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The aim of the present investigation is to define microstructure parameters, which control the effective transport properties in porous materials for energy technology. Recent improvements in 3D-imaging (FIB-nanotomography, synchrotron X-ray tomography) and image analysis (skeletonization and graph analysis, transport simulations) open new possibilities for the study of microstructure effects. In this study, we describe novel procedures for a quantitative analysis of constrictivity, which characterizes the so-called bottleneck effect. In a first experimental part, methodological tests are performed using a porous (La,Sr)CoO 3 material (SOFC cathode). The tests indicate that the proposed procedure for quantitative analysis of constrictivity gives reproducible results even for samples with inhomogeneous microstructures (cracks, gradient of porosity). In the second part, 3D analyses are combined with measurements of ionic conductivity by impedance spectroscopy. The investigations are preformed on membranes of electrolysis cells with porosities between 0.27 and 0.8. Surprisingly, the tortuosities remain nearly constant (1.6) for the entire range of porosity. In contrast, the constrictivities vary strongly and correlate well with the measured transport resistances. Hence, constrictivity represents the dominant microstructure parameter, which controls the effective transport properties in the analysed membrane materials. An empirical relationship is then derived for the calculation of effective transport properties based on phase volume fraction, tortuosity, and constrictivity.

The electrical conductivity of dense and nanoporous zirconia‐based thin films is compared to results obtained on bulk yttria stabilized zirconia (YSZ) ceramics. Different thin film preparation methods are used in order to vary grain size, grain shape, and porosity of the thin films. In porous films, a rather high conductivity is found at room temperature which decreases with increasing temperature to 120 °C. This conductivity is attributed to proton conduction along physisorbed water (Grotthuss mechanism) at the inner surfaces. It is highly dependent on the humidity of the surrounding atmosphere. At temperatures above 120 °C, the conductivity is thermally activated with activation energies between 0.4 and 1.1 eV. In this temperature regime the conduction is due to oxygen ions as well as protons. Proton conduction is caused by hydroxyl groups at the inner surface of the porous films. The effect vanishes above 400 °C, and pure oxygen ion conductivity with an activation energy of 0.9 to 1.3 eV prevails. The same behavior can also be observed in nanoporous bulk ceramic YSZ. In contrast to the nanoporous YSZ, fully dense nanocrystalline thin films only show oxygen ion conductivity, even down to 70 °C with an expected activation energy of 1.0 ± 0.1 eV. No proton conductivity through grain boundaries could be detected in these nanocrystalline, but dense thin films.

A solid oxide fuel cell (SOFC) is a solid-state energy conversion system that converts chemical energy into electrical energy and heat at elevated temperatures. Its bipolar cells are electrochemical devices with an anode, electrolyte, and cathode that can be arranged in a planar or tubular design with separated gas chambers for fuel and oxidant. Single chamber setups have bipolar cells with reaction selective electrodes and no separation between anode and cathode compartments. A nickel/yttria-stabilized-zirconia (YSZ) cermet is the most investigated and currently most widespread anode material for the use with hydrogen as fuel. In recent years, however, doped ceria cermet anodes with nickel or copper and ceria as the ceramic phase have been introduced together with ceria as electrolyte material for the use with hydrocarbon fuels. The state-of-the-art electrolyte material is YSZ of high ionic and nearly no electronic conductivity at temperatures between 800-1000 °C. In order to reduce SOFC system costs, a reduction of operation temperatures to 600-800 °C is desirable and electrolytes with higher ionic conductivities than YSZ are aimed for such as bismuth oxide, lanthanum gallate or mixed conducting ceria and the use of thin electrolytes. Proton conducting perovskites are researched as alternatives to conventional oxygen conducting electrolyte materials. At the cathode, the reduction of molecular oxygen takes place predominantly on the surface. Today's state-of-the-art cathodes are La x Sr 1-x MnO 3-d for SOFC operating at high temperature i.e. 800-1000 °C, or mixed conducting La x Sr 1-x Co y Fe 1-y O 3-d for intermediate temperature operation, i.e. 600-800 °C. Among the variety of alternative materials, Sm x Sr 1-x CoO 3-d and Ba x Sr 1-x Co x Fe 1-x O 3-d are perovskites that show very good oxygen reduction properties. This paper reviews the materials that are used in solid oxide fuel cells and their properties as well as novel materials that are potentially applied in the near future. The possible designs of single bipolar cells are also reviewed.

The mechanism and kinetics of oxygen reduction at thin dense two-dimensional La 0:52 Sr 0:48 Co 0:18 Fe 0:82 O 3Àd (LSCF) electrodes have been investigated in air between 500 and 700°C with electrochemical impedance spectroscopy and steady-state voltammetry. Dense and geometrically well-defined LSCF films with various thicknesses ranging between 16 and 766 nm have been prepared on cerium gadolinium oxide substrates by pulsed laser deposition and structured with photolithography. The current collection was ensured by a porous LSCF layer. A good agreement was found between the experimental data and the impedance of the reaction model calculated with statespace modelling for various electrode potentials and thicknesses. It was evidenced that oxygen adsorption, incorporation into the LSCF and bulk diffusion are ratedetermining while charge transfer at the electrode/electrolyte interface remains at quasi-equilibrium. The 16 and 60 nm thin dense LSCF electrodes appear to be more active towards oxygen reduction than thicker layers and porous films at 600 and 700°C.

The faradaic impedance of oxygen reduction has been simulated for thin dense two-dimensional La 0:52 Sr 0:48 Co 0:18 Fe 0:82 O 3Àd electrodes in air at 600°C. The reaction model accounts for the defect chemistry of the ceramic films and includes bulk and surface pathways. It was demonstrated that the contribution of the surface pathway to the reaction was negligible due to the small length of triple phase boundary gas/electrode/electrolyte.

Partially amorphous La 0.6 Sr 0.4 CoO 3-δ (LSC) thin-fi lm cathodes are fabricated using pulsed laser deposition and are integrated in free-standing micro-solid oxide fuel cells (micro-SOFC) with a 3YSZ electrolyte and a Pt anode. A low degree of crystallinity of the LSC layers is achieved by taking advantage of the miniaturization of the cells, which permits low-temperature operation (300-450 °C). Thermomechanically stable micro-SOFC are obtained with strongly buckled electrolyte membranes. The nanoporous columnar microstructure of the LSC layers provides a large surface area for oxygen incorporation and is also believed to reduce the amount of stress at the cathode/ electrolyte interface. With a high rate of failure-free micro-SOFC membranes, it is possible to avoid gas cross-over and open-circuit voltages of 1.06 V are attained. First power densities as high as 200-262 mW cm −2 at 400-450 °C are achieved. The area-specifi c resistance of the oxygen reduction reaction is lower than 0.3 Ω cm 2 at 400 °C around the peak power density. These outstanding fi ndings demonstrate that partially amorphous oxides are promising electrode candidates for the next-generation of solid oxide fuel cells working at low-temperatures.