Introducing Large Counteranions Enhances the Elastic Modulus of Imidazolium-Based Polymerized Ionic Liquids

Polymerized ionic liquids (PILs) are believed to be ideal solid-state polymer electrolytes, and hence experimental and computational studies have been widely undertaken to understand the relationship between the chemical structure and mechanical/dielectric properties and the ionic conductivity of PILs. However, it is still a challenge to understand the effect of counterion ionic volume on the material properties of PILs. Herein, we demonstrate the effect of the ionic volume ratio of counteranions to side-chain cations on linear viscoelastic response using three imidazolium-based PILs with different counteranions. We show that the elastic modulus is significantly enhanced at temperatures higher than glass transition temperature once the ionic volume of the counteranion exceeds that of the side-chain cation. Our results provide an additional strategy to improve mechanical properties of PILs, while maintaining relatively high ionic conductivity.