Regulation of Surface Defect Chemistry toward Stable Ni‐Rich Cathodes

Abstract Surface reconstruction of Ni‐rich layered oxides (NLO) degrades the cycling stability and safety of high‐energy‐density lithium‐ion batteries (LIBs), which challenges typical surface‐modification approaches to build a robust interface with electrochemical activity. Here, a strategy of leveraging the low‐strain analogues of Li‐ and Mn‐rich layered oxides (LMR) to reconstruct a stable surface on the Ni‐rich layered cathodes is proposed. The new surface structure not only consists of a gradient chemical composition but also contains a defect‐rich structure regarding the formation of oxygen vacancies and cationic ordering, which can simultaneously facilitate lithium diffusion and stabilize the crystal structure during the (de)lithiation. These features in the NLO lead to a dramatic improvement in electrochemical properties, especially the cyclability under high voltage cycling, exhibiting the 30% increase in capacity retention after 200 cycles at the current density of 1 C (3.0–4.6 V). The findings offer a facile and effective way to regulate defect chemistry and surface structure in parallel on Ni‐rich layered structure cathodes to achieve high‐energy density LIBs.