Composition effects in polyetherurethane-based solid polymer electrolytes

Abstract

Nuclear magnetic resonance spectroscopy (n.m.r.), dynamic mechanical thermal analysis (d.m.t.a.) and AC impedance techniques have been used in combination to probe the effect of electrolyte composition in an archetypal solid polymer electrolyte (SPE). A series of solid polymer electrolytes (SPEs) based on a urethane-crosslinked trifunctional poly(ethylene glycol) polymer host containing dissolved ionic species (LiClO 4 and LiCF 3SO 3) have been studied. D.m.t.a. has established that increasing LiClO 4 concentration causes a decrease in the polymer segmental mobility, owing to the formation of transient crosslinks via cation–polymer interaction. Investigation of the distribution of mechanical/structural relaxation times for the LiClO 4/polymer complex with d.m.t.a. reveals that increasing LiClO 4 concentration causes a slight broadening of the distribution, indicating a more heterogeneous environment. Results of n.m.r. 7Li T 1 and T 2 relaxation experiments support the idea that higher salt concentrations encourage ionic aggregation. This is of critical importance in determining the conductivity of the material since it affects the number of charge carriers available. Introduction of the plasticiser tetraglyme into the LiClO 4-based SPEs suppresses the glass transition temperature of the SPE, and causes a significant broadening of the relaxation time distribution (as measured by d.m.t.a.).