CN102709532B - Carbon-silicon composite anode material for preparing lithium ion battery and preparation method for carbon-silicon composite anode material - Google Patents
Carbon-silicon composite anode material for preparing lithium ion battery and preparation method for carbon-silicon composite anode material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011870 silicon-carbon composite anode material Substances 0.000 title abstract 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 122
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 114
- 239000010703 silicon Substances 0.000 claims abstract description 114
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 93
- 239000002131 composite material Substances 0.000 claims abstract description 81
- 239000002245 particle Substances 0.000 claims abstract description 31
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 26
- 239000004005 microsphere Substances 0.000 claims abstract description 16
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 14
- 230000014759 maintenance of location Effects 0.000 claims abstract description 12
- 239000003610 charcoal Substances 0.000 claims description 105
- 239000010406 cathode material Substances 0.000 claims description 65
- 239000003960 organic solvent Substances 0.000 claims description 53
- 239000007788 liquid Substances 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 34
- 239000002585 base Substances 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 26
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 239000006228 supernatant Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000011295 pitch Substances 0.000 claims description 10
- 239000010426 asphalt Substances 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000011294 coal tar pitch Substances 0.000 claims description 9
- 239000011331 needle coke Substances 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- 239000002006 petroleum coke Substances 0.000 claims description 9
- 239000006253 pitch coke Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 239000011863 silicon-based powder Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 239000010405 anode material Substances 0.000 abstract description 3
- 239000011258 core-shell material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- 239000011257 shell material Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- -1 glycol ester Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910021392 nanocarbon Inorganic materials 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000006257 cathode slurry Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000002010 green coke Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910015014 LiNiCoAlO Inorganic materials 0.000 description 1
- 229910013210 LiNiMnCoO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ORJLWVJIEZZMSJ-UHFFFAOYSA-N N=[S+]F.[Li] Chemical compound N=[S+]F.[Li] ORJLWVJIEZZMSJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical compound C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a carbon-silicon composite anode material for preparing a lithium ion battery and a preparation method for the carbon-silicon composite anode material. A carbon source of the composite anode material is an amphiphilic carbon material, and a silicon source of the composite anode material is crystalline silicon with a particle size of 3 to 10nm. The carbon-silicon composite anode material is in form of hard carbon microsphere, wherein the hard carbon microsphere has a core-shell structure taking carbon as a shell and taking silicon as a core, a particle size of 30 to 50nm and sphericity of 50 to 80 percent. The carbon-silicon composite anode material has specific capacity of 503 to 1,028mAh/g and 100-cycle capacity retention ratio of more than or equal to 85 percent. The carbon-silicon composite anode material has high specific capacity; and the prepared lithium ion battery is low in cost, and has the characteristics of high energy density, high multiplying power and high low-temperature performance.
Description
Technical field
The present invention relates to a kind of composite negative pole material for the preparation of lithium ion battery and preparation method thereof, more particularly, the present invention relates to a kind of charcoal silicon composite cathode material for the preparation of lithium ion battery and preparation method thereof, belong to technical field of lithium ion battery negative.
Background technology
Lithium rechargeable battery energy density is large, operating voltage is high, have extended cycle life, pollution-free, security performance good, make it be with a wide range of applications in the many-side such as portable electric appts, electric automobile, extensive energy storage, space technology, national defense industry, become the study hotspot of " 12 " period.
One of key technology of lithium ion battery is the research of anticathode material, thus improves the performance of battery.Graphite material has that good conductivity, degree of crystallinity are high, cheap, fail safe high, is topmost negative material during current business lithium ion battery is produced.But the theoretical capacity of graphite material is the highest only has 372mAh/g.Along with the development of society, the requirement of people to lithium battery energy density is more and more higher, and the capacity of graphite material constrains the further raising of lithium battery energy density to a certain extent.
With the graphite-phase ratio of existing market, silicium cathode in theory specific capacity can improve about 10 times, is about about 4000mAh/g.But what affect by discharge and recharge due to silicon volume changes greatly, electrode structure can be damaged, and therefore charge and discharge circulation life is shorter, be used alone be difficult to realize practical.In order to alleviate the destruction of silicium cathode in Lithium-ion embeding deintercalation process, using other materials to carry out coated to crystalline silicon is a kind of effective mode.Macrocell of Hitachi have developed the composite negative pole material with silicon dioxide and the coated crystalline silicon of charcoal, adopts silicon class material by negative pole, makes trendy battery capacity comparable the said firm original product improve 10%.Consider from the stability of negative material and the requirement of low cost, using Carbon Materials to carry out clad nano silicon grain is a kind of feasible method.The preparation method of carbon silicon composite cathode material mainly comprises thermal decomposition method, sol-gel process, high-energy mechanical ball milling method, chemical vapour deposition technique etc.
Eighties of last century end of the eighties, researcher finds, by the material such as pitch, green coke after red fuming nitric acid (RFNA)/sulfuric acid mixture process, can obtain being dissolved in part organic solvent, can be dissolved in again the material of alkaline aqueous solution.Based on this characteristic, this kind of material is referred to as amphipathic Carbon Materials by researcher.Due to amphipathic Carbon Materials be a kind of keep the precursor such as pitch, green coke solid advantageous while, also have both water-soluble, rich functional group's property, the carbonaceous material of the advantages such as thermosetting.Amphipathic Carbon Materials is preparing the use can avoiding organic solvent in Carbon Materials process, and reduce chemical levels, save oxidative stabilization process, have economy, energy-conservation, the feature of environmental protection, meets the requirement of green chemical industry.
In sum, in order to meet the demand of market to performance of lithium ion battery, promote the overall performance of lithium battery, with amphipathic Carbon Materials for charcoal source developing low-cost, be suitable for the charcoal silicon composite cathode material of volume production, and then development cost is cheap, what energy density was high is negative pole with charcoal silicon composite, and lithium ion battery is significantly.
It is 200510082822.X that State Intellectual Property Office discloses an application number in 2007.1.10, name is called " a kind of there is spherical nucleocapsid carbon-silicon composite material and method for making and purposes " patent of invention.This invention relates to a kind of carbon-silicon composite material, specifically relate to a kind of carbon-silicon composite material with spherical design, nucleocapsid structure, it is average grain diameter 1.2 ~ 53 microns, has the spheric granules of " nucleocapsid " structure, wherein, silicon accounts for 5 ~ 50wt% of particle gross weight, and carbon accounts for 50 ~ 95wt% of particle gross weight; Its kernel part is the spherical carbon granule of average grain diameter 1 ~ 45 micron; This carbon granule for being selected from graphitized intermediate-phase carbon bead, the mixture of a kind of, two kinds or the three kinds materials in hard carbon ball and spheroidization graphite; The thickness of its outer shell is 0.1 ~ 4 micron, and the silicon crystal grain being 10 nanometer ~ 4 micron by carbon and average grain diameter forms.This carbon-silicon composite material has on spherical carbon granule by being coated on inside after superfine silica powder and carbon dust compound pulping, obtained by pyrolysis and chemical vapour deposition (CVD).This material can be directly used in the negative active core-shell material of serondary lithium battery, also can by this material and other existing negative material used in combination, as the negative active core-shell material of serondary lithium battery.
Silicon is coated on the skin of charcoal by this technology, and being unfavorable for the embedding lithium bulking effect cushioning silicon with charcoal, is disadvantageous to the cyclicity of material; This materials'use pyrolysis and chemical meteorology deposition prepare charcoal silicon composite, and equipment is comparatively complicated, and energy consumption is large; This material granule is micron level, is unfavorable for the high-multiplying power discharge of battery.
It is 201110192069.5 that State Intellectual Property Office discloses an application number in 2012.2.15, the patent of invention that name is called " a kind of nano carbon microsphere cathode material of lithium ion cell and preparation method thereof ".This invention relates to a kind of nano carbon microsphere cathode material of lithium ion cell and preparation method thereof, belongs to lithium ion battery negative material technology.Described nano carbon microsphere cathode material of lithium ion cell is by the amphipathic Carbon Materials of coal tar pitch base, petroleum asphalt based amphipathic Carbon Materials, the amphipathic Carbon Materials of intermediate phase pitch-based, the amphipathic Carbon Materials of petroleum coke base, one among the amphipathic Carbon Materials of needle coke base and the amphipathic Carbon Materials of pitch coke base is through obtain solution, the steps such as stirring and rectifying separation are made, Nano carbon prepared by the present invention is micro-to be formed by the self assembly under capillary constraint of amphipathic Carbon Materials, therefore ball uniform particle sizes, good sphericity, as lithium ion battery negative material, there is high reversible capacity and excellent cycle performance.
Above-mentioned material is single carbon cathode material, due to the capacity bottleneck of Carbon Materials, limits the further raising of material specific capacity.
Summary of the invention
The present invention is intended to solve the problems of the prior art, there is provided a kind of and meet the demand of market to performance of lithium ion battery, can promote the energy density of lithium battery, development cost is cheap, have extended cycle life, the charcoal silicon composite cathode material for the preparation of lithium ion battery that specific capacity is large.
Another object of the present invention is to provide a kind of preparation method for the above-mentioned charcoal silicon composite for the preparation of lithium ion battery, and can reach apparatus and process simple, batch consistency is good, is suitable for the object of volume production.
In order to realize foregoing invention object, its concrete technical scheme is as follows:
For the preparation of a charcoal silicon composite cathode material for lithium ion battery, it is characterized in that: the charcoal source of described composite negative pole material is amphipathic Carbon Materials, and silicon source is the crystalline silicon of particle diameter 3 ~ 10nm; Described charcoal silicon composite cathode material is have that charcoal is shell, silicon is the nucleocapsid structure of core, and particle diameter is 30 ~ 50nm, and sphericity is the hard carbon microspheres of 50 ~ 80%; Described charcoal silicon composite cathode material specific capacity is 503 ~ 1028mAh/g, and circulate 100 capability retention >=85%.
Silicon source quality of the present invention is 3 ~ 35% of charcoal silicon composite cathode material gross mass.
Amphipathic Carbon Materials of the present invention is the multiple of one or any ratio in coal tar pitch base, petroleum asphalt based, intermediate phase pitch-based, petroleum coke base, needle coke base and the amphipathic Carbon Materials of pitch coke base.
Crystalline silicon of the present invention is monocrystalline silicon or the polysilicon of conventional selection.
For the preparation of a preparation method for the charcoal silicon composite cathode material of lithium ion battery, it is characterized in that: comprise following processing step:
A, multiple amphipathic Carbon Materials that is a kind of or arbitrary proportion to be joined in deionized water, and regulate the pH value of solution to be 10 ~ 14 with water-soluble alkali, make amphipathic Carbon Materials solution;
B, be the crystalline silicon powder that 1:100 ~ 1000 take that particle diameter is 3 ~ 10nm by the mass ratio of crystalline silicon and amphipathic Carbon Materials solution, join in amphipathic Carbon Materials solution and stir, obtain charcoal silicon mixed liquor;
C, get organic solvent with organic solvent volume than for 1:20 ~ 200 by charcoal silicon mixed liquor, under agitation, mixed liquor is joined in organic solvent, stop after 5 ~ 30min stirring, leave standstill, obtain the mixture of layering, supernatant liquid is the common molten thing of organic solvent and water, and lower floor's liquid is containing amphipathic Carbon Materials/silicon composite;
D, the supernatant liquid of the mixture of layering that step C is obtained and lower floor's fluid separation applications;
E, by the organic solvent evaporate to dryness of lower floor's liquid, obtain black gray expandable powder, be amphipathic Carbon Materials/silicon composite;
F, under an inert atmosphere amphipathic Carbon Materials/silicon composite obtained for step e is carried out charing and process, then naturally cool to room temperature, obtain the charcoal silicon composite cathode material for the preparation of lithium ion battery.
Water-soluble alkali described in steps A of the present invention is conventional potassium hydroxide, NaOH, ethylenediamine, potash, sodium carbonate or the cesium hydroxide selected.
Described in steps A of the present invention, the mass percent concentration of amphipathic Carbon Materials solution is 5 ~ 10%.
Stirring described in step B of the present invention is stirring 30 ~ 180min.
Mixing speed described in step C of the present invention is 300 ~ 1500r/min.
Organic solvent described in step C of the present invention is the low boiling-point and polarity organic solvent that can dissolve each other with water, refers to ethanol, acetone or methyl alcohol.
Supernatant liquid described in step C of the present invention is separated by separatory funnel with lower floor, and after supernatant liquid rectifying is separated, organic solvent can be recycled.
The organic solvent evaporate to dryness of lower floor's liquid is referred to the organic solvent evaporate to dryness of lower floor's liquid at 50 ~ 70 DEG C described in step e of the present invention.
Charing described in step F of the present invention is treated to and rises to 900 ~ 1400 DEG C with the heating rate of 1 ~ 10 DEG C/min and carry out charing process 20 ~ 60min.
The tube furnace that charing process described in step F of the present invention adopts routine to select, box type furnace or converter
Inert atmosphere described in step F of the present invention is conventional nitrogen atmosphere, argon gas atmosphere or the helium atmosphere selected.
The Advantageous Effects that the present invention brings:
1, the low in raw material price of the amphipathic Carbon Materials of the present invention's employing, abundance, is easy to realize large-scale industrial and produces;
2, the present invention adopts the multiple of one or any ratio in coal tar pitch base, petroleum asphalt based, intermediate phase pitch-based, petroleum coke base, needle coke base and pitch coke base to make amphipathic Carbon Materials, this preparation process does not need to add any surfactant, silicon nanoparticle can be made dispersed, and decrease the use of organic solvent to a certain extent, synthesis technique is made to become simple, and environmental protection;
3, synthesis technique of the present invention and the equipment of use simple, compared with the synthetic method of traditional charcoal silicon composite as chemical vapour deposition technique etc., production cost is more cheap;
4, the charcoal silicon composite cathode material that prepared by the present invention is formed by the self assembly under capillary constraint of amphipathic Carbon Materials, and therefore silicon is evenly distributed in charcoal, Stability Analysis of Structures;
5, the present invention selects the silicon and amphipathic Carbon Materials compound with more height ratio capacity, and then prepare charcoal nano silicon particles, the specific capacity of further raising material, the charcoal silicon composite cathode material specific capacity prepared is high, 503 ~ 1028mAh/g can be reached, and circulation 100 capability retentions are still not less than 85%;
6, not only cost is low for the lithium ion battery adopting charcoal silicon composite cathode material of the present invention to prepare, and there is high-energy-density feature, with the 1Ah battery that this material is prepared for negative pole, than reducing 5 ~ 10% with the 1Ah battery volume of native graphite (specific capacity 340mAh/g) negative pole, Mass lost 5 ~ 20%; The 1Ah battery volume being negative pole than nanometer anode material in application number 201110122069.5 patent reduces 3 ~ 8%, Mass lost 4 ~ 15%;
7, the lithium ion battery adopting charcoal silicon composite cathode material of the present invention to prepare has excellent multiplying power property, good cryogenic property;
8, preparation method provided by the invention and technological parameter system wherein can make apparatus and process simple, and batch consistency is good, is suitable for volume production.
Embodiment
embodiment 1
For the preparation of a charcoal silicon composite cathode material for lithium ion battery, the charcoal source of described composite negative pole material is amphipathic Carbon Materials, and silicon source is the crystalline silicon of particle diameter 3nm; Described charcoal silicon composite cathode material is have that charcoal is shell, silicon is the nucleocapsid structure of core, and particle diameter is 30nm, and sphericity is the hard carbon microspheres of 50%; Described charcoal silicon composite cathode material specific capacity is 503mAh/g, and circulate 100 capability retentions 85%.
embodiment 2
For the preparation of a charcoal silicon composite cathode material for lithium ion battery, the charcoal source of described composite negative pole material is amphipathic Carbon Materials, and silicon source is the crystalline silicon of particle diameter 10nm; Described charcoal silicon composite cathode material is have that charcoal is shell, silicon is the nucleocapsid structure of core, and particle diameter is 50nm, and sphericity is the hard carbon microspheres of 80%; Described charcoal silicon composite cathode material specific capacity is 1028mAh/g, and circulate 100 capability retentions 95%.
embodiment 3
For the preparation of a charcoal silicon composite cathode material for lithium ion battery, the charcoal source of described composite negative pole material is amphipathic Carbon Materials, and silicon source is the crystalline silicon of particle diameter 6.5nm; Described charcoal silicon composite cathode material is have that charcoal is shell, silicon is the nucleocapsid structure of core, and particle diameter is 40nm, and sphericity is the hard carbon microspheres of 65%; Described charcoal silicon composite cathode material specific capacity is 765.5mAh/g, and circulate 100 capability retentions 90%.
embodiment 4
For the preparation of a charcoal silicon composite cathode material for lithium ion battery, the charcoal source of described composite negative pole material is amphipathic Carbon Materials, and silicon source is the crystalline silicon of particle diameter 8nm; Described charcoal silicon composite cathode material is have that charcoal is shell, silicon is the nucleocapsid structure of core, and particle diameter is 32nm, and sphericity is the hard carbon microspheres of 73%; Described charcoal silicon composite cathode material specific capacity is 1001mAh/g, and circulate 100 capability retentions 93%.
embodiment 5
For the preparation of a charcoal silicon composite cathode material for lithium ion battery, the charcoal source of described composite negative pole material is amphipathic Carbon Materials, and silicon source is the crystalline silicon of particle diameter 3nm; Described charcoal silicon composite cathode material is have that charcoal is shell, silicon is the nucleocapsid structure of core, and particle diameter is 30nm, and sphericity is the hard carbon microspheres of 50%; Described charcoal silicon composite cathode material specific capacity is 503mAh/g, and circulate 100 capability retentions 85%.
Described silicon source quality of the present invention is 3% of charcoal silicon composite cathode material gross mass.
Described amphipathic Carbon Materials is the multiple of one or any ratio in coal tar pitch base, petroleum asphalt based, intermediate phase pitch-based, petroleum coke base, needle coke base and the amphipathic Carbon Materials of pitch coke base.
embodiment 6
For the preparation of a charcoal silicon composite cathode material for lithium ion battery, the charcoal source of described composite negative pole material is amphipathic Carbon Materials, and silicon source is the crystalline silicon of particle diameter 10nm; Described charcoal silicon composite cathode material is have that charcoal is shell, silicon is the nucleocapsid structure of core, and particle diameter is 50nm, and sphericity is the hard carbon microspheres of 80%; Described charcoal silicon composite cathode material specific capacity is 1028mAh/g, and circulate 100 capability retentions 95%.
Described silicon source quality of the present invention is 35% of charcoal silicon composite cathode material gross mass.
Described amphipathic Carbon Materials is the multiple of one or any ratio in coal tar pitch base, petroleum asphalt based, intermediate phase pitch-based, petroleum coke base, needle coke base and the amphipathic Carbon Materials of pitch coke base.
embodiment 7
For the preparation of a charcoal silicon composite cathode material for lithium ion battery, the charcoal source of described composite negative pole material is amphipathic Carbon Materials, and silicon source is the crystalline silicon of particle diameter 6.5nm; Described charcoal silicon composite cathode material is have that charcoal is shell, silicon is the nucleocapsid structure of core, and particle diameter is 40nm, and sphericity is the hard carbon microspheres of 65%; Described charcoal silicon composite cathode material specific capacity is 765.5mAh/g, and circulate 100 capability retentions 90%.
Described silicon source quality of the present invention is 19% of charcoal silicon composite cathode material gross mass.
Described amphipathic Carbon Materials is the multiple of one or any ratio in coal tar pitch base, petroleum asphalt based, intermediate phase pitch-based, petroleum coke base, needle coke base and the amphipathic Carbon Materials of pitch coke base.
embodiment 8
For the preparation of a charcoal silicon composite cathode material for lithium ion battery, the charcoal source of described composite negative pole material is amphipathic Carbon Materials, and silicon source is the crystalline silicon of particle diameter 8nm; Described charcoal silicon composite cathode material is have that charcoal is shell, silicon is the nucleocapsid structure of core, and particle diameter is 32nm, and sphericity is the hard carbon microspheres of 73%; Described charcoal silicon composite cathode material specific capacity is 1001mAh/g, and circulate 100 capability retentions 93%.
Described silicon source quality of the present invention is 21% of charcoal silicon composite cathode material gross mass.
Described amphipathic Carbon Materials is the multiple of one or any ratio in coal tar pitch base, petroleum asphalt based, intermediate phase pitch-based, petroleum coke base, needle coke base and the amphipathic Carbon Materials of pitch coke base.
embodiment 9
For the preparation of a preparation method for the charcoal silicon composite cathode material of lithium ion battery, comprise following processing step:
A, multiple amphipathic Carbon Materials that is a kind of or arbitrary proportion to be joined in deionized water, and regulate the pH value of solution to be 10 with water-soluble alkali, make amphipathic Carbon Materials solution;
B, be the crystalline silicon powder that 1:100 takes that particle diameter is 3nm by the mass ratio of crystalline silicon and amphipathic Carbon Materials solution, join in amphipathic Carbon Materials solution and stir, obtain charcoal silicon mixed liquor;
C, get organic solvent by charcoal silicon mixed liquor and organic solvent volume than for 1:20, under agitation, mixed liquor is joined in organic solvent, stop after 5min stirring, leave standstill, obtain the mixture of layering, supernatant liquid is the common molten thing of organic solvent and water, and lower floor's liquid is containing amphipathic Carbon Materials/silicon composite;
D, the supernatant liquid of the mixture of layering that step C is obtained and lower floor's fluid separation applications;
E, by the organic solvent evaporate to dryness of lower floor's liquid, obtain black gray expandable powder, be amphipathic Carbon Materials/silicon composite;
F, under an inert atmosphere amphipathic Carbon Materials/silicon composite obtained for step e is carried out charing and process, then naturally cool to room temperature, obtain the charcoal silicon composite cathode material for the preparation of lithium ion battery.
embodiment 10
For the preparation of a preparation method for the charcoal silicon composite cathode material of lithium ion battery, comprise following processing step:
A, multiple amphipathic Carbon Materials that is a kind of or arbitrary proportion to be joined in deionized water, and regulate the pH value of solution to be 14 with water-soluble alkali, make amphipathic Carbon Materials solution;
B, be the crystalline silicon powder that 1:1000 takes that particle diameter is 10nm by the mass ratio of crystalline silicon and amphipathic Carbon Materials solution, join in amphipathic Carbon Materials solution and stir, obtain charcoal silicon mixed liquor;
C, get organic solvent by charcoal silicon mixed liquor and organic solvent volume than for 1:200, under agitation, mixed liquor is joined in organic solvent, stop after 30min stirring, leave standstill, obtain the mixture of layering, supernatant liquid is the common molten thing of organic solvent and water, and lower floor's liquid is containing amphipathic Carbon Materials/silicon composite;
D, the supernatant liquid of the mixture of layering that step C is obtained and lower floor's fluid separation applications;
E, by the organic solvent evaporate to dryness of lower floor's liquid, obtain black gray expandable powder, be amphipathic Carbon Materials/silicon composite;
F, under an inert atmosphere amphipathic Carbon Materials/silicon composite obtained for step e is carried out charing and process, then naturally cool to room temperature, obtain the charcoal silicon composite cathode material for the preparation of lithium ion battery.
embodiment 11
For the preparation of a preparation method for the charcoal silicon composite cathode material of lithium ion battery, comprise following processing step:
A, multiple amphipathic Carbon Materials that is a kind of or arbitrary proportion to be joined in deionized water, and regulate the pH value of solution to be 12 with water-soluble alkali, make amphipathic Carbon Materials solution;
B, be the crystalline silicon powder that 1:550 takes that particle diameter is 6.5nm by the mass ratio of crystalline silicon and amphipathic Carbon Materials solution, join in amphipathic Carbon Materials solution and stir, obtain charcoal silicon mixed liquor;
C, get organic solvent by charcoal silicon mixed liquor and organic solvent volume than for 1:110, under agitation, mixed liquor is joined in organic solvent, stop after 17.5min stirring, leave standstill, obtain the mixture of layering, supernatant liquid is the common molten thing of organic solvent and water, and lower floor's liquid is containing amphipathic Carbon Materials/silicon composite;
D, the supernatant liquid of the mixture of layering that step C is obtained and lower floor's fluid separation applications;
E, by the organic solvent evaporate to dryness of lower floor's liquid, obtain black gray expandable powder, be amphipathic Carbon Materials/silicon composite;
F, under an inert atmosphere amphipathic Carbon Materials/silicon composite obtained for step e is carried out charing and process, then naturally cool to room temperature, obtain the charcoal silicon composite cathode material for the preparation of lithium ion battery.
embodiment 12
For the preparation of a preparation method for the charcoal silicon composite cathode material of lithium ion battery, comprise following processing step:
A, multiple amphipathic Carbon Materials that is a kind of or arbitrary proportion to be joined in deionized water, and regulate the pH value of solution to be 13 with water-soluble alkali, make amphipathic Carbon Materials solution;
B, be the crystalline silicon powder that 1:600 takes that particle diameter is 7nm by the mass ratio of crystalline silicon and amphipathic Carbon Materials solution, join in amphipathic Carbon Materials solution and stir, obtain charcoal silicon mixed liquor;
C, get organic solvent by charcoal silicon mixed liquor and organic solvent volume than for 1:180, under agitation, mixed liquor is joined in organic solvent, stop after 10min stirring, leave standstill, obtain the mixture of layering, supernatant liquid is the common molten thing of organic solvent and water, and lower floor's liquid is containing amphipathic Carbon Materials/silicon composite;
D, the supernatant liquid of the mixture of layering that step C is obtained and lower floor's fluid separation applications;
E, by the organic solvent evaporate to dryness of lower floor's liquid, obtain black gray expandable powder, be amphipathic Carbon Materials/silicon composite;
F, under an inert atmosphere amphipathic Carbon Materials/silicon composite obtained for step e is carried out charing and process, then naturally cool to room temperature, obtain the charcoal silicon composite cathode material for the preparation of lithium ion battery.
embodiment 13
On the basis of embodiment 9 ~ 12:
The mass percent concentration of described amphipathic Carbon Materials solution is 5% in step.
Stirring described is in stepb for stirring 30min.
Mixing speed described in step C is 300r/min.
Organic solvent described in step C is ethanol, acetone or methyl alcohol.
The organic solvent evaporate to dryness of lower floor's liquid is referred to the organic solvent evaporate to dryness of lower floor's liquid at 50 DEG C described in step e.
Charing described in step F be treated to the heating rate of 1 DEG C/min rise to 900 DEG C carry out charing process 20min.
embodiment 14
On the basis of embodiment 9 ~ 12:
The mass percent concentration of described amphipathic Carbon Materials solution is 10% in step.
Stirring described is in stepb for stirring 180min.
Mixing speed described in step C is 1500r/min.
Organic solvent described in step C is ethanol, acetone or methyl alcohol.
The organic solvent evaporate to dryness of lower floor's liquid is referred to the organic solvent evaporate to dryness of lower floor's liquid at 70 DEG C described in step e.
Charing described in step F be treated to the heating rate of 10 DEG C/min rise to 1400 DEG C carry out charing process 60min.
embodiment 15
On the basis of embodiment 9 ~ 12:
The mass percent concentration of described amphipathic Carbon Materials solution is 7.5% in step.
Stirring described is in stepb for stirring 105min.
Mixing speed described in step C is 900r/min.
Organic solvent described in step C is ethanol, acetone or methyl alcohol.
The organic solvent evaporate to dryness of lower floor's liquid is referred to the organic solvent evaporate to dryness of lower floor's liquid at 60 DEG C described in step e.
Charing described in step F be treated to the heating rate of 5.5 DEG C/min rise to 1150 DEG C carry out charing process 40min.
embodiment 16
On the basis of embodiment 9 ~ 12:
The mass percent concentration of described amphipathic Carbon Materials solution is 9% in step.
Stirring described is in stepb for stirring 170min.
Mixing speed described in step C is 1100r/min.
Organic solvent described in step C is ethanol, acetone or methyl alcohol.
The organic solvent evaporate to dryness of lower floor's liquid is referred to the organic solvent evaporate to dryness of lower floor's liquid at 65 DEG C described in step e.
Charing described in step F be treated to the heating rate of 7.5 DEG C/min rise to 1300 DEG C carry out charing process 55min.
embodiment 17
Amphipathic Carbon Materials preparation method (common process):
With coal tar pitch, petroleum asphalt, mesophase pitch, petroleum coke, needle coke and pitch coke for raw material, general known preparation method is adopted to prepare amphipathic Carbon Materials, concrete preparation process is as follows: by nitration mixture (with concentration be 65% red fuming nitric acid (RFNA) and concentration be 98% concentrated sulfuric acid volume ratio for 2:8 ~ 5:5 preparation) be heated to 50 ~ 100 DEG C, raw material is added by raw material and nitration mixture mass ratio 1:20 ~ 1:1, reaction 1 ~ 5h, reactant is poured into and dilutes 10 times of cessation reactions with ionized water, filter, gained filter cake spends deionized water to neutral; The solid matter obtained is joined in water-soluble alkali solution, to stir 1-5h at 50 ~ 100 DEG C, filter, keep the pH value of solution to be greater than 12 all the time in the process; Collect filtrate, in the filtrate obtained, drip water soluble acid (sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid etc.), regulate its pH value to 1, now have precipitation to generate; Centrifugation, spends deionized water to neutral, dries, obtain amphipathic Carbon Materials by the sediment obtained.
embodiment 18
Preparation method's (common process) of lithium ion battery:
A, namely charcoal silicon composite cathode material and conductive agent, binding agent, nonaqueous solvents mixing and stirring are obtained the charcoal silicon composite cathode slurry for the preparation of lithium ion battery; Namely positive active material and conductive agent, binding agent, nonaqueous solvents mixing and stirring are obtained the anode sizing agent for the preparation of lithium ion battery;
B, be evenly coated on two collectors respectively by charcoal silicon composite cathode slurry and anode sizing agent, dry, roll-in, obtains charcoal silicon composite cathode pole piece and anode pole piece.
C, positive pole, barrier film and negative pole are replaced lamination after, at pressure 0.2MPa, under temperature 60 C, hot pressing 1min, makes pole piece;
D, heat-sealing: adopt method known in those skilled in the art, put into aluminum plastic film bag by step pole piece and seal, being prepared into battery core;
E, once to change into: adopt method known in those skilled in the art, adopt 0.05C electric current that above-mentioned battery core is charged to 70%SOC state;
F, secondary heat treatment: be 0.2MPa at pressure by the battery core after once changing into, temperature is pressurization baking 3h at 60 DEG C, obtains lithium rechargeable battery.
G, partial volume: the method adopting those skilled in the art to know altogether tests out the capacity (rated capacity is 1Ah) of battery.
The consumption of the charcoal silicon composite cathode material described in step G and conductive agent, binding agent, nonaqueous solvents is counted with parts by weight:
Charcoal silicon composite cathode material 30 ~ 60 parts
Conductive agent 0.5 ~ 5 part
Binding agent 0.5 ~ 5 part
Nonaqueous solvents 30 ~ 69 parts.
The consumption of the positive active material described in step G and conductive agent, binding agent, nonaqueous solvents is counted with parts by weight:
Positive active material 30 ~ 60 parts
Conductive agent 0.5 ~ 5 part
Binding agent 0.5 ~ 5 part
Nonaqueous solvents 30 ~ 69 parts.
Described conductive agent is: a kind of or arbitrary proportion in carbon black, acetylene black, carbon fiber, flake graphite, carbon nano-tube several, preferred acetylene black and carbon nano-tube.
Described binding agent is: a kind of or arbitrary proportion in polyethylene glycol oxide, polyacrylonitrile, polyvinyl chloride, polystyrene, poly-ethyl acetate, polyvinylpyrrolidone, polymethyl methacrylate, polyacrylic acid glycol ester, Kynoar, polyhexafluoropropylene-vinylidene, poly-divinyl sulfide and their copolymer, derivative several, preferred Kynoar, polyhexafluoropropylene-vinylidene.
Described nonaqueous solvents is: one or more in nitrogen methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and alcohols, preferred nitrogen methyl pyrrolidone.
Positive active material in step G is cobalt acid lithium (LiCoO
2), LiFePO 4 (LiFePO
4), lithium nickelate (LiNiO
2), LiMn2O4 (LiMn
2o
4), ternary material (LiNiMnCoO
2or LiNiCoAlO
2) in one or more.
Collector described in step H is electrolytic copper foil or rolled copper foil, and thickness is 8 ~ 20 μm.
The thickness of the anode sizing agent on a current collector of the coating described in step H is 50 ~ 200 μm.
In step H, charcoal silicon composite cathode material coating thickness is 30-100 μm
Membrane layer of the present invention is polypropylene micro-porous film (PP), microporous polyethylene film (PE), glass mat or PP/PE/PP, and preferably, described barrier film is PP/PE/PP.
Electrolyte of the present invention contains lithium salts and nonaqueous solvents, and described lithium salts is lithium hexafluoro phosphate (LiPF
6), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), lithium perchlorate (LiClO
4), trifluoromethyl sulfonic acid lithium (EC), perfluoro butyl Sulfonic Lithium (LiCF
3sO
3), fluoro sulfimide lithium (LiN(CF
3sO
2)
2), a kind of or arbitrary proportion in lithium chloride (LiCl) and lithium iodide (LiI) several; Described nonaqueous solvents can be vinyl carbonate (EC), propylene carbonate (PC), gamma-butyrolacton (γ-GBL), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DMC) N-METHYLFORMAMIDE (DMF), N-N dimethylacetylamide (DMAC), acetonitrile (ACN), methyl-sulfoxide (DMSO) and other is fluorine-containing, a kind of or arbitrary proportion in the ring-type organic ester of sulfur-bearing or unsaturated bond several.
Claims (1)
1. for the preparation of a charcoal silicon composite cathode material for lithium ion battery, it is characterized in that: the charcoal source of described composite negative pole material is amphipathic Carbon Materials, and silicon source is the crystalline silicon of particle diameter 3 ~ 10nm; Described charcoal silicon composite cathode material is have the hard carbon microspheres that charcoal is shell, silicon is the nucleocapsid structure of core, and the particle diameter of described hard carbon microspheres is 30 ~ 50nm, and sphericity is 50 ~ 80%; Described charcoal silicon composite cathode material specific capacity is 503 ~ 1028mAh/g, and circulate 100 capability retention >=85%; Described silicon source quality is 3 ~ 35% of charcoal silicon composite cathode material gross mass; Described amphipathic Carbon Materials is the multiple of one or any ratio in coal tar pitch base, petroleum asphalt based, intermediate phase pitch-based, petroleum coke base, needle coke base and the amphipathic Carbon Materials of pitch coke base;
Described charcoal silicon composite cathode material is obtained by following methods:
A, multiple amphipathic Carbon Materials that is a kind of or arbitrary proportion to be joined in deionized water, and regulate the pH value of solution to be 10 ~ 14 with water-soluble alkali, make amphipathic Carbon Materials solution; The mass percent concentration of described amphipathic Carbon Materials solution is 5 ~ 10%;
B, be the crystalline silicon powder that 1:100 ~ 1000 take that particle diameter is 3 ~ 10nm by the mass ratio of crystalline silicon and amphipathic Carbon Materials solution, join in amphipathic Carbon Materials solution and stir 30 ~ 180min, obtain charcoal silicon mixed liquor;
C, get organic solvent with organic solvent volume than for 1:20 ~ 200 by charcoal silicon mixed liquor, under agitation, mixed liquor is joined in organic solvent, stop after 5 ~ 30min stirring, leave standstill, obtain the mixture of layering, supernatant liquid is the common molten thing of organic solvent and water, and lower floor's liquid is containing amphipathic Carbon Materials/silicon composite; Described mixing speed is 300 ~ 1500r/min; Described organic solvent is ethanol, acetone or methyl alcohol;
D, the supernatant liquid of the mixture of layering that step C is obtained and lower floor's fluid separation applications;
E, by the organic solvent evaporate to dryness of lower floor's liquid, obtain black gray expandable powder, be amphipathic Carbon Materials/silicon composite; Described refers to the organic solvent evaporate to dryness of lower floor's liquid the organic solvent evaporate to dryness of lower floor's liquid at 50 ~ 70 DEG C;
F, under an inert atmosphere amphipathic Carbon Materials/silicon composite obtained for step e is carried out charing and process, then naturally cool to room temperature, obtain the charcoal silicon composite cathode material for the preparation of lithium ion battery; Described charing is treated to and rises to 900 ~ 1400 DEG C with the heating rate of 1 ~ 10 DEG C/min and carry out charing process 20 ~ 60min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210178277.4A CN102709532B (en) | 2012-06-01 | 2012-06-01 | Carbon-silicon composite anode material for preparing lithium ion battery and preparation method for carbon-silicon composite anode material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210178277.4A CN102709532B (en) | 2012-06-01 | 2012-06-01 | Carbon-silicon composite anode material for preparing lithium ion battery and preparation method for carbon-silicon composite anode material |
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| Publication Number | Publication Date |
|---|---|
| CN102709532A CN102709532A (en) | 2012-10-03 |
| CN102709532B true CN102709532B (en) | 2015-06-03 |
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