Ionic conductivity and mobility in network polymers from poly(propylene oxide) containing lithium perchlorate

Abstract

Ionic conductivity σ and mobility μ in the amorphous network polymers from poly(propylene oxide) (PPO) containing lithium perchlorate (LiClO4) at the concentration of [LiClO4]/[PO unit]=0.042 and 0.076 were investigated by means of complex impedance and time-of-flight methods. The σ values of the PPO–LiClO4 complexes reached 10−5 S cm−1 at 70 °C. The temperature dependence of σ deviated from a single Arrhenius behavior above a critical temperature (−1 °C and 11 °C) which approximately corresponded to the glass transition temperature Tg. The μ values were relatively high and changed from 10−6 to 10−5 cm2 V−1 s−1 in the temperature range of 40–100 °C. The Nernst–Einstein equation correlated μ with the ionic diffusion coefficient D. The Williams–Landel–Ferry equation with C1≂5 and C2≂30–50 held with a temperature dependence of D in the order of 10−8–10−7 cm2 s−1. The change in the number of ionic carriers n with temperature obeyed the Arrhenius equation with the activation energy of 0.26 and 0.34 eV. The degree of dissociation for LiClO4 in the PPO networks was 1–6%, and the dissociation was facilitated in the low LiClO4 concentration complex. The temperature dependence of σ above Tg was interpreted quantitatively in terms of n and μ.