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CN114050251A - 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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CN114050251A
CN114050251A CN202111369228.4A CN202111369228A CN114050251A CN 114050251 A CN114050251 A CN 114050251A CN 202111369228 A CN202111369228 A CN 202111369228A CN 114050251 A CN114050251 A CN 114050251A
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silicon
composite micro
gas
nano structure
carbon
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CN114050251B (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

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Abstract

本发明公开了一种硅碳复合微纳米结构材料的制备方法，是将硅粉和金属粉充分研磨混合，然后进行球磨，冷却至室温后，得到硅/金属合金；将上述硅/金属合金置于管式炉中，通入四氯化硅气体，以及载气和碳源混合气体，于450~650℃下反应4~10h，将得到的产物用稀酸洗涤、过滤、水洗、干燥，除去副产物金属氯化物得到。本发明利用硅粉、金属粉、载气碳源和四氯化硅制备硅碳复合微纳米结构材料，复合材料作为锂离子电池的负极材料具有高效的导电网络，进而有效克服了硅导电性不良的问题，此外碳的充分包覆可以有效缓解充放电过程中的体积膨胀与抑制电极材料粉化，能充分维持电极结构完整性，循环稳定性得到提高，充分而有效的提升了电池的循环寿命。The invention discloses a preparation method of a silicon-carbon composite micro-nano structure material. The silicon powder and metal powder are fully ground and mixed, then ball-milled, and cooled to room temperature to obtain silicon/metal alloy; the silicon/metal alloy is placed in a In the tube furnace, pass silicon tetrachloride gas, and mixed gas of carrier gas and carbon source, react at 450~650℃ for 4~10h, wash the obtained product with dilute acid, filter, wash with water, dry, remove The by-product metal chloride is obtained. The invention uses silicon powder, metal powder, carrier gas carbon source and silicon tetrachloride to prepare silicon-carbon composite micro-nano structure material, and the composite material has an efficient conductive network as a negative electrode material of a lithium ion battery, thereby effectively overcoming the poor conductivity of silicon In addition, the sufficient coating of carbon can effectively alleviate the volume expansion during the charge and discharge process and inhibit the pulverization of the electrode material, fully maintain the structural integrity of the electrode, improve the cycle stability, and fully and effectively improve the cycle life of the battery. .

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 the 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 towards renewable clean energy sources 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 introduced the first generation of lithium ion batteries, which have dominated the competition with other batteries such as nickel hydride as power supplies for small electronic products. In recent years, lithium ion batteries have been widely used to provide 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 Hybrid Electric Vehicles (HEVs) and large energy storage areas.
Conventional lithium ion batteries are primarily comprised of a carbon-based negative electrode (typically graphite) containing a lithium salt (e.g., LiPF)6) And a lithium metal oxide positive electrode (typically LiCoO)2) And (4) forming. The theoretical specific capacity of the graphite is only 372 mAh/g, and the further requirements of related industries on the capacity and the performance of the lithium battery are difficult to meet, so that the development of a novel negative electrode material with high specific energy is particularly important. The negative electrode material has an important influence on the energy density, capacity, cycle performance and the like of the lithium ion battery. As a negative electrode material of a lithium ion battery, the following conditions should be satisfied: should have a lower potential, provide a lower discharge voltage, and thus be able to match the positive electrode material; when reacting with lithium, the crystal structure can not be changed significantly; the reaction is highly reversible; a large lithium ion diffusion coefficient; higher electron conductivity; a suitable density; a large amount of charge can be stored per unit mass.
Silicon-based (Si) materials have excellent electrochemical properties and are widely usedGreat researchers are concerned about and extensively research. The silicon has a lower voltage platform and ultrahigh theoretical specific capacity (the product is Li at room temperature)15Si4When it is 3600 mAh g-1) About 10 times (about 372 mAh g) that of the carbon-based material-1). Silicon is abundant in the earth's crust and therefore has a relatively low cost. However, there are still some challenges when using silicon as the negative electrodes of Lithium Ion Batteries (LIBs), including its intrinsically poor electrical conductivity, large volume change (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. In one aspect, a carbon-based material may serve as a matrix for buffering the bulk change of silicon during repeated lithium ion insertion/extraction: (>300%). On the other hand, the carbon component is advantageous for improving the conductivity of the electrode material. Many studies have well demonstrated that silicon carbon composites can significantly improve the conductivity of silicon materials and suppress the volume expansion of silicon. Among various carbon materials, two-dimensional graphene sheets can effectively reduce stress generated by volume expansion after being used as an auxiliary material of Si/C due to ultrahigh conductivity, excellent mechanical properties and stable chemical properties, so that a stable solid electrolyte interface is formed and lithium ion diffusion is further improved. For example, silicon nanoparticles prepared from bamboo leaves, at 8.4A g-1At a current density of 430 mAh g only-1The 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-1The reversible specific capacity of (a). The literature reports that a graphene-coated nano silicon/graphite composite material can be used for maintaining 445mAh g after circulating for 300 circles under the current density of 1C-1The reversible specific capacity and the capacity retention rate can reach 99.6 percent. Although graphene or redox graphene has the above advantages, graphene has high cost and a complex preparation process, and raw materials polluting the environment need to be introduced in the synthesis process. Therefore, large-scale, simple, inexpensive preparation of uniformly coated Si/C composites remains challenging.
However, the methods for preparing the Si/C composite disclosed in the above documents have problems that: the grain size of Si is large and uneven, the composite carbon structure is difficult to completely cover the surface of Si, and the improvement on the performance of Si is limited. It is therefore of particular importance to develop a simple method for complete carbon coating. There are many problems with the prior art methods for preparing Si/C composite materials, and therefore, there is a need for a Si/C preparation method that can overcome the above problems.
Disclosure of Invention
The invention aims to solve the problems that the particle size of Si in a Si/C compound is large and uneven, a compound carbon structure is difficult to completely coat on the surface of Si, the specific capacity is low, the improvement on the performance of Si is limited and the like, and provides a preparation method of a silicon-carbon compound micro-nano structure material with uniformly-coated carbon;
the invention also aims to provide application of the silicon-carbon composite micro-nano structure material as a negative electrode material of a lithium ion battery.
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, then carrying out 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 molar 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 (2) placing the silicon/metal alloy in a tubular furnace, introducing silicon tetrachloride gas and mixed gas of carrier gas and a carbon source, reacting for 4-10 hours at 450-650 ℃, washing, filtering, washing and drying the obtained product by using dilute acid, 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%. The introducing speed of the silicon tetrachloride gas and the mixed gas of the carrier gas and the carbon source is 300-500 mL/min. The diluted acid is one or a mixture of two or more of hydrochloric acid, nitric acid and sulfuric acid, and the concentration of the diluted acid is 0.1-5 mol/L. The drying is vacuum drying, and the drying temperature is 60-120 ℃.
Structure and performance of silicon-carbon composite micro-nano structure material
1. Structure of silicon-carbon composite micro-nano structure material
Fig. 1 is a TGA curve of the silicon-carbon composite micro-nanostructured material prepared by the invention. As can be seen from the TGA curve of the silicon-carbon composite micro-nanostructured material shown in fig. 1, the content of the silicon micro-nano particles in the silicon-carbon composite micro-nanostructured material is about 46%.
Fig. 2 is an SEM image of the silicon-carbon composite micro-nanostructured 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-nanostructured material. Fig. 3 is a TEM image of the silicon-carbon composite micro-nanostructured material prepared by the present invention. The TEM image of FIG. 3 also shows that the silicon micro-nano particles are uniformly coated by carbon.
2. Performance of silicon-carbon composite micro-nano structure material
The silicon-carbon composite micro-nano structure material is used as a negative electrode material of a 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 consisting of lithium salt and at least one of dimethyl carbonate, diethyl carbonate, ethylene carbonate, Biphenyl (BP), ethylene carbonate (VEC), Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), 1, 4-Butanesultone (BS), 1, 3-Propanesultone (PS), 1, 3- (1-Propylene) Sultone (PST), Ethylene Sulfate (ESA), Ethylene Sulfite (ESI), Cyclohexylbenzene (CHB), tert-butyl benzene (TBB), tert-amyl benzene (TPB) and Succinonitrile (SN); the lithium salt is lithium hexafluorophosphate (LiPF)6) Lithium bis (fluorosulfonamide) (LiFSI), lithium tetrafluoroborate (LiBF)4) Lithium bistrifluorosulfonamide (LiN (SO)2CF3)2) Lithium bis (oxalato) borate (LiBOB) and trifluoromethylLithium sulfonate (LiSO)3CF3) At least one of (1).
Fig. 4 shows the cycle performance of the silicon-carbon composite micro-nano structure material prepared by the invention under the current density of 0.1C. FIG. 4 shows that under the current density of 0.1C, the silicon-carbon composite micro-nano structure material has 1219.8 mAh g-1The reversible specific capacity of (a). The silicon-carbon composite micro-nano structure material has excellent cycle 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 an efficient conductive network, so that the problem of poor silicon conductivity is effectively overcome, in addition, the sufficient coating of carbon can effectively relieve the volume expansion in the charging and discharging processes and inhibit the electrode material from being pulverized, the structural integrity of the electrode can be fully maintained, the cycling 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 be used for simply and rapidly preparing a silicon-carbon composite micro-nano structure material from silicon powder, metal powder, a carrier gas carbon source and silicon tetrachloride by a solid-gas reaction method, and has wide application prospects in the fields of smart phones, notebook computers, portable cameras, green energy sources, aerospace and the like.
Drawings
Fig. 1 is a TGA curve of the silicon-carbon composite micro-nanostructured material prepared by the invention.
Fig. 2 is an SEM image of the silicon-carbon composite micro-nanostructured material prepared by the present invention.
Fig. 3 is a TEM image of the silicon-carbon composite micro-nanostructured material prepared by the present invention.
Fig. 4 is a cycle performance diagram of the silicon-carbon composite micro-nano structure material prepared by the invention under the current density of 0.1C.
Detailed Description
The preparation and performance of the silicon-carbon composite micro-nano structure material of the invention are further explained and explained by combining with the specific embodiment.
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 the mixture into a ball milling tank for planetary ball milling for 12 hours, and cooling the mixture to room temperature to obtain 1.42g of silicon/magnesium alloy (Mg)2Si）；
(2) Mixing the above silicon/magnesium alloy (Mg)2Si) is placed in a tube furnace, then mixed gas of silicon tetrachloride gas, argon gas and acetylene gas which are obtained by preheating to 65 ℃ is introduced, the introduction speed is 300-500 mL/min, chemical reaction is carried out at 450 ℃, and the reaction time is 10 hours; and 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 by-product magnesium chloride to obtain the silicon-carbon (Si @ C) composite micro-nano structure material.
(3) Taking the silicon-carbon (Si @ C) composite micro-nano structure material obtained in the step (2) as a negative electrode, combining ethylene carbonate and dimethyl carbonate as electrolyte, and lithium hexafluorophosphate (LiPF)6) And (5) assembling the lithium ion battery as a lithium salt. At a current density of 0.1C, after 100 cycles, the capacity 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 coarse silicon and 1.152g of metal magnesium powder, transferring the mixture into a ball milling tank for 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 tubular furnace, introducing mixed gas of silicon tetrachloride gas, argon gas and acetylene gas obtained by preheating to 65 ℃, introducing the mixed gas at the rate of 300-500 mL/min, and carrying out chemical reaction at 500 ℃ for 8 hours; and (3) transferring the obtained product to a beaker, adding 5-6mL of dilute sulfuric acid (0.5 mol/L), cleaning and stirring for 0.5-8 h, filtering, washing with water, drying, and removing a by-product magnesium chloride to obtain the silicon-carbon (Si @ C) composite micro-nano structure material.
(3) Taking the silicon-carbon (Si @ C) composite micro-nano structure material obtained in the step (2) as a negative electrode, combining ethylene carbonate and dimethyl carbonate as electrolyte, and lithium hexafluorophosphate (LiPF)6) And (5) assembling the lithium ion battery as a lithium salt. After 100 cycles at a current density of 0.1C, the capacity 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 coarse silicon and 1.152g of metal magnesium powder, transferring the mixture into a ball milling tank for 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 tubular furnace, introducing mixed gas of silicon tetrachloride gas, argon gas and acetylene gas obtained by preheating to 65 ℃, introducing the mixed gas at the rate of 300-500 mL/min, and carrying out chemical reaction at 550 ℃ for 6 hours; and (3) transferring the obtained product to a beaker, adding 10-15mL of dilute hydrochloric acid (0.5 mol/L), cleaning and stirring for 0.5-8 h, filtering, washing with water, drying, removing a by-product magnesium chloride, and repeatedly treating to obtain the silicon-carbon (Si @ C) composite micro/nano structure material.
(3) Taking the silicon-carbon (Si @ C) composite micro-nano structure material obtained in the step (2) as a negative electrode, combining ethylene carbonate and dimethyl carbonate as electrolyte, and lithium hexafluorophosphate (LiPF)6) And (5) assembling the lithium ion battery as a lithium salt. At a current density of 0.1C, after 100 cycles, the capacity was 819 mAh g-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 coarse silicon and 1.152g of metal magnesium powder, transferring the mixture into a ball milling tank for 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 tubular furnace, introducing mixed gas of silicon tetrachloride gas, argon gas and acetylene gas obtained by preheating to 65 ℃, introducing the mixed gas at the rate of 300-500 mL/min, and carrying out chemical reaction at the temperature of 600 ℃ for 6 hours; and 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 by-product magnesium chloride to obtain the silicon-carbon (Si @ C) composite micro-nano structure material.
(3) Taking the silicon-carbon (Si @ C) composite micro-nano structure material obtained in the step (2) as a negative electrode, combining ethylene carbonate and dimethyl carbonate as electrolyte, and lithium hexafluorophosphate (LiPF)6) And (5) assembling the lithium ion battery as a lithium salt. At the current density of 0.1C, after 100 cycles, the capacity is 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 coarse silicon and 1.152g of metal magnesium powder, transferring the mixture into a ball milling tank for 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 tubular furnace, introducing mixed gas of silicon tetrachloride gas, argon gas and methane gas obtained by preheating to 65 ℃, introducing the mixed gas at the rate of 300-500 mL/min, and carrying out chemical reaction at the temperature of 600 ℃ for 4 hours; and (3) 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 by-product magnesium chloride to obtain the silicon-carbon (Si @ C) composite micro-nano structure material.
(3) Taking the silicon-carbon (Si @ C) composite micro-nano structure material obtained in the step (2) as a negative electrode, combining ethylene carbonate and dimethyl carbonate as electrolyte, and lithium hexafluorophosphate (LiPF)6) And (5) assembling the lithium ion battery as a 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 coarse silicon and 1.152g of metal magnesium powder, transferring the mixture into a ball milling tank for 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 tubular furnace, introducing mixed gas of silicon tetrachloride gas, argon gas and propane gas obtained by preheating to 65 ℃, introducing the mixed gas at the rate of 300-500 mL/min, and carrying out chemical reaction at 650 ℃ for 4 hours; and 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 by-product magnesium chloride to obtain the silicon-carbon (Si @ C) composite micro-nano structure material.
(3) Taking the silicon-carbon (Si @ C) composite micro-nano structure material obtained in the step (2) as a negative electrode, combining ethylene carbonate and dimethyl carbonate as electrolyte, and lithium hexafluorophosphate (LiPF)6) And (5) assembling the lithium ion battery as a lithium salt. After 50 cycles at a current density of 0.1C, the capacity was 1018 mAh g-1。

Claims (10)

1.一种硅碳复合微纳米结构材料的制备方法，包括以下步骤：1. a preparation method of silicon-carbon composite micro-nano structure material, comprising the following steps: （1）将硅粉和金属粉充分研磨混合，然后进行球磨，冷却至室温后，得到硅/金属合金；(1) Fully grinding and mixing silicon powder and metal powder, then ball-milling, and cooling to room temperature to obtain silicon/metal alloy; （2）将上述硅/金属合金置于管式炉中，通入四氯化硅气体，以及载气和碳源混合气体，于450~650℃下反应4~10h，将得到的产物用稀酸洗涤、过滤、水洗、干燥，除去副产物金属氯化物，得到硅碳复合微纳米结构材料。(2) The above-mentioned silicon/metal alloy is placed in a tube furnace, and silicon tetrachloride gas, a mixed gas of carrier gas and carbon source are introduced, and the reaction is carried out at 450~650 ° C for 4~10 hours, and the obtained product is diluted with dilute gas. Acid washing, filtration, water washing and drying to remove the by-product metal chloride to obtain a silicon-carbon composite micro-nano structure material. 2.根据权利要求1所述的一种硅碳复合微纳米结构材料的制备方法，其特征在于：步骤（1）中，所述金属粉为锂、钠、镁、锌、铝粉中的至少一种；所述硅粉为商业微米级硅粉。2 . The method for preparing a silicon-carbon composite micro-nano structure material according to claim 1 , wherein in step (1), the metal powder is at least one of lithium, sodium, magnesium, zinc, and aluminum powder. 3 . One; the silicon powder is commercial micron-scale silicon powder. 3.根据权利要求1所述的一种硅碳复合微纳米结构材料的制备方法，其特征在于：步骤（1）中，所述硅粉和金属粉摩尔比为1:2~1:3。3 . The method for preparing a silicon-carbon composite micro-nano structure material according to claim 1 , wherein in step (1), the molar ratio of the silicon powder to the metal powder is 1:2 to 1:3. 4 . 4.根据权利要求1所述的一种硅碳复合微纳米结构材料的制备方法，其特征在于：步骤（1）中，所述球磨为行星式球磨，所述球磨时间为12~24h。4 . The method for preparing a silicon-carbon composite micro-nano structure material according to claim 1 , wherein in step (1), the ball milling is a planetary ball milling, and the ball milling time is 12-24 hours. 5 . 5.根据权利要求1所述的一种硅碳复合微纳米结构材料的制备方法，其特征在于：步骤（2）中，所述载气为氩气；所述碳源乙炔气体、甲烷气体、丙烷气体或丙烯气体；所述载气和碳源混合气体中，碳源的体积分数为5~10%。5 . The method for preparing a silicon-carbon composite micro-nano structure material according to claim 1 , wherein in step (2), the carrier gas is argon; the carbon source acetylene gas, methane gas, Propane gas or propylene gas; in the mixed gas of the carrier gas and the carbon source, the volume fraction of the carbon source is 5-10%. 6.根据权利要求1所述的一种硅碳复合微纳米结构材料的制备方法，其特征在于：步骤（2）中，所述四氯化硅气体，以及载气和碳源混合气体的通入速率为300~500mL/min。6 . The method for preparing a silicon-carbon composite micro-nano structure material according to claim 1 , wherein in step (2), the silicon tetrachloride gas, and the mixture gas of the carrier gas and the carbon source are passed through the gas. 7 . The input rate is 300~500mL/min. 7.根据权利要求1所述的一种硅碳复合微纳米结构材料的制备方法，其特征在于：步骤（2）中，所述稀酸为盐酸、硝酸或硫酸中的一种或两种及两种以上的混合溶液；所述稀酸的浓度为0.1~5mol/L。7 . The method for preparing a silicon-carbon composite micro-nano structure material according to claim 1 , wherein in step (2), the dilute acid is one or both of hydrochloric acid, nitric acid or sulfuric acid and the Two or more mixed solutions; the concentration of the dilute acid is 0.1 to 5 mol/L. 8.根据权利要求1所述的一种硅碳复合微纳米结构材料的制备方法，其特征在于：步骤（2）中，所述干燥为真空干燥，干燥温度为60~120℃。8 . The method for preparing a silicon-carbon composite micro-nano structure material according to claim 1 , wherein in step (2), the drying is vacuum drying, and the drying temperature is 60-120° C. 9 . 9.一种权利要求1~8任一项方法制备的硅碳复合微纳米结构材料作为锂离子电池的负极材料的应用。9. Application of the silicon-carbon composite micro-nano structure material prepared by any one of claims 1 to 8 as a negative electrode material for lithium ion batteries. 10.根据权利要求9所述的碳硅复合微纳米颗粒电极材料作为锂离子电池的负极材料的应用，其特征在于：所述锂离子电池的电解液为碳酸二甲酯、碳酸二乙酯、碳酸乙烯酯、联苯、碳酸乙烯亚乙酯、碳酸亚乙烯酯、氟代碳酸乙烯酯、1，4-丁磺酸内酯、1，3-丙磺酸内酯、1，3-（1-丙烯）磺内酯、硫酸乙烯酯、亚硫酸乙烯酯、环己基苯、叔丁基苯、叔戊基苯和丁二氰中的至少一种与锂盐组成的混合液；所述锂盐为六氟磷酸锂、双氟磺酰胺锂、四氟硼酸锂、双三氟磺酰胺锂、双乙二酸硼酸锂、三氟甲磺酸锂中的至少一种。10. The application of the carbon-silicon composite micro-nano particle electrode material according to claim 9 as a negative electrode material of a lithium ion battery, wherein the electrolyte of the lithium ion battery is dimethyl carbonate, diethyl carbonate, Ethylene carbonate, biphenyl, ethylene ethylene carbonate, vinylene carbonate, fluoroethylene carbonate, 1,4-butane sultone, 1,3-propane sultone, 1,3-(1 -propene) mixed solution composed of at least one of sultone, vinyl sulfate, vinyl sulfite, cyclohexylbenzene, t-butylbenzene, t-amylbenzene and butanedicyanide and a lithium salt; the lithium salt It is at least one of lithium hexafluorophosphate, lithium bisfluorosulfonamide, lithium tetrafluoroborate, lithium bistrifluorosulfonamide, lithium bisoxalatoborate, and lithium trifluoromethanesulfonate.
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