Interfacial Effects in Conductivity Measurements of Block Copolymer Electrolytes

The ionic conductivity in lamellar block copolymer electrolytes is often anisotropic, where the in-plane conductivity exceeds the through-plane conductivity by up to an order of magnitude. In a prior work, we showed significant anisotropy in the ionic conductivity of a lamellar block copolymer based on polystyrene (PS) and a polymer ionic liquid (PIL), and we proposed that the through-film ionic conductivity was depressed by layering of lamellar domains near the electrode surface. In the present work, we first tested that conclusion by measuring the through-plane ionic conductivity of two model PIL-based systems having controlled interfacial profiles using impedance spectroscopy. The measurements were not sensitive to changes in interfacial composition or structure, so anisotropy in the ionic conductivity of PS-block-PIL materials must arise from an in-plane enhancement rather than a through-plane depression. We then examined the origin of this in-plane enhancement with a series of PS-block-PIL materials, a P(S-r-IL) copolymer, and a PIL homopolymer, where impedance spectra were acquired with a top-contact electrode configuration. These studies show that enhanced in-plane ionic conductivities are correlated with the formation of an IL-rich wetting layer at the free surface, which presumably provides a low-resistance path for ion transport between the electrodes. Importantly, the enhanced in-plane ionic conductivities in these PS-block-PIL materials are consistent with simple geometric arguments based on properties of the PIL, while the through-plane values are an order of magnitude lower. Consequently, it is critical to understand how surface and bulk effects contribute to impedance spectroscopy measurements when developing structure–conductivity relations in this class of materials.