CN103236530B - Si-C composite material and preparation method thereof, lithium ion battery containing this material - Google Patents
Si-C composite material and preparation method thereof, lithium ion battery containing this material Download PDFInfo
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 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 21
- 239000000463 material Substances 0.000 title abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 173
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 94
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 78
- 239000002131 composite material Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000005538 encapsulation Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 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
- 239000003575 carbonaceous material Substances 0.000 claims description 12
- 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
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 6
- 230000035484 reaction time Effects 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 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
- 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 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000008103 glucose Substances 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
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011295 pitch Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052710 silicon Inorganic materials 0.000 abstract description 8
- 239000010703 silicon Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- 239000000843 powder Substances 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 235000013339 cereals Nutrition 0.000 description 8
- 238000013019 agitation Methods 0.000 description 6
- 230000004087 circulation Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 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
- 238000005516 engineering process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- -1 ethyl carbonate ester Chemical class 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000011366 tin-based material Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 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
- 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
- 230000005611 electricity Effects 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a kind of Si-C composite material and preparation method thereof, lithium ion battery containing this material, belong to technical field of lithium ion, the cycle performance of existing silicon-carbon composite cathode material and lithium ion battery prepared therefrom is poor, electric conductivity is low problem that it can solve.The preparation method of composite material of the present invention comprises the step of batch mixing, coated with silica step, carbon encapsulation steps and de-silicon dioxide layer step.The preparation method of Si-C composite material of the present invention utilizes reserved hole to hold the volumetric expansion in the embedding lithium process of silicon grain, and in hole dispersed electro-conductive network material with carbon element in advance, improve the conductivity of Si-C composite material, reach the phenomenon slowing down and even eliminate electroactive substance powder of detached because of volumetric expansion, effectively extend the cycle life of Si-C composite material.Si-C composite material of the present invention is prepared by said method.Lithium ion battery of the present invention comprises above-mentioned Si-C 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, lithium ion battery containing this material.
Background technology
At present, the lithium ion battery of production and application mainly adopts graphitized carbon to be negative material, but the lithium storage content of material is not high.With regard to graphite-based negative material, its larger layer structure space both provided place for the storage of lithium, also determined the characteristic of the low theoretical specific capacity (about 372mAh/g) of this material.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 just become study hotspot, particularly silica-base material due to its high specific discharge capacity (theoretical specific capacity of silica-base material and tin-based material is respectively 4200mAh/g and 990mAh/g).But the charge and discharge process Li-Si CR Critical bulk effect of electricity and powder of detached reduce efficiency and the cycle performance of battery.Develop the emphasis that siliceous composite material has become people's research, Research Thinking generally by silicon and other inactive metal (as Fe, Al, Cu etc.) form alloy (Wen Zhongsheng, Yang Jun, Liu Yu etc., silicon aluminium alloy/carbon composite material used for lithium ion battery negative electrode and preparation method thereof, Chinese Patent Application No.: CN03116070.0), or homogenize material is distributed in other active or non-active material and forms 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 No.: CN02112180.X), its cyclical stability can be improved to a certain extent.
Although said method alleviates the capacity attenuation of silicon based anode material to a certain extent, but its mechanism is all that simple physics compound or pyrocarbon are coated, all fundamentally can not suppress the bulk effect in charge and discharge process, after repeatedly circulating, capacity will start again decay rapidly.Therefore, a kind of technique is necessary to develop simple and effectively can suppress the preparation technology of the high power capacity silicon based anode material of the bulk effect of silicon.
Summary of the invention
The object of the invention is to solve the problem that the cycle performance of existing Si-C composite material and lithium ion battery prepared therefrom, electric conductivity are low, the preparation method of the Si-C composite material providing a kind of cycle performance, electric conductivity excellent.
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 and carries out batch mixing, obtain mixture;
2) coated with silica step:
The mixture obtained to step 1) adds silicon-conductive carbon net composites that inorganic acid reaction obtains coated with silica;
3) carbon encapsulation steps:
By step 2) coated with silica that obtains that silicon-conductive carbon net composites high molecular polymer carries out carbon is under heating coated;
4) de-silicon dioxide layer step:
What step 3) obtained carries out de-silicon dioxide layer through silicon dioxide and the coated silicon-conductive carbon net composites hydrofluoric acid of carbon, obtains Si-C composite material.
The present invention holds volumetric expansion in the embedding lithium process of silicon grain by utilizing reserved hole, and in hole dispersed electro-conductive network material with carbon element in advance, improve the conductivity of Si-C composite material, reach the phenomenon slowing down and even eliminate electroactive substance powder of detached because of volumetric expansion, effectively extend the cycle life of Si-C composite material; And conductive network is more conducive to the quick conduction of lithium ion, improves the conductivity of Si-C composite material; Synthesis technique is simple simultaneously, easy to implement.
Preferably, in described batch mixing step, described batch mixing is ultrasonic disperse 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, graphite.
Preferably, in coated with silica step, the described reaction time is 2h-4h, and described inorganic acid is hydrochloric acid or sulfuric acid.
Preferably, in 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, sucrose.
Preferably, in carbon encapsulation steps, the mass ratio of the silicon-conductive carbon net composites of described high molecular polymer and coated with silica is 1 ︰ (1-3), and the coated heating-up temperature of described carbon is 700 DEG C-900 DEG C.
Preferably, in de-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 de-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, and for existing Si-C composite material cycle performance, the low problem of electric conductivity, provides the Si-C composite material that a kind of cycle performance, electric conductivity are excellent.
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 prepared by said method.
Because Si-C composite material of the present invention is prepared by said method, its cycle performance, electric conductivity are better.
Technical problem to be solved by this invention also comprises, and for existing cycle performance of lithium ion battery, the low problem of electric conductivity prepared by Si-C composite material, provides the lithium ion battery that a kind of cycle performance, electric conductivity are excellent.
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.
Negative pole due to lithium ion battery of the present invention contains above-mentioned Si-C composite material, therefore its cycle performance, electric conductivity are better.
Accompanying drawing explanation
The schematic flow diagram of the preparation method of the Si-C composite material of Fig. 1 prepared by the embodiment of the present invention 1.
The discharge cycles performance curve of the Si-C composite material of Fig. 2 prepared by the embodiment of the present 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, the present embodiment provides a kind of preparation method of Si-C composite material, and it comprises the following steps:
1) batch mixing step:
Using silica flour and as the Graphene of conductive carbon material add mass concentration be 40% sodium silicate solution carry out ultrasonic wave dispersion 2h, obtain the mixture disperseed, 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 obtained to step 1) adds is the hydrochloric acid reaction 2h of 0.5M, and filtration washing obtains the silicon-conductive carbon net composites of coated with silica;
3) carbon encapsulation steps:
By step 2) silicon-conductive carbon net composites of coated with silica that obtains joins in polyvinyl chloride solution; wherein silicon-conductive carbon the net composites of coated with silica and the mass ratio of polyvinyl chloride are 1 ︰ 1; evaporate to dryness after stirring; porcelain boat is put into after gained solid porphyrize; 800 DEG C are warmed up under argon shield; constant temperature 3h at this temperature, obtains the silicon-conductive carbon net composites through the coated coated with silica of carbon.
4) de-silicon dioxide layer step:
Step 3) is obtained to join mass concentration through silicon dioxide and the coated silicon-conductive carbon net composites of carbon be in the hydrofluoric acid solution of 20%, 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, after drying, namely obtaining Si-C composite material.
Optionally, can continue with prepared Si-C composite material preparation experiment battery pole piece and test battery.
The process of preparation experiment battery pole piece is: by Si-C composite material and conductive agent acetylene black, binding agent PVDF(Kynoar) mix according to mass ratio 8 ︰ 1 ︰ 1, use NMP(1-N-methyl-2-2-pyrrolidone N-) this mixture is modulated into slurry, evenly be coated on Copper Foil, put into baking oven, dry 24 hours at 100 DEG C, taking-up is washed into pole piece, obtained experimental cell pole piece.
The process preparing test battery is: with the pole piece of above-mentioned preparation for experimental cell pole piece, be to electrode with lithium sheet, the solution of electrolyte to be concentration the be LiPF6 of 1.5mol/L, its solvent is EC(ethyl carbonate ester)+DMC(dimethyl carbonate), wherein EC(ethyl carbonate ester) and DMC(dimethyl carbonate) volume ratio be 1 ︰ 1, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
Cycle performance (under the constant current 0.1C) test data of Si-C composite material prepared by the present embodiment is shown in Fig. 2, and the first discharge specific capacity of Si-C composite material prepared by the present embodiment reaches 1207mAh/g, still remains on 967mAh/g after 100 circulations.
Embodiment 2
The present embodiment provides a kind of preparation method of Si-C composite material, and it comprises the following steps:
1) batch mixing step:
Using silica flour and as the carbon nano-tube of conductive carbon material, graphite (both mass ratioes are 1 ︰ 1) add mass concentration be 40% sodium silicate solution carry out ultrasonic wave dispersion 1h, obtain the mixture disperseed, 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 obtained to step 1) adds is the sulfuric acid reaction 2.5h of 0.5M, and filtration washing obtains the silicon-conductive carbon net composites of coated with silica;
3) carbon encapsulation steps:
By step 2) silicon-conductive carbon net composites of coated with silica that obtains joins in polymethyl methacrylate solution; wherein silicon-conductive carbon the net composites of coated with silica and the mass ratio of polymethyl methacrylate are 1 ︰ 2; evaporate to dryness after stirring; porcelain boat is put into after gained solid porphyrize; 750 DEG C are warmed up under argon shield; constant temperature 3h at this temperature, obtains the silicon-conductive carbon net composites through the coated coated with silica of carbon.
4) de-silicon dioxide layer step:
Step 3) is obtained to join mass concentration through silicon dioxide and the coated silicon-conductive carbon net composites of carbon be in the hydrofluoric acid solution of 5%, 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, after drying, namely obtaining Si-C composite material.
Optionally, can continue with prepared Si-C composite material preparation experiment battery pole piece and test battery.
Preparation experiment battery pole piece is identical with the method in embodiment 1 with test battery method.
The first discharge specific capacity of Si-C composite material prepared by the present embodiment reaches 1098mAh/g, still remains on 761mAh/g after 100 circulations.
Embodiment 3
The present embodiment provides a kind of preparation method of Si-C composite material, and it comprises the following steps:
1) batch mixing step:
Using silica flour and as the gas-phase growth of carbon fibre of conductive carbon material add mass concentration be 40% sodium silicate solution carry out ultrasonic wave dispersion 4h, obtain the mixture disperseed, 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 obtained to step 1) adds is the hydrochloric acid reaction 3h of 0.5M, and filtration washing obtains the silicon-conductive carbon net composites of coated with silica;
3) carbon encapsulation steps:
By step 2) silicon-conductive carbon net composites of coated with silica that obtains joins in polyacrylic acid solution; wherein silicon-conductive carbon the net composites of coated with silica and polyacrylic mass ratio are 1 ︰ 3; evaporate to dryness after stirring; porcelain boat is put into after gained solid porphyrize; 700 DEG C are warmed up under argon shield; constant temperature 3h at this temperature, obtains the silicon-conductive carbon net composites through the coated coated with silica of carbon.
4) de-silicon dioxide layer step:
Step 3) is obtained to join mass concentration through silicon dioxide and the coated silicon-conductive carbon net composites of carbon be in the hydrofluoric acid solution of 10%, 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, after drying, namely obtaining Si-C composite material.
Optionally, can continue with prepared Si-C composite material preparation experiment battery pole piece and test battery.
Preparation experiment battery pole piece is identical with the method in embodiment 1 with test battery method.
The first discharge specific capacity of Si-C composite material prepared by the present embodiment reaches 974mAh/g, still remains on 753mAh/g after 100 circulations.
Embodiment 4
The present embodiment provides a kind of preparation method of Si-C composite material, and it comprises the following steps:
1) batch mixing step:
Using silica flour and as the acetylene black of conductive carbon material add mass concentration be 40% sodium silicate solution carry out ultrasonic wave dispersion 3h, obtain the mixture disperseed, 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 obtained to step 1) adds is the sulfuric acid reaction 3.5h of 0.5M, and filtration washing obtains the silicon-conductive carbon net composites of coated with silica;
3) carbon encapsulation steps:
By step 2) silicon-conductive carbon net composites of coated with silica that obtains joins in polyacrylonitrile solution; wherein silicon-conductive carbon the net composites of coated with silica and the mass ratio of polyacrylonitrile are 1 ︰ 1.5; evaporate to dryness after stirring; porcelain boat is put into after gained solid porphyrize; 900 DEG C are warmed up under nitrogen protection; constant temperature 3h at this temperature, obtains the silicon-conductive carbon net composites through the coated coated with silica of carbon.
4) de-silicon dioxide layer step:
Step 3) is obtained to join mass concentration through silicon dioxide and the coated silicon-conductive carbon net composites of carbon be in the hydrofluoric acid solution of 30%, 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, after drying, namely obtaining Si-C composite material.
Optionally, can continue to continue preparation experiment battery pole piece and test battery with prepared Si-C composite material.
Preparation experiment battery pole piece is identical with the method in embodiment 1 with test battery method.
The first discharge specific capacity of Si-C composite material prepared by the present embodiment reaches 974mAh/g, still remains on 753mAh/g after 100 circulations.
Embodiment 5
The present embodiment provides a kind of preparation method of Si-C composite material, and it comprises the following steps:
1) batch mixing step:
Using silica flour and as the expanded graphite alkene of conductive carbon material add mass concentration be 40% sodium silicate solution carry out ultrasonic wave dispersion 2.5h, obtain the mixture disperseed, 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 μm;
2) coated with silica step:
Under agitation, the excessive concentration that the mixture of the dispersion obtained to step 1) adds is the hydrochloric acid reaction 4h of 0.5M, and filtration washing obtains the silicon-conductive carbon net composites of coated with silica;
3) carbon encapsulation steps:
By step 2) silicon-conductive carbon net composites of coated with silica that obtains joins in phenol resin solution; wherein silicon-conductive carbon the net composites of coated with silica and the mass ratio of phenolic resins are 1 ︰ 2.5; evaporate to dryness after stirring; porcelain boat is put into after gained solid porphyrize; 850 DEG C are warmed up under argon shield; constant temperature 3h at this temperature, obtains the silicon-conductive carbon net composites through the coated coated with silica of carbon.
4) de-silicon dioxide layer step:
Step 3) is obtained to join mass concentration through silicon dioxide and the coated silicon-conductive carbon net composites of carbon be in the hydrofluoric acid solution of 40%, 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, after drying, namely obtaining Si-C composite material.
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.
Preparation experiment battery pole piece is identical with the method in embodiment 1 with test battery method.
The first discharge specific capacity of Si-C composite material prepared by the present embodiment reaches 1172mAh/g, still remains on 838mAh/g after 100 circulations.
Embodiment 6
The present embodiment provides a kind of preparation method of Si-C composite material, and it comprises the following steps:
1) batch mixing step:
Using silica flour and as the graphite of conductive carbon material add mass concentration be 40% sodium silicate solution carry out ultrasonic wave dispersion 1.5h, obtain the mixture disperseed, 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 μm;
2) coated with silica step:
Under agitation, the excessive concentration that the mixture of the dispersion obtained to step 1) adds is the sulfuric acid reaction 2.8h of 0.5M, and filtration washing obtains the silicon-conductive carbon net composites of coated with silica;
3) carbon encapsulation steps:
By step 2) silicon-conductive carbon net composites of coated with silica that obtains joins in the solution (both mass ratioes are 1 ︰ 1) of glucose, sucrose; wherein the mass ratio of the silicon-conductive carbon net composites of coated with silica and glucose, sucrose is 1 ︰ 1.2; evaporate to dryness after stirring; porcelain boat is put into after gained solid porphyrize; 780 DEG C are warmed up under nitrogen protection; constant temperature 3h at this temperature, obtains the silicon-conductive carbon net composites through the coated coated with silica of carbon.
4) de-silicon dioxide layer step:
Step 3) is obtained to join mass concentration through silicon dioxide and the coated silicon-conductive carbon net composites of carbon be in the hydrofluoric acid solution of 15%, 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, after drying, namely obtaining Si-C composite material.
Optionally, can continue with prepared Si-C composite material preparation experiment battery pole piece and test battery.
Preparation experiment battery pole piece is identical with the method in embodiment 1 with test battery method.
The first discharge specific capacity of Si-C composite material prepared by the present embodiment reaches 986mAh/g, still remains on 759mAh/g after 100 circulations.
Si-C composite material prepared by the present invention utilizes reserved hole to hold the volumetric expansion in the embedding lithium process of silicon grain, and in hole dispersed electro-conductive network material with carbon element in advance, improve the conductivity of Si-C composite material, reach the phenomenon slowing down and even eliminate electroactive substance powder of detached because of volumetric expansion, effectively extend the cycle life of Si-C composite material; And conductive network is more conducive to the quick conduction of lithium ion, improves the conductivity of Si-C composite material.Synthesis technique is simple simultaneously, easy to implement.
Embodiment 7
The present embodiment provides a kind of Si-C composite material prepared by said method.
Embodiment 8
The present embodiment provides a kind of negative pole to contain the lithium ion battery of above-mentioned Si-C composite material, and this lithium ion battery also comprises the assembly of other necessity certainly, and such as, negative pole, barrier film, electrolyte and shell etc., repeat no more here.
Be understandable that, the illustrative embodiments that above execution mode is only used to principle of the present invention is described and adopts, but 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 are also considered as protection scope of the present invention.
Claims (9)
1. a preparation method for 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 and carries out batch mixing, obtain mixture, wherein, described conductive carbon material is gas-phase growth of carbon fibre;
2) coated with silica step:
To step 1) mixture that obtains adds silicon-conductive carbon net composites that inorganic acid reaction obtains coated with silica;
3) carbon encapsulation steps:
By step 2) coated with silica that obtains that silicon-conductive carbon net composites high molecular polymer carries out carbon is under heating coated;
4) de-silicon dioxide layer step:
By step 3) obtain carry out de-silicon dioxide layer through silicon dioxide and the coated silicon-conductive carbon net composites hydrofluoric acid of carbon, obtain 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 disperse 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 coated with silica step, the described reaction time is 2h-4h, and described inorganic acid is hydrochloric acid or sulfuric acid.
4. the preparation method of Si-C composite material as claimed in claim 1, it is characterized in that, in 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, sucrose.
5. the preparation method of Si-C composite material as claimed in claim 1, it is characterized in that, in carbon encapsulation steps, the mass ratio of the silicon-conductive carbon net composites of described high molecular polymer and coated with silica is 1 ︰ (1-3), and the coated heating-up temperature of described carbon is 700 DEG C-900 DEG C.
6. the preparation method of Si-C composite material as claimed in claim 1, it is characterized in that, in de-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.
7. the preparation method of Si-C composite material as claimed in claim 6, it is characterized in that, in de-silicon dioxide layer step, the mass concentration of described hydrofluoric acid is 10%-20%, and the reaction time is 2h-8h.
8. a Si-C composite material, is characterized in that, described Si-C composite material is prepared by the method in claim 1 ~ 7 described in any one.
9. a lithium ion battery, is characterized in that, its negative pole contains Si-C composite material according to claim 8.
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| CN104882594B (en) * | 2015-04-16 | 2017-07-07 | 中国人民解放军国防科学技术大学 | Three-dimensional grapheme hollow carbon sphere nano-complex and preparation method thereof |
| CN106450192A (en) * | 2016-10-14 | 2017-02-22 | 浙江天能能源科技股份有限公司 | Silicon/carbon composite material for lithium ion battery and preparation method and application thereof |
| CN106602014B (en) * | 2016-12-19 | 2019-01-29 | 长虹三杰新能源有限公司 | A kind of preparation method and battery of smart home lithium ion battery |
| CN107611366B (en) * | 2017-07-31 | 2019-11-19 | 宁夏西墨新材料科技有限公司 | A kind of preparation method of lithium ion battery negative material |
| CN107579214B (en) * | 2017-08-15 | 2020-05-19 | 武汉科技大学 | Method for preparing silicon-carbon composite material by taking silicate glass as raw material, product and application thereof |
| CN108439417B (en) * | 2018-04-20 | 2021-05-25 | 西安理工大学 | Preparation method of carbon nano tube coated silicon dioxide microsphere composite nano material |
| CN108677524A (en) * | 2018-05-02 | 2018-10-19 | 陕西金瑞烯科技发展有限公司 | A kind of preparation method of graphene polyester fiber |
| US20210167367A1 (en) * | 2018-08-30 | 2021-06-03 | Panasonic Intellectual Property Management Co., Ltd. | Negative electrode active material for secondary batteries and secondary battery |
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| CN111029558A (en) * | 2019-12-25 | 2020-04-17 | 广东凯金新能源科技股份有限公司 | Silicon-carbon composite negative electrode material with hollow core-shell structure and preparation method thereof |
| CN111366631B (en) * | 2020-03-02 | 2023-07-21 | 中北大学 | Determining adsorption performance of material by electrochemical polarization curve and/or electrochemical impedance spectrum |
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