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Halogen chemistry of solid electrolytes in all-solid-state batteries

Nature Reviews Chemistry volume 7, pages 826–842 (2023)Cite this article

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Abstract

All-solid-state batteries (ASSBs) using solid-state electrolytes, replacing flammable liquid electrolytes, are considered one of the most promising next-generation electrochemical energy storage devices because of their improved, inherent safety and energy density. A family of solid electrolytes incorporating halogens has attracted attention because of their potentially high ionic conductivity, good deformability and wide electrochemical windows. Although progress has been made for halogen-containing solid electrolytes (HSEs) in ASSBs, challenges in the preparations, characterizations and low-cost industrial scalability remain. In this Review, we focus on the development of halide battery chemistry, the preparation, modification and properties of HSEs, and issues with HSEs in ASSBs. The chemical action of halogen and ion transport mechanisms are discussed. Moreover, the main challenges and future development directions of halide-based ASSBs are discussed to pave the way for practical applications of HSEs for next-generation rechargeable batteries.

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Fig. 1: Monumental developments of HSEs over the years.
Fig. 2: Chemical properties and applications of halogens.
Fig. 3: Liquid-phase preparation procedures, typical structures and ion transport mechanisms in the Li–M–X system.
Fig. 4: Main preparation procedures, crystallography and ion transport pathways of LPSX-type HSEs (Li2S–P2S5–LiX system).
Fig. 5: Action mechanism of halogen-atomic substitution strategy in Li2S–P2S5 system.
Fig. 6: Performance analysis of experimentally assembled cells based on halogen-containing solid electrolytes.
Fig. 7: Interfacial composition and chemical stability of HSEs.

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Acknowledgements

H.T. thanks the Interdisciplinary Innovation Program of North China Electric Power University (No. XM2212315). C.X. thanks the National Natural Science Foundation of China (No. 51821004).

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Authors and Affiliations

  1. Key Laboratory of Power Station Energy Transfer Conversion and System of Ministry of Education and School of Energy Power and Mechanical Engineering, North China Electric Power University, Beijing, China

    Bijiao He, Fang Zhang, Yan Xin, Chao Xu & Huajun Tian

  2. National Energy Conservation Center, Beijing, China

    Xu Hu

  3. China Construction Third Engineering Group Co., Ltd, Wuhan, China

    Xin Wu

  4. NanoScience Technology Center, University of Central Florida, Orlando, FL, USA

    Yang Yang

  5. Department of Materials Science and Engineering, University of Central Florida, Orlando, FL, USA

    Yang Yang

  6. Renewable Energy and Chemical Transformation Cluster, University of Central Florida, Orlando, FL, USA

    Yang Yang

  7. Department of Chemistry, University of Central Florida, Orlando, FL, USA

    Yang Yang

  8. The Stephen W. Hawking Center for Microgravity Research and Education, University of Central Florida, Orlando, FL, USA

    Yang Yang

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Contributions

H.T., Y.X. and Y.Y. proposed the topic of the Review. B.H., F.Z., Y.X. and H.T. wrote the manuscript. C.X., X.H., Y.Y. and X.W. discussed the Review. All the authors agreed upon the final version of the manuscript.

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He, B., Zhang, F., Xin, Y. et al. Halogen chemistry of solid electrolytes in all-solid-state batteries. Nat Rev Chem 7, 826–842 (2023). https://doi.org/10.1038/s41570-023-00541-7

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