CN115959671A - Porous carbon network modified silicon monoxide composite negative electrode material and preparation and application thereof - Google Patents
Porous carbon network modified silicon monoxide composite negative electrode material and preparation and application thereof Download PDFInfo
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- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
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Images
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- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a porous carbon network modified silicon monoxide composite negative electrode material, and preparation and application thereof. Firstly, coating basic nickel oxide on the surface of a silica particle by a solvent method; then nickel oxide is generated by reaction at 350 ℃; then reducing in hydrogen atmosphere to obtain the metallic nickel-coated silicon monoxide particles; and finally, a carbon coating with a porous net structure grows on the surface of the metal nickel-coated silicon oxide particles in situ by adopting a plasma enhanced chemical vapor deposition method, so that the conductivity of the composite material is effectively improved. The porous carbon network modified silicon monoxide composite negative electrode material prepared by the invention has excellent structural stability and cycling stability, and effectively solves the problem of volume expansion of the silicon monoxide material in the charging and discharging processes.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a porous carbon network modified silicon monoxide composite negative electrode material, and a preparation method and application thereof.
Background
Compared with other rechargeable batteries, the lithium ion battery has higher energy density and working voltage and lower self-discharge and maintenance requirements, and is widely applied to various electronic equipment and electric automobiles. However, the graphite negative electrode currently commercialized has a lower theoretical specific capacity (372 mAh g) -1 ) Meanwhile, because the working potential is low, lithium dendrite is easy to generate, serious potential safety hazard is caused, and urgent requirements of application environments such as portable electronic equipment and electric automobiles on high energy density and high operation reliability cannot be met.
Si(SiO x ) The base material is considered as a new material which is most hopeful to replace the traditional graphite negative electrode due to abundant natural resources, high specific capacity and proper lithium intercalation potential. SiO in contrast to Si material x The material is inert due to in-situ formation during alloyingLithium oxide (Li) 2 O) and lithium silicate (Li) 4 SiO 4 ) Helping to build a stable Solid Electrolyte Interface (SEI) layer. But SiO x The negative electrode had a large volume change (about 200%) and poor electron conductivity (about 6.7X 10) -4 s cm -1 ) And the like, resulting in poor electrochemical performance. In order to solve the problems, the invention provides an in-situ reduction nickel oxide catalyst, which adopts a Plasma Enhanced Chemical Vapor Deposition (PECVD) method to grow a porous carbon network on the surface of a silicon oxide to relieve SiO x The volume of the material expands in the charging and discharging processes, so that a stable SEI film is promoted to be formed on the surface, and the cycling stability of the silicon monoxide negative electrode material is obviously improved.
Disclosure of Invention
The invention aims to provide a method for preparing a porous carbon network modified silicon monoxide composite cathode material by using in-situ reduced nickel oxide as a catalyst and adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method. The material has the advantages of high conductivity, high specific surface area and the like, and simultaneously relieves SiO x Volume effect of materials in lithium battery applications.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a porous carbon network modified silicon monoxide composite negative electrode material is provided, the composite negative electrode material is a carbon coating with a three-dimensional network structure attached to the surface of silicon monoxide particles, and the preparation method comprises the following steps:
step 1: pretreating the silica powder, namely dispersing the silica powder in 1mol/L KOH solution, stirring for 4 hours at room temperature, and washing the mixture to be neutral by using deionized water to obtain the silica powder with rough surface;
step 2: dispersing the silicon monoxide powder obtained in the step 1 in deionized water, and adding a mixed solution of nickel acetate and ammonium persulfate;
and 3, step 3: dissolving a certain amount of ammonia water solution in deionized water to dilute by 100 times, slowly dropwise adding the diluted ammonia water solution into the mixed solution obtained in the step (2), stirring at room temperature for 30min after dropwise adding is finished, washing with the deionized water to be neutral, and drying in an oven at 80 ℃ for 12 hours to obtain the silica powder with the surface attached with the basic nickel oxide;
and 4, step 4: placing the silicon oxide powder with the surface adhered with the basic nickel oxide obtained in the step 3 into a tubular furnace, growing a layer of carbon layer with a porous reticular structure in situ by adopting a plasma enhanced chemical vapor deposition method, and forming the silicon oxide composite material packaged by the carbon coating with the porous reticular structure, wherein the specific process comprises the following steps: placing the silicon monoxide powder with the surface adhered with the basic nickel oxide obtained in the step 3 into a porcelain boat, placing the porcelain boat into a tube furnace, heating the porcelain boat to 350 ℃ in an inert atmosphere to convert the basic nickel oxide into nickel oxide, introducing inert gas and reducing gas, and keeping the temperature for 60min to reduce the nickel oxide into a nickel simple substance; and continuously heating to 800-1000 ℃ in the mixed gas atmosphere, introducing carbon source gas and carrier gas to keep the air pressure in the tubular furnace between 100 and 110Pa, then turning on an inductively coupled plasma radio-frequency power supply, controlling the output power of the power supply to be 300W, controlling the carbon growth time to be 30min, turning off the inductively coupled plasma radio-frequency power supply after the reaction is finished, stopping introducing the carbon source gas and the carrier gas, and cooling to room temperature in the argon atmosphere to obtain the carbon coating packaged silicon monoxide composite cathode material with the three-dimensional network structure.
Preferably, the step 1 is performed by using a silica powder having a particle size of 1 to 10 μm.
Preferably, the inert gas in the step 4 is any one of argon, helium and neon, the flow rate is 200sccm, the reducing gas is hydrogen gas, and the flow rate is 20sccm.
Preferably, the carbon source gas in the step 4 is one or a mixture of several of methane, ethane and acetylene, the flow rate is 20sccm, the carrier gas is hydrogen, and the carrier gas assists ionization of the carbon source gas and has a flow rate of 10sccm.
Preferably, in the step 4, the heating rate of heating from room temperature to 350 ℃ is 2 ℃/min, the temperature is kept at 350 ℃ for 60min, and then the reduction gas hydrogen is introduced to reduce the nickel oxide.
Preferably, in the step 4, the heating rate from 350 ℃ to 800-1000 ℃ is 5 ℃/min, the temperature is kept at 800-1000 ℃ for 20min, and then carbon source gas is introduced.
Preferably, the mass ratio of nickel acetate to silica in step 2 is 1.
Preferably, an ammonia water solution with an initial concentration of 28% -37% is adopted in the step 3, wherein the molar ratio of the ammonia water solution to the nickel acetate is 2.
The invention also provides the porous carbon network modified silicon monoxide composite negative electrode material prepared by the preparation method.
The invention also provides application of the porous carbon network modified silicon monoxide composite negative electrode material in preparation of a secondary battery.
The beneficial effects of the invention are as follows: the method for synthesizing the nickel catalyst by adopting the solvent method is safe and reliable, has high repeatability, low price of raw materials and is environment-friendly, and the prepared metal nickel catalyst is obtained by reducing nickel oxide by hydrogen, and can rapidly grow the carbon coating with the three-dimensional network structure on the surface of the silicon oxide by utilizing a plasma enhanced chemical vapor deposition method under the catalytic action of the metal nickel. The carbon coating with the porous network structure improves the electric contact among active material particles microscopically, is beneficial to improving the electronic conductivity of the silicon monoxide, improves the solid-liquid interface contact macroscopically and is beneficial to promoting the rapid transfer of charges. In addition, the three-dimensional porous structure can effectively release the internal stress generated by the silicon oxide in the lithiation/delithiation process and relieve the volume swelling in the circulation process. Therefore, the composite material has excellent structural stability and cycle stability.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) picture of the porous carbon network modified silica composite anode material prepared by the method example 1 of the present invention.
FIG. 2 is a cycle curve of the porous carbon network modified silica composite anode material prepared in example 1 of the present invention at a current density of 1A/g.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The embodiment provides a preparation method of a porous carbon network modified silicon oxide composite negative electrode material, the composite negative electrode material is a carbon coating with a three-dimensional network structure attached to the surface of silicon oxide particles, and the preparation method comprises the following steps:
step 1: pretreating the silica powder, namely dispersing the silica powder in 1mol/L KOH solution, stirring for 4 hours at room temperature, and washing the mixture to be neutral by using deionized water to obtain the silica powder with rough surface;
step 2: dispersing the silicon monoxide powder obtained in the step 1 in deionized water, and adding a mixed solution of nickel acetate and ammonium persulfate;
and 3, step 3: dissolving a certain amount of ammonia water solution in deionized water to dilute by 100 times, slowly dropwise adding the diluted ammonia water solution into the mixed solution obtained in the step (2), stirring at room temperature for 30min after dropwise adding, washing with the deionized water to be neutral, and drying in an oven at 80 ℃ for 12 hours to obtain the silicon monoxide powder with the surface attached with the basic nickel oxide;
and 4, step 4: placing the silicon oxide powder with the surface adhered with the basic nickel oxide obtained in the step 3 into a tubular furnace, growing a layer of carbon layer with a porous reticular structure in situ by adopting a plasma enhanced chemical vapor deposition method, and forming the silicon oxide composite material packaged by the carbon coating with the porous reticular structure, wherein the specific process comprises the following steps: placing the silica powder with the surface adhered with the basic nickel oxide obtained in the step 3 into a porcelain boat, placing the porcelain boat into a tube furnace, heating the porcelain boat to 350 ℃ in an inert atmosphere to convert the basic nickel oxide into nickel oxide, introducing inert gas and reducing gas, and keeping the temperature for 60min to reduce the nickel oxide into a nickel simple substance; and continuously heating to 800-1000 ℃ in the atmosphere of mixed gas, introducing carbon source gas and carrier gas to keep the air pressure in the tubular furnace between 100 and 110Pa, then turning on an inductively coupled plasma radio-frequency power supply, wherein the power output power is 300W, the carbon growth time is 30min, turning off the inductively coupled plasma radio-frequency power supply after the reaction is finished, stopping introducing the carbon source gas and the carrier gas, and cooling to room temperature in the atmosphere of argon to obtain the silicon monoxide composite cathode material packaged by the carbon coating with the three-dimensional network structure.
In some embodiments, the step 1 is performed using a silica powder having a particle size of 1 to 10 μm.
In some embodiments, the inert gas in step 4 is any one of argon, helium and neon, and the flow rate is 200sccm, and the reducing gas is hydrogen, which plays a role of reducing nickel oxide, and the flow rate is 20sccm.
In some embodiments, the carbon source gas in step 4 is a mixed gas of one or more of methane, ethane and acetylene, and the carrier gas is hydrogen, and the carrier gas assists in ionization of the carbon source gas and has a flow rate of 10sccm.
In some embodiments, the heating rate of the step 4 from room temperature to 350 ℃ is 2 ℃/min, the temperature is kept at 350 ℃ for 60min, and then the reduction gas hydrogen is introduced for reduction of nickel oxide.
In some embodiments, the heating rate of step 4 from 350 ℃ to 800-1000 ℃ is 5 ℃/min, the temperature is maintained at 800-1000 ℃ for 20min, and then carbon source gas is introduced.
In some embodiments, the mass ratio of nickel acetate to silica in step 2 is 1.
In some embodiments, the ammonia solution with the initial concentration of 28% to 37% is used in the step 3, wherein the molar ratio of the ammonia solution to the nickel acetate is 2.
The porous carbon network modified silicon monoxide composite negative electrode material obtained by the preparation method can be used for preparing a secondary battery.
Example 1
The embodiment provides a preparation method of a porous carbon network modified silicon monoxide composite negative electrode material, wherein the composite negative electrode material is a carbon coating with a three-dimensional network structure attached to the surface of silicon monoxide particles, and the preparation method comprises the following steps:
step 1: pretreating the silica powder, namely dispersing the silica powder with the particle size of 1 mu m in a 1mol/L KOH solution, stirring for 4 hours at room temperature, and washing the mixture to be neutral by using deionized water to obtain the silica powder with rough surface;
step 2: dispersing the silicon monoxide powder obtained in the step 1 in deionized water, and adding a mixed solution of nickel acetate and ammonium persulfate; the mass ratio of nickel acetate to silica is 1.
And step 3: dissolving a certain amount of ammonia water solution in deionized water to dilute by 100 times, slowly dropwise adding the diluted ammonia water solution into the mixed solution obtained in the step (2), stirring at room temperature for 30min after dropwise adding, washing with the deionized water to be neutral, and drying in an oven at 80 ℃ for 12 hours to obtain the silicon monoxide powder with the surface attached with the basic nickel oxide;
and 4, step 4: putting the silicon oxide powder with the surface adhered with the basic nickel oxide obtained in the step 3 into a tube furnace, growing a layer of carbon layer with a porous net structure in situ by adopting a plasma enhanced chemical vapor deposition method, and forming the silicon oxide composite material packaged by the carbon coating with the porous net structure, wherein the specific process comprises the following steps: placing the silicon monoxide powder with the surface adhered with the basic nickel oxide obtained in the step 3 into a porcelain boat, placing the porcelain boat into a tube furnace, heating the porcelain boat to 350 ℃ at the heating rate of 2 ℃/min under the inert atmosphere, preserving the heat at 350 ℃ for 60min to convert the basic nickel oxide into nickel oxide, introducing inert gas and reducing gas, preserving the heat for 60min, and reducing the nickel oxide into a nickel simple substance; and continuously heating to 800 ℃ at the heating rate of 5 ℃/min in the mixed gas atmosphere, preserving the temperature for 20min at 800 ℃, then introducing a carbon source gas and a carrier gas to keep the air pressure in the tubular furnace between 100 and 110Pa, then turning on an inductively coupled plasma radio frequency power supply, wherein the output power of the power supply is 300W, the carbon growth time is 30min, turning off the inductively coupled plasma radio frequency power supply after the reaction is finished, stopping introducing the carbon source gas and the carrier gas, and cooling to room temperature in the argon atmosphere to obtain the carbon coating encapsulated silicon monoxide composite cathode material with the three-dimensional network structure.
The inert gas in the step 4 is argon gas, the flow rate is 200sccm, the reducing gas is hydrogen gas, and the flow rate is 20sccm.
The carbon source gas in the step 4 is methane, and the flow rate is 20sccm. The carrier gas was hydrogen at a flow rate of 10sccm.
Fig. 1 shows a Scanning Electron Microscope (SEM) picture of the porous carbon network modified silica composite anode material prepared in example 1, which shows that carbon layers on the surface are cross-linked with each other, and a porous network structure is present, so that abundant channels are provided for electron transport and ion diffusion, and the three-dimensional porous structure inhibits the volume expansion of silica to some extent.
Preparing the porous carbon network modified silicon monoxide composite negative electrode material into an electrode slice, assembling the prepared electrode slice into a battery in a glove box, and testing the electrochemical performance of the battery. The preparation method of the electrode slice specifically comprises the following steps: mixing the silicon monoxide material, the conductive agent and the binder according to the mass ratio of 8: 1 to prepare slurry, then coating the slurry on the rough surface of the copper foil, and baking the copper foil in a vacuum oven at 80 ℃ for 12 hours to prepare the electrode slice. The conductive agent comprises any one or more of conductive carbon black, ketjen black, carbon nano tubes and conductive graphite, the conductive carbon black is selected in the embodiment, the binder comprises sodium carboxymethylcellulose (CMC) and one or more of Styrene Butadiene Rubber (SBR), polyvinylidene fluoride (PVDF), sodium Alginate (SA) and polyacrylic acid (PAA), and the sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) are selected in the embodiment. Cutting the prepared electrode into small wafers with the diameter of 10mm, and placing the small wafers in a glove box with the oxygen and water contents lower than 0.01 ppm; a mixed solution obtained by dissolving Celgard-2500 serving as a diaphragm into a mixed solution with the volume ratio of EC to DEC to FEC of 1 to 2% of VC serving as an additive in a ratio of 3.
FIG. 2 shows the cycle performance curve of the porous carbon network modified silica composite anode material prepared in example 1 of the present invention at a current density of 1A/g. The porous carbon network modified silicon monoxide composite negative electrode material has the first discharge specific capacity of 2620.1mAh/g, the first charge specific capacity of 1896.4mAh/g and the first coulombic efficiency of 72.38%, the discharge reversible capacity is 377mAh/g after 300 cycles of circulation, and the capacity retention rate reaches 57.22%.
Example 2
The embodiment provides a preparation method of a porous carbon network modified silicon monoxide composite negative electrode material, the composite negative electrode material is a carbon coating with a three-dimensional network structure attached to the surface of silicon monoxide particles, and the preparation method comprises the following steps:
step 1: pretreating the silica powder, namely dispersing the silica powder with the particle size of 10 mu m in a 1mol/L KOH solution, stirring for 4 hours at room temperature, and washing the mixture to be neutral by using deionized water to obtain the silica powder with rough surface;
step 2: dispersing the silicon monoxide powder obtained in the step 1 in deionized water, and adding a mixed solution of nickel acetate and ammonium persulfate; the mass ratio of nickel acetate to silica is 1.
And step 3: dissolving a certain amount of ammonia water solution in deionized water to dilute by 100 times, slowly dropwise adding the diluted ammonia water solution into the mixed solution obtained in the step (2), stirring at room temperature for 30min after dropwise adding, washing with the deionized water to be neutral, and drying in an oven at 80 ℃ for 12 hours to obtain the silicon monoxide powder with the surface attached with the basic nickel oxide;
and 4, step 4: placing the silicon oxide powder with the surface adhered with the basic nickel oxide obtained in the step 3 into a tubular furnace, growing a layer of carbon layer with a porous reticular structure in situ by adopting a plasma enhanced chemical vapor deposition method, and forming the silicon oxide composite material packaged by the carbon coating with the porous reticular structure, wherein the specific process comprises the following steps: placing the silicon monoxide powder with the surface adhered with the basic nickel oxide obtained in the step 3 into a porcelain boat, placing the porcelain boat into a tube furnace, heating the porcelain boat to 350 ℃ at the heating rate of 2 ℃/min under the inert atmosphere, preserving the heat at 350 ℃ for 60min to convert the basic nickel oxide into nickel oxide, introducing inert gas and reducing gas, preserving the heat for 60min, and reducing the nickel oxide into a nickel simple substance; and continuously heating to 1000 ℃ at the heating rate of 5 ℃/min in the mixed gas atmosphere, preserving the temperature for 20min at 1000 ℃, then introducing a carbon source gas and a carrier gas to keep the air pressure in the tubular furnace between 100 and 110Pa, then turning on an inductively coupled plasma radio frequency power supply, wherein the output power of the power supply is 300W, the carbon growth time is 30min, turning off the inductively coupled plasma radio frequency power supply after the reaction is finished, stopping introducing the carbon source gas and the carrier gas, and cooling to room temperature in the argon atmosphere to obtain the carbon coating encapsulated silicon monoxide composite cathode material with the three-dimensional network structure.
The inert gas in the step 4 is helium, the flow rate is 200sccm, the reducing gas is hydrogen, and the flow rate is 20sccm.
The carbon source gas in the step 4 is ethane, and the flow rate is 20sccm. The carrier gas was hydrogen at a flow rate of 10sccm.
The preparation process of the electrode plate, the assembly and the test flow of the button cell are the same as those of the embodiment 1.
Example 3
The embodiment provides a preparation method of a porous carbon network modified silicon monoxide composite negative electrode material, wherein the composite negative electrode material is a carbon coating with a three-dimensional network structure attached to the surface of silicon monoxide particles, and the preparation method comprises the following steps:
step 1: pretreating the silica powder, namely dispersing the silica powder with the particle size of 1-10 mu m in 1mol/L KOH solution, stirring for 4 hours at room temperature, and washing the mixture to be neutral by using deionized water to obtain the silica powder with rough surface;
and 2, step: dispersing the silicon monoxide powder obtained in the step 1 in deionized water, and adding a mixed solution of nickel acetate and ammonium persulfate; the mass ratio of nickel acetate to silica is 1.
And step 3: dissolving a certain amount of ammonia water solution in deionized water to dilute by 100 times, slowly dropwise adding the diluted ammonia water solution into the mixed solution obtained in the step (2), stirring at room temperature for 30min after dropwise adding, washing with the deionized water to be neutral, and drying in an oven at 80 ℃ for 12 hours to obtain the silicon monoxide powder with the surface attached with the basic nickel oxide;
and 4, step 4: placing the silicon oxide powder with the surface adhered with the basic nickel oxide obtained in the step 3 into a tubular furnace, growing a layer of carbon layer with a porous reticular structure in situ by adopting a plasma enhanced chemical vapor deposition method, and forming the silicon oxide composite material packaged by the carbon coating with the porous reticular structure, wherein the specific process comprises the following steps: placing the silicon monoxide powder with the surface adhered with the basic nickel oxide obtained in the step 3 into a porcelain boat, placing the porcelain boat into a tube furnace, heating the porcelain boat to 350 ℃ at the heating rate of 2 ℃/min under the inert atmosphere, preserving the heat at 350 ℃ for 60min to convert the basic nickel oxide into nickel oxide, introducing inert gas and reducing gas, preserving the heat for 60min, and reducing the nickel oxide into a nickel simple substance; and continuously heating to 900 ℃ at the heating rate of 5 ℃/min in the mixed gas atmosphere, preserving the temperature for 20min at 900 ℃, then introducing a carbon source gas and a carrier gas to keep the air pressure in the tubular furnace between 100 and 110Pa, then turning on an inductively coupled plasma radio frequency power supply, wherein the output power of the power supply is 300W, the carbon growth time is 30min, turning off the inductively coupled plasma radio frequency power supply after the reaction is finished, stopping introducing the carbon source gas and the carrier gas, and cooling to room temperature in the argon atmosphere to obtain the carbon coating encapsulated silicon monoxide composite cathode material with the three-dimensional network structure.
The inert gas in the step 4 is helium gas and neon gas, the flow rate is 200sccm, the reducing gas is hydrogen gas, and the flow rate is 20sccm.
The carbon source gas in the step 4 is mixed gas of ethane and acetylene, and the flow rate is 20sccm. The carrier gas was hydrogen at a flow rate of 10sccm.
The preparation process of the electrode plate, the assembly and the test flow of the button cell are the same as those of the embodiment 1.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a porous carbon network modified silicon oxide composite negative electrode material is characterized in that the preparation method comprises the following steps:
step 1: pretreating the silica powder, namely dispersing the silica powder in 1mol/L KOH solution, stirring for 4 hours at room temperature, and washing the mixture to be neutral by using deionized water to obtain the silica powder with rough surface;
step 2: dispersing the silicon monoxide powder obtained in the step 1 in deionized water, and adding a mixed solution of nickel acetate and ammonium persulfate;
and 3, step 3: dissolving a certain amount of ammonia water solution in deionized water to dilute by 100 times, slowly dropwise adding the diluted ammonia water solution into the mixed solution obtained in the step (2), stirring at room temperature for 30min after dropwise adding, washing with the deionized water to be neutral, and drying in an oven at 80 ℃ for 12 hours to obtain the silicon monoxide powder with the surface attached with the basic nickel oxide;
and 4, step 4: putting the silicon oxide powder with the surface adhered with the basic nickel oxide obtained in the step 3 into a tube furnace, growing a layer of carbon layer with a porous net structure in situ by adopting a plasma enhanced chemical vapor deposition method, and forming the silicon oxide composite material packaged by the carbon coating with the porous net structure, wherein the specific process comprises the following steps: placing the silicon monoxide powder with the surface adhered with the basic nickel oxide obtained in the step 3 into a porcelain boat, placing the porcelain boat into a tube furnace, heating the porcelain boat to 350 ℃ in an inert atmosphere to convert the basic nickel oxide into nickel oxide, introducing inert gas and reducing gas, and keeping the temperature for 60min to reduce the nickel oxide into a nickel simple substance; and continuously heating to 800-1000 ℃ in the atmosphere of mixed gas, introducing carbon source gas and carrier gas to keep the air pressure in the tubular furnace between 100 and 110Pa, then turning on an inductively coupled plasma radio-frequency power supply, wherein the power output power is 300W, the carbon growth time is 30min, turning off the inductively coupled plasma radio-frequency power supply after the reaction is finished, stopping introducing the carbon source gas and the carrier gas, and cooling to room temperature in the atmosphere of argon to obtain the silicon monoxide composite cathode material packaged by the carbon coating with the three-dimensional network structure.
2. The preparation method of the porous carbon network modified silica composite anode material according to claim 1, characterized in that: the step 1 adopts the monox powder with the grain diameter of 1-10 mu m.
3. The preparation method of the porous carbon network modified silica composite anode material according to claim 1, characterized in that: the inert gas in the step 4 is any one of argon gas, helium gas and neon gas, the flow rate is 200sccm, the reducing gas is hydrogen gas, the effect of reducing the nickel oxide is achieved, and the flow rate is 20sccm.
4. The preparation method of the porous carbon network modified silica composite anode material according to claim 1, characterized in that: the carbon source gas in the step 4 is one or a mixture of several of methane, ethane and acetylene, the flow rate is 20sccm, the carrier gas is hydrogen, and the carrier gas assists the carbon source gas to ionize, and the flow rate is 10sccm.
5. The preparation method of the porous carbon network modified silica composite anode material according to claim 1, characterized in that: in the step 4, the temperature is raised from room temperature to 350 ℃ at the rate of 2 ℃/min, the temperature is kept at 350 ℃ for 60min, and then reducing gas hydrogen is introduced to reduce nickel oxide.
6. The preparation method of the porous carbon network modified silicon monoxide composite anode material according to claim 1, characterized in that: in the step 4, the heating rate of heating from 350 ℃ to 800-1000 ℃ is 5 ℃/min, the temperature is kept at 800-1000 ℃ for 20min, and then carbon source gas is introduced.
7. The preparation method of the porous carbon network modified silica composite anode material according to claim 1, characterized in that: in the step 2, the mass ratio of nickel acetate to silica is 1.
8. The preparation method of the porous carbon network modified silica composite anode material according to claim 1, characterized in that: in the step 3, an ammonia water solution with an initial concentration of 28% -37% is adopted, wherein the molar ratio of the ammonia water solution to the nickel acetate is 2.
9. A porous carbon network modified silica composite anode material obtained by the preparation method of any one of claims 1 to 8.
10. Use of a porous carbon network modified silica composite anode material as claimed in claim 9 in the manufacture of a secondary battery.
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