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

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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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Fig. 1: Increasing the O/M ratio from Li2MO3 to Li3MO4 in rocksalt oxides as a strategy to activate anionic redox.
Fig. 2: Structural evolution of Li3IrO4 on electrochemical insertion/deinsertion of Li.
Fig. 3: Irreversible capacity loss for total delithiation of Li3IrO4.
Fig. 4: Local structural evolution from operando EXAFS analysis at the Ir LIII edge.
Fig. 5: Participation of cationic and anionic redox processes during cycling studied by operando XANES.
Fig. 6: Ex situ EPR spectroscopy study of paramagnetic species at different states of charge.

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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

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.

Correspondence to Jean-Marie Tarascon.

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Supplementary Tables 1–4, Supplementary Figures 1–13

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Perez, A.J., Jacquet, Q., Batuk, D. et al. Approaching the limits of cationic and anionic electrochemical activity with the Li-rich layered rocksalt Li3IrO4 . Nat Energy 2, 954–962 (2017) doi:10.1038/s41560-017-0042-7

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