CN109390570B - Graphene-coated silicon and preparation method and application thereof - Google Patents
Graphene-coated silicon and preparation method and application thereof Download PDFInfo
- Publication number
- CN109390570B CN109390570B CN201811135354.1A CN201811135354A CN109390570B CN 109390570 B CN109390570 B CN 109390570B CN 201811135354 A CN201811135354 A CN 201811135354A CN 109390570 B CN109390570 B CN 109390570B
- Authority
- CN
- China
- Prior art keywords
- silicon
- graphene
- coated
- graphene oxide
- silicon particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
- 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 invention discloses graphene-coated silicon and a preparation method and application thereof, wherein the method comprises the following steps: the silicon particles with the surfaces coated with the silicon oxide passivation films generate silicon particles with positive charges under the modification of a surface modifier, the silicon particles with the positive charges and graphene oxide obtain silicon particles coated with graphene oxide in a self-assembly mode, and finally the silicon particles coated with the graphene oxide are subjected to high-temperature heating reduction treatment in a nitrogen atmosphere to obtain the silicon particles coated with the graphene oxide. According to the preparation method, silicon powder is used as a silicon source, an acid washing step is avoided in the process of preparing graphene coated silicon, no by-product is generated, the production process is environment-friendly, and the silicon utilization rate is high. In addition, the thermal reduction technology of the graphene oxide is mature, so that the production process is more controllable and suitable for large-scale production.
Description
Technical Field
The invention relates to the field of lithium battery silicon cathodes, in particular to graphene-coated silicon and a preparation method and application thereof.
Background
With the continuous improvement of the requirements of new energy automobiles on the endurance mileage in practical application, the high energy density becomes the future direction of the lithium ion battery, and the energy density of the traditional graphite cathode can not meet the requirements. The silicon-based material has the advantages of high density of 4200mAh/g, abundant raw materials, low cost, environmental friendliness and the like, and is expected to become a next-generation high-energy-density lithium battery cathode. During the process of lithium deintercalation, the volume change of silicon is huge and reaches 300%, which greatly limits the practical application of silicon cathode materials.
Graphene, as a novel carbon material, has the advantages of high specific surface area, excellent conductivity and mechanical properties, and the like, and can be widely applied to the field of positive and negative electrode materials in the aspect of charge conduction of lithium ion batteries. Graphene bagThe coating can provide a volume buffer framework for the silicon and also improve the conductivity of the negative electrode. Silicon is inert in chemical properties, and graphene is not easy to directly coat the surface of the silicon. Therefore, ACS appl, mater, interfaces, 2014, 6 (5), pp 3546-2Si as a by-product. However, the magnesiothermic reduction conditions employed in this process are highly susceptible to SiC formation and also involve the environmental contamination issues associated with by-products and acid wash by-products.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide graphene-coated silicon and a preparation method and application thereof, and aims to solve the problems that the existing preparation method of graphene-coated silicon is poor in environmental friendliness, large in number of byproducts and not suitable for large-scale production.
The technical scheme of the invention is as follows:
a preparation method of graphene-coated silicon comprises the following steps:
providing a silicon particle solution coated with a silicon oxide passivation film on the surface;
and (3) treating the silicon particle solution with a positive charge surfactant and a negative charge surfactant alternately, and obtaining the positively charged silicon particles through a Zeta potential test.
Dispersing the silicon particles with positive charges on the surface and graphene oxide in distilled water according to a preset mass ratio, and generating graphene oxide coated silicon by the silicon particles with positive charges on the surface and the graphene oxide in an electrostatic self-assembly manner;
and under the nitrogen atmosphere, heating the graphene oxide coated silicon at the temperature of 700-1200 ℃ to obtain the graphene coated silicon.
The preparation method of the graphene coated silicon comprises the steps of preparing a graphene coated silicon substrate, wherein the surfactant with positive charges is cetyl trimethyl ammonium bromide, dimethyl benzyl dodecyl ammonium bromide, benzyl triethyl ammonium chloride, octadecyl trimethyl ammonium chloride, benzalkonium bromide and N, one or more of N-dimethyldodecylamine, 3-aminopropyltrimethoxy siloxane, 3-aminopropyltriethoxy siloxane, organosilicon quaternary ammonium salt, bisimidazoline quaternary ammonium salt, lauramidopropyl ammonium sulfate, cationic polyacrylamide, PVP-Q cationic copolymer, polyethyleneimine quaternary ammonium salt, aliphatic triethanolamine acetate, dodecylamine acetate, quaternized panthenol, polydiallyldimethyl ammonium chloride, diethylaminoethyl acrylate ammonium chloride, dimethyl diallyl ammonium chloride and trialkyl ammonium chloride.
The preparation method of the graphene-coated silicon comprises the following steps of preparing a graphene-coated silicon substrate, wherein the graphene-coated silicon substrate is prepared from a graphene substrate, a graphene oxide substrate, and a graphene oxide substrate.
The preparation method of the graphene-coated silicon comprises the following steps of alternately treating the silicon particle solution with a positive charge surfactant and a negative charge surfactant, and obtaining the silicon particles with positive charges by a Zeta potential test method, wherein the step comprises the following steps:
mixing the silicon particle solution with the positively charged surfactant aqueous solution, oscillating for 1-30min, and cleaning and drying by using deionized water to obtain single-layer positively charged silicon particles;
mixing the single-layer positively-charged silicon particles with the negatively-charged surfactant aqueous solution, oscillating for 1-30min, and cleaning and drying with deionized water to obtain silicon particles with negative charges on the surfaces;
and repeating the steps to obtain silicon particles with positive charges of different layers, dispersing the silicon particles with the positive charges on the surface in water, testing the charge property by adopting a Zeta potential, and stopping the steps when the Zeta potential test result is more than 0.05 and less than 0.5.
The preparation method of the graphene-coated silicon comprises the step of preparing a silicon oxide passivation film, wherein the thickness of the silicon oxide passivation film is 1-1000 nm.
The preparation method of the graphene-coated silicon comprises the step of preparing the graphene-coated silicon, wherein the predetermined mass ratio of the silicon particles with positive charges on the surfaces to the graphene oxide is 0.5-3: 1.
The preparation method of the graphene-coated silicon comprises the step of heating at 700-1200 ℃ for 10min-5 h.
The preparation method of the graphene-coated silicon comprises the step of dispersing graphene oxide in distilled water to obtain the graphene oxide-coated silicon, wherein the concentration of the graphene oxide dispersed in distilled water is 0.5-10 mg/ml.
Graphene-coated silicon, wherein the graphene-coated silicon is prepared by the preparation method.
The application of the graphene-coated silicon is characterized in that the graphene-coated silicon is applied to preparation of a lithium battery cathode.
Has the advantages that: the invention takes silicon powder as a silicon source, and a thin silicon oxide passivation film is inevitably generated on the surface of the silicon powder in the processes of production, storage and transportation, namely, silicon particles (expressed as Si @ SiO) with the surface coated with the silicon oxide passivation film2) Said Si @ SiO2Generating Si @ SiO with positive charge under the modification of a surface modifier2Said Si @ SiO having a positive charge2Dispersing the graphene oxide particles and Graphene Oxide (GO) in distilled water according to a preset mass ratio, obtaining silicon particles (expressed as Si @ SiO2@ GO) coated by the graphene oxide in a self-assembly mode, and finally obtaining the silicon particles coated by the graphene oxide by high-temperature heating treatment of the Si @ SiO2@ GO in a nitrogen atmosphere. According to the preparation method, silicon powder is used as a silicon source, an acid washing step is avoided in the process of preparing graphene coated silicon, no by-product is generated, the production process is environment-friendly, and the silicon utilization rate is high. In addition, the thermal reduction technology of the graphene oxide is mature, so that the production process is more controllable and suitable for large-scale production.
Drawings
Fig. 1 is a flowchart of a preferred embodiment of a method for preparing graphene-coated silicon according to the present invention.
Fig. 2 is a schematic electron microscope view of the graphene oxide-coated silicon particle prepared in example 1 of the present invention.
Fig. 3 is a schematic electron microscope view of the graphene-coated silicon particles prepared in example 1 of the present invention.
Detailed Description
The invention provides graphene-coated silicon and a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a flowchart illustrating a method for preparing graphene-coated silicon according to a preferred embodiment of the present invention, wherein the method includes the following steps:
s10, providing a silicon particle solution with the surface coated with a silicon oxide passivation film;
s20, alternately treating the silicon particle solution with a positive charge surfactant and a negative charge surfactant, and obtaining the silicon particles with positive charges through a Zeta potential test;
s30, dispersing the silicon particles with positive charges on the surface and graphene oxide in distilled water according to a preset mass ratio, and generating graphene oxide coated silicon by the silicon particles with positive charges on the surface and the graphene oxide in an electrostatic self-assembly mode;
s40, heating the graphene oxide coated silicon at the temperature of 700-1200 ℃ in a nitrogen atmosphere to obtain the graphene coated silicon.
Specifically, the invention uses silicon powder as a silicon source, and the surface of the silicon powder inevitably generates a thin silicon oxide passivation film in the processes of production, storage and transportation, namely, silicon particles (expressed as Si @ SiO) with the surface coated with the silicon oxide passivation film are formed2) The silicon particles are endowed with positive charges on the surfaces through modification of a surface modifier, then the silicon particles coated with graphene oxide are formed in an electrostatic self-assembly mode, and finally the silicon particles coated with graphene oxide are obtained through a thermal reduction method. The method avoids the acid washing step in the process of preparing the graphene coated silicon, has no by-product, is environment-friendly in production process,the utilization rate of silicon is high. In addition, the thermal reduction technology of the graphene oxide is mature, so that the production process is more controllable and suitable for large-scale production.
In the present invention, silicon particles (Si @ SiO) are passivated by coating the surface with silicon oxide2) Dispersing in distilled water, and performing ultrasonic treatment for 30-180min to obtain uniformly dispersed Si @ SiO2An aqueous solution. Preferably, the Si @ SiO2The concentration of the aqueous solution is 0.5-3 mg/ml.
Further, by alternately treating the silicon particle solution with a positive charge surfactant and a negative charge surfactant, positively charged silicon particles were finally obtained by Zeta test. Specifically, in the present embodiment, a silicon oxide passivation film on the surface of a silicon particle is grafted alternately with a surfactant having positive and negative charges, thereby obtaining a silicon particle having a positive charge on the surface. Preferably, the concentration of the positively charged surfactant and the negatively charged surfactant are both 0.005 to 0.5 g/ml.
Further, the thickness of the silicon oxide passivation film on the surface of the silicon particles is 1-1000 nm. Preferably 400-800nm, such as 500nm, 600nm, 700 nm. Silica in this thickness range is more susceptible to grafting with surfactants, resulting in silicon particles with a positive surface charge.
In a preferred embodiment, the step of treating the silicon particle solution with a positively charged surfactant and a negatively charged surfactant alternately and obtaining positively charged silicon particles by the Zeta potential test method comprises:
mixing the silicon particle solution with the positively charged surfactant aqueous solution, oscillating for 1-30min, and cleaning and drying by using deionized water to obtain single-layer positively charged silicon particles; mixing the single-layer positively-charged silicon particles with the negatively-charged surfactant aqueous solution, oscillating for 1-30min, and cleaning and drying with deionized water to obtain silicon particles with negative charges on the surfaces; and repeating the steps to obtain silicon particles with positive charges of different layers, dispersing the silicon particles with the positive charges on the surface in water, testing the charge property by adopting a Zeta potential, and stopping the steps when the Zeta potential test result is more than 0.05 and less than 0.5.
As a specific embodiment, the silicon particle solution is mixed with a polydiallyldimethylammonium chloride (PDDA) aqueous solution to obtain positively charged silicon particles with a zeta potential of 0.05, i.e., PDDA + Si @ SiO2 particles. The single-layer positively-charged PDDA + Si @ SiO2 particles can be directly subjected to electrostatic self-assembly with graphene oxide to generate graphene oxide coated silicon.
As another specific embodiment, firstly, mixing the silicon particle solution with a polydiallyldimethylammonium chloride (PDDA) aqueous solution, oscillating at room temperature for 1-30min, and then washing and drying with deionized water to obtain single-layer positively charged silicon particles, namely PDDA + Si @ SiO2 particles; then mixing the single-layer positively charged silicon particles with the sodium polystyrene sulfonate aqueous solution, and cleaning and drying the mixture by using deionized water to obtain negatively charged silicon particles, namely PSS/PDDA-Si @ SiO2 particles; and finally, mixing the PSS/PDDA-Si @ SiO2 silicon particles with the polydiallyldimethylammonium chloride (PDDA) aqueous solution again, cleaning and drying by using deionized water to obtain two layers of positively charged silicon particles, namely PDDA/PSS/PDDA + Si @ SiO2 particles, wherein the aqueous solution is 0.12 in a Zeta potential test. Compared with a single-layer silicon particle with positive charges, the assembly efficiency of the graphene oxide coated silicon generated by the two layers of silicon particles with positive charges and graphene oxide in an electrostatic self-assembly mode is higher, and the utilization rate of silicon powder is high.
In the invention, the silicon particles with positive charges on the surface and the graphene oxide are dispersed in distilled water according to a predetermined mass ratio of 0.5-3:1, and the silicon particles with positive charges on the surface and the graphene oxide generate graphene oxide coated silicon in an electrostatic self-assembly mode. As a specific embodiment, dispersing silicon particles with positive charges on the surface and graphene oxide in distilled water according to the mass ratio of 2:1, and oscillating at room temperature for 30min-5h to obtain graphene oxide coated silicon (Si @ SiO2@ GO). Preferably, the concentrations of the silicon particles with positive charges on the surfaces and the graphene oxide after being dispersed in distilled water are both 0.5-10 mg/ml.
Further, the graphene oxide coated silicon is placed into an atmosphere furnace, and is subjected to heating reduction treatment at the temperature of 700-1200 ℃ in the nitrogen atmosphere for 10min-5h, so that the graphene oxide coated silicon is finally obtained. Due to the fact that the thermal reduction graphene oxide technology is mature, the preparation process of the graphene-coated silicon provided by the invention is more controllable, and is suitable for large-scale production. As a specific embodiment, the graphene oxide-coated silicon is placed in an atmosphere furnace, and is subjected to heating reduction treatment at a temperature of 1000 ℃ for 30min in a nitrogen atmosphere, so that the graphene oxide-coated silicon can be efficiently prepared.
Further, the invention also provides graphene-coated silicon prepared by any one of the preparation methods.
Furthermore, the invention also provides an application of the graphene-coated silicon, and the graphene-coated silicon is applied to preparation of a lithium battery cathode.
The following provides a further explanation of the preparation method of graphene-coated silicon according to the present invention by using specific examples:
example 1
2.5g of the purchased silicon powder was dispersed in 200ml of distilled water and ultrasonically dispersed for 1 hour to obtain component A. A1 mg/ml aqueous PDDA solution was prepared and designated as component B. Mixing the component A and the component B at room temperature, shaking for 60min, centrifuging, washing with distilled water for 2 times to obtain Si particles with positive charges, centrifuging, and drying. 2.5g of the dried silicon particles were dispersed in distilled water (2 mg/ml), mixed with 500ml (0.5mg/ml) of a graphene oxide solution,
and (3) performing electrostatic self-assembly at room temperature to obtain a silicon particle solution coated by the graphene oxide, and finally performing centrifugal drying to obtain silicon particles coated by the graphene oxide. And putting the silicon particles coated with the graphene oxide into an atmosphere furnace, and reducing for 1h at 1000 ℃ to obtain the silicon particles coated with the graphene oxide.
Example 2
2.5g of the purchased silicon powder is placed in an oven for heating at 150 ℃ for 10 minutes, and then dispersed in 200ml of distilled water, and subjected to ultrasonic dispersion for 1 hour to obtain a component A. A1 mg/ml aqueous PDDA solution was prepared and designated as component B. Prepare 1mg/ml sodium polystyrene sulfonate PSS aqueous solution, named as component C. Mixing 200ml of component A and 100ml of component B at room temperature, shaking for 60min, centrifuging, washing with distilled water for 2 times, mixing with 100ml of component C, washing for 2 times, mixing with component B to obtain Si particles with positive charges, centrifuging, and drying. Dispersing 2.5g of dried silicon particles into distilled water (2 mg/ml), mixing with 500ml of graphene oxide solution (0.5mg/ml), performing electrostatic self-assembly at room temperature to obtain graphene oxide-coated silicon particle solution, and finally performing centrifugal drying to obtain graphene oxide-coated silicon particles, wherein an electron microscope image of the graphene oxide-coated silicon particles is shown in fig. 2. And putting the graphene oxide-coated silicon particles into an atmosphere furnace, and reducing for 1h at 1000 ℃ to obtain the graphene-coated silicon particles, wherein an electron microscope image of the graphene-coated silicon particles is shown in fig. 3.
In summary, the silicon powder is used as a silicon source, and a thin silicon oxide passivation film is inevitably generated on the surface of the silicon powder in the processes of production, storage and transportation, namely, silicon particles (expressed as Si @ SiO) with the surface coated with the silicon oxide passivation film2) Said Si @ SiO2Generating Si @ SiO with positive charge under the modification of a surface modifier2Said Si @ SiO having a positive charge2Dispersing the graphene oxide particles and Graphene Oxide (GO) in distilled water according to a preset mass ratio, obtaining silicon particles (expressed as Si @ SiO2@ GO) coated by the graphene oxide in a self-assembly mode, and finally obtaining the silicon particles coated by the graphene oxide by high-temperature heating treatment of the Si @ SiO2@ GO in a nitrogen atmosphere. According to the preparation method, silicon powder is used as a silicon source, an acid washing step is avoided in the process of preparing graphene coated silicon, no by-product is generated, the production process is environment-friendly, and the silicon utilization rate is high. In addition, the thermal reduction technology of the graphene oxide is mature, so that the production process is more controllable and suitable for large-scale production.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of graphene-coated silicon is characterized by comprising the following steps:
providing a silicon particle solution coated with a silicon oxide passivation film on the surface;
mixing the silicon particle solution with a surfactant aqueous solution with positive charges, oscillating for 1-30min, and cleaning and drying by using deionized water to obtain single-layer silicon particles with positive charges;
mixing the single-layer positively-charged silicon particles with a negatively-charged surfactant aqueous solution, oscillating for 1-30min, and cleaning and drying with deionized water to obtain silicon particles with negative charges on the surfaces;
repeating the steps to obtain silicon particles with positive charges of different layers, dispersing the silicon particles with positive charges on the surface in water, testing the charge property by adopting a Zeta potential, and stopping the steps when the Zeta potential test result is more than 0.05 and less than 5;
dispersing the silicon particles with positive charges on the surface and graphene oxide in distilled water according to a preset mass ratio, and generating graphene oxide coated silicon by the silicon particles with positive charges on the surface and the graphene oxide in an electrostatic self-assembly manner;
heating the graphene oxide coated silicon at the temperature of 700-1200 ℃ in a nitrogen atmosphere to obtain graphene coated silicon;
the thickness of the silicon oxide passivation film is 400-800 nm;
the concentration of the positively charged surfactant is 0.005-0.5g/ml, and the concentration of the negatively charged surfactant is 0.005-0.5 g/ml.
2. The method of claim 1, wherein the positively charged surfactant is cetyltrimethylammonium bromide, dimethylbenzyldodecylammonium bromide, benzyltriethylammonium chloride, octadecyltrimethylammonium chloride, benzalkonium bromide, N-dimethyldodecylamine, 3-aminopropyltrimethoxysiloxane, 3-aminopropyltriethoxysiloxane, silicone quaternary ammonium salts, bisimidazoline quaternary ammonium salts, lauramidopropyl ammonium sulfate, cationic polyacrylamide, PVP-Q cationic copolymer, polyethyleneimine quaternary ammonium salt, aliphatic triethanolamine acetate, dodecylamine acetate, quaternized panthenol, polydiallyldimethylammonium chloride, diethylaminoethyl acrylate chloride, dimethyldiallylammonium chloride, di-allyltrimethylammonium chloride, poly-allyldodecylammonium chloride, poly-dodecyltrimethylammonium chloride, poly-allyltrimethylammonium chloride, poly-ethyleneimine quaternary ammonium chloride, poly-ethyleneimine, One or more of trialkyl ammonium chloride.
3. The method of claim 1, wherein the negatively charged surfactant is one or more of p-methylstyrene sulfonate, polystyrene sulfonate, dodecyl diphenyl oxide disulfonate, sodium 3-chloro-2-hydroxypropanesulfonate, polyether carboxylic acid surfactant, carboxymethyl cellulose salt, fatty carboxylate, alkyl phosphate hydroxyethyl ether, alkoxy phosphate, allyl alcohol ether phosphate, dialkyl phosphate, alkyl sulfosuccinic acid monoester disodium salt, sodium hexyl succinamide sulfonate, acrylic acid-propylene sulfonic acid-isopropenyl phosphoric acid copolymer, and polyacrylamide.
4. The method for preparing graphene-coated silicon according to claim 1, wherein the predetermined mass ratio of the silicon particles with positive charges on the surface to the graphene oxide is 0.5-3: 1.
5. The method as claimed in claim 1, wherein the heating treatment time at 700-1200 ℃ is 10min-5 h.
6. The method of claim 1, wherein the graphene oxide is dispersed in distilled water to a concentration of 0.5 to 10 mg/ml.
7. Graphene-coated silicon, characterized by being prepared by the preparation method of any one of claims 1 to 6.
8. Use of the graphene-coated silicon according to claim 7 for the preparation of a negative electrode for a lithium battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811135354.1A CN109390570B (en) | 2018-09-28 | 2018-09-28 | Graphene-coated silicon and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811135354.1A CN109390570B (en) | 2018-09-28 | 2018-09-28 | Graphene-coated silicon and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109390570A CN109390570A (en) | 2019-02-26 |
| CN109390570B true CN109390570B (en) | 2022-03-15 |
Family
ID=65419017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811135354.1A Active CN109390570B (en) | 2018-09-28 | 2018-09-28 | Graphene-coated silicon and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109390570B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109750178A (en) * | 2019-02-28 | 2019-05-14 | 华中科技大学 | A kind of preparation method and applications of graphene oxide enhancing nickel-based composite pow-der |
| CN110112408B (en) * | 2019-04-08 | 2021-03-12 | 新奥石墨烯技术有限公司 | Graphene-silicon composite material, preparation method thereof, electrode material and battery |
| CN110993930B (en) * | 2019-11-22 | 2021-09-24 | 芜湖天弋能源科技有限公司 | Preparation method of graphene-coated nano-silicon composite material and application of graphene-coated nano-silicon composite material as negative electrode material of lithium ion battery |
| CN111106352A (en) * | 2019-12-30 | 2020-05-05 | 国联汽车动力电池研究院有限责任公司 | Cross-linking type water-based binder for lithium ion battery and electrode prepared from cross-linking type water-based binder |
| CN112002885B (en) * | 2020-09-10 | 2022-03-01 | 中国空间技术研究院 | Silicon-carbon composite material, preparation method thereof and lithium ion battery |
| CN112185640B (en) * | 2020-09-23 | 2023-01-24 | 江西艾特磁材有限公司 | Method for coating magnetic powder core with sodium silicate |
| CN112978803A (en) * | 2021-02-23 | 2021-06-18 | 四川大学 | Preparation method of water-soluble superparamagnetic ferroferric oxide microspheres with positively charged surfaces |
| CN114613971B (en) * | 2022-03-31 | 2023-04-07 | 南京工业大学 | Preparation method and application of compact and stable pomegranate-shaped silicon-graphene composite electrode material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107204445A (en) * | 2017-05-26 | 2017-09-26 | 郑州中科新兴产业技术研究院 | A kind of lithium ion battery three-dimensional porous silicon-carbon cathode material and preparation method thereof |
| CN107611394A (en) * | 2017-09-08 | 2018-01-19 | 成都硅宝科技股份有限公司 | A kind of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating and preparation method thereof |
| CN107880484A (en) * | 2017-12-05 | 2018-04-06 | 中北大学 | A kind of composite modified high polymer material of nano-particle/graphene oxide and its preparation |
-
2018
- 2018-09-28 CN CN201811135354.1A patent/CN109390570B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107204445A (en) * | 2017-05-26 | 2017-09-26 | 郑州中科新兴产业技术研究院 | A kind of lithium ion battery three-dimensional porous silicon-carbon cathode material and preparation method thereof |
| CN107611394A (en) * | 2017-09-08 | 2018-01-19 | 成都硅宝科技股份有限公司 | A kind of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating and preparation method thereof |
| CN107880484A (en) * | 2017-12-05 | 2018-04-06 | 中北大学 | A kind of composite modified high polymer material of nano-particle/graphene oxide and its preparation |
Non-Patent Citations (2)
| Title |
|---|
| Facile electrostatic self-assembly of silicon/reduced graphene oxide porous composite by silica assist as high performance anode for Li-ion battery;Ming-Shan Wang et.al;《Applied Surface Science》;20180618;第379-389页 * |
| Three-Dimensional Interconnected Network of Graphene-Wrapped Porous Silicon Spheres: In Situ Magnesiothermic-Reduction Synthesis and Enhanced Lithium-Storage Capabilities;Ping Wu et. al;《Applied Materials & Interfaces》;20140131;第3546-3552页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109390570A (en) | 2019-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109390570B (en) | Graphene-coated silicon and preparation method and application thereof | |
| CN108172787B (en) | Monodisperse hollow nano silicon/carbon sphere and preparation method and application thereof | |
| CN109256535B (en) | Silicon @ carbon composite material with yolk shell structure and preparation and application thereof | |
| CN103474666B (en) | The preparation method of lithium ion battery anode active material | |
| CN106450251B (en) | A kind of lithium ion battery negative material and preparation method thereof | |
| CN105489394B (en) | The graphene nano wall preparation method for the plasma activated chemical vapour deposition strengthened based on electromagnetic field | |
| CN106025231B (en) | A kind of preparation method of hollow graphite alkene ball/sulphur composite material | |
| CN109994719B (en) | Phosphorus-doped MXene material and preparation method thereof | |
| CN102881881B (en) | Negative pole material of lithium ion battery, preparation method of material and lithium ion battery | |
| CN108305994B (en) | Coated graphite lithium ion battery negative electrode material and preparation method thereof | |
| CN103304149B (en) | A kind of method and coated substance of constructing hydrophobic coating at glass surface | |
| CN109502987A (en) | A method of high rigidity antireflective film is prepared based on hollow silica | |
| CN108172416A (en) | The preparation method and applications of three-dimensional carbon aerogels with porous tube wall nanotube | |
| CN105514382A (en) | Preparing method and application of silicon-based negative electrode material with SiO2 coating layer | |
| CN109081327A (en) | A kind of bowl-shape porous carbon microsphere and preparation method thereof | |
| CN106848282B (en) | Negative electrode material for non-aqueous electrolyte secondary battery and preparation method and application thereof | |
| CN205335089U (en) | Plasma chemical vapor deposition's graphite alkene nanometer wall based on electromagnetic field is reinforceed | |
| CN114975964A (en) | Polypyrrole-coated tin dioxide/nano carbon sphere negative electrode material, preparation method thereof and sodium ion battery | |
| CN108336313B (en) | Preparation method for preparing high-stability chain Fe3O4/C/red P structure sodium ion battery cathode material by using magnetic field as auxiliary technology | |
| CN108807872A (en) | A kind of preparation method of the silicon-carbon cathode material of the small spherical structure of caged | |
| CN106044783B (en) | A kind of preparation method of nanometer silica line | |
| CN108346789A (en) | Multiconductor nucleocapsid cavity structure anode material of lithium-ion battery and preparation method thereof | |
| CN112687861B (en) | Silicon oxide and preparation method and application thereof | |
| CN114566643A (en) | polyaniline-MXene-silicon nanoparticle composite material and preparation method and application thereof | |
| CN110449332A (en) | A kind of composite construction diamond thin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 518117 Longgang Road, Longgang District, Shenzhen, Guangdong (No. 1001) Applicant after: SHENZHEN 863 NEW MATERIAL TECHNOLOGY Co.,Ltd. Applicant after: SHENZHEN SAPAC INDUSTRY Co.,Ltd. Applicant after: Shenzhen Lihe Technology Innovation Co.,Ltd. Address before: 518117 Longgang Road, Longgang District, Shenzhen, Guangdong (No. 1001) Applicant before: SHENZHEN 863 NEW MATERIAL TECHNOLOGY Co.,Ltd. Applicant before: SHENZHEN SAPAC INDUSTRY Co.,Ltd. Applicant before: SHENZHEN BEAUTY STAR Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210622 Address after: No.1001 Longgang Avenue, Pingxi community, Pingdi street, Longgang District, Shenzhen, Guangdong 518000 Applicant after: SHENZHEN 863 NEW MATERIAL TECHNOLOGY Co.,Ltd. Applicant after: SHENZHEN SAPAC INDUSTRY Co.,Ltd. Applicant after: Shenzhen TONGCHAN Lixing Technology Group Co.,Ltd. Address before: 518117 Longgang Road, Longgang District, Shenzhen, Guangdong (No. 1001) Applicant before: SHENZHEN 863 NEW MATERIAL TECHNOLOGY Co.,Ltd. Applicant before: SHENZHEN SAPAC INDUSTRY Co.,Ltd. Applicant before: Shenzhen Lihe Technology Innovation Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |