Revisiting the Defect‑Rich Li─Mn─O Structure with Superior Kinetics for High‐Power Li‐Ion Batteries

Abstract Li‐rich cathode materials, characterized by dual anionic and cationic redox activities, present a promising pathway to surpass traditional capacity and voltage constraints for high‐energy‐density batteries. However, the activation of anionic redox often induces lattice oxygen release, precipitating irreversible structural transformations and compromised ion transport dynamics. In this work, a layered‐spinel intergrown structure is designed from an ion‐exchange process with great tunability, which induces the arrangement of the manganese oxide layer and combines the high‐capacity characteristics of the layer structure with superior stability provided by the spinel structure. Benefiting from expanded ion channels, the intergrown structure delivers an initial discharge capacity of 254.3 mAh g −1 at 0.1 C and retains a great high‐rate capability of 169.2 mAh g −1 at 5 C, which is superior to the reported Li‐rich manganese‐based cathode materials. This work delineates a systematic design framework for layered‐spinel intergrown architectures, leveraging their synergistic ion transport characteristics to achieve superior electrochemical performance in lithium‐ion batteries.