Synthesis, characterization and evaluation of cation-ordered LnBaCo₂O_5+δ as materials of oxygen permeation membranes and cathodes of SOFCs

LnBaCo₂O_5+δ (Ln = La, Pr, Nd, Sm, Gd, and Y) was synthesized via an EDTA-citrate complexing process. The particular Ln³⁺ dopant had a significant effect on the oxide's phase structure/stability, oxygen content, electrical conductivity, oxygen permeability, and cathode performance. Stable, cation-ordered oxides with layered lattice structures were obtained with medium-sized Ln³⁺ ions over a wide range of oxygen partial pressures, a property essential for applications as oxygen separation membranes and solid oxide fuel cell (SOFC) cathodes. PrBaCo₂O_5+δ demonstrated the highest oxygen flux (∼5.09 × 10^-7 mol cm^-2 s^-1 at 900 °C), but this value was still significantly lower than that of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ perovskite (∼3.1 × 10^-6 mol cm^-2 s^-1 at 900 °C). The observed difference was attributed to the much longer diffusion distance through a polycrystalline membrane with a layered lattice structure than through cubic perovskite because bulk diffusion was the rate-limiting step of permeation. An area-specific resistance of ∼0.213 Ω cm² was achieved at 600 °C with a PrBaCo₂O_5+δ cathode, suggesting that the layer-structured oxides were promising alternatives to ceramic membranes for SOFC cathodes.