Quantitative Evidence of Mobile Ion Hopping in Polymerized Ionic Liquids

Atomistic molecular dynamics simulations were performed, and an extensive set of analyses were undertaken to understand the ion transport mechanism in the polymerized ionic liquid poly(C₂VIm)Tf₂N. The ion hopping events were investigated at different time scales. Ion hopping was examined by monitoring the instantaneous cation-anion association and dissociation. Ion diffusion was subsequently evaluated with correlation functions and the calculation of relaxation times at different time scales. Dynamical heterogeneity in the mobility of the ions was observed with only a small portion of the anions classified as fast mobile ions. The mobile ions were characterized as the ones traveling farther than a certain distance during a characteristic period, which was much longer than the time scale of the instant ion pair dissociation. Effective hopping of the mobile ions contributed to the diffusivity which was dominated by interchain hopping and generally facilitated with five associating cations from two different polymer chains. Mobile anions had relatively fewer associating cations from more associating chains than immobile anions. The stringlike cooperative motion was observed in the mobile anions. The string length was determined to decrease with increasing temperature. These findings provided an in-depth understanding of the ion transport in polymerized ionic liquids and important information for the rational design of novel materials.