The effects of defects on the transport mechanisms of lithium ions in organic ionic plastic crystals

Organic ionic plastic crystals (OIPCs) consist of molecular ions of which interactions are strong enough to maintain crystalline order but are weak enough to allow the rotations of the molecular ions at sufficiently high temperatures. When defects such as Schottky vacancies and grain boundaries are introduced into OIPCs, the defects facilitate the transport of dopants such as Li⁺ ions, for which OIPCs are considered as strong candidates for solid electrolytes. The transport mechanism of dopant ions in OIPCs with defects, however, remains elusive at a molecular level partly because it is hard in experiments to track the dopant ions and control the types of defects systematically. In this work, we perform molecular dynamics simulations for 1,3-dimethylimidazolium hexafluorophosphate ([MMIM][PF₆]) OIPCs with Li⁺ ions doped and show that the transport mechanism of Li⁺ ions depends on the types and concentrations of defects. A high concentration of Schottky vacancies enhance the overall ion conduction, but decrease the transference number. The transference numbers of Li⁺ ions in [MMIM][PF₆] with grain boundaries are similar to that in [MMIM][PF₆] with 0.78 mol% point vacancies. We also find that the transport of ions in OIPCs is strongly heterogeneous and the time scales of the dynamic heterogeneity of the ions are sensitive to the types of defects.