Search

Novel thin film composite electrolyte membranes, prepared by dispersion of nano-sized SiO2 particles in the solid acid compound KH(PO3H), can be operated under both oxidizing and reducing conditions. Long-term stable proton conductivity is observed at not, vert, similar140 °C, i.e., slightly above the superprotonic phase transition temperature of KH(PO3H), under conditions of relatively low humidification (pH2O ≈ 0.02 atm).

Electrical conductivity studies have been performed of solid acid phosphites MH(PO3H) with M = Li+, Na+, K+, Rb+, Cs+, NH4+. Superprotonic conductivity following a phase transition in the temperature range from 120 to 190 °C is observed for the monoclinic forms, including Na+, K+, Rb+, Cs+ and NH4+ derivatives. At temperatures beyond the superprotonic transition temperature, thermal decomposition occurs in the case of the Na+, Rb+, and NH4+ salts. No superprotonic phase transition is observed for orthorhombic LiH(PO3H). The magnitude of the superprotonic conductivity of KH(PO3H) and CsH(PO3H), which is known to be stable under hydrogen atmospheres from literature, amounts to 4.2 · 10− 3 Ω− 1 cm− 1 (at 140 °C) and 3 · 10− 3 Ω− 1 cm− 1 (at 160 °C), respectively, which values are comparable to that of well known CsHSO4.

Dense La0.4Sr0.6Co0.2Fe0.8O3-δ oxygen-permeable membranes of different thickness were prepared by solid-state reaction. The oxygen flux facilitated by an oxygen partial pressure difference across the oxide membrane was measured at elevated temperatures. It is revealed that oxygen permeation flux is entirely controlled by the transport of oxide ions in the bulk of the membrane in the thickness range of 1.25−2.46 mm. When the thickness is decreased to 0.62 mm, it becomes jointly controlled by the oxygen exchange across the gas and solid interfaces. An electrochemical approach is adopted to analyze the thickness dependence of the oxygen flux. It is shown that the interfacial process is more sensitive to the change of temperature, as evidenced by the larger activation energy for the surface oxygen exchange (188.2 ± 2.2 kJ mol-1), than that for the bulk transport (93.7 ± 1.7 kJ mol-1).

A series of six cathodes Sr0.15La0.85MnO3 (SLM) on yttria-stabilized zirconia with different morphology of the electrode/electrolyte interface were characterized by ac impedance and dc polarization measurements. It is found that the electrode kinetics at elevated temperature (945°C) are governed by two serial processes. An activation process can be identified to occur at high cathodic overpotential, whereas a transport process competes with charge-transfer at comparatively low overpotential. Attention is drawn to the profound change in the electrocatalytic properties of Sr0.15La0.85MnO3 upon current passage and its influence in elucidation of the interfacial kinetics.

Zr0.84Y0.16O1.92−La0.8Sr0.2Cr0.5Fe0.5O3−δ (YSZ-LSCrF) dual-phase composite hollow fiber membranes were prepared by a combined phase-inversion and sintering method. The shell surface of the hollow fiber membrane was modified with Ce0.8Sm0.2O1.9 (SDC) via a drop−coating method. As the rate of oxygen permeation of the unmodified membrane is partly controlled by the surface exchange kinetics, coating of a porous layer of SDC on the shell side (oxygen reduction side) of the hollow fiber membrane was found to improve its oxygen permeability. Rate enhancements up to 113 and 48% were observed, yielding a maximum oxygen flux of 0.32 and 4.53 mL min−1 cm−2 under air/helium and air/CO gradients at 950 °C, respectively. Excess coating of SDC was found to induce significant gas phase transport limitations and hence lower the rate of oxygen permeation. A model was proposed to calculate the length of triple phase boundaries (TPBs) for the coated dual-phase composite membrane and to explain the effect of coating on the oxygen permeability.

Two processes in one space: Methane, the main component of natural gas, can be converted into syngas efficiently in a two-stage oxygen-permeable ceramic membrane reactor by means of integrated oxidation and reforming processes (see picture). This could be a cheaper alternative to the current steam-reforming of methane.

Electrical conductivity relaxation is used for monitoring the cubic-to-hexagonal phase transition in the perovskite-type oxide Ba0.5Sr0.5Co0.8Fe0.2O3−δ. After in situ annealing at 1173 K, at which temperature the cubic polymorph is stable, electrical conductivity relaxation experiments are conducted during long-term annealing at 1073 K. The decreases in the surface exchange and chemical diffusion coefficients with time due to the sluggish phase transition are found to be correlated. It is demonstrated that B-site doping with Zr to an amount as low as 3 mol % stabilizes the high-temperature perovskite cubic phase of Ba0.5Sr0.5Co0.8Fe0.2O3−δ, with preservation of its high oxygen transport and exchange properties.

This paper is the first part of a two part series, where the effects of varying the A-site dopant on the defect chemistry, the diffusion coefficient and the surface catalytic properties of the materials (La0.6Sr0.4 − xMx)0.99Co0.2Fe0.8O3 − δ, M = Sr, Ca (x = 0.05, 0.1), Ba (x = 0.1, 0.2) (LSMFC) have been investigated. In part I, the findings on the defect chemistry are reported, while the transport properties are reported in part II. Substitution of Sr2+ ions with Ca2+ ions (smaller ionic radius) and Ba2+ ions (larger ionic radius) strains the crystal structure differently for each composition while keeping the average valence of the cations constant. The Ba2+ containing materials show the largest oxygen loss at elevated temperatures, while the purely Sr2+ doped material showed the smallest oxygen loss. This was reflected in the partial oxidation entropy of the materials. The measured oxygen loss was modelled with point defect chemistry models. Measurements at very low pO2 showed several phase transitions.

The stabilizing and destabilizing mechanism in the action of acetylacetone on zirconium propoxide precursors is revealed; the nature of heteroleptic intermediates provides an explanation

The catalytic and electrocatalytic behavior of the La0.6Sr0.4Co0.8Fe0.2O3 (LSCF) perovskite deposited on yttria-stabilized zirconia (YSZ) was studied during the reaction of methane oxidation. Experiments were carried out in a well-mixed (CSTR) reactor at atmospheric pressure, in the 600–900°C range. When, instead of co-feeding with methane in the gas phase, oxygen was electrochemically supplied as O2−, considerable changes in the methane conversion and product selectivity were observed. Catalytic and electrocatalytic results were compared to those obtained when the LSCF served as a dense mixed-conducting membrane supplying oxygen to the methane feed stream because of the oxygen partial-pressure gradient across the membrane.

The interface microstructure of the state-of-the-art cathode material for solid oxide fuel cells, SrxLa1–xMnO3 (SLM), was investigated with respect to its electrochemical performance. The interface microstructure was characterized by grain size and coverage of SLM on the electrolyte surface. Variation of the grain size was obtained by using three different sintering temperatures, whereas variation of the coverage was obtained by using two powders with a different morphology. This resulted in a set of six cathode/electrolyte samples with different combinations of grain size and SLM coverage at the interface. The cathode overpotential, as a measure for the electrochemical performance, could not be related to the length of the three-phase boundary. Based on the constriction resistance occurring in the electrolyte a model was developed which provides an estimate for the width of the active three-phase boundary zone.This zone is most likely to extend outside the cathode particle across the zirconia surface. The width calculated in this way was found to vary in the range of 0.03 to 0.07 µm for the different electrode microstructures. It is argued that the actual values may be smaller by one or two orders of magnitude.

Oxygen permeation measurements in air/He gradients were performed on dense La1 ¿ xSrxFeO3 ¿ ¿ membranes in the composition range x = 0.1¿0.4 and temperature range 1123¿1323 K. Pretreatment of the lower oxygen partial pressure side of the membranes in a CO-containing atmosphere for several hours at 1273 K led to higher oxygen fluxes, which were in the range of 0.1¿4.5 mmol m¿2 s¿1. After treatment, the observed oxygen fluxes could be described in terms of bulk diffusion-limited permeation behaviour. Experimental evidence for a bulk-diffusion controlled flux was found from thickness dependence measurements on membranes with thicknesses between 0.5 mm and 2.0 mm. Model calculations, based on Wagner theory in conjunction with data of oxygen nonstoichiometry and vacancy diffusion coefficients from literature, were performed. The experimental flux values deviated from the model calculations with factors up to 2.5. Adjustment of the value of the vacancy diffusion coefficient led to good agreement between the experimental data and the model calculations. The calculated vacancy diffusion coefficients Dv0 were virtually independent of composition and were found to be in the range 5.3¿9.3 × 10¿6 cm2 s¿1.