锰基层状固溶体xLi2MnO3-(1-x)LiMO2(M=Mn、Ni、Co)由于其大于280mAh/g的超高比容量被认为是最有潜力的下一代正极材料，在锂离子电池关键技术方面具有重要科研价值和应用前景。目前限制其发展的一个重要因素是首次充电过程中4.5V处氧脱出后氧空位的形成和迁移造成局域离子重排，引起循环过程中的结构衍变，导致电压迟滞与容量衰减。本申请项目通过对材料进行离子互占位，解析氧与氧空位迁移，通过H-Li交换预处理/表层与导电聚合物形成H-O键，控制表面相从本体相分离，并对局域结构衍变进行研究；在此基础上，研究固溶体及修饰物在循环过程中不同元素化合价态变化、表面修饰物与固溶体晶格适配和调制的关系，揭示局域结构衍化规律、电压迟滞原因等基础科学问题。同时提出控制氧空位扩散与氧的不可逆脱出的具体措施，为稳定固溶体材料结构、提高能量密度及循环稳定性提供基础。

The manganese based layered solid solution system xLi2MnO3-(1-x)LiMO2(M=Mn、Ni、Co) is becoming the most promising cathode material of lithium ion batteries because of its anomalously high discharge capacity of more than 280 mAh/g and shows important scientific research value and application prospect. However, the further development of this series of material has been districted by the voltage hysteresis and capacity attenuation phenonenon, which is caused by the structure evolvement in the process of charge-discharge cycles because of the local ion rearrangement due to the formation and migration of oxygen vacancies at 4.5V of the first charging process. This project aims to explain the transferences of oxygen ions and oxygen vacancies and restrain the surface phase separation by the means of ion exchange at surface/bulk phases and H-Li exchange pretreatment / conductive polymer coating. Based on above, the valence state changes of different elements at the process of circulation and the lattice adaptation of modifications and solid solution were investigated, thus the causes of local structure evolvement and voltage hysteresis were revealed. At the same time, the measures to control the oxygen vacancy diffusion and irreversible oxygen ions loss were proposed. And the manganese based layered solid solution electrode material with good cycle stability and high energy density was developed according to theoretical basis of stabilizing the material structure.