JP5469347B2 - リチウム二次電池負極活物質の製造方法 - Google Patents
リチウム二次電池負極活物質の製造方法 Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims description 80
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 76
- 239000007773 negative electrode material Substances 0.000 title claims description 60
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000011148 porous material Substances 0.000 claims description 45
- 239000003575 carbonaceous material Substances 0.000 claims description 22
- 239000000571 coke Substances 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 13
- 239000003245 coal Substances 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 12
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 238000001069 Raman spectroscopy Methods 0.000 claims description 8
- 238000002441 X-ray diffraction Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 239000000295 fuel oil Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000011295 pitch Substances 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007770 graphite material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- -1 nickel metal hydride Chemical class 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-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
- 238000004458 analytical method Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
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- 229910021469 graphitizable carbon Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- 229910021382 natural graphite Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-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
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910005142 Li(HCF2CF2CH2OSO2)2N Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910015044 LiB Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- AQIHMSVIAGNIDM-UHFFFAOYSA-N benzoyl bromide Chemical compound BrC(=O)C1=CC=CC=C1 AQIHMSVIAGNIDM-UHFFFAOYSA-N 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011329 calcined coke Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
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- 238000007561 laser diffraction method Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
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- 238000009829 pitch coating Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
Description
石油系重質油および石炭系重質油のうちの少なくとも1つを原料とする炭素材からなり、X線回折による結晶面の間隔d002が0.340nm以上、C軸方向の結晶子サイズLc(110)が10nm以下、およびラマン分光法による1,360cm-1近傍の回折ピークの1,580cm-1近傍の回折ピークに対する強度比(R=I1360/I1580)が0.8〜1.2であり、表面の全細孔容積が0.02cc/g以上、10nm以下の細孔容積が0.01cc/g〜0.1cc/g、及び細孔面積が50m2/g以上であることを特徴とする、リチウム二次電池負極活物質に関する。
石炭系生コークスから炭素材を得る工程と、
前記炭素材を、不活性ガス雰囲気下、第1の温度で焼成して焼成体を得る工程と、
前記焼成体を酸素雰囲気下、第2の温度で表面酸化処理を行う工程とを具え、
X線回折による結晶面の間隔d002が0.340nm以上、C軸方向の結晶子サイズLc(110)が10nm以下、およびラマン分光法による1,360cm-1近傍の回折ピークの1,580cm-1近傍の回折ピークに対する強度比(R=I1360/I1580)が0.8〜1.2であり、表面の全細孔容積が0.02cc/g以上、10nm以下の細孔容積が0.01cc/g〜0.1cc/g、及び細孔面積が50m2/g以上であるリチウム二次電池負極活物質を製造することを特徴とする、リチウム二次電池負極活物質の製造方法である。
石油系重質油および石炭系重質油のうちの少なくとも1つの原料から炭素材を得る工程と、
前記炭素材を第1の温度で焼成して焼成体を得る工程と、
前記焼成体を酸素雰囲気下、第2の温度で表面酸化処理を行う工程とを具え、
X線回折による結晶面の間隔d002が0.340nm以上、C軸方向の結晶子サイズLc(110)が10nm以下、およびラマン分光法による1,360cm-1近傍の回折ピークの1,580cm-1近傍の回折ピークに対する強度比(R=I1360/I1580)が0.8〜1.2であり、表面の全細孔容積が0.02cc/g以上、10nm以下の細孔容積が0.01cc/g〜0.1cc/g、及び細孔面積が50m2/g以上であるリチウム二次電池負極活物質を製造することを特徴とする、リチウム二次電池負極活物質の製造方法である。
図1に示す簡易セルは、市販のCR2032型コイン電池と同じ構造であり、参照符号10は正極缶を、参照符号12は絶縁パッキンを、参照符号14は正極集電体を、参照符号16は正極を、参照符号18はセパレータを、参照符号20は負極を、参照符号22は負極集電体を、参照符号24は負極缶を、それぞれ示す。
細孔特性は、ユアサアイオニクス製細孔分布測定装置を用いて窒素脱着側等温線をBJH法解析に準拠して測定した。
キノリン不溶分を除去した精製ピッチを用いて、ディレードコーキング法によって製造した塊状コークスを、ジェットミルにて微粉砕、および整粒し、原料の生コークス粉末を得た。次いで、セラミック容器に得られた生コークス粉末を充填し、不活性雰囲気下焼成した。さらに、大気中で表面酸化処理を行った後、篩目開き45μmの超音波振動篩にて粗大粒子を除去することにより負極材料を得た。
表1に示すように、焼成温度、表面酸化処理温度、及び炭素材の種類を変更させ、上記実施例1同様にして負極材料を得るとともに負極電極を得、実施例1と同様にして特性評価を実施した。結果を表1に示す。なお、ピッチコートは、負極炭素材料端面で発生する電解液との副反応を抑制する目的のために実施したものであり、予め加熱した粉体混合機に生コークスとピッチとを配合し、加熱混合により実施した。
表2に示すように、焼成温度、表面酸化処理温度、及び炭素材の種類を変更させ、上記実施例1同様にして負極材料を得るとともに負極電極を得、実施例1と同様にして特性評価を実施した。結果を表2に示す。
12 絶縁パッキン
14 正極集電体
16 正極
18 セパレータ
20 負極
22 負極集電体
24 負極缶
Claims (4)
- リチウム二次電池負極活物質の製造方法であって、
石炭系生コークスから炭素材を得る工程と、
前記炭素材を、不活性ガス雰囲気下、第1の温度で焼成して焼成体を得る工程と、
前記焼成体を酸素雰囲気下、第2の温度で表面酸化処理を行う工程とを具え、
X線回折による結晶面の間隔d002が0.340nm以上、C軸方向の結晶子サイズLc(110)が10nm以下、およびラマン分光法による1,360cm-1近傍の回折ピークの1,580cm-1近傍の回折ピークに対する強度比(R=I1360/I1580)が0.8〜1.2であり、表面の全細孔容積が0.02cc/g以上、10nm以下の細孔容積が0.01cc/g〜0.1cc/g、及び細孔面積が50m2/g以上であるリチウム二次電池負極活物質を製造することを特徴とする、リチウム二次電池負極活物質の製造方法。 - 前記第1の温度は、900℃〜2000℃であることを特徴とする、請求項1に記載のリチウム二次電池負極活物質の製造方法。
- 前記第2の温度は、300℃〜800℃であることを特徴とする、請求項1又は2に記載のリチウム二次電池負極活物質の製造方法。
- 前記酸素雰囲気中の酸素濃度が、10体積%〜20体積%であることを特徴とする、請求項1〜3のいずれか一に記載のリチウム二次電池負極活物質の製造方法。
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