CN102491335A - Method for preparing silicon nanoparticles, anode material containing silicon nanoparticles, and lithium ion battery - Google Patents
Method for preparing silicon nanoparticles, anode material containing silicon nanoparticles, and lithium ion battery Download PDFInfo
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- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 93
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000010405 anode material Substances 0.000 title abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 94
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 47
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 45
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 230000007797 corrosion Effects 0.000 claims abstract description 15
- 238000005260 corrosion Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 64
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 64
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 229960001866 silicon dioxide Drugs 0.000 claims description 43
- 229910052786 argon Inorganic materials 0.000 claims description 32
- 238000007323 disproportionation reaction Methods 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 22
- 239000010439 graphite Substances 0.000 claims description 21
- 229910002804 graphite Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- 239000012530 fluid Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 6
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 30
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 30
- 238000005406 washing Methods 0.000 description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 21
- 239000010703 silicon Substances 0.000 description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 19
- 229910052744 lithium Inorganic materials 0.000 description 19
- 229910052710 silicon Inorganic materials 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- 230000004888 barrier function Effects 0.000 description 16
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- 239000008151 electrolyte solution Substances 0.000 description 16
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- 239000000243 solution Substances 0.000 description 16
- 230000003068 static effect Effects 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 208000012886 Vertigo Diseases 0.000 description 15
- 239000011889 copper foil Substances 0.000 description 15
- -1 ethyl carbonate ester Chemical class 0.000 description 15
- 239000013049 sediment Substances 0.000 description 15
- 239000002002 slurry Substances 0.000 description 15
- 238000009987 spinning Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910013870 LiPF 6 Inorganic materials 0.000 description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 9
- 239000011856 silicon-based particle Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 229910000077 silane Inorganic materials 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
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- 229910021487 silica fume Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent 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 relates to a method for preparing silicon nanoparticles, a anode material containing the silicon nanoparticles, and a lithium ion battery. The method comprises the following steps of: performing high-temperature disproportionated reaction of silicon monoxide, and removing silicon dioxide by corrosion, namely heating the silicon monoxide in the protective atmosphere to generate silicon-dioxide-wrapped silicon nanoparticles; and mixing the silicon-dioxide-wrapped silicon nanoparticles and corrosive liquid for corroding, corroding to remove the silicon dioxide, and separating to obtain the silicon nanoparticles. The lithium ion battery prepared on the basis of the silicon nanoparticles has high capacity and high circulating performance.
Description
Technical field
The invention belongs to battery manufacturing technology field, be specifically related to a kind of preparation method of silicon nanoparticle and contain the lithium ion battery negative material and the lithium ion battery of this silicon nanoparticle.
Background technology
Exhaustion day by day along with fossil oil; And the fast development of portable electric appts and electric vehicle; The research of new forms of energy such as power-supply battery has become the focus that the whole world is paid close attention to, and wherein lithium ion battery is because of its energy density is high, power density is high, good cycle, environmental friendliness, structure variation and excellent specific property such as cheap are used widely.With regard to the structure of lithium ion battery, it mainly is made up of positive pole, negative pole, barrier film and electrolytic solution, and can the electrode performance of negative material further improve the determinative that becomes restriction lithium ion battery performance.
To the demand for development of lithium-ion-power cell, require objectively that negative material has that heavy body, rapid rate discharge and recharge, characteristics such as high thermal stability and low cost.The more negative material of practical application is a carbon material at present; Like natural graphite, greying carbonaceous mesophase spherules etc.; Wherein the theoretical capacity of graphite cathode material is 372mAh/g; Actual capacity is at 320-350mAh/g, and high-rate charge-discharge capability is poor, has limited the development of lithium ion battery aspect heavy body and superpower.In non-carbon negative pole material, the theoretical capacity of silicon the highest (lithium storage content of silicon single crystal is 3800mAh/g), lithium and silicon form alloy Li
xSi (0＜x≤4.4) is when forming Li
4.4Theoretical capacity during the Si compound is up to 4200mAh/g, much larger than the theoretical capacity of graphite; But the alloying of Si-Li alloy and removal alloying are accompanied by huge volume change, and its volumetric expansion is up to 300%, the efflorescence render electrical electrode structure unstability of silicon and losing efficacy.Particularly common pure silicon, stable circulation is very poor, and the capacity that circulates after 5 times is just almost nil from reducing to more than the 3000mAh/g.
There are some researches show, consider, high-capacity material is prepared into the littler nanometer materials of size, then can effectively improve the electrochemistry cycle performance of material from dimensional effect.Nano-silicon refers to diameter less than 5 nanometers (10
-9M) crystal silicon particle has the purity height, and particle diameter is little, and characteristics such as be evenly distributed.The silicon of preparation nanoscale, can increase material specific surface area, reduce the diffusion length of lithium ion, improve the cycle performance of lithium ion battery.
Silicon nanoparticle is usually by the silane pyrolysis preparation, like the vapour deposition process of mentioning in U.S. Pat 4661335 (A) and the Chinese patent 200480034099.1 in the prior art.The principal reaction thing silane that this method adopts cost an arm and a leg and prepare that the vapour deposition furnace structure of silicon nanoparticle is complicated, difficult technique is with control, the uniform particle diameter property of prepared nanoscalar silicon particles is difficult to guarantee.When nanoscalar silicon particles was used to prepare lithium ion battery negative material, the particle diameter that requires silicon nanoparticle was between 3～50nm and low cost of manufacture, and existing vapour deposition process is difficult to produce the high-performance nano silicon grain that meets application requiring with lower cost.In addition; Chinese patent 03134724.X discloses a kind of method and device that utilizes anonizing to prepare nano silicon particles; Most silicon all are corroded and remove in this method; Cause productive rate very low, and adopt electrochemical erosion method can't realize volume production, be difficult to satisfy the demand of scale operation lithium ion battery nanoscalar silicon particles.
Application number be 98813207.9 Patent publish method of producing high purity silicon and device; This method is heated to more than 1000 ℃ silicon monoxide with below 1730 ℃; Make silicon monoxide produce disproportionation reaction; Resolve into liquid or solid silicon and solid silica, then the liquid silicon that generates is separated with solid silicon monoxide and/or silicon-dioxide under liquid state.Perhaps further heating more than the silicon fusing point with below 1730 ℃ after the disproportionation reaction.This method requires the reaction system sealing during disproportionation reaction is carried out.What this patent prepared is HIGH-PURITY SILICON, and for lithium ion battery electrode material, the raw material of so high purity not only can increase cost greatly but also can not obviously promote performance, is unnecessary therefore; On the other hand, the silicon that disproportionation is generated is fused into liquid silicon so that separate with solid silicon monoxide or silicon-dioxide, and liquid silicon cooling back forms bulk si, can not directly apply to lithium ion battery.
Summary of the invention
Technical problem to be solved by this invention is to the above-mentioned deficiency that exists in the prior art; A kind of preparation method of silicon nanoparticle is provided; It is simple to operate; Prepared silicon nanoparticle particle diameter is even, thus big, the good cycle of the ion cathode material lithium of silicon nanoparticle preparation and lithium ion battery specific storage.
The solution technical scheme that technical problem of the present invention adopted is that the preparation method of this silicon nanoparticle may further comprise the steps:
(1) the high temperature disproportionation reaction of silicon monoxide
Under protective atmosphere, silicon monoxide is heated, make it that disproportionation reaction take place, heating condition is 800-1300 ℃ of reaction 0.5-24h down, generates the silicon dioxide coated nano silicon grain;
(2) corrosion removes silicon-dioxide
The silicon dioxide coated nano silicon grain mixed with corrosive fluid carries out corrosion treatment, with silicon dioxide etching fall again through separate silicon nanoparticle.
Disproportionation reaction at high temperature takes place and generates silicon and silicon-dioxide in silicon monoxide, and the two evenly is mingled in together, forms the silicon dioxide coated nano silicon grain, and grain diameter is relevant with heating condition, is about four or five ten nanometers generally speaking.The used corrosive fluid of the present invention is the good solvent of silicon-dioxide, and can not dissolves silicon, remove silicon-dioxide with corrosive fluid and then obtain nanoscalar silicon particles, and particle size distribution is narrow.The present invention adopts the method for centrifugal settling to remove silicon-dioxide and corrosive fluid.
Preferably, heating condition is 950-1200 ℃ of reaction 1-12h down in the said step (1).
Preferably, protective atmosphere is the gas mixture of nitrogen, argon gas or argon gas and hydrogen in the said step (1).
Preferably, said step (2) gained silicon nanoparticle particle diameter is 5-100nm.
Preferably, corrosive fluid is the hydrofluoric acid aqueous solution of 3-40wt% in the said step (2), and add-on is pressed silicon-dioxide and hydrofluoric acid mol ratio 1: 4-1 in the product: 20 calculate, and the corrosion treatment time is 0.5-30h.Particularly, by disproportionation reaction equation 2SiO=SiO
2+ Si calculates the theoretical molar amount of product silicon-dioxide, again according to the reaction equation of silicon-dioxide and hydrofluoric acid: SiO
2+ 4HF=SiF
4↑+2H
2O calculates the theoretical molar amount that complete reaction is fallen the required hydrofluoric acid of silicon-dioxide.Remove silicon-dioxide for fully reacting, hydrofluoric acid can be suitably excessive.Can carry out ultimate analysis through the product after will corroding and judge whether corrosion is complete, and oxygen level is few more in the solids, and corrosion reaction is complete more.But residual silicon-dioxide does not influence its performance as negative material.
Further preferably, corrosive fluid is the hydrofluoric acid aqueous solution of 5-20wt% in the said step (2), and add-on is pressed silicon-dioxide and hydrofluoric acid mol ratio 1: 5-1 in the product: 12 calculate, and the corrosion treatment time is 0.5-12h.
Preferably; Corrosive fluid is Lithium Hydroxide MonoHydrate or Pottasium Hydroxide or the sodium hydroxide of 0.4-30wt% in the said step (2); Add-on is pressed silicon-dioxide and Lithium Hydroxide MonoHydrate or Pottasium Hydroxide or sodium hydroxide mol ratio 1: 1.5-1 in the product: 5 calculate, and the corrosion treatment time is 0.5-30h.
Further preferably, corrosive fluid is the sodium hydroxide of 1-30wt% in the said step (2), and add-on is pressed silicon-dioxide and Lithium Hydroxide MonoHydrate or Pottasium Hydroxide or sodium hydroxide mol ratio 1: 1.8-1 in the product: 3.5 calculate, and the corrosion treatment time is 0.5-12h.
Further preferably, corrosive fluid is the sodium hydroxide of 4-20wt% in the said step (2).
Use the silicon nanoparticle of method for preparing to can be used for preparing lithium ion battery negative material, electroconductibility, raising cycle performance of battery for increasing electrode materials adopt the static eliminator carbon black to mix with silicon nanoparticle.This ion cathode material lithium comprises: the silicon nanoparticle of 0.5-85wt% method for preparing, 5-85wt% median size are the graphite of 1-100 micron, 5-15wt% graphitized carbon black and 3-10wt% sticker.
Further preferably, said silicon nanoparticle is 0.5-20wt%, and graphite is 60-85wt%.
The present invention also provides the lithium ion battery with above-mentioned negative material preparation.Prepare the negative pole of lithium ion battery with above-mentioned negative material, be assembled into lithium ion battery again.Promptly this lithium ion battery comprises the negative pole for preparing battery with the above lithium ion battery negative material.
The invention has the beneficial effects as follows: use the silicon nanoparticle of simple and easy method preparation size as 5-100nm, this material can be used in the lithium ion battery negative material, can improve the specific storage and the cycle performance of lithium ion battery effectively.Specific storage is 1905-305mAh/g (promptly specific storage reaches as high as 1905mAh/g first) through testing first, and the specific storage that circulates after 100 times is 637-123mAh/g (promptly circulate 100 times after the highest 637mAh/g of remaining on).
Description of drawings
Fig. 1 is silicon nanoparticle preparation flow figure in specific embodiment of the present invention;
Fig. 2 is the x-ray diffraction pattern of silicon nanoparticle in specific embodiment of the present invention;
Fig. 3 is the electron scanning micrograph of silicon nanoparticle in specific embodiment of the present invention.
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.
Embodiment one
Carry out the preparation of silicon nanoparticle by preparation flow figure shown in Figure 1.Under nitrogen protection, 8.8g silicon monoxide SiO 800 ℃ of heating 24 hours, is carried out disproportionation reaction, get 8.8g brown granular shape product behind the naturally cooling, the gained granular disintegration is the coating that contains a plurality of silicon nanoparticles of coated with silica.With products therefrom with hydrofluoric acid (silicon-dioxide and hydrofluoric acid mol ratio are 1: the 4) stir process of 20g 40wt% 1 hour, the coating SiO that silicon nanoparticle is outer
2Erode (is coating SiO
2Dissolved by hydrofluoric acid).Centrifugal back seabed sediment silicon nanoparticle is with water washing three times, and upper layer substance is removed in all spinnings after each washing, and settling is dry, gets the brown silicon nanoparticle of 3.9g, and particle diameter is 80nm.
With gained silicon nanoparticle and graphite KS6, static eliminator Super P and sticker PVDF (pvdf) according to 40: 45: 8: 7 mass ratios mix (being respectively 0.12g, 0.135g, 0.024g, 0.021g); Add and be evenly coated on the Copper Foil after 1mL N-Methyl pyrrolidone (NMP) grinds to form slurry; 100 ℃ of following vacuum-drying 24 hours; Vacuum tightness is 0.02MPa, makes lithium ion battery and uses cathode pole piece.
With the lithium sheet is counter electrode, and electrolytic solution is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Record this battery first capacity be 600mAh/g, circulating also keeps 387mAh/g (test condition is a room temperature, and charge-discharge magnification is 0.1C) for 100 times.
Embodiment two
Under nitrogen protection, the 8.8g silicon monoxide 950 ℃ of heating 12 hours, is carried out disproportionation reaction, get brown product 8.8g behind the naturally cooling.With products therefrom with hydrofluoric acid (silicon-dioxide and hydrofluoric acid mol ratio are 1: the 6) stir process of 60g20wt% 2 hours, the coating SiO that silicon nanoparticle is outer
2Erode, centrifugal back seabed sediment is with water washing three times, and upper layer substance is removed in all spinnings after each washing, and settling is dry, gets the brown silicon nanoparticle of 3.3g, particle diameter 5nm.
With gained silicon nanoparticle and graphite KS6, static eliminator Super P and sticker PVDF according to 60: 25: 10: 5 mass ratios mix (being respectively 0.18g, 0.075g, 0.03g, 0.015g); Add and be evenly coated on the Copper Foil after 1mL N-Methyl pyrrolidone (NMP) grinds to form slurry; 100 ℃ of following vacuum-drying 24 hours; Vacuum tightness is 0.02MPa, makes lithium ion battery and uses cathode pole piece.
With the lithium sheet is counter electrode, and electrolytic solution is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Record this battery first capacity be 815mAh/g, circulating also keeps 313mAh/g (test condition is a room temperature, and charge-discharge magnification is 0.1C) for 100 times.
Embodiment three
Under argon shield, the 8.8g silicon monoxide 1000 ℃ of heating 10 hours, is carried out disproportionation reaction, get brown product 8.8g behind the naturally cooling.With products therefrom with hydrofluoric acid (silicon-dioxide and hydrofluoric acid mol ratio are 1: the 6) stir process of 60g20wt% 2 hours, the coating SiO that silicon nanoparticle is outer
2Erode, centrifugal back seabed sediment is with water washing three times, and upper layer substance is removed in all spinnings after each washing, and settling is dry, gets the brown silicon nanoparticle of 3.1g, particle diameter 40nm.
With gained silicon nanoparticle and graphite KS6, static eliminator Super P and sticker CMC (Walocel MT 20.000PV) according to 20: 60: 10: 10 mass ratios mix (being respectively 0.06g, 0.18g, 0.03g, 0.03g); Add and be evenly coated on the Copper Foil after 1mL N-Methyl pyrrolidone (NMP) grinds to form slurry; 100 ℃ of following vacuum-drying 24 hours; Vacuum tightness is 0.02MPa, makes lithium ion battery and uses cathode pole piece.
With the lithium sheet is counter electrode, and electrolytic solution is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Record this battery first capacity be 621mAh/g, circulating also keeps 407mAh/g (test condition is a room temperature, and charge-discharge magnification is 0.1C) for 100 times.
Embodiment four
Under argon shield, the 8.8g silicon monoxide 1050 ℃ of heating 8 hours, is carried out disproportionation reaction, get brown product 8.8g behind the naturally cooling.With products therefrom with hydrofluoric acid (silicon-dioxide and hydrofluoric acid mol ratio are 1: the 7) stir process of 140g10wt% 4 hours, the coating SiO that silicon nanoparticle is outer
2Erode, centrifugal back seabed sediment is with water washing three times, and upper layer substance is removed in all spinnings after each washing, and settling is dry, gets the brown silicon nanoparticle of 2.9g, and particle diameter is 45nm.
With gained silicon nanoparticle and graphite KS6, static eliminator Super P and sticker SBR (SBR emulsion) according to 1: 79: 10: 10 mass ratios mix (be respectively 0.003,0.237,0.03,0.03g); Add and be evenly coated on the Copper Foil after 1mL N-Methyl pyrrolidone (NMP) grinds to form slurry; 100 ℃ of following vacuum-drying 24 hours; Vacuum tightness is 0.02MPa, makes lithium ion battery and uses cathode pole piece.
With the lithium sheet is counter electrode, and electrolytic solution is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Record this battery first capacity be 403mAh/g, circulating also keeps 382mAh/g (test condition is a room temperature, and charge-discharge magnification is 0.1C) for 100 times.
Embodiment five
Under the gas mixture protection of argon gas and hydrogen, the 8.8g silicon monoxide 1050 ℃ of heating 6 hours, is carried out disproportionation reaction, get brown product 8.8g behind the naturally cooling.With products therefrom with hydrofluoric acid (silicon-dioxide and hydrofluoric acid mol ratio are 1: the 7.5) stir process of 500g 3wt% 3 hours, the coating SiO that silicon nanoparticle is outer
2Erode, centrifugal back seabed sediment is with water washing three times, and upper layer substance is removed in all spinnings after each washing, and settling is dry, gets the brown silicon nanoparticle of 2.9g, particle diameter 40nm.
With gained silicon nanoparticle and graphite KS6, static eliminator Super P and sticker SBR according to 15: 65: 10: 10 mass ratios mix (being respectively 0.045g, 0.195g, 0.03g, 0.03g); Add and be evenly coated on the Copper Foil after 1mL N-Methyl pyrrolidone (NMP) grinds to form slurry; 100 ℃ of following vacuum-drying 24 hours; Vacuum tightness is 0.02MPa, makes lithium ion battery and uses cathode pole piece.
With the lithium sheet is counter electrode, and electrolytic solution is EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution of 1mol/L LiPF6, 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.
Record this battery first capacity be 755mAh/g, circulating also keeps 637mAh/g (test condition is a room temperature, and charge-discharge magnification is 0.1C) for 100 times.
Embodiment six
Under argon shield, the 8.8g silicon monoxide 1100 ℃ of heating 6 hours, is carried out disproportionation reaction, get brown product 8.8g behind the naturally cooling.With products therefrom with hydrofluoric acid (silicon-dioxide and hydrofluoric acid mol ratio 1: the 9) stir process of 180g10wt% 2 hours, the coating SiO that silicon nanoparticle is outer
2Erode, centrifugal back seabed sediment is with water washing three times, and upper layer substance is removed in all spinnings after each washing, and settling is dry, gets the brown silicon nanoparticle of 2.9g, particle diameter 53nm.
With gained silicon nanoparticle and graphite KS6, static eliminator Super P and sticker SBR according to 30: 50: 5: 15 mass ratios mix (being respectively 0.09g, 0.15g, 0.015g, 0.045g); Add and be evenly coated on the Copper Foil after 1mL N-Methyl pyrrolidone (NMP) grinds to form slurry; 100 ℃ of following vacuum-drying 24 hours; Vacuum tightness is 0.02MPa, makes lithium ion battery and uses cathode pole piece.
With the lithium sheet is counter electrode, and electrolytic solution is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Record this battery first capacity be 905mAh/g, circulating also keeps 423mAh/g (test condition is a room temperature, and charge-discharge magnification is 0.1C) for 100 times.
Embodiment seven
Under argon shield, the 8.8g silicon monoxide 1100 ℃ of heating 4 hours, is carried out disproportionation reaction, get brown product 8.8g behind the naturally cooling.With products therefrom with hydrofluoric acid (silicon-dioxide and hydrofluoric acid mol ratio are 1: the 6) stir process of 240g5wt% 4 hours, the coating SiO that silicon nanoparticle is outer
2Erode, centrifugal back seabed sediment is with water washing three times, and upper layer substance is removed in all spinnings after each washing, and settling is dry, gets the brown silicon nanoparticle of 2.8g, particle diameter 51nm.
Fig. 2 is the x-ray diffraction pattern of present embodiment gained nano-silicon.Testing tool is a Rigaku D/MAX-2200 type x-ray diffractometer, and spectrogram is illustrated in the diffraction peak that has occurred five broads in the 20-80 ° of scope, and is consistent with the diffraction peak of crystalline state elemental silicon, proves that the gained nano silica fume is an elemental silicon.
Fig. 3 is the electron scanning micrograph of present embodiment gained nano-silicon; Testing tool is the S-4800 of a HIT field emission scanning electron microscope; From figure, can obviously find out the silicon grain subglobular; And big or small homogeneous, good dispersivity, median size is (10 little lattice length overalls are 500nm among Fig. 3) about 50nm.
With gained silicon nanoparticle and graphite KS6, static eliminator Super P and sticker CMC and SBR according to 0.5: 80: 9.5: 10 mass ratios mix (being respectively 0.0015g, 0.24g, 0.0285g, 0.03g); Add and be evenly coated on the Copper Foil after 1mL N-Methyl pyrrolidone (NMP) grinds to form slurry; 100 ℃ of following vacuum-drying 24 hours; Vacuum tightness is 0.02MPa, makes lithium ion battery and uses cathode pole piece.
With the lithium sheet is counter electrode, and electrolytic solution is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Record this battery first capacity be 385mAh/g, circulating also keeps 362mAh/g (test condition is a room temperature, and charge-discharge magnification is 0.1C) for 100 times.
Embodiment eight
Under argon shield, the 8.8g silicon monoxide 1150 ℃ of heating 3 hours, is carried out disproportionation reaction, get brown product 8.7g behind the naturally cooling.With products therefrom with hydrofluoric acid (silicon-dioxide and hydrofluoric acid mol ratio are 1: the 12) stir process of 240g10wt% 2 hours, the coating SiO that silicon nanoparticle is outer
2Erode, centrifugal back seabed sediment is with water washing three times, and upper layer substance is removed in all spinnings after each washing, and settling is dry, gets the brown silicon nanoparticle of 2.6g, particle diameter 65nm.
With gained silicon nanoparticle and graphite KS6, static eliminator Super P and sticker CMC and SBR according to 5: 75: 10: 10 mass ratios mix (being respectively 0.015g, 0.225g, 0.03g, 0.03g); Add and be evenly coated on the Copper Foil after 1mL N-Methyl pyrrolidone (NMP) grinds to form slurry; 100 ℃ of following vacuum-drying 24 hours; Vacuum tightness is 0.02MPa, makes lithium ion battery and uses cathode pole piece.
With the lithium sheet is counter electrode, and electrolytic solution is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Record this battery first capacity be 539mAh/g, circulating also keeps 503mAh/g (test condition is a room temperature, and charge-discharge magnification is 0.1C) for 100 times.
Embodiment nine
Under argon shield, the 8.8g silicon monoxide 1200 ℃ of heating 1 hour, is carried out disproportionation reaction, get brown product 8.7g behind the naturally cooling.With products therefrom with hydrofluoric acid (silicon-dioxide and hydrofluoric acid mol ratio are 1: the 9) stir process of 180g10wt% 3 hours, the coating SiO that silicon nanoparticle is outer
2Erode, centrifugal back seabed sediment is with water washing three times, and upper layer substance is removed in all spinnings after each washing, and settling is dry, gets the brown silicon nanoparticle of 2.7g, particle diameter 66nm.
With gained silicon nanoparticle and graphite KS6, static eliminator Super P and sticker PVDF according to 75: 5: 10: 10 mass ratios mix (being respectively 0.225g, 0.015g, 0.03g, 0.03g); Add and be evenly coated on the Copper Foil after 1mL N-Methyl pyrrolidone (NMP) grinds to form slurry; 100 ℃ of following vacuum-drying 24 hours; Vacuum tightness is 0.02MPa, makes lithium ion battery and uses cathode pole piece.
With the lithium sheet is counter electrode, and electrolytic solution is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Record this battery first capacity be 1905mAh/g, circulating also keeps 123mAh/g (test condition is a room temperature, and charge-discharge magnification is 0.1C) for 100 times.
Embodiment ten
Under argon shield, the 8.8g silicon monoxide 1300 ℃ of heating 0.5 hour, is carried out disproportionation reaction, get brown product 8.7g behind the naturally cooling.With products therefrom with hydrofluoric acid (silicon-dioxide and hydrofluoric acid mol ratio are 1: the 10) stir process of 200g10wt% 1 hour, the coating SiO that silicon nanoparticle is outer
2Erode, centrifugal back seabed sediment is with water washing three times, and upper layer substance is removed in all spinnings after each washing, and settling is dry, gets the brown silicon nanoparticle of 4.6g, particle diameter 57nm.
With gained silicon nanoparticle and graphite KS6, static eliminator Super P and sticker PVDF according to 40: 45: 8: 7 mass ratios mix (being respectively 0.12g, 0.135g, 0.024g, 0.021g); Add and be evenly coated on the Copper Foil after 1mL N-Methyl pyrrolidone (NMP) grinds to form slurry; 100 ℃ of following vacuum-drying 24 hours; Vacuum tightness is 0.02MPa, makes lithium ion battery and uses cathode pole piece.
With the lithium sheet is counter electrode, and electrolytic solution is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Record this battery first capacity be 305mAh/g, circulating also keeps 235mAh/g (test condition is a room temperature, and charge-discharge magnification is 0.1C) for 100 times.
Embodiment 11
Under argon shield, the 8.8g silicon monoxide 1300 ℃ of heating 0.5 hour, is carried out disproportionation reaction, get brown product 8.7g behind the naturally cooling.With products therefrom with sodium hydroxide (silicon-dioxide and sodium hydroxide mol ratio are 1: the 5) stir process of 250g4wt% 12 hours, the coating SiO that silicon nanoparticle is outer
2Erode, centrifugal back seabed sediment is with water washing three times, and upper layer substance is removed in all spinnings after each washing, and settling is dry, gets the brown silicon nanoparticle of 2.1g, particle diameter 56nm.
With gained silicon nanoparticle and graphite KS6, static eliminator Super P and sticker PVDF according to 20: 65: 8: 7 mass ratios mix (being respectively 0.06g, 0.195g, 0.024g, 0.021g); Add and be evenly coated on the Copper Foil after 1mL N-Methyl pyrrolidone (NMP) grinds to form slurry; 100 ℃ of following vacuum-drying 24 hours; Vacuum tightness is 0.02MPa, makes lithium ion battery and uses cathode pole piece.
With the lithium sheet is counter electrode, and electrolytic solution is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Record this battery first capacity be 705mAh/g, circulating also keeps 439mAh/g (test condition is a room temperature, and charge-discharge magnification is 0.1C) for 100 times.
Embodiment 12
Under argon shield, the 8.8g silicon monoxide 1100 ℃ of heating 2 hours, is carried out disproportionation reaction, get brown product 8.7g behind the naturally cooling.With products therefrom with sodium hydroxide (silicon-dioxide and sodium hydroxide mol ratio 1: the 4) stir process of 800g1wt% 30 hours, the coating SiO that silicon nanoparticle is outer
2Erode, centrifugal back seabed sediment is with water washing three times, and upper layer substance is removed in all spinnings after each washing, and settling is dry, gets the brown silicon nanoparticle of 2.6g, particle diameter 59nm.
With gained silicon nanoparticle and graphite KS6, static eliminator Super P and sticker PVDF according to 15: 70: 8: 7 mass ratios mix (being respectively 0.045g, 0.21g, 0.024g, 0.021g); Add and be evenly coated on the Copper Foil after 1mL N-Methyl pyrrolidone (NMP) grinds to form slurry; 100 ℃ of following vacuum-drying 24 hours; Vacuum tightness is 0.02MPa, makes lithium ion battery and uses cathode pole piece.
With the lithium sheet is counter electrode, and electrolytic solution is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Record this battery first capacity be 675mAh/g, circulating also keeps 473mAh/g (test condition is a room temperature, and charge-discharge magnification is 0.1C) for 100 times.
Embodiment 13
Under argon shield, the 8.8g silicon monoxide 1050 ℃ of heating 4 hours, is carried out disproportionation reaction, get brown product 8.7g behind the naturally cooling.With products therefrom with sodium hydroxide (silicon-dioxide and sodium hydroxide mol ratio 1: the 8) stir process of 80g20wt% 1 hour, the coating SiO that silicon nanoparticle is outer
2Erode, centrifugal back seabed sediment is with water washing three times, and upper layer substance is removed in all spinnings after each washing, and settling is dry, gets the brown silicon nanoparticle of 2.6g, particle diameter 61nm.
With gained silicon nanoparticle and graphite KS6, static eliminator Super P and sticker PVDF according to 3: 82: 8: 7 mass ratios mix (being respectively 0.03g, 0.246g, 0.024g, 0.021g); Add and be evenly coated on the Copper Foil after 1mL N-Methyl pyrrolidone (NMP) grinds to form slurry; 100 ℃ of following vacuum-drying 24 hours; Vacuum tightness is 0.02MPa, makes lithium ion battery and uses cathode pole piece.
With the lithium sheet is counter electrode, and electrolytic solution is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Record this battery first capacity be 405mAh/g, circulating also keeps 339mAh/g (test condition is a room temperature, and charge-discharge magnification is 0.1C) for 100 times.
Embodiment 14
Under argon shield, the 8.8g silicon monoxide 1000 ℃ of heating 5 hours, is carried out disproportionation reaction, get brown product 8.8g behind the naturally cooling.With products therefrom with sodium hydroxide (silicon-dioxide and sodium hydroxide mol ratio are 1: the 4) stir process of 20g40wt% 1 hour, the coating SiO that silicon nanoparticle is outer
2Erode, centrifugal back seabed sediment is with water washing three times, and upper layer substance is removed in all spinnings after each washing, and settling is dry, gets the brown silicon nanoparticle of 1.5g, particle diameter 43nm.
With gained silicon nanoparticle and graphite KS6, static eliminator Super P and sticker PVDF according to 20: 65: 8: 7 mass ratios mix (being respectively 0.06g, 0.195g, 0.024g, 0.021g); Add and be evenly coated on the Copper Foil after 1mL N-Methyl pyrrolidone (NMP) grinds to form slurry; 100 ℃ of following vacuum-drying 24 hours; Vacuum tightness is 0.02MPa, makes lithium ion battery and uses cathode pole piece.
With the lithium sheet is counter electrode, and electrolytic solution is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Record this battery first capacity be 517mAh/g, circulating also keeps 379mAh/g (test condition is a room temperature, and charge-discharge magnification is 0.1C) for 100 times.
Embodiment 15
Under argon shield, the 8.8g silicon monoxide 1000 ℃ of heating 5 hours, is carried out disproportionation reaction, get brown product 8.8g behind the naturally cooling.With products therefrom with sodium hydroxide (silicon-dioxide and sodium hydroxide mol ratio 1: the 7.5) stir process of 300g5wt% 1 hour, the coating SiO that silicon nanoparticle is outer
2Erode, centrifugal back seabed sediment is with water washing three times, and upper layer substance is removed in all spinnings after each washing, and settling is dry, gets the brown silicon nanoparticle of 3.0g, particle diameter 46nm.
With gained silicon nanoparticle and graphite KS6, static eliminator Super P and sticker PVDF according to 15: 70: 8: 7 mass ratios mix (being respectively 0.045g, 0.21g, 0.024g, 0.021g); Add and be evenly coated on the Copper Foil after 1mL N-Methyl pyrrolidone (NMP) grinds to form slurry; 100 ℃ of following vacuum-drying 24 hours; Vacuum tightness is 0.02MPa, makes lithium ion battery and uses cathode pole piece.
With the lithium sheet is counter electrode, and electrolytic solution is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Record this battery first capacity be 633mAh/g, circulating also keeps 453mAh/g (test condition is a room temperature, and charge-discharge magnification is 0.1C) for 100 times.
By above detailed description to the embodiment of the invention; Can understand the high problem of cost in the silicon nanoparticle production process that the invention solves; Adopt simple process to prepare the nanoscalar silicon particles of distribution homogeneous, solved simultaneously that siliceous negative material capacity is little in the lithium ion battery, cycle performance is poor, expansive problem.Compare with the lithium ion battery of common pure silicon preparation (circulate 5 times after capacity just almost nil from reducing to more than the 3000mAh/g), cyclical stability has had and has significantly improved.
It is understandable that above embodiment 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 (12)
1. the preparation method of a silicon nanoparticle is characterized in that may further comprise the steps:
(1) the high temperature disproportionation reaction of silicon monoxide
Under protective atmosphere, silicon monoxide is heated, make it that disproportionation reaction take place, heating condition is 800-1300 ℃ of reaction 0.5-24h down, generates the silicon dioxide coated nano silicon grain;
(2) corrosion removes silicon-dioxide
The silicon dioxide coated nano silicon grain mixed with corrosive fluid carries out corrosion treatment, with silicon dioxide etching fall again through separate silicon nanoparticle.
2. preparation method according to claim 1 is characterized in that heating condition is 950-1200 ℃ of reaction 1-12h down in the said step (1).
3. preparation method according to claim 1 is characterized in that protective atmosphere is the gas mixture of nitrogen, argon gas or argon gas and hydrogen in the said step (1).
4. preparation method according to claim 1 is characterized in that said step (2) gained silicon nanoparticle particle diameter is 5-100nm.
5. according to the arbitrary described preparation method of claim 1-4; It is characterized in that corrosive fluid is the hydrofluoric acid aqueous solution of 3-40wt% in the said step (2); Add-on is pressed silicon-dioxide and hydrofluoric acid mol ratio 1: 4-1 in the product: 20 calculate, and the corrosion treatment time is 0.5-30h.
6. preparation method according to claim 5 is characterized in that corrosive fluid is the hydrofluoric acid aqueous solution of 5-20wt% in the said step (2), and add-on is pressed silicon-dioxide and hydrofluoric acid mol ratio 1: 5-1 in the product: 12 calculate, and the corrosion treatment time is 0.5-12h.
7. according to the arbitrary described preparation method of claim 1-4; It is characterized in that corrosive fluid is Lithium Hydroxide MonoHydrate or Pottasium Hydroxide or the sodium hydroxide of 0.4-30wt% in the said step (2); Add-on is pressed silicon-dioxide and Lithium Hydroxide MonoHydrate or Pottasium Hydroxide or sodium hydroxide mol ratio 1: 1.5-1 in the product: 5 calculate, and the corrosion treatment time is 0.5-30h.
8. preparation method according to claim 7; It is characterized in that preferred corrosive fluid is the sodium hydroxide of 1-30wt% in the said step (2); Add-on is pressed silicon-dioxide and Lithium Hydroxide MonoHydrate or Pottasium Hydroxide or sodium hydroxide mol ratio 1: 1.8-1 in the product: 3.5 calculate, and the corrosion treatment time is 0.5-12h.
9. preparation method according to claim 8 is characterized in that corrosive fluid is the sodium hydroxide of 4-20wt% in the said step (2).
10. lithium ion battery negative material; It is characterized in that comprising the silicon nanoparticle of 0.5-85wt% with the arbitrary said method preparation of claim 1-9; The 5-85wt% median size is the graphite of 1-100 micron, 5-15wt% graphitized carbon black and 3-10wt% sticker.
11. lithium ion battery negative material according to claim 10 is characterized in that said silicon nanoparticle is 0.5-20wt%, graphite is 60-85wt%.
12. a lithium ion battery is characterized in that comprising the negative pole for preparing battery with claim 10 or 11 said lithium ion battery negative materials.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102790206A (en) * | 2012-08-22 | 2012-11-21 | 厦门大学 | Preparation method of nanoscale silicon materials for lithium ion battery cathode materials |
| CN103413922A (en) * | 2013-08-14 | 2013-11-27 | 宁波奈克斯特新材料科技有限公司 | Lithium ion battery negative electrode material and preparation method thereof |
| CN103626187A (en) * | 2013-12-03 | 2014-03-12 | 山东玉皇化工有限公司 | High specific capacity porous silica compound preparation method |
| CN108682837A (en) * | 2018-05-17 | 2018-10-19 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of lithium ion battery orienting stephanoporate silicon materials |
| CN109384231A (en) * | 2018-11-07 | 2019-02-26 | 苏州宇量电池有限公司 | A kind of preparation method of nano silicon material |
| CN109786727A (en) * | 2018-12-29 | 2019-05-21 | 湖南中科星城石墨有限公司 | A method of preparing high-purity nm silicon |
| CN111883764A (en) * | 2020-08-04 | 2020-11-03 | 黄杰 | Preparation method of nano silicon and application of nano silicon prepared by preparation method |
| CN113823781A (en) * | 2021-08-23 | 2021-12-21 | 惠州锂威新能源科技有限公司 | Composite negative electrode material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1284046A (en) * | 1997-12-25 | 2001-02-14 | 新日本制铁株式会社 | Process for prepn. of High-purity si and equipment therefor |
| CN101901919A (en) * | 2009-05-28 | 2010-12-01 | Toto株式会社 | Solid electrolyte fuel cell |
-
2011
- 2011-11-30 CN CN2011103997920A patent/CN102491335A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1284046A (en) * | 1997-12-25 | 2001-02-14 | 新日本制铁株式会社 | Process for prepn. of High-purity si and equipment therefor |
| CN101901919A (en) * | 2009-05-28 | 2010-12-01 | Toto株式会社 | Solid electrolyte fuel cell |
Non-Patent Citations (1)
| Title |
|---|
| 唐元洪等: "自组生长的硅纳米管的稳定性研究", 《研究快讯》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102790206A (en) * | 2012-08-22 | 2012-11-21 | 厦门大学 | Preparation method of nanoscale silicon materials for lithium ion battery cathode materials |
| CN103413922A (en) * | 2013-08-14 | 2013-11-27 | 宁波奈克斯特新材料科技有限公司 | Lithium ion battery negative electrode material and preparation method thereof |
| CN103626187A (en) * | 2013-12-03 | 2014-03-12 | 山东玉皇化工有限公司 | High specific capacity porous silica compound preparation method |
| CN103626187B (en) * | 2013-12-03 | 2016-03-30 | 山东玉皇盛世化工股份有限公司 | A kind of preparation method of height ratio capacity porous silicon oxide compound |
| CN108682837A (en) * | 2018-05-17 | 2018-10-19 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of lithium ion battery orienting stephanoporate silicon materials |
| CN108682837B (en) * | 2018-05-17 | 2021-07-06 | 合肥国轩高科动力能源有限公司 | Preparation method of directional porous silicon material for lithium ion battery |
| CN109384231A (en) * | 2018-11-07 | 2019-02-26 | 苏州宇量电池有限公司 | A kind of preparation method of nano silicon material |
| CN109786727A (en) * | 2018-12-29 | 2019-05-21 | 湖南中科星城石墨有限公司 | A method of preparing high-purity nm silicon |
| CN111883764A (en) * | 2020-08-04 | 2020-11-03 | 黄杰 | Preparation method of nano silicon and application of nano silicon prepared by preparation method |
| CN113823781A (en) * | 2021-08-23 | 2021-12-21 | 惠州锂威新能源科技有限公司 | Composite negative electrode material and preparation method thereof |
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Application publication date: 20120613 |