Flame spray synthesis and characterisation of stabilised ZrO2 and CeO2 electrolyte nanopowders for SOFC applications at intermediate temperatures

Zirconia (Y0.16Zr0.84O2, Sc0.2Zr0.8O2 and Sc0.2Ce0.01Zr0.79O2) and ceria (Gd0.2Ce0.8O2) based electrolyte materials are synthesised at production rates up to 260g h−1 by a liquid-fed one-step flame spray synthesis from water-based solutions, or cost-effective rare earth nitrates with a high water content. It was found that this one-step synthesis, based on an acetylene-supported flame is able to produce phase pure and highly crystalline, nanoscale electrolyte materials. The as-synthesised powders show a cubic lattice structure independent of production rates. Specific surface areas of the powders were adjusted between 20 and 60m2 g−2, where the latter is an upper limit for the further processing of the powders in terms of screen printing. The influence of process parameters on morphology, particle size, composition, crystallinity, lattice parameter, shrinkage behaviour and coefficient of thermal expansion of the as-synthesised powders were systematically investigated by transmission electron microscopy (TEM), nitrogen adsorption (BET), X-ray diffraction (XRD) and dilatometry. Electrochemical impedance spectroscopy (EIS) was applied at temperatures between 300°C and 900°C and confirmed the high quality and the competitive electrochemical behaviour of the produced powder

An electron hole doping and soft x-ray spectroscopy study on La1-xSrxFe0.75Ni0.25O3-{\delta}

The conductivity of the electron hole and polaron conductor La1-xSrxFe0.75Ni0.25O3-{\delta}, a potential cathode material for intermediate temperature solid oxide fuel cells, was studied for 0 <x < 1 and for temperatures 300 K <T < 1250 K. In LaSrFe-oxide, an ABO3 type perovskite, A-site substitu-tion of the trivalent La3+ by the divalent Sr2+ causes oxidation of Fe3+ towards Fe4+, which forms conducting electron holes. Here we have in addition a B-site substitution by Ni. The compound for x = 0.5 is identified as the one with the highest conductivity ({\sigma} ~ 678 S/cm) and lowest activation energy for polaron conductivity (Ep = 39 meV). The evolution of the electronic structure was monitored by soft x-ray Fe and oxygen K-edge spectroscopy. Homogeneous trend for the oxida-tion state of the Fe was observed. The variation of the ambient temperature conductivity and activation energy with relative Sr content (x) shows a correlation with the ratio of (eg/eg+t2g) in Fe L3 edge up to x=0.5. The hole doping process is reflected by an almost linear trend by the variation of the pre-peaks of the oxygen K-edge soft x-ray absorption spectra

Modeling the effect of molecular architecture of comb polymers on the behavior of Al2O3 dispersions using charge/composition factors (CCF)

Erworben im Rahmen der Schweizer Nationallizenzen (www.nationallizenzen.ch)In this work, we study the effect of periodicity and PEO side-chain length in four PMAA-PEO (sodium salt) comb polymers with known molecular architecture on Al2O3 colloidal dispersions in DI water. We introduce here charge composition factors (CCF) representing charge density of the comb polymers defined as (number of charged units in a repeating unit)/(molecular weight of a repeating unit). We find, for the first time to our knowledge, that the CCF can be used along with dispersant dosage to obtain explicit functions predicting the conductivity of the dispersants in solution, the zeta potential behavior during dispersant titrations, and the isoelectric point (IEP) of the dispersions. In addition, the dosage normalized by the CCF provides a basis for comparison for the dispersants to elucidate the trends found in adsorption and potentiometric titrations. Thus, the CCF can be used as a tool for the design of improved and new comb polymer molecular architectures

Oxygen transport in La0.5Sr0.5Fe1−yTiyO3− δ ( y =0.0, 0.2) membranes

The influence of partial substitution of Fe with Ti on the oxygen transport properties of La1−x Sr x FeO3 membranes was investigated in view of their application for oxygen separation. Samples of composition $$La_{{0.5}} Sr_{{0.5}} {\text{Fe}}_{{1 - y}} {\text{Ti}}_{y} {\text{O}}_{{3 - \delta }}$$ (y=0, 0.2) were prepared and their oxygen transport properties characterised by potential step relaxation and by oxygen permeation measurement in an air/argon gradient. With the first technique, chemical diffusion $${( {\widetilde{D}} )}$$ and surface exchange (k S) coefficients were obtained by fitting of the current relaxation data to a single expression valid over the complete time range. The Ti-substituted composition gave slightly larger values of $${\widetilde{D}}$$ and k S. The trend was opposite for the measured oxygen permeation flux. In the latter experience, ordering of oxygen vacancies was observed at lower temperature, reducing significantly the performance of the materia

Properties of B-site substituted La0.5Sr0.5FeO3−δ{\mathbf{La}}_{{0.5}} {\mathbf{Sr}}_{{0.5}} {\mathbf{FeO}}_{{3 - {\mathbf{\delta }}}} perovskites for application in oxygen separation membranes

Mixed ionic-electronic conducting $$La_{0.5} Sr_{0.5} Fe_{1 - x} B_x O_{3 - \delta }$$ (B: Al, Cr, Zr, Ga, Ti, Sn, Ta, V, Mg, and In with x = 0, 0.1, 0.2) perovskite materials were produced via solid-state synthesis. In order to study the effect of B-site substitution on the expansion behavior of these materials, their thermal expansion in air up to 900°C and isothermal expansion at the same temperature from air to Ar were measured by dilatometry. Ti and Ta were found to be the most effective substitutions in suppressing the isothermal expansion. The isothermal expansion at 900°C from air to Ar was reduced by 50% by substitution of 20% Ti or 10% Ta. Therefore, these compositions were further characterized by 4-probe total DC conductivity and permeation measurements under air/Ar gradient. The total conductivity of $$La_{0.5} Sr_{0.5} FeO_{3 - \delta }$$ was decreased by more than one order of magnitude at low temperatures and from 430S/cm, which is the maximum, to around 100S/cm at 500°C with the addition of Ti and Ta. The normalized oxygen permeation of LSF at 900°C decreased from 0.18 to 0.05μmol/cm2s and 0.07μmol/cm2s with the substitution of 20% Ti and 10% Ta, respectivel

Materials design for perovskite SOFC cathodes

Abstract: This article focuses on perovskite materials for application as cathode material in solid oxide fuel cells. In order to develop new promising materials it is helpful to classify already known perovskite materials according to their properties and to identify certain tendencies. Thereby, composition-dependent structural data and materials properties are considered. Structural data under consideration are the Goldschmidt tolerance factor, which describes the stability of perovskites with respect to other structures, and the critical radius and lattice free volume, which are used as geometrical measures of ionic conductivity. These calculations are based on the ionic radii of the constituent ions and their applicability is discussed. A potential map of perovskites as a tool to classify simple ABO3 perovskite materials according to their electrical conduction behavior is critically reviewed as a structured approach to the search for new cathode materials based on more complex perovskites with A and/or B-site substitutions. This article also covers the approaches used to influence electronic and the ionic conductivity. The advantage of mixed ionic electronic conductors in terms of the oxygen exchange reaction is addressed and their important properties, namely the oxygen-exchange coefficient and the oxygen diffusion coefficient, and their effect on the oxygen reduction reaction are presented. Graphical abstrac

Fe-resonant valence band photoemission and oxygen NEXAFS study on La1-xSrxFe0.75Ni0.25O3-{\delta}

Iron resonant valance band photoemission spectra of Sr substituted LaFe0.75Ni0.25 O3-{\delta} have been recorded across the Fe 2p - 3d absorption threshold to obtain Fe specific spectral information on the 3d projected partial density of states. Comparison with La1-xSrxFeO3 resonant VB PES literature data suggests that substitution of Fe by Ni forms electron holes which are mainly O 2p character. Substitution of La by Sr increases the hole concentration to an extent that the eg structure vanishes. The variation of the eg and t2g structures is paralleled by the changes in the electrical conductivity

The effect of solvent and electric field on the size distribution of iron oxide microdots: Exploitation of self-assembly strategies for photoelectrodes

An increasing number of technologies benefit from or require patterned surfaces on a micro- and nanoscale. Methods developed to structure polymer films can be adapted to fabricate low-cost patterned ceramics using nonlithographic techniques, for example, dewetting and phase separation in thin films. In this paper we describe a simple patterning process that does not require a template and is able to produce Fe2O3 microdots with a spatial periodicity. Our method involves the dewetting of a silicon substrate by a thin metal oxide precursor film, in which the liquid film breaks up because of fluctuations in the film thickness induced by solvent evaporation or an external applied electric field. The patterning is followed by a thermal treatment at 550 °C to produce crystalline Fe2O3 microdots with a diameter range of 200 nm to 3 μ

Manufacturing of tubular dead-end membranes by continuous thermoplastic extrusion

Dense and gastight dead-end tubular Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) membranes were fabricated by thermoplastic extrusion. Optimal feedstocks for the extrusion of dead-end tubular structures were obtained for a feedstock consisting of 89.83 wt% BSCF powder, 5.63 wt% ethylene vinyl acetate (EVA), 3.56 wt% paraffin wax (PW), and 0.98 wt% stearic acid (SA). Thermogravimetric analysis (TGA) was used to determine the thermal characteristics of the feedstock and to characterize the amount of binder removed during the wicking step. Straight and round dead-end tubular membranes with wall thickness of 0.5 mm could be achieved after sintering. The gastightness test showed that the membranes were leak-tight up to a pressure of 35 bar

Silica-based composite and mixed-oxide nanoparticles from atmospheric pressure flame synthesis

Binary TiO2/SiO2 and SnO2/SiO2 nanoparticles have been synthesized by feeding evaporated precursor mixtures into an atmospheric pressure diffusion flame. Particles with controlled Si:Ti and Si:Sn ratios were produced at various flow rates of oxygen and the resulting powders were characterized by BET (Brunauer-Emmett-Teller) surface area analysis, XRD, TEM and Raman spectroscopy. In the Si-O-Ti system, mixed oxide composite particles exhibiting anatase segregation formed when the Si:Ti ratio exceeded 9.8:1, while at lower concentrations only mixed oxide single phase particles were found. Arrangement of the species and phases within the particles correspond to an intermediate equilibrium state at elevated temperature. This can be explained by rapid quenching of the particles in the flame and is in accordance with liquid phase solubility data of Ti in SiO2. In contrast, only composite particles formed in the Sn-O-Si system, with SnO2 nanoparticles predominantly found adhering to the surface of SiO2 substrate nanoparticles. Differences in the arrangement of phases and constituents within the particles were observed at constant precursor mixture concentration and the size of the resultant segregated phase was influenced by varying the flow rate of the oxidant. The above effect is due to the variation of the residence time and quenching rate experienced by the binary oxide nanoparticles when varying the oxygen flow rate and shows the flexibility of diffusion flame aerosol reactor