Humidity-Controlled Water Uptake and Conductivities in Ion and Electron Mixed Conducting Polythiophene Films

Mixed conducting polymer films are of great interest in applications where an interface between electronic and ionic charge transport is needed, e.g., in bioelectronics, electrochemical energy applications, and photovoltaic device interfaces. The role of water on charge transport is of high relevance not only for aqueous environments but also for devices that are manufactured at ambient conditions with varying relative humidities. In this contribution, we present our results on the influence of controlled humidity changes on the mixed conductivity and correlation to the concomitant water uptake in the films. Two sulfonate-bearing polythiophene systems are studied: a self-made conjugated polyelectrolyte, poly(6-(thiophen-3-yl)hexane-1-sulfonate)-sodium (PTS-Na), and poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS) with different ratios of PEDOT and the polyelectrolyte PSS. Our data give clear evidence of the similarities between the aforementioned polythiophene systems and pure ionic membranes such as Nafion used in fuel cells. As such, a phase separation between the hydrophobic electronically conducting polythiophene phase and the hydrophilic water-swellable ion-conducting phase is proposed. Changing the humidity from dry conditions up to ∼90% relative humidity results in extremely high water uptakes of more than 90 wt %, which corresponds to ∼13 water molecules per sulfonate unit at maximum water uptake. Conversely, the electronic conductivity is less sensitive to increasing humidity, which is due to percolation pathways. The ionic conductivity strongly increases from 10^-10 S/cm at dry conditions to 10^-3 S/cm at around 30 wt % water content and then levels off at maximum conductivities of 10^-3-10^-2 S/cm up to water contents of 90 wt %.