CN103346302A - Lithium battery silicon-carbon nanotube composite cathode material as well as preparation method and application thereof - Google Patents
Lithium battery silicon-carbon nanotube composite cathode material as well as preparation method and application thereof Download PDFInfo
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Abstract
本发明公开了一种锂电池硅碳纳米管复合负极材料及其制备方法与应用。本发明通过将有机碳源和纳米硅按（0.4～9）:1的质量比混合搅拌均匀再加入催化剂得到混合浆料，再通过闭式循环喷雾干燥得到前驱体，将所得的前驱体在300～700℃保温1～5h，得到的样品再放入管式炉中，在气态有机碳源和N2、Ar2混合气氛下升温至500～900℃保温0.5～3h，自然冷却后得到所述锂电池硅碳纳米管复合负极材料。该锂电池硅碳纳米管复合负极材料的电化学性能优秀，首次充放电效率高达2000mAh/g以上，循环50周后仍然保持有1100mAh/g左右的可逆比容量，比容量高、循环性能好，成功解决了硅在实际制备锂离子电池负极的应用时存在的首次效率低、不可逆容量损失大和导电性能差的问题。
The invention discloses a lithium battery silicon-carbon nanotube composite negative electrode material, a preparation method and application thereof. In the present invention, the organic carbon source and nano-silicon are mixed and stirred evenly at a mass ratio of (0.4-9):1, and then the catalyst is added to obtain a mixed slurry, and then the precursor is obtained by closed-cycle spray drying, and the obtained precursor is heated at 300 ～700°C for 1～5h, the obtained sample was placed in a tube furnace, heated to 500～900°C for 0.5～3h under the mixed atmosphere of gaseous organic carbon source and N 2 , Ar 2 , and then naturally cooled to obtain the described Lithium battery silicon carbon nanotube composite negative electrode material. The silicon-carbon nanotube composite anode material for lithium batteries has excellent electrochemical performance, the first charge and discharge efficiency is as high as 2000mAh/g, and after 50 cycles, it still maintains a reversible specific capacity of about 1100mAh/g, with high specific capacity and good cycle performance. It has successfully solved the problems of low initial efficiency, large irreversible capacity loss and poor conductivity of silicon in the actual application of lithium-ion battery negative electrodes.
Description
技术领域technical field
本发明属于锂电池材料制备领域，具体涉及一种锂电池硅碳纳米管复合负极材料及其制备方法与应用。The invention belongs to the field of lithium battery material preparation, and in particular relates to a lithium battery silicon-carbon nanotube composite negative electrode material and a preparation method and application thereof.
背景技术Background technique
锂离子电池因其具有能量密度大、循环寿命长以及环境友好等优点成为一种理想的可再生能源。电极材料是决定锂离子电池综合性能的关键因素之一。目前商业化的碳负极材料已经接近其理论容量（372mAh/g），很难再有提升空间，与碳负极材料相比，单质硅的理论比容量高达4200mAh/g，因而成为了目前的研究热点。Lithium-ion batteries have become an ideal renewable energy source because of their high energy density, long cycle life, and environmental friendliness. Electrode materials are one of the key factors determining the overall performance of lithium-ion batteries. At present, commercialized carbon anode materials are close to their theoretical capacity (372mAh/g), and there is little room for improvement. Compared with carbon anode materials, the theoretical specific capacity of elemental silicon is as high as 4200mAh/g, so it has become a current research hotspot. .
目前硅基负极材料的嵌脱锂机理是硅与锂发生化学反应生成LixSi化合物，根据不同的嵌锂量共形成7种LixSi化合物，且每一种不同的LixSi化合物都具有不同的晶体结构。因此，随着充放电过程中脱嵌锂量及电位的不同将产生各种不同的合金化合物，从而引起材料结构的变化而导致极片粉化失效。特别是在嵌脱锂过程中，单质硅的体积膨胀效应高达300%，其首次充放电效率和循环稳定性能远不能达到商业应用化的要求。At present, the lithium insertion and removal mechanism of silicon-based negative electrode materials is that silicon and lithium undergo a chemical reaction to form Li x Si compounds. According to different lithium insertion amounts, a total of 7 Li x Si compounds are formed, and each different Li x Si compound has different crystal structures. Therefore, with the difference in the amount of intercalation and deintercalation of lithium and the potential during charge and discharge, various alloy compounds will be produced, which will cause changes in the material structure and lead to powdering failure of the pole piece. Especially in the process of intercalating and removing lithium, the volume expansion effect of elemental silicon is as high as 300%, and its first charge and discharge efficiency and cycle stability are far from meeting the requirements of commercial application.
碳纳米管（CNTs）具有良好的导电性能和机械强度，通过碳纳米管与纳米硅材料复合将有利于增强活性物质之间的电接触和交联强度，从而有效改善纳米硅基材料的导电性和颗粒之间的膨胀缓冲空间，对提高硅基材料首次效率和改进循环稳定性具有重要的促进作用。Carbon nanotubes (CNTs) have good electrical conductivity and mechanical strength. Combining carbon nanotubes with nano-silicon materials will help to enhance the electrical contact and cross-linking strength between active materials, thereby effectively improving the conductivity of nano-silicon-based materials. And the expansion buffer space between the particles plays an important role in improving the first-time efficiency and cycle stability of silicon-based materials.
近年来，人们对于碳纳米管和活性储锂材料的复合进行了很多有意义的探索研究，例如在文献（T.Cetinkaya,M.O.Guler,H.Akbulut.Microelectron.Eng.108:169–176(2013)）中，研究人员将多壁碳纳米管与纳米硅进行高能球磨，得到性能优异的硅碳纳米管复合材料，但是这种高能球磨只是将纳米硅颗粒和碳纳米管简单的机械混合，且在球磨过程中易破坏原料的形貌结构，不适宜工业化生产。申请号为201110378735.4的专利申请公开了一种锂离子电池硅碳负极材料及其制备方法，该发明通过将硅碳复合材料与天然石墨类材料混合制备出一种比容量为500mAh/g以上的硅碳负极材料。其中，硅碳复合材料由碳纳米管和/或碳纳米纤维沉积到纳米硅粉颗粒表面和/或嵌入到纳米硅粉颗粒之间形成核，并在核的表面包覆有碳层，这个过程需要经过多次粉碎、包覆处理，工艺复杂。In recent years, people have carried out a lot of meaningful research on the combination of carbon nanotubes and active lithium storage materials, for example in the literature (T.Cetinkaya, M.O.Guler, H.Akbulut.Microelectron.Eng.108:169–176(2013 )), the researchers performed high-energy ball milling of multi-walled carbon nanotubes and nano-silicon to obtain silicon-carbon nanotube composites with excellent properties, but this high-energy ball mill only simply mechanically mixed nano-silicon particles and carbon nanotubes, and The morphology and structure of the raw materials are easily damaged during the ball milling process, which is not suitable for industrial production. The patent application with the application number 201110378735.4 discloses a silicon-carbon negative electrode material for lithium-ion batteries and its preparation method. The invention prepares a silicon-carbon composite material with a specific capacity of more than 500mAh/g by mixing silicon-carbon composite materials with natural graphite materials. carbon anode material. Among them, the silicon-carbon composite material consists of carbon nanotubes and/or carbon nanofibers deposited on the surface of nano-silicon powder particles and/or embedded between nano-silicon powder particles to form a core, and the surface of the core is coated with a carbon layer. It needs to go through multiple crushing and coating treatments, and the process is complicated.
发明内容Contents of the invention
为克服现有技术中存在的不足之处，本发明的首要目的在于提供一种锂电池硅碳纳米管复合负极材料，该锂电池硅碳纳米管复合负极材料首次比容量达2000mAh/g以上。In order to overcome the deficiencies in the prior art, the primary purpose of the present invention is to provide a silicon-carbon nanotube composite negative electrode material for a lithium battery. The silicon-carbon nanotube composite negative electrode material for a lithium battery has a specific capacity of more than 2000mAh/g for the first time.
本发明的另一目的在于提供上述锂电池硅碳纳米管复合负极材料的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned silicon-carbon nanotube composite negative electrode material for a lithium battery.
本发明的再一目的在于提供上述锂电池硅碳纳米管复合负极材料的应用。Another object of the present invention is to provide the application of the silicon-carbon nanotube composite negative electrode material for lithium batteries.
为实现上述发明目的，本发明采用如下技术方案：In order to realize the above-mentioned purpose of the invention, the present invention adopts following technical scheme:
一种锂电池硅碳纳米管复合负极材料的制备方法，包括如下步骤：A method for preparing a silicon-carbon nanotube composite negative electrode material for a lithium battery, comprising the steps of:
（1）将有机碳源和催化剂溶于溶剂中得到溶液A；另取溶剂并加入分散剂溶解后将其加入到纳米硅液体中，超声0.5～2h，得到溶液B；然后将溶液B加入到溶液A中，得到混合浆料；其中纳米硅液体中溶剂为乙醇或乙二醇；(1) Dissolve the organic carbon source and catalyst in the solvent to obtain solution A; take another solvent and add a dispersant to dissolve it, then add it to the nano-silicon liquid, and ultrasonically for 0.5-2 hours to obtain solution B; then add solution B to the In the solution A, a mixed slurry is obtained; wherein the solvent in the nano-silicon liquid is ethanol or ethylene glycol;
（2）将步骤（1）得到的混合浆料搅拌0.5～3h，然后加入溶剂调节混合浆料的固体质量含量至10～30%，再将混合浆料干燥制粉，得到前驱体A；(2) Stir the mixed slurry obtained in step (1) for 0.5-3 hours, then add a solvent to adjust the solid mass content of the mixed slurry to 10-30%, and then dry the mixed slurry to obtain a precursor A;
（3）将步骤（2）获得的前驱体A在惰性气体中升温至300～700℃，保温1～5h后冷却至室温，得到前驱体B；(3) Precursor A obtained in step (2) is heated to 300-700°C in an inert gas, kept for 1-5 hours and then cooled to room temperature to obtain precursor B;
（4）将步骤（3）获得的前驱体B在气态有机碳源和惰性气体的混合气中升温至500～900℃，保温0.5～5h后冷却至室温，得到所述锂电池硅碳纳米管复合负极材料。(4) Precursor B obtained in step (3) is heated to 500-900°C in a mixture of gaseous organic carbon source and inert gas, kept for 0.5-5h and then cooled to room temperature to obtain the lithium battery silicon carbon nanotube Composite anode materials.
本发明制备方法在步骤（3）的热处理中生成了热解碳，在步骤（4）的热处理中生成了碳纳米管，而步骤（1）加入的催化剂在干燥过程中可以使得后续气相沉积的碳纳米管在硅碳微球的内部空隙和表面都可生长、结合的更加紧密。碳纳米管和热解碳的生成解决了现有技术中单质硅的体积膨胀效应高、首次充放电效率低和循环稳定性能差的问题，主要原因在于：首先，碳纳米管和热解碳可以有效的缓解脱嵌锂过程中硅的体积膨胀效应，抑制活性物质的粉化；其次，碳纳米管和热解碳可以提供电子传输的通道，能够提高活性物质硅的导电性。In the preparation method of the present invention, pyrolytic carbon is generated in the heat treatment of step (3), carbon nanotubes are generated in the heat treatment of step (4), and the catalyst added in step (1) can make the subsequent vapor deposition during the drying process Carbon nanotubes can grow and combine more tightly in the internal voids and surfaces of silicon carbon microspheres. The generation of carbon nanotubes and pyrolytic carbon solves the problems of high volume expansion effect of elemental silicon, low initial charge and discharge efficiency, and poor cycle stability in the prior art. The main reasons are: first, carbon nanotubes and pyrolytic carbon can It can effectively alleviate the volume expansion effect of silicon in the process of deintercalating lithium, and inhibit the pulverization of active materials; secondly, carbon nanotubes and pyrolytic carbon can provide electron transport channels, which can improve the conductivity of silicon as active materials.
本发明制备方法所得的锂电池硅碳纳米管复合负极材料具有优秀的电化学性能：首次充放电效率高、比容量高以及循环性能好。该锂电池硅碳纳米管复合负极材料的纳米硅嵌入在有机碳源热解形成的碳网基体中，基体内部和表面都生长有无序的碳纳米管，颗粒尺寸小于5μm。The lithium battery silicon-carbon nanotube composite negative electrode material obtained by the preparation method of the invention has excellent electrochemical properties: high initial charge and discharge efficiency, high specific capacity and good cycle performance. Nano-silicon of the silicon-carbon nanotube composite negative electrode material for a lithium battery is embedded in a carbon network matrix formed by pyrolysis of an organic carbon source, and disordered carbon nanotubes grow inside and on the surface of the matrix, and the particle size is less than 5 μm.
优选的，步骤（1）中所述的有机碳源和纳米硅的质量比为（0.4～9）:1；步骤（1）中所述催化剂用量为纳米硅质量的1%～3%，分散剂用量为纳米硅质量的1%；步骤（1）中所述纳米硅液体中纳米硅质量含量为10%，纳米硅的粒径为50～200nm。Preferably, the mass ratio of the organic carbon source and nano-silicon described in step (1) is (0.4-9):1; the amount of catalyst described in step (1) is 1%-3% of the mass of nano-silicon, dispersed The dosage of the agent is 1% of the mass of the nano-silicon; the mass content of the nano-silicon liquid in the step (1) is 10%, and the particle size of the nano-silicon is 50-200nm.
为发挥出纳米硅的高容量特点的同时，也可以保持很好的循环性能，步骤（1）中所述的有机碳源和纳米硅按（0.4～9）:1的质量比进行配比，纳米硅的粒径优选为50～200nm。In order to take advantage of the high capacity characteristics of nano-silicon while maintaining good cycle performance, the organic carbon source and nano-silicon described in step (1) are mixed according to the mass ratio of (0.4-9):1, The particle diameter of nano-silicon is preferably 50-200 nm.
优选的，步骤（1）中所述的有机碳源为酚醛树脂、柠檬酸或高温沥青；步骤（1）中所述的催化剂为乙酸镍、硫酸镍或乙酸铁；步骤（1）中所述的溶剂为无水乙醇、乙二醇和四氢呋喃中的一种或两种；步骤（1）中所述的分散剂为聚乙烯吡咯烷酮、聚乙烯亚胺、聚醚酰亚胺或十二烷基硫酸钠。Preferably, the organic carbon source described in step (1) is phenolic resin, citric acid or high-temperature pitch; the catalyst described in step (1) is nickel acetate, nickel sulfate or iron acetate; The solvent is one or both of absolute ethanol, ethylene glycol and tetrahydrofuran; the dispersant described in step (1) is polyvinylpyrrolidone, polyethyleneimine, polyetherimide or dodecylsulfuric acid sodium.
上述步骤（1）使用的溶剂具有能够将有机碳源和催化剂、或者分散剂完全溶解且具有沸点低、易挥发的特性的特性，并且溶剂的量至少能够将有机碳源和催化剂、或者分散剂完全溶于溶剂中。The solvent used in the above step (1) has the characteristics of being able to completely dissolve the organic carbon source and the catalyst or the dispersant and has a low boiling point and is volatile, and the amount of the solvent is at least capable of dissolving the organic carbon source and the catalyst or the dispersant Completely soluble in solvent.
此外在步骤（1）中的分散剂都为同时具有亲油亲水基团，并能使表面张力显著下降的物质，可以有效阻止纳米硅颗粒之间的团聚，起到很好的分散效果；在步骤（1）中超声的目的是为了更好的分散纳米硅，超声频率对本发明并无影响，不需特别限定。In addition, the dispersant in step (1) is a substance that has both lipophilic and hydrophilic groups and can significantly reduce the surface tension, which can effectively prevent the agglomeration of nano-silicon particles and achieve a good dispersion effect; The purpose of ultrasound in step (1) is to better disperse nano-silicon, and the frequency of ultrasound has no influence on the present invention, and no special limitation is required.
优选的，步骤（2）中所述的干燥方式为通过闭式循环喷雾干燥机进行干燥，所述闭式循环喷雾干燥机中雾化器的转速为20000～35000r/min，其进口温度为105～120℃，出口温度为80～90℃；步骤（2）中所述的搅拌速度为500～2000r/min，所述的溶剂为无水乙醇、乙二醇或四氢呋喃。Preferably, the drying method described in step (2) is to dry by a closed cycle spray dryer, the speed of the atomizer in the closed cycle spray dryer is 20000-35000r/min, and the inlet temperature is 105 ～120°C, the outlet temperature is 80～90°C; the stirring speed in step (2) is 500～2000r/min, and the solvent is absolute ethanol, ethylene glycol or tetrahydrofuran.
与普通的干燥方式相比，使用闭式循环喷雾干燥制备的粉体，纳米硅可以均匀的分散于有机碳源中，且粉体颗粒尺寸较为均一。并且混合浆料的固体质量含量为10～30%，该固体含量既不会太高而造成进料口堵塞，又不会太低浪费很长的时间，更适合闭式循环喷雾干燥法。Compared with the common drying method, the powder prepared by closed-cycle spray drying can be evenly dispersed in the organic carbon source, and the particle size of the powder is relatively uniform. And the solid mass content of the mixed slurry is 10-30%, which is neither too high to cause blockage of the feeding port, nor too low to waste a long time, and is more suitable for the closed cycle spray drying method.
优选的，步骤（3）中所述的惰性气体为纯度99.999%的氮气或纯度99.999%的氩气，其升温速率为1～5℃/min。Preferably, the inert gas described in step (3) is nitrogen with a purity of 99.999% or argon with a purity of 99.999%, and the heating rate is 1-5° C./min.
优选的，步骤（4）中所述的混合气中气态有机碳源为乙炔、甲烷、天然气和液化石油气中的一种以上，惰性气体为氮气或氩气，气态有机碳源和惰性气体的质量比为3:7～8:2；其中混合气的升温速率为1～5℃/min。Preferably, the gaseous organic carbon source in the mixed gas described in step (4) is more than one of acetylene, methane, natural gas and liquefied petroleum gas, the inert gas is nitrogen or argon, and the gaseous organic carbon source and inert gas The mass ratio is 3:7~8:2; the heating rate of the mixed gas is 1~5°C/min.
上述锂电池硅碳纳米管复合负极材料应用于锂离子电池负极片的制备；所述锂离子电池负极片的制备方法包括以下步骤：The silicon-carbon nanotube composite negative electrode material for the lithium battery is applied to the preparation of the negative electrode sheet of the lithium ion battery; the preparation method of the negative electrode sheet of the lithium ion battery comprises the following steps:
（1）将锂电池硅碳纳米管复合负极材料、粘结剂和导电剂按（70～80）：（20～10）：10的重量比进行混合，得到浆料；(1) Mixing the lithium battery silicon carbon nanotube composite negative electrode material, binder and conductive agent according to the weight ratio of (70-80): (20-10): 10 to obtain a slurry;
（2）将步骤（1）得到的浆料涂覆在铜箔上，并干燥5～24h，然后辊压、切片，得到所述锂离子电池负极片。(2) Coating the slurry obtained in step (1) on a copper foil, drying for 5-24 hours, and then rolling and slicing to obtain the negative electrode sheet of the lithium ion battery.
优选的，所述锂电池硅碳纳米管复合负极材料、粘结剂和导电剂的重量比为80:10:10。Preferably, the weight ratio of the lithium battery silicon carbon nanotube composite negative electrode material, binder and conductive agent is 80:10:10.
优选的，所述粘结剂为粘结剂LA132或聚偏二氟乙烯；所述导电剂为导电炭黑、导电液体或纳米碳。Preferably, the binder is binder LA132 or polyvinylidene fluoride; the conductive agent is conductive carbon black, conductive liquid or nano-carbon.
所述的粘结剂LA132为成都茵地乐公司生产的一款水系粘结剂；所述导电液体为市售常规的导电液体，所述纳米碳的粒径小于100nm。The binder LA132 is a water-based binder produced by Chengdu Yindile Company; the conductive liquid is a commercially available conventional conductive liquid, and the particle size of the nano-carbon is less than 100nm.
优选的，步骤（2）中所述的涂覆厚度为100～180微米；所述辊压的厚度为75～150微米；所述干燥方式为真空干燥，其温度为50～100℃。Preferably, the thickness of the coating in step (2) is 100-180 microns; the thickness of the rolling is 75-150 microns; the drying method is vacuum drying at a temperature of 50-100°C.
在本发明锂电池硅碳纳米管复合负极材料的制备过程中，所应用的分散剂、有机碳源的种类、前驱体烧结温度和喷雾干燥的工艺等条件均会对所制得的硅碳纳米管复合负极材料的结构、大小以及形貌产生很大影响，而产物的结构、大小和形貌又会对锂电池负极材料的性能产生极大的影响，进而影响到锂电池硅碳纳米管复合负极材料的首次充放电效率、比容量和循环性能。因此，在本发明中，发明人通过对分散剂种类、有机碳源的种类、喷雾干燥的工艺、烧结温度等工艺条件的优选，得到了一种首次充放电效率高、比容量高、循环性能好的锂电池硅碳纳米管复合负极材料。In the preparation process of the lithium battery silicon-carbon nanotube composite negative electrode material of the present invention, the conditions such as the applied dispersant, the type of organic carbon source, the sintering temperature of the precursor, and the process of spray drying will all affect the prepared silicon-carbon nanotube composite negative electrode material. The structure, size and shape of the tube composite negative electrode material have a great impact, and the structure, size and shape of the product will have a great impact on the performance of the lithium battery negative electrode material, which in turn affects the silicon carbon nanotube composite of the lithium battery. The first charge and discharge efficiency, specific capacity and cycle performance of negative electrode materials. Therefore, in the present invention, the inventors have obtained a kind of first charge and discharge efficiency, high specific capacity, cycle performance by optimizing process conditions such as the type of dispersant, the type of organic carbon source, the spray drying process, and the sintering temperature. Good lithium battery silicon carbon nanotube composite negative electrode material.
通过检测发现，本发明制备方法所得的锂电池硅碳纳米管复合负极材料首次比容量达2000mAh/g以上，远远高于目前商业化的石墨理论容量为372mAh/g。It is found through testing that the lithium battery silicon-carbon nanotube composite negative electrode material obtained by the preparation method of the present invention has a specific capacity of more than 2000mAh/g for the first time, which is far higher than the current commercial graphite theoretical capacity of 372mAh/g.
与现有技术相比本发明具有如下优点及有益效果：Compared with the prior art, the present invention has the following advantages and beneficial effects:
（1）本发明的锂电池硅碳纳米管复合负极材料制备工艺简单、成本低廉、适于工业化生产。(1) The silicon-carbon nanotube composite negative electrode material for lithium batteries of the present invention has a simple preparation process, low cost, and is suitable for industrial production.
（2）本发明的锂电池硅碳纳米管复合负极材料的电化学性能优秀，首次充放电效率高，比容量高（首次达2000mAh/g以上，目前商业化的石墨理论容量为372mAh/g）、循环性能好，成功解决了硅在实际制备锂离子电池负极的应用时存在的首次效率低、不可逆容量损失大和导电性能差的问题。(2) The silicon-carbon nanotube composite negative electrode material for lithium batteries of the present invention has excellent electrochemical performance, high charge and discharge efficiency for the first time, and high specific capacity (up to 2000mAh/g for the first time, and the theoretical capacity of commercialized graphite is 372mAh/g at present) , Good cycle performance, and successfully solved the problems of low initial efficiency, large irreversible capacity loss and poor conductivity of silicon in the actual application of lithium-ion battery negative electrodes.
附图说明Description of drawings
图1为实施例1制备的锂电池硅碳纳米管复合负极材料的SEM图谱；Fig. 1 is the SEM spectrum of the silicon carbon nanotube composite negative electrode material of lithium battery prepared in embodiment 1;
图2为实施例1制备的锂电池硅碳纳米管复合负极材料的XRD图谱；Fig. 2 is the XRD spectrum of the silicon carbon nanotube composite negative electrode material of lithium battery prepared in embodiment 1;
图3为模拟电池1的充放电循环性能图；FIG. 3 is a charge-discharge cycle performance diagram of the simulated battery 1;
图4为模拟电池2的充放电循环性能图；Fig. 4 is the charge-discharge cycle performance diagram of simulated battery 2;
图5为模拟电池3的充放电循环性能图；Fig. 5 is the charge-discharge cycle performance diagram of the simulated battery 3;
图6为模拟电池4的充放电循环性能图。FIG. 6 is a charge-discharge cycle performance graph of the simulated battery 4 .
具体实施方式Detailed ways
下面结合实施例与附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。The present invention will be further described in detail below in conjunction with the embodiments and accompanying drawings, but the embodiments of the present invention are not limited thereto.
实施例1Example 1
（一）制备锂电池硅碳纳米管复合负极材料，具体步骤如下：(1) Preparation of silicon-carbon nanotube composite negative electrode material for lithium battery, the specific steps are as follows:
（1）分别称取14.25g柠檬酸（C6H8O7·H2O）和0.05g乙酸镍（C4H6O4Ni·H2O）溶于100mL无水乙醇中，得到溶液A；称取0.02g分散剂聚乙烯吡咯烷酮溶于无水乙醇后加入到20g纳米硅液体（硅含量为2g）中，并超声30min得到溶液B，将溶液B倒入溶液A中，得到混合浆料；(1) Weigh 14.25g of citric acid (C 6 H 8 O 7 ·H 2 O) and 0.05g of nickel acetate (C 4 H 6 O 4 Ni · H 2 O) and dissolve them in 100mL of absolute ethanol to obtain a solution A: Weigh 0.02g of dispersant polyvinylpyrrolidone, dissolve it in absolute ethanol, add it to 20g of nano-silicon liquid (silicon content is 2g), and sonicate for 30min to obtain solution B, and pour solution B into solution A to obtain a mixed slurry material;
（2）在1000r/min的搅拌速度下将步骤（1）得到的混合浆料搅拌1h，然后加入无水乙醇调节混合浆料的固体含量约为15%（质量），在搅拌的条件下将混合浆料通过蠕动泵抽送至雾化器上进行离心式闭式循环喷雾干燥得到前驱体A；其中进料速度为15mL/min，进口温度为105℃，出口温度为80℃，雾化器转速为30000r/min；(2) Stir the mixed slurry obtained in step (1) for 1 hour at a stirring speed of 1000r/min, then add absolute ethanol to adjust the solid content of the mixed slurry to about 15% (mass), and mix The mixed slurry was pumped to the atomizer by a peristaltic pump for centrifugal closed cycle spray drying to obtain precursor A; the feed rate was 15mL/min, the inlet temperature was 105°C, the outlet temperature was 80°C, and the atomizer speed 30000r/min;
（3）将步骤（2）所得的前驱体A放入坩埚，转移至管式炉中，通入纯度99.999%的氮气并以3℃/min的速率升温至500℃后保温3h，然后自然冷却至室温，得到前驱体B；(3) Put the precursor A obtained in step (2) into a crucible, transfer it to a tube furnace, pass in nitrogen gas with a purity of 99.999%, raise the temperature to 500°C at a rate of 3°C/min, keep it warm for 3h, and then cool it naturally to room temperature to obtain precursor B;
（4）将步骤（3）所得的前驱体B再次转移到管式炉中，通入乙炔和氮气的混合气（其中氮气质量含量为30%），并以3℃/min的速率升温至700℃并保温3h，然后自然冷却到室温，得到所述锂电池硅碳纳米管复合负极材料。(4) The precursor B obtained in step (3) was transferred to the tube furnace again, and the mixed gas of acetylene and nitrogen (in which the mass content of nitrogen was 30%) was introduced, and the temperature was raised to 700 °C at a rate of 3 °C/min. ℃ and kept warm for 3 hours, and then naturally cooled to room temperature to obtain the silicon-carbon nanotube composite negative electrode material for a lithium battery.
（二）将最终获得的产物进行SEM形貌和XRD物相检测，SEM形貌检测结果如图1所示，XRD物相检测结果如图2所示。从图1可看到，在硅碳微球表面覆盖了无序的管状物。而从图2的XRD物相检测结果可看到，该图谱与碳纳米管的标准卡片JCPDSno.041-1487和硅的标准卡片JCPDSno.027-1402相吻合，表明所检测的产物中生成了无序管状物为碳纳米管。(2) The SEM morphology and XRD phase detection of the final product were carried out. The SEM morphology detection results are shown in Figure 1, and the XRD phase detection results are shown in Figure 2. It can be seen from Figure 1 that the surface of silicon carbon microspheres is covered with disordered tubes. From the XRD phase detection results of Fig. 2, it can be seen that the spectrum matches the standard card JCPDSno.041-1487 of carbon nanotubes and the standard card JCPDSno.027-1402 of silicon, indicating that no The sequential tubes are carbon nanotubes.
（三）制备锂电池负极片，具体步骤如下：(3) Preparation of lithium battery negative electrode sheet, the specific steps are as follows:
（1）将1.875g步骤（一）所制得的锂电池硅碳纳米管复合负极材料、2.5g粘结剂LA132（粘结剂固体含量为15%）和0.25g的导电炭黑均匀混合，调成浆料；(1) Mix 1.875g of silicon-carbon nanotube composite anode material for lithium batteries prepared in step (1), 2.5g of binder LA132 (solid content of binder is 15%) and 0.25g of conductive carbon black, into a paste;
（2）将步骤（1）制得的浆料涂覆在铜箔上，涂覆厚度为100微米，并在110℃下真空干燥8小时、辊压（厚度为80微米）制备成锂离子电池负极片1。(2) Coat the slurry prepared in step (1) on a copper foil with a coating thickness of 100 microns, dry it in vacuum at 110°C for 8 hours, and roll it (80 microns in thickness) to prepare a lithium-ion battery Negative plate 1.
实施例2Example 2
（一）制备锂电池硅碳纳米管复合负极材料，具体步骤如下：(1) Preparation of silicon-carbon nanotube composite negative electrode material for lithium battery, the specific steps are as follows:
（1）分别称取2.85g酚醛树脂和0.05g乙酸镍（C4H6O4Ni·H2O）溶于100mL无水乙醇中，得到溶液A；称取0.04g分散剂聚乙烯亚胺溶于无水乙醇后加入到40g纳米硅液体（硅含量为4g）中，并超声60min得到溶液B，将溶液B倒入溶液A中，得到混合浆料；(1) Dissolve 2.85g of phenolic resin and 0.05g of nickel acetate (C 4 H 6 O 4 Ni·H 2 O) in 100mL of absolute ethanol to obtain solution A; weigh 0.04g of dispersant polyethyleneimine After dissolving in absolute ethanol, add it to 40g of nano-silicon liquid (silicon content is 4g), and sonicate for 60min to obtain solution B, then pour solution B into solution A to obtain a mixed slurry;
（2）在1200r/min的搅拌速度下将步骤（1）得到的混合浆料搅拌1h，然后加入无水乙醇调节混合浆料的固体含量约为20%（质量），将混合浆料通过蠕动泵抽送至雾化器上进行离心式闭式循环喷雾干燥得到前驱体A；其中进料速度为15mL/min，进口温度为110℃，出口温度为82℃，雾化器转速为20000r/min；(2) Stir the mixed slurry obtained in step (1) for 1 hour at a stirring speed of 1200r/min, then add absolute ethanol to adjust the solid content of the mixed slurry to about 20% (mass), and pass the mixed slurry through peristalsis Pumped to the atomizer for centrifugal closed cycle spray drying to obtain precursor A; wherein the feed rate is 15mL/min, the inlet temperature is 110°C, the outlet temperature is 82°C, and the atomizer speed is 20000r/min;
（3）将步骤（2）所得的前驱体A放入坩埚，转移至管式炉中，通入纯度99.999%的氩气并以4℃/min的速率升温至300℃后保温5h，然后自然冷却至室温，得到前驱体B；(3) Put the precursor A obtained in step (2) into a crucible, transfer it to a tube furnace, pass in argon gas with a purity of 99.999%, and raise the temperature to 300°C at a rate of 4°C/min, keep it warm for 5h, and then naturally Cool to room temperature to obtain precursor B;
（4）将步骤（3）所得的前驱体B再次转移到管式炉中，通入甲烷和氩气的混合气（其中氩气质量含量为50%），并以2℃/min的速率升温至500℃并保温5h，然后自然冷却到室温，得到所述锂电池硅碳纳米管复合负极材料。(4) The precursor B obtained in step (3) was transferred to the tube furnace again, and the mixed gas of methane and argon (where the mass content of argon was 50%) was introduced, and the temperature was raised at a rate of 2°C/min to 500° C. and keep it warm for 5 hours, and then naturally cool to room temperature to obtain the silicon-carbon nanotube composite negative electrode material for a lithium battery.
（二）制备锂电池负极片，具体步骤如下：(2) Preparation of lithium battery negative electrode sheet, the specific steps are as follows:
（1）将1.875g步骤（一）所制得的锂电池硅碳纳米管复合负极材料、2.5g粘结剂LA132（粘结剂固体含量为15%）和0.25g的导电炭黑均匀混合，调成浆料；(1) Mix 1.875g of silicon-carbon nanotube composite anode material for lithium batteries prepared in step (1), 2.5g of binder LA132 (solid content of binder is 15%) and 0.25g of conductive carbon black, into a paste;
（2）将步骤（1）制得的浆料涂覆在铜箔上，涂覆厚度为100微米，并在110℃下真空干燥8小时、辊压（厚度为80微米）制备成锂离子电池负极片2。 (2) Coat the slurry prepared in step (1) on a copper foil with a coating thickness of 100 microns, dry it in vacuum at 110°C for 8 hours, and roll it (80 microns in thickness) to prepare a lithium-ion battery Negative plate 2.
实施例3Example 3
（一）制备锂电池硅碳纳米管复合负极材料，具体步骤如下：(1) Preparation of silicon-carbon nanotube composite negative electrode material for lithium battery, the specific steps are as follows:
（1）分别称取2.45g高温沥青和0.05g乙酸铁溶于四氢呋喃和无水乙醇中，得到溶液A；称取0.04g分散剂聚醚酰亚胺溶于无水乙醇后加入到40g纳米硅液体（硅含量为4g）中，并超声1.5h得到溶液B，将溶液B倒入溶液A中，得到混合浆料；(1) Weigh 2.45g of high-temperature asphalt and 0.05g of iron acetate and dissolve them in tetrahydrofuran and absolute ethanol to obtain solution A; weigh 0.04g of dispersant polyetherimide and dissolve them in absolute ethanol and add them to 40g of nano silicon Liquid (silicon content is 4g), and ultrasonic 1.5h to obtain solution B, solution B is poured into solution A to obtain a mixed slurry;
（2）在800r/min的搅拌速度下将步骤（1）得到的混合浆料搅拌2h，然后加入四氢呋喃调节混合浆料的固体含量约为25%（质量），将混合浆料通过蠕动泵抽送至雾化器上进行离心式闭式循环喷雾干燥得到前驱体A；其中进料速度为15mL/min，进口温度为115℃，出口温度为85℃，雾化器转速为35000r/min；(2) Stir the mixed slurry obtained in step (1) for 2 hours at a stirring speed of 800r/min, then add tetrahydrofuran to adjust the solid content of the mixed slurry to about 25% (mass), and pump the mixed slurry through a peristaltic pump To the atomizer for centrifugal closed cycle spray drying to obtain precursor A; wherein the feed rate is 15mL/min, the inlet temperature is 115°C, the outlet temperature is 85°C, and the atomizer speed is 35000r/min;
（3）将步骤（2）所得的前驱体A放入坩埚，转移至管式炉中，通入纯度99.999%的氮气并以5℃/min的速率升温至900℃后保温1h，然后自然冷却至室温，得到前驱体B；(3) Put the precursor A obtained in step (2) into a crucible, transfer it to a tube furnace, pass in nitrogen gas with a purity of 99.999%, raise the temperature to 900°C at a rate of 5°C/min, keep it warm for 1h, and then cool it naturally to room temperature to obtain precursor B;
（4）将步骤（3）所得的前驱体B再次转移到管式炉中，通入天然气和氮气的混合气（其中氮气质量含量为70%），并以5℃/min的速率升温至900℃并保温1h，然后自然冷却到室温，得到所述锂电池硅碳纳米管复合负极材料。(4) The precursor B obtained in step (3) was transferred to the tube furnace again, and the mixed gas of natural gas and nitrogen (in which the mass content of nitrogen was 70%) was introduced, and the temperature was raised to 900 °C at a rate of 5 °C/min. ℃ and kept warm for 1 h, then naturally cooled to room temperature to obtain the silicon-carbon nanotube composite negative electrode material for a lithium battery.
（二）制备锂电池负极片，具体步骤如下：(2) Preparation of lithium battery negative electrode sheet, the specific steps are as follows:
（1）将1.875g步骤（一）所制得的锂电池硅碳纳米管复合负极材料、2.5g粘结剂LA132（粘结剂固体含量为15%）和0.25g的导电炭黑均匀混合，调成浆料；(1) Mix 1.875g of silicon-carbon nanotube composite anode material for lithium batteries prepared in step (1), 2.5g of binder LA132 (solid content of binder is 15%) and 0.25g of conductive carbon black, into a paste;
（2）将步骤（1）制得的浆料涂覆在铜箔上，涂覆厚度为100微米，并在110℃下真空干燥8小时、辊压（厚度为80微米）制备成锂离子电池负极片3。(2) Coat the slurry prepared in step (1) on a copper foil with a coating thickness of 100 microns, dry it in vacuum at 110°C for 8 hours, and roll it (80 microns in thickness) to prepare a lithium-ion battery Negative plate 3.
实施例4（对比实施例）Embodiment 4 (comparative embodiment)
（一）制备锂电池硅碳复合负极材料，具体步骤如下：(1) Preparation of silicon-carbon composite anode materials for lithium batteries, the specific steps are as follows:
（1）分别称取14.25g柠檬酸（C6H8O7·H2O）和0.05g乙酸镍溶于100mL无水乙醇中，得到溶液A；称取0.02g分散剂十二烷基硫酸钠溶于无水乙醇后加入到20g纳米硅液体（硅含量为2g）中，并超声2h得到溶液B，将溶液B倒入溶液A中，得到混合浆料；(1) Dissolve 14.25g of citric acid (C 6 H 8 O 7 ·H 2 O) and 0.05g of nickel acetate in 100mL of absolute ethanol to obtain solution A; weigh 0.02g of dispersant lauryl sulfate Sodium was dissolved in absolute ethanol and added to 20g of nano-silicon liquid (silicon content: 2g), and ultrasonicated for 2 hours to obtain solution B, and solution B was poured into solution A to obtain a mixed slurry;
（2）在2000r/min的搅拌速度下将步骤（1）得到的混合浆料搅拌2h，然后加入无水乙醇调节混合浆料的固体含量约为15%，将混合浆料通过蠕动泵抽送至雾化器上进行离心式闭式循环喷雾干燥得到前驱体A；其中进料速度为15mL/min，进口温度为120℃，出口温度为90℃，雾化器转速为30000r/min；(2) Stir the mixed slurry obtained in step (1) for 2 hours at a stirring speed of 2000r/min, then add absolute ethanol to adjust the solid content of the mixed slurry to about 15%, and pump the mixed slurry to Precursor A was obtained by centrifugal closed-cycle spray drying on the atomizer; the feed rate was 15mL/min, the inlet temperature was 120°C, the outlet temperature was 90°C, and the atomizer speed was 30000r/min;
（3）将步骤（2）所得的前驱体A放入坩埚，转移至管式炉中，通入纯度99.999%的氮气并以3℃/min的速率升温至500℃后保温3h，然后自然冷却至室温，得到锂电池硅碳复合负极材料。(3) Put the precursor A obtained in step (2) into a crucible, transfer it to a tube furnace, pass in nitrogen gas with a purity of 99.999%, raise the temperature to 500°C at a rate of 3°C/min, keep it warm for 3h, and then cool it naturally to room temperature to obtain a silicon-carbon composite negative electrode material for a lithium battery.
（二）制备锂电池负极片，具体步骤如下：(2) Preparation of lithium battery negative electrode sheet, the specific steps are as follows:
（1）将1.875g步骤（一）所制得的锂电池硅碳纳米管复合负极材料、2.5g粘结剂LA132（粘结剂固体含量为15%）和0.25g的导电炭黑均匀混合，调成浆料；(1) Mix 1.875g of silicon-carbon nanotube composite anode material for lithium batteries prepared in step (1), 2.5g of binder LA132 (solid content of binder is 15%) and 0.25g of conductive carbon black, into a paste;
（2）将步骤（1）制得的浆料涂覆在铜箔上，涂覆厚度为100微米，并在110℃下真空干燥8小时、辊压（厚度为80微米）制备成锂离子电池负极片4。(2) Coat the slurry prepared in step (1) on a copper foil with a coating thickness of 100 microns, dry it in vacuum at 110°C for 8 hours, and roll it (80 microns in thickness) to prepare a lithium-ion battery Negative sheet 4.
上述实施例1～4中在锂电池负极片的制备中，粘结剂均选择为粘结剂LA138和导电剂均为导电炭黑，各原料的重量比相同，以及对锂电池负极片涂覆厚度和辊压厚度均相同，仅为了更好地对上述实施例的效果进行比较，而不是对粘结剂和导电剂种类、原料重量比以及锂电池负极片厚度的限定。In the above-mentioned Examples 1 to 4, in the preparation of the lithium battery negative electrode sheet, the binder is selected as the binder LA138 and the conductive agent is conductive carbon black, the weight ratio of each raw material is the same, and the lithium battery negative electrode sheet is coated with The thickness and rolling thickness are the same, only to better compare the effects of the above examples, rather than limiting the type of binder and conductive agent, the weight ratio of raw materials, and the thickness of the lithium battery negative electrode sheet.
效果实施例Effect example
将实施例1至4所得到的锂离子电池负极片分别以1mol/L LiPF6的三组分混合溶剂EC：DMC：EMC＝1：1：1（体积比v/v/v），溶液为电解液，聚丙烯微孔膜为隔膜，锂片为对电极组装成模拟电池1～4。The negative electrode sheets of lithium ion batteries obtained in Examples 1 to 4 were respectively mixed with a three-component mixed solvent EC of 1mol/L LiPF: DMC: EMC = 1: 1: 1 (volume ratio v/v/v), and the solution was electrolytic liquid, polypropylene microporous membrane as separator, and lithium sheet as counter electrode to assemble simulated batteries 1-4.
对模拟电池进行1～4进行循环性能测试，以LAND CT2001A（武汉金诺电子有限公司）为电池测试***，用100mA/g的电流密度进行恒电流充放电测试，电压范围为0.01～2.0V。Carry out 1-4 cycle performance tests on the simulated battery, use LAND CT2001A (Wuhan Jinnuo Electronics Co., Ltd.) as the battery test system, and conduct a constant current charge-discharge test with a current density of 100mA/g, and the voltage range is 0.01-2.0V.
图3为模拟电池1的充放电循环性能图，由图可知模拟电池1的锂离子电池比容量高，首次的放电和充电比容量分别为为2168.7mAh/g和1584.1mAh/g，首次循环效率为73%。循环50周，比容量还保持在1172mAh/g以上，循环性能好。Figure 3 is the charge-discharge cycle performance diagram of simulated battery 1. It can be seen from the figure that the lithium-ion battery of simulated battery 1 has a high specific capacity, the first discharge and charge specific capacities are 2168.7mAh/g and 1584.1mAh/g respectively, and the first cycle efficiency 73%. After 50 cycles, the specific capacity remains above 1172mAh/g, and the cycle performance is good.
图4为模拟电池2的充放电循环性能图，由图可知模拟电池2的锂离子电池比容量高，首次的放电和充电比容量分别为为2106.8mAh/g和1567.3mAh/g，首次循环效率为74%。循环50周，比容量还保持在1137mAh/g以上，循环性能好。Figure 4 is the charge-discharge cycle performance diagram of the simulated battery 2. It can be seen from the figure that the lithium-ion battery of the simulated battery 2 has a high specific capacity. The first discharge and charge specific capacities are 2106.8mAh/g and 1567.3mAh/g respectively. 74%. After 50 cycles, the specific capacity remains above 1137mAh/g, and the cycle performance is good.
图5为模拟电池3的充放电循环性能图，由图可知模拟电池3的锂离子电池比容量高，首次的放电和充电比容量分别为为2005.3mAh/g和1440.3mAh/g，首次循环效率为72%。循环50周，比容量还保持在1067mAh/g以上，循环性能好。Figure 5 is the charge-discharge cycle performance diagram of the simulated battery 3. It can be seen from the figure that the specific capacity of the lithium-ion battery of the simulated battery 3 is high. 72%. After 50 cycles, the specific capacity remains above 1067mAh/g, and the cycle performance is good.
图6为模拟电池4的充放电循环性能图，由图可知模拟电池4首次的放电和充电比容量分别为为2201.3mAh/g和1674.4mAh/g，首次循环效率为76%。循环50周，比容量仅有580mAh/g，循环性能较差。Fig. 6 is a charge-discharge cycle performance diagram of the simulated battery 4. It can be seen from the figure that the first discharge and charge specific capacities of the simulated battery 4 are 2201.3mAh/g and 1674.4mAh/g respectively, and the first cycle efficiency is 76%. After 50 cycles, the specific capacity is only 580mAh/g, and the cycle performance is poor.
模拟电池1～3的充放电循环性能优于模拟电池4的原因在于，实施例1至3的制备方法中，在步骤（3）的热处理中生成了热解碳，在步骤（4）的热处理中生成了碳纳米管，而步骤（1）加入的催化剂在干燥过程中可以使得后续气相沉积的碳纳米管在硅碳微球的内部空隙和表面都可生长、结合的更加紧密。而锂离子电池负极片1～3中所含的硅碳纳米管复合材料中无序的碳纳米管和热解碳起到了非常关键的作用：首先，碳纳米管和热解碳可以有效的缓解脱嵌锂过程中硅的体积膨胀效应，抑制活性物质的粉化；其次，碳纳米管和热解碳可以提供电子传输的通道，能够提高活性物质硅的导电性。The reason why the charge-discharge cycle performance of simulated batteries 1 to 3 is better than that of simulated battery 4 is that, in the preparation methods of Examples 1 to 3, pyrolytic carbon is generated in the heat treatment of step (3), and in the heat treatment of step (4) The carbon nanotubes are generated in the process, and the catalyst added in the step (1) can make the subsequent vapor-phase deposited carbon nanotubes grow and bond more tightly in the internal voids and surfaces of the silicon carbon microspheres during the drying process. The disordered carbon nanotubes and pyrolytic carbon in the silicon-carbon nanotube composites contained in the negative electrode sheets 1 to 3 of lithium-ion batteries play a very critical role: first, carbon nanotubes and pyrolytic carbon can effectively alleviate the The volume expansion effect of silicon during the lithium-deintercalation process inhibits the pulverization of the active material; secondly, carbon nanotubes and pyrolytic carbon can provide electron transport channels, which can improve the conductivity of the active material silicon.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.
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