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Amorphous iron fluorosulfate as a high-capacity cathode utilizing combined intercalation and conversion reactions with unexpectedly high reversibility

Nature Energy volume 8, pages 30–39 (2023)Cite this article

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Abstract

To achieve the desirable dual characteristics of high-capacity performance and low-cost production for the batteries of tomorrow, leveraging of multi-redox reactions of Earth-abundant transition metals in electrodes is fundamentally important. Here we identify an amorphous iron fluorosulfate electrode, a-LiFeSO4F, that can exploit both the intercalation and conversion reactions with a stable reversibility. The a-LiFeSO4F electrode delivers a capacity of 360 mAh g−1 with ~98.6% capacity retention after 200 cycles even at an elevated temperature (60 °C). In contrast to the conventional intercalation/conversion-type electrodes, the reversible cycle stability is attributed to the inherent amorphous structure of a-LiFeSO4F, whose structural integrity is not severely disturbed even after the conversion reaction, allowing its continuation as an intercalation host. We believe that this cycle stability of the intercalation/conversion reaction can be generally extended to various amorphous intercalation materials, offering new insights into the design of high-capacity electrodes through the exploitation of multi-mechanistic lithiation processes.

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Fig. 1: Characterization of a-LiFeSO4F.
Fig. 2: Redox activity of a-LiFeSO4F and polymorphs (tavorite and triplite).
Fig. 3: Ex situ analysis for investigation of mechanism.
Fig. 4: Electrochemical performance of a-LiFeSO4F.

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All data generated and analysed in this study are available within the article and its Supplementary Information.

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Acknowledgements

This work was mainly supported by the Samsung Research Funding Centre of Samsung Electronics under project number SRFC-TA1403-53. D.E. acknowledges supports from the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2021R1A6A3A13039400).

Author information

Authors and Affiliations

  1. Department of Materials Science and Engineering, Seoul National University, Seoul, Republic of Korea

    Jaehoon Heo, Insang Hwang, Donggun Eum, Hyeokjun Park, Jun-Hyuk Song, Seungju Yu, Kyungbae Oh, Giyun Kwon, Taehyun Hwang, Kun-Hee Ko & Kisuk Kang

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

    Sung-Kyun Jung

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

    Sung-Pyo Cho

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

    Giyun Kwon

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

    Kisuk Kang

  6. Center for Rechargeable Batteries, Institute of Engineering Research, College of Engineering, Seoul National University, Seoul, Republic of Korea

    Kisuk Kang

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

    Kisuk Kang

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Contributions

J.H., S.-K.J., I.H. and K.K. conceived and designed the experiments. J.H. prepared samples and carried out the main experiments. S.-P.C. conducted TEM analysis. J.H., D.E., H.P. and T.H. discussed the SXAS results. D.E., T.H. and K.-H.K. assisted with sample preparation. J.-H.S., S.Y. and K.O. carried out density functional theory calculation. J.H. and K.-H.K. discussed the XRD results. J.H., S.-K.J. and K.K. wrote the paper. D.E., S.-K.J., G.K. and K.K. revised or commented on the manuscript.

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Correspondence to Kisuk Kang.

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Heo, J., Jung, SK., Hwang, I. et al. Amorphous iron fluorosulfate as a high-capacity cathode utilizing combined intercalation and conversion reactions with unexpectedly high reversibility. Nat Energy 8, 30–39 (2023). https://doi.org/10.1038/s41560-022-01148-w

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