CN103337613A - Silicon-carbon composite material and preparation method thereof, and lithium ion battery - Google Patents
Silicon-carbon composite material and preparation method thereof, and lithium ion battery Download PDFInfo
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- CN103337613A CN103337613A CN2013102821840A CN201310282184A CN103337613A CN 103337613 A CN103337613 A CN 103337613A CN 2013102821840 A CN2013102821840 A CN 2013102821840A CN 201310282184 A CN201310282184 A CN 201310282184A CN 103337613 A CN103337613 A CN 103337613A
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 109
- 239000000463 material Substances 0.000 claims abstract description 105
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 87
- 230000007704 transition Effects 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 239000010703 silicon Substances 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 69
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 37
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 35
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 20
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 14
- 239000001095 magnesium carbonate Substances 0.000 claims description 14
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 14
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 13
- 229910021484 silicon-nickel alloy Inorganic materials 0.000 claims description 13
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 claims description 12
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 11
- XNRNVYYTHRPBDD-UHFFFAOYSA-N [Si][Ag] Chemical compound [Si][Ag] XNRNVYYTHRPBDD-UHFFFAOYSA-N 0.000 claims description 11
- 238000000354 decomposition reaction Methods 0.000 claims description 11
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 claims description 11
- 239000011667 zinc carbonate Substances 0.000 claims description 11
- 235000004416 zinc carbonate Nutrition 0.000 claims description 11
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 11
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 10
- 229930006000 Sucrose Natural products 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 239000005720 sucrose Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 229910000676 Si alloy Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- RDHFLXMETKTMPJ-UHFFFAOYSA-J silicon(4+);dicarbonate Chemical compound [Si+4].[O-]C([O-])=O.[O-]C([O-])=O RDHFLXMETKTMPJ-UHFFFAOYSA-J 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 44
- 239000000377 silicon dioxide Substances 0.000 abstract description 22
- 239000002210 silicon-based material Substances 0.000 abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052744 lithium Inorganic materials 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- 235000013312 flour Nutrition 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 239000000956 alloy Substances 0.000 description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 description 9
- 238000003763 carbonization Methods 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- -1 plumbi nitras Chemical compound 0.000 description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 239000001099 ammonium carbonate Substances 0.000 description 5
- 235000012501 ammonium carbonate Nutrition 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 5
- 230000004087 circulation Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 229940072033 potash Drugs 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 235000015320 potassium carbonate Nutrition 0.000 description 5
- 229910001631 strontium chloride Inorganic materials 0.000 description 5
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910018594 Si-Cu Inorganic materials 0.000 description 4
- 229910008465 Si—Cu Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 3
- 239000001639 calcium acetate Substances 0.000 description 3
- 229960005147 calcium acetate Drugs 0.000 description 3
- 235000011092 calcium acetate Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 description 2
- ZKHWPBZFJKPTCX-UHFFFAOYSA-N [Si].[Cu].[Sr] Chemical compound [Si].[Cu].[Sr] ZKHWPBZFJKPTCX-UHFFFAOYSA-N 0.000 description 2
- LZTIZMAEPFBXIL-UHFFFAOYSA-N [Si]=O.[Ba] Chemical compound [Si]=O.[Ba] LZTIZMAEPFBXIL-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- GSJMPHIKYICTQX-UHFFFAOYSA-N magnesium;oxosilicon Chemical compound [Mg].[Si]=O GSJMPHIKYICTQX-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910001427 strontium ion Inorganic materials 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000009829 pitch coating Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Images
Classifications
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- 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 silicon-carbon composite material and a preparation method thereof, and a lithium ion battery. The preparation method comprises following steps: (1) coating a silica-based material with a transition layer to obtain the transition layer-coated silica-based material; (2) coating the transition layer-coated silica-based material with carbon to obtain a carbon-transition layer-silicon based composite material; and (3) removing the transition layer to obtain the silicon-carbon composite material. The silicon-based material is coated with the transition layer, the transition layer is coated with the carbon, and the transition layer between the silicon-based material and the carbon is removed, so that a plurality of pores are formed between the silicon-based material and the carbon of the silicon-carbon composite material. The size of the pores between the silicon-based material and the carbon can be controlled precisely by setting the thickness of the transition layer according to micro-volume expansion theoretical value of the silicon-based material when lithium is embedded, so that volume effect of the silicon-carbon composite material is reduced effectively, and cycling performance of the lithium ion battery is further enhanced. The carbon of the silicon-carbon composite material is capable of increasing conductivity and rate capability of the composite material.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of Si-C composite material and preparation method thereof, lithium ion battery.
Background technology
At present, the lithium ion battery of commercial applications extensively adopts graphite or modified graphite as negative material.Lithium ion battery is in charge and discharge process, above-mentioned negative material volumetric expansion when the embedding lithium less (the embedding lithium coefficient of cubical expansion＜9%), show higher coulombic efficiency and cyclical stability preferably, but its theoretical maximum specific capacity only has 372mAh/g, thereby has limited the further raising of the specific energy of lithium ion battery.
The lithium ion battery negative material of height ratio capacity has become the key that improves battery performance, because silica-base material has higher specific capacity (the silicon theoretical specific capacity is 4200mAh/g), therefore silica-base material is considered to the most promising a kind of negative material, and has caused the extensive concern of battery material circle.But silica-base material has very big bulk effect (embedding lithium cubical expansivity〉300%) in the process of doff lithium, causes the efflorescence of silica-base material in the charging and discharging lithium battery process, obscission serious, makes cycle performance of battery sharply descend.
In the prior art, the process for preparing silicon/carbon/composite cathode material of silicon/carbon/graphite among the CN100379059C is: with being dispersed in the organic substance after silica flour and the graphite mixing, carry out high temperature cabonization again and handle, form silicon/carbon/graphite composite material; The process of preparation Si-C composite material is among the CN02112180.X: pitch is mixed the back high temperature sintering with silica flour, obtain Si-C composite material.Though silicon/carbon that method for preparing obtains/composite cathode material of silicon/carbon/graphite or Si-C composite material have improved the cyclical stability of lithium ion battery to a certain extent, still there are efflorescence, obscission.Use above-mentioned material as the lithium ion battery of negative material through after the charge and discharge cycles repeatedly, capacity begins rapid decay, does not fundamentally solve the bulk effect in the silicon-based anode material charge and discharge process.
Summary of the invention
Technical problem to be solved by this invention is at above shortcomings in the prior art, and a kind of Si-C composite material and preparation method thereof, lithium ion battery are provided.Have certain hole between the silica-based and carbon in the Si-C composite material that this preparation method obtains, reduced the bulk effect of Si-C composite material.
The technical scheme that solution the technology of the present invention problem adopts provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) at silica-base material transition zone is set, obtains the silica-base material that described transition zone coats;
(2) carbon coated outside the silica-base material that described transition zone coats obtains carbon-transition zone-silicon based composite material;
(3) remove described transition zone, obtain Si-C composite material.
Preferably, described step is specially:
(1) at silica-base material precipitation metal carbonate transition zone, obtains the silica-base material that this metal carbonate coats;
(2) carbon coated outside the silica-base material that described transition zone metal carbonate coats, obtain carbon-metal carbonate-silicon based composite material, wherein, the heat decomposition temperature of described transition zone metal carbonate be higher than described outside the silica-base material that described metal carbonate coats the temperature in the process of carbon coated;
(3) use acid solution to erode described metal carbonate, obtain Si-C composite material.
Preferably, the mass ratio of described silica-base material and described metal carbonate is (1: 9)～(2: 3).
Preferably, the mass ratio of described silica-base material and described metal carbonate is (1: 6.5)～(1: 3.2).
Preferably, the mass ratio of the described carbon in the described Si-C composite material and described silica-base material is (1: 19)～(9: 1).
Preferably, the mass ratio of the described carbon in the described Si-C composite material and described silica-base material is (3: 17)～(3: 2).
Preferably, described carbonate comprises any one or a few in magnesium carbonate, calcium carbonate, strontium carbonate, brium carbonate, zinc carbonate, the ceruse.
Preferably, described silica-base material comprises any one or a few in silicon, silicon monoxide, the silicon alloy.
Preferably, described silicon alloy is the silicon silver alloy, silicon copper, any one or a few in the silicon nickel alloy.
Preferably, described step (2) is specially: after the silica-base material that described metal carbonate is coated and carbon source mix, carry out calcination under nonoxidizing atmosphere, described calcination temperature is 250 ℃～800 ℃, be incubated 1～8 hour, obtain described carbon-metal carbonate-silicon based composite material.
Preferably, described carbon source is any one or a few in polyvinyl alcohol, sucrose, glucose, polyacrylonitrile, phenolic resins, polyvinyl chloride, the pitch.
Preferably, described step (1) is specially: with the aqueous solution of described silica-base material and slaine, add the carbonate deposition agent again, obtain the silica-base material that described metal carbonate coats.
Preferably, described slaine is one or more in calcium nitrate, barium nitrate, calcium acetate, calcium chloride, barium acetate, barium chloride, strontium chloride, strontium nitrate, strontium acetate, magnesium chloride, magnesium nitrate, magnesium acetate, zinc chloride, zinc nitrate, plumbi nitras, zinc sulfate, the lead acetate.
Preferably, described carbonate deposition agent is any one or a few in sodium carbonate, potash, the ammonium carbonate.
The present invention also provides a kind of Si-C composite material, and it is by above-mentioned preparation method's preparation.
The present invention also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
The preparation method of the Si-C composite material among the present invention is by arranging transition zone outside silica-base material, carbon coated outside transition zone is again removed between the silica-based and carbon in the Si-C composite material that the transition zone between silica-base material and the carbon obtains again and had certain hole.The thickness of transition zone is set according to silica-base material microvolume expanded size of theory when the embedding lithium, can accurately control the pore size between silica-based and the carbon, thereby effectively reduced the bulk effect of Si-C composite material, further improved the cycle performance of lithium ion battery.Carbon in this Si-C composite material has improved this conductivity of electrolyte materials and high rate performance.Carbon in this Si-C composite material has improved the Si-C composite material conductivity, has improved the high rate performance of Si-C composite material.
Description of drawings
Fig. 1 is the schematic diagram that material structure changes in the preparation Si-C composite material process in the embodiment of the invention 2;
Fig. 2 is the charge-discharge performance resolution chart of the lithium ion battery made of the Si-C composite material of the embodiment of the invention 2 preparation;
Fig. 3 is the high rate performance resolution chart of the lithium ion battery made of the Si-C composite material of the embodiment of the invention 2 preparation.
Among the figure: the 1-silica-base material; 2-calcium carbonate; 3-carbon; The 4-hole.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with the drawings and specific embodiments the present invention is described in further detail.
Present embodiment provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) at silica-base material transition zone is set, obtains the silica-base material that described transition zone coats;
(2) carbon coated outside the silica-base material that described transition zone coats obtains carbon-transition zone-silicon based composite material;
(3) remove described transition zone, obtain Si-C composite material.
Above-mentioned preparation method is by arranging transition zone outside silica-base material, carbon coated outside transition zone is again removed between the silica-based and carbon in the Si-C composite material that the transition zone between silica-base material and the carbon obtains again and had certain hole.The thickness of transition zone is set according to silica-base material microvolume expanded size of theory when the embedding lithium, can accurately control the pore size between silica-based and the carbon, thereby effectively reduced the bulk effect of Si-C composite material, further improved the cycle performance of lithium ion battery.Carbon in this Si-C composite material has improved this conductivity of electrolyte materials and high rate performance.Carbon in this Si-C composite material has improved the Si-C composite material conductivity, has improved the high rate performance of Si-C composite material.
Present embodiment prepares a kind of Si-C composite material by above-mentioned preparation method.
Present embodiment also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
Present embodiment provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) aqueous solution of preparation calcium chloride adds silica flour again, stirs to make silica flour be uniformly dispersed in the aqueous solution of calcium chloride.Under stirring, drip the aqueous solution of sodium carbonate in the said mixture, winnofil on silica flour, and the aqueous solution excessive 2% of the sodium carbonate that adds with guarantee in the aqueous solution the calcium ion precipitation fully, leave standstill 2 hours after, suction filtration or centrifugal, washing 3 times, after super-dry, obtain the silica-base material that calcium carbonate coats, wherein, the mass ratio of silica-base material and calcium carbonate is 1: 3.34.
(2) silica-base material that calcium carbonate is coated and sucrose add in the planetary ball mill, and with the rotating speed ball milling 5h of 280r/min, after mixing, this moment, sucrose was coated on outside the silica-base material of calcium carbonate coating.And then put into and carry out sintering under the nitrogen atmosphere, heating rate with 4 ℃/min is heated to 500 ℃, be incubated 4 hours, thereby make the sucrose carbonization become carbon, this moment is carbon coated outside the silica-base material that calcium carbonate coats, obtain carbon-to-carbon acid calcium-silicon based composite material, wherein, the heat decomposition temperature of calcium carbonate is 825 ℃.
(3) carbon-to-carbon acid calcium-silicon based composite material is added in the distilled water, after dispersed with stirring is even, again under stirring, to wherein dripping dilute hydrochloric acid solution calcium carbonate is corroded, and the dilute hydrochloric acid solution excessive 2% that adds to be to guarantee that calcium carbonate dissolves fully, carries out centrifugal, washing again 3 times, obtains Si-C composite material after super-dry, wherein, the mass ratio of the carbon in this Si-C composite material and silica-base material is 3: 1.
As shown in Figure 1, the preparation process of Si-C composite material: step (1) is winnofil 2 outside silica-base material 1 silica flour, obtains the silica-base material 1 that calcium carbonate 2 coats; Step (2) is carbon coated 3 outside the silica-base material 1 that calcium carbonate 2 coats, and generates carbon-to-carbon acid calcium-silicon based composite material; Step (3) erodes the calcium carbonate 2 in carbon-to-carbon acid calcium-silicon based composite material by dilute hydrochloric acid solution, obtains Si-C composite material.The Si-C composite material that obtains by this preparation method has nucleocapsid structure, wherein, carbon 3 is in the outside of silica-base material 1, and silica-base material 1 is the nuclear of this nucleocapsid structure, carbon 3 is the shell of this nucleocapsid mechanism, is the hole 4 of hollow between the silica-base material 1 in this nucleocapsid structure and the carbon 3.Hole 4 between shell in the Si-C composite material and the nuclear is the hole 4 between carbon 3 and the silica-base material 1, this hole 4 can accurately be controlled by above-mentioned preparation process, control in the step (1) at the thickness of the calcium carbonate 2 of silica-base material 1 precipitation by silica-base material 1 microvolume expanded size of theory when the embedding lithium and to control, this mainly is the volume of controlling calcium carbonate 2 by the quality that control is deposited in the calcium carbonate 2 on the silica-base material 1, for example: the quality that is deposited in the calcium carbonate 2 on the silica-base material 1 in the step (1) is more big, the thickness that just is deposited in the calcium carbonate 2 on the silica-base material 1 is more thick, and the carbon 3 of the Si-C composite material that obtains so at last and the hole 4 between the silica-base material 1 are also just more big.In step (2), outside the silica-base material 1 that calcium carbonate 2 coats, coat sucrose, and then under nitrogen atmosphere high temperature cabonization, the temperature of this carbonisation is mainly 500 ℃, and the heat decomposition temperature of calcium carbonate 2 is 825 ℃, so in the sucrose carbonisation, calcium carbonate 2 is stable existence and can thermal decomposition still, obtain carbon-to-carbon acid calcium-silicon composite by this step, silica-base material 1 is at innermost layer in this material, calcium carbonate 2 is at the skin of silica-base material 1, carbon 3 is at the skin of calcium carbonate 2, and just calcium carbonate 2 is between silica-base material 1 and carbon 3.Step erodes calcium carbonate 2 by watery hydrochloric acid in (3), erode calcium carbonate 2 like this after, just between silica-base material 1 and carbon 3, form certain hole 4.Not only comprise carbon 3 in this Si-C composite material, but also comprise silica-base material 1, because the volumetric expansion of carbon 3 is less, the specific capacity height of silica-base material 1, Si-C composite material has the advantage specific capacity height of silica-base material 1 like this, and the advantage volumetric expansion that this Si-C composite material while also has carbon 3 is less.This Si-C composite material volumetric expansion is little, be because comprise carbon 3 in this Si-C composite material on the one hand, so have the little advantage of the volumetric expansion of carbon 3, be that institute is so that the minimizing of the bulk effect of Si-C composite material owing to have certain hole 4 between the silica-base material 1 of Si-C composite material and the carbon 3 on the other hand.
In the above-mentioned steps (1) outside silica-base material 1 silica flour the method for winnofil 2 simple, use calcium chloride water and aqueous sodium carbonate all to belong to the little solution of corrosivity, and aqueous sodium carbonate makes that the reaction of calcium chloride precipitation is very easy to operation, cost is low, this step reaction efficiency is very high, few to less wastage, the waste reaction solution of raw material, make the preparation method of whole Si-C composite material be convenient to large-scale industrial production.The amount of winnofil 2 is very easy to control in the step (1), thereby the silica-base material 1 of the feasible Si-C composite material that finally makes and the hole 4 between the carbon 3 also are very easy to control.Has certain hole 4 between silica-base material 1 in the Si-C composite material that makes by said method and the carbon 3, so use the lithium ion battery of this Si-C composite material in charge and discharge process, effectively reduced the bulk effect of Si-C composite material, avoided the powder of detached phenomenon, this Si-C composite material has higher specific energy.According to silica-base material microvolume expanded size when the embedding lithium, can determine the space size of the volumetric expansion of the silica-base material 1 in corresponding this Si-C composite material of the reservation in this Si-C composite material, thereby can effectively alleviate volumetric expansion; Simultaneously, the housing in the Si-C composite material is carbon 3, and this carbon 3 has improved the conductivity of composite material, has improved high rate performance and the cycle life of material; The kernel of this Si-C composite material is silica-base material 1, and this silica-base material 1 has improved the specific capacity of composite material; Be that the Si-C composite material with nucleocapsid structure for preparing in the present embodiment has the advantage of the chemical property of silica-base material 1 and carbon 3 simultaneously.
Present embodiment prepares a kind of Si-C composite material by above-mentioned preparation method.
Present embodiment also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
The preparation method of battery pole piece is as follows:
With the gained Si-C composite material respectively with conductive agent acetylene black, binding agent PVDF(Kynoar) mix according to mass ratio 8:1:1, use the NMP(1-N-methyl-2-2-pyrrolidone N-) this mixture is modulated into slurry, evenly be coated on the Copper Foil, put into baking oven, dry 1h down at 80 ℃～120 ℃, take out and be washed into pole piece, 85 ℃ of vacuumize 12 hours, carry out compressing tablet, 85 ℃ of vacuumize 12 hours makes the Experimental cell pole piece.Be to electrode with the lithium sheet, electrolyte is the LiPF of 1.2mol/L
6EC(ethyl carbonate ester)+the DMC(dimethyl carbonate) (volume ratio 1:1) solution, barrier film is the celgard2400 film, is assembled into CR2025 type button cell in being full of the glove box of argon gas atmosphere.
As shown in Figure 2, this button cell is carried out the charge-discharge performance test: discharging and recharging by voltage is 0.01～1.5V, be under the condition of 0.1C (1C=700mA/g wherein at charging and discharging currents, the test program of battery is set according to the theoretical design capacity of battery in the present embodiment, obtained the value of material 1C again by the first charge-discharge test result), first discharge specific capacity is 839.78mAh/g, circulating, specific discharge capacity still remains on more than the 647.09mAh/g after 100 times, and the cyclical stability of battery is better.
As shown in Figure 3, this button cell is carried out the high rate performance test: discharging and recharging by voltage is 0.01～1.5V, and charging and discharging currents is respectively 0.1C, 0.2C, 0.5C, 1C, each multiplying power circulation 10 times, wherein, 1C=700mA/g.The high rate performance test result shows that the 0.1C specific discharge capacity is about 710.96mAh/g, and still more than 525mAh/g, the high rate performance of battery is better for the 1C specific discharge capacity.
Present embodiment provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) aqueous solution of preparation barium nitrate adds silicon monoxide (theoretical specific capacity of a silication silicon is about 1200mAh/g) again, stirs to make silicon monoxide be uniformly dispersed in the aqueous solution of barium nitrate.Under stirring, drip the aqueous solution of sodium carbonate in the said mixture, barium carbonate on silicon monoxide, and the aqueous solution excessive 2% of the sodium carbonate that adds with guarantee in the aqueous solution the barium ions precipitation fully, leave standstill 2 hours after, suction filtration or centrifugal, washing 3 times, after super-dry, obtain the silicon monoxide material that brium carbonate coats, wherein, the mass ratio of silicon monoxide and brium carbonate is 1: 6.5.
(2) after the silicon monoxide material that brium carbonate is coated and polyacrylonitrile mixed by hand-ground, this moment, polyacrylonitrile was coated on outside the silicon monoxide material of brium carbonate coating.And then put into and carry out sintering under the argon gas atmosphere, heating rate with 5 ℃/min is heated to 800 ℃, be incubated 2 hours, thereby make the polyacrylonitrile carbonization become carbon, this moment is carbon coated outside the silicon monoxide material that brium carbonate coats, obtain carbon-to-carbon acid barium-silicon monoxide composite material, wherein, the heat decomposition temperature of brium carbonate is 1300 ℃.
(3) carbon-to-carbon acid barium-silicon monoxide composite material is added in the distilled water, after dispersed with stirring is even, again under stirring, to wherein dripping dilute hydrochloric acid solution brium carbonate is corroded, and the dilute hydrochloric acid solution excessive 2% that adds to be to guarantee that brium carbonate dissolves fully, carries out centrifugal, washing again 3 times, obtains Si-C composite material after super-dry, wherein, the mass ratio of the carbon in this Si-C composite material and silicon monoxide is 1: 1.
Present embodiment prepares a kind of Si-C composite material by above-mentioned preparation method.
Present embodiment also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
According to the method for preparing button cell among the embodiment 2, the Si-C composite material that uses this Comparative Examples to make is made button cell as negative material, and this battery is carried out charge-discharge performance test: first discharge specific capacity has reached 998.651mAh/g, still remain on more than the 756.2mAh/g good cycling stability of this battery after 100 circulations.
Present embodiment provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) aqueous solution of preparation strontium chloride adds silicon copper again, stirs to make silicon copper be uniformly dispersed in the aqueous solution of strontium chloride.Under stirring, drip the aqueous solution of potash in the said mixture, precipitate strontium carbonate at silicon copper, and the aqueous solution excessive 2% of the potash that adds with guarantee in the aqueous solution the strontium ion precipitation fully, leave standstill 2 hours after, suction filtration or centrifugal, washing 3 times, after super-dry, obtain the Si-Cu alloy material that strontium carbonate coats, wherein, the mass ratio of silicon copper and strontium carbonate is 1: 4.5.
(2) Si-Cu alloy material that strontium carbonate is coated, phenolic resins and sucrose add magnetic agitation in the ethanol, after mixing, and drying, this moment, phenolic resins and sucrose were coated on outside the Si-Cu alloy material of strontium carbonate coating jointly.And then put into and carry out sintering under the hydrogen atmosphere, heating rate with 3 ℃/min is heated to 600 ℃, be incubated 5 hours, thereby make the equal carbonization of phenolic resins and sucrose become carbon, this moment is carbon coated outside the Si-Cu alloy material that strontium carbonate coats, obtain carbon-to-carbon acid strontium-silicon copper composite material, wherein, the heat decomposition temperature of strontium carbonate is 1100 ℃.
(3) carbon-to-carbon acid strontium-silicon copper composite material is added in the distilled water, after dispersed with stirring is even, again under stirring, to wherein dripping dilute hydrochloric acid solution strontium carbonate is corroded, and the dilute hydrochloric acid solution excessive 2% that adds to be to guarantee that strontium carbonate dissolves fully, carries out centrifugal, washing again 3 times, obtains Si-C composite material after super-dry, wherein, the mass ratio of the carbon in this Si-C composite material and silicon copper is 3: 17.
Silicon copper in this Si-C composite material is because it is alloy, this silicon copper is equivalent to copper facing on silicon, so silicon copper has good conductivity, and the theoretical specific capacity of silicon copper is about 4200mAh/g, therefore the Si-C composite material that includes this silicon copper has good conductivity, and then makes the lithium ion battery that uses this Si-C composite material have extraordinary cyclical stability (being that the life-span is long) and high rate capability.
Present embodiment prepares a kind of Si-C composite material by above-mentioned preparation method.
Present embodiment also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
According to the method for preparing button cell among the embodiment 2, the Si-C composite material that uses this Comparative Examples to make is made button cell as negative material, and this battery is carried out charge-discharge performance test: first discharge specific capacity has reached 2765.65mAh/g, still remain on more than the 1852.986mAh/g good cycling stability of this battery after 100 circulations.
Embodiment 5
Present embodiment provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) aqueous solution of preparation magnesium nitrate adds the mixture (wherein, the mass ratio of silica flour and silicon monoxide is 1: 1) of silica flour and silicon monoxide again, stirs to make silica flour and silicon monoxide all be uniformly dispersed in the aqueous solution of magnesium nitrate.Under stirring, again to the aqueous solution that wherein drips ammonium carbonate, equal precipitated magnesium carbonate on silica flour and silicon monoxide, and the aqueous solution excessive 2% of the ammonium carbonate that adds with guarantee in the aqueous solution the magnesium ion precipitation fully, leave standstill 2 hours after, suction filtration or centrifugal, washing 3 times, after super-dry, obtain the silicon monoxide material that silicon materials that magnesium carbonate coats and magnesium carbonate coat, wherein, the quality of silicon and silicon monoxide and with the mass ratio of magnesium carbonate be 1: 2.2.
(2) silicon materials that magnesium carbonate is coated and polyvinyl alcohol add in the planetary ball mill, with the rotating speed ball milling 6h of 300r/min, after mixing, at this moment, polyvinyl alcohol is coated on outside the silicon materials of magnesium carbonate coating, and polyvinyl alcohol is coated on outside the silicon monoxide material of magnesium carbonate coating.And then put into and carry out sintering under the nitrogen atmosphere, heating rate with 3 ℃/min is heated to 300 ℃, be incubated 2 hours, thereby make the polyvinyl alcohol carbonization become carbon, this moment the outer carbon coated of the silicon materials that magnesium carbonate coats and outside the silicon monoxide material of magnesium carbonate coating carbon coated, obtain the mixture of carbon-to-carbon acid magnesium-silicon composite material and carbon-to-carbon acid magnesium-silicon monoxide composite material, wherein, the heat decomposition temperature of magnesium carbonate is 350 ℃.
(3) mixture with carbon-to-carbon acid magnesium-silicon composite material and carbon-to-carbon acid magnesium-silicon monoxide composite material adds in the distilled water, after dispersed with stirring is even, again under stirring, to wherein dripping dilute hydrochloric acid solution magnesium carbonate is corroded, and the dilute hydrochloric acid solution excessive 2% that adds to be to guarantee that magnesium carbonate dissolves fully, carries out centrifugal, washing again 3 times, obtains Si-C composite material after super-dry, wherein, the quality of the carbon in this Si-C composite material and silicon and silicon monoxide and mass ratio be 1: 19.
Present embodiment prepares a kind of Si-C composite material by above-mentioned preparation method.
Present embodiment also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
According to the method for preparing button cell among the embodiment 2, the Si-C composite material that uses this Comparative Examples to make is made button cell as negative material, and this battery is carried out charge-discharge performance test: first discharge specific capacity has reached 1006.365mAh/g, still remain on more than the 805.6mAh/g good cycling stability of this battery after 100 circulations.
Embodiment 6
Present embodiment provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) aqueous solution of preparation calcium acetate adds the silicon silver alloy again, stirs to make the silicon silver alloy be uniformly dispersed in the aqueous solution of calcium acetate.Under stirring, drip the aqueous solution of potash in the said mixture, winnofil on the silicon silver alloy, and the aqueous solution excessive 2% of the potash that adds with guarantee in the aqueous solution the calcium ion precipitation fully, leave standstill 2 hours after, suction filtration or centrifugal, washing 3 times, after super-dry, obtain the silicon silver alloy that calcium carbonate coats, wherein, the mass ratio of silicon silver alloy and calcium carbonate is 2: 3.
(2) the silicon silver alloy that calcium carbonate is coated and pitch add in the planetary ball mill, and with the rotating speed ball milling 5h of 320r/min, after mixing, this moment, pitch-coating was outside the silicon silver alloy that calcium carbonate coats.And then put into and carry out sintering under the argon gas atmosphere, heating rate with 4 ℃/min is heated to 550 ℃, be incubated 8 hours, thereby make bitumencarb change into carbon, this moment is carbon coated outside the silicon silver alloy that calcium carbonate coats, obtain carbon-to-carbon acid calcium-silicon silver alloy composite material, wherein, the heat decomposition temperature of calcium carbonate is 825 ℃.
(3) carbon-to-carbon acid calcium-silicon silver alloy composite material is added in the distilled water, after dispersed with stirring is even, again under stirring, to wherein dripping dilute hydrochloric acid solution calcium carbonate is corroded, and the dilute hydrochloric acid solution excessive 2% that adds to be to guarantee that calcium carbonate dissolves fully, carries out centrifugal, washing again 3 times, obtains Si-C composite material after super-dry, wherein, the mass ratio of the carbon in this Si-C composite material and silicon silver alloy is 9: 1.
Present embodiment prepares a kind of Si-C composite material by above-mentioned preparation method.
Present embodiment also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
According to the method for preparing button cell among the embodiment 2, the Si-C composite material that uses this Comparative Examples to make is made button cell as negative material, and this battery is carried out charge-discharge performance test: first discharge specific capacity has reached 635.852mAh/g, still remain on more than the 552.56mAh/g good cycling stability of this battery after 100 circulations.
Embodiment 7
Present embodiment provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) aqueous solution of preparation strontium chloride adds silicon nickel alloy again, stirs to make silicon nickel alloy be uniformly dispersed in the aqueous solution of strontium chloride.Under stirring, drip the aqueous solution of ammonium carbonate in the said mixture, precipitate strontium carbonate at silicon nickel alloy, and the aqueous solution excessive 2% of the ammonium carbonate that adds with guarantee in the aqueous solution the strontium ion precipitation fully, leave standstill 2 hours after, suction filtration or centrifugal, washing 3 times, after super-dry, obtain the silicon nickel alloy material that strontium carbonate coats, wherein, the mass ratio of silicon nickel alloy and strontium carbonate is 1: 9.
(2) the silicon nickel alloy material that strontium carbonate is coated and polyvinyl chloride add in the planetary ball mill, and with the rotating speed ball milling 5h of 280r/min, after mixing, this moment, polyvinyl chloride was coated on outside the silicon nickel alloy material of strontium carbonate coating.And then put into and carry out sintering under the nitrogen atmosphere, heating rate with 4 ℃/min is heated to 650 ℃, be incubated 1 hour, thereby make the polyvinyl chloride carbonization become carbon, this moment is carbon coated outside the silicon nickel alloy material that strontium carbonate coats, obtain carbon-to-carbon acid strontium-silicon nickel alloy composite material, wherein, the heat decomposition temperature of strontium carbonate is 1100 ℃.
(3) carbon-to-carbon acid strontium-silicon nickel alloy composite material is added in the distilled water, after dispersed with stirring is even, again under stirring, to wherein dripping dilute hydrochloric acid solution strontium carbonate is corroded, owing to the nickel in the silicon nickel alloy also reacts with watery hydrochloric acid, so the dilute hydrochloric acid solution excessive 2% that adds is to guarantee all dissolvings fully of strontium carbonate and nickel, carry out again centrifugal, the washing 3 times, obtain Si-C composite material after super-dry, wherein, the carbon in this Si-C composite material and the mass ratio of silicon are 2: 3.
Present embodiment prepares a kind of Si-C composite material by above-mentioned preparation method.
Present embodiment also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
Embodiment 8
Present embodiment provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) mixed aqueous solution of preparation zinc nitrate and plumbi nitras adds silica flour again, stirs to make silica flour be uniformly dispersed in the mixed aqueous solution of zinc nitrate and plumbi nitras.Under stirring, drip the aqueous solution of sodium carbonate in the said mixture, this moment zinc nitrate and plumbi nitras generation coprecipitation reaction, on silica flour, precipitate zinc carbonate and ceruse simultaneously, and the aqueous solution excessive 2% of the sodium carbonate that adds all precipitates fully to guarantee zinc ion and lead ion in the aqueous solution, after leaving standstill 2 hours, suction filtration or centrifugal, the washing 3 times, after super-dry, obtain the common silicon materials that coat of zinc carbonate and ceruse, wherein, the quality of silicon and zinc carbonate and ceruse and mass ratio be 1: 3.2.
(2) zinc carbonate and the common silicon materials that coat of ceruse, glucose are added in the planetary ball mill, with the rotating speed ball milling 5h of 280r/min, after mixing, this moment, glucose was coated on outside zinc carbonate and the common silicon materials that coat of ceruse.And then put into and carry out sintering under the nitrogen atmosphere, heating rate with 4 ℃/min is heated to 250 ℃, be incubated 4 hours, thereby make the equal carbonization of glucose become carbon, this moment is carbon coated outside zinc carbonate and the common silicon materials that coat of ceruse, obtains carbon-to-carbon acid zinc/ceruse-silicon composite, wherein, the heat decomposition temperature of zinc carbonate is 300 ℃, and the heat decomposition temperature of ceruse is 315 ℃.
(3) carbon-to-carbon acid zinc/ceruse-silicon composite is added in the distilled water, after dispersed with stirring is even, again under stirring, to wherein dripping dilute nitric acid solution zinc carbonate, ceruse are corroded, and the dilute nitric acid solution excessive 2% that adds to be to guarantee all dissolvings fully of zinc carbonate and ceruse, carries out centrifugal, washing again 3 times, obtains Si-C composite material after super-dry, wherein, the mass ratio of the carbon in this Si-C composite material and silicon is 3: 2.
Present embodiment prepares a kind of Si-C composite material by above-mentioned preparation method.
Present embodiment also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
Be understandable that above execution mode only is the illustrative embodiments that adopts for principle of the present invention is described, yet the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement also are considered as protection scope of the present invention.
Claims (14)
1. the preparation method of a Si-C composite material is characterized in that, may further comprise the steps:
(1) at silica-base material transition zone is set, obtains the silica-base material that described transition zone coats;
(2) carbon coated outside the silica-base material that described transition zone coats obtains carbon-transition zone-silicon based composite material;
(3) remove described transition zone, obtain Si-C composite material.
2. the preparation method of Si-C composite material according to claim 1 is characterized in that, described step is specially:
(1) at described silica-base material precipitation metal carbonate transition zone, obtains the silica-base material that this metal carbonate coats;
(2) outside the silica-base material that described transition zone metal carbonate coats, coat described carbon, obtain carbon-metal carbonate-silicon based composite material, wherein, the heat decomposition temperature of described transition zone metal carbonate be higher than described outside the silica-base material that described metal carbonate coats the temperature in the process of carbon coated;
(3) use acid solution to erode described metal carbonate, obtain described Si-C composite material.
3. the preparation method of Si-C composite material according to claim 2 is characterized in that, the mass ratio of described silica-base material and described metal carbonate is (1: 9)～(2: 3).
4. the preparation method of Si-C composite material according to claim 3 is characterized in that, the mass ratio of described silica-base material and described metal carbonate is (1: 6.5)～(1: 3.2).
5. the preparation method of Si-C composite material according to claim 2 is characterized in that, the described carbon in the described Si-C composite material and the mass ratio of described silica-base material are (1: 19)～(9: 1).
6. the preparation method of Si-C composite material according to claim 5 is characterized in that, the described carbon in the described Si-C composite material and the mass ratio of described silica-base material are (3: 17)～(3: 2).
7. the preparation method of Si-C composite material according to claim 2 is characterized in that, described carbonate comprises any one or a few in magnesium carbonate, calcium carbonate, strontium carbonate, brium carbonate, zinc carbonate, the ceruse.
8. the preparation method of Si-C composite material according to claim 2 is characterized in that, described silica-base material comprises any one or a few in silicon, silicon monoxide, the silicon alloy.
9. the preparation method of Si-C composite material according to claim 8 is characterized in that, described silicon alloy is the silicon silver alloy, silicon copper, any one or a few in the silicon nickel alloy.
10. the preparation method of Si-C composite material according to claim 2, it is characterized in that, described step (2) is specially: the silica-base material that described metal carbonate is coated is with after carbon source is mixed, under nonoxidizing atmosphere, carry out calcination, described calcination temperature is 250 ℃～800 ℃, obtains described carbon-metal carbonate-silicon based composite material.
11. the preparation method of Si-C composite material according to claim 10 is characterized in that, described carbon source is any one or a few in polyvinyl alcohol, sucrose, glucose, polyacrylonitrile, phenolic resins, polyvinyl chloride, the pitch.
12. the preparation method of Si-C composite material according to claim 2, it is characterized in that, described step (1) is specially: with the aqueous solution of described silica-base material and slaine, add the carbonate deposition agent again, obtain the silica-base material that described metal carbonate coats.
13. a Si-C composite material is characterized in that, it is by any described preparation method's preparation of claim 1～12.
14. a lithium ion battery is characterized in that, its negative pole contains the described Si-C composite material of claim 13.
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