Role of Ordered Ni Atoms in Li Layers for Li‐Rich Layered Cathode Materials

Li‐rich layered oxide materials are promising candidates for high‐energy Li‐ion batteries. They show high capacities of over 200 mAh g−1 with the additional occupation of Li in their transition metal layers; however, the poor cycle performance induced by an irreversible phase transition limits their use in practical applications. In recent work, an atomic‐scale modified surface, in which Ni is ordered at 2c sites in the Li layers, significantly improves the performance in terms of reversible capacity and cycling stability. The role of the incorporated Ni on this performance, however, is not yet clearly understood. Here, the effects of the ordered Ni on Li battery performance are presented, based on first‐principles calculations and experimental observations. The Ni substitution suppresses the oxygen loss by moderating the oxidation of oxygen ions during the delithiation process and forms bonds with adjacent oxygen after the first deintercalation of Li ions. These NiO bonds contribute to the formation of a solid surface, resulting in the improved cycling stability. Moreover, the multivalent Ni suppresses Mn migration to the Li‐sites that causes the undesired phase transition. These findings from theoretical calculations and experimental observations provide insights to enhance the electrochemical performance of Li‐rich layered oxides. The regularly ordered Ni substitution in the Li‐rich layered oxide significantly improves the battery performance in terms of reversible capacity and cycling stability. The combinatorial study using first‐principles calculations and experiments reveals that Ni substitution effectively suppresses the oxygen loss and cation mixing that induces the undesired phase transition for the Li‐rich layered cathode materials.