CN104916826A - Silicon cathode material coated with graphene and preparation method thereof - Google Patents
Silicon cathode material coated with graphene and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 215
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 168
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000010406 cathode material Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 39
- 229910000077 silane Inorganic materials 0.000 claims description 39
- 239000000126 substance Substances 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 27
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 5
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- 238000012360 testing method Methods 0.000 description 9
- 229920001296 polysiloxane Polymers 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
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Abstract
The invention relates to the technical field of lithium-ion cathode material, in particular to silicon cathode material coated with graphene and a preparation method of the silicon cathode material coated with the grapheme. The preparation method comprises the following steps: A, preparing oxidized graphene suspension liquid; B, preparing nanometer silicon particle suspension liquid; and C, preparing silicon cathode material coated with grapheme. The preparation method adopts the electrostatic self-assembly synthetic technology and is wide in source of raw material, low in price, simple in synthetic method, easy for control of process conditions, strong in operability and good in repeatability. The silicon cathode material coated with grapheme is high in specific capacity and good in cycle performance and rate capability, wherein the specific discharge capacity for the first time under the electric current density of 0.01-1.2V, 200mA/g can reach 2746mAh/g, and the specific discharge capacity after 100 times of cycles can maintain 803.8mAh/g.
Description
Technical field
The present invention relates to ion cathode material lithium technical field, be specifically related to a kind of graphene coated silicium cathode material and preparation method thereof.
Background technology
Lithium ion battery, because advantages such as its high-energy-density, high power density, long lives, is the most promising energy storage chemical cell.Although lithium ion nineteen ninety just starts commercialization, its energy-storage property still can not meet the needs of people, and especially at electrical vehicular power power supply, these need on the electrokinetic cell of more macro-energy density and power density.Meanwhile, as the widely used battery of portable electric appts, lithium ion battery also needs to improve constantly its performance to meet the performance requirement and the market demand that improve constantly.Therefore, exploitation high performance lithium ion battery, becomes study hotspot in recent years.The research direction of one of them key is exactly the negative material that research and development have more height ratio capacity, more high charge-discharge speed, more long circulating useful life.
Silicon is its higher theoretical specific capacity (theoretical capacity is 4200mAh/g) as the sharpest edges of lithium ion battery negative material, but its in charge and discharge process because volumetric expansion easily causes structural deterioration, capacity sharp-decay.Modification at present for high power capacity silicium cathode material mainly adopts the methods such as surface modification, doping, compound to form system that is coated or high degree of dispersion, by improving the mechanical property of material, to alleviate the internal stress of volumetric expansion generation in removal lithium embedded process to the destruction of material structure, thus improve its electrochemical cycle stability.
Strong K sea nurse (AndreK.Geim) of peace moral etc. of Univ Manchester UK in 2004 obtains independently Graphene with mechanical split the law.The scientist of physics, chemistry, Material Field starts systematic research to Graphene since then.Graphene is the carbon six-membered cyclic two-dimensional structure that sp2 hydridization is formed, and is the basic building block of most of carbon class material, particularly graphite type material (as zero dimension fullerene, one-dimensional nano carbon pipe, three-dimensional graphite).Each C atom of Graphene is connected by very strong δ key covalent bond and other three C atoms, therefore makes Graphene have fabulous mechanical strength.The remaining p orbital electron of each C atom, define the large π key of delocalization of conjugation in the direction vertical with graphene planes, electronics can move freely in crystal, makes Graphene have good conductivity.Although Graphene is proved can with monoatomic two-dimensional structure individualism, because the calorifics undulation dispersed, Graphene can be caused to produce the out-of-flatness of feature, or even gauffer and curling.On the one hand, scientists study can control the substrate of Graphene gauffer, and studies the relation between charge mobility and gauffer.On the other hand, utilize the fold of Graphene intrinsic and curling microstructure, composite graphite alkene and other materials, prepare graphene composite material, has the excellent properties that unit material is different.
Therefore, be necessary graphene coated silicium cathode material researching and developing a kind of specific capacity height and good cycling stability and preparation method thereof, solve the deficiencies in the prior art.
Summary of the invention
In order to overcome the shortcoming and defect existed in prior art, the object of the present invention is to provide a kind of preparation method of graphene coated silicium cathode material, this preparation method adopts electrostatic self-assembled synthetic technology, raw material sources are extensive, cheap, synthetic method is simple, and process conditions are easy to control, workable, reproducible.
The object of the present invention is to provide a kind of graphene coated silicium cathode material, this graphene coated silicium cathode material specific capacity is high, cycle performance and high rate performance excellent, at 0.01-1.2V, under 200mA/g current density, first discharge specific capacity reaches 2746mAh/g, remains on 803.8mAh/g through 100 circulation specific discharge capacities.
Object of the present invention is achieved through the following technical solutions: a kind of preparation method of graphene coated silicium cathode material, comprises the steps:
A, preparation graphene oxide suspension:
A1, under the condition of ice-water bath, in the concentrated sulfuric acid, add SPA, stir, then add graphite, stir, more slowly add potassium permanganate powder, stir 30-60min, be then warming up to 45-55 DEG C, stir 20-28h, obtain reactant;
A2, the reactant that steps A 1 obtains be cooled to room temperature and slowly pour in the mixed liquor of frozen water and hydrogen peroxide, then centrifugation, and wash with watery hydrochloric acid, being then washed till pH value with deionized water is 6.8-7.2, the product obtained, 45-55 DEG C of vacuumize, obtains graphite oxide;
A3, by graphite oxide ultrasonic disperse obtained for steps A 2 in deionized water, form graphene oxide suspension;
B, prepare silicon nanoparticle suspension:
B1, under the condition of ice-water bath, add the concentrated sulfuric acid, stir in hydrogen peroxide, then add simple substance silicon nanoparticle, continue to stir, centrifuge washing, obtains the silicon nanoparticle processed after drying;
B2, by the silicon nanoparticle ultrasonic disperse of step B1 process in absolute ethyl alcohol, heating water bath, slowly drips coupling agent, and constant temperature stirs 8-16h, cooling, suction filtration, the silicon nanoparticle of obtained coupling agent finishing after dry;
B3, the silicon nanoparticle ultrasonic disperse of coupling agent finishing that obtained by step B2 in deionized water, form the silicon nanoparticle suspension of silane coupler finishing;
C, prepare graphene coated silicium cathode material:
C1, the silicon nanoparticle suspension of the silane coupler finishing graphene oxide suspension that steps A 3 is obtained obtained with step B3 mix, and stir, centrifuge washing, obtains mixture;
C2, the mixture obtained by step C1 carry out high-temperature process under protective atmosphere, prepare graphene coated silicium cathode material.
Preferably, in described steps A 1, the mass ratio of graphite and potassium permanganate is 1-3:2-6, and the addition of the concentrated sulfuric acid is 60-360mL/1-3g graphite, and the volume ratio of SPA and the concentrated sulfuric acid is 1-4:6-36.
The present invention is by controlling at 1-3:2-6 by the mass ratio of graphite and potassium permanganate, the addition of the concentrated sulfuric acid controls at 60-360mL/1-3g graphite, the volume ratio of SPA and the concentrated sulfuric acid is 1-4:6-36, can form graphite oxide better, improves graphite oxide yield and purity.More preferred, the mass ratio of graphite and potassium permanganate is 2:4, and the addition of the concentrated sulfuric acid is 210mL/2g graphite.
Preferably, in described steps A 2, the mass fraction of hydrogen peroxide is 10%-30%, and the volume ratio of frozen water and hydrogen peroxide is 120-400:10-30, and the mass fraction of watery hydrochloric acid is 3%-6%.
The present invention is by controlling at 10%-30% by the mass fraction of hydrogen peroxide, and the volume ratio of frozen water and hydrogen peroxide controls at 120-400:10-30, can improve reactivity and the purification effect of graphite oxide, obtained graphite oxide yield and purity high.More preferred, the mass fraction of hydrogen peroxide is 20%, and the volume ratio of frozen water and hydrogen peroxide is 260:20.
The present invention is by controlling at 3%-6% by the mass fraction of watery hydrochloric acid, and clean result is good, can improve graphite oxide yield and purity.More preferred, the mass fraction of watery hydrochloric acid is 4.5%.
Preferably, in described steps A 3, the time of ultrasonic disperse is 30-120min, and in graphene oxide suspension, the concentration of graphene oxide is 0.1-1mg/mL.
The present invention by by the time controling of ultrasonic disperse at 30-120min, dispersion effect is good, and obtained graphene coated silicium cathode material specific capacity is high, cycle performance and high rate performance excellent.More preferred, the time of ultrasonic disperse is 75min.
The present invention is by controlling at 0.1-1mg/mL by the concentration of graphene oxide in graphene oxide suspension, it can better be combined by the silicon nanoparticle in the silicon nanoparticle suspension of silane coupler finishing, electronegative graphene oxide is made just to be coated on the surface of the silicon nanoparticle of positively charged, obtained graphene coated silicium cathode material specific capacity is high, cycle performance and high rate performance excellent.More preferred, in graphene oxide suspension, the concentration of graphene oxide is 0.5mg/mL.
Preferably, in described step B1, the mass fraction of hydrogen peroxide is 25%-35%, and the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 120-300:20-60, and the addition of simple substance silicon nanoparticle is the 0.3-0.5g/30-50mL concentrated sulfuric acid.The mass fraction of the concentrated sulfuric acid is 98%.
The present invention is by controlling at 25%-35% by the mass fraction of hydrogen peroxide, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide controls at 120-300:20-60, the addition of simple substance silicon nanoparticle is the 0.3-0.5g/30-50mL concentrated sulfuric acid, with the concentrated sulfuric acid/hydrogen peroxide mixed liquor process simple substance silicon nanoparticle with strong oxidizing property, the concentrated sulfuric acid/hydrogen peroxide mixed liquor can the surface of oxidizing simple substance silicon grain, elemental silicon surface is oxidized generates a large amount of silicone hydroxyl, obtained graphene coated silicium cathode material specific capacity is high, cycle performance and high rate performance excellent.More preferred, the mass fraction of hydrogen peroxide is 30%, and the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 210:40.
Preferably, in described step B2, the addition of absolute ethyl alcohol is the silicon nanoparticle of 100-300mL/0.1-0.3g process, and the volume ratio of coupling agent and absolute ethyl alcohol is 2-6:100-300, silane coupler is Silane coupling agent KH550, and the temperature of heating water bath is 65-75 DEG C.
The present invention is by controlling the silicon nanoparticle in 100-300mL/0.1-0.3g process by the addition of absolute ethyl alcohol, the volume ratio of coupling agent and absolute ethyl alcohol controls at 2-6:100-300, simple substance silicon nanoparticle through the concentrated sulfuric acid/hydrogen peroxide mixed liquor process is dispersed in absolute ethyl alcohol, heating water bath, add Silane coupling agent KH550 (gamma-aminopropyl-triethoxy-silane), now, silicone hydroxyl generation crosslinking condensation after the silicone hydroxyl on silicon nanoparticle surface and Silane coupling agent KH550 are hydrolyzed reacts, be connected to the surface of simple substance silicon nanoparticle, the aobvious alkalescence of amino of its end, make simple substance silicon nanoparticle surface band positive electricity, obtained graphene coated silicium cathode material specific capacity is high, cycle performance and high rate performance excellent.More preferred, the addition of absolute ethyl alcohol is the silicon nanoparticle of 200mL/0.2g process, and the volume ratio of coupling agent and absolute ethyl alcohol is 3:200.
The silane coupler that the present invention adopts can also be the silane coupler of other type, and any apparent replacement is all within protection scope of the present invention without departing from the inventive concept of the premise.
The present invention is by controlling at 65-75 DEG C by the temperature of heating water bath, heated by hydro-thermal, silicone hydroxyl generation crosslinking condensation after the silicone hydroxyl on silicon nanoparticle surface and Silane coupling agent KH550 are hydrolyzed reacts, be connected to the surface of simple substance silicon nanoparticle, the aobvious alkalescence of amino of its end, make simple substance silicon nanoparticle surface band positive electricity, obtained graphene coated silicium cathode material specific capacity is high, cycle performance and high rate performance excellent.More preferred, the temperature of heating water bath is 70 DEG C.
Preferably, in described step B3, in the silicon nanoparticle suspension of silane coupler finishing, the concentration of the silicon nanoparticle of silane coupler finishing is 2-6mg/mL.
The present invention is by controlling at 2-6mg/mL by the concentration of the silicon nanoparticle of silane coupler finishing in the silicon nanoparticle suspension of silane coupler finishing, it can better be combined by the graphene oxide in graphene oxide suspension, electronegative graphene oxide is made just to be coated on the surface of the silicon nanoparticle of positively charged, obtained graphene coated silicium cathode material specific capacity is high, cycle performance and high rate performance excellent.More preferred, in the silicon nanoparticle suspension of silane coupler finishing, the concentration of the silicon nanoparticle of silane coupler finishing is 4mg/mL.
Preferably, in described step C1, the volume ratio of the silicon nanoparticle suspension of graphene oxide suspension and silane coupler finishing is 100-300:10-50.
The present invention controls at 100-300:10-50 by the volume ratio of the silicon nanoparticle suspension by graphene oxide suspension and silane coupler finishing, the silicon nanoparticle of electronegative graphene oxide and positively charged passes through electrostatic interaction, attract each other, electronegative graphene oxide is just coated on the surface of the silicon nanoparticle of positively charged, obtained graphene coated silicium cathode material specific capacity is high, cycle performance and high rate performance excellent.More preferred, the volume ratio of the silicon nanoparticle suspension of graphene oxide suspension and silane coupler finishing is 200:30.
Preferably, in described step C2, the temperature of high-temperature process is 600-800 DEG C, and the time of high-temperature process is 1-6h, and protective atmosphere is the mist of nitrogen, argon gas or nitrogen and argon gas.
The present invention is by controlling at 600-800 DEG C by the temperature of high-temperature process, the time controling of high-temperature process is at 1-6h, the graphene oxide high temperature reduction being coated on silicon nanoparticle surface is prepared graphene coated silicium cathode material, obtained graphene coated silicium cathode material specific capacity is high, cycle performance and high rate performance excellent.More preferred, the temperature of high-temperature process is 700 DEG C, and the time of high-temperature process is 3h.
Protective atmosphere of the present invention can also be other protective gas, and any apparent replacement is all within protection scope of the present invention without departing from the inventive concept of the premise.
The preparation principle of graphene coated silicon grain negative material of the present invention adopts electrostatic self-assembled legal system standby: first, (surface of graphene oxide contains a large amount of hydroxyls graphite oxide ultrasonic disperse to be formed in deionized water electronegative aobvious acidity, carboxyls etc., can provide H in water
+ion, so graphene oxide is electronegative in water, its suspension is aobvious acid) graphene oxide suspension, with the concentrated sulfuric acid/hydrogen peroxide mixed liquor process simple substance silicon nanoparticle with strong oxidizing property, the concentrated sulfuric acid/hydrogen peroxide mixed liquor can the surface of oxidizing simple substance silicon grain, elemental silicon surface is oxidized generates a large amount of silicone hydroxyl, be dispersed in absolute ethyl alcohol through mixed liquor process simple substance silicon nanoparticle, heating water bath, add Silane coupling agent KH550 (gamma-aminopropyl-triethoxy-silane), now, silicone hydroxyl generation crosslinking condensation after the silicone hydroxyl on silicon nanoparticle surface and Silane coupling agent KH550 are hydrolyzed reacts, be connected to the surface of simple substance silicon nanoparticle, the aobvious alkalescence of amino of its end, make simple substance silicon nanoparticle surface band positive electricity, centrifugal, washing, again disperse in deionized water, form the silicon nanoparticle suspension of Silane coupling agent KH550 finishing, graphene oxide suspension is mixed with the silicon nanoparticle suspension of Silane coupling agent KH550 finishing, magnetic agitation, the silicon nanoparticle of electronegative graphene oxide and positively charged passes through electrostatic interaction, attract each other, electronegative graphene oxide is just coated on the surface of the silicon nanoparticle of positively charged, centrifugal, washing, drying, high-temperature process, prepares graphene coated silicium cathode material by the graphene oxide high temperature reduction being coated on silicon nanoparticle surface.
Preparation method of the present invention adopts electrostatic self-assembled synthetic technology, and raw material sources are extensive, cheap, and synthetic method is simple, and process conditions are easy to control, workable, reproducible.
A kind of graphene coated silicium cathode material, described graphene coated silicium cathode material obtains according to preparation method described above.
Graphene coated silicium cathode material specific capacity of the present invention is high, cycle performance and high rate performance excellent, under 0.01-1.2V, 200mA/g current density, first discharge specific capacity reaches 2746mAh/g, remains on 803.8mAh/g through 100 circulation specific discharge capacities.
Beneficial effect of the present invention is: preparation method of the present invention adopts electrostatic self-assembled synthetic technology, and raw material sources are extensive, cheap, and synthetic method is simple, and process conditions are easy to control, workable, reproducible.
Graphene coated silicium cathode material specific capacity of the present invention is high, cycle performance and high rate performance excellent, under 0.01-1.2V, 200mA/g current density, first discharge specific capacity reaches 2746mAh/g, remains on 803.8mAh/g through 100 circulation specific discharge capacities.
The present invention utilizes the obtained graphene coated silicium cathode material of electrostatic self-assembled method to have clad structure, thus the expansion of silicon electrode can be cushioned, Graphene has more excellent conductivity to strengthen the transmission efficiency of electronics in graphene coated silicon, is conducive to the storage lithium specific capacity and the cycle performance that improve graphene coated silicon.
The graphene coated silicium cathode material granule that the present invention utilizes electrostatic self-assembled method obtained is less, the specific area of graphene coated silicon can be improved, thus reduce the diffusion length of lithium ion in graphene coated silicon, be conducive to the storage lithium specific capacity improving graphene coated silicon, contribute to the infiltration of electrolyte, thus improve the electronic conductivity of graphene coated silicium cathode material, provide Research Thinking for seeking Novel cathode material for lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the projection Electronic Speculum figure of the graphene coated silicium cathode material that embodiment 1 obtains.
Fig. 2 is the standard powder diagram of the graphene coated silicium cathode material that embodiment 1 obtains.
Fig. 3 is the first charge-discharge curve chart of graphene coated silicium cathode material under 0.01-1.2V, 200mA/g current density that embodiment 1 obtains.
Fig. 4 is the cycle performance curve chart of graphene coated silicium cathode material under 0.01-1.2V, 200mA/g current density that embodiment 1 obtains.
Fig. 5 is the cycle performance curve chart of graphene coated silicium cathode material under 0.01-1.2V, 200mA/g current density that embodiment 2 obtains.
Fig. 6 is the cycle performance curve chart of graphene coated silicium cathode material under 0.01-1.2V, 200mA/g current density that embodiment 3 obtains.
Embodiment
For the ease of the understanding of those skilled in the art, below in conjunction with embodiment and accompanying drawing 1-6, the present invention is further illustrated, and the content that execution mode is mentioned not is limitation of the invention.
The tem analysis instrument used that the present invention adopts is the microscopic appearance that the JEOLJEM2010 type projection electron microscope (TEM) of Rigaku electronics corporation (JEOL) observes specimen surface, accelerating voltage is 200KV, sample preparation drips after adopting absolute ethyl alcohol dispersion on conducting resinl surface, air drying.
The instrument that the XRD analysis of the present invention's employing is used is the crystal phase structure that Beijing Pu Xi all purpose instrument Co., Ltd XD-2 type X-ray diffractometer (XRD) characterizes prepared end product.Test condition is Cu target, K α radiation, and 36kV, 30mA walk wide by 0.02
o, sweep limits 10 ~ 80
o.Sample is that powder is placed in the pressing of sample stage groove, direct-detection.
The charge-discharge test instrument used that the present invention adopts is the BTS51800 battery test system of new Weir Electronics Co., Ltd. of Shenzhen, and model is CT-3008W, in 0.01-1.2V voltage range, carry out electro-chemical test.
Embodiment 1
A preparation method for graphene coated silicium cathode material, comprises the steps:
A, preparation graphene oxide suspension: under the condition of ice-water bath, getting 3.0g graphite joins in the mixed liquor of 360mL sulfuric acid and 40mL SPA, stir, lentamente 6.0g potassium permanganate is joined in this mixed liquor, stir, then 50 DEG C are heated to, and mechanical agitation 24h, obtain reactant; Reactant be cooled to room temperature and slowly pour 400mL frozen water into and 30mL mass fraction is in the mixed liquor of the hydrogen peroxide of 30%, then this mixed liquor is carried out centrifugation, and wash with the HCl that 500mL mass fraction is 5%, then being washed till pH value with deionized water is about 7, the product obtained vacuumize at 50 DEG C of temperature, with except anhydrating, obtains graphite oxide; Taking appropriate graphite oxide is distributed in deionized water, and ultrasonic 30min is mixed with the graphene oxide suspension of 1.0mg/mL;
B, prepare silicon nanoparticle suspension: under the condition of ice-water bath, add the 10mL concentrated sulfuric acid, stir in 40mL hydrogen peroxide, then add 0.4g simple substance silicon nanoparticle, continue to stir 8h, centrifuge washing, obtains the silicon nanoparticle processed after drying; The silicon nanoparticle getting 0.2g process joins in 100mL absolute ethyl alcohol, ultrasonic disperse 30min, and water-bath 70 DEG C stirring, slowly drips 1mLKH550, and constant temperature stirs 12h, cooling, suction filtration, the silicon nanoparticle of obtained KH550 finishing after dry; Again the silicon nanoparticle suspension of the KH550 finishing being mixed with 1.0mg/mL is in deionized water disperseed;
C, prepare graphene coated silicium cathode material: mixed by the silicon nanoparticle suspension of the graphene oxide suspension of the 1.0mg/mL of 200mL with the KH550 finishing of the 1.0mg/mL of 800mL; stir 8h; centrifuge washing; the lower 700 DEG C of process 2h of argon atmosphere, prepare graphene coated silicium cathode material.
A kind of graphene coated silicium cathode material, described graphene coated silicium cathode material obtains according to preparation method described above.
As shown in Figure 1, silicon grain is about 50 ~ 300 nanometers, and by graphene coated; The XRD figure of graphene coated silicium cathode material as shown in Figure 2.28.5 °, 47.3 °, 56.2 °, 69.1 °, 76.5 ° of characteristic peaks belonging to elemental silicon, the characteristic peaks at 28.5 ° of places belong to Graphene.
The electrochemical property test of graphene coated silicium cathode material prepared by embodiment 1:
Graphene coated silicium cathode material embodiment 1 prepared and conductive carbon black, binding agent Vingon (PVDF) to mix in mass ratio at 8: 1: 1, add appropriate 1-METHYLPYRROLIDONE (NMP) again to stir, be applied on Copper Foil, dry at 90 DEG C in vacuum drying oven, obtain graphene coated silicium cathode material electrodes sheet at sheet-punching machine top shear blade.The electrode obtained is done negative pole, metal lithium sheet is positive pole, electrolyte is for containing 1MLiPF6/(EC+DMC) (volume ratio is 1: 1) mixed system, barrier film is microporous polypropylene membrane (Celgard2400), is assembled into 2025 type button cells in the glove box being full of argon gas (Ar).Charge-discharge performance test is carried out with Shenzhen's new Weir Electronics Co., Ltd. BTS51800 battery test system.
Can find out that from Fig. 3 and 4 this material first discharge specific capacity under 0.01-1.2V, 200mA/g current density reaches 2746mAh/g, maintain 803.8mAh/g through 100 circulation specific discharge capacities, there is good electrochemistry cycle performance.
Embodiment 2
A preparation method for graphene coated silicium cathode material, comprises the steps:
A, preparation graphene oxide suspension: under the condition of ice-water bath, getting 3.0g graphite joins in the mixed liquor of 360mL sulfuric acid and 40mL SPA, stir, lentamente 6.0g potassium permanganate is joined in this mixed liquor, stir, then 50 DEG C are heated to, and mechanical agitation 24h, obtain reactant; Reactant be cooled to room temperature and slowly pour 400mL frozen water into and 30mL mass fraction is in the mixed liquor of the hydrogen peroxide of 30%, then this mixed liquor is carried out centrifugation, and wash with the HCl that 500mL mass fraction is 5%, then being washed till pH value with deionized water is about 7, the product obtained vacuumize at 50 DEG C of temperature, with except anhydrating, obtains graphite oxide; Taking appropriate graphite oxide is distributed in deionized water, and ultrasonic 30min is mixed with the graphene oxide suspension of 1.0mg/mL.
B, prepare silicon nanoparticle suspension: under the condition of ice-water bath, add the 10mL concentrated sulfuric acid, stir in 40mL hydrogen peroxide, then add 0.4g simple substance silicon nanoparticle, continue to stir 8h, centrifuge washing, obtains the silicon nanoparticle processed after drying; The silicon nanoparticle getting 0.2g process joins in 100mL absolute ethyl alcohol, ultrasonic disperse 30min, and water-bath 70 DEG C stirring, slowly drips 1mLKH550, and constant temperature stirs 12h, cooling, suction filtration, the silicon nanoparticle of obtained KH550 finishing after dry; Again the silicon nanoparticle suspension of the KH550 finishing being mixed with 1.0mg/mL is in deionized water disperseed.
C, prepare graphene coated silicium cathode material: mixed by the silicon nanoparticle suspension of the graphene oxide suspension of the 1.0mg/mL of 150mL with the KH550 finishing of the 1.0mg/mL of 800mL; stir 8h; centrifuge washing; the lower 700 DEG C of process 2h of argon atmosphere, prepare graphene coated silicium cathode material.
A kind of graphene coated silicium cathode material, described graphene coated silicium cathode material obtains according to preparation method described above.
The electrochemical property test of graphene coated silicium cathode material prepared by embodiment 2:
Graphene coated silicium cathode material embodiment 2 prepared and conductive carbon black, binding agent Vingon (PVDF) to mix in mass ratio at 8: 1: 1, add appropriate 1-METHYLPYRROLIDONE (NMP) again to stir, be applied on Copper Foil, dry at 90 DEG C in vacuum drying oven, obtain graphene coated silicium cathode material electrodes sheet at sheet-punching machine top shear blade.The electrode obtained is done negative pole, metal lithium sheet is positive pole, electrolyte is for containing 1MLiPF6/(EC+DMC) (volume ratio is 1: 1) mixed system, barrier film is microporous polypropylene membrane (Celgard2400), is assembled into 2025 type button cells in the glove box being full of argon gas (Ar).Charge-discharge performance test is carried out with Shenzhen's new Weir Electronics Co., Ltd. BTS51800 battery test system.
As can be seen from Figure 5 the first discharge specific capacity of this material under 0.01-1.2V, 200mA/g current density reaches 3507.3mAh/g, maintains 630.5mAh/g through 100 circulation specific discharge capacities, shows that this material has good chemical property.
Embodiment 3
A preparation method for graphene coated silicium cathode material, comprises the steps:
A, preparation graphene oxide suspension: under the condition of ice-water bath, getting 3.0g graphite joins in the mixed liquor of 360mL sulfuric acid and 40mL SPA, stir, lentamente 6.0g potassium permanganate is joined in this mixed liquor, stir, then 50 DEG C are heated to, and mechanical agitation 24h, obtain reactant; Reactant be cooled to room temperature and slowly pour 400mL frozen water into and 30mL mass fraction is in the mixed liquor of the hydrogen peroxide of 30%, then this mixed liquor is carried out centrifugation, and wash with the HCl that 500mL mass fraction is 5%, then being washed till pH value with deionized water is about 7, the product obtained vacuumize at 50 DEG C of temperature, with except anhydrating, obtains graphite oxide; Taking appropriate graphite oxide is distributed in deionized water, and ultrasonic 30min is mixed with the graphene oxide suspension of 1.0mg/mL.
B, prepare silicon nanoparticle suspension: under the condition of ice-water bath, add the 10mL concentrated sulfuric acid, stir in 40mL hydrogen peroxide, then add 0.4g simple substance silicon nanoparticle, continue to stir 8h, centrifuge washing, obtains the silicon nanoparticle processed after drying; The silicon nanoparticle getting 0.2g process joins in 100mL absolute ethyl alcohol, ultrasonic disperse 30min, and water-bath 70 DEG C stirring, slowly drips 1mLKH550, and constant temperature stirs 12h, cooling, suction filtration, the silicon nanoparticle of obtained KH550 finishing after dry; Again the silicon nanoparticle suspension of the KH550 finishing being mixed with 1.0mg/mL is in deionized water disperseed.
C, prepare graphene coated silicium cathode material: mixed by the silicon nanoparticle suspension of the graphene oxide suspension of the 1.0mg/mL of 100mL with the KH550 finishing of the 1.0mg/mL of 800mL; stir 8h; centrifuge washing; the lower 700 DEG C of process 2h of argon atmosphere, prepare graphene coated silicium cathode material.
A kind of graphene coated silicium cathode material, described graphene coated silicium cathode material obtains according to preparation method described above.
The electrochemical property test of graphene coated silicium cathode material prepared by embodiment 3:
Graphene coated silicium cathode material embodiment 3 prepared and conductive carbon black, binding agent Vingon (PVDF) to mix in mass ratio at 8: 1: 1, add appropriate 1-METHYLPYRROLIDONE (NMP) again to stir, be applied on Copper Foil, dry at 90 DEG C in vacuum drying oven, obtain graphene coated silicium cathode material electrodes sheet at sheet-punching machine top shear blade.The electrode obtained is done negative pole, metal lithium sheet is positive pole, electrolyte is for containing 1MLiPF6/(EC+DMC) (volume ratio is 1: 1) mixed system, barrier film is microporous polypropylene membrane (Celgard2400), is assembled into 2025 type button cells in the glove box being full of argon gas (Ar).Charge-discharge performance test is carried out with Shenzhen's new Weir Electronics Co., Ltd. BTS51800 battery test system.
As can be seen from Figure 6 the first discharge specific capacity of this material under 0.01-1.2V, 200mA/g current density reaches 3378.7mAh/g, maintains 530.8mAh/g through 100 circulation specific discharge capacities, shows that this material has good chemical property.
Embodiment 4
A preparation method for graphene coated silicium cathode material, comprises the steps:
A, preparation graphene oxide suspension:
A1, under the condition of ice-water bath, in the concentrated sulfuric acid, add SPA, stir, then add graphite, stir, more slowly add potassium permanganate powder, stir 30min, be then warming up to 45 DEG C, stir 20h, obtain reactant;
A2, the reactant that steps A 1 obtains be cooled to room temperature and slowly pour in the mixed liquor of frozen water and hydrogen peroxide, then centrifugation, and wash with watery hydrochloric acid, being then washed till pH value with deionized water is 6.8, the product obtained, 45 DEG C of vacuumizes, obtains graphite oxide;
A3, by graphite oxide ultrasonic disperse obtained for steps A 2 in deionized water, form graphene oxide suspension;
B, prepare silicon nanoparticle suspension:
B1, under the condition of ice-water bath, add the concentrated sulfuric acid, stir in hydrogen peroxide, then add simple substance silicon nanoparticle, continue to stir, centrifuge washing, obtains the silicon nanoparticle processed after drying;
B2, by the silicon nanoparticle ultrasonic disperse of step B1 process in absolute ethyl alcohol, heating water bath, slowly drips coupling agent, and constant temperature stirs 8h, cooling, suction filtration, the silicon nanoparticle of obtained coupling agent finishing after dry;
B3, the silicon nanoparticle ultrasonic disperse of coupling agent finishing that obtained by step B2 in deionized water, form the silicon nanoparticle suspension of silane coupler finishing;
C, prepare graphene coated silicium cathode material:
C1, the silicon nanoparticle suspension of the silane coupler finishing graphene oxide suspension that steps A 3 is obtained obtained with step B3 mix, and stir, centrifuge washing, obtains mixture;
C2, the mixture obtained by step C1 carry out high-temperature process under protective atmosphere, prepare graphene coated silicium cathode material.
In described steps A 1, the mass ratio of graphite and potassium permanganate is 1:2, and the addition of the concentrated sulfuric acid is 60mL/1g graphite, and the volume ratio of SPA and the concentrated sulfuric acid is 1:6.
In described steps A 2, the mass fraction of hydrogen peroxide is 10%, and the volume ratio of frozen water and hydrogen peroxide is 120:10, and the mass fraction of watery hydrochloric acid is 3%.
In described steps A 3, the time of ultrasonic disperse is 30min, and in graphene oxide suspension, the concentration of graphene oxide is 0.1mg/mL.
In described step B1, the mass fraction of hydrogen peroxide is 25, and the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 120:20, and the addition of simple substance silicon nanoparticle is the 0.3g/30mL concentrated sulfuric acid.
In described step B2, the addition of absolute ethyl alcohol is the silicon nanoparticle of 100mL/0.1g process, and the volume ratio of coupling agent and absolute ethyl alcohol is 2:100, and silane coupler is Silane coupling agent KH550, and the temperature of heating water bath is 65 DEG C.
In described step B3, in the silicon nanoparticle suspension of silane coupler finishing, the concentration of the silicon nanoparticle of silane coupler finishing is 2mg/mL.
In described step C1, the volume ratio of the silicon nanoparticle suspension of graphene oxide suspension and silane coupler finishing is 100:10.
In described step C2, the temperature of high-temperature process is 600 DEG C, and the time of high-temperature process is 6h, and protective atmosphere is nitrogen.
A kind of graphene coated silicium cathode material, described graphene coated silicium cathode material obtains according to preparation method described above.
Embodiment 5
A preparation method for graphene coated silicium cathode material, comprises the steps:
A, preparation graphene oxide suspension:
A1, under the condition of ice-water bath, in the concentrated sulfuric acid, add SPA, stir, then add graphite, stir, more slowly add potassium permanganate powder, stir 45min, be then warming up to 50 DEG C, stir 24h, obtain reactant;
A2, the reactant that steps A 1 obtains be cooled to room temperature and slowly pour in the mixed liquor of frozen water and hydrogen peroxide, then centrifugation, and wash with watery hydrochloric acid, being then washed till pH value with deionized water is 7.0, the product obtained, 50 DEG C of vacuumizes, obtains graphite oxide;
A3, by graphite oxide ultrasonic disperse obtained for steps A 2 in deionized water, form graphene oxide suspension;
B, prepare silicon nanoparticle suspension:
B1, under the condition of ice-water bath, add the concentrated sulfuric acid, stir in hydrogen peroxide, then add simple substance silicon nanoparticle, continue to stir, centrifuge washing, obtains the silicon nanoparticle processed after drying;
B2, by the silicon nanoparticle ultrasonic disperse of step B1 process in absolute ethyl alcohol, heating water bath, slowly drips coupling agent, and constant temperature stirs 12h, cooling, suction filtration, the silicon nanoparticle of obtained coupling agent finishing after dry;
B3, the silicon nanoparticle ultrasonic disperse of coupling agent finishing that obtained by step B2 in deionized water, form the silicon nanoparticle suspension of silane coupler finishing;
C, prepare graphene coated silicium cathode material:
C1, the silicon nanoparticle suspension of the silane coupler finishing graphene oxide suspension that steps A 3 is obtained obtained with step B3 mix, and stir, centrifuge washing, obtains mixture;
C2, the mixture obtained by step C1 carry out high-temperature process under protective atmosphere, prepare graphene coated silicium cathode material.
In described steps A 1, the mass ratio of graphite and potassium permanganate is 2:4, and the addition of the concentrated sulfuric acid is 210mL/2g graphite, and the volume ratio of SPA and the concentrated sulfuric acid is 2.5:21.
In described steps A 2, the mass fraction of hydrogen peroxide is 20%, and the volume ratio of frozen water and hydrogen peroxide is 260:20, and the mass fraction of watery hydrochloric acid is 4.5%.
In described steps A 3, the time of ultrasonic disperse is 75min, and in graphene oxide suspension, the concentration of graphene oxide is 0.5mg/mL.
In described step B1, the mass fraction of hydrogen peroxide is 30%, and the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 210:40, and the addition of simple substance silicon nanoparticle is the 0.4g/40mL concentrated sulfuric acid.
In described step B2, the addition of absolute ethyl alcohol is the silicon nanoparticle of 200mL/0.2g process, and the volume ratio of coupling agent and absolute ethyl alcohol is 4:200, and silane coupler is Silane coupling agent KH550, and the temperature of heating water bath is 70 DEG C.
In described step B3, in the silicon nanoparticle suspension of silane coupler finishing, the concentration of the silicon nanoparticle of silane coupler finishing is 4mg/mL.
In described step C1, the volume ratio of the silicon nanoparticle suspension of graphene oxide suspension and silane coupler finishing is 200:30.
In described step C2, the temperature of high-temperature process is 700 DEG C, and the time of high-temperature process is 3h, and protective atmosphere is argon gas.
A kind of graphene coated silicium cathode material, described graphene coated silicium cathode material obtains according to preparation method described above.
Embodiment 6
A preparation method for graphene coated silicium cathode material, comprises the steps:
A, preparation graphene oxide suspension:
A1, under the condition of ice-water bath, in the concentrated sulfuric acid, add SPA, stir, then add graphite, stir, more slowly add potassium permanganate powder, stir 60min, be then warming up to 55 DEG C, stir 28h, obtain reactant;
A2, the reactant that steps A 1 obtains be cooled to room temperature and slowly pour in the mixed liquor of frozen water and hydrogen peroxide, then centrifugation, and wash with watery hydrochloric acid, being then washed till pH value with deionized water is 7.2, the product obtained, 55 DEG C of vacuumizes, obtains graphite oxide;
A3, by graphite oxide ultrasonic disperse obtained for steps A 2 in deionized water, form graphene oxide suspension;
B, prepare silicon nanoparticle suspension:
B1, under the condition of ice-water bath, add the concentrated sulfuric acid, stir in hydrogen peroxide, then add simple substance silicon nanoparticle, continue to stir, centrifuge washing, obtains the silicon nanoparticle processed after drying;
B2, by the silicon nanoparticle ultrasonic disperse of step B1 process in absolute ethyl alcohol, heating water bath, slowly drips coupling agent, and constant temperature stirs 16h, cooling, suction filtration, the silicon nanoparticle of obtained coupling agent finishing after dry;
B3, the silicon nanoparticle ultrasonic disperse of coupling agent finishing that obtained by step B2 in deionized water, form the silicon nanoparticle suspension of silane coupler finishing;
C, prepare graphene coated silicium cathode material:
C1, the silicon nanoparticle suspension of the silane coupler finishing graphene oxide suspension that steps A 3 is obtained obtained with step B3 mix, and stir, centrifuge washing, obtains mixture;
C2, the mixture obtained by step C1 carry out high-temperature process under protective atmosphere, prepare graphene coated silicium cathode material.
In described steps A 1, the mass ratio of graphite and potassium permanganate is 3:6, and the addition of the concentrated sulfuric acid is 360mL/3g graphite, and the volume ratio of SPA and the concentrated sulfuric acid is 4:36.
In described steps A 2, the mass fraction of hydrogen peroxide is 30%, and the volume ratio of frozen water and hydrogen peroxide is 400:30, and the mass fraction of watery hydrochloric acid is 6%.
In described steps A 3, the time of ultrasonic disperse is 120min, and in graphene oxide suspension, the concentration of graphene oxide is 1mg/mL.
In described step B1, the mass fraction of hydrogen peroxide is 35%, and the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 300:60, and the addition of simple substance silicon nanoparticle is the 0.5g/50mL concentrated sulfuric acid.
In described step B2, the addition of absolute ethyl alcohol is the silicon nanoparticle of 300mL/0.3g process, and the volume ratio of coupling agent and absolute ethyl alcohol is 6:300, and silane coupler is Silane coupling agent KH550, and the temperature of heating water bath is 75 DEG C.
In described step B3, in the silicon nanoparticle suspension of silane coupler finishing, the concentration of the silicon nanoparticle of silane coupler finishing is 6mg/mL.
In described step C1, the volume ratio of the silicon nanoparticle suspension of graphene oxide suspension and silane coupler finishing is 300:50.
In described step C2, the temperature of high-temperature process is 800 DEG C, and the time of high-temperature process is 1h, and protective atmosphere is the mist of nitrogen and argon gas.
A kind of graphene coated silicium cathode material, described graphene coated silicium cathode material obtains according to preparation method described above.
Above-described embodiment is the present invention's preferably implementation, and in addition, the present invention can also realize by alternate manner, and any apparent replacement is all within protection scope of the present invention without departing from the inventive concept of the premise.
Claims (10)
1. a preparation method for graphene coated silicium cathode material, is characterized in that: comprise the steps:
A, preparation graphene oxide suspension:
A1, under the condition of ice-water bath, in the concentrated sulfuric acid, add SPA, stir, then add graphite, stir, more slowly add potassium permanganate powder, stir 30-60min, be then warming up to 45-55 DEG C, stir 20-28h, obtain reactant;
A2, the reactant that steps A 1 obtains be cooled to room temperature and slowly pour in the mixed liquor of frozen water and hydrogen peroxide, then centrifugation, and wash with watery hydrochloric acid, being then washed till pH value with deionized water is 6.8-7.2, the product obtained, 45-55 DEG C of vacuumize, obtains graphite oxide;
A3, by graphite oxide ultrasonic disperse obtained for steps A 2 in deionized water, form graphene oxide suspension;
B, prepare silicon nanoparticle suspension:
B1, under the condition of ice-water bath, add the concentrated sulfuric acid, stir in hydrogen peroxide, then add simple substance silicon nanoparticle, continue to stir, centrifuge washing, obtains the silicon nanoparticle processed after drying;
B2, by the silicon nanoparticle ultrasonic disperse of step B1 process in absolute ethyl alcohol, heating water bath, slowly drips coupling agent, and constant temperature stirs 8-16h, cooling, suction filtration, the silicon nanoparticle of obtained coupling agent finishing after dry;
B3, the silicon nanoparticle ultrasonic disperse of coupling agent finishing that obtained by step B2 in deionized water, form the silicon nanoparticle suspension of silane coupler finishing;
C, prepare graphene coated silicium cathode material:
C1, the silicon nanoparticle suspension of the silane coupler finishing graphene oxide suspension that steps A 3 is obtained obtained with step B3 mix, and stir, centrifuge washing, obtains mixture;
C2, the mixture obtained by step C1 carry out high-temperature process under protective atmosphere, prepare graphene coated silicium cathode material.
2. the preparation method of a kind of graphene coated silicium cathode material according to claim 1, it is characterized in that: in described steps A 1, the mass ratio of graphite and potassium permanganate is 1-3:2-6, the addition of the concentrated sulfuric acid is 60-360mL/1-3g graphite, and the volume ratio of SPA and the concentrated sulfuric acid is 1-4:6-36.
3. the preparation method of a kind of graphene coated silicium cathode material according to claim 1, it is characterized in that: in described steps A 2, the mass fraction of hydrogen peroxide is 10%-30%, and the volume ratio of frozen water and hydrogen peroxide is 120-400:10-30, and the mass fraction of watery hydrochloric acid is 3%-6%.
4. the preparation method of a kind of graphene coated silicium cathode material according to claim 1, it is characterized in that: in described steps A 3, the time of ultrasonic disperse is 30-120min, and in graphene oxide suspension, the concentration of graphene oxide is 0.1-1mg/mL.
5. the preparation method of a kind of graphene coated silicium cathode material according to claim 1, it is characterized in that: in described step B1, the mass fraction of hydrogen peroxide is 25%-35%, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 120-300:20-60, and the addition of simple substance silicon nanoparticle is the 0.3-0.5g/30-50mL concentrated sulfuric acid.
6. the preparation method of a kind of graphene coated silicium cathode material according to claim 1, it is characterized in that: in described step B2, the addition of absolute ethyl alcohol is the silicon nanoparticle of 100-300mL/0.1-0.3g process, the volume ratio of coupling agent and absolute ethyl alcohol is 2-6:100-300, silane coupler is Silane coupling agent KH550, and the temperature of heating water bath is 65-75 DEG C.
7. the preparation method of a kind of graphene coated silicium cathode material according to claim 1, it is characterized in that: in described step B3, in the silicon nanoparticle suspension of silane coupler finishing, the concentration of the silicon nanoparticle of silane coupler finishing is 2-6mg/mL.
8. the preparation method of a kind of graphene coated silicium cathode material according to claim 1, it is characterized in that: in described step C1, the volume ratio of the silicon nanoparticle suspension of graphene oxide suspension and silane coupler finishing is 100-300:10-50.
9. the preparation method of a kind of graphene coated silicium cathode material according to claim 1; it is characterized in that: in described step C2; the temperature of high-temperature process is 600-800 DEG C, and the time of high-temperature process is 1-6h, and protective atmosphere is the mist of nitrogen, argon gas or nitrogen and argon gas.
10. a graphene coated silicium cathode material, is characterized in that: the preparation method of described graphene coated silicium cathode material according to any one of claim 1-9 obtains.
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