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Optimizing the p charge of S in p-block metal sulfides for sulfur reduction electrocatalysis

Nature Catalysis volume 6, pages 174–184 (2023)Cite this article

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Abstract

Understanding sulfur conversion chemistry is key to the development of sulfur-based high-energy-density batteries. However, unclear relationships between the electronic structure of the catalyst and its activity are the major problem. Here, we provide a direct correlation between the p electron gain of S in p-block metal sulfides and the apparent activation energies (Ea) for the sulfur reduction reaction (SRR), in particular, Li2Sn to Li2S conversion, which is the rate-determining step of the SRR. The maximum p charge occurs in bismuth sulfide and results in the lowest Ea and a high SRR rate in the cathode. Li–S batteries with the Bi2S3 catalyst work steadily at a high rate of 5.0C with a high-capacity retention of ~85% after 500 cycles. A high areal capacity of ~21.9 mAh cm−2 was obtained under a high sulfur loading of 17.6 mg cm−2 but a low electrolyte/sulfur ratio of 7.5 μl mg−1.

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Fig. 1: Electrocatalysis.
Fig. 2: Ex situ XPS spectra.
Fig. 3: Operando Raman measurements.
Fig. 4: Electronic properties of various p-MSs.
Fig. 5: Descriptor.
Fig. 6: Optimized electrochemical performance of Li–S batteries in the presence of a Bi2S3@rGO catalyst.

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

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Acknowledgements

This work was supported by the National Key R&D Program of China (2022YFA1503502 and 2021YFF0500600), National Natural Science Foundation of China (22025204, 51932005, 92034301, 52102283 and 52022041) and Innovation Program of the Shanghai Municipal Education Commission (2021-01-07-00-02-E00119).

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Author notes

  1. These authors contributed equally: Wuxing Hua, Tongxin Shang, Huan Li, Yafei Sun.

Authors and Affiliations

  1. The Education Ministry Key Laboratory of Resource Chemistry, Joint International Research Laboratory of Resource Chemistry of Ministry of Education, Shanghai Key Laboratory of Rare Earth Functional Materials, and Shanghai Frontiers Science Center of Biomimetic Catalysis, Shanghai Normal University, Shanghai, China

    Wuxing Hua, Tongxin Shang, Yafei Sun & Ying Wan

  2. Nanoyang Group, State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin, China

    Wuxing Hua, Huan Li, Yong Guo, Jingyi Xia, Chuannan Geng & Zhonghao Hu

  3. Center for the Physics of Low-Dimensional Materials, Henan Joint International Research Laboratory of New Energy Materials and Devices, School of Physics and Electronics, Henan University, Kaifeng, China

    Wuxing Hua

  4. Shenzhen Key Laboratory for Graphene-based Materials and Engineering Laboratory for Functionalized Carbon Materials, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen, China

    Linkai Peng, Zhiyuan Han & Wei Lv

  5. School of Marine Science and Technology, Tianjin University, Tianjin, China

    Chen Zhang

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Contributions

Y.W. and W.L. designed the research, supervised the experiments and edited the paper. W.H., T.S., H.L. and Y.S. planned the synthesis, tested the catalysts, analysed the X-ray absorption spectra and electrochemical data and wrote the paper. H.L. contributed to the DFT calculations and discussion on the electronic properties of the selected catalysts. L.P. and Z. Han assisted with the electrochemical data and the in situ Raman measurements when the revised version was prepared. All authors discussed the results and commented on the paper.

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Correspondence to Wei Lv or Ying Wan.

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Nature Catalysis thanks Jie Xiong and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Hua, W., Shang, T., Li, H. et al. Optimizing the p charge of S in p-block metal sulfides for sulfur reduction electrocatalysis. Nat Catal 6, 174–184 (2023). https://doi.org/10.1038/s41929-023-00912-9

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