Exploring the bottlenecks of anionic redox in Li-rich layered sulfides


Anionic redox chemistry has emerged as a new paradigm to design higher-energy lithium ion-battery cathode materials such as Li-rich layered oxides. However, they suffer from voltage fade, large hysteresis and sluggish kinetics, which originate intriguingly from the anionic redox activity itself. To fundamentally understand these issues, we decided to act on the ligand by designing new Li-rich layered sulfides Li1.33 – 2y/3Ti0.67 – y/3FeyS2, among which the y = 0.3 member shows sustained reversible capacities of ~245 mAh g−1 due to cumulated cationic (Fe2+/3+) and anionic (S2−/Sn, n < 2) redox processes. Moreover, its negligible initial cycle irreversibility, mitigated voltage fade upon long cycling, low voltage hysteresis and fast kinetics compare positively with its Li-rich oxide analogues. Moving from the oxygen ligand to the sulfur ligand thus partially alleviates the practical bottlenecks affecting anionic redox, although it penalizes the redox potential and energy density. Overall, these sulfides provide chemical clues to improve the holistic performance of anionic redox electrodes, which may guide us to ultimately exploit the energy benefits of oxygen redox.

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Fig. 1: Moving from Li-rich layered oxides to sulfides.
Fig. 2: Structural behaviour of the Li1.33 – 2y/3Ti0.67 – y/3FeyS2 series.
Fig. 3: Electrochemical behaviour of Li1.33 – 2y/3Ti0.67 – y/3FeyS2.
Fig. 4: Structural evolution upon Li (de)intercalation.
Fig. 5: Spectroscopic characterizations to identify the redox processes.
Fig. 6: Li-rich layered sulfide as a model material to study the practicability of anionic redox.
Fig. 7: Correlating the experimental observations in Li1.33 – 2y/3Ti0.67 – y/3FeyS2 with theoretical calculations.

Data availability

The authors declare that the main data supporting the findings of this study are available within the article and its Supplementary Information. Extra data are available from the corresponding authors on reasonable request.

Change history

  • 17 December 2019

    An amendment to this paper has been published and can be accessed via a link at the top of the paper.


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S.S. thanks the Réseau sur le Stockage Electrochimique de l’Energie (RS2E) for funding of a PhD. J.-M.T. acknowledges funding from the European Research Council (ERC) under (FP/2014)/ERC grant–project 670116-ARPEMA. 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. The sXAS and mRIXS experiments at BL8.0.1 used resources of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. V. Pumjakushin is acknowledged for his help on neutron diffraction experiment at SINQ. The authors thank M. Saubanère and M.-L. Doublet for fruitful discussions and the laboratory Chimie Théorique Methodes and Modélisaion (CTMM) at the Institut Claude Gerhardt Montpellier (ICGM) for computational facilities. J.C. and H.L. were supported by the National Science Foundation under grant no. DMR-1809372.

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S.S., G.A. and J.-M.T. conceived the idea and designed the experiments. S.S. carried out the synthesis. S.S., G.A. and S.T. performed the electrochemical studies. S.S. and G.R. performed the diffraction experiments and analysis. M.T.S. collected and analysed the Mössbauer spectra. H.L. performed the XAS experiments, and H.L., J.C. and S.S. interpreted the spectra. A.M.A. conducted and analysed the TEM and EELS studies. W.Y. and Y.H. performed the sXAS and mRIXS studies. D.F. conducted the XPS studies. J.V. conducted the DFT studies. S.S., G.A. and J.-M.T. wrote the manuscript. All authors discussed the experiments and edited the manuscript.

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Correspondence to Jean-Marie Tarascon.

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Supplementary Figs. 1–10, Supplementary Notes 1–3, Supplementary Tables 1–5 and refs. 1–15.

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Saha, S., Assat, G., Sougrati, M.T. et al. Exploring the bottlenecks of anionic redox in Li-rich layered sulfides. Nat Energy 4, 977–987 (2019). https://doi.org/10.1038/s41560-019-0493-0

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