CN108878815B - Composite lithium battery negative electrode material and preparation method thereof - Google Patents

Composite lithium battery negative electrode material and preparation method thereof Download PDF

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CN108878815B
CN108878815B CN201810619618.4A CN201810619618A CN108878815B CN 108878815 B CN108878815 B CN 108878815B CN 201810619618 A CN201810619618 A CN 201810619618A CN 108878815 B CN108878815 B CN 108878815B
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CN108878815A (en
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张翠媛
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Shimenn County Shun Chao Technology Development 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
    • 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
    • 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
    • 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 a composite lithium battery cathode material, which comprises the following components in percentage by weight: the nano-nonmetal material comprises a nano-nonmetal matrix, a metal dopant, inorganic silicate, polyvinylidene fluoride, a modifier, a carbonization regulator, a conductive agent, a binder and dopamine. The invention can shorten the lithium ion diffusion distance through the nanometer nonmetal substrate, improve the lithium ion diffusion coefficient, have better capacity performance under larger current, the metal dopant and polyvinylidene fluoride can make the metal particle adhere to the surface of the nanometer nonmetal substrate and utilize dopamine to coat, can reduce the contact resistance, play a role in dispersing at the same time, the electrochemical performance of the material, especially the rate performance, is greatly improved, can improve the whole conductivity, realize multiple crosslinking and self-repairing functions, the adverse effect that the silicon negative pole should change repeatedly in the charging and discharging process of the battery can be solved by adding the inorganic silicate, the cycle performance of the silicon-based negative pole material is improved, and the specific capacity attenuation capacity of the battery is small.

Description

Composite lithium battery negative electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a composite lithium battery cathode material. Meanwhile, the invention also relates to a preparation method of the composite lithium battery cathode material.
Background
Lithium batteries are a type of battery using a nonaqueous electrolyte solution with lithium metal or a lithium alloy as a negative electrode material. Because the chemical characteristics of lithium metal are very active, the requirements on the environment for processing, storing and using the lithium metal are very high. Therefore, lithium batteries have not been used for a long time. With the development of science and technology, lithium batteries become mainstream at present, and a negative electrode material is one of key materials for manufacturing the lithium ion batteries and is an important factor for determining the performance and the price of the lithium ion batteries. The current commercialized negative electrode material is mainly graphite, the actual capacity of which is close to the theoretical value (372mAh/g), and the capacity is remarkably reduced along with the increase of the cycle number, so that the increasing capacity and performance requirements of the lithium ion battery cannot be met. On the other hand, the lithium intercalation potential of the graphite carbon material is mainly concentrated in the range of 100-0mV (vs. Li/Li +), which is very close to the deposition potential of metallic lithium and is not beneficial to the safety of the battery, and the silicon-based negative electrode material can expand and contract by about 300% in volume in the lithiation/delithiation process, which directly causes the silicon-based negative electrode material to fall off from a conductive network easily and affects the cycle stability, and meanwhile, a solid electrolyte interface film (SEI) continuously generated on the surface of the silicon-based negative electrode material can also induce the rapid attenuation of the specific capacity of the silicon-based negative electrode material, thereby reducing the service life and being not beneficial to wide popularization and application.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a composite lithium battery negative electrode material and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
the formula of the composite lithium battery negative electrode material is as follows: 6-10 parts of a nano nonmetal matrix, 5-7 parts of a metal dopant, 4-8 parts of inorganic silicate, 3-9 parts of polyvinylidene fluoride, 2-4 parts of a modifier, 3-5 parts of a carbonization regulator, 2-6 parts of a conductive agent, 1-5 parts of an adhesive and 1-3 parts of dopamine.
Preferably, the nano non-metal matrix comprises one or more of boron carbide, silicon nitride, zinc oxide or calcium sulfate, and the nano non-metal matrix is modified by mixing and stirring with calcium hydroxide at 50-70 ℃ for 10-15 minutes before use.
Preferably, the metal dopant comprises one or more of silver nitrate, copper oxide or copper powder.
Preferably, the inorganic silicate is one or a mixture of bentonite, clay, montmorillonite and kaolin.
Preferably, the modifier is one or more of ethanol, methyl acrylate, phosphoric acid, methyl acrylate, potassium chloride and nitrogen dioxide.
Preferably, the carbonization regulator comprises one or more of alkane, ether compound, alcohol compound, carboxylic acid compound and inorganic nitrogen-containing compound, and the alkane is C1～C10The alkane, ether compound comprises one or more of methyl ether, ethyl ether, n-butyl ether and ethylene oxide, the alcohol compound comprises one or more of methanol, ethanol, propanol and furfuryl alcohol, and the carboxylic acid compound comprises one or more of formic acid, acetic acid, propionic acid, terephthalic acid, benzoic acid and citric acid.
Preferably, the adhesive is one or a mixture of two groups of styrene-butadiene rubber and carboxymethyl cellulose, and the conductive agent is acetylene black or conductive carbon black.
The invention also provides a preparation method of the composite lithium battery cathode material, which comprises the following steps:
s1, sequentially adding a conductive agent and dopamine into a reaction container containing a tris buffer solution, wherein the weight ratio of the dopamine to the conductive agent is 1: 3-5, uniformly stirring at room temperature, performing suction filtration, and drying at room temperature to obtain polydopamine-coated conductive agent particles, wherein the pH value of a trihydroxymethylaminomethane buffer solution is 8.4-8.6;
s2, mixing and stirring the nano non-metal matrix and the modifier for 5-10 minutes, adding the metal dopant, continuously stirring, heating the mixture to 160-200 ℃, drying, keeping the temperature for 2-4 hours, and taking out the mixture;
s3, adding a carbonization regulator into the mixture obtained in the step S2, and then heating and carbonizing the mixture in an inert gas atmosphere at the temperature of 600-1000 ℃ for 1-10 hours, wherein the inert gas is one of nitrogen, argon and helium;
s4, mixing the products in S1 and S3, adding the adhesive and the inorganic silicon salt aqueous solution, mixing and stirring for 15-25 minutes in a vacuum stirrer, adjusting the viscosity to 2000-4000 mPa & S, and sieving with a 100-140-mesh sieve to obtain a negative electrode gel-like mixture;
s5, finally, adding polyvinylidene fluoride into the product of S4, mixing and stirring for 6-8 minutes, heating to 60-80 ℃, adding N-methyl-2-pyrrolidone solvent, uniformly coating the solution on a copper foil, and pressing into tablets after vacuum drying treatment.
Preferably, the stirring is performed by a spiral stirrer driven by a variable frequency motor, and the stirring speed is 1000-2000 r/min.
Preferably, the vacuum drying treatment is specifically drying for 8-24 hours in a vacuum drying oven at a temperature of 80-140 ℃, and the pressure intensity of pressing is 5-10 MPa.
The invention has the technical effects and advantages that: compared with the traditional product, the composite lithium battery cathode material and the preparation method thereof provided by the invention can shorten the diffusion distance of lithium ions and improve the diffusion coefficient of the lithium ions through the nano nonmetal substrate, have better capacity performance under larger current, can ensure that metal particles are attached to the surface of the nano nonmetal substrate and are coated by dopamine, can reduce contact resistance and play a role of dispersion, greatly improve the electrochemical performance, particularly the rate capability, of the material and can improve the integral conductivity, realize multiple crosslinking and self-repairing functions, can solve the adverse effect of repeated volume change of a silicon cathode in the charging and discharging process of a battery by adding inorganic silicon salt, improve the cycle performance of the silicon-based cathode material, have small specific capacity attenuation capacity of the battery, have simple and practical preparation method and cheap and easily-obtained used materials, the method is convenient for preparing the cathode material with excellent electrochemical performance on a large scale, is safe and stable, has good conductivity, long service life and wide application range, and is beneficial to popularization.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Embodiments of the present invention are further described in detail with reference to the following table.
Figure BDA0001697714330000041
Table one: is the specific parts of the formula in the embodiment of the invention
Preparation conditions Stirring speed Temperature of carbonization Carbonization time Drying temperature Drying time Pressure of tabletting
Example 1 1000r/min 600℃ 1h 80℃ 8h 5MPa
Example 2 1500r/min 800℃ 5h 110℃ 16h 8MPa
Example 3 2000r/min 1000℃ 10h 140℃ 24h 10MPa
Table two: is a specific description of the reaction conditions in the preparation methods of the examples of the present invention
Example 1
The formula of the composite lithium battery negative electrode material is as follows: 6 parts of a nano nonmetal matrix, 5 parts of a metal dopant, 4 parts of an inorganic silicate, 3 parts of polyvinylidene fluoride, 2 parts of a modifier, 3 parts of a carbonization regulator, 2 parts of a conductive agent, 1 part of an adhesive and 1 part of dopamine.
Specifically, the nano non-metal matrix comprises one or more of boron carbide, silicon nitride, zinc oxide or calcium sulfate, and the nano non-metal matrix is modified by mixing and stirring with calcium hydroxide at 50 ℃ for 10 minutes before use.
Specifically, the metal dopant comprises one or more of silver nitrate, copper oxide or copper powder.
Specifically, the inorganic silicate is one or a mixture of bentonite, clay, montmorillonite and kaolin.
Specifically, the modifier is one or more of ethanol, methyl acrylate, phosphoric acid, methyl acrylate, potassium chloride and nitrogen dioxide.
Specifically, the carbonization regulator comprises one or more of alkane, ether compounds, alcohol compounds, carboxylic acid compounds and inorganic nitrogen-containing compounds, and the alkane is C1～C10The alkane, ether compound comprises one or more of methyl ether, ethyl ether, n-butyl ether and ethylene oxide, the alcohol compound comprises one or more of methanol, ethanol, propanol and furfuryl alcohol, and the carboxylic acid compound comprises one or more of formic acid, acetic acid, propionic acid, terephthalic acid, benzoic acid and citric acid.
Specifically, the adhesive is one or two groups of mixtures of styrene-butadiene rubber and carboxymethyl cellulose, and the conductive agent is acetylene black or conductive carbon black.
The invention also provides a preparation method of the composite lithium battery cathode material, which comprises the following steps:
s1, sequentially adding a conductive agent and dopamine into a reaction container containing a tris buffer solution, wherein the weight ratio of the dopamine to the conductive agent is 1: 3, uniformly stirring at room temperature, performing suction filtration, and drying at room temperature to obtain polydopamine-coated conductive agent particles, wherein the pH value of a trihydroxymethylaminomethane buffer solution is 8.4;
s2, mixing and stirring the nano nonmetal matrix and the modifier for 5 minutes, adding the metal dopant, continuously stirring, heating the mixture to 160 ℃, drying, keeping the temperature for 2 hours, and taking out the mixture;
s3, adding a carbonization regulator into the mixture obtained in the step S2, and then heating and carbonizing the mixture in an inert gas atmosphere at the temperature of 600 ℃ for 1 hour, wherein the inert gas is one of nitrogen, argon and helium;
s4, mixing the products of S1 and S3, adding a binder and an inorganic silicon salt aqueous solution, mixing and stirring in a vacuum stirrer for 15 minutes, adjusting the viscosity to 2000mPa & S, and sieving with a 100-mesh sieve to obtain a negative electrode gel-like mixture;
s5, finally, adding the polyvinylidene fluoride into the product of S4, mixing and stirring for 6 minutes, heating to 60 ℃, adding an N-methyl-2-pyrrolidone solvent, uniformly coating the solution on a copper foil, and pressing into tablets after vacuum drying treatment.
Specifically, what stir used is the helical agitator of inverter motor drive, and stirring speed is 1000 r/min.
Specifically, the vacuum drying treatment is drying for 8 hours in a vacuum drying oven at the temperature of 80 ℃, and the pressure of pressing is 5 MPa.
Example 2
The formula of the composite lithium battery negative electrode material is as follows: 8 parts of a nano nonmetal substrate, 6 parts of a metal dopant, 6 parts of an inorganic silicate, 6 parts of polyvinylidene fluoride, 3 parts of a modifier, 4 parts of a carbonization regulator, 4 parts of a conductive agent, 3 parts of an adhesive and 2 parts of dopamine.
Specifically, the nano non-metal matrix comprises one or more of boron carbide, silicon nitride, zinc oxide or calcium sulfate, and the nano non-metal matrix is modified by mixing and stirring with calcium hydroxide at 60 ℃ for 13 minutes before use.
Specifically, the metal dopant comprises one or more of silver nitrate, copper oxide or copper powder.
Specifically, the inorganic silicate is one or a mixture of bentonite, clay, montmorillonite and kaolin.
Specifically, the modifier is one or more of ethanol, methyl acrylate, phosphoric acid, methyl acrylate, potassium chloride and nitrogen dioxide.
Specifically, the carbonization regulator comprises one or more of alkane, ether compounds, alcohol compounds, carboxylic acid compounds and inorganic nitrogen-containing compounds, and the alkane is C1～C10The alkane, ether compound comprises one or more of methyl ether, ethyl ether, n-butyl ether and ethylene oxide, the alcohol compound comprises one or more of methanol, ethanol, propanol and furfuryl alcohol, and the carboxylic acid compound comprises one or more of formic acid, acetic acid, propionic acid, terephthalic acid, benzoic acid and citric acid.
Specifically, the adhesive is one or two groups of mixtures of styrene-butadiene rubber and carboxymethyl cellulose, and the conductive agent is acetylene black or conductive carbon black.
The invention also provides a preparation method of the composite lithium battery cathode material, which comprises the following steps:
s1, sequentially adding a conductive agent and dopamine into a reaction container containing a tris buffer solution, wherein the weight ratio of the dopamine to the conductive agent is 1: 4, uniformly stirring at room temperature, performing suction filtration, and drying at room temperature to obtain polydopamine-coated conductive agent particles, wherein the pH value of the trihydroxymethylaminomethane buffer solution is 8.5;
s2, mixing and stirring the nano non-metal matrix and the modifier for 8 minutes, adding the metal dopant, continuously stirring, heating the mixture to 180 ℃, drying, keeping the temperature for 3 hours, and taking out the mixture;
s3, adding a carbonization regulator into the mixture obtained in the step S2, and then heating and carbonizing the mixture in an inert gas atmosphere, wherein the heating and carbonizing temperature is 800 ℃, the heating and carbonizing time is 5 hours, and the inert gas is one of nitrogen, argon and helium;
s4, mixing the products of S1 and S3, adding a binder and an inorganic silicon salt aqueous solution, mixing and stirring in a vacuum stirrer for 20 minutes, adjusting the viscosity to 3000mPa & S, and sieving with a 120-mesh sieve to obtain a negative electrode gel-like mixture;
s5, finally, adding polyvinylidene fluoride into the product of S4, mixing and stirring for 7 minutes, heating to 70 ℃, adding an N-methyl-2-pyrrolidone solvent, uniformly coating the solution on a copper foil, and pressing into tablets after vacuum drying treatment.
Specifically, the stirring is carried out by a spiral stirrer driven by a variable frequency motor, and the stirring speed is 1500 r/min.
Specifically, the vacuum drying treatment is drying for 16h in a vacuum drying oven at the temperature of 110 ℃, and the pressure of pressing is 7 MPa.
Example 3
The formula of the composite lithium battery negative electrode material is as follows: 10 parts of a nano nonmetal matrix, 7 parts of a metal dopant, 8 parts of an inorganic silicate, 9 parts of polyvinylidene fluoride, 4 parts of a modifier, 5 parts of a carbonization regulator, 6 parts of a conductive agent, 5 parts of an adhesive and 3 parts of dopamine.
Specifically, the nano non-metal matrix comprises one or more of boron carbide, silicon nitride, zinc oxide or calcium sulfate, and the nano non-metal matrix is modified by mixing and stirring with calcium hydroxide at 70 ℃ for 15 minutes before use.
Specifically, the metal dopant comprises one or more of silver nitrate, copper oxide or copper powder.
Specifically, the inorganic silicate is one or a mixture of bentonite, clay, montmorillonite and kaolin.
Specifically, the modifier is one or more of ethanol, methyl acrylate, phosphoric acid, methyl acrylate, potassium chloride and nitrogen dioxide.
Specifically, the carbonization regulator comprises one or more of alkane, ether compounds, alcohol compounds, carboxylic acid compounds and inorganic nitrogen-containing compounds, and the alkane is C1～C10The alkane, ether compound comprises one or more of methyl ether, ethyl ether, n-butyl ether and ethylene oxide, the alcohol compound comprises one or more of methanol, ethanol, propanol and furfuryl alcohol, and the carboxylic acid compound comprises one or more of formic acid, acetic acid, propionic acid, terephthalic acid, benzoic acid and citric acid.
Specifically, the adhesive is one or two groups of mixtures of styrene-butadiene rubber and carboxymethyl cellulose, and the conductive agent is acetylene black or conductive carbon black.
The invention also provides a preparation method of the composite lithium battery cathode material, which comprises the following steps:
s1, sequentially adding a conductive agent and dopamine into a reaction container containing a tris buffer solution, wherein the weight ratio of the dopamine to the conductive agent is 1: 5, uniformly stirring at room temperature, performing suction filtration, and drying at room temperature to obtain polydopamine-coated conductive agent particles, wherein the pH value of a trihydroxymethylaminomethane buffer solution is 8.6;
s2, mixing and stirring the nano non-metal matrix and the modifier for 10 minutes, adding the metal dopant, continuously stirring, heating the mixture to 200 ℃, drying, keeping the temperature for 4 hours, and taking out the mixture;
s3, adding a carbonization regulator into the mixture obtained in the step S2, and then heating and carbonizing the mixture in an inert gas atmosphere, wherein the heating and carbonizing temperature is 1000 ℃, the heating and carbonizing time is 10 hours, and the inert gas is one of nitrogen, argon and helium;
s4, mixing the products of S1 and S3, adding a binder and an inorganic silicon salt aqueous solution, mixing and stirring in a vacuum stirrer for 25 minutes, adjusting the viscosity to 4000mPa & S, and sieving by a sieve of 140 meshes to obtain a negative electrode gel-like mixture;
s5, finally, adding polyvinylidene fluoride into the product of S4, mixing and stirring for 8 minutes, heating to 80 ℃, adding an N-methyl-2-pyrrolidone solvent, uniformly coating the solution on a copper foil, and pressing into tablets after vacuum drying treatment.
Specifically, the stirring is carried out by a spiral stirrer driven by a variable frequency motor, and the stirring speed is 2000 r/min.
Specifically, the vacuum drying treatment is drying for 24 hours in a vacuum drying oven at the temperature of 140 ℃, and the pressure of pressing is 10 MPa.
In summary, the following steps: compared with the traditional product, the composite lithium battery cathode material and the preparation method thereof provided by the invention can shorten the diffusion distance of lithium ions and improve the diffusion coefficient of the lithium ions through the nano nonmetal substrate, have better capacity performance under larger current, can ensure that metal particles are attached to the surface of the nano nonmetal substrate and are coated by dopamine, can reduce contact resistance and play a role of dispersion, greatly improve the electrochemical performance, particularly the rate capability, of the material and can improve the integral conductivity, realize multiple crosslinking and self-repairing functions, can solve the adverse effect of repeated volume change of a silicon cathode in the charging and discharging process of a battery by adding inorganic silicon salt, improve the cycle performance of the silicon-based cathode material, have small specific capacity attenuation capacity of the battery, have simple and practical preparation method and cheap and easily-obtained used materials, the method is convenient for preparing the cathode material with excellent electrochemical performance on a large scale, is safe and stable, has good conductivity, long service life and wide application range, and is beneficial to popularization.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.

Claims (3)

1. A preparation method of a composite lithium battery negative electrode material is characterized by comprising the following steps:
s1, sequentially adding a conductive agent and dopamine into a reaction container containing a tris buffer solution, wherein the weight ratio of the dopamine to the conductive agent is 1: 3-5, then uniformly stirring at room temperature, performing suction filtration, and drying at room temperature to obtain polydopamine-coated conductive agent particles, wherein the pH value of the trihydroxymethylaminomethane buffer solution is 8.4-8.6;
s2, mixing and stirring the nano non-metal matrix and the modifier for 5-10 minutes, adding the metal dopant, continuously stirring, heating the obtained mixture to 160-200 ℃, drying, keeping the temperature for 2-4 hours, and taking out the dried mixture;
s3, adding a carbonization regulator into the dried mixture obtained in the step S2, and then heating and carbonizing the mixture in an inert gas atmosphere at the temperature of 600-1000 ℃ for 1-10 hours, wherein the inert gas is one of nitrogen, argon and helium;
s4, mixing the products in S1 and S3, adding the adhesive and the inorganic silicon salt aqueous solution, mixing and stirring for 15-25 minutes in a vacuum stirrer, adjusting the viscosity to 2000-4000 mPa & S, and sieving with a 100-140-mesh sieve to obtain a negative electrode gel-like mixture;
s5, finally, adding polyvinylidene fluoride into the product obtained in the step S4, mixing and stirring for 6-8 minutes, heating to 60-80 ℃, adding an N-methyl-2-pyrrolidone solvent, uniformly coating the obtained solution on a copper foil, and pressing into tablets after vacuum drying;
the nanometer non-metal matrix comprises one or more of boron carbide, silicon nitride, zinc oxide or calcium sulfate, and the nanometer non-metal matrix is mixed and stirred with calcium hydroxide at the temperature of 50-70 ℃ for 10-15 minutes before use to be modified; the metal dopant comprises one or more of silver nitrate, copper oxide or copper powder; the inorganic silicate is one or a mixture of bentonite, clay, montmorillonite and kaolin; the modifier is one or more of methyl acrylate, phosphoric acid, potassium chloride and nitrogen dioxide; the carbonization regulator comprises one or more of alkane, ether compounds, alcohol compounds, carboxylic acid compounds and inorganic nitrogen-containing compounds, and the alkane is C1～C10The ether compound comprises one or more of methyl ether, ethyl ether, n-butyl ether and ethylene oxide, and the alcohol compound comprises methanol and ethanolOne or more of alcohol, propanol and furfuryl alcohol, and the carboxylic acid compound comprises one or more of formic acid, acetic acid, propionic acid, terephthalic acid, benzoic acid and citric acid; the adhesive is styrene butadiene rubber, and the conductive agent is acetylene black or conductive carbon black.
2. The method for preparing the negative electrode material of the composite lithium battery as claimed in claim 1, wherein the method comprises the following steps: the stirring is carried out by a spiral stirrer driven by a variable frequency motor, and the stirring speed is 1000-2000 r/min.
3. The method for preparing the negative electrode material of the composite lithium battery as claimed in claim 1, wherein the method comprises the following steps: the vacuum drying treatment is drying for 8-24 hours in a vacuum drying oven at the temperature of 80-140 ℃, and the pressing pressure is 5-10 MPa.
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