Influence of a rigid polystyrene block on the free volume and ionic conductivity of a gel polymer electrolyte based on poly(methyl methacrylate)-block-polystyrene

Diblock copolymers poly(methyl methacrylate)-block-polystyrene with three different molar ratios [poly(methyl methacrylate)/polystyrene (PS) = 1:1, 1:1.5, and 1:1.8] were synthesized by atom transfer radical polymerization and used as a polymer matrix for gel polymer electrolytes (GPEs). The positron annihilation lifetime spectroscopy was applied to determine the free-volume behaviors of different GPEs, respectively. We illustrated that a proper PS ratio may led to the formation of a high fraction of free volume, and the influence of the PS ratio on the free-volume fraction was caused by the different morphologies of the GPEs because of the different packing densities of the PS rigid block. The ionic conductivity was correlated with the free volume in the GPE through the study of the ionic conductivity dependence on the temperature; this followed the Vogel–Tamman–Fulcher equation. Moreover, an ionic conductive model was proposed, in which variations of the free-volume behavior provide different ionic-conducting abilities. Thermogravimetric analysis indicated that GPEs based on different block copolymers exhibited high liquid-electrolyte preservation properties.