CN115986069A - A kind of positive electrode pre-lithiation material for lithium ion battery and preparation method thereof - Google Patents
A kind of positive electrode pre-lithiation material for lithium ion battery and preparation method thereofDownload PDFInfo
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Abstract
Translated fromChinese
Description
Translated fromChinese技术领域technical field
本发明属于电化学能源材料技术领域，具体涉及一种锂离子电池用正极预锂化材料及其制备方法。The invention belongs to the technical field of electrochemical energy materials, and in particular relates to a positive electrode pre-lithiation material for lithium ion batteries and a preparation method thereof.
背景技术Background technique
锂离子电池由于其高比能量密度，轻便，使用寿命长和快充快放的特点，已广泛应用于人们的日常生活中，然而随着人们生活水平的提高，对锂离子电池提出了更高的要求：质量更轻、使用时间更长等；为了解决上述问题必须寻找能量密度更高的储能体系。Lithium-ion batteries have been widely used in people's daily life due to their high specific energy density, light weight, long service life and fast charging and quick discharge. However, with the improvement of people's living standards, higher requirements have been put forward for lithium-ion batteries. Requirements: lighter weight, longer service life, etc.; in order to solve the above problems, it is necessary to find an energy storage system with higher energy density.
为了开发高比能锂电池，硅、锡基等新一代高容量负极材料的研究和应用广泛开展。在实际的锂离子电池体系中，存储在正极中的锂离子在初始充电过程中转移到负极，在负极表面形成固体电解质中间相(SEI)，不可逆消耗了一部分活性锂，降低电池的容量和能量密度。此外，对于一些高容量负极如硅，还会面临不可逆的合金化反应以及颗粒粉化等问题，导致其首圈库伦效率进一步降低。为此，需要通过预锂化方法，在电池系统引入额外的活性锂，以补偿锂的初始损耗，提高电池的能量密度。目前常用的预锂化方法主要包括电化学、化学预锂化以及将预锂化添加剂用于电极。其中将预锂化添加剂加到负极或正极中，与工业电池制造技术兼容。一些代表性的负极预锂化材料表现出高的“供体”锂离子比容量，有望消除锂离子电池的初始活性锂损失，然而这些负极预锂化材料往往与制备电池浆料的极性溶剂反应，且在空气下不稳定，阻碍了其商业化应用。与负极预锂化相比，正极预锂化材料表现出更高的开路电压和更好的环境稳定性。此外，正极预锂化添加剂通常与NMP(正极浆料制备中常用的溶剂)有更好的相容性，具备良好的工业化前景。In order to develop high specific energy lithium batteries, the research and application of a new generation of high-capacity negative electrode materials such as silicon and tin-based materials have been widely carried out. In the actual lithium-ion battery system, the lithium ions stored in the positive electrode are transferred to the negative electrode during the initial charging process, forming a solid electrolyte interphase (SEI) on the surface of the negative electrode, which irreversibly consumes a part of the active lithium and reduces the capacity and energy of the battery. density. In addition, for some high-capacity negative electrodes such as silicon, problems such as irreversible alloying reactions and particle pulverization will also be faced, resulting in a further decrease in the first-cycle Coulombic efficiency. For this reason, it is necessary to introduce additional active lithium into the battery system by pre-lithiation method to compensate for the initial loss of lithium and increase the energy density of the battery. Currently commonly used pre-lithiation methods mainly include electrochemical, chemical pre-lithiation, and the use of pre-lithiation additives for electrodes. Among them, the pre-lithiation additive is added to the negative or positive electrode, which is compatible with industrial battery manufacturing technology. Some representative negative electrode pre-lithiation materials exhibit high "donor" lithium ion specific capacity, which is expected to eliminate the initial active lithium loss of lithium-ion batteries. However, these negative electrode pre-lithiation materials are often mixed with the polar solvents used to prepare battery Reaction, and instability in air hindered its commercial application. Compared with negative electrode prelithiation, cathode prelithiation materials exhibit higher open circuit voltage and better environmental stability. In addition, positive electrode pre-lithiation additives usually have better compatibility with NMP (a solvent commonly used in the preparation of positive electrode slurry), and have good industrialization prospects.
正极预锂化现在主要是通过在电极中加入预锂化试剂来进行的。评估预锂化试剂性能应从下述六个方面进行考虑：1)可使用的活性锂离子容量；2)预锂化试剂的化学和环境稳定性；3)预锂化材料可能涉及的安全性问题；4)预锂化试剂的分解产物和其导致的副反应；5)预锂化对其他电化学性能的潜在影响；6)预锂化技术和现有工艺的兼容性和可扩展性。The positive electrode pre-lithiation is now mainly carried out by adding a pre-lithiation reagent to the electrode. To evaluate the performance of prelithiation reagents, the following six aspects should be considered: 1) the available active lithium ion capacity; 2) the chemical and environmental stability of prelithiation reagents; 3) the possible safety issues involved in prelithiation materials ; 4) The decomposition products of pre-lithiation reagents and the side reactions caused by them; 5) The potential impact of pre-lithiation on other electrochemical properties; 6) The compatibility and scalability of pre-lithiation technology and existing processes.
正极预锂化试剂可分为如下三种。The positive electrode pre-lithiation reagents can be divided into the following three types.
一是富锂化合物如Li2NiO2，Li5FeO4等。其环境稳定性好，安全性好，与现有工艺的兼容性好。但是其比容量较低，降低电池整体的能量密度。而且其在电池体系中引入的过渡金属元素会影响电池的长期循环。2016年，美国阿贡国家实验室报道了Li5FeO4正极预锂化材料，其具有867mAh·g-1的理论容量，受到研究者的广泛关注。One is lithium-rich compounds such as Li2 NiO2 , Li5 FeO4 and so on. It has good environmental stability, good safety, and good compatibility with existing processes. However, its specific capacity is low, which reduces the overall energy density of the battery. Moreover, the transition metal elements introduced into the battery system will affect the long-term cycle of the battery. In 2016, the Argonne National Laboratory of the United States reported the Li5 FeO4 cathode pre-lithiated material, which has a theoretical capacity of 867mAh g-1 and has attracted extensive attention from researchers.
二是二元锂化合物，如Li2O，Li3N等。其比容量非常高，具有很高的预锂化效率。Li2O的理论比容量高达1797mAh·g-1。但是其易与空气发生反应，环境稳定性不好，大规模使用时的安全性堪忧。且分解过程中会产生气体，造成额外的副反应。The second is binary lithium compounds, such as Li2 O, Li3 N and so on. Its specific capacity is very high and it has high pre-lithiation efficiency. The theoretical specific capacity of Li2 O is as high as 1797mAh·g-1 . However, it is easy to react with air, the environment stability is not good, and the safety of large-scale use is worrying. And gas will be generated during the decomposition process, causing additional side reactions.
三是基于转化反应的复合添加剂。如通过熔融锂与氧化钴反应生成Co/Li2O复合物，容量可达到724mAh·g-1。但是这种方法得到的材料依旧会在电池体系中引入过渡金属杂质。此外，生产工艺复杂，需要惰性气氛和高温，不利于大规模工业化使用。The third is the compound additive based on conversion reaction. If the Co/Li2 O composite is formed by the reaction of molten lithium and cobalt oxide, the capacity can reach 724mAh·g-1 . However, the materials obtained by this method will still introduce transition metal impurities into the battery system. In addition, the production process is complex, requiring an inert atmosphere and high temperature, which is not conducive to large-scale industrial use.
综上所述，制备环境稳定性好，容量高的新型正极预锂化添加剂将有助于高能量密度锂电池的发展。In summary, the preparation of new positive electrode pre-lithiation additives with good environmental stability and high capacity will contribute to the development of high energy density lithium batteries.
发明内容Contents of the invention
为了避免现有技术的不足之处，本发明的目的在于提出一种锂离子电池用正极预锂化材料，可有效解决锂离子电池首圈活性锂损失、循环稳定性差的问题；本发明的另一个目的在于提供一种锂离子电池用正极预锂化材料的制备方法，所述方法操作简单，成本低，易实现工业化。In order to avoid the deficiencies of the prior art, the object of the present invention is to propose a positive electrode pre-lithiation material for lithium ion batteries, which can effectively solve the problems of loss of active lithium and poor cycle stability in the first cycle of lithium ion batteries; another aspect of the present invention One object is to provide a method for preparing a positive electrode pre-lithiation material for lithium-ion batteries, the method is simple to operate, low in cost, and easy to realize industrialization.
本发明的上述目的是通过以下技术方案实现的：Above-mentioned purpose of the present invention is achieved through the following technical solutions:
一种锂离子电池用正极预锂化材料，其中所述锂离子电池用正极预锂化材料为氟化碳通过化学锂化制备得到纳米级氟化锂和碳的复合物，其中氟化锂为20％～70％，碳30％～80％，所述百分比为质量百分比。优选地，氟化锂的粒度不大于200nm。A positive electrode pre-lithiation material for a lithium ion battery, wherein the positive electrode pre-lithiation material for a lithium ion battery is a composite of carbon fluoride prepared by chemical lithiation to obtain nanoscale lithium fluoride and carbon, wherein lithium fluoride is 20%-70%,
一种锂离子电池用正极预锂化材料的制备方法，包括以下步骤：A preparation method of positive electrode pre-lithiation material for lithium ion battery, comprising the following steps:
步骤1、配置锂化溶液：称取锂化试剂，将锂化试剂加入锂化溶剂中，搅拌溶解；Step 1. Configure the lithiation solution: weigh the lithiation reagent, add the lithiation reagent into the lithiation solvent, and stir to dissolve;
步骤2、将步骤1得到的溶液转移至惰性气氛中，加入锂金属，搅拌溶解；Step 2. Transfer the solution obtained in step 1 to an inert atmosphere, add lithium metal, and stir to dissolve;
步骤3、将氟化碳前驱体加入步骤2中得到的锂化溶液中，搅拌；Step 3, adding the carbon fluoride precursor into the lithiated solution obtained in step 2, and stirring;
步骤4、将步骤3得到的反应物依次使用四氢呋喃，水和乙醇离心清洗，再转移至鼓风烘箱中干燥，最终得到锂离子电池用正极预锂化材料。Step 4. The reactant obtained in step 3 is washed by tetrahydrofuran, water and ethanol in sequence, and then transferred to a blast oven for drying, finally obtaining a positive electrode pre-lithiation material for a lithium ion battery.
其中，所述步骤1中锂化试剂为萘或联苯；锂化溶剂为四氢呋喃。Wherein, the lithiation reagent in the step 1 is naphthalene or biphenyl; the lithiation solvent is tetrahydrofuran.
其中，所述步骤1中锂化试剂/四氢呋喃溶液的浓度为0.1～1M。Wherein, the concentration of the lithiation reagent/tetrahydrofuran solution in the step 1 is 0.1-1M.
其中，所述步骤2中锂金属与锂化试剂的摩尔比为3：1～1：1。Wherein, the molar ratio of lithium metal to lithiation reagent in the step 2 is 3:1˜1:1.
其中，所述步骤3中氟化碳前驱体的粒径小于5μm，氟碳比为0.6～1。Wherein, in the step 3, the particle size of the carbon fluoride precursor is less than 5 μm, and the fluorocarbon ratio is 0.6-1.
其中，所述步骤4中干燥温度不超过60℃。Wherein, the drying temperature in step 4 does not exceed 60°C.
本发明锂离子电池用正极预锂化材料，原料为氟化碳，简单易得，降低了生产成本，通过化学锂化方法原位生成氟化锂和碳复合物，可以使得氟化锂和碳实现纳米级的均匀复合，改善材料的导电性和电化学反应活性；氟化锂和碳对于空气和水均非常稳定，使得这种材料可以很好的兼容现有的电池生产工艺；补偿了电池体系中活性锂离子的消耗，从而改善了硅碳负极材料的循环性能。本发明锂离子电池用正极预锂化材料的制备方法，操作简单，成本低，易实现工业化。The positive electrode pre-lithiation material for lithium ion battery of the present invention, the raw material is carbon fluoride, which is simple and easy to obtain, and reduces the production cost. Lithium fluoride and carbon composites are generated in situ by the chemical lithiation method, which can make lithium fluoride and carbon Achieve nanoscale uniform compounding, improve the conductivity and electrochemical reactivity of the material; lithium fluoride and carbon are very stable to air and water, making this material well compatible with existing battery production processes; compensating the battery The consumption of active lithium ions in the system improves the cycle performance of silicon-carbon anode materials. The preparation method of the cathode pre-lithiation material for the lithium ion battery of the present invention has the advantages of simple operation, low cost and easy industrialization.
附图说明Description of drawings
图1为本发明实施例1提供的氟化锂/碳复合物的SEM结果；Fig. 1 is the SEM result of the lithium fluoride/carbon composite that the embodiment of the present invention 1 provides;
图2为本发明实施例1提供的氟化锂/碳复合物的X射线衍射测试结果；Fig. 2 is the X-ray diffraction test result of the lithium fluoride/carbon composite provided in Example 1 of the present invention;
图3为本发明实施例1提供的氟化锂/碳复合物的透射电镜暗场相结果；Fig. 3 is the transmission electron microscope dark field phase result of the lithium fluoride/carbon composite provided by Example 1 of the present invention;
图4为本发明实施例1提供的氟化锂/碳复合物的首圈充电曲线；Fig. 4 is the charging curve of the first lap of the lithium fluoride/carbon composite provided by Example 1 of the present invention;
图5为采用本发明实施例1提供的锂离子电池用正极预锂化材料掺入镍钴锰商业正极材料，匹配硅碳负极材料得到的全电池在0.2C倍率下的容量与库伦效率图。Figure 5 is a diagram of the capacity and coulombic efficiency of a full battery obtained by using the positive electrode pre-lithiation material for lithium-ion batteries provided in Example 1 of the present invention doped with nickel-cobalt-manganese commercial positive electrode materials and matched with silicon-carbon negative electrode materials at a rate of 0.2C.
具体实施方式Detailed ways
为了更清楚地理解本发明的目的、技术方案及优点，以下结合附图及实施例，对本发明进行进一步详细说明。In order to understand the purpose, technical solutions and advantages of the present invention more clearly, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments.
本发明提供一种锂离子电池用正极预锂化材料，由以下组分组成：氟化锂20％～70％，碳30％～80％，以上组分质量百分比之和为100％。所述氟化锂的粒度不大于200nm。The invention provides a positive electrode pre-lithiation material for a lithium ion battery, which is composed of the following components: 20% to 70% of lithium fluoride, 30% to 80% of carbon, and the sum of the mass percentages of the above components is 100%. The particle size of the lithium fluoride is not greater than 200nm.
另外，本发明还提供上述锂离子电池用正极预锂化材料的制备方法，包括以下步骤：In addition, the present invention also provides a preparation method for the above-mentioned positive electrode pre-lithiation material for lithium ion batteries, comprising the following steps:
步骤1、配置锂化溶液：称取锂化试剂，将锂化试剂加入锂化溶剂中，搅拌溶解；Step 1. Configure the lithiation solution: weigh the lithiation reagent, add the lithiation reagent into the lithiation solvent, and stir to dissolve;
步骤2、将步骤1得到的溶液转移至惰性气氛中，加入锂金属，搅拌溶解；Step 2. Transfer the solution obtained in step 1 to an inert atmosphere, add lithium metal, and stir to dissolve;
步骤3、将氟化碳前驱体加入步骤2中得到的锂化溶液中，搅拌；Step 3, adding the carbon fluoride precursor into the lithiated solution obtained in step 2, and stirring;
步骤4、将步骤3得到的反应物使用四氢呋喃，水和乙醇离心清洗，再转移至鼓风烘箱中干燥，最终得到锂离子电池用正极预锂化材料。Step 4. The reactant obtained in step 3 is centrifugally washed with tetrahydrofuran, water and ethanol, and then transferred to a blast oven for drying to finally obtain a positive electrode pre-lithiation material for a lithium ion battery.
实施例1Example 1
步骤1、配置锂化溶液：称取15.4g联苯，加入至100mL四氢呋喃试剂中，搅拌溶解；Step 1. Prepare lithiation solution: weigh 15.4g of biphenyl, add it to 100mL tetrahydrofuran reagent, and stir to dissolve;
步骤2、将步骤1得到的溶液转移至惰性气氛中，加入0.7g锂金属，搅拌至完全溶解；Step 2. Transfer the solution obtained in step 1 to an inert atmosphere, add 0.7g of lithium metal, and stir until completely dissolved;
步骤3、将1.4g氟化碳前驱体(CF0.88)加入步骤2中得到的锂化溶液中，搅拌2小时；Step 3. Add 1.4g of carbon fluoride precursor (CF0.88 ) into the lithiated solution obtained in step 2, and stir for 2 hours;
步骤4、将步骤3得到的反应物使用四氢呋喃，水和乙醇离心清洗，再转移至鼓风烘箱中干燥，最终得到锂离子电池用正极预锂化材料。Step 4. The reactant obtained in step 3 is centrifugally washed with tetrahydrofuran, water and ethanol, and then transferred to a blast oven for drying to finally obtain a positive electrode pre-lithiation material for a lithium ion battery.
SEM表征：SEM characterization:
将步骤4所得氟化锂/碳复合物进行SEM表征，结果如图1所示，可以看到材料为片层堆叠的多孔结构，利于与电解液的接触。The lithium fluoride/carbon composite obtained in step 4 was characterized by SEM, and the result is shown in Figure 1. It can be seen that the material is a porous structure with stacked sheets, which is conducive to contact with the electrolyte.
图2是步骤4所得氟化锂/碳复合物的X射线衍射图谱，可以确定材料的结晶相为氟化锂，无其它杂质，碳为无定形碳，不表现出XRD峰。材料的衍射峰较宽，根据谢乐公式计算，氟化锂颗粒的粒径小于10nm。Figure 2 is the X-ray diffraction spectrum of the lithium fluoride/carbon composite obtained in step 4. It can be determined that the crystalline phase of the material is lithium fluoride, without other impurities, and the carbon is amorphous carbon, which does not show XRD peaks. The diffraction peak of the material is relatively broad, and according to Scherrer's formula calculation, the particle size of lithium fluoride particles is less than 10nm.
图3是材料的透射电子显微镜表征结果。暗场相中的亮点为氟化锂颗粒，可见其粒径小于10nm，与XRD结果一致。且颗粒均匀的分散在碳基底上。Figure 3 is the transmission electron microscope characterization results of the material. The bright spots in the dark field phase are lithium fluoride particles, and its particle size is less than 10nm, which is consistent with the XRD results. And the particles are uniformly dispersed on the carbon substrate.
实施例2Example 2
步骤1、配置锂化溶液：称取12.8g萘，加入至100mL四氢呋喃试剂中，搅拌溶解；Step 1. Prepare lithiation solution: weigh 12.8g naphthalene, add it to 100mL tetrahydrofuran reagent, and stir to dissolve;
步骤2、将步骤1得到的溶液转移至惰性气氛中，加入0.7g锂金属，搅拌至完全溶解；Step 2. Transfer the solution obtained in step 1 to an inert atmosphere, add 0.7g of lithium metal, and stir until completely dissolved;
步骤3、将1.4g氟化碳前驱体(CF0.88)加入步骤2中得到的锂化溶液中，搅拌12小时；Step 3. Add 1.4g of carbon fluoride precursor (CF0.88 ) into the lithiated solution obtained in step 2, and stir for 12 hours;
步骤4、将步骤3得到的反应物使用四氢呋喃，水和乙醇离心清洗，再转移至鼓风烘箱中干燥，最终得到锂离子电池用正极预锂化材料；Step 4, the reactant obtained in step 3 is centrifugally cleaned with tetrahydrofuran, water and ethanol, and then transferred to a blast oven for drying, finally obtaining a positive electrode pre-lithiation material for a lithium ion battery;
实施例3Example 3
步骤1、配置锂化溶液：称取15.4g联苯，加入至1000mL四氢呋喃试剂中，搅拌溶解；Step 1. Prepare lithiation solution: weigh 15.4g of biphenyl, add it to 1000mL tetrahydrofuran reagent, and stir to dissolve;
步骤2、将步骤1得到的溶液转移至惰性气氛中，加入0.7g锂金属，搅拌至完全溶解；Step 2. Transfer the solution obtained in step 1 to an inert atmosphere, add 0.7g of lithium metal, and stir until completely dissolved;
步骤3、将1.4g氟化碳前驱体(CF0.88)加入步骤2中得到的锂化溶液中，搅拌12小时；Step 3. Add 1.4g of carbon fluoride precursor (CF0.88 ) into the lithiated solution obtained in step 2, and stir for 12 hours;
步骤4、将步骤3得到的反应物使用四氢呋喃，水和乙醇离心清洗，再转移至鼓风烘箱中干燥，最终得到锂离子电池用正极预锂化材料；Step 4, the reactant obtained in step 3 is centrifugally cleaned with tetrahydrofuran, water and ethanol, and then transferred to a blast oven for drying, finally obtaining a positive electrode pre-lithiation material for a lithium ion battery;
实施例4Example 4
步骤1、配置锂化溶液：称取15.4g萘，加入至500mL四氢呋喃试剂中，搅拌溶解；Step 1. Prepare lithiation solution: weigh 15.4g of naphthalene, add it to 500mL of tetrahydrofuran reagent, and stir to dissolve;
步骤2、将步骤1得到的溶液转移至惰性气氛中，加入0.7g锂金属，搅拌至完全溶解；Step 2. Transfer the solution obtained in step 1 to an inert atmosphere, add 0.7g of lithium metal, and stir until completely dissolved;
步骤3、将1.4g氟化碳前驱体(CF0.88)加入步骤2中得到的锂化溶液中，搅拌20小时；Step 3. Add 1.4g of carbon fluoride precursor (CF0.88 ) into the lithiated solution obtained in step 2, and stir for 20 hours;
步骤4、将步骤3得到的反应物使用四氢呋喃，水和乙醇离心清洗，再转移至鼓风烘箱中干燥，最终得到锂离子电池用正极预锂化材料；Step 4, the reactant obtained in step 3 is centrifugally cleaned with tetrahydrofuran, water and ethanol, and then transferred to a blast oven for drying, finally obtaining a positive electrode pre-lithiation material for a lithium ion battery;
充放电性能测试：Charge and discharge performance test:
将本发明实施例1～实施例3得到的锂离子电池用正极预锂化材料制作成极片。The positive electrode pre-lithiation materials for lithium ion batteries obtained in Examples 1 to 3 of the present invention were made into pole pieces.
极片的制作过程为，将正极预锂化材料、super-p和PVDF按质量比为8:1:1混合研磨，用N-甲基-2-乙基-吡咯烷酮(NMP)作为溶剂，搅拌4h后涂覆在铝箔上，真空干燥12h，切片为直径为12mm的圆片；The production process of the pole piece is to mix and grind the positive electrode pre-lithiated material, super-p and PVDF at a mass ratio of 8:1:1, use N-methyl-2-ethyl-pyrrolidone (NMP) as a solvent, and stir After 4 hours, it is coated on aluminum foil, dried in vacuum for 12 hours, and sliced into discs with a diameter of 12 mm;
装电池：在充满高纯氩气，水和氧浓度均小于0.1ppm的手套箱内，以金属锂片为负极，按照正极壳，正极片，隔膜，电解液，锂片，钢片，弹片，负极壳的组装次序，组装成2032钮扣电池。放置12h后，在恒电流模式下，电池的充电限制电压为5.0V，放电终止电压为3.0V。电流密度为20mAh/g下进行充放电性能测试。测试结果如图4所示，可以看出：实施例1充电容量在420mA h/g，说明其可以为电池体系中提供活性锂离子。Install the battery: in a glove box filled with high-purity argon gas, the concentration of water and oxygen is less than 0.1ppm, the metal lithium sheet is used as the negative electrode, according to the positive electrode shell, positive electrode sheet, diaphragm, electrolyte, lithium sheet, steel sheet, shrapnel, The assembly sequence of the negative shell is assembled into a 2032 button battery. After being placed for 12 hours, in the constant current mode, the charging limit voltage of the battery is 5.0V, and the discharge termination voltage is 3.0V. The charge and discharge performance test was carried out at a current density of 20mAh/g. The test results are shown in Figure 4. It can be seen that the charging capacity of Example 1 is 420mAh/g, indicating that it can provide active lithium ions for the battery system.
全电池测试：将实施例1得到的材料与LiNi5Co2Mn3O2(NCM523)按5：95的质量比混合，再将正极材料、super-p和PVDF按质量比为95:3:2混合研磨，制作成极片。再将正极与比容量为500mAh/g的硅碳负极材料匹配进行全电池测试。结果如图5所示，经过预锂化后电池的首圈效率由84％降至76％，100圈后的容量保持率由61％升至87％，说明预锂化试剂补偿了硅碳负极材料首圈以及长循环过程中的锂离子损耗。Full battery test: mix the material obtained in Example 1 with LiNi5 Co2 Mn3 O2 (NCM523) in a mass ratio of 5:95, and then mix the positive electrode material, super-p and PVDF in a mass ratio of 95:3: 2 Mix and grind to make pole pieces. Then match the positive electrode with the silicon carbon negative electrode material with a specific capacity of 500mAh/g to conduct a full battery test. The results are shown in Figure 5. After pre-lithiation, the first cycle efficiency of the battery decreased from 84% to 76%, and the capacity retention rate after 100 cycles increased from 61% to 87%, indicating that the pre-lithiation reagent compensated the silicon carbon negative electrode. Li-ion loss during the first cycle of the material and during long cycling.
可见，以本发明的技术方案制备的氟化锂/碳复合材料作为正极预锂化材料，其电学性能上将表现出容量高、循环稳定性好等优点。It can be seen that the lithium fluoride/carbon composite material prepared by the technical solution of the present invention is used as a positive electrode pre-lithiation material, and its electrical properties will show the advantages of high capacity and good cycle stability.
本发明的锂离子电池用正极预锂化材料，由氟化碳通过化学锂化方法制备得到纳米级氟化锂和碳的复合物；氟化锂提供容量，碳基底改变氟化锂分解的反应路径，提高导电性；增加了锂电池首次充电容量，减缓了循环过程中由活性锂损失造成的电化学性能衰减，从而改善了硅碳负极的循环性能；本发明提出的锂离子电池用正极预锂化材料，成本低，具有环境稳定性，易实现工业化。以上所述，仅为本发明的较佳实施例而已，并非用于限定本发明的保护范围。The positive electrode pre-lithiation material for lithium-ion batteries of the present invention is prepared from carbon fluoride through a chemical lithiation method to obtain a composite of nano-scale lithium fluoride and carbon; lithium fluoride provides capacity, and the carbon substrate changes the decomposition reaction of lithium fluoride path, improve conductivity; increase the first charge capacity of lithium battery, slow down the electrochemical performance attenuation caused by the loss of active lithium in the cycle process, thereby improving the cycle performance of silicon carbon negative electrode; Lithiated materials are low in cost, environmentally stable, and easy to realize industrialization. The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the protection scope of the present invention.
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