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Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2

Nature Chemistry volume 10, pages 288–295 (2018)Cite this article

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Abstract

The search for improved energy-storage materials has revealed Li- and Na-rich intercalation compounds as promising high-capacity cathodes. They exhibit capacities in excess of what would be expected from alkali-ion removal/reinsertion and charge compensation by transition-metal (TM) ions. The additional capacity is provided through charge compensation by oxygen redox chemistry and some oxygen loss. It has been reported previously that oxygen redox occurs in O 2p orbitals that interact with alkali ions in the TM and alkali-ion layers (that is, oxygen redox occurs in compounds containing Li+–O(2p)–Li+ interactions). Na2/3[Mg0.28Mn0.72]O2 exhibits an excess capacity and here we show that this is caused by oxygen redox, even though Mg2+ resides in the TM layers rather than alkali-metal (AM) ions, which demonstrates that excess AM ions are not required to activate oxygen redox. We also show that, unlike the alkali-rich compounds, Na2/3[Mg0.28Mn0.72]O2 does not lose oxygen. The extraction of alkali ions from the alkali and TM layers in the alkali-rich compounds results in severely underbonded oxygen, which promotes oxygen loss, whereas Mg2+ remains in Na2/3[Mg0.28Mn0.72]O2, which stabilizes oxygen.

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Figure 1: Structure of Na2/3[Mg0.28Mn0.72]O2.
Figure 2: Electrochemical behaviour of Na2/3[Mg0.28Mn0.72]O2.
Figure 3: The scanning tunnelling electron microscopy images show the structure of the charged Na2/3[Mg0.28Mn0.72]O2.
Figure 4: Gas loss of Na2/3[Mg0.28Mn0.72]O2 during electrochemical (de)sodiation.
Figure 5: Oxygen K-edge SXAS and RXIS spectroscopy of Na2/3[Mg0.28Mn0.72]O2.
Figure 6: Coordination around oxygen and O 2p orbitals.

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Acknowledgements

P.G.B. is indebted to the Engineering and Physical Sciences Research Council (EPSRC), including the SUPERGEN program, for financial support. We additionally thank the EPSRC for grant EP/K040375/1 for the ‘South of England Analytical Electron Microscope’. The authors thank N. Kumar, Max Planck Institute of Chemical Physics, for help with magnetic measurements. Synchrotron radiation experiments were performed at the ADRESS beamline of the Swiss Light Source at the Paul Scherrer Institute, Switzerland. We acknowledge technical and experimental support at the ADRESS beamline by L. Nue and M. Dantz. Part of this research was funded by the Swiss National Science Foundation through the Sinergia network Mott Physics Beyond the Heisenberg model and the NCCR MARVEL. The research leading to these results received funding from the European Community's Seventh Framework Programme (FP7/2007-2013) under Grant Agreement no. 290605 (CO-FUND: PSIFELLOW). The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, US Department of Energy, under Contract no. DE-AC02-05CH11231. The authors are also grateful to G. Cibin for contributing to the collection of hard XAS data.

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Author notes

  1. Urmimala Maitra and Robert A. House: These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Materials, University of Oxford, Parks Road, Oxford, OX1 3PH, UK

    Urmimala Maitra, Robert A. House, James W. Somerville, Nuria Tapia-Ruiz, Juan G. Lozano, Niccoló Guerrini, Rong Hao, Kun Luo, Liyu Jin, Miguel A. Pérez-Osorio, Feliciano Giustino, Matthew R. Roberts & Peter G. Bruce

  2. Department of Physics and Astronomy, Division of Molecular and Condensed Matter Physics, Uppsala University, Box 516, Uppsala, S-751 20, Sweden

    Felix Massel & Laurent C. Duda

  3. School of Physical Sciences, University of Kent, Canterbury, CT2 7NH, Kent, UK

    David M. Pickup, Silvia Ramos & Alan V. Chadwick

  4. Swiss Light Source, Paul Scherrer Institut, Villigen PSI, 5232, Switzerland

    Xingye Lu, Daniel E. McNally & Thorsten Schmitt

  5. Department of Chemistry, University of Oxford, Parks Road, Oxford, OX1 3PH, UK

    Peter G. Bruce

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Contributions

U.M., R.A.H. and M.R.R. contributed to all aspects of the research. L.C.D., N.G., J.W.S., F.M., K.L., R.H., L.J., U.M., D.E.M., X.L. and T.S. contributed to the measurement of the SXAS and RIXS spectroscopy. D.M.P., N.T.-R., S.R. and A.V.C. contributed to the data collection and analysis of hard XAS measurements. J.W.S., M.A.P.-O. and F.G. performed the DFT calculations. J.G.L. collected, processed and interpreted the STEM images. P.G.B., U.M., R.A.H., J.W.S., M.R.R. and L.C.D. interpreted the data. P.G.B. wrote the paper with contributions from U.M., R.A.H. and M.R.R. The project was supervised by P.G.B.

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Correspondence to Peter G. Bruce.

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Maitra, U., House, R., Somerville, J. et al. Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2. Nature Chem 10, 288–295 (2018). https://doi.org/10.1038/nchem.2923

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