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Ionic conductivity in crystalline polymer electrolytes

Nature volume 412, pages 520–523 (2001)Cite this article

Abstract

Polymer electrolytes are the subject of intensive study, in part because of their potential use as the electrolyte in all-solid-state rechargeable lithium batteries1. These materials are formed by dissolving a salt (for example LiI) in a solid host polymer such as poly(ethylene oxide) (refs 2, 3, 4, 5, 6), and may be prepared as both crystalline and amorphous phases. Conductivity in polymer electrolytes has long been viewed as confined to the amorphous phase above the glass transition temperature, Tg, where polymer chain motion creates a dynamic, disordered environment that plays a critical role in facilitating ion transport2,3,7,8,9. Here we show that, in contrast to this prevailing view, ionic conductivity in the static, ordered environment of the crystalline phase can be greater than that in the equivalent amorphous material above Tg. Moreover, we demonstrate that ion transport in crystalline polymer electrolytes can be dominated by the cations, whereas both ions are generally mobile in the amorphous phase10. Restriction of mobility to the lithium cation is advantageous for battery applications. The realization that order can promote ion transport in polymers is interesting in the context of electronically conducting polymers, where crystallinity favours electron transport11,12.

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Figure 1: The structure of the polymer electrolyte PEO6:LiAsF6.
Figure 2
Figure 3
Figure 4: NMR data.

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Acknowledgements

We thank the UK Engineering and Physical Sciences Research Council for financial support (P.G.B.) and the Overseas Research Scheme for an award (Z.G.).

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Authors and Affiliations

  1. School of Chemistry, University of St Andrews, North Haugh, St Andrews, KY16 9ST, Fife, UK

    Zlatka Gadjourova, Yuri G. Andreev & Peter G. Bruce

  2. School of Physics and Astronomy, University of St Andrews, North Haugh, St Andrews, KY16 9SS, Fife, UK

    David P. Tunstall

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  1. Zlatka Gadjourova
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  2. Yuri G. Andreev
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  3. David P. Tunstall
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  4. Peter G. Bruce
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Correspondence to Peter G. Bruce.

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Gadjourova, Z., Andreev, Y., Tunstall, D. et al. Ionic conductivity in crystalline polymer electrolytes. Nature 412, 520–523 (2001). https://doi.org/10.1038/35087538

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