Transition metal oxide cathodes such as layered LiCoO₂, spinel LiMn₂O₄ and olivine LiFePO₄ have been commercialized for several decades and widely used in the rechargeable Li-ion batteries (LIBs). While great theoretical efforts have been made using the density functional theory (DFT) method, leading to insightful understanding covering materials stability and functional properties, the lack of consistency in choices of functionals and/or convergence criteria makes it somewhat difficult to compare results. It is therefore highly useful to assess these established systems towards self-consistency, thus offering a reliable working basis for theoretical formulation of novel cathodes. Here in this work, we have carried out systematic DFT calculations on the basis of recently established framework covering both thermodynamic stability, functional properties and associated mechanisms. Efforts have been made in self-consistent selection of exchange–correlation (XC) functionals in terms of dependable accuracy with affordable computational cost, which is essential for high-throughput first-principles calculations. The outcome of the current work on three established cathode systems is in very good agreement with experimental data, and the methodology is to provide a solid basis for designing novel cathode materials without using costing non-local exchange–correlation functionals for structure-energy calculations.

过渡金属氧化物阴极，例如层状LiCoO ₂，尖晶石LiMn ₂ O ₄和橄榄石LiFePO ₄锂离子电池已经商业化了几十年，并广泛用于可充电锂离子电池（LIB）。尽管使用密度泛函理论（DFT）进行了巨大的理论努力，导致对材料稳定性和功能特性的见解深入，但是在功能选择和/或收敛标准方面缺乏一致性使得比较结果有些困难。因此，评估这些已建立的系统的自洽性非常有用，从而为新型阴极的理论配方提供了可靠的工作基础。在这项工作中，我们在最近建立的涵盖热力学稳定性，功能特性和相关机理的框架的基础上，进行了系统的DFT计算。在可靠一致的准确性和可承受的计算成本方面，人们一直在努力自洽选择交换相关（XC）功能，这对于高通量第一性原理计算至关重要。当前在三个已建立的阴极系统上的工作成果与实验数据非常吻合，该方法学为设计新型阴极材料提供了坚实的基础，而无需在结构能计算中使用成本高昂的非局部交换相关函数。