Computational Understandings of the Cation Configuration Dependent Redox Activities and Oxygen Dimerizations in Li$_{1.22}$Ni$_{0.22}$Mn$_{0.56}$O$_2$ Cathode

Abstract: Understanding the lattice oxygen dimerization is quite essential for the optimal design for the Li-rich Mn-based cathode materials. In this work, based on the density functional theory (DFT) calculations, a Ni-honeycomb Li-Ni-Mn cation configuration for Li${1.22}$Ni${0.22}$Mn${0.56}$O$_2$ cathode was carefully proposed and examined, which can coexist with the well-known Li-honeycomb structure in the experimentally synthesized Li${1.2}$Ni${0.2}$Mn${0.6}$O$2$ samples. Li-Ni-Mn cation configurations have significant impacts on oxygen redox activities and oxygen dimerizations in the delithiated Li$_x$Ni${0.22}$Mn$_{0.56}$O$_2$. There is no necessary consistency between the high lattice oxygen redox activity and easy oxygen dimerization, such as the Li-honeycomb structures showing higher redox activities and higher activation energy barriers to prohibit oxygen dimerizations than Ni-honeycomb structures. Avoiding the Ni-honeycomb structures with more favorable lattice oxygen dimerization and making full use of the Li-honeycomb structures with better redox activities is important to optimally design the high-performance Li-rich Mn-based cathode materials.