Modulation of Local Charge Distribution Stabilized the Anionic Redox Process in Mn-Based P2-Type Layered Oxides

An anionic redox reaction is an extraordinary method for obtaining high-energy-density cathode materials for sodium-ion batteries (SIBs). The commonly used inactive-element-doped strategies can effectively trigger the O redox activity in several layered cathode materials. However, the anionic redox reaction process is usually accompanied by unfavorable structural changes, large voltage hysteresis, and irreversible O2 loss, which hinders its practical application to a large extent. In the present work, we take the doping of Li elements into Mn-based oxide as an example and reveal the local charge trap around the Li dopant will severely impede O charge transfer upon cycling. To overcome this obstacle, additional Zn2+ codoping is introduced into the system. Theoretical and experimental studies show that Zn2+ doping can effectively release the charge around Li+ and homogeneously distribute it on Mn and O atoms, thus reducing the overoxidation of O and improving the stability of the structure. Furthermore, this change in the microstructure makes the phase transition more reversible. This study aimed to provide a theoretical framework for further improve the electrochemical performance of similar anionic redox systems and provide insights into the activation mechanism of the anionic redox reaction.