Owing to its mixed ionic and electronic conductivity and high thermochemical stability, La 0.6 Sr 0.4 FeO 3-δ (LSF64) is an attractive electrode material in solid oxide fuel/electrolysis cells (SOFCs/SOECs). Well defined thin film microelectrodes are used to compare the electrochemical properties of LSF64 in oxidizing and reducing conditions. The high electronic sheet resistance in hydrogen can be overcome by the use of an additional metallic current collector. With the sheet resistance being compensated, the area specific electrode resistance is similar in humidified hydrogen and oxygen containing atmospheres. Analysis of the chemical capacitance and the electrode resistance for current collectors on top and beneath the LSF64 thin film allow mechanistic conclusions on active zones and bulk defect chemistry. Cyclic gas changes between reducing and oxidizing conditions, performed on macroscopic LSF64 thin film electrodes with top current collector, reveal a strong degradation of the surface kinetics in synthetic air with very fast recovery in reducing atmosphere. Additional in-situ high-temperature powder XRD on LSF64 demonstrates the formation of small amounts of iron oxides in humidified hydrogen at elevated temperatures. Solid oxide fuel cells (SOFCs) are in the process of gaining more and more commercial success as highly efficient power generation systems. They transform the chemically bound energy of a fuel to electrical energy. Solid oxide electrolysis cells (SOECs) are the counter parts of SOFCs as they use electrical energy, e.g. excess energy from the grid, to form fuel by electrolysis. Owing to their very high efficiencies, also SOECs are promising devices in future energy technologies.
1Currently Ni/YSZ cermet electrodes are the standard electrodes in SOF/ECs for reducing conditions, but they are known to suffer from several problems, like sulfur poisoning (in SOFC operation), sintering, redox cycle stability etc.2 To find an alternative to Ni/YSZ could therefore be favorable for both SOFCs and SOECs.Electrodes in SOE/FCs have to meet numerous requirements: thermochemical stability over a wide oxygen partial pressure range, high catalytic activity for oxygen exchange reactions, compatibility with adjacent cell components, sufficiently high electronic and ionic conductivity, etc. Perovskite-type oxides such as LaMnO 3 , LaCoO 3 and LaFeO 3 based materials are used in state-of-the-art SOF/EC electrodes in oxygen atmosphere. Often they are mixed ionic and electronic conductors (MIECs), which is advantageous in SOF/ECs as the whole electrode surface area may become active in the oxygen exchange reaction. Employing such MIECs also in reducing atmosphere could be highly attractive. However, Sr-doped LaMnO 3 and LaCoO 3 are only stable under comparatively high oxygen partial pressures and thus not suited for the use in hydrogen. Fe 4+ states can be interpreted as electron holes (h • ) and those determine the electronic conductivity at high oxygen partial pressure as they are the majority mobile charge carrie...