A New Method to Measure Oxygen Surface Exchange Kinetics On Porous Mixed Conducting Oxides With Simple Determination of Microstructure Parameters.

Abstract

Oxygen exchange reaction on mixed conducting oxide is a critical reaction for many applications, yet measuring its rate constant remains poorly reliable by standard techniques. Here, a new technique that adapts the conductivity relaxation measurements on porous ceramics is proposed. Using a simple image analysis tool, it is possible to accurately determine the grain size distribution of the porous oxide, which is used in a new relaxation model that integrates relaxation times over that distribution. With such a model, it is possible to fit relaxation transients with the oxygen exchange reaction rate constant kchem as the only fitting parameter. With such rigidity, the output values of kchem are not sensitive to the fitting procedure, which does not require optimization. The model is proven to be applicable to various mixed conducting oxides and to a wide range of microstructures, yielding a remarkably low residual for all the porous ceramics considered. The procedure uses porous ceramics, therefore the derived kinetics are representative of ceramics used in real applications such as fuel cells, sensors, or catalysis.