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Exploiting the paddle-wheel mechanism for the design of fast ion conductors

Nature Reviews Materials volume 7, pages 389–405 (2022)Cite this article

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Abstract

As an indispensable component in solid-state devices, superionic conductors can exhibit liquid-like and exceptionally high alkali cation conductivity in their crystalline lattices. A fundamental understanding of the nature of superionic behaviour at the atomic level is crucial for exploiting this behaviour in new technologies such as solid-state batteries, but remains a major challenge. Studies of ion transport in numerous materials over the past three decades have provided insight into cation conduction mechanisms. These efforts have mainly emphasized the impact of the static framework on cation diffusivity, whereas the contribution from cation–anion interplay has been largely overlooked. However, recent reports have revealed intriguing observations of the influence of anion rotational dynamics on cation translational processes through the paddle-wheel mechanism. This Review aims to illuminate this rapidly evolving topic, providing a perspective and direction for future breakthroughs. We summarize the polyanion groups that exhibit anion rotational or reorientational features and describe the advanced techniques available for studying the interaction between cation diffusion and anion rotation. Moreover, we identify strategies to stabilize disordered superionic phases at room temperature, thus enabling the paddle-wheel mechanism to be exploited to achieve super-high conductivity in solid electrolytes.

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Fig. 1: Features of plastic crystals.
Fig. 2: Timeline of the discovery of rotor phases in simple organic and inorganic salts.
Fig. 3: Rotation of [SO4]2– and [PO4]3– polyanions in inorganic alkali ion conductors.
Fig. 4: Rotation of [BH4]– and [BnHn]2– polyanions in inorganic alkali ion conductors.
Fig. 5: Rotation of [PnS4]3– polyanions in Na11Sn2PnX12 (where Pn = P, Sb; X = S, Se) Na-ion conductors.
Fig. 6: Strategies for stabilizing rotor phases to room temperature.
Fig. 7: Evaluating the use of rotor phases in ASSBs.

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Acknowledgements

L.F.N. gratefully acknowledges generous financial support from the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the US Department of Energy (DOE), the Office of Science, Basic Energy Sciences. L.F.N. also thanks the Natural Sciences and Engineering Research Council of Canada (NSERC) for platform support through the Discovery Grant and Canada Research Chair programmes. Z.Z. acknowledges support from the National Natural Science Foundation of China (22109185) during the final stages of manuscript preparation.

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Authors and Affiliations

  1. Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada

    Zhizhen Zhang & Linda F. Nazar

  2. Waterloo Institute of Nanotechnology, University of Waterloo, Waterloo, Ontario, Canada

    Zhizhen Zhang & Linda F. Nazar

  3. Joint Center for Energy Storage Research, Argonne National Laboratory, Argonne, IL, USA

    Zhizhen Zhang & Linda F. Nazar

  4. School of Materials, Sun Yat-sen University, Guangzhou, P. R. China

    Zhizhen Zhang

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Z.Z. researched the data, and wrote the initial draft of the manuscript with input from L.F.N. All authors discussed the content, edited and reviewed the manuscript before submission.

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Zhang, Z., Nazar, L.F. Exploiting the paddle-wheel mechanism for the design of fast ion conductors. Nat Rev Mater 7, 389–405 (2022). https://doi.org/10.1038/s41578-021-00401-0

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