CN111224105A - Multi-stage carbon-coated and multi-time high-temperature-disproportionation-improved silicon-containing negative electrode material and preparation method and application thereof - Google Patents

Multi-stage carbon-coated and multi-time high-temperature-disproportionation-improved silicon-containing negative electrode material and preparation method and application thereof Download PDF

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CN111224105A
CN111224105A CN202010146035.1A CN202010146035A CN111224105A CN 111224105 A CN111224105 A CN 111224105A CN 202010146035 A CN202010146035 A CN 202010146035A CN 111224105 A CN111224105 A CN 111224105A
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silicon
temperature
carbon
disproportionation
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崔大祥
张道明
张芳
王亚坤
阳靖峰
卢玉英
焦靖华
葛美英
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Shanghai National Engineering Research Center for Nanotechnology 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
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    • 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 provides a multi-stage carbon-coated and multi-time high-temperature disproportionation improved silicon-containing cathode material, a preparation method and application thereof, wherein the molecular formula of the silicon-containing cathode material is as follows: SiO 2x（0<x<2) The multi-stage coating is characterized in that the surface of a silicon material is coated with a multi-layer carbon material, the material consists of silicon subjected to multiple high-temperature disproportionation and a carbon coating layer coated on the silicon, and the total content of carbon is 2-10 wt%. The multi-layer coated silicon-containing negative electrode material is formed by multi-stage coating and multi-time disproportionation, so that the characteristics of uneven coating of the silicon-containing material, inhibition of expansion of the silicon-containing material and the like are improved, and the gram volume of the silicon-containing material is continuously increased by multi-time disproportionation, so that the defects of cycle stability and expansion of the silicon-containing material are improved. The preparation method provided by the invention is simple, and the disproportionation and carbonization coating of the inferior silicon are synthesized into one stepThe method can be completed, can be prepared in the existing equipment, does not need to introduce new equipment, improves the material performance and saves the production cost.

Description

Multi-stage carbon-coated and multi-time high-temperature-disproportionation-improved silicon-containing negative electrode material and preparation method and application thereof
Technical Field
The invention relates to a inferior silicon negative electrode material and a preparation method for improving coating performance, in particular to a inferior silicon negative electrode material improved by multistage carbon coating and multiple high-temperature disproportionation, a preparation method and application thereof, and belongs to the technical field of lithium ion batteries.
Background
At present, a commercial lithium ion battery mainly adopts a graphite negative electrode material, but the theoretical specific capacity of the lithium ion battery is 372mAh/g and is close to the theoretical value of the graphite negative electrode material, so that the development potential of the graphite negative electrode material is limited, and the wide requirements of the whole energy industry on the high-specific-energy and high-power-density lithium ion battery are difficult to meet at present.
Therefore, in recent years, SiOxThe advantages of its use in Si-based anode materials for lithium ion batteries have also begun to emerge, with the introduction of oxygen, so that the first lithium insertion generates inert components, which also results in a reduction in absolute volume under the action of lithium de-insertion. SiO in contrast to elemental siliconxHas more practical potential and has high specific energy prospect for lithium ion battery materials. Currently, modification of the silicon is mainly focused on particle size control, material surface modification, material surface coating and the like.
Therefore, the inventor researches a preparation method of the improved inferior silicon negative electrode material by multistage carbon coating and multiple high-temperature disproportionation, the method is simple and convenient to operate, simple in process, suitable for industrial production, applied to the negative electrode material of the lithium battery, high in first-efficiency, large in gram-volume, good in cycle performance, capable of improving the material performance and capable of effectively saving the production cost.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a sub-silicon anode material with improved multi-stage carbon coating and multi-stage high-temperature disproportionation.
Yet another object of the present invention is to: provides a preparation method of the above-mentioned multi-stage carbon-coated and multi-high temperature disproportionation improved inferior silicon negative electrode material product.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: a multi-stage carbon-coated and multi-time high-temperature disproportionation improved silicon-free negative electrode material is characterized in that a multi-layer carbon material is coated on the surface of a silicon-free material, and the molecular formula of the silicon-free material is as follows: SiOx (0 < x < 2), the material obtained by multiple high-temperature disproportionation after the surface of the silicon material is coated with a multi-layer carbon material consists of silicon and a carbon coating layer coated on the silicon, wherein the total content of carbon is 2-10 wt%.
The invention also provides a preparation method of the multilevel carbon-coated and multi-time high-temperature disproportionation improved silicon-free cathode material, which comprises the following steps:
(1) selecting a silicon raw material and a carbon source raw material: the carbon source raw material is one or a composition of asphalt, glucose, polyvinylpyrrolidone and phenolic resin with micron-sized particle size; the particle size of the raw material of the inferior silicon is micron;
(2) preparing a multi-stage carbon-coated and multi-time high-temperature disproportionation improved silicon-containing negative electrode material: step one, adopting a wet mixing method, uniformly mixing a carbon source and a silicon material, carbonizing at a high temperature, and carrying out heat preservation coating to obtain a silicon material coated with a first carbon layer and disproportionated silicon; secondly, uniformly mixing the silicon material obtained in the first step and a second layer of carbon source raw material by adopting a wet coating method, and performing material carbon layer coating and silicon disproportionation by high-temperature carbonization and heat preservation, wherein the carbon source is a carbon source raw material which can be carbonized into a carbon layer in the high-temperature heat preservation process, and the first layer of carbon source raw material and the second layer of carbon source raw material are the same or different; in the process of carbonizing the coated carbon layer at high temperature, a step of disproportionating the inferior silicon is introduced, and the temperature is kept at the temperature at which the disproportionation of the inferior silicon occurs.
The multi-stage carbon coating and the multiple high-temperature disproportionation pass through the steps of the first step and the second step, and the material is subjected to multi-layer carbon coating and multiple silicon disproportionation processes by adopting multiple times of repetition.
The invention also provides an application of the improved silicon-containing negative electrode material based on the multi-stage carbon coating and the multi-time high-temperature disproportionation as the silicon-containing negative electrode material of the lithium ion battery.
The invention provides a preparation method of a multi-stage carbon-coated and multi-time high-temperature disproportionation improved silicon-containing cathode material, which is simple and convenient to operate and simple in process, completes carbonization coating and silicon-containing disproportionation in one step, is suitable for industrial production, is applied to a lithium battery cathode material, has high first-efficiency, large gram-volume and good cycle performance, improves the material performance, and can effectively save the production cost. The problems of nonuniform coating, charge-discharge expansion, poor cycle performance and the like of the current silicon-containing cathode material are solved.
Drawings
FIG. 1 is an SEM image of a carbon-coated silica material prepared in example 1; as can be seen, the fine particles are carbon particle material, and 1-2 microns are carbon-coated silicon material;
FIG. 2 is a graph showing the first charge-discharge efficiency and the first efficiency of the carbon-coated silylene material prepared in example 1; carrying out charge and discharge tests by using a new Wille battery test system, wherein the set cut-off voltage is 0.01-1.5V, and the used current multiplying power charge and discharge is 0.1C;
FIG. 3 is an SEM image of a carbon-coated silica material prepared in example 2; as can be seen, the fine particles are carbon particulate material, and 2-4 microns are carbon-coated silicon-containing material;
FIG. 4 is a graph showing the first charge-discharge efficiency and the first efficiency of the carbon-coated silylene material prepared in example 2; carrying out charge and discharge tests by using a new Wille battery test system, wherein the set cut-off voltage is 0.01-1.5V, and the used current multiplying power charge and discharge is 0.1C;
FIG. 5 is an SEM image of a carbon-coated silica material prepared in example 3; as can be seen, the fine particles are carbon particle material, and 1-3 microns are carbon-coated silicon material;
FIG. 6 is a graph showing the first charge/discharge and the first efficiency of the carbon-coated silylene material prepared in example 3, wherein the charge/discharge test was performed using a new Willebell test system, the cut-off voltage was set to 0.01-1.5V, and the current multiplying factor used was 0.1C.
Detailed Description
The present invention is described in detail by the following specific examples, but the scope of the present invention is not limited to these examples.
Example 1
A multi-stage carbon-coated and multi-time high-temperature disproportionation improved silicon-based negative electrode material is a silicon-based material with a surface coated with a multi-layer carbon material, and the molecular formula of the silicon-based material is as follows: SiOx (0 < x < 2), the material obtained by multiple high-temperature disproportionation consists of inferior silicon and a carbon coating coated on the inferior silicon, wherein, the total content of carbon is 2-10wt%, and the preparation method comprises the following steps:
(1) preparing materials: screening particle sizes of a silicon raw material and a carbon source raw material, wherein the particle size of the silicon raw material D50=2 microns, the particle size of a high-softening-point asphalt D50=5 μm, and the particle size of a low-softening-point asphalt D50=5 μm;
(2) preparing a multi-stage carbon-coated and multi-time high-temperature disproportionation improved silicon-containing negative electrode material: mixing materials by adopting a ball milling wet method, wherein the ball material ratio is 2:1, mixing a silicon material and high-softening-point asphalt, the mass ratio of the silicon material to the high-softening-point asphalt is 100:5, mixing the materials for 4 hours in alcohol, drying the materials in an oven at 80 ℃, placing the materials in a tubular furnace, keeping the temperature at 900 ℃ for 1 hour, increasing the temperature at the rate of 5 ℃/min, and naturally cooling the materials to normal temperature to obtain a silicon material coated with a first carbon layer and disproportionated silicon; and step two, mixing materials by a ball milling wet method, mixing the silicon material obtained in the step one with the low-softening-point asphalt at a ball-to-material ratio of 2:1, mixing the silicon material obtained in the step one with the low-softening-point asphalt at a mass ratio of 100:3 for 2h in alcohol, drying in an oven at 80 ℃, placing in a tube furnace, keeping the temperature at 900 ℃ for 1h at a heating rate of 5 ℃/min, and naturally cooling to normal temperature to obtain the silicon material subjected to carbon coating and disproportionation twice. As shown in FIG. 1, SEM shows that the fine particles are carbon particles and 1-2 microns are carbon-coated silica.
The product carbon-coated silicon material is mixed with a certain proportion of a binder (PAA, 40 wt%) and a conductive agent (SP, 10wt%) to prepare a working electrode, and the working electrode is stood for 24 hours after being assembled into a battery. Under the condition that the ambient temperature is 25 ℃, a new Wille battery test system is used for carrying out charge and discharge tests, the set cut-off voltage is 0.01-1.5V, and the current multiplying power charge and discharge is 0.1C. The first efficiency of the material half cell performance is 73.54% as shown in fig. 2, and compared with 60% of the first efficiency of the silicon raw material, the first efficiency of the material is obviously improved.
Example 2
A multi-stage carbon-coated and multi-time high-temperature disproportionation improved silicon-containing cathode material is prepared by the following steps:
(1) preparing materials: screening particle sizes of a silicon raw material and asphalt, wherein the particle size of the silicon raw material D50=2 microns, the particle size of the high-softening-point asphalt D50=5 μm, and the particle size of the low-softening-point asphalt D50=5 μm;
(2) preparing a multi-stage carbon-coated and multi-time high-temperature disproportionation improved silicon-containing negative electrode material: firstly, mixing materials by adopting a ball milling wet method, mixing a silicon material and low-softening-point asphalt at a ball-material ratio of 2:1, wherein the mass ratio of the silicon material to the low-softening-point asphalt is 100:4, mixing the materials in alcohol for 4 hours, uniformly mixing, drying in an oven at 80 ℃, then placing in a tube furnace, keeping the temperature at 900 ℃ for 1 hour, raising the temperature at the rate of 5 ℃/min, and naturally cooling to normal temperature to obtain a silicon material coated with a first carbon layer and disproportionated with silicon; and step two, mixing materials by a ball milling wet method, namely mixing the silicon material obtained in the step one with the high-softening-point asphalt at a ball-to-material ratio of 2:1, wherein the mass ratio of the silicon material obtained in the step one to the high-softening-point asphalt is 100:5, mixing the materials in alcohol for 2h, drying the materials in an oven at 80 ℃, placing the materials in a tube furnace, keeping the temperature at 900 ℃ for 1h at a heating rate of 5 ℃/min, and naturally cooling the materials to normal temperature to obtain the silicon material subjected to carbon coating and disproportionation twice, wherein fine particles are carbon particle materials and are carbon-coated silicon material with particle sizes of 2-4 microns as shown in figure 3.
The product carbon-coated silicon material is mixed with a certain proportion of a binder (PAA, 40 wt%) and a conductive agent (SP, 10wt%) to prepare a working electrode, and the working electrode is stood for 24 hours after being assembled into a battery. Under the condition that the ambient temperature is 25 ℃, a new Wille cell test system is used for carrying out charge-discharge test, the set cut-off voltage is 0.01-1.5V, the used current multiplying power charge-discharge is 0.1C, the first performance effect of the material half cell is 74.11 percent as shown in figure 4, and compared with the first performance of 60 percent of a silicon raw material, the first performance of the material is obviously improved.
Example 3
A multi-stage carbon-coated and multi-time high-temperature disproportionation improved silicon-containing cathode material is prepared by the following steps:
(1) preparing materials: screening the particle sizes of the silicon raw material and the asphalt, wherein the particle size of the silicon raw material D50=2 microns, the particle size of the asphalt D50=5 microns, and the particle size of the glucose is 1 micron;
(2) preparing a multi-stage carbon-coated and multi-time high-temperature disproportionation improved silicon-containing negative electrode material: firstly, mixing silicon monoxide and asphalt by adopting a ball milling wet method, mixing the silicon monoxide and the asphalt at a ball-to-material ratio of 2:1 and a mass ratio of 100:5 of the silicon monoxide to the asphalt with a high softening point, uniformly mixing the materials in alcohol for 4 hours, drying the materials in an oven at the temperature of 80 ℃, then placing the materials in a tube furnace, keeping the temperature at 900 ℃ for 1 hour at the heating rate of 5 ℃/min, and naturally cooling the materials to the normal temperature to obtain a silicon monoxide material coated with a first carbon layer and disproportionated silicon monoxide; and step two, mixing materials by a ball milling wet method, mixing the silicon material obtained in the step one with glucose at a ball-to-material ratio of 2:1 and a mass ratio of 100:9, mixing the materials in alcohol for 2 hours, drying the materials in an oven at 80 ℃, placing the materials in a tube furnace, keeping the temperature at 900 ℃ for 1 hour at a heating rate of 5 ℃/min, and naturally cooling the materials to the normal temperature. And obtaining the silicon material which is carbon-coated twice and disproportionated twice, wherein the SEM picture is shown in figure 5, fine particles are carbon particle materials, and 1-3 microns are carbon-coated silicon material.
The product carbon-coated silicon material is mixed with a certain proportion of a binder (PAA, 40 wt%) and a conductive agent (SP, 10wt%) to prepare a working electrode, and the working electrode is stood for 24 hours after being assembled into a battery. Under the condition that the ambient temperature is 25 ℃, a new Wille cell test system is used for carrying out charge and discharge tests, the set cut-off voltage is 0.01-1.5V, the used current multiplying power charge and discharge is 0.1C, the first effect of the material half cell performance is 72.5 percent as shown in figure 6, and compared with 60 percent of the first effect of a silicon raw material, the first effect of the material is obviously improved.

Claims (7)

1. The multi-stage carbon-coated and multi-time high-temperature disproportionation improved silicon-free cathode material is characterized in that the multi-stage carbon coating is a silicon-free material surface coated with a multi-layer carbon material, and the molecular formula of the silicon is as follows: SiOx (0 < x < 2), the material obtained by multiple high-temperature disproportionation after the surface of the silicon material is coated with a multi-layer carbon material consists of silicon and a carbon coating layer coated on the silicon, wherein the total content of carbon is 2-10 wt%.
2. The method for preparing the multi-stage carbon-coated and multi-stage high-temperature disproportionation improved negative electrode material of silicon as claimed in claim 1, which is characterized by comprising the following steps:
(1) selecting a silicon raw material and a carbon source raw material: the carbon source raw material is one or a composition of asphalt, glucose, polyvinylpyrrolidone and phenolic resin with micron-sized particle size; the particle size of the raw material of the inferior silicon is micron;
(2) preparing a multi-stage carbon-coated and multi-time high-temperature disproportionation improved silicon-containing negative electrode material: step one, adopting a wet mixing method, uniformly mixing a carbon source and a silicon material, carbonizing at a high temperature, and carrying out heat preservation coating to obtain a silicon material coated with a first carbon layer and disproportionated silicon; secondly, uniformly mixing the silicon material obtained in the first step and a second layer of carbon source raw material by adopting a wet coating method, and performing material carbon layer coating and silicon disproportionation by high-temperature carbonization and heat preservation, wherein the carbon source is a carbon source raw material which can be carbonized into a carbon layer in the high-temperature heat preservation process, and the first layer of carbon source raw material and the second layer of carbon source raw material are the same or different; in the process of carbonizing the coated carbon layer at high temperature, a step of disproportionating the inferior silicon is introduced, and the temperature is kept at the temperature at which the disproportionation of the inferior silicon occurs.
3. The method for preparing a multi-stage carbon-coated and multi-time high-temperature disproportionation modified silicon-less anode material as claimed in claim 2, wherein the multi-stage carbon coating and multi-time high-temperature disproportionation are processed by the steps of the first step and the second step, and the multi-stage carbon coating and multi-time high-temperature disproportionation are repeated for multiple times, so that the material is subjected to multi-layer carbon coating and multi-time silicon-less disproportionation.
4. The method for preparing the multi-stage carbon-coated and multi-stage high-temperature disproportionation improved sub-silicon anode material according to claim 2 or 3, characterized by comprising the following steps:
(1) preparing materials: screening particle sizes of a silicon raw material and a carbon source raw material, wherein the particle size of the silicon raw material D50=2 microns, the particle size of a high-softening-point asphalt D50=5 μm, and the particle size of a low-softening-point asphalt D50=5 μm;
(2) preparing a multi-stage carbon-coated and multi-time high-temperature disproportionation improved silicon-containing negative electrode material: mixing materials by adopting a ball milling wet method, wherein the ball material ratio is 2:1, mixing a silicon material and high-softening-point asphalt, the mass ratio of the silicon material to the high-softening-point asphalt is 100:5, mixing the materials for 4 hours in alcohol, drying the materials in an oven at 80 ℃, placing the materials in a tubular furnace, keeping the temperature at 900 ℃ for 1 hour, increasing the temperature at the rate of 5 ℃/min, and naturally cooling the materials to normal temperature to obtain a silicon material coated with a first carbon layer and disproportionated silicon; and step two, mixing materials by a ball milling wet method, mixing the silicon material obtained in the step one with the low-softening-point asphalt at a ball-to-material ratio of 2:1, mixing the silicon material obtained in the step one with the low-softening-point asphalt at a mass ratio of 100:3 for 2h in alcohol, drying in an oven at 80 ℃, placing in a tube furnace, keeping the temperature at 900 ℃ for 1h at a heating rate of 5 ℃/min, and naturally cooling to normal temperature to obtain the silicon material subjected to carbon coating and disproportionation twice.
5. The method for preparing the multi-stage carbon-coated and multi-stage high-temperature disproportionation improved sub-silicon anode material according to claim 2 or 3, characterized by comprising the following steps:
(1) preparing materials: screening particle sizes of a silicon raw material and asphalt, wherein the particle size of the silicon raw material D50=2 microns, the particle size of the high-softening-point asphalt D50=5 μm, and the particle size of the low-softening-point asphalt D50=5 μm;
(2) preparing a multi-stage carbon-coated and multi-time high-temperature disproportionation improved silicon-containing negative electrode material: firstly, mixing materials by adopting a ball milling wet method, mixing a silicon material and low-softening-point asphalt at a ball-material ratio of 2:1, wherein the mass ratio of the silicon material to the low-softening-point asphalt is 100:4, mixing the materials in alcohol for 4 hours, uniformly mixing, drying in an oven at 80 ℃, then placing in a tube furnace, keeping the temperature at 900 ℃ for 1 hour, raising the temperature at the rate of 5 ℃/min, and naturally cooling to normal temperature to obtain a silicon material coated with a first carbon layer and disproportionated with silicon; and step two, mixing materials by a ball milling wet method, namely mixing the silicon material obtained in the step one with the high-softening-point asphalt at a ball-to-material ratio of 2:1, wherein the mass ratio of the silicon material obtained in the step one to the high-softening-point asphalt is 100:5, mixing the materials in alcohol for 2 hours, drying the materials in an oven at 80 ℃, placing the materials in a tubular furnace, keeping the temperature at 900 ℃ for 1 hour, increasing the temperature at the rate of 5 ℃/min, and naturally cooling the materials to normal temperature to obtain the silicon material subjected to carbon coating and disproportionation twice.
6. The method for preparing the multi-stage carbon-coated and multi-stage high-temperature disproportionation improved sub-silicon anode material according to claim 2 or 3, characterized by comprising the following steps:
(1) preparing materials: screening the particle sizes of the silicon raw material and the asphalt, wherein the particle size of the silicon raw material D50=2 microns, the particle size of the asphalt D50=5 microns, and the particle size of the glucose is 1 micron;
(2) preparing a multi-stage carbon-coated and multi-time high-temperature disproportionation improved silicon-containing negative electrode material: firstly, mixing silicon monoxide and asphalt by adopting a ball milling wet method, mixing the silicon monoxide and the asphalt at a ball-to-material ratio of 2:1 and a mass ratio of 100:5 of the silicon monoxide to the asphalt with a high softening point, uniformly mixing the materials in alcohol for 4 hours, drying the materials in an oven at the temperature of 80 ℃, then placing the materials in a tube furnace, keeping the temperature at 900 ℃ for 1 hour at the heating rate of 5 ℃/min, and naturally cooling the materials to the normal temperature to obtain a silicon monoxide material coated with a first carbon layer and disproportionated silicon monoxide; and step two, mixing materials by a ball milling wet method, mixing the silicon material obtained in the step one with glucose at a ball-to-material ratio of 2:1 and a mass ratio of 100:9, mixing the materials in alcohol for 2 hours, uniformly mixing, drying in an oven at 80 ℃, placing in a tube furnace, keeping the temperature at 900 ℃ for 1 hour at a heating rate of 5 ℃/min, and naturally cooling to normal temperature to obtain the silicon material subjected to carbon coating and disproportionation twice.
7. Use of the multi-stage carbon-coated and multiple high temperature disproportionation modified siliconized negative electrode material of claim 1 as a siliconized negative electrode material for lithium ion batteries.
CN202010146035.1A 2020-03-05 2020-03-05 Multi-stage carbon-coated and multi-time high-temperature-disproportionation-improved silicon-containing negative electrode material and preparation method and application thereof Pending CN111224105A (en)

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