Micro-tubular Solid Oxide Fuel Cells with Nickelate Cathode-support

The shortage of natural resources, rising energy demands and global warming have created an urgent need for more efficient energy conversion devices and different energy resources to achieve a more sustainable and efficient economy. Solid Oxide Fuel Cells (SOFC) are one of the most promising devices for the direct conversion from chemical to electrical energy in conjunction with high system efficiencies. Micro-tubular SOFC have been investigated since roughly 15 years. In contrast to planar systems, which produce electricity in the kW to MW range and target utilisation in stationary applications such as CHP plants, micro-tubular SOFC systems can be envisaged for mobile application due to quick start-up/shutdown operation. While most micro-tubular cells are mechanically supported by the electrolyte or anode, only few researches have investigated cathode-supported cells due to challenging fabrication. In this work, the new cathode material neodymium nickelate (NNO), Nd1.95NiO4+δ, was used as mechanical support, which is a novelty of this work, for micro-tubular SOFC. Different fabrication routes were used to create small tubes of 2-6 mm diameter. These tubes were evaluated with respect to their gas-diffusion properties by a new, self-manufactured diffusion setup and a complementary permeation setup. In order to achieve an economical fabrication process, the low-cost dip-coating method was investigated for the deposition of thin films from wet-chemical suspensions to create entire SOFC single cells. As SOFCs require gas-tight electrolyte layers, cofiring of tubular substrates and thin films must be executed to allow sufficient shrinkage of the deposited electrolyte thin layers to full density. Various electrolyte and electrode powders were characterised in different solvents, dispersants and binders with respect to low-temperature sintering feasibility. The shrinkage of scandia-stabilised zirconia (ScSZ) powder was decreased to 18% to still deliver sufficient sintered density by optimisation of the green density (usually zirconia requires shrinkage of 25% and more for densification). The cofiring temperature depends on the densification behaviour of powders but also on reactivity between adjacent layers. The reactivity between gadolinia-doped ceria (GDC)-interlayers and different zirconia materials was tested and showed lower compatibility of yttria-stabilised zirconia (YSZ) with GDC than for ScSZ/GDC reaction couples, which has not been reported so far. The interface of NNO cathodes and GDC interlayers was analysed by reactivity mapping and quantitative phase analysis. The performance optimisation of NNO/GDC interfaces by exchange current density measurement of NNO-cathodes sintered at different temperatures on GDC pellets is a further contribution of this work. The reactivity and performance investigations provide clear guidelines for maximum allowable cosintering temperature. Some electrochemical single cell tests showed competitive area-specific resistances (ASR) of ca. 1 Ωcm2 but were limited unfortunately by the counterelectrode microstructure and current collection methods, which were not the focus of this work. Open-circuit voltages (OCV) were 0.6-1.1 V at 700 °C in dry hydrogen atmosphere for tubes prepared by extrusion but only 0.3 V for tubes prepared by slip-casting. The electrochemical performances were modest with only 0.035 W/cm2 power density at 700 °C for tubes prepared by extrusion due to the elevated resistances of the counterelectrode and current collection.

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