WO2022121137A1 - One-dimensional porous silicon-carbon composite negative electrode material, preparation method, and application thereof - Google Patents

One-dimensional porous silicon-carbon composite negative electrode material, preparation method, and application thereof Download PDF

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WO2022121137A1
WO2022121137A1 PCT/CN2021/080164 CN2021080164W WO2022121137A1 WO 2022121137 A1 WO2022121137 A1 WO 2022121137A1 CN 2021080164 W CN2021080164 W CN 2021080164W WO 2022121137 A1 WO2022121137 A1 WO 2022121137A1
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carbon composite
negative electrode
porous silicon
electrode material
dimensional porous
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French (fr)
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葛传长
仰永军
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广东凯金新能源科技股份有限公司
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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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/022—Electrodes made of one single microscopic fiber
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

Definitions

  • the invention relates to the field of electrode negative electrode materials, in particular to a one-dimensional porous silicon-carbon composite negative electrode material, a preparation method and an application thereof.
  • lithium-ion battery performance largely depends on the improvement of energy density and cycle life of lithium intercalation materials.
  • silicon has attracted more and more attention because it has the highest theoretical lithium intercalation capacity (4200 mAh/g).
  • silicon-based materials have a serious volume expansion problem, resulting in a significant decrease in the cycle stability of the electrode.
  • carbon materials as a buffer framework to improve the mechanical instability of silicon materials during the process of intercalation and delithiation has become an important research direction of silicon carbon materials.
  • silicon-carbon composites are usually prepared by pyrolysis, mechanical mixing/high-energy ball milling, etc., but the silicon particles are embedded in a dense carbon matrix, which is prone to structural rupture due to the volume expansion of silicon during charge and discharge.
  • mechanical stress is generated between the silicon carbon active layer and the rigid copper current collector layer, resulting in the pulverization and peeling of the silicon material, so the battery capacity drops sharply and the cycle ability is very poor. Therefore, the development of new silicon-carbon composite materials preparation methods is still an important problem to be solved by domestic anode companies.
  • a one-dimensional porous silicon-carbon composite negative electrode material is provided.
  • porous silicon as an active component, silicon/carbon composite fibers are prepared by electrospinning, which can effectively shorten the transmission distance of lithium ions and alleviate the The expansion problem of silicon during the lithium intercalation process improves the electrochemical performance of the material, protects the active silicon particles, and provides a preparation method for a high-performance silicon-carbon composite material and a silicon-carbon composite material, which greatly improves the structural stability and cycle stability of the electrode. .
  • the invention also provides a preparation method of one-dimensional porous silicon-carbon composite negative electrode material, which has simple and easy process, stable product performance and good application prospect.
  • a method for preparing a one-dimensional porous silicon-carbon composite negative electrode material includes the following steps: (1) mixing nano-SiO2, a surfactant and a high molecular polymer into a dispersant, and ultrasonically stirring and dispersing at room temperature to obtain a spinning solution, and passing through Electrospinning to obtain SiO2/polymer composite fibers; (2) subjecting the SiO2/polymer composite fibers obtained in step (1) to oxidative non-melting treatment, then pre-carbonizing at 400-600 ° C under the protection of inert gas, and cooling to obtain SiO2 /carbon composite fiber; (3) Mix the active metal powder with the SiO2/carbon composite fiber obtained in step (2) according to a certain mass ratio, and then reduce part of the SiO2 into silicon element by thermal reduction under inert gas, and then The Si/SiO2/carbon composite fiber material is obtained by pickling, water washing and drying; (4) the Si/carbon composite fiber obtained in step (3) is acid-washed with hydrofluoric acid, washed with water and
  • the particle size of the nano-SiO2 is 50-1000 nm; the purity of the nano-SiO2 is greater than 99.9%;
  • the surfactant is hexadecanetrimethyl bromide Ammonium, ethylene glycol, nonylphenol polyoxyethylene ether, bromohexadecylpyridine, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidyloxypropyltrimethoxysilane, ⁇ -( One of Methacryloxy)propyltrimethoxysilane, 3-Methacryloxypropylmethyldiethoxysilane or 3-Methacryloxypropylmethyldimethoxysilane or a combination of at least two kinds;
  • the high molecular polymer is linear high softening point (250-280 ° C) pitch, polyacrylonitrile, polystyrene, polyvinylpyrrolidone, polyvinyl butyral, polyvinyl alcohol,
  • the mass ratio of the nano-SiO2, surfactant and high molecular polymer is 10-60:0.5-3:100; the high molecular weight in the spinning solution
  • the polymer mass fraction concentration is 5-15%;
  • the ultrasonic stirring and dispersion are carried out at room temperature, the ultrasonic power is greater than 50W, and the stirring time is greater than 8 h;
  • the electrospinning conditions are: the distance between the syringe and the collector is 8- 15cm, the voltage is 10-20kV, the needle diameter is 0.3-0.8mm, the extrusion rate is 0.5-5.0mL/h, and the collector is metal foil.
  • the oxidative non-melting is to pre-oxidize for 1-6 hours in an air atmosphere at a heating rate of 0.5-5 °C/min to 200-300 °C; the pre-carbonization It is heated to 400-600°C at a heating rate of 3-5°C/min under an inert atmosphere, and kept for 2-6 hours.
  • the active metal powder is aluminum powder and/or magnesium powder; the mass ratio of the active metal powder to SiO2 is 5-35:100; the thermal reduction is In an inert atmosphere, the temperature is raised to 400-800°C for 2-6 hours; the acid washing and water washing are performed by using excess hydrochloric acid solution at 40-60°C for 1-3 hours, and then stirring and washing with pure water to filter the filtrate.
  • the pH is 6.5-7.0.
  • step (4) the hydrofluoric acid pickling and water washing are performed by using excess hydrofluoric acid solution to stir and react at room temperature for 0.5-2 hours to remove the remaining SiO2, and then use pure water Stir and wash and filter until the pH of the filtrate is 6.5-7.0.
  • step (3) and step (4) the drying is performed in a blast or vacuum electric heating drying oven, the drying temperature is 80-120°C, and the drying time is 4-12 hours;
  • step (4) the high-temperature heat treatment temperature is 600-1000° C.; the heating rate is 3-10° C./min; and the heat-treatment time is 4-8 hours.
  • the inert gas is one of nitrogen, helium, neon, argon, krypton and xenon or A combination of at least 2.
  • a one-dimensional porous silicon-carbon composite negative electrode material, the one-dimensional porous silicon-carbon composite negative electrode material is prepared by the preparation method.
  • An application of a one-dimensional porous silicon-carbon composite negative electrode material, and the used one-dimensional porous silicon-carbon composite negative electrode material is applied to a lithium ion battery negative electrode material.
  • the preparation process of the invention is simple, no additional coating modification is required, and large-scale production is easy; the formation of porous silicon is induced in situ by the metallothermic reduction and etching methods, and the high reversible capacity can be obtained while the silicon active component can be remarkably improved. stability, improve the intrinsic expansion effect of silicon, and avoid problems such as particle pulverization and structural collapse; through the electrospinning of the polymer matrix, a carbon fiber matrix with small diameter and uniform thickness can be obtained, which can better provide a buffer for silicon and improve Electronic conductivity.
  • the porous silicon/carbon composite negative electrode material of the present invention has the first reversible specific capacity greater than 750mAh/g, while the first cycle Coulombic efficiency is greater than 86%, has excellent cycle stability, and overcomes the problem of poor electrochemical stability of traditional silicon carbon negative electrode materials. There is a broad market in the fields of energy storage and electric vehicles.
  • Example 1 SiO2 with a particle size of 100 nm, hexadecyltrimethylammonium bromide, and polyacrylonitrile (Mw180000) were added to N,N-dimethylformamide solvent in a mass ratio of 20:1:100, Keep the solid content of polyacrylonitrile at 8%, then stir under the ultrasonic power of 80W for 12 hours to obtain the spinning solution, and use electrospinning (the distance between the syringe and the collector is 10cm, the voltage is 20kV, the needle diameter is 0.5mm, The extrusion rate was 3 mL/h, and the collector was aluminum foil) to obtain SiO2/polyacrylonitrile composite fibers; the fiber self-supporting film containing the silicon source was taken off as a whole and placed in a muffle furnace for pre-oxidation at 250 °C for 4 hours.
  • electrospinning the distance between the syringe and the collector is 10cm, the voltage is 20kV, the needle diameter is
  • the temperature was raised to 600°C at a heating rate of 3°C/min for 2 hours to obtain a SiO2/carbon composite fiber precursor.
  • 100) after fully mixing, put it in an atmosphere furnace, heat it to 750 °C for 4 hours under an argon atmosphere, wash the reaction product with excess hydrochloric acid, wash with water to neutral (pH 7) and dry to obtain a silicon-rich precursor.
  • Example 2 Add SiO2, ⁇ -aminopropyltriethoxysilane, and polyvinylpyrrolidone (Mw1300000) with a particle size of 100 nm to an ethanol solvent in a mass ratio of 30:1:100 to maintain the solid content of polyacrylonitrile 8%, and then stirred for 12 hours under the ultrasonic power of 80W to obtain the spinning solution, using electrospinning (the distance between the syringe and the collector was 10cm, the voltage was 20kV, the diameter of the needle was 0.5mm, and the extrusion rate was 5mL/h.
  • electrospinning the distance between the syringe and the collector was 10cm, the voltage was 20kV, the diameter of the needle was 0.5mm, and the extrusion rate was 5mL/h.
  • the collector is aluminum foil) to obtain SiO2/polyacrylonitrile composite fiber;
  • Example 3 Add SiO2, ⁇ -aminopropyltriethoxysilane, and polyvinyl alcohol (Mw120000) with a particle size of 100 nm into an ethanol solvent at a mass ratio of 40:1:100 to maintain the solid content of polyacrylonitrile 8%, and then stirred for 12 hours under the ultrasonic power of 80W to obtain the spinning solution. Electrospinning was used (the distance between the syringe and the collector was 10cm, the voltage was 20kV, the diameter of the needle was 0.5mm, and the extrusion rate was 3mL/h.
  • the collector is aluminum foil) to obtain SiO2/polyacrylonitrile composite fiber;
  • Example 4 SiO2, hexadecyltrimethylammonium bromide and polyacrylonitrile (Mw180000) with a particle size of 200 nm were added to N,N-dimethylformamide solvent in a mass ratio of 40:1:100, Keep the solid content of polyacrylonitrile at 8%, then stir under the ultrasonic power of 80W for 12 hours to obtain the spinning solution, and use electrospinning (the distance between the syringe and the collector is 10cm, the voltage is 20kV, the needle diameter is 0.5mm, The extrusion rate was 5 mL/h, and the collector was aluminum foil) to obtain SiO2/polyacrylonitrile composite fibers; the fiber self-supporting film containing the silicon source was taken off as a whole and placed in a muffle furnace for pre-oxidation at 250 °C for 4 hours.
  • electrospinning the distance between the syringe and the collector is 10cm, the voltage is 20kV, the needle diameter is 0.5mm
  • the temperature was raised to 600°C at a heating rate of 3°C/min for 2 hours to obtain a SiO2/carbon composite fiber precursor.
  • 100) after fully mixing, put it in an atmosphere furnace, heat it to 750 °C for 4 hours under an argon atmosphere, wash the reaction product with excess hydrochloric acid, wash with water to neutral (pH 7) and dry to obtain a silicon-rich precursor.
  • Example 5 SiO2 with a particle size of 300 nm, hexadecyltrimethylammonium bromide, and polyacrylonitrile (Mw180000) were added to N,N-dimethylformamide solvent in a mass ratio of 40:1:100, Keep the solid content of polyacrylonitrile at 8%, then stir under the ultrasonic power of 80W for 12 hours to obtain the spinning solution, and use electrospinning (the distance between the syringe and the collector is 10cm, the voltage is 20kV, the needle diameter is 0.5mm, The extrusion rate was 3 mL/h, and the collector was aluminum foil) to obtain SiO2/polyacrylonitrile composite fibers; the fiber self-supporting film containing the silicon source was taken off as a whole and placed in a muffle furnace for pre-oxidation at 250 °C for 4 hours.
  • electrospinning the distance between the syringe and the collector is 10cm, the voltage is 20kV, the needle diameter is
  • the temperature was raised to 600°C at a heating rate of 3°C/min for 2 hours to obtain a SiO2/carbon composite fiber precursor.
  • 100) after fully mixing, put it in an atmosphere furnace, heat it to 750 °C for 4 hours under an argon atmosphere, wash the reaction product with excess hydrochloric acid, wash with water to neutral (pH 7) and dry to obtain a silicon-rich precursor.
  • the temperature was raised to 600 °C at a heating rate of 3 °C/min for 2 hours to obtain a SiO2/carbon composite fiber precursor; the precursor was then carbonized at 950 °C for 4 hours under nitrogen protection, and then cooled to room temperature to obtain Contrast material.
  • the test method of the half-cell is as follows: the electrochemical performance test is carried out by the following method: take the materials prepared in Examples 1 to 5 and the comparative example as the negative electrode material, mix with the thickener CMC, the binder SBR, and the conductive agent (Super-P) Mix according to the mass ratio of 85:2:3:10, add an appropriate amount of deionized water as a dispersant to make a slurry, coat it on the copper foil, and prepare a negative electrode sheet by rolling and vacuum drying; use 1mol/L
  • Celgard polypropylene microporous membrane is used as the diaphragm.
  • a CR2032 button half-cell was made with a lithium sheet as the counter electrode.
  • the charge-discharge test of the button battery was carried out on the LAND battery test system of Wuhan Jinnuo Electronics Co., Ltd. At room temperature, it was first activated by charging and discharging at a constant current of 0.1C, and then charged and discharged at 1C for 500 cycles, and the charge-discharge voltage was 0.005 ⁇ 2.0V.
  • the reversible capacity of the silicon/carbon composite material of the present invention can be selectively regulated by the amount of silicon source introduced, the capacity is higher than 750mAh/g, the first Coulomb efficiency is higher than 86%, and after 500 times of charge and discharge After the cycle, the electrode capacity retention rate is greater than 84%, which is much higher than that of the comparative example, which shows that the one-dimensional porous silicon/carbon composite material of the present invention can effectively improve the capacity retention rate of the battery while ensuring high capacity, so that the The applied Li-ion battery exhibits good cycle stability.

Abstract

The present invention relates to the field of battery negative electrode materials, and in particular to a one-dimensional porous silicon-carbon composite negative electrode material, a preparation method, and an application thereof. Compared to the prior art, the present invention has a simple preparation process, does not require extra coating modifications, and is easy to produce on a large scale. The formation of porous silicon is induced in situ by means of a metal thermal reduction and etching method, the stability of a silicon active component can be remarkably improved while obtaining a high reversible capacity, the intrinsic expansion effect of silicon is improved, and problems such as particle pulverization, structure collapse, and the like are avoided. A carbon fiber matrix that has a small diameter and uniform thickness can be obtained by means of electrospinning a polymer matrix, and can provide a better buffering effect for the silicon, and the electron conductivity is improved. According to the porous silicon-carbon composite negative electrode material of the present invention, the first reversible specific capacity is greater than 750 mAh/g, and meanwhile the first cycle coulombic efficiency is greater than 86%. The porous silicon-carbon composite negative electrode material has excellent cycle stability, solves the problem of poor electrochemical stability of conventional silicon-carbon negative electrode materials, and has a wide market in the fields of energy storage and electric vehicles.

Description

一维多孔硅碳复合负极材料、制备方法及其应用One-dimensional porous silicon-carbon composite anode material, preparation method and application thereof
相关申请的交叉引用。CROSS-REFERENCE TO RELATED APPLICATIONS.
本申请要求于2020年12月10日提交中国专利局，申请号为202011434647.7，发明名称为“一维多孔硅碳复合负极材料、制备方法及其应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed on December 10, 2020, with the application number of 202011434647.7 and the invention titled "One-dimensional porous silicon-carbon composite anode material, preparation method and application", the entire content of which is Incorporated herein by reference.
技术领域technical field
本发明涉电极负极材料领域，特别是涉及一种一维多孔硅碳复合负极材料、制备方法及其应用。The invention relates to the field of electrode negative electrode materials, in particular to a one-dimensional porous silicon-carbon composite negative electrode material, a preparation method and an application thereof.
背景技术Background technique
近年来电动汽车等新型产业技术的迅速发展，对高性能动力锂离子电池的需求也越来越迫切。锂离子电池性能的改善在很大程度上取决于嵌锂材料能量密度和循环寿命的提高。在新型负极材料研究中，硅因为具有最高的理论嵌锂容量(4200 mAh/g)而越来越受瞩目。然而硅基材料在高程度脱嵌锂条件下，存在严重的体积膨胀问题，造成电极的循环稳定性大幅度下降。而以碳材料作为缓冲骨架，复合改善目前硅材料嵌脱锂过程中的机械不稳定性已成为硅碳材料重要研究方向。With the rapid development of new industrial technologies such as electric vehicles in recent years, the demand for high-performance power lithium-ion batteries is becoming more and more urgent. The improvement of lithium-ion battery performance largely depends on the improvement of energy density and cycle life of lithium intercalation materials. In the research of new anode materials, silicon has attracted more and more attention because it has the highest theoretical lithium intercalation capacity (4200 mAh/g). However, under the condition of high degree of lithium deintercalation, silicon-based materials have a serious volume expansion problem, resulting in a significant decrease in the cycle stability of the electrode. Using carbon materials as a buffer framework to improve the mechanical instability of silicon materials during the process of intercalation and delithiation has become an important research direction of silicon carbon materials.
技术问题technical problem
目前硅碳复合材料通常通过热解、机械混合/高能球磨等方法来制备，但是所述硅颗粒镶嵌在致密的碳基体中，在充放电期间由于硅的体积膨胀容易发生结构破裂，同时也会导致硅碳活性层与刚性铜集流体层间产生机械应力，导致硅材料粉化剥落，因此电池容量急剧下降，循环能力非常差。因此，开发新型硅碳复合材料制备方法依然是目前国内负极企业所要解决的重要问题。At present, silicon-carbon composites are usually prepared by pyrolysis, mechanical mixing/high-energy ball milling, etc., but the silicon particles are embedded in a dense carbon matrix, which is prone to structural rupture due to the volume expansion of silicon during charge and discharge. As a result, mechanical stress is generated between the silicon carbon active layer and the rigid copper current collector layer, resulting in the pulverization and peeling of the silicon material, so the battery capacity drops sharply and the cycle ability is very poor. Therefore, the development of new silicon-carbon composite materials preparation methods is still an important problem to be solved by domestic anode companies.
技术解决方案technical solutions
根据本申请的各种实施例，提供一种一维多孔硅碳复合负极材料，以多孔硅为活性成分，采用静电纺丝制备硅/碳复合纤维，能够有效地缩短锂离子的传输距离，缓解嵌锂过程硅的膨胀问题，提高材料的电化学性能，对活性硅颗粒进行保护，提供一种高性能硅碳复合材料制备方法及硅碳复合材料，大幅提高电极的结构稳定性和循环稳定性。According to various embodiments of the present application, a one-dimensional porous silicon-carbon composite negative electrode material is provided. Using porous silicon as an active component, silicon/carbon composite fibers are prepared by electrospinning, which can effectively shorten the transmission distance of lithium ions and alleviate the The expansion problem of silicon during the lithium intercalation process improves the electrochemical performance of the material, protects the active silicon particles, and provides a preparation method for a high-performance silicon-carbon composite material and a silicon-carbon composite material, which greatly improves the structural stability and cycle stability of the electrode. .
本发明还提供一种一维多孔硅碳复合负极材料的制备方法，其工艺简单易行，产品性能稳定，具有良好的应用前景。The invention also provides a preparation method of one-dimensional porous silicon-carbon composite negative electrode material, which has simple and easy process, stable product performance and good application prospect.
一种一维多孔硅碳复合负极材料的制备方法，包括如下步骤：（1）将纳米SiO2与表面活性剂、高分子聚合物混合加入分散剂中，室温超声搅拌分散后得到纺丝溶液，通过静电纺丝得到SiO2/聚合物复合纤维；（2）将步骤（1）所得SiO2/聚合物复合纤维进行氧化不熔化处理，然后在惰性气体保护下于400-600℃预碳化，降温后得到SiO2/碳复合纤维；（3）将活性金属粉按一定质量比与步骤（2）所得SiO2/碳复合纤维混合，然后在惰性气体下通过热还原的方法将其中的部分SiO2还原成为硅单质，再经过酸洗、水洗和干燥得到Si/SiO2/碳复合纤维材料；（4）将步骤（3）所得Si/碳复合纤维采用氢氟酸酸洗、水洗和干燥去除多余的SiO2，在碳纤维中形成嵌含有多孔硅纳米颗粒结构，最后在惰性气氛下600-1000℃高温热处理4-8小时，降至室温即得一维多孔硅/碳复合负极材料。A method for preparing a one-dimensional porous silicon-carbon composite negative electrode material includes the following steps: (1) mixing nano-SiO2, a surfactant and a high molecular polymer into a dispersant, and ultrasonically stirring and dispersing at room temperature to obtain a spinning solution, and passing through Electrospinning to obtain SiO2/polymer composite fibers; (2) subjecting the SiO2/polymer composite fibers obtained in step (1) to oxidative non-melting treatment, then pre-carbonizing at 400-600 ° C under the protection of inert gas, and cooling to obtain SiO2 /carbon composite fiber; (3) Mix the active metal powder with the SiO2/carbon composite fiber obtained in step (2) according to a certain mass ratio, and then reduce part of the SiO2 into silicon element by thermal reduction under inert gas, and then The Si/SiO2/carbon composite fiber material is obtained by pickling, water washing and drying; (4) the Si/carbon composite fiber obtained in step (3) is acid-washed with hydrofluoric acid, washed with water and dried to remove excess SiO2, and form in the carbon fiber The porous silicon nanoparticle structure is embedded, and finally, the one-dimensional porous silicon/carbon composite negative electrode material is obtained by heat treatment at a high temperature of 600-1000° C. for 4-8 hours in an inert atmosphere, and then lowered to room temperature.
在其中一个实施例中，在步骤（1）中，所述纳米SiO2的粒径为50-1000 nm；所述纳米SiO2的纯度大于99.9%；所述表面活性剂为溴化十六烷三甲基铵、乙二醇、壬基酚聚氧乙烯醚、溴代十六烷基吡啶、γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、3-甲基丙烯酰氧丙基甲基二乙氧基硅烷或3-甲基丙烯酰氧丙基甲基二甲氧基硅烷中的1种或至少2种的组合；所述高分子聚合物为线性高软化点（250-280℃）沥青、聚丙烯腈、聚苯乙烯、聚乙烯吡咯烷酮、聚乙烯醇缩丁醛、聚乙烯醇、聚甲基丙烯酸甲酯、聚偏氟乙烯、聚氨酯、聚酰亚胺中的1种或至少2种的组合；所述分散剂为水、乙醇、N，N-二甲基甲酰胺、四氢呋喃、丙酮、三氯化碳、N，N-二甲基乙酰胺中的1种或至少2种的组合。In one embodiment, in step (1), the particle size of the nano-SiO2 is 50-1000 nm; the purity of the nano-SiO2 is greater than 99.9%; the surfactant is hexadecanetrimethyl bromide Ammonium, ethylene glycol, nonylphenol polyoxyethylene ether, bromohexadecylpyridine, γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-( One of Methacryloxy)propyltrimethoxysilane, 3-Methacryloxypropylmethyldiethoxysilane or 3-Methacryloxypropylmethyldimethoxysilane or a combination of at least two kinds; the high molecular polymer is linear high softening point (250-280 ° C) pitch, polyacrylonitrile, polystyrene, polyvinylpyrrolidone, polyvinyl butyral, polyvinyl alcohol, polyvinyl One or a combination of at least two of methyl methacrylate, polyvinylidene fluoride, polyurethane, and polyimide; the dispersant is water, ethanol, N,N-dimethylformamide, tetrahydrofuran, acetone , carbon trichloride, and N,N-dimethylacetamide at least one kind or a combination of at least two kinds.
在其中一个实施例中，在步骤（1）中，所述纳米SiO2、表面活性剂与高分子聚合物的质量比为10-60:0.5-3:100；所述纺丝溶液中的高分子聚合物质量分数浓度为5-15%；所述的超声搅拌分散在室温下进行，超声功率大于50W，搅拌时间大于8 h；所述静电纺丝条件为：注射器与收集器的距离为8-15cm，电压为10-20kV，针头直径为0.3-0.8mm，挤出速率为0.5-5.0mL/h，收集器为金属箔。In one embodiment, in step (1), the mass ratio of the nano-SiO2, surfactant and high molecular polymer is 10-60:0.5-3:100; the high molecular weight in the spinning solution The polymer mass fraction concentration is 5-15%; the ultrasonic stirring and dispersion are carried out at room temperature, the ultrasonic power is greater than 50W, and the stirring time is greater than 8 h; the electrospinning conditions are: the distance between the syringe and the collector is 8- 15cm, the voltage is 10-20kV, the needle diameter is 0.3-0.8mm, the extrusion rate is 0.5-5.0mL/h, and the collector is metal foil.
在其中一个实施例中，在步骤（2）中，所述氧化不熔化是在空气气氛以0.5-5℃/min的升温速率升温至200-300℃预氧化1-6小时；所述预碳化是在惰性气氛下以3-5℃/min的升温速率升温至400-600℃，并保温2-6小时。In one embodiment, in step (2), the oxidative non-melting is to pre-oxidize for 1-6 hours in an air atmosphere at a heating rate of 0.5-5 ℃/min to 200-300 ℃; the pre-carbonization It is heated to 400-600°C at a heating rate of 3-5°C/min under an inert atmosphere, and kept for 2-6 hours.
在其中一个实施例中，在步骤（3）中，所述活性金属粉为铝粉和/或镁粉；所述活性金属粉与SiO2的质量比为5-35:100；所述热还原是在惰性气氛下升温至400-800℃反应2-6小时；所述酸洗、水洗是采用过量盐酸溶液在40-60℃下搅拌反应1-3小时，然后再用纯水搅拌洗涤过滤至滤液pH为6.5-7.0。In one embodiment, in step (3), the active metal powder is aluminum powder and/or magnesium powder; the mass ratio of the active metal powder to SiO2 is 5-35:100; the thermal reduction is In an inert atmosphere, the temperature is raised to 400-800°C for 2-6 hours; the acid washing and water washing are performed by using excess hydrochloric acid solution at 40-60°C for 1-3 hours, and then stirring and washing with pure water to filter the filtrate. The pH is 6.5-7.0.
在其中一个实施例中，在步骤（4）中，所述氢氟酸酸洗、水洗是采用过量氢氟酸溶液在室温下搅拌反应0.5-2小时，去除剩余的SiO2，然后再用纯水搅拌洗涤过滤至滤液pH为6.5-7.0。In one embodiment, in step (4), the hydrofluoric acid pickling and water washing are performed by using excess hydrofluoric acid solution to stir and react at room temperature for 0.5-2 hours to remove the remaining SiO2, and then use pure water Stir and wash and filter until the pH of the filtrate is 6.5-7.0.
在其中一个实施例中，在步骤（3）和步骤（4）中，所述干燥是在鼓风或真空电热干燥箱中进行，干燥温度为80-120℃，干燥时间为4-12小时；在步骤（4）中，所述高温热处理温度为600-1000℃；所述升温速率为3～10℃/min,；所述热处理时间为4-8小时。In one embodiment, in step (3) and step (4), the drying is performed in a blast or vacuum electric heating drying oven, the drying temperature is 80-120°C, and the drying time is 4-12 hours; In step (4), the high-temperature heat treatment temperature is 600-1000° C.; the heating rate is 3-10° C./min; and the heat-treatment time is 4-8 hours.
在其中一个实施例中，在步骤（2）、步骤（3）和步骤（4）中，所述的惰性气体为氮气、氦气、氖气、氩气、氪气和氙气中的1种或至少2种的组合。In one embodiment, in step (2), step (3) and step (4), the inert gas is one of nitrogen, helium, neon, argon, krypton and xenon or A combination of at least 2.
一种一维多孔硅碳复合负极材料，所述一维多孔硅碳复合负极材料由所述的制备方法制得。A one-dimensional porous silicon-carbon composite negative electrode material, the one-dimensional porous silicon-carbon composite negative electrode material is prepared by the preparation method.
一种一维多孔硅碳复合负极材料的应用，使用的一维多孔硅碳复合负极材料应用于锂离子电池负极材料。An application of a one-dimensional porous silicon-carbon composite negative electrode material, and the used one-dimensional porous silicon-carbon composite negative electrode material is applied to a lithium ion battery negative electrode material.
有益效果beneficial effect
本发明的制备工艺简单，无需额外包覆改性，易于规模化生产；通过金属热还原和刻蚀方法原位诱导多孔硅的形成，在获得高可逆容量的同时能够显著提高硅活性组分的稳定性，改善硅的本征膨胀效应，避免颗粒粉化和结构坍塌等问题；通过聚合物基体静电纺丝能够获得直径小且粗细均匀的碳纤维基体，可以更好地为硅提供缓冲作用，提高电子传导率。本发明的多孔硅/碳复合负极材料，首次可逆比容量大于750mAh/g，同时首次循环库仑效率大于86％，具备优异的循环稳定性，克服了传统硅碳负极材料电化学稳定性差的问题，在储能和电动汽车领域中市场广阔。The preparation process of the invention is simple, no additional coating modification is required, and large-scale production is easy; the formation of porous silicon is induced in situ by the metallothermic reduction and etching methods, and the high reversible capacity can be obtained while the silicon active component can be remarkably improved. stability, improve the intrinsic expansion effect of silicon, and avoid problems such as particle pulverization and structural collapse; through the electrospinning of the polymer matrix, a carbon fiber matrix with small diameter and uniform thickness can be obtained, which can better provide a buffer for silicon and improve Electronic conductivity. The porous silicon/carbon composite negative electrode material of the present invention has the first reversible specific capacity greater than 750mAh/g, while the first cycle Coulombic efficiency is greater than 86%, has excellent cycle stability, and overcomes the problem of poor electrochemical stability of traditional silicon carbon negative electrode materials. There is a broad market in the fields of energy storage and electric vehicles.
本发明的实施方式Embodiments of the present invention
为了便于理解本发明，下面将对本发明进行更全面的描述。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。In order to facilitate understanding of the present invention, the present invention will be described more fully below. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that a thorough and complete understanding of the present disclosure is provided.
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used herein in the description of the present invention are for the purpose of describing specific embodiments only, and are not intended to limit the present invention.
实施例1：将粒径为100nm的SiO2、溴化十六烷三甲基铵、聚丙烯腈（Mw180000）按照20:1:100的质量比加入N,N-二甲基甲酰胺溶剂中，保持聚丙烯腈的固含量为8%，然后在80W的超声功率下搅拌12小时得到纺丝液，采用静电纺丝（注射器与收集器的距离为10cm，电压为20kV，针头直径为0.5mm，挤出速率为3mL/h，收集器为铝箔）得到SiO2/聚丙烯腈复合纤维；将含有硅源的纤维自支撑体膜整块取下放入马弗炉中于250℃预氧化4小时，然后在氮气保护下以3℃/min升温速率升温至600℃预碳化2小时得到SiO2/碳复合纤维前驱体，将该前驱体与镁粉（其中镁粉与前驱体中SiO2的质量比为12:100）充分混合后置入气氛炉中，在氩气气氛下加热到750℃保温4小时，将反应产物经过过量盐酸洗涤、水洗至中性（pH=7）和干燥后得到富硅前驱体；将该富硅前驱体经过量氢氟酸刻蚀、水洗至中性（pH=7）和干燥后得到多孔硅/碳前驱体；再将该前驱体在氮气保护下于950℃碳化4小时，降至室温即得一维多孔硅/碳复合负极材料。Example 1: SiO2 with a particle size of 100 nm, hexadecyltrimethylammonium bromide, and polyacrylonitrile (Mw180000) were added to N,N-dimethylformamide solvent in a mass ratio of 20:1:100, Keep the solid content of polyacrylonitrile at 8%, then stir under the ultrasonic power of 80W for 12 hours to obtain the spinning solution, and use electrospinning (the distance between the syringe and the collector is 10cm, the voltage is 20kV, the needle diameter is 0.5mm, The extrusion rate was 3 mL/h, and the collector was aluminum foil) to obtain SiO2/polyacrylonitrile composite fibers; the fiber self-supporting film containing the silicon source was taken off as a whole and placed in a muffle furnace for pre-oxidation at 250 °C for 4 hours. Then, under nitrogen protection, the temperature was raised to 600°C at a heating rate of 3°C/min for 2 hours to obtain a SiO2/carbon composite fiber precursor. : 100) after fully mixing, put it in an atmosphere furnace, heat it to 750 °C for 4 hours under an argon atmosphere, wash the reaction product with excess hydrochloric acid, wash with water to neutral (pH=7) and dry to obtain a silicon-rich precursor. ; The silicon-rich precursor is etched with a large amount of hydrofluoric acid, washed with water to neutral (pH=7) and dried to obtain a porous silicon/carbon precursor; then the precursor is carbonized under nitrogen protection at 950 ° C for 4 hours , and the one-dimensional porous silicon/carbon composite anode material was obtained at room temperature.
实施例2：将粒径为100nm的SiO2、γ-氨丙基三乙氧基硅烷、聚乙烯吡咯烷酮（Mw1300000）按照30:1:100的质量比加入乙醇溶剂中，保持聚丙烯腈的固含量为8%，然后在80W的超声功率下搅拌12小时得到纺丝液，采用静电纺丝（注射器与收集器的距离为10cm，电压为20kV，针头直径为0.5mm，挤出速率为5mL/h，收集器为铝箔）得到SiO2/聚丙烯腈复合纤维；将含有硅源的纤维自支撑体膜整块取下放入马弗炉中于250℃预氧化4小时，然后在氮气保护下以3℃/min升温速率升温至600℃预碳化2小时得到SiO2/碳复合纤维前驱体，将该前驱体与镁粉（其中镁粉与前驱体中SiO2的质量比为15:100）充分混合后置入气氛炉中，在氩气气氛下加热到750℃保温4小时，将反应产物经过过量盐酸洗涤、水洗至中性（pH=7）和干燥后得到富硅前驱体；将该富硅前驱体经过量氢氟酸刻蚀、水洗至中性（pH=7）和干燥后得到多孔硅/碳前驱体；再将该前驱体在氮气保护下于950℃碳化4小时，降至室温即得一维多孔硅/碳复合负极材料。Example 2: Add SiO2, γ-aminopropyltriethoxysilane, and polyvinylpyrrolidone (Mw1300000) with a particle size of 100 nm to an ethanol solvent in a mass ratio of 30:1:100 to maintain the solid content of polyacrylonitrile 8%, and then stirred for 12 hours under the ultrasonic power of 80W to obtain the spinning solution, using electrospinning (the distance between the syringe and the collector was 10cm, the voltage was 20kV, the diameter of the needle was 0.5mm, and the extrusion rate was 5mL/h. , the collector is aluminum foil) to obtain SiO2/polyacrylonitrile composite fiber; the fiber self-supporting body film containing silicon source is taken off as a whole and placed in a muffle furnace for pre-oxidation at 250 ° C for 4 hours, and then under nitrogen protection for 3 hours ℃/min heating rate was heated to 600 ℃ for 2 hours and pre-carbonized to obtain SiO2/carbon composite fiber precursor, which was fully mixed with magnesium powder (the mass ratio of magnesium powder and SiO2 in the precursor was 15:100) and then placed Put it into an atmosphere furnace, heat it to 750°C for 4 hours under an argon atmosphere, wash the reaction product with excess hydrochloric acid, wash it with water to neutrality (pH=7) and dry to obtain a silicon-rich precursor; the silicon-rich precursor Porous silicon/carbon precursor is obtained after etching with a large amount of hydrofluoric acid, washing with water to neutrality (pH=7) and drying; the precursor is then carbonized at 950 °C for 4 hours under the protection of nitrogen, and then cooled to room temperature to obtain a porous silicon/carbon precursor. dimensional porous silicon/carbon composite anode material.
实施例3：将粒径为100nm的SiO2、γ-氨丙基三乙氧基硅烷、聚乙烯醇（Mw120000）按照40:1:100的质量比加入乙醇溶剂中，保持聚丙烯腈的固含量为8%，然后在80W的超声功率下搅拌12小时得到纺丝液，采用静电纺丝（注射器与收集器的距离为10cm，电压为20kV，针头直径为0.5mm，挤出速率为3mL/h，收集器为铝箔）得到SiO2/聚丙烯腈复合纤维；将含有硅源的纤维自支撑体膜整块取下放入马弗炉中于250℃预氧化4小时，然后在氮气保护下以3℃/min升温速率升温至600℃预碳化2小时得到SiO2/碳复合纤维前驱体，将该前驱体与镁粉（其中镁粉与前驱体中SiO2的质量比为20:100）充分混合后置入气氛炉中，在氩气气氛下加热到750℃保温4小时，将反应产物经过过量盐酸洗涤、水洗至中性（pH=7）和干燥后得到富硅前驱体；将该富硅前驱体经过量氢氟酸刻蚀、水洗至中性（pH=7）和干燥后得到多孔硅/碳前驱体；再将该前驱体在氮气保护下于950℃碳化4小时，降至室温即得一维多孔硅/碳复合负极材料。Example 3: Add SiO2, γ-aminopropyltriethoxysilane, and polyvinyl alcohol (Mw120000) with a particle size of 100 nm into an ethanol solvent at a mass ratio of 40:1:100 to maintain the solid content of polyacrylonitrile 8%, and then stirred for 12 hours under the ultrasonic power of 80W to obtain the spinning solution. Electrospinning was used (the distance between the syringe and the collector was 10cm, the voltage was 20kV, the diameter of the needle was 0.5mm, and the extrusion rate was 3mL/h. , the collector is aluminum foil) to obtain SiO2/polyacrylonitrile composite fiber; the fiber self-supporting body film containing silicon source is taken off as a whole and placed in a muffle furnace for pre-oxidation at 250 ° C for 4 hours, and then under nitrogen protection for 3 hours ℃/min heating rate was heated to 600 ℃ for 2 hours to obtain SiO2/carbon composite fiber precursor, which was fully mixed with magnesium powder (the mass ratio of magnesium powder and SiO2 in the precursor was 20:100) and then placed Put it into an atmosphere furnace, heat it to 750°C for 4 hours under an argon atmosphere, wash the reaction product with excess hydrochloric acid, wash it with water to neutrality (pH=7) and dry to obtain a silicon-rich precursor; the silicon-rich precursor Porous silicon/carbon precursor is obtained after etching with a large amount of hydrofluoric acid, washing with water to neutrality (pH=7) and drying; the precursor is then carbonized at 950 °C for 4 hours under the protection of nitrogen, and then cooled to room temperature to obtain a porous silicon/carbon precursor. dimensional porous silicon/carbon composite anode material.
实施例4：将粒径为200nm的SiO2、溴化十六烷三甲基铵、聚丙烯腈（Mw180000）按照40:1:100的质量比加入N,N-二甲基甲酰胺溶剂中，保持聚丙烯腈的固含量为8%，然后在80W的超声功率下搅拌12小时得到纺丝液，采用静电纺丝（注射器与收集器的距离为10cm，电压为20kV，针头直径为0.5mm，挤出速率为5mL/h，收集器为铝箔）得到SiO2/聚丙烯腈复合纤维；将含有硅源的纤维自支撑体膜整块取下放入马弗炉中于250℃预氧化4小时，然后在氮气保护下以3℃/min升温速率升温至600℃预碳化2小时得到SiO2/碳复合纤维前驱体，将该前驱体与镁粉（其中镁粉与前驱体中SiO2的质量比为20:100）充分混合后置入气氛炉中，在氩气气氛下加热到750℃保温4小时，将反应产物经过过量盐酸洗涤、水洗至中性（pH=7）和干燥后得到富硅前驱体；将该富硅前驱体经过量氢氟酸刻蚀、水洗至中性（pH=7）和干燥后得到多孔硅/碳前驱体；再将该前驱体在氮气保护下于950℃碳化4小时，降至室温即得一维多孔硅/碳复合负极材料。Example 4: SiO2, hexadecyltrimethylammonium bromide and polyacrylonitrile (Mw180000) with a particle size of 200 nm were added to N,N-dimethylformamide solvent in a mass ratio of 40:1:100, Keep the solid content of polyacrylonitrile at 8%, then stir under the ultrasonic power of 80W for 12 hours to obtain the spinning solution, and use electrospinning (the distance between the syringe and the collector is 10cm, the voltage is 20kV, the needle diameter is 0.5mm, The extrusion rate was 5 mL/h, and the collector was aluminum foil) to obtain SiO2/polyacrylonitrile composite fibers; the fiber self-supporting film containing the silicon source was taken off as a whole and placed in a muffle furnace for pre-oxidation at 250 °C for 4 hours. Then, under nitrogen protection, the temperature was raised to 600°C at a heating rate of 3°C/min for 2 hours to obtain a SiO2/carbon composite fiber precursor. : 100) after fully mixing, put it in an atmosphere furnace, heat it to 750 °C for 4 hours under an argon atmosphere, wash the reaction product with excess hydrochloric acid, wash with water to neutral (pH=7) and dry to obtain a silicon-rich precursor. ; The silicon-rich precursor is etched with a large amount of hydrofluoric acid, washed with water to neutral (pH=7) and dried to obtain a porous silicon/carbon precursor; then the precursor is carbonized under nitrogen protection at 950 ° C for 4 hours , and the one-dimensional porous silicon/carbon composite anode material was obtained at room temperature.
实施例5：将粒径为300nm的SiO2、溴化十六烷三甲基铵、聚丙烯腈（Mw180000）按照40:1:100的质量比加入N,N-二甲基甲酰胺溶剂中，保持聚丙烯腈的固含量为8%，然后在80W的超声功率下搅拌12小时得到纺丝液，采用静电纺丝（注射器与收集器的距离为10cm，电压为20kV，针头直径为0.5mm，挤出速率为3mL/h，收集器为铝箔）得到SiO2/聚丙烯腈复合纤维；将含有硅源的纤维自支撑体膜整块取下放入马弗炉中于250℃预氧化4小时，然后在氮气保护下以3℃/min升温速率升温至600℃预碳化2小时得到SiO2/碳复合纤维前驱体，将该前驱体与镁粉（其中镁粉与前驱体中SiO2的质量比为20:100）充分混合后置入气氛炉中，在氩气气氛下加热到750℃保温4小时，将反应产物经过过量盐酸洗涤、水洗至中性（pH=7）和干燥后得到富硅前驱体；将该富硅前驱体经过量氢氟酸刻蚀、水洗至中性（pH=7）和干燥后得到多孔硅/碳前驱体；再将该前驱体在氮气保护下于950℃碳化4小时，降至室温即得一维多孔硅/碳复合负极材料。Example 5: SiO2 with a particle size of 300 nm, hexadecyltrimethylammonium bromide, and polyacrylonitrile (Mw180000) were added to N,N-dimethylformamide solvent in a mass ratio of 40:1:100, Keep the solid content of polyacrylonitrile at 8%, then stir under the ultrasonic power of 80W for 12 hours to obtain the spinning solution, and use electrospinning (the distance between the syringe and the collector is 10cm, the voltage is 20kV, the needle diameter is 0.5mm, The extrusion rate was 3 mL/h, and the collector was aluminum foil) to obtain SiO2/polyacrylonitrile composite fibers; the fiber self-supporting film containing the silicon source was taken off as a whole and placed in a muffle furnace for pre-oxidation at 250 °C for 4 hours. Then, under nitrogen protection, the temperature was raised to 600°C at a heating rate of 3°C/min for 2 hours to obtain a SiO2/carbon composite fiber precursor. : 100) after fully mixing, put it in an atmosphere furnace, heat it to 750 °C for 4 hours under an argon atmosphere, wash the reaction product with excess hydrochloric acid, wash with water to neutral (pH=7) and dry to obtain a silicon-rich precursor. ; The silicon-rich precursor is etched with a large amount of hydrofluoric acid, washed with water to neutral (pH=7) and dried to obtain a porous silicon/carbon precursor; then the precursor is carbonized under nitrogen protection at 950 ° C for 4 hours , and the one-dimensional porous silicon/carbon composite anode material was obtained at room temperature.
对比实施例：将粒径为300nm的SiO2、溴化十六烷三甲基铵、聚丙烯腈（Mw180000）按照30:1:100的质量比加入N,N-二甲基甲酰胺溶剂中，保持聚丙烯腈的固含量为8%，然后在80W的超声功率下搅拌12小时得到纺丝液，采用静电纺丝（注射器与收集器的距离为10cm，电压为20kV，针头直径为0.5mm，挤出速率为3mL/h，收集器为铝箔）得到SiO2/聚丙烯腈复合纤维；将含有硅源的纤维自支撑体膜整块取下放入马弗炉中于250℃预氧化4小时，然后在氮气保护下以3℃/min升温速率升温至600℃预碳化2小时得到SiO2/碳复合纤维前驱体；再将该前驱体在氮气保护下于950℃碳化4小时，降至室温即得对比材料。Comparative example: SiO2, cetyltrimethylammonium bromide and polyacrylonitrile (Mw180000) with a particle size of 300nm were added to N,N-dimethylformamide solvent in a mass ratio of 30:1:100, Keep the solid content of polyacrylonitrile at 8%, then stir under the ultrasonic power of 80W for 12 hours to obtain the spinning solution, and use electrospinning (the distance between the syringe and the collector is 10cm, the voltage is 20kV, the needle diameter is 0.5mm, The extrusion rate was 3 mL/h, and the collector was aluminum foil) to obtain SiO2/polyacrylonitrile composite fibers; the fiber self-supporting film containing the silicon source was taken off as a whole and placed in a muffle furnace for pre-oxidation at 250 °C for 4 hours. Then, under nitrogen protection, the temperature was raised to 600 °C at a heating rate of 3 °C/min for 2 hours to obtain a SiO2/carbon composite fiber precursor; the precursor was then carbonized at 950 °C for 4 hours under nitrogen protection, and then cooled to room temperature to obtain Contrast material.
采用半电池测试方法对实施例1~5以及对比例中的硅/碳复合材料进行首次比容量、首次库伦效率以及循环性能测试，结果列于表1。半电池的测试方法为：电化学性能测试采用如下方法进行：取实施例1~5及对比例制备的材料作为负极材料，与增稠剂CMC、粘结剂SBR、导电剂（Super-P）按照85:2:3:10的质量比混合，加入适量的去离子水作为分散剂调成浆料，涂覆在铜箔上，经辊压、真空干燥制备成负极片；使用1mol/L的LiPF6三组分混合溶剂按EC:DMC:EMC=1:1:1 (V/V)并添加5%VC混合的电解液，采用Celgard聚丙烯微孔膜为隔膜，在氩气保护的手套箱中以锂片为对电极制成CR2032纽扣半电池。扣式电池的充放电测试在武汉金诺电子有限公司LAND电池测试***上进行，在常温条件，首先以0.1C恒流充放活化，而后以1C充放循环500次，充放电电压为0.005~2.0V。The first specific capacity, first coulombic efficiency and cycle performance tests were carried out on the silicon/carbon composite materials in Examples 1 to 5 and the comparative example by using the half-cell test method, and the results are listed in Table 1. The test method of the half-cell is as follows: the electrochemical performance test is carried out by the following method: take the materials prepared in Examples 1 to 5 and the comparative example as the negative electrode material, mix with the thickener CMC, the binder SBR, and the conductive agent (Super-P) Mix according to the mass ratio of 85:2:3:10, add an appropriate amount of deionized water as a dispersant to make a slurry, coat it on the copper foil, and prepare a negative electrode sheet by rolling and vacuum drying; use 1mol/L The three-component LiPF6 mixed solvent is EC:DMC:EMC=1:1:1 (V/V) and the electrolyte mixed with 5% VC is added. Celgard polypropylene microporous membrane is used as the diaphragm. A CR2032 button half-cell was made with a lithium sheet as the counter electrode. The charge-discharge test of the button battery was carried out on the LAND battery test system of Wuhan Jinnuo Electronics Co., Ltd. At room temperature, it was first activated by charging and discharging at a constant current of 0.1C, and then charged and discharged at 1C for 500 cycles, and the charge-discharge voltage was 0.005~ 2.0V.
表1。Table 1.
Figure 332043dest_path_image001
。
Figure 332043dest_path_image001
.
从表1实施例可以看出，本发明的硅/碳复合材料可逆容量可通过硅源的引入量进行选择性调控，容量高于750mAh/g，首次库伦效率大于86%，经过500次充放电循环后，电极容量保持率大于84%，远高于对比实施例，由此表明本发明的一维多孔硅/碳复合材料可以在保证高容量发挥的同时有效提高电池的容量保持率，使所应用的锂离子电池表现出良好的循环稳定性。It can be seen from the examples in Table 1 that the reversible capacity of the silicon/carbon composite material of the present invention can be selectively regulated by the amount of silicon source introduced, the capacity is higher than 750mAh/g, the first Coulomb efficiency is higher than 86%, and after 500 times of charge and discharge After the cycle, the electrode capacity retention rate is greater than 84%, which is much higher than that of the comparative example, which shows that the one-dimensional porous silicon/carbon composite material of the present invention can effectively improve the capacity retention rate of the battery while ensuring high capacity, so that the The applied Li-ion battery exhibits good cycle stability.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only represent several embodiments of the present invention, and the descriptions thereof are specific and detailed, but should not be construed as a limitation on the scope of the patent of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can also be made, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims (10)

  1. 一种一维多孔硅碳复合负极材料的制备方法，其特征在于，包括如下步骤：A method for preparing a one-dimensional porous silicon-carbon composite negative electrode material, characterized in that it comprises the following steps:
    （1）将纳米SiO 2与表面活性剂、高分子聚合物混合加入分散剂中，室温超声搅拌分散后得到纺丝溶液，通过静电纺丝得到SiO 2/聚合物复合纤维； (1) Mixing nano-SiO 2 with surfactant and high molecular polymer into dispersing agent, stirring and dispersing by ultrasonic at room temperature to obtain spinning solution, and obtaining SiO 2 /polymer composite fiber by electrospinning;
    （2）将步骤（1）所得SiO 2/聚合物复合纤维进行氧化不熔化处理，然后在惰性气体保护下于400-600℃预碳化，降温后得到SiO 2/碳复合纤维； (2) The SiO 2 /polymer composite fiber obtained in step (1) is subjected to oxidation infusion treatment, and then pre-carbonized at 400-600 ° C under the protection of inert gas, and the SiO 2 /carbon composite fiber is obtained after cooling;
    （3）将活性金属粉按一定质量比与步骤（2）所得SiO 2/碳复合纤维混合，然后在惰性气体下通过热还原的方法将其中的部分SiO2还原成为硅单质，再经过酸洗、水洗和干燥得到Si/SiO2/碳复合纤维材料； (3) Mix the active metal powder with the SiO 2 /carbon composite fiber obtained in step (2) in a certain mass ratio, and then reduce part of the SiO 2 into silicon element by thermal reduction under inert gas, and then go through acid washing, Wash and dry to obtain Si/SiO2/carbon composite fiber material;
    （4）将步骤（3）所得Si/碳复合纤维采用氢氟酸酸洗、水洗和干燥去除多余的SiO 2，在碳纤维中形成嵌含有多孔硅纳米颗粒结构，最后在惰性气氛下600-1000℃高温热处理4-8小时，降至室温即得一维多孔硅/碳复合负极材料。 (4) The Si/carbon composite fiber obtained in step (3) is acid-washed with hydrofluoric acid, washed with water and dried to remove excess SiO 2 , forming a structure containing porous silicon nanoparticles in the carbon fiber, and finally in an inert atmosphere for 600-1000 The one-dimensional porous silicon/carbon composite negative electrode material is obtained by heat treatment at a high temperature of ℃ for 4-8 hours and lowered to room temperature.
  2. 根据权利要求1所述的一维多孔硅碳复合负极材料的制备方法，其特征在于，在步骤（1）中，所述纳米SiO 2的粒径为50-1000 nm；所述纳米SiO 2的纯度大于99.9%；所述表面活性剂为溴化十六烷三甲基铵、乙二醇、壬基酚聚氧乙烯醚、溴代十六烷基吡啶、γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、3-甲基丙烯酰氧丙基甲基二乙氧基硅烷或3-甲基丙烯酰氧丙基甲基二甲氧基硅烷中的1种或至少2种的组合；所述高分子聚合物为线性高软化点（250-280℃）沥青、聚丙烯腈、聚苯乙烯、聚乙烯吡咯烷酮、聚乙烯醇缩丁醛、聚乙烯醇、聚甲基丙烯酸甲酯、聚偏氟乙烯、聚氨酯、聚酰亚胺中的1种或至少2种的组合；所述分散剂为水、乙醇、N，N-二甲基甲酰胺、四氢呋喃、丙酮、三氯化碳、N，N-二甲基乙酰胺中的1种或至少2种的组合。 The method for preparing a one-dimensional porous silicon-carbon composite negative electrode material according to claim 1, wherein in step (1), the particle size of the nano-SiO 2 is 50-1000 nm ; The purity is greater than 99.9%; the surfactant is cetyltrimethylammonium bromide, ethylene glycol, nonylphenol polyoxyethylene ether, bromohexadecylpyridine, γ-aminopropyltriethoxy Silane, gamma-glycidyloxypropyltrimethoxysilane, gamma-(methacryloyloxy)propyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, or 3- One or a combination of at least two of methacryloyloxypropylmethyldimethoxysilane; the high molecular polymer is linear high softening point (250-280°C) pitch, polyacrylonitrile, polyphenylene One or a combination of at least two of ethylene, polyvinylpyrrolidone, polyvinyl butyral, polyvinyl alcohol, polymethyl methacrylate, polyvinylidene fluoride, polyurethane, and polyimide; the dispersant It is one or a combination of at least two of water, ethanol, N,N-dimethylformamide, tetrahydrofuran, acetone, carbon trichloride, and N,N-dimethylacetamide.
  3. 根据权利要求1所述的一维多孔硅碳复合负极材料的制备方法，其特征在于，在步骤（1）中，所述纳米SiO 2、表面活性剂与高分子聚合物的质量比为10-60:0.5-3:100；所述纺丝溶液中的高分子聚合物质量分数浓度为5-15%；所述的超声搅拌分散在室温下进行，超声功率大于50W，搅拌时间大于8 h；所述静电纺丝条件为：注射器与收集器的距离为8-15cm，电压为10-20kV，针头直径为0.3-0.8mm，挤出速率为0.5-5.0mL/h，收集器为金属箔。 The method for preparing a one-dimensional porous silicon-carbon composite negative electrode material according to claim 1, wherein in step (1), the mass ratio of the nano-SiO 2 , the surfactant and the high molecular polymer is 10- 60:0.5-3:100; the mass fraction concentration of the high molecular polymer in the spinning solution is 5-15%; the ultrasonic stirring and dispersion are carried out at room temperature, the ultrasonic power is greater than 50W, and the stirring time is greater than 8 h; The electrospinning conditions are as follows: the distance between the syringe and the collector is 8-15cm, the voltage is 10-20kV, the diameter of the needle is 0.3-0.8mm, the extrusion rate is 0.5-5.0mL/h, and the collector is metal foil.
  4. 根据权利要求1所述的一维多孔硅碳复合负极材料的制备方法，其特征在于，在步骤（2）中，所述氧化不熔化是在空气气氛以0.5-5℃/min的升温速率升温至200-300℃预氧化1-6小时；所述预碳化是在惰性气氛下以3-5℃/min的升温速率升温至400-600℃，并保温2-6小时。The method for preparing a one-dimensional porous silicon-carbon composite negative electrode material according to claim 1, characterized in that, in step (2), the oxidative non-melting is performed by heating at a heating rate of 0.5-5°C/min in an air atmosphere Pre-oxidation at 200-300° C. for 1-6 hours; the pre-carbonization is to heat up to 400-600° C. at a heating rate of 3-5° C./min under an inert atmosphere, and keep the temperature for 2-6 hours.
  5. 根据权利要求1所述的一维多孔硅碳复合负极材料的制备方法，其特征在于，在步骤（3）中，所述活性金属粉为铝粉和/或镁粉；所述活性金属粉与SiO2的质量比为5-35:100；所述热还原是在惰性气氛下升温至400-800℃反应2-6小时；所述酸洗、水洗是采用过量盐酸溶液在40-60℃下搅拌反应1-3小时，然后再用纯水搅拌洗涤过滤至滤液pH为6.5-7.0。The method for preparing a one-dimensional porous silicon-carbon composite negative electrode material according to claim 1, wherein in step (3), the active metal powder is aluminum powder and/or magnesium powder; The mass ratio of SiO2 is 5-35:100; the thermal reduction is to be heated to 400-800 ° C under an inert atmosphere for 2-6 hours; the acid washing and water washing are to use excess hydrochloric acid solution to stir at 40-60 ° C The reaction was carried out for 1-3 hours, and then stirred and washed with pure water until the pH of the filtrate was 6.5-7.0.
  6. 根据权利要求1所述的一维多孔硅碳复合负极材料的制备方法，其特征在于，在步骤（4）中，所述氢氟酸酸洗、水洗是采用过量氢氟酸溶液在室温下搅拌反应0.5-2小时，去除剩余的SiO2，然后再用纯水搅拌洗涤过滤至滤液pH为6.5-7.0。The method for preparing a one-dimensional porous silicon-carbon composite negative electrode material according to claim 1, characterized in that, in step (4), the hydrofluoric acid pickling and water washing are performed by using excess hydrofluoric acid solution to stir at room temperature React for 0.5-2 hours, remove the remaining SiO2, then stir and wash with pure water and filter until the pH of the filtrate is 6.5-7.0.
  7. 根据权利要求1所述的一维多孔硅碳复合负极材料的制备方法，其特征在于，在步骤（3）和步骤（4）中，所述干燥是在鼓风或真空电热干燥箱中进行，干燥温度为80-120℃，干燥时间为4-12小时；在步骤（4）中，所述高温热处理温度为600-1000℃；所述升温速率为3～10℃/min,；所述热处理时间为4-8小时。The method for preparing a one-dimensional porous silicon-carbon composite negative electrode material according to claim 1, characterized in that, in steps (3) and (4), the drying is performed in a blast or vacuum electric heating drying oven, The drying temperature is 80-120°C, and the drying time is 4-12 hours; in step (4), the high-temperature heat treatment temperature is 600-1000°C; the heating rate is 3-10°C/min; the heat treatment The time is 4-8 hours.
  8. 根据权利要求1所述的一维多孔硅碳复合负极材料的制备方法，其特征在于，在步骤（2）、步骤（3）和步骤（4）中，所述的惰性气体为氮气、氦气、氖气、氩气、氪气和氙气中的1种或至少2种的组合。The method for preparing a one-dimensional porous silicon-carbon composite negative electrode material according to claim 1, wherein in step (2), step (3) and step (4), the inert gas is nitrogen, helium , Neon, Argon, Krypton and Xenon 1 or a combination of at least 2.
  9. 一种一维多孔硅碳复合负极材料，其特征在于，所述一维多孔硅碳复合负极材料由权利要求1-8任一项所述的制备方法制得。A one-dimensional porous silicon-carbon composite negative electrode material, characterized in that, the one-dimensional porous silicon-carbon composite negative electrode material is prepared by the preparation method according to any one of claims 1-8.
  10. 一种一维多孔硅碳复合负极材料的应用，其特征在于，使用如权利要求9的一维多孔硅碳复合负极材料应用于锂离子电池负极材料。An application of a one-dimensional porous silicon-carbon composite negative electrode material, characterized in that the one-dimensional porous silicon-carbon composite negative electrode material according to claim 9 is used in a lithium-ion battery negative electrode material.
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