CN102694200A - Silicon-based negative lithium-ion battery and manufacturing method thereof - Google Patents
Silicon-based negative lithium-ion battery and manufacturing method thereof Download PDFInfo
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Abstract
本发明公开了一种硅基负极锂离子电池及其制造方法。包括正极片、负极片、隔膜，以及电解液，其负极片包括负极集流体和分布在负极集流体上的负极活性物质，负极活性物质中包含碳硅复合材料；负极片中的活性物质涂层具有石墨涂层和硅碳负极涂层，构成具有复合涂层结构的负极片。并且在制作过程中加入含复合添加剂的电解液和首次充电时采用多段充电活化方式。本发明有利于提高硅碳复合负极的粘结性、加工性能，增强充放电过程中对体积变化的缓冲能力，提高硅基负极与电解液的相容性，改善负极表面SEI膜的形成与稳定性，提高硅基负极锂离子电池的电化学性能。
The invention discloses a silicon-based negative electrode lithium ion battery and a manufacturing method thereof. Including positive electrode sheet, negative electrode sheet, diaphragm, and electrolyte, its negative electrode sheet includes negative electrode current collector and negative electrode active material distributed on the negative electrode current collector, the negative electrode active material contains carbon silicon composite material; the active material coating in the negative electrode sheet It has a graphite coating and a silicon carbon negative electrode coating to form a negative electrode sheet with a composite coating structure. In addition, during the production process, an electrolyte solution containing composite additives is added and a multi-stage charging activation method is adopted when charging for the first time. The invention is beneficial to improve the adhesion and processability of the silicon-carbon composite negative electrode, enhance the buffering capacity for volume changes during charge and discharge, improve the compatibility between the silicon-based negative electrode and the electrolyte, and improve the formation and stability of the SEI film on the surface of the negative electrode and improve the electrochemical performance of silicon-based negative electrode lithium-ion batteries.
Description
技术领域 technical field
本发明涉及一种锂离子电池，尤其是涉及一种含硅负极的锂离子电池，本发明还涉及该硅基负极锂离子电池的制造方法。The invention relates to a lithium ion battery, in particular to a lithium ion battery containing a silicon negative electrode, and also relates to a manufacturing method of the silicon-based negative electrode lithium ion battery.
背景技术 Background technique
锂离子电池具有工作电压高、比能量高和循环寿命长等优点，近年来得到了迅速发展。随着移动设备向小型化和多功能化方向发展，同时随着电动汽车的快速发展和广泛应用，对于能量高、循环寿命长的锂离子电池的需求十分迫切。目前商业锂离子电池的主要负极材料石墨，由于理论容量低(372mAh/g)，高倍率充放电性能差，限制了锂离子电池能量的进一步提高。Lithium-ion batteries have the advantages of high working voltage, high specific energy and long cycle life, and have been developed rapidly in recent years. With the development of mobile devices towards miniaturization and multi-function, and with the rapid development and wide application of electric vehicles, there is an urgent need for lithium-ion batteries with high energy and long cycle life. At present, graphite, the main negative electrode material of commercial lithium-ion batteries, has low theoretical capacity (372mAh/g) and poor high-rate charge and discharge performance, which limits the further improvement of lithium-ion battery energy.
硅具有最高的理论比容量（4200mAh g-1）和较低的脱锂电位（<0.5V），成为最有潜力取代石墨的锂离子电池负极材料之一。但是在充放电过程中，硅会发生巨大的体积变化，导致材料粉化、剥落、失去电接触，容量衰减很快。为了减小硅材料的体积效应，人们尝试了多种方法，包括降低硅材料的粒径；将硅制成多孔材料；降低硅材料的维度；制备硅碳复合材料等。这些方法或者抑制了硅材料的体积膨胀，或者改善了颗粒之间的电接触，从而在一定程度上提高了硅基负极的循环稳定性和首次充放电效率。Silicon has the highest theoretical specific capacity (4200mAh g -1 ) and low delithiation potential (<0.5V), making it one of the most potential anode materials for lithium-ion batteries to replace graphite. However, during the charge and discharge process, silicon will undergo a huge volume change, resulting in material pulverization, peeling, loss of electrical contact, and rapid capacity decay. In order to reduce the volume effect of silicon materials, people have tried a variety of methods, including reducing the particle size of silicon materials; making silicon porous materials; reducing the dimensionality of silicon materials; preparing silicon-carbon composite materials, etc. These methods either suppress the volume expansion of silicon materials or improve the electrical contact between particles, thereby improving the cycle stability and initial charge-discharge efficiency of silicon-based anodes to a certain extent.
但是，由于硅基负极与传统碳负极在结构与性能上的巨大差异，传统方法制备硅基负极锂离子电池存在一系列问题：如粘结性差、极片脆、与传统电解液相容性差、循环性能差等。因此，研究开发与硅基负极相适应的锂离子电池制造工艺具有重要意义。However, due to the huge difference in structure and performance between silicon-based negative electrodes and traditional carbon negative electrodes, there are a series of problems in the preparation of silicon-based negative electrode lithium-ion batteries by traditional methods: such as poor adhesion, brittle pole pieces, poor compatibility with traditional electrolytes, Poor cycle performance, etc. Therefore, it is of great significance to research and develop a lithium-ion battery manufacturing process compatible with silicon-based negative electrodes.
发明内容 Contents of the invention
本发明所要解决的第一个技术问题是提供一种负极材料与集流体的粘结性高、负极片的柔韧性好、负极与电解液的相容性好和电池的电化学性能好的硅基负极锂离子电池。The first technical problem to be solved by the present invention is to provide a silicon material with high adhesion between the negative electrode material and the current collector, good flexibility of the negative electrode sheet, good compatibility between the negative electrode and the electrolyte, and good electrochemical performance of the battery. base negative lithium-ion battery.
本发明所要解决的第二个技术问题是提供一种制造该硅基负极锂离子电池的方法。The second technical problem to be solved by the present invention is to provide a method for manufacturing the silicon-based negative electrode lithium-ion battery.
为了解决上述第二个技术问题，本发明提供的硅基负极锂离子电池，包括：正极片、负极片、隔膜，以及电解液，正极片包括正极集流体和分布在正极集流体上的正极活性物质，负极片包括负极集流体和分布在负极集流体上的负极活性物质，所述的负极活性物质为设在所述的负极片上的含有硅碳复合材料的活性物质涂层，所述的活性物质涂层为包括石墨负极涂层和硅碳负极涂层的复合多层结构。In order to solve the above-mentioned second technical problem, the silicon-based negative electrode lithium-ion battery provided by the present invention includes: a positive electrode sheet, a negative electrode sheet, a diaphragm, and an electrolyte, and the positive electrode sheet includes a positive electrode current collector and a positive active active electrode distributed on the positive electrode current collector. material, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material distributed on the negative electrode current collector, the negative electrode active material is an active material coating containing a silicon-carbon composite material arranged on the negative electrode sheet, and the active material The substance coating is a composite multilayer structure including graphite negative electrode coating and silicon carbon negative electrode coating.
所述的石墨负极涂层和硅碳负极涂层的复合多层结构包括以下几种形式：石墨/硅碳复合材料、硅碳复合材料/石墨或石墨/硅碳复合材料/石墨。The composite multilayer structure of the graphite negative electrode coating and the silicon-carbon negative electrode coating includes the following forms: graphite/silicon-carbon composite material, silicon-carbon composite material/graphite or graphite/silicon-carbon composite material/graphite.
所述的石墨负极涂层包括平均粒径3-6μm的石墨、粘结剂和添加剂，其中石墨含量为90-96%；所述的硅碳负极涂层包括硅碳复合材料、粘结剂和添加剂。The graphite negative electrode coating includes graphite with an average particle size of 3-6 μm, a binder and additives, wherein the graphite content is 90-96%; the silicon-carbon negative electrode coating includes a silicon-carbon composite material, a binder and additive.
所述的石墨负极涂层的厚度为5-30μm，所述的硅碳负极涂层厚度为30-100μm。The thickness of the graphite negative electrode coating is 5-30 μm, and the thickness of the silicon carbon negative electrode coating is 30-100 μm.
所述的正极活性物质为过渡金属嵌锂氧化物或磷酸盐正极材料LiCoO2、LiMn2O4、LiFePO4、LiCo1-x-yNixMnyO2中的一种或几种，其中，x、y、x+y＜1。The positive electrode active material is one or more of transition metal lithium intercalation oxides or phosphate positive electrode materials LiCoO 2 , LiMn 2 O 4 , LiFePO 4 , LiCo 1-xy Ni x Mn y O 2 , where x , y, x+y<1.
所述的电解液中除了加入体积比为1%～3%的碳酸亚乙烯酯（VC）之外，还加入体积比为2%～4%的碳酸乙烯亚乙酯（VEC）、甲烷二磺酸亚甲酯（MMDS）中的一种或两种。In addition to adding vinylene carbonate (VC) with a volume ratio of 1% to 3%, the electrolyte solution also adds ethylene carbonate (VEC), methanedisulfone with a volume ratio of 2% to 4%. One or both of Methylene Dioxide (MMDS).
为了解决上述第二个技术问题，本发明提供的硅基负极锂离子电池的制造方法，包括正极片制备，负极片制备，组装，加注电解液，电池活化步骤，所述的负极片制备的步骤是：分别将石墨、粘结剂与添加剂配制成石墨负极浆料，将硅碳复合材料、粘结剂与添加剂配制成硅碳负极浆料；按以下3种方式之一涂敷：（1）在负极集流体铜箔表面涂敷一层石墨负极涂层，烘干；接着在石墨负极涂层表面涂敷一层硅碳负极涂层，烘干；（2）在负极集流体铜箔表面涂敷一层硅碳负极涂层，烘干；然后在硅碳负极涂层表面再涂敷一层石墨负极涂层，烘干；（3）在负极集流体铜箔表面涂敷一层石墨负极涂层，烘干；接着在石墨负极涂层表面涂敷一层硅碳负极涂层，烘干；然后在硅碳负极涂层表面再涂敷一层石墨负极涂层，烘干；上述几种涂敷方式得到的膜片经辊轧、分切得到复合多层结构负极片。In order to solve the above-mentioned second technical problem, the manufacturing method of the silicon-based negative electrode lithium-ion battery provided by the present invention includes positive electrode sheet preparation, negative electrode sheet preparation, assembly, electrolyte filling, battery activation steps, and the preparation of the negative electrode sheet The steps are: respectively prepare graphite, binder and additives into graphite negative electrode slurry, and prepare silicon carbon composite material, binder and additives into silicon carbon negative electrode slurry; apply in one of the following three ways: (1 ) Coating a layer of graphite negative electrode coating on the surface of the copper foil of the negative electrode current collector and drying; then coating a layer of silicon carbon negative electrode coating on the surface of the graphite negative electrode coating and drying; (2) coating the surface of the copper foil of the negative electrode current collector Apply a layer of silicon carbon negative electrode coating and dry; then apply a layer of graphite negative electrode coating on the surface of the silicon carbon negative electrode coating and dry; (3) Coat a layer of graphite negative electrode on the surface of the negative electrode current collector copper foil Coating, drying; then coating a layer of silicon carbon negative electrode coating on the surface of the graphite negative electrode coating, drying; then coating a layer of graphite negative electrode coating on the surface of the silicon carbon negative electrode coating, drying; the above-mentioned The diaphragm obtained by the coating method is rolled and cut to obtain a negative electrode sheet with a composite multi-layer structure.
所述的电池活化步骤采用首末段为小电流的多段充电活化。The battery activation step adopts multi-stage charging activation with the first and last stages being small current.
所述的多段充电活化是指：锂离子电池首次充电时采用首末段为小电流的多段充电活化，先0.05C恒流充电1小时，再0.2C恒流充电至4.0V，最后0.05C充电至4.2V完成首次充电。The multi-stage charging activation refers to: when the lithium-ion battery is charged for the first time, the first and last stages are multi-stage charging activation with a small current, first charge at a constant current of 0.05C for 1 hour, then charge at a constant current of 0.2C to 4.0V, and finally charge at 0.05C To 4.2V to complete the first charge.
采用上述技术方案的硅基负极锂离子电池及其制造方法，相对于现有技术，本发明具有以下积极效果：Compared with the prior art, the silicon-based negative electrode lithium-ion battery and its manufacturing method adopting the above-mentioned technical scheme, the present invention has the following positive effects:
（1）由于碳硅复合材料的比表面积比较大，通常情况下与集流体的粘结性能较差。本发明在负极集流体表面先涂敷一层石墨涂层，然后再涂敷碳硅复合负极涂层，有利于提高碳硅负极涂层的粘结性能。(1) Due to the relatively large specific surface area of the carbon-silicon composite material, the bonding performance with the current collector is generally poor. In the present invention, a layer of graphite coating is first coated on the surface of the negative electrode current collector, and then the carbon-silicon composite negative electrode coating is applied, which is beneficial to improving the bonding performance of the carbon-silicon negative electrode coating.
（2）本发明在涂敷碳硅复合负极涂层后，再涂敷一层石墨涂层，可以提高负极涂层与电解液的相容性。(2) In the present invention, after coating the carbon-silicon composite negative electrode coating, a layer of graphite coating is applied, which can improve the compatibility between the negative electrode coating and the electrolyte.
（3）本发明优选采用“石墨/硅碳复合材料/石墨”复合涂层结构，有利于提高硅基负极与集流体的粘结性，以及与电解液的相容性，并缓冲充电过程中硅的“膨胀-收缩”体积效应。(3) The present invention preferably adopts the "graphite/silicon-carbon composite material/graphite" composite coating structure, which is conducive to improving the adhesion between the silicon-based negative electrode and the current collector, as well as the compatibility with the electrolyte, and buffering the charging process. The "swell-shrink" volume effect of silicon.
（4）本发明采用石墨涂层与硅碳复合负极涂层，并在负极浆料中加入磷片石墨，改善了硅基负极的柔韧性和加工性能。(4) The present invention uses graphite coating and silicon-carbon composite negative electrode coating, and adds phosphorus flake graphite to the negative electrode slurry, which improves the flexibility and processing performance of the silicon-based negative electrode.
（5）本发明在首次充电时采用三段式充电，即首末阶段均采用小电流，使石墨及碳硅复合负极材料表面均能形成性能良好的致密SEI膜。(5) The present invention adopts a three-stage charging in the first charging, that is, a small current is used in the first and last stages, so that a dense SEI film with good performance can be formed on the surface of graphite and carbon-silicon composite negative electrode materials.
（6）本发明在电解液中加入复合添加剂，改善了石墨及碳硅复合负极材料的SEI膜。(6) The present invention adds composite additives to the electrolyte to improve the SEI film of graphite and carbon-silicon composite negative electrode materials.
通过上述方式，使得本发明中的硅基负极锂离子电池的能量密度比传统石墨负极锂离子电池的能量密度高出20%以上，循环性能达到与石墨负极锂离子电池相当。Through the above method, the energy density of the silicon-based negative electrode lithium ion battery in the present invention is more than 20% higher than that of the traditional graphite negative electrode lithium ion battery, and the cycle performance is equivalent to that of the graphite negative electrode lithium ion battery.
附图说明 Description of drawings
图1硅基负极复合涂层结构示意图Figure 1 Schematic diagram of the structure of silicon-based negative electrode composite coating
具体实施方式 Detailed ways
下面结合附图和实施例对本发明作进一步说明。The present invention will be further described below in conjunction with drawings and embodiments.
实施例1：Example 1:
以LiNi0.5Co0.3Mn0.2O2作为锂离子电池正极活性物质，与粘结剂、导电剂、添加剂、溶剂等混合配制成LiNi0.5Co0.3Mn0.2O2正极浆料，然后经涂敷、干燥、辊轧、分切，得到正极片。LiNi 0.5 Co 0.3 Mn 0.2 O 2 is used as the positive electrode active material of lithium ion battery, mixed with binder, conductive agent, additive, solvent, etc. to prepare LiNi 0.5 Co 0.3 Mn 0.2 O 2 positive electrode slurry, and then coated and dried , rolling, and slitting to obtain the positive electrode sheet.
以平均粒径为5μm的石墨作为锂离子电池负极活性物质，与粘结剂聚偏氟乙烯、Super P导电碳、添加剂磷片石墨按质量比为91∶5∶2∶2，与溶剂N-甲基吡咯烷酮等混合配制成石墨负极浆料。同时，以硅碳复合材料作为锂离子电池负极活性物质，与聚偏氟乙烯、Super P导电碳、添加剂磷片石墨按质量比为88∶7∶2∶3，与溶剂N-甲基吡咯烷酮等混合配制成硅碳复合负极浆料。Graphite with an average particle size of 5 μm is used as the negative electrode active material of lithium-ion batteries, and the mass ratio of the binder polyvinylidene fluoride, Super P conductive carbon, and additive phosphorus flake graphite is 91:5:2:2, and the solvent N- Methylpyrrolidone and the like are mixed to prepare graphite negative electrode slurry. At the same time, the silicon-carbon composite material is used as the negative electrode active material of lithium-ion batteries, and the mass ratio of polyvinylidene fluoride, Super P conductive carbon, and additive phosphorus flake graphite is 88:7:2:3, and the solvent N-methylpyrrolidone, etc. Mix and prepare silicon-carbon composite negative electrode slurry.
在负极集流体铜箔表面涂敷一层10μm厚的石墨负极涂层，烘干；接着在石墨负极涂层表面涂敷一层50μm厚硅碳负极涂层，烘干；然后在硅碳负极涂层表面再涂敷一层10μm厚的石墨负极涂层，烘干；然后再在铜箔的另一面按上述方法依次涂敷石墨负极涂层、硅碳负极涂层、石墨负极涂层，得到如图1所示的硅基负极。该图描述了硅基负极的截面结构，其中1为集流体铜箔，2为石墨负极涂层，3为硅碳负极涂层。所得负极膜片经辊轧、分切得到复合多层结构负极片。Coat a layer of 10 μm thick graphite negative electrode coating on the surface of the negative electrode current collector copper foil and dry it; then apply a layer of 50 μm thick silicon carbon negative electrode coating on the surface of the graphite negative electrode coating and dry it; then coat the silicon carbon negative electrode The surface of the layer is coated with a 10 μm thick graphite negative electrode coating and dried; then the other side of the copper foil is coated with a graphite negative electrode coating, a silicon carbon negative electrode coating, and a graphite negative electrode coating in sequence according to the above method, to obtain the following: The silicon-based negative electrode shown in Figure 1. This figure describes the cross-sectional structure of the silicon-based negative electrode, in which 1 is the current collector copper foil, 2 is the graphite negative electrode coating, and 3 is the silicon carbon negative electrode coating. The obtained negative electrode film is rolled and cut to obtain a negative electrode sheet with a composite multilayer structure.
将铝极耳焊接在正极片上，镍极耳焊接在负极片上，将焊接好极耳的正极片,负极片及隔离膜通过卷绕的方式，形成的电池芯，装配到铝壳中，并用激光焊接的方式将电池盖板与壳体焊接在一起。制作的电池型号为523450（厚度5.2mm，宽度34mm，长度50mm），标称容量1400mAh。The aluminum tab is welded on the positive electrode, the nickel tab is welded on the negative electrode, and the positive electrode, negative electrode and separator with the welded tab are wound to form a battery core, assembled into the aluminum shell, and laser The battery cover and the casing are welded together by welding. The battery model produced is 523450 (thickness 5.2mm, width 34mm, length 50mm), nominal capacity 1400mAh.
向经脱气除水等工序的电池中注入电解液，电解液浓度是1mol/L，锂盐为六氟磷酸锂（LiPF6），以碳酸乙烯酯（EC）、碳酸甲乙酯（EMC）和碳酸二甲酯（DMC）的混合物为溶剂，其中各碳酸酯的比例为DMC∶EMC∶EC=1∶1∶1，再在电解液中加入2%（体积比）的碳酸亚乙烯酯（VC）和3%碳酸乙烯亚乙酯（VEC）。Inject the electrolyte into the battery after degassing and water removal, the concentration of the electrolyte is 1mol/L, the lithium salt is lithium hexafluorophosphate (LiPF 6 ), ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dicarbonate The mixture of methyl ester (DMC) is the solvent, and the ratio of each carbonate is DMC:EMC:EC=1:1:1, and then 2% (volume ratio) of vinylene carbonate (VC) and 3% ethylene carbonate (VEC).
注液后按照首次充电时采用多段充电活化，先以70mA(0.05C)恒流充电1小时，再以280mA(0.2C)恒流充电至4.0V，最后以70mA(0.05C)充电至4.2V完成首次充电；然后按照常规方式进行压钢珠及充放电得到硅基负极锂离子电池。After liquid injection, use multi-stage charging to activate according to the first charging, first charge with 70mA (0.05C) constant current for 1 hour, then charge with 280mA (0.2C) constant current to 4.0V, and finally charge with 70mA (0.05C) to 4.2V Complete the first charge; then press the steel ball and charge and discharge according to the conventional method to obtain a silicon-based negative electrode lithium-ion battery.
所得硅基负极锂离子电池在室温下以700mA（0.5C）的电流放电，初始放电容量为1430mAh，以0.5C倍率循环500次后的容量保持率为83%。The resulting silicon-based negative lithium-ion battery was discharged at room temperature at a current of 700mA (0.5C), with an initial discharge capacity of 1430mAh, and a capacity retention rate of 83% after 500 cycles at a rate of 0.5C.
实施例2：Example 2:
以LiCoO2作为锂离子电池正极活性物质，与粘结剂、导电剂、添加剂、溶剂等混合配制成LiCoO2正极浆料，然后经涂敷、干燥、辊轧、分切，得到正极片。 LiCoO2 is used as the positive electrode active material of lithium-ion batteries, mixed with binders, conductive agents, additives, solvents, etc. to prepare LiCoO2 positive electrode slurry, and then coated, dried, rolled, and cut to obtain positive electrodes.
以平均粒径为3μm的石墨作为锂离子电池负极活性物质，与水系粘结剂（SBR浮液及CMC混合物）、添加剂磷片石墨按质量比为96∶2.5∶1，与去离子水等混合配制成石墨负极浆料。同时，以硅碳复合材料作为锂离子电池负极活性物质，水系粘结剂（SBR浮液及CMC混合物）、添加剂磷片石墨按质量比为93∶5∶2，与去离子水等混合配制成硅碳复合负极浆料。Graphite with an average particle size of 3 μm is used as the negative electrode active material of lithium-ion batteries, mixed with water-based binder (SBR floating liquid and CMC mixture), additive phosphorus flake graphite at a mass ratio of 96:2.5:1, and deionized water, etc. Prepare graphite negative electrode slurry. At the same time, the silicon-carbon composite material is used as the negative electrode active material of the lithium-ion battery, and the water-based binder (SBR floating liquid and CMC mixture), the additive phosphorus flake graphite, and the mass ratio of 93:5:2 are mixed with deionized water to prepare Silicon carbon composite negative electrode slurry.
在负极集流体铜箔表面涂敷一层5μm厚的石墨负极涂层，烘干；接着在石墨负极涂层表面涂敷一层95μm厚硅碳负极涂层，烘干；然后再在铜箔的另一面按上述方法依次涂敷石墨负极涂层、硅碳负极涂层。所得负极膜片经辊轧、分切得到复合多层结构负极片。Coat a layer of 5 μm thick graphite negative electrode coating on the surface of the negative electrode current collector copper foil, and dry it; then apply a layer of 95 μm thick silicon carbon negative electrode coating on the surface of the graphite negative electrode coating, and dry it; The other side is coated with graphite negative electrode coating and silicon carbon negative electrode coating sequentially according to the above method. The obtained negative electrode film is rolled and cut to obtain a negative electrode sheet with a composite multilayer structure.
将铝极耳焊接在正极片上，镍极耳焊接在负极片上，将焊接好极耳的正极片,负极片及隔离膜通过卷绕的方式，形成的电池芯，装配到铝壳中，并用激光焊接的方式将电池盖板与壳体焊接在一起。制作的电池型号为523450（厚度5.2mm，宽度34mm，长度50mm），标称容量1400mAh。The aluminum tab is welded on the positive electrode, the nickel tab is welded on the negative electrode, and the positive electrode, negative electrode and separator with the welded tab are wound to form a battery core, assembled into the aluminum shell, and laser The battery cover and the casing are welded together by welding. The manufactured battery model is 523450 (thickness 5.2mm, width 34mm, length 50mm), nominal capacity 1400mAh.
向经脱气除水等工序的电池中注入电解液，电解液浓度是1mol/L，锂盐为六氟磷酸锂（LiPF6），以碳酸乙烯酯（EC）、碳酸甲乙酯（EMC）和碳酸二甲酯（DMC）的混合物为溶剂，其中各碳酸酯的比例为DMC∶EMC∶EC=1∶1∶1，再在电解液中加入3%（体积比）的碳酸亚乙烯酯（VC）和2%甲烷二磺酸亚甲酯（MMDS）。Inject the electrolyte into the battery after degassing and water removal, the concentration of the electrolyte is 1mol/L, the lithium salt is lithium hexafluorophosphate (LiPF 6 ), ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dicarbonate The mixture of methyl ester (DMC) is the solvent, and the ratio of each carbonate is DMC:EMC:EC=1:1:1, and then 3% (volume ratio) of vinylene carbonate (VC) and 2% methylene methane disulfonate (MMDS).
注液后按照首次充电时采用多段充电活化，先以70mA(0.05C)恒流充电1小时，再以280mA(0.2C)恒流充电至4.0V，最后以70mA(0.05C)充电至4.2V完成首次充电；然后按照常规方式进行压钢珠及充放电得到硅基负极锂离子电池。After liquid injection, use multi-stage charging to activate according to the first charging, first charge with 70mA (0.05C) constant current for 1 hour, then charge with 280mA (0.2C) constant current to 4.0V, and finally charge with 70mA (0.05C) to 4.2V Complete the first charge; then press the steel ball and charge and discharge according to the conventional method to obtain a silicon-based negative electrode lithium-ion battery.
所得硅基负极锂离子电池在室温下以700mA（0.5C）的电流放电，初始放电容量为1460mAh，以0.5C倍率循环500次后的容量保持率为84%。The obtained silicon-based negative electrode lithium-ion battery was discharged at a current of 700mA (0.5C) at room temperature, with an initial discharge capacity of 1460mAh, and a capacity retention rate of 84% after 500 cycles at a rate of 0.5C.
实施例3：Example 3:
以LiNi0.8Co0.1Mn0.1O2和LiMn2O4作为锂离子电池正极活性物质，与粘结剂、导电剂、添加剂、溶剂等混合配制成正极浆料，然后经涂敷、干燥、辊轧、分切，得到正极片。LiNi 0.8 Co 0.1 Mn 0.1 O 2 and LiMn 2 O 4 are used as positive electrode active materials for lithium ion batteries, mixed with binders, conductive agents, additives, solvents, etc. to prepare positive electrode slurry, and then coated, dried, and rolled , slitting to obtain the positive electrode sheet.
以平均粒径为6μm的石墨作为锂离子电池负极活性物质，与聚偏氟乙烯、Super P导电碳、添加剂磷片石墨按质量比为91∶5∶2∶2，与溶剂N-甲基吡咯烷酮等混合配制成石墨负极浆料。同时，以硅碳复合材料作为锂离子电池负极活性物质，与聚偏氟乙烯、Super P导电碳、添加剂磷片石墨按质量比为88∶7∶2∶3，与溶剂N-甲基吡咯烷酮等混合配制成硅碳复合负极浆料。Graphite with an average particle size of 6 μm is used as the negative electrode active material of lithium-ion batteries, and the mass ratio of polyvinylidene fluoride, Super P conductive carbon, and additive phosphorus flake graphite is 91:5:2:2, and the solvent N-methylpyrrolidone etc. mixed to prepare graphite negative electrode slurry. At the same time, the silicon-carbon composite material is used as the negative electrode active material of lithium-ion batteries, and the mass ratio of polyvinylidene fluoride, Super P conductive carbon, and additive phosphorus flake graphite is 88:7:2:3, and the solvent N-methylpyrrolidone, etc. Mix and prepare silicon-carbon composite negative electrode slurry.
在负极集流体铜箔表面涂敷一层30μm厚的石墨负极涂层，烘干；接着在石墨负极涂层表面涂敷一层30μm厚硅碳负极涂层，烘干；然后在硅碳负极涂层表面再涂敷一层10μm厚的石墨负极涂层，烘干；然后再在铜箔的另一面按上述方法依次涂敷石墨负极涂层、硅碳负极涂层、石墨负极涂层，所得负极膜片经辊轧、分切得到复合多层结构负极片。Coat a layer of 30 μm thick graphite negative electrode coating on the surface of the copper foil of the negative electrode current collector, and dry it; then apply a layer of 30 μm thick silicon carbon negative electrode coating on the surface of the graphite negative electrode coating, and dry it; then coat the silicon carbon negative electrode The surface of the layer is coated with a 10 μm thick graphite negative electrode coating and dried; then the other side of the copper foil is coated with a graphite negative electrode coating, a silicon carbon negative electrode coating, and a graphite negative electrode coating in sequence according to the above method, and the obtained negative electrode The diaphragm is rolled and cut to obtain a negative electrode sheet with a composite multi-layer structure.
将铝极耳焊接在正极片上，镍极耳焊接在负极片上，将焊接好极耳的正极片,负极片及隔离膜通过卷绕的方式，形成的电池芯，装配到铝壳中，并用激光焊接的方式将电池盖板与壳体焊接在一起。制作的电池型号为523450（厚度5.2mm，宽度34mm，长度50mm），标称容量1400mAh。The aluminum tab is welded on the positive electrode, the nickel tab is welded on the negative electrode, and the positive electrode, negative electrode and separator with the welded tab are wound to form a battery core, assembled into the aluminum shell, and laser The battery cover and the casing are welded together by welding. The battery model produced is 523450 (thickness 5.2mm, width 34mm, length 50mm), nominal capacity 1400mAh.
向经脱气除水等工序的电池中注入电解液，电解液浓度是1mol/L，锂盐为六氟磷酸锂（LiPF6），以碳酸乙烯酯（EC）、碳酸甲乙酯（EMC）和碳酸二甲酯（DMC）的混合物为溶剂，其中各碳酸酯的比例为DMC∶EMC∶EC=1∶1∶1，再在电解液中加入2%（体积比）的碳酸亚乙烯酯（VC）和3%碳酸乙烯亚乙酯（VEC）。Inject the electrolyte into the battery after degassing and water removal, the concentration of the electrolyte is 1mol/L, the lithium salt is lithium hexafluorophosphate (LiPF 6 ), ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dicarbonate The mixture of methyl ester (DMC) is the solvent, and the ratio of each carbonate is DMC:EMC:EC=1:1:1, and then 2% (volume ratio) of vinylene carbonate (VC) and 3% ethylene carbonate (VEC).
注液后按照首次充电时采用多段充电活化，先以70mA(0.05C)恒流充电1小时，再以280mA(0.2C)恒流充电至4.0V，最后以70mA(0.05C)充电至4.2V完成首次充电；然后按照常规方式进行压钢珠及充放电得到硅基负极锂离子电池。After liquid injection, use multi-stage charging to activate according to the first charging, first charge with 70mA (0.05C) constant current for 1 hour, then charge with 280mA (0.2C) constant current to 4.0V, and finally charge with 70mA (0.05C) to 4.2V Complete the first charge; then press the steel ball and charge and discharge in a conventional manner to obtain a silicon-based negative electrode lithium-ion battery.
所得硅基负极锂离子电池在室温下以700mA（0.5C）的电流放电，初始放电容量为1480mAh，以0.5C倍率循环500次后的容量保持率为82%。The obtained silicon-based negative lithium-ion battery was discharged at room temperature at a current of 700mA (0.5C), with an initial discharge capacity of 1480mAh, and a capacity retention rate of 82% after 500 cycles at a rate of 0.5C.
实施例4：Example 4:
以LiNi1/3Co1/3Mn1/3O2和LiFePO4作为锂离子电池正极活性物质，与粘结剂、导电剂、添加剂、溶剂等混合配制成正极浆料，然后经涂敷、干燥、辊轧、分切，得到正极片。LiNi 1/3 Co 1/3 Mn 1/3 O 2 and LiFePO 4 are used as positive electrode active materials for lithium ion batteries, mixed with binders, conductive agents, additives, solvents, etc. to prepare positive electrode slurry, and then coated, Drying, rolling and slitting to obtain the positive electrode sheet.
以平均粒径为6μm的石墨作为锂离子电池负极活性物质，与聚偏氟乙烯、Super P导电碳、添加剂磷片石墨按质量比为91∶5∶2∶2，与溶剂N-甲基吡咯烷酮等混合配制成石墨负极浆料。同时，以硅碳复合材料作为锂离子电池负极活性物质，与聚偏氟乙烯、Super P导电碳、添加剂磷片石墨按质量比为88∶7∶2∶3，与溶剂N-甲基吡咯烷酮等混合配制成硅碳复合负极浆料。Graphite with an average particle size of 6 μm is used as the negative electrode active material of lithium-ion batteries, and the mass ratio of polyvinylidene fluoride, Super P conductive carbon, and additive phosphorus flake graphite is 91:5:2:2, and the solvent N-methylpyrrolidone etc. mixed to prepare graphite negative electrode slurry. At the same time, the silicon-carbon composite material is used as the negative electrode active material of lithium-ion batteries, and the mass ratio of polyvinylidene fluoride, Super P conductive carbon, and additive phosphorus flake graphite is 88:7:2:3, and the solvent N-methylpyrrolidone, etc. Mix and prepare silicon-carbon composite negative electrode slurry.
在负极集流体铜箔表面涂敷一层50μm厚硅碳负极涂层，烘干；然后在硅碳负极涂层表面再涂敷一层20μm厚的石墨负极涂层，烘干；然后再在铜箔的另一面按上述方法依次涂敷硅碳负极涂层、石墨负极涂层，所得负极膜片经辊轧、分切得到复合多层结构负极片。Coat a layer of 50 μm thick silicon carbon negative electrode coating on the surface of the negative electrode current collector copper foil, and dry; then coat a layer of 20 μm thick graphite negative electrode coating on the surface of the silicon carbon negative electrode coating, and dry; The other side of the foil is coated with silicon-carbon negative electrode coating and graphite negative electrode coating sequentially according to the above method, and the obtained negative electrode membrane is rolled and cut to obtain a composite multilayer structure negative electrode sheet.
将铝极耳焊接在正极片上，镍极耳焊接在负极片上，将焊接好极耳的正极片,负极片及隔离膜通过卷绕的方式，形成的电池芯，装配到铝壳中，并用激光焊接的方式将电池盖板与壳体焊接在一起。制作的电池型号为523450（厚度5.2mm，宽度34mm，长度50mm），标称容量1400mAh。The aluminum tab is welded on the positive electrode, the nickel tab is welded on the negative electrode, and the positive electrode, negative electrode and separator with the welded tab are wound to form a battery core, assembled into the aluminum shell, and laser The battery cover and the casing are welded together by welding. The battery model produced is 523450 (thickness 5.2mm, width 34mm, length 50mm), nominal capacity 1400mAh.
向经脱气除水等工序的电池中注入电解液，电解液浓度是1mol/L，锂盐为六氟磷酸锂（LiPF6），以碳酸乙烯酯（EC）、碳酸甲乙酯（EMC）和碳酸二甲酯（DMC）的混合物为溶剂，其中各碳酸酯的比例为DMC∶EMC∶EC=1∶1∶1，再在电解液中加入1%（体积比）的碳酸亚乙烯酯（VC）和4%碳酸乙烯亚乙酯（VEC）。Inject the electrolyte into the battery after degassing and water removal, the concentration of the electrolyte is 1mol/L, the lithium salt is lithium hexafluorophosphate (LiPF 6 ), ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dicarbonate A mixture of methyl esters (DMC) is a solvent, and the ratio of each carbonate is DMC:EMC:EC=1:1:1, and then 1% (volume ratio) of vinylene carbonate (VC) and 4% ethylene carbonate (VEC).
注液后按照首次充电时采用多段充电活化，先以70mA(0.05C)恒流充电1小时，再以280mA(0.2C)恒流充电至4.0V，最后以70mA(0.05C)充电至4.2V完成首次充电；然后按照常规方式进行压钢珠及充放电得到硅基负极锂离子电池。After liquid injection, use multi-stage charging to activate according to the first charging, first charge with 70mA (0.05C) constant current for 1 hour, then charge with 280mA (0.2C) constant current to 4.0V, and finally charge with 70mA (0.05C) to 4.2V Complete the first charge; then press the steel ball and charge and discharge in a conventional manner to obtain a silicon-based negative electrode lithium-ion battery.
所得硅基负极锂离子电池在室温下以700mA（0.5C）的电流放电，初始放电容量为1415mAh，以0.5C倍率循环500次后的容量保持率为85%。The resulting silicon-based negative lithium-ion battery was discharged at room temperature at a current of 700mA (0.5C), with an initial discharge capacity of 1415mAh, and a capacity retention rate of 85% after 500 cycles at a rate of 0.5C.
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