CN103236530A - Silicon-carbon composite material, preparation method thereof, and lithium ion battery containing material - Google Patents
Silicon-carbon composite material, preparation method thereof, and lithium ion battery containing material Download PDFInfo
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- CN103236530A CN103236530A CN2013101515227A CN201310151522A CN103236530A CN 103236530 A CN103236530 A CN 103236530A CN 2013101515227 A CN2013101515227 A CN 2013101515227A CN 201310151522 A CN201310151522 A CN 201310151522A CN 103236530 A CN103236530 A CN 103236530A
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 188
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 94
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 24
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 40
- 235000013312 flour Nutrition 0.000 claims description 30
- 239000004115 Sodium Silicate Substances 0.000 claims description 24
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 18
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000005538 encapsulation Methods 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
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- 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 4
- 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 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
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- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011295 pitch Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000013543 active substance Substances 0.000 abstract 1
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- 230000002035 prolonged effect Effects 0.000 abstract 1
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 235000013339 cereals Nutrition 0.000 description 8
- 230000004087 circulation Effects 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
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- 229910021641 deionized water Inorganic materials 0.000 description 6
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- 238000005516 engineering process Methods 0.000 description 6
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- 239000007787 solid Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- -1 ethyl carbonate ester Chemical class 0.000 description 3
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- 230000004888 barrier function Effects 0.000 description 2
- 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 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000011366 tin-based material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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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 provides a silicon-carbon composite material, a preparation method of the material, and a lithium ion battery containing the material, which belong to the technical field of lithium ion batteries, and can solve the problems that an existing silicon-carbon composite cathode material and a lithium ion battery prepared from the existing material are poor in cycle performance and conductivity performance. The preparation method of the composite material comprises the steps of mixing materials, coating silicon dioxide, coating carbon and taking a silicon dioxide layer off. The preparation method of the silicon-carbon composite material utilizes reserved holes to contain volume expansion during the course that silicon particles are embedded into lithium, and a conductive network carbon material is dispersed in the holes in advance, so that the conductivity of the silicon-carbon composite material is improved, the pulverization and dropping of an electrochemical active substance due to the volume expansion are alleviated and even eliminated, and the cycle life of the silicon-carbon composite material is prolonged effectively. The silicon-carbon composite material is prepared by the method; and the lithium ion battery contains the silicon-carbon composite material.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of lithium ion battery material and preparation method thereof, contain the lithium ion battery of this material.
Background technology
At present, produce the lithium ion battery that uses and mainly adopt graphitized carbon to be negative material, but the lithium storage content of material is not high.With regard to the graphite-based negative material, its bigger layer structure space has also determined the characteristic of the low theoretical specific capacity (about 372mAh/g) of this material both for the storage of lithium provides the place.Therefore, the high power capacity of development of new and high magnification negative material have very high research and value.Since long period, lithium alloy receives much attention as alternative negative material, silica-base material and tin-based material are just owing to its high specific discharge capacity (theoretical specific capacity of silica-base material and tin-based material is respectively 4200mAh/g and 990mAh/g) becomes research focus, particularly silica-base material.Yet the bulk effect that charge and discharge process Li-Si electrode is serious and powder of detached have reduced efficient and the cycle performance of battery.Developing siliceous composite material has become the emphasis of people's research, the research thinking generally with silicon and other inactive metal (as Fe, Al, Cu etc.) form alloy (Wen Zhongsheng, Yang Jun, Liu Yu etc., used as negative electrode of Li-ion battery silicon-aluminum/carbon composite and preparation method thereof, Chinese patent application number: CN03116070.0), or material evenly spread in other activity or the non-active material form composite material (as Si-C, Si-TiN etc.) (Yang Jun, Wen Zhongsheng, Liu Yu etc., the Si-C composite material of used as negative electrode of Li-ion battery height ratio capacity and preparation method, Chinese patent application number: CN02112180.X), can improve its cyclical stability to a certain extent.
Though said method has been alleviated the capacity attenuation of silicon-based anode material to a certain extent, but all to be simple physics compound or pyrocarbon coats for its mechanism, all can not fundamentally suppress the bulk effect in the charge and discharge process, through after the circulation repeatedly, capacity will begin again to decay rapidly.Therefore, it is simple and can effectively suppress the preparation technology of high power capacity silicon-based anode material of the bulk effect of silicon to be necessary to develop a kind of technology.
Summary of the invention
The objective of the invention is to solve the low problem of cycle performance, electric conductivity of existing Si-C composite material and lithium ion battery prepared therefrom, the preparation method of the good Si-C composite material of a kind of cycle performance, electric conductivity is provided.
The technical scheme that solution the technology of the present invention problem adopts is a kind of preparation method of Si-C composite material, and described preparation method comprises:
1) batch mixing step:
Silica flour and conductive carbon material are joined sodium silicate solution carry out batch mixing, obtain mixture;
2) coated with silica step:
The mixture that obtains to step 1) adds the network combined material of silicon-conductive carbon that inorganic acid reaction obtains coated with silica;
3) carbon encapsulation steps:
With step 2) the network combined material of silicon-conductive carbon of the coated with silica that obtains carries out carbon with high molecular polymer and coats under heating;
4) take off the silicon dioxide layer step:
The network combined material of silicon-conductive carbon through silicon dioxide and carbon coating that step 3) is obtained takes off silicon dioxide layer with hydrofluoric acid, obtains Si-C composite material.
The hole that the present invention reserves by utilization holds the volumetric expansion in the silicon grain embedding lithium process, and dispersed electro-conductive network material with carbon element in advance in hole, improved the conductivity of Si-C composite material, reach and slow down even eliminate electroactive substance because of the phenomenon of volumetric expansion powder of detached, effectively prolong the cycle life of Si-C composite material; And conductive network more is conducive to the quick conduction of lithium ion, has improved the conductivity of Si-C composite material; Synthesis technique is simple, easy to implement simultaneously.
Preferably, in described batch mixing step, described batch mixing is ultrasonic dispersion 1h-4h, and the mass ratio of silica flour and sodium metasilicate is 1 ︰ (5-10), and the mass ratio of conductive carbon material and silica flour is 1 ︰ (10-20).
Preferably, in described batch mixing step, described conductive carbon material is any one or a few in Graphene, carbon nano-tube, gas-phase growth of carbon fibre, acetylene black, expanded graphite, the graphite.
Preferably, in the coated with silica step, the described reaction time is 2h-4h, and described inorganic acid is hydrochloric acid or sulfuric acid.
Preferably, in the carbon encapsulation steps, described high molecular polymer is any one or a few in polyvinyl chloride, polymethyl methacrylate, polyacrylic acid, polyacrylonitrile, phenolic resins, pitch, glucose, the sucrose.
Preferably, in the carbon encapsulation steps, the mass ratio of the network combined material of silicon-conductive carbon of described high molecular polymer and coated with silica is 1 ︰ (1-3), and the heating-up temperature that described carbon coats is 700 ℃-900 ℃.
Preferably, in taking off the silicon dioxide layer step, the mass concentration of described hydrofluoric acid is 5%-40%, and the reaction time is 1h-10h, and hydrofluoric acid is (4-10) ︰ 1 with the amount of substance ratio of sodium metasilicate.
Preferably, in taking off the silicon dioxide layer step, the mass concentration of described hydrofluoric acid is 10%-20%, and the reaction time is 2h-8h.
Technical problem to be solved by this invention also comprises, at existing Si-C composite material cycle performance, the low problem of electric conductivity, provides a kind of cycle performance, the good Si-C composite material of electric conductivity.
The technical scheme that solution the technology of the present invention problem adopts is a kind of Si-C composite material, and this Si-C composite material is by method for preparing.
Because Si-C composite material of the present invention is by method for preparing, its cycle performance, electric conductivity are better.
Technical problem to be solved by this invention also comprises, at the existing low problem of lithium ion battery cycle performance, electric conductivity by the Si-C composite material preparation, provides a kind of cycle performance, the good lithium ion battery of electric conductivity.
The technical scheme that solution the technology of the present invention problem adopts is a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
Because the negative pole of lithium ion battery of the present invention contains above-mentioned Si-C composite material, so its cycle performance, electric conductivity are better.
Description of drawings
Fig. 1 is the preparation method's of the prepared Si-C composite material of the embodiment of the invention 1 schematic flow diagram.
Fig. 2 is the discharge cycles performance curve of the prepared Si-C composite material of the embodiment of the invention 1.
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.
Embodiment 1
As shown in Figure 1, present embodiment provides a kind of preparation method of Si-C composite material, and it may further comprise the steps:
1) batch mixing step:
With silica flour with to add mass concentration as the Graphene of conductive carbon material be that 40% sodium silicate solution carries out ultrasonic wave and disperses 2h, the mixture that obtains disperseing, wherein, the mass ratio of silica flour and sodium metasilicate is 1 ︰ 5, the mass ratio of Graphene and silica flour is 1 ︰ 15, and the average grain diameter of silica flour is 0.1nm;
2) coated with silica step:
Under agitation, the excessive concentration that the mixture of the dispersion that obtains to step 1) adds is the hydrochloric acid reaction 2h of 0.5M, and filtration washing obtains the network combined material of silicon-conductive carbon of coated with silica;
3) carbon encapsulation steps:
With step 2) the network combined material of silicon-conductive carbon of the coated with silica that obtains joins in the polyvinyl chloride solution; wherein the mass ratio of the network combined material of the silicon-conductive carbon of coated with silica and polyvinyl chloride is 1 ︰ 1; the back evaporate to dryness stirs; put into porcelain boat behind the gained solid porphyrize; be warmed up to 800 ℃ under the argon shield; constant temperature 3h under this temperature obtains the network combined material of silicon-conductive carbon through the coated with silica of carbon coating.
4) take off the silicon dioxide layer step:
It is in 20% the hydrofluoric acid solution that the network combined material of silicon-conductive carbon that coats through silicon dioxide and carbon that step 3) is obtained joins mass concentration, wherein, hydrofluoric acid is 4 ︰ 1 with the amount of substance ratio of sodium metasilicate, stirring reaction 10h, filter and fully wash with deionized water, namely obtain Si-C composite material after the drying.
Optionally, can continue with prepared Si-C composite material preparation experiment battery pole piece and test battery.
The preparation experiment battery with the process of pole piece is: with Si-C composite material and 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, dried 24 hours down at 100 ℃, taking-up is washed into pole piece, makes the Experimental cell pole piece.
The process of preparation test battery is: the pole piece with above-mentioned preparation is the Experimental cell pole piece, be to electrode with the lithium sheet, electrolyte is that concentration is the solution of the LiPF6 of 1.5mol/L, its solvent is EC(ethyl carbonate ester)+the DMC(dimethyl carbonate), EC(ethyl carbonate ester wherein) and the DMC(dimethyl carbonate) volume ratio be 1 ︰ 1, barrier film is the celgard2400 film, is assembled into CR2025 type button cell in being full of the glove box of argon gas atmosphere.
Cycle performance (under the constant current 0.1C) test data of the Si-C composite material of present embodiment preparation is seen Fig. 2, and the first discharge specific capacity of the Si-C composite material of present embodiment preparation has reached 1207mAh/g, still remains on 967mAh/g after 100 circulations.
Embodiment 2
Present embodiment provides a kind of preparation method of Si-C composite material, and it may further comprise the steps:
1) batch mixing step:
With silica flour with to add mass concentration as the carbon nano-tube of conductive carbon material, graphite (both mass ratioes are 1 ︰ 1) be that 40% sodium silicate solution carries out ultrasonic wave and disperses 1h, the mixture that obtains disperseing, wherein, the mass ratio of silica flour and sodium metasilicate is 1 ︰ 7, the mass ratio of carbon nano-tube, graphite and silica flour is 1 ︰ 20, and the average grain diameter of silica flour is 1nm;
2) coated with silica step:
Under agitation, the excessive concentration that the mixture of the dispersion that obtains to step 1) adds is the sulfuric acid reaction 2.5h of 0.5M, and filtration washing obtains the network combined material of silicon-conductive carbon of coated with silica;
3) carbon encapsulation steps:
With step 2) the network combined material of silicon-conductive carbon of the coated with silica that obtains joins in the polymethyl methacrylate solution; wherein the mass ratio of the network combined material of the silicon-conductive carbon of coated with silica and polymethyl methacrylate is 1 ︰ 2; the back evaporate to dryness stirs; put into porcelain boat behind the gained solid porphyrize; be warmed up to 750 ℃ under the argon shield; constant temperature 3h under this temperature obtains the network combined material of silicon-conductive carbon through the coated with silica of carbon coating.
4) take off the silicon dioxide layer step:
It is in 5% the hydrofluoric acid solution that the network combined material of silicon-conductive carbon that coats through silicon dioxide and carbon that step 3) is obtained joins mass concentration, wherein, hydrofluoric acid is 10 ︰ 1 with the amount of substance ratio of sodium metasilicate, stirring reaction 5h, filter and fully wash with deionized water, namely obtain Si-C composite material after the drying.
Optionally, can continue with prepared Si-C composite material preparation experiment battery pole piece and test battery.
The preparation experiment battery is identical with method among the embodiment 1 with pole piece and test battery method.
The first discharge specific capacity of the Si-C composite material of present embodiment preparation has reached 1098mAh/g, still remains on 761mAh/g after 100 circulations.
Embodiment 3
Present embodiment provides a kind of preparation method of Si-C composite material, and it may further comprise the steps:
1) batch mixing step:
With silica flour with to add mass concentration as the gas-phase growth of carbon fibre of conductive carbon material be that 40% sodium silicate solution carries out ultrasonic wave and disperses 4h, the mixture that obtains disperseing, wherein, the mass ratio of silica flour and sodium metasilicate is 1 ︰ 10, the mass ratio of gas-phase growth of carbon fibre and silica flour is 1 ︰ 10, and the average grain diameter of silica flour is 100nm;
2) coated with silica step:
Under agitation, the excessive concentration that the mixture of the dispersion that obtains to step 1) adds is the hydrochloric acid reaction 3h of 0.5M, and filtration washing obtains the network combined material of silicon-conductive carbon of coated with silica;
3) carbon encapsulation steps:
With step 2) the network combined material of silicon-conductive carbon of the coated with silica that obtains joins in the polyacrylic acid solution; wherein the network combined material of the silicon-conductive carbon of coated with silica and polyacrylic mass ratio are 1 ︰ 3; the back evaporate to dryness stirs; put into porcelain boat behind the gained solid porphyrize; be warmed up to 700 ℃ under the argon shield; constant temperature 3h under this temperature obtains the network combined material of silicon-conductive carbon through the coated with silica of carbon coating.
4) take off the silicon dioxide layer step:
It is in 10% the hydrofluoric acid solution that the network combined material of silicon-conductive carbon that coats through silicon dioxide and carbon that step 3) is obtained joins mass concentration, wherein, hydrofluoric acid is 6 ︰ 1 with the amount of substance ratio of sodium metasilicate, stirring reaction 1h, filter and fully wash with deionized water, namely obtain Si-C composite material after the drying.
Optionally, can continue with prepared Si-C composite material preparation experiment battery pole piece and test battery.
The preparation experiment battery is identical with method among the embodiment 1 with pole piece and test battery method.
The first discharge specific capacity of the Si-C composite material of present embodiment preparation has reached 974mAh/g, still remains on 753mAh/g after 100 circulations.
Embodiment 4
Present embodiment provides a kind of preparation method of Si-C composite material, and it may further comprise the steps:
1) batch mixing step:
With silica flour with to add mass concentration as the acetylene black of conductive carbon material be that 40% sodium silicate solution carries out ultrasonic wave and disperses 3h, the mixture that obtains disperseing, wherein, the mass ratio of silica flour and sodium metasilicate is 1 ︰ 8, the mass ratio of acetylene black and silica flour is 1 ︰ 12, and the average grain diameter of silica flour is 1000nm;
2) coated with silica step:
Under agitation, the excessive concentration that the mixture of the dispersion that obtains to step 1) adds is the sulfuric acid reaction 3.5h of 0.5M, and filtration washing obtains the network combined material of silicon-conductive carbon of coated with silica;
3) carbon encapsulation steps:
With step 2) the network combined material of silicon-conductive carbon of the coated with silica that obtains joins in the polyacrylonitrile solution; wherein the mass ratio of the network combined material of the silicon-conductive carbon of coated with silica and polyacrylonitrile is 1 ︰ 1.5; the back evaporate to dryness stirs; put into porcelain boat behind the gained solid porphyrize; be warmed up to 900 ℃ under the nitrogen protection; constant temperature 3h under this temperature obtains the network combined material of silicon-conductive carbon through the coated with silica of carbon coating.
4) take off the silicon dioxide layer step:
It is in 30% the hydrofluoric acid solution that the network combined material of silicon-conductive carbon that coats through silicon dioxide and carbon that step 3) is obtained joins mass concentration, wherein, hydrofluoric acid is 9 ︰ 1 with the amount of substance ratio of sodium metasilicate, stirring reaction 8h, filter and fully wash with deionized water, namely obtain Si-C composite material after the drying.
Optionally, can continue to continue preparation experiment battery pole piece and test battery with prepared Si-C composite material.
The preparation experiment battery is identical with method among the embodiment 1 with pole piece and test battery method.
The first discharge specific capacity of the Si-C composite material of present embodiment preparation has reached 974mAh/g, still remains on 753mAh/g after 100 circulations.
Embodiment 5
Present embodiment provides a kind of preparation method of Si-C composite material, and it may further comprise the steps:
1) batch mixing step:
With silica flour with to add mass concentration as the expanded graphite alkene of conductive carbon material be that 40% sodium silicate solution carries out ultrasonic wave and disperses 2.5h, the mixture that obtains disperseing, wherein, the mass ratio of silica flour and sodium metasilicate is 1 ︰ 9, the mass ratio of expanded graphite and silica flour is 1 ︰ 18, and the average grain diameter of silica flour is 10 μ m;
2) coated with silica step:
Under agitation, the excessive concentration that the mixture of the dispersion that obtains to step 1) adds is the hydrochloric acid reaction 4h of 0.5M, and filtration washing obtains the network combined material of silicon-conductive carbon of coated with silica;
3) carbon encapsulation steps:
With step 2) the network combined material of silicon-conductive carbon of the coated with silica that obtains joins in the phenol resin solution; wherein the mass ratio of the network combined material of the silicon-conductive carbon of coated with silica and phenolic resins is 1 ︰ 2.5; the back evaporate to dryness stirs; put into porcelain boat behind the gained solid porphyrize; be warmed up to 850 ℃ under the argon shield; constant temperature 3h under this temperature obtains the network combined material of silicon-conductive carbon through the coated with silica of carbon coating.
4) take off the silicon dioxide layer step:
It is in 40% the hydrofluoric acid solution that the network combined material of silicon-conductive carbon that coats through silicon dioxide and carbon that step 3) is obtained joins mass concentration, wherein, hydrofluoric acid is 8 ︰ 1 with the amount of substance ratio of sodium metasilicate, stirring reaction 2h, filter and fully wash with deionized water, namely obtain Si-C composite material after the drying.
Optionally, can continue with prepared Si-C composite material preparation experiment battery pole piece and test battery.
Optionally, can continue to continue preparation experiment battery pole piece and test battery with prepared Si-C composite material.
The preparation experiment battery is identical with method among the embodiment 1 with pole piece and test battery method.
The first discharge specific capacity of the Si-C composite material of present embodiment preparation has reached 1172mAh/g, still remains on 838mAh/g after 100 circulations.
Embodiment 6
Present embodiment provides a kind of preparation method of Si-C composite material, and it may further comprise the steps:
1) batch mixing step:
With silica flour with to add mass concentration as the graphite of conductive carbon material be that 40% sodium silicate solution carries out ultrasonic wave and disperses 1.5h, the mixture that obtains disperseing, wherein, the mass ratio of silica flour and sodium metasilicate is 1 ︰ 6, the mass ratio of graphite and silica flour is 1 ︰ 19, and the average grain diameter of silica flour is 5 μ m;
2) coated with silica step:
Under agitation, the excessive concentration that the mixture of the dispersion that obtains to step 1) adds is the sulfuric acid reaction 2.8h of 0.5M, and filtration washing obtains the network combined material of silicon-conductive carbon of coated with silica;
3) carbon encapsulation steps:
With step 2) the network combined material of silicon-conductive carbon of the coated with silica that obtains joins in the solution (both mass ratioes are 1 ︰ 1) of glucose, sucrose; wherein the mass ratio of the network combined material of the silicon-conductive carbon of coated with silica and glucose, sucrose is 1 ︰ 1.2; the back evaporate to dryness stirs; put into porcelain boat behind the gained solid porphyrize; be warmed up to 780 ℃ under the nitrogen protection; constant temperature 3h under this temperature obtains the network combined material of silicon-conductive carbon through the coated with silica of carbon coating.
4) take off the silicon dioxide layer step:
It is in 15% the hydrofluoric acid solution that the network combined material of silicon-conductive carbon that coats through silicon dioxide and carbon that step 3) is obtained joins mass concentration, wherein, hydrofluoric acid is 5 ︰ 1 with the amount of substance ratio of sodium metasilicate, stirring reaction 9h, filter and fully wash with deionized water, namely obtain Si-C composite material after the drying.
Optionally, can continue with prepared Si-C composite material preparation experiment battery pole piece and test battery.
The preparation experiment battery is identical with method among the embodiment 1 with pole piece and test battery method.
The first discharge specific capacity of the Si-C composite material of present embodiment preparation has reached 986mAh/g, still remains on 759mAh/g after 100 circulations.
The hole that the Si-C composite material utilization of the present invention's preparation is reserved holds the volumetric expansion in the silicon grain embedding lithium process, and dispersed electro-conductive network material with carbon element in advance in hole, improved the conductivity of Si-C composite material, reach and slow down even eliminate electroactive substance because of the phenomenon of volumetric expansion powder of detached, effectively prolong the cycle life of Si-C composite material; And conductive network more is conducive to the quick conduction of lithium ion, has improved the conductivity of Si-C composite material.Synthesis technique is simple, easy to implement simultaneously.
Embodiment 7
Present embodiment provides a kind of Si-C composite material by method for preparing.
Embodiment 8
The lithium ion battery that present embodiment provides a kind of negative pole to contain above-mentioned Si-C composite material, this lithium ion battery also comprises the assembly that other is necessary certainly, for example, negative pole, barrier film, electrolyte and shell etc. repeat no more here.
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 (10)
1. the preparation method of a Si-C composite material is characterized in that, described preparation method comprises:
1) batch mixing step:
Silica flour and conductive carbon material are joined sodium silicate solution carry out batch mixing, obtain mixture;
2) coated with silica step:
The mixture that obtains to step 1) adds the network combined material of silicon-conductive carbon that inorganic acid reaction obtains coated with silica;
3) carbon encapsulation steps:
With step 2) the network combined material of silicon-conductive carbon of the coated with silica that obtains carries out carbon with high molecular polymer and coats under heating;
4) take off the silicon dioxide layer step:
The network combined material of silicon-conductive carbon through silicon dioxide and carbon coating that step 3) is obtained takes off silicon dioxide layer with hydrofluoric acid, obtains Si-C composite material.
2. the preparation method of Si-C composite material as claimed in claim 1, it is characterized in that in described batch mixing step, described batch mixing is ultrasonic dispersion 1h-4h, the mass ratio of silica flour and sodium metasilicate is 1 ︰ (5-10), and the mass ratio of conductive carbon material and silica flour is 1 ︰ (10-20).
3. the preparation method of Si-C composite material as claimed in claim 1, it is characterized in that, in described batch mixing step, described conductive carbon material is any one or a few in Graphene, carbon nano-tube, gas-phase growth of carbon fibre, acetylene black, expanded graphite, the graphite.
4. the preparation method of Si-C composite material as claimed in claim 1 is characterized in that, in the coated with silica step, the described reaction time is 2h-4h, and described inorganic acid is hydrochloric acid or sulfuric acid.
5. the preparation method of Si-C composite material as claimed in claim 1, it is characterized in that, in the carbon encapsulation steps, described high molecular polymer is any one or a few in polyvinyl chloride, polymethyl methacrylate, polyacrylic acid, polyacrylonitrile, phenolic resins, pitch, glucose, the sucrose.
6. the preparation method of Si-C composite material as claimed in claim 1, it is characterized in that, in the carbon encapsulation steps, the mass ratio of the network combined material of silicon-conductive carbon of described high molecular polymer and coated with silica is 1 ︰ (1-3), and the heating-up temperature that described carbon coats is 700 ℃-900 ℃.
7. the preparation method of Si-C composite material as claimed in claim 1, it is characterized in that in taking off the silicon dioxide layer step, the mass concentration of described hydrofluoric acid is 5%-40%, reaction time is 1h-10h, and hydrofluoric acid is (4-10) ︰ 1 with the amount of substance ratio of sodium metasilicate.
8. the preparation method of Si-C composite material as claimed in claim 7 is characterized in that, in taking off the silicon dioxide layer step, the mass concentration of described hydrofluoric acid is 10%-20%, and the reaction time is 2h-8h.
9. a Si-C composite material is characterized in that, described Si-C composite material is by any described method preparation in the claim 1～8.
10. a lithium ion battery is characterized in that, its negative pole contains the described Si-C composite material of claim 9.
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