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Microscopic interactions in nanocomposite electrolytes

journal contribution
posted on 01.06.2001, 00:00 authored by A Best, J Adebahr, P Jacobsson, D MacFarlane, Maria ForsythMaria Forsyth
Nanocomposite electrolytes of a fully amorphous trifunctional polyether (3PEG) and poly- (methylene ethylene oxide) (PMEO) have been complexed with two lithium salts and nanoparticulate (~20 nm) fillers of TiO2 and Al2O3. Addition of the fillers to the polymer salt complexes shows a significant change in the conformational modes of both polymers, especially the D-LAM region between 200 and 400 cm-1, indicating a reduced segmental flexibility of the chain. These changes are more pronounced with the use of TiO2 than Al2O3. Incorporation of the nanoparticulate fillers to the electrolytes fails to influence the degree of ion association, suggesting that the number of charge carriers available for conduction in both polymers using both LiClO4 and LiCF3SO3 is not the source of any conductivity increase. Addition of the fillers, which was seen to increase the conductivity in PEO-based systems, generally lowers the conductivity in the present PMEO systems, while the addition of TiO2 has little or no effect except in the cases of 3PEG 1.5 and 1.25 mol/kg LiClO4. In this case, 10 wt % TiO2 provides a conductivity increase of half an order of magnitude at approximately 60 °C. We also report for the first time a Raman spectroscopy investigation into the PEO-based nanocomposite electrolytes. The present results are discussed in terms of the electrostatic interactions involving dielectric properties of the fillers, of special interest being the interactions between the polymer and the fillers and between the ionic species and the fillers, when the effect of crystallization can be ignored.

History

Journal

Macromolecules

Volume

34

Issue

13

Pagination

4549 - 4555

Publisher

American Chemical Society

Location

Washington, D.C.

ISSN

0024-9297

eISSN

1520-5835

Language

eng

Publication classification

C1.1 Refereed article in a scholarly journal

Copyright notice

2001, American Chemical Society