JP6567386B2 - Nitrogen-containing carbon material powder and method for producing the same - Google Patents
Nitrogen-containing carbon material powder and method for producing the same Download PDFInfo
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- JP6567386B2 JP6567386B2 JP2015201421A JP2015201421A JP6567386B2 JP 6567386 B2 JP6567386 B2 JP 6567386B2 JP 2015201421 A JP2015201421 A JP 2015201421A JP 2015201421 A JP2015201421 A JP 2015201421A JP 6567386 B2 JP6567386 B2 JP 6567386B2
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- Prior art keywords
- nitrogen
- carbon material
- containing carbon
- material powder
- slurry
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- 239000003575 carbonaceous material Substances 0.000 title claims description 142
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims description 137
- 239000000843 powder Substances 0.000 title claims description 104
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 239000011148 porous material Substances 0.000 claims description 128
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 99
- 238000010438 heat treatment Methods 0.000 claims description 74
- 239000002002 slurry Substances 0.000 claims description 71
- 238000000034 method Methods 0.000 claims description 67
- 239000002994 raw material Substances 0.000 claims description 65
- 229910052757 nitrogen Inorganic materials 0.000 claims description 58
- 150000003624 transition metals Chemical class 0.000 claims description 45
- 239000002243 precursor Substances 0.000 claims description 41
- 229910052723 transition metal Inorganic materials 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 17
- 239000000446 fuel Substances 0.000 claims description 16
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 15
- 238000010298 pulverizing process Methods 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 13
- 229910052753 mercury Inorganic materials 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 10
- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 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
- 230000010757 Reduction Activity Effects 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 16
- -1 hydrazide Chemical compound 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 150000002894 organic compounds Chemical class 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 8
- 238000002848 electrochemical method Methods 0.000 description 8
- 239000011164 primary particle Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000011324 bead Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 150000004687 hexahydrates Chemical class 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920000554 ionomer Polymers 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000005518 polymer electrolyte Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000004684 trihydrates Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910021576 Iron(III) bromide Inorganic materials 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 230000004931 aggregating effect Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 238000002459 porosimetry Methods 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000004685 tetrahydrates Chemical class 0.000 description 2
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- 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
- 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 description 1
- XIZOGMFSXFMCDT-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;iron(3+);trihydrate Chemical compound O.O.O.[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XIZOGMFSXFMCDT-UHFFFAOYSA-K 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 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
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229910021560 Chromium(III) bromide Inorganic materials 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- IDCVFEFEBHVLFK-UHFFFAOYSA-J Cl[Co](Cl)(Cl)Cl.[Cs] Chemical compound Cl[Co](Cl)(Cl)Cl.[Cs] IDCVFEFEBHVLFK-UHFFFAOYSA-J 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021582 Cobalt(II) fluoride Inorganic materials 0.000 description 1
- 229910021584 Cobalt(II) iodide Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- YUHSQCAUZQHEBD-UHFFFAOYSA-H F[Co](F)(F)(F)(F)F.[K] Chemical compound F[Co](F)(F)(F)(F)F.[K] YUHSQCAUZQHEBD-UHFFFAOYSA-H 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000004277 Ferrous carbonate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 1
- 229910021579 Iron(II) iodide Inorganic materials 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- FCJGCTIWVFWIOE-UHFFFAOYSA-N N#C[Fe](C#N)(C#N)(C#N)C#N Chemical compound N#C[Fe](C#N)(C#N)(C#N)C#N FCJGCTIWVFWIOE-UHFFFAOYSA-N 0.000 description 1
- ZVQGKGNJZAQHCJ-UHFFFAOYSA-N N.N.O.O.O.O.O.O.[Fe+2] Chemical compound N.N.O.O.O.O.O.O.[Fe+2] ZVQGKGNJZAQHCJ-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QDUFFVDHDBLUSO-UHFFFAOYSA-K O.O.O.O.O.O.Br[Fe](Br)Br Chemical compound O.O.O.O.O.O.Br[Fe](Br)Br QDUFFVDHDBLUSO-UHFFFAOYSA-K 0.000 description 1
- KAKQILYTDCSBHF-UHFFFAOYSA-N O.O.O.O.O.O.O.[Na+].[Fe+2] Chemical compound O.O.O.O.O.O.O.[Na+].[Fe+2] KAKQILYTDCSBHF-UHFFFAOYSA-N 0.000 description 1
- AYBWWLKXTXQVGS-UHFFFAOYSA-L O.O.O.[Fe++].[S-]C#N.[S-]C#N Chemical compound O.O.O.[Fe++].[S-]C#N.[S-]C#N AYBWWLKXTXQVGS-UHFFFAOYSA-L 0.000 description 1
- MCZRSTYQTGGHAT-UHFFFAOYSA-J O.O.O.[Fe+3].S(=O)(=O)([O-])[O-].S(=O)(=O)(O)O.S(=O)(=O)([O-])[O-].[Na+] Chemical compound O.O.O.[Fe+3].S(=O)(=O)([O-])[O-].S(=O)(=O)(O)O.S(=O)(=O)([O-])[O-].[Na+] MCZRSTYQTGGHAT-UHFFFAOYSA-J 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- TYRQHOOINMAEHH-UHFFFAOYSA-N [K].N#C[Fe](C#N)(C#N)(C#N)(C#N)C#N Chemical compound [K].N#C[Fe](C#N)(C#N)(C#N)(C#N)C#N TYRQHOOINMAEHH-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QLGCEAZZWDUTTM-UHFFFAOYSA-K azanium;iron(3+);tetrachloride Chemical compound [NH4+].[Cl-].[Cl-].[Cl-].[Cl-].[Fe+3] QLGCEAZZWDUTTM-UHFFFAOYSA-K 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- UZDWIWGMKWZEPE-UHFFFAOYSA-K chromium(iii) bromide Chemical compound [Cr+3].[Br-].[Br-].[Br-] UZDWIWGMKWZEPE-UHFFFAOYSA-K 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 description 1
- XSBRXEODRVITTI-UHFFFAOYSA-L cobalt(2+);diiodide;hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[I-].[I-] XSBRXEODRVITTI-UHFFFAOYSA-L 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- QOQSIXJUYVUEMP-UHFFFAOYSA-H cobalt(2+);diphosphate;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QOQSIXJUYVUEMP-UHFFFAOYSA-H 0.000 description 1
- INDBQWVYFLTCFF-UHFFFAOYSA-L cobalt(2+);dithiocyanate Chemical compound [Co+2].[S-]C#N.[S-]C#N INDBQWVYFLTCFF-UHFFFAOYSA-L 0.000 description 1
- 229910000335 cobalt(II) sulfate Inorganic materials 0.000 description 1
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical class C1(=CC=CC1)* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- YECVBNYAHYWPOD-UHFFFAOYSA-L diiodoiron;tetrahydrate Chemical compound O.O.O.O.I[Fe]I YECVBNYAHYWPOD-UHFFFAOYSA-L 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 235000019268 ferrous carbonate Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011899 heat drying method Methods 0.000 description 1
- 108010036302 hemoglobin AS Proteins 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- NDNPXAGLLVWKAD-UHFFFAOYSA-L iron(2+) dibromide hexahydrate Chemical compound O.O.O.O.O.O.[Fe](Br)Br NDNPXAGLLVWKAD-UHFFFAOYSA-L 0.000 description 1
- UENYKSLRDITUNR-UHFFFAOYSA-L iron(2+) diperchlorate hexahydrate Chemical compound O.O.O.O.O.O.[Fe+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O UENYKSLRDITUNR-UHFFFAOYSA-L 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- QSFQAAFFWCAFJP-UHFFFAOYSA-L iron(2+);carbonate;hydrate Chemical compound O.[Fe+2].[O-]C([O-])=O QSFQAAFFWCAFJP-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- NPLZZSLZTJVZSX-UHFFFAOYSA-L iron(2+);oxalate;dihydrate Chemical compound O.O.[Fe+2].[O-]C(=O)C([O-])=O NPLZZSLZTJVZSX-UHFFFAOYSA-L 0.000 description 1
- ZJBJXXOHBZEBIM-UHFFFAOYSA-H iron(3+) oxalate pentahydrate Chemical compound O.O.O.O.O.[Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZJBJXXOHBZEBIM-UHFFFAOYSA-H 0.000 description 1
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- GJMIMISVJLOUGG-UHFFFAOYSA-K iron(3+);triperchlorate;hexahydrate Chemical compound O.O.O.O.O.O.[Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O GJMIMISVJLOUGG-UHFFFAOYSA-K 0.000 description 1
- SUBFIBLJQMMKBK-UHFFFAOYSA-K iron(3+);trithiocyanate Chemical compound [Fe+3].[S-]C#N.[S-]C#N.[S-]C#N SUBFIBLJQMMKBK-UHFFFAOYSA-K 0.000 description 1
- VRWKTAYJTKRVCU-UHFFFAOYSA-N iron(6+);hexacyanide Chemical compound [Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] VRWKTAYJTKRVCU-UHFFFAOYSA-N 0.000 description 1
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 229920000368 omega-hydroxypoly(furan-2,5-diylmethylene) polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920001088 polycarbazole Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- LDQICAMJIICDLF-UHFFFAOYSA-N potassium;iron(2+);iron(3+);hexacyanide Chemical compound [K+].[Fe+2].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] LDQICAMJIICDLF-UHFFFAOYSA-N 0.000 description 1
- IGJRYXMMAMQEGY-UHFFFAOYSA-L potassium;iron(2+);sulfate Chemical compound [K+].[Fe+2].[O-]S([O-])(=O)=O IGJRYXMMAMQEGY-UHFFFAOYSA-L 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JFSUDVTVQZUDOP-UHFFFAOYSA-N tetrasodium;iron(2+);hexacyanide;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] JFSUDVTVQZUDOP-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021381 transition metal chloride Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
Description
本発明は、窒素含有炭素材料からなる粉体及びその製造方法に関する。 The present invention relates to a powder made of a nitrogen-containing carbon material and a method for producing the same.
固体高分子形燃料電池は、発電効率が高い、出力密度が高い、急速な起動停止が可能である、小型軽量化が可能であるといった利点を持ち、携帯用電源、移動用電源、小型定置用発電機等への適用が期待されている。 The polymer electrolyte fuel cell has advantages such as high power generation efficiency, high output density, rapid start / stop, small size and light weight. Portable power source, mobile power source, small stationary device Application to generators is expected.
固体高分子形燃料電池では、その正極で起こる酸素還元反応を促進するために、一般に白金又は白金合金が触媒として用いられるが、白金の資源量が極めて少なく、また高価であるために実用化への大きな障壁となっている。そこで、白金等の貴金属を必要としない燃料電池用電極触媒として窒素及び／又は遷移金属を含有することによって酸素還元活性を発現した炭素触媒が注目を集めている。 In a polymer electrolyte fuel cell, platinum or a platinum alloy is generally used as a catalyst in order to promote the oxygen reduction reaction occurring at the positive electrode. However, since the amount of platinum resources is extremely small and expensive, it is put to practical use. It has become a big barrier. Therefore, carbon catalysts that have developed oxygen reduction activity by containing nitrogen and / or transition metals have attracted attention as electrode catalysts for fuel cells that do not require noble metals such as platinum.
例えば、窒素原子を含む有機物と鉄及び／又はコバルトと、銅とを含む原料を炭素化して得られる炭素触媒が提案されている（例えば、特許文献１参照）。また、電子線マイクロアナライザによって得られる窒素原子と炭素原子との原子比が０．００５〜０．３でり、ＢＥＴ法によって求められる比表面積が４００ｍ2／ｇ以上であり、Ｘ線回折線図から求められる結晶化度が０．１以下である窒素含有炭素材料が提案されている（例えば、特許文献２参照）。 For example, a carbon catalyst obtained by carbonizing a raw material containing an organic substance containing nitrogen atoms, iron and / or cobalt, and copper has been proposed (see, for example, Patent Document 1). Further, the atomic ratio of nitrogen atoms to carbon atoms obtained by an electron beam microanalyzer is 0.005 to 0.3, the specific surface area determined by the BET method is 400 m 2 / g or more, and an X-ray diffraction diagram Has been proposed (see, for example, Patent Document 2).
ＩＵＰＡＣの触媒分野における規定では、直径２ｎｍ以下の細孔はミクロ孔、直径５０ｎｍ以上の細孔はマクロ孔、直径がその間のサイズの細孔はメソ孔と定義されている。このような炭素触媒の酸素還元活性を向上させる試みの一つとして、炭素触媒にメソ孔を形成する方法が知られている。例えば、特許文献３ではヘモグロビンを原料とする炭素触媒の合成において、造孔剤として微粒子状の酢酸マグネシウムを添加し、炭化後に生成する酸化マグネシウムを硫酸水溶液で煮沸して除去することによって１０ｎｍ以下のメソ孔を形成している。 According to the regulations in the catalyst field of IUPAC, pores having a diameter of 2 nm or less are defined as micropores, pores having a diameter of 50 nm or more are defined as macropores, and pores having a diameter in between are defined as mesopores. As one of attempts to improve the oxygen reduction activity of such a carbon catalyst, a method of forming mesopores in the carbon catalyst is known. For example, in Patent Document 3, in the synthesis of a carbon catalyst using hemoglobin as a raw material, particulate magnesium acetate is added as a pore-forming agent, and magnesium oxide produced after carbonization is removed by boiling with sulfuric acid aqueous solution to be 10 nm or less. Mesopores are formed.
しかしながら、従来の炭素触媒の酸素還元活性は未だ不十分である。 However, the oxygen reduction activity of conventional carbon catalysts is still insufficient.
そこで、本発明は上記事情に鑑みてなされたものであり、酸素還元活性の高い窒素含有炭素材料粉体及びその製造方法を提供することを目的とする。 Then, this invention is made | formed in view of the said situation, and it aims at providing the nitrogen-containing carbon material powder with high oxygen reduction activity, and its manufacturing method.
本発明者らは、上記課題を解決するためにメソ孔に着目して鋭意研究を重ねた結果、窒素吸着法による孔径２〜２０ｎｍの細孔容積に対する水銀圧入法による孔径２０〜５０ｎｍの細孔容積の比が大きい窒素含有炭素材料粉体が、燃料電池用電極等の用途において、高い酸素還元活性を有することを見出し、該粉体の工業的な製造方法を見出して、本発明を完成するに至った。 As a result of intensive studies focusing on mesopores in order to solve the above-mentioned problems, the present inventors have found that pores having a pore diameter of 20 to 50 nm by a mercury intrusion method with respect to a pore volume having a pore diameter of 2 to 20 nm by a nitrogen adsorption method. The nitrogen-containing carbon material powder having a large volume ratio is found to have high oxygen reduction activity in applications such as fuel cell electrodes, and an industrial production method for the powder is found to complete the present invention. It came to.
すなわち、本発明は、下記のとおりである。
〔１〕
下記式（１）で表される孔径２０〜５０ｎｍのメソ孔量の指標Ｉが０．６以上である窒素含有炭素材料粉体。
That is, the present invention is as follows.
[1]
A nitrogen-containing carbon material powder having an index I of mesopore volume of 20 to 50 nm represented by the following formula (1) of 0.6 or more.
（孔径２０〜５０ｎｍのメソ孔量の指標Ｉ）＝（水銀圧入法による細孔径（直径）２０〜５０ｎｍの細孔容積Ｖ1［ｃｃ／ｇ］）／（窒素吸着法による細孔径（直径）２〜２０ｎｍの細孔容積Ｖ2［ｃｃ／ｇ］）
・・・・式（１）
〔２〕
窒素原子と炭素原子との原子比（Ｎ／Ｃ）が、０．００５〜０．３である、前項〔１〕に記載の窒素含有炭素材料粉体。
〔３〕
遷移金属をさらに含む、前項〔１〕又は２に記載の窒素含有炭素材料粉体。
〔４〕
前記遷移金属が、鉄及び／又はコバルトを含む、前項〔３〕に記載の窒素含有炭素材料粉体。
〔５〕
前記遷移金属の含有量が、０．１〜２０質量％である、前項〔３〕又は〔４〕に記載の窒素含有炭素材料粉体。
〔６〕
窒素含有炭素材料を溶媒に分散させてスラリーを得るスラリー調製工程と、該スラリーから該溶媒を除去することで下記式（１）で表される孔径２０〜５０ｎｍのメソ孔量の指標Ｉが０．６以上の窒素含有炭素材料粉体を形成する細孔形成工程とを有する、前項〔１〕〜〔５〕のいずれか１項に記載の窒素含有炭素材料粉体の製造方法。
(Indicator I of mesopore volume of pore diameter 20-50 nm) = (pore diameter (diameter) by mercury intrusion method 20 pore diameter V 1 [cc / g]) / (pore diameter (diameter) by nitrogen adsorption method) 2-20 nm pore volume V 2 [cc / g])
.... Formula (1)
[2]
The nitrogen-containing carbon material powder according to [1], wherein the atomic ratio (N / C) of nitrogen atoms to carbon atoms is 0.005 to 0.3.
[3]
3. The nitrogen-containing carbon material powder according to [1] or 2 above, further comprising a transition metal.
[4]
The nitrogen-containing carbon material powder according to [3], wherein the transition metal contains iron and / or cobalt.
[5]
The nitrogen-containing carbon material powder according to [3] or [4], wherein the content of the transition metal is 0.1 to 20% by mass.
[6]
A slurry preparation step of obtaining a slurry by dispersing a nitrogen-containing carbon material in a solvent, and removing the solvent from the slurry results in an index I of a mesopore amount of a pore diameter of 20 to 50 nm represented by the following formula (1): 0 The method for producing nitrogen-containing carbon material powder according to any one of [1] to [5] above, further comprising a pore forming step of forming 6 or more nitrogen-containing carbon material powder.
（孔径２０〜５０ｎｍのメソ孔量の指標Ｉ）＝（水銀圧入法による細孔径（直径）２０〜５０ｎｍの細孔容積Ｖ1［ｃｃ／ｇ］）／（窒素吸着法による細孔径（直径）２〜２０ｎｍの細孔容積Ｖ2［ｃｃ／ｇ］）
・・・・式（１）
〔７〕
前記細孔形成工程が、噴霧乾燥機を用いて前記スラリーから前記溶媒を除去する工程を含む、前項〔６〕に記載の窒素含有炭素材料粉体の製造方法。
〔８〕
前記細孔形成工程が、振動乾燥機を用いて前記スラリーから前記溶媒を除去する工程を含む、前項〔６〕に記載の窒素含有炭素材料粉体の製造方法。
〔９〕
前記細孔形成工程が、前記スラリーに凝集剤を添加して凝集物を生成させ、その後濾過を行って前記凝集物を採取し、更に前記凝集物から前記溶媒を除去する工程を含む、前項〔６〕に記載の窒素含有炭素材料粉体の製造方法。
〔１０〕
前記スラリー調製工程が、窒素含有炭素材料を湿式粉砕する湿式粉砕工程を含む、前項〔６〕〜〔９〕のいずれか一項に記載の窒素含有炭素材料粉体の製造方法。
〔１１〕
炭素原料と、窒素原料と、を含む前駆体を熱処理して、窒素含有炭素材料を得る熱処理工程を有する、前項〔６〕〜〔１０〕のいずれか一項に記載の窒素含有炭素材料粉体の製造方法。
〔１２〕
前記前駆体が、アズルミン酸及び／又はジアミノマレオニトリルを含む、前項〔１１〕に記載の窒素含有炭素材料粉体の製造方法。
〔１３〕
前記熱処理工程が、前記前駆体を不活性ガス雰囲気下で熱処理する第１の熱処理工程と、前記第１の熱処理工程で処理された前駆体をアンモニア含有ガス雰囲気下で熱処理する第２の熱処理工程と、を含む、前項〔１１〕又は〔１２〕に記載の窒素含有炭素材料粉体の製造方法。
〔１４〕
前項〔１〕〜〔５〕のいずれか一項に記載の窒素含有炭素材料粉体を含む、電極。
〔１５〕
前項〔１〕〜〔５〕のいずれか一項に記載の窒素含有炭素材料粉体を含む、燃料電池用電極。
〔１６〕
前項〔１〕〜〔５〕のいずれか一項に記載の窒素含有炭素材料粉体を含む、固体高分子形燃料電池用電極。
(Indicator I of mesopore volume of pore diameter 20-50 nm) = (pore diameter (diameter) by mercury intrusion method 20 pore diameter V 1 [cc / g]) / (pore diameter (diameter) by nitrogen adsorption method) 2-20 nm pore volume V 2 [cc / g])
.... Formula (1)
[7]
The method for producing a nitrogen-containing carbon material powder according to [6] above, wherein the pore forming step includes a step of removing the solvent from the slurry using a spray dryer.
[8]
The method for producing a nitrogen-containing carbon material powder according to [6], wherein the pore forming step includes a step of removing the solvent from the slurry using a vibration dryer.
[9]
The pore forming step includes a step of adding an aggregating agent to the slurry to form an aggregate, then performing filtration to collect the aggregate, and further removing the solvent from the aggregate [ 6] The method for producing a nitrogen-containing carbon material powder according to [6].
[10]
The method for producing a nitrogen-containing carbon material powder according to any one of [6] to [9], wherein the slurry preparation step includes a wet pulverization step of wet-pulverizing the nitrogen-containing carbon material.
[11]
The nitrogen-containing carbon material powder according to any one of [6] to [10] above, which has a heat treatment step of heat-treating a precursor containing a carbon raw material and a nitrogen raw material to obtain a nitrogen-containing carbon material. Manufacturing method.
[12]
The method for producing a nitrogen-containing carbon material powder according to [11] above, wherein the precursor contains azulmic acid and / or diaminomaleonitrile.
[13]
The heat treatment step includes a first heat treatment step of heat-treating the precursor in an inert gas atmosphere, and a second heat treatment step of heat-treating the precursor treated in the first heat treatment step in an ammonia-containing gas atmosphere. The method for producing a nitrogen-containing carbon material powder according to [11] or [12] above.
[14]
An electrode comprising the nitrogen-containing carbon material powder according to any one of [1] to [5].
[15]
A fuel cell electrode comprising the nitrogen-containing carbon material powder according to any one of [1] to [5].
[16]
An electrode for a solid polymer fuel cell, comprising the nitrogen-containing carbon material powder according to any one of [1] to [5].
本発明によると、酸素還元活性の高い窒素含有炭素材料粉体及びその製造方法を提供することができる。 According to the present invention, a nitrogen-containing carbon material powder having a high oxygen reduction activity and a method for producing the same can be provided.
以下、本発明を実施するための形態（以下、単に「本実施形態」という。）について詳細に説明するが、本発明はこれに限定されるものではなく、その要旨を逸脱しない範囲で様々な変形が可能である。
〔窒素含有炭素材料粉体〕
本実施形態の窒素含有炭素材料粉体は、平均粒子径（平均凝集粒子径）は特に限定されない。しかしながら、取扱いの観点からは、平均粒子径が０．１〜１００μｍであることが好ましく、０．２〜２０μｍであることがより好ましく、０．３〜１０μｍであることが更に好ましい。
Hereinafter, a mode for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the scope of the present invention. Deformation is possible.
[Nitrogen-containing carbon material powder]
The nitrogen-containing carbon material powder of the present embodiment is not particularly limited in average particle size (average aggregate particle size). However, from the viewpoint of handling, the average particle size is preferably 0.1 to 100 μm, more preferably 0.2 to 20 μm, and still more preferably 0.3 to 10 μm.
本実施形態の窒素含有炭素材料粉体は、水銀圧入法による細孔径（直径）２０〜５０ｎｍの範囲の細孔の容積をＶ1［ｃｃ／ｇ］、窒素吸着法による細孔径（直径）２〜２０ｎｍの範囲の細孔の容積をＶ2［ｃｃ／ｇ］、孔径２０〜５０ｎｍのメソ孔量の指標Ｉ＝Ｖ1／Ｖ2としたときに、Ｉが０．６以上である。当該指標Ｉの上限は特に限定されないが、例えば５．０が挙げられる。従来技術の窒素含有炭素材料は、孔径２０〜５０ｎｍのメソ孔の形成が困難であるため、前記指標Ｉが比較的小さいものが多い。これに対し、本実施形態の窒素含有炭素材料粉体は、前記指標Ｉを大きくすることで、酸素還元活性を向上させるものである。 The nitrogen-containing carbon material powder according to the present embodiment has a pore volume (diameter) of 20 to 50 nm in pore diameter (diameter) by mercury intrusion method, V 1 [cc / g], and a pore diameter (diameter) of 2 by nitrogen adsorption method. When the volume of pores in the range of ˜20 nm is V 2 [cc / g] and the mesopore volume index I = V 1 / V 2 of pore diameters of 20-50 nm, I is 0.6 or more. Although the upper limit of the said parameter | index I is not specifically limited, For example, 5.0 is mentioned. In the conventional nitrogen-containing carbon material, it is difficult to form mesopores having a pore diameter of 20 to 50 nm, and therefore, the index I is often relatively small. On the other hand, the nitrogen-containing carbon material powder of the present embodiment improves the oxygen reduction activity by increasing the index I.
前記指標Ｉを大きくすることで酸素還元活性が向上する理由は明らかではないが、下記のように考えている。細孔径２０〜５０ｎｍの範囲の細孔は、反応物質である酸素が拡散しやすく、もう一つの反応物質であるプロトンを媒介するアイオノマーや水が浸透しやすいため、酸素還元反応に適した反応場であり、一方、細孔径２〜２０ｎｍの範囲の細孔は、酸素還元反応に適していないと推定される。したがって、前記指標Ｉを大きくすることで酸素還元活性が向上すると考えられる。 The reason why the oxygen reduction activity is improved by increasing the index I is not clear, but is considered as follows. The pores with a pore diameter in the range of 20 to 50 nm are suitable for oxygen reduction reaction because oxygen, which is a reactant, easily diffuses, and ionomers or water that mediate protons, which are another reactant, easily penetrate. On the other hand, it is estimated that pores having a pore diameter in the range of 2 to 20 nm are not suitable for the oxygen reduction reaction. Therefore, it is considered that the oxygen reduction activity is improved by increasing the index I.
なお、細孔形状として、入口が狭く、内部が広がっている場合があるが、圧入を利用する水銀圧入法では入口のみを評価し、毛管凝縮を利用する窒素吸着法では入口と内部とを別々に評価する。ここで、前記指標Ｉの算出においては、酸素の拡散、およびアイオノマーや水の浸透という観点から、入口のサイズが重要であるため、細孔径２０〜５０ｎｍの範囲の細孔は水銀圧入法によって測定する。一方、数ｎｍ以下の細孔は水銀圧入法では測定が困難であるため、細孔径２〜２０ｎｍの範囲の細孔は窒素吸着法で測定する。 As the pore shape, the inlet may be narrow and the inside may be widened. However, in the mercury intrusion method using press-fitting, only the inlet is evaluated, and in the nitrogen adsorption method using capillary condensation, the inlet and the inside are separated. To evaluate. Here, in the calculation of the index I, the size of the inlet is important from the viewpoints of oxygen diffusion and ionomer or water penetration, so pores in the pore diameter range of 20 to 50 nm are measured by the mercury intrusion method. To do. On the other hand, since pores of several nm or less are difficult to measure by the mercury intrusion method, pores having a pore diameter in the range of 2 to 20 nm are measured by the nitrogen adsorption method.
一方、窒素吸着法による細孔径（直径）２０〜５０ｎｍの範囲の細孔の容積をＶ3［ｃｃ／ｇ］とした場合、（水銀圧入法による細孔径２０〜５０ｎｍの細孔容積Ｖ1［ｃｃ／ｇ］）／（窒素吸着法による細孔径２０〜５０ｎｍの細孔容積Ｖ3［ｃｃ／ｇ］）で表されるＶ1とＶ3との比Ｉ’は、窒素含有炭素材料粉体が有する細孔径２０〜５０ｎｍの細孔のうち、入口が広い細孔の割合を表すと考えられる。そのため、本実施態様の窒素含有炭素材料粉体においては、前記比Ｉ’は１．０以上が好ましく、１．５以上がより好ましい。前記比Ｉ’の上限は特に限定されないが、例えば５．０が挙げられる。 On the other hand, when the volume of pores having a pore diameter (diameter) of 20 to 50 nm in the nitrogen adsorption method is V 3 [cc / g], the pore volume V 1 [pore diameter of 20 to 50 nm by mercury porosimetry is used. cc / g]) / (pore volume V 3 with a pore diameter of 20 to 50 nm by nitrogen adsorption method V 3 [cc / g]) The ratio I ′ between V 1 and V 3 is a nitrogen-containing carbon material powder. This is considered to represent the proportion of pores having a wide inlet among pores having a pore diameter of 20 to 50 nm. Therefore, in the nitrogen-containing carbon material powder of this embodiment, the ratio I ′ is preferably 1.0 or more, and more preferably 1.5 or more. The upper limit of the ratio I ′ is not particularly limited, but an example is 5.0.
また、本実施形態の窒素含有炭素材料粉体は、水銀圧入法による細孔径（直径）２０〜５０ｎｍの範囲の細孔の容積Ｖ1［ｃｃ／ｇ］が０．１００ｃｃ／ｇ以上であることが好ましく、０．２００ｃｃ／ｇ以上であることがより好ましく、０．３００ｃｃ／ｇ以上であることがさらに好ましい。前記容積Ｖ1の上限は特に限定されないが、例えば５．０ｃｃ／ｇが挙げられる。従来技術の窒素含有炭素材料は、細孔径（直径）２０〜５０ｎｍのメソ孔の形成が困難であるため、細孔径（直径）２０〜５０ｎｍのメソ孔量が比較的少ない。これに対し、本実施形態の窒素含有炭素材料粉体は、細孔径（直径）２０〜５０ｎｍのメソ孔量を多くすることで、酸素還元活性を向上させるものである。
〔原子比（Ｎ／Ｃ）〕
本実施形態の窒素含有炭素材料粉体中の窒素原子と炭素原子との原子比（Ｎ／Ｃ）は、好ましくは０．００５〜０．３であり、より好ましくは０．０１〜０．２であり、さらに好ましくは０．０２〜０．１５である。本実施形態の窒素含有炭素材料粉体は、前記原子比（Ｎ／Ｃ）が上記範囲内であることにより、酸素還元活性がより高くなる。前記原子比（Ｎ／Ｃ）は、後述する窒素含有炭素材料粉体の製造方法において、炭素原料と窒素原料との比率を調整することにより、制御することができる。また、原子比（Ｎ／Ｃ）は、後述する実施例に記載の方法により測定することができる。
〔遷移金属〕
本実施形態の窒素含有炭素材料粉体は、遷移金属をさらに含むことが好ましい。本実施形態の窒素含有炭素材料粉体は、窒素及び遷移金属を含むことによって高い酸素還元活性が発揮される。本実施形態の窒素含有炭素材料粉体において、遷移金属原子の含有率は、好ましくは０．１〜２０質量％であり、より好ましくは０．３〜１５質量％であり、さらに好ましくは０．５〜１０質量％である。本実施形態の窒素含有炭素材料粉体は、遷移金属原子の含有率が上記範囲内であることにより、酸素還元活性がより高くなる傾向にある。
The nitrogen-containing carbon material powder of the present embodiment has a pore volume V 1 [cc / g] in the range of pore diameter (diameter) of 20 to 50 nm by a mercury intrusion method of 0.100 cc / g or more. Is preferably 0.200 cc / g or more, more preferably 0.300 cc / g or more. The upper limit of the volume V 1 is not particularly limited, and examples thereof include 5.0 cc / g. Since it is difficult to form mesopores having a pore diameter (diameter) of 20 to 50 nm in the conventional nitrogen-containing carbon material, the amount of mesopores having a pore diameter (diameter) of 20 to 50 nm is relatively small. On the other hand, the nitrogen-containing carbon material powder of this embodiment improves the oxygen reduction activity by increasing the amount of mesopores having a pore diameter (diameter) of 20 to 50 nm.
[Atomic ratio (N / C)]
The atomic ratio (N / C) between nitrogen atoms and carbon atoms in the nitrogen-containing carbon material powder of the present embodiment is preferably 0.005 to 0.3, more preferably 0.01 to 0.2. More preferably, it is 0.02-0.15. The nitrogen-containing carbon material powder of the present embodiment has higher oxygen reduction activity when the atomic ratio (N / C) is within the above range. The atomic ratio (N / C) can be controlled by adjusting the ratio of the carbon raw material and the nitrogen raw material in the method for producing a nitrogen-containing carbon material powder described later. Moreover, atomic ratio (N / C) can be measured by the method as described in the Example mentioned later.
[Transition metal]
The nitrogen-containing carbon material powder of this embodiment preferably further contains a transition metal. The nitrogen-containing carbon material powder of the present embodiment exhibits high oxygen reduction activity by containing nitrogen and a transition metal. In the nitrogen-containing carbon material powder of the present embodiment, the transition metal atom content is preferably 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, and still more preferably 0.00. 5 to 10% by mass. The nitrogen-containing carbon material powder of the present embodiment tends to have higher oxygen reduction activity when the content of transition metal atoms is within the above range.
遷移金属原子としては、特に限定されないが、例えば、Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｍｎ，及び／又はＣｒが好ましく、Ｆｅ，Ｃｏ，及び／又はＣｕがより好ましく、Ｆｅ，及び／又はＣｏがさらに好ましい。このような遷移金属を含むことにより、窒素含有炭素材料粉体の酸素還元活性がより向上する傾向にある。なお、本実施形態において、遷移金属原子の含有率は後述の実施例に記載の方法により測定することができる。
〔細孔径分布〕
本実施形態の窒素含有炭素材料粉体は特定の細孔を有しており、その指標である細孔径２０〜５０ｎｍのメソ孔量の指標Ｉが０．６以上であり、０．６５以上であることが好ましく、０．７以上であることがより好ましい。本実施形態の窒素含有炭素材料粉体は、細孔径２０〜５０ｎｍのメソ孔量の指標Ｉが上記範囲内であることにより、酸素還元活性がより高くなる。この理由については明らかではないが、細孔径２０〜５０ｎｍのメソ孔にはアイオノマーが浸透しやすく、窒素含有炭素材料粉体が有する活性点へのプロトンの供給が促進される、及び／又は、細孔径２０〜５０ｎｍの細孔が酸素の拡散経路になるためと推察される。なお、ここで細孔とは一次粒子表面に穿たれた細孔であってもよいし、一次粒子が凝集している場合にその粒子間に形成される空隙であってもよい。細孔径２０〜５０ｎｍのメソ孔量の指標Ｉを上記範囲内とした窒素含有炭素材料粉体を得る方法としては、特に限定されないが、例えば、後述の窒素含有炭素材料粉体の製造方法が挙げられる。なお、本実施形態において、細孔径２０〜５０ｎｍのメソ孔量の指標Ｉは後述の実施例に記載の方法により測定することができる。
〔窒素含有炭素材料粉体の製造方法〕
本実施形態に係る窒素含有炭素材料粉体の製造方法は、窒素含有炭素材料を溶媒に分散させてスラリーを得るスラリー調製工程と、該スラリーから該溶媒を除去することで下記式（１）で表される孔径２０〜５０ｎｍのメソ孔量の指標Ｉが０．６以上の窒素含有炭素材料粉体を形成する細孔形成工程とを有する。
Although it does not specifically limit as a transition metal atom, For example, Fe, Co, Ni, Cu, Mn, and / or Cr are preferable, Fe, Co, and / or Cu are more preferable, Fe and / or Co are further preferable. By including such a transition metal, the oxygen reduction activity of the nitrogen-containing carbon material powder tends to be further improved. In addition, in this embodiment, the content rate of a transition metal atom can be measured by the method as described in the below-mentioned Example.
(Pore diameter distribution)
The nitrogen-containing carbon material powder of the present embodiment has specific pores, and the index I of the mesopore amount with a pore diameter of 20 to 50 nm, which is an index thereof, is 0.6 or more, and is 0.65 or more. It is preferable that it is 0.7 or more. The nitrogen-containing carbon material powder of the present embodiment has higher oxygen reduction activity when the index I of the mesopore amount with a pore diameter of 20 to 50 nm is within the above range. Although the reason for this is not clear, the ionomer easily penetrates into mesopores having a pore diameter of 20 to 50 nm, promotes the supply of protons to the active sites of the nitrogen-containing carbon material powder, and / or is fine. It is assumed that pores having a pore diameter of 20 to 50 nm become oxygen diffusion paths. Here, the pores may be pores formed on the surface of the primary particles, or may be voids formed between the particles when the primary particles are aggregated. A method for obtaining a nitrogen-containing carbon material powder having a mesopore volume index I having a pore diameter of 20 to 50 nm within the above range is not particularly limited, and examples thereof include a method for producing a nitrogen-containing carbon material powder described below. It is done. In the present embodiment, the mesopore amount index I having a pore diameter of 20 to 50 nm can be measured by the method described in the examples described later.
[Method for producing nitrogen-containing carbon material powder]
The method for producing a nitrogen-containing carbon material powder according to the present embodiment includes a slurry preparation step of obtaining a slurry by dispersing the nitrogen-containing carbon material in a solvent, and removing the solvent from the slurry by the following formula (1): And a pore forming step of forming a nitrogen-containing carbon material powder having a mesopore volume index I having a pore diameter of 20 to 50 nm represented by 0.6 or more.
（孔径２０〜５０ｎｍのメソ孔量の指標Ｉ）＝（水銀圧入法による孔径２０〜５０ｎｍの細孔容積Ｖ1［ｃｃ／ｇ］）／（窒素吸着法による孔径２〜２０ｎｍの細孔容積Ｖ2［ｃｃ／ｇ］）
・・・・式（１）
また、本実施形態に係る窒素含有炭素材料粉体の製造方法は、炭素原料と、窒素原料と、を含む前駆体を調製する前駆体調製工程、前記前駆体を焼成し窒素含有炭素材料を得る第１の熱処理工程、前記窒素含有炭素材料を分散させたスラリーを得るスラリー調製工程、前記窒素含有炭素材料を分散させたスラリーから溶媒を除去することで細孔を形成させ上記指標Ｉが０．６以上の窒素含有炭素材料粉体を形成させる細孔形成工程、並びに、前記細孔を形成した窒素含有炭素材料を更に熱処理する第２の熱処理工程を有することが好ましい。
〔前駆体調製工程〕
前駆体調製工程は、炭素原料及び窒素原料、又は、炭素原料、窒素原料及び遷移金属原料を複合化して前駆体を調製する工程である。
（前駆体）
前駆体は、炭素原料及び窒素原料を複合化したものであっても、炭素原料、窒素原料、及び遷移金属原料を複合化したものであってもよい。前駆体は、必要に応じて他の成分も含むことができる。他の成分としては、特に限定されないが、例えば、ホウ素及び／又はリンを含有する化合物などが挙げられる。
(Indicator I of mesopore volume of pore diameter 20-50 nm) = (pore volume V 1 [cc / g] by pore diameter 20-50 nm by mercury porosimetry) / (pore volume V of pore diameter 2-20 nm by nitrogen adsorption method) 2 [cc / g])
.... Formula (1)
Moreover, the manufacturing method of the nitrogen-containing carbon material powder which concerns on this embodiment is a precursor preparation process which prepares the precursor containing a carbon raw material and a nitrogen raw material, The said precursor is baked and a nitrogen-containing carbon material is obtained. A first heat treatment step, a slurry preparation step for obtaining a slurry in which the nitrogen-containing carbon material is dispersed, pores are formed by removing a solvent from the slurry in which the nitrogen-containing carbon material is dispersed, and the index I is 0. It is preferable to have a pore forming step for forming 6 or more nitrogen-containing carbon material powders, and a second heat treatment step for further heat-treating the nitrogen-containing carbon material having the pores formed therein.
[Precursor preparation step]
The precursor preparation step is a step of preparing a precursor by combining a carbon raw material and a nitrogen raw material, or a carbon raw material, a nitrogen raw material, and a transition metal raw material.
(precursor)
The precursor may be a composite of a carbon raw material and a nitrogen raw material, or a composite of a carbon raw material, a nitrogen raw material, and a transition metal raw material. The precursor can also contain other components as required. Although it does not specifically limit as another component, For example, the compound etc. which contain boron and / or phosphorus are mentioned.
炭素原料、窒素原料、及び遷移金属原料は、それぞれ炭素原子、窒素原子、遷移金属原子を含有しているものであれば特に限定されず、一種類の化合物を複数の原子の原料としてもよいし、ある原子の原料として複数の化合物を用いてもよい。例えば、炭素原子、窒素原子及び遷移金属原子を含有する金属フタロシアニンのみを前駆体としてもよいし、炭素原子を含有するカーボンブラックと炭素原子及び窒素原子を含有するポリアニリンとを複合化したものを前駆体としてもよい。 The carbon raw material, the nitrogen raw material, and the transition metal raw material are not particularly limited as long as they each contain a carbon atom, a nitrogen atom, and a transition metal atom, and one kind of compound may be used as a raw material for a plurality of atoms. A plurality of compounds may be used as a raw material for a certain atom. For example, only a metal phthalocyanine containing a carbon atom, a nitrogen atom and a transition metal atom may be used as a precursor, or a composite of carbon black containing a carbon atom and polyaniline containing a carbon atom and a nitrogen atom is used as a precursor. It may be a body.
ここで、「複合化」とは、炭素原料及び窒素原料、又は、炭素原料、窒素原料及び遷移金属原料が物理的に混合している状態であってもよいし、炭素原料及び窒素原料、又は、炭素原料、窒素原料及び遷移金属原料が化学結合を形成している状態であってもよいが、それぞれが均一に分散していることが好ましい。
（炭素原料）
炭素原料としては、特に限定されないが、例えば、炭化収率の高い有機化合物及び炭素材料そのものが挙げられる。ここで、「炭化収率の高い」とは、窒素ガス流通下で、１０００℃、１時間熱処理を施して得られる炭素材料の収率が１質量％以上のことをいう。
Here, “composite” may be a state in which a carbon raw material and a nitrogen raw material, or a carbon raw material, a nitrogen raw material and a transition metal raw material are physically mixed, a carbon raw material and a nitrogen raw material, or The carbon raw material, the nitrogen raw material, and the transition metal raw material may be in a state in which a chemical bond is formed, but it is preferable that they are uniformly dispersed.
(Carbon raw material)
Although it does not specifically limit as a carbon raw material, For example, the organic compound and carbon material itself with a high carbonization yield are mentioned. Here, “high carbonization yield” means that the yield of the carbon material obtained by heat treatment at 1000 ° C. for 1 hour under nitrogen gas flow is 1% by mass or more.
炭化収率の高い有機化合物としては、特に限定されないが、例えば、フェノール樹脂、ポリフルフリルアルコール、フラン、フラン樹脂、フェノールホルムアルデヒド樹脂、エポキシ樹脂、ポリ塩化ビニリデン、ポリチオフェン、ポリスルフォン、ポリビニルアルコール、ポリビニルブチラール、ポリエステル、ポリ乳酸、ポリエ−テル、ポリエーテルエーテルケトン、セルロース、カルボキシメチルセルロース、リグニン、ピッチ、ポリカルバゾール、ポリアクリル酸、ポリアクリル酸エステル、ポリメタクリル酸エステル及びポリメタクリル酸が挙げられる。 The organic compound having a high carbonization yield is not particularly limited. For example, phenol resin, polyfurfuryl alcohol, furan, furan resin, phenol formaldehyde resin, epoxy resin, polyvinylidene chloride, polythiophene, polysulfone, polyvinyl alcohol, polyvinyl butyral. , Polyester, polylactic acid, polyether, polyetheretherketone, cellulose, carboxymethylcellulose, lignin, pitch, polycarbazole, polyacrylic acid, polyacrylic acid ester, polymethacrylic acid ester and polymethacrylic acid.
炭化収率の高い炭素材料そのものとしては、特に限定されないが、例えば、黒鉛、活性炭、アモルファスカーボン、カーボンブラック、石炭、木炭、コークス、カーボンナノチューブ、フラーレン及びグラフェンが挙げられる。これらは１種を単独で又は２種以上を組み合わせて用いられる。
（窒素原料）
窒素原料としては、特に限定されないが、例えば、窒素原子を有する低分子の有機化合物、窒素原子を有する高分子の有機化合物を用いることができ、それらの２種以上の混合物であってもよい。
The carbon material itself having a high carbonization yield is not particularly limited, and examples thereof include graphite, activated carbon, amorphous carbon, carbon black, coal, charcoal, coke, carbon nanotube, fullerene, and graphene. These are used singly or in combination of two or more.
(Nitrogen raw material)
Although it does not specifically limit as a nitrogen raw material, For example, the low molecular organic compound which has a nitrogen atom, the high molecular organic compound which has a nitrogen atom can be used, and those 2 or more types of mixtures may be sufficient.
窒素原子を有する低分子の有機化合物としては、特に限定されないが、例えば、窒素原子を有する数平均分子量１０００未満の有機化合物が挙げられる。このような有機化合物としては、特に限定されないが、具体的には、例えば、ジアミノマレオニトリル、フタロシアニン、ポルフィリン、フェナントロリン、メラミン、アクリロニトリル、ピロール、ピリジン、ビニルピリジン、アニリン、イミダゾール、１−メチルイミダゾール、２−メチルイミダゾ−ル、ベンゾイミダゾ−ル、ピリダジン、ピリミジン、ピペラジン、キノキサリン、ピラゾール、モルホリン、ヒドラジン、ヒドラジド、尿素、サレン、トリアジン及びシアヌル酸が挙げられる。 Although it does not specifically limit as a low molecular organic compound which has a nitrogen atom, For example, the organic compound with a number average molecular weight less than 1000 which has a nitrogen atom is mentioned. Such an organic compound is not particularly limited, and specifically, for example, diaminomaleonitrile, phthalocyanine, porphyrin, phenanthroline, melamine, acrylonitrile, pyrrole, pyridine, vinylpyridine, aniline, imidazole, 1-methylimidazole, Examples include 2-methylimidazole, benzimidazole, pyridazine, pyrimidine, piperazine, quinoxaline, pyrazole, morpholine, hydrazine, hydrazide, urea, salen, triazine and cyanuric acid.
窒素原子を有する高分子の有機化合物としては、特に限定されないが、例えば、窒素原子を有する数平均分子量１０００以上の有機化合物が挙げられる。このような有機化合物としては、特に限定されないが、具体的には、例えば、アズルミン酸、ジアミノマレオニトリル重合体、メラミン樹脂、ポリアミドイミド樹脂、ポリアクリロニトリル、ポリアクリロニトリル−ポリメタクリル酸共重合体、ポリピロール、ポリビニルピロール、ポリビニルピリジン、ポリアニリン、ポリベンゾイミダゾ−ル、ポリイミド、ポリアミド、キチン、キトサン、ポリアミノ酸、絹、毛、核酸、ＤＮＡ、ＲＮＡ、ポリウレタン、ポリアミドアミン、ポリカルボジイミド、ポリビスマレイミド及びポリアミノビスマレイミドが挙げられる。本実施形態の窒素含有炭素材料粉体は、このような窒素原料を用いて製造することにより、原子比（Ｎ／Ｃ）を適切な範囲内に保つことができる。 Although it does not specifically limit as a high molecular organic compound which has a nitrogen atom, For example, the organic compound with a number average molecular weight 1000 or more which has a nitrogen atom is mentioned. Such an organic compound is not particularly limited. Specifically, for example, azulmic acid, diaminomaleonitrile polymer, melamine resin, polyamideimide resin, polyacrylonitrile, polyacrylonitrile-polymethacrylic acid copolymer, polypyrrole. , Polyvinyl pyrrole, polyvinyl pyridine, polyaniline, polybenzimidazole, polyimide, polyamide, chitin, chitosan, polyamino acid, silk, hair, nucleic acid, DNA, RNA, polyurethane, polyamidoamine, polycarbodiimide, polybismaleimide and polyaminobis Maleimide is mentioned. The nitrogen-containing carbon material powder of this embodiment can keep the atomic ratio (N / C) within an appropriate range by manufacturing using such a nitrogen raw material.
このなかでも、窒素原料及び炭素原料として、アズルミン酸及び／又はジアミノマレオニトリルを含むことが好ましく、ジアミノマレオニトリルがより好ましい。アズルミン酸及び／又はジアミノマレオニトリルを含むことにより、窒素含有炭素材料粉体の酸素還元活性がより向上する傾向にある。また、溶媒への溶解性がより高いジアミノマレオニトリルを含むことにより、遷移金属と窒素原料及び炭素原料との錯体形成が好適に進行し、ひいては、遷移金属がより均等に分散した窒素含有炭素材料粉体が得られるため、窒素含有炭素材料粉体の酸素還元活性がより向上する傾向にある。
（遷移金属原料）
遷移金属原料としては、特に限定されないが、例えば、遷移金属塩、遷移金属錯体を用いることができ、それらの２種類以上の混合物であってもよい。遷移金属としては、特に限定されないが、例えば、Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｍｎ，Ｃｒが好ましく、Ｆｅ，Ｃｏ，Ｃｕがより好ましく、Ｆｅ，Ｃｏがさらに好ましい。遷移金属塩としては、特に限定されないが、例えば、遷移金属の塩化物、臭化物、ヨウ化物、硝酸化物、硫酸化物、リン酸化物、酢酸化物、シアン化物が挙げられる。遷移金属錯体としては、例えば、遷移金属のアセチルアセトン錯体、シクロペンタジエニル錯体、フタロシアニン錯体、ポルフィリン錯体、フェナントロリン錯体が挙げられる。本実施形態の窒素含有炭素材料粉体は、このような遷移金属を用いて製造することにより、酸素還元活性がより向上する傾向にある。
Among these, it is preferable that azurmic acid and / or diaminomaleonitrile is included as a nitrogen raw material and a carbon raw material, and diaminomaleonitrile is more preferable. By including azulmic acid and / or diaminomaleonitrile, the oxygen reduction activity of the nitrogen-containing carbon material powder tends to be further improved. Further, by containing diaminomaleonitrile having higher solubility in a solvent, the complex formation of the transition metal with the nitrogen raw material and the carbon raw material proceeds favorably, and consequently the nitrogen-containing carbon material in which the transition metal is more evenly dispersed. Since powder is obtained, the oxygen reduction activity of the nitrogen-containing carbon material powder tends to be further improved.
(Transition metal raw material)
Although it does not specifically limit as a transition metal raw material, For example, a transition metal salt and a transition metal complex can be used, and those 2 or more types of mixtures may be sufficient. Although it does not specifically limit as a transition metal, For example, Fe, Co, Ni, Cu, Mn, and Cr are preferable, Fe, Co, and Cu are more preferable, Fe and Co are further more preferable. The transition metal salt is not particularly limited, and examples thereof include transition metal chlorides, bromides, iodides, nitrates, sulfates, phosphates, acetates, and cyanides. Examples of transition metal complexes include transition metal acetylacetone complexes, cyclopentadienyl complexes, phthalocyanine complexes, porphyrin complexes, and phenanthroline complexes. The nitrogen-containing carbon material powder of the present embodiment tends to improve the oxygen reduction activity by producing using such a transition metal.
具体的な鉄塩としては、特に限定されないが、例えば、塩化鉄（ＩＩ）、塩化鉄（ＩＩ）四水和物、塩化鉄（ＩＩＩ）、塩化鉄（ＩＩＩ）六水和物、臭化鉄（ＩＩ）、臭化鉄（ＩＩ）六水和物、臭化鉄（ＩＩＩ）、臭化鉄（ＩＩＩ）六水和物、ヘキサシアノ鉄（ＩＩ）酸アンモニウム三水和物、ヘキサシアノ鉄（ＩＩ）酸カリウム三水和物、ヘキサシアノ鉄（ＩＩＩ）酸アンモニウム、ヘキサシアノ鉄（ＩＩＩ）カリウム、ヘキサシアノ鉄（ＩＩ）酸ナトリウム十水和物、ヘキサシアノ鉄（ＩＩＩ）酸ナトリウム一水和物、硝酸鉄（ＩＩ）六水和物、硝酸鉄（ＩＩＩ）九水和物、チオシアン酸鉄（ＩＩＩ）、炭酸鉄（ＩＩ）、炭酸鉄（ＩＩ）一水和物、ヘキサクロロ鉄（ＩＩＩ）酸メチルアンモニウム、テトラクロロ鉄（ＩＩ）酸テトラメチルアンモニウム、ペンタシアノニトロシル鉄（ＩＩＩ）酸カリウム二水和物、ヘキサシアノ鉄（ＩＩ）酸カリウム鉄（ＩＩＩ）水和物、ペンタシアノニトロシル鉄（ＩＩＩ）酸ナトリウム二水和物、アンミンペンタシアノ鉄（ＩＩ）酸ナトリウム三水和物、アクアペンタシアノ鉄（ＩＩ）酸ナトリウム七水和物、チオシアン酸鉄（ＩＩ）三水和物、酢酸鉄、シュウ酸鉄（ＩＩＩ）五水和物、シュウ酸鉄（ＩＩ）二水和物、クエン酸鉄（ＩＩＩ）三水和物、ヨウ化鉄（ＩＩ）、ヨウ化鉄（ＩＩ）四水和物、硫酸鉄（ＩＩＩ）、硫酸鉄（ＩＩＩ）九水和物、テトラクロロ鉄（ＩＩ）酸アンモニウム、過塩素酸鉄（ＩＩ）六水和物、過塩素酸鉄（ＩＩＩ）六水和物、アクアペンタフルオロ鉄（ＩＩＩ）酸カリウム、硫酸カリウム鉄（ＩＩＩ）十二水和物、ビス（スルファト）鉄（ＩＩ）二アンモニウム六水和物、トリス（硫酸）鉄（ＩＩＩ）酸ナトリウム三水和物、リン酸鉄（ＩＩＩ）二水和物、リン酸鉄（ＩＩ）八水和物、硫酸鉄（ＩＩ）七水和物、など等が例示できるが挙げられる。好ましくは、塩化鉄（ＩＩ）、塩化鉄（ＩＩＩ）、臭化鉄（ＩＩ）、臭化鉄（ＩＩＩ）、硝酸鉄（ＩＩＩ）九水和物が例示できるが挙げられる。 Specific iron salts are not particularly limited. For example, iron (II) chloride, iron (II) chloride tetrahydrate, iron (III) chloride, iron (III) chloride hexahydrate, iron bromide (II), iron (II) bromide hexahydrate, iron (III) bromide, iron (III) bromide hexahydrate, ammonium hexacyanoferrate (II) trihydrate, iron hexacyanoferrate (II) Potassium acid trihydrate, ammonium hexacyanoferrate (III), potassium hexacyanoiron (III), sodium hexacyanoferrate (II) decahydrate, sodium hexacyanoferrate (III) monohydrate, iron nitrate (II ) Hexahydrate, iron (III) nitrate nonahydrate, iron (III) thiocyanate, iron (II) carbonate, iron (II) carbonate monohydrate, methylammonium hexachloroferrate (III), tetrachloro Tetramethy iron (II) acid Ammonium, potassium pentacyanonitrosyl iron (III) dihydrate, potassium iron (III) hexacyanoferrate (II), sodium pentacyanonitrosyl iron (III) dihydrate, ammine pentacyanoiron ( II) Sodium acid trihydrate, aquapentacyanoiron iron (II) sodium heptahydrate, iron (II) thiocyanate trihydrate, iron acetate, iron (III) oxalate pentahydrate, oxalic acid Iron (II) dihydrate, iron (III) citrate trihydrate, iron (II) iodide, iron (II) iodide tetrahydrate, iron (III) sulfate, iron (III) sulfate nine Hydrates, ammonium tetrachloroferrate (II), iron (II) perchlorate hexahydrate, iron (III) perchlorate hexahydrate, potassium aquapentafluoroiron (III), potassium iron sulfate (III) Twelve water Bis (sulfato) iron (II) diammonium hexahydrate, tris (sulfate) iron (III) sodium trihydrate, iron (III) phosphate dihydrate, iron (II) phosphate eight Examples thereof include hydrates, iron (II) sulfate heptahydrate, and the like. Preferable examples include iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) bromide, and iron (III) nitrate nonahydrate.
具体的なコバルト塩としては、特に限定されないが、例えば、ヘキサシアノコバルト（ＩＩＩ）酸カリウム、硝酸コバルト（ＩＩ）六水和物、フッ化コバルト（ＩＩ）、臭化コバルト（ＩＩ）、臭化コバルト（ＩＩ）六水和物、炭酸コバルト（ＩＩ）、チオシアン酸コバルト（ＩＩ）三水和物、酢酸コバルト（ＩＩ）四水和物、酢酸コバルト（ＩＩＩ）、塩化コバルト（ＩＩ）、塩化コバルト（ＩＩ）六水和物、テトラクロロコバルト（ＩＩ）酸セシウム、ヘキサフルオロコバルト（ＩＩＩ）酸カリウム、ヨウ化コバルト（ＩＩ）、ヨウ化コバルト（ＩＩ）六水和物、ヘキサニトロコバルト（ＩＩＩ）酸カリウム、リン酸コバルト（ＩＩ）、リン酸コバルト（ＩＩ）八水和物、硫酸コバルト（ＩＩ）、硫酸コバルト（ＩＩ）七水和物、等が例示できるが挙げられる。好ましくは、塩化コバルト（ＩＩ）、臭化コバルト（ＩＩ）、硝酸コバルト（ＩＩ）六水和物が例示できるが挙げられる。 Specific cobalt salts are not particularly limited. For example, potassium hexacyanocobalt (III) acid, cobalt (II) nitrate hexahydrate, cobalt (II) fluoride, cobalt (II) bromide, cobalt bromide. (II) hexahydrate, cobalt carbonate (II), cobalt thiocyanate (II) trihydrate, cobalt acetate (II) tetrahydrate, cobalt acetate (III), cobalt chloride (II), cobalt chloride ( II) Hexahydrate, cesium tetrachlorocobalt (II), potassium hexafluorocobalt (III), cobalt (II) iodide, cobalt (II) iodide hexahydrate, hexanitrocobalt (III) acid Examples include potassium, cobalt (II) phosphate, cobalt (II) phosphate octahydrate, cobalt (II) sulfate, cobalt (II) sulfate heptahydrate, etc. It can can be mentioned. Preferred examples include cobalt (II) chloride, cobalt (II) bromide, and cobalt (II) nitrate hexahydrate.
具体的なニッケル塩としては、特に限定されないが、例えば、塩化ニッケル（ＩＩ）、塩化ニッケル（ＩＩ）六水和物、臭化ニッケル（ＩＩ）、硝酸ニッケル（ＩＩ）六水和物等が挙げられる。 Specific nickel salts are not particularly limited, and examples thereof include nickel chloride (II), nickel chloride (II) hexahydrate, nickel bromide (II), nickel nitrate (II) hexahydrate and the like. It is done.
具体的な銅塩としては、特に限定されないが、例えば、塩化銅（ＩＩ）、塩化銅（ＩＩ）二水和物、臭化銅（ＩＩ）、硝酸銅（ＩＩ）二水和物等が挙げられる。 Specific copper salts are not particularly limited, and examples include copper (II) chloride, copper (II) chloride dihydrate, copper (II) bromide, copper nitrate (II) dihydrate, and the like. It is done.
具体的なマンガン塩としては、特に限定されないが、例えば、塩化マンガン（ＩＩ）、臭化マンガン（ＩＩ）、硝酸マンガン（ＩＩ）四水和物等が挙げられる。 Specific examples of the manganese salt include, but are not limited to, manganese chloride (II), manganese bromide (II), manganese nitrate (II) tetrahydrate, and the like.
具体的なクロム塩としては、特に限定されないが、例えば、塩化クロム（III）、臭化クロム（III）、硝酸クロム（III）九水和物等が挙げられる。 Specific examples of the chromium salt include, but are not limited to, chromium (III) chloride, chromium (III) bromide, and chromium (III) nitrate nonahydrate.
前駆体中の遷移金属原子の含有量は、好ましくは０．０１質量％〜１０質量％であり、より好ましくは０．０３質量％〜５質量％であり、さらに好ましくは０．０５質量％〜３質量％である。前駆体中の遷移金属原子の含有量が上記範囲内であることにより、窒素含有炭素材料粉体の酸素還元活性がより向上する傾向にある。 The content of the transition metal atom in the precursor is preferably 0.01% by mass to 10% by mass, more preferably 0.03% by mass to 5% by mass, and further preferably 0.05% by mass to 3% by mass. When the content of the transition metal atom in the precursor is within the above range, the oxygen reduction activity of the nitrogen-containing carbon material powder tends to be further improved.
また、用いる炭素原料及び窒素原料によって、熱処理工程によって得られる窒素含有炭素材料中の窒素含有量が大きく異なるため、窒素含有炭素材料粉体の窒素原子と炭素原子との原子比（Ｎ／Ｃ）が上記範囲になるよう炭素原料と窒素原料との比率を調整することが好ましい。原子比（Ｎ／Ｃ）は、原子比（Ｎ／Ｃ）の高い窒素原料を用いる及び／又は前駆体中の窒素原料の比率を上げることにより大きく制御することができ、原子比（Ｎ／Ｃ）の低い窒素原料を用いる及び／又は前駆体中の窒素原料の比率を下げることにより小さく制御することができる。 Moreover, since the nitrogen content in the nitrogen-containing carbon material obtained by the heat treatment step varies greatly depending on the carbon raw material and nitrogen raw material used, the atomic ratio (N / C) of nitrogen atoms to carbon atoms in the nitrogen-containing carbon material powder It is preferable to adjust the ratio of the carbon raw material and the nitrogen raw material so that is in the above range. The atomic ratio (N / C) can be largely controlled by using a nitrogen raw material having a high atomic ratio (N / C) and / or increasing the ratio of the nitrogen raw material in the precursor. ) And / or lowering the ratio of the nitrogen source in the precursor can be controlled to be small.
窒素原料、炭素原料、及び遷移金属原料の複合化の方法としては、特に限定されないが、例えば、各原料が予め複合化した原料を前駆体として用いる方法、各原料を溶媒に溶かした後に蒸発乾固する方法、各原料をボールミル等で物理混合する方法等が挙げられる。また、複合化方法としては、特に限定されないが、例えば、一つの溶媒に全ての原料を溶解させてもよいが、それぞれ異なる溶媒に各原料を溶解させた後に各溶媒を混合してもよい。「各原料が予め複合化した」とは、例えば鉄フタロシアニン錯体のように単独の化合物で窒素原料、炭素原料及び遷移金属原料になるものを前駆体として用いる場合を指す。 The method for compounding the nitrogen material, the carbon material, and the transition metal material is not particularly limited. For example, a method using a material in which each material is compounded in advance as a precursor, evaporating and drying each material in a solvent. Examples thereof include a method of solidifying, a method of physically mixing each raw material with a ball mill or the like. The composite method is not particularly limited. For example, all raw materials may be dissolved in one solvent, but the respective solvents may be mixed after dissolving the respective raw materials in different solvents. “Each raw material is pre-complexed” refers to a case where a single compound such as an iron phthalocyanine complex that becomes a nitrogen raw material, a carbon raw material, and a transition metal raw material is used as a precursor.
溶媒として用いることができるものとしては、特に限定されないが、例えば、各原料の溶解度が高いものを好ましく用いることができる。溶媒は、１種類の溶液単独で用いてもよいし、２種以上の溶液を併用してもよい。
〔熱処理工程〕
熱処理工程は、炭素原料と、窒素原料と、を含む前駆体を熱処理して、窒素含有炭素材料を得る工程である。熱処理工程は、一段階の熱処理であってもよいが、二段階以上の熱処理であってもよい。また、熱処理工程を二段階以上で行う場合は、その間に他の工程を組み込んでもよい。熱処理工程は、前記前駆体を不活性ガス雰囲気下で熱処理する第１の熱処理工程と、前記第１の熱処理工程で処理された前駆体をアンモニア含有ガス雰囲気下で熱処理する第２の熱処理工程と、を含むことが好ましい。
Although what can be used as a solvent is not specifically limited, For example, what has high solubility of each raw material can be used preferably. As the solvent, one type of solution may be used alone, or two or more types of solutions may be used in combination.
[Heat treatment process]
The heat treatment step is a step of obtaining a nitrogen-containing carbon material by heat-treating a precursor containing a carbon raw material and a nitrogen raw material. The heat treatment step may be a one-step heat treatment, but may be a two-step or more heat treatment. Moreover, when performing a heat processing process in two or more steps, you may incorporate another process in the meantime. The heat treatment step includes a first heat treatment step of heat-treating the precursor in an inert gas atmosphere, and a second heat treatment step of heat-treating the precursor treated in the first heat treatment step in an ammonia-containing gas atmosphere; It is preferable to contain.
このなかでも、熱処理工程において、前駆体を不活性ガス雰囲気下で熱処理する第１の熱処理工程と、前記第１の熱処理工程で得られた窒素含有炭素材料を溶媒に分散させたスラリーを得るスラリー調製工程と、前記スラリーから溶媒を除去することで細孔を形成して前記指標Ｉが０．６以上の窒素含有炭素材料粉体を得る細孔形成工程と、前記細孔を形成した窒素含有炭素材料粉体をアンモニア含有ガス雰囲気下で熱処理する第２の熱処理工程とをこの順に行なうことが好ましい。不活性ガス雰囲気下における第１の熱処理工程は主に炭素化を目的とするものであり、アンモニア含有ガス雰囲気下における第２の熱処理工程は主に賦活化を目的とするものであり、このような熱処理工程を行うことで、酸素還元活性により優れる窒素含有炭素材料粉体が得られる傾向にある。
（第１の熱処理工程）
第１の熱処理工程は、前記前駆体を不活性ガス雰囲気下で熱処理する。上記不活性ガスとしては、特に限定されないが、例えば、窒素、希ガス、真空等を用いることができる。不活性ガス雰囲気下における熱処理温度は、好ましくは４００〜１５００℃であり、より好ましくは５００〜１４００℃であり、さらに好ましくは５５０〜１３００℃である。熱処理温度が４００℃以上であることにより、前駆体の炭素化が十分に進行する傾向にある。また、熱処理温度が１５００℃以下であることにより、十分な収率が得られる傾向にある。
Among these, in the heat treatment step, a first heat treatment step in which the precursor is heat-treated in an inert gas atmosphere, and a slurry for obtaining a slurry in which the nitrogen-containing carbon material obtained in the first heat treatment step is dispersed in a solvent. A preparation step, a pore formation step of forming a pore by removing the solvent from the slurry to obtain a nitrogen-containing carbon material powder having an index I of 0.6 or more, and a nitrogen-containing material in which the pore is formed It is preferable to perform in this order the second heat treatment step of heat treating the carbon material powder in an ammonia-containing gas atmosphere. The first heat treatment step in the inert gas atmosphere is mainly for the purpose of carbonization, and the second heat treatment step in the ammonia-containing gas atmosphere is mainly for the purpose of activation. By performing an appropriate heat treatment step, a nitrogen-containing carbon material powder that is superior in oxygen reduction activity tends to be obtained.
(First heat treatment step)
In the first heat treatment step, the precursor is heat-treated in an inert gas atmosphere. Although it does not specifically limit as said inert gas, For example, nitrogen, a noble gas, a vacuum etc. can be used. The heat treatment temperature in an inert gas atmosphere is preferably 400 to 1500 ° C, more preferably 500 to 1400 ° C, and further preferably 550 to 1300 ° C. When the heat treatment temperature is 400 ° C. or higher, the carbonization of the precursor tends to proceed sufficiently. Further, when the heat treatment temperature is 1500 ° C. or less, a sufficient yield tends to be obtained.
不活性ガス雰囲気下における熱処理時間は、好ましくは５分〜５０時間であり、より好ましくは１０分〜２０時間であり、さらに好ましくは２０分〜１０時間である。熱処理時間が５分以上であることにより、前駆体の炭素化が十分に進行する傾向にある。また、熱処理時間が５０時間以下であることにより、十分な収率が得られる傾向にある。
（第２の熱処理工程）
第２の熱処理工程は、第１の熱処理工程で処理された前駆体をアンモニア含有ガス雰囲気下で熱処理する。第２の熱処理工程における熱処理の対象は、上述したとおり細孔形成工程を行った後の窒素含有炭素材料粉体であってもよい。
The heat treatment time in an inert gas atmosphere is preferably 5 minutes to 50 hours, more preferably 10 minutes to 20 hours, and further preferably 20 minutes to 10 hours. When the heat treatment time is 5 minutes or longer, carbonization of the precursor tends to proceed sufficiently. Moreover, it exists in the tendency for sufficient yield to be acquired because heat processing time is 50 hours or less.
(Second heat treatment step)
In the second heat treatment step, the precursor treated in the first heat treatment step is heat-treated in an ammonia-containing gas atmosphere. The target of the heat treatment in the second heat treatment step may be the nitrogen-containing carbon material powder after the pore formation step as described above.
アンモニア含有ガスとしては、特に限定されないが、例えば、アンモニアのみ、又はアンモニアを窒素や希ガスで希釈したガスを用いることが好ましい。アンモニア含有ガス雰囲気下における熱処理温度は、好ましくは６００〜１２００℃であり、より好ましくは７００〜１１００℃であり、さらに好ましくは８００〜１０５０℃である。熱処理温度が６００℃以上であることにより、前記細孔を形成した窒素含有炭素材料粉体の賦活化が十分に進行し、酸素還元活性により優れる窒素含有炭素材料粉体が得られる傾向にある。また、熱処理温度が１２００℃以下であることにより、十分な収率が得られる傾向にある。 The ammonia-containing gas is not particularly limited. For example, it is preferable to use only ammonia or a gas obtained by diluting ammonia with nitrogen or a rare gas. The heat treatment temperature in an ammonia-containing gas atmosphere is preferably 600 to 1200 ° C, more preferably 700 to 1100 ° C, and still more preferably 800 to 1050 ° C. When the heat treatment temperature is 600 ° C. or higher, activation of the nitrogen-containing carbon material powder having the pores proceeds sufficiently, and a nitrogen-containing carbon material powder that is superior in oxygen reduction activity tends to be obtained. Moreover, it exists in the tendency for sufficient yield to be acquired because heat processing temperature is 1200 degrees C or less.
アンモニア含有ガス雰囲気下における熱処理時間は、好ましくは５分〜５時間であり、より好ましくは１０分〜３時間であり、さらに好ましくは１５分〜２時間である。熱処理時間が５分以上であることにより、前記細孔を形成した窒素含有炭素材料粉体の賦活化が十分に進行し、酸素還元活性により優れる窒素含有炭素材料粉体が得られる傾向にある。また、熱処理時間が５時間以下であることにより、十分な収率が得られる傾向にある。
（遷移金属除去工程）
不活性ガス雰囲気下における第１の熱処理工程及び／又はアンモニア含有ガス雰囲気下における第２の熱処理工程の前後には、塩酸や硫酸等を用いて遷移金属の一部を除去してもよい。特に、熱処理によって表面に遷移金属粒子が生成する場合には、結晶化度増大の抑制の観点から、該熱処理工程後に遷移金属粒子を除去することが好ましい。遷移金属粒子のできやすさは遷移金属の種類、濃度、分散性、又は熱処理温度等によって変化する。また、遷移金属粒子の除去率を高めるために、不活性ガス雰囲気下での第１の熱処理工程及び／又はアンモニア含有ガス雰囲気下での第２の熱処理工程を複数のサブ工程に分割し、熱処理工程と遷移金属除去工程とを繰り返し行うことも好ましい。
〔スラリー調製工程〕
スラリー調製工程では、窒素含有炭素材料を溶媒に分散させてスラリーを得るが、スラリー中での窒素含有炭素材料粒子の平均粒子径（凝集している場合は平均凝集径）によって後の細孔形成工程で形成される細孔径が変化する。したがって、スラリー中の窒素含有炭素材料粒子の平均粒子径の調整、及びスラリー中での分散を行うことが好ましい。スラリー中の平均粒子径の調整方法は、前駆体調製工程において前駆体の平均粒子径を制御してもよいし、熱処理工程後の窒素含有炭素材料を粉砕して調整してもよい。また、平均粒子径の調整とスラリー中での分散は個別に行ってもよいし、同時に行ってもよい。このなかでも、スラリー調製工程が、窒素含有炭素材料を湿式粉砕する湿式粉砕工程を含むことが好ましく、具体的には、例えば、第１の熱処理工程後の窒素含有炭素材料を湿式粉砕し、スラリー中の平均粒子径の調整とスラリー中での分散とを同時に行う方法が、生産性の観点から好ましい。
The heat treatment time in an ammonia-containing gas atmosphere is preferably 5 minutes to 5 hours, more preferably 10 minutes to 3 hours, and even more preferably 15 minutes to 2 hours. When the heat treatment time is 5 minutes or longer, the activation of the nitrogen-containing carbon material powder having the pores proceeds sufficiently, and a nitrogen-containing carbon material powder that is superior in oxygen reduction activity tends to be obtained. Moreover, it exists in the tendency for sufficient yield to be acquired because heat processing time is 5 hours or less.
(Transition metal removal process)
Before and after the first heat treatment step in the inert gas atmosphere and / or the second heat treatment step in the ammonia-containing gas atmosphere, a part of the transition metal may be removed using hydrochloric acid, sulfuric acid, or the like. In particular, when transition metal particles are generated on the surface by heat treatment, it is preferable to remove the transition metal particles after the heat treatment step from the viewpoint of suppressing increase in crystallinity. The ease with which transition metal particles can be produced varies depending on the type, concentration, dispersibility, or heat treatment temperature of the transition metal. Further, in order to increase the removal rate of the transition metal particles, the first heat treatment step in the inert gas atmosphere and / or the second heat treatment step in the ammonia-containing gas atmosphere is divided into a plurality of sub-steps, and the heat treatment is performed. It is also preferable to repeat the process and the transition metal removing process.
[Slurry preparation process]
In the slurry preparation process, a nitrogen-containing carbon material is dispersed in a solvent to obtain a slurry, but the subsequent pore formation is based on the average particle diameter of the nitrogen-containing carbon material particles in the slurry (the average agglomerated diameter if aggregated) The pore diameter formed in the process changes. Therefore, it is preferable to adjust the average particle diameter of the nitrogen-containing carbon material particles in the slurry and to disperse in the slurry. The method for adjusting the average particle size in the slurry may control the average particle size of the precursor in the precursor preparation step, or may be adjusted by pulverizing the nitrogen-containing carbon material after the heat treatment step. Further, the adjustment of the average particle diameter and the dispersion in the slurry may be performed individually or simultaneously. Among these, the slurry preparation step preferably includes a wet pulverization step of wet-pulverizing the nitrogen-containing carbon material. Specifically, for example, the nitrogen-containing carbon material after the first heat treatment step is wet-pulverized to obtain a slurry. A method in which the adjustment of the average particle diameter therein and the dispersion in the slurry are simultaneously performed is preferable from the viewpoint of productivity.
孔径２０〜５０ｎｍのメソ孔量の指標Ｉを０．６以上にする観点から、スラリー中の窒素含有炭素材料の平均粒子径（凝集粒子を含まない一次粒子の平均粒子径を意味する。）は６０〜８００ｎｍであることが好ましく、８０〜６００ｎｍであることがより好ましく、１００〜５００ｎｍであることが更に好ましい。同様に、スラリー中での平均凝集径も６０〜８００ｎｍであることが好ましく、８０〜６００ｎｍであることがより好ましく、１００〜５００ｎｍであることが更に好ましい。 From the viewpoint of setting the mesopore volume index I having a pore diameter of 20 to 50 nm to 0.6 or more, the average particle diameter of the nitrogen-containing carbon material in the slurry (meaning the average particle diameter of the primary particles not including aggregated particles). The thickness is preferably 60 to 800 nm, more preferably 80 to 600 nm, and still more preferably 100 to 500 nm. Similarly, the average aggregate diameter in the slurry is preferably 60 to 800 nm, more preferably 80 to 600 nm, and still more preferably 100 to 500 nm.
前駆体調製工程において前駆体の平均粒子径を制御する場合は、特に限定されないが、例えば、炭素原料、窒素原料及び遷移金属原料を含む溶液をスプレードライヤーにて造粒する方法や、重合によって微粒子を得る方法を用いることができる。 When controlling the average particle size of the precursor in the precursor preparation step, it is not particularly limited. For example, a method of granulating a solution containing a carbon raw material, a nitrogen raw material and a transition metal raw material with a spray dryer, or fine particles by polymerization Can be used.
また、粉砕方法としては、特に限定されないが、例えば、前駆体又は窒素含有炭素材料を、乾式ボールミル、乾式ジェットミル、湿式ビーズミル、湿式ジェットミル等にて粉砕する方法が挙げられる。投入可能な粒子径及び粉砕後の粒子径は粉砕装置によって異なるため、造粒法や複数の粉砕装置を組み合わせて段階的に微粒化することができる。乾式粉砕の場合は、必要に応じて分級してもよい。生産性の観点から、スラリー中の平均粒子径の調整とスラリー中での分散とを同時に行うことができる、湿式ビーズミル、湿式ジェットミルが好ましい。 The pulverization method is not particularly limited, and examples thereof include a method of pulverizing the precursor or the nitrogen-containing carbon material with a dry ball mill, a dry jet mill, a wet bead mill, a wet jet mill or the like. Since the particle diameter that can be charged and the particle diameter after pulverization differ depending on the pulverizing apparatus, it can be atomized stepwise by combining a granulation method and a plurality of pulverizing apparatuses. In the case of dry pulverization, classification may be performed as necessary. From the viewpoint of productivity, a wet bead mill or a wet jet mill that can simultaneously adjust the average particle diameter in the slurry and disperse in the slurry is preferable.
スラリー中での分散方法としては、特に限定されないが、例えば、撹拌羽根による撹拌、メカニカルホモジナイザーや超音波ホモジナイザーによる分散、湿式ビーズミル、湿式ジェットミル等による粉砕と分散等が挙げられる。 The dispersion method in the slurry is not particularly limited, and examples thereof include stirring by a stirring blade, dispersion by a mechanical homogenizer or an ultrasonic homogenizer, and pulverization and dispersion by a wet bead mill, a wet jet mill or the like.
溶媒は窒素含有炭素材料が分散しやすいものが好ましく、特に限定されないが、例えば、水、エタノール、イソプロピルアルコールやこれらの混合溶媒が挙げられる。
〔細孔形成工程〕
本実施形態の窒素含有炭素材料粉体の製造方法は、スラリー調製工程で得られたスラリーから該溶媒を除去することで上記指標Ｉが０．６以上の窒素含有炭素材料粉体を形成する細孔形成工程を有する。
The solvent is preferably one in which the nitrogen-containing carbon material is easily dispersed, and is not particularly limited, and examples thereof include water, ethanol, isopropyl alcohol, and a mixed solvent thereof.
[Pore formation process]
The method for producing a nitrogen-containing carbon material powder according to this embodiment is a method for forming a nitrogen-containing carbon material powder having an index I of 0.6 or more by removing the solvent from the slurry obtained in the slurry preparation step. It has a hole forming step.
当該細孔形成工程において、前記窒素含有炭素材料を溶媒に分散させたスラリーから前記溶媒を除去する際に、窒素含有炭素材料の一次粒子が凝集して凝集粒子を形成し、一次粒子間に細孔が形成される。溶媒を除去する方法によって形成される細孔径および細孔量が変化し、細孔径２０〜５０ｎｍのメソ孔量の指標Ｉを０．６以上にする観点から、溶媒除去方法としては、噴霧乾燥機を用いる方法、振動乾燥機を用いる方法、または、スラリーに凝集剤を添加して凝集物を生成させ、その後濾過を行って前記凝集物を採取し、更に前記凝集物から溶媒を除去する方法が好ましい。
（噴霧乾燥機を用いる方法）
細孔形成工程は、噴霧乾燥機を用いて前記スラリーから前記溶媒を除去する工程を含むことが好ましい。
In the pore forming step, when the solvent is removed from the slurry in which the nitrogen-containing carbon material is dispersed in a solvent, primary particles of the nitrogen-containing carbon material aggregate to form aggregated particles, and fine particles are formed between the primary particles. A hole is formed. From the viewpoint of changing the pore diameter and the amount of pores formed by the method for removing the solvent and setting the index I of the mesopore amount of the pore diameter of 20 to 50 nm to 0.6 or more, the solvent removing method is a spray dryer. , A method using a vibration dryer, or a method in which a flocculant is added to a slurry to produce an agglomerate, followed by filtration to collect the agglomerate, and further removing the solvent from the agglomerate. preferable.
(Method using spray dryer)
The pore forming step preferably includes a step of removing the solvent from the slurry using a spray dryer.
噴霧乾燥機を用いる方法により細孔径２０〜５０ｎｍのメソ孔量の指標Ｉを０．６以上にするためには、噴霧するスラリー中の窒素含有炭素材料の濃度が０．１〜５０質量％であることが好ましく、０．５〜２０質量％であることがより好ましく、１〜１５質量％であることが更に好ましい。窒素含有炭素材料の酸化を防止する観点から、噴霧乾燥に使用する熱風の温度は３００℃以下であることが好ましく、２５０℃以下であることがより好ましい。噴霧乾燥機で乾燥した凝集物の平均凝集径は、取扱いの観点から０．１〜１００μｍであることが好ましく、０．２〜２０μｍであることがより好ましく、０．３〜１０μｍであることが更に好ましい。
（振動乾燥機を用いる方法）
細孔形成工程は、振動乾燥機を用いて前記スラリーから前記溶媒を除去する工程を含むことが好ましい。
In order to set the mesopore volume index I having a pore diameter of 20 to 50 nm to 0.6 or more by a method using a spray dryer, the concentration of the nitrogen-containing carbon material in the slurry to be sprayed is 0.1 to 50% by mass. Preferably, it is 0.5 to 20% by mass, and more preferably 1 to 15% by mass. From the viewpoint of preventing oxidation of the nitrogen-containing carbon material, the temperature of the hot air used for spray drying is preferably 300 ° C. or less, and more preferably 250 ° C. or less. From the viewpoint of handling, the average aggregate diameter of the aggregates dried by the spray dryer is preferably 0.1 to 100 μm, more preferably 0.2 to 20 μm, and preferably 0.3 to 10 μm. Further preferred.
(Method using vibration dryer)
The pore forming step preferably includes a step of removing the solvent from the slurry using a vibration dryer.
振動乾燥機で２０〜５０ｎｍのメソ孔量の指標Ｉを０．６以上にするためには、スラリー調製工程で得られたスラリーを装置に投入した後にゆっくりと濃縮してゲル状にし、その後装置を振動させる方法が好ましい。振動を与えずにゆっくりと濃縮することにより孔径２０〜５０ｎｍのメソ孔が形成され、その後振動を与えることによって、取扱いやすい粉末状の凝集物が得られる。
（凝集剤−濾過−加熱乾燥する方法）
細孔形成工程は、前記スラリーに凝集剤を添加して凝集物を生成させ、その後濾過を行って前記凝集物を採取し、更に前記凝集物から前記溶媒を除去する工程を含むことが好ましい。
In order to make the index I of the mesopore amount of 20 to 50 nm with a vibration dryer to 0.6 or more, the slurry obtained in the slurry preparation step is charged into the apparatus and then slowly concentrated to a gel, and then the apparatus The method of vibrating is preferred. By slowly concentrating without applying vibration, mesopores having a pore diameter of 20 to 50 nm are formed, and then by applying vibration, an easy-to-handle powdery aggregate is obtained.
(Flocculant-Filtration-Heat drying method)
The pore forming step preferably includes a step of adding an aggregating agent to the slurry to form an aggregate, then filtering to collect the aggregate, and further removing the solvent from the aggregate.
窒素含有炭素材料の凝集剤としては酸が好ましく、その中でも加熱乾燥で容易に除去できる塩酸、硝酸、ギ酸、酢酸を用いることが好ましい。添加量としてはスラリー中のプロトン濃度が１０-5〜１０-2ｍｏｌ／Ｌとなる量が好ましい。スラリーを撹拌しながら凝集剤を添加し、５分間〜２４時間静置した後に濾過を行うことが好ましい。濾過方法としては、特に限定されず、例えば、加圧濾過、減圧濾過等の通常の方法用いることができ、また濾材も濾紙、濾布、メンブレンフィルター等を用いることができる。濾過した後に加熱下で溶媒を除去するが、これも特に限定されず、加熱乾燥、真空乾燥等を適宜選択できる。
〔電極〕
本実施形態の電極は、上記窒素含有炭素材料粉体を含む。本実施形態の電極は、燃料電池用電極であることが好ましく、固体高分子形燃料電池用電極であることがより好ましい。上記窒素含有炭素材料粉体を含む本実施形態の燃料電池用電極の製造方法は特に限定されず、窒素含有炭素材料粉体、アイオノマー及び溶媒からなるインクを調製し、そのインクを転写シート又はガス拡散電極に塗布し、乾燥するといった一般的な方法を用いることができる（例えば、特開２０１２−４３６１２号公報参照）。
〔用途〕
本実施形態に係る窒素含有炭素材料粉体は、燃料電池用電極等に好適に用いることができる。本実施形態に係る窒素含有炭素材料粉体を含む燃料電池用電極は、高い酸素還元性を有する。酸素還元触媒から酸素還元電極、燃料電池等を得る方法は、特に限定されず、一般的な固体高分子形燃料電池の作製法を用いることができる。
As the flocculant of the nitrogen-containing carbon material, an acid is preferable. Among them, hydrochloric acid, nitric acid, formic acid, and acetic acid that can be easily removed by heating and drying are preferably used. The addition amount is preferably such that the proton concentration in the slurry is 10 −5 to 10 −2 mol / L. It is preferable to perform filtration after adding the flocculant while stirring the slurry and allowing to stand for 5 minutes to 24 hours. The filtration method is not particularly limited, and for example, a normal method such as pressure filtration or vacuum filtration can be used, and filter paper, filter cloth, membrane filter, or the like can be used as the filter medium. The solvent is removed under heating after the filtration, but this is not particularly limited, and heat drying, vacuum drying, and the like can be appropriately selected.
〔electrode〕
The electrode of this embodiment includes the nitrogen-containing carbon material powder. The electrode of the present embodiment is preferably a fuel cell electrode, and more preferably a polymer electrolyte fuel cell electrode. The method for producing the fuel cell electrode of the present embodiment containing the nitrogen-containing carbon material powder is not particularly limited, and an ink comprising a nitrogen-containing carbon material powder, an ionomer and a solvent is prepared, and the ink is transferred to a transfer sheet or gas. A general method of applying to a diffusion electrode and drying can be used (for example, refer to JP 2012-43612 A).
[Use]
The nitrogen-containing carbon material powder according to the present embodiment can be suitably used for fuel cell electrodes and the like. The fuel cell electrode including the nitrogen-containing carbon material powder according to the present embodiment has high oxygen reducing ability. A method for obtaining an oxygen reduction electrode, a fuel cell and the like from the oxygen reduction catalyst is not particularly limited, and a general method for producing a polymer electrolyte fuel cell can be used.
以下に実施例等を挙げて本実施形態をさらに詳細に説明するが、これらは例示的なものであり、本実施形態は以下の実施例に限定されるものではない。当業者は、以下に示す実施例に様々な変更を加えて本実施形態として実施することができ、係る変更は本発明の範囲に包含される。 Hereinafter, the present embodiment will be described in more detail with reference to examples and the like. However, these are illustrative, and the present embodiment is not limited to the following examples. A person skilled in the art can implement the present embodiment by making various modifications to the examples described below, and such modifications are included in the scope of the present invention.
分析方法は以下のとおりとした。
（Ｖ1測定）
ＪＩＳ Ｒ１６５５「ファインセラミックスの水銀圧入法による成形体気孔径分布試験方法」に従って実施例及び比較例で得られた窒素含有炭素材料粉体の細孔径分布を測定し、細孔径（直径）２０〜５０ｎｍの範囲の細孔容積を積算しＶ1［ｃｃ／ｇ］とした。
The analysis method was as follows.
(V 1 measurement)
The pore size distribution of the nitrogen-containing carbon material powders obtained in Examples and Comparative Examples was measured in accordance with JIS R1655 “Test Method for Molded Body Pore Size Distribution by Mercury Intrusion Method of Fine Ceramics”, and pore size (diameter) of 20-50 nm. V 1 [cc / g] was obtained by integrating the pore volume in the range of.
測定装置には島津製作所製のオートポアＩＶ９５００を使用した。
（Ｖ2、Ｖ3測定）
ＪＩＳ Ｚ８８３１−２「粉体（固体）の細孔径分布及び細孔特性−第２部：ガス吸着によるメソ細孔及びマクロ細孔の測定方法」に従って、吸着ガスに窒素を用い、ＢＪＨ法にて実施例及び比較例で得られた窒素含有炭素材料粉体の細孔径分布を測定した。細孔径（直径）２〜２０ｎｍの範囲の細孔容積を積算しＶ2［ｃｃ／ｇ］とした。同様に細孔径（直径）２０〜５０ｎｍの範囲の細孔容積を積算しＶ3［ｃｃ／ｇ］とした。
Autopore IV9500 manufactured by Shimadzu Corporation was used as the measuring device.
(V 2 and V 3 measurement)
According to JIS Z8831-2 “Pore size distribution and pore characteristics of powder (solid) —Part 2: Measurement method of mesopores and macropores by gas adsorption”, using nitrogen as the adsorbed gas and using the BJH method The pore size distribution of the nitrogen-containing carbon material powders obtained in the examples and comparative examples was measured. The pore volume in the range of pore diameter (diameter) of 2 to 20 nm was integrated to obtain V 2 [cc / g]. Similarly, the pore volume in the range of pore diameter (diameter) of 20 to 50 nm was integrated to obtain V 3 [cc / g].
測定装置にはカンタクローム製のオートソーブ３ＭＰを使用した。
（孔径２０〜５０ｎｍのメソ孔量の指標Ｉ）
実施例及び比較例で得られた窒素含有炭素材料粉体について、Ｉ＝Ｖ1／Ｖ2とした。同様にＩ’＝Ｖ1／Ｖ3とした。
（Ｎ／Ｃ測定）
ＪＩＳ Ｍ８８１９「石炭類及びコークス類−機器分析装置による元素分析方法」に従って実施例及び比較例で得られた窒素含有炭素材料粉体中の炭素及び窒素の質量濃度を測定した。これを原子比に換算したものをＮ／Ｃとした。
An autosorb 3MP manufactured by Cantachrome was used as a measuring device.
(Indicator I of mesopore size with a pore diameter of 20 to 50 nm)
The resulting nitrogen-containing carbon material powder in the examples and comparative examples were as I = V 1 / V 2. Similarly, I ′ = V 1 / V 3 .
(N / C measurement)
The mass concentrations of carbon and nitrogen in the nitrogen-containing carbon material powders obtained in the examples and comparative examples were measured according to JIS M8819 “Coal and cokes—elemental analysis method using instrumental analyzer”. N / C was calculated by converting this to an atomic ratio.
測定装置にはヤナコテクニカルサイエンス製のＣＨＮコーダーＭＴ−６を使用した。
（遷移金属の含有率測定）
実施例及び比較例で得られた窒素含有炭素材料粉体を空気流通下９００℃で１時間熱処理して炭素及び窒素を焼き飛ばし、残渣を王水に溶解させてＩＣＰ発光分光分析することによって窒素含有炭素材料粉体中の遷移金属の含有率を測定した。
A CHN coder MT-6 manufactured by Yanaco Technical Science was used as a measuring device.
(Measurement of transition metal content)
The nitrogen-containing carbon material powders obtained in the examples and comparative examples were heat-treated at 900 ° C. for 1 hour under air flow to burn off carbon and nitrogen, and the residue was dissolved in aqua regia and analyzed by ICP emission spectroscopy. The transition metal content in the carbon material powder was measured.
測定装置にはエスアイアイ・ナノテクノロジー製のＳＰＳ３５２０ＵＶ−ＤＤを使用した。
（平均粒子径測定）
実施例及び比較例で得られたスラリー中の窒素含有炭素材料粒子を水／エタノール混合溶媒中で一次粒子まで分散させ、これを銅メッシュ上で乾燥させ、走査型電子顕微鏡（日立製作所製、製品名Ｓ−４８００）で写真撮影した。この中から無作為に１００個の一次粒子を抽出し、各々の円相当径を面積平均したものを平均粒子径とした。
（電気化学測定）
実施例及び比較例で用いた、電極作製法及び回転電極法によるリニアスイープボルタンメトリーの測定方法（北斗電工の回転リングディスク電極装置「ＨＲ−３０１」、ポテンショスタット「ＨＺ−５０００」を使用。）を以下に示す。まず、バイアル瓶に、実施例又は比較例で作製した窒素含有炭素材料凝集体５ｍｇを秤取し、そこに、ガラスビーズをスパチュラ一杯、５質量％ナフィオン分散液（シグマアルドリッチジャパン製）を５０μＬ、並びにイオン交換水及びエタノールをそれぞれ１５０μＬずつ添加し、それらの混合物に２０分間超音波を照射してスラリーを作製した。このスラリーを４μＬ秤取し、回転電極のガラス状炭素上（０．２８２８ｃｍ2）に塗布し、飽和水蒸気下で乾燥した。乾燥後の回転電極を作用極とし、可逆水素電極（ＲＨＥ）を参照極として、炭素電極を対極とした。０．５Ｍ硫酸を電解液とし、その電解液に酸素を３０分間バブリングした後、掃引速度５ｍＶ／ｓ、回転速度１５００ｒｐｍで１．１Ｖから０Ｖまで掃引して電気化学測定を行った。当該電気化学測定において、０．８Ｖでの電流密度の絶対値が大きい（酸素の還元電流はマイナスの値となる）ほど、窒素含有炭素材料粉体の酸素還元活性が高いと判定した。
［比較例１］
＜前駆体調製工程＞
２Ｌのナス型フラスコにジアミノマレオニトリル２０ｇ、塩化鉄（ＩＩ）０．０４５ｇ及びメタノール５００ｇを加え、室温で１２時間撹拌した。その後、５０℃の水浴中にて、ロータリーエバポレーターを用いて溶媒を除去し、真空乾燥機にて８０℃で２時間乾燥させて前駆体を得た。
＜第１の熱処理工程＞
調製した前駆体のうち２０ｇをアルミナボートに載置し、それをボックス炉に収容した。炉内を大気圧、１ＮＬ／ｍｉｎの窒素流通下で６０分間かけて室温から９００℃まで昇温し、９００℃のまま１時間保持することで４．１ｇの窒素含有炭素材料を得た。
＜平均粒子径調整工程＞
上記窒素含有炭素材料を遊星ボールミル（フリッチュ・ジャパン（株）製のＰｕｌｖｅｒｉｓｅｔｔｅ−５を使用）にて直径１０ｍｍのジルコニアボールを用いて乾式粉砕することにより、平均粒子径を９８０ｎｍに調整した窒素含有炭素材料粉体を得た。
＜第２の熱処理工程＞
上記の平均粒子径を調整した窒素含有炭素材料粉体２．０ｇを石英ボートに載置し、それを内径３６ｍｍの石英管状炉に収容した。炉内を大気圧、１ＮＬ／ｍｉｎのアンモニアガス流通下で６０分間かけて室温から９７５℃まで昇温し、９７５℃のまま１時間保持した。当該熱処理後の窒素含有炭素材料粉体について、孔径２０〜５０ｎｍのメソ孔量の指標Ｉの算出と電気化学測定とを行った結果を表１に示す。
［実施例１］
＜スラリー調製工程＞
比較例１の平均粒子調整工程で得られた窒素含有炭素材料粉体をビーズミル（寿工業（株）製のウルトラアペックスミルを使用）にてさらに湿式粉砕した。具体的には比較例１の平均粒子調整工程で得られた窒素含有炭素材料粉体１０ｇ、イオン交換水３００ｍＬ、エタノール３００ｍＬからなるスラリーを直径０．３ｍｍのジルコニアビーズで粉砕し平均粒子径２９０ｎｍの窒素含有炭素材料粒子を含むスラリーを得た。
＜細孔形成工程：噴霧乾燥機＞
前記スラリー調製工程で得られたスラリーを噴霧乾燥機（藤崎電機（株）製のＭＤＬ−０１５ＭＧＣを使用）にて乾燥した。具体的には、乾燥ガスとして２００℃に加熱した窒素を３５０Ｌ／ｍｉｎ、噴霧ガスとして窒素を３６Ｌ／ｍｉｎ、スラリーを１５ｇ／ｍｉｎ流して噴霧乾燥した。
＜第２の熱処理工程＞
上記の噴霧乾燥で得られた窒素含有炭素材料粉体を比較例１の第２の熱処理工程と同様の方法にて熱処理した。当該熱処理後の窒素含有炭素材料粉体について、孔径２０〜５０ｎｍのメソ孔量の指標Ｉの算出と電気化学測定とを行った結果を表１に示す。
［実施例２］
＜細孔形成工程：振動乾燥機＞
実施例１のスラリー調製工程で得られたスラリーを振動乾燥機（中央化工機（株）製のまめかんＶＵ型を使用）にて乾燥した。具体的には、実施例１のスラリー調製工程で得られたスラリー５０ｇを振動乾燥機に投入し、６０℃の温水で振動乾燥機を加熱しながら、真空ポンプで１０ｋＰａに減圧して乾燥を行った。３０分後にスラリーがゲル状になった段階で、２ｋＰａまで減圧し、振動乾燥機を１５０Ｈｚで振動させた。
＜第２の熱処理工程＞
上記の振動乾燥で得られた窒素含有炭素材料粉体を比較例１の第２の熱処理工程と同様の方法にて熱処理した。当該熱処理後の窒素含有炭素材料粉体について、孔径２０〜５０ｎｍのメソ孔量の指標Ｉの算出と電気化学測定とを行った結果を表１に示す。
［実施例３］
＜細孔形成工程：凝集剤−濾過−加熱乾燥＞
実施例１のスラリー調製工程で得られたスラリー２５０ｇに、水を５５０ｇ加えマグネチックスターラーで５分撹拌した。次に０．１Ｍの希塩酸を１０ｇ添加し、５分撹拌後、撹拌を止めて１晩静置した。孔径１μｍのＰＴＦＥ製メンブレンフィルターで減圧濾過し、フィルター上の残渣を８０℃で真空乾燥した。得られた窒素含有炭素材料は板状であるため、メノウ乳鉢で粉砕した。
＜第２の熱処理工程＞
上記の凝集剤−濾過−加熱乾燥−粉砕で得られた窒素含有炭素材料粉体を比較例１の第２の熱処理工程と同様の方法にて熱処理した。当該熱処理後の窒素含有炭素材料粉体について、孔径２０〜５０ｎｍのメソ孔量の指標Ｉの算出と電気化学測定とを行った結果を表１に示す。
［比較例２］
＜細孔形成工程：ロータリーエバポレーター＞
実施例１のスラリー調製工程で得られたスラリー２５０ｇを５００ｃｃのナスフラスコに投入して、ロータリーエバポレーター（日本ビュッヒ（株）製のＲ−２１０を使用）にて乾燥した。具体的には５０℃の水浴にて加温しながら、５０ｋＰａまで減圧した。
＜第２の熱処理工程＞
上記のロータリーエバポレーター乾燥で得られた窒素含有炭素材料粉体を比較例１の第２の熱処理工程と同様の方法にて熱処理した。当該熱処理後の窒素含有炭素材料粉体について、孔径２０〜５０ｎｍのメソ孔量の指標Ｉの算出と電気化学測定とを行った結果を表１に示す。
SPS3520UV-DD made by SII Nano Technology was used as the measuring device.
(Average particle size measurement)
The nitrogen-containing carbon material particles in the slurry obtained in Examples and Comparative Examples were dispersed to primary particles in a water / ethanol mixed solvent, dried on a copper mesh, and scanned with an electron microscope (manufactured by Hitachi, Ltd., product) The photograph was taken under the name S-4800). From this, 100 primary particles were randomly extracted, and the average particle diameter was obtained by averaging the respective equivalent circle diameters.
(Electrochemical measurement)
The linear sweep voltammetry measurement method (using Hokuto Denko's rotating ring disk electrode device “HR-301” and potentiostat “HZ-5000”) used in the examples and comparative examples by the electrode preparation method and the rotating electrode method is used. It is shown below. First, 5 mg of nitrogen-containing carbon material aggregates prepared in Examples or Comparative Examples were weighed into a vial, and a glass bead full of spatula, 5% by mass Nafion dispersion (manufactured by Sigma Aldrich Japan) 50 μL, In addition, 150 μL each of ion-exchanged water and ethanol were added, and the mixture was irradiated with ultrasonic waves for 20 minutes to prepare a slurry. 4 μL of this slurry was weighed, applied onto glassy carbon (0.2828 cm 2 ) of the rotating electrode, and dried under saturated steam. The dried rotating electrode was the working electrode, the reversible hydrogen electrode (RHE) was the reference electrode, and the carbon electrode was the counter electrode. 0.5M sulfuric acid was used as an electrolyte, and oxygen was bubbled through the electrolyte for 30 minutes, and then the electrochemical measurement was performed by sweeping from 1.1 V to 0 V at a sweep speed of 5 mV / s and a rotation speed of 1500 rpm. In the electrochemical measurement, it was determined that the oxygen reduction activity of the nitrogen-containing carbon material powder was higher as the absolute value of the current density at 0.8 V was larger (the reduction current of oxygen was a negative value).
[Comparative Example 1]
<Precursor preparation step>
To a 2 L eggplant-shaped flask, 20 g of diaminomaleonitrile, 0.045 g of iron (II) chloride and 500 g of methanol were added and stirred at room temperature for 12 hours. Then, the solvent was removed using a rotary evaporator in a 50 ° C. water bath, and the precursor was obtained by drying at 80 ° C. for 2 hours using a vacuum dryer.
<First heat treatment step>
20 g of the prepared precursor was placed on an alumina boat and accommodated in a box furnace. The furnace was heated from room temperature to 900 ° C. over 60 minutes under a nitrogen flow of 1 NL / min at atmospheric pressure, and kept at 900 ° C. for 1 hour to obtain 4.1 g of a nitrogen-containing carbon material.
<Average particle size adjustment step>
The above nitrogen-containing carbon material is dry-ground using a zirconia ball having a diameter of 10 mm in a planetary ball mill (Pulverisete-5 manufactured by Fritsch Japan Co., Ltd.), so that the average particle diameter is adjusted to 980 nm. Material powder was obtained.
<Second heat treatment step>
2.0 g of the nitrogen-containing carbon material powder having the above average particle diameter adjusted was placed on a quartz boat and accommodated in a quartz tube furnace having an inner diameter of 36 mm. The inside of the furnace was heated from room temperature to 975 ° C. over 60 minutes under an atmospheric pressure, 1 NL / min ammonia gas flow, and kept at 975 ° C. for 1 hour. Table 1 shows the results of calculation of the mesopore volume index I and the electrochemical measurement of the nitrogen-containing carbon material powder after the heat treatment with a pore diameter of 20 to 50 nm.
[Example 1]
<Slurry preparation process>
The nitrogen-containing carbon material powder obtained in the average particle adjustment step of Comparative Example 1 was further wet pulverized with a bead mill (using an ultra apex mill manufactured by Kotobuki Industries Co., Ltd.). Specifically, a slurry composed of 10 g of the nitrogen-containing carbon material powder obtained in the average particle adjustment step of Comparative Example 1, 300 mL of ion-exchanged water, and 300 mL of ethanol was pulverized with zirconia beads having a diameter of 0.3 mm and an average particle size of 290 nm. A slurry containing nitrogen-containing carbon material particles was obtained.
<Pore forming step: spray dryer>
The slurry obtained in the slurry preparation step was dried with a spray dryer (using MDL-015MGC manufactured by Fujisaki Electric Co., Ltd.). Specifically, nitrogen heated to 200 ° C. as a drying gas was 350 L / min, nitrogen was sprayed as 36 L / min, and the slurry was sprayed and dried at 15 g / min.
<Second heat treatment step>
The nitrogen-containing carbon material powder obtained by spray drying was heat-treated in the same manner as in the second heat treatment step of Comparative Example 1. Table 1 shows the results of calculation of the mesopore volume index I and the electrochemical measurement of the nitrogen-containing carbon material powder after the heat treatment with a pore diameter of 20 to 50 nm.
[Example 2]
<Pore formation process: Vibration dryer>
The slurry obtained in the slurry preparation step of Example 1 was dried with a vibration dryer (Mamekan VU type manufactured by Chuo Kako Co., Ltd. was used). Specifically, 50 g of the slurry obtained in the slurry preparation step of Example 1 was put into a vibration dryer, and dried by reducing the pressure to 10 kPa with a vacuum pump while heating the vibration dryer with hot water at 60 ° C. It was. When the slurry became a gel after 30 minutes, the pressure was reduced to 2 kPa, and the vibration dryer was vibrated at 150 Hz.
<Second heat treatment step>
The nitrogen-containing carbon material powder obtained by the above vibration drying was heat-treated by the same method as the second heat treatment step of Comparative Example 1. Table 1 shows the results of calculation of the mesopore volume index I and the electrochemical measurement of the nitrogen-containing carbon material powder after the heat treatment with a pore diameter of 20 to 50 nm.
[Example 3]
<Pore forming step: flocculant-filtration-heat drying>
To 250 g of the slurry obtained in the slurry preparation step of Example 1, 550 g of water was added and stirred with a magnetic stirrer for 5 minutes. Next, 10 g of 0.1 M dilute hydrochloric acid was added, and after stirring for 5 minutes, stirring was stopped and the mixture was allowed to stand overnight. The residue was filtered under reduced pressure with a PTFE membrane filter having a pore size of 1 μm, and the residue on the filter was vacuum dried at 80 ° C. Since the obtained nitrogen-containing carbon material was plate-shaped, it was pulverized with an agate mortar.
<Second heat treatment step>
The nitrogen-containing carbon material powder obtained by the above flocculant-filtration-heat drying-crushing was heat-treated in the same manner as in the second heat treatment step of Comparative Example 1. Table 1 shows the results of calculation of the mesopore volume index I and the electrochemical measurement of the nitrogen-containing carbon material powder after the heat treatment with a pore diameter of 20 to 50 nm.
[Comparative Example 2]
<Pore forming process: rotary evaporator>
250 g of the slurry obtained in the slurry preparation step of Example 1 was put into a 500 cc eggplant flask and dried using a rotary evaporator (R-210 manufactured by Nihon Buch Co., Ltd.). Specifically, the pressure was reduced to 50 kPa while heating in a 50 ° C. water bath.
<Second heat treatment step>
The nitrogen-containing carbon material powder obtained by the above rotary evaporator drying was heat-treated in the same manner as in the second heat treatment step of Comparative Example 1. Table 1 shows the results of calculation of the mesopore volume index I and the electrochemical measurement of the nitrogen-containing carbon material powder after the heat treatment with a pore diameter of 20 to 50 nm.
本発明の窒素含有炭素材料粉体は、燃料電池用電極材料として、産業上の利用可能性を有する。 The nitrogen-containing carbon material powder of the present invention has industrial applicability as a fuel cell electrode material.
Claims (10)
前記遷移金属が、鉄及び／又はコバルトを含み、
前記遷移金属の含有量が、０．１〜２０質量％である窒素含有炭素材料粉体。
（孔径２０〜５０ｎｍのメソ孔量の指標Ｉ）＝（水銀圧入法による細孔径（直径）２０〜５０ｎｍの細孔容積Ｖ1［ｃｃ／ｇ］）／（窒素吸着法による細孔径（直径）２〜２０ｎｍの細孔容積Ｖ2［ｃｃ／ｇ］）
・・・・式（１） Index I mesopores of pore size 20~50nm represented by the following formula (1) is Ri der 0.6 or higher, includes a transition metal,
The transition metal comprises iron and / or cobalt;
The nitrogen-containing carbon material powder whose content of the said transition metal is 0.1-20 mass% .
(Indicator I of mesopore volume of pore diameter 20-50 nm) = (pore diameter (diameter) by mercury intrusion method 20 pore diameter V 1 [cc / g]) / (pore diameter (diameter) by nitrogen adsorption method) 2-20 nm pore volume V 2 [cc / g])
.... Formula (1)
前記スラリー調製工程において、前記スラリー中の窒素含有炭素材料の平均粒子径が６０〜８００ｎｍであり、
前記細孔形成工程が、（Ｉ）噴霧乾燥機を用いて前記スラリーから前記溶媒を除去する工程、（ＩＩ）振動乾燥機を用いて前記スラリーから前記溶媒を除去する工程、又は（ＩＩＩ）前記スラリーに凝集剤を添加して凝集物を生成させ、その後濾過を行って前記凝集物を採取し、更に前記凝集物から前記溶媒を除去する工程を含む、請求項１又は２に記載の窒素含有炭素材料粉体の製造方法。
（孔径２０〜５０ｎｍのメソ孔量の指標Ｉ）＝（水銀圧入法による細孔径（直径）２０〜５０ｎｍの細孔容積Ｖ1［ｃｃ／ｇ］）／（窒素吸着法による細孔径（直径）２〜２０ｎｍの細孔容積Ｖ2［ｃｃ／ｇ］）
・・・・式（１） A slurry preparation step of obtaining a slurry by dispersing a nitrogen-containing carbon material in a solvent, and removing the solvent from the slurry results in an index I of a mesopore amount of a pore diameter of 20 to 50 nm represented by the following formula (1): 0 possess a pore forming step of forming a .6 or more nitrogen-containing carbon material powder,
In the slurry preparation step, the average particle diameter of the nitrogen-containing carbon material in the slurry is 60 to 800 nm,
The pore forming step includes (I) a step of removing the solvent from the slurry using a spray dryer, (II) a step of removing the solvent from the slurry using a vibration dryer, or (III) 3. The nitrogen-containing product according to claim 1 , further comprising a step of adding a flocculant to the slurry to form an aggregate, and then performing filtration to collect the aggregate and further removing the solvent from the aggregate. Production method of carbon material powder.
(Indicator I of mesopore volume of pore diameter 20-50 nm) = (pore diameter (diameter) by mercury intrusion method 20 pore diameter V 1 [cc / g]) / (pore diameter (diameter) by nitrogen adsorption method) 2-20 nm pore volume V 2 [cc / g])
.... Formula (1)
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