Abstract
Elucidating the mechanisms governing sulfur redox reactions is important for the development of high-energy-density Li||S batteries. Despite progress, the kinetics of the solid-solid conversion from Li2S2 to Li2S remain poorly understood. This work demonstrates that spin-state transitions within reaction intermediates are the key factor of the sluggish kinetics. Guided by density functional theory and machine-learning-assisted catalyst screening, we find a negative correlation between the spin moment of the catalyst and the Gibbs free energy barrier for the Li2S2 to Li2S conversion. Among a series of dual-metal doped catalysts, a Co,Ni-doped MoS2 catalyst, with its high spin moment, modulates the spin states of the reactants, reducing the high free-energy barrier associated with spin-state transitions. Therefore, Li||S batteries incorporating this catalyst show accelerated sulfur conversion, particularly during solid-solid transitions, suppressed polysulfide shuttling, and have stable electrochemical performance. A pouch cell achieves a capacity of 13.2 Ah and a specific energy of 435 Wh kg-1. These findings show mechanistic understanding into the role of spin moments in sulfur conversion, enabling to design efficient and durable catalysts for Li||S batteries.
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All data supporting the findings of this study are provided within the article and its Supplementary Information. The data underlying the graphs in the main Figures and Supplementary Figs. are provided in the Source Data file associated with this paper. Source data are provided with this paper.
Code availability
The codes of machine learning models and data processing used in this study are available on Zenodo62 and at: https://doi.org/10.5281/zenodo.18681112.
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Acknowledgements
This work was supported by the Science and Technology Development Fund (FDCT) of Macao S.A.R (0046/2019/AFJ, 0007/2021/AGJ, 0070/2023/AFJ, and 0022/2023/RIB1), Multi-Year Research Grants (File no. MYRG-GRG2024-00166-IAPME and MYRG-GRG2025-00136-IAPME) from the Research Services and Knowledge Transfer Office at the University of Macau, the Science and Technology Innovation Committee of Shenzhen Municipality (SGCX20250526152800001), the SIAT International Joint Lab Project, Shenzhen Science and Technology Program (KQTD20221101093647058), the funding provided by Prince Mohammad Bin Fahd University, and the High-Performance Computing Cluster (HPCC) of Information and Communication Technology Office (ICTO) at University of Macau.
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K.-N.H., K.-S.H., Y.-M.S., and H.-M.C. conceived and supervised this work. Q.-B.J., H.-F.X. planned the synthesis, tested the catalysts, electrochemical data, and wrote the paper with the assistance of L.-W.L., K.G., C.-Y.Z., Y.-S.Z., M.-D.W., J.Z, M.-K.L., and C.-Z.Y. H.-F.X. and Y.-M.S. carried out theoretical calculations. X.-Y.Y. carried out the machine learning simulations. C.W. carried out XAS. Z.-L.L. tested the pouch cells. K.-T.S. and H.-F.L. carried out the temperature-dependent magnetic susceptibility measurement and the M-T data analysis. All authors participated in the analysis of experimental data and discussion of the results, as well as in the writing and revision of the manuscript.
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Jiang, Q., Xu, H., Ye, X. et al. Breaking the rate limiting barrier in lithium||sulfur batteries via spin state engineering. Nat Commun (2026). https://doi.org/10.1038/s41467-026-70974-3
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DOI: https://doi.org/10.1038/s41467-026-70974-3
