Filipe M. Figueiredo

Ceria-based materials for solid oxide fuel cells

This paper is focused on the comparative analysis of data on electronic and ionic conduction in gadolinia-doped ceria (CGO) ceramics as well as on the electrochemical properties of various oxide electrodes in contact with ceria-based solid electrolytes. Properties of electrode materials, having thermal expansion compatible with that of doped ceria, are briefly reviewed. At temperatures below 1000 K, Ce0.90Gd0.10O2−δ (CGO10) was found to possess a better stability at reduced oxygen pressures than Ce0.80Gd0.20O2−δ (CGO20). Incorporation of small amounts of praseodymium oxide into Ce0.80Gd0.20O2−δ leads to a slight improvement of the stability of CGO20 at intermediate temperatures, but the difference between electrolytic domain boundaries of the Pr-doped material and CGO10 is insignificant. Since interaction of ceria-based ceramis with electrode materials, such as lanthanum-strontium manganites, may result in the formation of low-conductive layers at the electrode/electrolyte interface, optimization of electrode fabrication conditions is needed. A good electrochemical activity in contact with CGO20 electrolyte was pointed out for electrodes of perovskite-type La0.8Sr0.2Fe0.8Co0.2O3−δ and LaFe0.5Ni0.5O3−δ, and LaCoO3−δ/La2Zr2O7 composites; surface modification of the electrode layers with praseodymium oxide results in considerable decrease of cathodic overpotentials. Using highly-dispersed ceria for the activation of SOFC anodes significantly improves the fuel cell performance.

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

Abstract Gadolinia-doped ceria electrolyte Ce 0.8 Gd 0.2 O 2− δ (CGO) and perovskite-type mixed conductor La 0.8 Sr 0.2 Fe 0.8 Co 0.2 O 3− 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 La 0.7 Sr 0.3 MnO 3− δ /Ce 0.8 Gd 0.2 O 2− 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 Permeability of Ce0.8Gd0.2 O 2 − δ ‐ La0.7Sr0.3MnO3 − δ Composite Membranes

(CGO) and (LSM) possess similar thermal expansion coefficients and were thus combined in dual‐phase membranes for oxygen separation. Studies of oxygen permeation through CGO‐LSM composite ceramics, containing similar volume fractions of the phases, showed that the oxygen transfer is limited by the bulk ionic conductivity. The oxygen conduction in the composites depends strongly on processing conditions, decreasing with interdiffusion of the phase components. Blocking oxygen ionic conduction is assumed to be due to formation of layers with low ionic conductivity at the CGO grain boundaries, caused by diffusion of lanthanum and strontium into CGO. The permeation fluxes through CGO‐LSM membranes at high feed‐side oxygen pressures (1–50 atm) exhibit Wagner‐type behavior and exceed significantly the oxygen permeability at lower oxygen pressures.

Ionic conductivity of La(Sr)Ga(Mg,M)O3−δ (M=Ti, Cr, Fe, Co, Ni): effects of transition metal dopants

Abstract Oxygen-ion conductivity of the perovskite-type solid solutions (La,Sr)Ga1−zM2O3−δ (M=Ti, Cr, Fe, Co; z=0–0.20), LaGa1−y−zMgyMzO3−δ (M=Cr, Fe, Co; y=0.10–0.20, z=0.35–0.60) and LaGa1−zNizO3−δ (z=0.20–0.50) was studied using the techniques of oxygen permeation, Faradaic efficiency, ion-blocking electrode and the e.m.f. of oxygen concentration cells. Oxygen-ion transference numbers vary from 2×10−6 to 0.98 throughout the series and p-type electronic conductivity increases with increasing transition metal content. Substitution of Ga with higher valence cations (Ti, Cr) decreases ionic conductivity whereas small amounts of Fe or Co (∼5%) increase ionic conductivity. For higher transition metal contents, lower levels of oxygen-ion conductivity and an increase in the activation energy, EA, for ionic transport, from 60 (5%-doped) to 230 kJ/mol (>40%-doped) are observed. In heavily doped phases, EA tends to decrease with temperature and, above 1170 K, values are similar to the undoped phase suggesting that an order–disorder transition takes place. Factors affecting the observed ionic conductivity trends are discussed.

Surface modification of La0.3Sr0.7CoO3−δ ceramic membranes

The dependence of oxygen permeability of dense La 0 . 3 Sr 0 . 7 CoO 3 - Φ ceramics on membrane thickness indicates significant surface exchange limitations to the permeation fluxes, which suggests a possibility to increasemembrane performance by surface activation. The cobaltite membranes with various porous layers applied onto the permeate-side surface were tested at 850-1120 K. Silver-modified La 0 . 3 Sr 0 . 7 CoO 3 membranes showed enhanced permeation at temperatures above 950 K; deposition of porous layers of PrO x and Pr 0 . 7 Sr 0 . 3 CoO 3 - Φ had no positive effect. The maximum oxygen permeability at 850-1120 K was observed in the case of porous La 0 . 3 Sr 0 . 7 CoO 3 - Φ layers with surface density about 10 mg cm - 2 . These results suggest that the surface exchange of lanthanum-strontium cobaltite membranes under an oxygen chemical potential gradient is limited by both oxygen sorption at the surface and ion diffusion through the surface oxide layers. Oxygen permeability of La 0 . 3 Sr 0 . 7 CoO 3 - Φ ceramics was found to increase with increasing grain size due to decreasing grain-boundary resistance to ionic transport.

Electron–hole conduction in Pr-doped Ce(Gd)O2−δ by faradaic efficiency and emf measurements

Abstract Non-negligible electrode polarisation in faradaic efficiency and emf electrochemical cells used for transport number determination results in apparent ion transference numbers which are lower than the true values. However, appropriate modifications of these techniques combined with use of electrodes having a high polarisation resistance, enable a precise determination of even minor electronic contributions to the total conductivity of solid electrolytes. Experimental modification of the faradaic efficiency method, taking into account the electrode polarisation resistance, is proposed and verified using Ce 0.80 Gd 0.18 Pr 0.02 O 2− δ ceramics. Substitution of 2% gadolinium cations in the lattice of Ce 0.80 Gd 0.20 O 2− δ solid electrolyte with praseodymium was found to increase the p-type electronic conductivity by 2.5–4 times, while the activation energy for the electron–hole transport decreases from 145 to 125 kJ mol −1 . The oxygen ion transference numbers of Ce 0.80 Gd 0.18 Pr 0.02 O 2− δ in air vary in the range 0.996–0.970 at 873–1223 K, decreasing with increasing temperature. No significant effect of co-doping with praseodymium on the ionic conductivity, crystal lattice and thermal expansion of ceria solid electrolyte was found.

Mixed electronic and ionic conductivity of LaCo(M)O3 (M=Ga, Cr, Fe or Ni): IV. Effect of preparation method on oxygen transport in LaCoO3−δ

Abstract Measurements of oxygen permeation through dense LaCoO 3− δ membranes prepared by different routes (standard ceramic or from organic precursors) showed a considerable role of processing conditions and microstructure on permeation fluxes. The higher permeability observed in ceramics produced by the ceramic route was attributed to a lower grain-boundary resistance to oxygen transport. Experimental data were also compared with results of numerical modeling of oxygen transport in LaCoO 3− δ , based on isotopic diffusion data in single crystals. Ionic conduction in ceramics with smaller grain size is lower than in single crystals, suggesting a significant grain boundary resistance. In contrast, oxygen permeability of LaCoO 3− δ prepared by the standard ceramic synthesis route, involving higher sintering temperatures is higher than expected. This suggests easy diffusion along grain boundaries. The influence of the ceramic microstructure on total electrical conductivity and thermal expansion of lanthanum cobaltite ceramics was found negligible.

Bulk and grain boundary conductivity of Ca0.97Ti1−xFexO3−δ materials

Abstract Polycrystalline Ca 0.97 Ti 1− x Fe x O 3− δ samples with x =0, 0.01, 0.035, 0.07 and 0.15 were prepared by a conventional ceramic route and characterised by impedance spectroscopy at different temperatures in air. Spectra obtained for samples with low iron contents ( x

Oxygen permeability and Faradaic efficiency of Ce0.8Gd0.2O2–δ–La0.7Sr0.3MnO3–δ composites

Composite Ce0.8Gd0.2O2−δ (CGO, solid electrolyte) and La0.7Sr0.3MnO3−δ (LSM, electronic conductor) ceramics were tested as dual-phase membranes for oxygen separation. Oxygen permeation through CGO–LSM composite ceramics containing similar percentages of both phases is limited by bulk ionic transport. In contrast to electronic transport, oxygen ion transport in these composites depends strongly on processing conditions, decreasing with interdiffusion of components. Oxygen ions are blocked by low ionic conductivity layers formed by diffusion of cations of LSM to the contacts between CGO grains. Testing of CGO–LSM membranes at high oxygen pressures (1–50 atm) showed that the composite ceramics are stable in these conditions and exhibit Wagner-type permeation fluxes.

Processing, microstructure and properties of LaCoO3-δ ceramics

Abstract Dense lanthanum cobaltite ceramics with different microstructures were prepared using several processing procedures, including chemical and ceramic synthesis routes. XRD, SEM, dilatometry, total electrical conductivity and oxygen permeability measurements were used for the characterization of these materials. Submicrometer size LaCoO 3− δ powders obtained via a cellulose-precursor technique or a combustion synthesis process showed much higher sinterability and poor compactability with respect to the powder prepared by the standard ceramic procedure. The influence of the processing route on crystal lattice, electronic conductivity and thermal expansion of LaCoO 3− δ ceramics was negligible. At the same time, the preparation technique significantly affects the ceramic microstructure and the oxygen ionic conductivity. LaCoO 3− δ membranes prepared via the standard ceramic technique, involving higher sintering temperatures, exhibit significantly higher oxygen permeation fluxes than ceramics prepared from organic precursors. This behavior was attributed to the effect of grain-boundary resistivity to ionic transport, which decreases with increasing sintering temperature and grain size, as commonly found for oxide solid electrolytes.