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Alkali metal crystalline polymer electrolytes

Nature Materials volume 8, pages 580–584 (2009)Cite this article

Abstract

Polymer electrolytes have been studied extensively because uniquely they combine ionic conductivity with solid yet flexible mechanical properties, rendering them important for all-solid-state devices including batteries, electrochromic displays and smart windows1,2,3. For some 30 years, ionic conductivity in polymers was considered to occur only in the amorphous state above Tg. Crystalline polymers were believed to be insulators. This changed with the discovery of Li+ conductivity in crystalline poly(ethylene oxide)6:LiAsF6 (refs 4, 5). However, new crystalline polymer electrolytes have proved elusive, questioning whether the 6:1 complex has particular structural features making it a unique exception to the rule that only amorphous polymers conduct. Here, we demonstrate that ionic conductivity in crystalline polymers is not unique to the 6:1 complex by reporting several new crystalline polymer electrolytes containing different alkali metal salts (Na+, K+ and Rb+), including the best conductor poly(ethylene oxide)8:NaAsF6 discovered so far, with a conductivity 1.5 orders of magnitude higher than poly(ethylene oxide)6:LiAsF6. These are the first crystalline polymer electrolytes with a different composition and structures to that of the 6:1 Li+ complex.

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Figure 1: Conductivity data of 8:1 complexes of PEO (methoxy end-capped, average Mn=1,000) with NaAsF6, NaPF6, KAsF6 and RbAsF6.
Figure 2: PXRD data.
Figure 3: The structure of PEO8:NaAsF6.
Figure 4: DSC curve for PEO8:NaAsF6.
Figure 5: PXRD data collected at several temperatures above and below the knee in the conductivity plot of PEO8:NaAsF6, Fig. 1.
Figure 6

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Acknowledgements

The authors are grateful to J. K. Cockcroft, University College London, for collecting variable-temperature PXRD data. P.G.B. is indebted to the EPSRC and the EU for financial support.

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Authors and Affiliations

  1. EaStCHEM, School of Chemistry, The Purdie Building, University of St. Andrews, KY16 9ST, UK

    Chuhong Zhang, Stephen Gamble, David Ainsworth, Alexandra M. Z. Slawin, Yuri G. Andreev & Peter G. Bruce

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  1. Chuhong Zhang
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Correspondence to Peter G. Bruce.

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Zhang, C., Gamble, S., Ainsworth, D. et al. Alkali metal crystalline polymer electrolytes. Nature Mater 8, 580–584 (2009). https://doi.org/10.1038/nmat2474

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