CN102800851A - Silicon carbon composite material and preparation method thereof, lithium ion battery containing same - Google Patents
Silicon carbon composite material and preparation method thereof, lithium ion battery containing same Download PDFInfo
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- CN102800851A CN102800851A CN2012102944691A CN201210294469A CN102800851A CN 102800851 A CN102800851 A CN 102800851A CN 2012102944691 A CN2012102944691 A CN 2012102944691A CN 201210294469 A CN201210294469 A CN 201210294469A CN 102800851 A CN102800851 A CN 102800851A
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 177
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 89
- 239000010703 silicon Substances 0.000 claims abstract description 76
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 76
- 239000002131 composite material Substances 0.000 claims abstract description 56
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 43
- 239000007789 gas Substances 0.000 claims description 28
- 235000012239 silicon dioxide Nutrition 0.000 claims description 19
- 235000013312 flour Nutrition 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- 238000005229 chemical vapour deposition Methods 0.000 claims description 9
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 239000007833 carbon precursor Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 69
- 239000000463 material Substances 0.000 abstract description 25
- 239000011248 coating agent Substances 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 239000011258 core-shell material Substances 0.000 abstract 1
- 239000011863 silicon-based powder Substances 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 38
- 229910052786 argon Inorganic materials 0.000 description 19
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 18
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 15
- 229910052744 lithium Inorganic materials 0.000 description 15
- 230000004087 circulation Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000003595 mist Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 5
- 150000001721 carbon Chemical class 0.000 description 4
- 150000003376 silicon Chemical class 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black 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
- 239000010405 anode material Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 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
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- -1 ethyl carbonate ester Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011366 tin-based material Substances 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 containing the material. The preparation method of the silicon carbon composite material comprises the following steps: (1) calcining silicon powder in oxygen-containing atmosphere to obtain a composite material with silica-coated silicon; (2) coating the composite material with silica-coated silicon by carbon; (3) corroding the silica with excessive hydrofluoric acid to obtain the silicon carbon composite material. The preparation process of the silicon carbon composite material is simple; the preparation of the composite material with silica-coated silicon by partial oxidation of silicon is simple, and controllable in silicon oxidation degree; the silica layer of the material obtained after coating the composite material with silica-coated silicon by carbon is easy to remove; and a core shell structure with a certain gap between the carbon layer and the silicon is obtained. The preparation process is simple; the silicon carbon composite material prepared by the preparation method has better electrochemical properties; batteries prepared by the silicon carbon composite material have better cycle performance.
Description
Technical field
The invention belongs to battery manufacturing technology field, the lithium ion battery that is specifically related to a kind of height ratio capacity Si-C composite material and preparation method thereof and uses this Si-C composite material to prepare.
Background technology
At present; It is negative material that the lithium ion battery of practical application mainly adopts graphitized carbon; The layer structure space that the graphite-based negative material is bigger is that the storage of lithium provides the place, the big characteristic that has determined the low theoretical specific capacity (about 372mAh/g) of this material of this layer structure.Therefore, high power capacity and powerful negative material have very high research and use value.For a long time, silica-based and tin-based material are just owing to its high specific discharge capacity (theoretical specific capacity of silicon and tin is respectively 4200mAh/g and 990mAh/g) becomes research focus, particularly silica-base material.Yet silicium cathode is accompanied by serious volumetric expansion and contraction in the doff lithium process, causes the electroactive material powder of detached on the electrode, finally causes capacity attenuation.For improving the cyclical stability of silica-base material; Developing siliceous alloy and composite material has become the emphasis of people's research; The research thinking generally is that silicon and other inactive metals (like Fe, Al, Cu etc.) are formed alloy (Wen Zhongsheng, Yang Jun, Liu Yu etc.; Used as negative electrode of Li-ion battery silicon-aluminum/carbon composite and preparation method thereof; One Chinese patent application number: CN03116070.0), or silicon materials are evenly spread to form composite materials such as Si-C, Si-TiN (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 in other activity or the non-active material; One Chinese patent application number: CN02112180.X), these alloys and composite material 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.
Summary of the invention
Technical problem to be solved by this invention is to the above-mentioned deficiency that exists in the prior art, the lithium ion battery that a kind of Si-C composite material and preparation method thereof is provided and is prepared by this Si-C composite material.This preparation technology is simple, and prepared Si-C composite material can effectively suppress the volumetric expansion of silicium cathode, big, the good cycle of corresponding lithium ion battery specific capacity.
Solving the technical scheme that technical problem of the present invention adopted is a kind of preparation method of Si-C composite material, may further comprise the steps:
(1), obtains the composite material of coated with silica silicon with silica flour calcination under oxygen-containing atmosphere;
(2) with the composite material carbon coated of said coated with silica silicon;
(3) corrode said silicon dioxide with excessive hydrofluoric acid, obtain Si-C composite material.
Preferably, the particle diameter of the silica flour in the said step (1) is 0.005 ~ 50 μ m.
Preferably, the particle diameter of the silica flour in the said step (1) is 5 ~ 50nm.
Preferably, the calcination temperature in the said step (1) is 400 ~ 600 ℃, and calcination time is 0.5 ~ 2 hour.
Preferably, the heating rate in the said step (1) is 5 ~ 10 ℃/minute.
Preferably, in the said step (2) on the composite material of said coated with silica silicon the method for carbon coated be: with the organic carbon precursor mix with the composite material of said coated with silica silicon the back calcination; Perhaps through chemical vapour deposition technique carbon coated on the composite material of said coated with silica silicon.
Preferably; Said chemical vapour deposition technique in the method for carbon coated on the composite material of said coated with silica silicon is: under the vacuum condition; In the composite material of said coated with silica silicon, feed carbon-source gas, under 550 ~ 900 ℃ temperature, pyrolysis carbon-source gas 10 ~ 100 minutes.
Preferably; Said chemical vapour deposition technique in the method for carbon coated on the composite material of said coated with silica silicon is: the composite material of said coated with silica silicon is heated to 500 ~ 700 ℃ under vacuum; Feed carbon-source gas then; Elevated temperature is 50 ~ 200 ℃ again, pyrolysis carbon-source gas 10 ~ 100 minutes.
Preferably, the heating rate in the said chemical vapour deposition technique is 5 ~ 10 ℃/minute.
Preferably, said carbon-source gas is the mist of argon gas and acetylene, and wherein the volume ratio of argon gas and acetylene is 9: 1.
Preferably, the hydrofluoric concentration in the hydrofluoric acid in the said step (3) is 5wt% ~ 10wt%.
Preferably, the content of the carbon in the said Si-C composite material that obtains in the said step (3) is 3wt% ~ 10wt%.
The present invention also provides a kind of Si-C composite material, and it is by above-mentioned described method preparation.
The present invention also provides a kind of lithium ion battery, and its negative pole contains above-mentioned described Si-C composite material, even prepare the negative pole of lithium ion battery with above-mentioned Si-C composite material, is assembled into lithium ion battery again.
Beneficial effect of the present invention: the preparation process of this Si-C composite material is simple; Wherein the preparation of the composite material of generation coated with silica silicon is simple behind the silicon generation partial oxidation; The degree of oxidation of silicon is controlled easily; And the material on the composite material of this coated with silica silicon after the carbon coated is prone to remove silicon dioxide layer, and this Si-C composite material has certain lithium storage content, and this is because it has used the dispersible carrier of the carbon class material of electrochemical reversible doff lithium stable performance as active material.Si-C composite material discharge and recharge characteristic possess carrier carbon material and silicon class material separately discharge and recharge characteristic and compound characteristics, so possess the high lithium storage content characteristic of silicon class material and the high cyclical stability of carbon class material simultaneously.
The Si-C composite material that use the present invention makes is as the negative pole of lithium ion battery; Can make the specific capacity and the cycle performance of lithium ion battery have marked improvement; By the battery of made of the present invention, first discharge specific capacity is high, and stable; First discharge specific capacity still remains on 600 ~ 830mAh/g at 970 ~ 1410mAh/g after 100 circulations.
Description of drawings
Fig. 1 is the sketch map that material structure changes in the preparation Si-C composite material process in the embodiment of the invention 1;
Fig. 2 is the sketch map that the material structure of the doff lithium of Si-C composite material in charge and discharge process of preparation in the embodiment of the invention 1 changes;
The charge-discharge performance resolution chart of the lithium ion battery that Fig. 3 processes for the Si-C composite material of preparation in the embodiment of the invention 1.
Among the figure: 1-silicon; The 2-silicon dioxide layer; The 3-carbon-coating; The composite material of 4-coated with silica silicon; The 5-Si-C composite material; 6-Li
xSi.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, the present invention is described in further detail below in conjunction with accompanying drawing and embodiment.
Embodiment 1
Present embodiment provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) take by weighing the silica flour that a certain amount of particle diameter is 5 μ m, the speed with 7 ℃/minute under Muffle furnace air atmosphere is warmed up to 480 ℃, and calcination 1.2 hours obtains the composite material 4 of coated with silica silicon.
(2) composite material 4 of coated with silica silicon is placed on the central authorities of tube furnace; Tube furnace is evacuated to furnace pressure smaller or equal to 0.01 atmospheric pressure; Be warming up to 500 ℃ with 7 ℃/minute speed then, feed the mist (wherein, the volume ratio of argon gas and acetylene is 9: 1) of argon gas and acetylene this moment; Again furnace temperature is raise 50 ℃, and be incubated 100 minutes.Carbon-coating 3 through chemical vapour deposition technique coats on the composite material 4 of coated with silica silicon is even, and carbon-coating 3 quality of deposition are better.
(3) use the hydrofluoric acid corrode silicon dioxide of excessive concentration as 9wt%, the content that obtains the carbon in the Si-C composite material is 6wt%.The degree of oxidation of the silicon 1 in the step (1) is easy to control, and the amount that changes into silicon dioxide through control silicon 1 partial oxygen can obtain the ratio of silicon 1 and silicon dioxide in the composite material 4 of coated with silica silicon.Like this after coating carbon-coating 3 erodes silicon dioxide layer 2 again on the composite material 4 of coated with silica silicon; Can be through different silicon in the composite material 4 of regulating coated with silica silicon 1 and silicon dioxide ratio, and the size in the space between adjustment carbon-coating 3 and the silicon 1.
As shown in Figure 1; At first silicon 1 takes place to generate silicon dioxide layer 2 on the surface of silicon behind the partial oxidation in air; Generate the composite material 4 of coated with silica silicon, on the composite material 4 of coated with silica silicon, coat carbon-coating 3 through chemical vapor deposition processes then, erode silicon dioxide layer 2 with hydrofluoric acid again; Form the nucleocapsid structure that certain gap is arranged between carbon-coating 3 and the silicon 1, obtain Si-C composite material 5.
Gained Si-C composite material 5 is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10; With NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry; Evenly be coated on the Copper Foil, 100 ℃ of vacuumize 24 hours makes Experimental cell and uses pole piece.With the lithium sheet is to electrode; Electrolyte is the LiPF6 solution of 1mol/L; Solvent is EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1), and barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Be illustrated in figure 2 as the sketch map of the material structure variation of the doff lithium of Si-C composite material in charge and discharge process in the embodiment of the invention 1.The negative material of this battery is a Si-C composite material 5, and the structure of this Si-C composite material 5 is for there being the nucleocapsid structure of certain gap between carbon-coating 3 and silicon 1.When lithium cell charging, lithium ion is embedded in the Si-C composite material 5, and the silicon in lithium ion and the Si-C composite material generates Li
xSi6, silicon 1 volume expanding in so original nucleocapsid structure, the space in the nucleocapsid structure can hold the Li that generates after silicon expands
xSi6.When lithium battery discharged, lithium ion took off embedding from the space of Si-C composite material 5, and the nucleocapsid structure of Si-C composite material 5 is stable existence still.In the whole charging and discharging process of lithium battery, the porous crack mechanism of Si-C composite material 5 has effectively suppressed the bulk effect of silicon 1, and the powder phenomenon-tion of the negative material of having avoided causing owing to volumetric expansion has improved the cycle performance of lithium ion battery.
Be illustrated in figure 3 as the charge-discharge performance resolution chart of the lithium ion battery that the silicon-carbon composite cathode material of present embodiment preparation makes; First discharge specific capacity has reached 1407mAh/g; For the second time specific discharge capacity just drops to about 1120mAh/g, and this mainly is to generate solid electrolyte membrane (SEI film) and part irreversible reaction (silicon grain that does not coat like part splits and comes off, composite material in have small amount of oxygen to combine the generation lithia with lithium) first in the discharge process to cause.But along with cycle-index increases, the decay of battery specific capacity is also not obvious, still remains on 720mAh/g after 100 circulations after the first charge-discharge.
The preparation process of this Si-C composite material 5 is simple; Wherein the preparation of the composite material 4 of generation coated with silica silicon is simple behind the silicon 1 generation partial oxidation; The degree of oxidation of silicon 1 is controlled easily; And the material on the composite material 4 of this coated with silica silicon after the carbon coated is prone to remove silicon dioxide layer 2, and this Si-C composite material 5 has certain lithium storage content, and this is because it has used the dispersible carrier of the carbon class material of electrochemical reversible doff lithium stable performance as active material.Si-C composite material 5 discharge and recharge characteristic possess carrier carbon material and silicon class material separately discharge and recharge characteristic and compound characteristics, so possess the high lithium storage content characteristic of silicon class material and the high cyclical stability of carbon class material simultaneously.
Embodiment 2
Present embodiment provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) particle diameter that takes by weighing 1000 grams is the silica flour of 5 μ m, and the speed with 7 ℃/minute under Muffle furnace air atmosphere is warmed up to 500 ℃, and calcination 1.5 hours obtains the composite material of coated with silica silicon.
(2) the phenolic resins ball milling with the composite material of coated with silica silicon and 80 grams mixes, under the inert atmosphere 700 ℃ of following high temperature sinterings 3 hours.
(3) use the hydrofluoric acid corrode silicon dioxide of excessive concentration as 7wt%, the content that obtains the carbon in the Si-C composite material is 9wt%.
The manufacture method of CR2025 type button cell such as embodiment 1 press the battery of present embodiment method made, and first discharge specific capacity has reached 1232mAh/g, still remain on 833mAh/g after 105 circulations.
Present embodiment provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) take by weighing the silica flour that a certain amount of particle diameter is 30nm, the speed with 8 ℃/minute under Muffle furnace air atmosphere is warmed up to 550 ℃, and calcination 2 hours obtains the composite material of coated with silica silicon.
(2) composite material of coated with silica silicon is placed on the central authorities of tube furnace; Tube furnace is evacuated to furnace pressure smaller or equal to 0.01 atmospheric pressure; The mist that feed argon gas and acetylene this moment (wherein; The volume ratio of argon gas and acetylene is 9: 1), be warming up to 700 ℃ with 8 ℃/minute speed then, and be incubated 50 minutes.
(3) use the hydrofluoric acid corrode silicon dioxide of excessive concentration as 8wt%, the content that obtains the carbon in the Si-C composite material is 7wt%.
The manufacture method of CR2025 type button cell such as embodiment 1 press the battery of present embodiment method made, and first discharge specific capacity has reached 1017mAh/g, still remain on 674mAh/g after 105 circulations.
Embodiment 4
Present embodiment provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) take by weighing the silica flour that a certain amount of particle diameter is 0.05 μ m, the speed with 10 ℃/minute under Muffle furnace air atmosphere is warmed up to 400 ℃, and calcination 0.5 hour obtains the composite material of coated with silica silicon.
(2) composite material of coated with silica silicon is placed on the central authorities of tube furnace; Tube furnace is evacuated to furnace pressure smaller or equal to 0.01 atmospheric pressure; The mist that feed argon gas and acetylene this moment (wherein; The volume ratio of argon gas and acetylene is 9: 1), be warming up to 550 ℃ with 10 ℃/minute speed then, and be incubated 100 minutes.
(3) use the hydrofluoric acid corrode silicon dioxide of excessive concentration as 5wt%, the content that obtains the carbon in the Si-C composite material is 3wt%.
The manufacture method of CR2025 type button cell such as embodiment 1 press the battery of present embodiment method made, and first discharge specific capacity has reached 1098mAh/g, still remain on 631mAh/g after 105 circulations.
Embodiment 5
Present embodiment provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) take by weighing the silica flour that a certain amount of particle diameter is 50nm, the speed with 6 ℃/minute under Muffle furnace air atmosphere is warmed up to 450 ℃, and calcination 1 hour obtains the composite material of coated with silica silicon.
(2) composite material of coated with silica silicon is placed on the central authorities of tube furnace; Tube furnace is evacuated to furnace pressure smaller or equal to 0.01 atmospheric pressure; The mist that feed argon gas and acetylene this moment (wherein; The volume ratio of argon gas and acetylene is 9: 1), be warming up to 600 ℃ with 6 ℃/minute speed then, and be incubated 70 minutes.
(3) use the hydrofluoric acid corrode silicon dioxide of excessive concentration as 7wt%, the content that obtains the carbon in the Si-C composite material is 9wt%.
The manufacture method of CR2025 type button cell such as embodiment 1 press the battery of present embodiment method made, and first discharge specific capacity has reached 974mAh/g, still remain on 601mAh/g after 105 circulations.
Embodiment 6
Present embodiment provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) take by weighing the silica flour that a certain amount of particle diameter is 50 μ m, the speed with 9 ℃/minute under Muffle furnace air atmosphere is warmed up to 600 ℃, and calcination 0.8 hour obtains the composite material of coated with silica silicon.
(2) composite material of coated with silica silicon is placed on the central authorities of tube furnace; Tube furnace is evacuated to furnace pressure smaller or equal to 0.01 atmospheric pressure; Be warming up to 700 ℃ with 9 ℃/minute speed then, feed the mist (wherein, the volume ratio of argon gas and acetylene is 9: 1) of argon gas and acetylene this moment; Again furnace temperature is raise 100 ℃, and be incubated 30 minutes.
(3) use the hydrofluoric acid corrode silicon dioxide of excessive concentration as 6wt%, the content that obtains the carbon in the Si-C composite material is 5wt%.
The manufacture method of CR2025 type button cell such as embodiment 1 press the battery of present embodiment method made, and first discharge specific capacity has reached 1128mAh/g, still remain on 759mAh/g after 105 circulations.
Embodiment 7
Present embodiment provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) take by weighing the silica flour that a certain amount of particle diameter is 25 μ m, the speed with 5 ℃/minute under Muffle furnace air atmosphere is warmed up to 470 ℃, and calcination 1.5 hours obtains the composite material of coated with silica silicon.
(2) composite material of coated with silica silicon is placed on the central authorities of tube furnace; Tube furnace is evacuated to furnace pressure smaller or equal to 0.01 atmospheric pressure; Be warming up to 600 ℃ with 5 ℃/minute speed then, feed the mist (wherein, the volume ratio of argon gas and acetylene is 9: 1) of argon gas and acetylene this moment; Again furnace temperature is raise 130 ℃, and be incubated 10 minutes.
(3) use the hydrofluoric acid corrode silicon dioxide of excessive concentration as 8wt%, the content that obtains the carbon in the Si-C composite material is 10wt%.
The manufacture method of CR2025 type button cell such as embodiment 1 press the battery of present embodiment method made, and first discharge specific capacity has reached 1087mAh/g, still remain on 631mAh/g after 105 circulations.
Embodiment 8
Present embodiment provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) take by weighing the silica flour that a certain amount of particle diameter is 5nm, the speed with 7 ℃/minute under Muffle furnace air atmosphere is warmed up to 500 ℃, and calcination 1.8 hours obtains the composite material of coated with silica silicon.
(2) composite material of coated with silica silicon is placed on the central authorities of tube furnace; Tube furnace is evacuated to furnace pressure smaller or equal to 0.01 atmospheric pressure; The mist that feed argon gas and acetylene this moment (wherein; The volume ratio of argon gas and acetylene is 9: 1), be warming up to 900 ℃ with 7 ℃/minute speed then, and be incubated 10 minutes.
(3) use the hydrofluoric acid corrode silicon dioxide of excessive concentration as 5wt%, the content that obtains the carbon in the Si-C composite material is 8wt%.
The manufacture method of CR2025 type button cell such as embodiment 1 press the battery of present embodiment method made, and first discharge specific capacity has reached 1359mAh/g, still remain on 791mAh/g after 105 circulations.
Embodiment 9
Present embodiment provides a kind of preparation method of Si-C composite material, may further comprise the steps:
(1) take by weighing the silica flour that a certain amount of particle diameter is 2.5 μ m, the speed with 10 ℃/minute under Muffle furnace air atmosphere is warmed up to 580 ℃, and calcination 1.3 hours obtains the composite material of coated with silica silicon.
(2) composite material of coated with silica silicon is placed on the central authorities of tube furnace; Tube furnace is evacuated to furnace pressure smaller or equal to 0.01 atmospheric pressure; Be warming up to 550 ℃ with 10 ℃/minute speed then, feed the mist (wherein, the volume ratio of argon gas and acetylene is 9: 1) of argon gas and acetylene this moment; Again furnace temperature is raise 200 ℃, and be incubated 60 minutes.
(3) use the hydrofluoric acid corrode silicon dioxide of excessive concentration as 10wt%, the content that obtains the carbon in the Si-C composite material is 4wt%.
The manufacture method of CR2025 type button cell such as embodiment 1 press the battery of present embodiment method made, and first discharge specific capacity has reached 1247mAh/g, still remain on 796mAh/g after 105 circulations.
Embodiment 10
Present embodiment provides a kind of Si-C composite material, in fact by method for preparing.
Embodiment 11
Present embodiment provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
Certainly, also should comprise other material known such as positive electrode, collector, element etc. in the lithium ion battery of this enforcement.
It is 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 the one of ordinary skilled in the art, under the situation that does not break away from spirit of the present invention and essence, can make various modification and improvement, these modification also are regarded as protection scope of the present invention with improving.
Claims (10)
1. the preparation method of a Si-C composite material is characterized in that, may further comprise the steps:
(1), obtains the composite material of coated with silica silicon with silica flour calcination under oxygen-containing atmosphere;
(2) with the composite material carbon coated of said coated with silica silicon;
(3) corrode said silicon dioxide with excessive hydrofluoric acid, obtain Si-C composite material.
2. the preparation method of Si-C composite material according to claim 1 is characterized in that, the particle diameter of the silica flour in the said step (1) is 0.005 ~ 50 μ m.
3. the preparation method of Si-C composite material according to claim 2 is characterized in that, the particle diameter of the silica flour in the said step (1) is 5 ~ 50nm.
4. the preparation method of Si-C composite material according to claim 1 is characterized in that, the calcination temperature in the said step (1) is 400 ~ 600 ℃, and calcination time is 0.5 ~ 2 hour.
5. the preparation method of Si-C composite material according to claim 1 is characterized in that, in the said step (2) on the composite material of said coated with silica silicon the method for carbon coated be:
The organic carbon precursor is mixed the back calcination with the composite material of said coated with silica silicon;
Perhaps
Through chemical vapour deposition technique carbon coated on the composite material of said coated with silica silicon.
6. the preparation method of Si-C composite material according to claim 5; It is characterized in that; Said chemical vapour deposition technique in the method for carbon coated on the composite material of said coated with silica silicon is: under the vacuum condition; In the composite material of said coated with silica silicon, feed carbon-source gas, under 550 ~ 900 ℃ temperature, pyrolysis carbon-source gas 10 ~ 100 minutes.
7. the preparation method of Si-C composite material according to claim 5; It is characterized in that; Said chemical vapour deposition technique in the method for carbon coated on the composite material of said coated with silica silicon is: the composite material of said coated with silica silicon is heated to 500 ~ 700 ℃ under vacuum; Feed carbon-source gas then, elevated temperature is 50 ~ 200 ℃ again, pyrolysis carbon-source gas 10 ~ 100 minutes.
8. the preparation method of Si-C composite material according to claim 1 is characterized in that, the content of the carbon in the said Si-C composite material that obtains in the said step (3) is 3wt% ~ 10wt%.
9. a Si-C composite material is characterized in that, it is by any described method preparation of 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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