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Volume 134, 2007
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Factors influencing the conductivity of crystalline polymer electrolytes

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Crystalline polymer electrolytes conduct, in contrast to the established view for 30 years. The crystalline polymer poly(ethylene oxide)6:LiXF6, X = P, As, Sb is composed of tunnels formed from pairs of (CH2–CH2–O)n chains, within which the Li+ ions reside and along which they may migrate. The anions are located outside the tunnels. PEO6:LiXF6 formed from PEO of average molecular weight 1000 Da has an average chain length of 40 Å compared with a typical crystallite size of 2500 Å, hence low molecular weight materials have many chain ends within a crystallite. More chain ends increase conductivity. Materials composed of polydispersed PEO (chains of different lengths) of average molecular weight 1000 Da exhibit a conductivity one order of magnitude greater than monodispersed materials of the same molecular weight. Replacing the –OCH3 groups on the chain ends with –OC2H5 increases the conductivity by a further order of magnitude. Conductivity may also be increased by isovalent or aliovalent doping of the 6 : 1 complexes in which XF6 is replaced by N(SO2CF3)2 or SiF2−6, respectively.

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The article was received on 09 Feb 2006, accepted on 28 Mar 2006 and first published on 03 Aug 2006

Article type: Paper
DOI: 10.1039/B601945E
Faraday Discuss., 2007,134, 143-156

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    Factors influencing the conductivity of crystalline polymer electrolytes

    E. Staunton, Y. G. Andreev and P. G. Bruce, Faraday Discuss., 2007, 134, 143
    DOI: 10.1039/B601945E

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