WO2020151093A1 - 一种硅碳复合材料及其制法 - Google Patents

一种硅碳复合材料及其制法 Download PDF

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WO2020151093A1
WO2020151093A1 PCT/CN2019/082319 CN2019082319W WO2020151093A1 WO 2020151093 A1 WO2020151093 A1 WO 2020151093A1 CN 2019082319 W CN2019082319 W CN 2019082319W WO 2020151093 A1 WO2020151093 A1 WO 2020151093A1
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silicon
carbon
composite material
nano
coating
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PCT/CN2019/082319
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English (en)
French (fr)
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晏荦
郑安华
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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Priority to JP2021508047A priority Critical patent/JP7068546B2/ja
Priority to KR1020207030015A priority patent/KR102533003B1/ko
Publication of WO2020151093A1 publication Critical patent/WO2020151093A1/zh
Priority to US17/343,763 priority patent/US11851332B2/en

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    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Definitions

  • the invention relates to the technical field of new energy materials, in particular to a silicon-carbon composite material and a preparation method thereof.
  • Chinese patent CN105552323A discloses a silicon/silicon oxycarbide/carbon anode material and its preparation method and application. Ultra-small silicon oxygen carbon nanoparticles are uniformly dispersed in a carbon matrix as a buffer matrix, while silicon nanoparticles are It is uniformly embedded in the carbon/silicon-oxy-carbon buffer matrix. Although the negative electrode active material has high capacity and good cycle performance, its first-time efficiency is low, which limits its application in lithium-ion batteries.
  • Chinese Patent CN104103821B discloses a method for preparing silicon carbon anode material.
  • a metal catalyst is used to first decompose the silicon source to prepare the precursor Si-SiO x , and then the Si-SiOx prepared by the reaction and the carboxylated carbon matrix are combined with a carrier gas.
  • the precursor of the silicon-carbon anode material is prepared, and the silicon-carbon anode material is finally coated with carbon.
  • This method can prepare high-capacity nano-silicon, but the nano-silicon cannot be uniformly distributed on the surface of the carbon matrix , There are hidden dangers such as unsatisfactory cycle performance and high volume expansion.
  • the purpose of the present invention is to provide a silicon-carbon composite material and its preparation method in view of the above-mentioned shortcomings of the prior art, which adopts vapor phase simultaneous deposition to form a silicon-carbon composite material precursor, and then performs carbon coating to form a silicon-carbon composite material similar to a dragon fruit structure.
  • Carbon composite material has the advantages of high first efficiency, low expansion and long cycle, which slows down the growth of silicon material grains during heat treatment, effectively avoids the pulverization of the material during the cycle, and alleviates the volume expansion of silicon-based materials The effect improves the cycle performance, conductivity and rate performance of the material.
  • a silicon-carbon composite material is a composite material similar to a dragon fruit structure, and includes a matrix core, a silicon-carbon composite shell and a coating layer.
  • the silicon-carbon composite shell is uniformly dispersed by a number of nano-silicon particles.
  • the nano-silicon particles are formed by the high-temperature cracking of a silicon source
  • the conductive carbon is formed by the high-temperature cracking of an organic carbon source
  • the coating layer is a carbon coating layer
  • the carbon coating layer is at least one
  • the thickness of a single layer is 0.2-3 ⁇ m.
  • the single layer thickness of the carbon coating layer is further preferably 0.2-2 ⁇ m, particularly preferably 0.2-1 ⁇ m.
  • the dragon fruit-like structure can effectively alleviate the volume effect of silicon-based materials during the charging and discharging process, thereby effectively avoiding the powdering of the material during the cycle.
  • a good carbon conductive network can improve the conductivity of the material and improve the material
  • the rate performance alleviates the volume expansion effect of silicon-based materials and improves the cycle performance.
  • the particle size D50 of the silicon-carbon composite material is 2-20 ⁇ m, more preferably 2-15 ⁇ m, particularly preferably 2-10 ⁇ m; the specific surface area is 1-30 m2/g, further preferably 2-20 m2/g, It is particularly preferably 2-8m2/g; the true density is 1-3g/cm3, more preferably 1.5-2.5g/cm3, particularly preferably 2.0-2.5g/cm3; the particle size of the matrix core of the silicon-carbon composite material D50 is 2-18 ⁇ m, more preferably 2-15 ⁇ m, and particularly preferably 2-8 ⁇ m.
  • the matrix core is any one or two of nano silicon, nano silicon oxide, or nano conductive carbon material
  • nano silicon is single crystal nano silicon with a grain size of 1-40 nm, and a grain size of 1 Any one or more of -40 nm polycrystalline nano silicon or amorphous nano silicon, further preferably 2-20 nm, particularly preferably 2-10 nm
  • nano-silicon particle size D50 is 5-300 nm, more preferably 10-200 nm, It is particularly preferably 10-100nm
  • X in nano-silica SiOx is 0.8-1.5, preferably 0.8-1.3, particularly preferably 0.8-1.1
  • nano-conductive carbon material is any of conductive carbon black, carbon nanotubes and graphene One kind.
  • the single crystal nano silicon is a single crystal nano silicon wire prepared on a gold-plated silicon wafer by a chemical vapor deposition method.
  • the nano-conductive carbon material graphene is a graphene composite material loaded with amorphous carbon.
  • the method for preparing the graphene composite material loaded with amorphous carbon adopts a monolithic uniformly dispersed graphene oxide solution mixed with amorphous carbon, stirred at room temperature, and after drying, it is carried out under an inert gas atmosphere. After preheating and cooling, it is placed in a reducing atmosphere for reduction reaction, and it is obtained by cooling.
  • a method for preparing the aforementioned silicon-carbon composite material which includes the following steps:
  • S1 Put the core of the substrate in a CVD furnace, under a protective atmosphere, heat up to 400-1200°C at 1-15°C/min, simultaneously vapor-deposit nano-silicon particles and conductive carbon, hold for 0.5-20h, and naturally cool to room temperature to obtain Silicon carbon composite material precursor;
  • the simultaneous vapor deposition of nano-silicon particles and conductive carbon layer can pass the carbon source and the silicon source at the same time in a certain ratio, or alternately pass the carbon source and the silicon source.
  • the synchronous vapor deposition of nano silicon particles and conductive carbon is formed by a certain ratio of 1:1 to 99, at a rate of 0.5 to 20.0 L/min at the same time or alternately through the organic carbon source and the silicon source;
  • the silicon source mentioned is one or more of SiH4, SiHCl 3 , Si 2 H 6 , Si 3 H 8 , SiCl 4 , Si 2 Cl 6 , SiH 2 Cl or SiH 3 Cl.
  • the CVD furnace is a rotary furnace with a rotation speed of 0.2-5.0 rpm;
  • the protective gas is one or more of nitrogen, helium, neon, argon, krypton, and xenon;
  • the organic carbon source gas is methane, ethane, propane, isopropane, butane, isobutane, ethylene, propylene, acetylene, butene, vinyl chloride, vinyl fluoride, vinyl difluoride, ethyl chloride, fluoroethane, One or more of difluoroethane, methyl chloride, fluoromethane, difluoromethane, trifluoromethane, methylamine, formaldehyde, benzene, toluene, xylene, styrene, and phenol.
  • the carbon coating is any one of pyrolysis carbon coating, gas phase carbon coating or liquid carbon coating, wherein the high temperature pyrolysis coating adopts primary carbon coating or secondary carbon coating
  • the coating amount of the second carbon coating is 0.1-10 times the coating amount of the first carbon coating by mass
  • the thickness of the coating layer is 10-2000nm.
  • it is 10-1500 nm, Especially preferably, it is 10-1000 nm.
  • the two carbon coatings can also be coated with liquid carbon first and then coated with vapor carbon, or can be coated with vapor carbon first and then coated with liquid carbon.
  • the liquid phase carbon coating process includes: mixing and dispersing the organic carbon source, the material to be coated, and the solvent uniformly by a high-speed disperser to form a slurry, spray drying the slurry, and then heat treatment. Pass high-purity protective gas into the atmosphere furnace, heat up to 400-1200°C at a heating rate of ⁇ 10°C for sintering, keep it for 0.5-10h, and cool to room temperature naturally to obtain a liquid-phase coating product; the organic carbon source is cracked The mass of carbon accounts for 1 to 99% by weight of the total mass of the pyrolysis carbon from the organic carbon source and the composite material to be coated; the added amount of the solvent is adjusted to control the solid content of the slurry to be 5 to 50%.
  • the organic carbon source during liquid coating is sucrose, glucose, citric acid, phenolic resin, epoxy resin, pitch, polypyrrole, polypyrrolidone, polyaniline, polyacrylonitrile, polydopamine, polyvinyl alcohol.
  • the solvent is one or more of water, alcohol solvent, ketone solvent, alkane solvent, N-methylpyrrolidone, tetrahydrofuran, toluene, and alcohol solvent is ethanol, methanol, One or more of ethylene glycol, isopropanol, n-octanol, allyl alcohol, and octanol.
  • Ketone solvents are acetone, methyl methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketone, methyl isoacetone, and cyclohexyl
  • Alkane solvents are one or more of cyclohexane, n-hexane, isoheptane, 3,3-dimethylpentane, and 3-methylhexane.
  • the protective gas is one or more of nitrogen, argon, and argon-hydrogen mixed gas;
  • the process of gas-phase carbon coating includes: placing the object to be coated in a CVD furnace, introducing protective gas, and raising the temperature to 500-1200°C at a rate of 1-15°C/min and a rate of 0.5-20.0L/min.
  • the organic carbon source gas is introduced at a feed rate of min, kept for 0.5-20 hours, and naturally cooled to room temperature to obtain a gas-phase coated product.
  • the CVD furnace is a rotary furnace with a rotation speed of 0.2 to 5.0 rpm;
  • the protective gas is one of nitrogen, helium, neon, argon, krypton, and xenon.
  • the organic carbon source gas is methane, ethane, propane, isopropane, butane, isobutane, ethylene, propylene, acetylene, butene, vinyl chloride, vinyl fluoride, vinyl difluoride, ethyl chloride, One or more of fluoroethane, difluoroethane, methyl chloride, fluoromethane, difluoromethane, trifluoromethane, methylamine, formaldehyde, benzene, toluene, xylene, styrene, and phenol.
  • the dragon fruit-like silicon-carbon composite material of the present invention includes a matrix shell core, a silicon-carbon composite outer core and a coating layer.
  • the silicon-carbon composite shell is formed by uniformly dispersing nano-silicon particles in conductive carbon, wherein Low-temperature deposited nano-silicon contains a large amount of amorphous silicon, and the volume expansion of amorphous nano-silicon is small, thereby effectively avoiding the pulverization of the material during the cycle, improving the cycle performance of the material, and the internal conductive matrix can improve the conductivity of the material. Improve the rate performance of the material, alleviate the volume expansion effect of silicon-based materials and enhance the cycle performance.
  • the silicon-carbon composite material with dragon fruit-like structure of the present invention is firstly simultaneously vapor-deposited to obtain nano-silicon particles uniformly dispersed in the conductive carbon layer, and finally is coated to obtain a dragon fruit-like structure silicon-carbon composite material.
  • the lithium ion battery prepared by using this material can exhibit good cycle performance and rate performance.
  • Figure 1 is an electron microscope picture of the silicon-based composite material in Example 1 of the present invention.
  • Example 2 is the first charge-discharge curve of the silicon-based composite material in Example 1 of the present invention
  • Figure 3 is a cycle performance curve of the silicon-based composite material in Example 1 of the present invention.
  • Example 4 is an electron microscope picture of the silicon-based composite material in Example 3 of the present invention.
  • Figure 5 is an XRD picture of the silicon-based composite material in Example 3 of the present invention.
  • FIG. 6 is the first charge and discharge curve of the silicon-based composite material in Example 3 of the present invention.
  • FIGS. 1-6 and the specific embodiments described herein are only used to explain the present invention, and not to limit the scope of the present invention. Those skilled in the art make some non-essential changes or adjustments with reference to the embodiments of the present invention. , Still belongs to the protection scope of the present invention.
  • the solid content of the mixture is 20%, the mixture is spray-dried, the sprayed material is heat-treated, the high-purity protective gas nitrogen is introduced into the atmosphere furnace, the temperature is raised to 900°C at 4°C/min, and the temperature is kept for 3h. Naturally cooled to room temperature to obtain a silicon-carbon composite material.
  • the solid content of the mixture is 20%, the mixture is spray-dried, the sprayed material is heat-treated, the high-purity protective gas nitrogen is introduced into the atmosphere furnace, the temperature is raised to 900°C at 4°C/min, and the temperature is kept for 3h. Naturally cool to room temperature to obtain a silicon-based composite material.
  • the solid content of the mixture is 20%, the mixture is spray-dried, the sprayed material is heat-treated, the high-purity protective gas nitrogen is introduced into the atmosphere furnace, the temperature is raised to 900°C at 4°C/min, and the temperature is kept for 3h. Naturally cool to room temperature to obtain a silicon-based composite material.
  • the solid content of the mixture is 20%, the mixture is spray-dried, the sprayed material is heat-treated, the high-purity protective gas nitrogen is introduced into the atmosphere furnace, the temperature is raised to 900°C at 4°C/min, and the temperature is kept for 3h. Naturally cool to room temperature to obtain a silicon-based composite material.
  • High-purity nitrogen was introduced, methane gas was introduced at a rate of 0.5 L/min, and SiH 4 gas was introduced at a rate of 1.5 L/min for 1 hour, and cooled to room temperature naturally to obtain a precursor.
  • the solid content of the mixture is 20%, the mixture is spray-dried, the sprayed material is heat-treated, the high-purity protective gas nitrogen is introduced into the atmosphere furnace, the temperature is raised to 900°C at 4°C/min, and the temperature is kept for 3h. Naturally cool to room temperature to obtain a silicon-based composite material.
  • protective gas nitrogen enter high-purity nitrogen, enter methane gas at a rate of 0.5L/min, enter SiH 4 gas at a rate of 1.5L/min for 1h, then stop feeding SiH 4 gas, continue to enter methane gas at a rate of 0.5L/min, and keep it warm for 2h.
  • SiH 4 gas Stop feeding SiH 4 gas
  • the solid content of the mixture is 20%, the mixture is spray-dried, the sprayed material is heat-treated, the high-purity protective gas nitrogen is introduced into the atmosphere furnace, the temperature is raised to 900°C at 4°C/min, and the temperature is kept for 3h. Naturally cool to room temperature to obtain a silicon-based composite material.
  • 5% (calculated according to the percentage of the mass of organic cracked carbon to the total mass of the silicon-based composite material) pitch, 95% precursor and alcohol are mixed and dispersed uniformly by a high-speed disperser to form a mixture, which is controlled by adjusting the amount of alcohol added
  • the solid content of the mixture is 20%, the mixture is spray-dried, the sprayed material is heat-treated, the high-purity protective gas nitrogen is introduced into the atmosphere furnace, the temperature is raised to 900°C at 4°C/min, and the temperature is kept for 3h. Naturally cool to room temperature to obtain a silicon-based composite material.
  • NMP N-methylpyrrolidone
  • the button battery charge and discharge test was performed on the LANHE battery test system of Wuhan Landian Electronics Co., Ltd. Under normal temperature conditions, 0.1C constant current charge and discharge, and the charge and discharge voltage is limited to 0.005 to 1.5V.
  • expansion rate (pole piece thickness after 50 cycles-pole piece thickness before the cycle) / (pole piece thickness before the cycle-copper foil thickness) * 100%.
  • Table 1 shows the performance test evaluation results of Comparative Examples 1 to 2 and Examples 1 to 6

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Abstract

一种硅碳复合材料，该硅碳复合材料为类似火龙果结构的复合材料，包括基体核心、硅碳复合外壳和包覆层，硅碳复合外壳是由若干纳米硅颗粒均匀弥散式分散在导电碳中而形成，纳米硅颗粒由硅源高温裂解形成，所述的导电碳由有机碳源高温裂解形成，包覆层为碳包覆层，碳包覆层至少为一层，单层厚度为0.2-3μm。与现有技术相比，该复合材料采用气相同步沉积形成硅碳复合材料前驱体，再进行碳包覆形成类似火龙果结构的硅碳复合材料，具有高首效、低膨胀和长循环等优点，减缓了热处理过程中硅材料晶粒长大，有效的避免了材料在循环过程中的粉化，缓解了硅基材料的体积膨胀效应，提升了材料的循环性能、导电性能和倍率性能。

Description

一种硅碳复合材料及其制法 技术领域
本发明涉及新能源材料技术领域，特别涉及一种硅碳复合材料及其制法。
背景技术
二次电池已广泛应用于便携式电子产品中，随着便携式电子产品小型化发展及二次电池在航空、军事及汽车产业中的需求日益增大，电池的容量和能量密度均亟待大幅度提高。目前商业化负极材料主要为石墨类材料，但因其理论容量较低(372mAh/g)，无法满足于市场的需求。近年来，人们的目光瞄准新型高比容量负极材料：储锂金属及其氧化物(如Sn，Si)和锂过渡金属磷化物，Si因具有高的理论比容量(4200mAh/g)而成为最具潜力的可替代石墨类材料之一，但是Si基在充放电过程中存在巨大的体积效应，易发生破裂和粉化，从而丧失与集流体的接触，造成循环性能急剧下降。因此，如何降低体积膨胀效应和提升循环性能对硅材料在锂离子电池中的应用有重大意义。
现有技术中，中国专利CN105552323A公开一种硅/碳氧化硅/碳负极材料及其制备方法和应用，采用超小硅氧碳纳米粒子均匀分散在碳基质中作为缓冲基质，而硅纳米粒子则被均匀镶嵌在碳/硅氧碳缓冲基质中，虽然该负极活性材料具有容量高和循环性能较好，但是其的首次效率偏低，限制了它在锂离子电池中的应用。中国专利CN104103821B公开一种硅碳负极材料的制备方法，采用金属催化剂先将硅源分解制得前驱体Si-SiO x，再通过载气将反应制备的Si-SiOx与羧基化处理的碳基体在动态旋转沉积室中复合，制得硅碳负 极材料的前驱体，最后经过碳包覆得到硅碳负极材料，这种方法可以制备高容量的纳米硅，但是纳米硅无法均匀分布在碳基体的表面，存在循环性能不理想和较高的体积膨胀等隐患。
有鉴于此，确有必要开发一种硅碳复合材料及制法以克服来现有技术Si基材料在充放电过程中存在巨大的体积效应、易发生破裂和粉化、丧失与集流体的接触，造成循环性能急剧下降，以及硅基负极活性材料体积效应大和电导率低等导致循环性能差以及倍率性能差等技术难题。
发明内容
本发明的目的在于，针对现有技术的上述不足，提供一种硅碳复合材料及其制法，采用气相同步沉积形成硅碳复合材料前驱体，再进行碳包覆形成类似火龙果结构的硅碳复合材料，具有高首效、低膨胀和长循环等优点，减缓了热处理过程中硅材料晶粒长大，有效的避免了材料在循环过程中的粉化，缓解了硅基材料的体积膨胀效应，提升了材料的循环性能、导电性能和倍率性能。
本发明为达到上述目的所采用的技术方案是：
一种硅碳复合材料，该硅碳复合材料为类似火龙果结构的复合材料，包括基体核心、硅碳复合外壳和包覆层，所述的硅碳复合外壳是由若干纳米硅颗粒均匀弥散式分散在导电碳中而形成，纳米硅颗粒由硅源高温裂解形成，所述的导电碳由有机碳源高温裂解形成，所述的包覆层为碳包覆层，碳包覆层至少为一层，单层厚度为0.2-3μm。优选所述碳包覆层单层厚度进一步优选为0.2-2μm，特别优选为0.2-1μm。类火龙果结构能有效的缓解硅基材料在充放电过程中的体积效应，从而有效的避免了材料在循环过程中的粉化，良好的碳导电网络，能提高材料的导电性，改善材料的倍率性能，缓解了硅 基材料的体积膨胀效应和提升了循环性能。
优选地，所述的硅碳复合材料的粒度D50为2-20μm，进一步优选为2-15μm，特别优选为2-10μm；比表面积为1-30m2/g，进一步优选为2-20m2/g，特别优选为2-8m2/g；真密度为1-3g/cm3，进一步优选为1.5-2.5g/cm3，特别优选为2.0-2.5g/cm3；所述的硅碳复合材料的基体核心的粒度D50为2-18μm，进一步优选为2-15μm，特别优选为2-8μm。
优选地，所述的基体核心为纳米硅或纳米氧化亚硅或纳米导电碳材料中任一种或两种，纳米硅为晶粒大小为1-40nm的单晶纳米硅、晶粒大小为1-40nm的多晶纳米硅或非晶纳米硅中任一种或多种，进一步优选为2-20nm，特别优选为2-10nm；纳米硅粒度D50为5-300nm，进一步优选为10-200nm，特别优选为10-100nm；纳米氧化亚硅SiOx中X为0.8-1.5，优选为0.8-1.3，特别优选为0.8-1.1；纳米导电碳材料为导电炭黑、碳纳米管和石墨烯中的任一种。
优选地，所述的单晶纳米硅是采用化学气相沉积法在镀金硅片上制备而成的单晶纳米硅丝。
优选地，所述的纳米导电碳材料石墨烯是负载非晶态碳的石墨烯复合材料。
优选地，所述的负载非晶态碳的石墨烯复合材料的制法采用以单片层均匀分散的氧化石墨烯溶液与非晶态碳混合，室温搅拌，干燥之后，在惰性气体氛围下进行预热处理、冷却后置于还原气氛下进行还原反应，冷却即得。
一种前述硅碳复合材料的制法，其包括下列步骤：
S1：将基体核心置于CVD炉中，在保护气氛下，以1～15℃/min升温至 400～1200℃同步气相沉积纳米硅颗粒和导电碳，保温0.5～20h，自然冷却至室温，得到硅碳复合材料前驱体；
S2：将硅碳复合材料前驱体进行碳包覆，即得硅碳复合材料；
优选地，所述的同步进行气相沉积纳米硅粒子和导电碳层，可以按一定比列同时通入碳源和硅源，也可以交替通入碳源和硅源。其中，同步气相沉积纳米硅颗粒和导电碳是通过按一定比例可以为1:1—99，以0.5～20.0L/min速率同时通入或交替通入有机碳源和硅源而形成的；所述的硅源为SiH4、SiHCl 3、Si 2H 6、Si 3H 8、SiCl 4、Si 2Cl 6、SiH 2Cl或SiH 3Cl中的一种或几种。进一步优选地，所述CVD炉为回转炉，回转速度为0.2～5.0rpm；所述保护性气体为氮气、氦气、氖气、氩气、氪气、氙气中的一种或几种；所述有机碳源气体为甲烷、乙烷、丙烷、异丙烷，丁烷，异丁烷、乙烯、丙烯、乙炔、丁烯、氯乙烯，氟乙烯，二氟乙烯、氯乙烷，氟乙烷，二氟乙烷、氯甲烷，氟甲烷，二氟甲烷，三氟甲烷，甲胺，甲醛、苯、甲苯、二甲苯、苯乙烯、苯酚中的一种或几种。
优选地，所述的碳包覆为高温裂解碳包覆或气相碳包覆或液相碳包覆中的任一种，其中所述高温裂解包覆采用一次碳包覆或者二次碳包覆，采用二次碳包覆时，第二次碳包覆的包覆量按质量计为第一次碳包覆的包覆量的0.1～10倍，包覆层的厚度为10～2000nm，进一步优选为10～1500nm，特别优选为10～1000nm。两次碳包覆还可以先采用液相碳包覆后采用气相碳包覆，或者可以先采用气相碳包覆后采用液相碳包覆。
优选地，所述的液相碳包覆的过程包括：将有机物碳源、待包覆物与溶剂利用高速分散机混合分散均匀，形成浆料，对浆料进行喷雾干燥，再进行 热处理，在气氛炉中通入高纯保护性气体，以≦10℃的升温速率升温至400～1200℃进行烧结，保温0.5～10h，自然冷却至室温，得到液相包覆产物；所述有机物碳源裂解碳的质量占有机物碳源裂解碳与待包覆物生成复合材料的总质量的1～99wt％；所述溶剂的添加量为调节控制浆料的固含量为5～50％。
进一步优选，液相包覆时所述有机物碳源为蔗糖、葡萄糖、柠檬酸、酚醛树脂、环氧树脂、沥青、聚吡咯、聚吡咯烷酮、聚苯胺、聚丙烯腈、聚多巴胺、聚乙烯醇中的一种或几种；所述溶剂为水、醇类溶剂、酮类溶剂、烷类溶剂、N-甲基吡咯烷酮、四氢呋喃、甲苯中的一种或几种，醇类溶剂为乙醇、甲醇、乙二醇、异丙醇、正辛醇、丙烯醇、辛醇中的一种或几种，酮类溶剂为丙酮、甲基丁酮、甲基异丁酮、甲乙酮、甲异丙酮、环已酮、甲已酮中的一种或几种，烷类溶剂为环己烷、正己烷、异庚烷、3,3-二甲基戊烷、3-甲基己烷中的一种或几种；保护性气体为氮气、氩气、氩氢混合气体中的一种或几种；
优选地，所述的气相碳包覆的过程包括：将待包覆物置于CVD炉中，通入保护性气体，以1～15℃/min升温至500～1200℃，以0.5～20.0L/min通入速率通入有机碳源气体，保温0.5～20h，自然冷却至室温，得到气相包覆产物。
进一步优选，气相碳包覆时所述CVD炉为回转炉，回转速度为0.2～5.0rpm；所述保护性气体为氮气、氦气、氖气、氩气、氪气、氙气中的一种或几种；所述有机碳源气体为甲烷、乙烷、丙烷、异丙烷，丁烷，异丁烷、乙烯、丙烯、乙炔、丁烯、氯乙烯，氟乙烯，二氟乙烯、氯乙烷，氟乙烷，二氟乙烷、氯甲烷，氟甲烷，二氟甲烷，三氟甲烷，甲胺，甲醛、苯、甲苯、 二甲苯、苯乙烯、苯酚中的一种或几种。
与现有技术相比，本发明的有益效果是：
1.本发明的类火龙果结构的硅碳复合材料，包括基体壳心、硅碳复合外核和包覆层，硅碳复合外壳由纳米硅颗粒均匀弥散地分散在导电碳中而形成，其中低温沉积纳米硅中含有大量的非晶硅，非晶纳米硅体积膨胀小，从而有效的避免了材料在循环过程中的粉化，改善材料的循环性能，内部导电基体能提高材料的导电性，改善材料的倍率性能，缓解了硅基材料的体积膨胀效应和提升了循环性能。
2.本发明的类火龙果结构的硅碳复合材料先同步进行气相沉积得到纳米硅粒子均匀弥散的分布在导电碳层中，最后进行包覆处理，得到类火龙果结构的硅碳复合材料，采用该材料制备锂离子电池可以表现出良好的循环性能和倍率性能。
上述是发明技术方案的概述，以下结合附图与具体实施方式，对本发明做进一步说明。
附图说明
图1为本发明实施例1中硅基复合材料电镜图片；
图2为本发明实施例1中硅基复合材料首次充放电曲线；
图3为本发明实施例1中硅基复合材料循环性能曲线；
图4为本发明实施例3中硅基复合材料电镜图片；
图5为本发明实施例3中硅基复合材料XRD图片；
图6为本发明实施例3中硅基复合材料首次充放电曲线。
具体实施方式：
为了使本发明的目的和技术方案及优点更加清楚明白，以下结合实施例和附图作详细说明。应当理解，参照图1-6和此处所描述的具体实施例仅仅 用以解释本发明，并不用于限定本发明的范围，本领域的技术人员参照本发明实施例作出一些非本质的改动或调整，仍属于本发明的保护范围。
比较例1
将200g粒径D50＝50nm的纳米硅材料置于回转炉中，调节回转速度为1.5rpm，通入保护性气体氮气，以5℃/min升温至900℃，分别以4.0L/min速率通入高纯氮，1.5L/min速率通入甲烷气体20min，保温3h，自然冷却至室温，得到硅碳复合材料。
比较例2
将200g粒径D50＝50nm的纳米硅材料置于回转炉中，调节回转速度为1.5rpm，通入保护性气体氮气，以5℃/min升温至900℃，分别以4.0L/min速率通入高纯氮，1.5L/min速率通入甲烷气体20min，保温3h，自然冷却至室温，得到前驱体。将15％(按有机物裂解碳的质量占所述硅基复合材料总质量的百分比计算)沥青、85％前驱体和酒精利用高速分散机混合分散均匀形成混合料，通过调节酒精的添加量来控制混合料的固含量为20％，对混合料进行喷雾干燥，对喷雾后的物料进行热处理，在气氛炉中通入高纯保护性气体氮气，以4℃/min升温至900℃，保温3h，自然冷却至室温，得到硅碳复合材料。
实施例1
将200g粒径D50＝50nm的纳米硅材料置于回转炉中，调节回转速度为1.5rpm，通入保护性气体氮气，以5℃/min升温至700℃，分别以4.0L/min速率通入高纯氮，0.5L/min速率通入甲烷气体，0.5L/min速率通入SiH 4气体2h，自然冷却至室温，得到前驱体。将15％(按有机物裂解碳的质量占所述硅基复合材料总质量的百分比计算)沥青、85％前驱体和酒精利用高速分散机混合分散均匀形成混合料，通过调节酒精的添加量来控制混合料的固含量为20％，对混合料进行喷雾干燥，对喷雾后的物料进行热处理，在气氛炉中通入高纯保护性气体氮气，以4℃/min升温至900℃，保温3h，自然冷却至室温，得到硅基复合材料。
实施例2
将200g粒径D50＝100nm的纳米硅材料置于回转炉中，调节回转速度为1.5rpm，通入保护性气体氮气，以5℃/min升温至650℃，分别以4.0L/min速率通入高纯氮，0.5L/min速率通入甲烷气体，1.5L/min速率通入SiH 4气体1h，自然冷却至室温，得到前驱体。将15％(按有机物裂解碳的质量占所述硅基复合材料总质量的百分比计算)沥青、85％前驱体和酒精利用高速分散机混合分散均匀形成混合料，通过调节酒精的添加量来控制混合料的固含量为20％，对混合料进行喷雾干燥，对喷雾后的物料进行热处理，在气氛炉中通入高纯保护性气体氮气，以4℃/min升温至900℃，保温3h，自然冷却至室温，得到硅基复合材料。
实施例3
将100g导电炭黑材料置于回转炉中，调节回转速度为1.5rpm，通入保护性气体氮气，以5℃/min升温至650℃，分别以4.0L/min速率通入高纯氮，0.5L/min速率通入甲烷气体，1.5L/min速率通入SiHCl 3气体1h，自然冷却至室温，得到前驱体。将15％(按有机物裂解碳的质量占所述硅基复合材料总质量的百分比计算)沥青、85％前驱体和酒精利用高速分散机混合分散均匀形成混合料，通过调节酒精的添加量来控制混合料的固含量为20％，对混合料进行喷雾干燥，对喷雾后的物料进行热处理，在气氛炉中通入高纯保护性气体氮气，以4℃/min升温至900℃，保温3h，自然冷却至室温，得到硅基复合材料。
实施例4
将150g粒径D50＝100nm的纳米氧化硅材料置于回转炉中，调节回转速度为1.5rpm，通入保护性气体氮气，以5℃/min升温至650℃，分别以4.0L/min速率通入高纯氮，0.5L/min速率通入甲烷气体，1.5L/min速率通入SiH 4气体1h，自然冷却至室温，得到前驱体。将15％(按有机物裂解碳的质量占所述硅基复合材料总质量的百分比计算)沥青、85％前驱体和酒精利用高速分散机混合分散均匀形成混合料，通过调节酒精的添加量来控制混合料的固含量为20％，对混合料进行喷雾干燥，对喷雾后的物料进行热处理，在气氛炉中通入高纯保护性气体氮气，以4℃/min升温至900℃，保温3h，自然冷却至 室温，得到硅基复合材料。
实施例5
将150g粒径D50＝100nm的纳米氧化硅材料置于回转炉中，调节回转速度为1.5rpm，通入保护性气体氮气，以5℃/min升温至650℃，分别以4.0L/min速率通入高纯氮，0.5L/min速率通入甲烷气体，1.5L/min速率通入SiH 4气体1h，之后停止通入SiH 4气体，继续以0.5L/min速率通入甲烷气体，保温2h，自然冷却至室温，得到前驱体。将15％(按有机物裂解碳的质量占所述硅基复合材料总质量的百分比计算)沥青、85％前驱体和酒精利用高速分散机混合分散均匀形成混合料，通过调节酒精的添加量来控制混合料的固含量为20％，对混合料进行喷雾干燥，对喷雾后的物料进行热处理，在气氛炉中通入高纯保护性气体氮气，以4℃/min升温至900℃，保温3h，自然冷却至室温，得到硅基复合材料。
实施例6
将150g粒径D50＝100nm的纳米氧化硅材料置于回转炉中，调节回转速度为1.5rpm，通入保护性气体氮气，以5℃/min升温至650℃，以4.0L/min速率通入高纯氮，每隔10min交替以0.5L/min速率通入甲烷气体，1.5L/min速率通入SiH4气体1.5h，之后停止通入SiH4气体，保温2h，自然冷却至室温，得到前驱体。将5％(按有机物裂解碳的质量占所述硅基复合材料总质量的百分比计算)沥青、95％前驱体和酒精利用高速分散机混合分散均匀形成混合料，通过调节酒精的添加量来控制混合料的固含量为20％，对混合料进行喷雾干燥，对喷雾后的物料进行热处理，在气氛炉中通入高纯保护性气体氮气，以4℃/min升温至900℃，保温3h，自然冷却至室温，得到硅基复合材料。
采用以下方法对比较例1～2及实施例1～6进行测试：
取比较例1～2及实施例1～6制备的材料作为负极材料，与粘结剂聚偏二氟乙烯(PVDF)、导电剂(Super-P)按照70:15:15的质量比混合，加入适量的N-甲基吡咯烷酮(NMP)作为溶剂调成浆料，涂覆在铜箔上，并经真空干燥、辊压，制备成负极片；采用金属锂片作为对电极，使用1mol/L的 LiPF6三组分混合溶剂按EC:DMC:EMC＝1:1:1(v/v)混合的电解液，采用聚丙烯微孔膜为隔膜，在充满惰性气体手套箱中组装成CR2032型扣式电池。扣式电池的充放电测试在武汉市蓝电电子股份有限公司LANHE电池测试系统上，在常温条件，0.1C恒流充放电，充放电电压限制在0.005～1.5V。
采用如下方法测试和计算材料体积膨胀率：膨胀率＝(50周循环后极片厚度-循环前极片厚度)/(循环前极片厚度-铜箔厚度)*100％。
测试结果如表1所示：
表1为比较例1～2及实施例1～6性能测试评价结果
Figure PCTCN2019082319-appb-000001
根据上述说明书的揭示和教导，本发明所属领域的技术人员还可以对上述实施方式进行变更和修改。因此，上述说明并非对发明的限制，本发明并不局限于上面揭示和描述的具体实施方式，对发明的一些修改和变更如本技术领域的普通技术人员在实施例的实质范围内对各原料的等效替换及辅助成分的添加、具体方式的选择等做出的变化、改型、添加或替换等变型，也应当落入本发明的权利要求的保护范围内。

Claims (10)

  1. 一种硅碳复合材料，其特征在于，该硅碳复合材料为类似火龙果结构的复合材料，包括基体核心、硅碳复合外壳和包覆层，所述的硅碳复合外壳是由若干纳米硅颗粒均匀弥散式分散在导电碳中而形成，纳米硅颗粒由硅源高温裂解形成，所述的导电碳由有机碳源高温裂解形成，所述的包覆层为碳包覆层，碳包覆层至少为一层，单层厚度为0.2-3μm。
  2. 如权利要求1所述的硅碳复合材料，其特征在于，所述的硅碳复合材料的粒度D50为2-20μm，比表面积为1-30m 2/g，真密度为1-3g/cm 3，所述的硅碳复合材料的基体核心的粒度D50为2-18μm。
  3. 如权利要求1所述的硅碳复合材料，其特征在于，所述的基体核心为纳米硅或纳米氧化亚硅或纳米导电碳材料中任一种或两种，纳米硅为晶粒大小为1-40nm的单晶纳米硅、晶粒大小为1-40nm的多晶纳米硅或非晶纳米硅中任一种或多种，纳米硅粒度D50为5-300nm，纳米氧化亚硅SiOx中X为0.8-1.5，纳米导电碳材料为导电炭黑、碳纳米管和石墨烯中的任一种。
  4. 如权利要求3所述的硅碳复合材料，其特征在于，所述的单晶纳米硅是采用化学气相沉积法在镀金硅片上制备而成的单晶纳米硅丝。
  5. 如权利要求3所述的硅碳复合材料，其特征在于，所述的纳米导电碳材料石墨烯是负载非晶态碳的石墨烯复合材料。
  6. 如权利要求5所述的硅碳复合材料，其特征在于，所述的负载非晶态碳的石墨烯复合材料的制法采用以单片层均匀分散的氧化石墨烯溶液与非晶态碳混合，室温搅拌，干燥之后，在惰性气体氛围下进行预热处理、冷却后置于还原气氛下进行还原反应，冷却即得。
  7. 一种权利要求1-6任一所述硅碳复合材料的制法，其特征在于，包括下列步骤：
    S1：将基体核心置于CVD炉中，在保护气氛下，以1～15℃/min升温至400～1200℃同步气相沉积纳米硅颗粒和导电碳，保温0.5～20h，自然冷却，得到硅碳复合材料前驱体；
    S2：将硅碳复合材料前驱体进行碳包覆，即得硅碳复合材料；
    其中，同步气相沉积纳米硅颗粒和导电碳是通过按一定比例以0.5～20.0L/min速率同时通入或交替通入有机碳源和硅源而形成的；所述的硅源为SiH 4、SiHCl 3、Si2H 6、Si 3H 8、SiCl 4、Si 2Cl 6、SiH 2Cl或SiH 3Cl中的一种或几种。
  8. 如权利要求7所述的硅碳复合材料的制法，其特征在于，所述的碳包覆为高温裂解碳包覆或气相碳包覆或液相碳包覆中的任一种，其中所述高温裂解包覆采用一次碳包覆或者二次碳包覆，采用二次碳包覆时，第二次碳包覆的包覆量按质量计为第一次碳包覆的包覆量的0.1～10倍，包覆层的厚度为10～2000nm。
  9. 如权利要求8所述的硅碳复合材料的制法，其特征在于，所述的液相碳包覆的过程包括：将有机物碳源、待包覆物与溶剂利用高速分散机混合分散均匀，形成浆料，对浆料进行喷雾干燥，再进行热处理，在气氛炉中通入高纯保护性气体，以≦10℃的升温速率升温至400～1200℃进行烧结，保温0.5～10h，自然冷却至室温，得到液相包覆产物；所述有机物碳源裂解碳的质量占有机物碳源裂解碳与待包覆物生成复合材料的总质量的1～99wt％；所述溶剂的添加量为调节控制浆料的固含量为5～50％。
  10. 如权利要求8所述硅碳复合材料的制法，其特征在于，所述的气相碳包覆的过程包括：将待包覆物置于CVD炉中，通入保护性气体，以1～15℃/min升温至500～1200℃，以0.5～20.0L/min通入速率通入有机碳源气体，保温0.5～20h，自然冷却至室温，得到气相包覆产物。
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