锂离子电池石墨类碳负极的容量衰减机制研究-化学工程与技术专业毕业论文.docxVIP

哈尔滨工业大学工学博士学位论文 哈尔滨工业大学工学博士学位论文 Abs Abstract 万方数据 万方数据 万方数据 万方数据 离子，这两个因素引起长期循环过程中锂沉积物的生成。锂沉积物的厚度可达几 十到上百微米，阻碍了锂离子的嵌入，并引起 MCMB 层从集流体上的局部剥离， 使得电池的 Rb 略有增加，Rf 和 Rct 明显增加，导致负极容量的衰减。2400 次循环 后负极 MCMB 的容量衰减大于正极 LiCoO2，负极表面 SEI 膜的生长是负极容量 衰减的主要原因，占容量损失的 68%。 在长期充放电循环过程中，LiCoO2/石墨电池负极材料的 d002 小幅度增加，Lc 小幅度降低，La 未出现明显变化。循环至 600 次时，石墨表面出现不均匀分布的 锂沉积物，而且随着循环的进行不断生长。锂沉积物表面的 SEI 膜成分和石墨表 面的 SEI 膜成分相似。锂沉积物的出现消耗电池中的电解液，降低电池的离子导 电性，而且其本身的形成也会消耗电池中的活性锂，引起电池的容量衰减。随着 充放电循环的进行，石墨材料的剥落引起负极活性材料的减少，使得锂沉积物出 现在石墨电极表面。LiCoO2/石墨电池的正极和负极对电池长期循环容量衰减的影 响最大，其次是电解液，负极对电池性能衰减的影响大于正极。 关键词：锂离子电池；碳材料；容量衰减；SEI 膜；锂沉积物 II Abstract The lithium ion battery has some advantages such as high voltage, high energy density, few pollution and so on. It has been applied in the fields of electronic products and electric vehicle. The capacity of lithium ion battery decreased gradually during use. If the reasons for the capacity loss were explored, the preparation of the battery would be improved targetedly and lithium ion batteries with high capacity and long life could be obtained, which is of great importance. In this paper, capacity loss mechanisms of mesocarbon microbeads (MCMB) and graphite anodes applied in lithium ion battery widely were studied. The changes of electrochemical properties of the anodes during the long-term charge/discharge cycling were examined by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) tests. Then the growth of solid electrolyte interface (SEI) film on the surface of the anode, structure changes and the growth of the lithium deposits were studied using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and so on. The capacity fade behaviors of MCMB were studied by the long-term charging and discharging of MCMB coin cells. The results indicated that d002 and Lc of MCMB bulk increased and the degree of graphitization decreased slightly with the cycling, while d110 and La did not change obviously, and the disorder ex