WO2007043311A1 - 窒素含有炭素材料およびその製造方法 - Google Patents
窒素含有炭素材料およびその製造方法 Download PDFInfo
- Publication number
- WO2007043311A1 WO2007043311A1 PCT/JP2006/318842 JP2006318842W WO2007043311A1 WO 2007043311 A1 WO2007043311 A1 WO 2007043311A1 JP 2006318842 W JP2006318842 W JP 2006318842W WO 2007043311 A1 WO2007043311 A1 WO 2007043311A1
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- WO
- WIPO (PCT)
- Prior art keywords
- nitrogen
- carbon material
- peak
- containing carbon
- intensity
- Prior art date
Links
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 181
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 238000000034 method Methods 0.000 title description 53
- 239000002253 acid Substances 0.000 claims abstract description 64
- 238000001237 Raman spectrum Methods 0.000 claims abstract description 47
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 32
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 26
- 238000010000 carbonizing Methods 0.000 claims abstract description 19
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 16
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 230000014509 gene expression Effects 0.000 claims abstract description 8
- 239000007772 electrode material Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims description 51
- 238000010586 diagram Methods 0.000 claims description 45
- 238000002835 absorbance Methods 0.000 claims description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 238000001069 Raman spectroscopy Methods 0.000 claims description 22
- 238000000862 absorption spectrum Methods 0.000 claims description 21
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 13
- 238000000026 X-ray photoelectron spectrum Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 103
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 52
- 229910052799 carbon Inorganic materials 0.000 abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 26
- 239000001257 hydrogen Substances 0.000 abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 26
- 150000001721 carbon Chemical group 0.000 abstract description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 29
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- 238000003763 carbonization Methods 0.000 description 19
- 239000000126 substance Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 239000002994 raw material Substances 0.000 description 18
- 238000011084 recovery Methods 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 238000000160 carbon, hydrogen and nitrogen elemental analysis Methods 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 12
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 11
- 239000011229 interlayer Substances 0.000 description 11
- 230000000379 polymerizing effect Effects 0.000 description 11
- 239000010453 quartz Substances 0.000 description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000000746 purification Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 125000002560 nitrile group Chemical group 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 4
- 239000012776 electronic material Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 150000001247 metal acetylides Chemical class 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
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- 239000011347 resin Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- 239000004640 Melamine resin Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- -1 nitrogen-containing compound Chemical class 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N Aminoantipyrine Natural products CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910016523 CuKa Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000005260 alpha ray Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 238000005868 electrolysis reaction Methods 0.000 description 2
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- 238000011049 filling Methods 0.000 description 2
- 239000007849 furan resin Substances 0.000 description 2
- 125000002887 hydroxy group Chemical class [H]O* 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000003345 natural gas Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229960005222 phenazone Drugs 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- FQOBINBWTPHVEO-UHFFFAOYSA-N pyrazino[2,3-b]pyrazine Chemical compound N1=CC=NC2=NC=CN=C21 FQOBINBWTPHVEO-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 101000578940 Homo sapiens PDZ domain-containing protein MAGIX Proteins 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
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 125000000815 N-oxide group Chemical group 0.000 description 1
- 102100028326 PDZ domain-containing protein MAGIX Human genes 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 101150107341 RERE gene Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000003178 carboxy group Chemical class [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 230000001678 irradiating effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 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 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- GKKCIDNWFBPDBW-UHFFFAOYSA-M potassium cyanate Chemical compound [K]OC#N GKKCIDNWFBPDBW-UHFFFAOYSA-M 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
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- 239000011863 silicon-based powder Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 239000011232 storage material Substances 0.000 description 1
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- 125000003944 tolyl group Chemical group 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0234—Carbonaceous material
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- C01—INORGANIC CHEMISTRY
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C01P2006/80—Compositional purity
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- Nitrogen-containing carbon material and method for producing the same
- the present invention relates to a nitrogen-containing carbon material useful as an electrode material or the like and a method for producing the same.
- carbon materials have been mainly used as adsorbents, etc., but electronic properties such as conductivity, basic properties such as physical properties, high thermal conductivity, low thermal expansion coefficient, lightness, heat resistance, etc.
- electronic properties such as conductivity, basic properties such as physical properties, high thermal conductivity, low thermal expansion coefficient, lightness, heat resistance, etc.
- applications are being studied.
- due to the physical properties of electronic materials they have been used or studied in the field of electronic materials such as negative electrodes for lithium ion secondary batteries and electrodes for capacitors.
- Such a carbon material is produced by carbonization using coconut shells, coal coatas, coal or petroleum pitch, furan resin, phenol resin, and the like as raw materials.
- a method for producing a nitrogen-containing carbon material mainly, (1) a chemical vapor deposition (CVD) method using a low-molecular nitrogen-containing organic compound as a raw material, and (2) a low-molecular nitrogen-containing organic compound is used.
- CVD chemical vapor deposition
- a method of polymerizing as a raw material and carbonizing the obtained rosin is known.
- the CVD method itself is not suitable for industrial mass production, and in the process of CVD, halogen-containing compounds such as chlorine are used. If used, there is a problem with corrosion of the material, which is preferable.
- an expensive resin that is, a monomer that is a raw material of the resin is manufactured by a multistage reaction, the manufacturing process is complicated, or a large amount of monomer is industrially produced.
- carbides are produced using rosin as a raw material, there is a problem in that enormous amounts of raw materials and energy are consumed up to the production of carbon materials, taking into account the basic raw material power process.
- the polymerization process is complex, the nitrogen-containing carbon material obtained by carbonization consumes more and more raw materials and energy. Therefore, it is expensive and unsatisfactory to supply for various applications.
- the nitrogen-containing carbon material obtained by CVD generally has a high hydrogen content with a low nitrogen content.
- -tolyl groups and halogen groups remain, and the interplanar distance of the layered structure tends to be shortened.
- Patent Document 6 Patent Document 9, and Patent Document 5
- pyrrole, 2, 3, 6, 7-tetracyanol 1, 4, 5, 8-tetraazanaphthalene, acetonitrile, and bromide-tolyl are used as raw materials.
- the nitrogen content is low or the hydrogen content is high.
- the peak position of the diffraction angle (2 ⁇ ) corresponding to the (002) plane is 26.5 ° (the inter-surface distance is 3.36 angstroms). Equivalent) and the distance between layers is short.
- Patent Document 11 discloses a production example of a nitrogen-containing carbon material obtained by a method in which pyrrole is polymerized and carbonized at a high temperature.
- the peak position of the diffraction angle (2 0) corresponding to the (002) plane is 26.0 °, which corresponds to the inter-plane distance of 3.42 angstroms.
- the laser Raman spectrum of the nitrogen-containing carbon material is also disclosed, the peak position, and 1600 cm- 1 corresponding to crystalline, a 1350 cm _1 corresponding to amorphous, almost peak There is no shift.
- the peak separation of 160 OCM _1 and 1350 cm _1 is clear. In other words, the half width of the Raman peak is narrow.
- Patent Document 4 discloses a nitrogen-containing carbon material produced by CVD, such as N vinyl 2 pyrrolidone. According to the laser Raman's vector data of the obtained nitrogen-containing carbon material, the nitrogen-containing carbon material has a peak in 1350 cm _1, the half-value width with a sharp half-width and 97cm _1, Ru. Patent Document 4 also discloses an example of producing a nitrogen-containing carbon material by pulverizing graphite powder in a high-pressure nitrogen atmosphere at a very strong crushing acceleration. However, the half-value width of 1350 cm _1 is not included. ! /, Has a relatively sharp half-value width of 87 cm_1 .
- the nitrogen-containing carbon material obtained by the conventional technique has (i) a low nitrogen content. High hydrogen content, containing nitrile groups and halogen groups, (ii) short distance between (002) planes measured by X-ray diffraction, and (iii) laser Raman
- the nitrogen-containing carbon material satisfies at least one of the following four characteristics: the measured spectrum peak is not shifted, and (iv) the peak half-width is small and the crystallinity is high.
- Non-graphitizable carbon also referred to as hard carbon
- this is known to be advantageous for improving electric capacity (for example, non-patent document 2).
- propylene carbonate having excellent low-temperature operating characteristics can be used as a solvent for an electrolytic solution due to low crystallinity (for example, Non-Patent Document 3).
- a large interlayer distance is advantageous for the formation of an interlayer compound.
- it is advantageous for insertion and removal of lithium ions between layers.
- Patent Document 1 Japanese Patent Laid-Open No. 2001-80914
- Patent Document 2 JP-A-10-21918
- Patent Document 3 Japanese Patent Laid-Open No. 2004-168587
- Patent Document 4 Japanese Patent Laid-Open No. 2005-798
- Patent Document 5 Japanese Patent Laid-Open No. 2003-277026
- Patent Document 6 Japanese Patent Laid-Open No. 7-90588
- Patent Document 7 JP-A-9-27317
- Patent Document 8 Japanese Patent Application Laid-Open No. 2004-342463
- Patent Document 9 Japanese Patent Laid-Open No. 2003-137524
- Patent Document 10 Japanese Unexamined Patent Publication No. 2000-1306
- Patent Document 11 JP-A-8-165111
- Patent Document 12 Japanese Unexamined Patent Application Publication No. 2004-362802
- Patent Document 13 JP-A-8-180866
- Patent Document 14 Japanese Unexamined Patent Publication No. 2005-239456
- Non-patent document 1 High-capacity secondary battery for automobiles P140 CMC Publishing (2003)
- Non-patent document 2 Carbon material for negative electrode for lithium ion secondary battery p4 Realize (
- Non Patent Literature 3 Carbon material for negative electrode for lithium ion secondary battery pl l Realize (1996)
- the present invention utilizes a force directly derived from natural gas, a naphtha cracker fraction and! /! Basic chemical raw material, or a monomer produced as a by-product thereof. Furthermore, it is characterized in that the polymerization process and the subsequent powder process of the polymer are simple production methods, and the recovery rate of carbides is high in the carbonization process of the obtained powdered polymer. The purpose is to provide a method for producing energy- and resource-saving nitrogen-containing carbon materials.
- Another object of the present invention is to provide a method for producing a nitrogen-containing carbon material that is industrially simple and can be mass-produced.
- the present invention also relates to a laser Raman having a layered structure in which the content of nitrogen atoms is high, the content of hydrogen atoms is low, and the residual ratio of tolyl groups and halogen groups is low, and the interlayer distance is long.
- An object is to provide a novel nitrogen-containing carbon material having a specific peak shift in the spectrum.
- the present invention is as follows.
- a nitrogen-containing carbon material characterized by satisfying the following conditions (i), (ii) and (iii) in the nitrogen-containing carbon material:
- the half-value width of the peak P1 is characterized in that it is a 200 to 400 _ 1 (3) or a nitrogen-containing carbon material charge according to (4),
- the half-value width of the peak P2 is characterized in that it is a 30 ⁇ 200cm _ 1 (3) ⁇ (5)!, Nitrogen, according to whether the deviation 3 ⁇ 4 including talent,
- the intensity Q3 absorbance peak S3 in wavenumber 2800 to 3000 cm _ 1 the ratio of the intensity Q1 of the absorbance of the peak S1 of 1550 ⁇ 1640cm _ 1 (Q3ZQ1) is at 0.10 or less
- the intensity Q4 absorbance peak S4 of wavenumber 3000 ⁇ 3500cm _ 1 the ratio of the intensity Q1 of the absorbance of the peak S1 of 1550 ⁇ 1640cm _ 1 (Q4ZQ1) is at 0.80 or less
- the nitrogen-containing carbon material according to any one of (3) to (10),
- the production method of the present invention is produced as a by-product in the production process of monomers such as acrylonitrile, etc., and has been used as a polymer raw material, which has not been utilized in the past. It is.
- the production method of the present invention is an efficient production method that is easy to produce because the polymer as a precursor is easily polymerized and has a high recovery rate of carbides in the carbonization step of the polymer. Since the obtained nitrogen-containing carbon material is a further powder, there is no need for a molding step such as a resin and fiberizing step and a subsequent pulverizing step, and the handleability is excellent.
- the nitrogen-containing carbon material of the present invention has a layered structure in which the nitrogen atom content is high, the hydrogen atom content is low, the nitrile group residual ratio is low, and the interlayer distance is long. It is a novel nitrogen-containing carbon material that has a specific peak shift and a promising peak that is considered to exhibit an index of crystallinity.
- the present invention is characterized by being produced by carbonizing azulmic acid in an inert gas atmosphere. This is a nitrogen-containing carbon material.
- the present invention is a method for producing a nitrogen-containing carbon material, which is produced by carbonizing azulmic acid in an inert gas atmosphere.
- the present invention is a nitrogen-containing carbon material characterized by satisfying the following conditions (1), (2) and (3):
- the abundance ratio of carbon atoms, nitrogen atoms, and hydrogen atoms is determined using a CHN analyzer.
- the nitrogen-containing carbon material that does not satisfy the formula (I) is that (H / C) is large, is short, or (NZC) is small, and the conjugated system is sufficiently developed. ! /, Or a low nitrogen content! /, Which is unfavorable.
- the atomic ratio of nitrogen atoms to carbon atoms (NZC) and the atomic ratio of hydrogen atoms to carbon atoms (HZC) preferably satisfy the following relational expressions.
- a nitrogen-containing carbon material that does not satisfy the formula (IV) is not preferable because it consumes a large amount of equipment, resources, and energy in the production process of azulmic acid and the carbonization process of azulmic acid.
- Expressions (I) to (VI) are derived as a range surrounding the embodiment of FIG. 15 in the embodiment. That is, it is a region surrounded by a line substantially parallel to the inclination of the line connecting the examples.
- (H / C) is 0.01-0.5, more preferably 0.05-0.40, and even more preferably 0.05-0.35. Particularly preferred is ⁇ or 0.05 to 0.15.
- (NZC) is 0.03 ⁇ : L 0, preferably 0.05 ⁇ 0.7, more preferably 0.08 ⁇ 0.
- the nitrogen-containing carbon material according to the present invention is small! /, (H / C), it is large.
- NZC NZC
- the nitrogen-containing carbon material according to the present invention may contain elements other than carbon atoms, nitrogen atoms, and hydrogen atoms.
- the content of other elements is preferably 15% by weight or less, more preferably 7% by weight or less, particularly preferably 100% by weight or less with respect to 100% by weight of the nitrogen-containing carbon material according to the present invention. Or less than 3% by weight.
- Examples of other elements include oxygen elements. This oxygen element often exists in the form of a carboxyl group or a hydroxyl group. When used in electronic materials, if these functional groups are large, irreversible adsorption occurs, which is not preferable. The presence of halogen elements such as chlorine and bromine is preferable because of corrosion of the material.
- the content of halogen element is preferably 10% by weight or less, more preferably 3% by weight or less, still more preferably 1% by weight or less, and particularly preferably 0.1% by weight or less.
- the diffraction angle (2 ⁇ ) is 23.5. It has a peak at a position of -25. 5 ° and a peak at a position of 23.7-25. 0, preferably S, and more preferably has a peak at 23.9-24. 5 °. It is preferable that the peak has a high intensity at a diffraction angle (2 ⁇ ) of 15 to 50 °.
- the nitrogen-containing carbon material according to the present invention has a layered structure.
- interlayer distance is equivalent to 3.49-3.78 angstroms
- preferred interlayer distance is equivalent to 3.56-3.75 angstroms
- more preferred interlayer distance is equivalent to 3. 64-3.7.72 angstroms.
- a large interlayer distance is advantageous for forming an intercalation compound.
- the nitrogen-containing carbon material according to the present invention has a wave number of 1000 to 2000 cm _ 1 in the laser Raman spectrum diagram! peak P1 between 355 ⁇ 1385cm _ 1, even with the peak P2 between 1550 ⁇ 1620cm _ 1! ⁇ U without small with two major peaks.
- the ratio of (LZH1) described later is 0.70 to 0.95, preferably 0.86 to 0.93, particularly The preferred range is 0.88 to 0.91.
- the ratio of (LZH1) in the laser Raman spectrum diagram of the nitrogen-containing carbon material according to the present invention is a value related to the half width of the peak. The full width at half maximum is small! /, And the value power of (L / H1) is reduced, the full width at half maximum is increased, and the value of (L / H1) is increased.
- (LZH1) is used as an index of the full width at half maximum, but the full width at half maximum can also be measured by performing peak separation. Peak separation is a well-known Lorentz function, Gaussian function, etc. It can be done using the method. It can be easily understood by those skilled in the art that a function having a high fitting ratio may be appropriately used for peak separation!
- the half width of the peak P 1, 200 to 400 _1 force transducer preferred, preferably from 250 ⁇ 350Cm _1 force, preferably especially 270 to it is a 320cm _1.
- the ratio of (LZH2) described later is 0.60 to 0.90, more preferably 0.63 to 0.85. And particularly preferably from 0.75 to 0.84.
- the ratio of (LZH2) in the laser Raman spectrum of the nitrogen-containing carbon material according to the present invention is a value related to the half width of the peak. If the full width at half maximum is small, the value force S of (LZH2) is small, and if the full width at half maximum is large, the value of (LZH2) is large.
- (LZH2) is used as an index of half width, but half width can be measured by performing peak separation. Peak separation can be performed using known methods such as Lorentz function and Gaussian function. It can be easily understood by those skilled in the art that a function having a high fitting rate is appropriately used for peak separation.
- the half width of the peak P 2 preferably 30 ⁇ 200Cm _1 force S, preferably from 80 ⁇ 170Cm _1 force S, particularly preferably 100 ⁇ 150cm _1 .
- P2 is the Raman shift in the laser Raman spectrum diagram is the main two peaks between from 1,340 to 162 OCM _1.
- P1 is a peak between 1355 ⁇ 1385cm _1
- P2 is a peak between 1550 ⁇ 1620cm _1.
- the peak intensity using an Ar laser (wavelength 540 nm, 2 mW), Bimusai's 5, the operation range 1000 ⁇ 2000Cm _1, is lasers one Raman spectral diagram force measurement obtained when measured accumulated time 5 minutes.
- FIG. 1 shows a schematic diagram of an example of a laser Raman spectrum of the nitrogen-containing carbon material according to the present invention.
- FIG. 1 is a diagram for explaining the ratio of (LZH1) and (LZH2) used in the present invention, and is a laser Raman spectrum diagram obtained from the nitrogen-containing carbon material according to the present invention. It is not something to limit.
- B1 is the intensity value of 1000 to 1300 cm _1 / J
- B2 is 1700 It is the minimum of the intensity value between ⁇ 2000cm _1.
- the base line in the laser Raman spectrum used in the present invention is a straight line connecting Bl and B2.
- Cl and C2 shown in FIG. 1 are the intersections of a perpendicular line and a baseline drawn from the peaks P1 and P2 to the Raman shift axis, respectively.
- D is the minimum intensity value between the peaks P1 and P2
- M force is the intersection of the perpendicular line drawn to the Raman shift axis and the baseline
- the height L is the perpendicular line drawn to the M force Raman shift axis.
- the length to the intersection of the baseline Specifically, in the laser Raman spectrum diagram illustrated in Fig. 1, it is the length of the line segment MD.
- the height HI is the length from the point P1 to the intersection of the vertical line and the baseline that are lowered to the Raman shift axis.
- the length of the line segment P1C1 corresponds to the height HI.
- Height H2 is the length from P2 to the intersection of the perpendicular line and the baseline that descends from the Raman shift axis.
- the length of the line segment P2C 2 corresponds to the height H2.
- the nitrogen-containing carbon material according to the present invention includes Nls XPS spectra obtained by X-ray photoelectron spectroscopy (XPS) [40! 0 ⁇ 0.3 eV, and 398. 0 ⁇ 0.5 eV [Preferably having a peak. More preferred are 401.0 ⁇ 0.2 eV and 398.0 ⁇ 0.3 eV, and particularly preferred are 401.0 ⁇ 0. LeV and 398.0 ⁇ 0. LeV.
- the peak near 401eV corresponds to the nitrogen element of Center type and Valley type
- the peak near 398eV corresponds to the nitrogen element of Top type (for example, Carbon 40 C, 597-608 ( This means that nitrogen atoms exist as quaternized nitrogen or pyridine nitrogen in the plane and end of the plane of the carbon network, respectively, in the nitrogen-containing carbon material according to the present invention.
- XPS is an X-ray source: A1 tube (A1— ⁇ ⁇ -ray), tube voltage: 15 kV, tube current: 10 mA, analysis area: 600 m X 300 m Ellipse, capture region: Nls, Cls, Pass-Energy: 20eV, defined as the value measured with energy correction at the C Is peak position.
- the nitrogen-containing carbon material according to the present invention in the infrared absorption spectrum wavenumber force 1550-16 giving the maximum value of the peak intensity of the absorbances at wave numbers of 150 0 ⁇ 1800cm _1 It is preferably 40 cm.
- the nitrogen-containing carbon material contact the infrared absorption spectrum, Te, and strength Q2 absorbance peak S2 of wavenumber from 2,200 to 22 80 cm _1, the intensity Q1 of the absorbance of the peak S1 at 1550 ⁇ 1640Cm _1
- the ratio (Q2ZQ1) force is preferably 0.07 or less. More preferably, it is 0.05 or less, and particularly preferably 0.02 or less.
- the absorbance peak at a wave number of 2200 to 2280 cm_1 is a peak derived from a nitrile group, and is preferably small.
- the nitrogen-containing carbon material has an absorbance peak S3 intensity Q3 at a wave number of 2800-30 OOcnT 1 and an absorbance peak S1 intensity Q1 at 1550-1640 cm _1 in an infrared absorption spectrum diagram.
- the ratio (Q3ZQ1) force is preferably 0.10 or less. More preferably, it is 0.05 or less, and particularly preferably 0.02 or less.
- the absorbance peak at a wave number of 2800 to 3000 cm_1 is a peak derived from the C—H group, and is preferably small.
- the nitrogen-containing carbon material has an absorbance peak S4 intensity Q4 at a wave number of 3000 to 35 OOcnT 1 and an absorbance peak S1 intensity Q1 at 1550 to 1640 cm _1 in an infrared absorption spectrum diagram.
- the ratio (Q4ZQ1) force is preferably 0.80 or less. More preferably, it is 0.70 or less, and particularly preferably 0.6 or less.
- Absorbance peaks at wave numbers 3000 to 3500 cm _1 are peaks derived from N—H groups and O—H groups, and are preferably small.
- the intensity Q1 of the peak S1 is defined as follows.
- the A1 and the point indicating the minimum absorbance of 1000 to 1200 _1, shall be the point showing the minimum absorbance between 1700 ⁇ 1900Cm _1 to A2.
- Baseline A1A2 is a straight line connecting Al and A2.
- E1 is the intersection of the base line A1A2 and the perpendicular line drawn from the peak S1 to the wave number axis of the infrared absorption spectrum.
- the intensity Q1 of the peak S1 is the length of the line segment S1E1 from the S1 to the intersection E1 of the perpendicular line and the baseline drawn down from the wave number axis of the infrared absorption spectrum.
- the intensity Q2 of the peak S2 is defined as follows. The A3 and the point indicating the minimum absorbance 2100 ⁇ 2200cm _1, it shall be the point showing the minimum absorbance between 2280 ⁇ 2400Cm _1 to A4. Baseline A3 A4 is a straight line connecting A3 and A4. [0065] Next, E2 is the intersection of the perpendicular line drawn from the peak S2 to the wave number axis of the infrared absorption spectrum and the baseline A3A4. The intensity Q2 of the peak S2 is the length of the line segment S2E2 from the S2 to the intersection E2 of the perpendicular line and the baseline drawn from the wave number axis of the infrared absorption spectrum.
- the intensity Q3 of the peak S3 is defined as follows.
- Baseline A5A6 is a straight line connecting A5 and A6.
- E3 is the intersection of the perpendicular line drawn from the peak S3 to the wave number axis of the infrared absorption spectrum and the baseline A5A6.
- the intensity Q3 of the peak S3 is the length of the line segment S3E3 from the S3 to the intersection E3 of the vertical line and the baseline drawn down from the wave number axis of the infrared absorption spectrum.
- the intensity Q4 of the peak S4 is defined as follows.
- Baseline A7A8 is a straight line connecting A7 and A8.
- E4 is the intersection of the base line A7A8 and a perpendicular line drawn from the peak S4 to the wave number axis of the infrared absorption spectrum.
- the intensity Q4 of the peak S4 is the length of the line segment S4E4 from the S4 to the intersection E4 of the perpendicular line and the baseline drawn down to the wave number axis of the infrared absorption spectrum.
- the nitrogen-containing carbon material of the present invention is a nitrogen-containing carbon material having the characteristics defined in the present invention, any production method and starting material will not be used.
- it can be produced mainly by carbonizing azulmic acid obtained by polymerizing hydrocyanic acid.
- FIG. 2 shows a schematic diagram of a process for producing a nitrogen-containing carbon material according to the present invention.
- the production method according to the present invention includes a step of polymerizing a raw material containing hydrocyanic acid in step S10 and a step of carbonizing the azulmic acid obtained in step S10 (step S12).
- step S10 The hydrocyanic acid used in step S10 of the production method according to the present invention is not limited to the following method. Any one produced by a known method can be used.
- this method is used in a method of producing acrylonitrile or metataronitrile by a gas phase catalytic reaction in which propylene, isobutylene, tert-butyl alcohol, propane or isobutane is reacted with ammonia or an oxygen-containing gas in the presence of a catalyst. What is produced can be used. For this reason, the hydrocyanic acid used in step S10 can be obtained very inexpensively.
- a raw material that produces hydrocyanic acid by an ammonium acid reaction such as methanol may be supplied to the reactor.
- hydrocyanic acid produced by the Andrewsso method in which methane, which is a main component of natural gas, is reacted with ammonia and an oxygen-containing gas in the presence of a catalyst can be used.
- This method is also a method for obtaining hydrocyanic acid at a very low price because of using methane.
- the azulmic acid used in step S12 of the production method according to the present invention is not limited to the following method! /, But is a black to black brown hydrocyanic acid polymer obtained by polymerizing a raw material mainly containing hydrocyanic acid. Yes (see step S10).
- the raw material containing hydrocyanic acid used in the present invention has an abundance ratio of other polymerizable substances to hydrocyanic acid of 40% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less. Particularly preferably, it is 1% by weight or less.
- Azulmic acid can be produced by polymerizing hydrocyanic acid by various methods (see step S10). For example, heating liquefied hydrocyanic acid or aqueous hydrocyanic acid solution or leaving it for a long time, adding a base, irradiating light, emitting high energy, various discharges, electrolysis of aqueous potassium cyanide solution, etc.
- known methods see, for example, Angew. Chem. 72 ⁇ , 379-384 (1960) and references thereof, and vacuum science, 16 ⁇ , 64-22 (1969) and references thereof. The described method can be illustrated.
- a base examples include sodium hydroxide, potassium hydroxide, cyanate sodium, cyanate potassium, triethylamine and the like. I'll do it.
- Azulmic acid can also be produced by recovering it from the purification process power of hydrocyanic acid produced as a by-product in the process of ammonic acid such as propylene.
- (Chemical Formula 1) is a linear structure
- (Chemical Formula 2) and (Chemical Formula 3) are ladder structures
- (C) 4 and (Chemical Formula 5) are structures condensed between ladders.
- there is a structure in which condensation occurs between structures condensed between ladders and a structure in which bonds or condensation occur between (Chemical Formula 1), (Chemical Formula 2), (Chemical Formula 3), (Chemical Formula 4), and (Chemical Formula 5). It is estimated that there will be.
- composition of azulmic acid used in the present invention can be measured using a CHN analyzer.
- (Weight% of nitrogen element) Z (wt% of carbon element) is preferably between 0.2 and 1.0. Or from 0 3 to 0.9, and particularly preferably from 0 4 to 0.9.
- (Weight of hydrogen element. / O) (Weight% of carbon element) is preferably 0.03 to 02, more preferably 005 to 015, and particularly preferably 008 to 011.
- Azunoremin acid used in the present invention Te per cent Rere laser Raman scan Bae click Bok Honoré view of wavenumber 1000 ⁇ 2000cm one 1, Ramanshifu Bok force 1300 ⁇ : I400cm _1, 1500 ⁇ : 1600cm- 1 of pins in position It is preferable to have a peak at a position of 1360 to 1380 cm—1530 to: 1550 cm— 1 .
- FIG. 3 shows a schematic diagram of an example of a laser Raman spectrum of aznoremic acid used in the present invention.
- Azunoremin acid used in the present invention in the laser Raman spectrum of wave numbers 1000 ⁇ 2000c m _1, a peak P3 between 1300 ⁇ 1400Cm- 1, that peak P4 between 1500 ⁇ 1600Cm _1 Preferably it has at least two major peaks.
- a peak P3 is 1350 ⁇ 1390Cm _1
- peak P4 is 151 0 ⁇ : 1570cm- located between 1, more preferably the peak P3 force 360 ⁇ 1380cm one 1, peak P 4 months 1530 ⁇ 1550Cm- 1 ⁇ ⁇
- (H3ZH4), (L1 / H3) and (L1 / H4) shown in Fig. 3 use Ar laser (wavelength 540nm, 2mW), beam size 5 //, operation range 1000-2000cm — ⁇ , the peak ratio of the laser Raman spectrum obtained when the measurement time is 5 minutes, and is defined as follows.
- B3 is a minimum intensity value of 1000 to 1300 cm- 1
- B4 is a minimum intensity value of 1700 to 2000 cm_1 .
- the base line in the laser Raman spectrum used in the present invention is a straight line connecting B3 and B4.
- C3 and C4 shown in Fig. 3 are the intersections of the perpendicular line and the baseline where the peak P3 and P4 forces are also lowered on the Raman shift axis, respectively.
- D1 is the intersection of the minimum intensity value Ml between peaks P3 and P4 from the perpendicular to the Raman shift axis and the baseline, and the height L1 is the perpendicular and baseline drawn from Ml to the Raman shift axis.
- the length to the intersection of is Specifically, it is the length of the line segment MIDI in the laser Raman spectrum diagram illustrated in Fig. 3.
- the height H3 is the length from the peak P3 to the intersection of the perpendicular line drawn down to the Raman shift axis and the baseline, and corresponds to the line segment P3C3.
- Height H4, P4 force is also on the Raman shift axis
- the ratio of azulmic acid used in the present invention is 0.5 to 1.0, preferably 0.6 to 0.9, and more preferably 0.7 to 0.8. . Further, it (Ll / H3) i of azulmic acid used in the present invention is 0.4 to 0.9, preferably 0.6 to 0.8, and more preferably 0.65 to 0.75. It is. On the other hand, the ratio (L1ZH4) of azulmic acid used in the present invention is 0.70 to 0.99, preferably 0.80 to 0.95, and more preferably 0.65 to 0.75. .
- the azulmic acid used in the present invention has a diffraction angle (2 0) of 26.8 ⁇ 1 ° in the range of 10 to 50 ° in the X-ray diffraction diagram obtained by using CuKa rays as an X-ray source.
- a strong peak is shown at the position, preferably at 26.8 ⁇ 0.5 °, and more preferably at the position of 26.8 ⁇ 0.2 °.
- the azurmic acid used in the present invention has a diffraction angle (2 0) of 12.3 in the range of 10 to 50 ° in the X-ray diffraction diagram obtained using the CuK strand as the X-ray source.
- a peak also appears at the ⁇ 1 ° position, preferably at the 12.3 ⁇ 0.5 ° position.
- the azulmic acid used in the present invention is subjected to peak separation using a well-known function having a high fitting rate such as a Lorentz function or a Gaussian function in its X-ray diffraction diagram, and the half-width of the peak is in a specific range. Preferably to be in.
- the position at 26.8 ⁇ 1 ° after peak separation was performed using a Lorentz function or a Gaussian function with a high power fit factor.
- the full width at half maximum of the peak is 6 to 12 °, preferably 8 to 10 °, and more preferably 8.5 to 9.5 °.
- the X-ray diffraction pattern of azulmic acid used in the present invention suggests that the azulmic acid has a layered structure.
- Such an example is not known in the precursor before the carbonization of the nitrogen-containing carbon material.
- such a structure of the precursor before carbonization is advantageous in that it exhibits characteristics of a layered structure, a high nitrogen content, and a low hydrogen content. Inferred.
- the azulmic acid used in the present invention is preferably 30% by weight or less, more preferably 10% by weight or less, particularly preferably, when Soxhlet extraction is carried out for 5 hours in black mouth form. Is less than 1% by weight.
- the eluted fraction is a low molecular weight compound or a linear polymer, and a large amount of eluted fraction means that the degree of polymerization is increased.
- the azulmic acid used in the present invention is not limited to the following, but can be obtained by polymerizing a raw material mainly containing hydrocyanic acid.
- the method of polymerizing hydrocyanic acid is suitable as a method for producing azulmic acid having the above-mentioned laser Raman spectrum having a specific peak and X-ray diffraction pattern.
- the carbonization method of azulmic acid used in the present invention is not limited to the following, but a rotating furnace, a tunnel furnace, a tubular furnace, a fluidized firing furnace, etc. are used, and azulmic acid is not used. It is carried out by heat treatment in an active gas atmosphere in the range of 600 to 3000 ° C, preferably 700 to 2000 ° C, more preferably 750 to 1500 ° C, and particularly preferably 800 to L 100 ° C.
- the inert gas include, but are not limited to, the following gases: inert gases such as nitrogen, argon, helium, neon, carbon dioxide, and vacuum, and nitrogen gas is preferred.
- the inert gas is circulated, although it may be stationary or circulated.
- the oxygen concentration in the inert gas is preferably 5% or less, more preferably 1% or less, and particularly preferably lOOOppm or less.
- the carbonization time is in the range of 10 seconds to 100 hours, preferably 5 minutes to 10 hours, more preferably 15 minutes to 5 hours, and even more preferably 30 minutes to 2 hours.
- the pressure in the carbonization process is 0.01 to 5 MPa, preferably 0.75 to LMPa, more preferably LMPa, 0.08 to 0.3 MPa, particularly preferably ⁇ to 0.009 to 0.1 5 MPa. is there.
- High-pressure treatment is not preferable because it has a diamond structure composed of sp3 orbitals.
- a stabilization treatment may be performed in which heat treatment is performed in air at a relatively low temperature.
- a nitrogen-containing carbon material satisfying a high nitrogen content and a low hydrogen content can be obtained without stabilization treatment.
- the nitrogen-containing carbon material produced by the production method according to the present invention preferably has a layered structure constituted by sp2 orbitals.
- the production method according to the present invention is a method for producing a nitrogen-containing carbon material including a step of carbonizing azulmic acid.
- the azulmic acid can be obtained by polymerizing a raw material containing hydrocyanic acid.
- the method for producing a nitrogen-containing carbon material according to the present invention is suitable for producing a nitrogen-containing carbon material satisfying the following (1), (2) and (3):
- NZC nitrogen atom to carbon atom
- HZC hydrogen atom to carbon atom
- azulmic acid was recovered in the step shown in FIG.
- this crude hydrocyanic acid vapor (10) was maintained at 40-50 ° C through a heated pipe, and sulfur dioxide gas 0.035KgZh and nitrogen gas 18m3Zh were added as stabilizers, and the gas in the lower part of the hydrocyanic acid absorption tower 7 was Sent to the phase.
- the cyanide absorption tower 7 has a diameter of 0.5 m, a height of 9 m, 10 trays, and a multi-tube falling liquid film cooling zone of 0.5 m.
- Absorbent (11) was sent to the top of the cyanate absorber 7 after cooling 3000 kgZh of the bottom of the cyanide refiner 3 to 104 ° C to 5 ° C.
- the amount of hydrocyanic acid contained in the evolved gas l l lkgZh (14) from the top of the hydrocyanic acid absorption tower 7 was ⁇ m or less.
- the analysis apparatus and analysis conditions in the examples are as follows.
- the Raman spectrum was measured under the following conditions by crushing the sample with an agate mortar and mounting it on a powder cell.
- the X-ray diffraction pattern was measured under the following conditions after pulverizing the sample with an agate mortar and filling the powder cell.
- the XPS spectrum was measured under the following conditions after pulverizing the sample with an agate mortar and filling the powder cell.
- Equipment ESCALAB250 manufactured by Thermo Electron
- X-ray source A1 tube (A1— ⁇ ⁇ -ray), tube voltage: 15 kV, tube current: 10 mA, analysis area: 600 m X 300 m ellipse, capture area: Nls, Cls, Pas s— Energy: 20eV.
- a Varian Co. FTS575CZUMA500, transmission method, MCT detector was measured under the conditions of a resolution 4 cm _ 1. Samples were prepared using KBr with a spectrum easily measured, diluted to a concentration (about 100 times), and tableted at a press pressure of 200 kgZcm2.
- composition of azulmic acid obtained in the above production example was 40.0% by weight of carbon element, 29.8% by weight of nitrogen element, and 4.1% by weight of hydrogen element. Since the adsorbed water remains under the dry conditions here, the difference is probably due to the oxygen and hydrogen elements of the adsorbed water.
- FIG. 5 shows a laser Raman spectrum of azulmic acid obtained in the production example of the present invention. From the laser Raman spectrum shown in FIG. 5, the azulmic acid obtained in the above production example was 1000 to 2000 cm _1 . 1375cm _ 1 [This is strong!
- FIG. 6 shows an X-ray diffraction pattern of azulmic acid obtained in the production example of the present invention.
- the azulmic acid obtained in the above production example from the X-ray diffraction pattern shown in Fig. 6 has a strong peak at 27.0 ° between 5 and 50 °, and a broad peak around 12.3 °. It was.
- the nitrogen-containing carbon material obtained in Example 1 was carbon element: 68.6% by weight, nitrogen element: 24.0% by weight, and hydrogen element: 1.8% by weight.
- the atomic ratio of nitrogen to carbon (NZC) is 0.30.
- the atomic ratio of hydrogen atoms to carbon atoms (HZ C) is 0.31.
- FIG. 7 shows a laser Raman spectral diagram of the nitrogen-containing carbon material obtained in Example 1 of the present invention. From the laser Raman spectrum diagram shown in FIG. 7, the nitrogen-containing carbon material obtained in Example 1, between the 1000 ⁇ 2000Cm _1, around 1355 cm _1, has a peak near 1570cm _1, (LZH1) is 0. 85.
- Fig. 8 shows the result of fitting the above-mentioned laser Raman spectrum diagram with a Gaussian function with 2 peaks.
- Full width at half maximum of the peak of 1355cm _1 is 302cm _1
- full width at half maximum of the peak of 1570cm _ 1 was 137cm _1. It can be seen that the full width at half maximum is very large, in addition to a large chemical shift compared to ordinary carbon materials.
- FIG. 9 shows an X-ray diffraction pattern of the nitrogen-containing carbon material obtained in Example 1 of the present invention.
- the nitrogen-containing carbon material obtained in Example 1 is 5 Between -50 °, it had a main peak around 25.0 ° and a peak around 44.7 °. From the entire X-ray diffraction pattern, it can be seen that the film has a layered structure.
- FIG. 10 shows an XPS spectrum diagram of N 1 s of the nitrogen-containing carbon material obtained in Example 1 of the present invention.
- the nitrogen-containing carbon material obtained in Example 1 has peaks at positions of 398. OeV and 40.7 eV between 392 and 410 eV. Had.
- Nitrogen-containing carbon material obtained in Example 1 there are wave number providing the maximum value of the peak intensity of the absorbance in 1612 cm _1 at a wave number 1500 ⁇ 1800cm _1, Q2 peak, Q3 peak was not observed, (Q2ZQ1) Was less than 0.01 and (Q3ZQ1) was less than 0.01. (Q4 ZQ1) was 0.50.
- the nitrogen-containing carbon material obtained in Example 2 was carbon element: 89.2% by weight, nitrogen element: 8.7% by weight, and hydrogen element: 0.8% by weight.
- the atomic ratio of nitrogen to carbon (NZC) is 0.085.
- the atomic ratio (HZC) of hydrogen atoms to carbon atoms is 0.10.
- FIG. 11 shows a laser Raman spectrum diagram of the nitrogen-containing carbon material obtained in Example 2 of the present invention.
- Laser Raman spectral diagram force I Chikararu so shown in FIG. 11, the nitrogen-containing carbon material obtained second embodiment 2, among the 1000 ⁇ 2000Cm _1, near 1382cm _1, 15 It had a peak near 85 cm and (LZH1) was 0 88.
- Fig. 12 shows the result of fitting the above-mentioned laser Raman spectrum diagram with a Gaussian function with 2 peaks.
- the half-value width of the peak of 1382cm _1 is 298cm- 1
- the half-value width of the peak of 1585Cm- 1 was 122cm- 1. It can be seen that the full width at half maximum is very large, in addition to a large chemical shift compared to ordinary carbon materials.
- FIG. 13 shows an X-ray diffraction pattern of the nitrogen-containing carbon material obtained in Example 2 of the present invention.
- the nitrogen-containing carbon material obtained in Example 2 has a major peak between 24 and 1 ° between 5 and 50 °, and also around 44 and 3 °. It had a peak. It can be seen that it has a very large interlayer structure. It can be seen from the entire diffractogram that it has a layered structure.
- FIG. 14 shows an NLS XPS spectrum diagram of the nitrogen-containing carbon material obtained in Example 2 of the present invention. As shown in FIG. 14, the nitrogen-containing carbon material obtained in Example 2 has peaks at 398.0 eV and 401.0 eV between 392 and 410 eV. Had.
- the wave number giving the maximum peak intensity of the absorbance at wave number isoo isoocn 1 is 1612 cm -1 , and the Q2 peak and Q3 peak are not observed (Q2 / Q1) was less than 0.01 and (Q3 / Q1) force was less than 0.01. (Q4 / Q1) was 0.47.
- the nitrogen-containing carbon material obtained in Example 3 was carbon element: 56.6% by weight, nitrogen element: 32.1% by weight, hydrogen element: 2.2% by weight.
- the atomic ratio of nitrogen to carbon (NZC) is 0.30.
- the atomic ratio of hydrogen atoms to carbon atoms (HZ C) is 0.31.
- Nitrogen-containing carbon material obtained in Example 3 of the present invention among the 1000 ⁇ 2000Cm _1, around 1 360 cm _1, has a peak near 1593cm _1, (LZH1) was 0.76.
- the nitrogen-containing carbon material obtained in Example 3 of the present invention had a major peak around 25.1 ° and a peak around 44.3 ° between 5 and 50 °. The fact that it has a very large interlayer structure is surprising.
- Melamine rosin with the highest nitrogen content was carbonized as a precursor of nitrogen-containing carbon materials. That is, 12 g of melamine resin was filled in a quartz tube having an inner diameter of 25 mm, and carbonized at 800 ° C. in the same manner as in Example 1 to obtain 1.5 g of a nitrogen-containing carbon material. The recovery rate is 13%.
- the nitrogen-containing carbon material obtained in Comparative Example 1 was carbon element: 68.2% by weight, nitrogen element: 17.9% by weight, and hydrogen element: 1.9% by weight.
- the atomic ratio (NZC) of nitrogen to carbon is 0.22.
- the ratio of the number of hydrogen atoms to carbon atoms (HZ C) is 0.35.
- a quartz tube with an inner diameter of 25 mm was filled with 12 g of melamine resin, and carbonized at 1000 ° C. in the same manner as in Example 2 to obtain 1. Og of a nitrogen-containing carbon material. Recovery rate is 8%
- the nitrogen-containing carbon material obtained in Comparative Example 2 was carbon element: 78.2% by weight, nitrogen element: 7.8% by weight, and hydrogen element: 1.5% by weight.
- the atomic ratio of nitrogen to carbon (NZC) is 0.080.
- the atomic ratio (HZC) of hydrogen atoms to carbon atoms is 0.23.
- a quartz tube having an inner diameter of 25 mm was filled with 12 g of polyarlin and carbonized at 800 ° C. in the same manner as in Example 1 to obtain 2.8 g of a nitrogen-containing carbon material.
- the recovery rate is 23%.
- the nitrogen-containing carbon material obtained in Comparative Example 3 was carbon element: 77.3% by weight, nitrogen element: 7.5% by weight, and hydrogen element: 2.0% by weight.
- the atomic ratio of nitrogen to carbon (NZC) is 0.08.
- the atomic ratio of hydrogen atoms to carbon atoms (HZC) is 0.31.
- the nitrogen-containing carbon material obtained in Comparative Example 4 was carbon element: 92.0% by weight, nitrogen element: 2.7% by weight, and hydrogen element: 1.0% by weight.
- the atomic ratio of nitrogen to carbon (NZC) is 0.02.
- the atomic ratio of hydrogen atoms to carbon atoms (HZC) is 0.13.
- a quartz tube having an inner diameter of 25 mm was filled with 12 g of polyatari mouth-tolyl and carbonized at 800 ° C. in the same manner as in Example 1 to obtain 4 g of a nitrogen-containing carbon material.
- the recovery rate is 33%.
- the nitrogen-containing carbon material obtained in Comparative Example 5 was carbon element: 77.0% by weight, nitrogen element: 13.9% by weight, and hydrogen element: 1.8% by weight.
- the ratio of the number of nitrogen atoms to carbon atoms (NZC) is 0.15.
- the atomic ratio of hydrogen atoms to carbon atoms (HZ C) is 0.28.
- a quartz tube with an inner diameter of 25 mm was filled with 12 g of polyacrylonitrile and carbonized at 1000 ° C. in the same manner as in Example 2 to obtain 2.9 g of a nitrogen-containing carbon material.
- the recovery rate is 24%.
- the nitrogen-containing carbon material obtained in Comparative Example 6 was carbon element: 89.9% by weight, nitrogen element: 6.0% by weight, and hydrogen element: 1.2% by weight.
- the atomic ratio of nitrogen to carbon (NZC) is 0.057.
- the atomic ratio of hydrogen atoms to carbon atoms (HZC) is 0.16.
- a quartz tube with an inner diameter of 25 mm was filled with 12 g of wholly aromatic polyimide, and carbonized at 800 ° C. in the same manner as in Example 1 to obtain 6.9 g of a nitrogen-containing carbon material.
- the recovery rate is 58%.
- the nitrogen-containing carbon material obtained in Comparative Example 7 was carbon element: 80.5% by weight, nitrogen element: 3.8% by weight, and hydrogen element: 2.0% by weight.
- the atomic ratio of nitrogen to carbon (NZC) is 0.04.
- the atomic ratio of hydrogen atoms to carbon atoms (HZC) is 0.30.
- a quartz tube with an inner diameter of 25 mm was filled with 12 g of wholly aromatic polyimide, and carbonized at 1000 ° C. in the same manner as in Example 2 to obtain 6.4 g of a nitrogen-containing carbon material.
- the recovery rate is 54%.
- the nitrogen-containing carbon material obtained in Comparative Example 8 was composed of carbon element: 86.1% by weight, nitrogen. Element: 1.8% by weight, hydrogen element: 1.0% by weight.
- the atomic ratio of nitrogen to carbon (NZC) is 0.02.
- the atomic ratio of hydrogen atoms to carbon atoms (HZC) is 0.14.
- the nitrogen-containing carbon material obtained in the example and the nitrogen-containing carbon material obtained in the comparative example are compared with the horizontal axis of (HZC) and the vertical axis of (N / C).
- the nitrogen-containing carbon material of the present invention has a high nitrogen content even though the hydrogen content is low.
- the nitrogen-containing carbon material according to the present invention has a specific laser Raman spectrum in which the nitrogen atom content is high, the hydrogen atom content is low, the nitrile group content is low, and the interlayer distance is large.
- an electrode material such as a lithium ion secondary battery negative electrode, a capacitor electrode, and a fuel cell electrode.
- the production method according to the present invention is useful as a method for producing a nitrogen-containing carbon material satisfying a high nitrogen content and a low hydrogen content while satisfying the economical efficiency of production.
- the production method according to the present invention includes a step of polymerizing a raw material containing hydrocyanic acid in step S10 and a step of carbonizing the azulmic acid obtained in step S10 (step S12).
- the process for producing azulmic acid from hydrocyanic acid is used in order to produce azulmic acid because the hydrocyanic acid used in step S10 is a direct derivative from basic chemical raw materials and is also a by-product in the production of monomers and the like.
- This is a method for producing a precursor of a nitrogen-containing carbon material that consumes less amounts and resources.
- cyanide is easily polymerized, so the polymerization process is simple, and the resulting polymer is obtained as a smooth powder, so it is easy to handle, and there is also a process for making powder such as a pulverization process. It is unnecessary.
- a polymer of cyanic acid which has not been used in the past, will be used effectively.
- the present invention is a method for producing a nitrogen-containing carbon material with high energy consumption and low resource consumption in the carbonization step of step S12.
- FIG. 1 shows a schematic diagram of an example of a laser Raman spectrum of a nitrogen-containing carbon material according to the present invention.
- FIG. 2 shows a schematic view of a process for producing a nitrogen-containing carbon material according to the present invention.
- FIG. 3 shows a schematic diagram of an example of a laser Raman spectrum of azulmic acid used in the present invention.
- FIG. 4 is a diagram schematically illustrating a cyanic acid purification step and an azulmic acid recovery step performed in the present invention.
- FIG. 5 shows a laser Raman spectrum of azulmic acid obtained in the production example of the present invention.
- FIG. 6 shows an X-ray diffraction pattern of azulmic acid obtained in the production example of the present invention.
- FIG. 7 shows a laser Raman spectrum of the nitrogen-containing carbon material obtained in Example 1 of the present invention.
- FIG. 8 is a diagram showing the result of fitting the laser Raman spectrum obtained in Example 1 of the present invention with a Gaussian function with a peak number of 2.
- FIG. 8 is a diagram showing the result of fitting the laser Raman spectrum obtained in Example 1 of the present invention with a Gaussian function with a peak number of 2.
- FIG. 9 shows an X-ray diffraction pattern of the nitrogen-containing carbon material obtained in Example 1 of the present invention.
- FIG. 10 shows an NLS XPS spectrum diagram of the nitrogen-containing carbon material obtained in Example 1 of the present invention.
- FIG. 11 shows a laser romance vector diagram of the nitrogen-containing carbon material obtained in Example 2 of the present invention.
- FIG. 12 is a diagram showing a result obtained by fitting the laser Raman spectrum obtained in Example 2 of the present invention with a Gaussian function with a peak number of 2.
- FIG. 12 is a diagram showing a result obtained by fitting the laser Raman spectrum obtained in Example 2 of the present invention with a Gaussian function with a peak number of 2.
- FIG. 13 shows an X-ray diffraction pattern of the nitrogen-containing carbon material obtained in Example 2 of the present invention.
- FIG. 14 shows an NLS XPS spectrum diagram of the nitrogen-containing carbon material obtained in Example 2 of the present invention.
- FIG. 15 is a diagram comparing the nitrogen-containing carbon material obtained in the example and the nitrogen-containing carbon material obtained in the comparative example, with (HZC) on the horizontal axis and (NZC) on the vertical axis. Indicates. Explanation of symbols
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JP2007539852A JP4766701B2 (ja) | 2005-09-30 | 2006-09-22 | 窒素含有炭素材料およびその製造方法 |
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CN109342472A (zh) * | 2018-12-21 | 2019-02-15 | 四川聚创石墨烯科技有限公司 | 一种碳质材料综合检测方法 |
CN109342484A (zh) * | 2018-12-21 | 2019-02-15 | 四川聚创石墨烯科技有限公司 | 一种掺杂氧化石墨烯属性检测方法 |
CN114824165B (zh) * | 2022-06-30 | 2022-10-14 | 宁德新能源科技有限公司 | 负极极片、电化学装置及电子设备 |
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US8092771B2 (en) | 2007-03-28 | 2012-01-10 | Asahi Kasei Chemicals Corporation | Nitrogen-containing carbon material and process for producing the same |
JP2008239419A (ja) * | 2007-03-28 | 2008-10-09 | Asahi Kasei Chemicals Corp | 水素貯蔵方法および装置 |
US8900754B2 (en) | 2007-03-28 | 2014-12-02 | Asahi Kasei Chemicals Corporation | Electrode, and lithium ion secondary battery, electric double layer capacitor and fuel cell using the same |
JP5291617B2 (ja) * | 2007-03-28 | 2013-09-18 | 旭化成ケミカルズ株式会社 | リチウムイオン二次電池用、電気二重層キャパシタ用又は燃料電池用の電極、並びに、それを用いたリチウムイオン二次電池、電気二重層キャパシタ及び燃料電池 |
JP2010111518A (ja) * | 2008-11-04 | 2010-05-20 | Asahi Kasei Chemicals Corp | 窒素含有炭素材料及びその製造方法 |
JP2011256093A (ja) * | 2010-06-11 | 2011-12-22 | Asahi Kasei Chemicals Corp | 窒素含有炭素材料 |
JP2012216330A (ja) * | 2011-03-31 | 2012-11-08 | Kumamoto Univ | 非水系二次電池用電極材料 |
JP2012221735A (ja) * | 2011-04-08 | 2012-11-12 | Kumamoto Univ | 燃料電池用電極触媒 |
JP2012246185A (ja) * | 2011-05-27 | 2012-12-13 | Asahi Kasei Chemicals Corp | アズルミン酸混合液及びその製造方法 |
JP2014156381A (ja) * | 2013-02-18 | 2014-08-28 | Asahi Kasei Chemicals Corp | 青酸重合物及びその製造方法 |
JP2015157717A (ja) * | 2014-02-21 | 2015-09-03 | 旭化成ケミカルズ株式会社 | 窒素含有炭素材料及びその製造方法、並びに燃料電池用電極 |
WO2015137377A1 (ja) * | 2014-03-11 | 2015-09-17 | 旭化成ケミカルズ株式会社 | 窒素含有炭素材料及びその製造方法、並びに、スラリー、インク、及び燃料電池用電極 |
JPWO2015137377A1 (ja) * | 2014-03-11 | 2017-04-06 | 旭化成株式会社 | 窒素含有炭素材料及びその製造方法、並びに、スラリー、インク、及び燃料電池用電極 |
US10727495B2 (en) | 2014-03-11 | 2020-07-28 | Asahi Kasei Kabushiki Kaisha | Nitrogen-containing carbon material and process for producing nitrogen-containing carbon material, and slurry, ink, and electrode for fuel cell |
JP2021066618A (ja) * | 2019-10-18 | 2021-04-30 | 旭化成株式会社 | 多孔質炭素材料、多孔質炭素材料の製造方法、複合体、複合体の製造方法、リチウム硫黄電池用の正極、及びリチウム硫黄電池 |
JP7328865B2 (ja) | 2019-10-18 | 2023-08-17 | 旭化成株式会社 | 多孔質炭素材料、多孔質炭素材料の製造方法、複合体、複合体の製造方法、リチウム硫黄電池用の正極、及びリチウム硫黄電池 |
Also Published As
Publication number | Publication date |
---|---|
KR20080044313A (ko) | 2008-05-20 |
KR20100116235A (ko) | 2010-10-29 |
EP1939141A1 (en) | 2008-07-02 |
US20090112020A1 (en) | 2009-04-30 |
KR101134339B1 (ko) | 2012-04-09 |
JP4766701B2 (ja) | 2011-09-07 |
EP2527294A1 (en) | 2012-11-28 |
EP2527294B1 (en) | 2013-12-04 |
EP1939141A4 (en) | 2012-03-21 |
CN101277900A (zh) | 2008-10-01 |
JPWO2007043311A1 (ja) | 2009-04-16 |
KR101016586B1 (ko) | 2011-02-22 |
US8034976B2 (en) | 2011-10-11 |
CN101277900B (zh) | 2013-01-23 |
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