Regulating Oxygen Redox Chemistry through the Synergistic Effect of Transition‐Metal Vacancy and Substitution Element for Layered Oxide Cathodes

Abstract Reversible oxygen redox (OR) is considered as a paradigmatic avenue to boost the energy densities of layered oxide cathodes. However, its activation is largely coupled with the local coordination environment around oxygen, which is usually accompanied with irreversible oxygen release and unfavorable structure distortion. Herein, it is revealed that the synergistic effect of transition‐metal (TM) vacancy and substitution element for modulating the OR activity and reversibility of layered Na 0.67 MnO 2 through multimodal o perando synchrotron characterizations and electrochemical investigations. It is disclosed that TM vacancy can not only suppress the complicated phase transition but also stimulate the OR activity by creating nonbonding O 2p states via the Na─O─vacancy configurations. Notably, the substitution element plays a decisive role for regulating the reversibility of vacancy‐boosted OR activity: the presence of strong Al─O bonds stabilizes the Mn‐O motifs by sharing O with Al in the rigid Mn─O─Al frameworks, which mitigates TM migration and oxygen release induced by TM vacancy, leading to enhanced OR reversibility; while the introduction of weak Zn─O bonds exacerbates TM migration and irreversible oxygen release. This work clarifies the critical role of both TM vacancy and substitution element for regulating the OR chemistry, providing an effective avenue for designing high‐performance cathodes employing anionic redox.