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Surface-localized phase mediation accelerates quasi-solid-state reaction kinetics in sulfur batteries

Nature Chemistry volume 17, pages 614–623 (2025)Cite this article

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Abstract

Lithium–sulfur batteries promise high energy density storage but show poor stabilities owing to uncontrolled polysulfide dissolution. Although limiting polysulfide solvation to establish quasi-solid-state sulfur reaction can decouple electrode reactions from the electrolyte volume, this approach suffers from slow reaction kinetics. Here we propose a surface-localized polysulfide-solvation strategy to mediate the reaction of ‘quasi-solid’ polysulfide by leveraging an organic phase mediator with a weakly solvating electrolyte. This electrolyte restricts polysulfide dissolution globally while the phase mediator complexes with the surface polysulfide, promoting polysulfide solvation at the surface and facilitating fast surface-localized solution-phase sulfur reactions. Lithium–sulfur batteries using surface-localized phase mediation show excellent rate performance with 494 mA h g−1-sulfur at 16 C and stabilized cycling for 300 cycles with 90.2% capacity retention. The strategy enables steady operation of a 2.4 Ah 331 Wh kg−1 pouch cell. Our work highlights the advantages of surface phase mediation in controlling electrode reaction pathways and kinetics via electrolyte rational design.

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Fig. 1: Schematics of the proposed surface-localized solvation-mediated QSSSR.
Fig. 2: Characterizations of the electrolyte solvation structure.
Fig. 3: Electrode reaction behaviour using LiTFSI–CPME and LiTFSI–DME electrolytes.
Fig. 4: The phase-mediating effects in the BDTS–LiTFSI–CPME electrolyte.
Fig. 5: Operando X-ray investigations on the sulfur speciation dynamics.
Fig. 6: Electrochemical performances of Li–S cells in the BDTS–LiTFSI–CPME electrolyte.

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The data analysed and generated during the current study are included in the paper and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant number 92372115 to Q.P.) and the National Key R&D Program of China (grant number 2021YFB2500200 to Q.P.). We also acknowledge the National Natural Science Foundation of China (22075002 to Q.P.; 52203347 to Yatao Liu; 51825201 and 52227802 to R.Z.; 22409006 to M.H.), the Beijing Natural Science Foundation (number Z220020 to Q.P.), the Opening Foundation of State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology (oic-202401006 to Yatao Liu), the China Postdoctoral Science Foundation (2021M690001 to Yatao Liu) and the China National Petroleum Corporation-Peking University Strategic Cooperation Project of Fundamental Research (to Q.P.). We appreciate S. Lv for the valuable discussions on the interactions between BDTSRed and polysulfides. We acknowledge the Beijing Synchrotron Radiation Facility (BSRF, 4B7A beamline) and L. Zheng and C. Ma for the XANES measurements and analysis.

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Authors and Affiliations

  1. Beijing Key Laboratory for Theory and Technology of Advanced Battery Materials, School of Materials Science and Engineering, Peking University, Beijing, China

    Yatao Liu, Yun An, Yifeng An, Mengxue He, Yongfeng Jia, Xufeng Hong, Yumei Liu, Song Gao, Ruqiang Zou & Quanquan Pang

  2. State Key Laboratory of Organic-Inorganic Composites, College of Chemical Engineering, Beijing University of Chemical Technology, Beijing, China

    Yatao Liu & Yunfeng Lu

  3. School of Advanced Materials, Peking University, Shenzhen Graduate School, Shenzhen, China

    Chi Fang, Yaokun Ye & Jiaxin Zheng

  4. International Center of Quantum Materials, School of Physics, Peking University, Beijing, China

    Yizhou Hao & Jianhao Chen

  5. Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing, China

    Yunfeng Lu

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Contributions

Yatao Liu, R.Z. and Q.P. conceived the idea and designed the experiments. Yatao Liu performed the experiments. Yun An conducted the AIMD simulations. Yun An and Y.Y. conducted the DFT calculations. C.F., Y.Y. and J.Z. conducted the classical MD simulations. Yifeng An, M.H., X.H., Yumei Liu and S.G. helped with the spectroscopy studies. Yatao Liu, M.H. and Y.J. assembled the pouch cells. Y.H. and J.C. synthesized the graphene material for pouch cell assembly. All authors discussed the results and contributed to the data analysis. Yatao Liu, Q.P., R.Z. and Y. Lu wrote the paper with contributions from all authors. R.Z. and Q.P. supervised this work.

Corresponding authors

Correspondence to Ruqiang Zou or Quanquan Pang.

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Extended data

Extended Data Fig. 1 Evaluation of BDTS-LiTFSI-CPME electrolyte under rigid conditions.

(a-c) Li–S coin cells with fixed discharge capacity at 55 °C: (a) with 5.0 μL mg-1 electrolyte and 2.0 mg cm-2 -sulfur (discharge/charge rate of 0.3 C/0.2 C); (b) with 5.0 μL mg-1 electrolyte and 3.0 mg cm-2 -sulfur (discharge/charge rate of 0.3 C/0.1 C). (c) with 4.0 μL mg-1 electrolyte and 5.1 mg cm-2 -sulfur (discharge/charge rate of 0.1 C/0.1 C). (d) The performance of a 2.4 Ah-level pouch Li–S cells operated at 40 °C (3.0 μL mg-1, detailed parameters shown in Supplementary Table 3); the inset shows the digital photo of the pouch cell.

Source data

Supplementary information

Supplementary Information

Supplementary Figs. 1–24, discussion, Tables 1–9, Notes 1 and 2, and methods.

Supplementary Video 1

The dynamic AIMD trajectory after equilibrium for 1 M LiTFSI–CPME electrolyte.

Supplementary Video 2

The dynamic AIMD trajectory after equilibrium for 1 M LiTFSI–DME electrolyte.

Supplementary Data 1

The settings in the AIMD input file for CPME- and DME-based electrolytes.

Source data

Source Data Fig. 2

Statistical source data.

Source Data Fig. 3

Statistical source data.

Source Data Fig. 4

Statistical source data.

Source Data Fig. 5

Statistical source data.

Source Data Fig. 6

Statistical source data.

Source Data Extended Data Fig. 1

Statistical source data.

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Liu, Y., An, Y., Fang, C. et al. Surface-localized phase mediation accelerates quasi-solid-state reaction kinetics in sulfur batteries. Nat. Chem. 17, 614–623 (2025). https://doi.org/10.1038/s41557-025-01735-w

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