Theory of Ion-Mediated Segmental Localization, Activated Structural Relaxation, and the Glass Transition in Polymerized Ionic Liquids

We combine polymer integral equation theory for structural correlations with a force-level theory for activated segmental relaxation to construct a microscopic theory for how ions modify the onset of segmental localization, the polymer alpha relaxation time, and glass transition temperature, Tg, in dry polymerized ionic liquids (PolyILs). Our most important findings concerning the behavior of Tg are (i) a weak dependence on anion–cation Coulomb attraction strength due to strong decoupling of ion and segmental dynamics, (ii) strong reduction with increasing mobile ion size due to both plasticization effects and weakening of ion-modified monomer caging, and (iii) increase with backbone rigidity and intrachain dynamic cooperativity. We quantitatively estimate Tg variations as ion size and polymer static and dynamic rigidity are widely varied. The experimental data of 19 PolyILs are organized into a specific pattern consistent with the theoretical predictions with glass transition temperatures varying over a very wide range (∼250 K) as observed experimentally. Based on the theoretical results, suggestions are made concerning the search for high conductivity Li- or Na-based PolyILs based on further lowering of Tg via new polymer synthesis. Calculations of the alpha time as a function of packing fraction reveal the dynamic fragility increases for larger mobile ions, a more flexible backbone, and/or a smaller degree of intrachain dynamic cooperativity, as a consequence of the increasing importance of collective elasticity in determining the activation barrier. An analysis of transient segmental localization and a crossover to activated dynamics reveals similar, but not identical, trends as predicted at the laboratory vitrification timescale.