Anionic redox in Li-rich and Na-rich transition metal oxides (A-rich-TMOs) has emerged as a new paradigm to increase the energy density of rechargeable batteries. Ever since, numerous electrodes delivering extra anionic capacity beyond the theoretical cationic capacity have been reported. Unfortunately, most often the anionic capacity achieved in charge is partly irreversible in discharge. A unified picture of anionic redox in A-rich-TMOs is designed here to identify the electronic origin of this irreversibility and to propose new directions to improve the cycling performance of the electrodes. The electron localization function is introduced as a holistic tool to unambiguously locate the oxygen lone pairs in the structure and follow their participation in the redox activity of A-rich-TMOs. The charge-transfer gap of transition metal oxides is proposed as the pertinent observable to quantify the amount of extra capacity achievable in charge and its reversibility in discharge, irrespective of the material chemical composition. From this generalized approach, we conclude that the reversibility of the anionic capacity is limited to a critical number of O holes per oxygen, hO ≤ 1/3.
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The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.
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The authors acknowledge the RS2E institution and the Agence Nationale pour la Recherche (ANR)—DeliRedox no. ANR-14-CE05-0020—for supporting this work. Part of this work was supported by the EU through the POROUS4APP project—H2020-NMP-PILOT-2015 no. 686163.
The authors declare no competing interests.
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Ben Yahia, M., Vergnet, J., Saubanère, M. et al. Unified picture of anionic redox in Li/Na-ion batteries. Nat. Mater. 18, 496–502 (2019). https://doi.org/10.1038/s41563-019-0318-3
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