The dynamics that govern the attractive feature of ion transport in polymerized ionic liquids (PILs) at faster timescales than the structural relaxation of the polymer matrix material is still somewhat of a mystery. From the chemistry of the monomeric ions to their coordination with the free counter ions, and in conjunction with ion conformational changes, this study aims to unravel the mechanism of ion transport among the intertwining polymer chains as a function of monomeric ionic liquid (IL) concentration blended with a polymerized counterpart. By employing the monomeric cation chemistries of 1-ethyl-3-vinylimidazolium, 1,2-methyl-3-vinylimidazolium and [2-(Methacryloyloxy)ethyl]dimethyl ethylammonium with counter anions of bis(trifluoromethane)sulfonimide, trifluoromethanesulfonate or hexafluorophosphate, assorted blends of these polymerized and monomeric ILs at various concentrations display curious thermodynamic and eutectic-like transitions that correspond to shifts in the ion-hopping timescales as probed with differential scanning calorimetry and broadband dielectric spectroscopy. The changes in anion-cation coordination at characteristic concentrations for each blend and the structural changes associated with the dynamic glass transition that accompany these changes are measured <i>via</i> particular Raman emission bands and with oscillatory shear rheology, respectively. These results give insights into the mechanism of ion transport in PIL systems to better tune the desired physicochemical properties of these systems such as ionic conductivity.

Blends of monomeric ionic liquids with their polymerized counterparts: Unraveling ion transport mechanisms with broadband dielectric spectroscopy

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.