In situ studies of fuel oxidation in solid oxide fuel cells.

Existing electrochemical experiments and models of fuel oxidation postulate about the importance of different oxidation pathways and relative fuel conversion efficiencies, but specific information is often lacking. Experiments described below present the first direct, in situ measurements of relevant chemical species formed on solid oxide fuel cell (SOFC) cermet anodes operating with both butane and CO fuel feeds. Raman spectroscopy is used to acquire vibrational spectra from SOFC anodes at 715 degrees C during operation. Both C4H10 and CO form graphitic intermediates. In the limit of a large oxide flux, excess butane forms ordered graphite but only transiently. At higher cell potentials (e.g., less current being drawn) ordered and disordered graphite form on the Ni cermet anode following exposure to butane, and under open circuit voltage (OCV) conditions the graphite persists indefinitely. The chemistry of CO oxidation is such that ordered graphite and a Ni-COO intermediate form only at intermediate cell potentials. Concurrent voltammetry studies show that the formation of graphite with butane at OCV leads first to decreased cell performance after exposure to 25 cm3 butane, then recovered performance after 75 cm3. CO voltammetry data show that at lower potentials the oxide flux through the YSZ electrolyte is sufficient to oxidize the Ni in the anode especially near the interface with the electrolyte.