Uncovering the Critical Role of Ni on Surface Lattice Stability in Anionic Redox Active Li_1.2Ni_0.2Mn_0.6O₂

ABSTRACT Anionic redox reaction (ARR) can provide extra capacity beyond transition metal (TM) redox in lithium‐rich TM oxide cathodes. Practical ARR application is much hindered by the structure instability, particularly at the surface. Oxygen release has been widely accepted as the ringleader of surficial structure instability. However, the role of TM in surface stability has been much overlooked, not to mention its interplay with oxygen release. Herein, TM dissolution and oxygen release are comparatively investigated in Li_1.2Ni_0.2Mn_0.6O₂. Ni is verified to detach from the lattice counter‐intuitively despite the overwhelming stoichiometry of Mn, facilitating subsequent oxygen release of the ARR process. Intriguingly, surface reorganization occurs following regulated Ni dissolution, enabling the stabilization of the surface and elimination of oxygen release in turn. Accordingly, a novel optimization strategy is proposed by adding a relaxation step at 4.50 V within the first cycle procedure. Battery performance can be effectively improved, with voltage decay suppressed from 3.44 mV/cycle to 1.60 mV/cycle, and cycle stability improved from 66.77% to 90.01% after 100 cycles. This work provides new perspectives for clarifying ARR surface instability and guidance for optimizing ARR performance.