Surface Segregation and Phase Formation in Thin Films of SOFC Cathode Materials

"A limiting factor for Solid Oxide Fuel Cell (SOFC) performance is the oxygen reduction reaction (ORR) at the cathode surface. Changes in the surface composition and structure on annealing at 800°C has been studied, since these can influence the ORR. Idealized single crystals of cathode materials La0.8Sr0.2MnO3 (LSM) and La1-xSrxCoyFe1-yO3 (LSCF) were grown as heteroepitaxial thin films on lattice matched single crystal substrates. Changes upon heating the films to operating temperature and pressures were characterized using various synchrotron x-ray techniques. Total Reflection X-ray Fluorescence (TXRF) measurements, which probe compositional changes, were made at high temperature in real time. The LSM surfaces were found to develop manganese enrichment when heated. Highly strontium doped LSCF were found to develop strontium-rich surfaces. HArd X-ray PhotoElectron Spectroscopy (HAXPES) was used to investigate the electronic structure of the materials. Highly strontium doped LSCF precipitates a surface strontium phase that contains both oxide and carbonate contributions.IntroductionSolid oxide fuel cells (SOFCs) are chemical to electrical energy conversion devices that could potentially reshape how energy demands are fulfilled. SOFCs have a potential efficiency over 70%, fuel flexibility, low emissions, and low degradation over long time scales. Commonly, SOFCs are operated at high temperatures (above 800°C). At these temperatures expensive housing is needed to contain an operating stack as well as coatings to contain the oxidation of the metallic interconnects. Lowering the temperature of an operating device would allow for more conventional materials to be used, thus lowering overall cost. Understanding the reaction kinetics of the oxygen reduction reaction at the surface of the cathode is vital to designing a system that will perform well at lower temperatures. A commercialization goal is to reduce operating temperatures without sacrificing performance.In order to exploit the advantages of SOFCs, an understanding is needed of the surface chemical states of cations on the surface of the cathode and how this relates to the oxygen reduction reaction (ORR):"