CN102709532A - 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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- CN102709532A CN102709532A CN2012101782774A CN201210178277A CN102709532A CN 102709532 A CN102709532 A CN 102709532A CN 2012101782774 A CN2012101782774 A CN 2012101782774A CN 201210178277 A CN201210178277 A CN 201210178277A CN 102709532 A CN102709532 A CN 102709532A
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- charcoal
- silicon composite
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- wood
- lithium ion
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 55
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 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 148
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 140
- 239000010703 silicon Substances 0.000 claims abstract description 140
- 239000002131 composite material Substances 0.000 claims abstract description 107
- 239000002245 particle Substances 0.000 claims abstract description 30
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 239000004005 microsphere Substances 0.000 claims abstract description 15
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 13
- 230000014759 maintenance of location Effects 0.000 claims abstract description 12
- 239000003610 charcoal Substances 0.000 claims description 205
- 239000000463 material Substances 0.000 claims description 131
- 239000002994 raw material Substances 0.000 claims description 94
- 239000010406 cathode material Substances 0.000 claims description 70
- 239000003960 organic solvent Substances 0.000 claims description 53
- 239000002585 base Substances 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 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
- 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
- 239000011302 mesophase 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
- 238000000926 separation method Methods 0.000 claims description 8
- 238000010438 heat treatment 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
- 238000012545 processing Methods 0.000 claims description 6
- 239000011863 silicon-based powder Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 abstract 2
- 239000011258 core-shell material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- 239000002904 solvent 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
- 239000002153 silicon-carbon composite material Substances 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
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000007770 graphite material Substances 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 229910021392 nanocarbon Inorganic materials 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 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
- 239000006182 cathode active material Substances 0.000 description 2
- 239000006257 cathode slurry Substances 0.000 description 2
- 238000006243 chemical reaction 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
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 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
- 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
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 239000011295 pitch Substances 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
- 238000011160 research Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical compound C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 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
- ZPOLNCDBPYJDSE-UHFFFAOYSA-N 3-[4-[bis(2-chloroethyl)amino]phenyl]-2-formamidopropanoic acid Chemical compound O=CNC(C(=O)O)CC1=CC=C(N(CCCl)CCCl)C=C1 ZPOLNCDBPYJDSE-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
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
- 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
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 238000013461 design Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 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
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 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
- 238000005087 graphitization Methods 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
- 238000009776 industrial production Methods 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
- BMANCNNUKXPJTN-UHFFFAOYSA-N lithium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BMANCNNUKXPJTN-UHFFFAOYSA-N 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
- 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
- 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
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 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
- 239000007787 solid Substances 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
- 238000005406 washing Methods 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 that is used to prepare lithium ion battery and preparation method thereof; More particularly; The present invention relates to a kind of charcoal silicon composite cathode material that is used to prepare lithium ion battery and preparation method thereof, belong to the lithium ion battery negative material technical field.
Background technology
The lithium rechargeable battery energy density is big, operating voltage is high, have extended cycle life, pollution-free, security performance good; It is with a wide range of applications in many-sides such as portable electric appts, electric automobile, extensive energy storage, space technology, national defense industry, becomes the research focus during " 12 ".
One of key technology of lithium ion battery is the research of anticathode material, thereby improves the performance of battery.Graphite material has characteristics such as good conductivity, degree of crystallinity are high, cheap, fail safe height, be commercial at present produce with lithium ion battery in topmost negative material.Has only 372mAh/g but the theoretical capacity of graphite material is the highest.Along with the development of society, people require increasingly highly to the lithium battery energy density, and the capacity of graphite material has restricted the further raising of lithium battery energy density to a certain extent.
Compare with the graphite of existing marketization, silicium cathode specific capacity in theory can improve about 10 times, is about about 4000mAh/g.But because that the silicon volume is discharged and recharged the variation that influences is bigger, electrode structure can be damaged, so charge and discharge circulation life is shorter, uses separately to be difficult to realize practicability.Embed the destruction of taking off silicium cathode in the embedding process in order to alleviate lithium ion, using other materials that crystalline silicon is coated is a kind of effective and efficient manner.Macrocell of Hitachi has developed the composite negative pole material that coats crystalline silicon with silicon dioxide and charcoal, adopts silicon class material through negative pole, makes the comparable the said firm of trendy battery capacity original product improve 10%.Consider that from the stability of negative material and requirement cheaply using the raw material of wood-charcoal material to come the 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, the researcher finds, after materials such as pitch, green coke are handled through red fuming nitric acid (RFNA)/sulfuric acid mixture, can obtain being dissolved in the part organic solvent, can be dissolved in the material of alkaline aqueous solution again.Based on this characteristic, the researcher is referred to as amphipathic raw material of wood-charcoal material with this type material.Because amphipathic raw material of wood-charcoal material is a kind of when keeping the intrinsic advantages of precursor such as pitch, green coke, also had both water-soluble, rich functional group's property, the carbonaceous material of advantages such as thermosetting.Amphipathic raw material of wood-charcoal material is the use that in preparation raw material of wood-charcoal material process, can avoid organic solvent, reduces the chemical reagent consumption, saves the oxidative stabilization process, has economy, and energy-conservation, the characteristics of environmental protection meet the requirement of green chemical industry.
In sum; In order to satisfy the demand of market to the lithium ion battery performance; Promoting the overall performance of lithium battery, is charcoal source developing low-cost with amphipathic raw material of wood-charcoal material, is suitable for the charcoal silicon composite cathode material of volume production; And then development cost is cheap, and what energy density was high is that the lithium ion battery of negative pole is very significant with the charcoal silicon composite.
It is 200510082822.X that State Intellectual Property Office discloses an application number in 2007.1.10, and name is called the patent of invention of " a kind of carbon-silicon composite material and method for making and purposes with spherical nucleocapsid ".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; The spheric granules that it is 1.2～53 microns of average grain diameters, have " nucleocapsid " structure; Wherein, silicon accounts for 5～50wt% of particle gross weight, and carbon accounts for 50～95wt% of particle gross weight; Its kernel partly is the carbon granule of the sphere of 1～45 micron of average grain diameter; This carbon granule is for being selected from graphitization mesocarbon bead, a kind of, two kinds or three kinds of mixtures of material in hard carbon ball and the spheroidization graphite; The thickness of its outer shell is 0.1～4 micron, is that the silicon crystal grain of 10 nanometers～4 micron is formed by carbon and average grain diameter.This carbon-silicon composite material is to have on the spherical carbon granule being coated on inside behind superfine silica powder and the compound pulping of carbon dust, obtains through pyrolysis and chemical vapour deposition (CVD).This material can directly be used for the secondary lithium battery cathode active material, also can the existing negative material of this material and other be mixed use, as the secondary lithium battery cathode active material.
This technology is coated on the skin of charcoal with silicon, is unfavorable for cushioning with charcoal the embedding lithium bulking effect of silicon, is disadvantageous to the cyclicity of material; This material uses pyrolysis and chemical meteorology deposition to prepare the charcoal silicon composite, and equipment is comparatively complicated, and energy consumption is big; This material granule is a 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, and name is called the patent of invention of " a kind of lithium ion cell nano carbon microspheres negative material and preparation method thereof ".This invention relates to a kind of lithium ion cell nano carbon microspheres negative material and preparation method thereof, belongs to the lithium ion battery negative material technology.Described lithium ion cell nano carbon microspheres negative material is processed by the steps such as a kind of process obtain solution, stirring and rectifying separation among the amphipathic raw material of wood-charcoal material of coal tar pitch base, petroleum asphalt based amphipathic raw material of wood-charcoal material, the amphipathic raw material of wood-charcoal material of mesophase pitch base, the amphipathic raw material of wood-charcoal material of petroleum coke base, the amphipathic raw material of wood-charcoal material of needle coke base and the amphipathic raw material of wood-charcoal material of pitch coke base; The nanometer charcoal of the present invention's preparation is little to be formed by the self assembly under capillary constraint of amphipathic raw material of wood-charcoal material; Therefore the spherolite footpath evenly; Good sphericity has high reversible capacity and good cycle performance as lithium ion battery negative material.
Above-mentioned material is single carbon cathode material, because the capacity bottleneck of raw material of wood-charcoal material has limited the further raising of material specific capacity.
Summary of the invention
The present invention is intended to solve the problems of the prior art; A kind of demand that satisfies market to the lithium ion battery performance is provided, can promotes the energy density of lithium battery, development cost is cheap; Have extended cycle life the charcoal silicon composite cathode material that is used to prepare lithium ion battery that specific capacity is big.
Another object of the present invention provides that a kind of it is simple to reach apparatus and process to the above-mentioned preparation method who is used to prepare the charcoal silicon composite of lithium ion battery, and batch high conformity is suitable for the purpose of volume production.
In order to realize the foregoing invention purpose, its concrete technical scheme is following:
A kind of charcoal silicon composite cathode material that is used to prepare lithium ion battery is characterized in that: the charcoal source of described composite negative pole material is amphipathic raw material of wood-charcoal material, and the silicon source is the crystalline silicon of particle diameter 3～10nm; Described charcoal silicon composite cathode material is that to have charcoal be shell, the silicon nucleocapsid structure for nuclear, and particle diameter is 30～50nm, and sphericity is 50～80% hard carbon microspheres; Described charcoal silicon composite cathode material specific capacity is 503～1028mAh/g, and capability retention >=85% circulates 100 times.
Silicon source quality of the present invention is 3～35% of a charcoal silicon composite cathode material gross mass.
Amphipathic raw material of wood-charcoal material of the present invention is one or any ratio multiple in coal tar pitch base, petroleum asphalt based, mesophase pitch base, petroleum coke base, needle coke base and the amphipathic raw material of wood-charcoal material of pitch coke base.
Crystalline silicon of the present invention is conventional monocrystalline silicon or the polysilicon of selecting.
A kind of preparation method who is used to prepare the charcoal silicon composite cathode material of lithium ion battery is characterized in that: comprise following processing step:
A, a kind of multiple amphipathic raw material of wood-charcoal material of or arbitrary proportion is joined in the deionized water, and to use the pH value of water-soluble alkali regulator solution be 10～14, process amphipathic raw material of wood-charcoal material solution;
B, be that 1:100～1000 take by weighing the crystalline silicon powder that particle diameter is 3～10nm, join in the amphipathic raw material of wood-charcoal material solution and stir, obtain charcoal silicon mixed liquor by the mass ratio of crystalline silicon and amphipathic raw material of wood-charcoal material solution;
C, be that organic solvent is got in 1:20～200 by charcoal silicon mixed liquor and organic solvent volume ratio; Under agitation, mixed liquor is joined in the organic solvent, stop behind 5～30min stirring; Leave standstill; Obtain the mixture of layering, supernatant liquid is the molten altogether thing of organic solvent and water, and lower floor's liquid contains amphipathic raw material of wood-charcoal material/silicon composite;
Supernatant liquid and lower floor's fluid separation applications of the mixture of D, layering that step C is obtained;
E, with the organic solvent evaporate to dryness of lower floor's liquid, obtain grey black toner end, be amphipathic raw material of wood-charcoal material/silicon composite;
F, the amphipathic raw material of wood-charcoal material/silicon composite that under inert atmosphere, step e is made carry out charing to be handled, and naturally cools to room temperature then, obtains to be used to prepare the charcoal silicon composite cathode material of lithium ion battery.
Water-soluble alkali described in the steps A of the present invention is conventional potassium hydroxide, NaOH, ethylenediamine, potash, sodium carbonate or the cesium hydroxide of selecting.
The mass percent concentration of amphipathic raw material of wood-charcoal material solution is 5～10% described in the steps A of the present invention.
Stirring described in the step B of the present invention is for stirring 30～180min.
Mixing speed described in the step C of the present invention is 300～1500r/min.
The low boiling-point and polarity organic solvent of organic solvent described in the step C of the present invention for dissolving each other with water is meant ethanol, acetone or methyl alcohol.
Supernatant liquid described in the step C of the present invention separates through separatory funnel with lower floor, and after the supernatant liquid rectifying separation, organic solvent can be recycled.
The organic solvent evaporate to dryness with lower floor's liquid described in the step e of the present invention is meant under 50～70 ℃ the organic solvent evaporate to dryness with lower floor's liquid.
Charing described in the step F of the present invention is treated to heating rate with 1～10 ℃/min and rises to 900～1400 ℃ and carry out charing and handle 20～60min.
Charing described in the step F of the present invention is handled and is adopted conventional tube furnace, box type furnace or the converter of selecting
Inert atmosphere described in the step F of the present invention is conventional nitrogen atmosphere, argon gas atmosphere or the helium atmosphere of selecting.
The useful technique effect that the present invention brings:
1, the cost of material of the amphipathic raw material of wood-charcoal material of the present invention's employing is cheap, and the source is abundant, is easy to realize large-scale industrial production;
What 2, the present invention adopted one or any ratio in coal tar pitch base, petroleum asphalt based, mesophase pitch base, petroleum coke base, needle coke base and the pitch coke base multiplely processes amphipathic raw material of wood-charcoal material; This preparation process need not add any surfactant; Silicon nanoparticle is evenly disperseed; And reduced the use of organic solvent to a certain extent, make synthesis technique become simply, and environmental protection;
3, synthesis technique of the present invention and use equipment are simple, and compared with the synthetic method of traditional charcoal silicon composite such as chemical vapour deposition technique etc., production cost is more cheap;
4, the charcoal silicon composite cathode material of the present invention's preparation is formed by the self assembly under capillary constraint of amphipathic raw material of wood-charcoal material, so silicon is evenly distributed Stability Analysis of Structures in charcoal;
5, it is compound that the present invention selects silicon and amphipathic raw material of wood-charcoal material with height ratio capacity more for use; And then preparation charcoal nano silicon particles; Further improve the specific capacity of material; The charcoal silicon composite cathode material specific capacity of preparing is high, can reach 503～1028mAh/g, and 100 capability retentions that circulate still is not less than 85%;
6, not only cost is low for the lithium ion battery of employing charcoal silicon composite cathode material preparation of the present invention; And has a high-energy-density characteristic; With this material is the 1Ah battery of negative pole preparation; 1Ah battery volume than with native graphite (specific capacity 340mAh/g) negative pole has reduced 5～10%, and quality has reduced 5～20%; Than nanometer negative material in application number 201110122069.5 patents is that the 1Ah battery volume of negative pole has reduced 3～8%, and quality has reduced 4～15%;
7, adopt the lithium ion battery of charcoal silicon composite cathode material preparation of the present invention to have good multiplying power property, good cryogenic property;
8, preparation method provided by the invention and technological parameter system wherein can make that apparatus and process is simple, and batch high conformity is suitable for volume production.
Embodiment
Embodiment 1
A kind of charcoal silicon composite cathode material that is used to prepare lithium ion battery, the charcoal source of described composite negative pole material are amphipathic raw material of wood-charcoal material, and the silicon source is the crystalline silicon of particle diameter 3nm; Described charcoal silicon composite cathode material is that to have charcoal be shell, the silicon nucleocapsid structure for nuclear, and particle diameter is 30nm, and sphericity is 50% hard carbon microspheres; Described charcoal silicon composite cathode material specific capacity is 503mAh/g, and capability retention 85% circulates 100 times.
Embodiment 2
A kind of charcoal silicon composite cathode material that is used to prepare lithium ion battery, the charcoal source of described composite negative pole material are amphipathic raw material of wood-charcoal material, and the silicon source is the crystalline silicon of particle diameter 10nm; Described charcoal silicon composite cathode material is that to have charcoal be shell, the silicon nucleocapsid structure for nuclear, and particle diameter is 50nm, and sphericity is 80% hard carbon microspheres; Described charcoal silicon composite cathode material specific capacity is 1028mAh/g, and capability retention 95% circulates 100 times.
Embodiment 3
A kind of charcoal silicon composite cathode material that is used to prepare lithium ion battery, the charcoal source of described composite negative pole material are amphipathic raw material of wood-charcoal material, and the silicon source is the crystalline silicon of particle diameter 6.5nm; Described charcoal silicon composite cathode material is that to have charcoal be shell, the silicon nucleocapsid structure for nuclear, and particle diameter is 40nm, and sphericity is 65% hard carbon microspheres; Described charcoal silicon composite cathode material specific capacity is 765.5mAh/g, and capability retention 90% circulates 100 times.
Embodiment 4
A kind of charcoal silicon composite cathode material that is used to prepare lithium ion battery, the charcoal source of described composite negative pole material are amphipathic raw material of wood-charcoal material, and the silicon source is the crystalline silicon of particle diameter 8nm; Described charcoal silicon composite cathode material is that to have charcoal be shell, the silicon nucleocapsid structure for nuclear, and particle diameter is 32nm, and sphericity is 73% hard carbon microspheres; Described charcoal silicon composite cathode material specific capacity is 1001mAh/g, and capability retention 93% circulates 100 times.
Embodiment 5
A kind of charcoal silicon composite cathode material that is used to prepare lithium ion battery, the charcoal source of described composite negative pole material are amphipathic raw material of wood-charcoal material, and the silicon source is the crystalline silicon of particle diameter 3nm; Described charcoal silicon composite cathode material is that to have charcoal be shell, the silicon nucleocapsid structure for nuclear, and particle diameter is 30nm, and sphericity is 50% hard carbon microspheres; Described charcoal silicon composite cathode material specific capacity is 503mAh/g, and capability retention 85% circulates 100 times.
Described silicon source quality of the present invention is 3% of a charcoal silicon composite cathode material gross mass.
Described amphipathic raw material of wood-charcoal material is one or any ratio multiple in coal tar pitch base, petroleum asphalt based, mesophase pitch base, petroleum coke base, needle coke base and the amphipathic raw material of wood-charcoal material of pitch coke base.
Embodiment 6
A kind of charcoal silicon composite cathode material that is used to prepare lithium ion battery, the charcoal source of described composite negative pole material are amphipathic raw material of wood-charcoal material, and the silicon source is the crystalline silicon of particle diameter 10nm; Described charcoal silicon composite cathode material is that to have charcoal be shell, the silicon nucleocapsid structure for nuclear, and particle diameter is 50nm, and sphericity is 80% hard carbon microspheres; Described charcoal silicon composite cathode material specific capacity is 1028mAh/g, and capability retention 95% circulates 100 times.
Described silicon source quality of the present invention is 35% of a charcoal silicon composite cathode material gross mass.
Described amphipathic raw material of wood-charcoal material is one or any ratio multiple in coal tar pitch base, petroleum asphalt based, mesophase pitch base, petroleum coke base, needle coke base and the amphipathic raw material of wood-charcoal material of pitch coke base.
Embodiment 7
A kind of charcoal silicon composite cathode material that is used to prepare lithium ion battery, the charcoal source of described composite negative pole material are amphipathic raw material of wood-charcoal material, and the silicon source is the crystalline silicon of particle diameter 6.5nm; Described charcoal silicon composite cathode material is that to have charcoal be shell, the silicon nucleocapsid structure for nuclear, and particle diameter is 40nm, and sphericity is 65% hard carbon microspheres; Described charcoal silicon composite cathode material specific capacity is 765.5mAh/g, and capability retention 90% circulates 100 times.
Described silicon source quality of the present invention is 19% of a charcoal silicon composite cathode material gross mass.
Described amphipathic raw material of wood-charcoal material is one or any ratio multiple in coal tar pitch base, petroleum asphalt based, mesophase pitch base, petroleum coke base, needle coke base and the amphipathic raw material of wood-charcoal material of pitch coke base.
Embodiment 8
A kind of charcoal silicon composite cathode material that is used to prepare lithium ion battery, the charcoal source of described composite negative pole material are amphipathic raw material of wood-charcoal material, and the silicon source is the crystalline silicon of particle diameter 8nm; Described charcoal silicon composite cathode material is that to have charcoal be shell, the silicon nucleocapsid structure for nuclear, and particle diameter is 32nm, and sphericity is 73% hard carbon microspheres; Described charcoal silicon composite cathode material specific capacity is 1001mAh/g, and capability retention 93% circulates 100 times.
Described silicon source quality of the present invention is 21% of a charcoal silicon composite cathode material gross mass.
Described amphipathic raw material of wood-charcoal material is one or any ratio multiple in coal tar pitch base, petroleum asphalt based, mesophase pitch base, petroleum coke base, needle coke base and the amphipathic raw material of wood-charcoal material of pitch coke base.
Embodiment 9
A kind of preparation method who is used to prepare the charcoal silicon composite cathode material of lithium ion battery comprises following processing step:
A, a kind of multiple amphipathic raw material of wood-charcoal material of or arbitrary proportion is joined in the deionized water, and to use the pH value of water-soluble alkali regulator solution be 10, process amphipathic raw material of wood-charcoal material solution;
B, be that 1:100 takes by weighing the crystalline silicon powder that particle diameter is 3nm, join in the amphipathic raw material of wood-charcoal material solution and stir, obtain charcoal silicon mixed liquor by the mass ratio of crystalline silicon and amphipathic raw material of wood-charcoal material solution;
C, be that 1:20 gets organic solvent by charcoal silicon mixed liquor and organic solvent volume ratio; Under agitation, mixed liquor is joined in the organic solvent, stop behind the 5min stirring; Leave standstill; Obtain the mixture of layering, supernatant liquid is the molten altogether thing of organic solvent and water, and lower floor's liquid contains amphipathic raw material of wood-charcoal material/silicon composite;
Supernatant liquid and lower floor's fluid separation applications of the mixture of D, layering that step C is obtained;
E, with the organic solvent evaporate to dryness of lower floor's liquid, obtain grey black toner end, be amphipathic raw material of wood-charcoal material/silicon composite;
F, the amphipathic raw material of wood-charcoal material/silicon composite that under inert atmosphere, step e is made carry out charing to be handled, and naturally cools to room temperature then, obtains to be used to prepare the charcoal silicon composite cathode material of lithium ion battery.
Embodiment 10
A kind of preparation method who is used to prepare the charcoal silicon composite cathode material of lithium ion battery comprises following processing step:
A, a kind of multiple amphipathic raw material of wood-charcoal material of or arbitrary proportion is joined in the deionized water, and to use the pH value of water-soluble alkali regulator solution be 14, process amphipathic raw material of wood-charcoal material solution;
B, be that 1:1000 takes by weighing the crystalline silicon powder that particle diameter is 10nm, join in the amphipathic raw material of wood-charcoal material solution and stir, obtain charcoal silicon mixed liquor by the mass ratio of crystalline silicon and amphipathic raw material of wood-charcoal material solution;
C, be that 1:200 gets organic solvent by charcoal silicon mixed liquor and organic solvent volume ratio; Under agitation, mixed liquor is joined in the organic solvent, stop behind the 30min stirring; Leave standstill; Obtain the mixture of layering, supernatant liquid is the molten altogether thing of organic solvent and water, and lower floor's liquid contains amphipathic raw material of wood-charcoal material/silicon composite;
Supernatant liquid and lower floor's fluid separation applications of the mixture of D, layering that step C is obtained;
E, with the organic solvent evaporate to dryness of lower floor's liquid, obtain grey black toner end, be amphipathic raw material of wood-charcoal material/silicon composite;
F, the amphipathic raw material of wood-charcoal material/silicon composite that under inert atmosphere, step e is made carry out charing to be handled, and naturally cools to room temperature then, obtains to be used to prepare the charcoal silicon composite cathode material of lithium ion battery.
Embodiment 11
A kind of preparation method who is used to prepare the charcoal silicon composite cathode material of lithium ion battery comprises following processing step:
A, a kind of multiple amphipathic raw material of wood-charcoal material of or arbitrary proportion is joined in the deionized water, and to use the pH value of water-soluble alkali regulator solution be 12, process amphipathic raw material of wood-charcoal material solution;
B, be that 1:550 takes by weighing the crystalline silicon powder that particle diameter is 6.5nm, join in the amphipathic raw material of wood-charcoal material solution and stir, obtain charcoal silicon mixed liquor by the mass ratio of crystalline silicon and amphipathic raw material of wood-charcoal material solution;
C, be that 1:110 gets organic solvent by charcoal silicon mixed liquor and organic solvent volume ratio; Under agitation, mixed liquor is joined in the organic solvent, stop behind the 17.5min stirring; Leave standstill; Obtain the mixture of layering, supernatant liquid is the molten altogether thing of organic solvent and water, and lower floor's liquid contains amphipathic raw material of wood-charcoal material/silicon composite;
Supernatant liquid and lower floor's fluid separation applications of the mixture of D, layering that step C is obtained;
E, with the organic solvent evaporate to dryness of lower floor's liquid, obtain grey black toner end, be amphipathic raw material of wood-charcoal material/silicon composite;
F, the amphipathic raw material of wood-charcoal material/silicon composite that under inert atmosphere, step e is made carry out charing to be handled, and naturally cools to room temperature then, obtains to be used to prepare the charcoal silicon composite cathode material of lithium ion battery.
Embodiment 12
A kind of preparation method who is used to prepare the charcoal silicon composite cathode material of lithium ion battery comprises following processing step:
A, a kind of multiple amphipathic raw material of wood-charcoal material of or arbitrary proportion is joined in the deionized water, and to use the pH value of water-soluble alkali regulator solution be 13, process amphipathic raw material of wood-charcoal material solution;
B, be that 1:600 takes by weighing the crystalline silicon powder that particle diameter is 7nm, join in the amphipathic raw material of wood-charcoal material solution and stir, obtain charcoal silicon mixed liquor by the mass ratio of crystalline silicon and amphipathic raw material of wood-charcoal material solution;
C, be that 1:180 gets organic solvent by charcoal silicon mixed liquor and organic solvent volume ratio; Under agitation, mixed liquor is joined in the organic solvent, stop behind the 10min stirring; Leave standstill; Obtain the mixture of layering, supernatant liquid is the molten altogether thing of organic solvent and water, and lower floor's liquid contains amphipathic raw material of wood-charcoal material/silicon composite;
Supernatant liquid and lower floor's fluid separation applications of the mixture of D, layering that step C is obtained;
E, with the organic solvent evaporate to dryness of lower floor's liquid, obtain grey black toner end, be amphipathic raw material of wood-charcoal material/silicon composite;
F, the amphipathic raw material of wood-charcoal material/silicon composite that under inert atmosphere, step e is made carry out charing to be handled, and naturally cools to room temperature then, obtains to be used to prepare the charcoal silicon composite cathode material of lithium ion battery.
Embodiment 13
On the basis of embodiment 9～12:
Mass percent concentration at amphipathic raw material of wood-charcoal material solution described in the steps A is 5%.
Be stirring 30min in the stirring described in the step B.
In the mixing speed described in the step C is 300r/min.
At the organic solvent described in the step C is ethanol, acetone or methyl alcohol.
Be meant under 50 ℃ organic solvent evaporate to dryness at the organic solvent evaporate to dryness described in the step e with lower floor's liquid with lower floor's liquid.
Being treated to heating rate with 1 ℃/min in the charing described in the step F rises to 900 ℃ and carries out charing and handle 20min.
Embodiment 14
On the basis of embodiment 9～12:
Mass percent concentration at amphipathic raw material of wood-charcoal material solution described in the steps A is 10%.
Be stirring 180min in the stirring described in the step B.
In the mixing speed described in the step C is 1500r/min.
At the organic solvent described in the step C is ethanol, acetone or methyl alcohol.
Be meant under 70 ℃ organic solvent evaporate to dryness at the organic solvent evaporate to dryness described in the step e with lower floor's liquid with lower floor's liquid.
Being treated to heating rate with 10 ℃/min in the charing described in the step F rises to 1400 ℃ and carries out charing and handle 60min.
Embodiment 15
On the basis of embodiment 9～12:
Mass percent concentration at amphipathic raw material of wood-charcoal material solution described in the steps A is 7.5%.
Be stirring 105min in the stirring described in the step B.
In the mixing speed described in the step C is 900r/min.
At the organic solvent described in the step C is ethanol, acetone or methyl alcohol.
Be meant under 60 ℃ organic solvent evaporate to dryness at the organic solvent evaporate to dryness described in the step e with lower floor's liquid with lower floor's liquid.
Being treated to heating rate with 5.5 ℃/min in the charing described in the step F rises to 1150 ℃ and carries out charing and handle 40min.
Embodiment 16
On the basis of embodiment 9～12:
Mass percent concentration at amphipathic raw material of wood-charcoal material solution described in the steps A is 9%.
Be stirring 170min in the stirring described in the step B.
In the mixing speed described in the step C is 1100r/min.
At the organic solvent described in the step C is ethanol, acetone or methyl alcohol.
Be meant under 65 ℃ organic solvent evaporate to dryness at the organic solvent evaporate to dryness described in the step e with lower floor's liquid with lower floor's liquid.
Being treated to heating rate with 7.5 ℃/min in the charing described in the step F rises to 1300 ℃ and carries out charing and handle 55min.
Embodiment 17
Amphipathic raw material of wood-charcoal preparation method for material (common process):
With coal tar pitch, petroleum asphalt, mesophase pitch, petroleum coke, needle coke and pitch coke is raw material; Adopt general known preparation method to prepare amphipathic raw material of wood-charcoal material; Concrete preparation process is following: nitration mixture (be 65% red fuming nitric acid (RFNA) with concentration and concentration is that 98% concentrated sulfuric acid volume ratio is that 2:8～5:5 prepares) is heated to 50～100 ℃; Press raw material and nitration mixture mass ratio 1:20～1:1 adds raw material, reaction 1～5h pours reactant with 10 times of cessation reactions of ionized water dilution into; Filter, the washing of gained cakes with deionized water is to neutral; The solid matter that obtains is joined in the water-soluble alkali solution, under 50～100 ℃, to stir 1-5h, filter, the pH value that in this process, keeps solution is all the time greater than 12; Collect filtrating, in the filtrating that obtains, drip water soluble acid (sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid etc.), regulate its pH value to 1, have this moment deposition to generate; Centrifugation, the sediment that obtains is extremely neutral with deionized water wash, and oven dry promptly gets amphipathic raw material of wood-charcoal material.
Embodiment 18
The preparation method of lithium ion battery (common process):
A, charcoal silicon composite cathode material and conductive agent, binding agent, nonaqueous solvents mixing and stirring are promptly got the charcoal silicon composite cathode slurry that is used to prepare lithium ion battery; Positive active material and conductive agent, binding agent, nonaqueous solvents mixing and stirring are promptly got the anode sizing agent that is used to prepare lithium ion battery;
B, charcoal silicon composite cathode slurry and anode sizing agent evenly are coated in respectively on two collectors, oven dry, roll-in obtains charcoal silicon composite cathode pole piece and anode pole piece.
C, positive pole, barrier film and negative pole replaced lamination after, at pressure 0.2MPa, 60 ℃ of following hot pressing 1min of temperature process pole piece;
D, heat-sealing: adopt method known in those skilled in the art, the step pole piece is put into aluminum plastic film bag and heat-sealing, be prepared into electric core;
E, once change into: adopt method known in those skilled in the art, adopt the 0.05C electric current that above-mentioned electric core is charged to the 70%SOC attitude;
F, secondary heat treatment: the electric core after will once changing into is 0.2MPa at pressure, and temperature is 60 ℃ of pressurization baking 3h down, obtains lithium rechargeable battery.
G, partial volume: the method that adopts those skilled in the art to know altogether tests out the capacity (rated capacity is 1Ah) of battery.
Consumption at the charcoal silicon composite cathode material described in the step G and conductive agent, binding agent, nonaqueous solvents is counted with parts by weight:
30～60 parts of charcoal silicon composite cathode materials
0.5～5 part of conductive agent
0.5～5 part of binding agent
30～69 parts of nonaqueous solventss.
Consumption at the positive active material described in the step G and conductive agent, binding agent, nonaqueous solvents is counted with parts by weight:
30～60 parts of positive active materials
0.5～5 part of conductive agent
0.5～5 part of binding agent
30～69 parts of nonaqueous solventss.
Described conductive agent is: several kinds of a kind of or arbitrary proportion in carbon black, acetylene black, carbon fiber, flake graphite, the CNT, preferred acetylene black and CNT.
Described binding agent is: polyethylene glycol oxide, polyacrylonitrile, polyvinyl chloride, polystyrene, gather ethyl acetate, polyvinylpyrrolidone, polymethyl methacrylate, polyacrylic acid glycol ester, Kynoar, polyhexafluoropropylene-vinylidene, gather divinyl sulfide and their copolymer, several kinds of a kind of or arbitrary proportion in the derivative, preferred Kynoar, polyhexafluoropropylene-vinylidene.
Described nonaqueous solvents is: one or more in n-formyl sarcolysine base pyrrolidones (NMP), dimethyl formamide (DMF), DEF (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and the 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 the step H is electrolytic copper foil or rolled copper foil, and thickness is 8～20 μ m.
The thickness that is coated in the anode sizing agent on the collector described in the step H is 50～200 μ m.
Charcoal silicon composite cathode material coating thickness is 30-100 μ m among the step H
Membrane layer of the present invention is polypropylene micro-porous film (PP), microporous polyethylene film (PE), glass mat or PP/PE/PP, and preferred, said 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 acid lithium (LiCF
3SO
3), fluoro sulfimide lithium (LiN (CF
3SO
2)
2), several kinds of a kind of or arbitrary proportion in lithium chloride (LiCl) and the lithium iodide (LiI); Said nonaqueous solvents can for vinyl carbonate (EC), propylene carbonate (PC), gamma-butyrolacton (γ-GBL), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DMC) N-NMF (DMF), N-N dimethylacetylamide (DMAC), acetonitrile (ACN), methyl-sulfoxide (DMSO) and other are fluorine-containing, several kinds of a kind of or arbitrary proportion in the ring-type organic ester of sulfur-bearing or unsaturated bond.
Claims (10)
1. charcoal silicon composite cathode material that is used to prepare lithium ion battery, it is characterized in that: the charcoal source of described composite negative pole material is amphipathic raw material of wood-charcoal material, and the silicon source is the crystalline silicon of particle diameter 3～10nm; Described charcoal silicon composite cathode material is that to have charcoal be shell, the silicon nucleocapsid structure for nuclear, and particle diameter is 30～50nm, and sphericity is 50～80% hard carbon microspheres; Described charcoal silicon composite cathode material specific capacity is 503～1028mAh/g, and capability retention >=85% circulates 100 times.
2. be used to prepare the charcoal silicon composite cathode material of lithium ion battery according to claim 1 for one kind, it is characterized in that: described silicon source quality of the present invention is 3～35% of a charcoal silicon composite cathode material gross mass.
3. be used to prepare the charcoal silicon composite cathode material of lithium ion battery according to claim 1 for one kind, it is characterized in that: described amphipathic raw material of wood-charcoal material is one or any ratio multiple in coal tar pitch base, petroleum asphalt based, mesophase pitch base, petroleum coke base, needle coke base and the amphipathic raw material of wood-charcoal material of pitch coke base.
4. a kind of preparation method who is used to prepare the charcoal silicon composite cathode material of lithium ion battery according to claim 1 is characterized in that: comprise following processing step:
A, a kind of multiple amphipathic raw material of wood-charcoal material of or arbitrary proportion is joined in the deionized water, and to use the pH value of water-soluble alkali regulator solution be 10～14, process amphipathic raw material of wood-charcoal material solution;
B, be that 1:100～1000 take by weighing the crystalline silicon powder that particle diameter is 3～10nm, join in the amphipathic raw material of wood-charcoal material solution and stir, obtain charcoal silicon mixed liquor by the mass ratio of crystalline silicon and amphipathic raw material of wood-charcoal material solution;
C, be that organic solvent is got in 1:20～200 by charcoal silicon mixed liquor and organic solvent volume ratio; Under agitation, mixed liquor is joined in the organic solvent, stop behind 5～30min stirring; Leave standstill; Obtain the mixture of layering, supernatant liquid is the molten altogether thing of organic solvent and water, and lower floor's liquid contains amphipathic raw material of wood-charcoal material/silicon composite;
Supernatant liquid and lower floor's fluid separation applications of the mixture of D, layering that step C is obtained;
E, with the organic solvent evaporate to dryness of lower floor's liquid, obtain grey black toner end, be amphipathic raw material of wood-charcoal material/silicon composite;
F, the amphipathic raw material of wood-charcoal material/silicon composite that under inert atmosphere, step e is made carry out charing to be handled, and naturally cools to room temperature then, obtains to be used to prepare the charcoal silicon composite cathode material of lithium ion battery.
5. a kind of preparation method who is used to prepare the charcoal silicon composite cathode material of lithium ion battery according to claim 4, it is characterized in that: the mass percent concentration at amphipathic raw material of wood-charcoal material solution described in the steps A is 5～10%.
6. a kind of preparation method who is used to prepare the charcoal silicon composite cathode material of lithium ion battery according to claim 4 is characterized in that: in the stirring described in the step B for stirring 30～180min.
7. a kind of preparation method who is used to prepare the charcoal silicon composite cathode material of lithium ion battery according to claim 4, it is characterized in that: in the mixing speed described in the step C is 300～1500r/min.
8. a kind of preparation method who is used to prepare the charcoal silicon composite cathode material of lithium ion battery according to claim 4, it is characterized in that: at the organic solvent described in the step C is ethanol, acetone or methyl alcohol.
9. a kind of preparation method who is used to prepare the charcoal silicon composite cathode material of lithium ion battery according to claim 4 is characterized in that: be meant under 50～70 ℃ the organic solvent evaporate to dryness with lower floor's liquid at the organic solvent evaporate to dryness with lower floor's liquid described in the step e.
10. a kind of preparation method who is used to prepare the charcoal silicon composite cathode material of lithium ion battery according to claim 4 is characterized in that: be treated to heating rate with 1～10 ℃/min in the charing described in the step F and rise to 900～1400 ℃ and carry out charing and handle 20～60min.
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| JP2010501970A (en) * | 2006-08-22 | 2010-01-21 | ビーティーアール・ニュー・エナジー・マテリアルズ・インク | Silicon / carbon composite cathode material for lithium ion battery and method for producing the same |
| CN102332571A (en) * | 2011-09-21 | 2012-01-25 | 广东达之邦新能源技术有限公司 | Silicon-carbon compound cathode material and manufacturing method thereof as well as lithium ion battery and cathode piece |
| CN102351163A (en) * | 2011-07-11 | 2012-02-15 | 中国东方电气集团有限公司 | Nano carbon microsphere cathode material of lithium ion cell and its preparation method |
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| JP2010501970A (en) * | 2006-08-22 | 2010-01-21 | ビーティーアール・ニュー・エナジー・マテリアルズ・インク | Silicon / carbon composite cathode material for lithium ion battery and method for producing the same |
| CN102351163A (en) * | 2011-07-11 | 2012-02-15 | 中国东方电气集团有限公司 | Nano carbon microsphere cathode material of lithium ion cell and its preparation method |
| CN102332571A (en) * | 2011-09-21 | 2012-01-25 | 广东达之邦新能源技术有限公司 | Silicon-carbon compound cathode material and manufacturing method thereof as well as lithium ion battery and cathode piece |
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| CN103011127A (en) * | 2012-12-08 | 2013-04-03 | 天津大学 | Preparation method of asphalt hard carbon material for lithium ion battery cathode |
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