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Cation-doped ZnS catalysts for polysulfide conversion in lithium–sulfur batteries

Nature Catalysis volume 5, pages 555–563 (2022)Cite this article

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Abstract

Catalytic conversion of polysulfides is regarded as a crucial approach to enhancing kinetics and suppressing the shuttle effect in lithium–sulfur (Li–S) batteries. However, the activity prediction of Li–S catalysts remains elusive owing to the lack of mechanistic understanding of activity descriptors. Here, we report a volcano-shaped relationship between polysulfide adsorption ability and catalytic activity. In conjunction with theoretical analysis, we distinguish catalytic and anchoring effects to delineate the role of adsorption and emphasize the passivation of catalysts. These findings enable us to develop a composite catalyst, Co0.125Zn0.875S, which shows higher performance than simple binary compounds. Such a fundamental understanding of the intrinsic link between polysulfide adsorption and catalytic activity offers a rational viewpoint for designing Li–S catalysts and tuning their activities.

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Fig. 1: Schematic illustration of catalyst design.
Fig. 2: Catalyst design and activity characterizations.
Fig. 3: Mechanistic studies on catalytic processes.
Fig. 4: Kinetic analysis of polysulfide conversion on catalyst surface.
Fig. 5: Electrochemical properties of Li–S batteries using M0.125Zn0.875S catalysts.

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Source data are provided with this paper. All other data are available from the authors upon reasonable request.

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Acknowledgements

We acknowledge the financial support of the National Key Research and Development Program of China (2020YFA0406104) and the National Natural Science Foundation of China (22075131). The numerical calculations were carried out at the computing facilities in the High-Performance Computing Center (HPCC) of Nanjing University. Work at Argonne National Laboratory was supported by the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office under the US-China Clean Energy Research Center (CERC-CVC2) programme. Argonne National Laboratory is operated for the DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357.

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Authors and Affiliations

  1. State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, China

    Zihan Shen & Huigang Zhang

  2. National Laboratory of Solid State Microstructures, Collaborative Innovation Center of Advanced Microstructures, College of Engineering and Applied Sciences, Nanjing University, Nanjing, China

    Xin Jin, Jiaming Tian, Shuo Zhang, Xing Fan & Hong Lu

  3. Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA

    Matthew Li, Yifei Yuan & Jun Lu

  4. Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China

    Susu Fang & Weigao Xu

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Contributions

H.Z. and Z.S. conceived the idea and designed the project. Z.S., X.J. and J.T. performed the catalyst synthesis and carried out the electrochemical experiments. Z.S., M.L., Y.Y. and S.Z. conducted the morphology and structural characterizations. Z.S., H.Z. and X.J. conducted the DFT calculations and microkinetic modelling. S.F., X.F., W.X. and H.L. assisted with the the ex situ Raman measurements and analysed the spectra. H.Z. and J.L. supervised the project and wrote the manuscript. All authors analysed the data and discussed the results.

Corresponding authors

Correspondence to Jun Lu or Huigang Zhang.

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Nature Catalysis thanks Mahbub Islam, Harry Hoster and Qianfan Zhang for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–28, Tables 1–4 and Notes 1–4.

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TEM size analysis.

Supplementary Data 1

Atomic coordinates in the used models

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Electrochemical data.

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UV–vis spectra and calculation results.

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Modelling results.

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Electrochemical data.

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Shen, Z., Jin, X., Tian, J. et al. Cation-doped ZnS catalysts for polysulfide conversion in lithium–sulfur batteries. Nat Catal 5, 555–563 (2022). https://doi.org/10.1038/s41929-022-00804-4

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