Improvement of solid oxide fuel cells strongly relies on the development of cathode materials with high catalytic activity for the oxygen reduction reaction. Excellent activity was found for perovskite-type oxides such as LaSrCoO (LSC), but performance degradation, probably caused by surface composition changes, hinders exploitation of the full potential of LSC. This study reveals that the potentially very high activity of the LSC surface can be traced back to few very active sites. Already tiny amounts of SrO, for example, 4% of a monolayer, deposited on an LSC surface, lead to severe deactivation. Co, on the other hand, causes (re-)activation, suggesting that active sites are strongly related to Co being present at the surface. These insights could be gained by a novel method to measure changes of the electrochemical performance of thin film electrodes in situ, while modifying their surface: impedance spectroscopy measurements during deposition of well-defined fractions of monolayers of Sr-, Co- and La-oxides by single laser pulses in a pulsed laser deposition chamber.

Correlation between the surface chemistry of LSC thin films analyzed by LEIS and ICP-MS and the oxygen exchange kinetics.

In this study, the contribution of grain boundaries to the oxygen reduction and diffusion kinetics of La0.8Sr0.2MnO3 (LSM) thin films is investigated. Polycrystalline LSM thin films with columnar grains of different grain sizes as well as epitaxial thin films were prepared by pulsed laser deposition. (18)O tracer exchange experiments were performed at temperatures from 570 °C to 810 °C and subsequently analyzed by secondary ion mass spectrometry (SIMS). The isotope concentration depth profiles of polycrystalline films clearly indicate contributions from diffusion and surface exchange in grains as well as in grain boundaries. Measured depth profiles were analyzed by finite element modeling and revealed the diffusion coefficients D and oxygen exchange coefficients k of both the grain bulk and grain boundaries. Values obtained for grain boundaries (Dgb and kgb) are almost three orders of magnitude higher than those of the grains (Dg and kg). Hence, grain boundaries may not only facilitate fast oxygen diffusion but also fast oxygen exchange kinetics. Variation of the A-site stoichiometry ((La0.8Sr0.2)0.95MnO3) did not lead to large changes of the kinetic parameters. Properties found for epitaxial layers without grain boundaries (Db and kb) are close to those of the grains in polycrystalline layers.

Symmetric cells with porous La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) electrodes on Gd 0.1 Ce 0.9 O 1.95 (GDC) electrolytes were aged at 800 • C for 800 hours in ambient air. Electrochemical impedance spectroscopy (EIS) measurements performed periodically at 700 • C showed a continuous increase of the polarization resistance from 0.15 to 0.34 · cm 2 . Three-dimensional (3D) tomographic analysis using focused ion beam-scanning electron microscopy (FIB-SEM) showed negligible changes due to the ageing, suggesting that the observed resistance increase was not caused by electrode morphological evolution. However, an increased amount, by a factor of 3, of a water-soluble Sr rich surface phase on the aged LSCF electrode was detected by an etching procedure coupled with inductively coupled plasma-optical emission spectrometry (ICP-OES). The electrochemical analysis in combination with the microstructural parameters determined by FIB-SEM was used to examine the effect of Sr segregation on the rate of oxygen surface exchange, based on the Adler-Lane-Steele (ALS) model. 1-6However, a number of MIEC materials including LSCF exhibit Sr surface segregation, which has been proposed to hinder the oxygen surface exchange process. [7][8][9][10][11] This is believed to be an important issue for the stability of advanced SOFCs utilizing MIEC cathodes. Still, most of the Sr segregation observations have been made on thin film samples, where it is straightforward to measure surface composition using techniques such as X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and secondary ion mass spectrometry (SIMS).12-15 Recently Rupp et al. 16 reported a novel technique utilizing chemical etching with on-line inductively coupled plasma optical emission spectrometry (ICP-OES) detection to successfully quantify Sr-rich surface phases on dense La 0.6 Sr 0.4 CoO 3-δ (LSC) thin films. There is only one report of a measurement of a practical porous LSCF electrode that showed Sr segregation, measured via XPS, along with electrochemical performance degradation. 11The distinction between thin film and bulk electrode samples is potentially important. Thin films are often characterized by columnar growth with very high grain boundary densities, they may exhibit significant stress, and the thermal history is usually very different from that of porous electrodes (preparation mostly below 800• C). Although the measured properties of well-prepared polycrystalline thin-film electrodes normally agree reasonably well with values from bulk materials, 17 in some cases such as epitaxial thin film electrodes, properties may deviate significantly.18 Also, SOFC stacks with LSCF cathodes have been shown to provide reasonably stable long-term performance, 19 an observation that appears to be at odds with the Sr segregation and related degradation observed for thin-film LSCF.In this work, we investigated the degradation mechanisms, especially Sr surface segregation, of porous LSCF cathodes. LSCF symmetric-electrode cells with Gd 0.1 Ce 0.9 ...

a Cation diffusion was investigated in La 0.6 Sr 0.4 CoO 3Àd (LSC) thin films on (100) yttria stabilized zirconia in the temperature range 625-800 1C. Isotopic ( 86 Sr) and elemental tracers (Fe, Sm) were used to establish diffusion profiles of the cations in bi-and multi-layered thin films. The profiles were analyzed by time of flight-secondary ion mass spectrometry (ToF-SIMS). Grain and grain boundary diffusion coefficients of the cations were determined for LSC thin films with columnar grains -diffusion along grain boundaries is shown to be about three orders of magnitude faster than in grains. This could be verified for thin films with different grain size.A-and B-site cations showed very similar temperature dependencies with activation energies of B3.5 eV for bulk and B4.1 eV for grain boundary diffusion. The importance of cation diffusivities for surface segregation of Sr and thus for a major degradation mechanism of LSC cathodes in solid oxide fuel cells is discussed.

Chemical capacitance measurements are used to study the defect chemistry of La0.6Sr0.4FeO3–δ thin films and their polarization (η) and pO2 dependence. Important point defects are oxygen vacancies (), electrons (e′) and holes (h˙).

The temperature dependent conductivity of yttria stabilized zirconia (YSZ) exhibits a bending in Arrhenius' plots which is frequently discussed in terms of free and associated oxygen vacancies. However, the very high doping concentration in YSZ leads to such a strong defect interaction that the concept of free vacancies becomes highly questionable. Therefore, the temperature dependent conductivity of YSZ is reconsidered. The conductivity of YSZ with different doping concentration was measured in a broad temperature range. The data are analyzed in terms of two different barrier heights that have to be passed along an average path of an oxygen vacancy in YSZ (two barrier model). For 8-10 mol% yttria, the two barriers are in the range of 0.6 eV and 1.1-1.2 eV, respectively. The conductivity and thus the barrier heights also depend on the cooling rate after a high temperature pre-treatment. This indicates that different frozen-in distributions of dopants affect the vacancy motion by different energy landscapes. Temporarily existing defect configurations, possibly with a strong effect of repulsive oxygen vacancy interaction, are suggested as the reason of high barriers. Future dynamic ab-initio calculations may reveal whether this modified model of the YSZ conductivity is mechanistically meaningful. Yttria stabilized zirconia (YSZ) is among the most important ion conducting solids and acts as a kind of model material representing fast oxide ion conductors. Owing to this model character of YSZ, but also due to its application in solid oxide fuel cells (SOFCs), solid oxide electrolysis cells (SOECs) and oxygen sensors, a vast amount of papers can be found dealing with its oxide ion conduction. The ionic conductivity is based on the motion of oxygen vacancies, introduced by Y 3+ ions replacing Zr 4+ . For concentrations above ca. 8 mol%, yttria doping also stabilizes the cubic structure down to room temperature. A detailed review of the science of YSZ and related materials is far beyond the scope of this paper but a few important facts regarding the ionic conductivity of zirconia-based solid electrolytes can be briefly summarized as follows:1-9 i) Doping concentrations above ca. 8 mol% Y 2 O 3 lead to a decrease of the conductivity, despite increasing oxygen vacancy concentration. ii) The conductivity not only depends on the vacancy concentration but also on the kind of dopant. For example, Sc-doped zirconia shows significantly higher conductivity than YSZ. iii) The temperature dependence of the conductivity cannot be described by a single activation energy (E act ) but shows higher E act values at lower temperatures.Numerous theoretical studies were performed in order to understand these experimental observations and to get a deeper insight into defect thermodynamics and kinetics of doped zirconia and of the closely related ceria-based ion conductors, see e.g. Refs. 10-29. Those model studies employed different simulation approaches such as molecular dynamics (MD), density functional theory (DFT) and kinetic Monte Carl...

Surface composition of La0.6Sr0.4CoO3−δ electrodes investigated by means of a novel on-line in situ etching procedure with ICP-OES analysis.