Ion transport in polymerized ionic liquids: a comparison of polycation and polyanion systems

The correlation among chemical structure, mesoscale structure, and ion transport in 1,2,3-triazole-based polymerized ionic liquids (polyILs) featuring comparable polycation and polyanion backbones is investigated by wide-angle X-ray scattering (WAXS), differential scanning calorimetry, and broadband dielectric spectroscopy (BDS). Above the glass transition temperature, T_g, higher ionic conductivity is observed in polycation polyILs compared to their polyanion counterparts, and ion conduction is enhanced by increasing the counterion volume in both polycation or polyanion polyILs. Below T_g, polyanions show lower activation energy associated with ion conduction. However, the validity of the Barton-Nakajima-Namikawa relation indicates that hopping conduction is the dominant charge transport mechanism in all the polyILs studied. While a significant transition from a Vogel-Fulcher-Tammann to Arrhenius type of thermal activation is observed below T_g, the decoupling index, often used to quantify the extent to which segmental dynamics and ion conduction are correlated, remains unaltered for the polyILs studied, suggesting that this index may not be a general parameter to characterize charge transport in polymerized ionic liquids. Furthermore, detailed analyses of the WAXS results indicate that both the mobile ion type and the structure of the pendant groups control mesoscale organization. These findings are discussed within the framework of recent models, which account for the subtle interplay between electrostatic and elastic forces in determining ion transport in polyILs. The findings demonstrate the intricate balance between the chemical structure and interactions in polyILs that determine ion conduction in this class of polymer electrolytes.