Limitations of charge-transfer models for mixed-conducting oxygen electrodes

A framework is presented for defining charge-transfer and non-charge-transfer processes in solid state electrochemical systems. We examine why charge-transfer models have difficulty modeling non-charge-transfer effects, and walk through several examples including the ALS model for oxygen reduction on a porous mixed-conducting oxygen electrode. These examples illustrate that electrode 'overpotential' is often better described in terms of macroscopic thermodynamic gradients of chemical species. In the case of a porous mixed conducting oxygen electrode, oxygen reduction is limited by chemical reaction and diffusion, and may occur up to 20 microns from the electrochemical (charge-transfer) interface. (C) 2000 Elsevier Science B.V. All rights reserved.