Assessment of bismuth oxide-based electrolytes for composite gas separation membranes

Oxide + salt composites can be used in CO2 and NOx separation membranes, where high oxide-ion conductivity is crucial to improve performance. Pursuing this goal, the stability of three different bismuth oxide-based electrolytes (Cu + V, Y and Yb-doped) against molten alkali carbonates (Li, Na, K) or nitrates (Na, K) was tested firing them in the 450–550 °C temperature range, and with endurance tests up to 100 h. A well-known ceria-based composite was used as reference (CGO - Ce0.9Gd0.1O1.95). Oxides and composites were studied by X-ray diffraction, scanning electron microscopy and impedance spectroscopy (in air, 140–650 °C temperature range). Bi2Cu0.10V0.90O5.35 easily reacts with molten salts. Bi0.75Y0.25O1.5 and Bi0.75Yb0.25O1.5 have higher stability against molten carbonates and complete stability against molten nitrates. The Y-doped oxide stability against the molten carbonates was enhanced changing the molten salt composition (Y2O3 additions) and using lower firing temperatures. Above all, composites based on Y or Yb-doped Bi2O3 with molten alkali nitrates showed impressive 6× or 3× higher electrical conductivity at 290 °C, in air (4.88 × 10−2 and 2.41 × 10−2 S cm−1, respectively) than CGO-based composites (7.72 × 10−3 S cm−1), qualifying as promising materials for NOx separation membranes.publishe

Evaluation of porous ceramic cathode layers for solid oxide fuel cells

Sr0.15La0.85MnO3 layers with 2 and 10 u thickness, deposited on zirconia based electrolytes, were evaluated as cathodes for high temperature applications. Different electrode layers were characterized in terms of thickness, porosity, three phase boundary line per unit area (TPBL), and concentration polarization behavior. Electrodes with maximum porosity and TPBL exhibit minimum concentration polarization losses at constant current density

Oxygen transport in Ce0.8Gd0.2O2 - δ-based composite membranes

Gadolinia-doped ceria electrolyte Ce0.8Gd0.2O2 - δ (CGO) and perovskite-type mixed conductor La0.8Sr0.2Fe0.8Co0.2O3 - δ (LSFC), having compatible thermal expansion coefficients (TECs), were combined in dual-phase ceramic membranes for oxygen separation. Oxygen permeability of both LSFC and composite LSFC/CGO membranes at 970-1220 K was found to be limited by the bulk ambipolar conductivity. LSFC exhibits a relatively low ionic conductivity and high activation energy for ionic transport (∼ 200 kJ/mol) in comparison with doped ceria. As a result, oxygen permeation through LSFC/CGO composite membranes, containing similar volume fractions of the phases, is determined by the ionic transport in CGO. The permeation fluxes through LSFC/CGO and La0.7Sr0.3MnO3 - δ/Ce0.8Gd0.2O2 - δ (LSM/CGO) composites have comparable values. An increase in the p-type electronic conductivity of ceria in oxidizing conditions, which can be achieved by co-doping with variable-valence metal cations, such as Pr, leads to a greater permeability. The oxygen ionic conductivity of the composites consisting of CGO and perovskite oxides depends strongly of processing conditions, decreasing with interdiffusion of the phase components, particularly lanthanum and strontium cations from the perovskite into the CGO phase

Oxygen ionic conduction in brownmillerite CaAl0.5Fe0.5O2.5+δ

The oxygen permeability of CaAl0.5Fe0.5O2.5+δ brownmillerite membranes at 1123-1273 K was found to be limited by the bulk ionic conduction, with an activation energy of 170 kJ/mol. The ion transference numbers in air are in the range 2 × 10-3 to 5 × 10-3. The analysis of structural parameters showed that the ionic transport in the CaAl0.5Fe0.5O2.5+δ lattice is essentially along the c axis. The largest ion-migration channels are found in the perovskite-type layers formed by iron-oxygen octahedra, though diffusion in tetrahedral layers of the brownmillerite structure is also possible. Heating up to 700-800 K in air leads to losses of hyperstoichiometric oxygen, accompanied with a drastic expansion and, probably, partial disordering of the CaAl0.5Fe0.5O2.5+δ lattice. The average thermal expansion coefficients of CaAl0.5Fe0.5O2.5+δ ceramics in air are 16.7 × 10-6 and 12.6 × 10-6 K-1 at 370-850 and 930-1300 K, respectively

Oxygen permeability of LaGa0.65Ni0.20Mg0.15O3-δ ceramics: Effect of synthesis method

Oxygen ionic transport in dense LaGa0.65Ni0.20Mg0.15O3-δ membranes, prepared by the standard ceramic synthesis technique and via glycine-nitrate process (GNP), was studied using measurements of the total conductivity, oxygen permeation and faradaic efficiency (FE). At 1223 K oxygen transfer through LaGa0.65Ni0.20Mg0.15O3-δ ceramics is mainly determined by the bulk ambipolar conductivity, while decreasing temperature leads to a greater role of the surface exchange rate. In spite of moderate difference in the ceramic microstructures, the surface exchange limitations are considerably higher for the membranes prepared by the standard ceramic route compared to GNP-synthesized material. Thermal expansion and partial ionic and electronic conductivities were found essentially independent of the synthesis method. The level of oxygen ionic conduction in LaGa0.65Ni0.20Mg0.15O3-δ, characterized by the activation energy of about 150 kJ/mol and ion transference numbers in the range 1 × 10-3-5 × 10-2 at 973-1223 K, is higher than that in La(Ga,Ni)O3-δ perovskites and comparable to La2NiO4-based phases

Structural characterization of mixed conducting perovskites La(Ga,M)O3-δ ( M = Mn, Fe, Co, Ni)

Comparative analysis of the structure refinement results of perovskite-like LaGa0.5M0.5O3-δ (M = Mn, Fe, Co, Ni) and data on other LaGaO3-based phases, heavily doped with transition metal cations, shows that on doping the structural changes in these oxides follow common trends for the perovskite-type systems. The maximum ionic conductivity, observed in various perovskites when the tolerance factor values are approximately 0.96-0.97, was found to correlate with the transition from orthorhombic to rhombohedral structure and maximum lattice distortion. The perovskite unit cell distortion near the orthorhombic-rhombohedral phase boundary may hence play a positive role in the ionic transport processes. © 2002 Elsevier Science Ltd. All rights reserved