具有类似石墨褶皱蜂巢层状结构的黑磷储钠负极材料具有超高的比容量(2596mAh/g)和良好的大电流充放电性能，是一类极具潜力的钠离子电池负极材料。然而体相黑磷充放电过程会发生较大体积膨胀致使电极粉化，造成电池容量快速衰减，成为制约该类材料实用化的壁垒。本项目运用第一性原理计算结合从头算分子动力学模拟方法，对不同结构和组成的黑磷负极材料的微观结构和钠化过程进行理论模拟计算，从热力学和动力学角度对该类材料的组成-微结构-储钠性能-动力学特性-结构形变之间的构效关系进行系统研究，阐明二维磷烯主体的表面效应和夹层石墨烯载体的协同作用对材料热力学稳定性和动态结构演变的影响，获得黑磷储钠负极材料容量衰减机理；在此基础上，开展以氮掺杂石墨烯为载体的黑磷储钠材料的微观结构设计和性能调控研究，探明二维纳米复合化等微观结构调控手段对黑磷电化学性能提升的作用方式和本质，为高性能储钠负极材料的研发提供理论依据。

Due to the high theoretical specific capacity of 2596 mAh/g and high-rate capability, the black phosphorus with a puckered honeycomb structure similar to graphite have been considered as a potential anode material for sodium ion batteries (NIBs). However, the large volume change during the sodiation process results in electrode degradation and rapid capacity fading, which greatly limited practical applications. In this proposal, two types of 2D nanoscale phospherene-based anode materials will be carefully explored based on first-principle calculations combined with ab initio molecular dynamics simulations. To gain insight into the capacity fading mechanism of phospherene-based anode materials, the relationship between composition, structure, sodium storage property, kinetics characteristics, and dynamic structural evolution will be systematically investigated by theoretical simulation of the sodiation process. Furthermore, a strategy by constructing a sandwich-like phospherene-based anode materials with N-doped grapheme(NG) substrate is proposed to improve the cycling stablility and electrochemical performance of electrode materials, becauae of NG’s high electrical conductivity and numerous active sites. We expect that the fundamental findings from this computational works will lead to a better understanding of essential effect of nano-composite technologies to the electrochemical properties improvement and provide useful guidelines in further designing and developments of high-performance phosphorus-based anode materials for NIBs.