High‐Energy Earth‐Abundant Cathodes with Enhanced Cationic/Anionic Redox for Sustainable and Long‐Lasting Na‐Ion Batteries

Layered iron/manganese‐based oxides are a class of promising cathode materials for sustainable batteries due to their high energy densities and earth abundance. However, the stabilization of cationic and anionic redox reactions in these cathodes during cycling at high voltage remain elusive. Here, an electrochemically/thermally stable P2‐Na0.67Fe0.3Mn0.5Mg0.1Ti0.1O2 cathode material with zero critical elements is designed for sodium‐ion batteries (NIBs) to realize a highly reversible capacity of ≈210 mAh g−1 at 20 mA g−1 and good cycling stability with a capacity retention of 74% after 300 cycles at 200 mA g−1, even when operated with a high charge cut‐off voltage of 4.5 V versus sodium metal. Combining a suite of cutting‐edge characterizations and computational modeling, it is shown that Mg/Ti co‐doping leads to stabilized surface/bulk structure at high voltage and high temperature, and more importantly, enhances cationic/anionic redox reaction reversibility over extended cycles with the suppression of other undesired oxygen activities. This work fundamentally deepens the failure mechanism of Fe/Mn‐based layered cathodes and highlights the importance of dopant engineering to achieve high‐energy and earth‐abundant cathode material for sustainable and long‐lasting NIBs. A high‐energy and earth‐abundant Na0.67Fe0.3Mn0.5Mg0.1Ti0.1O2 cathode is developed, which shows significantly improved cycling stability at a high charge cut‐off voltage of 4.5 V versus Na. Multiscale characterization reveals that the Mg/Ti co‐doping improves the surface and bulk structural stability and enhances the cationic and anionic redox reaction reversibility during prolong cycling.