<div>In this work, we investigate the dynamics of ion motion in “doubly-polymerized” ionic liquids (DPILs) in which both charged species of an ionic liquid are covalently linked to the same polymer chains. Broadband dielectric spectroscopy is used to characterize these materials over a broad frequency and temperature range, and their behavior is compared to that of conventional “singly-polymerized” ionic liquids (SPILs) in which only one of the charged species is attached to the polymer chains. Polymerization of the DPIL decreases the bulk ionic conductivity by four orders of magnitude relative to both SPILs. The timescales for local ionic rearrangement are similarly found to be approximately four orders of magnitude slower in the DPILs than in the SPILs, and the DPILs also have a lower static dielectric constant. These results suggest that copolymerization of the ionic monomers affects ion motion on both the bulk and the local scales, with ion pairs serving to form strong physical crosslinks between the polymer chains. This study provides quantitative insight into the energetics and timescales of ion motion that drive the phenomenon of “ion locking” currently under investigation for new classes of organic electronics.</div>
Pyr1,xTFSI Ionic Liquids (x = 1–8): A Computational Chemistry Study
