JP6889408B2 - 鉄酸化物−炭素複合体粒子粉末及びその製造方法 - Google Patents
鉄酸化物−炭素複合体粒子粉末及びその製造方法 Download PDFInfo
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- JP6889408B2 JP6889408B2 JP2017550380A JP2017550380A JP6889408B2 JP 6889408 B2 JP6889408 B2 JP 6889408B2 JP 2017550380 A JP2017550380 A JP 2017550380A JP 2017550380 A JP2017550380 A JP 2017550380A JP 6889408 B2 JP6889408 B2 JP 6889408B2
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- Prior art keywords
- iron oxide
- carbon
- particle powder
- iron
- particles
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- 239000000843 powder Substances 0.000 title claims description 103
- MAQAUGBCWORAAB-UHFFFAOYSA-N [C+4].[O-2].[Fe+2].[O-2].[O-2] Chemical compound [C+4].[O-2].[Fe+2].[O-2].[O-2] MAQAUGBCWORAAB-UHFFFAOYSA-N 0.000 title claims description 81
- 239000011246 composite particle Substances 0.000 title claims description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000002245 particle Substances 0.000 claims description 136
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 102
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 98
- 229910052799 carbon Inorganic materials 0.000 claims description 60
- 239000002041 carbon nanotube Substances 0.000 claims description 32
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- 229910000859 α-Fe Inorganic materials 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 6
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 claims description 2
- 150000002506 iron compounds Chemical class 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 75
- 235000013980 iron oxide Nutrition 0.000 description 43
- 229910052742 iron Inorganic materials 0.000 description 36
- 239000012071 phase Substances 0.000 description 29
- 239000010953 base metal Substances 0.000 description 26
- 239000002131 composite material Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 16
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- 239000011019 hematite Substances 0.000 description 10
- 229910052595 hematite Inorganic materials 0.000 description 10
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- -1 iron carbides Chemical class 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 238000007600 charging Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229940078494 nickel acetate Drugs 0.000 description 5
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- 238000001694 spray drying Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000007833 carbon precursor Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
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- FLDSMVTWEZKONL-AWEZNQCLSA-N 5,5-dimethyl-N-[(3S)-5-methyl-4-oxo-2,3-dihydro-1,5-benzoxazepin-3-yl]-1,4,7,8-tetrahydrooxepino[4,5-c]pyrazole-3-carboxamide Chemical compound CC1(CC2=C(NN=C2C(=O)N[C@@H]2C(N(C3=C(OC2)C=CC=C3)C)=O)CCO1)C FLDSMVTWEZKONL-AWEZNQCLSA-N 0.000 description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
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- 229920006369 KF polymer Polymers 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
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- 229910000905 alloy phase Inorganic materials 0.000 description 3
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- 238000006243 chemical reaction Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000003915 liquefied petroleum gas Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
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- 239000002608 ionic liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
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- 150000002739 metals Chemical class 0.000 description 2
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- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
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- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical class [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 206010022971 Iron Deficiencies Diseases 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910004008 NLi Inorganic materials 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
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- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical class Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical class [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- 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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
- H01G11/46—Metal oxides
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
- Compounds Of Iron (AREA)
Description
FeO3/2 + 3Li+ + 3e− ⇔ Fe + (3/2)Li2O・・・(1)
試料中の炭素含有量は、炭素・硫黄分析装置EMIA−2200型(株式会社堀場製作所製)を用いて測定した。
X線回折(XRD)装置D8 ADVANCE(BRUKER社製)で測定を行い、リートベルト解析によって試料中の結晶相の同定を行った。炭素はアモルファス相として存在するものと、カーボンナノチューブやグラファイト起因の結晶相として存在するものがあった。炭素以外の結晶相である鉄酸化物、α−Fe、Fe3C、及びNiFe(テトラテーナイト)の重量分率を算出した。100重量%から試料中の炭素含有量を引いた値を前記結晶相の含有量とみなし、得られた重量分率から試料中の各相の含有量を見積もった。最も高い質量分率の鉄酸化物を主相とし、該結晶子サイズを算出した。
レーザー回折散乱式粒度分布測定装置LMS−2000e((株)セイシン企業製)を用いて試料のD50を測定した。
試料の凝集粒子同士が積層しないようにシート上に分散・固定させ、電界放射型走査型電子顕微鏡S−4800((株)日立ハイテクノロジー製)を用いて、該試料を観察した。
粒子粉末の圧縮成型体密度は2.00gの試料を直径20mmφの治具で、2〜20kNの加圧範囲内で、2kNずつ変えて圧粉し、各圧力に対して成型体厚さを測定し、得られた成型体の体積から算出した。前記加圧状態で、体積抵抗率を、抵抗率計測器ロレスタGP(三菱化学アナリテック(株))で4端子法、10Vで計測した。
母材粒子の鉄含有粒子Bを600℃で炭素源Cと120分間接触させた後、400℃で安定化処理を行い(製法X)、鉄酸化物−炭素複合体粒子粉末1を得た。表1に粉体特性を示すように、鉄酸化物粒子の結晶相はヘマタイトとマグネタイトの混相であり、鉄酸化物として31.3重量%含んでおり、α−Feの相は検出されず、残りの68.7重量%は炭素であった。また、図2に示すように、SEM観察でカーボンナノチューブが該鉄酸化物粒子と複合化しているのを確認した。凝集粒子径は16.0μmであった。
母材粒子の鉄含有粒子Bを600℃で炭素源Cと120分間接触させた後、450℃で安定化処理を行い、鉄酸化物−炭素複合体粒子粉末2を得た。
鉄含有粒子AとBとを混合し、圧縮剪断応力の印加を行うことによって母材粒子を作製した。600℃で炭素源Dと60分間接触させた後、400℃で安定化処理を行い、鉄酸化物−炭素複合体粒子粉末3を得た。
鉄含有粒子AとBとを混合し、圧縮剪断応力の印加を行うことによって母材粒子を作製した。600℃−60分間で炭素源Dと接触させた後、450℃で安定化処理を行い、鉄酸化物−炭素複合体粒子粉末4を得た。
母材粒子の鉄含有粒子Bを600℃で炭素源Cと水素との混合ガス(体積比1:1)に60分間接触させた後、400℃で安定化処理を行い、鉄酸化物−炭素複合体粒子粉末5を得た。
母材粒子の鉄含有粒子Bを600℃で炭素源Cと水素との混合ガスに45分間接触させた後、400℃で安定化処理を行い、鉄酸化物−炭素複合体粒子粉末6を得た。
母材粒子の鉄含有粒子Bを600℃で炭素源Cと水素との混合ガスに90分間接触させた後、250〜350℃で安定化処理を行い、鉄酸化物−炭素複合体粒子粉末7を得た。
母材粒子の鉄含有粒子Bを600℃で炭素源Cと水素との混合ガスに80分間接触させた後、350℃で安定化処理を行い、鉄酸化物−炭素複合体粒子粉末8を得た。
鉄含有粒子Aを、ポリビニルアルコール500、完全けん化型(和光純薬工業株式会社製)、及び酢酸ニッケル(関西触媒化学株式会社製)と分散させ、スプレードライで造粒して母材粒子を作製した。650℃で炭素源Dと20分間接触させた後、250℃〜400℃で安定化処理を行い、鉄酸化物−炭素複合体粒子粉末9を得た。
鉄含有粒子A、ポリビニルアルコール及び酢酸ニッケルを水に分散させ、スプレードライで造粒して母材粒子を作製した。650℃で炭素源Dと10分間接触させた後、250℃〜400℃で安定化処理を行い、鉄酸化物−炭素複合体粒子粉末10を得た。
鉄含有粒子A、ポリビニルアルコール及び酢酸ニッケルを水に分散させ、スプレードライで造粒して母材粒子を作製した。650℃で炭素源Dと30分間接触させた後、250℃〜400℃で安定化処理を行い、鉄酸化物−炭素複合体粒子粉末11を得た。図3に示すSEM写真から分かるように、鉄酸化物とカーボンナノチューブが複合化されていた。
鉄含有粒子A、ポリビニルアルコール及び酢酸ニッケルを水に分散させ、スプレードライで造粒して母材粒子を作製した。650℃で炭素源Dと20分間接触させた後、250℃〜400℃で安定化処理を行い、鉄酸化物−炭素複合体粒子粉末12を得た。得られた該試料のXRDによるヘマタイトとマグネタイトの重量比は90.9:9.1であった。
鉄酸化物粒子Aと鉄酸化物粒子Bとを混合し、圧縮剪断応力の印加を行うことによって母材粒子を作製した。600℃で40分間炭素源Dと接触させた後、250℃〜350℃で安定化処理を行い、鉄酸化物−炭素複合体粒子粉末13を得た。XRDにより25重量%のFe3Cの相も確認された。
母材粒子の鉄含有粒子Bを、600℃で120分間炭素源Cと接触させ、鉄酸化物−炭素複合体粒子粉末21を得た。
鉄含有粒子AとBとを混合し、圧縮剪断応力の印加を行うことによって母材粒子を作製した。600℃で60分間炭素源Dと接触させ、鉄酸化物−炭素複合体粒子粉末22を得た。
鉄含有粒子AとBとを混合し、圧縮剪断応力の印加を行うことによって母材粒子を作製した。600℃で45分間炭素源Dと接触させて、鉄酸化物−炭素複合体粒子粉末23を得た。
鉄含有粒子AとBとを混合し、圧縮剪断応力の印加を行うことによって母材粒子を作製した。600℃で45分間炭素源Dと接触させた後、250〜350℃で安定化処理を行い、鉄酸化物−炭素複合体粒子粉末24を得た。
母材粒子の鉄含有粒子Bを、600℃で炭素源Cと水素との混合ガスに70分間接触させた後、350℃で安定化処理を行い、鉄酸化物−炭素複合体粒子粉末25を得た。
鉄含有粒子A、ポリビニルアルコール及び酢酸ニッケルを水に分散させ、スプレードライで造粒して母材粒子を作製した。500℃の熱処理を行い、鉄酸化物−炭素複合体粒子粉末26を得た。得られた該試料のXRDによるヘマタイトとマグネタイトの重量比は91.8:8.2であり、実施例12と同程度の結晶相の重量比であった。
母材粒子の鉄含有粒子Aを、600℃で20分間炭素源Dと接触させた後、250℃〜400℃で安定化処理を行い、鉄酸化物−炭素複合体27を得た。
鉄酸化物−炭素複合体9(実施例9、炭素含有量33.8重量%)および鉄酸化物−炭素複合体10(実施例10、炭素含有量10.8重量%)の粉体抵抗率を比較する為に、鉄酸化物−炭素複合体26(比較例6)にデンカブラックHS−100(デンカ株式会社製)を加えて、各々炭素含有量が約11重量%、約34重量%となる様にメノウ乳鉢で混合し、鉄酸化物−炭素混合物31及び32を作製した(各々、表2の比較例6−1と6−2で、各々炭素含有量10.3と31.8重量%)。圧縮形成体密度に対する体積抵抗率をプロットした結果を図4に示す。鉄酸化物−炭素複合体9及び鉄酸化物−炭素複合体10は、鉄酸化物−炭素混合物31及び鉄酸化物−炭素混合物32に対して、同程度の圧縮成型体密度に対し良好な導電性を示した。
鉄酸化物−炭素複合体12を95質量部に、呉羽化学製KFポリマーL9305(ポリフッ化ビニリデン樹脂(PVDF)を5質量%含有したN−メチルピロリドン(NMP)溶液品)を5質量部として加え、プラネタリーミキサーにて混練し、固形分濃度を約21重量%に調整した後、高純度銅箔上に200μmのドクターブレードを用いて塗布した。塗布後の電極シートを乾燥させた後、ロールプレスを用いて、電極に対し線圧15kN/mmでプレスし、さらにこれを120℃、1時間真空乾燥した後、2032コインセル用15mmφに打ち抜くことによって、電極41を作製した。
鉄酸化物−炭素複合体26を76.1質量部に、呉羽化学製KFポリマーL9305を4.9質量部に、導電剤としてデンカブラックHS−100を19.0質量部にして互いに加え、プラネタリーミキサーにて混練し、固形分濃度を約21重量%に調整した後、高純度銅箔上に200μmのドクターブレードを用いて塗布した。塗布後の電極シートを乾燥させた後、ロールプレスを用いて、電極に対し線圧15kN/mmでプレスし、さらにこれを120℃、1時間真空乾燥した後、2032コインセル用として15mmφに打ち抜くことによって、電極42を作製した。
鉄酸化物−炭素複合体26を75.4質量部に、呉羽化学製KFポリマーL9305を5質量部に、導電剤としてカーボンナノチューブを19.6質量部にして互いに加え、プラネタリーミキサーにて混練し、固形分濃度を約21重量%に調整した後、高純度銅箔上に200μmのドクターブレードを用いて塗布した。塗布後の電極シートを乾燥させた後、ロールプレスを用いて、電極に対し線圧15kN/mmでプレスし、さらにこれを120℃、1時間真空乾燥した後、2032コインセル用として15mmφに打ち抜くことによって、電極43を作製した。
Claims (1)
- 鉄酸化物−炭素複合体粒子粉末の製造方法であって、母材となる鉄化合物粒子粉末に熱処理でカーボンナノチューブを複合化させる工程を含み、得られる鉄酸化物−炭素複合体粒子粉末は、FeOx(0<x≦1.6)で表わされる鉄酸化物粒子粉末の少なくとも1種を含む鉄酸化物−炭素複合体粒子粉末であって、鉄酸化物の含有量が25〜96重量%であり、炭素の一部がカーボンナノチューブであり、α−Feの含有量が3重量%以下である鉄酸化物−炭素複合体粒子粉末の製造方法。
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