Multiple time constant modelling of a printed conducting polymer electrode

Constant phase elements (CPE) are routinely used to describe the frequency response of electrochemical systems. However, this approach is often scientifically unsatisfactory because the physical origin of the phase is unclear. Here we observe CPE-like behaviour in a conducting polymer poly(3,4-ethylenedioxythiophene)/poly(styrene-4-sulfonate) (PEDOT:PSS) film that was inkjet printed onto paper to form a flexible electrochemical double layer capacitor electrode. We show that the response of the electrochemically active film can also be described using a physical model with multiple parallel finite RC (resistor–capacitor) transmission lines whose lengths and time constants are determined by the distribution of the measured film thickness. The modeled volumetric capacitance and ionic conductivity match those determined experimentally, suggesting that the physical origin of the constant phase response is a distribution of mass transport limited time constants.

► Thickness variations in a porous electrode produce a constant phase element (CPE)-like response. ► Model with parallel finite RC (resistor–capacitor) transmission lines produces a CPE-like response. ► Demonstration of an inkjet printed flexible electrochemical double layer capacitor electrode.