Manganese Oxide Formation in Lanthanum Strontium Manganite-Yttria-Stabilized Zirconia SOFC Cathodes

Abstract

Microstructural changes in the cathode adjacent to the cathode–electrolyte interface were studied in SOFCs with lanthanum strontium manganite (LSM)/Y2O3-stabilized ZrO2 (YSZ) composite cathodes after long-term operation (1.3 to 2.0 kh) with steam (1 to 3 pct H2O) added to the cathode gas. We specifically sought to understand why the degradation rate (the increase of area specific resistance with time) was markedly higher at lower temperatures (e.g., 1073 K (800 °C)) than at higher temperatures (e.g., 1198 K (925 °C)). Transmission electron microscopy, combined with X-ray energy-dispersive spectroscopy and electron energy-loss spectroscopy, was used to detect and identify submicron MnxOy precipitates. The particles were shown to be Mn3O4 in cells operated at 1198 K (925 °C), and both Mn3O4 and Mn2O3 in cells operated at 1073 K (800 °C). In a cell exposed for 5 kh at 1198 K (925 °C) to a cathode atmosphere of 1.1 pct H2O at 4 bara, MnxOy precipitates were uniformly distributed across the cathode. On the other hand, in an identical cell exposed to the same conditions but operated continuously at 380 mA cm−2, MnxOy precipitates were observed almost exclusively within about 3 µm of the electrolyte/cathode interface. Whether MnxOy formation is causative or simply correlative with the steam effect remains an important question for future work.