Importance of oxygen spillover for fuel oxidation on Ni/YSZ anodes in solid oxide fuel cells.

Using first principles simulations and the Monte Carlo method, the optimal structure of the triple-phase boundaries (TPB) of the Ni/Yttria-Stabilized Zirconia (YSZ) anode in solid oxide fuel cells (SOFCs) is determined. Based on the new TPB microstructures we reveal different reaction pathways for H2 and CO oxidation. In contrast to what was believed in previous theoretical studies, we find that the O spillover from YSZ to Ni plays a vital role in electrochemical reactions. The H2 oxidation reaction can proceed very rapidly, by means of both the H and O spillovers, whereas the CO oxidation can only proceed through the O spillover pathway. Further understanding of the roles of defects and dopants allows us to explain puzzling experimental observations and to predict ways to improve the catalytic performance of SOFCs.