Mixed ionic-electronic YSZ/Ni composite for SOFC anodes with high electrical conductivity

The preparation of the ZrO(2):8 mol % Y(2)O(3)/NiO (YSZ/NiO) composites by a modified liquid mixture technique is reported. Nanometric NiO particles dispersed over the yttria-stabilized zirconia (YSZ) were prepared, resulting in dense sintered specimens with no solid solution formation between the oxides. Such a feature allowed for the electrical characterization of the composites in a wide range of relative volume fraction, temperature, and oxygen partial pressure. The main results indicate that the composites have high electrical conductivity, and the transport properties in these mixed ionic-electronic (MIEC) composites are strongly dependent on the relative volume fraction of the phases, microstructure, and temperature. These parameters should hence be taken into consideration for the optimized design of MIEC composites for electrochemical applications. In this context, the composite was reduced under H(2) for the preparation of high-conductivity YSZ/Ni cermets for use as solid oxide fuel cell anode material with relatively low metal content. (c) 2005 the Electrochemical Society. [DOI:10.1149/1.2149312] All rights reserved.

Electrical properties of YSZ/NiO composites prepared by a liquid mixture technique

We report the preparation and characterization of yttria-stabilized zirconia/nickel oxide composites (YSZ/NiO). This composite is the precursor material of the cermet YSZ/Ni, which is used as solid oxide fuel cell anode material. The performance of the anode is strongly dependent on the microstructural properties of the cermet. Therefore, the control of the microstructure of the YSZ/NiO composite is a key step for the fabrication of high-performance anodes. In this study, the composites were prepared by a modified liquid mixture technique. Scanning electron microscopy analysis evidenced the good dispersion of the phases and that NiO nanoparticles are spread over the YSZ surface. Sintered pellets were studied by X-ray diffraction and impedance spectroscopy. The main results show that the composite is comprised of a well-dispersed mixture of the two phases. The electrical conductivity data show that there is a strong dependence of the transport mechanism on the relative composition of phases. (c) 2005 Elsevier Ltd. All rights reserved.

Microstructural and electrical properties of the sofc anode precursor YSZ/NiO composite prepared by A liquid mixture technique

A detailed study of the microstructural and electrical properties of the yttria-stabilized zirconia/nickel oxide (YSZ/NiO) composite was performed. This material is the precursor to the solid oxide fuel cell anode cermet YSZ/Ni. A liquid mixture technique was developed to produce the YSZ/NiO composite to fabricate high-performance SOFC anodes. This technique resulted in fine and homogeneous powders and specimens with high electrical conductivity. The combined results showed that this technique is suitable for the production of the anode cermet.

Sintering of cobalt and strontium doped lanthanum chromite obtained by combustion synthesis

Lanthanum chromite (LaCrO3) is one of the most adequate materials for use as interconnector in solid oxide fuel cell (SOFC) applications, due to its intrinsic properties, namely its good electrical conductivity and resistance to environment conditions in fuel cell operations. Due to difficulties in sintering, additives are usually added to help in the densification process. In this work, the influence of added cobalt and strontium, in the sintering of LaCrO3 obtained by combustion synthesis was studied. The starting materials were respectively nitrates of chromium, lanthanum, cobalt and strontium, and urea was used as fuel. The results show that by increasing the strontium and cobalt concentrations it is possible to reduce the temperature of sintering. Using both additives, the sintering processes took place in lesser times than normally used for this material, as well as greater values of density were attained.

Síntese e caracterização da cerâmica 'Ti IND. x''('Sm IND. 0,2''Ce IND. 0,8') IND. (1-x)''O IND. (2-Б) para aplicação como anodo em células a combustível de óxido sólido

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Análise do 'LA''CR'O IND.3' dopado com 'SR' e 'CO',preparados via reação de combustão, utilizando difração de raios X com aplicação do método de Rietveld

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudo do crescimento de nanofitas de céria dopada com gadolínio por sistema de aquecimento por micro-ondas

O óxido de cério (céria) tem atraído atenção devido às suas importantes aplicações, como em células a combustível de óxido sólido, catalisadores de gases de exaustão de automóveis, catalisadores para a obtenção de hidrogênio, bloqueadores de raios ultravioleta, biomateriais, entre outros. Controlar os métodos de síntese da céria é de grande importância para explicar ou prever essas propriedades. Desta forma, o objetivo deste trabalho foi estudar o crescimento de nanofitas de óxido de cério em um sistema hidrotérmico assistido por micro-ondas, no qual 8 min foram obtidas nanofitas com comprimentos próximos a 330 nm, em 130 ºC e pressão de 3 atm. Os resultados colaboram para pesquisas em reformadores para obtenção de etanol e/ou anodos de células combustíveis de óxido sólido.

Análise técnica, econômica e ecológica do uso de biogás em célula a combustível de óxido sólido (SOFC)

Pós-graduação em Engenharia Mecânica - FEG

Densification and enhancement of the grain boundary conductivity of gadolinium-doped barium cerate by ultra fast flash grain welding

Doped barium cerate is a promising solid electrolyte for intermediate temperature fuel cells as a protonic conductor. However, it is difficult to sinter it to high density at a reasonable temperature. Moreover, it presents a high grain boundary resistivity at intermediate temperatures. Flash grain welding was applied to compacted samples, starting from a temperature of 910 degrees C and applying, for a short time, an ac electric polarization of 40 V, 1000 Hz. At that frequency, the resulting current flows through the grain boundaries promoting a welding via a local Joule heating. A large decrease of the grain boundary resistivity was observed by impedance spectroscopy. Scanning electron microscopy observations of polished and etched surfaces revealed highly sintered regions. Attempts were also made to combine flash grain welding with conventional sintering. (C) 2012 Elsevier Ltd. All rights reserved.

X-ray absorption spectroscopy study on La0.6Sr0.4CoO3 and La0.6Sr0.4Co1¡yFeyO3 nanotubes and nanorods for IT-SOFC cathodes.

In the last years, extensive research has been devoted to develop novel materials and structures with high electrochemical performance for intermediate-temperatures solid-oxide fuel cells (IT-SOFCs) electrodes. In recent works, we have investigated the structural and electrochemical properties of La0:6Sr0:4CoO3 (LSCO) and La0:6Sr0:4Co1¡yFeyO3 (LSCFO) nanostructured cathodes, finding that they exhibit excellent electrocatalytic properties for the oxygen reduction reaction [1,2]. These materials were prepared by a pore-wetting technique using polycarbonate porous membranes as templates. Two average pore sizes were used: 200 nm and 800 nm. Our scanning electronic microscopy (SEM) study showed that the lower pore size yielded nanorods, while nanotubes were obtained with the bigger pore size. All the samples were calcined at 1000oC in order to produce materials with the desired perovskite-type crystal structure. In this work, we analyze the oxidation states of Co and Fe and the local atomic order of LSCO and LSCFO nanotubes and nanowires for various compositions. For this pur- pose we performed XANES and EXAFS studies on both Co and Fe K edges. These measurements were carried out at the D08B-XAFS2 beamline of the Brazilian Synchrotron Light Laboratory (LNLS). XANES spectroscopy showed that Co and Fe only change slightly their oxidation state upon Fe addition. Surprisingly, XANES results indicated that the content of oxygen vacancies is low, even though it is well-known that these materials are mixed ionic-electronic conductors. EXAFS results were consistent with those expected according to the rhombohedral crystal structure determined in previous X-ray powder dffraction investigations. [1] M.G. Bellino et al, J. Am. Chem. Soc. 129 (2007) 3066 [2] J.G. Sacanell et al., J. Power Sources 195 (2010) 1786

In-situ XANES experiments on Ni K-edge in mesoporous ZrO2-CeO2:Ni.

Ordered mesoporous ZrO2-CeO2 mixed oxides are potential candidates for catalytic applications. These systems, used as anodes in solid oxide fuel cells (SOFC), may lead to better performance of SOFCs, due to an enhancement on surface area, aiming to achieve a lower working temperature. The aim of this studies is to evaluate the reduction capacity of Ni2+ to Ni in ZrO2-x(mol)%CeO2 (x=50 and 90) samples impregnated with 60(wt.)%NiO. The synthesis was made with Zr and Ce chloride precursors, HCl aqueous solution, Pluronic P123, NH4OH to adjust the pH (3-4) and a teflon autoclave to perform a hydrothermal treatment (80oC/48h). The samples were dried and calcined, until 540oC in N2 and 4 hours in air. The NiO impregnation was made with an ethanol dispersion of Ni(NO3)£6H2O. The powder was calcinated in air until 350oC for 2 hours. Temperature-resolved XANES data at the Ni K-edge were collected at the DXAS beam line of the LNLS in transmission mode, using a Si(111) monochromator and a CCD detector. Sample preparation consisted of mixing »6mg of the powder samples with boron nitride and pressing into pellets. The data were acquired during an experiment of temperature programmed reduction (TPR) under a 5% H2/He until 600oC and mixtures of 20%CH4:5%O2/He, at temperatures from 400 to 600oC. All the reactions were monitored with a mass spectrometer. The data was analyzed with a linear combination fit of 2 standards for each valence number using Athena software. The Ni K-edge experiments demonstrated that for both contents of CeO2, NiO embedded in the porous zirconia-ceria matrix reduces at lower temperatures than pure NiO, revealing that the ZrO2-CeO2 support improves the reduction of impregnated NiO. Ni was oxidized to NiO after all reactions with methane and oxygen. Hydrogenated carbonaceous species were detected, but under reducing conditions, the hydrocarbon compounds are removed. The reaction of total oxidation of methane CH4:O2 (1:2 ratio) was observed at lower temperatures (around 400oC) for both samples.

Structural and textural studies of NiO impregnation in mesoporous ZrO2-CeO2 for catalysis applications.

The synthesis of zirconia-based ordered mesoporous structures for catalytic applications is a research area under development. These systems are also potential candidates as anodes in intermediate temperature solid oxide fuel cells (it-SOFC) due to an enhancement on their surface area [1-4]. The structural features of mesoporous zirconia-ceria materials in combination with oxygen storage/release capacity (OSC) are crucial for various catalytic reactions. The direct use of hydrocarbons as fuel for the SOFC (instead of pure H2), without the necessity of reforming and purification reactors can improve global efficiency of these systems [4]. The X-ray diffraction data showed that ZrO2-x%CeO2 samples with x>50 are formed by a larger fraction of the cubic phase (spatial group Fm3m), while for x<50 the major crystalline structure is the tetragonal phase (spatial group P42/nmc). The crystallite size of the cubic phase increases with increase in ceria content. The tetragonal crystallite size decreases when ceria content increases. After impregnation, the Rietveld analysis showed a NiO content around 60wt.% for all samples. The lattice parameters for the ZrO2 tetragonal phase are lower for higher ZrO2 contents, while for all samples the cubic NiO and CeO2 parameters do not present changes. The calculated densities are higher for higher ceria content, as expected. The crystallite size of NiO are similar (~20nm) for all samples and 55nm for the NiO standard. Nitrogen adsorption experiments revealed a broader particle size distribution for higher CeO2 content. The superficial area values were around 35m2/g for all samples, the average pore diameter and pore volumes were higher when increasing ceria content. After NiO impregnation the particle size distribution was the same for all samples, with two pore sizes, the first around 3nm and a broader peak around 10nm. The superficial area increased to approximately 45m2/g for all samples, and the pore volume was also higher after impregnation and increased when ceria content increased. These results point up that the impregnation of NiO improves the textural characteristics of the pristine material. The complementary TEM/EDS images present a homogeneous coating of NiO particles over the ZrO2-x%CeO2 support, showing that these samples are excellent for catalysis applications. [1] D. Y. Zhao, J. Feng, Q. Huo, N. Melosh, G. H. Fredrickson, B. F. Chmelka, G. D. Stucky, Science 279, 548-552 (1998). [2] C. Yu, Y. Yu, D. Zhao, Chem. Comm. 575-576 (2000). [3] A. Trovarelli, M. Boaro, E. Rocchini, C. de Leitenburg, G. Dolcetti, J. Alloys Compd. 323-324 (2001) 584-591. [4] S. Larrondo, M. A. Vidal, B. Irigoyen, A. F. Craievich, D. G. Lamas, I. O. Fábregas, et al. Catal. Today 107–108 (2005) 53-59.

Structural and reduction studies of ZrO2-CeO2:Ni for application in SOFC anodes.

Zirconia-ceria solid-solutions are extensively used as promoters for three-way catalysts, which are applied in the control of NOx, CO and hydrocarbons emission from automotive exhausts. In addition, thesematerials can be used as anodes in solid oxide fuel cells (SOFCs) operated with hydrocarbons. There areonly few works on ZrO2-CeO2 ordered mesoporous materials for catalytic applications and for anodes inSOFCs. The interest in these anodes relies on the fact that ZrO2-CeO2materials are mixed ionic/electronic conductors in reducing atmosphere and, therefore, fuel oxidation is produced on its entire surface, while it only occurs in the [anode/electrolyte/gas] interface (triple-phase boundaries) for electronic conductors. In this work, a synthesis method was developed usingZr and Ce chloride precursors, HCl aqueous solution, Pluronic P123 as the structure directing agent, NH4OH to adjust the pH (3-4) and a Teflon autoclave to perform hydrothermal treatment (80ºC/48 hours). The samples were dried and calcined, until 540ºC in N2and 4 hours in air. The X-ray diffraction data showed that powders with higher CeO2 content are formed by a larger fraction of the cubic CeO2 phase, while for a lower CeO2content the major crystalline structure is the tetragonal ZrO2 phase. The NiO impregnation was made with an ethanol dispersion of Ni(NO3)×6H2O. The resulting powder was calcinated in air until 350ºC for 2 hours. Temperature-programmed reduction (TPR) data were collected in order to evaluate the reduction profiles of ZrO2-x%CeO2:Ni samples in H2/Ar atmosphere. Results showed lower reduction temperatures for all ceria content in samples comparing to a NiO standard.

The Effect of Various Electrode Microstructure Parameters on the Effective Conductivity and Three-Phase Boundary Density of Infiltrated SOFC Electrodes

Solid oxide fuel cell (SOFC) technology has the potential to be a significant player in our future energy technology repertoire based on its ability to convert chemical energy into electrical energy. Infiltrated SOFCs, in particular, have demonstrated improved performance and at lower cost than traditional SOFCs. An infiltrated electrode comprises porous ceramic scaffolding (typically constructed from the oxygen ion conducting material) that is infiltrated with electron conducting and catalytic particles. Two important SOFC electrode properties are effective conductivity and three phase boundary density (TPB). Researchers study these electrode properties separately, and fail to recognize them as competing properties. This thesis aims to (1) develop a method to model the TPB density and use it to determine the effect of porosity, scaffolding particle size, and pore former size on TPB density as well as to (2) compare the effect of porosity, scaffolding particle size, and pore former size on TPB density and effective conductivity to determine a desired set of parameters for infiltrated SOFC electrode performance. A computational model was used to study the effect of microstructure parameters on the effective conductivity and TPB density of the infiltrated SOFC electrode. From this study, effective conductivity and TPB density are determined to be competing properties of SOFC electrodes. Increased porosity, scaffolding particle size, and pore former particle size increase the effective conductivity for a given infiltrate loading above percolation threshold. Increased scaffolding particle size and pore former size ratio, however, decreases the TPB density. The maximum TPB density is achievable between porosities of 45% and 60%. The effect of microstructure parameters are more prominent at low loading with scaffolding particle size being the most significant factor and pore former size ratio being the least significant factor.

Looking at Chemistry in Hard to See Places: Understanding Energy Conversion at 1400° Celsius

Solid oxide fuel cells (SOFCs) are promising devices for stationary and portable power and heat generation, because they can use complex fuels such as hydro-carbons, CO, and alcohols. Extreme, non-equilibrium conditions and high tem-peratures (≥ 700 ˚C) required for SOFC operation hamper efforts to understand the mechanisms of component degradation in SOFCs. This talk focuses on new insights into SOFC chemistry and the conversion of carbon-containing fuels (both hydrocarbons and oxygenated) into electricity, carbon dioxide and water, gleaned from a combination of techniques including electrochemical impedance spectroscopy, voltammetry, and vibrational Raman scattering.