JP2013165057A - リチウム2次電池用負極活物質、その製造方法およびこれを含むリチウム2次電池 - Google Patents
リチウム2次電池用負極活物質、その製造方法およびこれを含むリチウム2次電池 Download PDFInfo
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- JP2013165057A JP2013165057A JP2013001869A JP2013001869A JP2013165057A JP 2013165057 A JP2013165057 A JP 2013165057A JP 2013001869 A JP2013001869 A JP 2013001869A JP 2013001869 A JP2013001869 A JP 2013001869A JP 2013165057 A JP2013165057 A JP 2013165057A
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- silicon oxide
- active material
- negative electrode
- electrode active
- oxide particles
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 63
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 145
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 132
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 129
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 56
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000010703 silicon Substances 0.000 claims abstract description 55
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 230000007423 decrease Effects 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
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- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 6
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- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
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- 229910052712 strontium Inorganic materials 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
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- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- JYVXNLLUYHCIIH-ZCFIWIBFSA-N R-mevalonolactone, (-)- Chemical compound C[C@@]1(O)CCOC(=O)C1 JYVXNLLUYHCIIH-ZCFIWIBFSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920005993 acrylate styrene-butadiene rubber polymer Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229910021475 bohrium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229910021473 hassium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 229940057061 mevalonolactone Drugs 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- GHZRKQCHJFHJPX-UHFFFAOYSA-N oxacycloundecan-2-one Chemical compound O=C1CCCCCCCCCO1 GHZRKQCHJFHJPX-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910021481 rutherfordium Inorganic materials 0.000 description 1
- 229910021477 seaborgium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/049—Manufacturing of an active layer by chemical means
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M4/1315—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. LiCoOxFy
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M4/13915—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. LiCoOxFy
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
【解決手段】本発明の一実施形態によるリチウム2次電池用負極活物質は、シリコン(Si)相および酸素(O)相を有するシリコンオキシド粒子を含み、前記シリコンオキシド粒子は、粒子の表面から粒子の中心に行くほど前記シリコン(Si)相の原子%が減少し、前記酸素(O)相の原子%が増加する濃度勾配を有し、前記シリコンオキシド粒子の表面と前記シリコン(Si)相の原子%が55原子%である深さとの間の距離は、前記シリコンオキシド粒子の粒径の2〜20%である。
【選択図】図1
Description
LiaMnGbO2(上記式中、0.90≦a≦1.8および0.001≦b≦0.1である);LiaMn2GbO4(上記式中、0.90≦a≦1.8および0.001≦b≦0.1である);QO2;QS2;LiQS2;V2O5;LiV2O5;LiTO2;LiNiVO4;Li(3−f)J2(PO4)3(0≦f≦2);Li(3−f)Fe2(PO4)3(0≦f≦2);およびLiFePO4。
前記芳香族炭化水素系有機溶媒は、ベンゼン、フルオロベンゼン、1,2−ジフルオロベンゼン、1,3−ジフルオロベンゼン、1,4−ジフルオロベンゼン、1,2,3−トリフルオロベンゼン、1,2,4−トリフルオロベンゼン、クロロベンゼン、1,2−ジクロロベンゼン、1,3−ジクロロベンゼン、1,4−ジクロロベンゼン、1,2,3−トリクロロベンゼン、1,2,4−トリクロロベンゼン、ヨードベンゼン、1,2−ジヨードベンゼン、1,3−ジヨードベンゼン、1,4−ジヨードベンゼン、1,2,3−トリヨードベンゼン、1,2,4−トリヨードベンゼン、トルエン、フルオロトルエン、2,3−ジフルオロトルエン、2,4−ジフルオロトルエン、2,5−ジフルオロトルエン、2,3,4−トリフルオロトルエン、2,3,5−トリフルオロトルエン、クロロトルエン、2,3−ジクロロトルエン、2,4−ジクロロトルエン、2,5−ジクロロトルエン、2,3,4−トリクロロトルエン、2,3,5−トリクロロトルエン、ヨードトルエン、2,3−ジヨードトルエン、2,4−ジヨードトルエン、2,5−ジヨードトルエン、2,3,4−トリヨードトルエン、2,3,5−トリヨードトルエン、キシレンまたはこれらの組み合わせを使用することができる。
〔実施例1〕
SiO粉末を1000℃およびAr雰囲気下で1時間熱処理を行った。前記熱処理した粉末100gをエタノール40体積%水溶液350mLに分散させた。300rpmの速度に撹拌しながら1ml/分の流量で49体積%HF溶液50mLを添加した。添加完了後、そのまま放置して追加的に30分間反応させた。反応完了後、減圧ろ過装置を利用して5Lの蒸溜水を透過させて粉末を洗浄してシリコンオキシド粒子粉末を得た。
前記49体積%HF水溶液100mLを添加したことを除いては、実施例1と同様な方法でシリコンオキシド粒子粉末を得た。
前記49体積%HF水溶液200mLを添加したことを除いては、実施例1と同様な方法でシリコンオキシド粒子粉末を得た。
前記HF水溶液の添加流量を0.5ml/分にしたことを除いては、実施例1と同様な方法でシリコンオキシド粒子粉末を得た。
前記HF水溶液の添加流量を2.0ml/分にしたことを除いては、実施例1と同様な方法でシリコンオキシド粒子粉末を得た。
SiO粉末を1000℃およびAr雰囲気下で1時間熱処理を行ってシリコンオキシド粒子粉末を得た。
SiO粉末を1000℃およびAr雰囲気下で1時間熱処理を行った。前記熱処理した粉末100gをエタノール40体積%水溶液350mLに分散させた。49体積%HF水溶液50mLを一度に添加した。添加後、30分間反応させた。反応完了後、減圧ろ過装置を利用して5Lの蒸溜水を透過させて粉末を洗浄してシリコンオキシド粒子粉末を得た。
図2A〜図2Cは、実施例1で製造されたシリコンオキシド粒子の透過電子顕微鏡(TEM)写真であり、それぞれ明視野像、暗視野像および高分解能イメージである。
実施例1〜5と比較例1および2で製造された各シリコンオキシド粒子についてX線光電子分光法(XPS)を実施して、シリコン(Si)相および酸素(O)相についてのXPS測定結果から、粒子の表面で粒子の中心に向かう深さに応じたシリコン(Si)相の原子%濃度および酸素(O)相の原子%濃度のグラフを得た。
−分析機器:ESCA 250 spectrometer
−分析チャンバー内の圧力:8*10−10mbar
−使用放射線:monochromatic Alkα
−X線の活性エネルギー:1486.8eV
−分析面積:500μm2
−XPS分析の表面層の大略的な厚さ:約5nm
−深さ条件:Ar+イオンビームスパッタリング3keV)により深さプロファイルを得る。SiO2に対して決定される前記スパッタリング速度は10nm/minである。
実施例1〜5、比較例1および2により製造されたシリコンオキシド粒子粉末をリチウム2次電池用負極活物質を使用して、2016コイン型半電池を製造した。極板組成は、活物質:導電材:バインダー=80:10:10(重量比)にし、導電材にはデンカブラックを使用し、バインダーにはポリイミドを使用し、溶媒としてはN−メチル−2−ピロリドンを使用して、極板を製作した。対極としては、リチウム金属を使用し、中間にセパレ−タ−を挿入して電解液を注入しシーリングして電池を完成させた。電解液としては、EC(エチレンカーボネート)/EMC(エチルメチルカーボネート)/DMC(ジメチルカーボネート)=3/3/4(体積比)を使用し、これにはフルオロエチレンカーボネート(FEC)添加剤が5体積%含まれている。
前記各リチウム2次電池を25℃で、0.5Cにて充放電を50回実施しながらサイクル寿命特性を評価して図10に示し、最初のサイクルに対する効率を計算して下記表2に示した。
112…負極
113…セパレータ
114…正極
120…電池容器
140…封入部材
Claims (21)
- シリコン(Si)相および酸素(O)相を有するシリコンオキシド粒子を含み、
前記シリコンオキシド粒子は、粒子の表面から粒子の中心に行くほど前記シリコン(Si)相の原子%が減少し、前記酸素(O)相の原子%が増加する濃度勾配を有し、
前記シリコンオキシド粒子の表面と前記シリコン(Si)相の原子%が55原子%である深さとの間の距離は、前記シリコンオキシド粒子の粒径の2〜20%である、
リチウム2次電池用負極活物質。 - 前記シリコンオキシド粒子の表面での前記シリコン(Si)相の原子%は、前記シリコンオキシド粒子の表面での前記酸素(O)相の原子%よりも高い、請求項1に記載のリチウム2次電池用負極活物質。
- 前記シリコンオキシド粒子の表面からの深さによる前記シリコン(Si)相の原子%のグラフにおいて、
前記シリコンオキシド粒子の表面から前記シリコン(Si)相の原子%が55原子%である深さまでのシリコン(Si)相の原子%の積分値は、5,000〜40,000nm・原子%である、請求項1に記載のリチウム2次電池用負極活物質。 - 前記シリコンオキシド粒子の表面と前記シリコン(Si)相の原子%が55原子%である深さとの間の距離は、前記シリコンオキシド粒子の粒径の6〜12%である、請求項1に記載のリチウム2次電池用負極活物質。
- 前記シリコンオキシド粒子の表面と前記シリコン(Si)相の原子%が55原子%である深さとの間の距離は、100〜1000nmである、請求項1に記載のリチウム2次電池用負極活物質。
- 前記シリコンオキシド粒子は、結晶性シリコン(Si)および非結晶性シリコン酸化物を含み、
前記結晶性シリコン(Si)の濃度は、前記シリコンオキシド粒子の表面に行くほど増加する、請求項1に記載のリチウム2次電池用負極活物質。 - 前記シリコンオキシド粒子は、空隙を含む、請求項1に記載のリチウム2次電池用負極活物質。
- 前記シリコンオキシド粒子は、10〜500m2/gの比表面積を有する、請求項1に記載のリチウム2次電池用負極活物質。
- 前記シリコンオキシド粒子は、SiOx(xは、0.5〜1.5である)で表される、請求項1に記載のリチウム2次電池用負極活物質。
- 前記負極活物質は、アルカリ金属、アルカリ土類金属、13族〜16族元素、遷移金属、希土類元素およびこれらの組み合わせから選択された一つをさらに含む、請求項1に記載のリチウム2次電池用負極活物質。
- 前記シリコンオキシド粒子は、0.1〜100μmの平均粒径を有する、請求項1に記載のリチウム2次電池用負極活物質。
- 請求項1〜11のいずれか一項に記載の負極活物質を含む負極;
正極活物質を含む正極;および
非水電解質
を含む、リチウム2次電池。 - ケイ素酸化物を不活性雰囲気で熱処理して結晶性シリコン(Si)相およびシリコン酸化物相を含むシリコンオキシド粒子を製造する段階;
前記シリコンオキシド粒子を第1溶媒に分散させて混合溶液を製造する段階;および
前記混合溶液にエッチャントを添加する段階
を含む、リチウム2次電池用負極活物質の製造方法。 - 前記シリコンオキシド粒子は、SiO粉末を含む、請求項13に記載のリチウム2次電池用負極活物質の製造方法。
- 前記熱処理は、800〜1300℃の温度で行われる、請求項13に記載のリチウム2次電池用負極活物質の製造方法。
- 前記第1溶媒は、水溶液を含む、請求項13に記載のリチウム2次電池用負極活物質の製造方法。
- 前記シリコンオキシド粒子および前記エッチャントのモル比は、10:1〜1:10である、請求項13に記載のリチウム2次電池用負極活物質の製造方法。
- 前記エッチャントは、0.05〜5ml/分の流量で前記混合溶液に添加される、請求項13に記載のリチウム2次電池用負極活物質の製造方法。
- 前記エッチャントは、酸または少なくとも一つのF原子を含有する物質を含む、請求項13に記載のリチウム2次電池用負極活物質の製造方法。
- 前記エッチャントは、エッチャント物質および第2溶媒を含むエッチャント溶液を含み、
前記第1溶媒および前記第2溶媒の総体積と前記エッチャント物質の体積との体積比は、1:1〜30:1である、請求項13に記載のリチウム2次電池用負極活物質の製造方法。 - 前記エッチャント溶液は、少なくとも一つのF原子を有し、0.5〜12M濃度を有するエッチャント物質を含む第1溶液、または前記第1溶液のエッチング速度と同一なエッチング速度を有する第2溶液を含む、請求項20に記載のリチウム2次電池用負極活物質の製造方法。
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