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Polymeric Electrolytes and Polyelectrolytes: Salt Concentration and Domain Effects on Conductivity

Published online by Cambridge University Press:  21 February 2011

Mark A. Ratner ,
Stephen D. Druger  and
A. Nitzan
Mark A. Ratner
Affiliation:
Department of Chemistry and Materials Research Center, Northwestern University, Evanston, IL 60208
Stephen D. Druger
Affiliation:
Department of Chemistry and Materials Research Center, Northwestern University, Evanston, IL 60208
A. Nitzan
Affiliation:
Department of Chemistry, Tel Aviv University, Tel Aviv, Israel
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Abstract

Solvent-free polymer electrolytes and polyelectrolytes are usually studied at quite high ionic concentrations, (into the range above 1M). Under these conditions, correlation effects arising from ion-polymer and ion-ion interactions are expected to be important in the mechanism of conductivity. We sketch some specific ionic effects, separating those actittg on the mobility from those effecting carrier concentration. Mobility effects include reduction of the fluidity due to the effective cross-linking by cations, screening of applied fields due to high ionic concentrations, frictional drag due to counterion motion, and in some polymer hosts, lowered local availability of cation solvation sites due to reduction of the number of coordinating basic oxygens. Reduction of the carrier density from its stoichipmetric value can be discussed in terms of a generalized ion-pairing model. Though the concentrations usually studied are so high that Debye-Huckel theory is invalid and the stoichiometric average cation-anion separation is smaller than the Bjerrum length (a situation in which ordinary electrolyte theory considers all ions paired), nevertheless consideration in terms of contact ion pairs, solvent separated ion pairs and mean stoichiometric separation can be used to compute the effective concentration of carriers. Estimates based on an electrostatic continuum, cavity model for the binding energy of a pair describe the reduction of effective carrier number observed in poly (propylene oxide) materials.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 135: Symposium M – Solid State Ionics I , 1988 , 13
Copyright
Copyright © Materials Research Society 1989

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