In situ characterization of electrochemical processes of solid oxide fuel cells

Solid oxide fuel cells (SOFCs) represent a next generation energy source with high energy conversion efficiency, low pollutant emission, good flexibility with a wide variety of fuels, and excellent modularity suitable for distributed power generation. As an electrochemical energy conversion device, SOFC’s performance and reliability depend sensitively on the catalytic activity and stability of the electrode materials. To date, however, the development of electrode materials and microstructures is still based largely on trial-and-error methods because of inadequate understanding of the mechanisms of the electrode processes. Identifying key descriptors/properties of electrode materials or functional heterogeneous interfaces, especially under in situ conditions, may provide guidance to the design of electrode materials and microstructures. This thesis aims to gain insight into the electrochemical and catalytic processes occurring on the electrode surfaces using unique characterization tools with superior sensitivity, high spatial resolution, and excellent surface specificity applicable under in situ/operando conditions. Carbon deposition on nickel-based anodes is investigated with in situ Raman spectroscopy and SERS. Analysis shows a rapid nucleation of carbon deposition upon exposure to small amount of propane. Such nucleation process is sensitive to the presence of surface coating (e.g., GDC) and the concentration of steam. In particular, operando analysis of the Ni-YSZ boundary indicates special function of the interface for coking initiation and reformation. The coking-resistant catalysts (BaO, BZY, and BZCYYb) are systematically studied using in situ Raman spectroscopy, SERS, and EFM. In particular, time-resolved Raman analysis of the surface functional groups (-OH, -CO3, and adsorbed carbon) upon exposure to different gas atmospheres provides insight into the mechanisms related to carbon removal. The morphology and distribution of early stage carbon deposition are investigated with EFM, and the impact of BaO surface modification is evaluated. The surface species formed as a result of sulfur poisoning on nickel-based anode are examined with SERS. To identify the key factors responsible for sulfur tolerance, model cells with welldefined electrode-electrolyte interfaces are systematically studied. The Ni-BZCYYb interface exhibits superior sulfur tolerance. The oxygen reduction kinetics on LSCF, a typical cathode material of SOFC, is studied using model cells with patterned electrodes. The polarization behaviors of these micro- electrodes, as probed using a micro-probe impedance spectroscopy system, were correlated with the systematically varied geometries of the electrodes to identify the dominant paths for oxygen reduction under different electrode configurations. Effects of different catalyst modifications are also evaluated to gain insight into the mechanisms that enhance oxygen reduction activity. The causes of performance degradation of LSCF cathodes over long term operation are investigated using SERS. Spectral features are correlated with the formation of surface contamination upon the exposure to air containing Cr vapor, H2O, and CO2. Degradation in cathode performance occurs under normal operating conditions due to the poisoning effect of Cr from the interconnect between cells and the high operating temperature. The surface-modified LSCF cathode resists surface reactions with Cr vapor that impairs electrode performance, suggesting promising ways to mitigate performance degradation.Ph.D