, and 150 ⁇ L of ethanol were added in an appropriate amount, and this mixed solution was used as a catalyst slurry. Prepared.
- a binder solution Nafion (registered trademark), DuPont
- a small amount of catalyst slurry is sucked with a pipette, applied to a disk electrode (diameter 5 mm) of a rotating ring disk electrode device (RRDE-1, SC-5, limited thickness company), and dried to produce a working electrode. did.
- a platinum electrode was used as the ring electrode.
- As the electrolyte solution a 1 M sulfuric acid aqueous solution in which oxygen was dissolved at room temperature was used.
- the electrode was rotated at a rotation speed of 1500 rpm, and the current when the potential was swept at a sweep speed of 0.5 mV / sec was recorded as a function of the potential. Further, from the obtained polarization curve, a voltage at which a reduction current of ⁇ 10 ⁇ A / cm 2 flowed was recorded as an oxygen reduction start potential. The current density when a voltage of 0.7 V was applied was also recorded. Further, the number n of electrons involved in the reaction was calculated by the following formula (I). In this formula (I), I D and I R are each disk current and ring current at the potential 0V. N is the capture rate, and was 0.372256.
- FIG. 2 shows an example of the relationship between voltage and current density obtained by the rotating ring disk electrode method.
- FIG. 2A shows the results for four types of Pc / Co catalysts
- FIG. 2B shows the results for four types of PVP / Fe / KB catalysts, Q / Co / KB catalysts, and Q-Ph / Co / KB catalysts. Results are shown.
- the horizontal axis represents voltage (V vs. NHE), and the vertical axis represents current density (mA / cm 2 ) at each voltage.
- a carbon catalyst in which a larger current flows at a higher voltage means that the performance as a catalyst is higher.
- FIG. 3 shows an example of the results of evaluating the current density (mA / cm 2 ), oxygen reduction initiation potential (V), and number of electrons involved in the reaction when 0.7 V is applied for each carbon catalyst. .
- Example 5 In the same manner as in Example 1 described above, a raw material containing a polyvinylpyridine iron complex and ketjen black and containing 50% by weight of the ketjen black was obtained. Then, in the same manner as in Example 1 described above, this raw material was heated to raise the temperature, and held at 500 ° C., 600 ° C., 700 ° C., 800 ° C., 900 ° C. or 1000 ° C. for 1 hour in a nitrogen atmosphere.
- the composition thus obtained was pulverized and sieved, followed by metal removal treatment, and six types of carbon catalysts having different carbonization temperatures (PVP / Fe / KB ( C500), PVP / Fe / KB (C600), PVP / Fe / KB (C700), PVP / Fe / KB (C800), PVP / Fe / KB (C900), PVP / Fe / KB (C1000)) It was.
- Example 1 a part of the four types of carbon catalysts produced at a carbonization temperature of 700 ° C. to 1000 ° C. was subjected to heat treatment.
- the heating temperature in the heat treatment was 700 ° C.
- the oxygen reduction activity of each carbon catalyst was evaluated similarly to the above-mentioned Example 4.
- FIG. 4 shows four types of carbon catalysts produced at a carbonization temperature of 700 ° C. to 1000 ° C. and not subjected to heat treatment, and four types of catalysts produced at a carbonization temperature of 700 ° C. to 1000 ° C. and subjected to heat treatment.
- An example of the result of evaluating the oxygen reduction starting potential (V) and the number of electrons involved in the reaction is shown. As shown in FIG. 4, it was shown that the oxygen reduction activity of the carbon catalyst is improved by performing the heat treatment.
- Example 6 In the same manner as in Example 3 described above, two types of carbon catalysts (Pc / Co (C800) catalyst and Pc / Co (C1000) catalyst) carbonized at 800 ° C. or 1000 ° C. were obtained. Similarly, a carbon catalyst (Pc / Fe (C800) catalyst) carbonized at 800 ° C. was obtained by using an iron phthalocyanine complex instead of a cobalt phthalocyanine complex. And the oxygen reduction activity of each carbon catalyst was evaluated similarly to the above-mentioned Example 4.
- FIG. 5 shows an example of the results of evaluating the current density (mA / cm 2 ) and the oxygen reduction starting potential (V) when 0.7 V is applied for each carbon catalyst. As shown in FIG. 5, it was confirmed that each carbon catalyst has oxygen reduction activity.
- Example 7 Of the carbon catalysts obtained in Example 5 above, eight types of carbon catalysts, ketjen black used in the production of the carbon catalyst, and each of the three types of carbon catalysts obtained in Example 6 were crystallized. The distribution of the child size La was evaluated.
- a sample of the carbon catalyst was placed in a concave portion of a glass sample plate and pressed with a slide glass, and the concave portion was uniformly filled so that the surface thereof coincided with the reference surface.
- the glass sample plate was fixed to a wide-angle X-ray diffraction sample stage so that the shape of the filled carbon catalyst sample did not collapse.
- X-ray diffraction measurement was performed using an X-ray diffraction apparatus (Rigaku RINT2100 / PC, Rigaku Corporation).
- the applied voltage and current to the X-ray tube were 32 kV and 20 mA, respectively.
- the sampling interval was 0.1 °
- the scanning speed was 0.1 ° / min
- the measurement angle range (2 ⁇ ) was 5 to 100 °.
- CuK ⁇ was used as the incident X-ray.
- the procedure of the analysis method proposed by Diamond basically consists of (1) intensity measurement of 11 bands of a sample, (2) correction of measured intensity, and (3) model network surface expected to exist in the sample. (4) Calculation of theoretical scattering intensity from the assumed model network surface, (5) Least square fitting of the obtained measured intensity by the theoretical scattering intensity, (6) Model network surface from the weight of each theoretical scattering intensity It consists of six steps of calculating the weight fraction and average network surface size. Therefore, the data to be analyzed first was read and smoothed and absorbed. The smoothing process was performed 7 times, and the absorption correction was performed using the theoretical absorption coefficient 4.219.
- the two-dimensional lattice constant is generally set to a value between the lattice constants of benzene and ideal graphite, approximately 0.240 to 0.24612 nm.
- the Ruland coefficient indicates the integral width of the function representing the passband of the energy of the used monochromator, and generally takes a value of 0 to 1.
- 0.24412 nm was selected as an initial set value of the lattice constant a 0 as a value close to the lattice constant of a general carbonaceous material.
- 0.05 was selected as the default value of the coefficient of Rand.
- model network surface was selected.
- the theoretical strength can be calculated and executed using three types of model network surfaces: a benzene / coronene base model, a pyrene base model, and a mixed model.
- a benzene / coronene base model as shown in FIG. 6 was used.
- the scattering intensity of the model network surface (approximately 0.25 nm to 7 nm) having an odd multiple size (1, 3, 5... 25, 27, 29 times) of the two-dimensional lattice constant a 0 is calculated. Is possible.
- the crystallite size La distribution of 7.2 nm or less is 0.245 nm, 0.736 nm, 1.223 nm, 1.719 nm, 2.210 nm, 2.700 nm, 3.200 nm, 3.683 nm, 4.174 nm, Crystallite size percentages of 4.665 nm, 5.156 nm, 5.647 nm, 6.138 nm, 6.630 nm and 7.110 nm were obtained.
- FIG. 7 shows the crystallites obtained for each of the eight types of carbon catalysts produced in Example 5 above at a carbonization temperature of 700 to 1000 ° C. and the ketjen black used in the production of the carbon catalysts.
- An example of size La distribution is shown.
- 7A, C, E, and G show the results for carbon catalysts that were produced at carbonization temperatures of 700 ° C., 800 ° C., 900 ° C., and 1000 ° C. and were not heat treated, respectively
- FIGS. 7B, D, F, and H Show the results for carbon catalysts produced at carbonization temperatures of 700 ° C., 800 ° C., 900 ° C. and 1000 ° C. and heat treated at 700 ° C., respectively
- FIG. 7I shows the results for Ketjen Black.
- FIG. 8 shows an example of the distribution of crystallite size La obtained for the three types of carbon catalysts obtained in Example 6 described above.
- FIGS. 8A, B, and C show the results for the Pc / Co (C800) catalyst, the Pc / Co (C1000) catalyst, and the Pc / Fe (C800) catalyst that were not heat treated, respectively.
- FIG. 9 shows the ratio (%) of the crystallite size La in each range in the crystallite size La distribution obtained for the 13 types of carbon catalysts and ketjen black that were analyzed.
- 10 types of carbon catalysts (PVP / Fe / KB) produced using raw materials containing polyvinyl pyridine, iron and ketjen black tend to be different from other carbon catalysts. Crystallite size La distribution.
- the ratio of the crystallite size La in the range of 1 to 5 nm is as high as 60 to 100%, and the ratio in the range of 2 to 5 nm is also high as 30 to 100%.
- the ratio of the crystallite size La within the range of 1 to 5 nm was as high as 80 to 100%, and the ratio within the range of 2 to 5 nm was also high as 80 to 100%.
- the ratio of less than 1 nm and the ratio of more than 5 nm were as low as 20% or less, respectively.
- thermoplastic resin polyvinylpyridine
- a conductive carbon material Ketjen Black
- the PVP / Fe / KB catalyst subjected to the heat treatment had a crystallite size La distribution different from that of the PVP / Fe / KB catalyst not subjected to the heat treatment. That is, for example, the heat-treated PVP / Fe / KB catalyst has a high ratio of crystallite size La in the range of 2 to 5 nm as high as 80 to 100% and a ratio of less than 2 nm as low as 10% or less. It had a characteristic crystallite size La distribution.
- the PVP / Fe / KB catalyst subjected to the heat treatment has a unique crystal structure in which the ratio of the crystallite size La within the range of 3 to 5 nm is as high as 70% or more and the ratio of less than 3 nm is as low as 20% or less. It had a child size La distribution.
- Example 8 For each of the PVP / Fe / KB catalyst produced in Example 1 and not heat-treated, the Q / Co / KB catalyst produced in Example 2 and the ketjen black used in the production thereof, Observation with a microscope was performed.
- FIG. 10 shows an example of a photograph taken with a scanning electron microscope (SEM).
- FIG. 10A is an SEM photograph of a raw material that is a mixture of an iron complex of polyvinylpyridine and ketjen black
- FIG. 10B is an SEM photograph of the raw material heated to 300 ° C.
- FIG. 10C is a graph after carbonization. It is a SEM photograph of a PVP / Fe / KB catalyst.
- FIG. 10D is a SEM photograph of the Q / Co / KB catalyst.
- the surface of the ketjen black is a thin film carbon formed by carbonization of the polyvinylpyridine iron complex layer. Covered by structure.
- Ketjen Black after the surface of Ketjen Black was coated with the polyvinylpyridine iron complex, it contracted with carbonization, and as a result, a nano-level adhesion interface was formed well between Ketjen Black and the carbon structure. It was.
- This Hirsch method is a method proposed by Hirsch in 1954 in order to evaluate the average number of layers and the distribution of carbon nets in a sample having a relatively small net size such as coal or pitch. .
- ketjen black usually has about two layers of carbon network surface, it was considered that a carbon structure composed of about one or two layers of carbon network surface was formed on the surface of the ketjen black. And it was thought that the thin film of such a carbon structure formed the active point of the catalyst.
- the Q / Co / KB catalyst was configured by adhering carbonized aggregates on the surface of ketjen black. Therefore, in the PVP / Fe / KB catalyst, it was confirmed that remarkably good contact was achieved between the ketjen black and the carbon structure as compared with the Q / Co / KB catalyst.
- FIG. 11 shows an example of a photograph taken with a transmission electron microscope (TEM).
- FIG. 11A is a TEM photograph of a PVP / Fe / KB catalyst
- FIG. 11B is a TEM photograph of Q / Co / KB
- FIG. 11C is a TEM photograph of Ketjen Black alone.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
- Fuel Cell (AREA)
Abstract
Description
1.5gのビニルピリジンを20mLのジメチルホルムアミドに溶解させた後、70℃で5日間かけて高分子化を行い、ポリビニルピリジンを得た。このポリビニルピリジンに0.65gの塩化鉄六水和物を加え、室温で24時間攪拌することによりポリビニルピリジン鉄錯体を得た。
10gの8-キノリノール(オキシン)と、10gのホルムアルデヒドと、1gのシュウ酸二水和物を容積100mLのナスフラスコに入れ、100℃で一晩還流させた。次いで、1MのHClを5.5mL加え、同様に一晩還流させた。得られた固体を吸引ろ過し、蒸留水で3回洗浄し、一晩真空乾燥させて、高分子(Q高分子)を得た。
300mLのアセトンに3.275gのフェノ-ル樹脂(群栄化学工業株式会社)を加え、超音波を照射して溶解させた。さらに、1.0gのコバルトフタロシアニン錯体(東京化成工業株式会社)を加え、超音波を照射しながらロ-タリ-エバポレ-タ-を用いて40℃で溶媒を除去した。その後、残された組成物を温度80℃で24時間真空乾燥することにより、フェノ-ル樹脂を含有するコバルトフタロシアニン錯体を合成した。
実施例1で得られた5種類の炭素触媒、実施例2で得られた2種類の炭素触媒、実施例3で得られた4種類の炭素触媒のそれぞれについて、酸素還元活性を評価した。すなわち、まず、粉末状の炭素触媒を5mg量り取り、これに50μLのバインダー溶液(ナフィオン(登録商標)、デュポン株式会社)、150μLの水、150μLのエタノールを適量加え、この混合溶液を触媒スラリーとして調製した。
上述の実施例1と同様にして、ポリビニルピリジン鉄錯体とケッチェンブラックとを含有し、当該ケッチェンブラックを50重量%含有する原料を得た。そして、上述の実施例1と同様に、この原料を加熱して昇温し、窒素雰囲気下、500℃、600℃、700℃、800℃、900℃又は1000℃で1時間保持した。
上述の実施例3と同様にして、800℃又は1000℃で炭素化された2種類の炭素触媒(Pc/Co(C800)触媒、Pc/Co(C1000)触媒)を得た。また、同様に、コバルトフタロシアニン錯体に代えて、鉄フタロシアニン錯体を用いることにより、800℃で炭素化された炭素触媒(Pc/Fe(C800)触媒)を得た。そして、上述の実施例4と同様に、各炭素触媒の酸素還元活性を評価した。
上述の実施例5で得られた炭素触媒のうち8種類の炭素触媒、当該炭素触媒の製造に用いられたケッチェンブラック、及び実施例6で得られた3種類の炭素触媒の各々について、結晶子サイズLaの分布を評価した。
上述の実施例1で製造され熱処理が施されていないPVP/Fe/KB触媒、実施例2で製造されたQ/Co/KB触媒及びこれらの製造に用いられたケッチェンブラックのそれぞれについて、電子顕微鏡による観察を行った。
Claims (15)
- 導電性炭素材料と、
前記導電性炭素材料の表面を被覆する炭素構造と、
を有する
ことを特徴とする炭素触媒。 - 前記炭素構造を構成する炭素網面の7.2nm以下の結晶子サイズLa分布において、1~5nmの割合が50%以上である
ことを特徴とする請求項1に記載された炭素触媒。 - 前記結晶子サイズLa分布において、1nm未満の割合が40%以下である
ことを特徴とする請求項2に記載された炭素触媒。 - 前記炭素構造は、熱可塑性樹脂と金属と前記導電性炭素材料とを含有する原料を加熱して炭素化することにより形成された炭素構造である
ことを特徴とする請求項1乃至3のいずれかに記載された炭素触媒。 - 請求項1乃至4のいずれかに記載された炭素触媒が担持されている
ことを特徴とする電極。 - 請求項5に記載された電極を有する
ことを特徴とする電池。 - 熱可塑性樹脂と金属と導電性炭素材料とを含有する原料を加熱することにより、溶融した前記熱可塑性樹脂で前記導電性炭素材料の表面を被覆するとともに、前記導電性炭素材料の表面で前記熱可塑性樹脂を炭素化して、炭素触媒を得る
ことを特徴とする炭素触媒の製造方法。 - 前記熱可塑性樹脂は、前記金属に配位可能な高分子配位子であり、
前記原料は、前記熱可塑性樹脂が前記金属に配位して形成された錯体を含有する
ことを特徴とする請求項7に記載された炭素触媒の製造方法。 - 前記熱可塑性樹脂は、その分子内に配位原子として1又は複数の窒素原子を含む
ことを特徴とする請求項8に記載された炭素触媒の製造方法。 - 前記熱可塑性樹脂は、ポリビニルピリジン、サレン重合物、ポリピロール、ポリビニルピロール、3-メチルポリピロール、ポリビニルカルバゾール、ポリアミド、ポリアニリン、ポリビスマレイミド、ポリアミドイミドからなる群より選択される1種又は2種以上を含有する
ことを特徴とする請求項9に記載された炭素触媒の製造方法。 - 前記導電性炭素材料は、カーボンブラックである
ことを特徴とする請求項7乃至10のいずれかに記載された炭素触媒の製造方法。 - 前記金属は遷移金属である
ことを特徴とする請求項7乃至11のいずれかに記載された炭素触媒の製造方法。 - 炭素化により得られた前記炭素触媒に前記金属を除去する処理を施す工程と、
前記処理が施された前記炭素触媒に熱処理を施すことにより前記炭素触媒の活性を向上させる工程と、
をさらに含む
ことを特徴とする請求項7乃至12のいずれかに記載された炭素触媒の製造方法。 - 前記熱処理は、前記炭素触媒を300~1500℃の範囲内の温度で加熱することにより行う
ことを特徴とする請求項13に記載された炭素触媒の製造方法。 - 請求項7乃至14のいずれかに記載された方法により製造された
ことを特徴とする炭素触媒。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/131,928 US9711803B2 (en) | 2008-12-02 | 2009-11-24 | Carbon catalyst, method for manufacturing the carbon catalyst, and electrode and battery using the carbon catalyst |
EP09830323.3A EP2371449B1 (en) | 2008-12-02 | 2009-11-24 | Carbon catalyst, method for manufacturing the carbon catalyst, and electrode and battery using the carbon catalyst |
CA2745163A CA2745163C (en) | 2008-12-02 | 2009-11-24 | Carbon catalyst, method for manufacturing the carbon catalyst, and electrode and battery using the carbon catalyst |
JP2010541295A JP4979817B2 (ja) | 2008-12-02 | 2009-11-24 | 炭素触媒及びその製造方法、これを用いた電極及び電池 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008307848 | 2008-12-02 | ||
JP2008-307848 | 2008-12-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010064556A1 true WO2010064556A1 (ja) | 2010-06-10 |
Family
ID=42233207
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/069778 WO2010064556A1 (ja) | 2008-12-02 | 2009-11-24 | 炭素触媒及びその製造方法、これを用いた電極及び電池 |
Country Status (5)
Country | Link |
---|---|
US (1) | US9711803B2 (ja) |
EP (1) | EP2371449B1 (ja) |
JP (1) | JP4979817B2 (ja) |
CA (1) | CA2745163C (ja) |
WO (1) | WO2010064556A1 (ja) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011006281A (ja) * | 2009-06-25 | 2011-01-13 | Teijin Ltd | 炭素材料及びその製造方法 |
JP2012146670A (ja) * | 2010-07-15 | 2012-08-02 | Showa Denko Kk | 燃料電池用触媒およびその用途 |
JP2013008650A (ja) * | 2011-06-23 | 2013-01-10 | Nagasaki Institute Of Applied Science | 燃料電池触媒坦持体および燃料電池 |
CN103118974A (zh) * | 2010-06-17 | 2013-05-22 | 拜耳知识产权有限责任公司 | 用于碱性电解质中的氧气还原反应的不含金属的碳催化剂 |
WO2013077165A1 (ja) * | 2011-11-25 | 2013-05-30 | 国立大学法人群馬大学 | 金属担持用担体、金属担持触媒、メタネーション反応装置及びこれらに関する方法 |
WO2013089026A1 (ja) * | 2011-12-12 | 2013-06-20 | パナソニック株式会社 | 炭素系材料、電極触媒、酸素還元電極触媒、ガス拡散電極、水溶液電解装置、並びに炭素系材料の製造方法 |
EP2647428A1 (en) * | 2010-11-29 | 2013-10-09 | National University Corporation Gunma University | Carbon catalyst for hydrogen production, method for producing catalyst, and method for producing hydrogen using catalyst |
WO2014006908A1 (ja) * | 2012-07-06 | 2014-01-09 | パナソニック株式会社 | 炭素系材料、電極触媒、電極、ガス拡散電極、電気化学装置、燃料電池、並びに炭素系材料の製造方法 |
WO2014020915A1 (ja) * | 2012-08-01 | 2014-02-06 | 東洋インキScホールディングス株式会社 | 電池触媒用組成物及びその製造方法、電極材料、並びに燃料電池 |
WO2015079956A1 (ja) * | 2013-11-29 | 2015-06-04 | 日清紡ホールディングス株式会社 | アルカリ型燃料電池用炭素触媒及びその製造方法、並びにアルカリ型燃料電池用電極及びアルカリ型燃料電池 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011132676A1 (ja) * | 2010-04-20 | 2011-10-27 | 日清紡ホールディングス株式会社 | 直接型燃料電池のカソード用炭素触媒並びにこれを用いた直接型燃料電池用カソード及び直接型燃料電池 |
WO2013160719A1 (en) | 2012-04-26 | 2013-10-31 | Indian Institute Of Technology Madras | Metal-alloy graphene nanocomposites and methods for their preparation and use |
WO2016086234A1 (en) * | 2014-11-30 | 2016-06-02 | The Texas A&M University System | Non-noble element catalysts and methods for making |
KR101692852B1 (ko) * | 2015-07-02 | 2017-01-06 | 인하대학교 산학협력단 | 코발트 기반 산소환원반응용 촉매 및 이의 제조방법 |
RU2708398C1 (ru) * | 2018-12-10 | 2019-12-06 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | Металл-несодержащий тонкопленочный фотокатализатор восстановления молекулярного кислорода и способ его получения |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007018801A (ja) * | 2005-07-06 | 2007-01-25 | Gs Yuasa Corporation:Kk | 固体高分子形燃料電池用触媒混合体の製造方法およびその製造方法で得られた触媒混合体を含む電極を用いた固体高分子形燃料電池 |
JP2007026746A (ja) | 2005-07-13 | 2007-02-01 | Gunma Univ | 燃料電池用電極触媒の製造方法及びその方法で製造された電極触媒並びにその電極触媒を用いた燃料電池 |
JP2007207662A (ja) | 2006-02-03 | 2007-08-16 | Gunma Univ | 燃料電池用電極触媒及びその製造方法並びに該触媒を用いた燃料電池 |
JP2008282725A (ja) | 2007-05-11 | 2008-11-20 | Gunma Univ | 炭素系燃料電池用電極触媒の製造方法 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4756898A (en) | 1987-04-30 | 1988-07-12 | The United States Of America As Represented By The United States Department Of Energy | Low density microcellular carbon or catalytically impregnated carbon foams and process for their prepartion |
JP3544237B2 (ja) | 1995-02-09 | 2004-07-21 | 独立行政法人 科学技術振興機構 | 巨大フラーレンの製造方法 |
JPH09249407A (ja) | 1996-03-14 | 1997-09-22 | Toyota Central Res & Dev Lab Inc | 黒鉛複合物およびその製造方法 |
JP3601581B2 (ja) | 1999-06-11 | 2004-12-15 | 東洋紡績株式会社 | バナジウム系レドックスフロー電池用炭素電極材 |
TW574764B (en) * | 2002-01-25 | 2004-02-01 | Toyo Tanso Co | Negative electrode material for lithium ion secondary battery |
JP3837076B2 (ja) | 2002-02-26 | 2006-10-25 | 純一 尾崎 | 燃料電池用電極触媒及びそれを用いた燃料電池 |
JP3969658B2 (ja) | 2003-06-27 | 2007-09-05 | 純一 尾崎 | 燃料電池用電極触媒、それを用いた燃料電池および電極 |
WO2006046656A1 (ja) * | 2004-10-28 | 2006-05-04 | Mitsubishi Chemical Corporation | 球状炭素粒子およびその集合体 |
JP4591504B2 (ja) | 2005-02-03 | 2010-12-01 | トヨタ自動車株式会社 | 触媒材料およびその製造方法 |
US7718155B2 (en) | 2005-10-06 | 2010-05-18 | Headwaters Technology Innovation, Llc | Carbon nanostructures manufactured from catalytic templating nanoparticles |
US7887771B2 (en) | 2005-10-06 | 2011-02-15 | Headwaters Technology Innovation, Llc | Carbon nanorings manufactured from templating nanoparticles |
CA2642226A1 (en) | 2006-02-17 | 2007-08-30 | Monsanto Technology Llc | Transition metal-containing catalysts and processes for their preparation and use as fuel cell catalysts |
JP2008173606A (ja) | 2007-01-22 | 2008-07-31 | Toyota Motor Corp | 触媒材料及びその製造方法 |
EP2371448B1 (en) | 2008-12-02 | 2019-07-03 | Nisshinbo Holdings Inc. | Carbon catalyst, method for manufacturing the carbon catalyst, and electrode and battery using the carbon catalyst |
-
2009
- 2009-11-24 CA CA2745163A patent/CA2745163C/en active Active
- 2009-11-24 JP JP2010541295A patent/JP4979817B2/ja active Active
- 2009-11-24 EP EP09830323.3A patent/EP2371449B1/en active Active
- 2009-11-24 WO PCT/JP2009/069778 patent/WO2010064556A1/ja active Application Filing
- 2009-11-24 US US13/131,928 patent/US9711803B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007018801A (ja) * | 2005-07-06 | 2007-01-25 | Gs Yuasa Corporation:Kk | 固体高分子形燃料電池用触媒混合体の製造方法およびその製造方法で得られた触媒混合体を含む電極を用いた固体高分子形燃料電池 |
JP2007026746A (ja) | 2005-07-13 | 2007-02-01 | Gunma Univ | 燃料電池用電極触媒の製造方法及びその方法で製造された電極触媒並びにその電極触媒を用いた燃料電池 |
JP2007207662A (ja) | 2006-02-03 | 2007-08-16 | Gunma Univ | 燃料電池用電極触媒及びその製造方法並びに該触媒を用いた燃料電池 |
JP2008282725A (ja) | 2007-05-11 | 2008-11-20 | Gunma Univ | 炭素系燃料電池用電極触媒の製造方法 |
Non-Patent Citations (9)
Title |
---|
"Abstracts of Annual Meeting of the Carbon Society of Japan, 28 November 2008 (28. 11.2008)", vol. 35TH, article RIEKO KOBAYASHI ET AL.: "PVP Kinzoku Sakutai o Mochiita Tansokei Shokubai ni Okeru Tanso Tantai no Hyomen Jotai ga Sanso Kangen Kassei e Oyobosu Eikyo", pages: 124 - 125, XP008169391 * |
HIROYUKI FUJIMOTO, CARBON ANALYZER D SERIES, Retrieved from the Internet <URL:http://www.asahi-net.or.jp/-qn6h-fjmt> |
HIROYUKI FUJIMOTO, CARBON, vol. 192, 2000, pages 125 - 129 |
HIROYUKI FUJIMOTO, CARBON, vol. 228, 2007, pages 185 - 194 |
R. DIAMOND, ACTA. CRYST., vol. 10, 1957, pages 359 - 363 |
R. DIAMOND, ACTA. CRYST., vol. 11, 1958, pages 129 - 138 |
R. DIAMOND, PH.D. DISSERTATION, UNIVERSITY OF CAMBRIDGE, 1956 |
R. DIAMOND, PHIL. TRANS. ROY. SOC. LONDON, vol. A252, 1960, pages 193 - 223 |
See also references of EP2371449A4 |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011006281A (ja) * | 2009-06-25 | 2011-01-13 | Teijin Ltd | 炭素材料及びその製造方法 |
CN103118974A (zh) * | 2010-06-17 | 2013-05-22 | 拜耳知识产权有限责任公司 | 用于碱性电解质中的氧气还原反应的不含金属的碳催化剂 |
JP2012146670A (ja) * | 2010-07-15 | 2012-08-02 | Showa Denko Kk | 燃料電池用触媒およびその用途 |
EP2647428A4 (en) * | 2010-11-29 | 2014-06-11 | Univ Gunma Nat Univ Corp | CARBON CATALYST FOR HYDROGEN PRODUCTION, PROCESS FOR PRODUCTION OF CATALYST, AND PROCESS FOR PRODUCTION OF HYDROGEN USING CATALYST |
EP2647428A1 (en) * | 2010-11-29 | 2013-10-09 | National University Corporation Gunma University | Carbon catalyst for hydrogen production, method for producing catalyst, and method for producing hydrogen using catalyst |
US9050583B2 (en) | 2010-11-29 | 2015-06-09 | National University Corporation Gunma University | Carbon catalyst for hydrogen production, method for producing catalyst, and method for producing hydrogen using catalyst |
JP2013008650A (ja) * | 2011-06-23 | 2013-01-10 | Nagasaki Institute Of Applied Science | 燃料電池触媒坦持体および燃料電池 |
WO2013077165A1 (ja) * | 2011-11-25 | 2013-05-30 | 国立大学法人群馬大学 | 金属担持用担体、金属担持触媒、メタネーション反応装置及びこれらに関する方法 |
JP2013111496A (ja) * | 2011-11-25 | 2013-06-10 | Gunma Univ | 金属担持用担体、金属担持触媒、メタネーション反応装置及びこれらに関する方法 |
WO2013089026A1 (ja) * | 2011-12-12 | 2013-06-20 | パナソニック株式会社 | 炭素系材料、電極触媒、酸素還元電極触媒、ガス拡散電極、水溶液電解装置、並びに炭素系材料の製造方法 |
JP5677589B2 (ja) * | 2011-12-12 | 2015-02-25 | パナソニック株式会社 | 炭素系材料、電極触媒、酸素還元電極触媒、ガス拡散電極、水溶液電解装置、並びに炭素系材料の製造方法 |
WO2014006908A1 (ja) * | 2012-07-06 | 2014-01-09 | パナソニック株式会社 | 炭素系材料、電極触媒、電極、ガス拡散電極、電気化学装置、燃料電池、並びに炭素系材料の製造方法 |
CN104321276A (zh) * | 2012-07-06 | 2015-01-28 | 松下知识产权经营株式会社 | 碳基材料、电极催化剂、电极、气体扩散电极、电化学装置、燃料电池及碳基材料的制备方法 |
JPWO2014006908A1 (ja) * | 2012-07-06 | 2016-06-02 | パナソニックIpマネジメント株式会社 | 炭素系材料、電極触媒、電極、ガス拡散電極、電気化学装置、燃料電池、並びに炭素系材料の製造方法 |
US9929411B2 (en) | 2012-07-06 | 2018-03-27 | Panasonic Intellectual Property Management Co., Ltd. | Carbon-based material, electrode catalyst, electrode, gas diffusion electrode, electrochemical device, fuel battery, and process for producing carbon-based material |
JP2014042910A (ja) * | 2012-08-01 | 2014-03-13 | Toyo Ink Sc Holdings Co Ltd | 炭素触媒造粒体、炭素触媒造粒体の製造方法、及び該炭素触媒造粒体を用いた触媒インキ並びに燃料電池 |
WO2014020915A1 (ja) * | 2012-08-01 | 2014-02-06 | 東洋インキScホールディングス株式会社 | 電池触媒用組成物及びその製造方法、電極材料、並びに燃料電池 |
WO2015079956A1 (ja) * | 2013-11-29 | 2015-06-04 | 日清紡ホールディングス株式会社 | アルカリ型燃料電池用炭素触媒及びその製造方法、並びにアルカリ型燃料電池用電極及びアルカリ型燃料電池 |
JP2015106512A (ja) * | 2013-11-29 | 2015-06-08 | 日清紡ホールディングス株式会社 | アルカリ型燃料電池用炭素触媒及びその製造方法、並びにアルカリ型燃料電池用電極及びアルカリ型燃料電池 |
Also Published As
Publication number | Publication date |
---|---|
US20110229766A1 (en) | 2011-09-22 |
EP2371449B1 (en) | 2020-04-15 |
CA2745163C (en) | 2019-01-22 |
EP2371449A4 (en) | 2016-09-28 |
CA2745163A1 (en) | 2010-06-10 |
JPWO2010064556A1 (ja) | 2012-05-10 |
US9711803B2 (en) | 2017-07-18 |
JP4979817B2 (ja) | 2012-07-18 |
EP2371449A1 (en) | 2011-10-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4979817B2 (ja) | 炭素触媒及びその製造方法、これを用いた電極及び電池 | |
JP4979816B2 (ja) | 炭素触媒及びその製造方法、これを用いた電極及び電池 | |
Ban et al. | Efficient Co–N/PC@ CNT bifunctional electrocatalytic materials for oxygen reduction and oxygen evolution reactions based on metal–organic frameworks | |
KR101367602B1 (ko) | 탄소 촉매 및 그 제조 방법, 그리고 이것을 이용한 전극 및 전지 | |
US8993164B2 (en) | Support for catalyst supporting, carrier with supported catalyst, electrode, and battery | |
JP5481646B2 (ja) | 炭素触媒、燃料電池、蓄電装置 | |
CN1286202C (zh) | 燃料电池用电极催化剂、使用它的燃料电池及电极 | |
WO2011055739A1 (ja) | 炭素触媒並びにその製造方法及びこれを用いた電極並びに電池 | |
JP2007207662A (ja) | 燃料電池用電極触媒及びその製造方法並びに該触媒を用いた燃料電池 | |
Wang et al. | Enhancing the catalytic performance of Pt/C catalysts using steam-etched carbon blacks as a catalyst support | |
JP5689379B2 (ja) | 触媒担持用担体、触媒担持体、電極及び電池 | |
Liu et al. | In-situ synthesis of conductive Fe-MOFs on the carbon nanotubes/carbon cloth as high-performance catalyst for alkaline oxygen evolution | |
JP5732667B2 (ja) | 炭素触媒の製造方法 | |
WO2007072739A1 (ja) | マンガン酸化物ナノ粒子分散材料及び電極の製造方法 | |
Li et al. | In situ preparation of multi-wall carbon nanotubes/Au composites for oxygen electroreduction | |
Kongi et al. | Highly active Ag-MnOx/C catalysts for oxygen electroreduction |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09830323 Country of ref document: EP Kind code of ref document: A1 |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2745163 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13131928 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2010541295 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009830323 Country of ref document: EP |