Boosting Reversibility of Mn‐Based Tunnel‐Structured Cathode Materials for Sodium‐Ion Batteries by Magnesium Substitution

Electrochemical irreversibility and sluggish mobility of Na+ in the cathode materials result in poor cycle stability and rate capability for sodium‐ion batteries. Herein, a new strategy of introducing Mg ions into the hinging sites of Mn‐based tunnel‐structured cathode material is designed. Highly reversible electrochemical reaction and phase transition in this cathode are realized. The resulted Na0.44Mn0.95Mg0.05O2 with Mg2+ in the hinging Mn‐O5 square pyramidal exhibits promising cycle stability and rate capability. At a current density of 2 C, 67% of the initial discharge capacity is retained after 800 cycles (70% at 20 C), much improved than the undoped Na0.44MnO2. The improvement is attribute to the enhanced Na+ diffusion kinetics and the lowered desodiation energy after Mg doping. Highly reversible charge compensation and structure evolution are proved by synchrotron‐based X‐ray techniques. Differential charge density and atom population analysis of the average electron number of Mn indicate that Na0.44Mn0.95Mg0.05O2 is more electron‐abundant in Mn 3d orbits near the Fermi level than that in Na0.44MnO2, leading to higher redox participation of Mn ions. Na0.44Mn0.95Mg0.05O2 as a novel cathode material for sodium‐ion batteries is designed and synthesized aiming to effectively facilitate Na+ diffusion and lower desodiation energy. Structure evolution of tunnel‐type cathode during high rate charging/discharging is revealed for the first time, enabling high rate capability and cycle stability with the help of Mg.