Open AccessBoosting Reversibility of Mn‐Based Tunnel‐Structured Cathode Materials for Sodium‐Ion Batteries by Magnesium Substitution
Author(s) -
Li XunLu,
Bao Jian,
Li YiFan,
Chen Dong,
Ma Cui,
Qiu QiQi,
Yue XinYang,
Wang QinChao,
Zhou YongNing
Publication year - 2021
Publication title -
advanced science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.388
H-Index - 100
ISSN - 2198-3844
DOI - 10.1002/advs.202004448
Subject(s) - cathode , electrochemistry , materials science , ion , electrode , chemistry , organic chemistry
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.