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Composition effects in polyetherurethane-based solid polymer electrolytes
journal contributionposted on 01.12.1998, 00:00 authored by S Ng, Maria ForsythMaria Forsyth, D MacFarlane, M Garcia, M Smith, J Strange
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 (LiClO4 and LiCF3SO3) have been studied. D.m.t.a. has established that increasing LiClO4 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 LiClO4/polymer complex with d.m.t.a. reveals that increasing LiClO4 concentration causes a slight broadening of the distribution, indicating a more heterogeneous environment. Results of n.m.r. 7Li T1 and T2 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 LiClO4-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.).