CN114050251B - Preparation and application of silicon-carbon composite micro-nano structure material - Google Patents

Preparation and application of silicon-carbon composite micro-nano structure material Download PDF

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CN114050251B
CN114050251B CN202111369228.4A CN202111369228A CN114050251B CN 114050251 B CN114050251 B CN 114050251B CN 202111369228 A CN202111369228 A CN 202111369228A CN 114050251 B CN114050251 B CN 114050251B
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composite micro
nano structure
carbon
structure material
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CN114050251A (en
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刘现玉
陈洁
尚琼
王润清
马明广
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Lanzhou City University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

Abstract

The invention discloses a preparation method of a silicon-carbon composite micro-nano structure material, which comprises the steps of fully grinding and mixing silicon powder and metal powder, then performing ball milling, and cooling to room temperature to obtain silicon/metal alloy; and (3) placing the silicon/metal alloy in a tube furnace, introducing silicon tetrachloride gas and mixed gas of carrier gas and carbon source, reacting for 4-10 hours at 450-650 ℃, washing the obtained product with dilute acid, filtering, washing with water, drying, and removing by-product metal chloride. According to the invention, silicon powder, metal powder, a carrier gas carbon source and silicon tetrachloride are used for preparing the silicon-carbon composite micro-nano structure material, the composite material is used as a negative electrode material of a lithium ion battery, and has a high-efficiency conductive network, so that the problem of poor silicon conductivity is effectively overcome, in addition, the full coating of carbon can effectively relieve the volume expansion in the charge and discharge process and inhibit the pulverization of the electrode material, the structural integrity of the electrode can be fully maintained, the cycle stability is improved, and the cycle life of the battery is fully and effectively prolonged.

Description

Preparation and application of silicon-carbon composite micro-nano structure material
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a silicon-carbon composite micro-nano structure material; the invention also relates to application of the silicon-carbon composite micro-nano structure material as a negative electrode material of a lithium ion battery.
Background
The increasing global energy consumption, limited supply of fossil fuels and the requirement to reduce carbon content emissions have increased the demand for renewable energy sources such as nuclear, wind, solar, tidal, fuel cells and secondary batteries. The trend to use renewable clean energy is increasing worldwide, but this requires more intensive research into the physical and chemical properties of the materials. Since the beginning of the 90 s of the 20 th century, sony has pushed out the first generation of lithium ion batteries, which have been dominant in competing with other batteries, such as nickel hydrogen, for power supply as small electronic products. In recent years, lithium ion batteries have been widely used to provide electrical power to various types of small portable electronic devices such as notebook computers, smart phones, and camcorders. In addition, they have also been used in the field of Hybrid Electric Vehicles (HEVs) and large energy storage.
Conventional lithium ion batteries are composed primarily of a carbon-based negative electrode (typically graphite) containing a lithium salt (e.g., liPF 6 ) Carbonate-based organic electrolyte and lithium metal oxide positive electrode (usually LiCoO) 2 ) Composition is prepared. The theoretical specific capacity of graphite is only 372 mAh/g, and further requirements of related industries on the capacity and performance of lithium batteries are difficult to meet, so that the development of novel cathode materials with high specific energy is particularly important. The negative electrode material has important influence on the energy density, capacity, cycle performance and the like of the lithium ion battery. The following conditions should be applied as a negative electrode material of a lithium ion battery: should have a low potential to provide a low discharge voltage so as to be able to match the positive electrode material; when reacting with lithium, the crystal structure cannot be changed significantly; the reaction is highly reversible; a larger lithium ion diffusion coefficient; higher electron conductivity; a suitable density; a unit mass can store a large amount of charge.
Silicon-based (Si) materials have excellent electrochemical properties themselves, and have been focused and widely studied by vast researchers. Silicon has a lower voltage plateau and an ultrahigh theoretical specific capacity (the product at room temperature is Li) 15 Si 4 At 3600 mAh g -1 ) About 10 times (about 372 mAh g) -1 ). Silicon content in crustIs abundant and therefore has a relatively low cost. However, there are still challenges when using silicon as the negative electrode of Lithium Ion Batteries (LIBs), including its intrinsically poor conductivity, large volume changes (about 300%), and instability of the solid electrolyte membrane (SEI), which can lead to destruction of the electrode structure and loss of energy storage.
Compounding silicon with carbon-based materials is one of the common solutions. On the one hand, the carbon-based material can be used as a matrix for buffering large volume changes of silicon during repeated lithium ion insertion/extraction>300%). On the other hand, the carbon component contributes to improvement of the conductivity of the electrode material. Many studies have fully demonstrated that silicon-carbon composites can significantly increase the electrical conductivity of silicon materials and inhibit the volume expansion of silicon. In various carbon materials, the two-dimensional graphene sheet can effectively reduce the stress generated by volume expansion after being used as an auxiliary material of Si/C due to the ultrahigh conductivity, excellent mechanical property and stable chemical property of the two-dimensional graphene sheet, form a stable solid electrolyte interface and further improve the diffusion of lithium ions. For example, silicon nanoparticles prepared from bamboo leaves, at 8.4A g -1 Can only display 430 mAh g at current density -1 Is a reversible capacity of (a). After the silicon nano particles are coated by carbon and redox graphene, 1400 mAh g can be obtained under the same current density -1 Is a reversible specific capacity of (a). Literature reports that a graphene-coated nano silicon/graphite composite material can keep 445mAh g after 300 circles of circulation under the current density of 1C -1 The reversible specific capacity of the catalyst can reach 99.6 percent. Although graphene or redox graphene has the advantages, the cost of graphene is high, the preparation process is complex, and raw materials polluting the environment need to be introduced in the synthesis process. Thus, large-scale, simple, inexpensive preparation of uniformly coated Si/C composites remains challenging.
However, the method for preparing the Si/C composite disclosed in the above document has problems in that: the grain size of Si is bigger and nonuniform, the composite carbon structure is difficult to be completely coated on the surface of Si, and the performance improvement of Si is limited. It is therefore particularly important to develop a simple method of complete carbon coating. There are a number of problems associated with the prior art methods for preparing Si/C composites, and therefore, a need exists for a Si/C preparation method that overcomes the above problems.
Disclosure of Invention
The invention aims to solve the problems that the grain size of Si in a Si/C compound is large and nonuniform, a composite carbon structure is difficult to completely cover the surface of Si, the specific capacity is low, the performance improvement of Si is limited, and the like, and provides a preparation method of a silicon-carbon composite micro-nano structure material uniformly coated by carbon;
the invention further aims to provide application of the silicon-carbon composite micro-nano structure material as a negative electrode material of a lithium ion battery.
1. Preparation of carbon silicon (Si@C) composite micro-nano particle electrode material
The preparation method of the silicon-carbon composite micro-nano structure material comprises the following steps:
(1) And fully grinding and mixing the silicon powder and the metal powder, performing ball milling, and cooling to room temperature to obtain the silicon/metal alloy. Wherein the metal powder is at least one of lithium, sodium, magnesium, zinc and aluminum powder; the silicon powder is commercial micron-sized silicon powder; the mol ratio of the silicon powder to the metal powder is 1:2-1:3; the ball milling is planetary ball milling, and the ball milling time is 12-24 hours.
(2) And placing the silicon/metal alloy in a tube furnace, introducing silicon tetrachloride gas and mixed gas of carrier gas and carbon source, reacting for 4-10 hours at 450-650 ℃, washing the obtained product with dilute acid, filtering, washing with water, drying, and removing by-product metal chloride to obtain the silicon-carbon composite micro-nano structure material.
The carrier gas is argon; the carbon source is acetylene gas, methane gas, propane gas or propylene gas; and in the mixed gas of the carrier gas and the carbon source, the volume fraction of the carbon source is 5-10%. And the introducing rate of the silicon tetrachloride gas and the mixed gas of the carrier gas and the carbon source is 300-500 mL/min. The dilute acid is one or two or more than two of hydrochloric acid, nitric acid or sulfuric acid, and the concentration of the dilute acid is 0.1-5 mol/L. The drying is vacuum drying, and the drying temperature is 60-120 ℃.
2. Structure and performance of silicon-carbon composite micro-nano structure material
1. Structure of silicon-carbon composite micro-nano structure material
FIG. 1 shows the TGA curve of the silicon-carbon composite micro-nano-structure material prepared by the invention. As can be seen from the TGA curve of the silicon-carbon composite micro-nano structure material in fig. 1, the content of the silicon micro-nano particles in the silicon-carbon composite micro-nano structure material is about 46%.
Fig. 2 is an SEM image of the silicon-carbon composite micro-nano structure material prepared by the present invention. As can be seen from the SEM image of fig. 2, the silicon nanoparticles are uniformly distributed in the carbon, forming a uniform silicon-carbon composite micro-nanostructure material. Fig. 3 is a TEM image of a silicon carbon composite micro-nano structured material prepared according to the present invention. The uniform coating of the silicon micro-nano particles with carbon can also be seen from the TEM image of fig. 3.
2. Performance of silicon-carbon composite micro-nano structure material
And taking the silicon-carbon composite micro-nano structure material as a negative electrode material of the lithium ion battery. And assembling the silicon-carbon composite micro-nano structure material and the electrolyte into the lithium ion battery. The electrolyte of the lithium ion battery is a mixed solution of lithium salt and at least one of dimethyl carbonate, diethyl carbonate, ethylene carbonate, biphenyl (BP), ethylene carbonate (VEC), ethylene carbonate (VC), fluoroethylene carbonate (FEC), 1, 4-Butyl Sultone (BS), 1, 3-Propane Sultone (PS), 1,3- (1-Propylene) Sultone (PST), ethylene Sulfate (ESA), ethylene Sulfite (ESI), cyclohexylbenzene (CHB), tert-butylbenzene (TBB), tert-pentylbenzene (TPB) and Ding Erqing (SN); the lithium salt is lithium hexafluorophosphate (LiPF) 6 ) Lithium bis (fluorosulfonamide) (LiSSI), lithium tetrafluoroborate (LiBF) 4 ) Lithium bistrifluorosulfonamide (LiN (SO) 2 CF 3 ) 2 ) Lithium bis (oxalato) borate (LiBOB), lithium triflate (LiSO) 3 CF 3 ) At least one of them.
FIG. 4 shows the cycle performance of the prepared SiC composite micro-nano structure material under the current density of 0.1C. FIG. 4 shows that at a current density of 0.1CThe silicon-carbon composite micro-nano structure material has 1219.8 mAh g -1 Is a reversible specific capacity of (a). The silicon-carbon composite micro-nano structure material is proved to have excellent circulation stability.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention has the advantages of easily obtained raw materials, simple process and low cost, greatly improves the production efficiency and safety, can fully meet the requirements of modern industrial production, realizes commercial large-scale production, and has wide application prospect.
2. According to the invention, a solid-gas reaction method is adopted, silicon powder, metal powder, a carrier gas carbon source and silicon tetrachloride are utilized to prepare the silicon-carbon composite micro-nano structure material, the composite material has a high-efficiency conductive network, the problem of poor conductivity of silicon is further effectively overcome, in addition, the full cladding of carbon can effectively relieve the volume expansion in the charge-discharge process and inhibit the pulverization of electrode materials, the structural integrity of the electrode can be fully maintained, the cycle stability is improved, and the cycle life of the battery is fully and effectively prolonged.
3. The invention provides a universally applicable method, which can simply and rapidly prepare silicon powder, metal powder, carrier gas carbon source and silicon tetrachloride into the silicon-carbon composite micro-nano structure material by a solid-gas reaction method, and has wide application prospect in the fields of smart phones, notebook computers, portable cameras, green energy sources, aerospace and the like.
Drawings
FIG. 1 shows the TGA curve of the silicon-carbon composite micro-nano-structure material prepared by the invention.
Fig. 2 is an SEM image of the silicon-carbon composite micro-nano structure material prepared by the present invention.
Fig. 3 is a TEM image of a silicon-carbon composite micro-nano structure material prepared according to the present invention.
FIG. 4 is a graph showing the cycle performance of the silicon-carbon composite micro-nano structure material prepared by the invention at a current density of 0.1C.
Detailed Description
The preparation and the performance of the silicon-carbon composite micro-nano structure material are further explained and illustrated below by combining specific examples.
Example 1
A preparation method of a silicon-carbon (Si@C) composite micro-nano structure material comprises the following specific steps:
(1) Fully grinding and mixing 0.56g of commercial micron-sized crude silicon and 1.152g of metal magnesium powder, transferring into a ball milling tank for planetary ball milling for 12 hours, cooling to room temperature, and obtaining 1.42g of silicon/magnesium alloy (Mg 2 Si）；
(2) The above silicon/magnesium alloy (Mg 2 Si) placing the mixture in a tubular furnace, then introducing a mixed gas of silicon tetrachloride gas, argon gas and acetylene gas which are preheated to 65 ℃, wherein the introducing rate is 300-500 mL/min, and carrying out chemical reaction at 450 ℃ for 10h; transferring the obtained product to a beaker, adding 50-60mL of dilute hydrochloric acid (0.1 mol/L), cleaning, stirring for 0.5-8 h, filtering, washing with water, drying, and removing a byproduct magnesium chloride to obtain the silicon-carbon (Si@C) composite micro-nano structural material.
(3) Taking the silicon-carbon (Si@C) composite micro-nano structural material in the step (2) as a negative electrode, combining ethylene carbonate and dimethyl carbonate as electrolyte, and lithium hexafluorophosphate (LiPF) 6 ) And (3) assembling the lithium ion battery for lithium salt. At a current density of 0.1C, the capacity after 100 cycles was 652 mAh g -1 。
Example 2
A preparation method of a silicon-carbon (Si@C) composite micro-nano structure material comprises the following specific steps:
(1) Fully grinding and mixing 0.56g of commercial micron-sized crude silicon and 1.152g of metal magnesium powder, transferring the mixture into a ball milling tank, performing planetary ball milling for 15 hours, and cooling the mixture to room temperature to obtain 1.382g of silicon/magnesium alloy;
(2) Placing the silicon/magnesium alloy in a tube furnace, then introducing a mixed gas of silicon tetrachloride gas, argon gas and acetylene gas which is obtained by preheating to 65 ℃, and carrying out chemical reaction at 500 ℃ for 8 hours at the rate of 300-500 mL/min; transferring the obtained product to a beaker, adding 5-6mL of dilute sulfuric acid (0.5 mol/L), cleaning, stirring for 0.5-8 h, filtering, washing with water, drying, and removing a byproduct magnesium chloride to obtain the silicon-carbon (Si@C) composite micro-nano structural material.
(3) Taking the silicon-carbon (Si@C) composite micro-nano structural material in the step (2) as a negative electrode, combining ethylene carbonate and dimethyl carbonate as electrolyte, and lithium hexafluorophosphate (LiPF) 6 ) And (3) assembling the lithium ion battery for lithium salt. At a current density of 0.1C, the capacity after 100 cycles was 783 mAh g -1 。
Example 3
A preparation method of a silicon-carbon (Si@C) composite micro-nano structure material comprises the following specific steps:
(1) Fully grinding and mixing 0.56g of commercial micron-sized crude silicon and 1.152g of metal magnesium powder, transferring the mixture into a ball milling tank, performing planetary ball milling for 20 hours, and cooling the mixture to room temperature to obtain 1.33g of silicon/magnesium alloy;
(2) Placing the silicon/magnesium alloy in a tube furnace, then introducing a mixed gas of silicon tetrachloride gas, argon gas and acetylene gas which is obtained by preheating to 65 ℃, and carrying out chemical reaction at 550 ℃ for 6 hours at the rate of 300-500 mL/min; transferring the obtained product to a beaker, adding 10-15mL of dilute hydrochloric acid (0.5 mol/L), cleaning, stirring for 0.5-8 h, filtering, washing with water, drying, removing a byproduct magnesium chloride, and repeatedly treating to obtain the silicon-carbon (Si@C) composite micro-nano structural material.
(3) Taking the silicon-carbon (Si@C) composite micro-nano structural material in the step (2) as a negative electrode, combining ethylene carbonate and dimethyl carbonate as electrolyte, and lithium hexafluorophosphate (LiPF) 6 ) And (3) assembling the lithium ion battery for lithium salt. At a current density of 0.1C, the capacity was 819 mAh g after 100 cycles -1 。
Example 4
A preparation method of a silicon-carbon (Si@C) composite micro-nano structure material comprises the following specific steps:
(1) Fully grinding and mixing 0.56g of commercial micron-sized crude silicon and 1.152g of metal magnesium powder, transferring the mixture into a ball milling tank, performing planetary ball milling for 24 hours, and cooling the mixture to room temperature to obtain 1.19g of silicon/magnesium alloy;
(2) Placing the silicon/magnesium alloy in a tube furnace, then introducing a mixed gas of silicon tetrachloride gas, argon gas and acetylene gas which is preheated to 65 ℃, wherein the introducing rate is 300-500 mL/min, and carrying out chemical reaction at 600 ℃ for 6 hours; transferring the obtained product to a beaker, adding 50-60mL of dilute hydrochloric acid (0.1 mol/L), cleaning, stirring for 0.5-8 h, filtering, washing with water, drying, and removing a byproduct magnesium chloride to obtain the silicon-carbon (Si@C) composite micro-nano structural material.
(3) Taking the silicon-carbon (Si@C) composite micro-nano structural material in the step (2) as a negative electrode, combining ethylene carbonate and dimethyl carbonate as electrolyte, and lithium hexafluorophosphate (LiPF) 6 ) And (3) assembling the lithium ion battery for lithium salt. At a current density of 0.1C, the capacity after 100 cycles was 807 mAh g -1 。
Example 5
A preparation method of a silicon-carbon (Si@C) composite micro-nano structure material comprises the following specific steps:
(1) Fully grinding and mixing 0.56g of commercial micron-sized crude silicon and 1.152g of metal magnesium powder, transferring the mixture into a ball milling tank, performing planetary ball milling for 12 hours, and cooling the mixture to room temperature to obtain 1.43g of silicon/magnesium alloy;
(2) Placing the silicon/magnesium alloy in a tube furnace, then introducing a mixed gas of silicon tetrachloride gas, argon gas and methane gas which is preheated to 65 ℃, wherein the introducing rate is 300-500 mL/min, and carrying out chemical reaction at 600 ℃ for 4 hours; transferring the product to a beaker, adding 50-60mL of dilute hydrochloric acid (0.1 mol/L), cleaning, stirring for 0.5-8 h, filtering, washing with water, drying, and removing a byproduct magnesium chloride to obtain the silicon-carbon (Si@C) composite micro-nano structural material.
(3) Taking the silicon-carbon (Si@C) composite micro-nano structural material in the step (2) as a negative electrode, combining ethylene carbonate and dimethyl carbonate as electrolyte, and lithium hexafluorophosphate (LiPF) 6 ) And (3) assembling the lithium ion battery for lithium salt. At a current density of 0.1C, after 50 cycles, the capacity was 1219.8 mAh g -1 。
Example 6
A preparation method of a silicon-carbon (Si@C) composite micro-nano structure material comprises the following specific steps:
(1) Fully grinding and mixing 0.56g of commercial micron-sized crude silicon and 1.152g of metal magnesium powder, transferring the mixture into a ball milling tank, performing planetary ball milling for 22 hours, and cooling the mixture to room temperature to obtain 1.21g of silicon/magnesium alloy;
(2) Placing the silicon/magnesium alloy in a tube furnace, then introducing a mixed gas of silicon tetrachloride gas, argon gas and propane gas which is preheated to 65 ℃, wherein the introducing rate is 300-500 mL/min, and carrying out chemical reaction at 650 ℃ for 4 hours; transferring the obtained product to a beaker, adding 50-60mL of dilute hydrochloric acid (0.1 mol/L), cleaning, stirring for 0.5-8 h, filtering, washing with water, drying, and removing a byproduct magnesium chloride to obtain the silicon-carbon (Si@C) composite micro-nano structural material.
(3) Taking the silicon-carbon (Si@C) composite micro-nano structural material in the step (2) as a negative electrode, combining ethylene carbonate and dimethyl carbonate as electrolyte, and lithium hexafluorophosphate (LiPF) 6 ) And (3) assembling the lithium ion battery for lithium salt. At a current density of 0.1C, the capacity was 1018 mAh g after 50 cycles -1 。

Claims (4)

1. The preparation method of the silicon-carbon composite micro-nano structure material comprises the following steps:
(1) Fully grinding and mixing silicon powder and metal magnesium powder, performing ball milling, and cooling to room temperature to obtain silicon/magnesium alloy;
(2) Placing the silicon/magnesium alloy in a tube furnace, introducing silicon tetrachloride gas and mixed gas of carrier gas and methane, reacting for 4-10 hours at 450-650 ℃, washing the obtained product with dilute acid, filtering, washing with water, drying, and removing by-product metal magnesium chloride to obtain the silicon-carbon composite micro-nano structure material;
in the step (1), the silicon powder is commercial micron-sized silicon powder, the molar ratio of the silicon powder to the metal magnesium powder is 1:2-1:3, the ball milling is planetary ball milling, and the ball milling time is 12-24 hours;
in the step (2), the carrier gas is argon; and in the mixed gas of the carrier gas and the methane, the volume fraction of the methane is 5-10%, and the introducing rate of the silicon tetrachloride gas and the mixed gas of the carrier gas and the methane is 300-500 mL/min.
2. The method for preparing the silicon-carbon composite micro-nano structure material according to claim 1, which is characterized in that: in the step (2), the dilute acid is one or two or more than two of hydrochloric acid, nitric acid and sulfuric acid; the concentration of the dilute acid is 0.1-5 mol/L.
3. The method for preparing the silicon-carbon composite micro-nano structure material according to claim 1, which is characterized in that: in the step (2), the drying is vacuum drying, and the drying temperature is 60-120 ℃.
4. Use of a silicon-carbon composite micro-nano structure material prepared by the method of any one of claims 1-3 as a negative electrode material of a lithium ion battery.
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