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Coupling structural evolution and oxygen-redox electrochemistry in layered transition metal oxides

Nature Materials volume 21, pages 664–672 (2022)Cite this article

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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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Fig. 1: Structural and electrochemical properties of NLMO and NLTMO.
Fig. 2: Comparison of out-of-plane cation disorder in NLMO and NLTMO.
Fig. 3: Redox stabilization mechanisms of oxidized lattice oxygen.
Fig. 4: Quantification of the contribution of each oxygen stabilization mechanism in NLMO and NLTMO.
Fig. 5: Oxygen dimerization generated by in-plane cation disorder in NLMO.

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All relevant experimental and theoretical data within the article will be provided by the corresponding author on reasonable request.

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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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Authors and Affiliations

  1. Department of Materials Science and Engineering, Research Institute of Advanced Materials (RIAM), Seoul National University, Seoul, Republic of Korea

    Donggun Eum, Byunghoon Kim, Jun-Hyuk Song, Hyeokjun Park, Ho-Young Jang, Sung Joo Kim, Myeong Hwan Lee, Jae Hoon Heo, Sung Kwan Park, Kyungbae Oh, Do-Hoon Kim & Kisuk Kang

  2. Center for Nanoparticle Research, Institute for Basic Science (IBS), Seoul National University, Seoul, Republic of Korea

    Donggun Eum, Byunghoon Kim, Myeong Hwan Lee, Kyungbae Oh, Do-Hoon Kim & Kisuk Kang

  3. National Center for Inter-University Research Facilities, Seoul National University, Seoul, Republic of Korea

    Sung-Pyo Cho

  4. Department of Energy Engineering, School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan, Republic of Korea

    Jaehyun Park & Seok Ju Kang

  5. Lawrence Berekely National Laboratory, Berekely, CA, USA

    Youngmin Ko

  6. Ulsan Advanced Energy Technology R&D Center, Korea Institute of Energy Research, Ulsan, Republic of Korea

    Jinsoo Kim

  7. Institute of Engineering Research, College of Engineering, Seoul National University, Seoul, Republic of Korea

    Kisuk Kang

  8. School of Chemical and Biological Engineering, College of Engineering, Seoul National University, Seoul, Republic of Korea

    Kisuk Kang

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  1. Donggun Eum
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Contributions

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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Correspondence to Kisuk Kang.

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Supplementary Notes 1–9, Figs. 1–29, Tables 1–8 and refs. 1–12.

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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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