Superstructure formation and variation in Ni–GDC cermet anodes in SOFC

Abstract

The microstructures and spatial distributions of constituent elements at the anode in solid oxide fuel cells (SOFCs) have been characterized by analytical transmission electron microscopy (TEM). High resolution TEM observations demonstrate two different types of superstructure formation in grain interiors and at grain boundaries. Energy-filtered TEM elemental imaging qualitatively reveals that mixture zones exist at metal–ceramic grain boundaries, which is also quantitatively verified by STEM energy dispersive X-ray spectroscopy. It was apparent that both metallic Ni and the rare-earth elements Ce/Gd in gadolinium-doped ceria can diffuse into each other with equal diffusion lengths (about 100 nm). This will lead to the existence of mutual diffusion zones at grain boundaries, accompanied by a change in the valence state of the diffusing ions, as identified by electron energy-loss spectroscopy (EELS). Such mutual diffusion is believed to be the dominant factor that gives rise to superstructure formation at grain boundaries, while a different superstructure is formed at grain interiors, as a consequence solely of the reduction of Ce⁴⁺ to Ce³⁺ during H₂ treatment. This work will enhance the fundamental understanding of microstructural evolution at the anode, correlating with advancements in sample preparation in order to improve the performance of SOFC anodes.