Revisiting the NaNiMnO Cathode: Oxygen Redox Chemistry and Oxygen Release Suppression.

Sodium layered transition metal oxides have been considered as promising cathode materials for sodium ion batteries due to their large capacity and high operating voltage. However, mechanism investigations of chemical evolution and capacity failure at high voltage are inadequate. As a representative cathode, NaNiMnO, the capacity contribution at a 4.2 V plateau has long been assigned to the redox of the Ni/Ni couple, while at the same time it suffers large irreversible capacity loss during the initial discharging process. In this work, we prove that the capacity at the 4.2 V plateau is contributed to the irreversible O/O /O evolution based on in situ differential electrochemical mass spectrometry and density functional theory calculation results. Besides, a phenomenon of oxygen release and subsequent surface lattice densification is observed, which is responsible for the large irreversible capacity loss during the initial cycle. Furthermore, the oxygen release is successfully suppressed by Fe substitution due to the formation of a unique Fe-(O-O) species, which effectively stabilizes the reversibility of the O/O redox at high operating voltage. Our findings provide a new understanding of the chemical evolution in layered transition metal oxides at high operating voltage. Increasing the covalency of the TM-O bond has been proven to be effective in suppressing the oxygen release and hence improving the electrochemical performance.