WO2021129125A1 - 一种中空核壳结构硅碳复合负极材料及其制备方法 - Google Patents

一种中空核壳结构硅碳复合负极材料及其制备方法 Download PDF

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WO2021129125A1
WO2021129125A1 PCT/CN2020/124577 CN2020124577W WO2021129125A1 WO 2021129125 A1 WO2021129125 A1 WO 2021129125A1 CN 2020124577 W CN2020124577 W CN 2020124577W WO 2021129125 A1 WO2021129125 A1 WO 2021129125A1
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silicon
parts
negative electrode
carbon composite
electrode material
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French (fr)
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仰永军
葛传长
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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
    • H01M4/628—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 technical field of lithium ion battery negative electrode materials, in particular to a hollow core-shell structure silicon-carbon composite negative electrode material and a preparation method thereof.
  • Lithium-ion batteries have become an ideal power source for digital products, cordless power tools, and new energy vehicles due to their advantages of high working voltage, high specific energy, good circulation, and long service life.
  • the negative electrode material used commercially is graphite material, and its theoretical specific capacity is only 372mAh/g. It is increasingly difficult to meet the requirements of high-performance lithium-ion batteries. Therefore, the search for high-capacity negative electrode materials has become an important research direction.
  • Si-based materials have the highest theoretical specific capacity among materials currently studied. Pure silicon has a theoretical specific capacity of 4200mAh/g, which is considered to be the most promising high-capacity anode material for lithium-ion batteries.
  • the conductivity of pure silicon is low.
  • silicon used as a negative electrode material will have a volume expansion of 300-400%, resulting in failure of the material structure, and the battery cycle performance cannot meet commercial requirements.
  • the common practice in the industry is to use a mixture of silicon and carbon materials, that is, silicon-carbon composite materials. The good electrical conductivity of carbon materials is used to improve the poor conductivity of elemental silicon, and on the other hand, the silicon-carbon composite materials are reduced.
  • Patent CN103367727A discloses a lithium-ion battery silicon-carbon anode material and a preparation method thereof.
  • the anode material is obtained by pyrolyzing nano-silicon, graphite and organic carbon sources. However, the material still has high expansion rate, rate and cycle performance. Poor and other issues.
  • Patent CN1891668 discloses a carbon-silicon composite material with a spherical core-shell structure and its preparation method and use.
  • the carbon-silicon composite material is a composite of ultrafine silicon powder and carbon powder into a slurry and then coated with spherical carbon particles inside The above is obtained by pyrolysis and chemical vapor deposition.
  • This method has a certain improvement on the shortcomings of poor cycle performance of existing silicon-carbon composites, but the selected spherical carbon does not have a significant buffering effect on the volume change of silicon, and the contact interface between silicon-carbon is not strong, making The cycle performance of silicon-carbon composites still cannot meet actual needs.
  • the purpose of the present invention is to provide a hollow core-shell structured silicon-carbon composite anode material and a preparation method thereof.
  • the present invention limits the expansion of nano-silicon particles and greatly improves the structural stability and cycle stability of the silicon-carbon anode pole piece.
  • the preparation method of the present invention has simple and easy process, stable product performance, and good application prospects, so as to solve the problems raised in the background art.
  • a hollow core-shell structure silicon-carbon composite negative electrode material including the following mass parts of raw materials:
  • the volume average particle diameter D50 of the silicon powder is 1-10 ⁇ m;
  • the surfactant is cetyltrimethylammonium bromide, polyethylene glycol, nonylphenol polyoxyethylene ether, bromodecyl Hexaalkylpyridine, emulsifier OP-10, Tween 20, Tween 80, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxy
  • One or at least two of propyl silane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -(methacryloxy)propyltrimethoxysilane The combination; the mass ratio of the surfactant and the silicon powder is 0.05:100 to 5:100.
  • the abrasive is one or a combination of at least two of water, ethanol, ethylene glycol, N-methylpyrrolidone, glycerin, isopropanol, isoamyl alcohol, methyl naphthalene, and washing oil;
  • the solid content of the silicon powder in the abrasive is 5-18%; the ball mill adopts wet ultra-fine grinding; the end point of the ball mill is determined as the volume average particle size D50 of the silicon particles in the obtained nano-silicon slurry is 50- 500nm.
  • the soluble resin is one or a combination of at least two of phenolic resin, epoxy resin, and acrylic resin;
  • the additive is a linear structure high molecular polymer, specifically polyvinyl alcohol, polycarbonate, polyvinyl alcohol, and polycarbonate.
  • the foaming agent is one or a combination of at least two of sodium bicarbonate, ammonium bicarbonate, potassium bicarbonate, ammonium carbonate, and calcium bicarbonate;
  • the dispersant is water, ethanol, One or a combination of at least two of N,N-dimethylformamide.
  • the mass ratio of silicon and soluble resin in the nano-silicon slurry in the dispersion liquid is 5-30:100; the mass ratio of the additive to the soluble resin in the dispersion liquid is 1-5:100; the dispersion The mass ratio of the foaming agent to the soluble resin in the liquid is 0.05 to 0.3:100; the mass fraction concentration of the soluble resin in the dispersion liquid is 3 to 10%.
  • Another technical solution to be solved by the present invention is: a preparation method of a hollow core-shell structure silicon-carbon composite negative electrode material, including the following steps:
  • S102 Disperse the nano silicon slurry obtained in S101, soluble resin, additives, and foaming agent into the dispersant according to a certain mass ratio, and form a homogeneous dispersion under high-speed stirring;
  • S103 Spray-dry the dispersion obtained in S102 under certain conditions to obtain nano-silicon/resin microspheres, and the obtained microspheres are carbonized at 750-1100°C under the protection of inert gas, cooled to room temperature and sieved to obtain a hollow core-shell structure Silicon carbon composite anode material.
  • the stirring of S102 adopts a high-speed mixer, the stirring speed is 500-2000 rpm; the stirring and mixing time is 2-6 hours.
  • the spray drying conditions of S103 are the inlet temperature of 120 ⁇ 250°C, the atomization pressure of 2 ⁇ 10MPa; the carbonization treatment is carried out in an atmosphere furnace, and the temperature is increased to carbonization at a rate of 0.5 ⁇ 20°C/min under the protection of inert gas. Temperature: The carbonization temperature is 750-1100°C, and the carbonization time is 2-6 hours.
  • the inert gas is one or a combination of at least two of nitrogen, helium, neon, argon, krypton and xenon.
  • the sieve is divided into a standard sieve with 80 mesh or more, and the sieve is taken off.
  • the present invention prepares a hollow core-shell structure silicon-carbon composite anode material with low expansion rate, high consistency and good conductivity through spray granulation.
  • the surface of the nano-silicon has a carbon coating layer, which improves the interface connectivity between the nano-particles.
  • the nano-silicon particles themselves are wrapped in a spherical carbon capsule. There is a space between the silicon particles and the outer shell of the carbon capsule, which can effectively contain the volume of silicon. Expansion improves the structural stability of the material.
  • the formed special core-shell structure reduces the specific surface area of the silicon-carbon composite negative electrode material, avoids the direct contact of the silicon material with the electrolyte, and reduces the occurrence of side reactions.
  • the silicon-carbon composite anode material of the present invention used as a lithium-ion battery anode material has high capacity, high rate, high cycle stability, and greatly improves the electrochemical performance of silicon carbon.
  • the present invention has simple preparation process, uniform particle size, good dispersibility, short production process, no harsh conditions, low cost, and easy industrialization.
  • Figure 1 is a flow chart of the preparation method of the present invention
  • Figure 2 is a distribution diagram of silicon particles prepared by the present invention in a carbon shell.
  • a hollow core-shell structure silicon-carbon composite negative electrode material including the following mass parts of raw materials:
  • the silicon powder with a volume average particle size D50 of 5 ⁇ m, metallic Li, expanded graphite, ⁇ -aminopropyltriethoxysilane, and water are mixed according to the mass ratio of 100:1.5:1000 and then ultrafine.
  • microsphere powder into an atmosphere furnace, heat it up to 980°C at 2°C/min under nitrogen atmosphere for 4 hours, cool to room temperature and pass through a 300-mesh standard sieve to obtain a hollow core-shell silicon-carbon composite with uniform particle size distribution material.
  • a hollow core-shell structure silicon-carbon composite negative electrode material including the following mass parts of raw materials:
  • the nano-silicon slurry with a diameter D50 of 150nm the obtained nano-silicon (converted from the nano-silicon slurry), polyvinylpyrrolidone (Mw630000), ammonium bicarbonate and phenolic resin according to the mass ratio of 20:2.5:0.2:100 mixed into the high-speed shear
  • adding water and make a slurry with a resin solid content of 8% at a speed of 1500r/min and then use spray drying to complete the spray granulation at an inlet temperature of 150°C and an atomization pressure of 6MPa to obtain hollow nano-silicon /Resin microspheres.
  • microsphere powder into an atmosphere furnace, heat it up to 980°C at 2°C/min under nitrogen atmosphere for 4 hours, cool to room temperature and pass through a 300-mesh standard sieve to obtain a hollow core-shell silicon-carbon composite with uniform particle size distribution material.
  • a hollow core-shell structure silicon-carbon composite negative electrode material including the following mass parts of raw materials:
  • Silicon/resin microspheres Put the obtained microsphere powder into an atmosphere furnace, heat it up to 980°C at 2°C/min under nitrogen atmosphere for 4 hours, cool to room temperature and pass through a 300-mesh standard sieve to obtain a hollow core-shell silicon-carbon composite with uniform particle size distribution material.
  • a hollow core-shell structure silicon-carbon composite negative electrode material including the following mass parts of raw materials:
  • microsphere powder into an atmosphere furnace, heat it up to 980°C at 2°C/min under nitrogen atmosphere for 4 hours, cool to room temperature and pass through a 300-mesh standard sieve to obtain a hollow core-shell silicon-carbon composite with uniform particle size distribution material.
  • a hollow core-shell structure silicon-carbon composite negative electrode material including the following mass parts of raw materials:
  • the nano-silicon slurry with a particle size D50 of 100nm, the obtained nano-silicon (converted from the nano-silicon slurry), polyvinyl alcohol (Mw75000) and phenolic resin according to the mass ratio of 15:3:100 are mixed into the high-speed shearing disperser, Add water and make a slurry with a resin solid content of 8% at a rotation speed of 1500r/min, and then use spray drying to complete spray granulation at an inlet temperature of 150°C and an atomization pressure of 6MPa.
  • the obtained powder was put into an atmosphere furnace, heated at 2°C/min to 980°C for 4 hours in a nitrogen atmosphere, cooled to room temperature, and passed through a standard 300 mesh sie
  • a hollow core-shell structure silicon-carbon composite negative electrode material including the following mass parts of raw materials:
  • a hollow core-shell structure silicon-carbon composite negative electrode material including the following mass parts of raw materials:
  • the silicon-carbon composite materials in Examples 1 to 4 and Comparative Examples 1 to 3 were tested for particle size, specific surface area, first specific capacity, first coulombic efficiency, and cycle performance using the half-cell test method. The results are listed in Table 1.
  • the name and model of the instrument used in the test are: particle size: Malvern laser particle size analyzer MS2000; specific surface area: Kantar specific surface area analyzer NOVA2000e.
  • the CR2032 button half-cell battery is made with lithium sheet as the counter electrode in the glove box.
  • the charge and discharge test of the button battery was carried out on the LAND battery test system of Wuhan Jinnuo Electronics Co., Ltd. Under normal temperature conditions, first charge and discharge at a constant current of 0.1C for activation, and then charge and discharge at 0.5C for 200 cycles, with a charge and discharge voltage of 0.005 ⁇ 2.0V.
  • Comparative Examples 1 to 3 The capacity retention rate of Comparative Examples 1 to 3 (51.4-75.6%) is significantly worse than the capacity retention rate of Examples 1 to 4 (89.2-90.6%). This is because the nano-silicon is completely wrapped in the dense carbon shell in the examples. Inside, the complete hollow core-shell structure can buffer the expansion of silicon during charging and discharging, improve the structural stability and conductivity of the negative electrode material, thereby improving the cycle performance of the battery.
  • the preparation method of the present invention first prepares nano-silicon slurry, and then stirs and disperses the nano-silicon slurry with soluble resin, additives and foaming agent at a high speed according to an appropriate ratio (adjusted according to the different capacity requirements of the material), and then obtains by spray drying
  • the nano silicon/resin microspheres are then carbonized at a specific temperature under the protection of inert gas to obtain a hollow core-shell structure silicon-carbon composite negative electrode material.
  • the nano-silicon in the composite material has a carbon coating layer on the surface and is wrapped in a hollow carbon capsule, which reserves space for lithium-intercalation expansion of the nano-silicon, and improves the structural stability of the material during charging and discharging.
  • the preparation method of the invention has simple process, short process, easy operation, small equipment investment, wide source of raw materials, low cost, stable product properties, and is suitable for industrialized production.

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Abstract

本发明公开了一种中空核壳结构硅碳复合负极材料及其制备方法，将硅粉、金属Li、膨胀石墨、表面活性剂和研磨剂混合后进行球磨制得纳米硅浆料；将所得纳米硅浆料和可溶性树脂、添加剂、发泡剂按照一定的质量比分散到分散剂中，并在高速搅拌下形成均质分散液；对所得分散液在一定条件下进行喷雾干燥得到纳米硅/树脂微球，所得微球在惰性气体保护下，于750～1100℃进行碳化处理，降温至室温过筛得到中空核壳结构硅碳复合负极材料。本发明制备出的硅碳复合负极材料具有形貌规整、粒径均匀、表面光滑、硅分布均匀、高容量、循环稳定性好的优点。

Description

一种中空核壳结构硅碳复合负极材料及其制备方法 技术领域
本发明涉及锂离子电池负极材料技术领域，特别涉及一种中空核壳结构硅碳复合负极材料及其制备方法。
背景技术
锂离子电池因具有工作电压高、比能量高、循环性好、使用寿命长等优点而成为数码产品、无绳电动工具、新能源汽车的理想电源。目前商业上使用的负极材料为石墨材料，其理论比容量仅有372mAh/g，越来越难以满足高性能锂离子电池的要求，因此寻找高容量负极材料成为一个重要的研究方向。
在现有改进技术中，Si基材料是目前人们所研究材料中理论比容量最高的，纯硅的理论比容量为4200mAh/g，被认为是最有希望的高容量的锂离子电池负极材料。但是纯硅电导率低，在充放电过程中，作为负极材料的硅会具有300～400％的体积膨胀，导致材料结构失效，电池循环性能无法满足商用需求。针对以上两方面问题，业内普遍做法是采用硅与碳类材料混合，即硅碳复合材料，利用碳材料良好的导电性改善单质硅的电导率差的问题，另一方面减小硅碳复合材料中硅的比例，减少硅的绝对膨胀对材料的刚性损坏。专利CN103367727A公开了一种锂离子电池硅碳负极材料及其制备方法，该负极材料是通过将纳米硅、石墨和有机碳源混合热解而得，但材料依然存在膨胀率高、倍率和循环性能差等问题。专利CN1891668公开了一种具有球形核壳结构的碳硅复合材料及其制法和用途，该碳硅复合材料是将超细硅粉与碳粉复合成浆后包覆在内部具有球形的碳颗粒上，通过热解和化学气相沉积而得。该法对现有硅碳复合材料循环性能差的缺点有一定的改善，但选用的球形碳对硅的体积变化并未起到显著的缓冲作用，且硅碳间的接触界面并不牢固，使得硅碳复合材料的循环性能仍然不能满足实际需求。
因此，为了有效缓解硅在充放电过程中因体积膨胀而导致材料粉化、结构 坍塌等问题，研发一种具有高容量、高倍率、长循环特性的锂离子电池硅碳负极材料是行业内急待解决的技术难题。
发明内容
本发明的目的在于提供一种中空核壳结构硅碳复合负极材料及其制备方法，本发明对纳米硅颗粒膨胀进行限域保护，大幅提高硅碳负极极片的结构稳定性和循环稳定性。本发明的制备方法工艺简单易行，产品性能稳定，具有良好的应用前景，以解决上述背景技术中提出的问题。
为实现上述目的，本发明提供如下技术方案：
一种中空核壳结构硅碳复合负极材料，包括如下质量份数的原材料：
金属Li 25份、硅粉25份、膨胀石墨25份、表面活性剂5份、研磨剂5份、可溶性树脂5份、添加剂4份、发泡剂3份、分散剂3份。
进一步地，所述硅粉的体积平均粒径D50为1～10μm；所述表面活性剂为溴化十六烷三甲基铵、聚乙二醇、壬基酚聚氧乙烯醚、溴代十六烷基吡啶、乳化剂OP-10、吐温20、吐温80、3-甲基丙烯酰氧丙基甲基二乙氧基硅烷、3-甲基丙烯酰氧丙基甲基二甲氧基硅烷、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)丙基三甲氧基硅烷中的1种或至少2种的组合；所述表面活性剂与硅粉的质量比为0.05:100～5:100。
进一步地，所述研磨剂为水、乙醇、乙二醇、N-甲基吡咯烷酮、甘油、异丙醇、异戊醇、甲基萘、洗油中的1种或至少2种的组合；所述硅粉在研磨剂中的固含量为5～18％；所述球磨采用湿法超细磨；所述球磨终点判定条件为所得纳米硅浆料中硅颗粒的体积平均粒径D50为50～500nm。
进一步地，所述可溶性树脂为酚醛树脂、环氧树脂、丙烯酸树脂中的1种或至少2种的组合；所述添加剂为线性结构高分子聚合物，具体为聚乙烯醇、聚碳酸酯、聚丙烯腈、聚丙烯酰胺、聚乙二醇、聚苯乙烯、聚乙烯吡咯烷酮、聚乙烯醇缩丁醛、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；所述发泡剂为碳酸氢钠、碳酸氢铵、碳酸氢钾、碳酸铵、碳酸氢钙中的1种或至少2种的组合；所述分散剂为水、乙醇、N，N-二甲基甲酰胺中的1种或至少2种的组合。
进一步地，所述分散液中纳米硅浆料中的硅和可溶性树脂的质量比为5～30:100；所述分散液中添加剂与可溶性树脂的质量比为1～5:100；所述分散液中发泡剂与可溶性树脂的质量比为0.05～0.3:100；所述分散液中可溶性树脂的质量分数浓度为3～10％。
本发明要解决的另一种技术方案为：一种中空核壳结构硅碳复合负极材料的制备方法，包括如下步骤：
S101：将硅粉、金属Li、膨胀石墨、表面活性剂和研磨剂混合后进行球磨制得纳米硅浆料；
S102：将S101所得纳米硅浆料和可溶性树脂、添加剂、发泡剂按照一定的质量比分散到分散剂中，并在高速搅拌下形成均质分散液；
S103：对S102所得分散液在一定条件下进行喷雾干燥得到纳米硅/树脂微球，所得微球在惰性气体保护下，于750～1100℃进行碳化处理，降温至室温过筛得到中空核壳结构硅碳复合负极材料。
进一步地，S102的搅拌采用高速混料机，搅拌转速为500-2000rpm；搅拌混合时间为2-6小时。
进一步地，S103的喷雾干燥的条件为进风温度120～250℃，雾化压力2～10MPa；碳化处理在气氛炉中进行，在惰性气体保护下以0.5～20℃/min的速率升温至碳化温度；碳化温度为750～1100℃，碳化时间为2～6小时。
进一步地，所述惰性气体为氮气、氦气、氖气、氩气、氪气和氙气中的1种或至少2种的组合。
进一步地，所述筛分为过80目以上的标准筛网，取筛下料。
与现有技术相比，本发明的有益效果是：
1.本发明针对现有技术中硅碳负极材料膨胀率高、导电性差等问题，通过喷雾造粒制备出膨胀率低、一致性高、导电率好的中空核壳结构硅碳复合负极材料。纳米硅表面有碳包覆层，提高了纳米颗粒间的界面连接性，同时纳米硅颗粒本身被包裹在球形碳囊中，硅颗粒与碳囊外壳间留有间距，能够有效地容纳硅的体积膨胀，提高材料的结构稳定性，同时所形成的特殊核壳结构降低了硅碳复合负极材料的比表面积，避免了硅材料直接与电解液接触，减少了副反应的发生。
2.本发明硅碳复合负极材料用作锂离子电池负极材料具有高容量，高倍率，高循环稳定性能，极大改善了硅碳的电化学性能。
3.本发明与现有技术相比，制备工艺简单，所得颗粒尺寸大小均匀，分散性好，生产流程短，无苛刻条件，成本较低，易于工业化。
附图说明
图1为本发明的制备方法流程图；
图2为本发明制备的硅颗粒在碳壳中分布图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
一种中空核壳结构硅碳复合负极材料，包括如下质量份数的原材料：
金属Li 25份、硅粉25份、膨胀石墨25份、表面活性剂5份、研磨剂5份、可溶性树脂5份、添加剂4份、发泡剂3份、分散剂3份。
如图1，将体积平均粒径D50为5μm的硅粉、金属Li、膨胀石墨、γ-氨丙基三乙氧基硅烷、水按照100:1.5:1000的质量份数比混合后进行超细磨得 到体积平均粒径D50为100nm的纳米硅浆料，将所得纳米硅(由纳米硅浆料折算)、聚乙烯醇(Mw75000)、碳酸氢铵和酚醛树脂按质量比15:3:0.2:100混合投入高速剪切分散机中，加入水并在1500r/min转速下制成树脂固含量为8％的浆料，然后采用喷雾干燥在进风温度150℃，雾化压力6MPa下完成喷雾造粒得到中空纳米硅/树脂微球。将所得微球粉体投入气氛炉中，在氮气氛围下以2℃/min升温至980℃处理4小时，降温至室温后过300目标准筛得到粒径分布均匀的中空核壳结构硅碳复合材料。
实施例2
一种中空核壳结构硅碳复合负极材料，包括如下质量份数的原材料：
金属Li 25份、硅粉25份、膨胀石墨25份、表面活性剂5份、研磨剂5份、可溶性树脂5份、添加剂4份、发泡剂3份、分散剂3份。
将体积平均粒径D50为5μm的硅粉、金属Li、膨胀石墨、溴化十六烷三甲基铵、水按照100:1.5:1000的质量份数比混合后进行超细磨得到体积平均粒径D50为150nm的纳米硅浆料，将所得纳米硅(由纳米硅浆料折算)、聚乙烯吡咯烷酮(Mw630000)、碳酸氢铵和酚醛树脂按质量比20:2.5:0.2:100混合投入高速剪切分散机中，加入水并在1500r/min转速下制成树脂固含量为8％的浆料，然后采用喷雾干燥在进风温度150℃，雾化压力6MPa下完成喷雾造粒得到中空纳米硅/树脂微球。将所得微球粉体投入气氛炉中，在氮气氛围下以2℃/min升温至980℃处理4小时，降温至室温后过300目标准筛得到粒径分布均匀的中空核壳结构硅碳复合材料。
实施例3
一种中空核壳结构硅碳复合负极材料，包括如下质量份数的原材料：
金属Li 25份、硅粉25份、膨胀石墨25份、表面活性剂5份、研磨剂5份、可溶性树脂5份、添加剂4份、发泡剂3份、分散剂3份。
将体积平均粒径D50为5μm的硅粉、金属Li、膨胀石墨、γ-氨丙基三 乙氧基硅烷、水按照100:1.5:1000的质量份数比混合后进行超细磨得到体积平均粒径D50为100nm的纳米硅浆料，将所得纳米硅(由纳米硅浆料折算)、聚乙烯醇(Mw75000)、碳酸氢铵和酚醛树脂按质量比25:3:0.15:100混合投入高速剪切分散机中，加入水并在1500r/min转速下制成树脂固含量为8％的浆料，然后采用喷雾干燥在进风温度150℃，雾化压力6MPa下完成喷雾造粒得到中空纳米硅/树脂微球。将所得微球粉体投入气氛炉中，在氮气氛围下以2℃/min升温至980℃处理4小时，降温至室温后过300目标准筛得到粒径分布均匀的中空核壳结构硅碳复合材料。
实施例4
一种中空核壳结构硅碳复合负极材料，包括如下质量份数的原材料：
金属Li 25份、硅粉25份、膨胀石墨25份、表面活性剂5份、研磨剂5份、可溶性树脂5份、添加剂4份、发泡剂3份、分散剂3份。
将体积平均粒径D50为5μm的硅粉、金属Li、膨胀石墨、γ-氨丙基三乙氧基硅烷、水按照100:1.5:1000的质量份数比混合后进行超细磨得到体积平均粒径D50为150nm的纳米硅浆料，将所得纳米硅(由纳米硅浆料折算)、聚丙烯酰胺(Mw5000000)、碳酸氢铵和环氧树脂按质量比20:2:0.2:100混合投入高速剪切分散机中，加入水并在1500r/min转速下制成树脂固含量为8％的浆料，然后采用喷雾干燥在进风温度160℃，雾化压力6MPa下完成喷雾造粒得到中空纳米硅/树脂微球。将所得微球粉体投入气氛炉中，在氮气氛围下以2℃/min升温至980℃处理4小时，降温至室温后过300目标准筛得到粒径分布均匀的中空核壳结构硅碳复合材料。
对比实施例1
一种中空核壳结构硅碳复合负极材料，包括如下质量份数的原材料：
金属Li 25份、硅粉25份、膨胀石墨25份、表面活性剂5份、研磨剂5份、可溶性树脂5份、添加剂4份、发泡剂3份、分散剂3份。
将体积平均粒径D50为5μm的硅粉、金属Li、膨胀石墨、γ-氨丙基三乙氧基硅烷、水按照100:1.5:1000的质量份数比混合后进行超细磨得到体积平均粒径D50为100nm的纳米硅浆料，将所得纳米硅(由纳米硅浆料折算)、聚乙烯醇(Mw75000)和酚醛树脂按质量比15:3:100混合投入高速剪切分散机中，加入水并在1500r/min转速下制成树脂固含量为8％的浆料，然后采用喷雾干燥在进风温度150℃，雾化压力6MPa下完成喷雾造粒。将所得粉体投入气氛炉中，在氮气氛围下以2℃/min升温至980℃处理4小时，降温至室温后过300目标准筛得到对比材料。
对比实施例2
一种中空核壳结构硅碳复合负极材料，包括如下质量份数的原材料：
金属Li 25份、硅粉25份、膨胀石墨25份、表面活性剂5份、研磨剂5份、可溶性树脂5份、添加剂4份、发泡剂3份、分散剂3份。
将体积平均粒径D50为5μm的硅粉、金属Li、膨胀石墨、γ-氨丙基三乙氧基硅烷、水按照100:1.5:1000的质量份数比混合后进行超细磨得到体积平均粒径D50为100nm的纳米硅浆料，将所得纳米硅(由纳米硅浆料折算)、聚乙烯醇(Mw75000)、碳酸氢铵和酚醛树脂按质量比35:3:0.2:100混合投入高速剪切分散机中，加入水并在1500r/min转速下制成树脂固含量为8％的浆料，然后采用喷雾干燥在进风温度150℃，雾化压力6MPa下完成喷雾造粒。将所得粉体投入气氛炉中，在氮气氛围下以2℃/min升温至980℃处理4小时，降温至室温后过300目标准筛得到对比材料。
对比实施例3
一种中空核壳结构硅碳复合负极材料，包括如下质量份数的原材料：
金属Li 25份、硅粉25份、膨胀石墨25份、表面活性剂5份、研磨剂5份、可溶性树脂5份、添加剂4份、发泡剂3份、分散剂3份。
将体积平均粒径D50为5μm的硅粉、金属Li、膨胀石墨、γ-氨丙基三 乙氧基硅烷、水按照100:1.5:1000的质量份数比混合后进行超细磨得到体积平均粒径D50为100nm的纳米硅浆料，将所得纳米硅(由纳米硅浆料折算)、聚乙烯醇(Mw75000)、碳酸氢铵和酚醛树脂按质量比15:3:0.5:100混合投入高速剪切分散机中，加入水并在1500r/min转速下制成树脂固含量为8％的浆料，然后采用喷雾干燥在进风温度150℃，雾化压力6MPa下完成喷雾造粒。将所得粉体投入气氛炉中，在氮气氛围下以2℃/min升温至980℃处理4小时，降温至室温后过300目标准筛得到对比材料。
采用半电池测试方法对实施例1～4以及对比例1～3中的硅碳复合材料进行粒径、比表面积、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。测试所使用的仪器名称及型号为：粒径：马尔文激光粒度分析仪MS2000；比表面积：康塔比表面积测定仪NOVA2000e。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1～4及对比例1～3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电池测试系统上进行，在常温条件，首先以0.1C恒流充放活化，而后以0.5C充放循环200次，充放电电压为0.005～2.0V。
表1
Figure PCTCN2020124577-appb-000001
Figure PCTCN2020124577-appb-000002
从表1可以看出，本发明实施例制备出的材料比容量及首次库伦效率明显优于对比例，其原因在于实施例1～4所得硅碳复合材料表面光滑，球形形貌完整(如图2，图2中M表示为碳壳，N表示为硅颗粒)，这种完整结构可以减小材料比表面积，有效避免硅活性材料和电解液之间的副反应，提高了材料的克容量发挥和首次库伦效率。从测试结果还可以看出实施例1～4的方法制备的硅碳复合负极材料具有更好的循环容量保持率。对比例1～3的容量保持率(51.4-75.6％)明显差于实施例1～4的容量保持率(89.2-90.6％)，这是因为实施例中纳米硅被完全包裹在致密的碳壳内部，完整的中空核壳结构可缓冲充放电过程中硅的膨胀，提高负极材料的结构稳定性、导电率，从而提高了电池的循环性能。
本发明的制备方法首先制备纳米硅浆料，然后按照适当比例(根据材料的不同容量需求来调节)将纳米硅浆料与可溶性树脂、添加剂和发泡剂高速搅拌分散均匀，再通过喷雾干燥得到纳米硅/树脂微球，然后在惰性气体保护下经特定温度碳化处理即得到中空核壳结构硅碳复合负极材料。该复合材料中纳米硅表面有碳包覆层，同时被包裹在中空的碳囊中，为纳米硅的嵌锂膨胀预留了空间，提高了材料在充放电过程中的结构稳定性。首次循环过程中仅在碳壳外表形成SEI膜，有效提高了所制备的负极材料的库伦效率和循环 稳定性。本发明的制备方法工艺简单、流程短、操作容易、设备投资较小、原料来源广泛且成本低，产品性质稳定，适宜工业化生产。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明披露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (10)

  1. 一种中空核壳结构硅碳复合负极材料，其特征在于，包括如下质量份数的原材料：
    金属Li 25份、硅粉25份、膨胀石墨25份、表面活性剂5份、研磨剂5份、可溶性树脂5份、添加剂4份、发泡剂3份、分散剂3份。
  2. 如权利要求1所述的中空核壳结构硅碳复合负极材料，其特征在于，所述硅粉的体积平均粒径D50为1～10μm；所述表面活性剂为溴化十六烷三甲基铵、聚乙二醇、壬基酚聚氧乙烯醚、溴代十六烷基吡啶、乳化剂OP-10、吐温20、吐温80、3-甲基丙烯酰氧丙基甲基二乙氧基硅烷、3-甲基丙烯酰氧丙基甲基二甲氧基硅烷、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)丙基三甲氧基硅烷中的1种或至少2种的组合；所述表面活性剂与硅粉的质量比为0.05:100～5:100。
  3. 如权利要求1所述的中空核壳结构硅碳复合负极材料，其特征在于，所述研磨剂为水、乙醇、乙二醇、N-甲基吡咯烷酮、甘油、异丙醇、异戊醇、甲基萘、洗油中的1种或至少2种的组合；所述硅粉在研磨剂中的固含量为5～18％；所述球磨采用湿法超细磨；所述球磨终点判定条件为所得纳米硅浆料中硅颗粒的体积平均粒径D50为50～500nm。
  4. 如权利要求1所述的中空核壳结构硅碳复合负极材料，其特征在于，所述可溶性树脂为酚醛树脂、环氧树脂、丙烯酸树脂中的1种或至少2种的组合；所述添加剂为线性结构高分子聚合物，具体为聚乙烯醇、聚碳酸酯、聚丙烯腈、聚丙烯酰胺、聚乙二醇、聚苯乙烯、聚乙烯吡咯烷酮、聚乙烯醇缩丁醛、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；所述发泡剂为碳酸氢钠、碳酸氢铵、碳酸氢钾、碳酸铵、碳酸氢钙中的1种或至少2种的组合；所述分散剂为水、乙醇、N，N-二甲基甲酰胺中的1种或至少2种的组合。
  5. 如权利要求1所述的中空核壳结构硅碳复合负极材料，其特征在于， 所述分散液中纳米硅浆料中的硅和可溶性树脂的质量比为5～30:100；所述分散液中添加剂与可溶性树脂的质量比为1～5:100；所述分散液中发泡剂与可溶性树脂的质量比为0.05～0.3:100；所述分散液中可溶性树脂的质量分数浓度为3～10％。
  6. 一种如权利要求1-5任一项所述的中空核壳结构硅碳复合负极材料的制备方法，其特征在于，包括如下步骤：
    S101：将硅粉、金属Li、膨胀石墨、表面活性剂和研磨剂混合后进行球磨制得纳米硅浆料；
    S102：将S101所得纳米硅浆料和可溶性树脂、添加剂、发泡剂按照一定的质量比分散到分散剂中，并在高速搅拌下形成均质分散液；
    S103：对S102所得分散液在一定条件下进行喷雾干燥得到纳米硅/树脂微球，所得微球在惰性气体保护下，于750～1100℃进行碳化处理，降温至室温过筛得到中空核壳结构硅碳复合负极材料。
  7. 如权利要求6所述的一种中空核壳结构硅碳复合负极材料的制备方法，其特征在于，S102的搅拌采用高速混料机，搅拌转速为500-2000rpm；搅拌混合时间为2-6小时。
  8. 如权利要求6所述的一种中空核壳结构硅碳复合负极材料的制备方法，其特征在于，S103的喷雾干燥的条件为进风温度120～250℃，雾化压力2～10MPa；碳化处理在气氛炉中进行，在惰性气体保护下以0.5～20℃/min的速率升温至碳化温度；碳化温度为750～1100℃，碳化时间为2～6小时。
  9. 如权利要求6所述的一种中空核壳结构硅碳复合负极材料的制备方法，其特征在于，所述惰性气体为氮气、氦气、氖气、氩气、氪气和氙气中的1种或至少2种的组合。
  10. 如权利要求6所述的一种中空核壳结构硅碳复合负极材料的制备方法，其特征在于，所述筛分为过80目以上的标准筛网，取筛下料。
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