Enhanced Cycling Stability in the Anion Redox Material P3‐Type Zn‐Substituted Sodium Manganese Oxide

Sodium layered oxides showing oxygen redox activity are promising positive electrodes for sodium‐ion batteries (SIBs). However, structural degradation typically results in limited reversibility of the oxygen redox activity. Herein, the effect of Zn‐doping on the electrochemical properties of P3‐type sodium manganese oxide, synthesised under air and oxygen is investigated for the first time. Air‐Na0.67Mn0.9Zn0.1O2 and Oxy‐Na0.67Mn0.9Zn0.1O2 exhibit stable cycling performance between 1.8 and 3.8 V, each maintaining 96 % of their initial capacity after 30 cycles, where Mn3+/Mn4+ redox dominates. Increasing the voltage range to 1.8–4.3 V activates oxygen redox. For the material synthesised under air, oxygen redox activity is based on Zn, with limited reversibility. The additional transition metal vacancies in the material synthesised under oxygen result in enhanced oxygen redox reversibility with small voltage hysteresis. These results may assist the development of high‐capacity and structurally stable oxygen redox‐based materials for SIBs. The effect of Zn‐substitution on the electrochemical properties of P3‐Na0.67Mn0.9Zn0.1O2, synthesised under air and oxygen has been studied. Both materials exhibit stable cycling between 1.8–3.8 V, where Mn3+/Mn4+ redox dominates and increasing the voltage range to 1.8–4.3 V activates oxygen redox. Additional transition metal vacancies in the material synthesised under oxygen give enhanced oxygen redox reversibility with small voltage hysteresis.