CN108232141B - High-compaction lithium ion battery silicon-carbon composite negative electrode material and preparation method thereof - Google Patents
High-compaction lithium ion battery silicon-carbon composite negative electrode material and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
Description
技术领域technical field
本发明属于电池技术领域，具体涉及一种高压实的硅碳复合负极材料和其制备方法以及含有所述硅碳复合材料的电池负极和锂离子电池。The invention belongs to the technical field of batteries, and in particular relates to a high-compact silicon-carbon composite negative electrode material and a preparation method thereof, as well as a battery negative electrode and a lithium ion battery containing the silicon-carbon composite material.
背景技术：Background technique:
锂离子电池由于具有高比容量、高能量密度和功率密度、无自放电、绿色环保等优点，已经成为目前科学研究和工业开发的热点。随着便携式电子产品、电动交通工具以及储能电站等领域的快速发展，锂离子电池的能量密度、功率密度和循环寿命等性能指标也需要进一步提升。目前商业化锂离子电池中负极材料主要是石墨类材料，而石墨类材料的理论容量为372mAh/g，限制了锂离子电池能量密度的进一步提高。因此，开发高容量的负极材料是解决当今社会能源问题的关键。Due to the advantages of high specific capacity, high energy density and power density, no self-discharge, and green environmental protection, lithium-ion batteries have become a hot spot in current scientific research and industrial development. With the rapid development of portable electronic products, electric vehicles, and energy storage power stations, performance indicators such as energy density, power density, and cycle life of lithium-ion batteries also need to be further improved. At present, the anode materials in commercial lithium-ion batteries are mainly graphite-based materials, and the theoretical capacity of graphite-based materials is 372mAh/g, which limits the further improvement of the energy density of lithium-ion batteries. Therefore, the development of high-capacity anode materials is the key to solving energy problems in today's society.
以硅基材料为代表的新型高比容量负极材料受到了人们的广泛关注。硅基负极材料具有高的储锂容量和较低的电压平台，是非常理想的下一代锂离子电池负极材料。然而，硅基材料在脱嵌锂过程中具有巨大的体积膨胀率(>300％)和低的电导率，而且其首圈库伦效率很低，导致其至今没有得到广泛的使用。目前的解决办法通常是将硅基材料与碳材料进行复合来提高材料的导电性和循环稳定性：碳材料的电导率高，与常规电解液兼容性好，将硅基材料均匀的分散在碳材料中能显著提升复合材料整体的导电性；硅基材料均匀的分散在碳材料中，碳材料能有效的缓冲硅基材料的体积膨胀，从而降低复合材料整体的体积膨胀率，提升复合材料的循环稳定性。因此，硅基材料与碳材料的复合得到了广泛的研究，但是在不影响其容量发挥的前提下，开发一种低成本、可大规模制备、耐高压实的硅碳复合材料仍是所属领域的技术难题。New high specific capacity anode materials represented by silicon-based materials have received extensive attention. Silicon-based anode materials have high lithium storage capacity and low voltage platform, and are very ideal anode materials for next-generation lithium-ion batteries. However, silicon-based materials have a huge volume expansion rate (>300%) and low electrical conductivity during lithium deintercalation, and their first-cycle Coulombic efficiency is very low, so they have not been widely used so far. The current solution is usually to compound silicon-based materials with carbon materials to improve the electrical conductivity and cycle stability of the materials: carbon materials have high electrical conductivity, good compatibility with conventional electrolytes, and uniformly disperse silicon-based materials in carbon materials. The overall conductivity of the composite material can be significantly improved in the material; the silicon-based material is uniformly dispersed in the carbon material, and the carbon material can effectively buffer the volume expansion of the silicon-based material, thereby reducing the overall volume expansion rate of the composite material and improving the composite material. Cyclic stability. Therefore, the composite of silicon-based materials and carbon materials has been widely studied, but under the premise of not affecting its capacity, the development of a low-cost, large-scale preparation, high-pressure-resistant silicon-carbon composite material is still a part of technical problems in the field.
CN103123967A公开了一种锂离子电池SiO/C复合负极材料及其制备方法，步骤包括：将石墨、正硅酸乙酯、聚乙烯吡咯烷酮在溶剂中分散均匀；调节pH值至8-9，除去溶剂后在惰性气氛下热解；将柠檬酸的乙醇溶液与上述产物混合，球磨后在惰性气氛下热解即得到SiO/C复合负极材料。该发明采用液态的正硅酸乙酯为硅源，使水解产生的氧化硅能更均匀的分散在石墨中，再通过热解柠檬酸的乙醇溶液引入碳源，克服了现有的SiO/C复合负极材料循环稳定性差以及煅烧温度高的缺点，提供了一种比容量高和循环稳定性好的锂离子电池SiO/C复合负极材料及其制备方法。但该方法需要多次去除溶剂及惰性气氛下热解的步骤，操作过程繁琐，同时该方法以正硅酸乙酯为硅源，水解产物的氧含量不易控制，不利于商业化。CN103022446A公开了一种锂离子电池硅氧化物/碳负极材料及其制备方法，该发明公开的锂离子电池硅氧化物/碳负极材料是具有核壳结构的三层复合材料，采用石墨材料为内核，多孔硅氧化物为中间层，有机热解碳为最外包覆层；其制备方法包括多孔SiOx的制备及碳包覆工艺；但该方法需要加入活性金属以还原部分SiOx，所得生成物结构虽然对硅颗粒在充放电过程中的体积膨胀效应能进行自吸收，但是活性金属的引入会大大降低该材料的质量比容量，同时提高了材料的整体活性，使制备难度增加，商业化困难。CN105655564A公开了一种具有核壳结构的SiOx/C复合材料及其制备方法，该发明中的SiOx颗粒表面具有非晶态的导电碳层，且所述硅碳复合材料颗粒之间具有自由空间，可以缓冲充放电过程中产生的巨大的体积膨胀，从而提高材料的循环性能。然而，该材料的制备过程需要在SiOx颗粒表面在有机碳源气体、氢气和惰性气体环境中包覆非晶态的导电碳层，该方法效率低且对设备要求高，不适合大规模制备；而且该发明公开的材料为具有空隙的核壳结构，在用作高压实密度的负极材料时很难保持原有的形貌，循环性能较差。CN103123967A discloses a lithium ion battery SiO/C composite negative electrode material and a preparation method thereof. The steps include: dispersing graphite, ethyl orthosilicate and polyvinyl pyrrolidone evenly in a solvent; adjusting the pH value to 8-9, and removing the solvent and then pyrolyzed in an inert atmosphere; the ethanol solution of citric acid is mixed with the above product, and after ball milling, the SiO/C composite negative electrode material is obtained by pyrolysis in an inert atmosphere. The invention adopts liquid ethyl orthosilicate as the silicon source, so that the silicon oxide produced by hydrolysis can be more uniformly dispersed in the graphite, and then the carbon source is introduced through the ethanol solution of pyrolysis citric acid, which overcomes the existing SiO/C Due to the disadvantages of poor cycle stability and high calcination temperature of the composite negative electrode material, a SiO/C composite negative electrode material for lithium ion batteries with high specific capacity and good cycle stability and a preparation method thereof are provided. However, this method requires multiple steps of removing the solvent and pyrolysis in an inert atmosphere, and the operation process is cumbersome. At the same time, the method uses ethyl orthosilicate as the silicon source, and the oxygen content of the hydrolyzate is difficult to control, which is unfavorable for commercialization. CN103022446A discloses a lithium ion battery silicon oxide/carbon negative electrode material and a preparation method thereof. The lithium ion battery silicon oxide/carbon negative electrode material disclosed in the invention is a three-layer composite material with a core-shell structure, and a graphite material is used as the core , the porous silicon oxide is the middle layer, and the organic pyrolytic carbon is the outermost coating layer; the preparation method includes the preparation of porous SiOx and the carbon coating process; but this method needs to add active metal to reduce part of the SiOx , and the resulting Although the material structure can self-absorb the volume expansion effect of silicon particles during the charging and discharging process, the introduction of active metals will greatly reduce the mass specific capacity of the material, and at the same time improve the overall activity of the material, making it more difficult to prepare and commercialize difficulty. CN105655564A discloses a SiO x /C composite material with a core-shell structure and a preparation method thereof. In the invention, the surface of the SiO x particles has an amorphous conductive carbon layer, and the silicon-carbon composite material particles have free space, which can buffer the huge volume expansion generated during the charging and discharging process, thereby improving the cycling performance of the material. However, the preparation process of this material requires an amorphous conductive carbon layer to be coated on the surface of SiO x particles in an organic carbon source gas, hydrogen and an inert gas environment, which is inefficient and requires high equipment and is not suitable for large-scale preparation. Moreover, the material disclosed in the invention is a core-shell structure with voids, and it is difficult to maintain the original morphology when used as a negative electrode material with high compaction density, and the cycle performance is poor.
本发明使用硅基材料与碳材料二次造粒及表面包覆的方法制备出片状的硅碳复合负极材料。与其他制备方法相比，该方法简单高效，得到的片状材料本身结构稳固，在高压实体系下也能保持材料原来的形貌而不破碎，使材料具有更好的循环性能和压实性能，而且片状材料的倍率性能也更为优异。在作为锂离子电池负极材料时，即使在1.5g/cm3的高压实密度条件下依然表现出高的充放电容量和优异的循环和倍率性能。The invention uses the method of secondary granulation and surface coating of silicon-based material and carbon material to prepare a sheet-shaped silicon-carbon composite negative electrode material. Compared with other preparation methods, the method is simple and efficient, and the obtained sheet material itself has a stable structure, and can maintain the original shape of the material without breaking under the high-pressure compaction system, so that the material has better cycle performance and compaction. performance, and the rate performance of the sheet material is also more excellent. When used as a negative electrode material for lithium-ion batteries, it still exhibits high charge-discharge capacity and excellent cycle and rate performance even under the condition of a high compaction density of 1.5 g/ cm3 .
发明内容SUMMARY OF THE INVENTION
本发明的目的在于解决现有硅基复合材料循环性能和压实性能不佳的问题，提供了一种高压实的硅碳复合负极材料及其制备方法，从而提升当前锂离子电池负极材料的循环寿命和能量密度。The purpose of the present invention is to solve the problems of poor cycle performance and compaction performance of existing silicon-based composite materials, and to provide a high-compact silicon-carbon composite negative electrode material and a preparation method thereof, thereby improving the current negative electrode material for lithium ion batteries. Cycle life and energy density.
为实现上述发明目的，本发明提供了一种高压实的硅碳复合负极材料的制备方法，包括如下步骤：In order to achieve the above purpose of the invention, the present invention provides a method for preparing a high-compact silicon-carbon composite negative electrode material, comprising the following steps:
1)将硅基材料、聚二烯丙基二甲基氯化铵和水混合球磨，二者结合后得到硅基材料颗粒表面带正电荷的浆料A；1) The silicon-based material, polydiallyl dimethyl ammonium chloride and water are mixed and ball-milled, and the two are combined to obtain a positively charged slurry A on the surface of the silicon-based material particle;
2)将碳材料、表面活性剂和水混合球磨，得到碳材料表面带负电荷的浆料B；2) mixing and ball milling the carbon material, surfactant and water to obtain a negatively charged slurry B on the surface of the carbon material;
3)将浆料A与浆料B混合并加入粘合剂球磨，再加入适量水调节至合适的固含量喷雾干燥得到黑色粉末；3) mixing slurry A and slurry B and adding a binder for ball milling, then adding an appropriate amount of water to adjust to a suitable solid content and spray drying to obtain black powder;
4)对上述黑色粉末高温热解后进行表面包覆处理，再热解后即得高压实的锂离子电池硅碳复合负极材料。4) After the above-mentioned black powder is pyrolyzed at a high temperature, a surface coating treatment is performed, and after pyrolysis, a high-compression silicon-carbon composite negative electrode material for a lithium ion battery is obtained.
步骤(1)中，所述硅基材料为无定形硅、硅的氧化物、硅纳米颗粒、硅薄膜、硅纳米管、硅纳米线、多孔硅、中空结构的硅中的一种或多种组合，优选为无定形硅、硅的氧化物、硅纳米颗粒、多孔硅中的一种或多种组合。In step (1), the silicon-based material is one or more of amorphous silicon, silicon oxides, silicon nanoparticles, silicon thin films, silicon nanotubes, silicon nanowires, porous silicon, and hollow-structured silicon A combination, preferably one or more combinations of amorphous silicon, silicon oxides, silicon nanoparticles, and porous silicon.
步骤(1)中，所述聚二烯丙基二甲基氯化铵的分子量为50000-300000，优选为100000-200000。In step (1), the molecular weight of the polydiallyldimethylammonium chloride is 50000-300000, preferably 100000-200000.
步骤(1)中，所述浆料A的固含量为15-30％，优选为20-25％。In step (1), the solid content of the slurry A is 15-30%, preferably 20-25%.
步骤(2)中，所述碳材料为中间相碳微球、硬碳、软碳、鳞片石墨、晶质石墨、石墨烯、碳纳米管、乙炔黑中的一种或多种组合，优选为鳞片石墨、石墨烯、中间相碳微球、乙炔黑中的一种或几种组合。In step (2), the carbon material is one or more combinations of mesocarbon microspheres, hard carbon, soft carbon, flake graphite, crystalline graphite, graphene, carbon nanotubes, and acetylene black, preferably One or a combination of flake graphite, graphene, mesocarbon microspheres, and acetylene black.
步骤(2)中，所述表面活性剂为阴离子型表面活性剂与非离子型表面活性剂组合，如十二烷基硫酸钠与聚乙烯吡咯烷酮组合、十二烷基硫酸钠与聚乙二醇组合、阴离子型聚丙烯酰胺和聚乙烯吡咯烷酮组合、阴离子型聚丙烯酰胺与聚乙二醇组合，优选为十二烷基硫酸钠与聚乙烯吡咯烷酮组合、阴离子型聚丙烯酰胺与聚乙二醇组合。In step (2), the surfactant is a combination of anionic surfactants and non-ionic surfactants, such as the combination of sodium lauryl sulfate and polyvinylpyrrolidone, sodium lauryl sulfate and polyethylene glycol. combination, combination of anionic polyacrylamide and polyvinylpyrrolidone, combination of anionic polyacrylamide and polyethylene glycol, preferably sodium lauryl sulfate and polyvinylpyrrolidone, combination of anionic polyacrylamide and polyethylene glycol .
步骤(2)中，所述浆料B的固含量为15-30％，优选为20-25％。In step (2), the solid content of the slurry B is 15-30%, preferably 20-25%.
步骤(3)中，所述粘合剂为沥青、酚醛树脂、壳聚糖、蔗糖、葡萄糖、淀粉、聚糠醇中的一种或多种组合，优选为沥青、酚醛树脂、壳聚糖中的一种或多种组合。In step (3), the binder is one or more combinations of asphalt, phenolic resin, chitosan, sucrose, glucose, starch, and polyfurfuryl alcohol, preferably asphalt, phenolic resin, and chitosan. one or more combinations.
步骤(3)中，所述固含量为10-20％，优选为14-18％。In step (3), the solid content is 10-20%, preferably 14-18%.
步骤(3)中，所述混合浆料中硅基材料的含量为10-40wt％。In step (3), the content of the silicon-based material in the mixed slurry is 10-40 wt%.
步骤(1)-(3)中，所述球磨为行星式高能球磨，所用的氧化锆球直径为0.1-10mm。In steps (1)-(3), the ball mill is a planetary high-energy ball mill, and the diameter of the zirconia balls used is 0.1-10 mm.
步骤(1)-(3)中，所述球磨机的转速为300-800r/min，优选为400-600r/min。In steps (1)-(3), the rotational speed of the ball mill is 300-800 r/min, preferably 400-600 r/min.
步骤(1)-(2)中，所述球磨时间为0.5-2h，优选为1-1.5h。In steps (1)-(2), the ball milling time is 0.5-2h, preferably 1-1.5h.
步骤(3)中，所述球磨时间为2-6h，优选为3-5h。In step (3), the ball milling time is 2-6h, preferably 3-5h.
步骤(3)中，所述喷雾干燥为离心式喷雾干燥，转速为10000-30000r/min，优选为18000-26000r/min。In step (3), the spray drying is centrifugal spray drying, and the rotational speed is 10000-30000 r/min, preferably 18000-26000 r/min.
步骤(3)中，所述喷雾干燥进气口温度为160～300℃，优选为180-250℃，所述喷雾干燥出料口温度为80～120℃，优选为90-100℃，溶剂蒸发量为20-60L/h，优选为30-50L/h。In step (3), the temperature of the spray drying inlet is 160-300°C, preferably 180-250°C, the temperature of the spray-drying outlet is 80-120°C, preferably 90-100°C, and the solvent evaporates. The amount is 20-60 L/h, preferably 30-50 L/h.
步骤(4)中，所述热解的温度为600-1200℃，优选为800-1000℃；In step (4), the temperature of the pyrolysis is 600-1200°C, preferably 800-1000°C;
步骤(4)中，所述热解升温速度为0.5-10℃/min，优选为1-8℃/min。In step (4), the heating rate of the pyrolysis is 0.5-10°C/min, preferably 1-8°C/min.
步骤(4)中，所述热解的保温时间为2-8h，优选为3-6h。In step (4), the holding time of the pyrolysis is 2-8h, preferably 3-6h.
步骤(4)中，所述热解设备为气氛箱式炉、回转炉、管式炉或推板窑中的一种。In step (4), the pyrolysis equipment is one of an atmosphere box furnace, a rotary furnace, a tube furnace or a push-plate kiln.
步骤(4)中，所述热解是在惰性气氛保护下进行的，所述惰性气氛为氮气、氩气、氦气中的一种或多种的组合。In step (4), the pyrolysis is carried out under the protection of an inert atmosphere, and the inert atmosphere is one or a combination of nitrogen, argon, and helium.
步骤(4)中，所述表面包覆的方法包括固相包覆法和气相包覆法；所述固相包覆法的包覆剂为煤沥青、石油沥青、针状焦或石油焦中的一种或多种；所述气相包覆法为化学气相沉积法，包覆剂为乙炔或甲烷中的一种或两种。In step (4), the surface coating method includes a solid phase coating method and a gas phase coating method; the coating agent of the solid phase coating method is coal tar, petroleum tar, needle coke or petroleum coke. One or more of; the vapor coating method is chemical vapor deposition method, and the coating agent is one or both of acetylene or methane.
步骤(4)中，所述固相包覆的设备为固相包覆机；所述气相包覆的设备为CVD化学气相沉积炉。In step (4), the solid-phase coating equipment is a solid-phase coating machine; the gas-phase coating equipment is a CVD chemical vapor deposition furnace.
步骤(4)中，所述固相包覆的包覆剂的用量为复合材料质量的5-20wt％，优选8-15wt％。In step (4), the amount of the solid-phase-coated coating agent is 5-20 wt %, preferably 8-15 wt % of the mass of the composite material.
步骤(4)中，所述表面包覆的包覆层为无定形碳；所述的包覆层厚度为10-300nm。In step (4), the coating layer coated on the surface is amorphous carbon; the thickness of the coating layer is 10-300 nm.
步骤(4)中，所述气相包覆的气体质量流量为20-1000sccm，优选100-600sccm。In step (4), the gas mass flow rate of the gas phase coating is 20-1000 sccm, preferably 100-600 sccm.
本发明还提供了一种由上述制备方法制得的高压实的硅碳复合负极材料。本发明的硅碳复合材料为硅基材料和碳材料组成的片状结构，其中，硅基材料均匀地分散在碳材料中。The present invention also provides a high-compact silicon-carbon composite negative electrode material prepared by the above preparation method. The silicon-carbon composite material of the present invention is a sheet-like structure composed of a silicon-based material and a carbon material, wherein the silicon-based material is uniformly dispersed in the carbon material.
本发明所提供的应用是高压实的硅碳复合材料作为锂离子电池负极材料的应用，所述锂离子电池含有本发明提供的硅碳复合负极材料或由本发明制备方法制备的硅碳复合负极材料。The application provided by the present invention is the application of a high-compression silicon-carbon composite material as a negative electrode material for a lithium ion battery, and the lithium ion battery contains the silicon-carbon composite negative electrode material provided by the present invention or the silicon-carbon composite negative electrode prepared by the preparation method of the present invention. Material.
与现有技术相比，本发明提供的硅碳复合材料的制备方法的优势在于：制备方法简单，原料易得，适宜大规模生产，实用化程度高，且制得的硅碳复合材料为片状结构，本身结构稳固，在高压实体系下也能保持材料原来的形貌而不破碎，使材料具有更好的循环性能和压实性能，而且片状材料的倍率性能也更为优异。在作为锂离子电池负极材料时，即使在1.5g/cm3的高压实密度条件下依然表现出高的充放电容量和优异的循环和倍率性能。Compared with the prior art, the advantages of the preparation method of the silicon-carbon composite material provided by the present invention are that the preparation method is simple, the raw materials are easily obtained, it is suitable for large-scale production, the degree of practicability is high, and the prepared silicon-carbon composite material is a sheet. It has a stable structure and can maintain the original shape of the material under high-pressure compaction system without breaking, so that the material has better cycle performance and compaction performance, and the rate performance of the sheet material is also more excellent. When used as a negative electrode material for lithium-ion batteries, it still exhibits high charge-discharge capacity and excellent cycle and rate performance even under the condition of a high compaction density of 1.5 g/ cm3 .
附图说明Description of drawings
图1为本发明实施例1制得的高压实的硅碳复合负极材料的扫描电子显微镜照片。FIG. 1 is a scanning electron microscope photograph of the high-compact silicon-carbon composite negative electrode material prepared in Example 1 of the present invention.
图2为本发明实施例1制得的高压实的硅碳复合负极材料的高倍数扫描电子显微镜照片。2 is a high-magnification scanning electron microscope photograph of the high-compression silicon-carbon composite negative electrode material prepared in Example 1 of the present invention.
图3为本发明实施例1制得的高压实的硅碳复合负极材料作为锂离子电池负极材料时的充放电曲线。3 is a charge-discharge curve of the high-compact silicon-carbon composite negative electrode material prepared in Example 1 of the present invention as a negative electrode material for a lithium ion battery.
图4为本发明实施例1制得的高压实的硅碳复合负极材料作为锂离子电池负极材料时的循环性能曲线。4 is a cycle performance curve of the high-compact silicon-carbon composite negative electrode material prepared in Example 1 of the present invention as a negative electrode material for a lithium ion battery.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步说明，但本发明并不限于以下实施例。The present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited to the following embodiments.
下述实施例中所述实验方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials can be obtained from commercial sources unless otherwise specified.
下述实施例和对比例制备所得高压实的硅碳复合负极材料的电化学性能均按照下述方法进行测试：将制备得到的高压实的硅碳复合负极材料、碳黑和羧甲基纤维素(CMC)粘结剂以质量比90：5：5混合配成浆料，均匀地涂敷到铜箔集流体上，并经真空干燥、辊压至压实密度为1.5g/cm3，制备成工作电极；以锂金属薄片作为对电极，玻璃纤维膜(购自英国Whatman公司)作为隔膜，1mol/L LiPF6(溶剂为体积比1：1的碳酸乙烯酯和碳酸二甲酯混合液)作为电解液，在氩气氛围的德国布劳恩惰性气体手套箱中组装成扣式电池。The electrochemical properties of the high-compacted silicon-carbon composite negative electrode material prepared by the following examples and comparative examples are all tested according to the following method: the prepared high-compacted silicon-carbon composite negative electrode material, carbon black and carboxymethyl Cellulose (CMC) binder is mixed with a mass ratio of 90:5:5 to prepare a slurry, which is uniformly coated on the copper foil current collector, dried in vacuum and rolled to a compacted density of 1.5g/ cm3 , prepared into a working electrode; lithium metal flakes are used as counter electrodes, glass fiber membranes (purchased from Whatman, UK) are used as separators, 1mol/L LiPF6 (solvent is a mixture of ethylene carbonate and dimethyl carbonate with a volume ratio of 1:1) ) as the electrolyte, and assembled into a button cell in an inert gas glove box in Braun, Germany under an argon atmosphere.
将上述装配的电池在LAND充放电测试仪上进行充放电测试。The battery assembled above was charged and discharged on a LAND charge and discharge tester.
实施例1Example 1
将1kg粒径为50～100nm的SiOx颗粒、200g聚二烯丙基二甲基氯化铵和5L水球磨1h混合均匀得到浆料A；同时将2kg粒径为1～10um的薄层鳞片石墨、100g十二烷基硫酸钠、200g聚乙烯吡咯烷酮和10L水球磨1h混合均匀得到浆料B；将浆料A和B混合均匀后加入7.5L水和500g沥青球磨3h得到固含量为15％的均匀浆料；将得到的浆料进行喷雾干燥处理去除水分；在氮气保护的条件下，以2℃/min的升温速度升温至900℃并保温热解3h得到黑色粉末；将该黑色粉末置于CVD包覆炉中，以500sccm的气体质量流量通入乙炔气，在900℃下沉积3h；将包覆后的材料置于氮气保护的条件下，以3℃/min的升温速度升温至1000℃并保温3h，自然冷却得到片状高压实的硅碳复合负极材料。Mix 1kg of SiO x particles with a particle size of 50-100nm, 200g of polydiallyldimethylammonium chloride and 5L water ball mill for 1h to obtain slurry A; at the same time, 2kg of thin-layer flakes with a particle size of 1-10um are mixed. Graphite, 100g sodium dodecyl sulfate, 200g polyvinylpyrrolidone and 10L water ball mill for 1h to obtain slurry B; 7.5L water and 500g asphalt are added to ball mill for 3h to obtain a solid content of 15% after mixing slurry A and B evenly The obtained slurry was spray-dried to remove moisture; under nitrogen protection, the temperature was raised to 900°C at a heating rate of 2°C/min and thermally decomposed for 3h to obtain black powder; the black powder was placed in In the CVD coating furnace, acetylene gas was introduced at a gas mass flow of 500sccm, and deposited at 900 °C for 3 hours; the coated material was placed under nitrogen protection, and the temperature was increased to 1000 at a heating rate of 3 °C/min. ℃ and heat preservation for 3h, and natural cooling to obtain a sheet-like high-compacted silicon-carbon composite negative electrode material.
用扫描电镜(SEM，日本电子扫描电镜JEOL-6701F)分析复合材料的形貌，图1为制得的高压实的硅碳复合负极材料的扫描电镜照片，该复合材料为片状，表面致密且粒度均匀，粒径范围为5～20um。图2为该复合材料的高倍数扫描电镜照片，从图中可以看出该复合材料中的SiOx颗粒和薄层鳞片石墨均匀分布且融合为整体。Scanning electron microscope (SEM, JEOL-6701F) was used to analyze the morphology of the composite material. Figure 1 is a scanning electron microscope photo of the prepared high-compact silicon-carbon composite negative electrode material. The composite material is sheet-like and has a dense surface. And the particle size is uniform, the particle size range is 5 ~ 20um. FIG. 2 is a high-magnification scanning electron microscope photograph of the composite material. It can be seen from the figure that the SiO x particles and the thin-layer flake graphite in the composite material are uniformly distributed and integrated into a whole.
对发明所得的片状高压实的硅碳复合负极材料进行电化学分析测试，结果如图3所示。充放电区间为0～2V，压实密度为1.5g/cm3，在电流密度300mA/g(0.5C)下充放电，材料容量可达596.4mAh/g，首圈库伦效率为88.2％，且循环50圈容量保持率为97.9％(如图4)，证明本发明所得复合材料具有较高的容量、优异的循环性能和压实性能。所得片状高压实的硅碳复合负极材料在扣式电池中的测试结果列于表2。Electrochemical analysis and test were performed on the sheet-like high-compacted silicon-carbon composite negative electrode material obtained by the invention, and the results are shown in FIG. 3 . The charge-discharge range is 0-2V, the compaction density is 1.5g/cm 3 , and the material capacity can reach 596.4mAh/g under the current density of 300mA/g (0.5C), and the first cycle Coulomb efficiency is 88.2%, and The capacity retention rate after 50 cycles is 97.9% (as shown in Figure 4), which proves that the composite material obtained in the present invention has high capacity, excellent cycle performance and compaction performance. The test results of the obtained sheet-like high-compacted silicon-carbon composite negative electrode material in a button cell are listed in Table 2.
实施例2Example 2
制备浆料B时表面活性剂组合由100g十二烷基硫酸钠与200g聚乙烯吡咯烷酮组合改为100g阴离子型聚丙烯酰胺与200g聚乙二醇组合，其他制备步骤同实施例1。所得材料的电化学性能测试结果列于表2。When preparing slurry B, the surfactant combination was changed from the combination of 100g sodium lauryl sulfate and 200g polyvinylpyrrolidone to the combination of 100g anionic polyacrylamide and 200g polyethylene glycol, and other preparation steps were the same as those in Example 1. The electrochemical performance test results of the obtained materials are listed in Table 2.
对比例1Comparative Example 1
制备浆料A时不加聚二烯丙基二甲基氯化铵，其他制备步骤同实施例1。所得材料的电化学性能测试结果列于表2。When preparing slurry A, polydiallyl dimethyl ammonium chloride was not added, and other preparation steps were the same as those in Example 1. The electrochemical performance test results of the obtained materials are listed in Table 2.
对比例2Comparative Example 2
制备浆料B时不加阴离子型表面活性剂十二烷基硫酸钠，其他制备步骤同实施例1。所得材料的电化学性能测试结果列于表2。When preparing slurry B, the anionic surfactant sodium lauryl sulfate was not added, and other preparation steps were the same as those in Example 1. The electrochemical performance test results of the obtained materials are listed in Table 2.
对比例3Comparative Example 3
制备浆料B时不加非离子型表面活性剂聚乙烯吡咯烷酮，其他制备步骤同实施例1。所得材料的电化学性能测试结果列于表2。The nonionic surfactant polyvinylpyrrolidone was not added during the preparation of slurry B, and other preparation steps were the same as those in Example 1. The electrochemical performance test results of the obtained materials are listed in Table 2.
对比例4Comparative Example 4
制备浆料B时不加任何表面活性剂，其他制备步骤同实施例1。所得材料的电化学性能测试结果列于表2。No surfactant was added during the preparation of slurry B, and other preparation steps were the same as in Example 1. The electrochemical performance test results of the obtained materials are listed in Table 2.
实施例3Example 3
将浆料A和浆料B混合时加入的粘合剂沥青改为酚醛树脂，其他制备步骤同实施例1。所得材料的电化学性能测试结果列于表2。The binder pitch added when slurry A and slurry B were mixed was changed to phenolic resin, and other preparation steps were the same as those in Example 1. The electrochemical performance test results of the obtained materials are listed in Table 2.
实施例4Example 4
将浆料A和浆料B混合时加入的粘合剂沥青改为壳聚糖，其他制备步骤同实施例1。所得材料的电化学性能测试结果列于表2。The binder pitch added when slurry A and slurry B were mixed was changed to chitosan, and other preparation steps were the same as those in Example 1. The electrochemical performance test results of the obtained materials are listed in Table 2.
对比例5Comparative Example 5
将浆料A和浆料B混合时不加入粘合剂，其他制备步骤同实施例1。所得材料的电化学性能测试结果列于表2。No binder was added when slurry A and slurry B were mixed, and other preparation steps were the same as those in Example 1. The electrochemical performance test results of the obtained materials are listed in Table 2.
实施例5Example 5
表面包覆时将CVD气相包覆改为将黑色粉末与500g煤沥青混合均匀后加入固相包覆机中进行固相包覆，其他制备步骤同实施例1。所得材料的电化学性能测试结果列于表2。During surface coating, the CVD gas phase coating was changed to mix the black powder with 500 g of coal tar pitch uniformly and then add it into a solid-phase coating machine for solid-phase coating, and other preparation steps were the same as those in Example 1. The electrochemical performance test results of the obtained materials are listed in Table 2.
对比例6Comparative Example 6
不进行表面包覆，其他制备步骤同实施例1。所得材料的电化学性能测试结果列于表2。No surface coating was performed, and other preparation steps were the same as those in Example 1. The electrochemical performance test results of the obtained materials are listed in Table 2.
表1实施例和对比例所用原材料The raw materials used in Table 1 Examples and Comparative Examples
注：PDDA为制备浆料A时使用的聚二烯丙基二甲基氯化铵的英文缩写Note: PDDA is the English abbreviation of polydiallyldimethylammonium chloride used in the preparation of slurry A
表2、高压实的硅碳复合负极材料的电化学性能测试结果Table 2. Electrochemical performance test results of high-compacted silicon-carbon composite anode materials
综上所述，本发明的制备方法简单高效，得到的片状材料本身结构稳固，电化学性能优异，在高压实体系下也具有很好的循环性能。To sum up, the preparation method of the present invention is simple and efficient, and the obtained sheet-like material has a stable structure, excellent electrochemical performance, and good cycle performance in a high-pressure compact system.
申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。The applicant declares that the present invention illustrates the detailed process equipment and process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process equipment and process flow. Process flow can be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.
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