RESUMEN
Minimizing the overpotential at the air electrode of solid oxide fuel cells (SOFC) is one of the key challenges regarding a broad applicability of this technology. Next to novel materials and geometry optimization, surface modification is a promising and flexible method to alter the oxygen exchange kinetics at SOFC cathode surfaces. Despite extensive research, the mechanism behind the effect of surface decorations is still under debate. Moreover, for Sr decoration, previous studies yielded conflicting results, reporting either a beneficial or a detrimental impact on the oxygen exchange kinetics. In this contribution, in situ impedance spectroscopy during pulsed laser deposition was used to investigate the effect of Sr containing decorations under different deposition conditions. Depending on deposition temperature and interactions with the gas phase, opposing effects of Sr decoration were found. In combination with near-ambient pressure X-ray photoelectron spectroscopy and non-ambient X-ray diffractometry, it was possible to trace this phenomenon back to different chemical environments of the surface Sr. At high temperatures, Sr is deposited as SrO, which can have a beneficial effect on the oxygen exchange kinetics. At low temperatures, SrCO3 adsorbates are formed from trace amounts of CO2 in the measurement atmosphere, causing a decrease of the oxygen exchange rate. These results are in excellent agreement with the concept of surface acidity as a descriptor for the effect of surface decorations, providing further insight into the oxygen exchange kinetics on SOFC cathode surfaces and its degradation. In addition, this study shows that Sr segregation itself initially does not lead to performance degradation but that segregated SrO readily reacts with acidic compounds, reducing the catalytic capability of mixed conducting oxides.
RESUMEN
La0.6Sr0.4FeO3-δ (LSF) electrodes were grown on different electrolyte substrates by pulsed laser deposition (PLD) and their oxygen exchange reaction (OER) resistance was tracked in real-time by in situ PLD impedance spectroscopy (i-PLD) inside the PLD chamber. This enables measurements on pristine surfaces free from any contaminations and the direct observation of thickness dependent properties. As substrates, yttria-stabilized zirconia single crystals (YSZ) were used for polycrystalline LSF growth and La0.95Sr0.05Ga0.95Mg0.05O3-δ (LSGM) single crystals or YSZ single crystals with a 5 nm buffer-layer of Gd0.2Ce0.8O2-δ for epitaxial LSF film growth. While polycrystalline LSF electrodes show a constant OER resistance in a broad thickness range, epitaxially grown LSF electrodes exhibit a continuous and strong increase of the OER resistance with film thickness until ≈60 nm. In addition, the activation energy of the OER resistance increases by 0.23 eV compared to polycrystalline LSF. High resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) measurements reveal an increasing contraction of the out-of-plane lattice parameter in the epitaxial LSF electrodes over electrode thickness. Defect thermodynamic simulations suggest that the decrease of the LSF unit cell volume is accompanied by a lowering of the oxygen vacancy concentration, explaining both the resistive increase and the increased activation energy.
RESUMEN
In this study, five different mixed conducting cathode materials were grown as dense thin films by pulsed laser deposition (PLD) and characterized via in situ impedance spectroscopy directly after growth inside the PLD chamber (i-PLD). This technique enables quantification of the oxygen reduction kinetics on pristine and contaminant-free mixed conducting surfaces. The measurements reveal excellent catalytic performance of all pristine materials with polarization resistances being up to two orders of magnitude lower than those previously reported in the literature. For instance, on dense La0.6Sr0.4CoO3-δ thin films, an area specific surface resistance of â¼0.2 Ω cm2 at 600 °C in synthetic air was found, while values usually >1 Ω cm2 are measured in conventional ex situ measurement setups. While surfaces after i-PLD measurements were very clean, ambient pressure X-ray photoelectron spectroscopy (AP-XPS) measurements found that all samples measured in other setups were contaminated with sulfate adsorbates. In situ impedance spectroscopy during AP-XPS revealed that already trace amounts of sulfur present in high purity gases accumulate quickly on pristine surfaces and lead to strongly increased surface polarization resistances, even before the formation of a SrSO4 secondary phase. Accordingly, the inherent excellent catalytic properties of this important class of materials were often inaccessible so far. As a proof of concept, the fast kinetics observed on sulfate-free surfaces were also realized in ex situ measurements with a gas purification setup and further reduces the sulfur concentration in the high purity gas.
RESUMEN
The oxygen exchange reaction mechanism on truly pristine surfaces of SOFC cathode materials (La0.6Sr0.4CoO3-δ = LSC, La0.6Sr0.4FeO3-δ = LSF, (La0.6Sr0.4)0.98Pt0.02FeO3-δ = Pt:LSF, SrTi0.3Fe0.7O3-δ = STF, Pr0.1Ce0.9O2-δ = PCO and La0.6Sr0.4MnO3-δ = LSM) was investigated employing in situ impedance spectroscopy during pulsed laser deposition (i-PLD) over a wide temperature and p(O2) range. Besides demonstrating the often astonishing catalytic capabilities of the materials, it is possible to discuss the oxygen exchange reaction mechanism based on experiments on clean surfaces unaltered by external degradation processes. All investigated materials with at least moderate ionic conductivity (i.e. all except LSM) exhibit polarization resistances with very similar p(O2)- and T-dependences, mostly differing only in absolute value. In combination with non-equilibrium measurements under polarization and defect chemical model calculations, these results elucidate several aspects of the oxygen exchange reaction mechanism and refine the understanding of the role oxygen vacancies and electronic charge carriers play in the oxygen exchange reaction. It was found that a major part of the effective activation energy of the surface exchange reaction, which is observed during equilibrium measurements, originates from thermally activated charge carrier concentrations. Electrode polarization was therefore used to control defect concentrations and to extract concentration amended activation energies, which prove to be drastically different for oxygen incorporation and evolution (0.26 vs. 2.05 eV for LSF).
RESUMEN
Accelerating the oxygen reduction kinetics of solid oxide fuel cell (SOFC) cathodes is crucial to improve their efficiency and thus to provide the basis for an economically feasible application of intermediate temperature SOFCs. In this work, minor amounts of Pt were doped into lanthanum strontium ferrite (LSF) thin film electrodes to modulate the material's oxygen exchange performance. Surprisingly, Pt was found to be incorporated on the B-site of the perovskite electrode as non metallic Pt4+. The polarization resistance of LSF thin film electrodes with and without additional Pt surface doping was compared directly after film growth employing in situ electrochemical impedance spectroscopy inside a PLD chamber (i-PLD). This technique enables observation of the polarization resistance of pristine electrodes unaltered by degradation or any external contamination of the electrode surface. Moreover, growth of multi-layers of materials with different compositions on the very same single crystalline electrolyte substrate combined with in situ impedance measurements allow excellent comparability of different materials. Even a 5 nm layer of Pt doped LSF (1.5 at% Pt), i.e. a Pt loading of 80 ng cm-2, improved the polarization resistance by a factor of about 2.5. In addition, p(O2) and temperature dependent impedance measurements on both pure and Pt doped LSF were performed in situ and obtained similar activation energies and p(O2) dependence of the polarization resistance, which allow us to make far reaching mechanistic conclusions indicating that Pt4+ introduces additional active sites.
RESUMEN
Perovskite-type oxide materials (nominal composition ABO3) are a very versatile class of materials, and their properties are tuneable by varying and doping A- and B-site cations. When the B-site contains easily reducible cations (e.g. Fe, Co or Ni), these can exsolve under reducing conditions and form metallic nanoparticles on the surface. This process is very interesting as a novel route for the preparation of catalysts, since oxide surfaces decorated with finely dispersed catalytically active (often metallic) nanoparticles are a key requirement for excellent catalyst performance. Five doped perovskites, namely, La0.9Ca0.1FeO3-δ, La0.6Ca0.4FeO3-δ, Nd0.9Ca0.1FeO3-δ, Nd0.6Ca0.4FeO3-δ and Nd0.6Ca0.4Fe0.9Co0.1O3-δ, have been synthesized and characterized by experimental and theoretical methods with respect to their crystal structures, electronic properties, morphology and exsolution behaviour. All are capable of exsolving Fe and/or Co. Special emphasis has been placed on the influence of the A-site elemental composition on structure and exsolution capability. Using Nd instead of La increased structural distortions and, at the same time, hindered exsolution. Increasing the amount of Ca doping also increased distortions and additionally changed the Fe oxidation states, resulting in exsolution being shifted to higher temperatures as well. Using the easily reducible element Co as the B-site dopant significantly facilitated the exsolution process and led to much smaller and homogeneously distributed exsolved particles. Therefore, the Co-doped perovskite is a promising material for applications in catalysis, even more so as Co is catalytically a highly active element. The results show that fine-tuning of the perovskite composition will allow tailored exsolution of nanoparticles, which can be used for highly sophisticated catalyst design.
RESUMEN
A single crystalline SrTiO3 working electrode in a zirconia-based solid oxide electrochemical cell is illuminated by UV light at temperatures of 360-460 °C. In addition to photovoltaic effects, this leads to the build-up of a battery-type voltage up to more than 300 mV. After switching off UV light, this voltage only slowly decays. It is caused by UV-induced oxygen incorporation into the mixed conducting working electrode and thus by changes of the oxygen stoichiometry δ in SrTiO3-δ under UV illumination. These changes of the oxygen content could be followed in time-dependent voltage measurements and also manifest themselves in time-dependent resistance changes during and after UV illumination. Discharge currents measured after UV illumination reveal that a large fraction of the existing oxygen vacancies in SrTiO3 become filled under UV light. Additional measurements on cells with TiO2 thin film electrodes show the broader applicability of this novel approach for transforming light into chemical energy and thus the feasibility of solid oxide photoelectrochemical cells (SOPECs) in general and of a "light-charged oxygen battery" in particular.
RESUMEN
An array of analytical methods including surface area determination by gas adsorption using the Brunauer, Emmett, Teller (BET) method, combustion analysis, XRD, ToF-SIMS, TEM and impedance spectroscopy has been used to investigate the interaction of gadolinia doped ceria (GDC) with hydrogen sulphide containing reducing atmospheres. It is shown that sulphur is incorporated into the GDC bulk and might lead to phase changes. Additionally, high concentrations of silicon are found on the surface of model composite microelectrodes. Based on these data, a model is proposed to explain the multi-facetted electrochemical degradation behaviour encountered during long term electrochemical measurements. While electrochemical bulk properties of GDC stay largely unaffected, the surface polarisation resistance is dramatically changed, due to silicon segregation and reaction with adsorbed sulphur.
RESUMEN
ABSTRACT: A solid oxide electrolysis cell (SOEC) with a model-type La0.6Sr0.4FeO3-δ thin-film cathode (working electrode) on an yttria-stabilized zirconia electrolyte and a porous La0.6Sr0.4Co0.2Fe0.8O3-δ counterelectrode was operated in wet argon gas at the cathode. The hydrogen formation rate in the cathode compartment was quantified by mass spectrometry. Determination of the current as well as outlet gas composition revealed the electrochemical reduction of some residual oxygen in the cathodic compartment. Quantitative correlation between gas composition changes and current flow was possible. At 640 °C a water-to-hydrogen conversion rate of ca. 4 % was found at -1.5 V versus a reversible counterelectrode in 1 % oxygen. Onset of hydrogen formation could already be detected at voltages as low as -0.3 V. This reflects a fundamental difference between steam electrolysis and electrolysis of liquid water: substantial hydrogen production in a SOEC is already possible at pressures much below ambient. This causes difficulties in determining the cathodic overpotential of such a cell.
RESUMEN
In this study the electrochemically active region of oxygen incorporation into yttria stabilized zirconia (YSZ) was visualized by means of (18)O tracer incorporation experiments on dense Pt thin film microelectrodes combined with ToF-SIMS analysis. The localization and the shape of the incorporation zone were found to strongly depend on the polarization of the electrode. In case of lower overpotentials the active zone next to the three phase boundary (TPB) was frame-shaped and located beneath the Pt electrode. Increases in polarization led to an extension of the incorporation zone along the free YSZ surface. Owing to the low temperature of 300-330 °C a profile-broadening caused by diffusion in YSZ could be minimized and quantitatively separated from the measured profiles. The TPB-width (i.e. the decay length of electrochemical activity) was determined to be approximately 1.0-1.3 µm at these temperatures.