Interrogating the Structure and Dynamics of the Semiconducting Polymer–Electrolyte Interphase

How the physicochemical nature of the interphase between a soft semiconducting polymer and electrolyte changes as a function of the chemistries of these components, passive swelling, applied electric fields, and charge-carrier injection into the polymer remain outstanding questions that need to be resolved to design materials systems that can achieve high charge and ion transport. Here we will discuss recent advances in understanding the formation and dynamics of the polymer–electrolyte interphase through the development of multiscale modeling approaches. Quantum chemical calculations are used to describe the nature of the charge carriers (i.e., polarons) in the semiconducting polymers, including how the dielectric environment and interactions with counterions impact polaron (de)localization. We then develop and deploy molecular dynamics (MD) simulations to examine dynamic features of polymer swelling by the electrolyte as a function of applied electric fields and charge-carrier injection into the polymer.