Generalized Poisson-Nernst-Planck-Based Physical Model of the O2|LSM|YSZ Electrode

The paper presents a generalized Poisson-Nernst-Planck model of an yttria-stabilized zirconia electrolyte developed from first principles of nonequilibrium thermodynamics which allows for spatial resolution of the space charge layer. It takes into account limitations in oxide ion concentrations due to the limited availability of oxygen vacancies. The electrolyte model is coupled with a reaction kinetic model describing the triple phase boundary with electron conducting lanthanum strontium manganite and gaseous phase oxygen. By comparing the outcome of numerical simulations based on different formulations of the kinetic equations with the results of EIS and CV measurements we attempt to discern the existence of separate surface lattice sites for oxygen adatoms and surface oxides from the assumption of shared ones. Moreover, we show that the mass-action kinetics model is sensitive to oxygen partial pressure unlike exponential kinetics models. The resulting model is fitted to a dataset of EIS and CVs spanning multiple temperatures and pressures, using various relative weights of EIS and CV data in the fitness function. The model successfully describes the physics of the interface around the OCV.

Activation of Porous Pt Electrodes Deposited on YSZ Electrolyte by Nitric Acid Treatment

The effect of nitric acid treatment on the electrochemical performance of porous Pt electrodes deposited on YSZ (abbreviation from yttria stabilized zirconia) electrolyte was investigated. Two identical symmetrical Pt/YSZ/Pt cells with porous Pt electrodes were fabricated, after which the electrodes of the first cell were kept as sintered, while those of the second cell were impregnated with HNO3 solution. The electrochemical behavior of the prepared electrodes was studied using impedance spectroscopy and cyclic voltammetry. Significant reduction of the polarization resistance of the HNO3-treated electrodes was revealed. The observed enhancement of the electrochemical performance of porous Pt electrodes was assumed to be caused by adsorption of NOx-species on YSZ and Pt surfaces, which promotes oxygen molecules dissociation and transport to the triple phase boundary by the “relay-race” mechanism. The obtained results allow for considering the nitric acid treatment of a porous Pt electrode as an effective way of electrode activation.