Abstract
The design of superionic conductors has been largely focused on static structural features, with the dynamic ion transport mechanism less explored. Here, we explore a paradigm that harnesses the polyanion rotations to trigger the dynamically disordered Li sublattice as well as the liquid-like cation diffusion for superior ionic conductivity in crystals. A descriptor called rotation tolerance factor was proposed as a predictive metric for identifying the potential fast-rotating anion clusters with the low mass and reduced valence charge for given structural frameworks. Guided by this factor, halides with rotational polyanions, namely Li3Y(SH)6, Li3Y(NH2)6, Li2Zr(NH2)6, and an oxide (Li6.5La3Zr2O11.5(NH2)0.5) have been designed with synergistic polyanion rotation and Li⁺ sublattice disorder, which lead to enhanced Li ionic conductivities at room temperature compared to the counterparts without polyanions. The experimentally synthesized NH2- incorporated Li2ZrCl5.92(NH2)0.08 demonstrates a four-fold higher conductivity over Li2ZrCl6 control, enabling all-solid-state Li-In | |LiCoO2 and Li-In | |LiNi0.88Co0.09Mn0.03O2 cells with 96.5% and 97.4% capacity retention after 190 cycles at 140 and 200 mA g-1, respectively. This work provides an insight that flexible anion rotations could promote the dynamically disordered lithium sublattice distribution as well as the ionic conductivity.
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Data availability
The data generated in this study are provided in the Supplementary Information/Source Data file. Source data provided with this paper. Source data are provided with this paper.
Code availability
The machine learning molecular dynamics simulations were performed using open-source software packages, including LAMMPS, MLIP, Pymatgen and MAML, available at https://www.lammps.org, https://instadeepai.github.io/mlip/http://pymatgen.org and https://github.com/materialyzeai/maml. Additional scripts, structures, and relevant details are available at https://doi.org/10.5281/zenodo.18802601.
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Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (52573251, 523B2106, 52072240), Science and Technology Commission of Shanghai Municipality (23DZ1200800), the National Key R&D Program (2025YFF0516300) and the Materials Genome Initiative Center at Shanghai Jiao Tong University. All simulations were carried out with computational resources from Shanghai Jiao Tong University High Performance Computing Center.
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C.G., H.Z. conceived the project and designed the simulations and experiments. J.Z, J.L. and Y.Z. conducted the experiments. C.G. carried out DFT simulations and data analysis. R.O. assisted with the analyses. C.G. wrote the manuscript. F.H. and H.Z. supervised the project. All authors contributed to the review and editing of the manuscript.
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Guan, C., Zong, J., Li, J. et al. Triggering dynamically disordered lithium sublattice in superionic conductors. Nat Commun (2026). https://doi.org/10.1038/s41467-026-71304-3
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DOI: https://doi.org/10.1038/s41467-026-71304-3
