Low‐Electronegativity Cationic High‐Entropy Doping to Trigger Stable Anion Redox Activity for High‐Ni Co‐Free Layered Cathodes in Li‐Ion Batteries

LiNi0.8 Co0.1 Mn0.1 O2 (NCM-811) exhibits the highest capacity in commercial lithium-ion batteries (LIBs), and the high Ni content (80 %) provides the only route for high energy density. However, the cationic structure instability arisen from the increase of Ni content (>80 %) limits the further increase of the capacity, and inevitable O2 release related to anionic structure instability hinders the utilization of anion redox activity. Here, by comparing various combinations of high-entropy dopants substituted Co element, we propose a low-electronegativity cationic high-entropy doping strategy to fabricate the high-Ni Co-free layered cathode (LiNi0.8 Mn0.12 Al0.02 Ti0.02 Cr0.02 Fe0.02 O2 ) that exhibits much higher capacity and cycling stability. Configurational disorder originated from cationic high-entropy doping in transition metal (TM) layer, anchors the oxidized lattice oxygen ((O2 )n- ) to preserve high (O2 )n- content, triggering the anion redox activity. Electron transfer induced by applying TM dopants with lower electronegativity than that of Co element, increases the electron density of O in TM-O octahedron (TM-O6 ) configuration to reach higher (O2 )n- content, resulting in the higher anion redox activity. With exploring the stabilization effect on both cations and anions of high-entropy doping and low-electronegativity cationic modified anion redox activity, we propose an innovative and variable pathway for rationally tuning the properties of commercial cathodes.