Polarization-Induced Interfacial Reactions Between Nickel and Selenium in Ni/Zirconia SOFC Anodes and Comparison with Sulfur Poisoning

Three distinctly different characteristic responses of a nickel/yttria-stabilized zirconia (Ni/YSZ) cermet anode to the presence of hydrogen selenide in synthetic coal gas were observed, depending on temperature (650-800oC), H2Se concentration (0-40 ppm), and especially on the extent of anodic polarization (0 to ~0.5 V). The first level of response was characterized by a rapid but modest decrease in power density to a new steady state, with no further degradation observed in tests up to 700 hours in duration. Mostly observed at high temperatures, low H2Se concentrations, and low anodic polarizations, this response level was similar to effects caused by the presence of H2S, but with slower onset and lower reversibility. Higher anodic polarization at a constant current could trigger a second level of response characterized by oscillatory behavior involving cycles of rapid performance loss followed by rapid recovery. Oscillations at the constant current density were accompanied by the appearance and disappearance of a new feature in the electrochemical impedance spectrum with a summit frequency of ~100 Hz. Oscillatory behavior ceased when the current density was lowered. Such behavior was not observed for cells operated at a constant potential of similar magnitude, though. A third level of response, irreversible cell failure, could be induced by further increases in anodic polarization, additionally favored by low temperature and high H2Se concentration. Post-test analyses of failed cells by electron microscopy revealed the extensive microstructural changes including the appearance of nickel oxide and nickel selenide alteration phases, only at the anode/electrolyte interface. From bulk thermochemical considerations the formation of nickel selenides could not be expected. Local chemical conditions created at the anode/electrolyte interface appear to be of overriding importance with respect to the extent of Ni/YSZ anode interactions with H2Se in coal gas.