Reversible anionic (oxygen) redox in lithium-rich cathode oxides has been becoming a blooming research topic to further boost the energy density in lithium-ion batteries. There are numerous experimental observations and theoretical calculations to illustrate the importance of defects on anionic redox activity, but how the defects on the surface and bulk control the kinetics of anionic redox is not well understood. Here, we uncover this intriguing ambiguity on the correlation among defects states, Li-ion diffusion, and oxygen redox reaction. It is found that the surface-defective microstructure has fast Li-ion diffusion to achieve superior cationic redox activities/kinetics, whereas the bulk-defective microstructure corresponds to a slow Li-ion diffusion to result in poor cationic redox activities/kinetics. By contrast, both surface and bulk defects can be of benefit to the enhancement of oxygen redox activities/kinetics. Moreover, a positive correlation is also established among charge-transfer resistance, interface reaction charge-transfer activation energy, and oxygen redox activity in these electrode materials. This study on defect-anionic activity provides a new insight for controlling anionic redox reaction in lithium-rich cathode materials for real-world application.
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