Electrochemical Behavior of Symmetric Electrical Double-Layer Capacitors and Pseudocapacitors and Identification of Transport Anomalies in the Interconnected Ionic and Electronic Phases Using the Impedance Technique

A double-channel transmission line impedance model was applied to the study of supercapacitors to investigate the charge transport characteristics in the ionic and electronic conductors forming the electrode/solution interface. The macro homogeneous description of two closely mixed phases (Paasch–Micka–Gersdorf model) was applied to study the influence of disordered materials on the charge transport anomalies during the interfacial charge–discharge process. Different ex situ techniques were used to characterize the electrode materials used in electrical double-layer (EDLC) and pseudocapacitor (PC) devices. Two time constants in the impedance model were adequate to represent the charge transport in the different phases. The interfacial impedance considering frequency dispersion and blocked charge transfer conditions adequately described the charge storage at the interface. Deviations from the normal (Fickian) transport involving the ionic and electronic charge carriers were identified by the dispersive parameters (e.g., n and s exponents) used in the impedance model. The ionic and electronic transports were affected when the carbon-based electrical double-layer capacitor was converted into a composite with strong pseudocapacitive characteristics after the decoration process using NiO. The overall capacitance increased from 2.62 F g(−1) to 536 F g(−1) after the decoration. For the first time, the charge transport anomalies were unequivocally identified in porous materials used in supercapacitors with the impedance technique.