The influence of reduction conditions on a Ni-YSZ SOFC anode microstructure and evolution

Ni-YSZ cermets are the most widespread material used as SOFC anodes. These materials are generally fabricated through the reduction of a NiO-YSZ composite, but the reduction conditions have a great effect in the final microstructure of the electrode. In the present work several conditions were explored to reduce microtubular anode supports produced via extrusion in order to find a suitable microstructure for SOFC anodes. Samples were reduced in pure and diluted H2, either dry or humidified at temperatures ranging from 400 to 800°C while their DC conductivity was being monitored. The highest value of peak conductivity was measured in the sample reduced in humidified pure hydrogen at 800°C, but it experienced more severe conductivity degradation that other samples. The best value for the duration of the test was obtained for the sample reduced in dry diluted hydrogen at 800°C.Authors would like to thank the project MAT2012-30763, financed by the Spanish Government (Ministerio de Economía y Competitividad) and the Feder program of the European Union.Peer Reviewe

Highly stable microtubular cells for portable solid oxide fuel cell applications

In this work, extruded support tubes based on Nickel Oxide-YSZ (yttria stabilized-zirconia) were manufactured by Powder Extrusion Moulding (PEM). An YSZ layer is then deposited by dip coating as the electrolyte and subsequently, standard La0.8Sr0.2MnO3-δ (LSM)/YSZ composites were deposited by dip coating as oxygen electrodes. Microstructure of the anode support was optimized in order to achieve the maximum fuel utilization and as a consequence, a high performance of the cells. Experiments as a function of the fuel composition showed power densities above 500 mWcm−2 at 800 °C at 0.7 V, with high fuel utilization (∼75%). Long-term durability studies were also performed for a period above 1000 hours. The experiment was conducted at 800 °C using pure humidified hydrogen at a fixed voltage of 0.8 V. It was observed that the current density of the cell is significantly evolving during the initial period of about 100 hours, as a consequence of reconditioning of nickel particles at the anode support. Once the system is stabilized, no degradation was observed up to 1000 hours under operating conditions, obtaining current densities in the range of 400 mAcm−2 at 0.8 V and 800 °C.The project MAT2015-68078-R, financed by the Spanish Government (Ministerio de Economía y Competitividad) and the Feder program of the European Union, is also acknowledged.Peer Reviewe

The influence of the reducing conditions on the final microstructure and performance of nickel-yttria stabilized zirconia cermets

Ni-YSZ (yttria stabilized zirconia) cermets are the most widespread composite materials to be used as SOFC fuel electrodes. These materials are generally fabricated by the reduction of NiO to Ni in a NiO-YSZ composite, where the reducing conditions have a great effect in the final microstructure of the electrode. In the present work, several reducing conditions were explored in order to find the most suitable microstructure for anode-supported microtubular solid oxide fuel cells (SOFCs). Samples were firstly reduced in either pure or diluted H (dry or humidified), at temperatures ranging from 400 to 800 °C while their DC conductivity was monitored. The highest conductivity value was measured for the sample reduced in pure humidified hydrogen at 800 °C. However, this sample experienced conductivity degradation in comparison with samples reduced under dry conditions. For the studied temperature range, nucleation of nano-porous nickel particles is firstly formed during reduction. However, from our experiments it was concluded that those nanoparticles are not stable with time, at least at temperatures between 600 °C and 800 °C. Electrochemical characterization of complete microtubular cells under real wet conditions was also performed under current load, confirming that the microstructure of the Ni-YSZ cermet is still evolving during operation.Authors would like to thank the project MAT2015-68078-R, financed by the Spanish Government (Ministerio de Economía y Competitividad) and the Feder program of the European Union.Peer Reviewe

Editorial

Víctor Orera was our first teacher and scientific father in the laboratory. With him we also learned that research, like any human activity, must be honest and contribute to improving the world around us. He was very passionate about science, dedicated and naturally optimistic. When we were having a bad day at the lab, he had a knack for finding the silver lining in an apparently unsuccessful outcome. Until retirement, he was the leader of our Research Group, Processing and Characterization of Structural and Functional Ceramics, PROCACEF, at the Institute of Materials Science of Aragon, ICMA, an institute that he contributed to found and develop. ICMA has recently become part of the Aragon Institute of Nanoscience and Materials (INMA), from where we write these words..

CFD simulation of a reversible solid oxide microtubular cell

Trabajo presentado al 10th European Solid Oxide Fuell Cell Forum celebrado en Lucerna (Suiza) del 26 al 29 de Junio de 2012.In this work, the authors introduce a comprehensive model and the corresponding 3D numerical tool for the simulation of reversible micro-tubular solid oxide fuel cells. It is based on a previous in-house model for SOFC [1], to which some new features has been added to extend its applicability to SOEC. The model considers the following physical phenomena: (i) fluid flow through channels and porous media; (ii) multicomponent mass transfer within channels and electrodes; (iii) heat transfer due to conduction, convection and radiation; (iv) charge motion; and (v) electrochemical reaction. The numerical algorithm to solve this mathematical model is implemented in OpenFOAM, an open source CFD toolbox based on the finite-volume method.Peer reviewe

Investigation of Graded La2NiO4+ Cathodes to Improve SOFC Electrochemical Performance

Mixed ionic and electronic conducting MIEC oxides are promising materials for use as cathodes in solid oxide fuel cells SOFCs due to their enhanced electrocatalytic activity compared with electronic conducting oxides. In this paper, the MIEC oxide La2NiO4+ was prepared by the sol-gel route. Graded cathodes were deposited onto yttria-stabilized zirconia YSZ pellets by dip-coating, and electrochemical impedance spectroscopy studies were performed to characterize the symmetrical cell performance. By adapting the slurries, cathode layers with different porosities and thicknesses were obtained. A ceria gadolinium oxide CGO barrier layer was introduced, avoiding insulating La2Zr2O7 phase formation and thus reducing resistance polarization of the cathode. A systematic correlation between microstructure, composition, and electrochemical performance of these cathodes has been performed. An improvement of the electrochemical performance has been demonstrated, and a reduction in the area specific resistance ASR by a factor of 4.5 has been achieved with a compact interlayer of La2NiO4+ between the dense electrolyte and the porous La2NiO4+ cathode layer. The lowest observed ASR of 0.11 cm2 at 800°C was obtained from a symmetrical cell composed of a YSZ electrolyte, a CGO interlayer, an intermediate compact La2NiO4+ layer, a porous La2NiO4+ electrode layer, and a current collection layer of platinum paste

Anode supported microtubular solid oxide fuel cells running on methane

Trabajo presentado al "III Iberian Symposium on Hydrogen, Fuel Cells and Advanced Batteries" celebrado en Zaragoza (España) del 27 al 30 de Junio de 2011.We would like to thank grants MAT2009-14324-C0.2-01 and CIT-120000-2007-50 financed by the Spanish Government and Feder program of the European Community for funding project. M. A. Laguna-Bercero would also like to thank the JAEprogram (CSIC) for financial support.Peer Reviewe

Electrochemical performance of Nd1.95NiO4+δ cathode supported microtubular solid oxide fuel cells

Nd1.95NiO4+δ (NNO) cathode supported microtubular cells were fabricated and characterized. This material presents superior oxygen transport properties in comparison with other commonly used cathode materials. The supporting tubes were fabricated by cold isostatic pressing (CIP) using NNO powders and corn starch as pore former. The electrolyte (GDC, gadolinia doped ceria based) was deposited by wet powder spraying (WPS) on top of pre-sintered tubes and then co-sintered. Finally, a NiO/GDC suspension was dip-coated and sintered as the anode. Optimization of the cell fabrication process is shown. Power densities at 750°C of ~40 mWcm-2 at 0.5V were achieved. These results are the first electrochemical measurements reported using NNO cathode-supported microtubular cells. Further developments of the fabrication process are needed for this type of cells in order to compete with the standard microtubular solid oxide fuel cells (SOFC).The authors thank grant MAT2009-14324-C02-01 and MAT2012-30763, financed by the Spanish Government (Ministerio de Ciencia e Innovación) and Feder program of the European Community, for funding the project.Peer Reviewe

Microtubular SOFC based on an extruded support

Trabajo presentado al "IV Iberian Symposium on Hydrogen, Fuel Cells and Advanced Batteries" celebrado en Estoril (Portugal) del 26 al 28 de junio de 2013.In this work the processing route for an anode supported microtubular solid oxide fuel cell is adjusted. The fuel cell composition and microstructure design is based on previous work. In this work we have developed microtubular cells based on an extruded support. Firstly, Ni-YSZ anode was manufactured by Powder Extrusion Moulding (PEM). Feedstock composition and extruding parameters were adjusted to obtain tubular green bodies. An YSZ layer was then deposited as the electrolyte and the sintering parameters were optimized to obtain a dense layer. An active area of ~1 cm2 LSMYSZ was deposited as the cathode and its electrochemical performance was measured using pure hydrogen as fuel, yielding a power output at 0.5V of 0.7Wcm-2 at 8500C.Authors would like to thank financial support received from MICINN and Feder program of the European Community (MAT2010-19837-C06 and MAT2012-30763 projects), Madrid regional government (MATERYENER S2009 PPQ-1626 program), and also grant GA-LC-035/2012, financed by the Aragón Government and La Caixa Foundation.Peer Reviewe

Effect of synthesis conditions on electrical and catalytical properties of perovskites with high value of A-site cation size mismatch

et al.The perovskite La0.15Sm0.35Sr0.08Ba0.42FeO3-δ has been prepared by the glycine nitrate route, varying the calcination temperature, fuel/oxidizer ratio and cooling rate, in order to study the sample preparation influence on the properties in the context of their application as a electrode material for SOFCs. The obtained materials have been characterized by X-ray diffraction, scanning electron microscopy, electrical and BET surface area measurements, and also the reaction between oxygen and CO, which can occur in SOFCs during the conversion of chemical energy into electrical energy. As overall results, all the samples present a phase segregation showing two perovskites with rhombohedral structure. SEM images show a well-necked morphology of the powders which are composed of nanosized particles and agglomerations of grains. The BET specific surface area of the samples decreases as calcination temperature increases, as well as for the quenched sample. The measured electronic conductivity values (<50 S/cm) are characteristic for samples with these high values of σ(r) (A cation size disorder). The catalytic activity tests for the CO oxidation reaction showed a T50% (“light-off temperature”, defined as the temperature at which 50% conversion of CO is achieved) value about 440°C–450 °C, CO conversion reaching 100% at approximately 600 °C for all the prepared perovskites. Then, for the La0.15Sm0.35Sr0.08Ba0.42FeO3-δ perovskite, CO conversion temperature is lower than usual SOFCs operating temperature. This points out to the technological interest of these materials in the framework of reducing the operating temperature of SOFCs.This research has been funded by the Ministerio de Ciencia e Innovación (CONSOLIDER-INGENIO 2010 CSD2009-00013), Ministerio de Economía y Competitividad (MAT2013-42092-R and MAT2012-30763), the Feder program of the Europen Union and Dpto. Educación, Política Lingüística y Cultura of the Basque Goverment (IT-630-13). The authors thank for technical and human support provided by SGIker of UPV/EHU. K. Vidal thanks UPV/EHU for funding.Peer Reviewe