Performance Degradation in Proton-Conducting Ceramic Electrochemical Cells

Abstract

Proton-conducting ceramics are a promising new class of electrochemical cells with a lower-temperature operational range in comparison to more-conventional solid-oxide or molten-carbonate counterparts. In the past, we have successfully demonstrated the scalability of this technology from the button-cell to the lab-scale stacks shown in the figure, along with strong performance and stability over thousands of hours under methane fuel at 550 ºC. This encouraging result was achieved through careful tuning of materials, fabrication procedures, and operating conditions. We have found that the degradation rates of protonic-ceramics stacks can be intense, especially at lower temperatures under fuel-cell operating mode. We have observed lower degradation rates under electrolysis operation, and at higher operating temperatures. These are both perhaps counterintuitive; lower-temperature operation is expected to improve the long-term stability, and degradation is typically more pronounced for more-common solid-oxide electrolyzers. In this presentation, we will review our studies on the root causes of performance degradation in protonic ceramics, and approaches to mitigate degradation. Previous work on performance degradation in oxygen-ion conducting electroceramics provides clues into the sources of degradation in protonic ceramics. That said, a number of degradation mechanisms are avoided by the nature of the protonic-ceramic device. For example, our microstructural characterizations reveal no nickel coarsening or agglomeration in the fuel electrode, likely due to the lower-temperature operation near 550 ºC. Operating conditions are shown to have a large impact on degradation rates in our protonic-ceramics; such conditions provide important clues about degradation’s root causes. Electrochemical Impedance Spectroscopy reveals how the slow kinetics of the electrochemical processes are closely tied to the degradation behaviors observed in our experiments. While we will continue to explore our root causes of degradation in proton-conducting electrochemical cells, we also report the impact of a gadolinium-doped ceria (GDC) interlayer on improving the durability of the cells, especially at low temperatures. This is perhaps a surprising, as GDC is a common O2--conducting material, and perhaps ill-matched to protonic ceramics. Regardless, the presence of the GDC layer at the air electrode - electrolyte interface has proven to be an effective strategy for minimizing protonic-ceramics degradation throughout our research, falling to 1.2% / 1000 hr for the methane-fueled stack at 600 ºC. While the root causes of this performance improvement remain unclear, we find the use of the GDC interlayer to impactful in reducing performance degradation in protonic ceramics. Figure 1