Preparation of La0.75Sr0.25Cr0.5Mn0.5O3−δ fine powders by carbonate coprecipitation for solid oxide fuel cells

A range of La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ (LSCM) powders is prepared by the carbonate coprecipitation method for use as anodes in solid oxide fuel cells. The supersaturation ratio (R = [(NH₄)₂CO₃]/([La³⁺] + [Sr²⁺] + [Cr³⁺] + [Mn²⁺])) during the coprecipitation determines the relative compositions of La, Sr, Cr, and Mn. The composition of the precursor approaches the stoichiometric one at the supersaturation range of 4 ≤ R ≤ 12.5, whereas Sr and Mn components are deficient at R < 4 and excessive at R = 25. The fine and phase-pure LSCM powders are prepared by heat treatment at very low temperature (1000 °C) at R = 7.5 and 12.5. By contrast, the solid-state reaction requires a higher heat-treatment temperature (1400 °C). The catalytic activity of the LSCM electrodes is enhanced by using carbonate-derived powders to manipulate the electrode microstructures.     

Preparation of lanthanum tungstate membranes by tape casting technique

Lanthanum tungstate materials have been reported to show exceptional mixed proton and electron conducting behaviour at elevated temperatures and making them attractive for dense hydrogen gas separation membranes. In this work preparation of planar asymmetric lanthanum tungstate membranes was addressed. For this purpose carbon black and rice starch pore formers were evaluated for optimum substrate gas permeability. It was found that carbon black pore former results in higher level of effective porosity. Stabilization of fine lanthanum tungstate powder in ethanol based solvent media was carried out to find out optimum surfactant quantity for tape casting slurry. By combining lanthanum tungstate tapes with and without pore former defect free asymmetric membranes were produced by conventional sintering.     

Stability and performance of infiltrated La0.8Sr0.2CoxFe1−xO3 electrodes with and without Sm0.2Ce0.8O1.9 interlayers

The chemical stability of composite electrodes produced by the infiltration of La_0.8Sr_0.2Co_xFe_1−xO₃ (LSCF) into a porous yttria-stabilized zirconia (YSZ) scaffold were investigated as a function of the Co:Fe ratio in the LSCF and the LSCF calcination temperature. XRD and impedance spectroscopy results indicate that for an LSCF calcination temperature of 1123 K, reactions between the LSCF and YSZ do not occur to a significant extent. Reactions producing La₂Zr₂O₇ and SrZrO₃ at the interface were observed, however, for a calcination temperature of 1373 K and x values greater than 0.2. In addition to determining the conditions for which reactions between LSCF and YSZ occur, the effectiveness of infiltrated SDC interlayers in preventing reactions at the LSCF-YSZ interface and their influence on the overall performance of LSCF/YSZ composite electrodes was studied.     

Thermogravimetric relaxation study of the proton conductor lanthanum tungstate,La28−xW4+xO54+δv2−δ, x = 0.85

Diffusion- and surface exchange coefficients for incorporation and transport of protons and water in lanthanum tungstate, La_27.15W_4.85O_55.28v_0.73 have been determined from thermogravimetric relaxation. Tracer diffusion of protons has proved to be considerably faster than chemical diffusion of water, whereas the tracer surface exchange process is somewhat slower than its chemical counterpart. Consequently, tracer relaxations display larger critical thicknesses than the chemical ones and are moreover found to be predominantly surface controlled. The activation energy of the chemical diffusion coefficient changes above 700 °C and this transition and a corresponding change in its water vapor dependency are discussed in light of chemical diffusion of water. The activation energy of the chemical surface exchange coefficient under reducing conditions is the half of that under oxidizing. Platinum nano particles have proved to increase the rate of water incorporation under reducing conditions.     

Sintering behavior and phase transformation of YSZ-LZ composite coatings

Sintering behavior and phase transformations in yttria-stabilized zirconia (YSZ)-based thermal barrier coatings (TBCs) control their applications in gas turbines operated at high working temperatures required for improved fuel efficiency. In this work, to control the sintering behavior and reduce phase transformations in YSZ-based TBCs, lanthanum zirconate (LZ) powder was blended with the YSZ feedstock powder, and YSZ-LZ composite coatings were fabricated using the air plasma spraying method. The influence of mixture weight ratio of YSZ to LZ (75:25, 50:50, and 25:75) on the sintering behavior and phase stability of the composite coatings was investigated through the isothermal exposure test at 1100, 1300, and 1400 °C. The as-coated composites showed the pyrochlore and tetragonal phases, indicating that the phases are LZ and YSZ, respectively. As the exposure temperature was increased, the phase transformation of YSZ from the tetragonal phase to the monoclinic phase was accelerated. The content of monoclinic phase was changed with the increasing LZ content after thermal exposure at 1300 and 1400 °C. In addition, the composites showed different sintering and bridging behaviors at the adjacent splats with the LZ content. The composites prepared with the blended feedstock powders of LZ and YSZ produced an obvious effect on the phase stability and mechanical properties.     

The role of manganese substitution on the redox behavior of La0.6Sr0.4Fe0.8Mn0.2O3-δ

Perovskite oxides such as ferrites have been widely investigated for their remarkable electrochemical activity as SOFC electrodes. However, their phase instability in reducing conditions remains an issue for anode application. The role of Mn substitution into B-site of La_0.6Sr_0.4FeO_3-δ (LSF) perovskite oxide was investigated. New insights on the structural evolution of La_0.6Sr_0.4Fe_0.8Mn_0.2O_3-δ (LSFMn) upon high temperature reduction were revealed. In oxidizing atmosphere, Mn substitution reduces the oxygen vacancy concentration while, switching to reducing conditions, it drives the transition from rhombohedral perovskite to single Ruddlesden-Popper phase, affecting the Fe⁰ exsolution. Redox-cycles of LSFMn were investigated and the properties of re-oxidized compounds were highlighted. The effect of Mn substitution on perovskite conductivity was also evaluated both in oxidizing and reducing conditions.     

Direct Applicability of La0.6Sr0.4CoO3 – δ Thin Film Cathode to Yttria Stabilised Zirconia Electrolytes at T ≤ 650 °C

For investigating the direct applicability of highly active cobalt containing cathodes on YSZ electrolytes at a lower processing and operating temperature range (T ≤ 650 °C), we fabricated a thin film lanthanum strontium cobalt oxide (LSC) cathode on an yttria stabilised zirconia (YSZ)‐based solid oxide fuel cell (SOFC) via pulsed laser deposition (PLD). Its electrochemical performance (5.9 mW cm^–2 at 0.7 V, 650 °C) was significantly inferior to that (595 mW cm^–2 at 0.7 V, 650 °C) of an SOFC with a thin (t ∼ 200 nm) gadolinium doped ceria (GDC) buffer layer in between the LSC thin film cathode and the YSZ electrolyte. It implies that even though the cathode processing and cell operating temperatures were strictly controlled not to exceed 650 °C, the direct application of LSC on YSZ should be avoided. The origin of the cell performance deterioration is thoroughly studied by glancing angle X‐ray diffraction (GAXRD) and transmission electron microscopy (TEM), and the decomposition of the cathode and diffusion of La and Sr into YSZ were observed when LSC directly contacted YSZ.