76 research outputs found
Neutron diffraction structural study of the apatite-type oxide ion conductor, La8Y2Ge6O27: location of the interstitial oxide ion site
Apatite-type rare earth silicates/germanates have attracted considerable interest recently due to their high oxide ion conductivities. Despite evidence in support of a conduction mechanism involving interstitial oxide ions, the exact location of the interstitial oxide ion sites continues to attract controversy. In this paper we report a neutron diffraction structural study for the high oxygen excess compound, La8Y2Ge6O27. The structural model indicates that the oxide ions are located between the GeO4 tetrahedra, leading to significant localised distortions. These results, coupled with recent modelling studies, hence, support the conclusion that oxide ion migration proceeds via these tetrahedra
Apatite germanates doped with tungsten: Synthesis, structure, and conductivity
et al.High oxygen content apatite germanates, La10Ge 6-xWxO27+x, have been prepared by doping on the Ge site with W. In addition to increasing the oxygen content, this doping strategy is shown to result in stabilisation of the hexagonal lattice, and yield high conductivities. Structural studies of La10Ge 5.5W0.5O27.5 show that the interstitial oxygen sites are associated to a different degree with the Ge/WO4 tetrahedra, leading to five coordinate Ge/W and significant disorder for the oxygen sites associated with these units. Raman spectroscopy studies suggest that in the case of the WO5 units, the interstitial oxygen is more tightly bonded and therefore not as mobile as in the case of the GeO5 units, thus not contributing significantly to the conduction process. © 2011 The Royal Society of Chemistry.Financial support from Spanish project MAT2007-64486-C07-02 is acknowledged.Peer Reviewe
Dealing with degradation in solid oxide electrochemical cells: novel materials and spectroscopic probes
In this PhD thesis, we have focused on two of the main issues regarding solid oxide fuel cells and electrolysers. On the one hand, the high temperatures at which they work (800-1000ºC) is detrimental for their long-term performance, and novel combinations of electrolyte and oxygen electrode materials have been tested in order to establish their suitability to work in intermediate temperature (600-800ºC) solid oxide fuel cells. On the other hand, degradation issues affect these devices greatly when working in the electrolyser mode, often assigned to the development of high oxygen partial pressures within the electrolyte. Regarding this topic, we have developed an analytical procedure to monitor the oxygen activity inside a YSZ electrolyte using redox dopants as spectroscopic probes and used it in cells tested in different conditions in the electrolysis mode.First, an aluminium-doped lanthanum silicate compound (LSAO) with the apatite structure was chosen as electrolyte, and eight different strontium and cobalt-free compounds with a perovskite structure with the general formula LaMxN1-xO3 (where M: Fe, Mn, Cr; and N: Ni, Cu) were selected to be tested with the apatite electrolyte. The solid-state synthesis of the apatite and perovskite-type compounds was optimised, achieving perovskite compounds free from secondary phases or decomposition, both in powder form and also after sintering them in pellet form, as it was proven by X-ray diffraction and Raman spectroscopy. The chemical compatibility of the electrolyte and electrode materials was tested by mixing and heating the powders at temperatures above the operational and sintering ones, and no reaction between the compounds took place, as proven again by X-ray diffraction. The thermomechanical compatibility between sintered materials was tested by dilatometry, and no big differences could be found regarding the thermal expansion behaviour of the apatite and perovskites in a wide range of temperatures.Then, the electrochemical performance of the compounds was tested by electrochemical impedance spectroscopy. The LSAO ionic conductivity at intermediate temperatures (9.4·10-3 S·cm-1 at 800ºC) was close to the one shown by a conventional YSZ electrolyte, and the electrical conductivity of the oxygen electrode materials ranged from 10 to 100 S·cm-1 at 800ºC, with activation energies in the high temperature range between 0.1 and 0.3 eV. Among the perovskite materials, the ones containing manganese and copper showed the highest electrical conductivities and the lowest activation energies. The iron-containing compounds (LFN and LFC) exhibited a different activation behaviour with temperature than the rest of the compounds.The following step consisted on manufacturing symmetrical cells with the apatite electrolyte and perovskite electrodes. For that purpose, slurries of the electrode materials were prepared and the electrolyte pellet was coated with them by dip-coating and sintered. The microstructure of the cells was checked in terms of electrode thickness, porosity, particle size, and adherence of the electrodes. Among the compositions tested, LFC showed the lowest ASR with just 4.3 Ω·cm2 at 700ºC, value comparable to the state-of-the-art oxygen electrodes. When applying a small DC bias, the activation energies of the electrodes decreased, as well as their polarization resistances. Promising results were found in this thesis about novel electrolyte/electrode combinations for IT-SOFC, with room for improvement regarding electrode microstructure and the fabrication of composite electrodes with the LFC material.In order to examine the degradation issues concerning SOEC devices, the research began with finding a suitable spectroscopic probe that allowed us to track the oxygen activity in the cells. First, the optical signals in a YSZ electrolyte doped with redox ions were investigated. The objective was to select the ones suitable to track the oxygen activity, allow for a detection in the backscattering configuration and be operative at high temperatures. The samples tested in this part of the thesis were either commercial or solidified on purpose YSZ single-crystals doped with Ce, Mn, Mn-Nd, V or Tb; or polycrystalline ceramics of Tb or Pr-doped YSZ.Among the commercial samples, it was found that YSZ-Ce showed strong change in its optical signal upon redox treatment, and the Ce3+ backscattering signal could be used to monitor the oxygen activity, although the signal disappeared at temperatures above 300ºC. In the case of YSZ-Mn and YSZ-V, even though a change in the optical signal upon oxidation/reduction could be found, there were no backscattering signals that could be used for tracking the oxygen activity. The luminescence of minority rare earth dopants in these samples (Pr3+, Er3+ or Nd3+) was measured and a change in the backscattering signal could be observed upon redox treatment. Nevertheless, the quantification of these signals would have been complicated due to a possible interaction with the major dopants, and these commercial samples were not used to track the oxygen activity within the electrolyte.In the case of praseodymium-doped YSZ, a change in optical signal was observed by diffuse reflectance, and bands due to Pr3+ and Pr4+ could be found. In the case of backscattering signal, Pr3+ ions exhibited an intense luminescence band which decreases upon oxidation to Pr4+, and this signal held up to 700ºC. This could be useful to make in-situ or in-operando measurements of the oxygen activity inside the electrolyte. Nevertheless, ion-ion interaction and concentration quenching of the luminescence band prevented an easy quantification of the oxygen activity, and this probe was also discarded.Terbium-doped YSZ was found suitable in order to track the oxygen activity within YSZ. Changes in optical and luminescence signals could be observed and attributed to different oxidation states of terbium (Tb3+ and Tb4+) upon redox treatments. Tb3+ was not affected by concentration quenching and a quantitative analysis could be carried out. It was found that Tb4+ absorbance was proportional to PO2^(1⁄4), as expected for the electron trapping model. A relation between the Tb3+ luminescence intensity and the oxygen partial pressure could be found, and it proved to be useful in the high PO2 range (10-4-100 bar). Terbium was therefore the selected probe in order to carry out the electrochemical experiments to detect degradation mechanisms in electrolysers.3%Tb-doped 8YSZ shows appropriate oxide ion conductivity to be used as the electrolyte in solid oxide cells. Then, an electrolyte-supported solid oxide cell was prepared using a LSM/YSZ composite for the oxygen electrode and a NiO/YSZ composite for the fuel electrode, and its electrochemical properties were tested in a bicameral cell at 800ºC. Using EIS and changing the atmosphere in the oxygen side, the electrochemical properties of the system were described, and the polarization resistance of each electrode was assigned. After those measurements, several experiments were carried out polarising different cells using a range of biases in the electrolyser mode. When a steady-state was reached around 48 hours after applying a constant voltage, cells were quenched to freeze the high temperature polarization state.The post-mortem cells were analysed in terms of the Tb3+ luminescence across the electrolyte thickness. The luminescence values were transformed into oxygen partial pressures using the relation mentioned above and profiles of the oxygen activity within the electrolyte could be obtained. These measurements were noisy and a couple of corrections were made in order to obtain a suitable signal. An edge-correction due to the loss of signal near the electrodes and a saturation correction due to microstructural aspects of the cell were applied. The method presented here has potential to visualize PO2 profiles in SOEC. Further experiments should be done in order to achieve higher accuracies.Finally, numerical solutions to the transport equations for describing the oxygen activity within the electrolyte were found and compared with the experimental results. It was found that the simulations assuming polarization resistances as derived from EIS spectra at the beginning of the CA experiments did not agree with the oxygen activity profiles obtained from the luminescence experiments. By analysing the SEM micrographs of the post-mortem cells, we could find that the most degradation had occurred near the fuel electrode. The nickel particles tended to agglomerate, especially for high polarization biases, and the porosity of the electrode decreased with applied bias. Besides, cracks within the electrolyte were found near this electrode and even a complete delamination of the fuel electrode was observed for the highest polarization experiment. These observations allowed us to assign a higher polarization resistance to the fuel electrode and then the numerical model results were closer to the results of the luminescence measurements. In order to get better insights of the degradation conditions of the cell while working on electrolyser mode, more experiments should be done.<br /
Understanding the complex structural features and phase changes in Na2Mg2(SO4)3:a combined single crystal and variable temperature powder diffraction and Raman spectroscopy study
Sodium mixed metal sulphates have attracted considerable attention, both in terms of mineralogy and more recently due to interest in Na ion containing materials for battery applications. The phase, Na 2 Mg 2 (SO 4 ) 3 , has been previously reported to undergo a phase change to langbeinite at high temperatures, which is interesting given that usually the langbeinite structure is only adopted when large alkali metal ions, e.g. K, Cs, are present. Nevertheless the room temperature structure of this phase has remained elusive, and so in this work, we report a detailed structural study of this system. We show that room temperature Na 2 Mg 2 (SO 4 ) 3 can only be prepared by quenching from high temperature, with slow cooling leading to phase separation to give the previously unreported systems, Na 2 Mg(SO 4 ) 2 and Na 2 Mg 3 (SO 4 ) 4 . We report the structures of quenched Na 2 Mg 2 (SO 4 ) 3 (monoclinic, P2 1 ), as well as Na 2 Mg(SO 4 ) 2 (triclinic, P1¯) and Na 2 Mg 3 (SO 4 ) 4 (orthorhombic, Pbca), detailing their complex structural features. Furthermore, we report a study of the thermal evolution of quenched Na 2 Mg 2 (SO 4 ) 3 with temperature through variable temperature XRD and Raman studies, which shows a complex series of phase transitions, highlighting why this phase has proven so elusive to characterise previously, and illustrating the need for detailed characterisation of such sulphate systems
Interstitial oxide ion distribution and transport mechanism in aluminum-doped neodymium silicate apatite electrolytes
et al.Rare earth silicate apatites are one-dimensional channel structures that show potential as electrolytes for solid oxide fuel cells (SOFC) due to their high ionic conductivity at intermediate temperatures (500-700 °C). This advantageous property can be attributed to the presence of both interstitial oxygen and cation vacancies, that create diffusion paths which computational studies suggest are less tortuous and have lower activation energies for migration than in stoichiometric compounds. In this work, neutron diffraction of NdAlSiO (0 ≤ x ≤ 1.5) single crystals identified the locations of oxygen interstitials, and allowed the deduction of a dual-path conduction mechanism that is a natural extension of the single-path sinusoidal channel trajectory arrived at through computation. This discovery provides the most thorough understanding of the O transport mechanism along the channels to date, clarifies the mode of interchannel motion, and presents a complete picture of O percolation through apatite. Previously reported crystallographic and conductivity measurements are re-examined in the light of these new findings.We are pleased to acknowledge the Agency for Science, Technology and Research (A*STAR) PSF grant 082 101 0021 “Optimization of Oxygen Sublattices in Solid Oxide Fuel Cell Apatite Electrolytes” for funding the work and the Ministry of Education (MOE) Tier 2 grant T208B1212 for enabling the purchase of a single crystal X-ray diffractometer.Peer Reviewe
Synthesis and structures of sodium containing K<sub>2-x</sub>Na<sub>x</sub>Mg<sub>2</sub>(SO<sub>4</sub>)<sub>3</sub> langbeinite phases
Formation of apatite oxynitrides by the reaction between apatite-type oxide ion conductors, La8+xSr2-x(Si/Ge)6O26+x/2, and ammonia
Following growing interest in the use of ammonia as a fuel in Solid Oxide Fuel Cells (SOFCs), we have investigated the possible reaction between the apatite silicate/germanate electrolytes, La8+xSr2-x(Si/Ge)6O26+x/2, and NH3 gas. We examine how the composition of the apatite phase affects the reaction with ammonia. For the silicate series, the results showed a small degree of N incorporation at 600○C, while at higher temperatures (800○C), substantial N incorporation was observed. For the germanate series, partial decomposition was observed after heating in ammonia at 800○C, while at the lower temperature (600○C), significant N incorporation was observed. For both series, the N content in the resulting apatite oxynitride was shown to increase with increasing interstitial oxide ion content (x) in the starting oxide. The results suggest that the driving force for the nitridation process is to remove the interstitial anion content, such that for the silicates the total anion (O+N) content in the oxynitrides approximates to 26.0, the value for an anion stoichiometric apatite. For the germanates, lower total anion contents are observed in some cases, consistent with the ability of the germanates to accommodate anion vacancies. The removal of the mobile interstitial oxide ions on nitridation suggests problems with the use of apatite-type electrolytes in SOFCs utilising NH3 at elevated temperatures
Caracterización, integración y comportamiento de nuevos materiales tipo oxiapatita en una pila de combustible de óxido sólido microtubular
Una SOFC (Solid Oxide Fuel Cell) o pila de combustible de óxido sólido, es el tipo de pila de hidrógeno más eficiente actualmente. Normalmente, su temperatura de trabajo se encuentra entre los 600 ºC y 1000 ºC, lo cual conlleva un problema de estabilidad termoquímica de los componentes y sus interfases, que acaba derivando en una disminución de la efectividad y duración de la celda. Una posible solución que se está estudiando en el ICMA, en el grupo de Procesado y Caracterización de Cerámicas Estructurales y Funcionales (grupo de investigación dentro del cual se va a realizar este proyecto), es sustituir el material del electrolito que se utiliza actualmente, la YSZ (circona estabilizada con itria), por nuevos materiales de tipo oxiapatita, los cuales presentan mejores valores de conducción de los iones de oxígeno a temperaturas intermedias, lo que permitiría bajar el punto de operación del sistema al rango de los 700 - 800ºC. Sin embargo, estos materiales presentan importantes limitaciones en su procesado, debido fundamentalmente a su difícil densificación, lo que hace necesario un estudio minucioso de su proceso de sinterización. En este proyecto se estudiarán dos oxiapatitas en concreto: La9.67Si6O26.5 y La9.67Si3Ge3O26.5 El objetivo principal de este proyecto es fabricar una pila microtubular soportada sobre ánodo con este nuevo tipo de material. Para ello habrá que: 1. Sintetizar las oxiapatitas, realizando las mezclas, moliendas y tratamientos térmicos adecuados, comprobando después su cristalinidad mediante difracción de rayos X y espectroscopia Raman así como sus propiedades de conducción iónica mediante espescroscopia de impedancias (EIS). 2. Caracterizar y optimizar la morfología del polvo de los compuestos obtenidos para su posterior utilización en la fabricación de las pilas. Para ello, se estudiará la distribución del tamaño de partícula, se realizarán ensayos de dilatometría para determinar las temperaturas de sinterización del electrolito y por último, se realizarán ensayos de reología de las suspensiones para optimizar el proceso de dipcoating por el que se depositarán el electrolito y el cátodo sobre el ánodo. 3. Una vez optimizados los parámetros, se fabricarán los ánodos de NiO y oxiapatita, mediante CIP (prensado isostático en frío). Posteriormente,se depositará el electrolito sobre el ánodo mediante la técnica de dipcoating y por último, se depositará el cátodo (mezcla de Pr2NiO4 y oxiapatita) sobre el electrolito. La integración entre las diferentes capas que la componen , así como los espesores de cada una de las fases, se estudiará mediante técnicas de microscopia óptica y de barrido (SEM). 4. Finalmente, si la integración de las multicapas resulta ser adecuada, se realizará la caracterización electroquímica mediante el control del voltaje a circuito abierto (OCV), medidas de las curvas intensidad-voltage (I-V). El objetivo global de este proyecto es que el estudiante adquiera los conocimientos necesarios para trabajar en un laboratorio de fabricación y caracterización de materiales cerámicos
Optimización de cátodos de pilas de combustible SOFC mediante infiltración de catalizadores
El presente proyecto tiene como objetivo el estudio del efecto de la adición de nanopartículas metálicas u óxidos metálicos sobre el comportamiento del electrodo de aire (cátodo) en una pila de combustible de óxido sólido (SOFC). Para llevar a cabo este propósito se procederá a la fabricación de una pila plana simétrica con dos cátodos (en vez de ánodo y cátodo como en las pilas convencionales) depositados mediante la técnica de screen-printing y de dip-coating, y a los cuales se les incorporarán posteriormente nanopartículas metálicas a partir de sus sales por técnicas de infiltración. Los procedimientos que han sido llevados a cabo para la elaboración de una celda simétrica han sido los siguientes: Partiendo de sustratos comerciales de YSZ (circona estabilizada con itria), se cortarán con láser electrolitos planos circulares a los cuales se les aplicarán las suspensiones de electrodo basadas en LSM (manganita de lantano y estroncio) e YSZ mediante las técnicas de dip-coating y de screen-printing. Esta última técnica de fabricación favorece la reproducibilidad y automatización del proceso. A continuación se procede a la caracterización microestructural de los electrodos y de su interfase con el electrolito de YSZ, para comprobar la homogeneidad de la deposición, tamaño y distribución de las fases, y adherencia con la YSZ. Para ello se observarán las muestras en el microscopio electrónico de barrido (SEM) que nos permitirán establecer cuáles son las mejores condiciones de trabajo (proporción LSM/YSZ, espesor de electrodo, temperatura de sinterizado y porosidad). Como parte central del proyecto, se procede a la incorporación mediante técnicas de infiltración a vacío de sales metálicas que favorecerán las reacciones electroquímicas en el electrodo, reduciendo así su resistencia de polarización. En este paso se parte de disoluciones de nitrato de cobalto, cerio, manganeso y praseodimio que tras un tratamiento térmico formen nanopartículas metálicas o de óxido metálico. Posteriormente se procede a caracterizar y optimizar las infiltraciones mediante el uso de la espectroscopia de impedancias. Los resultados obtenidos muestran que las disoluciones con una carga de sales metálicas de 2,5 μmoles por electrodo reducen en mayor medida la resistencia eléctrica de las pilas de combustible tipo SOFC. Finalmente, tras analizar todas las sales metálicas infiltradas se comprueba que la infiltración de sales metálicas de cerio son las que mejores resultados presentan. Las mejorías obtenidas son del orden del 30 % cuando nos encontramos a “bajas temperaturas” (700 ºC). En el caso de altas temperaturas (900 ºC) las mejorías siguen siendo notables, un 18 % respecto a una celda sin infiltrar. Se concluye por tanto que la infiltración de catalizadores en los cátodos de las pilas de combustible de tipo SOFC mejoran su comportamiento debido a un incremento de la catálisis de la reducción del oxígeno
Synthesis of new Ln<sub>4</sub>(Al<sub>2</sub>O<sub>6</sub>F<sub>2</sub>)O<sub>2</sub> (Ln = Sm, Eu, Gd) phases with a cuspidine-related structure
The first fluorination of the cuspidine-related phases of Ln4(Al2O7□)O2 (where Ln = Sm, Eu, Gd) is reported. A low-temperature reaction with poly(vinyl-idene difluoride) lead to the fluorine being substituted in place of oxygen and inserted into the vacant position between the dialuminate groups. X-ray photoelectron spectroscopy shows the presence of the F 1s photoelectron together with an increase in Al 2p and rare-earth 4d binding energies supporting F incorporation. Energy-dispersive X-ray spectroscopy analyses are consistent with the formula Ln4(Al2O6F2)O2, confirming that substitution of one oxygen by two fluoride atoms has been achieved. Rietveld refinements show an expansion in the cell upon fluorination and confirm that the incorporation of fluoride in the Ln4(Al2O7□)O2 structure results in changes in Al coordination from four to five. Thus, the isolated tetrahedral dialuminate Al2O7 groups are converted to chains of distorted square-based pyramids. These structural results are also discussed based on Raman spectra.This research was funded by the Ministerio de Economía, Industria y Competitividad (MAT2016-76739-R) (AEI/FEDER, UE), and Departamento de Educación of the Basque Government (IT-630–13). The authors thank SGIker of UPV/EHU for technical and personnel support. A. Mora´nRuiz thanks UPV/EHU for funding.Peer reviewe
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