Mixed-conducting LSC/CGO and Ag/CGO composites for passive oxygen separation membranes

Abstract

Dense ceramic oxygen separation membranes can pass oxygen perm-selectively at elevated temperature and have potential for improving the performance and reducing the cost of several industrial processes: such as the conversion of natural gas to syngas, or to separate oxygen from air for oxy-fuel combustion in electricity generation (to reduce NOx emissions and facilitate CO2 sequestration). These pressure-driven solid state membranes are based on fast oxygen-ion conducting ceramics, but also need a compensating flow of electrons. Dual-phase composites are attractive since they provide an extra degree of freedom, compared with single phase membranes, for optimising the overall membrane performance. In this study, composites containing gadolinia doped ceria (CGO, Ce0.9Gd0.1O2- ) and either strontium-doped lanthanum cobaltite (LSC, La0.9Sr0.1CoO3- or La0.6Sr0.4CoO3- ) or silver (Ag) were investigated for possible application as oxygen separation membranes in oxy-fuel combustion system. These should combine the high oxygen ion conductivity of CGO with the high electronic conductivity and fast oxygen surface exchange of LSC or silver. Dense mixed-conducting composite materials of LSC/CGO (prepared by powder mixing and sintering) and Ag/CGO composites (prepared by silver plus copper oxide infiltration method) showed high relative density (above 95%), low background gas leakage and also good electrical conduction. The percolation threshold of the electronic conducting component was determined to be approximately 20 vol.% for both LSC compositions and 14 vol.% for Ag. Isotopic exchange and depth profiling by secondary ion mass spectrometry was used to investigated the oxygen tracer diffusion (D*) and surface exchange coefficient (k*) of the composites. Composites just above the electronic percolation threshold exhibited high solid state oxygen diffusivity, fast surface exchange activity moderate thermal expansion and sufficient mechanical strength thus combining the benefits of their constituent materials. The preliminary work on oxygen permeation measurement showed that the reasonable magnitude of oxygen fluxes is possible to be achieved. This indicates that the composites of LSC/CGO and Ag/CGO are promising for further development as passive oxygen separation membranes.