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Correlating ligand-to-metal charge transfer with voltage hysteresis in a Li-rich rock-salt compound exhibiting anionic redox

Nature Chemistry volume 13, pages 1070–1080 (2021)Cite this article

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Abstract

Anionic redox is a double-edged sword for Li-ion cathodes because it offers a transformational increase in energy density that is also negated by several detrimental drawbacks to its practical implementation. Among them, voltage hysteresis is the most troublesome because its origin is still unclear and under debate. Herein, we tackle this issue by designing a prototypical Li-rich cation-disordered rock-salt compound Li1.17Ti0.33Fe0.5O2 that shows anionic redox activity and exceptionally large voltage hysteresis while exhibiting a partially reversible Fe migration between octahedral and tetrahedral sites. Through combined in situ and ex situ spectroscopic techniques, we demonstrate the existence of a non-equilibrium (adiabatic) redox pathway enlisting Fe3+/Fe4+ and O redox as opposed to the equilibrium (non-adiabatic) redox pathway involving sole O redox. We further show that the charge transfer from O(2p) lone pair states to Fe(3d) states involving sluggish structural distortion is responsible for voltage hysteresis. This study provides a general understanding of various voltage hysteresis signatures in the large family of Li-rich rock-salt compounds.

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Fig. 1: Structure and electrochemistry of LTFO compound.
Fig. 2: Reversible Fe migration.
Fig. 3: Redox mechanism characterized by in situ 57Fe Mössbauer spectroscopy and ex situ HAXPES.
Fig. 4: GITT analysis of LTFO from the 1st discharge to the 2nd charge process.
Fig. 5: In situ characterizations of the electronic and geometric structural evolutions during relaxation.
Fig. 6: Kinetic and thermodynamic picture of voltage hysteresis.
Fig. 7: Theoretical calculations of the redox process of LTFO.

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All of the data supporting the findings of this study are available within the paper and the Supplementary Information.  Source data are provided with this paper.

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Acknowledgements

XAS experiments were performed on the ROCK beamline (financed by the French National Research Agency (ANR) as a part of the ‘Investissements d’Avenir’ programme, reference: ANR-10-EQPX-45) at the SOLEIL Synchrotron, France under proposals #20171234 and #20190596. HAXPES measurements were performed on the GALAXIES beamline at the SOLEIL Synchrotron, France under proposals #20171035 and #20190646. This research used resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility, operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Extraordinary facility operations were supported in part by the DOE Office of Science through the National Virtual Biotechnology Laboratory, a consortium of DOE national laboratories focused on the response to COVID-19, with funding provided by the Coronavirus CARES Act. Access to TEM facilities was granted by the Advance Imaging Core Facility of Skoltech. We highly appreciate help from I. Aguilar for measuring ICP-AES and help from D. Ceolin and J. Sottmann with HAXPES experiments. The authors thank D. Xia for his earlier advice and G. Assat and J. Vergnet for fruitful discussions. A.M.A and A.V.M are grateful to the Russian Science Foundation for financial support (grant 20-43-01012). J.-M.T and B.L. acknowledge funding from the European Research Council (ERC) (FP/2014)/ERC Grant-Project 670116-ARPEMA.

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Authors and Affiliations

  1. Chimie du Solide-Energie, UMR 8260, Collège de France, Paris, France

    Biao Li, Gwenaëlle Rousse & Jean-Marie Tarascon

  2. Réseau sur le Stockage Electrochimique de l’Energie (RS2E), Amiens, France

    Biao Li, Moulay Tahar Sougrati, Gwenaëlle Rousse, Rémi Dedryvère, Antonella Iadecola, Marie-Liesse Doublet & Jean-Marie Tarascon

  3. ICGM, Univ Montpellier, CNRS, ENSCM, Montpellier, France

    Moulay Tahar Sougrati & Marie-Liesse Doublet

  4. Sorbonne Université, Paris, France

    Gwenaëlle Rousse & Jean-Marie Tarascon

  5. Center for Energy Science and Technology, Skolkovo Institute of Science and Technology, Moscow, Russia

    Anatolii V. Morozov & Artem M. Abakumov

  6. IPREM, E2S-UPPA, CNRS, University of Pau & Pays Adour, Pau, France

    Rémi Dedryvère

  7. Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Technische Universität München, Garching, Germany

    Anatoliy Senyshyn

  8. Electrochemistry Laboratory, Paul Scherrer Institute, Villigen PSI, Switzerland

    Leiting Zhang

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Contributions

B.L. and J.-M.T. conceived the idea and designed the experiments. B.L. prepared the samples and did the electrochemical tests. M.T.S. collected and analysed the Mössbauer data. G.R. analysed the crystal structures and diffraction patterns. A.V.M. and A.M.A. performed the TEM studies and interpreted the data. A.I. and R.D. collected and analysed the XAS and HAXPES data. A.S. collected the NPD data. L.Z. performed the OEMS experiment and did the analysis. M.-L.D. developed the theoretical framework and B.L. carried out the DFT calculations. J.-M.T., M.-L.D., A.M.A. and B.L. discussed the results and wrote the paper with contributions from all authors.

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Correspondence to Jean-Marie Tarascon.

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Peer review information Nature Chemistry thanks Naoaki Yabuuchi and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Li, B., Sougrati, M.T., Rousse, G. et al. Correlating ligand-to-metal charge transfer with voltage hysteresis in a Li-rich rock-salt compound exhibiting anionic redox. Nat. Chem. 13, 1070–1080 (2021). https://doi.org/10.1038/s41557-021-00775-2

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