Boosting Reversibility of Mn‐Based Tunnel‐Structured Cathode Materials for Sodium‐Ion Batteries by Magnesium Substitution
Xun‐Lu Li, Jian Bao, Yifan Li, Dong Chen, Cui Ma, Qi‐Qi Qiu, Xinyang Yue, Qinchao Wang, Yong‐Ning Zhou
Abstract
Abstract 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 Na 0.44 Mn 0.95 Mg 0.05 O 2 with Mg 2+ in the hinging Mn‐O 5 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 Na 0.44 MnO 2 . 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 Na 0.44 Mn 0.95 Mg 0.05 O 2 is more electron‐abundant in Mn 3d orbits near the Fermi level than that in Na 0.44 MnO 2 , leading to higher redox participation of Mn ions.