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Overcoming the conversion reaction limitation at three-phase interfaces using mixed conductors towards energy-dense solid-state Li–S batteries

Nature Materials volume 24, pages 243–251 (2025)Cite this article

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Abstract

Lithium–sulfur (Li–S) all-solid-state batteries (ASSBs) hold great promise for next-generation safe, durable and energy-dense battery technology. However, solid-state sulfur conversion reactions are kinetically sluggish and primarily constrained to the restricted three-phase boundary area of sulfur, carbon and solid electrolytes, making it challenging to achieve high sulfur utilization. Here we develop and implement mixed ionic–electronic conductors (MIECs) in sulfur cathodes to replace conventional solid electrolytes and invoke conversion reactions at sulfur–MIEC interfaces in addition to traditional three-phase boundaries. Microscopic and tomographic analyses reveal the emergence of mixed-conducting domains embedded in sulfur at sulfur–MIEC boundaries, helping promote the thorough conversion of active sulfur into Li2S. Consequently, substantially improved active sulfur ratios (up to 87.3%) and conversion degrees (>94%) are achieved in Li–S ASSBs with high discharge capacity (>1,450 mAh g–1) and long cycle life (>1,000 cycles). The strategy is also applied to enhance the active material utilization of other conversion cathodes.

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Fig. 1: Illustration of the sulfur cathode using MIEC.
Fig. 2: The origin of the low sulfur utilization.
Fig. 3: Materials characterization.
Fig. 4: Electrochemical evaluation of Li–S ASSBs at 60 °C.
Fig. 5: Post-characterization of S-C-MIEC20 cathodes.

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Data availability

The data supporting the findings of this study are available within the article and its Supplementary Information. Computational data are available via figshare at https://doi.org/10.6084/m9.figshare.27257931 (ref. 55).

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Acknowledgements

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy, through Advanced Battery Materials Research (BMR) program award number DE-EE0008862 (Da. Wang, L.-J.J., R.K. and Do. Wang) and Battelle-Pacific Northwest National Laboratory subcontract award 680628 (Battery500 Consortium, Da. Wang, L.-J.J., L.Y., A.S., A.T.N. and Do. Wang). We gratefully acknowledge the computing resources provided on Bebop, a high-performance computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory. This research used 8-BM of the National Synchrotron Light Source II, a US Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract number DE-SC0012704 (D. Wierzbicki and Y.D.). The APT characterization performed at EMSL, a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research, was supported by the US DOE Office of Electricity (OE) under contract DE-AC05-76RL01830 (B.G. and X.L.) through Pacific Northwest National Laboratory project number 70247 (Long Duration and Cost Competitive Energy Storage). In addition, we thank C. George, J. L. Gray and J. Meyet from the Pennsylvania State University for their instrument assistance.

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Authors and Affiliations

  1. Department of Mechanical Engineering, The Pennsylvania State University, University Park, PA, USA

    Daiwei Wang, Rong Kou, Meng Liao, Lei Ye, Heng Jiang, Shuhua Shan & Donghai Wang

  2. Pacific Northwest National Laboratory, Richland, WA, USA

    Bharat Gwalani & Xiaolin Li

  3. National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, NY, USA

    Dominik Wierzbicki & Yonghua Du

  4. Department of Chemical Engineering, University of Illinois at Chicago, Chicago, IL, USA

    Vijay Singh, Tomas Rojas & Anh T. Ngo

  5. Materials Science Division, Argonne National Laboratory, Argonne, IL, USA

    Vijay Singh, Tomas Rojas & Anh T. Ngo

  6. Department of Chemical Engineering, The Pennsylvania State University, University Park, PA, USA

    Li-Ji Jhang

  7. Department of Materials Science and Engineering, The Pennsylvania State University, University Park, PA, USA

    Alexander Silver

  8. Department of Mechanical Engineering, Southern Methodist University, Dallas, TX, USA

    Donghai Wang

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Contributions

Da. Wang and Do. Wang conceived the idea and designed the experiments. B.G. and X.L. conducted the APT experiments. D.Wierzbicki and Y.D. carried out the XAS characterization and analysis. Da. Wang., L.-J.J., A.S. and L.Y. prepared the materials, assembled the batteries and conducted electrochemical tests. V.S., T.R. and A.T.N. designed and performed the simulation. Da. Wang carried out the TEM experiments. M.L. and H.J. conducted the XRD analysis. Da. Wang and R.K. performed the SEM tests. Da. Wang performed the quantitative analysis of dead sulfur. S.S. and Da. Wang designed the Swagelok cell for electrochemical testing. Da. Wang, Do. Wang and X.L. wrote the paper with comments from all authors.

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Correspondence to Donghai Wang.

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Nature Materials thanks Yan Yao and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–39, Tables 1–11 and Notes 1–8.

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Wang, D., Gwalani, B., Wierzbicki, D. et al. Overcoming the conversion reaction limitation at three-phase interfaces using mixed conductors towards energy-dense solid-state Li–S batteries. Nat. Mater. 24, 243–251 (2025). https://doi.org/10.1038/s41563-024-02057-x

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