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Lithium superionic conductors with corner-sharing frameworks

Abstract

Superionic lithium conductivity has only been discovered in a few classes of materials, mostly found in thiophosphates and rarely in oxides. Herein, we reveal that corner-sharing connectivity of the oxide crystal structure framework promotes superionic conductivity, which we rationalize from the distorted lithium environment and reduced interaction between lithium and non-lithium cations. By performing a high-throughput search for materials with this feature, we discover ten new oxide frameworks predicted to exhibit superionic conductivity—from which we experimentally demonstrate LiGa(SeO3)2 with a bulk ionic conductivity of 0.11 mS cm−1 and an activation energy of 0.17 eV. Our findings provide insight into the factors that govern fast lithium mobility in oxide materials and will accelerate the development of new oxide electrolytes for all-solid-state batteries.

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Fig. 1: Crystal structures of known superionic conductors with CS frameworks.
Fig. 2: Screening for new superionic conductors with a CS framework and experimental verification of LiGa(SeO3)2.
Fig. 3: Lithium environment in oxide materials with 2,822 CS and 5,750 non-CS frameworks.
Fig. 4: Effect of distorted lithium environment on the energy landscape.
Fig. 5: Structural features of CS framework and their RR channels.

Data availability

All relevant data within the article are available from the corresponding author upon reasonable request. Source data are provided with this paper and within the Supplementary Information.

Code availability

A sample code to perform our analysis on the geometry of tetrahedral/octahedral environment is provided in the Supplementary Information.

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Acknowledgements

This research utilized the resources of the National Energy Research Scientific Computing Center (NERSC), a US Department of Energy Office of Science User facility operated under contract no. DE-AC02-05CH11231, and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant no. ACI-1548562. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231. K. Jun gratefully acknowledges support from a a Kwanjeong Educational Foundation scholarship.

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Authors

Contributions

Y.W. initially proposed the concept. K.J. carried out all of the calculations with the help of Y.X. Y.X. implemented the site identifying algorithm. Y.S. synthesized the conductor. Y.S., Y.Z. and R.K. densified the pellet. Y.S. performed the electrochemical characterization and analysed the results with Y.Z., K.J., H.K. and L.J.M. G.C., Y.W. and D.I. supervised the project. K.J., Y.S., Y.W. and G.C. wrote the manuscript with contributions and revisions from all authors.

Corresponding authors

Correspondence to Yan Wang or Gerbrand Ceder.

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The authors declare no competing interests.

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

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Supplementary information

Supplementary Information

Supplementary Figs. 1–22, Tables 1–6, Notes 1–7 and references.

Source data

Source Data Fig. 2

XRD data, EIS data and Arrhenius plot.

Source Data Fig. 3

Distribution of the CSM and volume.

Source Data Fig. 4

Dependence of EKRA on CSM and volume.

Source Data Fig. 5

Polyhedral packing ratio, site ratio and percentile of RR-channel dimensions.

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Jun, K., Sun, Y., Xiao, Y. et al. Lithium superionic conductors with corner-sharing frameworks. Nat. Mater. 21, 924–931 (2022). https://doi.org/10.1038/s41563-022-01222-4

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