CN1903793A - Carbon silicon composite material, its preparation method and use - Google Patents

Abstract

Translated fromChinese

本发明涉及一种碳硅复合材料，其包括硅基体，及在其上生长的碳纳米管或纳米碳纤维；所述的硅基体的平均粒径为100nm～100μm；所述的碳纳米管或纳米碳纤维的直径为1～200nm，长度为10nm～100μm；所述的碳纳米管为单壁，双壁或多壁。该碳硅复合材料的制备方法有多种，可以将催化剂负载到硅材料上，或是将催化剂与硅颗粒混合或制成合金后，再使用化学气相沉积方法沉积碳纳米管或纳米碳纤维。该碳硅复合材料结合了基体硅材料具有稳定的结构，表面生长的纳米碳管或纳米碳纤维具有较大比表面积和较大空隙率的优点，在能量储存与转换器件中，可以作为锂离子电池的负极材料，也作为各种燃料电池催化剂的载体。The invention relates to a carbon-silicon composite material, which includes a silicon substrate, and carbon nanotubes or carbon nanofibers grown thereon; the average particle diameter of the silicon substrate is 100 nm to 100 μm; the carbon nanotubes or nanometer The carbon fiber has a diameter of 1-200nm and a length of 10nm-100μm; the carbon nanotube is single-walled, double-walled or multi-walled. There are many methods for preparing the carbon-silicon composite material. The catalyst can be loaded on the silicon material, or the catalyst can be mixed or alloyed with silicon particles, and then carbon nanotubes or carbon nanofibers can be deposited by chemical vapor deposition. The carbon-silicon composite material combines the stable structure of the matrix silicon material, and the carbon nanotubes or nano-carbon fibers grown on the surface have the advantages of large specific surface area and large porosity. In energy storage and conversion devices, it can be used as a lithium-ion battery. It is also used as a negative electrode material for various fuel cell catalysts.

Description

Translated fromChinese

一种碳硅复合材料及其制备方法和用途A carbon-silicon composite material and its preparation method and application

技术领域technical field

本发明涉及一种碳硅复合材料，及其制备方法和用途。The invention relates to a carbon-silicon composite material, its preparation method and application.

背景技术Background technique

硅和碳这两种元素在宇宙中的蕴含量非常丰富，分别居第三位和第七位，因而将这两种材料商业化具有非常可观的前景，但是在实际应用过程中，如作为锂离子电池负极材料时，虽然硅具有非常高的质量比容量，但是硅的电导率非常低，并且循环时会产生巨大的体积变化，使得材料的循环性能非常差，这限制了硅材料在锂离子电池负极材料中的应用；与此相对的是，碳材料有非常好的锂离子嵌入和脱出的可逆性，但是它的容量相对来说较低，这不能满足日益发展的社会对高比能量电池的要求，尽管目前广泛采用碳材料作为锂离子电池的负极材料，但是随着社会的发展这种材料低容量的问题逐渐变得紧迫起来，因而需要寻找一种高能、廉价的材料来取代目前常用的负极材料。These two elements, silicon and carbon, are very abundant in the universe, ranking third and seventh respectively, so the commercialization of these two materials has very promising prospects, but in practical applications, such as lithium As an anode material for ion batteries, although silicon has a very high mass specific capacity, the conductivity of silicon is very low, and a huge volume change will occur during cycling, making the cycle performance of the material very poor, which limits the use of silicon in lithium-ion batteries. Application in battery negative electrode materials; in contrast, carbon materials have very good reversibility of lithium ion intercalation and extraction, but its capacity is relatively low, which cannot meet the needs of the growing society for high specific energy batteries Although carbon materials are currently widely used as negative electrode materials for lithium-ion batteries, the problem of low capacity of this material has gradually become urgent with the development of society. Therefore, it is necessary to find a high-energy, cheap material to replace the current commonly used carbon materials. negative electrode material.

发明内容Contents of the invention

本发明的目的在于克服现有技术单独使用硅材料或碳材料作为锂离子电池的负极材料时都不能满足需要的缺陷，从而提供一种具有较大比表面积和较大空隙率、可以充分发挥硅和碳的功能、在硅颗粒表面生长碳纳米管或纳米碳纤维的碳硅复合材料，及其制备方法和用途。The purpose of the present invention is to overcome the defect that the existing technology can not meet the needs when using silicon material or carbon material alone as the negative electrode material of lithium ion battery, thereby providing a kind of material with large specific surface area and large porosity, which can fully utilize silicon and carbon functions, a carbon-silicon composite material in which carbon nanotubes or carbon nanofibers are grown on the surface of silicon particles, and a preparation method and use thereof.

本发明的目的是通过如下的技术方案实现的：The purpose of the present invention is achieved through the following technical solutions:

本发明提供一种碳硅复合材料，其包括硅基体，及在其上生长的碳纳米管或纳米碳纤维；所述的硅基体的平均粒径为100nm～100μm；所述的碳纳米管或纳米碳纤维的直径为1～200nm，长度为10nm～100μm；所述的碳纳米管为单壁，双壁或多壁。The invention provides a carbon-silicon composite material, which includes a silicon substrate, and carbon nanotubes or carbon nanofibers grown thereon; the average particle diameter of the silicon substrate is 100 nm to 100 μm; the carbon nanotubes or nanometer The carbon fiber has a diameter of 1-200nm and a length of 10nm-100μm; the carbon nanotube is single-walled, double-walled or multi-walled.

所述的基体硅颗粒的形貌既可为不规则的，也可以为规则的，优选的几何外形为球形。The morphology of the matrix silicon particles can be irregular or regular, and the preferred geometric shape is spherical.

所述的碳纳米管或纳米碳纤维既可以具有笔直的几何外观，也可以具有弯曲或螺旋的几何外观；既可以垂直基体硅颗粒表面定向生长，也可以非定向生长。The carbon nanotubes or carbon nanofibers can have a straight geometric appearance, or a curved or helical geometric appearance; they can grow vertically to the surface of the silicon particles in an orientation, or grow in a non-directional manner.

本发明提供一种所述碳硅复合材料的制备方法，具体包括如下步骤：The invention provides a method for preparing the carbon-silicon composite material, which specifically includes the following steps:

1)催化剂溶液的配制1) Preparation of catalyst solution

使用选自蒸馏水、乙醇、甲醇、异丙醇、乙二醇或丙三醇中的一种或几种溶剂配制0.0001～0.1M的催化剂溶液；Use one or several solvents selected from distilled water, ethanol, methanol, isopropanol, ethylene glycol or glycerol to prepare a 0.0001-0.1M catalyst solution;

所述的催化剂为选自Fe(NO₃)₃·9H₂O，FeSO₄·7H₂O，FeCl₃·6H₂O，Co(NO₃)₂·6H₂O，Co(CH₃COO)₂·4H₂O，Ni(NO₃)₂·6H₂O，(NH₄)₆Mo₇O₂₄·4H₂O中的一种或几种；The catalyst is selected from Fe(NO₃ )₃ 9H₂ O, FeSO₄ 7H₂ O, FeCl₃ 6H₂ O, Co(NO₃ )₂ 6H₂ O, Co(CH₃ COO)₂ One or more of 4H₂ O, Ni(NO₃ )₂ , 6H₂ O, (NH₄ )₆ Mo₇ O₂₄ , 4H₂ O;

2)催化剂负载2) Catalyst loading

将作为基体材料的硅材料加入到步骤1)制得的催化剂溶液中，所述的催化剂与硅的质量比为1∶1～1000，搅拌30分钟～20小时，静置5～72小时，分离、干燥，得到催化剂负载的硅材料；Add the silicon material as the matrix material to the catalyst solution prepared in step 1), the mass ratio of the catalyst to silicon is 1:1 to 1000, stir for 30 minutes to 20 hours, let stand for 5 to 72 hours, and separate , drying to obtain a catalyst-supported silicon material;

所述的硅基体的平均粒径为100nm～100μm；The average particle size of the silicon matrix is 100 nm to 100 μm;

3)化学气相沉积3) Chemical vapor deposition

将步骤2)得到的物质放置在一耐热容器中(如石墨舟，氧化铝舟)，然后装入气密性好的管式炉，充入氩气或氩气与氢气的混合气，或以氨气进行预处理，然后程序升温至500～1200℃温度；升到目标温度后，将气体转换为碳源气体(乙炔、乙烯、甲烷或一氧化碳)或者转换为氩气、氮气或氢气与上述碳源气体的混合气，恒温20分钟至48小时进行化学气相沉积后，自然冷却至室温。The material obtained in step 2) is placed in a heat-resistant container (such as a graphite boat, an alumina boat), and then a tube furnace with good airtightness is packed into it, and a mixture of argon or argon and hydrogen is charged, or Pretreatment with ammonia, and then temperature program to 500 ~ 1200 ℃ temperature; after rising to the target temperature, the gas is converted to carbon source gas (acetylene, ethylene, methane or carbon monoxide) or converted to argon, nitrogen or hydrogen and the above The mixed gas of carbon source gas is kept at a constant temperature for 20 minutes to 48 hours for chemical vapor deposition, and then naturally cooled to room temperature.

本发明提供另一种所述碳硅复合材料的制备方法，具体包括如下步骤：The present invention provides another method for preparing the carbon-silicon composite material, which specifically includes the following steps:

1)化学镀溶液的配制1) Preparation of electroless plating solution

使用选自蒸馏水、乙醇、甲醇、异丙醇、乙二醇或丙三醇中的一种或几种溶剂配制0.0001～0.1M的Fe(NO₃)₃·9H₂O，Co(NO₃)₂·6H₂O或Ni(NO₃)₂·6H₂O溶液；配制含有柠檬酸三钠和乙酸钠的蒸馏水溶液；所述的柠檬酸三钠和乙酸钠的浓度均为0.0001～1M；然后将前者滴加到后者中，搅拌均匀，得到混合溶液A；Use one or several solvents selected from distilled water, ethanol, methanol, isopropanol, ethylene glycol or glycerol to prepare 0.0001～0.1M Fe(NO₃ )₃ 9H₂ O, Co(NO₃ )₂ · 6H₂ O or Ni(NO₃ )₂ · 6H₂ O solution; prepare a distilled aqueous solution containing trisodium citrate and sodium acetate; the concentrations of the trisodium citrate and sodium acetate are both 0.0001-1M; then Add the former dropwise to the latter and stir evenly to obtain a mixed solution A;

使用蒸馏水将氢氧化钠和硼氢化钠配制成还原剂溶液B；其中的氢氧化钠的浓度1.5～15M，硼氢化钠的浓度为0.0001～1M；Using distilled water to prepare sodium hydroxide and sodium borohydride into reducing agent solution B; the concentration of sodium hydroxide in it is 1.5-15M, and the concentration of sodium borohydride is 0.0001-1M;

2)催化剂的负载2) Catalyst loading

将作为基体材料的硅材料加入到步骤1)制得的混合溶液A中，搅拌，升温至25～95℃，调节溶液的pH＝4～12，然后滴加步骤1)制备的还原剂溶液B，待滴加完，继续搅拌10分钟～2小时，分离，干燥，得到催化剂负载的硅材料；加入的硅材料、溶液A、溶液B的比例为1g∶40～100ml∶10～50ml；Add the silicon material as the matrix material to the mixed solution A prepared in step 1), stir, raise the temperature to 25-95°C, adjust the pH of the solution to 4-12, and then add the reducing agent solution B prepared in step 1) dropwise , until the dropwise addition is completed, continue to stir for 10 minutes to 2 hours, separate and dry to obtain a catalyst-supported silicon material; the ratio of the added silicon material, solution A, and solution B is 1g: 40-100ml: 10-50ml;

所述的硅基体的平均粒径为100nm～100μm；The average particle size of the silicon matrix is 100 nm to 100 μm;

3)化学气相沉积3) Chemical vapor deposition

将步骤2)得到的物质放置在一耐热容器中(如石墨舟，氧化铝舟)，然后装入气密性好的管式炉，充入氩气或氩气与氢气的混合气，然后程序升温至500～1200℃温度；升到目标温度后，将气体转换为碳源气体(乙炔、乙烯、甲烷或一氧化碳)或者转换为氩气、氮气或氢气与上述碳源气体的混合气，恒温20分钟至48小时进行化学气相沉积后，自然冷却至室温。The material obtained in step 2) is placed in a heat-resistant container (such as a graphite boat, an alumina boat), then a tube furnace with good airtightness is packed into it, and a mixture of argon or argon and hydrogen is charged, and then The temperature is programmed to rise to 500-1200°C; after reaching the target temperature, the gas is converted into a carbon source gas (acetylene, ethylene, methane or carbon monoxide) or a mixture of argon, nitrogen or hydrogen and the above carbon source gas, and the temperature is constant. After 20 minutes to 48 hours of chemical vapor deposition, naturally cool to room temperature.

本发明提供再一种所述碳硅复合材料的制备方法，具体包括如下步骤：The present invention provides another method for preparing the carbon-silicon composite material, which specifically includes the following steps:

1)催化剂的混合1) Mixing of catalysts

将选自Fe、Co、Ni、Mo金属粉末的一种或几种与作为基体材料的硅颗粒混合均匀(可以用手磨、球磨或振动磨)，混合5分钟～50小时，金属与基体材料的质量比为1∶1～1000；Mix one or more metal powders selected from Fe, Co, Ni, Mo with silicon particles as the matrix material (hand milling, ball milling or vibration milling can be used), mix for 5 minutes to 50 hours, the metal and the matrix material The mass ratio is 1:1～1000;

所述的硅基体的平均粒径为100nm～100μm；The average particle size of the silicon matrix is 100 nm to 100 μm;

2)化学气相沉积2) Chemical vapor deposition

将步骤1)得到的物质放置在一耐热容器中(如石墨舟，氧化铝舟)，然后装入气密性好的管式炉，充入氩气或氩气与氢气的混合气，然后程序升温至700～1200℃温度；升到目标温度后，将气体转换为碳源气体(乙炔、乙烯、甲烷或一氧化碳)或者转换为氩气、氮气或氢气与上述碳源气体的混合气，恒温20分钟至48小时进行化学气相沉积后，自然冷却至室温。The material obtained in step 1) is placed in a heat-resistant container (such as a graphite boat, an alumina boat), and then a tube furnace with good airtightness is packed into it, and a mixture of argon or argon and hydrogen is charged, and then The temperature is programmed to rise to 700-1200°C; after reaching the target temperature, the gas is converted into a carbon source gas (acetylene, ethylene, methane or carbon monoxide) or a mixture of argon, nitrogen or hydrogen and the above carbon source gas, at constant temperature After 20 minutes to 48 hours of chemical vapor deposition, naturally cool to room temperature.

本发明提供还一种所述碳硅复合材料的制备方法，具体包括如下步骤：The present invention provides a method for preparing the carbon-silicon composite material, which specifically includes the following steps:

1)含催化剂元素合金的制备1) Preparation of alloys containing catalyst elements

将选自Fe、Co、Ni、Mo金属粉末的一种或几种与作为基体材料的硅颗粒混合均匀，然后进行球磨30分钟～500小时，转速为100～3000rpm，金属与基体材料的质量比为1∶0.001～1000；Mix one or several metal powders selected from Fe, Co, Ni, Mo with silicon particles as the base material, and then perform ball milling for 30 minutes to 500 hours at a speed of 100 to 3000rpm. The mass ratio of metal to base material 1:0.001～1000;

所述的硅基体的平均粒径为100nm～100μm；The average particle size of the silicon matrix is 100 nm to 100 μm;

2)化学气相沉积2) Chemical vapor deposition

将步骤1)得到的物质放置在一耐热容器中(如石墨舟，氧化铝舟)，然后装入气密性好的管式炉，充入氩气或氩气与氢气的混合气，然后程序升温至700～1200℃温度；升到目标温度后，将气体转换为碳源气体(乙炔、乙烯、甲烷或一氧化碳)或者转换为氩气、氮气或氢气与上述碳源气体的混合气，恒温20分钟至48小时进行化学气相沉积后，自然冷却至室温。The material obtained in step 1) is placed in a heat-resistant container (such as a graphite boat, an alumina boat), and then a tube furnace with good airtightness is packed into it, and a mixture of argon or argon and hydrogen is charged, and then The temperature is programmed to rise to 700-1200°C; after reaching the target temperature, the gas is converted into a carbon source gas (acetylene, ethylene, methane or carbon monoxide) or a mixture of argon, nitrogen or hydrogen and the above carbon source gas, at constant temperature After 20 minutes to 48 hours of chemical vapor deposition, naturally cool to room temperature.

使用上述方法可以得到本发明的碳硅复合材料，其为在具有微米或纳米尺寸的硅颗粒表面生长着一维纳米碳纤维或碳纳米管的具有毛绒球外观的微纳或纳纳复合材料。这种硅/碳微纳和纳纳复合材料，在硅颗粒上生长碳纳米管，形成笼装的复合结构，一方面利用了碳纳米管优越的导电性，使得它能弥补硅颗粒导电性差的问题，另一方面由于碳纳米管直接生长在硅颗粒上使得两者接触性更好，不容易由于外力的作用的分离，这与单纯的两相混合有根本的区别。因而以它作为材料在某些领域，尤其是锂离子电池负极材料的应用方面能够取得非常理想的效果。并且采用这两种材料制备的复合材料既能做到价格低廉，又能持续发展。The carbon-silicon composite material of the present invention can be obtained by using the above method, which is a micro-nano or nano-composite material with the appearance of a fluffy ball, in which one-dimensional nano-carbon fibers or carbon nanotubes are grown on the surface of silicon particles with a micron or nanometer size. This kind of silicon/carbon micro-nano and nano-nano composite material grows carbon nanotubes on silicon particles to form a caged composite structure. The problem, on the other hand, because the carbon nanotubes grow directly on the silicon particles, the contact between the two is better, and it is not easy to separate due to the action of external force, which is fundamentally different from the simple two-phase mixing. Therefore, using it as a material can achieve very ideal results in some fields, especially in the application of lithium-ion battery negative electrode materials. And the composite material prepared by using these two materials can not only achieve low price, but also can develop continuously.

此外，该复合材料结合了基体硅材料具有稳定的结构，表面生长的纳米碳管或纳米碳纤维具有较大比表面积和较大空隙率的优点，同时又避免了单纯碳纳米管在应用时容易团聚，不易分散的缺点。从而在作为催化剂载体，化学电源和超级电容器中的电极材料等方面，显示了很好的动力学性能，热稳定性，化学稳定性和结构稳定性。In addition, the composite material combines the stable structure of the matrix silicon material, and the carbon nanotubes or carbon nanofibers grown on the surface have the advantages of large specific surface area and large porosity, while avoiding the easy agglomeration of simple carbon nanotubes during application , the disadvantage of not being easy to disperse. Therefore, it shows good kinetic performance, thermal stability, chemical stability and structural stability in terms of being used as a catalyst carrier, a chemical power source and an electrode material in a supercapacitor.

本发明的优点还在于：在核心硅表面生长的一维纳米碳纤维和碳纳米管(单壁，双壁或多壁)的直径，长度，长径比，密度可通过催化剂在基体碳表面负载时催化剂的粒径，含量，分布和化学气相沉积的所采用的载气的种类，流量，不同载气成份的比例，反应的温度和时间来加以调控。本发明所采用的工艺简单，重复性好，所需仪器设备都是化学和材料工业常用的设备。所制备出的产品纯度高，几何结构可控，质量稳定，适合于工业化大规模生产。The present invention also has the advantages that: the diameter of one-dimensional carbon nanofibers and carbon nanotubes (single-walled, double-walled or multi-walled) grown on the core silicon surface, the length, the aspect ratio, and the density can be supported by the catalyst on the carbon surface of the matrix. The particle size, content, distribution of the catalyst and the type of carrier gas used in chemical vapor deposition, the flow rate, the proportion of different carrier gas components, the reaction temperature and time are regulated. The process adopted in the present invention is simple and has good repeatability, and the required instruments and equipment are all commonly used equipment in the chemical and material industries. The prepared product has high purity, controllable geometric structure and stable quality, and is suitable for large-scale industrial production.

本发明提供的碳硅复合材料，在能量储存与转换器件中，可以作为锂离子电池的负极材料，也作为各种燃料电池催化剂的载体。The carbon-silicon composite material provided by the invention can be used as the negative electrode material of the lithium ion battery and as the carrier of various fuel cell catalysts in energy storage and conversion devices.

附图说明Description of drawings

图1为实施例1制备的硅/碳复合材料的场发射扫描电子显微形貌；Fig. 1 is the field emission scanning electron micrograph of the silicon/carbon composite material that embodiment 1 prepares;

图2为实施例1制备的硅/碳复合材料放大32500倍的场发射扫描电子显微形貌。Fig. 2 is the field emission scanning electron microscopic appearance of the silicon/carbon composite material prepared in Example 1 with a magnification of 32500 times.

具体实施方式Detailed ways

实施例1：称取0.001g Fe粉和10g硅颗粒(其平均粒径为5μm)，研磨5小时，然后将所得的物料放置在一石墨舟中，再装入管式炉中，充入氩气，流量为20sccm，程序升温至800℃后，将气体转换为甲烷和氢气的混合气，其比例为1∶20(v/v)，总流量为300sccm，恒温20分钟进行化学气相沉积后，将气体转换为氩气，自然冷却至室温，所得产物即硅/多壁碳纳米管复合材料，其中多壁碳纳米管的平均直径为8nm，长度为60μm。其在场发射扫描电子显微中的形貌如图1所示，在高放大倍数的场发射扫描电子显微中的形貌如图2所示，可见该碳硅复合材料为具有毛绒球外观的复合材料，且分散性好。Embodiment 1: take by weighing 0.001g Fe powder and 10g silicon particle (its average particle diameter is 5 μ m), grind 5 hours, then the material of gained is placed in a graphite boat, then packs into tube furnace, fills with argon Gas, the flow rate is 20 sccm, after the temperature is programmed to 800 ° C, the gas is converted into a mixture of methane and hydrogen, the ratio is 1:20 (v/v), the total flow rate is 300 sccm, and the chemical vapor deposition is carried out at a constant temperature for 20 minutes. The gas is converted into argon, and naturally cooled to room temperature, and the obtained product is a silicon/multi-walled carbon nanotube composite material, wherein the average diameter of the multi-walled carbon nanotube is 8 nm, and the length is 60 μm. Its morphology in field emission scanning electron microscopy is shown in Figure 1, and its morphology in high-magnification field emission scanning electron microscopy is shown in Figure 2. It can be seen that the carbon-silicon composite material has the appearance of a plush ball Composite material with good dispersion.

将所述的材料作为锂离子电池的负极材料使用。负极的制备方法描述如下：硅/多壁碳纳米管复合材料，碳黑与聚偏氟乙烯的环己烷溶液在常温常压下混合形成浆料，均匀涂敷于作为集流体的铜箔衬底上，所得的薄膜厚度约70μm.将得到的薄膜在150℃下烘干后，在20Kg/cm²下压紧，继续在150℃下烘干12小时。烘干后硅/多壁碳纳米管复合材料，碳黑与聚偏氟乙烯的重量百分比为80∶5∶15，然后将薄膜裁剪为面积为1cm²的圆形薄片作为负极。Said material is used as negative electrode material of lithium ion battery. The preparation method of the negative electrode is described as follows: the silicon/multi-walled carbon nanotube composite material, the cyclohexane solution of carbon black and polyvinylidene fluoride are mixed at normal temperature and pressure to form a slurry, and evenly coated on the copper foil lining as the current collector On the bottom, the thickness of the obtained film is about 70 μm. After drying the obtained film at 150° C., press it at 20 Kg/cm² and continue to dry it at 150° C. for 12 hours. After drying the silicon/multi-walled carbon nanotube composite material, the weight percentage of carbon black and polyvinylidene fluoride is 80:5:15, and then the film is cut into a circular sheet with an area of 1 cm² as the negative electrode.

将商品正极材料LiCoO₂与乙炔黑和10％聚偏氟乙烯(PVDF)的环己烷溶液在常温常压下混合形成浆料(活性材料∶乙炔黑∶PVDF＝75∶15∶10)，均匀涂敷于铝箔衬底上，所得的薄膜厚度约50～60μm，作为电池的正极。电解液为1mol LiPF₆溶于1L EC和DMC的混合溶剂中(体积比1∶1)。将所有电池材料，包括正极，负极，电池壳，隔膜，干燥后在充氩手套箱中或干燥间中添加电解液组装成实验电池。The commercial cathode material_LiCoO2 was mixed with acetylene black and 10% polyvinylidene fluoride (PVDF) cyclohexane solution at normal temperature and pressure to form a slurry (active material: acetylene black: PVDF = 75:15:10), uniform Coated on the aluminum foil substrate, the thickness of the obtained film is about 50-60 μm, and it is used as the positive electrode of the battery. The electrolyte solution is 1mol LiPF₆ dissolved in 1L EC and DMC mixed solvent (volume ratio 1:1). All battery materials, including positive electrode, negative electrode, battery case, and diaphragm, were dried and then added electrolyte in an argon-filled glove box or a drying room to assemble an experimental battery.

实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为950mAh/g，1C的可逆容量为560mAh/g，显示了较好的动力学行为。The experimental battery is subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 950mAh/g, and its reversible capacity at 1C is 560mAh/g, showing good kinetic behavior.

实施例2：称取0.001g Fe粉和10g硅颗粒(其平均粒径为10μm)，研磨5小时，然后将所得的物料放置在三氧化二铝舟中，再装入管式炉中，充入氩气，化学气相沉积过程同实施例1，化学气相沉积的时间为2小时，硅/多壁碳纳米管复合材料，其中多壁碳纳米管的平均直径为15nm，长度为160μm。Embodiment 2: take by weighing 0.001g Fe powder and 10g silicon particle (its average particle diameter is 10 μ m), grind 5 hours, then the material of gained is placed in the aluminum oxide boat, then packs in the tube furnace, fills Enter argon gas, the chemical vapor deposition process is the same as in Example 1, and the chemical vapor deposition time is 2 hours. Silicon/multi-walled carbon nanotube composite material, wherein the average diameter of the multi-walled carbon nanotubes is 15 nm, and the length is 160 μm.

如实施例1所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为930mAh/g，1C的可逆容量为560mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 1, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 930mAh/g, and its reversible capacity at 1C is 560mAh/g, showing good kinetic behavior.

实施例3：称取0.001g Fe粉和10g硅颗粒(其平均粒径为100nm)，研磨5小时，然后将所得的物料放置在三氧化二铝舟中，再装入管式炉中，充入氩气和氢气的混合气，其比例为85∶15(v/v)，程序升温至700℃后，将气体转换为乙烯，流量为50sccm，恒温2小时进行化学气相沉积后，将气体转换为氮气，自然冷却至室温，所得产物即硅/多壁碳纳米管复合材料，其中多壁碳纳米管的平均直径为17nm，长度为70μm。Embodiment 3: take by weighing 0.001g Fe powder and 10g silicon particle (its average particle diameter is 100nm), grind 5 hours, then the material of gained is placed in the aluminum oxide boat, then packs in the tube furnace, fully Enter a mixture of argon and hydrogen, the ratio of which is 85:15 (v/v). After the temperature is programmed to 700 ° C, the gas is converted to ethylene, and the flow rate is 50 sccm. After chemical vapor deposition at a constant temperature for 2 hours, the gas is converted to Nitrogen, naturally cooled to room temperature, the resulting product is silicon/multi-walled carbon nanotube composite material, wherein the average diameter of the multi-walled carbon nanotubes is 17 nm, and the length is 70 μm.

如实施例1所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为880mAh/g，1C的可逆容量为570mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 1, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 880mAh/g, and its reversible capacity at 1C is 570mAh/g, showing good kinetic behavior.

实施例4：称取0.001g Ni粉和5.9g硅颗粒(其平均粒径为5μm)，研磨5小时，然后将所得的物料放置在一石墨舟中，再装入管式炉中，充入氩气，化学气相沉积过程同实施例1，化学气相沉积的时间为50分钟，所得产物即硅/多壁碳纳米管复合材料，其中多壁碳纳米管的平均直径为5nm，长度为80μm。Embodiment 4: take by weighing 0.001g Ni powder and 5.9g silicon particle (its average particle diameter is 5 μ m), grind 5 hours, then the material of gained is placed in a graphite boat, then packs in the tube furnace, fills Argon gas, the chemical vapor deposition process is the same as in Example 1, the chemical vapor deposition time is 50 minutes, and the resulting product is a silicon/multi-walled carbon nanotube composite material, wherein the average diameter of the multi-walled carbon nanotubes is 5 nm, and the length is 80 μm.

如实施例1所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为790mAh/g，1C的可逆容量为680mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 1, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 790mAh/g, and its reversible capacity at 1C is 680mAh/g, showing good kinetic behavior.

实施例5：称取0.001gCo粉和10g硅颗粒(其平均粒径为100μm)，研磨5小时，然后将所得的物料放置在一石墨舟中，再装入管式炉中，充入氩气，化学气相沉积过程同实施例1，化学气相沉积的时间为50分钟，所得产物即硅/单壁碳纳米管复合材料，其中单壁碳纳米管的平均直径为1nm，长度为70μm。Example 5: Weigh 0.001g of Co powder and 10g of silicon particles (its average particle size is 100 μm), grind for 5 hours, then place the resulting material in a graphite boat, then pack it into a tube furnace, and fill it with argon , The chemical vapor deposition process is the same as in Example 1, the chemical vapor deposition time is 50 minutes, and the resulting product is a silicon/single-walled carbon nanotube composite material, wherein the average diameter of the single-walled carbon nanotubes is 1 nm, and the length is 70 μm.

如实施例1所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/单壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为1000mAh/g，1C的可逆容量为880mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 1, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/single-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 1000mAh/g, and its reversible capacity at 1C is 880mAh/g, showing good kinetic behavior.

实施例6：称取0.001g Mo粉和10g硅颗粒(其平均粒径为50μm)，研磨5小时，然后将所得的物料放置在一石墨舟中，再装入管式炉中，充入氩气，化学气相沉积过程同实施例1，化学气相沉积的时间为50分钟，所得产物即硅/多壁碳纳米管复合材料，其中多壁碳纳米管的平均直径为8nm，长度为100μm。Embodiment 6: take by weighing 0.001g Mo powder and 10g silicon particle (its average particle diameter is 50 μ m), grind 5 hours, then the material of gained is placed in a graphite boat, then packs into tube furnace, fills with argon Gas, the chemical vapor deposition process is the same as in Example 1, the chemical vapor deposition time is 50 minutes, and the resulting product is a silicon/multi-walled carbon nanotube composite material, wherein the average diameter of the multi-walled carbon nanotubes is 8 nm, and the length is 100 μm.

如实施例1所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为860mAh/g，1C的可逆容量为580mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 1, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 860mAh/g, and its reversible capacity at 1C is 580mAh/g, showing good kinetic behavior.

实施例7：称取0.001gMo粉和10g硅颗粒(其平均粒径为100μm)，研磨50小时，然后将所得的物料放置在一石墨舟中，再装入管式炉中，充入氩气，化学气相沉积过程同实施例1，化学气相沉积的时间为48小时，所得产物即硅/多壁碳纳米管复合材料，其中多壁碳纳米管的平均直径为200nm，长度为20μm。Embodiment 7: Take by weighing 0.001g Mo powder and 10g silicon particles (its average particle diameter is 100 μ m), grind for 50 hours, then place the material of gained in a graphite boat, then pack into tube furnace, fill with argon , The chemical vapor deposition process is the same as in Example 1, the chemical vapor deposition time is 48 hours, and the resulting product is a silicon/multi-walled carbon nanotube composite material, wherein the average diameter of the multi-walled carbon nanotubes is 200nm and the length is 20 μm.

如实施例1所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为960mAh/g，1C的可逆容量为780mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 1, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 960mAh/g, and its reversible capacity at 1C is 780mAh/g, showing good kinetic behavior.

实施例8：称取0.001g Fe粉和0.001gMo粉和10g硅颗粒(其平均粒径为5μm)，研磨15分钟，然后将所得的物料放置在一石墨舟中，再装入管式炉中，充入氩气，化学气相沉积过程同实施例1，化学气相沉积的时间为50分钟，所得产物即硅/多壁碳纳米管复合材料，其中多壁碳纳米管的平均直径为15nm，长度为46μm。Embodiment 8: take by weighing 0.001g Fe powder and 0.001g Mo powder and 10g silicon particle (its average particle diameter is 5 μ m), grind 15 minutes, then the material of gained is placed in a graphite boat, then packs in the tube furnace , filled with argon, the chemical vapor deposition process was the same as in Example 1, and the time of chemical vapor deposition was 50 minutes, and the resulting product was a silicon/multi-walled carbon nanotube composite material, wherein the average diameter of the multi-walled carbon nanotubes was 15nm, and the length is 46 μm.

如实施例1所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为890mAh/g，1C的可逆容量为630mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 1, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 890mAh/g, and its reversible capacity at 1C is 630mAh/g, showing good kinetic behavior.

实施例9：称取0.001gFe粉和0.001gMo粉和10g硅颗粒(其平均粒径为5μm)，研磨5小时，然后将所得的物料放置在一石墨舟中，再装入管式炉中，充入氩气，化学气相沉积过程同实施例1，化学气相沉积的时间为2小时，所得产物即硅/多壁碳纳米管复合材料，其中多壁碳纳米管的平均直径为1nm，长度为100μm。Embodiment 9: take by weighing 0.001g Fe powder and 0.001g Mo powder and 10g silicon particle (its average particle diameter is 5 μ m), grind 5 hours, then the material of gained is placed in a graphite boat, then packs in the tube furnace, Charge into argon, the chemical vapor deposition process is the same as embodiment 1, and the time of chemical vapor deposition is 2 hours, and the gained product is the silicon/multi-walled carbon nanotube composite material, wherein the average diameter of the multi-walled carbon nanotube is 1nm, and the length is 100 μm.

如实施例1所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为980mAh/g，1C的可逆容量为780mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 1, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 980mAh/g, and its reversible capacity at 1C is 780mAh/g, showing good kinetic behavior.

实施例10：称取1g Fe粉和1g硅颗粒(其平均粒径为5μm)，研磨5小时，然后将所得的物料放置在一石墨舟中，再装入管式炉中，充入氩气，流量为20sccm，程序升温至500℃后，将气体转换为氢气和一氧化碳的混合气(1∶6，v/v)，总流量为300sccm，恒温50分钟进行化学气相沉积后，自然冷却至室温；即得产物硅/碳纳米纤维复合材料，碳纳米纤维的平均直径为6nm，长度为50μm。Embodiment 10: take by weighing 1g Fe powder and 1g silicon particle (its average particle diameter is 5 μ m), grind 5 hours, then the material of gained is placed in a graphite boat, then packs into tube furnace, fills with argon , the flow rate is 20sccm, after the temperature is programmed to 500°C, the gas is converted into a mixture of hydrogen and carbon monoxide (1:6, v/v), the total flow rate is 300sccm, the chemical vapor deposition is carried out at a constant temperature for 50 minutes, and then naturally cooled to room temperature ; The resulting silicon/carbon nanofiber composite material has an average diameter of 6 nm and a length of 50 μm.

如实施例1所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/碳纳米纤维复合材料作为负极活性材料，其在0.1C的可逆容量为1050mAh/g，1C的可逆容量为780mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 1, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/carbon nanofiber composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 1050mAh/g, and its reversible capacity at 1C is 780mAh/g, showing good kinetic behavior.

实施例11：称取0.001g Fe粉和10g硅颗粒(其平均粒径为5μm)，研磨20小时，然后将所得的物料放置在一石墨舟中，再装入管式炉中，充入氩气，流量为20sccm，充入氩气，程序升温至900℃后，将气体转换为甲烷，流量为100sccm，恒温48小时进行化学气相沉积后，将气体转换为氩气，自然冷却至室温，所得产物即硅/单壁碳纳米管复合材料，其中单壁碳纳米管的平均直径为10.3nm，长度为60μm。Embodiment 11: take by weighing 0.001g Fe powder and 10g silicon particle (its average particle diameter is 5 μ m), grind 20 hours, then the material of gained is placed in a graphite boat, then packs into tube furnace, fills with argon Gas, the flow rate is 20sccm, filled with argon, after the temperature is programmed to 900°C, the gas is converted to methane, the flow rate is 100sccm, after chemical vapor deposition at a constant temperature for 48 hours, the gas is converted to argon, and naturally cooled to room temperature, the obtained The product is a silicon/single-wall carbon nanotube composite material, wherein the average diameter of the single-wall carbon nanotube is 10.3 nm, and the length is 60 μm.

如实施例1所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/单壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为1050mAh/g，1C的可逆容量为860mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 1, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/single-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 1050mAh/g, and its reversible capacity at 1C is 860mAh/g, showing good kinetic behavior.

实施例12：称取0.001g Fe粉和10g硅颗粒(其平均粒径为5μm)，研磨5小时，然后将所得的物料放置在一石墨舟中，再装入管式炉中，充入氩气，流量为20sccm，程序升温至1200℃后，将气体转换为甲烷和氢气的混合气，其比例为3∶2(v/v)，总流量为100sccm，恒温50分钟进行化学气相沉积后，将气体转换为氩气，自然冷却至室温，所得产物即硅/双壁碳纳米管复合材料，其中双壁碳纳米管的平均直径为5.5nm，长度为80μm。Embodiment 12: take by weighing 0.001g Fe powder and 10g silicon particle (its average particle diameter is 5 μm), grind 5 hours, then the material of gained is placed in a graphite boat, then packs into tube furnace, fills with argon Gas, the flow rate is 20 sccm, after the temperature is programmed to 1200 ° C, the gas is converted into a mixed gas of methane and hydrogen, the ratio is 3:2 (v/v), the total flow rate is 100 sccm, and the chemical vapor deposition is carried out at a constant temperature for 50 minutes. The gas is converted into argon, and naturally cooled to room temperature, and the obtained product is a silicon/double-walled carbon nanotube composite material, wherein the average diameter of the double-walled carbon nanotube is 5.5 nm, and the length is 80 μm.

如实施例1所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/双壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为1000mAh/g，1C的可逆容量为800mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 1, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/double-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 1000mAh/g, and its reversible capacity at 1C is 800mAh/g, showing good kinetic behavior.

实施例13：称取0.0001mol Fe(NO₃)₃·9H₂O放入烧杯中，加入1000ml蒸馏水，搅拌溶解；然后再称取0.0001mol柠檬酸三钠和0.0001mol乙酸钠，并加入1000ml的蒸馏水，搅拌溶解；然后将前者滴加到后者中，搅拌，得到被还原的溶液；再称取60g氢氧化钠加入到1000ml蒸馏水中，再称取0.0001mol硼氢化钠加入到上述的碱性溶液，得到还原剂溶液。将20g硅粉(平均粒径为10μm)加入到被还原溶液中搅拌，并升温至95℃，同时开始滴加硼氢化钠溶液，并控制pH＝11，持续搅拌10分钟，分离、干燥；将所得物质放置在一氧化铝舟中，然后装入管式炉，充入氩气，流量为80sccm，程序升温至900℃后，将气体转换为甲烷和氢气的混合气，其比例为5∶20(v/v)，总流量为100sccm，恒温40分钟进行化学气相沉积后，将气体转换为氩气，自然冷却至室温，所得产物即硅/多壁碳纳米管复合材料，其中多壁碳纳米管的平均直径为18nm，长度为75μm。Example 13: Weigh 0.0001mol Fe(NO₃ )₃ 9H₂ O into a beaker, add 1000ml of distilled water, stir to dissolve; then weigh 0.0001mol of trisodium citrate and 0.0001mol of sodium acetate, and add 1000ml of Distilled water, stir to dissolve; then add the former dropwise to the latter, stir to obtain the reduced solution; then weigh 60g sodium hydroxide and add it to 1000ml distilled water, then weigh 0.0001mol sodium borohydride and add it to the above-mentioned alkaline solution to obtain a reducing agent solution. Add 20g of silicon powder (with an average particle size of 10 μm) into the reduced solution and stir, and raise the temperature to 95°C. At the same time, start to add sodium borohydride solution dropwise, and control the pH=11, keep stirring for 10 minutes, separate and dry; The resulting substance was placed in an alumina boat, then loaded into a tube furnace, filled with argon, with a flow rate of 80 sccm, and after the temperature was programmed to 900 ° C, the gas was converted into a mixture of methane and hydrogen, the ratio of which was 5:20 (v/v), the total flow rate is 100 sccm, after chemical vapor deposition at a constant temperature for 40 minutes, the gas is converted into argon, and naturally cooled to room temperature. The resulting product is a silicon/multi-walled carbon nanotube composite material, in which The tubes have an average diameter of 18 nm and a length of 75 μm.

如实施例1所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为970mAh/g，1C的可逆容量为770mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 1, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as the negative electrode active material, and its reversible capacity at 0.1C is 970mAh/g, and the reversible capacity at 1C is 770mAh/g, showing good kinetic behavior.

实施例14：称取0.01mol Fe(NO₃)₃·9H₂O放入烧杯中，加入10ml蒸馏水，搅拌溶解；然后再称取0.01mol柠檬酸三钠和0.01mol乙酸钠，并加入10ml的蒸馏水，搅拌溶解；然后将前者滴加到后者中，搅拌，得到被还原的溶液；再称取6g氢氧化钠加入到10ml蒸馏水中，再称取0.01mol硼氢化钠加入到上述的碱性溶液，得到还原剂溶液。将0.5g硅粉(平均粒径为10μm)加入到被还原溶液中搅拌，并升温至70℃，同时开始滴加硼氢化钠溶液，并控制pH＝8，持续搅拌2小时，分离、干燥；将所得物质放置在一氧化铝舟中，然后装入管式炉，充入氩气，流量为80sccm，程序升温至900℃后，将气体转换为氢气和一氧化碳的混合气(1∶6，v/v)，总流量为100sccm，恒温40分钟进行化学气相沉积后，自然冷却至室温，即得产物硅/碳纳米纤维复合材料，碳纳米纤维的平均直径为12nm，长度为35μm。Example 14: Weigh 0.01mol Fe(NO₃ )₃ 9H₂ O into a beaker, add 10ml of distilled water, stir to dissolve; then weigh 0.01mol of trisodium citrate and 0.01mol of sodium acetate, and add 10ml of Distilled water, stir to dissolve; then add the former dropwise to the latter, stir to obtain the reduced solution; then weigh 6g sodium hydroxide and add it to 10ml distilled water, then weigh 0.01mol sodium borohydride and add it to the above alkaline solution to obtain a reducing agent solution. Add 0.5g of silicon powder (with an average particle size of 10 μm) into the reduced solution, stir, and raise the temperature to 70°C. At the same time, start to add sodium borohydride solution dropwise, and control the pH=8, keep stirring for 2 hours, separate and dry; The resulting substance is placed in an alumina boat, then loaded into a tube furnace, filled with argon, the flow rate is 80sccm, and after the temperature is programmed to 900°C, the gas is converted into a mixture of hydrogen and carbon monoxide (1:6, v /v), the total flow rate is 100 sccm, after chemical vapor deposition at constant temperature for 40 minutes, it is naturally cooled to room temperature to obtain the product silicon/carbon nanofiber composite material, the average diameter of carbon nanofibers is 12nm, and the length is 35 μm.

如实施例1所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/碳纳米纤维复合材料作为负极活性材料，其在0.1C的可逆容量为930mAh/g，1C的可逆容量为770mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 1, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/carbon nanofiber composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 930mAh/g, and its reversible capacity at 1C is 770mAh/g, showing good kinetic behavior.

实施例15：称取0.001mol Fe(NO₃)₃·9H₂O放入烧杯中，加入100ml乙醇，搅拌溶解；然后再称取0.001mol柠檬酸三钠和0.001mol乙酸钠，并加入100ml的乙醇，搅拌溶解；然后将前者滴加到后者中，搅拌，得到被还原的溶液；再称取6g氢氧化钠加入到20ml乙二醇中，再称取0.01mol硼氢化钠加入到上述的碱性溶液，得到还原剂溶液。将2g硅粉(平均粒径为10μm)加入到被还原溶液中搅拌，并升温至70℃，同时开始滴加硼氢化钠溶液，并控制pH＝4，持续搅拌2小时，分离、干燥；将所得物质放置在一氧化铝舟中，然后装入管式炉，充入氩气，流量为80sccm，程序升温至700℃后，将气体转换为甲烷，流量为100sccm，恒温20分钟进行化学气相沉积后，将气体转换为氩气，自然冷却至室温，所得产物即硅/单壁碳纳米管复合材料，其中单壁碳纳米管的平均直径为5nm，长度为50nm。Example 15: Weigh 0.001mol Fe(NO₃ )₃ 9H₂ O into a beaker, add 100ml of ethanol, stir to dissolve; then weigh 0.001mol of trisodium citrate and 0.001mol of sodium acetate, and add 100ml of Ethanol, stir to dissolve; then add the former dropwise to the latter, stir to obtain the reduced solution; then weigh 6g of sodium hydroxide and add it to 20ml of ethylene glycol, then weigh 0.01mol of sodium borohydride and add it to the above alkaline solution to obtain a reducing agent solution. Add 2g of silicon powder (with an average particle size of 10 μm) into the reduced solution and stir, and raise the temperature to 70°C. At the same time, start to add sodium borohydride solution dropwise, and control the pH=4, keep stirring for 2 hours, separate and dry; The resulting substance was placed in an alumina boat, then loaded into a tube furnace, filled with argon, with a flow rate of 80 sccm, and after the temperature was programmed to 700°C, the gas was converted into methane with a flow rate of 100 sccm, and the chemical vapor deposition was carried out at a constant temperature for 20 minutes Afterwards, the gas was changed to argon, and naturally cooled to room temperature, and the obtained product was a silicon/single-walled carbon nanotube composite material, wherein the average diameter of the single-walled carbon nanotubes was 5 nm, and the length was 50 nm.

如实施例1所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/单壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为900mAh/g，1C的可逆容量为750mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 1, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/single-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 900mAh/g, and its reversible capacity at 1C is 750mAh/g, showing good kinetic behavior.

实施例16：称取0.01mol Fe(NO₃)₃·9H₂O放入烧杯中，加入100ml蒸馏水，搅拌溶解；然后再称取0.2mol柠檬酸三钠和0.5mol乙酸钠，并加入50ml的蒸馏水，搅拌溶解；然后将前者滴加到后者中，搅拌，得到被还原的溶液；再称取6g氢氧化钠加入到40ml蒸馏水中，再称取0.05mol硼氢化钠加入到上述的碱性溶液，得到还原剂溶液。将2g硅粉(平均粒径为10μm)加入到被还原溶液中搅拌，并升温至70℃，同时开始滴加硼氢化钠溶液，并控制pH＝12，持续搅拌10分钟，分离、干燥；将所得物质放置在一氧化铝舟中，然后装入管式炉，充入氩气，流量为80sccm，程序升温至900℃后，将气体转换为甲烷和氢气的混合气，其比例为3∶2(v/v)，总流量为100sccm，恒温40分钟进行化学气相沉积后，将气体转换为氩气，自然冷却至室温，所得产物即硅/双壁碳纳米管复合材料，其中双壁碳纳米管的平均直径为3.5nm，长度为800nm。Example 16: Weigh 0.01mol Fe(NO₃ )₃ 9H₂ O into a beaker, add 100ml of distilled water, stir to dissolve; then weigh 0.2mol of trisodium citrate and 0.5mol of sodium acetate, and add 50ml of Distilled water, stir to dissolve; then add the former dropwise to the latter, stir to obtain the reduced solution; then weigh 6g sodium hydroxide and add it to 40ml distilled water, then weigh 0.05mol sodium borohydride and add it to the above-mentioned alkaline solution to obtain a reducing agent solution. Add 2g of silicon powder (with an average particle size of 10 μm) into the reduced solution and stir, and raise the temperature to 70°C. At the same time, start to add sodium borohydride solution dropwise, and control the pH=12, keep stirring for 10 minutes, separate and dry; The resulting substance was placed in an alumina boat, then loaded into a tube furnace, filled with argon, with a flow rate of 80 sccm, and after the temperature was programmed to 900 ° C, the gas was converted into a mixture of methane and hydrogen, the ratio of which was 3:2 (v/v), the total flow rate is 100 sccm, after chemical vapor deposition at a constant temperature for 40 minutes, the gas is converted into argon, and naturally cooled to room temperature, the resulting product is a silicon/double-walled carbon nanotube composite material, wherein the double-walled carbon The tubes have an average diameter of 3.5 nm and a length of 800 nm.

如实施例1所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/双壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为970mAh/g，1C的可逆容量为800mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 1, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/double-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 970mAh/g, and its reversible capacity at 1C is 800mAh/g, showing good kinetic behavior.

实施例17：称取0.01mol Co(NO₃)₂·6H₂O放入烧杯中，加入100ml甲醇，搅拌溶解；然后再称取0.2mol柠檬酸三钠和0.5mol乙酸钠，并加入50ml异丙醇，搅拌溶解；然后将前者滴加到后者中，搅拌，得到被还原的溶液；再称取6g氢氧化钠加入到20ml蒸馏水中，再称取0.01mol硼氢化钠加入到上述的碱性溶液，得到还原剂溶液。将2g硅粉(平均粒径为10μm)加入到被还原溶液中搅拌，并升温至75℃，同时开始滴加硼氢化钠溶液，并控制pH＝10，持续搅拌30分钟，分离、干燥；将所得物质放置在一氧化铝舟中，然后装入管式炉，充入氩气，流量为80sccm，程序升温至900℃后，将气体转换为甲烷和氢气的混合气，其比例为3∶2(v/v)，总流量为100sccm，恒温40分钟进行化学气相沉积后，将气体转换为氩气，自然冷却至室温，所得产物即硅/双壁碳纳米管复合材料，其中双壁碳纳米管的平均直径为6.5nm，长度为120μm。Example 17: Weigh 0.01mol Co(NO₃ )₂ ·6H₂ O into a beaker, add 100ml methanol, stir to dissolve; then weigh 0.2mol trisodium citrate and 0.5mol sodium acetate, and add 50ml iso propanol, stirring and dissolving; then add the former dropwise to the latter, stirring to obtain the reduced solution; then weigh 6g sodium hydroxide and add it to 20ml distilled water, then weigh 0.01mol sodium borohydride and add it to the above alkali neutral solution to obtain a reducing agent solution. Add 2g of silicon powder (average particle size of 10 μm) into the reduced solution and stir, and raise the temperature to 75°C, at the same time start to add sodium borohydride solution dropwise, and control the pH=10, keep stirring for 30 minutes, separate and dry; The resulting substance was placed in an alumina boat, then loaded into a tube furnace, filled with argon, with a flow rate of 80 sccm, and after the temperature was programmed to 900 ° C, the gas was converted into a mixture of methane and hydrogen, the ratio of which was 3:2 (v/v), the total flow rate is 100 sccm, after chemical vapor deposition at a constant temperature for 40 minutes, the gas is converted into argon, and naturally cooled to room temperature, the resulting product is a silicon/double-walled carbon nanotube composite material, wherein the double-walled carbon The tubes have an average diameter of 6.5 nm and a length of 120 μm.

如实施例1所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/双壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为970mAh/g，1C的可逆容量为790mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 1, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/double-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 970mAh/g, and its reversible capacity at 1C is 790mAh/g, showing good kinetic behavior.

实施例18：称取0.01mol Ni(NO₃)₂·6H₂O放入烧杯中，加入100ml甲醇，搅拌溶解；然后再称取0.2mol柠檬酸三钠和0.5mol乙酸钠，并加入50ml甲醇，搅拌溶解；然后将前者滴加到后者中，搅拌，得到被还原的溶液；再称取6g氢氧化钠加入到20ml甲醇中，再称取0.01mol硼氢化钠加入到上述的碱性溶液，得到还原剂溶液。将2g硅粉(平均粒径为10μm)加入到被还原溶液中搅拌，并保持其与室温相等为25℃，同时开始滴加硼氢化钠溶液，并控制pH＝9，持续搅拌30分钟，分离、干燥；将所得物质放置在一氧化铝舟中，然后装入管式炉，充入氩气，流量为80sccm，程序升温至1200℃后，将气体转换为甲烷和氢气的混合气，其比例为3∶2(v/v)，总流量为100sccm，恒温48小时进行化学气相沉积后，将气体转换为氩气，自然冷却至室温，所得产物即硅/双壁碳纳米管复合材料，其中双壁碳纳米管的平均直径为5nm，长度为160μm。Example 18: Weigh 0.01mol Ni(NO₃ )₂ ·6H₂ O into a beaker, add 100ml methanol, stir to dissolve; then weigh 0.2mol trisodium citrate and 0.5mol sodium acetate, and add 50ml methanol , stir to dissolve; then add the former dropwise to the latter, stir to obtain the reduced solution; then weigh 6g of sodium hydroxide and add it to 20ml of methanol, then weigh 0.01mol of sodium borohydride and add it to the above alkaline solution , to obtain a reducing agent solution. Add 2g of silicon powder (average particle size 10μm) into the reduced solution and stir, and keep it equal to room temperature at 25°C, and at the same time start to add sodium borohydride solution dropwise, and control the pH=9, keep stirring for 30 minutes, separate , drying; the resulting substance is placed in an alumina boat, then loaded into a tube furnace, filled with argon, the flow rate is 80sccm, after the temperature is programmed to 1200 ° C, the gas is converted into a mixture of methane and hydrogen, the ratio It is 3:2 (v/v), the total flow rate is 100 sccm, after chemical vapor deposition at constant temperature for 48 hours, the gas is converted into argon, and naturally cooled to room temperature, the resulting product is silicon/double-walled carbon nanotube composite material, wherein Double-walled carbon nanotubes have an average diameter of 5 nm and a length of 160 μm.

如实施例1所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/双壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为1000mAh/g，1C的可逆容量为900mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 1, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/double-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 1000mAh/g, and its reversible capacity at 1C is 900mAh/g, showing good kinetic behavior.

实施例19：称取0.001mol Co(NO₃)₂·6H₂O和0.000015mol(NH₄)₆Mo₇O₂₄·4H₂O，于烧杯中，加入100ml乙醇，搅拌溶解，然后加入1g硅粉，其平均粒径为10μm，搅拌2小时，静置约72小时后，分离、干燥；将所得物质放置在一石墨舟中，然后装入管式炉，充入氩气和氢气的混合气(200∶5，v/v)，总流量为300sccm，程序升温至500℃后，将气体转换为氢气和一氧化碳的混合气(1∶4，v/v)，总流量为300sccm，恒温20分钟进行化学气相沉积后，自然冷却至室温；即得产物硅/碳纳米纤维复合材料，碳纳米纤维的平均直径为10nm，长度为20μm。Example 19: Weigh 0.001mol Co(NO₃ )₂ ·6H₂ O and 0.000015mol (NH₄ )₆ Mo₇ O₂₄ ·4H₂ O into a beaker, add 100ml of ethanol, stir to dissolve, and then add 1g of silicon powder with an average particle size of 10 μm, stirred for 2 hours, left to stand for about 72 hours, then separated and dried; the obtained material was placed in a graphite boat, and then loaded into a tube furnace, filled with a mixture of argon and hydrogen (200:5, v/v), the total flow is 300sccm, after the temperature is programmed to 500°C, the gas is converted into a mixture of hydrogen and carbon monoxide (1:4, v/v), the total flow is 300sccm, and the temperature is kept constant for 20 minutes After chemical vapor deposition, it was naturally cooled to room temperature; the resulting silicon/carbon nanofiber composite material had an average diameter of 10 nm and a length of 20 μm.

将所述的材料作为锂离子电池的负极材料使用。负极的制备方法如实施例1。Said material is used as negative electrode material of lithium ion battery. The preparation method of the negative electrode is as in Example 1.

将商品正极材料LiFePO₄与乙炔黑和10％聚偏氟乙烯(PVDF)的环己烷溶液在常温常压下混合形成浆料(活性材料∶乙炔黑∶PVDF＝75∶15∶10)，均匀涂敷于铝箔衬底上，所得的薄膜厚度约20～60μm，作为电池的正极。电解液为1mol LiPF₆溶于1L EC和DMC的混合溶剂中(体积比1∶1)。将所有电池材料，包括正极，负极，电池壳，隔膜，干燥后在充氩手套箱中或干燥间中添加电解液组装成实验电池。The commercial cathode material LiFePO₄ was mixed with acetylene black and 10% polyvinylidene fluoride (PVDF) cyclohexane solution at normal temperature and pressure to form a slurry (active material: acetylene black: PVDF = 75:15:10), uniform Coated on the aluminum foil substrate, the thickness of the obtained film is about 20-60 μm, and it is used as the positive electrode of the battery. The electrolyte solution is 1mol LiPF₆ dissolved in 1L EC and DMC mixed solvent (volume ratio 1:1). All battery materials, including positive electrode, negative electrode, battery case, and diaphragm, were dried and then added electrolyte in an argon-filled glove box or a drying room to assemble an experimental battery.

实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/碳纳米纤维复合材料作为负极活性材料，其在0.1C的可逆容量为550mAh/g，1C的可逆容量为300mAh/g，显示了较好的动力学行为。The experimental battery is subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/carbon nanofiber composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 550mAh/g, and its reversible capacity at 1C is 300mAh/g, showing good kinetic behavior.

实施例20：称取0.003mol Co(NO₃)₂·6H₂O和0.000045mol(NH₄)₆Mo₇O₂₄·4H₂O，于烧杯中，加入100ml乙醇中，搅拌溶解，然后加入1g硅颗粒，其平均粒径为20μm，搅拌30分钟，静置约24小时后，分离、干燥；化学气相沉积过程同实施例19，化学气相沉积的时间为2h，所得产物即硅/碳纳米纤维复合材料，纳米碳纤维的平均直径为50nm，长度为100μm。Example 20: Weigh 0.003mol Co(NO₃ )₂ ·6H₂ O and 0.000045mol (NH₄ )₆ Mo₇ O₂₄ ·4H₂ O into a beaker, add to 100ml ethanol, stir to dissolve, then add 1g Silicon particles, whose average particle size is 20 μm, are stirred for 30 minutes, left to stand for about 24 hours, separated and dried; the chemical vapor deposition process is the same as in Example 19, and the chemical vapor deposition time is 2h, and the resulting product is silicon/carbon nanofibers Composite material, the average diameter of carbon nanofibers is 50nm, and the length is 100μm.

如实施例19所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/碳纳米纤维复合材料作为负极活性材料，其在0.1C的可逆容量为920mAh/g，1C的可逆容量为750mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 19, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/carbon nanofiber composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 920mAh/g, and its reversible capacity at 1C is 750mAh/g, showing good kinetic behavior.

实施例21：称取0.012mol Co(NO₃)₂·6H₂O和0.00018mol(NH₄)₆Mo₇O₂₄·4H₂O，于烧杯中，加入120ml乙醇，搅拌溶解，然后加入1g硅颗粒，其平均粒径为1cm，搅拌1小时，静置约72小时后，分离、干燥；化学气相沉积过程同实施例19，其中氢气和一氧化碳混合气的总流量为500sccm，化学气相沉积的时间为2小时，所得产物即硅/碳纳米纤维复合材料，纳米碳纤维的平均直径为200nm，长度为100μm。Example 21: Weigh 0.012mol Co(NO₃ )₂ ·6H₂ O and 0.00018mol (NH₄ )₆ Mo₇ O₂₄ ·4H₂ O into a beaker, add 120ml of ethanol, stir to dissolve, and then add 1g of silicon Particles, whose average particle size is 1cm, stirred for 1 hour, left to stand for about 72 hours, separated and dried; the chemical vapor deposition process is the same as in Example 19, wherein the total flow of hydrogen and carbon monoxide mixed gas is 500 sccm, the time of chemical vapor deposition After 2 hours, the obtained product is silicon/carbon nanofiber composite material, the average diameter of carbon nanofibers is 200 nm, and the length is 100 μm.

称取实施例21所得硅/双壁碳纳米管复合材料0.5g，加入溶解有0.2g K₂PtCl₆的200ml乙二醇溶液中，充分搅拌1小时后，于160℃在氩气保护下回流约6小时，自然冷却至室温后，将产物以乙醇反复冲洗，所得产物即硅/双壁碳纳米管复合材料负载纳米Pt，Pt负载量为14.5wt.％，Pt高度分散于其表面，其平均直径为4.9nm。将上述溶液中K₂PtCl₆的含量提高到0.8g，则硅/多壁碳纳米管复合材料表面的Pt负载量可达到18wt.％，Pt的平均直径为6.9nm，用于质子交换摸燃料电池中，其催化活性是美国ETEK公司所生产的Pt/Vulcan XC-72催化剂(负载量为60wt.％)的0.35倍；用于二甲醚燃料电池中，其催化活性是美国ETEK公司所生产的Pt/Vulcan XC-72催化剂(负载量为60wt.％)的0.6倍。。Weigh 0.5 g of the silicon/double-walled carbon nanotube composite material obtained in Example 21, add 0.2 g K₂ PtCl₆ into 200 ml of ethylene glycol solution, stir thoroughly for 1 hour, and then reflux at 160° C. under the protection of argon About 6 hours, after naturally cooling to room temperature, the product was repeatedly washed with ethanol, and the resulting product was a silicon/double-walled carbon nanotube composite material loaded with nano-Pt, with a Pt loading of 14.5wt.%, and Pt was highly dispersed on its surface. The average diameter is 4.9 nm. Increase the content of K₂ PtCl₆ in the above solution to 0.8g, then the Pt load on the surface of the silicon/multi-walled carbon nanotube composite material can reach 18wt.%, and the average diameter of Pt is 6.9nm, which is used for proton exchange and fuel In the battery, its catalytic activity is 0.35 times that of the Pt/Vulcan XC-72 catalyst (loading capacity is 60wt.%) produced by the American ETEK company; when used in a dimethyl ether fuel cell, its catalytic activity is 0.35 times that of the American ETEK company produced 0.6 times that of the Pt/Vulcan XC-72 catalyst (loading capacity is 60wt.%). .

实施例22：称取0.01786mol FeSO₄·7H₂O于烧杯中，加入178.6ml甲醇，搅拌溶解，然后加入1g硅颗粒，其平均粒径为1μm，搅拌30min，静置约24小时后，分离、干燥；将所得干燥料放置在三氧化二铝舟中，然后装入管式炉中，充入氩气，流量为100sccm，程序升温至1000℃后，将气体转换为甲烷，流量为100sccm，恒温48小时进行化学气相沉积后，将气体转换为氩气，自然冷却至室温，所得产物即硅/单壁碳纳米管复合材料，其中单壁碳纳米管的平均直径为1nm，长度为100μm。Example 22: Weigh 0.01786mol FeSO₄ 7H₂ O into a beaker, add 178.6ml of methanol, stir to dissolve, then add 1g of silicon particles with an average particle size of 1 μm, stir for 30min, and after standing for about 24 hours, separate , drying; the resulting dried material is placed in an aluminum oxide boat, then packed into a tube furnace, filled with argon, and the flow rate is 100 sccm, after the program is heated to 1000 ° C, the gas is converted into methane, and the flow rate is 100 sccm, After chemical vapor deposition at a constant temperature for 48 hours, the gas was changed to argon and cooled to room temperature naturally. The resulting product was a silicon/single-walled carbon nanotube composite material, wherein the average diameter of the single-walled carbon nanotubes was 1 nm and the length was 100 μm.

将实施例22的硅/单壁碳纳米管复合材料与导电乙炔黑、聚偏氟乙烯以质量比85∶5∶10混合并压制到泡沫镍上制备成电极，以6M KOH为电解液，在0.9V时，获得最大比电容量为110F/g，功率密度为12kW/g，能量密度为4.3Wh/g，表现出良好的电双层特性，是一种非常有潜力的超级电容器材料。The silicon/single-walled carbon nanotube composite material of Example 22 was mixed with conductive acetylene black and polyvinylidene fluoride at a mass ratio of 85:5:10 and pressed onto nickel foam to prepare an electrode, with 6M KOH as the electrolyte, in At 0.9V, the maximum specific capacitance is 110F/g, the power density is 12kW/g, and the energy density is 4.3Wh/g. It shows good electric double layer characteristics and is a very potential supercapacitor material.

实施例23：称取0.01786mol FeSO₄·7H₂O于烧杯中，加入1786ml乙二醇，搅拌溶解，然后加入1000g硅颗粒，其平均粒径为1μm，搅拌20h，静置约24小时后，分离、干燥；化学气相沉积过程同实施例22，化学气相沉积的时间为1小时，所得产物即硅/单壁碳纳米管复合材料，其中单壁碳纳米管的平均直径为1.2nm，长度为80nm。Example 23: Weigh 0.01786mol FeSO₄ ·7H₂ O into a beaker, add 1786ml of ethylene glycol, stir to dissolve, then add 1000g of silicon particles with an average particle size of 1 μm, stir for 20h, and let it stand for about 24 hours, Separation and drying; the chemical vapor deposition process is the same as in Example 22, the time of chemical vapor deposition is 1 hour, and the resulting product is a silicon/single-walled carbon nanotube composite material, wherein the average diameter of the single-walled carbon nanotubes is 1.2nm, and the length is 80nm.

称取实施例23所得硅/双壁碳纳米管复合材料0.5g，加入溶解有0.2g K₂PtCl₆的200ml乙二醇溶液中，充分搅拌1小时后，于160℃在氩气保护下回流约6小时，自然冷却至室温后，将产物以乙醇反复冲洗，所得产物即硅/双壁碳纳米管复合材料负载纳米Pt，Pt负载量为6wt.％，Pt高度分散于其表面，其平均直径为5.6nm。将上述溶液中K₂PtCl₆的含量提高到0.8g，则硅/多壁碳纳米管复合材料表面的Pt负载量可达到24wt.％，Pt的平均直径为8.6nm，用于质子交换摸燃料电池中，其催化活性是美国ETEK公司所生产的Pt/Vulcan XC-72催化剂(负载量为60wt.％)的0.75倍。Weigh 0.5 g of the silicon/double-walled carbon nanotube composite material obtained in Example 23, add it into 200 ml of ethylene glycol solution in which 0.2 g K₂ PtCl₆ is dissolved, stir thoroughly for 1 hour, and then reflux at 160° C. under the protection of argon After about 6 hours, after naturally cooling to room temperature, the product was repeatedly washed with ethanol, and the resulting product was silicon/double-walled carbon nanotube composite material loaded with nano-Pt, and the Pt loading was 6wt.%, and Pt was highly dispersed on its surface, and its average The diameter is 5.6nm. Increase the content of K₂ PtCl₆ in the above solution to 0.8g, then the Pt load on the surface of the silicon/multi-walled carbon nanotube composite can reach 24wt.%, and the average diameter of Pt is 8.6nm, which is used for proton exchange and fuel In the battery, its catalytic activity is 0.75 times that of the Pt/Vulcan XC-72 catalyst (loaded at 60wt.%) produced by ETEK, USA.

实施例24：称取0.00027mol FeCl₃·6H₂O和0.00025mol Co(CH₃COO)₂·4H₂O于烧杯中，加入60ml乙醇，搅拌溶解，然后加入1g硅颗粒，其平均粒径为1μm，搅拌2小时，静置约72小时后，分离、干燥；将所得干燥料放置在一石墨舟中，然后装入管式炉中，充入氩气，流量为100sccm，程序升温至1200℃后，将气体转换为甲烷和氢气的混合气，其比例为3∶2(v/v)，总流量为100sccm，恒温30分钟进行化学气相沉积后，将气体转换为氩气，自然冷却至室温，所得产物即硅/双壁碳纳米管复合材料，其中双壁碳纳米管的平均直径为2.5nm，长度为60μm。Example 24: Weigh 0.00027mol FeCl₃ ·6H₂ O and 0.00025mol Co(CH₃ COO)₂ ·4H₂ O into a beaker, add 60ml of ethanol, stir to dissolve, then add 1g of silicon particles, the average particle size is 1 μm, stirred for 2 hours, after standing for about 72 hours, separated and dried; the obtained dry material was placed in a graphite boat, then put into a tube furnace, filled with argon, the flow rate was 100sccm, and the temperature was raised to 1200°C Finally, the gas is converted into a mixture of methane and hydrogen, the ratio of which is 3:2 (v/v), the total flow rate is 100 sccm, after chemical vapor deposition at a constant temperature for 30 minutes, the gas is converted into argon, and naturally cooled to room temperature , the resulting product is silicon/double-walled carbon nanotube composite material, wherein the average diameter of double-walled carbon nanotubes is 2.5 nm, and the length is 60 μm.

如实施例19所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/双壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为970mAh/g，1C的可逆容量为860mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 19, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/double-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 970mAh/g, and its reversible capacity at 1C is 860mAh/g, showing good kinetic behavior.

实施例25：称取0.00054mol FeCl₃·6H₂O和0.0005mol Co(CH₃COO)₂·4H₂O于烧杯中，加入120ml乙醇，搅拌溶解，然后加入1g硅颗粒，其平均粒径为5μm，搅拌2小时，静置约72小时后，分离、干燥；化学气相沉积过程同实施例24，化学气相沉积的时间为1小时，所得产物即硅/双壁碳纳米管复合材料，其中双壁碳纳米管的平均直径为6nm，长度为100μm。Example 25: Weigh 0.00054mol FeCl₃ ·6H₂ O and 0.0005mol Co(CH₃ COO)₂ ·4H₂ O into a beaker, add 120ml of ethanol, stir to dissolve, then add 1g of silicon particles, the average particle size is 5 μm, stirred for 2 hours, left to stand for about 72 hours, separated and dried; the chemical vapor deposition process was the same as in Example 24, and the chemical vapor deposition time was 1 hour, and the resulting product was a silicon/double-walled carbon nanotube composite material, wherein the double-walled carbon nanotube The walled carbon nanotubes have an average diameter of 6 nm and a length of 100 μm.

称取实施例25所得硅/双壁碳纳米管复合材料0.5g，加入溶解有0.2g K₂PtCl₆的200ml乙二醇溶液中，充分搅拌1小时后，于160℃在氩气保护下回流约6小时，自然冷却至室温后，将产物以乙醇反复冲洗，所得产物即硅/双壁碳纳米管复合材料负载纳米Pt，Pt负载量为12wt.％，Pt高度分散于其表面，其平均直径为6.7nm。将上述溶液中K₂PtCl₆的含量提高到0.8g，则硅/多壁碳纳米管复合材料表面的Pt负载量可达到22wt.％，Pt的平均直径为7.2nm，用于质子交换摸燃料电池中，其催化活性是美国ETEK公司所生产的Pt/Vulcan XC-72催化剂(负载量为60wt.％)的0.2倍。Weigh 0.5 g of the silicon/double-walled carbon nanotube composite material obtained in Example 25, add it into 200 ml of ethylene glycol solution in which 0.2 g K₂ PtCl₆ is dissolved, stir thoroughly for 1 hour, and then reflux at 160° C. under the protection of argon About 6 hours, after naturally cooling to room temperature, the product was washed repeatedly with ethanol, and the resulting product was silicon/double-walled carbon nanotube composite material loaded with nano-Pt, and the Pt loading was 12wt.%, and Pt was highly dispersed on its surface, and its average The diameter is 6.7nm. Increase the content of K₂ PtCl₆ in the above solution to 0.8g, then the Pt load on the surface of the silicon/multi-walled carbon nanotube composite can reach 22wt.%, and the average diameter of Pt is 7.2nm, which is used for proton exchange and fuel In the battery, its catalytic activity is 0.2 times that of the Pt/Vulcan XC-72 catalyst (loading capacity: 60wt.%) produced by the American ETEK company.

实施例26：称取0.0009mol Ni(NO₃)₂·6H₂O于烧杯中，加入100ml甲醇，搅拌溶解，然后加入1g硅颗粒，其平均粒径为20μm，搅拌30分钟，静置约48小时后，分离、干燥；将所得干燥料放置在一石墨舟中，然后装入管式炉中，抽真空后，充入氩气和氢气的混合气，其比例为92∶8(v/v)，总流量为100sccm，程序升温至400℃温度后，将气体转换为氨气，流量为50sccm，恒温20分钟进行预处理后，将气体转换为乙炔，流量为20sccm，在相同温度下恒温20分钟进行化学气相沉积后，将气体转换为氩气，自然冷却至室温，所得产物即新型碳绒球材料，为硅/多壁碳纳米管复合材料，其中碳纳米管定向生长在硅表面，其平均直径为50nm，长度为50μm。Example 26: Weigh 0.0009mol Ni(NO₃ )₂ ·6H₂ O into a beaker, add 100ml of methanol, stir to dissolve, then add 1g of silicon particles with an average particle size of 20μm, stir for 30 minutes, and let stand for about 48 Hours later, separate and dry; the resulting dried material is placed in a graphite boat, then packed into a tube furnace, and after vacuuming, it is filled with a mixture of argon and hydrogen in a ratio of 92:8 (v/v ), the total flow rate is 100sccm, after the temperature is programmed to 400°C, the gas is converted to ammonia with a flow rate of 50sccm, and after pretreatment at a constant temperature for 20 minutes, the gas is converted to acetylene with a flow rate of 20sccm and kept at the same temperature for 20sccm After chemical vapor deposition in minutes, the gas is converted into argon, and cooled naturally to room temperature. The resulting product is a new type of carbon pompom material, which is a silicon/multi-walled carbon nanotube composite material, in which carbon nanotubes grow oriented on the silicon surface. The average diameter is 50 nm and the length is 50 μm.

如实施例19所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为940mAh/g，1C的可逆容量为840mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 19, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 940mAh/g, and its reversible capacity at 1C is 840mAh/g, showing good kinetic behavior.

实施例27：称取0.0004mol Ni(NO₃)₂·6H₂O于烧杯中，加入50ml甲醇，搅拌溶解，然后加入1g硅颗粒，其平均粒径为20μm，搅拌30分钟，静置约48小时后，分离、干燥；化学气相沉积过程同实施例26，化学气相沉积的时间为1小时，所得产物即硅/多壁碳纳米管复合材料，其中碳纳米管定向生长在硅表面，其平均直径为20nm，长度为100μm。Example 27: Weigh 0.0004mol Ni(NO₃ )₂ ·6H₂ O into a beaker, add 50ml of methanol, stir to dissolve, then add 1g of silicon particles with an average particle size of 20μm, stir for 30 minutes, and let stand for about 48 After one hour, separate and dry; the chemical vapor deposition process is the same as in Example 26, and the chemical vapor deposition time is 1 hour, and the resulting product is a silicon/multi-walled carbon nanotube composite material, wherein the carbon nanotubes grow oriented on the silicon surface, and the average The diameter is 20nm and the length is 100μm.

如实施例19所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为990mAh/g，1C的可逆容量为880mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 19, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as the negative electrode active material, and its reversible capacity at 0.1C is 990mAh/g, and its reversible capacity at 1C is 880mAh/g, showing good kinetic behavior.

实施例28：称取0.001mol Fe(NO₃)₃·9H₂O于烧杯中，加入100ml异丙醇，搅拌溶解，然后加入1g硅颗粒，其平均粒径为2μm，搅拌30分钟，静置约72小时后，分离、干燥；将所得干燥料放置在一石墨舟中，然后装入管式炉中，充入氩气和氢气的混合气，其比例为200∶28(v/v)，总流量为100sccm，程序升温至500℃后，将气体转换为氩气和乙炔的混合气，其比例为100∶9(v/v)，总流量为190sccm，恒温50分钟进行化学气相沉积后，自然冷却至室温，所得产物即硅/多壁碳纳米管复合材料，其中多壁碳纳米管在硅表面为非定向生长，其平均直径为50nm，长度为20μm。Example 28: Weigh 0.001mol Fe(NO₃ )₃ 9H₂ O into a beaker, add 100ml of isopropanol, stir to dissolve, then add 1g of silicon particles with an average particle size of 2μm, stir for 30 minutes, and let stand After about 72 hours, separate and dry; the resulting dry material is placed in a graphite boat, then loaded into a tube furnace, filled with a mixture of argon and hydrogen, the ratio of which is 200:28 (v/v), The total flow rate is 100sccm, after the temperature is programmed to 500°C, the gas is converted into a mixture of argon and acetylene, the ratio is 100:9 (v/v), the total flow rate is 190sccm, and the chemical vapor deposition is carried out at a constant temperature for 50 minutes. Naturally cooled to room temperature, the resulting product is a silicon/multi-walled carbon nanotube composite material, wherein the multi-walled carbon nanotubes grow non-directionally on the silicon surface, with an average diameter of 50 nm and a length of 20 μm.

称取实施例28所得硅/多壁碳纳米管复合材料0.5g，加入溶解有0.2g K₂PtCl₆的200ml乙二醇溶液中，充分搅拌1小时后，于160℃在氩气保护下回流约6小时，自然冷却至室温后，将产物以乙醇反复冲洗，所得产物即硅/多壁碳纳米管复合材料负载纳米Pt，Pt负载量为12wt.％，Pt高度分散于其表面，其平均直径为3.5nm。将上述溶液中K₂PtCl₆的含量提高到0.8g，则硅/多壁碳纳米管复合材料表面的Pt负载量可达到25wt.％，Pt的平均直径为3.7nm，用于直接甲醇燃料电池中，其对甲醇电化学氧化的催化活性与美国ETEK公司所生产的Pt/Vulcan XC-72催化剂(负载量为60wt.％)相当。Weigh 0.5 g of the silicon/multi-walled carbon nanotube composite material obtained in Example 28, add 0.2 g K₂ PtCl₆ into 200 ml of ethylene glycol solution, stir thoroughly for 1 hour, and then reflux at 160° C. under the protection of argon About 6 hours, after naturally cooling to room temperature, the product was washed repeatedly with ethanol, and the resulting product was a silicon/multi-walled carbon nanotube composite material loaded with nano-Pt, and the Pt loading was 12wt.%. The Pt was highly dispersed on its surface, and its average The diameter is 3.5nm. Increase the content of K₂ PtCl₆ in the above solution to 0.8g, then the Pt load on the surface of the silicon/multi-walled carbon nanotube composite material can reach 25wt.%, and the average diameter of Pt is 3.7nm, which is used in direct methanol fuel cells Among them, its catalytic activity for the electrochemical oxidation of methanol is equivalent to that of the Pt/Vulcan XC-72 catalyst (loaded at 60wt.%) produced by ETEK, USA.

实施例29：称取0.0002mol Fe(NO₃)₃·9H₂O于烧杯中，加入20ml异丙醇，搅拌溶解，然后加入1g硅颗粒，其平均粒径为20μm，搅拌30分钟，静置约72小时后，分离、干燥；化学气相沉积过程同实施例28，化学气相沉积的时间为2小时，所得产物即为硅/多壁碳纳米管复合材料，其中多壁碳纳米管的平均直径为10nm，长度为100μm。Example 29: Weigh 0.0002mol Fe(NO₃ )₃ 9H₂ O into a beaker, add 20ml of isopropanol, stir to dissolve, then add 1g of silicon particles with an average particle size of 20μm, stir for 30 minutes, and let stand After about 72 hours, separate and dry; the chemical vapor deposition process is the same as in Example 28, the chemical vapor deposition time is 2 hours, and the resulting product is a silicon/multi-walled carbon nanotube composite material, wherein the average diameter of the multi-walled carbon nanotubes It is 10nm and the length is 100μm.

如实施例19所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为980mAh/g，1C的可逆容量为800mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 19, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 980mAh/g, and its reversible capacity at 1C is 800mAh/g, showing good kinetic behavior.

实施例30：称取0.0006mol Fe(NO₃)₃·9H₂O于烧杯中，加入60ml异丙醇，搅拌溶解，然后加入1g硅颗粒，其平均粒径为20μm，搅拌30分钟，静置约48小时后，分离、干燥；化学气相沉积过程同实施例28，化学气相沉积的时间为30分钟，所得产物即硅/多壁碳纳米管复合材料，其中多壁碳纳米管的平均直径为30nm，长度为50μm 。Example 30: Weigh 0.0006mol Fe(NO₃ )₃ 9H₂ O into a beaker, add 60ml of isopropanol, stir to dissolve, then add 1g of silicon particles with an average particle size of 20μm, stir for 30 minutes, and let stand After about 48 hours, separate and dry; the chemical vapor deposition process is the same as in Example 28, and the chemical vapor deposition time is 30 minutes, and the resulting product is a silicon/multi-walled carbon nanotube composite material, wherein the average diameter of the multi-walled carbon nanotubes is 30nm and a length of 50μm.

如实施例19所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为1000mAh/g，1C的可逆容量为890mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 19, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 1000mAh/g, and its reversible capacity at 1C is 890mAh/g, showing good kinetic behavior.

实施例31：称取0.0002molg Fe(NO₃)₃·9H₂O于烧杯中，加入20ml异丙醇，搅拌溶解，然后加入1g硅颗粒，其平均粒径为10μm，搅拌30分钟后，静置约24小时后，分离、干燥；化学气相沉积过程同实施例28，化学气相沉积的时间为20分钟，所得产物即硅/多壁碳纳米管复合材料，其中多壁碳纳米管的平均直径为10nm，长度为5μm。Example 31: Weigh 0.0002molg Fe(NO₃ )₃ 9H₂ O into a beaker, add 20ml of isopropanol, stir to dissolve, then add 1g of silicon particles with an average particle size of 10μm, stir for 30 minutes, and After leaving for about 24 hours, separate and dry; the chemical vapor deposition process is the same as in Example 28, and the chemical vapor deposition time is 20 minutes, and the resulting product is a silicon/multi-walled carbon nanotube composite material, wherein the average diameter of the multi-walled carbon nanotube is It is 10nm and the length is 5μm.

如实施例19所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为950mAh/g，1C的可逆容量为770mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 19, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 950mAh/g, and its reversible capacity at 1C is 770mAh/g, showing good kinetic behavior.

实施例32：称取0.0001mol Fe(NO₃)₃·9H₂O于烧杯中，加入20ml乙二醇，搅拌溶解，然后加入1g硅颗粒，其平均粒径为10μm，搅拌30分钟后，静置约24小时后，分离、干燥；化学气相沉积过程同实施例28，化学气相沉积的时间为20分钟，所得产物即硅/多壁碳纳米管复合材料，其中多壁碳纳米管的平均直径为10nm，长度为500nm。Example 32: Weigh 0.0001mol Fe(NO₃ )₃ 9H₂ O into a beaker, add 20ml of ethylene glycol, stir to dissolve, then add 1g of silicon particles with an average particle size of 10μm, stir for 30 minutes, then statically After leaving for about 24 hours, separate and dry; the chemical vapor deposition process is the same as in Example 28, and the chemical vapor deposition time is 20 minutes, and the resulting product is a silicon/multi-walled carbon nanotube composite material, wherein the average diameter of the multi-walled carbon nanotube is is 10nm and the length is 500nm.

如实施例19所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为938mAh/g，1C的可逆容量为596mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 19, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 938mAh/g, and its reversible capacity at 1C is 596mAh/g, showing good kinetic behavior.

实施例33：称取0.0001mol Fe(NO₃)₃·9H₂O于烧杯中，加入20ml丙三醇，搅拌溶解，然后加入1g硅颗粒，其平均粒径为10μm，搅拌30分钟后，静置约24小时后，分离、干燥；化学气相沉积过程同实施例28，化学气相沉积的时间为20分钟，所得产物即硅/多壁碳纳米管复合材料，其中多壁碳纳米管的平均直径为10nm，长度为100nm。Example 33: Weigh 0.0001mol Fe(NO₃ )₃ 9H₂ O into a beaker, add 20ml of glycerol, stir to dissolve, then add 1g of silicon particles with an average particle size of 10μm, stir for 30 minutes, then statically After leaving for about 24 hours, separate and dry; the chemical vapor deposition process is the same as in Example 28, and the chemical vapor deposition time is 20 minutes, and the resulting product is a silicon/multi-walled carbon nanotube composite material, wherein the average diameter of the multi-walled carbon nanotube is is 10nm and the length is 100nm.

如实施例19所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为1100mAh/g，1C的可逆容量为960mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 19, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 1100mAh/g, and its reversible capacity at 1C is 960mAh/g, showing good kinetic behavior.

实施例34：称取0.0006mol Fe(NO₃)₃·9H₂O和0.0004mol Ni(NO₃)₂·6H₂O于烧杯中，加入60ml甲醇，搅拌溶解，然后加入0.06g硅颗粒，其平均粒径为50μm，搅拌2小时，静置约60小时后，分离、干燥；将所得干燥料放置在一石墨舟中，然后装入管式炉中，充入氩气和氢气的混合气，其比例为85∶15(v/v)，程序升温至700℃后，将气体转换为乙烯，流量为50sccm，恒温2小时进行化学气相沉积后，将气体转换为氮气，自然冷却至室温，所得产物即硅/多壁碳纳米管复合材料，其中多壁碳纳米管的平均直径为20nm，长度为100μm。Example 34: Weigh 0.0006mol Fe(NO₃ )₃ 9H₂ O and 0.0004mol Ni(NO₃ )₂ 6H₂ O in a beaker, add 60ml of methanol, stir to dissolve, then add 0.06g of silicon particles, the The average particle size is 50 μm, stirred for 2 hours, left to stand for about 60 hours, separated and dried; the obtained dried material was placed in a graphite boat, then loaded into a tube furnace, filled with a mixture of argon and hydrogen, The ratio is 85:15 (v/v), after the temperature is programmed to 700°C, the gas is converted to ethylene, the flow rate is 50 sccm, after chemical vapor deposition at a constant temperature for 2 hours, the gas is converted to nitrogen, and naturally cooled to room temperature, the obtained The product is a silicon/multi-walled carbon nanotube composite material, wherein the average diameter of the multi-walled carbon nanotubes is 20 nm and the length is 100 μm.

如实施例19所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为970mAh/g，1C的可逆容量为840mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 19, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 970mAh/g, and its reversible capacity at 1C is 840mAh/g, showing good kinetic behavior.

实施例35：称取0.0006mol Fe(NO₃)₃·9H₂O和0.0004mol Ni(NO₃)₂·6H₂O于烧杯中，加入60ml甲醇、乙醇和丙三醇(3∶2∶1，v/v)，搅拌溶解，然后加入6g硅颗粒，其平均粒径为50μm，搅拌2小时，静置约60小时后，分离、干燥；化学气相沉积过程同实施例34，所得产物即硅/多壁碳纳米管复合材料，其中多壁碳纳米管平均直径为20nm，长度为100μm。Example 35: Weigh 0.0006mol Fe(NO₃ )₃ 9H₂ O and 0.0004mol Ni(NO₃ )₂ 6H₂ O in a beaker, add 60ml of methanol, ethanol and glycerol (3:2:1 , v/v), stirred and dissolved, then added 6g of silicon particles, the average particle size of which was 50 μm, stirred for 2 hours, left to stand for about 60 hours, separated and dried; the chemical vapor deposition process was the same as in Example 34, and the resulting product was silicon /Multi-walled carbon nanotube composite material, wherein the multi-walled carbon nanotubes have an average diameter of 20nm and a length of 100μm.

如实施例19所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为928mAh/g，1C的可逆容量为720mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 19, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 928mAh/g, and its reversible capacity at 1C is 720mAh/g, showing good kinetic behavior.

实施例36：称取1g Fe粉和1000g硅颗粒(平均粒径为20μm)，以3000rpm球磨30min，得到合金颗粒，化学气相沉积过程同实施例34，所得产物即硅/多壁碳纳米管复合材料，其中多壁碳纳米管平均直径为2nm，长度为20nm。Embodiment 36: Take by weighing 1g Fe powder and 1000g silicon particle (average particle diameter is 20 μm), with 3000rpm ball milling 30min, obtain alloy particle, chemical vapor deposition process is the same as embodiment 34, and the obtained product is silicon/multi-walled carbon nanotube compound material, wherein the multi-walled carbon nanotubes have an average diameter of 2nm and a length of 20nm.

如实施例19所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为960mAh/g，1C的可逆容量为800mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 19, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as an anode active material, and its reversible capacity at 0.1C is 960mAh/g, and its reversible capacity at 1C is 800mAh/g, showing good kinetic behavior.

实施例37：称取1000g Ni粉和1g硅颗粒(平均粒径为1μm)，以300rpm球磨100小时，得到合金颗粒，将所得干燥料放置在一石墨舟中，然后装入管式炉中，充入氩气和氢气的混合气，其比例为100∶28(v/v)，总流量为100sccm，程序升温至1200℃后，将气体转换为氩气和乙炔的混合气，其比例为100∶9(v/v)，总流量为100sccm，恒温20分钟进行化学气相沉积后，自然冷却至室温，所得产物即硅/多壁碳纳米管复合材料，其中多壁碳纳米管在硅表面为非定向生长，其平均直径为5nm，长度为20μm。Example 37: Weigh 1000g of Ni powder and 1g of silicon particles (average particle size is 1 μm), and ball mill for 100 hours at 300rpm to obtain alloy particles, place the resulting dry material in a graphite boat, and then pack it into a tube furnace, Inflate the mixed gas of argon and hydrogen, the ratio is 100:28 (v/v), the total flow rate is 100sccm, after the temperature is programmed to 1200°C, the gas is converted into the mixed gas of argon and acetylene, the ratio is 100 : 9 (v/v), the total flow rate is 100 sccm, after chemical vapor deposition at a constant temperature for 20 minutes, it is naturally cooled to room temperature, and the resulting product is a silicon/multi-walled carbon nanotube composite material, wherein the multi-walled carbon nanotube is on the silicon surface. Non-directional growth with an average diameter of 5 nm and a length of 20 μm.

如实施例19所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/多壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为940mAh/g，1C的可逆容量为810mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 19, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/multi-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 940mAh/g, and its reversible capacity at 1C is 810mAh/g, showing good kinetic behavior.

实施例38：称取1g Ni粉和1g硅颗粒(平均粒径为10μm)，以100rpm球磨500小时，得到合金颗粒，将所得干燥料放置在一石墨舟中，然后装入管式炉中，充入氩气，流量为100sccm，程序升温至900℃后，将气体转换为甲烷和氢气的混合气，其比例为5∶2(v/v)，总流量为100sccm，恒温48小时进行化学气相沉积后，将气体转换为氩气，自然冷却至室温，所得产物即硅/双壁碳纳米管复合材料，其中双壁碳纳米管的平均直径为25nm，长度为100μm。Example 38: Weigh 1g of Ni powder and 1g of silicon particles (average particle size is 10 μm), and ball mill for 500 hours at 100rpm to obtain alloy particles, place the resulting dry material in a graphite boat, and then pack it into a tube furnace, Fill with argon with a flow rate of 100 sccm. After the temperature is programmed to 900°C, the gas is converted into a mixture of methane and hydrogen, the ratio of which is 5:2 (v/v), the total flow rate is 100 sccm, and the chemical vapor phase is carried out at a constant temperature for 48 hours. After deposition, the gas was changed to argon, and naturally cooled to room temperature, and the obtained product was a silicon/double-walled carbon nanotube composite material, wherein the double-walled carbon nanotubes had an average diameter of 25 nm and a length of 100 μm.

如实施例19所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/双壁碳纳米管复合材料作为负极活性材料，其在0.1C的可逆容量为990mAh/g，1C的可逆容量为840mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 19, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/double-walled carbon nanotube composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 990mAh/g, and its reversible capacity at 1C is 840mAh/g, showing good kinetic behavior.

实施例39：称取1g Ni粉、1g Co粉、1g Mo粉和100g硅颗粒(平均粒径为5μm)，以300rpm球磨200小时，得到合金颗粒，将所得物质放置在一石墨舟中，然后装入管式炉，充入氩气和氢气的混合气(100∶17，v/v)，总流量为100sccm，程序升温至500℃后，将气体转换为氢气和一氧化碳的混合气(1∶4，v/v)，总流量为300sccm，恒温50分钟进行化学气相沉积后，自然冷却至室温；即得产物硅/碳纳米纤维复合材料，碳纳米纤维的平均直径为21nm，长度为80μm。Example 39: Weigh 1g of Ni powder, 1g of Co powder, 1g of Mo powder and 100g of silicon particles (average particle size is 5 μm), and ball mill for 200 hours at 300rpm to obtain alloy particles, place the resulting material in a graphite boat, and then Load into the tube furnace, charge the mixed gas of argon and hydrogen (100:17, v/v), the total flow rate is 100 sccm, after the temperature is programmed to 500 ° C, the gas is converted into a mixed gas of hydrogen and carbon monoxide (1: 4, v/v), the total flow rate is 300sccm, after chemical vapor deposition at a constant temperature for 50 minutes, it is naturally cooled to room temperature; the product silicon/carbon nanofiber composite material is obtained, the average diameter of carbon nanofibers is 21nm, and the length is 80 μm.

如实施例19所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/碳纳米纤维复合材料作为负极活性材料，其在0.1C的可逆容量为1000mAh/g，1C的可逆容量为890mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 19, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/carbon nanofiber composite material is used as the negative electrode active material, and its reversible capacity at 0.1C is 1000mAh/g, and its reversible capacity at 1C is 890mAh/g, showing good kinetic behavior.

实施例40：称取1g Ni粉、4g Mo粉和100g硅颗粒(平均粒径为5μm)，以1500rpm球磨50小时，得到合金颗粒，将所得物质放置在一石墨舟中，然后装入管式炉，充入氩气和氢气的混合气(100∶17，v/v)，总流量为100sccm，程序升温至1000℃后，将气体转换为氢气和一氧化碳的混合气(1∶4，v/v)，总流量为300sccm，恒温5小时进行化学气相沉积后，自然冷却至室温；即得产物硅/碳纳米纤维复合材料，碳纳米纤维的平均直径为13nm，长度为60μm。Example 40: Weigh 1g of Ni powder, 4g of Mo powder and 100g of silicon particles (average particle size is 5 μm), and ball mill at 1500rpm for 50 hours to obtain alloy particles, place the resulting material in a graphite boat, and then pack it into a tube The furnace is filled with a mixture of argon and hydrogen (100:17, v/v), with a total flow rate of 100 sccm, and after the temperature is programmed to 1000 ° C, the gas is converted into a mixture of hydrogen and carbon monoxide (1:4, v/v v), the total flow rate is 300sccm, the chemical vapor deposition is carried out at constant temperature for 5 hours, and then naturally cooled to room temperature; the product silicon/carbon nanofiber composite material is obtained, the average diameter of carbon nanofibers is 13nm, and the length is 60μm.

如实施例19所述进行正极和负极的制备，并组装电池进行测试，实验电池由受计算机控制的自动充放电仪进行充放电循环测试。充电截止电压为4.2V，放电截止电压为2.0V。研究证明，所述硅/碳纳米纤维复合材料作为负极活性材料，其在0.1C的可逆容量为1000mAh/g，1C的可逆容量为840mAh/g，显示了较好的动力学行为。The positive and negative electrodes were prepared as described in Example 19, and the battery was assembled for testing. The experimental battery was subjected to a charge-discharge cycle test by an automatic charge-discharge instrument controlled by a computer. The charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.0V. Studies have proved that the silicon/carbon nanofiber composite material is used as a negative electrode active material, and its reversible capacity at 0.1C is 1000mAh/g, and its reversible capacity at 1C is 840mAh/g, showing good kinetic behavior.

Claims (9)

1, a kind of silicon﹠amp, it comprises silicon substrate, reaches carbon nanotubes grown or carbon nano fiber thereon; The median size of described silicon substrate is 100nm～100 μ m; The diameter of described carbon nanotube or carbon nano fiber is 1～200nm, and length is 10nm～100 μ m; Described carbon nanotube is a single wall, double-walled or many walls.

2, silicon﹠amp as claimed in claim 1 is characterized in that: the geometric shape of described matrix silicon grain is for spherical.

3, silicon﹠amp as claimed in claim 1 is characterized in that: described carbon nanotube or carbon nano fiber have straight geometry appearance, or have the geometry appearance of bending or spiral.

4, the preparation method of the described silicon﹠amp of a kind of claim 1 specifically comprises the steps:

1) preparation of catalyst solution

Use is selected from the catalyst solution of one or more solvent preparations 0.0001～0.1M in distilled water, ethanol, methyl alcohol, Virahol, ethylene glycol or the glycerol;

Described catalyzer is for being selected from Fe (NO₃)₃9H₂O, FeSO₄7H₂O, FeCl₃6H₂O, Co (NO₃)₂6H₂O, Co (CH₃COO)₂4H₂O, Ni (NO₃)₂6H₂O, (NH₄)₆Mo₇O₂₄4H₂Among the O one or more;

2) catalyst cupport

To join as the silicon materials of body material in the catalyst solution that step 1) makes, the mass ratio of described catalyzer and silicon is 1: 1～1000, stirs 30 minutes～20 hours, leaves standstill 5～72 hours, separates, drying, obtains the silicon materials of catalyst cupport;

The median size of described silicon substrate is 100nm～100 μ m;

3) chemical vapour deposition

With step 2) material that obtains is placed in the thermally resistant container, and the tube furnace of packing into then charges into the gas mixture of argon gas or argon gas and hydrogen, or carries out pre-treatment, temperature programming to 500 then～1200 ℃ temperature with ammonia; After being raised to target temperature, gas being converted to carbon-source gas or being converted to the gas mixture of argon gas, nitrogen or hydrogen and carbon-source gas, constant temperature 20 minutes naturally cools to room temperature after carrying out chemical vapour deposition to 48 hours.

5, the preparation method of the described silicon﹠amp of a kind of claim 1 specifically comprises the steps:

1) preparation of chemical plating solution

Use is selected from the Fe (NO of one or more solvent preparations 0.0001～0.1M in distilled water, ethanol, methyl alcohol, Virahol, ethylene glycol or the glycerol₃)₃9H₂O, Co (NO₃)₂6H₂O or Ni (NO₃)₂6H₂O solution; Preparation contains the distilled water solution of trisodium citrate and sodium acetate; The concentration of described trisodium citrate and sodium acetate is 0.0001～1M; Then the former is added drop-wise among the latter, stirs, obtain mixed solution A;

Use distilled water that sodium hydroxide and sodium borohydride are mixed with reductant solution B; Concentration sodium hydroxide 1.5～15M wherein, the concentration of sodium borohydride is 0.0001～1M;

2) load of catalyzer

To join as the silicon materials of body material in the mixed solution A that step 1) makes, stir, be warming up to 25～95 ℃, the pH=4 of regulator solution～12 drip the reductant solution B that step 1) prepares then, wait to drip, continue to stir 10 minutes～2 hours, separate, drying obtains the silicon materials of catalyst cupport; The ratio of the silicon materials that add, solution A, solution B is 1g: 40～100ml: 10～50ml;

The median size of described silicon substrate is 100nm～100 μ m;

3) chemical vapour deposition

With step 2) material that obtains is placed in the thermally resistant container, and the tube furnace that the resistance to air loss of packing into then is good charges into the gas mixture of argon gas or argon gas and hydrogen, temperature programming to 500 then～1200 ℃ temperature; After being raised to target temperature, gas being converted to carbon-source gas or being converted to the gas mixture of argon gas, nitrogen or hydrogen and carbon-source gas, constant temperature 20 minutes naturally cools to room temperature after carrying out chemical vapour deposition to 48 hours.

6, the preparation method of the described silicon﹠amp of a kind of claim 1 specifically comprises the steps:

1) mixing of catalyzer

One or more that are selected from Fe, Co, Ni, Mo metal-powder are mixed with silicon grain as body material, mixed 5 minutes～50 hours, the mass ratio of metal and body material is 1: 1～1000;

The median size of described silicon substrate is 100nm～100 μ m;

2) chemical vapour deposition

The material that step 1) is obtained is placed in the thermally resistant container, and the tube furnace that the resistance to air loss of packing into then is good charges into the gas mixture of argon gas or argon gas and hydrogen, temperature programming to 700 then～1200 ℃ temperature; After being raised to target temperature, gas being converted to carbon-source gas or being converted to the gas mixture of argon gas, nitrogen or hydrogen and carbon-source gas, constant temperature 20 minutes naturally cools to room temperature after carrying out chemical vapour deposition to 48 hours.

7, the preparation method of the described silicon﹠amp of a kind of claim 1 specifically comprises the steps:

1) contains the preparation of catalyst elements alloy

One or more that are selected from Fe, Co, Ni, Mo metal-powder are mixed with silicon grain as body material, carried out ball milling then 30 minutes～500 hours, rotating speed is 100～3000rpm, and the mass ratio of metal and body material is 1: 0.001～1000;

The median size of described silicon substrate is 100nm～100 μ m;

2) chemical vapour deposition

The material that step 1) is obtained is placed in the thermally resistant container, and the tube furnace that the resistance to air loss of packing into then is good charges into the gas mixture of argon gas or argon gas and hydrogen, temperature programming to 700 then～1200 ℃ temperature; After being raised to target temperature, gas being converted to carbon-source gas or being converted to the gas mixture of argon gas, nitrogen or hydrogen and carbon-source gas, constant temperature 20 minutes naturally cools to room temperature after carrying out chemical vapour deposition to 48 hours.

8, the described silicon﹠amp of one of claim 1～3 in energy storage and switching device as the purposes of the negative material of lithium ion battery.

9, the described silicon﹠amp of one of claim 1～3 is as the purposes of the carrier of various fuel-cell catalysts.

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