CN106887569A - A kind of new structure graphene coated nano silicon particles and preparation method thereof - Google Patents

A kind of new structure graphene coated nano silicon particles and preparation method thereof Download PDF

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CN106887569A
CN106887569A CN201710097153.6A CN201710097153A CN106887569A CN 106887569 A CN106887569 A CN 106887569A CN 201710097153 A CN201710097153 A CN 201710097153A CN 106887569 A CN106887569 A CN 106887569A
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nano silicon
silicon particles
graphene
silica flour
new structure
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童磊
余德馨
郑安华
杜辉玉
郑远辉
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Shanghai Shanshan Technology Co Ltd
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Shanghai Shanshan Technology Co Ltd
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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
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 present invention relates to lithium ion battery electrode material field, more particularly to a kind of new structure graphene coated nano silicon particles and preparation method thereof, it is characterised in that：By being coated on the redox graphene of outer layer/carbon shell, the nano silicon particles core in redox graphene/carbon shell, and redox graphene/cavity layer between carbon shell and nano silicon particles core is constituted.Compared with prior art, silicon grain surface oxide layer thickness is easily controllable for the present invention；The silica flour of surface oxidation is readily dispersed in solvent, and the hydroxyl of particle surface makes it easily be combined with dressing agent；The Graphene of particle surface cladding increased the electrical contact between particle and particle, particle and collector, be conducive to the reduction impedance of composite inner electron transmission；The carbon that dressing agent carbochain Pintsch process is produced forms the shell with some strength together with Graphene, advantageously forms the SEI of stabilization.

Description

A kind of new structure graphene coated nano silicon particles and preparation method thereof
Technical field
The present invention relates to lithium ion battery electrode material field, more particularly to a kind of new structure graphene coated silicon nanometer Particle and preparation method thereof.
Background technology
With the development of portable mobile apparatus and electric automobile, people are close for higher energy density and more power The energy storing device demand of degree is more and more urgent, and the lithium ion battery (372mAh/g) with graphite as negative pole cannot meet Consumption demand, therefore, find capacity negative material higher extremely urgent.Silicon materials are because the theoretical lithium storage content of its superelevation (4200mAh/g) and rich in natural resources, it is considered to be most potential as lithium ion battery negative material of new generation, but silicon material Also there is following problem demanding prompt solution using upper as negative material in material：Used as a kind of semi-conducting material, it leads 1 silicon Electrically mutually poor, electron transfer rate is slow, and high rate performance will necessarily be reduced during as lithium ion battery negative material；2 in charge and discharge In electric process, due to the insertion/deintercalation of lithium ion, silicon materials volume is caused to change (cubical expansivity up to more than 300%), This volume change repeatedly inevitably result in active material particle internal structure collapse, reduce active material particle between contact, Cause active material particle and collector to depart from, ultimately cause that capacity attenuation, high rate performance reduction and safety etc. are a series of to ask Topic；3 unstable active material particle surfaces cause the excessive formation of SEI, cause irreversible capacitance loss.On solving Problem is stated, it is necessary to silicon materials are carried out with the modification of the following aspects：1 enough void space adapt to Volume Changes；2 Compliant conductive host material improves electric conductivity；3Si surface protections to form stabilization and thin SEI to promote.
Graphene as a kind of new two-dimensional material, due to its unique electricity, calorifics and mechanical characteristic and turn into silicon The ideal chose of material modification.The A of Chinese patent CN 105489869 disclose a kind of preparation side of Graphene-silicon composite Method, the preparation method mainly includes：Amino modified modification is carried out to silicon nanoparticle surface using silane coupler；After modifying Nano-silicon mix with graphene oxide solution and coated；High-temperature calcination obtains silicon nanoparticle Surface coating under inert atmosphere Graphene-the silicon composite of graphene layer.This composite increases because the Graphene on nano silicon particles surface is present Electric conductivity, the Graphene of full cladding forms to silicon nanoparticle a kind of constraint and reduces grain structure structure collapses because of expansion Burst.But the material is not still solved, and the material internal electrical contact that volumetric expansion causes is reduced, material and collector depart from, The problems such as SEI films are unstable, reduces its commercialized possibility.
Ding etc. by building the swollen space structure of new appearance from the volumetric expansion of nano silicon particles is sponged, so as to solve The material internal that volumetric expansion is caused makes electrical contact with the problems such as reduction, material and collector depart from, SEI films are unstable (X.Ding, et Al.Nano Energy, 2016,27：647-657).The preparation method of material is as follows：1. nano silicon particles are wrapped using Copper Foil It is placed into high temperature furnace, under the high temperature conditions melts Copper Foil and be coated on nano silicon particles surface；2. with methane gas as carbon source, Mixing H2With Ar gases, by the method for CVD in copper Surface Creation graphene layer；3. Cu layers is etched away come structure using salpeter solution Build white space obtain can self-absorption volumetric expansion composite.The composite capacity is high and good cycle, but Preparation condition is difficult to control, and highly energy-consuming is difficult mass production, the waste liquor contamination environment of ion containing Cu of generation.
Therefore, a kind of preparation method is sought on the basis of electric conductivity is improved simple, can be prepared on a large scale, environmental protection The preparation method for being capable of the Graphene-silicon composite of self-absorption Volume Changes is significant.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, there is provided a kind of preparation method, so as to get electrode material energy The volumetric expansion of silicon is fallen in enough effectively self-absorptions.
To achieve the above object, a kind of new structure graphene coated nano silicon particles are designed, it is characterised in that：By coating Redox graphene/carbon shell in outer layer, the nano silicon particles core in redox graphene/carbon shell, and reduction Graphene oxide/cavity layer between carbon shell and nano silicon particles core is constituted.
A kind of preparation method of new structure graphene coated nano silicon particles, it is characterised in that comprise the following steps：
Step one, surface oxidation：Silica flour is inserted in high temperature furnace, under the conditions of oxygen-containing atmosphere, with 300-1000 DEG C of insulation 0.5-20.0h, it is the silica flour of 8wt%-57wt% that oxygen content is obtained；
Step 2, prepare silica flour solution：Silica flour after above-mentioned high temperature oxidation process is added in dispersant and ultrasound point Dissipate to obtain silica flour solution；Concentration of the described silica flour in dispersant is 0.1-10.0mg/ml；Described dispersant uses water or nothing Water-ethanol or the two arbitrary volume than mixed solution；
Step 3, surface modification：Dressing agent is added in above-mentioned silica flour solution, and constant temperature stirring 1-24h obtains mixed solution； The temperature of described constant temperature is 20-80 DEG C, and the quality of described dressing agent is the 25%~100% of siliceous amount；
Step 4, prepare dispersion liquid：After by the mixed solution vacuum filtration after stirring, unmodified dressing agent is washed away, so Suction filtration thing is distributed in water afterwards, it is the dispersion liquid of 0.5-10.0mg/ml that concentration is obtained；
Step 5, GO claddings：Take silica flour quality 20%-100% graphene oxide solution drop in step 4 point In dispersion liquid, 1-24h is stirred, precipitated product is collected by centrifugation and is vacuum dried；Described graphene oxide solution concentration is 0.5- 2.0mg/ml；
Step 6, reduction and carbonization：Desciccate is inserted in high temperature furnace, 700-900 DEG C is warming up under an inert atmosphere, protected Warm 1.0-3.0h, obtains the silicon composite of graphene coated；
Step 7, HF etchings：The silicon composite that graphene coated will be obtained adds concentration molten for the diluted hydrofluoric acid of 5wt% In liquid, drying fully is washed after reaction, that is, obtain the graphene coated nano silicon particles composite with new structure；It is described Dilute hydrofluoric acid solution in hydrofluoric acid amount for silica flour quality 20%-143%.
Described silica flour is obtained by ball milling, Ball-milling Time 4.0-48.0h, and it is 0.05-50.0um's that particle diameter is obtained Silica flour.
Oxygen-containing atmosphere is one kind or several mixing in compressed air, synthesis of air, oxygen, vapor.
Described dressing agent is that the macromolecule organic containing amino is included but is not limited only to polyvinylpyrrolidone, polyphenyl One or more in vinyl sulfonic acid sodium, diallyl dimethyl ammoniumchloride.
Described dressing agent is the silane coupler containing amino, and the described silane coupler containing amino is γ-ammonia Propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane, N- β (aminoethyl)-γ-aminopropyltrimethoxysilane, N- β (aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N- β (aminoethyl)-gamma-aminopropyl-triethoxy-silane, N- β (ammonia second Base)-γ-aminopropyltriethoxy dimethoxysilane, aminoethyl aminoethylaminopropyl trimethoxy silane or the alkane of polyamino alkyl three One kind in TMOS.
The concentration of described dispersion liquid is 0.5-2.0mg/ml.
Graphene oxide in the graphene oxide solution uses Hummers methods, Brodie methods or Staudenmaie methods It is obtained.
The lamella size of the graphene oxide in the graphene oxide solution is 0.1-20.0um.
The lamella size of the graphene oxide in the graphene oxide solution is 0.5-5.0um.
The present invention compared with prior art, 1, silicon grain surface oxide layer thickness it is easily controllable；2nd, the silica flour of surface oxidation It is readily dispersed in solvent, the hydroxyl of particle surface makes it easily be combined with dressing agent；3rd, the Graphene of particle surface cladding increases Add the electrical contact between particle and particle, particle and collector, be conducive to the reduction impedance of composite inner electron transmission；4、 The carbon that dressing agent carbochain Pintsch process is produced forms the shell with some strength together with Graphene, advantageously forms stabilization SEI；5th, the self-absorption that the space structure that the self-sacrifice of silicon oxide layer is formed is beneficial to silicon volumetric expansion, reduce as lithium from The battery Volume Changes caused during sub- GND；6th, the removal of silicon oxide layer avoids it and electric conductivity and capacity density is born Face rings；The capability retention of the graphene coated nano silicon particles of preparation is high, good cycle；Rate charge-discharge simultaneously high Performance and security performance allow its range of application to be widened to electric automobile field, extensive market from consumption electronic product；And system Preparation Method is simple, easy to operate, be easy to implement large-scale production.
Brief description of the drawings
Fig. 1 is to take turns doing shown structural representation after respective handling in the present invention to silicon, signified in the direction of arrows, point Be not the structural representation after silicon grain schematic diagram, silicon grain surface oxidation, the structural representation after surface modification, GO cladding after Structural representation, reduction and carbonization after structural representation, HF etching after structural representation, charge expansion after structural representation Figure.
Fig. 2 is the G@SiO2@Si scanning of materials electron microscopic pictures of the embodiment of the present invention 1.
Fig. 3 is the new structure graphene coated silicon grain cycle performance curve of the embodiment of the present invention 1.
Specific embodiment
In conjunction with accompanying drawing and the invention will be further described.
Embodiment 1
Referring to Fig. 1, the preparation method of new structure graphene coated nano silicon particles uses following preparation process：
Material prepares：Piece goods silicon and 6mm mill balls are taken, after mixing with the proportioning of ratio of grinding media to material 15: 1, in 400r/min Rotating speed under ball milling 7h, sift out powder and use the type laser diffraction analyzer test material particle size range of Malvern 3000, through survey Examination is obtained, and made silica flour particle diameter is in the range of 0.5-20.0um.
Step one, surface oxidation：Obtained silica flour is fitted into silica crucible and is put into high temperature furnace, is progressively warming up to Start to be passed through compressed air after 900 DEG C and be incubated 1h, the silica flour of surface oxidation is obtained after cooling, it is molten using PULSE HEATING noble gas Melt-infrared absorption test oxygen content, it is 42.8% to test its oxygen content.
Step 2, prepare silica flour solution：The silica flour for taking 1 part of surface oxidation of mass fraction is added to ultrasound in deionized water Dispersion 30min, obtains silica flour solution；
Step 3, surface modification：To 0.5 part of kayexalate of mass fraction of addition and constant temperature in above-mentioned dispersion liquid Stirring 4.0h；
Step 4, prepare dispersion liquid：After stirring terminates, with deionized water filtering and washing three times, unreacted polyphenyl is removed , be scattered in filtering and washing product in deionized water afterwards and be configured to the dispersion liquid of 1.0mg/ml by vinyl sulfonic acid sodium；
Step 5, GO claddings：Take 0.2 part of mass fraction graphene oxide be scattered in deionized water in be configured to 1.0mg/ The graphene oxide solution of ml, during graphene oxide solution to be dropped to above-mentioned dispersion liquid under stirring, completion of dropwise addition After stir 6.0h；Stirring removes uncoated graphene oxide solution after terminating using centrifuge, collects sediment and in vacuum Dried in baking oven, obtain GO@SiO@Si composites；
Step 6, reduction and carbonization：By dry GO@SiO2@Si composites are inserted in high temperature furnace, under an inert atmosphere 900 DEG C are warming up to, 1h is incubated, G@SiO are obtained2@Si composites, as shown in Figure 2；
Step 7, HF etchings：Concentration is the dilute hydrofluoric acid solution etching G@SiO of 5.0wt%2@Si composites, and Washing drying, finally gives the composite of the graphene coated silicon grain with new structure.The sky formed after wherein etching Cavity layer is used as the swollen space of appearance.
Chemical property is adopted and tested with the following method：Graphene coated silicon grain composite, the conduction that will be prepared Agent, binding agent and CMC plus are coated in Cu substrates after deionized water stirs into uniform sizing material according to 95: 2: 2: 1 mass ratio, Electrode slice is made through drying, rolling, cutting；It is positive pole, the LiPF of 1mol/L to use lithium piece6Solution is electrolyte, polypropylene is micro- Pore membrane is barrier film, is assembled into CR2025 type button cells, and in Wuhan Jin Nuo Electronics Co., Ltd.s, LAND battery test systems are enterprising Row test.Test condition is as follows：Voltage range 0.01-2.5V, current density 200mA/g, circulate 50 circulations of test material Performance, as shown in Figure 3.What the Volumetric expansion of material was obtained by the following method：Volumetric expansion=(after circulation in 50 weeks Pole piece thickness before pole piece thickness-circulation)/(pole piece thickness-copper thickness before circulation) × 100%.
Embodiment 2
Material preparation condition such as embodiment 1, difference be silica flour used for ball milling 4h is obtained, use Malvern 3000 type laser diffraction analyzer test material particle size ranges, obtain after tested, and made silica flour particle diameter is in 0.6-50um scopes It is interior.
Electro-chemical test is carried out using the identical method of same embodiment 1 and compares material volume bulking effect.
Embodiment 3
Material preparation condition such as embodiment 1, difference is that silica flour oxidization time is 0.5h, using PULSE HEATING noble gas It is 28.3% that melting-infrared absorption tests its oxygen content.
Electro-chemical test is carried out using the identical method of same embodiment 1 and compares material volume bulking effect.
Embodiment 4
Material preparation condition such as embodiment 1, difference is to add 1 part of kayexalate of mass fraction.
Electro-chemical test is carried out using the identical method of same embodiment 1 and compares material volume bulking effect.
Embodiment 5
Material preparation condition such as embodiment 1, difference is that dressing agent used is the γ-ammonia in silane coupler system Propyl trimethoxy silicane.
Electro-chemical test is carried out using the identical method of same embodiment 1 and compares material volume bulking effect.
Embodiment 6
Material preparation condition such as embodiment 1, difference is to use 1 part of graphene oxide solution of mass fraction.
Electro-chemical test is carried out using the identical method of same embodiment 1 and compares material volume bulking effect.
Embodiment 7
Material preparation condition such as embodiment 1, difference is graphene oxide layer size ＞ Sum used.
Electro-chemical test is carried out using the identical method of same embodiment 1 and compares material volume bulking effect.
Comparative example 1
Material prepares：Piece goods silicon and 6mm mill balls are taken, after mixing with the proportioning of ratio of grinding media to material 15: 1, in 400r/min Rotating speed under ball milling 7h, sift out powder and use the type laser diffraction analyzer test material particle size range of Malvern 3000, through survey Examination is obtained, and made silica flour particle diameter is in the range of 0.5-20.0um.
Prepare silica flour solution：The silica flour for taking 1 part of mass fraction is added in the mixed solution that water/ethanol volume ratio is 1: 1 Ultrasonic disperse 30min；
Surface modification：To 0.5 part of kayexalate of mass fraction is added in above-mentioned dispersion liquid, simultaneously constant temperature is stirred 4.0h, stirring uses deionized water filtering and washing three times after terminating, and removes unreacted kayexalate；
Prepare dispersion liquid：Filtering and washing product is scattered in deionized water afterwards and is configured to the dispersion of 1.0mg/ml Liquid.
GO is coated：The GO for taking 0.2 part of mass fraction is scattered in deionized water the GO solution for being configured to 1.0mg/ml, During GO solution dropped into above-mentioned dispersion liquid under stirring, 6.0h is stirred after completion of dropwise addition.Stirring uses centrifugation after terminating Machine removes uncoated GO, collects sediment and is dried in vacuum drying oven, obtains GO@Si composites.
Reduction and carbonization：Dry GO@Si composites are inserted in high temperature furnace, 900 DEG C are warming up under an inert atmosphere, protected Warm 1h, obtains G@Si composites.
Electro-chemical test is carried out using the identical method of same embodiment 1 and compares material volume bulking effect.
Comparative example 2
Material prepares：Piece goods silicon and 6mm mill balls are taken, after mixing with the proportioning of ratio of grinding media to material 15: 1, in 400r/min Rotating speed under ball milling 7h, sift out powder and use the type laser diffraction analyzer test material particle size range of Malvern 3000, through survey Examination is obtained, and made silica flour particle diameter is in the range of 0.5-20.0um.Obtained silica flour is fitted into silica crucible and high temperature is put into In stove, start to be passed through compressed air after being progressively warming up to 900 DEG C and be incubated 1h, the silica flour of surface oxidation is obtained after cooling, use PULSE HEATING inert gas fusion-infrared absorption test oxygen content, it is 42.8% to test its oxygen content.
Prepare the silica flour solution of surface oxidation：The silica flour for taking 1 part of surface oxidation of mass fraction is added in deionized water Ultrasonic disperse 30min, is configured to the silica flour solution of the surface oxidation of 1.0mg/ml.
GO is coated：The GO for taking 0.2 part of mass fraction is scattered in deionized water the GO solution for being configured to 1.0mg/ml, is stirring Mix during GO solution dropped into above-mentioned dispersion liquid under state, 6h is stirred after completion of dropwise addition.Stirring terminates rear suction filtration and in vacuum Dried in baking oven, obtain GO@SiO2@Si composites.
Reduction and carbonization：Dry GO@SiO2@Si composites are inserted in high temperature furnace, 900 are warming up under an inert atmosphere DEG C, 1.0h is incubated, obtain G@SiO2@Si composites.
HF is etched：G@SiO2@Si composites are etched using hydrofluoric acid solution and wash drying, finally give with new The composite of the graphene coated silicon grain of structure.
Electro-chemical test is carried out using the identical method of same embodiment 1 and compares material volume bulking effect.
Comparative example 3
Material preparation condition such as embodiment 1, difference is that the G SiO2 Si composites for obtaining do not use hydrogen fluorine Harsh eating away silicon dioxide layer.
Electro-chemical test is carried out using the identical method of same embodiment 1 and compares material volume bulking effect.
The Electrochemical results of the negative material prepared by embodiment 1~7 and comparative example 1~3 are as shown in table 1.
Table 1
From above Electrochemical results, the method for the invention prepare with as the cavity layer for holding swollen space Graphene coated nano silicon particles material, it has excellent chemical property and circulation as lithium ion battery negative material Stability.In composite preparation process of the present invention, the particle diameter and oxidization time of selected silicon grain influence the thickness of oxide layer Spend, and then influence is held swollen space size and the species of specific discharge capacity dressing agent and the size of GO lamellas of material and can then be influenceed The Surface coating effect of particle, and then influence the pattern of material；The consumption of dressing agent and GO can influence the change of material phosphorus content Change, and then influence the overall electric conductivity of material.Therefore, the related preparation condition of rational adjustment, can just design required electrode Material.
Below specific explanation has been carried out to presently preferred embodiments of the present invention, but the present invention is not limited only to the reality Example is applied, those skilled in the art associates other specific embodiment parties of the invention by would not require any inventive effort Formula, is all contained in the application claim limited range.

Claims (10)

1. a kind of new structure graphene coated nano silicon particles, it is characterised in that：By the reduction-oxidation graphite for being coated on outer layer Alkene/carbon shell, the nano silicon particles core in redox graphene/carbon shell, and redox graphene/carbon shell are received with silicon Cavity layer composition between rice grain core.
2. a kind of preparation method of new structure graphene coated nano silicon particles as claimed in claim 1, it is characterised in that： Comprise the following steps：
Step one, surface oxidation：Silica flour is inserted in high temperature furnace, under the conditions of oxygen-containing atmosphere, with 300-1000 DEG C of insulation 0.5- 20.0h, it is the silica flour of 8wt%-57wt% that oxygen content is obtained；
Step 2, prepare silica flour solution：Silica flour after above-mentioned high temperature oxidation process is added in dispersant and ultrasonic disperse is obtained Silica flour solution；Concentration of the described silica flour in dispersant is 0.1-10.0mg/ml；Described dispersant uses water or anhydrous second Alcohol or the two arbitrary volume than mixed solution；
Step 3, surface modification：Dressing agent is added in above-mentioned silica flour solution, and constant temperature stirring 1-24h obtains mixed solution；It is described Constant temperature temperature be 20-80 DEG C, the quality of described dressing agent is the 25%~100% of siliceous amount；
Step 4, prepare dispersion liquid：After by the mixed solution vacuum filtration after stirring, unmodified dressing agent is washed away, then will Suction filtration thing is distributed in water, and it is the dispersion liquid of 0.5-10.0mg/ml that concentration is obtained；
Step 5, GO claddings：Take the dispersion liquid that the graphene oxide solution of silica flour quality 20%-100% is dropped in step 4 In, 1.0-24.0h is stirred, precipitated product is collected by centrifugation and is vacuum dried；Described graphene oxide solution concentration is 0.5- 2.0mg/ml；
Step 6, reduction and carbonization：Desciccate is inserted in high temperature furnace, 700-900 DEG C, insulation are warming up under an inert atmosphere 1.0-3.0h, obtains the silicon composite of graphene coated；
Step 7, HF etchings：The silicon composite that graphene coated will be obtained adds the dilute hydrofluoric acid solution that concentration is 5wt% In, fully wash drying after reaction, that is, obtain the graphene coated nano silicon particles composite with new structure；Described The amount of hydrofluoric acid is the 20%-143% of silica flour quality in dilute hydrofluoric acid solution.
3. the preparation method of new structure graphene coated nano silicon particles as claimed in claim 2, it is characterised in that：It is described Silica flour be by ball milling obtain, Ball-milling Time 4.0-48.0h, be obtained particle diameter for 0.05-50.0um silica flour.
4. the preparation method of new structure graphene coated nano silicon particles as claimed in claim 2, it is characterised in that：It is oxygen-containing Atmosphere is one kind or several mixing in compressed air, synthesis of air, oxygen, vapor.
5. the preparation method of new structure graphene coated nano silicon particles as claimed in claim 2, it is characterised in that：It is described Dressing agent be the macromolecule organic containing amino include but be not limited only to polyvinylpyrrolidone, kayexalate, One or more in diallyl dimethyl ammoniumchloride.
6. the preparation method of new structure graphene coated nano silicon particles as claimed in claim 2, it is characterised in that：It is described Dressing agent be the silane coupler containing amino, the described silane coupler containing amino is γ-aminopropyl trimethoxy Silane, gamma-aminopropyl-triethoxy-silane, N- β (aminoethyl)-γ-aminopropyltrimethoxysilane, N- β (aminoethyl)-γ- Aminopropyltriethoxy dimethoxysilane, N- β (aminoethyl)-gamma-aminopropyl-triethoxy-silane, N- β (aminoethyl)-γ-ammonia third In ylmethyl dimethoxysilane, aminoethyl aminoethylaminopropyl trimethoxy silane or polyamino alkyltrialkoxysilaneand It is a kind of.
7. the preparation method of new structure graphene coated nano silicon particles as claimed in claim 2, it is characterised in that：It is described Dispersion liquid concentration be 0.5-2.0mg/ml.
8. the preparation method of new structure graphene coated nano silicon particles as claimed in claim 2, it is characterised in that：It is described Graphene oxide in graphene oxide solution is obtained using Hummers methods, Brodie methods or Staudenmaie methods.
9. the preparation method of the new structure graphene coated nano silicon particles as described in any one of claim 2~8, its feature It is：The lamella size of the graphene oxide in the graphene oxide solution is 0.1-20.0um.
10. the preparation method of the new structure graphene coated nano silicon particles as described in any one of claim 2~8, it is special Levy and be：The lamella size of the graphene oxide in the graphene oxide solution is 0.5-5.0um.
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