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Abstract Anionic redox chemistry presents a promising approach to enhancing the energy density of oxide cathode materials. However, anionic redox reactions invariably lead to O 2 formation, either as free gaseous O 2 or trapped molecular O 2 , which destabilizes the material's structure. Here, this critical challenge is addressed by constructing a crystal structure with both gradient redox activity and de‐clustered redox‐active oxygen. This design strategy is directly validated by operando differential electrochemical mass spectrometry and ex situ 50 K electron paramagnetic resonance, revealing no release of O 2 or trapped O 2 in the 4.5 V P2‐type sodium manganese‐based layered oxide. Notably, the material exhibits a highly reversible capacity of 247 mA h g −1 at 20 mA g −1 and exceptional capacity retention of 91.4% after 300 cycles at 300 mA g −1 . In situ X‐ray diffraction further suggests that the absence of O 2 formation suppresses the typical P2‐O2 phase transition, resulting in a minimal lattice volume change of only 0.5%. Ex situ neutron diffraction studies and theoretical calculations further elucidate that the locally ordered lattice is well‐preserved, attributable to reduced cationic migrations during cycling.
Li et al. (Mon,) studied this question.