Direct observation of lithium polysulfides in lithium–sulfur batteries using operando X-ray diffraction


In the on going quest towards lithium-battery chemistries beyond the lithium-ion technology, the lithium–sulfur system is emerging as one of the most promising candidates. The major outstanding challenge on the route to commercialization is controlling the so-called polysulfide shuttle, which is responsible for the poor cycling efficiency of the current generation of lithium–sulfur batteries. However, the mechanistic understanding of the reactions underlying the polysulfide shuttle is still incomplete. Here we report the direct observation of lithium polysulfides in a lithium–sulfur cell during operation by means of operando X-ray diffraction. We identify signatures of polysulfides adsorbed on the surface of a glass-fibre separator and monitor their evolution during cycling. Furthermore, we demonstrate that the adsorption of the polysulfides onto SiO2 can be harnessed for buffering the polysulfide redox shuttle. The use of fumed silica as an electrolyte additive therefore significantly improves the specific charge and Coulombic efficiency of lithium–sulfur batteries.

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Figure 1: Typical voltage profile of a Li–S cell and the corresponding reaction mechanisms.
Figure 2: Operando XRD measurements of a Li–S cell.
Figure 3: Operando XRD measurements of a Li–S cell using SiO2 as electrolyte additive.
Figure 4: Microscale changes in the morphology of glass fibres.
Figure 5: Nanoscale changes in the glass-fibre morphology.
Figure 6: Operando XRD measurements of a Li–S cell after multiple cycles (8th and 33rd cycle).
Figure 7: Cycling performance of Li–S cells with and without SiO2 electrolyte additive.


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The authors acknowledge the financial support of the Swiss National Science Foundation (Project No. 200021_144292) and thank Robert Bosch GmbH for providing lithium PSs. The authors would like to express their gratitude to P. Novák for fruitful discussions about Li–S batteries. H. Kaiser and C. Junker are acknowledged for their help with all technical aspects of this study. C. Goudet-Prunier is thanked for her help in writing the manuscript. S. Sallard is acknowledged for help and contributions to the experimental part of the study.

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C.V., J.C. and R.B. conceived the project. J.C. and C.V. designed the experimental set-up for operando XRD, built the experimental set-up and performed the experiments. C.M. performed the XPS and TEM analyses. C.V., J.C. and R.B. analysed the data. C.V. and J.C. wrote the manuscript, with contributions from R.B., S.T. and L.G.

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Correspondence to Claire Villevieille.

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The authors declare no competing financial interests.

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Supplementary Figures 1–5, Supplementary Notes, Supplementary References. (PDF 460 kb)

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Conder, J., Bouchet, R., Trabesinger, S. et al. Direct observation of lithium polysulfides in lithium–sulfur batteries using operando X-ray diffraction. Nat Energy 2, 17069 (2017).

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