CN107565115B - Preparation method of silicon-carbon negative electrode material, silicon-carbon negative electrode material and lithium ion battery - Google Patents
Preparation method of silicon-carbon negative electrode material, silicon-carbon negative electrode material and lithium ion battery Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion batteries, and relates to a preparation method of a silicon-carbon negative electrode material, the silicon-carbon negative electrode material and a lithium ion battery. The preparation method of the silicon-carbon negative electrode material provided by the invention comprises the following steps: (a) heating SiO to make it generate disproportionation reaction to generate c-SiO; (b) placing the C-SiO in a chemical vapor deposition furnace, heating the furnace in a protective atmosphere, introducing a carbon source after the temperature is raised to a reaction temperature, and carrying out vapor deposition reaction to obtain C-SiO/C, wherein the carbon source is a liquid or solid compound; (c) and corroding the C-SiO/C by using corrosive liquid to obtain the silicon-carbon negative electrode material C-SiO/Si/C. The invention has simple process and easy operation, and the prepared silicon-carbon cathode material has the high lithium storage property of silicon materials and the high cycle stability of carbon materials, and has high specific capacity, good conductivity and good cycle performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a silicon-carbon negative electrode material, the silicon-carbon negative electrode material and a lithium ion battery.
Background
In the existing secondary battery system, the lithium ion battery is the most competitive secondary battery at present, both from the viewpoint of development space and from the viewpoint of technical indexes such as service life, specific energy, operating voltage and self-discharge rate. With the continuous development of electronic technology, higher requirements are also put forward on lithium ion batteries, and higher energy density, better cycle life, better high and low temperature charge and discharge performance, better safety performance and the like are required, so that the positive electrode and negative electrode materials for the lithium ion batteries are required to be further developed and perfected.
At present, most of lithium ion battery negative electrode materials in practical application are carbon materials, such as natural graphite, graphitized mesocarbon microbeads and the like. In the non-carbon negative electrode material, silicon has extremely high theoretical specific capacity and a lower lithium storage reaction voltage platform, and the silicon is widely distributed in nature, and the content of the silicon in the crust is second to that of oxygen, so the silicon-based negative electrode material is a novel high-energy material with great development prospect. However, the electronic conductivity and ionic conductivity of silicon are low, resulting in poor kinetics of electrochemical reactions; the cycle stability of ordinary pure silicon is poor. And the phase change and volume expansion of silicon in the lithiation process can generate larger stress, so that the electrode is broken and pulverized, the resistance is increased, and the cycle performance is suddenly reduced.
At present, silicon powder and a carbon source material are subjected to ball milling and mixing and then pyrolyzed to prepare a silicon-carbon composite material, so that the volume expansion phenomenon in the charging and discharging processes of a battery is relieved, and the cycle performance of the silicon-based material is improved. However, the existing preparation method of the silicon-carbon composite material has certain disadvantages, such as limited selection range of carbon source, high cost, poor effect, unobvious improvement of cycle performance and the like; in addition, the method has complex operation steps, difficult control of the reaction process and poor stability, and is not beneficial to industrial development and application.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a silicon-carbon negative electrode material, which has simple process and easy operation, and the prepared silicon-carbon negative electrode material has the high lithium storage characteristics of silicon materials and the high cycle stability of carbon materials, high specific capacity and good reaction kinetics performance.
The second purpose of the invention is to provide a silicon-carbon negative electrode material, which can effectively inhibit the volume expansion of a silicon negative electrode, has excellent conductivity, high specific capacity and good cycle performance.
A third object of the present invention is to provide a lithium ion battery having a high specific capacity, a good cycle performance, and an excellent electrochemical performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
according to one aspect of the present invention, the present invention provides a method for preparing a silicon-carbon anode material, comprising the steps of:
(a) heating SiO to make it generate disproportionation reaction to generate c-SiO;
(b) placing the C-SiO in a chemical vapor deposition furnace, heating the furnace in a protective atmosphere, introducing a carbon source after the temperature is raised to a reaction temperature, and carrying out a vapor deposition reaction to obtain C-SiO/C;
(c) and corroding the C-SiO/C by using corrosive liquid to obtain the silicon-carbon negative electrode material C-SiO/Si/C.
According to a further preferable technical scheme, the particle size of the silicon monoxide matrix material is 400-600 meshes, preferably 450-550 meshes, and further preferably 500 meshes.
As a further preferable technical scheme, in the step (a), the specific process of disproportionation reaction of SiO is as follows:
putting the SiO into a heating device, heating to 80-120 ℃ at a heating rate of 2-8 ℃/min, preserving heat for 0.5-2 h, heating to 700-1000 ℃ at a heating rate of 2-8 ℃/min, preserving heat for 1-3 h, and cooling to room temperature to obtain c-SiO;
preferably, the heating device is provided with a quartz boat, a zirconia boat or an alumina boat.
As a further preferable technical scheme, in the step (b), the content of C in the C-SiO/C is 3-10 wt%;
preferably, the carbon source is any one of polystyrene, glucose, sucrose, phenolic resin, epoxy resin, ferrocene ethanol solution, ferrocene acetone solution, cobalt nitrate ethanol solution, benzene, toluene or xylene;
preferably, the reaction temperature is 700-1200 ℃;
preferably, the chemical vapor deposition furnace is a tube furnace, a rotary furnace or a muffle furnace;
preferably, the protective atmosphere is any one of nitrogen, helium, argon or neon.
As a further preferred technical scheme, the carbon source is polystyrene, and the specific process for obtaining the C-SiO/C through vapor deposition reaction comprises the following steps:
ball-milling the c-SiO and the copper powder, and uniformly mixing to obtain a mixture; placing the mixture on one side of a chemical vapor deposition furnace, and placing the polystyrene on the other side of the chemical vapor deposition furnace; purifying for 0.3-1 h under a protective atmosphere, heating the mixture to 700-900 ℃ at a heating rate of 3-7 ℃/min, heating the polystyrene region to 300-500 ℃, preserving the heat for 2-4 h, and cooling to room temperature to obtain C-SiO/C;
preferably, the method further comprises a copper powder pretreatment step, wherein micron-sized copper powder is subjected to ultrasonic cleaning for 20-40 min by using an acetone solution, then is subjected to ultrasonic cleaning for 10-30 min by using an acid solution with the concentration of 20% -40%, and then is cleaned by using water, dried and subjected to ball milling with c-SiO;
preferably, the method further comprises a step of removing copper powder, wherein the cooled sample is placed in ferric chloride solution to remove the copper powder, and then is washed by acid solution with the concentration of 5% -15% and water respectively to obtain the C-SiO/C;
preferably, the C-SiO/C is composed of a C-SiO matrix and graphene uniformly distributed on the C-SiO matrix.
As a further preferable technical scheme, the carbon source is ferrocene ethanol solution, and the specific process for obtaining C-SiO/C through vapor deposition reaction comprises the following steps:
placing the C-SiO in a chemical vapor deposition furnace, purifying for 0.3-1 h under protective atmosphere, heating to 900-1100 ℃ at the heating rate of 3-7 ℃/min, introducing a ferrocene ethanol solution, carrying out vapor deposition reaction for 2-5 h, removing a carbon source, and cooling to room temperature to obtain C-SiO/C;
preferably, the concentration range of the ferrocene ethanol solution is 5-20 mg/mL;
preferably, the method further comprises the step of heating the ferrocene ethanol solution at 40-60 ℃, and then introducing the heated ferrocene ethanol solution into a chemical vapor deposition furnace for vapor deposition reaction;
preferably, the C-SiO/C is composed of a C-SiO matrix and carbon nanotubes uniformly distributed on the C-SiO matrix.
As a further preferable technical scheme, the carbon source is toluene, and the specific process for obtaining the C-SiO/C through vapor deposition reaction comprises the following steps:
placing the C-SiO in a chemical vapor deposition furnace, purifying for 0.3-1 h under protective atmosphere, heating to 700-1000 ℃ at a heating rate of 3-7 ℃/min, introducing toluene, carrying out vapor deposition reaction for 1-4 h, removing a carbon source, and cooling to room temperature to obtain the C-SiO/C;
preferably, the method further comprises the steps of heating the toluene at 40-60 ℃, and introducing the toluene into a chemical vapor deposition furnace for vapor deposition reaction;
preferably, the C-SiO/C consists of a C-SiO matrix and amorphous carbon uniformly distributed on the C-SiO matrix.
As a further preferable technical solution, in the step (c), the etching solution is a hydrofluoric acid aqueous solution with a concentration of 3wt% to 20wt%, preferably a hydrofluoric acid aqueous solution with a concentration of 5wt% to 10 wt%;
preferably, the mass ratio of the C-SiO/C to the hydrofluoric acid is 1: 1.2-1.5, wherein the time of corrosion treatment is 5-30 min;
preferably, the corrosion treatment further comprises the steps of washing with water and drying, and the drying temperature is preferably 90-120 ℃.
According to another aspect of the invention, the invention also provides a silicon-carbon negative electrode material prepared by the preparation method of the silicon-carbon negative electrode material.
According to another aspect of the invention, the invention also provides a lithium ion battery, and the negative electrode of the lithium ion battery comprises the silicon-carbon negative electrode material.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method, silicon monoxide is used as a raw material, and the porous silicon-carbon composite cathode material is obtained through high-temperature disproportionation reaction, vapor deposition reaction with a carbon source and corrosion operation steps in sequence; compared with the commonly used gaseous carbon source in the prior art, the carbon source is a carbon-containing liquid or solid compound, the method has the advantages of wide raw material source, low cost, environment-friendly raw materials, easy operation and convenient control of the preparation process, simple and feasible process conditions and low energy consumption, and the prepared silicon-carbon cathode material has the high lithium storage property of silicon materials and the high cycle stability, high specific capacity and good reaction kinetics performance of carbon materials.
2. According to the silicon-carbon cathode material, the carbon layer is loaded on the surface of the silicon substrate material, so that the carbon layer not only improves the conductivity of the material, but also can prevent silicon nuclei from being broken and scattered, effectively prevents the composite material from being broken and crushed due to volume change in the charging and discharging processes, improves the silicon volume effect, ensures the structural stability of the material, and improves the electrochemical reaction dynamic performance of the material; in addition, the surface chemical structure of the silicon-based material is improved, the direct contact between the silicon-based material and electrolyte is reduced, a stable, thin and compact solid electrolyte membrane is promoted to be formed on the surface of the electrode, and the interface compatibility of the electrode/electrolyte is improved, so that the cycle performance of the electrode is improved.
3. The invention has simple process, good repeatability, no complex equipment in the whole production process, low production cost, high efficiency, good stability of the prepared product, convenient large-scale industrial production and good application prospect in lithium ion batteries.
4. The lithium ion battery and the silicon-carbon cathode material provided by the invention have the advantages of low cost, stable performance, high specific capacity, good conductivity, long cycle life and excellent electrochemical performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is an XRD pattern (X-ray diffraction pattern) of the silicon-carbon negative electrode material provided in example 3 of the present invention, with diffraction angles on the abscissa and intensity on the ordinate; in the figure, XRD patterns of a base material SiO, disproportionation generated C-SiO, vapor deposition obtained C-SiO/C and corrosion obtained C-SiO/Si/C are represented from bottom to top in sequence;
fig. 2 is an SEM (Scanning electron microscope) image of the silicon carbon negative electrode material provided in embodiment 3 of the present invention; FIGS. 2(a) and 2(b) are SEM images of vapor deposition-derived C-SiO/C and etching-derived C-SiO/Si/C, respectively;
FIG. 3 shows the charging and discharging cycle curves of the lithium ion battery made of the silicon-carbon negative electrode material prepared in example 3 of the present invention at times 1, 10 and 20, and the abscissa shows the specific capacity (mA. h. g)－1) The ordinate is the voltage (V); FIGS. 3(a), 3(b) and 3(C) are graphs showing the cycle curves of SiO as a base material, C-SiO/C obtained by vapor deposition and C-SiO/Si/C obtained by etching, respectively;
FIG. 4 is a graph of cycle number versus specific discharge capacity of a lithium ion battery made of the silicon-carbon negative electrode material prepared in example 3 of the present invention, wherein the abscissa represents the cycle number and the ordinate represents the specific discharge capacity (mA. h. g)－1)。
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but those skilled in the art will understand that the following embodiments and examples are only illustrative of the present invention and should not be construed as limiting the scope of the present 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. The specification of the conditions is carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In a first aspect, the present embodiment provides a method for preparing a silicon-carbon anode material, including the following steps:
(a) heating SiO to make it generate disproportionation reaction to generate c-SiO;
(b) placing the C-SiO in a chemical vapor deposition furnace, heating the furnace in a protective atmosphere, introducing a carbon source after the temperature is raised to a reaction temperature, and carrying out a vapor deposition reaction to obtain C-SiO/C; wherein the carbon source is a solid or liquid compound;
(c) and corroding the C-SiO/C by using corrosive liquid to obtain the silicon-carbon negative electrode material C-SiO/Si/C.
The silicon-carbon cathode material prepared by the preparation method of the silicon-carbon cathode material provided by the invention can overcome the defect that the silicon material and the carbon material which are independently used as the cathode material of the lithium ion battery in the prior art can not meet the requirement, can fully exert the functions of silicon and carbon, and has better structural stability. On one hand, the excellent conductivity of the carbon layer is utilized, the problem of poor conductivity of silicon particles is solved, and the conductivity of the material is improved; on the other hand, an electrochemical reaction interface is increased through a silicon substrate material, the electrochemical reaction dynamic performance of the material is improved, and the cycle performance of the electrode is improved; in addition, the surface of the silicon substrate material is uniformly loaded with the carbon layer, so that the surface structure of silicon can be improved, the direct contact between the silicon and electrolyte is reduced, a stable, thin and compact solid electrolyte membrane is promoted to be formed on the surface of the electrode, the interface compatibility of the electrode/electrolyte is improved, and the cycle performance of the electrode is further improved.
Compared with the common matrix material and gaseous carbon source in the prior art, the method has the advantages of wide raw material source, low cost, easy and feasible operation process, low energy consumption and easy large-scale industrial production.
According to the invention, SiO is subjected to high-temperature disproportionation reaction to generate c-SiO, wherein the c-SiO represents silicon and silicon dioxide, and silicon particles are uniformly distributed in a silicon dioxide matrix, so that the generation of some side reactants can be effectively avoided.
And then placing the C-SiO and a carbon source in a chemical vapor deposition furnace for vapor deposition reaction to obtain C-SiO/C, wherein the C-SiO/C represents that a layer of C (carbon layer) is uniformly loaded on the surface of the C-SiO material. According to the invention, different types of carbon sources can be selected, and chemical vapor deposition is carried out at a proper reaction temperature and time to deposit carbon in different forms, so that silicon carbon materials with different conductivities, circulation performances and specific capacities can be prepared.
Then, etching (or called as etching) the C-SiO/C by using an etching solution to remove silicon dioxide and prevent the agglomeration of silicon particles, thereby preparing the porous silicon-carbon material C-SiO/Si/C; wherein C-SiO/Si/C represents a silicon-carbon material obtained by removing silicon dioxide from C-SiO/C through corrosion. In the invention, the pore size of the silicon-carbon material can be adjusted by controlling the etching time.
In an alternative embodiment, the particle size of the silica matrix material is 400 to 600 mesh, preferably 450 to 550 mesh, and more preferably 500 mesh.
In one embodiment, the silica matrix material optionally has a particle size of 400 mesh, 450 mesh, 500 mesh, 550 mesh, or 600 mesh.
The average particle size of the silicon monoxide matrix material in the embodiment is about 500 meshes, the raw materials are easy to obtain, the subsequent operation is facilitated, and the prepared material has good structural stability and dynamic performance.
In an alternative embodiment, in step (a), the disproportionation reaction of SiO is carried out by:
putting the SiO into a heating device, heating to 80-120 ℃ at a heating rate of 2-8 ℃/min, preserving heat for 0.5-2 h, heating to 700-1000 ℃ at a heating rate of 2-8 ℃/min, preserving heat for 1-3 h, and cooling to room temperature to obtain c-SiO;
preferably, the SiO is placed in a heating device, the temperature is raised to 90-110 ℃ at the heating rate of 4-6 ℃/min under the atmosphere of air, nitrogen or argon, the temperature is maintained for 1-1.5 h, then the temperature is raised to 750-850 ℃ at the same heating rate, the temperature is maintained for 1.5-2.5 h, and then the temperature is cooled to room temperature to obtain c-SiO;
preferably, the heating device is provided with a quartz boat, a zirconia boat or an alumina boat.
By adopting a sectional type atmosphere heating mode, the generation of some side reactants can be effectively avoided, the content of fine particles can be controlled, and the disproportionation reaction effect is better.
The heating apparatus in this embodiment may be a tube furnace equipped with a quartz boat, a zirconia boat, an alumina boat, or the like, and the heating apparatus may be configured to heat the SiO in the high temperature resistant quartz boat, zirconia boat, or alumina boat.
In a specific embodiment, optionally, the silicon monoxide is placed in a quartz boat, a zirconium oxide boat or an aluminum oxide boat, and the temperature is raised to 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃ at a temperature raising rate of 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min or 8 ℃/min in the air atmosphere, and the temperature is maintained for 0.5h, 1h, 1.5h or 2h, and then raised to 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ or 1000 ℃ at the same temperature raising rate, and the temperature is maintained for 1h, 1.5h, 2h, 2.5h or 3h, and then cooled to room temperature, so as to obtain the c-SiO.
Here, the "room temperature" in the present invention means a temperature of 20 to 30 ℃. The cooling to room temperature is preferably carried out by natural cooling.
In an alternative embodiment, in step (b), the C content of the C-SiO/C is 3wt% to 10 wt%;
preferably, the carbon source is any one of polystyrene, glucose, sucrose, phenolic resin, epoxy resin, ferrocene ethanol solution, ferrocene acetone solution, cobalt nitrate ethanol solution, benzene, toluene or xylene;
preferably, the reaction temperature is 700-1200 ℃;
preferably, the chemical vapor deposition furnace is a tube furnace, a rotary furnace or a muffle furnace;
preferably, the protective atmosphere is any one of nitrogen, helium, argon or neon.
The vapor deposition reaction time is different, and the required mass ratio of the c-SiO to the carbon source or the proportion of the carbon source is also different. Under the condition of a certain vapor deposition reaction time, C-SiO/C with different weight percentage contents of C can be obtained by changing the mass ratio of C-SiO to the carbon source.
In one embodiment, the reaction temperature for vapor deposition is, optionally, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ or 1200 ℃.
The carbon sources in the invention can be roughly divided into three types, one type is polystyrene solid carbon sources, the second type is ferrocene ethanol solution, and the third type is methylbenzene. Wherein, the polystyrene comprises polystyrene or polypropylene ethylene; the ferrocene ethanol solution comprises a ferrocene ethanol solution, a ferrocene acetone solution, a ferrocene methanol solution, a ferric nitrate ethanol solution, a cobalt nitrate ethanol solution and the like, wherein the ferrocene, ferric nitrate and cobalt nitrate are used as catalysts, the methanol, the ethanol and the acetone are used as solvents, and the ferrocene ethanol solution can also comprise a combination of similar iron sulfate, propanol and other catalysts and solvents; toluenes include benzene, toluene, xylene, and the like; in addition, the carbon source in the present invention also includes glucose, sucrose, phenol resin, epoxy resin and the like, and the operating conditions of vapor deposition are similar to those of toluene carbon sources.
The invention mainly loads three carbon layers with different forms on the silicon matrix material through the three carbon sources. The following description will be made by taking polystyrene, ferrocene ethanol solution and toluene as examples; it is understood that the carbon source is not limited to these three carbon sources, and may be any one of the carbon sources described above.
In an alternative embodiment, the carbon source is polystyrene, and the specific process for obtaining C-SiO/C by vapor deposition reaction is as follows:
ball-milling the c-SiO and the copper powder, and uniformly mixing to obtain a mixture; placing the mixture on one side of a chemical vapor deposition furnace, and placing the polystyrene on the other side of the chemical vapor deposition furnace; purifying for 0.3-1 h under a protective atmosphere, heating the mixture to 700-900 ℃ at a heating rate of 3-7 ℃/min, heating the polystyrene region to 300-500 ℃, preserving the heat for 2-4 h, and cooling to room temperature to obtain C-SiO/C;
preferably, the method further comprises a copper powder pretreatment step, wherein micron-sized copper powder is subjected to ultrasonic cleaning for 20-40 min by using an acetone solution, then is subjected to ultrasonic cleaning for 10-30 min by using a hydrochloric acid solution with the concentration of 20% -40%, and then is cleaned by using water, dried and subjected to ball milling with c-SiO;
preferably, the method further comprises a step of removing copper powder, wherein the cooled sample is placed in ferric chloride solution to remove the copper powder, and then is washed by hydrochloric acid solution with the concentration of 5% -15% and water respectively to obtain the C-SiO/C;
preferably, the C-SiO/C is composed of a C-SiO matrix and graphene uniformly distributed on the C-SiO matrix.
The copper powder in this embodiment can play a catalytic role to produce graphene-like carbon. The polystyrene is used as a carbon source, and the multi-layer graphene sheet is loaded on the surface of the c-SiO by vapor deposition in the operation mode.
In one embodiment, optionally, the purification is performed under a protective atmosphere for 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1h, and the mixture is heated to 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃ at a heating rate of 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min or 7 ℃/min, the polystyrene zone is heated to 300 ℃, 350 ℃, 400 ℃, 450 ℃ or 500 ℃, and cooled to room temperature after 2h, 3h or 4h of heat preservation.
In a specific embodiment, optionally, the micron-sized copper powder is subjected to ultrasonic cleaning for 20min, 25min, 30min, 35min or 40min by using an acetone solution, and then is subjected to ultrasonic cleaning for 10min, 15min, 20min, 25min or 30min by using a hydrochloric acid solution with the concentration of 20%, 30% or 40%, and then the copper powder is washed by water and dried. Wherein, the water is preferably deionized water, and the drying is preferably vacuum drying.
In an alternative embodiment, the carbon source is ferrocene ethanol solution, and the specific process for obtaining C-SiO/C through vapor deposition reaction is as follows:
placing the C-SiO in a chemical vapor deposition furnace, purifying for 0.3-1 h under protective atmosphere, heating to 900-1100 ℃ at the heating rate of 3-7 ℃/min, introducing a ferrocene ethanol solution, carrying out vapor deposition reaction for 2-5 h, removing a carbon source, and cooling to room temperature to obtain C-SiO/C;
preferably, the concentration range of the ferrocene ethanol solution is 5-20 mg/mL;
preferably, the method further comprises the step of heating the ferrocene ethanol solution at 40-60 ℃, and then introducing the heated ferrocene ethanol solution into a chemical vapor deposition furnace for vapor deposition reaction;
preferably, the C-SiO/C is composed of a C-SiO matrix and carbon nanotubes uniformly distributed on the C-SiO matrix.
Preferably, before the vapor deposition reaction process, heating the ferrocene ethanol solution in a water bath at 45-55 ℃, wherein the water bath heating is continuously performed in the vapor deposition reaction process until the carbon source is removed and the water bath heating is removed at the same time after the vapor deposition reaction is finished. The ferrocene in the embodiment can play a catalytic role, and the carbon nano tube is loaded on the surface of the c-SiO by taking ferrocene ethanol solution as a carbon source and carrying out vapor deposition through the operation mode.
In a specific embodiment, optionally, purifying for 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1h under a protective atmosphere, heating to 900 ℃, 950 ℃, 1000 ℃, 1050 ℃ or 1100 ℃ at a heating rate of 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min or 7 ℃/min, introducing a ferrocene ethanol solution, performing a vapor deposition reaction for 2h, 3h, 4h or 5h, removing a carbon source, and naturally cooling to room temperature.
In one embodiment, the ferrocene alcohol solution is optionally at a concentration of 5mg/mL, 10mg/mL, 15mg/mL or 20 mg/mL.
In an alternative embodiment, the carbon source is toluene, and the specific process for obtaining C-SiO/C by vapor deposition reaction is as follows:
placing the C-SiO in a chemical vapor deposition furnace, purifying for 0.3-1 h under protective atmosphere, heating to 700-1000 ℃ at a heating rate of 3-7 ℃/min, introducing toluene, carrying out vapor deposition reaction for 1-4 h, removing a carbon source, and cooling to room temperature to obtain the C-SiO/C;
preferably, the method further comprises the steps of heating the toluene at 40-60 ℃, and introducing the toluene into a chemical vapor deposition furnace for vapor deposition reaction;
preferably, the C-SiO/C consists of a C-SiO matrix and amorphous carbon uniformly distributed on the C-SiO matrix.
Preferably, before the vapor deposition reaction process, the toluene is heated in a water bath at 45-55 ℃, the water bath heating is continuously performed in the vapor deposition reaction process until the carbon source is removed and the water bath heating is removed at the same time after the vapor deposition reaction is completed.
The toluene is used as a carbon source, and the amorphous carbon is loaded on the surface of the c-SiO by vapor deposition in the operation mode.
In a specific embodiment, optionally, purifying for 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1h under a protective atmosphere, heating to 700 ℃, 750 ℃, 00 ℃, 850 ℃, 900 ℃, 950 ℃ or 1000 ℃ at a heating rate of 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min or 7 ℃/min, introducing toluene, performing a vapor deposition reaction for 1h, 2h, 3h or 4h, removing a carbon source, and naturally cooling to room temperature.
In one embodiment, the toluene is optionally heated in a water bath at 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C or 60 deg.C.
In an optional embodiment, in the step (c), the etching solution is 3wt% to 20wt% of hydrofluoric acid aqueous solution, preferably 5wt% to 10wt% of hydrofluoric acid aqueous solution;
preferably, the mass ratio of the C-SiO/C to the hydrofluoric acid is 1: 1.2-1.5, wherein the time of corrosion treatment is 5-30 min;
preferably, the corrosion treatment further comprises the steps of washing with water and drying, and the drying temperature is preferably 90-120 ℃.
The silicon dioxide can be removed by etching to prepare a porous silicon carbon material, and generally, hydrofluoric acid can be slightly excessive relative to C-SiO/C; under a certain hydrofluoric acid concentration, the aperture size of the silicon-carbon material can be adjusted by controlling the etching time.
In a specific embodiment, the concentration of the hydrofluoric acid aqueous solution is optionally 3wt%, 4 wt%, 5wt%, 6 wt%, 8 wt%, 10wt%, 12 wt%, 14 wt%, 15 wt%, 16 wt%, 18 wt% or 20 wt%.
In one embodiment, the etching treatment time is optionally 5min, 10min, 15min, 20min, 25min or 30 min.
In one embodiment, optionally, the drying is preferably vacuum drying at a temperature of 90 ℃, 100 ℃, 110 ℃ or 120 ℃.
In a second aspect, the present embodiment provides a silicon-carbon negative electrode material, which is prepared by the above-described preparation method of the silicon-carbon negative electrode material.
In a third aspect, the present embodiment provides a lithium ion battery, including a positive electrode, a negative electrode, a separator, and an electrolyte, where the negative electrode includes the above-described silicon carbon negative electrode material.
In the second and third aspects of the present embodiment, the lithium ion battery negative electrode material may refer to the prior art for the remaining components and structure, except for using the above silicon carbon negative electrode material as an active material; the anode, the cathode and the lithium ion battery structure and the preparation method thereof can refer to the conventional technology, and the difference from the conventional technology is only that the silicon-carbon anode material obtained by the preparation method of the silicon-carbon anode material in the first aspect is added into the lithium ion battery anode material.
The silicon-carbon cathode material prepared by the technical scheme has better electrochemical performance, is used as a cathode material of a lithium ion battery, and has the advantages of low cost, stable performance, good conductivity, high specific capacity and long cycle life.
According to the invention, different carbon micro-morphologies are deposited by adopting different carbon sources, so that the silicon-carbon material with different conductivity, specific capacity and cycle performance is prepared; and the carbon-silicon cathode materials with different microscopic grain sizes are prepared through different corrosion times, so that the performance of the battery is improved. By adopting the technical scheme, the prepared silicon-carbon negative electrode material has the optimal pore size of 3.2nm, the average particle size of 8.85 mu m and the first discharge specific capacity of over 980 mA.h/g at room temperature.
The present invention will be further described with reference to specific examples, comparative examples and the accompanying drawings.
Example 1
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(a) disproportionation reaction: taking silicon monoxide as a base material, wherein the granularity of the silicon monoxide base material is 450 meshes, and heating the silicon monoxide to ensure that the silicon monoxide generates disproportionation reaction to generate c-SiO;
(b) vapor deposition reaction: placing the C-SiO in a chemical vapor deposition furnace, purifying for 0.5h under the protection of argon, heating to 1000 ℃ at the heating rate of 5 ℃/min, introducing a ferrocene ethanol solution, and carrying out vapor deposition reaction for 3h to obtain C-SiO/C, wherein the content of C in the C-SiO/C is 5 wt%;
(c) and (3) corrosion: and (3) placing the C-SiO/C into a hydrofluoric acid aqueous solution with the concentration of 5wt%, stirring and soaking for 10min, washing with deionized water, and drying at the temperature of 100 ℃ to obtain the silicon-carbon negative electrode material C-SiO/Si/C.
Example 2
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(a) disproportionation reaction: using silicon monoxide as a base material, wherein the granularity of the silicon monoxide base material is 500 meshes, and heating the silicon monoxide to ensure that the silicon monoxide generates disproportionation reaction to generate c-SiO;
(b) vapor deposition reaction: placing the C-SiO in a chemical vapor deposition furnace, purifying for 0.5h under the protection of argon, heating to 800 ℃ at the heating rate of 5 ℃/min, introducing toluene, and carrying out vapor deposition reaction for 2h to obtain C-SiO/C, wherein the content of C in the C-SiO/C is 6 wt%;
(c) and (3) corrosion: and placing the C-SiO/C into a 5wt% hydrofluoric acid aqueous solution, stirring and soaking for 15min, washing with deionized water, and drying at 100 ℃ to obtain the silicon-carbon negative electrode material C-SiO/Si/C.
Example 3
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(a) disproportionation reaction: taking silicon monoxide as a base material, wherein the granularity of the silicon monoxide base material is 500 meshes, putting the silicon monoxide into a heating device with an alumina boat, heating to 100 ℃ at a heating rate of 5 ℃/min under the argon atmosphere, preserving heat for 1h, then heating to 800 ℃ at the same heating rate, preserving heat for 2h, cooling to room temperature, and carrying out disproportionation reaction on the silicon monoxide to generate c-SiO in the process;
(b) vapor deposition reaction: ball-milling the c-SiO and the copper powder, and uniformly mixing to obtain a mixture; placing the mixture on one side of a double-temperature-zone tube furnace, and placing polystyrene on the other side of the double-temperature-zone tube furnace; purifying for 0.5h under the protection of argon, heating the mixture area to 800 ℃ at the heating rate of 5 ℃/min, heating the polystyrene area to 400 ℃, preserving the heat for 3h, and naturally cooling to room temperature to obtain C-SiO/C; wherein the C content of the C-SiO/C is 7 wt%;
the obtained C-SiO/C consists of a C-SiO substrate and a plurality of graphene sheets uniformly distributed on the C-SiO substrate;
(c) and (3) corrosion: placing C-SiO/C in a hydrofluoric acid aqueous solution with the concentration of 5wt%, wherein the mass ratio of the C-SiO/C to the hydrofluoric acid is 1: 1.2, stirring and soaking for 10min, washing with deionized water, and drying in vacuum at 100 ℃ to obtain the silicon-carbon negative electrode material C-SiO/Si/C.
Example 4
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(a) disproportionation reaction: taking silicon monoxide as a base material, wherein the granularity of the silicon monoxide base material is 600 meshes, putting the silicon monoxide into a tubular furnace with a zirconia boat, heating to 120 ℃ at a heating rate of 6 ℃/min under the argon atmosphere, preserving heat for 2h, then heating to 900 ℃ at the same heating rate, preserving heat for 3h, and cooling to room temperature, wherein the silicon monoxide is subjected to disproportionation reaction to generate c-SiO in the process;
steps (b) and (c) were the same as in example 3.
Example 5
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(b) vapor deposition reaction: ultrasonically cleaning micron-sized copper powder for 30min by using an acetone solution, ultrasonically cleaning the copper powder for 20min by using a hydrochloric acid solution with the concentration of 30%, cleaning the copper powder by using deionized water, and drying the copper powder in vacuum;
ball-milling the c-SiO and the dried copper powder, and uniformly mixing to obtain a mixture; placing the mixture on one side of a double-temperature-zone tube furnace, and placing polystyrene on the other side of the double-temperature-zone tube furnace; purifying for 1h under the protection of argon-hydrogen mixed gas, heating the mixture area to 750 ℃ at a heating rate of 3 ℃/min, heating the polystyrene area to 300 ℃, preserving heat for 2h, and naturally cooling to room temperature;
placing the cooled sample in ferric chloride solution to remove copper powder, and washing with 10% hydrochloric acid solution and water respectively to obtain C-SiO/C; wherein the C content of the C-SiO/C is 8 wt%;
the obtained C-SiO/C consists of a C-SiO substrate and a plurality of graphene sheets uniformly distributed on the C-SiO substrate;
steps (a) and (c) are the same as in example 3.
Example 6
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(b) vapor deposition reaction: ultrasonically cleaning micron-sized copper powder for 40min by using an acetone solution, ultrasonically cleaning the copper powder for 30min by using a hydrochloric acid solution with the concentration of 40%, cleaning the copper powder by using deionized water, and drying the copper powder in vacuum;
ball-milling the c-SiO and the dried copper powder, and uniformly mixing to obtain a mixture; placing the mixture on one side of a double-temperature-zone tube furnace, and placing polystyrene on the other side of the double-temperature-zone tube furnace; purifying for 0.3h under the protection of helium gas, heating the mixture area to 900 ℃ at a heating rate of 7 ℃/min, heating the polystyrene area to 500 ℃, preserving heat for 4h, and naturally cooling to room temperature;
placing the cooled sample in ferric chloride solution to remove copper powder, and washing with 15% hydrochloric acid solution and water respectively to obtain C-SiO/C; wherein the C content of the C-SiO/C is 8 wt%;
the obtained C-SiO/C consists of a C-SiO substrate and a plurality of graphene sheets uniformly distributed on the C-SiO substrate;
steps (a) and (c) are the same as in example 3.
Example 7
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(c) and (3) corrosion: placing C-SiO/C in 10wt% hydrofluoric acid aqueous solution, wherein the mass ratio of the C-SiO/C to the hydrofluoric acid is 1: 1.5, stirring and soaking for 5min, washing with deionized water, and drying in vacuum at 90 ℃ to obtain the silicon-carbon negative electrode material C-SiO/Si/C.
Steps (a) and (b) are the same as in example 3.
Example 8
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(b) vapor deposition reaction: placing C-SiO in a rotary furnace, purifying for 1h under the nitrogen protection atmosphere, heating to 1100 ℃ at the heating rate of 6 ℃/min, placing the ferrocene ethanol solution in a water bath at 50 ℃ for heating, introducing the ferrocene ethanol solution, carrying out vapor deposition reaction for 5h, removing a carbon source, and cooling to room temperature to obtain C-SiO/C; wherein the concentration of the ferrocene ethanol solution is 10 mg/mL;
the obtained C-SiO/C consists of a C-SiO substrate and carbon nano tubes uniformly distributed on the C-SiO substrate;
steps (a) and (c) are the same as in example 3.
Example 9
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(b) vapor deposition reaction: placing C-SiO in a rotary furnace, purifying for 0.6h under the protection of argon, heating to 1000 ℃ at the heating rate of 4 ℃/min, placing toluene in a water bath at 50 ℃ for heating, introducing toluene, carrying out vapor deposition reaction for 4h, removing a carbon source, and cooling to room temperature to obtain C-SiO/C; wherein the C content in the C-SiO/C is 6 wt%;
the obtained C-SiO/C consists of a C-SiO matrix and amorphous carbon uniformly distributed on the C-SiO matrix;
steps (a) and (c) are the same as in example 3.
Example 10
A method for preparing a silicon-carbon negative electrode material, which is the same as in example 8 except that the ferrocene ethanol solution in the step (b) is replaced by a cobalt nitrate ethanol solution.
Example 11
A method of manufacturing a silicon carbon negative electrode material, which was the same as in example 9 except that toluene was replaced with xylene in the step (b).
Comparative example 1
The preparation method of the silicon-carbon anode material is different from the step (a) in the embodiment 3, and the rest steps are the same as the embodiment 3.
(a) Disproportionation reaction: using 500-mesh SiO as base material, putting the SiO in a heating device, and carrying out disproportionation reaction at 1500 ℃ for 6h to obtain c-SiO.
Comparative example 2
The preparation method of the silicon-carbon anode material is different from the step (b) in the embodiment 3, and the rest steps are the same as the embodiment 3.
(b) Vapor deposition reaction: and mixing the C-SiO and the copper powder, placing the mixture in a chemical vapor deposition furnace, heating the mixture to 1000 ℃ at the heating rate of 10 ℃/min under the protection of argon, introducing a polystyrene carbon source, carrying out chemical vapor deposition reaction for 6 hours, and cooling the mixture to room temperature to obtain the C-SiO/C.
Comparative example 3
A method for preparing a silicon-carbon negative electrode material, which is different from the embodiment 9 in the step (b), and the rest steps are the same as the embodiment 9.
(b) Vapor deposition reaction: and (3) placing the C-SiO and the toluene in a chemical vapor deposition furnace, carrying out vapor deposition reaction for 8 hours under the condition of argon protective atmosphere and 650 ℃, and cooling to room temperature to obtain the C-SiO/C.
Comparative example 4
A method for preparing a silicon-carbon negative electrode material, which is different from the embodiment 3 in the step (c), and the rest steps are the same as the embodiment 3.
(c) And (3) corrosion: placing C-SiO/C in a 30 wt% hydrofluoric acid aqueous solution, wherein the mass ratio of the C-SiO/C to the hydrofluoric acid is 1: 1.01, stirring and soaking for 60min, washing with deionized water, and drying at 125 ℃ to obtain the silicon-carbon negative electrode material C-SiO/Si/C.
Comparative example 5
A preparation method of a silicon-carbon cathode material adopts a preparation method of a carbon-silicon composite material in the prior art; comprises the steps of high-temperature disproportionation reaction of silicon monoxide and corrosion removal of silicon dioxide to prepare the carbon-silicon composite material.
The silicon-carbon anode materials prepared in the examples and the comparative examples are subjected to XRD test and SEM scanning test. The details will be described only with reference to example 3. The XRD patterns of the base material SiO, disproportionation-generated C-SiO, vapor-deposition-obtained C-SiO/C and corrosion-obtained C-SiO/Si/C in example 3 are represented in sequence from bottom to top in FIG. 1. From the spectrogram in fig. 1, it can be seen that SiO has a wider diffraction peak with low diffraction intensity at 20-30 °, indicating that SiO is in an amorphous state; the c-SiO obtained after the high-temperature disproportionation reaction has diffraction peaks at 28 degrees and 47 degrees and 56 degrees except for diffraction peaks at 20-30 degrees, which shows that the SiO undergoes the disproportionation reaction at high temperature and comprises crystalline silicon and amorphous silicon oxide (silicon dioxide); without much change in the diffraction peak morphology after vapor deposition and etching.
FIGS. 2(a) and 2(b) show SEM images of C-SiO/C and C-SiO/Si/C, respectively, in example 3. As can be seen from FIG. 2, after vapor deposition, the obtained C-SiO/C composite material maintains the particle morphology of the raw material after a layer of carbon is loaded on the surface of the C-SiO, but the particle surface becomes a little rough; and the surface appearance of the silicon-carbon cathode material C-SiO/Si/C obtained after corrosion is better.
Electrochemical performance test
The silicon-carbon anode materials prepared in examples 1-11 and comparative examples 1-5 were used to prepare half-cells, and their relevant electrochemical performances were tested, and the test results are shown in table 1. Wherein, the preparation of the half cell: the button cell is assembled by taking an active material as a positive electrode and a lithium sheet as a negative electrode, a conductive carbon Super 'p' is adopted as a conductive agent, a diaphragm is celgard2400, and 1mol/L LiPF is adopted as an electrolyte6Conductive salt and DMC: DEC: EC (wt%) ═ 1: 1: 1. The test conditions were: the charge-discharge cut-off voltage is 0.01-1.5V, the first charge-discharge specific capacity is tested under the state of 0.1C, the cycle efficiency is tested for 50 times under the state of 0.5C, and the test results are shown in Table 1.
TABLE 1 electrochemical Performance test results
As can be seen from Table 1, the silicon-carbon negative electrode material provided by the invention has the advantages of high initial charge-discharge specific capacity, long cycle life and good stability; the electrochemical performance of the silicon-carbon anode materials prepared in the examples 1 to 11 of the invention is obviously due to the comparative examples 1 to 5. Specifically, the preparation method of the silicon-carbon anode material provided by the invention is not only superior to the existing preparation method of the silicon-carbon anode material, but also within the ranges of the disproportionation reaction operation mode, the vapor deposition reaction operation mode and the corrosion operation parameters defined by the invention, the prepared silicon-carbon anode material has more excellent electrochemical performance, higher specific capacity and better cycling stability.
Further, FIG. 3(a), FIG. 3(b) and FIG. 3(C) show charge and discharge cycle curves of 1 st, 10 th and 20 th times for SiO as a base material, C-SiO/C obtained by vapor deposition and C-SiO/Si/C obtained by etching in example 3, respectively; fig. 4 shows their cycle number-discharge specific capacity plots. It can be further seen from fig. 3 and 4 that under the same test conditions, the finally obtained silicon-carbon negative electrode material C-SiO/Si/C has high specific capacity and better cycle stability.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (16)
1. The preparation method of the silicon-carbon negative electrode material is characterized by comprising the following steps of:
(a) heating SiO to make it generate disproportionation reaction to generate c-SiO;
the specific process of the disproportionation reaction of the silicon monoxide comprises the following steps:
putting the SiO into a heating device, heating to 80-120 ℃ at a heating rate of 2-8 ℃/min, preserving heat for 0.5-2 h, heating to 700-1000 ℃ at a heating rate of 2-8 ℃/min, preserving heat for 1-3 h, and cooling to room temperature to obtain c-SiO;
(b) ball-milling the c-SiO and the copper powder, and uniformly mixing to obtain a mixture; placing the mixture on one side of a chemical vapor deposition furnace, and placing polystyrene on the other side of the chemical vapor deposition furnace; purifying for 0.3-1 h in protective atmosphere, heating the mixture to 700-900 ℃ in the protective atmosphere at a heating rate of 3-7 ℃/min, heating the polystyrene to 300-500 ℃, keeping the temperature for 2-4 h, cooling to room temperature, placing the cooled sample in ferric chloride solution to remove copper powder, and washing with 5-15% acid solution and water respectively to obtain C-SiO/C;
the content of C in the C-SiO/C is 3 to 10 weight percent;
(c) and corroding the C-SiO/C by using corrosive liquid to obtain the silicon-carbon negative electrode material C-SiO/Si/C.
2. The preparation method of the silicon-carbon anode material as claimed in claim 1, wherein the particle size of the silicon monoxide matrix material is 400-600 meshes.
3. The preparation method of the silicon-carbon anode material as claimed in claim 1, wherein the particle size of the silicon monoxide matrix material is 450-550 meshes.
4. The method for preparing silicon-carbon anode material according to claim 1, wherein the particle size of the silicon monoxide matrix material is 500 meshes.
5. The method for preparing a silicon-carbon anode material according to claim 1, wherein the heating device is provided with a quartz boat, a zirconia boat or an alumina boat.
6. The preparation method of the silicon-carbon anode material according to claim 1, wherein the chemical vapor deposition furnace is a tube furnace, a rotary furnace or a muffle furnace.
7. The method for preparing the silicon-carbon anode material according to claim 1, wherein the protective atmosphere is any one of nitrogen, helium, argon or neon.
8. The method for preparing a silicon-carbon anode material according to claim 1,
the method further comprises a copper powder pretreatment step, wherein micron-sized copper powder is subjected to ultrasonic cleaning for 20-40 min by using an acetone solution, then is subjected to ultrasonic cleaning for 10-30 min by using an acid solution with the concentration of 20% -40%, and then is cleaned by using water, dried and then is subjected to ball milling with c-SiO.
9. The method for preparing the silicon-carbon negative electrode material as claimed in claim 1, wherein the C-SiO/C is composed of a C-SiO matrix and graphene uniformly distributed on the C-SiO matrix.
10. The method for preparing the silicon-carbon anode material according to any one of claims 1 to 9, wherein in the step (c), the etching solution is a hydrofluoric acid aqueous solution with a concentration of 3wt% to 20 wt%.
11. The method for preparing the silicon-carbon anode material according to claim 10, wherein the etching solution is a hydrofluoric acid aqueous solution with a concentration of 5wt% to 10 wt%.
12. The method for preparing the silicon-carbon anode material according to claim 10, wherein the mass ratio of C-SiO/C to hydrofluoric acid is 1: 1.2-1.5, and the time of the corrosion treatment is 5-30 min.
13. The method for preparing silicon-carbon anode material according to claim 10, further comprising the steps of washing with water and drying after the etching treatment.
14. The method for preparing the silicon-carbon negative electrode material as claimed in claim 13, wherein the drying temperature is 90-120 ℃.
15. A silicon-carbon negative electrode material, which is characterized by being prepared by the preparation method of the silicon-carbon negative electrode material as claimed in any one of claims 1 to 14.
16. A lithium ion battery, characterized in that its negative electrode comprises the silicon carbon negative electrode material of claim 15.
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| CN108682837B (en) * | 2018-05-17 | 2021-07-06 | 合肥国轩高科动力能源有限公司 | Preparation method of directional porous silicon material for lithium ion battery |
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| CN111777061B (en) * | 2019-04-04 | 2022-03-11 | 江苏载驰科技股份有限公司 | Silicon monoxide composite material, preparation method and application thereof |
| CN112652744A (en) * | 2019-10-12 | 2021-04-13 | 江苏天奈科技股份有限公司 | Preparation method of high-capacity high-cycle lithium battery negative electrode material and lithium battery |
| CN112803015A (en) * | 2019-11-14 | 2021-05-14 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
| CN111403708B (en) * | 2020-03-25 | 2021-11-30 | 广东凯金新能源科技股份有限公司 | Lithium ion battery silicon monoxide composite negative electrode material and preparation method thereof, and lithium ion battery |
| CN112635731B (en) * | 2020-12-17 | 2021-11-02 | 浙江锂宸新材料科技有限公司 | Preparation method of composite nano-silicon negative electrode material based on conductive carbon aerogel and product thereof |
| CN113023738A (en) * | 2021-03-03 | 2021-06-25 | 昆山宝创新能源科技有限公司 | Silicon-based composite material, preparation method thereof and battery |
| CN114864869A (en) * | 2022-05-30 | 2022-08-05 | 上海瑞浦青创新能源有限公司 | Negative electrode and preparation method and application thereof |
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