Mathematical modeling of oxygen transport in solid oxide fuel cells

摘要

This thesis develops mathematical models to describe the electrochemical performance of a solid oxide fuel cell cathode based on electrochemical kinetics and mass transfer. The individual effects of various coupled processes are investigated. A one-dimensional model is developed based on porous electrode theory. Two different mechanisms are investigated for the charge transfer reaction. One of these assumes that intermediately adsorbed oxygen atoms are reduced at the electrode/electrolyte interface, similar to the models proposed for metal electrodes. Simulated polarization curves exhibit limited currents due to depletion of oxygen adsorbates at high cathodic overvoltages. An empirical correlation is confirmed to exist between the limiting current an the oxygen partial pressure, however, a similar correlation often assumed to exist between the measured polarization resistance and the oxygen partial pressure could not be justified. For the other model, oxygen vacancies are assumed to be exchanged directly at the electrode/electrolyte interface. The electrochemical behaviour is improved by reducing the oxygen partial pressure, due to increased vacancy concentration of the electrode material. Simulated polarization curves exhibit Tafel-like slopes in the cathodic direction, which are due to polarization concentration, and not activation polarization in the conventional sense. Anodic limiting currents are predicted due to lack of available free sites for vacancy exchange at the cathode side. The thesis also presents a theoretical treatment of current and potential distributions in simple two-dimensional cell geometries, and a two-dimensional model for a porous electrode-electrolyte system for investigation of the effect of interfacial diffusion of adsorbates along the electrode/electrolyte interface. 172 refs., 60 figs., 11 tabs.