Abstract
Lithium halide solid electrolytes have garnered significant attention owing to their high ionic conductivity and positive electrode compatibility. However, achieving target ionic conductivity typically requires high lithium concentration (>4.3 wt%) within optimal structure, which raises costs and exacerbates air sensitivity. Here, we leverage anion clusters to synthesize a series of amorphous halide electrolytes xLi2SO4-ZrCl4, with optimal ionic conductivities of 1.5 mS cm-1 at 30 °C and a significantly reduced lithium content of 2.4 wt%, alongside good air stability. Through neutron/synchrotron X-ray experiments, first-principles calculations and machine learning-accelerated molecular dynamics simulations, we reveal a disordered backbone of [ZraCl4a(SO4)]2- (1 ≤ a ≤ 4) that enables fast Li-ion diffusion via under-coordinated oxygen sites. All-solid-state lithium batteries employing these electrolytes and LiNi0.8Co0.1Mn0.1O2 positive electrode exhibit 81.1% capacity retention after 1400 cycles at 1 C (60 min) and 30 °C. Our findings reveal anion-cluster chemistry as an approach that transforms solid electrolyte design for advanced batteries, bridging materials science with practical energy storage innovation.
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The authors declare that all the relevant data are available within the paper and its Supplementary Information file or from the corresponding author upon request. Source data are provided within this paper. The training datasets and the pretrained MACE model are available in https://doi.org/10.5281/zenodo.1834487277. Source data are provided with this paper.
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Acknowledgements
W.X. acknowledges the financial supports from the National Natural Science Foundation of China (22472079, W2441017), the Zhejiang Provincial Natural Science Foundation of China (LY23B030003), the Natural Science Foundation of Ningbo (2023J200). S.W. acknowledges the National Natural Science Foundation of China (52573249). F.W. acknowledges the China Postdoctoral Science Foundation (2025M780087). The calculations were supported by the High-performance Computing Platform of Eastern Institute of Technology, Ningbo. Synchrotron total scattering measurements were carried out on beamline BL08W at SPring-8 under proposal Nos. 2021B2006 and 2023A2341. The authors thank the staff members of the Multi-Physics Instrument (http://english.ihep.cas.cn/csns/fa/in/202109/t20210915_283259.html) at the China Spallation Neutron Source (CSNS), for providing technical support and assistance in data collection and analysis. The authors thank Wenhan Guo and Xue Tian from the Dongguan Key Laboratory of Interdisciplinary Science for Advanced Materials and Large-Scale Scientific Facilities, School of Physical Sciences, Great Bay University, for the help with the differential electrochemical mass spectrometry measurements.
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W.T. and W.X. conceived and designed the experiments. F.W., S.W. and W.X. developed the workflow for analyzing the amorphous structure and carried out all the calculations. W.T., S.L., and J.T. performed synchrotron data acquisition, analysis and discussion. J.L., W.Y. and W.X. conducted nPDF characterizations and analysis. Z.S. and Y.L. prepared air stability experiments. H.J., C.Z. and H.Z. provided guidance for data and image processing. F.H., P.Y. and F.R. participated in the discussions. W.T. and F.W. wrote the original manuscript. Z.M. and X.S. edited the manuscript. All authors commented the manuscript. X.S. and W.X. supervised the whole project.
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Tang, W., Wang, F., Liang, S. et al. Polyanion-stabilized amorphous halide electrolytes with low lithium content for all-solid-state lithium batteries. Nat Commun (2026). https://doi.org/10.1038/s41467-026-69737-x
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DOI: https://doi.org/10.1038/s41467-026-69737-x
