Oxygen transport and exchange in oxide ceramics

Abstract Oxygen transport in most oxide ceramics incorporated in solid oxide fuel cells (SOFC) involves the movement of oxygen ion vacancies. It is the relative magnitude of oxygen ion vacancy and electronic charge carrier concentrations and mobilities which determines whether oxide materials can function as effective electrolyte or electrode components. Examination of relevant data suggests that zirconia- and ceria-based electrolytes are unlikely to be replaced in SOFC systems operating in the temperature range 450–950 °C. Oxygen ion vacancies are also involved in the cathodic reduction of oxygen and influence the magnitude of the associated exchange current density which can be measured by isotopic oxygen exchange measurements. Oxygen vacancy concentrations are also implicated in thermal expansion coefficient values and chemical stability considerations. It follows that optimisation of the cathode composition requires many conflicting requirements to be satisfied. However for operation at 800 °C, electrolyte, electrode and bipolar plate materials are available to ensure power densities approaching 0.5 W cm −2 . In contrast, direct methanol SOFC systems operating at 500 °C necessitate the development of alternative electrode materials. The successful exploitation of our knowledge about oxygen ion vacancy transport in ceramic oxides has now stimulated research into the role of protons in oxide lattices, and it is postulated that protonic/hydroxyl ion transport could be important in the development of alternative anode components.