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Delocalized electron holes on oxygen in a battery cathode

Nature Energy volume 8, pages 351–360 (2023)Cite this article

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Abstract

Oxide ions in transition metal oxide cathodes can store charge at high voltage offering a route towards higher energy density batteries. However, upon charging these cathodes, the oxidized oxide ions condense to form molecular O2 trapped in the material. Consequently, the discharge voltage is much lower than charge, leading to undesirable voltage hysteresis. Here we capture the nature of the electron holes on O2− before O2 formation by exploiting the suppressed transition metal rearrangement in ribbon-ordered Na0.6[Li0.2Mn0.8]O2. We show that the electron holes formed are delocalized across the oxide ions coordinated to two Mn (O–Mn2) arranged in ribbons in the transition metal layers. Furthermore, we track these delocalized hole states as they gradually localize in the structure in the form of trapped molecular O2 over a period of days. Establishing the nature of hole states on oxide ions is important if truly reversible high-voltage O-redox cathodes are to be realized.

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Fig. 1: Structure and electrochemistry of Na0.6[Li0.2Mn0.8]O2.
Fig. 2: SQUID magnetometry.
Fig. 3: 17O NMR spectra and DFT-modelled electron spin densities.
Fig. 4: Time-dependent evolution of 17O NMR.
Fig. 5: Oxygen K-edge spectroscopy.
Fig. 6: Delocalized electron holes on O.

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All the data generated or analysed during this study are included in the published article and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

We are indebted to the Engineering and Physical Sciences Research Council (EPSRC), the Henry Royce Institute for Advanced Materials (EP/R00661X/1, EP/S019367/1, EP/R010145/1, EP/L019469/1) and the Faraday Institution (FIRG007, FIRG008, FIRG016) for financial support. We thank the HEC Materials Chemistry Consortium (EP/R029431/1) for supercomputer facilities. We acknowledge Diamond Light Source for time on I21 under proposal MM25589-1. This project was supported by the Royal Academy of Engineering under the Research Fellowship scheme. B.J.M. acknowledges support from the Royal Society (UF130329 and URF\R\191006). For the purpose of open access, the author has applied a CC BY public copyright licence to any author accepted manuscript (AAM) version arising from this submission.

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Authors and Affiliations

  1. Department of Materials, University of Oxford, Oxford, UK

    Robert A. House, Gregory J. Rees, John-Joseph Marie, M. Saiful Islam & Peter G. Bruce

  2. Department of Chemistry, University of Bath, Bath, UK

    Kit McColl & Benjamin J. Morgan

  3. Diamond Light Source, Harwell, UK

    Mirian Garcia-Fernandez, Abhishek Nag & Ke-Jin Zhou

  4. Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, Oxford, UK

    Simon Cassidy & Peter G. Bruce

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Contributions

R.A.H. planned and conducted the synthesis and characterization work. R.A.H. and S.C. planned and conducted the SQUID measurements. R.A.H. prepared the 17O-labelled samples and G.J.R. performed and fitted the 17O MAS NMR. R.A.H. and J.-J.M. in close collaboration with M.G-F., A.N. and K.-J.Z. conducted the RIXS and XAS measurements. K.M. conducted the DFT computation and NMR shift modelling with the support of B.J.M. and M.S.I. R.A.H. and P.G.B. wrote the manuscript with contributions from all authors.

Corresponding authors

Correspondence to Robert A. House or Peter G. Bruce.

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Nature Energy thanks Wei Kong Pang, Dong-Hwa Seo and Stefan Topolovec for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Note, Tables 1 and 2 and Figs. 1–11.

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SQUID source data.

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House, R.A., Rees, G.J., McColl, K. et al. Delocalized electron holes on oxygen in a battery cathode. Nat Energy 8, 351–360 (2023). https://doi.org/10.1038/s41560-023-01211-0

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