CN107611394B - Carbon-coated core-shell structure nano silicon/graphene composite negative electrode material and preparation method thereof - Google Patents
Carbon-coated core-shell structure nano silicon/graphene composite negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carbon-coated core-shell structure nano silicon/graphene composite negative electrode material and a preparation method thereof. The composite negative electrode material which has the advantages of high coulombic efficiency, excellent cycle performance and the like is prepared through a simple process.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a carbon-coated core-shell structure nano silicon/graphene composite negative electrode material and a preparation method thereof.
Background
At present, the specific capacity of the anode material of the commercial lithium ion battery basically reaches the limit value, and the rapid promotion is difficult to occur, so the development of the cathode material plays a crucial role in the safety, the energy density and the service life of the battery.
The theoretical gram capacity of the silicon-based material in the existing negative electrode material can reach 4200mAh/g (Li)22Si5) And the lithium ion battery cathode material has good safety (the potential of lithium-intercalated silicon is lower than 0.5V, the problem of solvent molecule co-intercalation does not exist), rich raw material reserves and low cost, and is one of the lithium ion battery cathode materials with the greatest development prospect. However, in the process of charging and discharging, silicon can undergo huge volume change (100% -300%), which causes the materials to be pulverized, peeled off, lose electric contact and have fast capacity attenuation, so the research of the silicon cathode mainly focuses on how to reduce the volume effect of the silicon material and improve the cycle performance of the silicon material.
In order to inhibit the volume expansion of silicon, ensure the stable structure of the material in the charging and discharging process and maintain good electric contact among silicon material particles, between the material and electrolyte and between the material and a current collector. Various methods have been tried for this purpose, including the preparation of amorphous silicon thin films, nano-silicon, porous silicon, silicon oxides, silicon-containing non-metallic compounds, silicon-containing metallic compounds, silicon/carbon composites, silicon/metal (active or inert) composites, and the like. Lithium ions rapidly pass through the boundaries of silicon crystal grains during lithium intercalation and are combined with silicon to form an amorphous lithium silicon compound, the silicon grains are not recrystallized during lithium removal, no phase change exists, and reversible expansion and contraction of local volume are greatly reduced, so that the cycle performance of the material is improved. The graphene has a two-dimensional honeycomb lattice structure and is higher than the reversible lithium storage capacity (the theoretical specific capacity is 372mAh/g) of graphite; reducing the number of layers is beneficial for obtaining higher reversible capacity. The research finds that: both sides of the graphene sheet layer can adsorb 1 Li+Therefore, the theoretical specific capacity of the graphene is twice that of the graphite, namely 744 mAh/g. Although the graphene has higher theoretical specific capacity, if the graphene is independently used as a negative electrode material of a lithium ion battery, the problems of large irreversible specific capacity, voltage hysteresis and the like need to be solved. However, graphene has a very high specific surface area (2600 m)2/g), excellent electron conduction performance, good thermal property and mechanical property, and the nano silicon is compounded with the nano siliconThe material structure change caused by silicon volume expansion in the process of lithium removal can be relieved, and the electron transmission rate of the nano silicon cathode is improved, so that the electrochemical performance of the nano silicon is improved. However, the biggest problem faced by this method is how to effectively and uniformly distribute the active silicon nanoparticles in the matrix, and avoid the local area caused by the aggregation of silicon particles from particle expansion or contraction, thereby causing the loss of electrical contact between particles and the deterioration of material properties.
Patent CN103400970A discloses a nano silicon/graphene lithium ion battery cathode material and a preparation method thereof. The preparation process comprises the following steps: (1) dissolving metallic lithium and a cosolvent in a dehydrated first solvent under an argon atmosphere to prepare an electronic solution; (2) dropwise adding silicon tetrachloride into the reactor in the step (1) under an argon atmosphere to obtain a suspension of nano silicon particles with the particle size of 10-100 nm in an electronic solution; (3) preparing graphite oxide or graphene turbid liquid by taking water as a dispersing agent, adding nitric acid, performing ultrasonic treatment, washing to be neutral, performing vacuum drying, and performing ultrasonic treatment on the obtained product and a second solvent to prepare a gel sample solution; (4) dropwise adding the colloidal solution prepared in the step (3) into the solution prepared in the step (2), stirring, and dispersing nano silicon and graphene through ultrasonic treatment; (5) and (4) carrying out differential centrifugal separation, vacuum filtration and drying on the mixed solution obtained in the step (4), and calcining in an argon-protected tubular furnace to obtain the composite electrode material. Although the problem of uniform dispersion of nano-silicon particles is solved to a certain extent, the obtained composite material still has the defects of low first efficiency and poor cycle performance, about 40% of capacity attenuation still exists after 100 cycles, and the preparation process is complex.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a carbon-coated core-shell structure nano silicon/graphene composite negative electrode material with good cycle stability and a preparation method thereof, so that the prepared material has the advantages of high coulombic efficiency and excellent cycle performance.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a carbon-coated core-shell structure nano silicon/graphene composite negative electrode material comprises the following steps:
(1) preparing nano silicon dioxide dispersion liquid or silicate solution by using nano silicon dioxide or silicate as a silicon source through cationic surfactant modification, mixing the nano silicon dioxide dispersion liquid or silicate solution with graphene oxide sol, and realizing uniform adsorption of the nano silicon dioxide or silicate on graphene oxide sheet layers through electrostatic self-assembly to obtain a quasi-two-dimensional structural unit silicon dioxide/graphene oxide composite material or a silicate/graphene oxide composite material; the nano silicon dioxide dispersion liquid or the silicate solution is mixed with the graphene oxide sol by convection mixing compounding in a T-shaped tubular reactor;
(2) drying the silicon dioxide/graphene oxide composite material or the silicate/graphene oxide composite material of the quasi-two-dimensional structural unit, putting the dried silicon dioxide/graphene oxide composite material or the silicate/graphene oxide composite material into molten salt under the protection of nitrogen, reducing the silicon dioxide or the silicate and the graphene oxide simultaneously by adopting a low-temperature in-situ reduction technology, spheroidizing the nano silicon/graphene of the quasi-two-dimensional structural unit by utilizing the characteristics of easy lamination and spheroidization of the graphene to form a core-shell structure nano silicon/graphene composite material which is laminated layer by layer, and carrying out acid washing after the reaction is finished; the step of pickling is to clean the nano silicon/graphene composite material by using a dilute hydrochloric acid solution;
(3) in a spheroidizing device, the reduced nano silicon/graphene composite material is subjected to composite coating with a certain amount of graphite and a carbon source material, and then the nano silicon/graphene composite negative electrode material with the carbon-coated core-shell structure is obtained by carbonization under the protection of inert gas.
In the step (1) of the preparation method of the carbon-coated core-shell structure nano silicon/graphene composite negative electrode material, the particle size of the nano silicon dioxide is less than or equal to 10nm, the concentration of the solution prepared from the silicate is 10-80 mg/ml, and the mass ratio of the nano silicon dioxide or the silicate to the cationic surfactant is 100: (1-20) carrying out ultrasonic mixing treatment for 0.5-1 h to obtain the nano silicon dioxide dispersion liquid or the silicate solution.
In the step (1) of the preparation method of the carbon-coated core-shell structure nano silicon/graphene composite negative electrode material, the cationic surfactant is dodecyl trimethyl ammonium bromide, 3-aminopropyl triethyl silane, dodecyl dimethyl benzyl ammonium chloride or polydimethyl diallyl ammonium chloride.
In the step (1) of the preparation method of the carbon-coated core-shell structure nano silicon/graphene composite negative electrode material, the graphene oxide sol is prepared by a Hummers method, the concentration of the graphene oxide sol is 1-5 mg/ml, and the mass ratio of solid matters in the graphene oxide sol to nano silicon dioxide or silicate modified by a cationic surfactant is 0.10-0.5: 1.
In the step (2) of the preparation method of the carbon-coated core-shell structure nano silicon/graphene composite negative electrode material, the molten salt is aluminum chloride and aluminum powder, and the in-situ reduction at low temperature refers to mixing the silicon dioxide/graphene oxide composite material or silicate/graphene oxide composite material, aluminum chloride and aluminum powder according to the mass ratio of the silicon source to the aluminum chloride to the aluminum powder of 1:8:0.8, and then preserving heat for 5-10 hours at the temperature of 150-250 ℃.
In the step (3) of the preparation method of the carbon-coated core-shell structure nano silicon/graphene composite negative electrode material, the carbon source material is one or more than two of asphalt, sucrose, glucose, polyvinyl alcohol, polyethylene glycol, phenolic resin, polyacrylonitrile, polypyrrole and polyaniline; the mass ratio of the carbon source material to the graphite is 0.5-2: 10, and the mass ratio of the nano silicon/graphene composite material to the graphite is 0.5-2: 10.
In the step (3) of the preparation method of the carbon-coated core-shell structure nano silicon/graphene composite negative electrode material, the carbonization conditions are as follows: heating to 600-900 ℃ at a heating rate of 2-5 ℃/min, and preserving heat for 2-10 h.
The spheroidizing device used in the step (3) is a spray dryer.
In the preparation method of the carbon-coated core-shell structure nano silicon/graphene composite negative electrode material, the mass content of silicon in the carbon-coated core-shell structure nano silicon/graphene composite negative electrode material is 5-20%.
The carbon-coated core-shell structured nano silicon/graphene composite negative electrode material obtained by the preparation method is a spherical three-dimensional structure of a nano silicon/graphene composite raw material.
The carbon-coated core-shell structured nano silicon/graphene composite negative electrode material is used for manufacturing a lithium ion battery negative electrode plate.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the invention, silicon dioxide or silicate is used as a silicon source, the silicon dioxide or silicate is compounded with graphene oxide sol, and the carbon-coated core-shell structure nano silicon/graphene composite negative electrode material is obtained through carbon coating or compounding, so that the specific surface area of graphene can be greatly reduced, and the first efficiency of the composite negative electrode material is improved.
According to the preparation method of the core-shell structure nano silicon/graphene composite negative electrode material, the nano silicon dioxide or silicate is uniformly adsorbed on a graphene oxide sheet layer through electrostatic self-assembly, the low-temperature in-situ reduction technology is adopted, the prepared composite material realizes the nano dispersion of silicon nanoparticles in a graphene substrate layer, the phenomenon that the particles are expanded or contracted in a local area due to the agglomeration of the silicon particles to cause the loss of electric contact among the particles and the deterioration of material performance is avoided, meanwhile, because the granularity of the selected nano silicon particles is small enough, even if the nano silicon particles are pulverized, a large proportion of silicon materials can be well contacted with the graphene, the island effect can be effectively avoided, and the nano composite negative electrode material with higher capacity and better stability, rate capability and cycle performance is obtained.
The preparation method of the carbon-coated core-shell structure nano silicon/graphene composite anode material has the advantages of simple process, easiness in operation, safety, environmental friendliness, large-scale production and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
This example uses the surfactant poly dimethyl diallyl ammonium chloride and nano silica particles with a diameter of less than 10 nm. Firstly, 0.16g of surfactant poly dimethyl diallyl ammonium chloride is weighed and dispersed in distilled water, after the surfactant poly dimethyl diallyl ammonium chloride is fully stirred for a period of time, 0.9g of nano silicon dioxide is added, ultrasonic dispersion is carried out for 0.5h, centrifugal separation, cleaning and drying are carried out, and the cation modified nano silicon dioxide material is obtained.
2mg/ml of graphene oxide sol is prepared by a Hummers method. And adding the prepared cation modified nano silicon dioxide material into 100ml of graphene oxide sol, stirring and mixing uniformly, and freeze-drying to prepare nano silicon dioxide/graphene oxide powder.
And (3) uniformly mixing the prepared nano silicon dioxide/graphene oxide powder with 7.2g of aluminum chloride and 0.72g of aluminum powder, keeping the temperature of 200 ℃ for 5 hours in an argon atmosphere, and naturally cooling to room temperature. And cleaning the obtained material with a dilute hydrochloric acid solution to prepare the nano silicon/graphene composite material.
Weighing 0.5g of asphalt to dissolve in distilled water, adding 5g of graphite material and the nano silicon/graphene composite material, stirring for 3 hours at the speed of 1000r/min to obtain mixed slurry, and performing spray drying on the mixed slurry through a peristaltic pump under the stirring condition to obtain a precursor: the inlet temperature of the spray drying is 220 ℃, and the outlet temperature of the spray drying is 100-120 ℃.
And carbonizing the prepared precursor in a high-temperature atmosphere furnace, gradually heating from room temperature to 900 ℃ at a heating rate of 5 ℃/min under the protection of a high-purity Ar gas atmosphere, keeping the temperature for 3 hours, cooling to room temperature, taking out, and grinding to obtain the carbon-coated core-shell structured nano silicon/graphene composite negative electrode material.
The preparation method of the lithium ion battery comprises the following steps:
and uniformly stirring the prepared negative electrode material with a conductive agent (SP) and a binder (CMC/SBR) to prepare electrode slurry, uniformly coating the slurry on a copper foil current collector with the thickness of 9 mu m, drying for 12h at 105 ℃ under a vacuum condition, and cutting to obtain a negative electrode sheet. A 2032 type button cell is formed in a glove box filled with high-purity argon gas. The button cell is tested by the Xinwei cell test system for the charge and discharge performance, the charge and discharge cut-off voltage range is 5 mV-1.5V, the test temperature is 25 ℃, and the same test method is adopted in the following embodiments.
Example 2
This example uses the surfactant dodecyl dimethyl benzyl ammonium chloride and nano silica particles with a diameter of less than 10 nm. Firstly, 0.16g of surfactant dodecyl dimethyl benzyl ammonium chloride is weighed and dispersed in distilled water, after the surfactant dodecyl dimethyl benzyl ammonium chloride is fully stirred for a period of time, 0.8g of nano silicon dioxide is added, ultrasonic dispersion is carried out for 0.5h, centrifugal separation, cleaning and drying are carried out, and the cation modified nano silicon dioxide material is obtained.
2mg/ml of graphene oxide sol is prepared by a Hummers method. And adding the prepared cation modified nano silicon dioxide material into 100ml of graphene oxide sol, stirring and mixing uniformly, and freeze-drying to prepare nano silicon dioxide/graphene oxide powder.
Uniformly mixing the prepared nano silicon dioxide/graphene oxide powder with 6.4g of aluminum chloride and 0.64g of aluminum powder, keeping the temperature of 250 ℃ for 5 hours in an argon atmosphere, and naturally cooling to room temperature. And cleaning the obtained material with a dilute hydrochloric acid solution to prepare the nano silicon/graphene composite material.
Weighing 1g of glucose, dissolving in distilled water, adding 6g of graphite material and the nano silicon/graphene composite material, stirring for 3 hours at the speed of 1000r/min to obtain mixed slurry, and performing spray drying on the mixed slurry through a peristaltic pump under the stirring condition to obtain a precursor: the inlet temperature of the spray drying is 220 ℃, and the outlet temperature of the spray drying is 100-120 ℃.
And carbonizing the prepared precursor in a high-temperature atmosphere furnace, gradually heating from room temperature to 600 ℃ at a heating rate of 2 ℃/min under the protection of high-purity Ar atmosphere, keeping the temperature for 10 hours, cooling to room temperature, taking out and grinding to obtain the carbon-coated core-shell structured nano silicon/graphene composite negative electrode material.
Example 3
This example uses the surfactant 3-aminopropyltriethylsilane and nano silica particles with a diameter of less than 10 nm. Firstly, 0.16g of surfactant 3-aminopropyltriethylsilane is weighed and dispersed in distilled water, after the surfactant 3-aminopropyltriethylsilane is fully stirred for a period of time, 0.8g of nano-silica is added, ultrasonic dispersion is carried out for 1 hour, centrifugal separation, cleaning and drying are carried out, and the cation modified nano-silica material is obtained.
5mg/ml of graphene oxide sol is prepared by a Hummers method. And adding the prepared cation modified nano silicon dioxide material into 20ml of graphene oxide solution, stirring and mixing uniformly, and freeze-drying to prepare nano silicon dioxide/graphene oxide powder.
Uniformly mixing the prepared nano silicon dioxide/graphene oxide powder with 6.4g of aluminum chloride and 0.64g of aluminum powder, keeping the temperature of 200 ℃ for 5 hours in an argon atmosphere, and naturally cooling to room temperature. And cleaning the obtained material with a dilute hydrochloric acid solution to prepare the nano silicon/graphene composite material.
Weighing 0.7g of cane sugar, dissolving in distilled water, adding 3.5g of graphite material and the nano silicon/graphene composite material, stirring for 3 hours at the speed of 1000r/min to obtain mixed slurry, and performing spray drying on the mixed slurry through a peristaltic pump under the stirring condition to obtain a precursor: the inlet temperature of the spray drying is 220 ℃, and the outlet temperature of the spray drying is 100-120 ℃.
And carbonizing the prepared precursor in a high-temperature atmosphere furnace, gradually heating from room temperature to 800 ℃ at a heating rate of 3 ℃/min under the protection of a high-purity Ar gas atmosphere, keeping the temperature for 3 hours, cooling to room temperature, taking out and grinding to obtain the carbon-coated core-shell structured nano silicon/graphene composite negative electrode material.
Example 4
This example uses the surfactant dodecyl dimethyl benzyl ammonium chloride and nano silica particles with a diameter of less than 10 nm. Firstly, 0.16g of surfactant dodecyl dimethyl benzyl ammonium chloride is weighed and dispersed in distilled water, after the surfactant dodecyl dimethyl benzyl ammonium chloride is fully stirred for a period of time, 0.8g of nano silicon dioxide is added, ultrasonic dispersion is carried out for 1 hour, centrifugal separation, cleaning and drying are carried out, and the cation modified nano silicon dioxide material is obtained.
2mg/ml of graphene oxide sol is prepared by a Hummers method. And adding the prepared cation modified nano silicon dioxide material into 100ml of graphene oxide sol, stirring and mixing uniformly, and freeze-drying to prepare nano silicon dioxide/graphene oxide powder.
Uniformly mixing the prepared nano silicon dioxide/graphene oxide powder with 6.4g of aluminum chloride and 0.64g of aluminum powder, keeping the temperature of 250 ℃ for 5 hours in an argon atmosphere, and naturally cooling to room temperature. And cleaning the obtained material with a dilute hydrochloric acid solution to prepare the nano silicon/graphene composite material.
Weighing 1g of phenolic resin, dissolving in absolute ethyl alcohol, adding 7g of graphite material and the nano silicon/graphene material, stirring for 3 hours at the speed of 1000r/min to obtain mixed slurry, and performing spray drying on the mixed slurry through a peristaltic pump under the stirring condition to obtain a precursor: the inlet temperature of the spray drying is 220 ℃, and the outlet temperature of the spray drying is 100-120 ℃.
Carbonizing the prepared precursor in a high-temperature atmosphere furnace: under the protection of high-purity Ar gas atmosphere, gradually heating from room temperature to 700 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 3 hours, cooling to room temperature, taking out and grinding to obtain the carbon-coated core-shell structured nano silicon/graphene composite negative electrode material.
Example 5
The present example uses the surfactants poly dimethyl diallyl ammonium chloride and glass fibers. Firstly, 0.16g of surfactant poly dimethyl diallyl ammonium chloride is weighed and dispersed in distilled water, after the surfactant poly dimethyl diallyl ammonium chloride is fully stirred for a period of time, 0.8g of glass fiber is added, ultrasonic dispersion is carried out for 1h, centrifugal separation, cleaning and drying are carried out, and the cation modified nano glass fiber material is obtained.
2mg/ml of graphene oxide sol is prepared by a Hummers method. And adding the prepared cation modified glass fiber material into 100ml of graphene oxide sol, stirring and mixing uniformly, and freeze-drying to prepare the nano glass fiber/graphene oxide powder.
And (3) uniformly mixing the prepared glass fiber/graphene oxide powder with 6.4g of aluminum chloride and 0.64g of aluminum powder, keeping the temperature of 250 ℃ for 6 hours in an argon atmosphere, and naturally cooling to room temperature. And cleaning the obtained material with a dilute hydrochloric acid solution to prepare the nano silicon/graphene composite material.
Weighing 1g of phenolic resin, dissolving in absolute ethyl alcohol, adding 7g of graphite material and the nano silicon/graphene material, stirring for 3 hours at the speed of 1000r/min to obtain mixed slurry, and performing spray drying on the mixed slurry through a peristaltic pump under the stirring condition to obtain a precursor: the inlet temperature of the spray drying is 220 ℃, and the outlet temperature of the spray drying is 100-120 ℃.
Carbonizing the prepared precursor in a high-temperature atmosphere furnace: under the protection of high-purity Ar gas atmosphere, gradually heating from room temperature to 700 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 3 hours, cooling to room temperature, taking out and grinding to obtain the carbon-coated core-shell structured nano silicon/graphene composite negative electrode material.
The electrochemical performance test results of the composite negative electrode material prepared in the above examples when used in a lithium ion battery are shown in table 1:
TABLE 1 electrochemical Performance test results
As can be seen from Table 1, the composite negative electrode material obtained by the preparation method of the invention has high reversible capacity and excellent cycle performance when used in a lithium ion battery. The cathode material prepared by the optimized preparation method of the invention has good electrochemical performance when being used for a lithium ion battery.
Although the invention has been described herein with reference to illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure. More specifically, various variations and modifications may be made to the component parts and/or arrangements of the subject combination arrangement within the scope of the disclosure herein. In addition to variations and modifications in the component parts and/or arrangements, other uses will also be apparent to those skilled in the art.
Claims (9)
1. A preparation method of a carbon-coated core-shell structure nano silicon/graphene composite anode material is characterized by comprising the following steps:
(1) preparing nano silicon dioxide dispersion liquid or silicate solution by using nano silicon dioxide or silicate as a silicon source through cationic surfactant modification, mixing the nano silicon dioxide dispersion liquid or silicate solution with graphene oxide sol, and realizing uniform adsorption of the nano silicon dioxide or silicate on graphene oxide sheet layers through electrostatic self-assembly to obtain a silicon dioxide/graphene oxide composite material or a silicate/graphene oxide composite material; the particle size of the nano silicon dioxide is less than or equal to 10 nm; the mass ratio of the solid matter in the graphene oxide sol to the nano silicon dioxide or silicate modified by the cationic surfactant is 0.10-0.5: 1;
(2) drying the silicon dioxide/graphene oxide composite material or the silicate/graphene oxide composite material, putting the dried silicon dioxide/graphene oxide composite material or the silicate/graphene oxide composite material into molten salt under the protection of nitrogen, carrying out in-situ reduction at the temperature of 150-250 ℃ to obtain a nano silicon/graphene composite material, and carrying out acid washing after the reaction is finished;
(3) in a spheroidization device, carrying out composite coating on the reduced nano silicon/graphene composite material and a certain amount of graphite and carbon source material, and then carbonizing under the protection of inert gas to obtain a carbon-coated nano silicon/graphene composite negative electrode material with a core-shell structure; the carbon source material is one or more than two of asphalt, sucrose, glucose, polyvinyl alcohol, polyethylene glycol, phenolic resin, polyacrylonitrile, polypyrrole and polyaniline.
2. The preparation method of the carbon-coated core-shell structure nano silicon/graphene composite anode material according to claim 1, wherein the mass ratio of the nano silicon dioxide or silicate to the cationic surfactant in the step (1) is 100: (1-20) carrying out ultrasonic mixing treatment for 0.5-1 h to obtain the nano silicon dioxide dispersion liquid or the silicate solution.
3. The preparation method of the carbon-coated core-shell structure nano silicon/graphene composite anode material according to claim 1, wherein the cationic surfactant in the step (1) is dodecyl trimethyl ammonium bromide, 3-aminopropyl triethyl silane, dodecyl dimethyl benzyl ammonium chloride or polydimethyl diallyl ammonium chloride.
4. The preparation method of the carbon-coated core-shell structure nano silicon/graphene composite anode material according to claim 1, wherein the concentration of the graphene oxide sol in the step (1) is 1-5 mg/ml.
5. The preparation method of the carbon-coated core-shell structure nano silicon/graphene composite anode material according to claim 1, wherein the molten salt in the step (2) is aluminum chloride and aluminum powder, and the in-situ reduction at low temperature is performed by mixing the silicon dioxide/graphene oxide composite material or the silicate/graphene oxide composite material, the aluminum chloride and the aluminum powder according to the mass ratio of the silicon source to the aluminum chloride to the aluminum powder of 1:8:0.8, and then keeping the temperature at 150-250 ℃ for 5-10 h.
6. The preparation method of the carbon-coated core-shell structure nano silicon/graphene composite negative electrode material according to claim 1, wherein the mass ratio of the carbon source material to the graphite in the step (3) is 0.5-2: 10, and the mass ratio of the nano silicon/graphene composite material to the graphite is 0.5-2: 10.
7. The preparation method of the carbon-coated core-shell structure nano silicon/graphene composite anode material according to claim 1, wherein the carbonization conditions in the step (3) are as follows: heating to 600-900 ℃ at a heating rate of 2-5 ℃/min, and preserving heat for 2-10 h.
8. The preparation method of the carbon-coated core-shell structure nano silicon/graphene composite negative electrode material according to claim 1, wherein the mass content of silicon in the carbon-coated core-shell structure nano silicon/graphene composite negative electrode material is 5-20%.
9. The carbon-coated core-shell structured nano silicon/graphene composite negative electrode material prepared by the preparation method of any one of claims 1 to 8.
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