Role of Tethered Ion Placement on Polymerized Ionic Liquid Structure and Conductivity: Pendant versus Backbone Charge Placement

The role of ion placement was systematically investigated in imidazolium bis­(trifluoromethane)­sulfonimide (ImTFSI) polymerized ionic liquids (PILs) containing pendant charges and charges in the backbone (sometimes called ionenes). The backbone PILs were synthesized via a facile step growth route, and pendant PILs were synthesized via RAFT. Both PILs were designed to have nearly identical charge density, and the conductivity was found to be substantially enhanced in the backbone PIL systems even after accounting for differences in the glass transition temperature (T_g). Wide-angle X-ray scattering (WAXS) revealed an invariance in the location of the amorphous halo between the two systems, while the anion–anion correlation peak was shifted to lower scattering wavevector (q) in the backbone PILs. This indicates an increase in the correlation length of ions and is consistent with charge transport along a more correlated pathway following the polymer backbone. Due to the linear nature of the backbone PILs, crystallization was observed and correlated with changes in conductivity. Upon crystallization, the conductivity dropped, and eventually, two populations of mobile ions were observed and attributed to ions in the amorphous and near-crystallite regions. The present work demonstrates the important role of ion placement on local structure and conductivity as well as the ability of backbone PILs to be used as controllable optical or dielectric materials based on crystallization or processing history.