Effects of copper doping on microstructural evolution and oxygen permeability of Ce0.8Sm0.2O2-δ-Sm0.6Sr0.4Fe1-xCuxO3-δ dual-phase oxygen permeable membranes

Abstract

Ce0.8Sm0.2O2-δ(wt.70 %)-Sm0.6Sr0.4Fe1-xCuxO3-δ(wt.30 %) (SDC-SSFC) dual-phase oxygen permeable membranes were prepared by one-pot EDTA-citric acid combined complexing method. Effects of copper doping content on crystallographic phase, microstructure and oxygen permeability were deeply investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) combined with energy-dispersive X-ray spectroscopy (EDXS). Systematic studies reveal that SDC as oxygen ion conductors and SSFC as electron conductor display an excellent synergistic effect only if a suitable doping content of copper was adopted. It can be found that Ce0.8Sm0.2O2-δ-Sm0.6Sr0.4Fe0.9Cu0.1O3-δ exhibits the highest oxygen permeation flux of up to about 0.61 ml cm−2 at 950 °C and lower oxygen permeation activation energy, which displays nearly a two-fold increase in oxygen permeability compared with the sample without any copper doping. If the copper doping content in B-site of SSFC perovskite exceeds about 30 %, a third phase, i.e., CuO, would appear in the bulk of SDC-SSFC dual-phase membrane and the grain size of CuO tend to gradually increase which would degrade the oxygen permeability of SDC-SSFC dual-phase membrane. Kinetical analysis showed that the critical membrane thickness (Lc) of Ce0.8Sm0.2O2-δ-Sm0.6Sr0.4Fe0.9Cu0.1O3-δ membrane is close to approximately 0.6 mm, i.e., if the membrane thickness is larger than 0.6 mm, its rate-determining step would transform into the bulk-diffusion exchange from surface exchange. Meanwhile, Ce0.8Sm0.2O2-δ-Sm0.6Sr0.4Fe0.9Cu0.1O3-δ membrane exhibits a stable oxygen permeation flux of up to 0.32 ml cm−2·min−1 in pure CO2 atmosphere for more than 120 h without any degradation.