CN111900348B - Method for preparing silicon-carbon composite material based on ball milling method and application thereof - Google Patents

Method for preparing silicon-carbon composite material based on ball milling method and application thereof Download PDF

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CN111900348B
CN111900348B CN202010672502.4A CN202010672502A CN111900348B CN 111900348 B CN111900348 B CN 111900348B CN 202010672502 A CN202010672502 A CN 202010672502A CN 111900348 B CN111900348 B CN 111900348B
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CN111900348A (en
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宋燕
杨桃
李圆
刘占军
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Shanxi Institute of Coal Chemistry of CAS
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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
    • H01M4/364—Composites as mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • B02C17/10—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with one or a few disintegrating members arranged in the container
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B02C23/06—Selection or use of additives to aid disintegrating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

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Abstract

The invention relates to a method for preparing a silicon-carbon composite material based on a ball milling method and application thereof, belongs to the technical field of lithium ion batteries, and particularly relates to a silicon-carbon composite material prepared by the ball milling method in an air atmosphere and application thereof to a lithium ion battery cathode material, which solve the technical problem that the silicon-carbon composite material prepared by the ball milling method needs inert atmosphere protection. The solution is as follows: the nano silicon powder and the carbon material are mixed, and the high-content silicon-carbon composite is directly prepared in the air atmosphere by a ball milling method without inert atmosphere protection by adding the high-temperature molten salt phase-change heat storage material. The method reduces the filling of inert atmosphere, reduces the requirements on ball milling equipment, and ensures the content of silicon in the silicon-carbon composite material, thereby being beneficial to improving the specific capacity value of the composite material.

Description

Method for preparing silicon-carbon composite material based on ball milling method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a method for preparing a silicon-carbon composite material based on a ball milling method and application thereof.
Background
Energy storage and conversion devices have become a focus of research due to the irreversible consumption of fossil energy. At present, lithium ion batteries occupy an indispensable part in electronic devices, wherein silicon has a theoretical specific capacity of 4200mAh/g, which causes thinking of numerous scholars and enterprises for replacing commercial graphitic carbon negative electrode materials, but the volume expansion of about 400% causes irreversible capacity loss, so that the cycling stability of the materials is limited when the materials are used as lithium ion battery negative electrodes.
The silicon-carbon composite material can better improve the defect of poor silicon circulation stability, and the addition of carbon can improve the conductivity of the material, thereby improving the rate capability of the material. At present, the common industrial preparation method of the silicon-carbon composite material is a mechanical ball milling method. Since silicon is readily oxidized to silicon dioxide under heating, the presence of silicon dioxide, which is an electrochemically inert substance, affects the realization of the material capacity. Mechanical ball milling generates a large amount of heat due to the high speed operation of the beads, and in order to reduce or avoid the formation of silica, ball milling is generally carried out in an inert atmosphere (such as argon or nitrogen), which poses challenges to ball mill equipment and production costs.
Disclosure of Invention
In order to overcome the defects of the prior art and solve the technical problem that the silicon-carbon composite material needs to be protected by inert atmosphere when prepared by a ball milling method, the invention provides a method for preparing the silicon-carbon composite material based on the ball milling method, which has low cost, high silicon content and high performance and can be produced in a large scale, and an application thereof.
The design concept of the invention is as follows: the high-temperature fused salt phase-change heat storage material is added into the silicon-carbon mixture, the mechanical ball milling can be carried out in the direct air atmosphere without the protection of inert atmosphere, and compared with the ball milling in the air atmosphere without the high-temperature fused salt phase-change heat storage material, the silicon content in the obtained silicon-carbon product is greatly protected. The high-temperature molten salt phase-change heat storage material is uniformly dispersed in the silicon-carbon mixture, so that direct impact of heat on silicon is avoided, the formation of silicon dioxide is reduced, the content of silicon in the mixture is protected, and the capacity of a product is improved. According to the invention, silicon-carbon compounds with different silicon contents can be obtained by adjusting the mass percentage of the high-temperature molten salt phase-change heat storage material in the mixture, so that the electrochemical performance is adjusted.
The invention is realized by the following technical scheme.
A method for preparing a silicon-carbon composite material based on a ball milling method is disclosed, wherein: the process of preparing the silicon-carbon composite material based on the ball milling method does not need inert atmosphere protection, the high-temperature fused salt phase-change heat storage material is uniformly mixed with the nano silicon powder and the carbon material, and ball milling is directly carried out in the air atmosphere under the protection of the high-temperature fused salt phase-change heat storage material, so that the silicon-carbon composite material with higher silicon content is prepared.
A method for preparing a silicon-carbon composite material based on a ball milling method comprises the following steps:
s1, uniformly mixing the silicon nano powder, the carbon material and the high-temperature molten salt phase-change heat storage material, and putting the mixture into a ball milling device, wherein the atmosphere of the ball milling device is air, the mass ratio of the nano silicon powder to the carbon material is 1:9-2:1, the mass ratio of the nano silicon powder to the high-temperature molten salt phase-change heat storage material is 1:500-1:50, the rotating speed of the ball milling device is set to be 100r/min-1000r/min, and the ball milling time is set to be 0.5h-18h, and ball milling is carried out on the mixed material;
and S2, after the ball milling in the step S1 is finished, separating the obtained mixture and the small ball particles, placing the obtained mixture in a hydrofluoric acid solution, stirring, washing for multiple times by deionized water until the washing liquid is neutral, simultaneously washing away the high-temperature molten salt type phase change heat storage material, and drying the obtained material to obtain the silicon-carbon composite material.
Further, the high-temperature molten salt phase-change heat storage material is one or more of potassium chloride, sodium carbonate, sodium sulfate and calcium chloride. Any obvious replacement of the high-temperature molten salt phase-change heat storage material without departing from the concept of the invention shall be within the protection scope of the invention.
Further, the carbon material is one of amorphous carbon or graphitic carbon. Any obvious replacement of the carbon source without departing from the inventive concept is intended to be within the scope of the present invention.
Further, in the step S1, the particle size of the nano silicon powder is 30 to 100 nm.
Further, in the step S2, the volume fraction of the hydrofluoric acid solution is 5% to 40%, and the stirring time is 1 to 10 hours.
The silicon-carbon composite material prepared by the method is applied to batteries, electrode materials, energy storage elements or portable electronic equipment.
Further, the battery is a lithium ion battery; the electrode material is a negative electrode material; the energy storage element is a lithium ion battery; the portable electronic device is a camera, a camcorder, a mobile phone, an MP3 or an MP4 device.
The battery assembled by the silicon-carbon composite material prepared by the invention comprises the following components: fully mixing and grinding the silicon-carbon composite material prepared by the steps with conductive agent superconducting carbon black, adhesive carboxymethyl cellulose and a small amount of water to form uniform paste, coating the paste on a copper foil current collector to be used as a working electrode, and taking a metal lithium sheet as a counter electrode to prepare the button cell.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the silicon-carbon composite electrode material is prepared by a mechanical ball milling method under the air atmosphere by adding the high-temperature molten salt phase-change heat storage material, and the content of silicon in the composite can be fully ensured without the protection of inert atmosphere, so that the realization of high specific capacity of the silicon-carbon negative electrode material is ensured.
Drawings
FIG. 1 is a thermogravimetric comparison graph of the silicon content in a silicon carbon composite after ball milling with sodium chloride and without sodium chloride in example 1;
FIG. 2 is a charge-discharge curve diagram of the silicon-carbon negative electrode material prepared in example 1 at a current density of 200 mA/g;
fig. 3 is a graph of the cycling stability of the silicon carbon anode material prepared in example 1.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. Unless otherwise specified, the examples follow conventional experimental conditions. In addition, it will be apparent to those skilled in the art that various modifications or improvements can be made to the material components and amounts in these embodiments without departing from the spirit and scope of the invention as defined in the appended claims.
Example 1
A method for preparing a silicon-carbon composite material based on a ball milling method comprises the following steps: 200mg of silicon powder with the particle size of 100nm, 800mg of graphite powder and 20g of sodium chloride are uniformly mixed, put into a ball milling tank in an air atmosphere and ball milled for 8 hours at the rotating speed of 500 r/min. And after the ball milling is finished, screening the mixture and the small balls, putting the obtained mixture into a hydrofluoric acid solution with the volume fraction of 20%, stirring for 1h, washing the obtained product with deionized water for multiple times until the solution is neutral, simultaneously washing away sodium chloride, performing suction filtration, and drying to obtain the silicon-carbon negative electrode material.
Fig. 1 is a thermogravimetric comparison graph of the silicon content in the silicon-carbon composite after adding sodium chloride and ball milling without sodium chloride, and it can be seen that the addition of sodium chloride is helpful for protecting the silicon content in the air atmosphere, thereby being helpful for improving the specific capacity of the composite material.
Electrochemical performance testing of the silicon carbon composite material prepared in example 1:
the silicon-carbon composite material prepared in example 1 was mixed with conductive agent superconducting carbon black and binder carboxymethyl cellulose (CMC) at a mass ratio of 8:1:1, added with an appropriate amount of deionized water, ground into slurry, coated on a copper foil, and dried in a vacuum oven at 80 ℃. The obtained electrode is a negative electrode, the metal lithium sheet is a positive electrode, and the electrolyte is 1MLiPF6V. (EC + DMC) (volume ratio 1: 1) mixed system, separator polypropylene membrane (Celgard 2400), assembled into 2016 type button cell in a glove box filled with argon.
As can be seen from figure 2, the material has the first discharge specific capacity of 1144mAh/g under the current density of 200mA/g and 0.01-3.0V. FIG. 3 is a graph showing the cycling stability of the silicon-carbon composite material between 0.01V and 3V.
Example 2
A method for preparing a silicon-carbon composite material based on a ball milling method comprises the following steps: 200mg of silicon powder with the particle size of 30nm, 1.8g of graphite powder and 10g of potassium chloride are uniformly mixed, put into a ball milling tank in an air atmosphere and ball milled for 6 hours at the rotating speed of 100 r/min. And after the ball milling is finished, screening the mixture and the small balls, putting the obtained mixture into a hydrofluoric acid solution with the volume fraction of 5%, stirring for 10 hours, washing the obtained product with deionized water for multiple times until the solution is neutral, simultaneously washing away potassium chloride, performing suction filtration and drying, and obtaining the silicon-carbon negative electrode material.
Electrochemical performance testing of the silicon carbon composite material prepared in example 2:
the silicon-carbon composite material prepared in example 2 was mixed with conductive agent superconducting carbon black and binder carboxymethyl cellulose (CMC) at a mass ratio of 8:1:1, added with an appropriate amount of deionized water, ground into slurry, coated on a copper foil, and dried in a vacuum oven at 80 ℃. The obtained electrode is a negative electrode, the metal lithium sheet is a positive electrode, and the electrolyte is 1MLiPF6V. (EC + DMC) (volume ratio 1: 1) mixed system, separator polypropylene membrane (Celgard 2400), assembled into 2016 type button cell in a glove box filled with argon.
Thermogravimetry of the material in an air atmosphere shows that the silicon content is 9.6 percent, which is basically the same as the theoretical silicon content. The first discharge specific capacity reaches 750mAh/g under the current density of 0.01-3.0V and 200 mA/g.
Example 3
A method for preparing a silicon-carbon composite material based on a ball milling method comprises the following steps: 200mg of silicon powder with the particle size of 100nm, 100mg of graphite powder and 100g of sodium sulfate are uniformly mixed, put into a ball milling tank in an air atmosphere and are ball milled for 18 hours at the rotating speed of 100 r/min. And after the ball milling is finished, screening the mixture and the small balls, putting the obtained mixture into a hydrofluoric acid solution with the volume fraction of 20%, stirring for 6h, washing the obtained product with deionized water for multiple times until the solution is neutral, simultaneously washing sodium sulfate, performing suction filtration and drying to obtain the silicon-carbon negative electrode material.
Electrochemical performance testing of the silicon carbon composite material prepared in example 3:
the silicon-carbon composite material prepared in example 3 was mixed with conductive agent superconducting carbon black and binder carboxymethyl cellulose (CMC) at a mass ratio of 8:1:1, added with an appropriate amount of deionized water, ground into slurry, coated on a copper foil, and dried in a vacuum oven at 80 ℃. The obtained electrode is a negative electrode, the metal lithium sheet is a positive electrode, and the electrolyte is 1MLiPF6V (EC + DMC) (volume ratio 1: 1) mixed system, the diaphragm is polypropylene film (Celga)rd 2400) were assembled into a 2016 type button cell in a glove box filled with argon.
Thermogravimetry of the material in an air atmosphere shows that the silicon content is 59.2%, and the first discharge specific capacity of the material reaches 2304mAh/g under the current density of 0.01-3.0V and 200 mA/g.
Example 4
A method for preparing a silicon-carbon composite material based on a ball milling method comprises the following steps: 200mg of silicon powder with the particle size of 50nm, 1.8g of amorphous carbon obtained by high-temperature carbonization of phenolic resin at 700 ℃ and 100g of calcium chloride are uniformly mixed, put into a ball milling tank in an air atmosphere and ball milled for 8 hours at the rotating speed of 1000 r/min. And after the ball milling is finished, screening the mixture and the small balls, putting the obtained mixture into a hydrofluoric acid solution with the volume fraction of 20%, stirring for 1h, washing the obtained product with deionized water for multiple times until the solution is neutral, washing away calcium chloride, performing suction filtration, and drying to obtain the silicon-carbon negative electrode material.
Electrochemical performance testing of the silicon carbon composite material prepared in example 4:
the silicon-carbon composite material prepared in example 4 was mixed with conductive agent superconducting carbon black and binder carboxymethyl cellulose (CMC) at a mass ratio of 8:1:1, added with an appropriate amount of deionized water, ground into slurry, coated on a copper foil, and dried in a vacuum oven at 80 ℃. The obtained electrode is a negative electrode, the metal lithium sheet is a positive electrode, and the electrolyte is 1MLiPF6V. (EC + DMC) (volume ratio 1: 1) mixed system, separator polypropylene membrane (Celgard 2400), assembled into 2016 type button cell in a glove box filled with argon.
Thermogravimetry of the material in an air atmosphere shows that the silicon content is 8.5%, and the first discharge specific capacity of the material reaches 549mAh/g under the current density of 0.01-3.0V and 200 mA/g.
Example 5
A method for preparing a silicon-carbon composite material based on a ball milling method comprises the following steps: 200mg of silicon powder with the particle size of 50nm, 1.8g of amorphous carbon obtained by 700-degree carbonization of polyvinylpyrrolidone and 100g of sodium carbonate are uniformly mixed, put into a ball milling tank in an air atmosphere and ball milled for 0.5h at the rotating speed of 1000 r/min. And after the ball milling is finished, screening the mixture and the small balls, putting the obtained mixture into a hydrofluoric acid solution with the volume fraction of 20%, stirring for 1h, washing the obtained product with deionized water for multiple times until the solution is neutral, simultaneously washing away sodium carbonate, performing suction filtration and drying to obtain the silicon-carbon negative electrode material.
Electrochemical performance testing of the silicon carbon composite material prepared in example 5:
the silicon-carbon composite material prepared in example 5 was mixed with conductive agent superconducting carbon black and binder carboxymethyl cellulose (CMC) at a mass ratio of 8:1:1, added with an appropriate amount of deionized water, ground into slurry, coated on a copper foil, and dried in a vacuum oven at 80 ℃. The obtained electrode is a negative electrode, the metal lithium sheet is a positive electrode, and the electrolyte is 1MLiPF6V. (EC + DMC) (volume ratio 1: 1) mixed system, separator polypropylene membrane (Celgard 2400), assembled into 2016 type button cell in a glove box filled with argon.
Thermogravimetry of the material in an air atmosphere shows that the silicon content is 9.2%, and the first discharge specific capacity of the material reaches 1450mAh/g under the current density of 0.01-3.0V and 200 mA/g.
Example 6
A method for preparing a silicon-carbon composite material based on a ball milling method comprises the following steps: 200mg of silicon powder with the particle size of 50nm and 400mg of amorphous carbon obtained by high-temperature carbonization of cane sugar at 700 ℃, 50g of potassium chloride and 50g of sodium chloride are uniformly mixed, put into a ball milling tank in an air atmosphere and ball milled for 8 hours at the rotating speed of 1000 r/min. And after the ball milling is finished, screening the mixture and the small balls, putting the obtained mixture into a hydrofluoric acid solution with the volume fraction of 20%, stirring for 1h, washing the obtained product with deionized water for multiple times until the solution is neutral, washing away potassium chloride and sodium chloride, performing suction filtration, and drying to obtain the silicon-carbon negative electrode material.
Electrochemical performance testing of the silicon carbon composite material prepared in example 6:
mixing the silicon-carbon composite material prepared in the example 6 with conductive agent superconducting carbon black and adhesive carboxymethyl cellulose (CMC) according to the mass ratio of 8:1:1, adding a proper amount of deionized water, grinding into slurry, coating the slurry on a copper foilDrying in a vacuum oven at 80 ℃. The obtained electrode is a negative electrode, the metal lithium sheet is a positive electrode, and the electrolyte is 1MLiPF6V. (EC + DMC) (volume ratio 1: 1) mixed system, separator polypropylene membrane (Celgard 2400), assembled into 2016 type button cell in a glove box filled with argon.
Thermogravimetry of the material in an air atmosphere shows that the silicon content is 29.8%, and the first discharge specific capacity of the material reaches 1755mAh/g under the current density of 0.01-3.0V and 200 mA/g.
Example 7
A method for preparing a silicon-carbon composite material based on a ball milling method comprises the following steps: 200mg of silicon powder with the particle size of 100nm, 800mg of amorphous carbon obtained by high-temperature carbonization of coal pitch at 800 ℃, 15g of sodium chloride and 5g of calcium chloride are uniformly mixed, put into a ball milling tank in an air atmosphere and ball milled for 8 hours at the rotating speed of 500 r/min. And after the ball milling is finished, screening the mixture and the small balls, putting the obtained mixture into a hydrofluoric acid solution with the volume fraction of 20%, stirring for 1h, washing the obtained product with deionized water for multiple times until the solution is neutral, simultaneously washing away sodium chloride and calcium chloride, performing suction filtration, and drying to obtain the silicon-carbon negative electrode material.
Electrochemical performance testing of the silicon carbon composite material prepared in example 7:
the silicon-carbon composite material prepared in example 7 was mixed with conductive agent superconducting carbon black and binder carboxymethyl cellulose (CMC) at a mass ratio of 8:1:1, added with an appropriate amount of deionized water, ground into slurry, coated onto a copper foil, and dried in a vacuum oven at 80 ℃. The obtained electrode is a negative electrode, the metal lithium sheet is a positive electrode, and the electrolyte is 1MLiPF6V. (EC + DMC) (volume ratio 1: 1) mixed system, separator polypropylene membrane (Celgard 2400), assembled into 2016 type button cell in a glove box filled with argon.
Thermogravimetry of the material under air atmosphere showed that the silicon content was 15.2%. The material has the first discharge specific capacity of 1346mAh/g under the current density of 0.01-3.0V and 200 mA/g.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (7)

1. A method for preparing a silicon-carbon composite material based on a ball milling method is characterized by comprising the following steps: the preparation method comprises the steps of preparing a silicon-carbon composite material based on a ball milling method, wherein inert atmosphere protection is not needed in the process of preparing the silicon-carbon composite material, uniformly mixing a high-temperature molten salt phase-change heat storage material with nano silicon powder and a carbon material, and directly carrying out ball milling in an air atmosphere under the protection of the high-temperature molten salt phase-change heat storage material to prepare the silicon-carbon composite material;
The method specifically comprises the following steps:
s1, uniformly mixing the silicon nano powder, the carbon material and the high-temperature molten salt phase-change heat storage material, and putting the mixture into a ball milling device, wherein the atmosphere of the ball milling device is air, the mass ratio of the nano silicon powder to the carbon material is 1:9-2:1, the mass ratio of the nano silicon powder to the high-temperature molten salt phase-change heat storage material is 1:500-1:50, the rotating speed of the ball milling device is set to be 100r/min-1000r/min, and the ball milling time is set to be 0.5h-18h, and ball milling is carried out on the mixed material;
and S2, after the ball milling in the step S1 is finished, separating the obtained mixture and the small ball particles, placing the obtained mixture in a hydrofluoric acid solution, stirring, washing for multiple times by deionized water until the washing liquid is neutral, simultaneously washing away the high-temperature molten salt type phase change heat storage material, and drying the obtained material to obtain the silicon-carbon composite material.
2. The method for preparing the silicon-carbon composite material based on the ball milling method according to claim 1, wherein the method comprises the following steps: the high-temperature molten salt type phase change heat storage material is one or more of potassium chloride, sodium carbonate, sodium sulfate and calcium chloride.
3. The method for preparing the silicon-carbon composite material based on the ball milling method according to claim 1, wherein the method comprises the following steps: the carbon material is one of amorphous carbon or graphitic carbon.
4. The method for preparing the silicon-carbon composite material based on the ball milling method according to claim 1, wherein the method comprises the following steps: in the step S1, the particle size of the nano silicon powder is 30-100 nm.
5. The method for preparing the silicon-carbon composite material based on the ball milling method according to claim 1, wherein the method comprises the following steps: in the step S2, the volume fraction of the hydrofluoric acid solution is 5% -40%, and the stirring time is 1-10 h.
6. The silicon-carbon composite material prepared by the method of claim 1 is applied to an electrode material, an energy storage element or a portable electronic device.
7. Use of the silicon-carbon composite material according to claim 6, characterized in that: the electrode material is a negative electrode material; the energy storage element is a lithium ion battery; the portable electronic device is a camera, a camcorder, a mobile phone, an MP3 or an MP4 device.
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