Ceria-based Nanostructured Materials for Low-Temperature Solid Oxide Fuel Cells (2012)

As one of the most efficient and environmentally benign energy conversion devices, solid oxide fuel cells (SOFC) have attracted much attention in recent years. Conventional SOFC with yttria-stabilized zirconia as electrolyte require high operation temperature (800-1000 °C), which causes significant problems like material degradation, as well as other technological complications and economic barrier for wider applications. Therefore, there is a broad interest in reducing the operation temperature of SOFCs. One of the most promising ways to develop low-temperature SOFCs (LTSOFC) is to explore effective materials for each component with improved properties. So in this thesis, we are aiming to design and fabricate ceria-based nanocomposite materials for electrolyte and electrodes of LTSOFC by a novel nanocomposite approach. In the first part of the thesis, novel core-shell doped ceria/Na2CO3 nanocomposite was fabricated and investigated as electrolytes materials of LTSOFC. Two types of doped ceria were selected as the main phase for nanocomposite: samarium doped ceria (SDC) and calcium doped ceria (CDC). The core-shell SDC/Na2CO3 nanocomposite particles are smaller than 100 nm with amorphous Na2CO3 shell of 4~6 nm in thickness. The ionic conductivity of nanocomposite electrolytes were investigated by EIS and four-probe d.c. method, which demonstrated much enhanced ionic conductivities compared to the single phase oxides. The thermal stability of such nanocomposite has also been investigated based on XRD, BET, SEM and TGA characterization after annealing samples at various temperatures. Such nanocomposite was applied in LTSOFCs with an excellent power density of 0.8 Wcm-2 at 550 °C. The high performances together with notable thermal stability prove the doped ceria/Na2CO3 nanocomposite as a potential electrolyte material for long-term LTSOFCs. In the second part of the thesis, a novel template-, surfactant-free chemical synthetic route has been successfully developed for the controlled synthesis of hierarchically structured CeO2 with nanowires and mesoporous microspheres morphologies. The new synthetic route was designed by utilizing the chelate formation between cerium ion and various carboxylates forms of citric acid. Then, hierarchically structured cerium oxide with morphologies of nanowires and mesoporous microspheres can be obtained by thermal decomposition of the two kinds of precursors. Moreover, by doping with desired elements, SDC nanowires and SDC-CuO mesoporous microspheres were prepared and used for electrolyte and anode materials, respectively, based on their unique properties depending on their morphologies. When SDC nanowires/Na2CO3 composite were applied as electrolyte for single SOFC, and it exhibited maximum power density of 522 mWcm-2 at 600 °C, which is much better than the state-of-the-art SOFCs using doped ceria as electrolytes. Besides, the mesoporous CuO-SDC composite anode was synthesized by our microwave-assisted method, which shows good phase homogeneity of both SDC and CuO. When it was applied for fuel cells, the cell had better performance than conventional CuO-SDC anode prepared by solid state method. The whole work of this thesis aims to provide a new methodology for the entire SOFC community. It is notable that our work has attracted considerable attention after publication of several attached papers. The results in this thesis may benefit the development of LTSOFC and expand the related research to a new horizon.