Titanium Substitution Facilitating Oxygen and Manganese Redox in Sodium Layered Oxide Cathode

Abstract Sodium layered oxide with anion redox activity (SLO‐A) stands out as a promising cathode material for sodium‐ion batteries due to its impressive capacity and high voltage resulting from Mn‐ and O‐redox processes. However, the SLO‐A faces significant challenges in cycling stability and rate performance, primarily due to the poor reversibility and sluggish kinetics of the O‐redox. In this study,a novel Ti‐doped material, Na 2/3 Li 2/9 Mn 53/72 Ti 1/24 O 2 (NLMTO), exhibiting remarkable characteristics such as a notable rate capacity (130 mAh g −1 at 3C, where 1C equals 200 mA g −1 ) and excellent cycling retention (85.4% after 100 cycles at 0.5C) is introduced. Employing electrochemical differential analyses, the contributions to the superior performance arising from the Mn‐ and O‐redox processes are quantitatively delineated. The optimized performance of NLMTO is attributed, in part, to the enhanced stability of both bulk and interface structures. The introduction of Ti through substitution not only contributes to this stability but also allows for the fine‐tuning of the material's electron configurations. This is achieved by augmenting the density of states near the Fermi energy level, as well as elevating the O 2p and Mn 3d orbits. This research advances sodium‐ion battery technology.