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Ion Association in Polymer Electrolytes; A Raman Study of Poly (Propylene Oxide) Based Complexes

Published online by Cambridge University Press:  21 February 2011

M. Kakihana ,
S. Schantz ,
L.M. Torell  and
L. Borjesson
M. Kakihana
Affiliation:
Department of Physics, Chalmers University of Technology, S -412 96 Gothenburg, Sweden
S. Schantz
Affiliation:
Department of Physics, Chalmers University of Technology, S -412 96 Gothenburg, Sweden
L.M. Torell
Affiliation:
Department of Technology, Uppsala University, Box 534, S-751 21 Uppsala, Sweden
L. Borjesson
Affiliation:
Department of Physics, Chalmers University of Technology, S -412 96 Gothenburg, Sweden
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Abstract

Raman spectra of a series of PPO-LiClO4 and PPO-NaCF3SO3 complexes have been obtained for different temperatures and salt concentrations to study the various ion associations of the dopant salt. It was found that ion-ion interactions dramatically influenced the internal symmetric stretching modes ν1 of the anions. Splitting of ν1 into a multicomponent band was observed. The intensity profile of the band was found to change rapidly with salt concentration and temperature. A three component band analysis led to the identification of dissociated ions, ion pairs and multiple ion aggregates, respectively. Increased ion association with increased temperature and/or salt concentration was observed for both LiCIO4- and NaCF3SO3- complexes. It is likely to initiate the phase separation and salt precipitation observed in many salt-polymer complexes at higher temperatures. Considerably stronger ion-ion interaction was observed in the NaCF3SO3-system than in the LiCIO4-complex, which may explain the lower conductivities reported for PPO-NaCF3SO3 electrolytes. The drastic conductivity drop observed in both systems at higher salt concentrations can however only partly be due to a decreased concentration of “free” ions, the major effect being attributed to decreased ion mobility.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 135: Symposium M – Solid State Ionics I , 1988 , 351
Copyright
Copyright © Materials Research Society 1989

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