WO2022151648A1 - High-capacity highly stable silicon-carbon negative electrode material and preparation method therefor - Google Patents

High-capacity highly stable silicon-carbon negative electrode material and preparation method therefor Download PDF

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WO2022151648A1
WO2022151648A1 PCT/CN2021/099089 CN2021099089W WO2022151648A1 WO 2022151648 A1 WO2022151648 A1 WO 2022151648A1 CN 2021099089 W CN2021099089 W CN 2021099089W WO 2022151648 A1 WO2022151648 A1 WO 2022151648A1
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silicon
negative electrode
electrode material
capacity
carbon negative
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PCT/CN2021/099089
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French (fr)
Chinese (zh)
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M2004/026—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 battery anode materials, in particular to a high-capacity and high-stability silicon carbon anode material and a preparation method thereof.
  • Li-ion batteries Compared to other rechargeable batteries, such as NiCd and NiMH, Li-ion batteries have higher energy density, higher operating voltage, limited self-discharge and lower maintenance requirements.
  • Lithium-ion battery is a relatively mature rechargeable battery at present. It not only has the characteristics of high specific capacity, long cycle life, no memory effect, and low self-discharge rate, but also has low pollution and meets environmental protection requirements. It can be widely used in electric vehicles, aerospace, biomedical engineering and other fields. A large number of studies have shown that the key to the performance of energy storage power supply is energy storage density and power density, while the energy storage density of ion batteries depends to a large extent on the specific capacity of positive and negative materials.
  • Lithium-ion batteries have revolutionized portable electronics over the past two decades and have the potential to have a huge impact on vehicle energization.
  • state-of-the-art Li-ion batteries (such as LiCoO2/graphite batteries) cannot meet the requirements of automotive electrification, which requires high energy density and high power density with long cycle life.
  • silicon is one of the most promising anode candidates for next-generation lithium-ion batteries. This is due to its low voltage distribution and high theoretical capacity (3590 mAh/g for Li15Si4 phase at room temperature), which is about 10 times (about 372 mAh/g) of carbonaceous materials (including graphite, pyrolytic carbon and mesophase pitch). g).
  • silicon also has the highest volume capacity (9786mAh/cm3, calculated based on the initial volume of silicon).
  • silicon is the second largest element in the earth's crust, which is environmentally friendly and non-toxic. Therefore, mass production of silicon at low cost is not a problem.
  • the practical application of silicon anodes is currently hindered by multiple challenges, including large volume changes ( ⁇ 300%) during lithiation/delithiation, low intrinsic conductivity, and solid electrolyte interface (SEI) instability. Large volume changes can result in particle pulverization, loss of electrical contact with conductive additives or current collectors, or even debonding from current collectors. Repeated volume expansion and contraction can also lead to fracture and reformation of the SEI layer around the particles, resulting in continuous depletion of electrolyte, increased impedance and capacity fading.
  • SEI solid electrolyte interface
  • the present invention provides a high-capacity and high-stability silicon-carbon negative electrode material, which is a multi-level carbon-coated silicon nanoparticle composite structure, which expands silicon nanoparticles from zero dimension to three dimensions, maintains stable structure.
  • the invention also provides a preparation method of a high-capacity and high-stability silicon carbon anode material, which is simple and convenient to prepare, and the prepared material combines multiple advantages such as large specific surface, high electrical conductivity and good structural stability, and effectively relieves the volume expansion of the silicon anode , keep the structure stable.
  • the silicon carbon negative electrode material comprises a plurality of spherical composite particles and an organic cracked carbon layer coated on the outside of a plurality of the first composite particles; the spherical composite particles include an inner core layer, For the carbonaceous material layer wrapped outside the inner core layer, the mass ratio of the inner core layer and the carbonaceous material layer is (3-65):1.
  • the organic cracked carbon layer is an organic carbon source
  • the organic carbon source is one or more of glucose, citric acid, polyacrylonitrile and pitch.
  • a further improvement to the above technical solution is that the mass ratio of the inner core layer and the carbonaceous material layer is (4-60):1, the inner core layer is nano-silicon, and the carbonaceous material layer includes graphite and graphene.
  • a method for preparing a high-capacity and high-stability silicon-carbon negative electrode material comprising the steps of: mixing nano-silicon and carbonaceous material after ball milling to obtain a powdery mixture, and mixing the powdery mixture with an organic carbon source solution, a nitrogen source and a surfactant After shaking, shaking and ultrasonically dispersing, a mixed solution is obtained; the mixed solution is subjected to a solvothermal reaction, and then solid-liquid separation is performed to obtain a solid substance; the solid substance is calcined to obtain a silicon carbon negative electrode material.
  • a further improvement to the above technical solution is that the mass ratio of the inner core layer and the carbonaceous material layer is (4-55):1) the inner core layer is nano-silicon, and the carbonaceous material layer includes graphite and graphene.
  • a further improvement to the above technical solution is that the speed of the ball milling is 250-650r/min, and the time of the ball milling is 32-40h.
  • the nitrogen source is one or more of 2,4,6-trichlorotriazine, 2,4,6-triazide triazine, melamine, and dicyandiamide
  • the surfactants include cetyltrimethylammonium bromide and alkyl polyethers.
  • a further improvement to the above technical scheme is that, in parts by mass, the ratio of the powdery mixture to the organic carbon source is 1: (11-15), and the ratio of the powdery mixture to the nitrogen source is (10-35 ): 1, the ratio of the powdery mixture to the surfactant is (1300-1600): 1, and the filling ratio of the solvothermal reaction is 35-80%.
  • reaction temperature of the solvothermal reaction is 220-300° C., and the reaction time is 4-18 h.
  • a further improvement to the above technical solution is that the calcination temperature is 650-1200° C., and the calcination time is 6-9 hours.
  • the present invention confines silicon nanoparticles in carbon materials, relieves the huge pressure caused by volume expansion in the conductive process, forms a stable solid electrolyte interface film (SEI), and maintains the structural stability of electrode materials; carbonaceous materials have good
  • SEI solid electrolyte interface film
  • the electrical conductivity makes the material prepared by the present invention avoid the inherent low conductivity of silicon while improving the stability. Therefore, the material prepared by the present invention combines multiple advantages such as large specific surface area, high conductivity and good structural stability. , effectively relieve the volume expansion of the silicon anode and keep the structure stable.
  • FIG. 1 is a schematic structural diagram of the high-capacity and high-stability silicon-carbon negative electrode material of the present invention.
  • a high-capacity and high-stability silicon-carbon negative electrode material includes a plurality of spherical composite particles 10 and an organic cracked carbon layer 20 coated on the outside of the plurality of first composite particles;
  • the spherical composite particles 10 include an inner core layer 11 and a carbonaceous material layer 12 wrapped around the outer core of the inner core layer 11 .
  • the mass ratio of the inner core layer 11 and the carbonaceous material layer 12 is (3-65):1.
  • the organic cracked carbon layer 20 is an organic carbon source, and the organic carbon source is one or more of glucose, citric acid, polyacrylonitrile and pitch.
  • the mass ratio of the inner core layer 11 and the carbonaceous material layer 12 is (4-60):1, the inner core layer 11 is nano-silicon, and the carbonaceous material layer 12 includes graphite and graphene.
  • the present invention confines silicon nanoparticles in carbon materials, relieves the huge pressure caused by volume expansion in the conductive process, forms a stable solid electrolyte interface film (SEI), and maintains the structural stability of electrode materials; carbonaceous materials have good
  • SEI solid electrolyte interface film
  • the electrical conductivity makes the material prepared by the present invention avoid the inherent low conductivity of silicon while improving the stability. Therefore, the material prepared by the present invention combines multiple advantages such as large specific surface area, high conductivity and good structural stability. , effectively relieve the volume expansion of the silicon anode and keep the structure stable.
  • a method for preparing a high-capacity and high-stability silicon-carbon negative electrode material comprising the steps of: mixing nano-silicon and carbonaceous material after ball milling to obtain a powdery mixture, and mixing the powdery mixture with an organic carbon source solution, a nitrogen source and a surfactant After shaking, shaking and ultrasonically dispersing, a mixed solution is obtained; the mixed solution is subjected to a solvothermal reaction, and then solid-liquid separation is performed to obtain a solid substance; the solid substance is calcined to obtain a silicon carbon negative electrode material.
  • the mass ratio of the inner core layer 11 and the carbonaceous material layer 12 is (4-55):1, the inner core layer 11 is nano-silicon, and the carbonaceous material layer 12 includes graphite and graphene.
  • the speed of the ball milling is 250-650r/min, and the time of the ball milling is 32-40h.
  • the nitrogen source is one or more of 2,4,6-trichlorotriazine, 2,4,6-triazide triazine, melamine, and dicyandiamide, and the surfactant includes hexadecane trimethylammonium bromide and alkyl polyethers.
  • the ratio of the powdery mixture to the organic carbon source is 1:(11-15)
  • the ratio of the powdery mixture to the nitrogen source is (10-35):1
  • the powdery mixture The ratio of surfactant and surfactant is (1300-1600): 1, and the filling ratio of the solvothermal reaction is 35-80%.
  • the reaction temperature of the solvothermal reaction is 220-300° C., and the reaction time is 4-18 h.
  • the calcination temperature is 650-1200°C, and the calcination time is 6-9h.
  • the mass ratio is 15:1, and the mixed powder is obtained after ball milling.
  • the ball milling rate is 400r/min, and the ball milling time is 2h; the ball-milled powder, glucose, 2,4,6-trichlorotriazine Mix with CTAB according to mass ratio; mixed powder: glucose is 1:11, mixed powder: 2,4,6-trichlorotriazine is 20:1, mixed powder: CTAB is 1300:1; shake well, after ultrasonic dispersion
  • the hydrothermal reaction was carried out, the filling ratio was 60%, the reaction temperature was 220 °C, and the reaction time was 10 h to obtain a mixed suspension; the mixed suspension was centrifuged and dried to obtain a solid substance; the solid substance was calcined in an argon atmosphere for 7 h , the calcination temperature is 750 °C, and the silicon carbon negative electrode material is obtained.
  • the mass ratio is 20:1, and the mixed powder is obtained after ball milling, the ball milling rate is 400r/min, and the ball milling time is 2h; the ball-milled powder, glucose, 2,4,6-trichlorotriazine Mix with CTAB according to mass ratio; mixed powder: glucose is 1:11, mixed powder: 2,4,6-trichlorotriazine is 20:1, mixed powder: CTAB is 1300:1; shake well, after ultrasonic dispersion
  • the hydrothermal reaction was carried out, the filling ratio was 60%, the reaction temperature was 220 °C, and the reaction time was 10 h to obtain a mixed suspension; the mixed suspension was centrifuged and dried to obtain a solid substance; the solid substance was calcined in an argon atmosphere for 7 h , the calcination temperature is 750 °C, and the silicon carbon negative electrode material is obtained.
  • the mass ratio is 30:1, and the mixed powder is obtained after ball milling, the ball milling rate is 400r/min, and the ball milling time is 2h; the ball-milled powder, glucose, 2,4,6-trichlorotriazine Mix with CTAB according to mass ratio; mixed powder: glucose is 1:11, mixed powder: 2,4,6-trichlorotriazine is 20:1, mixed powder: CTAB is 1300:1; shake well, after ultrasonic dispersion Hydrothermal reaction was carried out, the filling ratio was 60%, the reaction temperature was 220°C, and the reaction time was 10h to obtain a mixed suspension; the mixed suspension was centrifuged and dried to obtain a solid substance; the solid substance was calcined for 7h in an argon atmosphere , the calcination temperature is 750 °C, and the silicon carbon negative electrode material is obtained.
  • the mixed nano-silicon and carbonaceous materials are first mixed and then ball-milled.
  • the silicon nano-particles can be well dispersed in the carbonaceous materials such as conductive graphite microflakes, which improves the electrical conductivity and effectively alleviates the Structural collapse and pulverization of silicon-based materials due to volume changes.
  • the organic carbon source solution such as glucose can be aggregated into large spheres and coated on the surface of the silicon-graphite composite material to form a multi-level structure, and the silicon nanoparticles can be expanded from zero to three dimensions.
  • a three-dimensional conductive network is formed, so as to give full play to the good conductive properties of graphite and fast charge transfer.
  • the composite material is a structure in which a small ball is enclosed in a large ball, and the specific surface area of the sphere is large, so the multi-level composite material has a high specific surface area, which is conducive to the full contact between the electrolyte and the composite material and the rapid exchange of lithium ions; in the solvothermal reaction
  • a nitrogen source such as 2,4,6-trichlorotriazine was introduced, which alleviated the conduction loss caused by graphene defects to a certain extent and contributed to the rapid transfer of charges; surfactants such as hexadecyl triazine
  • CTAB methyl ammonium bromide
  • the carbonaceous material may lose carbon to form a hollow structure, and the porous structure can ensure that the electrolyte and active materials are fully infiltrated for smooth lithium ion exchange.
  • the most important thing is that the silicon nanoparticles are strictly confined in the carbon material, which can largely relieve the huge stress caused by the volume expansion, form a stable solid electrolyte interface film (SEI), and maintain the structural stability of the electrode material.
  • SEI solid electrolyte interface film
  • the silicon-carbon composite material undergoes two carbon composites, one for ball milling and one for solvothermal reaction, which can not only control its structure to be a multi-level silicon-carbon composite material, but also effectively increase the ratio of sp2 and sp3 hybrid carbon, thereby improving the silicon carbon.

Abstract

A high-capacity highly stable silicon-carbon negative electrode material, which relates to the field of battery negative electrode materials. The silicon-carbon negative electrode material comprises a plurality of spherical composite particles (10), and an organic pyrolytic carbon layer (20) coated on the exterior of the plurality of spherical composite particles (10); and the spherical composite particles (10) comprise kernel layers (11), and carbonaceous material layers (12) that package the exterior of the kernel layers (11), the mass ratio of the kernel layers (11) to the carbonaceous material layers (12) being (3-65):1. The described material is a multi-stage carbon-coated silicon nanoparticle composite structure, silicon nanoparticles are expanded from zero-dimensional to three-dimensional, and the structure is kept stable. Also provided is a preparation method for a high-capacity highly stable silicon-carbon negative electrode material. The preparation is simple and convenient, and the prepared material combines multiple advantages such as a large specific surface, high conductivity and good structure stability, effectively mitigates the volume expansion of a silicon negative electrode, and keeps the structure stable.

Description

一种高容量高稳定性硅碳负极材料及其制备方法A kind of high capacity and high stability silicon carbon anode material and preparation method thereof
相关申请的交叉引用。CROSS-REFERENCE TO RELATED APPLICATIONS.
本申请要求于2021年1月14日提交中国专利局，申请号为202110048704.6，发明名称为“一种高容量高稳定性硅碳负极材料及其制备方法”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 January 14, 2021, with the application number of 202110048704.6 and the invention titled "A high-capacity and high-stability silicon carbon anode material and its preparation method", all of which The contents are incorporated herein by reference.
技术领域technical field
本发明涉及电池负极材料领域，特别是涉及一种高容量高稳定性硅碳负极材料及其制备方法。The invention relates to the field of battery anode materials, in particular to a high-capacity and high-stability silicon carbon anode material and a preparation method thereof.
背景技术Background technique
21世纪来，最严峻问题是能源和环境。目前，全球约80％的能源消耗依赖于石油、煤炭、天然气等不可再生资源，这不仅使不可再生资源的存储量大幅减少，还引发了严重的环境、气候和健康安全等问题，而不可再生的能源会造成大面积的环境污染，所以开发新型的可再生能源尤为必要。太阳能、风能等可再生资源虽无污染，但因其不稳定性，不能持续供应能量。于是，作为新一代高效储能***的可充电电池成为解决这一问题的关键。In the 21st century, the most serious problems are energy and environment. At present, about 80% of the global energy consumption depends on non-renewable resources such as oil, coal and natural gas, which not only greatly reduces the storage of non-renewable resources, but also causes serious environmental, climate and health and safety problems. The energy will cause a large area of environmental pollution, so the development of new renewable energy is particularly necessary. Although renewable resources such as solar energy and wind energy are non-polluting, they cannot continuously supply energy due to their instability. Therefore, rechargeable batteries as a new generation of high-efficiency energy storage systems have become the key to solving this problem.
技术问题technical problem
与其他可再充电电池相比，如镍镉和镍氢电池，锂离子电池具有更高的能量密度，更高的工作电压，有限的自放电和更低的维护要求。锂离子电池是目前发展较为成熟的可充电电池。它不仅具有比容量高、循环寿命长、无记忆效应、自放电率低等特点，而且污染小，符合环保要求，能广泛应用于电动汽车、航空航天、生物医学工程等领域。大量研究表明，储能电源性能的好坏关键在于储能密度和功率密度，而离子电池的储能密度较大程度上取决于正负极材料的比容量。锂离子电池在过去的二十年里已经彻底革新了便携式电子设备，并有可能对车辆通电产生巨大影响。尽管具有突出的潜力，最先进的锂离子电池(如LiCoO2/石墨电池)不能满足汽车电气化的要求，同时需要高能量密度和高功率密度，同时具有较长的循环寿命。在这种情况下，硅是下一代锂离子电池最有前景的负极候选材料之一。这是由于其低的电压分布和高的理论容量(室温下Li15Si4相为3590mAh/g)，这是碳质材料(包括石墨，热解碳和中位相沥青)的约10倍(约372mA h/g)。除锂金属以外，硅还具有最高的体积容量(9786mAh/cm3，基于硅的初始体积计算)。另外，硅是地壳中第二大元素，环保无毒。因此，以低成本批量生产硅不是问题。然而，硅负极的实际应用目前受到多种挑战的阻碍，包括锂化/脱锂过程中大量的体积变化(约300％)，低固有电导率和固体电解质界面(SEI)的不稳定性。大体积变化会导致颗粒粉碎，与导电添加剂或集电器的电接触丧失，甚至从集电器上剥离。反复的体积膨胀和收缩也会导致颗粒周围SEI层的断裂和再形成，从而导致电解质的连续消耗，阻抗增加和容量衰减。Compared to other rechargeable batteries, such as NiCd and NiMH, Li-ion batteries have higher energy density, higher operating voltage, limited self-discharge and lower maintenance requirements. Lithium-ion battery is a relatively mature rechargeable battery at present. It not only has the characteristics of high specific capacity, long cycle life, no memory effect, and low self-discharge rate, but also has low pollution and meets environmental protection requirements. It can be widely used in electric vehicles, aerospace, biomedical engineering and other fields. A large number of studies have shown that the key to the performance of energy storage power supply is energy storage density and power density, while the energy storage density of ion batteries depends to a large extent on the specific capacity of positive and negative materials. Lithium-ion batteries have revolutionized portable electronics over the past two decades and have the potential to have a huge impact on vehicle energization. Despite their outstanding potential, state-of-the-art Li-ion batteries (such as LiCoO2/graphite batteries) cannot meet the requirements of automotive electrification, which requires high energy density and high power density with long cycle life. In this context, silicon is one of the most promising anode candidates for next-generation lithium-ion batteries. This is due to its low voltage distribution and high theoretical capacity (3590 mAh/g for Li15Si4 phase at room temperature), which is about 10 times (about 372 mAh/g) of carbonaceous materials (including graphite, pyrolytic carbon and mesophase pitch). g). Besides lithium metal, silicon also has the highest volume capacity (9786mAh/cm3, calculated based on the initial volume of silicon). In addition, silicon is the second largest element in the earth's crust, which is environmentally friendly and non-toxic. Therefore, mass production of silicon at low cost is not a problem. However, the practical application of silicon anodes is currently hindered by multiple challenges, including large volume changes (~300%) during lithiation/delithiation, low intrinsic conductivity, and solid electrolyte interface (SEI) instability. Large volume changes can result in particle pulverization, loss of electrical contact with conductive additives or current collectors, or even debonding from current collectors. Repeated volume expansion and contraction can also lead to fracture and reformation of the SEI layer around the particles, resulting in continuous depletion of electrolyte, increased impedance and capacity fading.
技术解决方案technical solutions
根据本申请的各种实施例，本发明提供一种高容量高稳定性硅碳负极材料，该材料为多级碳包覆硅纳米颗粒复合结构，将硅纳米颗粒从零维扩展至三维，保持结构稳定。本发明还提供一种高容量高稳定性硅碳负极材料的制备方法，制备简单便捷，制得的材料结合了大比表面、高导电性和良好结构稳定等多重优势，有效缓解硅负极体积膨胀，保持结构稳定。According to various embodiments of the present application, the present invention provides a high-capacity and high-stability silicon-carbon negative electrode material, which is a multi-level carbon-coated silicon nanoparticle composite structure, which expands silicon nanoparticles from zero dimension to three dimensions, maintains stable structure. The invention also provides a preparation method of a high-capacity and high-stability silicon carbon anode material, which is simple and convenient to prepare, and the prepared material combines multiple advantages such as large specific surface, high electrical conductivity and good structural stability, and effectively relieves the volume expansion of the silicon anode , keep the structure stable.
一种高容量高稳定性硅碳负极材料，所述硅碳负极材料包括若干球状复合颗粒、包覆于若干所述第一复合颗粒外部的有机裂解碳层；所述球状复合颗粒包括内核层、包裹于所述内核层外部的碳质材料层，所述内核层和碳质材料层的质量比为(3-65)：1。A high-capacity and high-stability silicon carbon negative electrode material, the silicon carbon negative electrode material comprises a plurality of spherical composite particles and an organic cracked carbon layer coated on the outside of a plurality of the first composite particles; the spherical composite particles include an inner core layer, For the carbonaceous material layer wrapped outside the inner core layer, the mass ratio of the inner core layer and the carbonaceous material layer is (3-65):1.
对上述技术方案的进一步改进为，所述有机裂解碳层为有机碳源，所述有机碳源为葡萄糖、柠檬酸、聚丙烯腈和沥青中的一种或多种。A further improvement to the above technical solution is that the organic cracked carbon layer is an organic carbon source, and the organic carbon source is one or more of glucose, citric acid, polyacrylonitrile and pitch.
对上述技术方案的进一步改进为，所述内核层和碳质材料层的质量比为(4-60)：1，所述内核层为纳米硅，所述碳质材料层包括石墨和石墨烯。A further improvement to the above technical solution is that the mass ratio of the inner core layer and the carbonaceous material layer is (4-60):1, the inner core layer is nano-silicon, and the carbonaceous material layer includes graphite and graphene.
一种高容量高稳定性硅碳负极材料的制备方法，包括如下步骤：混合纳米硅与碳质材料球磨后得到粉状混合物，将粉状混合物与有机碳源溶液、氮源和表面活性剂混合后震荡摇匀并超声分散，得到混合溶液；将混合溶液进行溶剂热反应后固液分离，得到固体物质；煅烧固体物质，得到硅碳负极材料。A method for preparing a high-capacity and high-stability silicon-carbon negative electrode material, comprising the steps of: mixing nano-silicon and carbonaceous material after ball milling to obtain a powdery mixture, and mixing the powdery mixture with an organic carbon source solution, a nitrogen source and a surfactant After shaking, shaking and ultrasonically dispersing, a mixed solution is obtained; the mixed solution is subjected to a solvothermal reaction, and then solid-liquid separation is performed to obtain a solid substance; the solid substance is calcined to obtain a silicon carbon negative electrode material.
对上述技术方案的进一步改进为，所述内核层和碳质材料层的质量比为(4-55)：1，所述内核层为纳米硅，所述碳质材料层包括石墨和石墨烯。A further improvement to the above technical solution is that the mass ratio of the inner core layer and the carbonaceous material layer is (4-55):1, the inner core layer is nano-silicon, and the carbonaceous material layer includes graphite and graphene.
对上述技术方案的进一步改进为，所述球磨的速率为250-650r/min，球磨的时间为32-40h。A further improvement to the above technical solution is that the speed of the ball milling is 250-650r/min, and the time of the ball milling is 32-40h.
对上述技术方案的进一步改进为，所述氮源为2,4,6-三氯三嗪、2,4,6-三叠氮三嗪、三聚氰胺、双氰胺中的一种或多种，所述表面活性剂包括十六烷基三甲基溴化铵和烷基聚醚。A further improvement to the above technical solution is that the nitrogen source is one or more of 2,4,6-trichlorotriazine, 2,4,6-triazide triazine, melamine, and dicyandiamide, The surfactants include cetyltrimethylammonium bromide and alkyl polyethers.
对上述技术方案的进一步改进为，以质量份数计，所述粉状混合物与有机碳源的比例为1：(11-15)，所述粉状混合物和氮源的比例为(10-35)：1，所述粉末状混合物和表面活性剂的比例为(1300-1600)：1，所述溶剂热反应的填充比为35-80％。A further improvement to the above technical scheme is that, in parts by mass, the ratio of the powdery mixture to the organic carbon source is 1: (11-15), and the ratio of the powdery mixture to the nitrogen source is (10-35 ): 1, the ratio of the powdery mixture to the surfactant is (1300-1600): 1, and the filling ratio of the solvothermal reaction is 35-80%.
对上述技术方案的进一步改进为，所述溶剂热反应的反应温度为220-300℃，反应时间为4-18h。A further improvement to the above technical solution is that the reaction temperature of the solvothermal reaction is 220-300° C., and the reaction time is 4-18 h.
对上述技术方案的进一步改进为，所述煅烧的温度为650-1200℃，煅烧时间为6-9h。A further improvement to the above technical solution is that the calcination temperature is 650-1200° C., and the calcination time is 6-9 hours.
有益效果beneficial effect
本发明将硅纳米颗粒被限制在碳材料中，缓解导电过程中体积膨胀带来的巨大压力，形成稳定的固体电解质界面膜(SEI)，保持电极材料的结构稳定性；碳质材料具有良好的导电性，使得本发明制得的材料在提高稳定性的同时，规避了硅固有的低电导率，因此本发明制得的材料结合了大比表面积、高导电性和良好结构稳定性等多重优势，有效缓解硅负极体积膨胀，保持结构稳定。The present invention confines silicon nanoparticles in carbon materials, relieves the huge pressure caused by volume expansion in the conductive process, forms a stable solid electrolyte interface film (SEI), and maintains the structural stability of electrode materials; carbonaceous materials have good The electrical conductivity makes the material prepared by the present invention avoid the inherent low conductivity of silicon while improving the stability. Therefore, the material prepared by the present invention combines multiple advantages such as large specific surface area, high conductivity and good structural stability. , effectively relieve the volume expansion of the silicon anode and keep the structure stable.
附图说明Description of drawings
为了更好地描述和说明这里公开的那些发明的实施例和/或示例，可以参考一幅或多幅附图。用于描述附图的附加细节或示例不应当被认为是对所公开的发明、目前描述的实施例和/或示例以及目前理解的这些发明的最佳模式中的任何一者的范围的限制。In order to better describe and illustrate embodiments and/or examples of those inventions disclosed herein, reference may be made to one or more of the accompanying drawings. The additional details or examples used to describe the drawings should not be construed as limiting the scope of any of the disclosed inventions, the presently described embodiments and/or examples, and the best mode presently understood of these inventions.
图1为本发明的高容量高稳定性硅碳负极材料的结构示意图。FIG. 1 is a schematic structural diagram of the high-capacity and high-stability silicon-carbon negative electrode material of the present invention.
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.
如图1所示，一种高容量高稳定性硅碳负极材料，所述硅碳负极材料包括若干球状复合颗粒10、包覆于若干所述第一复合颗粒外部的有机裂解碳层20；所述球状复合颗粒10包括内核层11、包裹于所述内核层11外部的碳质材料层12，所述内核层11和碳质材料层12的质量比为(3-65)：1。As shown in FIG. 1, a high-capacity and high-stability silicon-carbon negative electrode material includes a plurality of spherical composite particles 10 and an organic cracked carbon layer 20 coated on the outside of the plurality of first composite particles; The spherical composite particles 10 include an inner core layer 11 and a carbonaceous material layer 12 wrapped around the outer core of the inner core layer 11 . The mass ratio of the inner core layer 11 and the carbonaceous material layer 12 is (3-65):1.
所述有机裂解碳层20为有机碳源，所述有机碳源为葡萄糖、柠檬酸、聚丙烯腈和沥青中的一种或多种。The organic cracked carbon layer 20 is an organic carbon source, and the organic carbon source is one or more of glucose, citric acid, polyacrylonitrile and pitch.
所述内核层11和碳质材料层12的质量比为(4-60)：1，所述内核层11为纳米硅，所述碳质材料层12包括石墨和石墨烯。The mass ratio of the inner core layer 11 and the carbonaceous material layer 12 is (4-60):1, the inner core layer 11 is nano-silicon, and the carbonaceous material layer 12 includes graphite and graphene.
本发明将硅纳米颗粒被限制在碳材料中，缓解导电过程中体积膨胀带来的巨大压力，形成稳定的固体电解质界面膜(SEI)，保持电极材料的结构稳定性；碳质材料具有良好的导电性，使得本发明制得的材料在提高稳定性的同时，规避了硅固有的低电导率，因此本发明制得的材料结合了大比表面积、高导电性和良好结构稳定性等多重优势，有效缓解硅负极体积膨胀，保持结构稳定。The present invention confines silicon nanoparticles in carbon materials, relieves the huge pressure caused by volume expansion in the conductive process, forms a stable solid electrolyte interface film (SEI), and maintains the structural stability of electrode materials; carbonaceous materials have good The electrical conductivity makes the material prepared by the present invention avoid the inherent low conductivity of silicon while improving the stability. Therefore, the material prepared by the present invention combines multiple advantages such as large specific surface area, high conductivity and good structural stability. , effectively relieve the volume expansion of the silicon anode and keep the structure stable.
一种高容量高稳定性硅碳负极材料的制备方法，包括如下步骤：混合纳米硅与碳质材料球磨后得到粉状混合物，将粉状混合物与有机碳源溶液、氮源和表面活性剂混合后震荡摇匀并超声分散，得到混合溶液；将混合溶液进行溶剂热反应后固液分离，得到固体物质；煅烧固体物质，得到硅碳负极材料。A method for preparing a high-capacity and high-stability silicon-carbon negative electrode material, comprising the steps of: mixing nano-silicon and carbonaceous material after ball milling to obtain a powdery mixture, and mixing the powdery mixture with an organic carbon source solution, a nitrogen source and a surfactant After shaking, shaking and ultrasonically dispersing, a mixed solution is obtained; the mixed solution is subjected to a solvothermal reaction, and then solid-liquid separation is performed to obtain a solid substance; the solid substance is calcined to obtain a silicon carbon negative electrode material.
所述内核层11和碳质材料层12的质量比为(4-55)：1，所述内核层11为纳米硅，所述碳质材料层12包括石墨和石墨烯。The mass ratio of the inner core layer 11 and the carbonaceous material layer 12 is (4-55):1, the inner core layer 11 is nano-silicon, and the carbonaceous material layer 12 includes graphite and graphene.
所述球磨的速率为250-650r/min，球磨的时间为32-40h。The speed of the ball milling is 250-650r/min, and the time of the ball milling is 32-40h.
所述氮源为2,4,6-三氯三嗪、2,4,6-三叠氮三嗪、三聚氰胺、双氰胺中的一种或多种，所述表面活性剂包括十六烷基三甲基溴化铵和烷基聚醚。The nitrogen source is one or more of 2,4,6-trichlorotriazine, 2,4,6-triazide triazine, melamine, and dicyandiamide, and the surfactant includes hexadecane trimethylammonium bromide and alkyl polyethers.
以质量份数计，所述粉状混合物与有机碳源的比例为1：(11-15)，所述粉状混合物和氮源的比例为(10-35)：1，所述粉末状混合物和表面活性剂的比例为(1300-1600)：1，所述溶剂热反应的填充比为35-80％。In parts by mass, the ratio of the powdery mixture to the organic carbon source is 1:(11-15), the ratio of the powdery mixture to the nitrogen source is (10-35):1, and the powdery mixture The ratio of surfactant and surfactant is (1300-1600): 1, and the filling ratio of the solvothermal reaction is 35-80%.
所述溶剂热反应的反应温度为220-300℃，反应时间为4-18h。The reaction temperature of the solvothermal reaction is 220-300° C., and the reaction time is 4-18 h.
所述煅烧的温度为650-1200℃，煅烧时间为6-9h。The calcination temperature is 650-1200°C, and the calcination time is 6-9h.
实施例1。Example 1.
混合硅与石墨微片，质量比为15：1，球磨后得到混合粉末，球磨速率为400r/min，球磨时间为2h；将球磨后的粉末、葡萄糖、2,4,6-三氯三嗪和CTAB按照质量比混合；混合粉末：葡萄糖为1:11，混合粉末：2,4,6-三氯三嗪为20:1，混合粉末：CTAB为1300:1；震荡摇匀，超声分散后进行水热反应，填充比为60％，反应温度220℃，反应时间10h，得到混合悬浊液；将混合悬浊液离心并干燥后得到固体物质；将固体物质在氩气气氛下，煅烧7h，煅烧温度为750℃，得到硅碳负极材料。Mix silicon and graphite flakes, the mass ratio is 15:1, and the mixed powder is obtained after ball milling. The ball milling rate is 400r/min, and the ball milling time is 2h; the ball-milled powder, glucose, 2,4,6-trichlorotriazine Mix with CTAB according to mass ratio; mixed powder: glucose is 1:11, mixed powder: 2,4,6-trichlorotriazine is 20:1, mixed powder: CTAB is 1300:1; shake well, after ultrasonic dispersion The hydrothermal reaction was carried out, the filling ratio was 60%, the reaction temperature was 220 °C, and the reaction time was 10 h to obtain a mixed suspension; the mixed suspension was centrifuged and dried to obtain a solid substance; the solid substance was calcined in an argon atmosphere for 7 h , the calcination temperature is 750 ℃, and the silicon carbon negative electrode material is obtained.
实施例2。Example 2.
混合硅与石墨微片，质量比为20：1，球磨后得到混合粉末，球磨速率为400r/min，球磨时间为2h；将球磨后的粉末、葡萄糖、2,4,6-三氯三嗪和CTAB按照质量比混合；混合粉末：葡萄糖为1:11，混合粉末：2,4,6-三氯三嗪为20:1，混合粉末：CTAB为1300:1；震荡摇匀，超声分散后进行水热反应，填充比为60％，反应温度220℃，反应时间10h，得到混合悬浊液；将混合悬浊液离心并干燥后得到固体物质；将固体物质在氩气气氛下，煅烧7h，煅烧温度为750℃，得到硅碳负极材料。Mix silicon and graphite flakes, the mass ratio is 20:1, and the mixed powder is obtained after ball milling, the ball milling rate is 400r/min, and the ball milling time is 2h; the ball-milled powder, glucose, 2,4,6-trichlorotriazine Mix with CTAB according to mass ratio; mixed powder: glucose is 1:11, mixed powder: 2,4,6-trichlorotriazine is 20:1, mixed powder: CTAB is 1300:1; shake well, after ultrasonic dispersion The hydrothermal reaction was carried out, the filling ratio was 60%, the reaction temperature was 220 °C, and the reaction time was 10 h to obtain a mixed suspension; the mixed suspension was centrifuged and dried to obtain a solid substance; the solid substance was calcined in an argon atmosphere for 7 h , the calcination temperature is 750 ℃, and the silicon carbon negative electrode material is obtained.
实施例3。Example 3.
混合硅与石墨微片，质量比为30：1，球磨后得到混合粉末，球磨速率为400r/min，球磨时间为2h；将球磨后的粉末、葡萄糖、2,4,6-三氯三嗪和CTAB按照质量比混合；混合粉末：葡萄糖为1:11，混合粉末：2,4,6-三氯三嗪为20:1，混合粉末：CTAB为1300:1；震荡摇匀，超声分散后进行水热反应，填充比为60％，反应温度220℃，反应时间10h，得到混合悬浊液；将混合悬浊液离心并干燥后得到固体物质；将固体物质在氩气气氛下，煅烧7h，煅烧温度为750℃，得到硅碳负极材料。Mix silicon and graphite flakes, the mass ratio is 30:1, and the mixed powder is obtained after ball milling, the ball milling rate is 400r/min, and the ball milling time is 2h; the ball-milled powder, glucose, 2,4,6-trichlorotriazine Mix with CTAB according to mass ratio; mixed powder: glucose is 1:11, mixed powder: 2,4,6-trichlorotriazine is 20:1, mixed powder: CTAB is 1300:1; shake well, after ultrasonic dispersion Hydrothermal reaction was carried out, the filling ratio was 60%, the reaction temperature was 220°C, and the reaction time was 10h to obtain a mixed suspension; the mixed suspension was centrifuged and dried to obtain a solid substance; the solid substance was calcined for 7h in an argon atmosphere , the calcination temperature is 750 ℃, and the silicon carbon negative electrode material is obtained.
本发明的制备过程首先将混合的纳米硅和碳质材料混合后球磨，球磨过程中，硅纳米颗粒能良好的分散在碳质材料如导电石墨微片中，提高导电性的同时也有效缓解了硅基材料由于体积变化所引起的结构坍塌和粉化。在溶剂热过程中，在高温高压条件下，有机碳源溶液如葡萄糖能聚合成大球包覆在硅-石墨复合材料表面，形成多级结构，将硅纳米颗粒从零维拓展至三维，构筑了三维导电网络，从而充分发挥石墨良好的导电特性，快速进行电荷传输。并且复合材料为大球中包小球的结构，球体的比表面积大，因此该多级复合材料具有高比表面积，有利于电解液和复合材料的充分接触和锂离子快速交换；在溶剂热反应过程中，引入了氮源如2,4,6-三氯三嗪，一定程度上缓解了石墨烯缺陷带来的导电损失，有助于电荷的快速传输；表面活性剂如十六烷基三甲基溴化铵(CTAB)的引入有助于硅纳米颗粒的分散，使碳包覆得更加均匀，从而提高结构稳定性。从碳源来看，葡萄糖价格低廉、绿色环保，易与硅发生相互作用，更好地包覆其上。此外，在高温煅烧过程中经历热解反应，碳质材料在局部可能碳缺失而形成空洞结构，多孔结构可以保证电解液和活性物质充分浸润，进行畅通的锂离子交换。最重要的是硅纳米颗粒被严格的限制在碳材料中，可在很大程度上缓解体积膨胀带来的巨大应力，形成稳定的固体电解质界面膜(SEI)，保持电极材料的结构稳定性。硅碳复合材料经过两次碳复合，一次为球磨，一次为溶剂热反应，不仅能调控其结构为多级硅碳复合材料，还能有效增加sp2与sp3杂化碳的比例，从而提高硅碳负极结构稳定性和导电性。In the preparation process of the present invention, the mixed nano-silicon and carbonaceous materials are first mixed and then ball-milled. During the ball-milling process, the silicon nano-particles can be well dispersed in the carbonaceous materials such as conductive graphite microflakes, which improves the electrical conductivity and effectively alleviates the Structural collapse and pulverization of silicon-based materials due to volume changes. In the solvothermal process, under the condition of high temperature and high pressure, the organic carbon source solution such as glucose can be aggregated into large spheres and coated on the surface of the silicon-graphite composite material to form a multi-level structure, and the silicon nanoparticles can be expanded from zero to three dimensions. A three-dimensional conductive network is formed, so as to give full play to the good conductive properties of graphite and fast charge transfer. In addition, the composite material is a structure in which a small ball is enclosed in a large ball, and the specific surface area of the sphere is large, so the multi-level composite material has a high specific surface area, which is conducive to the full contact between the electrolyte and the composite material and the rapid exchange of lithium ions; in the solvothermal reaction In the process, a nitrogen source such as 2,4,6-trichlorotriazine was introduced, which alleviated the conduction loss caused by graphene defects to a certain extent and contributed to the rapid transfer of charges; surfactants such as hexadecyl triazine The introduction of methyl ammonium bromide (CTAB) facilitates the dispersion of silicon nanoparticles and makes the carbon coating more uniform, thereby improving the structural stability. From the perspective of carbon source, glucose is cheap, green and environmentally friendly, and it is easy to interact with silicon to better coat it. In addition, during the high-temperature calcination process, the carbonaceous material may lose carbon to form a hollow structure, and the porous structure can ensure that the electrolyte and active materials are fully infiltrated for smooth lithium ion exchange. The most important thing is that the silicon nanoparticles are strictly confined in the carbon material, which can largely relieve the huge stress caused by the volume expansion, form a stable solid electrolyte interface film (SEI), and maintain the structural stability of the electrode material. The silicon-carbon composite material undergoes two carbon composites, one for ball milling and one for solvothermal reaction, which can not only control its structure to be a multi-level silicon-carbon composite material, but also effectively increase the ratio of sp2 and sp3 hybrid carbon, thereby improving the silicon carbon. Anode structural stability and electrical conductivity.
上述实施方式仅为本发明的优选实施方式，不能以此来限定本发明保护的范围，本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。The above-mentioned embodiments are only preferred embodiments of the present invention, and cannot be used to limit the scope of protection of the present invention. Any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention belong to the scope of the present invention. Scope of protection claimed.

Claims (10)

  1. 一种高容量高稳定性硅碳负极材料，其特征在于，所述硅碳负极材料包括若干球状复合颗粒、包覆于若干所述第一复合颗粒外部的有机裂解碳层；所述球状复合颗粒包括内核层、包裹于所述内核层外部的碳质材料层，所述内核层和碳质材料层的质量比为(3-65)：1。A high-capacity and high-stability silicon-carbon negative electrode material, characterized in that the silicon-carbon negative electrode material comprises a plurality of spherical composite particles and an organic cracked carbon layer coated on the outside of a plurality of the first composite particles; the spherical composite particles It includes an inner core layer and a carbonaceous material layer wrapped outside the inner core layer, and the mass ratio of the inner core layer and the carbonaceous material layer is (3-65):1.
  2. 根据权利要求1所述的高容量高稳定性硅碳负极材料，其特征在于，所述有机裂解碳层为有机碳源，所述有机碳源为葡萄糖、柠檬酸、聚丙烯腈和沥青中的一种或多种。The high-capacity and high-stability silicon carbon negative electrode material according to claim 1, wherein the organic cracked carbon layer is an organic carbon source, and the organic carbon source is glucose, citric acid, polyacrylonitrile and pitch. one or more.
  3. 根据权利要求1所述的高容量高稳定性硅碳负极材料，其特征在于，所述内核层和碳质材料层的质量比为(4-60)：1，所述内核层为纳米硅，所述碳质材料层包括石墨和石墨烯。The high-capacity and high-stability silicon-carbon negative electrode material according to claim 1, wherein the mass ratio of the inner core layer and the carbonaceous material layer is (4-60): 1, and the inner core layer is nano-silicon, The carbonaceous material layer includes graphite and graphene.
  4. 一种高容量高稳定性硅碳负极材料的制备方法，其特征在于，包括如下步骤：混合纳米硅与碳质材料球磨后得到粉状混合物，将粉状混合物与有机碳源溶液、氮源和表面活性剂混合后震荡摇匀并超声分散，得到混合溶液；将混合溶液进行溶剂热反应后固液分离，得到固体物质；煅烧固体物质，得到硅碳负极材料。A method for preparing a high-capacity and high-stability silicon-carbon negative electrode material, comprising the steps of: mixing nano-silicon and carbonaceous material after ball milling to obtain a powdery mixture, mixing the powdery mixture with an organic carbon source solution, a nitrogen source and a After mixing, the surfactants are shaken, shaken, and ultrasonically dispersed to obtain a mixed solution; the mixed solution is subjected to a solvothermal reaction and then subjected to solid-liquid separation to obtain a solid substance; the solid substance is calcined to obtain a silicon carbon negative electrode material.
  5. 根据权利要求4所述的高容量高稳定性硅碳负极材料的制备方法，其特征在于，所述内核层和碳质材料层的质量比为(4-55)：1，所述内核层为纳米硅，所述碳质材料层包括石墨和石墨烯。The method for preparing a high-capacity and high-stability silicon carbon negative electrode material according to claim 4, wherein the mass ratio of the inner core layer and the carbonaceous material layer is (4-55): 1, and the inner core layer is Nano silicon, the carbonaceous material layer includes graphite and graphene.
  6. 根据权利要求4所述的高容量高稳定性硅碳负极材料的制备方法，其特征在于，所述球磨的速率为250-650r/min，球磨的时间为32-40h。The method for preparing a high-capacity and high-stability silicon-carbon negative electrode material according to claim 4, wherein the ball milling rate is 250-650 r/min, and the ball milling time is 32-40 h.
  7. 根据权利要求4所述的高容量高稳定性硅碳负极材料的制备方法，其特征在于，所述氮源为2,4,6-三氯三嗪、2,4,6-三叠氮三嗪、三聚氰胺、双氰胺中的一种或多种，所述表面活性剂包括十六烷基三甲基溴化铵和烷基聚醚。The method for preparing a high-capacity and high-stability silicon carbon negative electrode material according to claim 4, wherein the nitrogen source is 2,4,6-trichlorotriazine, 2,4,6-triazide triazine One or more of oxazine, melamine, and dicyandiamide, and the surfactant includes cetyltrimethylammonium bromide and alkyl polyether.
  8. 根据权利要求4所述的高容量高稳定性硅碳负极材料的制备方法，其特征在于，以质量份数计，所述粉状混合物与有机碳源的比例为1：(11-15)，所述粉状混合物和氮源的比例为(10-35)：1，所述粉末状混合物和表面活性剂的比例为(1300-1600)：1，所述溶剂热反应的填充比为35-80％。The method for preparing a high-capacity and high-stability silicon carbon negative electrode material according to claim 4, wherein, in parts by mass, the ratio of the powdery mixture to the organic carbon source is 1: (11-15), The ratio of the powdery mixture to the nitrogen source is (10-35): 1, the ratio of the powdery mixture to the surfactant is (1300-1600): 1, and the filling ratio of the solvothermal reaction is 35- 80%.
  9. 根据权利要求4所述的高容量高稳定性硅碳负极材料的制备方法，其特征在于，所述溶剂热反应的反应温度为220-300℃，反应时间为4-18h。The method for preparing a high-capacity and high-stability silicon carbon negative electrode material according to claim 4, wherein the reaction temperature of the solvothermal reaction is 220-300°C, and the reaction time is 4-18h.
  10. 根据权利要求4所述的高容量高稳定性硅碳负极材料的制备方法，其特征在于，所述煅烧的温度为650-1200℃，煅烧时间为6-9h。The method for preparing a high-capacity and high-stability silicon carbon negative electrode material according to claim 4, wherein the calcining temperature is 650-1200°C, and the calcining time is 6-9h.
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