Surface Activity and Bulk Defect Chemistry of Solid Oxide Fuel Cell Cathodes

In the first half of this thesis, a new robotic instrument called a scanning impedance probe is presented that can acquire electrochemical impedance spectra in automated fashion from hundreds of thin film microelectrodes with systematically varied properties. Results from this instrument are presented for three catalyst compositions that are commonly considered for use in state-of-the-art solid oxide fuel cell cathodes. For (La<sub>0.8sub>Sr<sub>0.2sub>)<sub>0.95sub>Mn<sub>O3+δsub> (LSM), the impedance spectra are well fit by a through-the-film reaction pathway. Transport rates are extracted, and the surface activity towards oxygen reduction is found to be correlated with the number of exposed grain boundary sites, suggesting that grain boundaries are more surface-active than grains. For La<sub>0.5sub>Sr<sub>0.5sub>Co<sub>O3-δsub> (LSC), the surface activity degrades ~50x initially and then stabilizes at a comparable activity to that of previously measured Ba<sub>0.5sub>Sr<sub>0.5sub>Co<sub>0.8sub>Fe<sub>0.2O3-δsub> films. For Sr<sub>0.06sub>Nb<sub>0.06sub>Bi<sub>1.87sub>O<sub>3sub> (SNB), an example of a doped bismuth oxide, the activity of the metal-SNB boundary is measured.

In the second half of this thesis, SrCo<sub>0.9sub>Nb<sub>0.1sub>O<sub>3-δsub> is selected as a case study of perovskites containing Sr and Co, which are the most active oxygen reduction catalysts known. Several bulk properties are measured, and synchrotron data are presented that provide strong evidence of substantial cobalt-oxygen covalency at high temperatures. This covalent bonding may be the underlying source of the high surface activity.