Self-Passivation of a LiNiO₂ Cathode for a Lithium-Ion Battery through Zr Doping

A self-passivating Li2ZrO3 layer with a thickness of 5–10 nm, which uniformly encapsulates the surfaces of LiNiO2 cathode particles, is spontaneously formed by introducing excess Zr (1.4 atom %). A thin layer of Li2ZrO3 on the surface is converted into a stable impedance-lowering solid–electrolyte interphase layer during subsequent cycles. The Zr-doped LiNiO2 cathode with an initial discharge capacity of 233 mA·h·g–1 exhibited significantly improved capacity retention (86% after 100 cycles) and thermal stability, compared to the undoped LiNiO2. While the spontaneously formed Zr-rich coating layer provides surface protection, the Zr ions in the LiNiO2 lattice delay the detrimental phase transition occurring in the deeply charged state of LiNiO2 and partially suppress the anisotropic strain emerging from the phase transition. Further optimization of the proposed simultaneous coating and doping strategy can mitigate the inherent structural instability of the LiNiO2 cathode, making it a promising high-energy-density cathode for electric vehicles.