Ion Transport in Pendant and Backbone Polymerized Ionic Liquids

Polymerized ionic liquids (PILs) are single-ion conductors in which one of the ionic species is tethered to the polymer chain while the other is free to be transported. The ionic species can either be directly incorporated into the polymeric backbone (backbone PILs) or placed as pendant groups to the chain (pendant PILs). Here, we examined the morphology, conductivity, and rheology of imidazolium-based pendant and backbone PILs. We found that pendant PILs yielded higher ionic conductivity when scaled to T_g, but backbone PILs exhibited higher ionic conductivity on an absolute temperature scale, likely because of differences in the T_gs of the two systems. We also found that ion transport for backbone PILs was coupled to the segmental dynamics below T_g, where the decoupling of ionic conductivity from segmental relaxation was observed for pendant PILs. The results of this study will help the community to better understand the role of the PIL structure on conductivity to work toward the ultimate goal of designing high-performance solid polymer electrolytes.