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Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li2IrO3

Nature Materials volume 16, pages 580–586 (2017)Cite this article

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Abstract

Lithium-ion battery cathode materials have relied on cationic redox reactions until the recent discovery of anionic redox activity in Li-rich layered compounds which enables capacities as high as 300 mAh g−1. In the quest for new high-capacity electrodes with anionic redox, a still unanswered question was remaining regarding the importance of the structural dimensionality. The present manuscript provides an answer. We herein report on a β-Li2IrO3 phase which, in spite of having the Ir arranged in a tridimensional (3D) framework instead of the typical two-dimensional (2D) layers seen in other Li-rich oxides, can reversibly exchange 2.5 e− per Ir, the highest value ever reported for any insertion reaction involving d-metals. We show that such a large activity results from joint reversible cationic (Mn+) and anionic (O2)n− redox processes, the latter being visualized via complementary transmission electron microscopy and neutron diffraction experiments, and confirmed by density functional theory calculations. Moreover, β-Li2IrO3 presents a good cycling behaviour while showing neither cationic migration nor shearing of atomic layers as seen in 2D-layered Li-rich materials. Remarkably, the anionic redox process occurs jointly with the oxidation of Ir4+ at potentials as low as 3.4 V versus Li+/Li0, as equivalently observed in the layered α-Li2IrO3 polymorph. Theoretical calculations elucidate the electrochemical similarities and differences of the 3D versus 2D polymorphs in terms of structural, electronic and mechanical descriptors. Our findings free the structural dimensionality constraint and broaden the possibilities in designing high-energy-density electrodes for the next generation of Li-ion batteries.

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Figure 1: Structure of β-LixIrO3.
Figure 2: Electrochemical data for β-LixIrO3.
Figure 3: XPS analysis.
Figure 4: Local structure of β-LixIrO3.
Figure 5: Cycling behaviour of β-LixIrO3.
Figure 6: Electronic structures and computed voltages.

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Acknowledgements

The authors thank Q. Jacquet for fruitful discussions and V. Pomjakushin for his valuable help in neutron diffraction experiments. This work is based on experiments performed at the Swiss Spallation Neutron Source SINQ, Paul Scherrer Institute, Villigen, Switzerland. Use of the 11-BM mail service of the APS at Argonne National Laboratory was supported by the US Department of Energy under contract No. DE-AC02-06CH11357 and is greatly acknowledged. J.-M.T. acknowledges funding from the European Research Council (ERC) (FP/2014)/ERC Grant-Project 670116-ARPEMA. E.M. acknowledges financial support from the Fonds de Recherche du Québec—Nature et Technologies.

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Authors and Affiliations

  1. Collège de France, Chimie du Solide et de l’Energie, UMR 8260, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France

    Paul E. Pearce, Arnaud J. Perez, Gwenaelle Rousse, Dmitry Batuk, Eric McCalla & Jean-Marie Tarascon

  2. Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, 80039 Amiens Cedex, France

    Paul E. Pearce, Arnaud J. Perez, Gwenaelle Rousse, Mathieu Saubanère, Dominique Foix, Eric McCalla, Marie-Liesse Doublet & Jean-Marie Tarascon

  3. Sorbonne Universités—UPMC Univ Paris 06, 4 Place Jussieu, F-75005 Paris, France

    Paul E. Pearce, Arnaud J. Perez, Gwenaelle Rousse & Jean-Marie Tarascon

  4. Institut Charles Gerhardt, UMR 5253, CNRS and Université de Montpellier, Place Eugène Bataillon, F-34095 Montpellier, France

    Mathieu Saubanère & Marie-Liesse Doublet

  5. EMAT, University of Antwerp, Groenenborgerlaan 171, B-2020, Antwerp, Belgium

    Dmitry Batuk, Artem M. Abakumov & Gustaaf Van Tendeloo

  6. IPREM/ECP (UMR 5254), Université de Pau, 2 Avenue Pierre Angot, 64053 Pau Cedex 9, France

    Dominique Foix

  7. CEMS, University of Minnesota, 421 Washington Avenue, Minneapolis, Minnesota 55455, USA

    Eric McCalla

  8. Skolkovo Institute of Science and Technology, 3 Nobel Street, 143026 Moscow, Russia

    Artem M. Abakumov

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  1. Paul E. Pearce
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Contributions

P.E.P. and J.-M.T. carried out the synthesis; P.E.P., A.J.P. and J.-M.T. did the electrochemical work; E.M. and G.R. conducted the structural analysis; M.S. and M.-L.D. did the DFT calculations; D.B., A.M.A. and G.V.T. did the TEM study; D.F. collected and analysed the XPS spectra; G.R. and J.-M.T. wrote the manuscript and all authors discussed the experiments and final manuscript.

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Correspondence to Jean-Marie Tarascon.

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Pearce, P., Perez, A., Rousse, G. et al. Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li2IrO3. Nature Mater 16, 580–586 (2017). https://doi.org/10.1038/nmat4864

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