The local free volume, glass transition, and ionic conductivity in a polymer electrolyte: A positron lifetime study

Abstract

The size of free-volume holes in neat poly[(ethylene glycol)23dimethacrylate] [poly((EG)23DMA)] and in the same polymer doped with 0.6 mol/kg LiCF3SO3 have been studied as a function of temperature in the range between 100 and 370 K using positron annihilation lifetime spectroscopy. The results are compared with differential scanning calorimetry and ionic conductivity measurements. In both systems, the hole volume νh shows a typical glass-transition behavior, i.e., a small linear increase with temperature below the glass transition temperature Tg and a steeper increase above Tg. From these measurements Tg was estimated to be 233 K (neat polymer) and 240 K (polymer with salt) and the coefficients of the thermal expansion of the hole volume were determined. The fractional free volume (f=0.080) and the number density of holes (Nh=0.6 nm−3) were also estimated. Below Tg the average hole volume of the polymer electrolyte is larger than in the neat polymer. This is consistent with the bulky character of the CF3SO3− anion. Above Tg the salt-doped system shows the lower hole volume of the two systems, probably caused by a reduced segmental mobility as a consequence of the interactions of the Li+ ions with the ethylene oxide units of the polymer. Based on the free-volume theory of Cohen–Turnbull the ionic conductivity σ is correlated with the mean hole volume νh. A linear relation between log(σT 0.5) and 1/νh was observed to be valid for variations of the conductivity over several orders of magnitudes. From these plots critical hole sizes of γν*=0.65 nm3 (neat polymer) and 0.87 nm3 (polymer-salt system) were estimated. The parameters B and T0 of the Vogel–Tamman–Fulcher equation were also determined, as well as the apparent activation volume ΔVapp by pressure-dependent conductivity measurements. The cationic transference number in the polymer-salt system was determined by pulsed field gradient-nuclear magnetic resonance to be t+≈0.3.