Phase Composition and Transport Properties of oxide ion conductors based on Sr1-xKxGeO3-x/2

Oxide ion conductors have been increasingly studied because of their potential applications in different electrochemical devices, such as, oxygen sensors, membranes for oxygen separation and components of fuel cells. Solid Oxide Fuel Cells (SOFCs) are electrochemical devices that operate at high temperatures, 600-1000 ºC, with higher efficiency for electrical generation than conventional systems based on fuel combustion. The high operating temperatures of the SOFC is mainly due to the limited ionic conductivity of the electrolyte. Zr0.84Y0.16O1.92 (YSZ) is the electrolyte most widely used in commercial systems due to its high stability and oxide ion conductivity at elevated temperatures (900-1000 ºC). However, there is a great interest in the development of devices with lower operation temperatures (600-800 ºC) to overcome collateral problems like difficulties in cell sealing or shorter lifetime of the components caused by the high operation temperature of YSZ. The high oxide ion conductivities recently reported in Na- and K-doped strontium silicates and germanates, make them potentially suitable for SOFC electrolytes. In this work, the structure, microstructure and electrical properties of Sr1-xKxGeO3-x/2 (x = 0.0, 0.1, 0.15 and 0.2) compounds have been re-investigated. The materials have been prepared by conventional ceramic and freeze-drying precursor methods. Different phases are stabilized depending on the synthetic method and the sintering temperature. Samples prepared by freeze-drying at 700 ºC exhibit a triclinic structure, which transforms to a mixture of monoclinic and trigonal related phases on heating at 1000 ºC. The presence of some broad diffractions peaks, which are not fitted in the Rietveld analysis, indicates the existence of an amorphous or low-crystalline phase (ACn) that have been quantified by an external standard procedure (G-factor approach). The homogeneity and chemical composition of the samples were checked by scanning electron microscopy combined with energy dispersive spectroscopy (EDX). The total conductivity of these materials was studied by impedance spectroscopy.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Structural analysis and sintering aids effects in La2Ce2O7 proton conductors

Global warming is an important problem that has to be solved without delay. The development of environmental-friendly energy technology is needed to deal with this issue. Solid Oxide Fuel Cells (SOFC) technology has been proposed as a real alternative to fossil fuel combustion. Proton conductors like La2Ce2O7 (LDC), has several advantages in comparison with BaCeO3 due to its high stability in H2O or CO2 conditions [1]. Furthermore, for industry application is necessary to low the high sintering temperature of typical electrolyte materials. La2Ce2O7 was synthesized by the freeze-drying precursor method and calcination conditions have been optimized to obtain single phase with high compaction at 1400 ºC for 1h. A fully characterization has been carried out using X-ray powder diffraction and scanning electron microscopy. The total conductivity was determined by complex impedance spectroscopy in dry and wet air. Transmission Electron Microscopy (TEM) was used to clarify certainly the structure of La2Ce2O7 due to its still unknown. SAEDs patterns revealed a disordered fluorite, not appearing secondary reflections typical of pyrochlore superstructure, finishing the controversy around the correct structure in this material [2,3]. Moreover, an exhaustive study about lowering the sintering temperature with Co and Zn as sintering aids has been investigated obtaining electrolytes that can be used for SOFC. The sintering aids were impregnated using cobalt and zinc nitrates in ethanol media. Both sintering aids allow for obtain high dense pellets lowering the sintering temperature 300 ºC and 400 ºC for samples with cobalt and zinc, respectively, without compromising the electrical and microstructural properties (Fig 1).Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Ce0.8Gd0.2O2‐δ / La0.6Sr0.4CoO3 Heterostructures prepared by pulsed laser deposition

Oxide interfaces have received greater attention due to the possibility to obtain properties that are very different from bulk materials. Due to the wide variety of electronic and ionic phenomena than can be detected at the interfaces, such materials have many technological applications [1]. Attention is being drawn to oxide heterostructures, a new family of artificial materials where electronic and ionic properties can be modulated at the interfaces by varying the characteristics of the layers [2, 3]. Slight variations in the near anionic-cationic order might take place if there exists strained interfaces. The interest in multilayared heterostructures derives from the mobility deffects and the space-charge-zone effects at the interfaces. In addition, a new degree of freedom related to the capacitive and resistive contributions is provided as a consequence of the size effects of these artificial structures. In the present work, for the first time, we investigate the structure, microstructure and electrical properties of a new family of heterostructured materials with alternated thin layers of La0.6Sr0.4CoO3 (LSC) and Ce0.8Gd0.2O2-δ (CGO) deposited by pulsed laser deposition on (110) NdGaO3 (NGO) single crystal substrates. In order to evaluate the interfacial contribution to ionic-electronic conductivity and know what is actually happens at the interface of MIECs, different heterostructures were prepared by varying both the number of bilayers (N) and the total thickness of the samples (N = 2 and 5; and the thickness were 50, 100 and 300 nm).Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Novel microstructural strategies to enhance the electrochemical performance of La0.8Sr0.2MnO3-δ cathodes

Solid oxide fuel cells (SOFCs) are one of the most efficient technologies for direct conversion of fuels to electricity. La0.8Sr0.2MnO3-δ (LSM) is the cathode material most widely used in SOFCs [1], however, LSM exhibits high activation energy for oxygen reduction reaction (ORR) and low ionic conductivity, which limits its application at reduced temperatures. In this material the electrochemically active reaction sites are restricted to the triple-phase boundary (TPB) near the electrolyte/electrode interface, where the electrolyte, air and electrode meet. Different strategies have been investigated to enlarge the TPB area of LSM, such as the production of nanocrystalline powders by precursor routes, preparation of composites by infiltration methods and thin films [2-4]. Here we present and compare innovative procedures to extend the TPB of LSM in contact with yttria-stabilized zirconia electrolyte: i) nanocrystalline LSM films deposited by spray-pyrolysis on polished YSZ electrolyte; ii) the addition of polymethyl methacrylate microspheres as pore formers during the spray-pyrolysis deposition to further increase the porosity of these films and (iii) the deposition of LSM by spray-pyrolysis on porous backbones of Zr0.84Y0.16O1.92 (YSZ), Ce0.9Gd0.1O1.95 (CGO) and Bi1.5Y0.5O3- (BYO) electrolytes previously fixed onto the YSZ electrolyte. The most remarkable peculiarity of this novel preparation method, compared to the traditional impregnation, is the formation of LSM thick film of 500 nm on the electrode surface (Fig. 1), which improves the electrical conductivity of the composite cathode. Thus, the optimization of this novel method would be an alternative to the classical infiltration with several advantages for the industry of planar SOFCs allowing the deposition of a wide variety of ceramic films over large areas with more uniform distribution of the catalyst, lower cost and only one deposition step is required to form the electrode. The morphology and electrochemical performance of the electrode have been investigated by scanning electron microscopy and impedance spectroscopy. Very low values of area specific resistance were obtained ranging from 1.4 cm2 for LSM deposited on polished YSZ to 0.06 cm2 for LSM deposited onto BYO backbone at a measured temperature of 650 ºC. This electrodes exhibit high performance even after annealing at 950 ºC making them interesting for applications at intermediate temperatures.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Influence of Nb-doping on the structural and electrical properties of lanthanum molybdates, La5.4MoO11.1

Nowadays, hydrogen is receiving a great deal of attention as an energy carrier. Commonly, it is obtained by hydrocarbons reforming, such as natural gas, coal and biomass. However, the resulting hydrogen needs to be purified to remove by-products and impurities, increasing the production costs. An alternative for hydrogen production is proton-conducting ceramics, where hydrogen separation takes place via a chemical potential gradient across the membrane.1, 2 In this work, Nb-doped La6MoO12--based compounds have been investigated as part of a new family of materials very competitive as SOFC electrolyte and hydrogen separation membranes.3 These materials, La5.4Mo1-xNbxO11.1-x/2 (x = 0.05, 0.10, 0.15 y 0.20) were synthesized by the freeze-drying precursor method and calcination conditions have been optimized to obtain single phases. A complete characterization has been carried out using X-Ray powder diffraction and scanning and transmission electron microscopy. The total conductivity was determined by complex impedance spectroscopy at different atmospheres. Different polymorphs are obtained as a function of the cooling rate and the dopant amount. The samples cooled by quenching are cubic with a fluorite-type structure (Fm3 ̅m) and the ones cooled at 50 y 0.5 ºC•min-1 are rhombohedral (R1 and R2 polymorphs). For niobium contents higher than x = 0.10 the R1 polymorph is stabilised at cooling rates equal or inferior to 50 ºC•min-1. For all three series, the incorporation of niobium into La5.4MoO11.1 increases the conductivity, reaching the best values for x=0.10 and the sample obtained by quenching.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Solid Oxide Fuel Cells based on Lanthanum Tungstates Electrolytes

Lanthanum tungstate with composition La27W4NbO55- (LWNO) has been tested as proton conductor electrolyte for Solid Oxide Fuel Cells (SOFCs). For this purpose, different electrodes and composite electrodes are considered, including: La0.8Sr0.2MnO3-, La0.6Sr0.4Co1-xFexO3-, La0.5Sr0.5Cr0.5Mn0.5O3-, SrFe0.75Nb0.25O3- and NiO. Chemical compatibility between the cell components is investigated by X-ray powder diffraction (XRPD) and energy dispersive spectroscopy (EDS). Furthermore, area specific resistance (ASR) of the different electrodes is determined in symmetrical cells by impedance spectroscopy. XRPD and EDS analysis do not reveal significant bulk reactivity between most of these electrodes and LWNO electrolyte in the typical operating temperature range of a SOFC (600-900 ºC). However, minor interdiffusion of elements at the electrolyte/electrode interface affects both the ohmic losses and electrode polarization of the cells. ASR values are significantly improved by using a buffer layer of Ce0.8Gd0.2O1.9, between the electrolyte and electrode materials, to prevent reactivity. A single cell with 350 µm thick electrolyte, NiO-Ce0.8Gd0.2O1.9 anode and La0.6Sr0.4Co0.8Fe0.2O3- cathode, generates maximum power densities of 140 and 18 mWcm-2 at 900 and 650 ºC, respectively.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Compatibility and performance of SOFCs based on lanthanum tungstates

Rare-earth tungstates with general composition “Ln6WO12” have attracted great attention in last few years due to their relatively high mixed proton-electron conductivity [1, 2]. One of the main ad-vantages of these electrolytes, compared to the traditional perovskites based on BaCeO3, is that they exhibit high tolerance towards CO2 and H2S environments. Therefore, this material is a potential electrolyte for proton conducting solid oxide fuel cells (PC-SOFC). In this work, the lanthanum tungstate with com-position La27W4NbO55-δ (LWNO) has been tested as proton conductor electrolyte [3]. For this purpose, different electrodes and composite electrodes have been considered, including: La0.8Sr0.2MnO3-δ, La0.6Sr0.4Co1-xFexO3-δ, La0.5Sr0.5Cr0.5Mn0.5O3-δ, SrFe0.75Nb0.25O3-δ and NiO. Chemical compatibility between the cell compo-nents is investigated by X-ray powder diffraction (XRPD) and energy dispersive spectroscopy (EDS). Furthermore, area specific resistance (ASR) of the different electrodes is determined in symmetrical cells by impedance spectroscopy. XRPD and EDS analysis do not reveal significant bulk reactivity between most of these electrodes and LWNO electrolyte in the typical operating temperature range of a SOFC (600-900 ºC). However, minor interdiffusion of elements at the electrolyte/electrode interface affects both the ohmic losses and electrode polarization of the symmetric cells. ASR values are significantly improved by using a buffer layer of Ce0.8Gd0.2O1.9, between the electrolyte and electrode materials, to prevent reactivity. A single cell with 350 µm thick electrolyte, NiO-Ce0.8Gd0.2O1.9 anode and La0.6Sr0.4Co0.8Fe0.2O3-δ cathode, generates maximum power densities of 140 and 18 mWcm-2 at 900 and 650 ºC, respectively. Hence, lanthanum tungstates could be competitive proton conductors for PC-SOFCs with similar performance to those based on BaZrO3 if thin film electrolytes are used.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Influence of lanthanum doping on the structure and transport properties of CeO2

LaxCe1-xO2-x/2 materials are oxide and/or proton conductors depending on the La-content and they are of interest for numerous electrochemical applications at high temperatures, including membranes for hydrogen separation and fuel cell electrolytes. Samples with low La-content exhibit (x0.4) crystallize with cubic fluorite type structure; while for x>0.4 the structure is still unclear. The crystal structure of these materials is still unknown, some authors reported that the materials exhibit fluorite type structure in the whole compositional range. However, another authors reported a pyrochlore type structure for x0.5. The stabilization of the fluorite or pyrochlore type structure depends mainly on the oxygen sublattice and the vacancy ordering1. In this contribution, LaxCe1-xO2-δ (0<x0.7) materials are prepared by the freeze-drying precursor method and the sintering conditions have been optimized to obtain dense ceramic samples. A complete structural characterization has been carried out by X-ray powder diffraction and scanning electron microscopy. The average structure determined by conventional XRD indicates that the materials are single fluorite compounds for x0.6. However, the local structure determined by combined electron diffraction and HRTEM is more complex. The SAED patterns reveal diffuse scatterings for x0.5 that have been associated with O-vacancy ordering, leading to a superstructure relative to a single fluorite . This finding is further confirmed by the HRTEM images in the same zone axis. Thermogravimetric and Raman analysis confirmed an increase of oxygen vacancy concentration with La-doping. The overall conductivity was determined by complex impedance spectroscopy in different atmospheres. The samples with high La-content exhibit an important proton contribution at low temperature. In addition, all samples are mixed ion-electronic conductors in hydrogen containing atmosphereUniversidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Effect of preparation conditions on the polymorphism and transport properties of lanthanum molybdates

In this work, La6MoO12-based compounds were investigated as part of a new family of materials very competitive as hydrogen separation membranes [1,2]. La5.4MoO11.1 was synthesized by the freeze-drying precursor method and the calcination conditions were optimized in order to obtain single phases. Several cooling rates were applied and different polymorphs were obtained: a simple cubic fluorite symmetry (Fm-3m) for the sample cooled by quenching, and two different rhombohedral (R-3) space groups for the samples cooled at 50 ºC•min-1 and 0.5 ºC•min-1 (see Figure below). For the quenched sample, the Rietveld refinement was satisfactory in a Fm-3m space group. For the other two compositions no structural model was available and were indexed in a R-3 space group, however some small reflections were not given any intensity by the model used. Transmission electron microscopy confirmed the presence of superstructures for those samples. All ceramic materials were obtained with relative densities close to 100% after sintering at 1500 ºC. Stability studies demonstrated that all three polymorphs were stable in oxidizing and reducing conditions at 800 ºC for 48 hours. The three samples present a significant proton contribution to the conductivity at temperatures lower than 800 ºC. These results were confirmed by thermogravimetric analysis. The highest conductivity values were observed for the samples prepared by quenching. The three polymorphs display a small p-type electronic contribution to the overall conductivity in oxidizing conditions and n-type electronic one in very reducing conditions, much more significant for the samples cooled by quenching and at 50 ºC•min-1.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Nanocrystalline cathodes for PC-SOFCs based on BCZY

Perovskites based on BaCeO3-δ exhibit the highest proton conductivity among this class of materials, however, they are susceptible to hydration and carbonation in presence of water vapor and CO2 [1]. In contrast, the chemical stability of BaZrO3-based protonic conductors is better, but they require sintering temperatures as high as 1700 ºC and suffer from high intrinsic grain boundary resistance, limiting the final performance. Partial substitution of Zr for Ce in Ba(Ce0.9-xZrx)Y0.2O3-δ allows obtaining electrolytes with both high proton conductivity and good chemical stability. The performance of a PC-SOFC at low temperatures depends significantly on the ohmic resistance of the electrolyte, although it can be lowered by reducing the electrolyte thickness. Another important limiting factor is the increase of the cathode polarization resistance due to the thermally activated nature of the oxygen reduction reaction. For this reason, it is essential to obtain high efficiency cathodes operating at reduced temperatures. In this work, BaCe0.6Zr0.2Y0.2O3-δ (BCZY) powders were prepared by freeze-drying precursor method. These powders were mixed with a Zn-containing solution as sintering additive in order to obtain dense pellets with submicrometric grain size at only 1200 ºC. After that, La0.6Sr0.4Co0.8Fe0.2O3 nanocrystalline electrodes were deposited symmetrically onto dense pellets BCZY by conventional spray-pyrolysis [3]. The structure, microstructure and electrochemical properties of these electrodes have been examined by XRD, FE-SEM and impedance spectroscopy. The stability of these electrodes at intermediate temperatures was evaluated as a function of time. These nanocrystalline cathodes exhibit a substantial improvement of the electrode polarization resistance with respect to the same materials prepared by screen-printing method at high sintering temperatures, e.g. 0.7 and 3.2 cm2 at 600 ºC for LSCF cathodes prepared by spray-pyrolysis and screen-printing method respectively (Figure). An anode supported cell with composition LSCF/BCZY/NiO-BCZY was also prepared to test the electrochemical performance.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech