Abstract
Lattice oxygen redox offers an unexplored way to access superior electrochemical properties of transition metal oxides (TMOs) for rechargeable batteries. However, the reaction is often accompanied by unfavourable structural transformations and persistent electrochemical degradation, thereby precluding the practical application of this strategy. Here we explore the close interplay between the local structural change and oxygen electrochemistry during short- and long-term battery operation for layered TMOs. The substantially distinct evolution of the oxygen-redox activity and reversibility are demonstrated to stem from the different cation-migration mechanisms during the dynamic de/intercalation process. We show that the π stabilization on the oxygen oxidation initially aids in the reversibility of the oxygen redox and is predominant in the absence of cation migrations; however, the π-interacting oxygen is gradually replaced by σ-interacting oxygen that triggers the formation of O–O dimers and structural destabilization as cycling progresses. More importantly, it is revealed that the distinct cation-migration paths available in the layered TMOs govern the conversion kinetics from π to σ interactions. These findings constitute a step forward in unravelling the correlation between the local structural evolution and the reversibility of oxygen electrochemistry and provide guidance for further development of oxygen-redox layered electrode materials.
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Acknowledgements
This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (no. NRF-2019M3E6A1064522), and Creative Materials Discovery Program through the NRF funded by the Ministry of Science, ICT and Future Planning (grant no. NRF-2017M3D1A1039553). This research was supported by the Institute for Basic Science (grant no. IBS-R006-A2) and Korea Electric Power Corporation (grant no. R20XO02-31).
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D.E. and K.K. conceived the basic idea for this project and led the research. D.E. performed the material synthesis, electrochemical testing and structural/spectroscopic characterization including HRPD, XANES, STXM and Raman analyses. B.K. conducted the DFT calculations. B.K., J.-H.S., H.P. and H.-Y.J. discussed and provided fundamental ideas for the overall study. S.J. Kim and S.-P.C. performed the STEM measurements. S.J. Kim contributed to the interpretation of the results. J.P. and S.J. Kang measured and processed the DEMS data. M.H.L. and J.H.H. provided constructive advice for the experimental design for the structural characterization. H.-Y.J. and Y.K. assisted with processing of the SQUID and DEMS results, respectively. S.K.P., J.K., K.O. and D.-H.K. offered valuable comments on this project. D.E. and K.K. wrote the paper. K.K. supervised all aspects of the research.
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Eum, D., Kim, B., Song, JH. et al. Coupling structural evolution and oxygen-redox electrochemistry in layered transition metal oxides. Nat. Mater. 21, 664–672 (2022). https://doi.org/10.1038/s41563-022-01209-1
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DOI: https://doi.org/10.1038/s41563-022-01209-1
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