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Approaching the limits of cationic and anionic electrochemical activity with the Li-rich layered rocksalt Li3IrO4

Nature Energyvolume 2pages954962 (2017) | Download Citation

Abstract

The Li-rich rocksalt oxides Li2MO3 (M = 3d/4d/5d transition metal) are promising positive-electrode materials for Li-ion batteries, displaying capacities exceeding 300 mAh g–1 thanks to the participation of the oxygen non-bonding O(2p) orbitals in the redox process. Understanding the oxygen redox limitations and the role of the O/M ratio is therefore crucial for the rational design of materials with improved electrochemical performances. Here we push oxygen redox to its limits with the discovery of a Li3IrO4 compound (O/M = 4) that can reversibly take up and release 3.5 electrons per Ir and possesses the highest capacity ever reported for any positive insertion electrode. By quantitatively monitoring the oxidation process, we demonstrate the material’s instability against O2 release on removal of all Li. Our results show that the O/M parameter delineates the boundary between the material’s maximum capacity and its stability, hence providing valuable insights for further development of high-capacity materials.

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Acknowledgements

We thank P. Pearce for providing the β-Li2IrO3 and L. Lemarquis for helping in the DEMS experiment. We are particularly grateful to S. Belin, V. Briois and L. Stievano for helpful discussions on XAS analysis and synchrotron SOLEIL (France) for providing beamtime at the ROCK beamline (financed by the French National Research Agency (ANR) as part of the ‘Investissements d’Avenir’ programme, reference: ANR-10-EQPX-45). A.J.P and A.I. acknowledge the GdR C(RS)2 for the workshop organized on a chemometric approach for XAS data analysis. V. Nassif is acknowledged for her help during neutron diffraction experiments performed at Institut Laue Langevin on D1B. 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 gratefully acknowledged. This work has been performed with the support of the European Research Council (ERC) (FP/2014)/ERC Grant-Project 670116-ARPEMA.

Author information

Affiliations

  1. Collège de France, Chimie du Solide et Energie, UMR 8260, 11 place Marcelin Berthelot, 75005, Paris, France

    • Arnaud J. Perez
    • , Quentin Jacquet
    • , Dmitry Batuk
    • , Gwenaëlle Rousse
    •  & Jean-Marie Tarascon
  2. Sorbonne Universités - UPMC Univ. Paris 06, 4 Place Jussieu, 75005, Paris, France

    • Arnaud J. Perez
    • , Quentin Jacquet
    • , Gwenaëlle Rousse
    •  & Jean-Marie Tarascon
  3. Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, Amiens, France

    • Arnaud J. Perez
    • , Quentin Jacquet
    • , Antonella Iadecola
    • , Matthieu Saubanère
    • , Gwenaëlle Rousse
    • , Dominique Larcher
    • , Hervé Vezin
    • , Marie-Liesse Doublet
    •  & Jean-Marie Tarascon
  4. EMAT, University of Antwerp, Groenenborgerlaan 171, 2020, Antwerp, Belgium

    • Dmitry Batuk
  5. Institut Charles Gerhardt, CNRS UMR 5253, Université Montpellier, Place E. Bataillon, 34095, Montpellier, France

    • Matthieu Saubanère
    •  & Marie-Liesse Doublet
  6. Laboratoire de Réactivité et Chimie des Solides, UMR CNRS 7314, 33 Rue Saint Leu, 80039, Amiens, France

    • Dominique Larcher
  7. Université Lille 1, CNRS UMR 8516-LASIR, 59655, Villeneuve d’Ascq, France

    • Hervé Vezin

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Contributions

A.J.P. carried out the synthesis; A.J.P., Q.J., D.L. and J.-M.T. designed and performed the electrochemical studies; A.J.P., Q.J. and G.R. performed the diffraction experiments and analysis; A.J.P., Q.J. and A.I. carried out the X-ray absorption study; D.B. collected and analysed the TEM images; H.V. collected and analysed the EPR spectra; M.S. and M.-L.D. conducted the DFT study; A.J.P. and J.-M.T. wrote the manuscript and all authors discussed the experiments and edited the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Jean-Marie Tarascon.

Supplementary information

  1. Supplementary Information

    Supplementary Tables 1–4, Supplementary Figures 1–13

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DOI

https://doi.org/10.1038/s41560-017-0042-7