Oxygen potential transition in mixed conducting oxide electrolyte

It is generally assumed that oxygen potential in a thin oxide electrolyte follows a linear distribution between electrodes. Jacobsen and Mogensen have shown, however, that this is not the case for thin zirconia membranes in solid oxide electrochemical cells. Here we demonstrate that there is a ubiquitous oxygen potential transition rooted in the p-type/n-type transition of electronic conductivity inside mixed conducting oxides, and that the transition is extremely sensitive to electrode potential and current density. It is also remarkably sensitive to the conductivity ratio of electrons and holes, as well as their association with lattice oxygens and vacancies, which tends to increase the oxygen flow. Direct evidence of a sharp oxygen potential transition has been found in an equally sharp grain size transition in electrically loaded zirconia. More broadly speaking, the oxygen potential transition is akin to a first-order phase transition. Therefore, it will suffer interface instability, especially in high-current-density devices. These findings provide new opportunities to understand several disparate observations in the literature, from microstructural degradation and stress distribution in solid oxide fuel/electrolyzer cells, to field-assisted sintering, to conducting filaments in resistance memory, to dendrite formation in electrochemical cells.