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Reversible anionic redox chemistry in high-capacity layered-oxide electrodes

Abstract

Li-ion batteries have contributed to the commercial success of portable electronics and may soon dominate the electric transportation market provided that major scientific advances including new materials and concepts are developed. Classical positive electrodes for Li-ion technology operate mainly through an insertion–deinsertion redox process involving cationic species. However, this mechanism is insufficient to account for the high capacities exhibited by the new generation of Li-rich (Li1+xNiyCozMn(1−xyz)O2) layered oxides that present unusual Li reactivity. In an attempt to overcome both the inherent composition and the structural complexity of this class of oxides, we have designed structurally related Li2Ru1−ySnyO3 materials that have a single redox cation and exhibit sustainable reversible capacities as high as 230 mA h g−1. Moreover, they present good cycling behaviour with no signs of voltage decay and a small irreversible capacity. We also unambiguously show, on the basis of an arsenal of characterization techniques, that the reactivity of these high-capacity materials towards Li entails cumulative cationic (Mn+→M(n+1)+) and anionic (O2−→O22−) reversible redox processes, owing to the ds p hybridization associated with a reductive coupling mechanism. Because Li2MO3 is a large family of compounds, this study opens the door to the exploration of a vast number of high-capacity materials.

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Figure 1: Structural aspects of the Li2Ru1−ySnyO3 solid solution.
Figure 2: Electrochemical performance of Li2Ru1−ySnyO3.
Figure 3: Li-driven structural behaviour on cycling.
Figure 4: Microscopy and Mössbauer measurements for spotting the evolution of Li2Ru1−ySnyO3 electrodes on cycling.
Figure 5: Detection of anionic redox species.
Figure 6: Reductive coupling mechanism, calculations accounting for superoxo-like species and measured oxygen release.

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Acknowledgements

We thank E. Clot (ICG) and O. Eisenstein (ICG) for helpful discussions about the reductive elimination mechanism, Y. Klein (IMPMC) for discussions about Ru oxides and J-N. Chotard (LRCS) for discussions about crystal structures and X-ray diffraction.

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M.S., K.R., C.P.L. and A.S.P. carried out the synthesis, M.S. and J-M.T. conducted the electrochemical work and J-M.T. designed the research approach; G.R. analysed the crystal structures and diffraction patterns; H.V. collected and analysed the EPR spectra; M.T.S. collected and analysed the Mössbauer data; D.F. and D.G. collected and analysed the XPS spectra; W.W. performed the pressure cell experiments: M.B.H. and L.D. carried out the TEM studies: M-L.D. conducted the DFT calculations and developed the theoretical framework; M-L.D., G.R. and J-M.T. wrote the manuscript and all authors discussed the experiments and final manuscript.

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Correspondence to J-M. Tarascon.

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Sathiya, M., Rousse, G., Ramesha, K. et al. Reversible anionic redox chemistry in high-capacity layered-oxide electrodes. Nature Mater 12, 827–835 (2013). https://doi.org/10.1038/nmat3699

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