Polymer Architecture Induced Trade-off Between Conductivities and Transference Numbers in Salt-doped Polymeric Ionic Liquids*

Recent experiments have demonstrated that polymeric ionic liquids which share the same cation and anion but possessing different architectures can exhibit markedly different conductivity and transference numbers characteristics when doped with lithium salt. In this study, we used atomistic molecular simulations on polymer chemistries inspired by the experiments to probe the mechanistic origins underlying the competition between conductivity and transference numbers. Our results indicate that the architecture of the polycationic ionic liquid plays a subtle, but crucial role in modulating the anion-cation interactions, especially their dynamical coordination characteristics. Chemistries leading to longer-lived anion-cation coordinations relative to lithium-anion coordinations lead to lower conductivities and higher transference numbers. Our results suggest that higher conductivities are accompanied by lower transference numbers and vice versa, revealing that alternative approaches may need to be considered to break this trade-off in salt-doped polyILs.