Papers by Author: Detlev Stöver

Abstract: Solid oxide fuel cells (SOFCs) enable environmentally friendly energy to be produced with high efficiency. The market entry of SOFC systems depends on the functionality of the components and on the costs. The SOFC has not yet reached market maturity. This presentation focuses on the possibilities for manufacturing SOFCs with high power outputs and long-term durability by using manufacturing technologies feasible in industry. For the past 15 years, FZ Jülich has been developing large-size so-called anode-supported SOFCs (up to 200 x 200 mm²) with reproducibly high power output (> 2 A/cm² at 800°C). Novel technologies for high-capacity manufacturing such as tape casting and roller coating have been introduced. Additionally, newly developed thin-film techniques have led to power outputs of more than 3 A/cm² at 800°C and more than 1.5 A/cm² below 700°C. These high power densities open up new possibilities for the operation of SOFCs at low temperatures to ensure low degradation and therefore long lifetimes.

Abstract: The green density and roughness of green ceramic layers determine their mechanical and micro structural properties after final sintering. These properties can be measured precisely by laser profilometry. The green density of thin layers (20-50 µm) could quickly be determined as accurately as 0.5% theoretical density. The influence of paste parameters (powder conditioning, solid content, binder, and dispersing agent) on the green density was studied systematically for electrolyte pastes (8 mol.-% yttria stabilised zirconia = 8YSZ) typically used in solid oxide fuel cell applications. It could be shown that a minimal binder content is required to achieve acceptable green densities. Pre-calcination of the powder yielded also significantly higher film densities. Dispersant agents contributed to a smoother surface in any case, however a significant effect on the packing density was only observed for the fine, non-calcined powder.

Abstract: Conventional thermal barrier coating (TBC) systems consist of a duplex structure with a metallic bondcoat and a ceramic, heat isolative topcoat. In modern TBCs the ceramic topcoat is further divided into layers with different functions. One example is the double layer system in which conventional yttria stabilized zirconia (YSZ) is used as bottom and new materials as pyrochlores or perovskites are used as topcoat layers. These systems demonstrated an improved temperature capability compared to standard YSZ. Examples of such systems will be shown. In modern gas turbines the increased temperatures and gas pressures lead to an increased fraction of radiative heat flow. Coatings with increased reflectivity can be used to avoid the direct heating of the metallic substrates by this radiation. An effective method to produce such coatings is suspension plasma spraying. These reflective coatings are deposited on top of the TBC system and will lead to a further grading and improved performance of the coating.

Abstract: Up to now, Solid Oxide Fuel Cell (SOFC) materials and processing does not meet the cost goals for commercialization. This resulted in a worldwide increase in R&D activities dealing with advanced materials and effective manufacturing methods. The present paper describes efforts to process novel SOFC materials as well as optimization of well known ones. The R&D trends are explained for key components such as anode, electrolyte, cathode, contact- and protective layers. Typical SOFC manufacturing methods include tape casting, extrusion, calendaring and axial pressing. Each of these techniques has advantages and limitations. Examples for the highly efficient use of these methods are given for electrolyte supported cells as well as anode and cathode supported designs. An evaluation in reference to automation, process complexity and costs is given under the present limiting factors. Exemplary the processing by tape casting and the micro structural fine tuning of an advanced anode-supported system is discussed in detail. To produce the layered components of an SOFC, techniques like screen printing, wet powder spraying, PVD and CVD are under development. While the layer properties are excellent, PVD and CVD are nowadays too expensive in some cases, due to the low deposition rates. If thin layers are required, these techniques become interesting under cost considerations. The effectiveness of a PVD interlayer between electrolyte and high power density cathodes is shown in comparison to a sintered layer. In thin electrolyte concepts, the cathode becomes the power limiting component at operating temperatures below around 750°C. Thus new cathode materials and adjusted processing parameters are under development. The possibilities to manufacture advanced cathode layers by screen printing, wet powder spraying and other wet chemical methods are discussed. As an example screen printing of LSCF is described which results in a high power density cathode layer for low temperature SOFC operation. Finally, future needs to achieve the technical and economic goals are summarized.

Abstract: Due to their direct conversion of electrochemical into electrical energy solid oxide fuel cells (SOFCs) have great potential for a future additional energy supply. Even in the last two years numerous developers of SOFCs, both industry and research institutions, have demonstrated long-term stable operation of stacks of various dimensions (ranging from 1 to 125 kWel, with durations of up to 25000 hours of operation). Besides technical proof, single component availability (cells, bipolar plates, sealing…), stable and low-aging operation, as well as cost efficient manufacturing of the components is becoming more and more evident in preparation for a market launch. Close cooperation between SOFC stack developers, SOFC users and manufacturers of powders, semifinished parts or stack components is a prerequisite for success. Within a collaboration project funded by the German Federal Ministry of Economics and Labor (BMWA) the development of an SOFC as an auxiliary power unit (APU) is being promoted. The industrial users are BMW for automotive applications and Liebherr for use in construction vehicles or aircraft. The content of this presentation will be the transfer of the manufacturing knowledge developed at Research Center Jülich to CeramTec; including on the one hand the problems and limitations and, on the other hand the successes and positive perceptions. In detail, the transfer of, for example tape casting and screen printing will be addressed, powder characteristics concerning paste or slip formulation and special tests with reference to SOFCs are presented, and single cell tests of various cells manufactured with different powders or fabrication processes are described. Additionally, some remarks will concern different priorities in either R&D or industry (e.g. R&D: high power density; industry: reproducibility), process windows for manufacturing and the search for alternative fabrication methods.

Abstract: The lifetime under thermal cycling of a system consisting of an air plasma sprayed thermal barrier coating (TBC) deposited on a metallic bondcoat (BC) is determined by the subcritical growth of micro-cracks near the interface between both coatings. This growth mainly occurs during the cooling down phase, as shown by the acoustic emission monitoring during the thermal cycling. The factors controlling the stress level leading to the crack growth are the local curvature of the metallic-ceramic interface, the growth of an oxide scale (TGO) at such interface and the sintering of the TBC, the two last processes occurring during the high temperature cycle phase. Implementing all these factors, a model based on Finite Element Method (FEM) calculations is presented where growing cracks are incorporated by assigning soft properties to the FEM cells occupied by the cracks. Determining the growth direction for the maximum energy release rate at every cooling down step, the current crack extension during the cycling is tracked until it reaches a characteristic length corresponding to the TBC failure. The influence by the metallic-ceramic interface roughness and by the temperature gradient across the TBC is discussed.