Gradient and De‐Clustered Anionic Redox Enabled Undetectable O₂ Formation in 4.5 V Sodium Manganese Oxide Cathodes

Abstract

Anionic redox chemistry presents a promising approach to enhancing the energy density of oxide cathode materials. However, anionic redox reactions invariably lead to O2 formation, either as free gaseous O2 or trapped molecular O2, 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 O2 or trapped O2 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 O2 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.