The role of the double layer for the pseudocapacitance of the hydrogen adsorption on platinum

Pseudocapacitances such as the hydrogen adsorption on platinum (HAoPt) are associated with faradaic chemical processes that appear as capacitive in their potentiodynamic response, which was reported to result from the kinetics of adsorption processes. This study discusses an alternative interpretation of the partly capacitive response of the HAoPt that is based on the proton transport of ad- or desorbed hydrogen in the double layer. Potentiodynamic perturbations of equilibrated surface states of the HAoPt lead to typical double layer responses with the characteristic resistive-capacitive relaxations that overshadow the fast adsorption kinetics. A potential-dependent double layer representation by a dynamic transmission line model incorporates the HAoPt in terms of capacitive contributions and can computationally reconstruct the charge exchanged in full range cyclic voltammetry data. The coupling of charge transfer with double layer dynamics displays a novel physicochemical theory to explain the phenomenon of pseudocapacitance and the mechanisms in thereon based supercapacitors.