Development of functional layers for direct ethanol solid oxide fuel cells

Abstract

This thesis explores the synthesis and application of cerium oxide as a material in solid oxide fuel cells (SOFC) with tailored properties to decrease the processing temperature and improve the effectiveness of the catalytic and electrochemical reactions. Three approaches were investigated: i) a precipitation route for the synthesis of gadolinium doped ceria (CGO) with a sintering aid, ii) shape control of nanoceria by a hydrothermal route and application of the materials as an SOFC electrolyte and as catalytic layer for direct operation of an SOFC with ethanol, and iii) the application of a doped ceria barrier layer and nanostructured layer by a physical deposition method. The precipitation route showed to be efficient for the synthesis of nanometric ceria and the addition of Fe2O3 enhanced the sintering mechanism. It was inferred that Fe mostly segregates at the grain boundary interfaces of CGO, therefore, decreasing the grain boundary energy and favouring the elimination of the solid-gas interface. Nonetheless, Fe-rich phase precipitates were found to enhance the electronic contribution of CGO. Thus, the use of transition metal oxide as a sintering aid in ceria-based electrolytes should be controlled to avoid changes in charge transport in the electrolyte. The hydrothermal route was investigated as a novel approach to controlling the densification mechanism in the material. Through this simple route, CGO nanorods and nanocubes were synthesized by controlling the temperature. The CGO nanorods exhibited high surface energy, promoting mass diffusion at lower temperatures leading to a rapid densification and were therefore successfully applied as an electrolyte material in an electrolyte supported SOFC fully sintered at 1150 ºC operating at intermediate temperature. On the other hand, the CGO nanocubes had a very low sintering activity, attributed to their higher surface stability. The CGO nanorods and the CGO nanocubes were further evaluated to be applied as support materials for Ni-based catalysts in the steam reforming reaction of ethanol at intermediate temperature. The Ni catalyst on the CGO nanorod support displayed the highest activity after a heat treatment analogous to that for processing SOFCs. Hence, it was employed as a catalytic layer in an SOFC operating directly with ethanol. It was demonstrated that the fuel cell remained stable under operating condition with a continuous flow of anhydrous ethanol. Nanostructured doped ceria functional layers deposited by pulsed laser deposition (PLD) were applied as a barrier layer and as a cathode interlayer. The deposition of such functional layers was shown to enhance the cell's performance, having a role in both the durability, and increasing the oxygen reduction reaction sites. In summary, this thesis contributes towards the development of nanomaterials with tailored properties for application as functional layers of high performance SOFC.