A method for independently obtaining electronic and ionic contributions to electrical conductivity in thin-film samples comprised of carbon black (CB) mixed with polymer electrolyte is reported. The method relies upon careful control of the nature of the contact between the sample and the current-carrying electrodes. Electronic conductivities are derived from currents obtained using electronically-conductive glassy carbon electrodes to contact the sample, whereas ionic conductivities are derived from currents obtained using ionically-conductive Nafion electrodes to contact the sample. Conditions under which the measured currents are free from interference from redox reactions at the electrodes and capacitive charging at electrode-electrolyte interfaces are discussed. Electrical conduction was studied in a series of composite carbon black/polymer samples under conditions of fixed temperature and variable relative humidity (RH). For samples containing 10–20 weight percent carbon black dispersed in Nafion, electronic conductivity was higher than ionic conductivity at all RH values tested (25–100% RH). Ionic conductivity increased with increasing RH in a manner consistent with expectation from prior studies on Nafion membranes, whereas electronic conductivity decreased with increasing RH due to water swelling and weakened electrical contacts among carbon particles in the network.
Shetzline, J. A., & Creager, S. E. (2014). Quantifying Electronic and Ionic Conductivity Contributions in Carbon/Polyelectrolyte Composite Thin Films. Journal of The Electrochemical Society, 161(14), H917–H923. https://doi.org/10.1149/2.0621414jes