CN114613972A - Silicon carbide oxide negative electrode material for lithium ion battery and preparation method thereof - Google Patents

Silicon carbide oxide negative electrode material for lithium ion battery and preparation method thereof Download PDF

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Publication number
CN114613972A
CN114613972A CN202210363025.2A CN202210363025A CN114613972A CN 114613972 A CN114613972 A CN 114613972A CN 202210363025 A CN202210363025 A CN 202210363025A CN 114613972 A CN114613972 A CN 114613972A
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Prior art keywords
silicon monoxide
lithium ion
negative electrode
ion battery
electrode material
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岳之浩
金晨鑫
周浪
徐国军
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Gongqingcheng Optical Hydrogen Storage Technology Research Institute Of Nanchang University
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Gongqingcheng Optical Hydrogen Storage Technology Research Institute Of Nanchang University
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Priority to CN202210363025.2A priority Critical patent/CN114613972A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes

Abstract

The invention discloses a preparation method of a silicon carbide oxide negative electrode material for a lithium ion battery, which comprises the following steps: (1) placing the silicon monoxide particles in a vacuum heat treatment furnace; (2) after the set temperature is reached, introducing a gaseous carbon source to coat a carbon layer on the surface of the silicon monoxide particles; (3) after the set temperature is reached, introducing a gaseous nitrogen source to simultaneously dope nitrogen into the carbon layer and the silicon monoxide particles; the invention also discloses the silicon monoxide carbon cathode material for the lithium ion battery, which is prepared by the method. The preparation method of the negative electrode material can improve the overall conductivity of the negative electrode material, and can obviously inhibit the volume expansion effect of the negative electrode material, so that the electrochemical performance of the silicon monoxide negative electrode material is expected to be improved.

Description

Silicon carbide oxide negative electrode material for lithium ion battery and preparation method thereof
Technical Field
The invention relates to the technical field of new energy materials, in particular to a silicon carbide oxide negative electrode material for a lithium ion battery and a preparation method thereof.
Background
Graphite-based negative electrode materials widely used in industry cannot meet the requirements of high-energy density lithium ion batteries due to low specific capacity (372 mAh/g). Therefore, many researchers are studying new anode materials such as silicon-based anode materials. Wherein, the silicon oxide (SiO)x0 < x < 2) negative electrode materials are of great interest due to their high theoretical specific capacity (2100mAh/g) and relatively excellent cycle life. However, the silicon oxide negative electrode material still has the problems of poor conductivity and severe volume expansion during charge and discharge. In the existing solutions, a pure carbon coating method is mostly adopted to modify a silicon oxide material, but the conductivity of the silicon oxide negative electrode material cannot be fundamentally improved.
Disclosure of Invention
The invention aims to provide a silicon carbide oxide negative electrode material for a lithium ion battery and a preparation method thereof aiming at the defects of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a silicon monoxide carbon negative electrode material for a lithium ion battery comprises the following steps:
step (1), putting the silicon monoxide particles into a vacuum heat treatment furnace;
step (2), after the set temperature is reached, introducing a gaseous carbon source to coat a carbon layer on the surface of the silicon monoxide particles;
and (3) introducing a gaseous nitrogen source after the set temperature is reached, so that nitrogen is doped into the carbon layer and the silicon monoxide particles simultaneously.
Further, the vacuum heat treatment furnace is preferably a rotary vacuum tube furnace.
Further, the set temperature in the step (2) is preferably 600-.
Further, the gaseous carbon source in the step (2) is preferably acetylene or methane.
Further, the carbon layer formed in the step (2) preferably has a thickness of 5 to 20 nm.
Further, the set temperature in the step (3) is preferably 700-1000 ℃.
Further, the gaseous nitrogen source in the step (3) is preferably ammonia gas.
Further, the mass content of the nitrogen element formed in the step (3) is 0.01-1%.
The invention also provides a silicon carbide oxide cathode material for the lithium ion battery, which is prepared by the method.
The method comprises the steps of sequentially filling a gaseous carbon source and a gaseous nitrogen source in a high-temperature environment to form a uniform carbon coating layer on the surface of the silicon oxide particles, and then doping nitrogen into the carbon layer and the silicon oxide to form the silicon oxide carbon negative electrode material for the lithium ion battery.
The gaseous carbon source is adopted for thermal decomposition and then is deposited on the surface of the silicon oxide particles, so that the silicon oxide particles are isolated from the electrolyte, the direct contact between the silicon oxide negative electrode material and the electrolyte can be avoided, and the repeated formation of an SEI film is avoided. Compared with the conventional liquid-phase carbon coating method, the gaseous carbon coating method can make the thickness of the carbon layer more uniform and controllable. The nitrogen doping has the function of improving the conductivity of the silicon monoxide particles and the conductivity of the coated carbon layer.
The beneficial effects of the invention include:
(1) the preparation method of the cathode material can dope nitrogen into the carbon layer and the silicon monoxide particles simultaneously, can fundamentally and obviously improve the conductivity of the material, and can obviously inhibit volume expansion in the charging and discharging processes.
(2) The negative electrode material structure of the present invention is expected to have both excellent cycle stability and rate characteristics.
Drawings
FIG. 1 is a schematic structural diagram of the present invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings.
Example 1
The preparation method of the silicon monoxide carbon negative electrode material for the lithium ion battery shown in the attached figure 1 is as follows: (1) putting the silica particles with the particle size of 1 mu m into a rotary vacuum tube furnace; (2) when the temperature reaches 900 ℃, introducing acetylene to coat a carbon layer with the thickness of 5nm on the surface of the silicon monoxide particles; (3) and (3) introducing ammonia gas at 900 ℃ without changing the temperature, and doping nitrogen into the carbon layer and the silicon monoxide, wherein the nitrogen content is 0.5%. The first discharge capacity of the prepared negative electrode material is 2000mAh/g, the capacity retention rate is 90% after the negative electrode material is cycled for 300 times at 0.5C, and the capacity retention rate is 84% after the negative electrode material is cycled for 300 times at 2C.
Example 2
The preparation method of the silicon monoxide carbon negative electrode material for the lithium ion battery shown in the attached figure 1 is as follows: (1) putting the silicon monoxide particles with the particle size of 1 mu m into a rotary vacuum tube furnace; (2) introducing methane after the temperature reaches 1000 ℃ to coat a carbon layer with the thickness of 10nm on the surface of the silicon monoxide particles; (3) and (3) introducing ammonia gas at 1000 ℃ without changing the temperature, and doping nitrogen into the carbon layer and the silicon monoxide, wherein the nitrogen content is 0.8%. The first discharge capacity of the prepared negative electrode material is 1860mAh/g, the capacity retention rate is 91% after the negative electrode material is cycled for 300 times at 0.5C, and the capacity retention rate is 86% after the negative electrode material is cycled for 300 times at 2C.
Example 3
The preparation method of the silicon monoxide carbon negative electrode material for the lithium ion battery shown in the attached figure 1 comprises the following steps: (1) putting the silicon monoxide particles with the particle size of 1 mu m into a rotary vacuum tube furnace; (2) when the temperature reaches 900 ℃, methane is introduced to coat a carbon layer with the thickness of 8nm on the surface of the silicon monoxide particles; (3) and (3) introducing ammonia gas after the temperature is raised to 1000 ℃, and doping nitrogen into the carbon layer and the silicon monoxide, wherein the nitrogen content is 0.6%. The first discharge capacity of the prepared negative electrode material is 1900mAh/g, the capacity retention rate of 88% after 0.5C circulation and 300 times and the capacity retention rate of 81% after 2C circulation and 300 times.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (9)

1. A preparation method of a silicon carbide oxide negative electrode material for a lithium ion battery is characterized by comprising the following steps:
step (1), putting the silicon monoxide particles into a vacuum heat treatment furnace;
step (2), after the set temperature is reached, introducing a gaseous carbon source to coat a carbon layer on the surface of the silicon monoxide particles;
and (3) introducing a gaseous nitrogen source after the set temperature is reached, so that nitrogen is doped into the carbon layer and the silicon monoxide particles simultaneously.
2. The method for preparing the silicon monoxide carbon anode material for the lithium ion battery according to claim 1, wherein the vacuum heat treatment furnace is a rotary vacuum tube furnace.
3. The method for preparing a silicon monoxide carbon anode material for a lithium ion battery as claimed in claim 1, wherein the set temperature in the step (2) is 600-1000 ℃.
4. The method for preparing a silicon monoxide carbon anode material for a lithium ion battery according to claim 1, wherein the gaseous carbon source in the step (2) is acetylene or methane.
5. The method for preparing a silicon monoxide carbon anode material for a lithium ion battery according to claim 1, wherein the carbon layer formed in the step (2) has a thickness of 5-20 nm.
6. The method for preparing a silicon monoxide carbon anode material for a lithium ion battery as claimed in claim 1, wherein the set temperature in the step (3) is 700-1000 ℃.
7. The method for preparing a silicon monoxide carbon anode material for a lithium ion battery according to claim 1, wherein the gaseous nitrogen source in the step (3) is ammonia gas.
8. The preparation method of the silicon monoxide carbon negative electrode material for the lithium ion battery, according to claim 1, characterized in that the nitrogen element formed in the step (3) is contained in an amount of 0.01-1% by mass.
9. A silicon monoxide carbon negative electrode material for a lithium ion battery, which is characterized by being prepared by the preparation method of any one of claims 1 to 8.
CN202210363025.2A 2022-04-08 2022-04-08 Silicon carbide oxide negative electrode material for lithium ion battery and preparation method thereof Pending CN114613972A (en)

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CN113363430A (en) * 2020-03-06 2021-09-07 溧阳天目先导电池材料科技有限公司 Soft carbon coated boron-doped silicon-based negative electrode material and preparation method and application thereof
CN113809312A (en) * 2020-06-15 2021-12-17 溧阳天目先导电池材料科技有限公司 Nitrogen-doped soft carbon-coated silicon-based lithium ion negative electrode material and preparation method and application thereof
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