Abstract
Silicon-based solid-state batteries are promising next-generation high-energy-density technologies. However, poor (electro)chemical compatibility between silicon negative electrodes and solid electrolytes (e.g., Li6PS5Cl) plus sluggish interfacial kinetics severely limits their reversibility and Coulombic efficiency. Here, we propose a surface halogenation strategy that transforms the native amorphous SiO2 passivation layer on silicon particles into a functional Al(Si)OCl composite surface via controlled reaction with AlCl3. This artificial interphase reconciles interfacial incompatibility and enables fast ionic/electronic transport, suppressing irreversible lithium loss. The optimized negative electrode achieves a high initial Coulombic efficiency of 94.3% in half-cells and 85.6% initial Coulombic efficiency (86.6% with pre-lithiation) in full cells paired with LiNi0.88Co0.09Mn0.03O2. Enhanced reversibility further delivers long-term cyclability. The optimized negative electrode delivers 86% capacity retention and 99.998% average Coulombic efficiency over 200 cycles. Even at high-loading ( > 10 mAh cm-2, and no adhesives/conductive carbon/electrolyte), it retains 72% capacity after 500 cycles. The full cells maintain 80% capacity after 200 cycles at 1 C, with an average Coulombic efficiency exceeding 99.95%. The versatility of this halogenation strategy underscores halide chemistry’s broad potential in advancing high-performance, reversible silicon-based solid-state batteries.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (22075268, 22409173, 22472079, W2441017), the Key R&D Program of Zhejiang (2024SSYS0050), the Zhejiang Provincial Natural Science Foundation of China (LQ24B030015), and Zhejiang Provincial Postdoctoral Science Foundation (ZJ2024026).
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H.L. conceived and designed the experimental work and prepared the manuscript. Y.L. revised the Figures. G.H. and Y.L. provided technical guidance for solid-state battery assembly processes. C.X. and L.Z. performed NDP characterization. H.H. revised the manuscript. H.Z. supplemented the interfacial reaction calculation. W.X. and N.L. supervised the overall project and revised the manuscript. All authors have given approval to the final version of the manuscript.
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Li, H., Li, Y., Hu, G. et al. Surface halogenation engineering for reversible silicon-based solid-state batteries. Nat Commun (2025). https://doi.org/10.1038/s41467-025-67985-x
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DOI: https://doi.org/10.1038/s41467-025-67985-x
