A new approach to the understanding of ion transport in semicrystalline polymer electrolytes

Despite the conventional wisdom that ion transport in polymer electrolytes is mediated primarily by polymer segmental motion, we have performed measur ements on semicrystalline complexes of poly(ethylene oxide) (PEO) with LII which suggest that transport occurs preferentially along the PEO helical ax is, at least in the crystalline phase. The principal basis for this claim i s an observed enhancement by a factor of 5-20 in electrical conductivity in stretched polymer electrolyte films. The effect of uniaxial stress on the polymer electrolyte long and short range structures was investigated by X-r ay diffraction and Li-7 nuclear magnetic resonance (NMR) spectroscopy. Stre tching results in partial alignment of the PEO helices and also induces sma ll but observable changes in the Li+ solvation sheath. These results are co rrelated with the ionic conductivity enhancement in the stretched polymer, (C) 2000 Elsevier Science B.V. All rights reserved.