CN108470891B - Method for preparing silicon-carbon negative electrode material based on micron silicon dioxide - Google Patents

Method for preparing silicon-carbon negative electrode material based on micron silicon dioxide Download PDF

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CN108470891B
CN108470891B CN201810219122.8A CN201810219122A CN108470891B CN 108470891 B CN108470891 B CN 108470891B CN 201810219122 A CN201810219122 A CN 201810219122A CN 108470891 B CN108470891 B CN 108470891B
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washing
silicon
silicon dioxide
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CN108470891A (en
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吴振国
吴晨
郭孝东
向伟
钟本和
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Nanchong Zhongxin New Energy Technology Co ltd
Sichuan University
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Sichuan University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The method for preparing the silicon-carbon anode material based on the micron silicon dioxide comprises the following steps: 1) according to SiO2: carbon source: water (30-80): (5-15): (60-120) preparing slurry, grinding for 4-5 h by a wet method, and freeze-drying to obtain nano-scale SiO2(ii) a 2) Carbonizing the material obtained in the step 1) at high temperature to obtain SiO2@ C material, further according to SiO2@ C: mg: carrying out magnesiothermic reduction on NaCl at the mass ratio of 1:1: 1-1: 1:10 at 600-750 ℃, and then carrying out acid washing, washing and drying to obtain Si @ C nanoparticles; 3) and (3) ultrasonically mixing the nano particles obtained in the step (2) with a graphene oxide solution, and carrying out spray thermal cracking, coating and reduction to obtain the material. The invention has the advantages of low cost, simple operation, difficult agglomeration, good product structure stability, and strong conductivity and ion transmission capability of the material, and can maintain the original appearance of the sample.

Description

Method for preparing silicon-carbon negative electrode material based on micron silicon dioxide
Technical Field
The invention belongs to the field of preparation of silicon-carbon cathode materials, and particularly relates to a method for preparing a silicon-carbon cathode material based on micron silicon dioxide.
Background
The silicon-based material is a high-performance lithium ion battery cathode material with great potential, has the highest known theoretical specific capacity (4200mAh/g) and lower lithium intercalation potential (0.1Vvs. Li/Li +), is rich in resources and is environment-friendly. However, the silicon negative electrode is accompanied by huge volume change (up to 300%) in the lithium extraction process, which can cause the silicon particles to be crushed and pulverized, so that the electrode material loses electric activity and shows extremely poor cycle stability; in addition, the electrical conductivity of silicon itself is notHigh and poor rate characteristics, which seriously affects the application of silicon materials as the negative electrode materials of lithium ion batteries. Silicon carbon composites have been extensively studied as an effective way to alleviate the above problems. In the preparation and performance research of a high-performance silicon-carbon composite negative electrode material for a lithium ion battery, a master thesis of Shanghai university of transportation, 2013), a spherical porous silicon/graphene @ carbon (Si/GNS @ C) composite material is prepared by using two different silicon sources, namely nano silicon powder and mesoporous silica (SBA-15), but the carbon-coating method is a chemical vapor deposition method, and the method is not easy to industrially popularize and apply; the ceramic Huachao et al (the magnesiothermic reduction method for preparing the porous silicon-carbon composite cathode material, the silicate academic newspaper, in the 08 th year 2013) uses mesoporous SiO2The silicon-carbon material is prepared by direct magnesiothermic reduction of a silicon source due to the nanoscale SiO2The preparation of the magnesium-containing catalyst is mostly prepared by hydrolyzing a biomass silicon source or Tetraethoxysilane (TEOS), and formed particles are easy to agglomerate, so that the preparation cost is high, and the thermal reaction effect of magnesium is not ideal.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the method for preparing the silicon-carbon cathode material based on the micron silicon dioxide, and the method has the advantages of low cost, easiness in industrial production, small volume expansion of the prepared product and strong conductivity.
In order to achieve the purpose, the invention adopts the technical scheme that:
the method for preparing the silicon-carbon anode material based on the micron silicon dioxide comprises the following steps:
the method comprises the following steps: according to the weight ratio of silicon dioxide: carbon source: water (30-80): (5-15): (60-120), respectively weighing silicon dioxide with the particle size of 50-100 um, a carbon source and water to prepare slurry, grinding for 4-5 hours by using a sand mill wet method, and freeze-drying to obtain nano-scale SiO2
Step two: carbonizing the product obtained in the step one at high temperature to obtain SiO2@ C material, then according to SiO2@ C: mg: carrying out magnesiothermic reduction on NaCl in a mass ratio of 1:1: 1-1: 1:10 at 600-750 ℃, and then carrying out acid washing, washing and drying to obtain Si @ C nanoparticles;
step three: and ultrasonically mixing the Si @ C nano particles prepared in the step two with a graphene oxide solution, and then carrying out coating reduction by using a spray thermal cracking technology to prepare the Si @ C @ G material.
Further, the carbon source is one of glucose, phenolic resin, polyvinylpyrrolidone and polyacrylonitrile.
Further, the temperature for freeze-drying in step one was-45 ℃.
Further, the high-temperature carbonization in the second step is carried out at 450-700 ℃ for 2-4 h.
Further, the acid washing and washing process in the second step is as follows: removing impurities by 2mol/L hydrochloric acid, washing with 5% hydrofluoric acid for 30min, and removing unreacted SiO2Finally, washing the mixture to be neutral by using deionized water and ethanol.
Further, the process of the coating reduction in the third step is as follows: spraying with ultrasonic wave to realize granulation, and mixing with the obtained spherical particles2And introducing the/Ar mixed gas as a carrier gas into a 600-800 ℃ vertical tube furnace for coating reduction operation, and finally collecting the Si @ C @ G material through an electrostatic field.
The invention has the beneficial effects that:
the invention utilizes micron-sized SiO2The raw material is ground by a wet method to prepare the material, the cost is low, the operation is simple, and the problem of dependence on a biomass silicon source or nano-scale SiO prepared by TEOS hydrolysis is solved2Easy agglomeration, high preparation cost and non-ideal magnesium thermal reaction effect in the later period; and the original appearance of the sample can be maintained through a freeze drying technology, so that the method has a commercial prospect.
Selecting an organic polymer carbon source, carbonizing to obtain porous SiO coated with a three-dimensional porous structure2The material @ C controls the generation of SiC by controlling the amount of NaCl serving as a fluxing agent, is favorable for maintaining the structural stability of the material in the charging and discharging process, and meanwhile, the macromolecular carbon source is favorable for buffering volume expansion.
Si @ C by spray pyrolysisAnd compounding with graphene, and performing secondary coating. In the course of the ultrasonic spraying process,the granulation function can be effectively realized, and spherical particles with uniform particles are obtained; and graphene oxide in carrier gas Ar/H2Under the reduction action of gas, graphene is generated and coated on the surface of the Si @ C material, so that the conductivity and ion transmission capability of the material are enhanced, the disadvantage of poor conductivity of the silicon-based material is better improved, and the silicon-carbon composite material with excellent performance is obtained.
Drawings
FIG. 1 is a plot of particle size distribution after sanding;
FIG. 2 is an X-ray diffraction pattern of magnesium after heating at different NaCl additions;
FIG. 3 is a magnified view of the particle size after spray drying of Si @ C.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
Weighing SiO230g of polyvinylpyrrolidone, 5g of polyvinylpyrrolidone and 120mL of water are put into a sand mill, wet-ground for 4h, separated, put into a refrigerator for freezing and freeze-dried for two days and two nights at the temperature of-45 ℃ in a freeze-drying machine.
Putting the product after cold drying into a tube furnace, calcining for 4 hours at 450 ℃ in an inert atmosphere to obtain SiO2@ C material, then according to SiO2The mass ratio of @ C to Mg to NaCl is 1:1:1, the magnesium thermal reduction is carried out for 4h at the temperature of 650 ℃ in an inert atmosphere, the washing is carried out for 8h in 2M hydrochloric acid solution, and the magnesium thermal reaction by-product is removed; adding the solution after acid washing into hydrofluoric acid solution with the mass fraction of 5% for washing for 0.5h to remove incompletely reacted SiO2Washing with deionized water and ethanol solution, filtering to neutrality, placing in a vacuum oven, and vacuum drying at 80 deg.C for 12h to obtain the Si @ C composite material.
Weighing the Si @ C composite material and graphene oxide according to the mass ratio of 10:1, adding the materials into 20mL of water, and carrying out ultrasonic treatment for 15min to fully disperse the materials in the water solution. Spraying the mixed solution into a tubular furnace by using a spray thermal cracking device, and carrying out H reaction at 800 DEG C2/And reducing under the reducing action of Ar mixed carrier gas to prepare Si @ C @ G particles, and collecting under the action of an electrostatic field.
Example 2
Weighing SiO240g of polyvinylpyrrolidone, 10g of polyvinylpyrrolidone and 120mL of water are mixed in a sand mill, wet-ground for 4h, separated, frozen in a refrigerator, and freeze-dried in a freeze-drying machine at-45 ℃ for two days and two nights.
Putting the product after cold drying into a tube furnace, calcining for 4 hours at 450 ℃ in an inert atmosphere to obtain SiO2@ C material, then according to SiO2The mass ratio of @ C to Mg to NaCl is 1:1:1, the magnesium thermal reduction is carried out for 4h at the temperature of 650 ℃ in an inert atmosphere, the washing is carried out for 8h in 2M hydrochloric acid solution, and the magnesium thermal reaction by-product is removed; adding the solution after acid washing into hydrofluoric acid solution with the mass fraction of 5% for washing for 0.5h to remove incompletely reacted SiO2Washing with deionized water and ethanol solution, filtering to neutrality, placing in a vacuum oven, and vacuum drying at 80 deg.C for 12h to obtain the Si @ C composite material.
Weighing the Si @ C composite material and graphene oxide according to the mass ratio of 10:1, adding the materials into 20mL of water, and carrying out ultrasonic treatment for 15min to fully disperse the materials in the water solution. Spraying the mixed solution into a tubular furnace by using a spray thermal cracking device, and carrying out H reaction at 800 DEG C2And reducing under the reducing action of the/Ar mixed carrier gas to prepare Si @ C @ G particles, and collecting under the action of an electrostatic field.
Example 3
Weighing SiO260g of polyvinylpyrrolidone, 5g of polyvinylpyrrolidone and 120mL of water are mixed in a sand mill, wet-ground for 4h, separated, frozen in a refrigerator, and freeze-dried in a freeze-drying machine at-45 ℃ for two days and two nights.
Placing the product after cold drying in a tube furnace, calcining for 4 hours at 500 ℃ in inert atmosphere to obtain SiO2@ C material, then according to SiO2@ C: mg: the mass ratio of NaCl is 1:1:3, carrying out magnesiothermic reduction for 4h at 650 ℃ in an inert atmosphere, washing for 8h in 2M hydrochloric acid solution, and removing magnesium thermal reaction byproducts; adding the solution after acid washing into hydrofluoric acid solution with the mass fraction of 5% for washing for 0.5h to remove incompletely reacted SiO2Washing with deionized water and ethanol solution, filtering to neutrality, placing in a vacuum oven,and (3) drying for 12h in vacuum at the temperature of 80 ℃ to obtain the Si @ C composite material.
Weighing the Si @ C composite material and graphene oxide according to the mass ratio of 10:1, adding the materials into 20mL of water, and carrying out ultrasonic treatment for 15min to fully disperse the materials in the water solution. Spraying the mixed solution into a tubular furnace by using a spray thermal cracking device, reducing the mixed solution under the reducing action of H2/Ar mixed carrier gas at 800 ℃ to prepare Si @ C @ G particles, and collecting the particles under the action of an electrostatic field.
Example 4
Weighing SiO280g of polyvinylpyrrolidone, 5g of polyvinylpyrrolidone and 100mL of water are mixed in a sand mill, wet grinding is carried out for 5h, after separation, the mixture is frozen in a refrigerator and is frozen and dried for two days and two nights in a freeze dryer at the temperature of minus 45 ℃.
Placing the product after cold drying in a tube furnace, calcining for 3h at 500 ℃ in inert atmosphere to obtain SiO2@ C material, then according to SiO2@ C: mg: the mass ratio of NaCl is 1:1:5, carrying out magnesiothermic reduction for 4h at 700 ℃ in an inert atmosphere, washing for 8h in 2M hydrochloric acid solution, and removing magnesium thermal reaction byproducts; adding the solution after acid washing into hydrofluoric acid solution with the mass fraction of 5% for washing for 0.5h to remove incompletely reacted SiO2Washing with deionized water and ethanol solution, filtering to neutrality, placing in a vacuum oven, and vacuum drying at 80 deg.C for 12h to obtain the Si @ C composite material.
Weighing the Si @ C composite material and graphene oxide according to the mass ratio of 10:1, adding the materials into 20mL of water, and carrying out ultrasonic treatment for 15min to fully disperse the materials in the water solution. Spraying the mixed solution into a tubular furnace by using a spray thermal cracking device, and carrying out H reaction at 800 DEG C2And reducing under the reducing action of the/Ar mixed carrier gas to prepare Si @ C @ G particles, and collecting under the action of an electrostatic field.
Example 5
Weighing SiO260g of polyvinylpyrrolidone, 5g of polyvinylpyrrolidone and 100mL of water are mixed in a sand mill, wet-ground for 4h, separated, frozen in a refrigerator, and freeze-dried in a freeze-drying machine at-45 ℃ for two days and two nights.
Placing the cold-dried product in a tube furnace, and calcining at 450 ℃ in an inert atmosphereBurning for 4h to obtain SiO2@ C material, then according to SiO2@ C: mg: the mass ratio of NaCl is 1:1:10, the magnesium thermal reduction is carried out for 4h at the temperature of 700 ℃ in an inert atmosphere, the washing is carried out for 8h in 2M hydrochloric acid solution, and the magnesium thermal reaction by-product is removed; adding the solution after acid washing into hydrofluoric acid solution with the mass fraction of 5% for washing for 0.5h to remove incompletely reacted SiO2Washing with deionized water and ethanol solution, filtering to neutrality, placing in a vacuum oven, and vacuum drying at 80 deg.C for 12h to obtain the Si @ C composite material.
Weighing the Si @ C composite material and graphene oxide according to the mass ratio of 10:1, adding the materials into 20mL of water, and carrying out ultrasonic treatment for 15min to fully disperse the materials in the water solution. Spraying the mixed solution into a tubular furnace by using a spray thermal cracking device, reducing the mixed solution under the reducing action of H2/Ar mixed carrier gas at 700 ℃ to prepare Si @ C @ G particles, and collecting the particles under the action of an electrostatic field.
FIG. 1 is a distribution diagram of the particle size after sanding, and the particle size test of the particles after 5h sanding in example 4 is selected, and the results show that the sanding can ensure that the micron-sized SiO particles are obtained2The average grain diameter of the grinding fluid is about 200nm, and the grinding fluid has a better grinding effect.
FIG. 2 is an X-ray diffraction pattern of magnesium after heating at different NaCl additions showing that the addition of NaCl affects the formation of SiC, and that an increase in NaCl addition favors the reduction of SiC.
Fig. 3 is an enlarged view of the particle size after Si @ C spray drying, and it can be seen that a fluffy spherical material is formed, thus facilitating relief of the volume expansion of the material.

Claims (4)

1. The method for preparing the silicon-carbon anode material based on the micron silicon dioxide is characterized by comprising the following steps of:
the method comprises the following steps: according to the weight ratio of silicon dioxide: carbon source: water (30-80): (5-15): (60-120), respectively weighing silicon dioxide with the particle size of 50-100 um, a carbon source and water to prepare slurry, grinding for 4-5 hours by using a sand mill wet method, and freeze-drying to obtain nano-scale SiO2
Step two: subjecting the product obtained in the step one to high temperature carbonTo obtain SiO2@ C material, then according to SiO2@ C: mg: carrying out magnesiothermic reduction on NaCl in a mass ratio of 1:1: 1-1: 1:10 at 600-750 ℃, and then carrying out acid washing, washing and drying to obtain Si @ C nanoparticles; the pickling and washing process comprises the following steps: removing impurities by 2mol/L hydrochloric acid, washing with 5% hydrofluoric acid for 30min, and removing unreacted SiO2Finally, washing the mixture to be neutral by using deionized water and ethanol;
step three: ultrasonically and uniformly mixing the Si @ C nano particles prepared in the step two with a graphene oxide solution, and then performing coating reduction by using a spray thermal cracking technology to prepare a Si @ C @ G material; the process of coating reduction comprises the following steps: spraying with ultrasonic wave to realize granulation, and mixing with the obtained spherical particles2And introducing the/Ar mixed gas as a carrier gas into a 600-800 ℃ vertical tube furnace for coating reduction operation, and finally collecting the Si @ C @ G material through an electrostatic field.
2. The method for preparing the silicon-carbon anode material based on the micron silicon dioxide as claimed in claim 1, wherein the carbon source is one of glucose, phenolic resin, polyvinylpyrrolidone and polyacrylonitrile.
3. The method for preparing a silicon carbon negative electrode material based on micron silicon dioxide as claimed in claim 1, wherein the temperature of the freeze drying in the first step is-45 ℃.
4. The method for preparing the silicon-carbon anode material based on the micron silicon dioxide as claimed in claim 1, wherein the high-temperature carbonization in the second step is performed at 450-700 ℃ for 2-4 h.
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CN109399601B (en) * 2018-09-14 2021-12-21 江苏大学 Preparation method and application of nitrogen-phosphorus co-doped biochar material
CN112582615B (en) * 2020-12-10 2022-09-06 广东凯金新能源科技股份有限公司 One-dimensional porous silicon-carbon composite negative electrode material, preparation method and application thereof
CN113036137A (en) * 2021-03-05 2021-06-25 昆山宝创新能源科技有限公司 Lithium ion battery cathode material and preparation method and application thereof
CN113998702B (en) * 2021-10-13 2023-10-13 昆明理工大学 Method for preparing Si/C anode material by taking micro silicon powder as raw material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105958036A (en) * 2016-07-07 2016-09-21 天津普兰能源科技有限公司 Preparation method for carbon-coated silicon negative electrode material for lithium ion battery
CN106374088A (en) * 2016-10-14 2017-02-01 浙江天能能源科技股份有限公司 Method for preparing silicon/carbon composite material with magnesiothermic reduction process
CN106848273A (en) * 2017-01-19 2017-06-13 深圳市沃特玛电池有限公司 A kind of preparation method of Si-C composite material
CN107240677A (en) * 2016-03-28 2017-10-10 国家纳米科学中心 A kind of micro-nano structure carbon silicon complex microsphere and its production and use

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107240677A (en) * 2016-03-28 2017-10-10 国家纳米科学中心 A kind of micro-nano structure carbon silicon complex microsphere and its production and use
CN105958036A (en) * 2016-07-07 2016-09-21 天津普兰能源科技有限公司 Preparation method for carbon-coated silicon negative electrode material for lithium ion battery
CN106374088A (en) * 2016-10-14 2017-02-01 浙江天能能源科技股份有限公司 Method for preparing silicon/carbon composite material with magnesiothermic reduction process
CN106848273A (en) * 2017-01-19 2017-06-13 深圳市沃特玛电池有限公司 A kind of preparation method of Si-C composite material

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