Imitating Architectural Mortise‐Tenon Structure for Stable Ni‐Rich Layered Cathodes

Abstract Ni‐rich layered oxides are the most promising cathodes for Li‐ion batteries, but chemo‐mechanical failures during cycling and large first‐cycle capacity loss hinder their applications in high‐energy batteries. Herein, by introducing spinel‐like mortise‐tenon structures into the layered phase of LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811), the adverse volume variations in cathode materials can be significantly suppressed. Meanwhile, these mortise‐tenon structures play the role of the expressway for fast lithium‐ion transport, which is substantiated by experiments and calculations. Moreover, the particles with mortise‐tenon structures usually terminate with the most stable (003) facet. The new cathode exhibits a discharge capacity of 215 mAh g⁻¹ at 0.1 C with an initial Coulombic efficiency of 97.5%, and capacity retention of 82.2% after 1200 cycles at 1 C. This work offers a viable lattice engineering to address the stability and low initial Coulombic efficiency of the Ni‐rich layered oxides, and facilitates the implementation of Li‐ion batteries with high‐energy density and long durability.