Operando X-ray Diffraction Studies of the Mg-Ion Migration Mechanisms in Spinel Cathodes for Rechargeable Mg-Ion Batteries

A promising high-voltage spinel oxide cathode material MgCrMnO₄ with 18% Mg/Mn inversion was synthesized successfully. A new custom operando battery device was designed to study the cation migration mechanisms of the MgCrMnO₄ cathode using 0.1 M Mg(TPFA)₂ electrolyte dissolved in triglyme and activated carbon as the anode. For the first time in multivalent batteries, high-quality operando diffraction data enabled the accurate quantification of cation contents in the host structure. Besides the exceptional reversibility of 12% Mg²⁺ insertion in Mg_1-<i>x</i>CrMnO₄ (<i>x</i> ≤ 1), a partially reversible insertion of excess Mg²⁺ during overdischarging was also observed. Moreover, the insertion/extraction reaction was experimentally shown to be accompanied by a series of cation redistributions in the spinel framework, which were further supported by density functional theory calculations. The inverted Mn is believed to be directly involved in the cation migrations, which would cause voltage hysteresis and irreversible structural evolution after overdischarging. Tuning the Mg/Mn inversion rate could provide a direct path to further optimize spinel oxide cathodes for Mg-ion batteries, and more generally, the operando techniques developed in this work should play a key role in understanding the complex mechanisms involved in multivalent ion insertion systems.