CN112952073A - Yolk-shell type carbon-coated silicon composite negative electrode material and preparation method thereof - Google Patents

Yolk-shell type carbon-coated silicon composite negative electrode material and preparation method thereof Download PDF

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CN112952073A
CN112952073A CN202110439019.6A CN202110439019A CN112952073A CN 112952073 A CN112952073 A CN 112952073A CN 202110439019 A CN202110439019 A CN 202110439019A CN 112952073 A CN112952073 A CN 112952073A
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carbon
yolk
silicon
coated silicon
composite
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龚晓辉
郑渊博
蒋海东
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Ningxia Baichuan New Material Co ltd
Jiangsu Baichuan High Tech New Materials Co ltd
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Ningxia Baichuan New Material Co ltd
Jiangsu Baichuan High Tech New Materials 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a yolk-shell type carbon-coated silicon composite negative electrode material and a preparation method thereof, wherein firstly, silicon alloy powder and a carbon material are mixed and dispersed under the action of a binder to obtain carbon material-coated silicon alloy composite powder; then carrying out heat treatment on the composite powder in an inert atmosphere to carbonize the binder; adding the heat-treated composite powder into a metal corrosion solution, stirring and dispersing to remove metal in the composite powder; and sequentially filtering, washing and drying the composite powder without the metal, and finally carrying out heat treatment to completely carbonize organic matters in the composite to obtain the yolk-shell type carbon-coated silicon composite negative electrode material. The preparation method of the yolk-shell type carbon-coated silicon composite negative electrode material is low in cost and easy to realize, and the prepared composite negative electrode material is of a yolk-shell type structure, has high enough compressive strength, and is high in battery capacity and good in cycle performance when applied to a lithium ion battery.

Description

Yolk-shell type carbon-coated silicon composite negative electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to a yolk-shell type carbon-coated silicon composite cathode material and a preparation method thereof.
Background
The lithium ion battery has the advantages of high working voltage, large energy density, long cycle life and the like, so that the lithium ion battery becomes an ideal power supply for portable electronic equipment, electric vehicles and energy storage systems, and the development of a novel electrode material with high specific energy, good safety and low cost is the core content in the research field of the lithium ion battery. The main cathode material of the current commercial lithium ion battery is graphite, and the further improvement of the energy of the lithium ion battery is limited due to the low theoretical capacity (372 mAh/g) and the poor high-rate charge-discharge performance of the graphite.
Silicon has extremely high theoretical specific capacity (4200 mAh/g) and lower delithiation potential (less than 0.5V relative to Li/Li)+) In recent years, it has become one of the popular negative electrode materials for lithium ion batteries. However, the silicon undergoes a large volume change during the lithium intercalation and deintercalation cycle, which results in the structural degradation of the electrode, and further causes the capacity of the electrode to decline rapidly, limiting the practical application of the silicon material.
In order to buffer the volume change of silicon in battery application, the following methods are commonly used: (1) carbon coating (for example, patent CN101710617A, CN105576209A, CN 101244814A), carbon material is often used as coating material because of its strong conductive ability, no influence on lithium ion conduction, and high strength, but it needs to use nano-silicon powder to avoid the silicon particles from breaking under expansion/contraction stress, and the cost of nano-silicon powder is extremely high; (2) by using low-cost silicon oxide materials and carbon coatings thereof (such as CN103474631A, CN103035917B and CN 103219504A), silicon oxide is converted into simple substance silicon with lithium storage capacity during battery formation, associated lithium silicate and lithium oxide become buffers coated outside silicon, but the reaction of reducing silicon oxide into silicon needs to consume extra energy, so that the first charge and discharge efficiency of the materials is low, and the generated lithium silicate and lithium oxide are electric insulators and influence the charge transmission in electrodes. Since the volume of fully lithiated silicon is as much as 4 times the original volume, simple coating is not sufficient to provide effective buffering, and further optimization of the structure of the silicon-based anode material is necessary.
Disclosure of Invention
The invention aims to provide a preparation method of a yolk-shell type carbon-coated silicon composite negative electrode material, which is low in cost and easy to realize, wherein the prepared composite negative electrode material is a yolk-shell type structure taking silicon as a yolk and carbon as a shell, has high enough compressive strength, and is high in battery capacity and good in cycle performance when applied to a lithium ion battery.
The technical scheme adopted by the invention for solving the problems is as follows: a preparation method of a yolk-shell type carbon-coated silicon composite negative electrode material comprises the following steps:
(1) mixing and dispersing silicon alloy powder and a carbon material under the action of a binder to obtain carbon material coated silicon alloy composite powder;
(2) carrying out heat treatment on the composite powder obtained in the step (1) in an inert atmosphere to carbonize a binder;
(3) adding the composite powder subjected to heat treatment in the step (2) into a metal corrosive liquid, stirring and dispersing, and dissolving and removing metals in the composite;
(4) and (4) sequentially filtering, washing and drying the reactant in the step (3), and then carrying out heat treatment on the purified reactant to completely carbonize the organic matters in the compound.
Preferably, the particle size of the silicon alloy powder is not more than 2 μm, wherein the silicon alloy is silicon-aluminum alloy, silicon-aluminum alloy derivatives, silicon-zinc alloy derivatives, silicon-tin alloy or silicon-tin alloy derivatives, and the volume ratio of silicon to metal is 1: 3.
Preferably, the carbon material is at least one of graphite, mesocarbon microbeads, soft carbon, hard carbon, conductive carbon, carbon nanotubes and graphene.
Preferably, the binder is at least one of phenolic resin, phenolic resin prepolymer, polyacrylonitrile, polyacrylic acid, polyacrylonitrile-polyacrylic acid copolymer, starch, glucose and asphalt.
Preferably, the amount of the silicon alloy powder added is not more than the total mass of the carbon material and the binder.
Preferably, the mixing and dispersing method is ball milling or spray drying.
Preferably, the metal corrosion solution is a solution having both oxidizing property and weak acidity, and the metal corrosion solution is at least one of an acid solution, an iron (III) salt aqueous solution, a copper (II) salt aqueous solution, and a cobalt (III) salt aqueous solution, wherein the acid solution is a water-soluble acid, specifically hydrochloric acid, sulfuric acid, nitric acid, or acetic acid.
Adding the heat-treated composite powder in the step (3) into the metal corrosion liquid in batches, dropwise adding hydrogen peroxide and hydrochloric acid into the reaction liquid after each batch of heat-treated composite powder (carbon-coated alloy composite) is corroded to regenerate the corrosion liquid, and then adding the heat-treated composite powder for reaction.
More preferably, the metal corrosion solution is an iron (III) salt aqueous solution, and the iron (III) salt aqueous solution is an iron trichloride aqueous solution.
Preferably, the heat treatment temperature in the step (2) is controlled to be 300 ℃ to the melting point of the silicon alloy, and the heat treatment temperature in the step (4) is controlled to be 1400 ℃ to the melting point of the silicon alloy.
The invention also aims to provide a yolk-shell type carbon-coated silicon composite negative electrode material which is prepared according to the preparation method.
Compared with the prior art, the invention has the advantages that:
(1) the invention adopts the low-cost and easily-obtained silicon-aluminum alloy micro powder as the raw material of the cathode material, so that the cost is low; in addition, after the composite powder of the carbon material coated silicon alloy is subjected to heat treatment and carbonization and is treated by a metal corrosive liquid, metal between a carbon shell and a silicon core is removed, and nanoscale simple substance silicon is left without reduction and activation in battery formation as silicon oxide, wherein when weakly acidic aqueous solution containing iron (III) salt, copper (II) salt or cobalt (III) salt is used as the metal corrosive liquid, the generation of hydrogen bubbles can be avoided, and the integrity of the composite particle carbon shell is facilitated.
(2) After the composite powder of the carbon material coated silicon alloy is subjected to heat treatment and carbonization and is treated by a metal corrosive liquid, metal between a carbon shell and a silicon core is removed, and nano-scale elemental silicon is left, so that the preparation method takes metal components as a cavity template, the stable carbon shell is completely removed after the outside of alloy particles is formed, and the originally occupied volume becomes a cavity between the carbon shell and the silicon core, so that the prepared cathode material is of a yolk-shell type structure (the elemental silicon is taken as a yolk, the carbon material is taken as a shell, and a cavity is formed between the yolk and the shell), has sufficiently high compressive strength, does not collapse or break after rolling (a pole piece of a lithium ion battery usually needs to be rolled to reduce the thickness, enhance the adhesion of an electrode material to a current collector and reduce the internal resistance), and ensures the structural integrity of the material and the performance of the battery.
(3) The composite cathode material prepared by the invention has a cavity for accommodating lithiated silicon, the volume change of a silicon core is limited in the particle, the extrusion of the expansion of the silicon core to a carbon coating layer is eliminated/reduced, and the stability of an electrode microstructure is ensured.
(4) The preparation method adopts two heat treatments, wherein the first heat treatment is the heat treatment of the composite powder of the silicon alloy coated by the carbon material in the inert atmosphere, the temperature is controlled to be 300 ℃ to the melting point of the silicon alloy, so that the carbon shell is partially carbonized, the carbon shell is prevented from being dissolved by corrosive liquid in the subsequent metal corrosion process, and the second heat treatment is the heat treatment of a purified reactant in the inert atmosphere, the temperature is controlled to be 1400 ℃ to further carbonize the carbon shell, eliminate harmful chemical groups in carbon components and improve the electrical properties of the material.
Drawings
Fig. 1 is a scanning electron microscope image of a yolk-shell carbon-coated silicon composite negative electrode material in example 1 of the present invention.
Fig. 2 is a transmission electron microscope image of the yolk-shell carbon-coated silicon composite negative electrode material in example 1 of the present invention.
Fig. 3 is an X-ray photoelectron spectrum of the yolk-shell carbon-coated silicon composite negative electrode material in example 1 of the present invention.
Fig. 4 is an X-ray diffraction spectrum of the yolk-shell type carbon-coated silicon composite negative electrode material in example 1 of the present invention.
Fig. 5 shows the specific capacity change of the yolk-shell carbon-coated silicon composite negative electrode material and the electrode prepared from the mixture of silicon and graphite powder before and after rolling under the constant current charge-discharge cycle of 0.1C.
Fig. 6 is an electron microscope image of an electrode prepared from the yolk-shell carbon-coated silicon composite negative electrode material of example 1 of the present invention after 100 cycles of charge and discharge at 0.1C before rolling (without rolling).
Fig. 7 is an electron microscope image of an electrode prepared from the yolk-shell carbon-coated silicon composite negative electrode material of example 1 of the present invention after being rolled for 100 0.1C charge-discharge cycles.
Fig. 8 is a process flow chart of the yolk-shell carbon-coated silicon composite negative electrode material of the invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1
A preparation method of a yolk-shell type carbon-coated silicon composite negative electrode material comprises the following steps:
(1) 60 g of silicon aluminum alloy powder (1 μm, 21wt.% Si) and an ethanol solution (50 wt.%) containing 24 g of resol were mixed and ball milled for 6 h, 40.7 g of graphite powder (2000 mesh) was added, ball milled for 12 h, vacuum dried at 40 ℃ to remove ethanol, and ball milled for 12 h after complete removal of ethanol.
(2) The fine powder of the composite particles was sieved out using a 300 mesh sieve, and vacuum treated at 160 ℃ for 8 hours to further polymerize the phenolic resin to convert it to a thermosetting polymer, after which the composite powder was heat treated in a tube furnace at 550 ℃ under nitrogen for 5 hours.
(3) Slowly adding the heat-treated composite powder obtained in the step (2) into a 1 mol/L ferric trichloride aqueous solution in batches, stirring and dispersing, slowly adding 30% hydrogen peroxide aqueous solution dropwise with the yellow ferric trichloride reduced into almost colorless ferrous chloride by aluminum, oxidizing the ferrous chloride to regenerate the ferric trichloride, recovering the solution to be dark yellow, adding hydrochloric acid dropwise to keep the pH value of the solution at 1 so as to maintain the solubility of various salts in a reaction system, and finishing the reaction when the solution color does not become light any more, namely the metallic aluminum is considered to be consumed.
(4) And (3) carrying out ultrafiltration on the reactant in the step (3) through a polytetrafluoroethylene filter membrane with the aperture of 0.45 mu m, collecting a solid, sequentially washing the solid with dilute hydrochloric acid and water, drying the solid in a vacuum oven at 80 ℃, and further carrying out heat treatment on the obtained product for 8 hours at 900 ℃ in nitrogen atmosphere to obtain black powder (the mass ratio of silicon to pyrolytic carbon to graphite is 19:19.6: 61.4).
The resol is prepared by the following method: 187.7 g of formaldehyde solution (37-40 wt.%), 156.9 g of phenol and 33.7 g of triethylamine are added into a flask, the mixture is stirred and reacted for 9 hours at 85 ℃, the reaction solution is poured into 1L of water, a brownish red paste is separated out, the upper layer of water is removed, the lower layer of paste crude product is washed by dilute hydrochloric acid and water in sequence until the pH value of the washing solution is less than 7, and the washing solution is dried in vacuum at 40 ℃ to obtain a light yellow transparent solid (154 g, the yield is 82%).
As shown in fig. 1 and 2, scanning electron micrographs and transmission electron micrographs of the yolk-shell type carbon-coated silicon composite negative electrode material of example 1 were obtained, respectively.
As shown in fig. 3, an X-ray photoelectron spectrum of the yolk-shell carbon-coated silicon composite negative electrode material in example 1 shows that the silicon content of the surface of the composite negative electrode material is much lower than the whole silicon content, which indicates that the exposed silicon is very little and is basically covered by the carbon shell; the exposed trace silicon consists of elemental silicon and silicon dioxide.
As shown in fig. 4, the X-ray diffraction spectrum of the yolk-shell carbon-coated silicon composite negative electrode material in example 1 is seen from the figure, in which the main components of the composite negative electrode material are graphite and silicon, aluminum is not contained, and no silica is detected, indicating that the amount of silica detected by X-ray photoelectron spectroscopy is very small, and only exists on the surface of exposed silicon, and the diffraction signal of pyrolytic carbon is weak and is not obvious in the spectrum.
As shown in fig. 5, the specific capacity of the yolk-shell carbon-coated silicon composite negative electrode material and the electrode prepared from the mixture of silicon and graphite powder before and after rolling changes under the constant current charge-discharge cycle of 0.1C.
The reference substance silicon and graphite powder mixture consists of silicon powder and graphite powder in a mass ratio of 2:8, the electrode formula is silicon carbon to conductive carbon to polyvinylidene fluoride =8:1:1 (mass ratio), the performance of the material is inspected through a silicon carbon electrode | | | metal lithium half battery, and the electrolyte of the battery is 1 mol/L LiPF without any additive6EC/DMC/DEC (volume ratio 1:1: 1) solution, and the membrane is a polyethylene wet membrane with the thickness of 16 mu m.
As shown in fig. 6 and 7, the electron micrographs are respectively the electron micrographs of the electrode prepared from the yolk-shell type carbon-coated silicon composite negative electrode material in example 1 after being subjected to 100 times of 0.1C charge-discharge cycles before rolling (without rolling) and after the electrolyte, the SEI material and the binder are washed away, and the electron micrographs of the electrode prepared from the yolk-shell type carbon-coated silicon composite negative electrode material in example 1 of the present invention after being subjected to 100 times of 0.1C charge-discharge cycles after rolling and after the electrolyte, the SEI material and the binder are washed away.
Example 2
A preparation method of a yolk-shell type carbon-coated silicon composite negative electrode material comprises the following steps:
(1) 60 g of silicon aluminum alloy powder (1 μm, 21wt.% Si) and an ethanol solution (50 wt.%) containing 6 g of acrylonitrile-acrylic acid copolymer were mixed and ball-milled for 6 h, 74 g of graphite powder (2000 mesh) was added, ball-milled for 12 h, vacuum-dried at 40 ℃ to remove ethanol, and ball-milled for 12 h after complete removal of ethanol.
(2) The fine powder of the composite particles was sieved out using a 300 mesh sieve, and the composite powder was heat-treated in a tube furnace at 550 ℃ under a nitrogen atmosphere for 5 hours.
(3) Slowly adding the heat-treated composite powder obtained in the step (2) into a 3 mol/L copper dichloride aqueous solution in batches, stirring and dispersing, gradually lightening the color of the solution (the reaction may generate brown copper (II) and copper (I) conjugates which can slow down the reaction as blue copper dichloride is reduced into colorless cuprous chloride by aluminum, heating the solution to accelerate the decomposition of the substances), slowly dropwise adding 30% hydrogen peroxide aqueous solution, oxidizing the cuprous chloride to regenerate the cupric chloride to recover the solution into blue, dropwise adding hydrochloric acid to keep the pH of the solution at 1 so as to maintain the solubility of various salts in the reaction system, and finishing the reaction when the color of the solution is not lightened any more, namely, the metallic aluminum is considered to be consumed.
(4) And (3) carrying out ultrafiltration on the reactant in the step (3) through a polytetrafluoroethylene filter membrane with the aperture of 0.45 mu m, collecting the solid, sequentially washing the solid with dilute hydrochloric acid and water, drying the solid in a vacuum oven at 80 ℃, and further carrying out heat treatment on the obtained product for 8 hours at 900 ℃ in nitrogen atmosphere to obtain black powder.
Wherein, the acrylonitrile-acrylic acid copolymer is prepared by the following method: adding 75.0 g of polyacrylonitrile, 250 g of hydrochloric acid (36-38 wt.%), and 35 g of water into a flask, stirring at 80 ℃ for reaction for 72 hours, adding 250 mL of water after the reaction is finished to precipitate a solid, dissolving the solid with boiling water, cooling, pouring out a water layer to wash the solid until the pH value of a washing liquid is more than 3, and then drying in vacuum at 80 ℃ to obtain 89 g of light yellow transparent solid.
In addition to the above embodiments, the present invention also includes other embodiments, and any technical solutions formed by equivalent transformation or equivalent replacement should fall within the scope of the claims of the present invention.

Claims (10)

1. A preparation method of a yolk-shell type carbon-coated silicon composite negative electrode material is characterized by comprising the following steps of: the method comprises the following steps:
(1) mixing and dispersing silicon alloy powder and a carbon material under the action of a binder to obtain carbon material coated silicon alloy composite powder;
(2) carrying out heat treatment on the composite powder obtained in the step (1) in an inert atmosphere to carbonize a binder;
(3) adding the composite powder subjected to heat treatment in the step (2) into a metal corrosive liquid, stirring and dispersing, and dissolving and removing metals in the composite;
(4) and (4) sequentially filtering, washing and drying the reactant in the step (3), and then carrying out heat treatment on the purified reactant to completely carbonize the organic matters in the compound.
2. The method for preparing a yolk-shell carbon-coated silicon composite anode material according to claim 1, wherein the method comprises the following steps: the grain size of the silicon alloy powder is not more than 2 mu m, wherein the silicon alloy is silicon-aluminum alloy, silicon-aluminum alloy derivatives, silicon-zinc alloy derivatives, silicon-tin alloy or silicon-tin alloy derivatives, and the volume ratio of silicon to metal is 1: 3.
3. The method for preparing a yolk-shell carbon-coated silicon composite anode material according to claim 1, wherein the method comprises the following steps: the carbon material is at least one of graphite, mesocarbon microbeads, soft carbon, hard carbon, conductive carbon, carbon nanotubes and graphene.
4. The method for preparing a yolk-shell carbon-coated silicon composite anode material according to claim 1, wherein the method comprises the following steps: the binder is at least one of phenolic resin, phenolic resin prepolymer, polyacrylonitrile, polyacrylic acid, polyacrylonitrile-polyacrylic acid copolymer, starch, glucose and asphalt.
5. The method for preparing a yolk-shell carbon-coated silicon composite anode material according to claim 1, wherein the method comprises the following steps: the addition amount of the silicon alloy powder is not more than the total mass of the carbon material and the adhesive.
6. The method for preparing a yolk-shell carbon-coated silicon composite anode material according to claim 1, wherein the method comprises the following steps: the mixing and dispersing method is ball milling or spray drying.
7. The method for preparing a yolk-shell carbon-coated silicon composite anode material according to claim 1, wherein the method comprises the following steps: the metal corrosion solution is a solution with oxidizability and weak acidity, and the metal corrosion solution is at least one of an acid solution, an iron (III) saline solution, a copper (II) saline solution and a cobalt (III) saline solution.
8. The method for preparing a yolk-shell carbon-coated silicon composite anode material according to claim 7, wherein the method comprises the following steps: the metal corrosion liquid is iron (III) salt water solution, and the iron (III) salt water solution is ferric trichloride water solution.
9. The method for preparing a yolk-shell carbon-coated silicon composite anode material according to claim 1, wherein the method comprises the following steps: the heat treatment temperature in the step (2) is controlled to be 300 ℃ to the melting point of the silicon alloy, and the heat treatment temperature in the step (4) is controlled to be 1400 ℃ to the melting point of the silicon alloy.
10. A yolk-shell type carbon-coated silicon composite negative electrode material is characterized in that: the compound is prepared by the preparation method of any one of claims 1 to 9.
CN202110439019.6A 2021-04-23 2021-04-23 Yolk-shell type carbon-coated silicon composite negative electrode material and preparation method thereof Pending CN112952073A (en)

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Application publication date: 20210611