Low thermal expansion transition metal oxides for reduced temperature solid oxide fuel cell cathodes

Solid oxide fuel cells (SOFCs) are power generation devices that offer many great advantages compared to lower temperature fuel cells; for example, they are able to operate at high efficiencies without the use of expensive precious metal catalysts, and are also able to directly utilize hydrocarbon fuels without the need of an external reformer. Unfortunately, the conventional high operating temperature of these devices (T ≈ 1000 °C) requires the use of expensive, specialized materials that can withstand these high temperatures. This issue has generated considerable interest in reducing the operating temperature of these devices to the intermediate-temperature (600 – 800 °C) to allow for the use of less-expensive materials, such as stainless steel. However, the conventionally utilized SOFC cathode materials exhibit poor electrochemical performance at these reduced temperatures. Currently considered alternative intermediate temperature cathodes, such as Ba₀.₅Sr₀.₅Co₀.₈Fe₀.₂O₃₋δ (BSCF), offer improved performance, but have a large thermal expansion coefficient (TEC), leading to cell failure. In light of these issues, this dissertation focuses on the development of low TEC cathodes for intermediate temperature SOFCS (IT-SOFCs). The primary focus of this dissertation is on the swedenborgite-type RBaCo₃MO₇₊δ (R = Y, In, and Ca; M = Zn and Fe) series of cathodes. Due to their tetrahedrally-coordinated M site, the cobalt ions in these materials do not undergo a spin-state transition, and have TECs similar to conventional SOFC electrolyte materials. The long-term phase stability of these materials was addressed, and it was discovered that a slight In substitution significantly promoted phase stability. In the Y₁₋[subscript x] In [subscript x] BaCo₃ZnO₇₊δ series, it was observed that x = 0.1 successfully stabilized the phase without observable degradation of performance. Similarly, a high-Ca content material (Y₀.₅In₀.₁Ca₀.₄BaCo₃ZnO₇₊δ) was successfully stabilized, though Ca is known to destabilize the phase; furthermore, this compound showed improved performance compared to YBaCo₃ZnO₇₊δ. Lastly, the replacement of the performance-inhibiting Zn with Fe was investigated, and the Y₀.₉In₀.₁BaCo₃Zn₀.₆Fe₀.₄O₇₊δ sample showed low temperature performance rivaling BSCF. Other work in this dissertation focuses on the application of functional silver materials for use in SOFCs, with good performance; these materials were easily manufactured, and they showed performance drastically greater than the conventionally utilized platinum.