Replication Data for: What is the Role of Relative Humidity on Conductivity in Polymer Electrolytes?

Replication Data for: What is the Role of Relative Humidity on Conductivity in Polymer Electrolytes?
Abstract: Ion transport properties in polymer electrolytes have been widely studied under rigorously dry and highly waterswollen conditions. However, the transition between these extremes, i.e., the low hydration regime, is still poorly understood at the molecular level and relevant to applications ranging from battery electrolytes to electrophoretic separations. In this study, we apply atomistic molecular dynamics simulations to probe the role of hydration on ion mobilities and conductivities in LiTFSI-doped polyethers at low water content (less than 10% water by volume), which corresponds to 0−80% relative humidity conditions. With increasing water content, Li+ ions exhibit two distinct regimes in their mobilities. At low water content, the majority of the Li+ ions are weakly hydrated (two or fewer water molecules per Li+ ion), maintaining strong interactions with their polymer solvation cage, and therefore exhibit only a weak increase in mobility relative to dry conditions. As water content increases, Li+ ions form complete hydration shells, residing within water-rich domains that promote faster mobilities. Further, Li+ mobilities increase more significantly in polymer electrolytes composed of more hydrophilic polymers and higher salt concentrations due to the formation of larger water-rich domains. In contrast, TFSI− has comparatively weak interactions with both the polymer and water, exhibiting a monotonic increase in mobility as a function of water content. Overall, these results help clarify the molecular mechanisms underlying ionic mobilities and conductivities in polymer electrolytes at low water content.