Academic literature on the topic 'Ag/CGO'

As a result of a successful collaboration between the University of St Andrews and HEXIS AG over the past >10 years, an alternative solid oxide fuel cell (SOFC) fuel electrode material (to the state-of-the-art Ni/CGO fuel electrode) has been intensively researched and developed 1 at a button cell scale (1 cm2 active area), 2 tested under harsh operating conditions and upscaled to short stack scale (5 cells each of 100 cm2 active area), 1,3 in addition to being integrated into full combined heat and power units (60 cells each of 100 cm2 active area) with nominal 1-1.5 kW power outputs. 3,4 This highly robust fuel electrode comprises a La0.20Sr0.25Ca0.45TiO3 (LSCTA-) ‘backbone’ with cerium gadolinium oxide (CGO) and Rh impregnates, offering stability toward redox/thermoredox/thermal cycling, overload or stress testing, degradation comparable to the state-of-the-art SOFCs and exposure to sulphurised natural gas. 1 This material, therefore, addresses many of the challenges presented by the Ni/CGO fuel electrodes. Given the success of this material as a SOFC fuel electrode and the growing demand for production of ‘green’ hydrogen and synthesis gas through high-temperature electrolysis, 5 it is also desirable to assess its performance in solid oxide electrolysis cells (SOECs). In this paper, the authors present a comprehensive study of the performance of SOECs containing the aforementioned titanate-based fuel electrodes. Firstly, testing of button cell scale SOECs (1 cm2 active area) in pure CO2 and H2O/H2 mixtures, carried out at the University of St Andrews and HEXIS AG, will be outlined, including promising initial test data from VI curves and AC impedance spectroscopic analysis. Subsequently, information on durability testing of the aforementioned SOECs will be provided. This data indicates that high degradation is observed during testing in H2O/H2/N2 mixtures when employing a LSM-YSZ/LSM air electrode, most likely due to delamination caused by oxygen evolution at the triple phase boundary between LSM and YSZ particles and at the air electrode-electrolyte interface, which is significantly minimised by replacement with a LSCF-CGO air electrode. Finally, upscaling of this technology to a 5 x 5 cm footprint SOEC (16 cm2 active area) containing the aforementioned fuel electrode, a stabilised zirconia electrolyte and a LSCF-CGO air electrode will be outlined. Encouraging results from a ~600 hour test at 850 °C will be presented, including operation in 54 % H2O:46 % CO2 and pure CO2 at 1.47 V, as well as in 51 % H2O:49 % N2 at 1.29 V (without the use of a reducing gas). References 1 R. Price, M. Cassidy, J. G. Grolig, G. Longo, U. Weissen, A. Mai and J. T. S. Irvine, Advanced Energy Materials, 2021, 11, 2003951. 2 R. Price, M. Cassidy, J. G. Grolig, A. Mai and J. T. S. Irvine, J. Electrochem. Soc., 2019, 166, F343–F349. 3 M. C. Verbraeken, B. Iwanschitz, E. Stefan, M. Cassidy, U. Weissen, A. Mai and J. T. S. Irvine, Fuel Cells, 2015, 5, 682–688. 4 R. Price, H. Bausinger, G. Longo, U. Weissen, M. Cassidy, J. G. Grolig, A. Mai and J. T. S. Irvine, In Preparation, 2022. 5 J. B. Hansen, Faraday Discuss., 2015, 182, 9 – 48.

The future renewable energy system relies on devices capable of energy conversion and storage. Solid oxide fuel cells (SOFCs) convert the chemical energy of a fuel into electricity and heat with high electrical efficiency. The fuel flexibility of SOFCs allows for the use of not only hydrogen, but also C-containing fuels, including biogas and green fuels from power-to-X. Such fuels contain trace amounts of sulfur, either being present from the original source or added for safety reasons as odorant, which causes loss of performance in state-of-the-art (SoA) SOCFs with Ni-based cermet fuel electrodes, due to sulfur adsorption on the Ni. An upstream desulfurization unit mitigates this problem in commercial SOFC-systems, increasing CAPEX and system complexity. Hence, alternative S-tolerant fuel electrode materials are highly desirable. All-ceramic doped strontium titanates perovskite compounds (ABO3) are interesting candidates due to their high electronic conductivity and chemical stability. Among these, La0.4Sr0.4Fe0.03Ni0.03Ti0.94O3 (LSFNT), is particularly interesting, due to its B-site exsolution of electrocatalytically active Fe and Ni nanoparticles under reducing conditions. However, the electrochemical activity from the exsoluted catalyst is not sufficient and integration of additional electrocatalyst by infiltration ensures electrochemical performance comparable to SoA. In this study, the electrochemical performance and sulfur tolerance of three different, electrolyte supported cells are examined: Cell 1 contains a standard Ni/CGO cermet fuel electrode, Cell 2 contains a LSFNT electrode backbone with Ni:CGO electrocatalyst and Cell 3 contains LSFNT electrode backbone with Fe-Ni:CGO electrocatalyst.. Fe is added to the Ni:CGO to investigate if alloy formation on the nanoscale can improve the sulfur tolerance. All the cells contain LSM-YSZ oxygen electrodes. The cells were integrated in a short, 5-cell stack and tested at HEXIS AG. The fuel was a natural gas directly supplied from the grid, pre-reformed in a catalytic partial oxidation (CPOx) unit, where a desulfurization unit was connected or by-passed for determining the sulfur tolerance. The electrochemical performance was investigated for each cell in the stack individually by iV-curves and electrochemical impedance spectroscopy (EIS) with and without the use of an upstream desulfurization unit. This was followed by a durability test for ca. 400 hours with sulfur exposure. While the initial performances with short term exposure to sulfur indicate reversible degradation on both types of infiltrated LSFNT fuel electrodes, Cell 1 with the Ni/CGO cermet fuel electrode experiences loss of performance related to an increase in the Ohmic resistance. Cell 1 together with Cell 2 (LSFNT infiltrated with Ni:CGO) are both stable over several hundred hours of operation in sulfur, whereas accelerated degradation of cell voltage is observed on Cell 3 where Fe is present in the infiltrate. Details on electrochemical behavior during the durability test and origins of degradation will be presented together with a microstructural analysis. Figure 1

AbstractDelafossite semiconductors have attracted substantial attention in the field of electro-optics owing to their unique properties and availability of p-type materials that are applicable for solar cells, photocatalysts, photodetectors (PDs) and p-type transparent conductive oxides (TCOs). The CuGaO2 (CGO), as one of the most promising p-type delafossite materials, has appealing electrical and optical properties. In this work, we are able to synthesize CGO with different phases by adopting solid-state reaction route using sputtering followed by heat treatment at different temperatures. By examining the structural properties of CGO thin films, we found that the pure delafossite phase appears at the annealing temperature of 900 °C. While at lower temperatures, delafossite phase can be observed, but along with spinel phase. Furthermore, their structural and physical characterizations indicate an improvement of material-quality at temperatures higher than 600 °C. Thereafter, we fabricated a CGO-based ultraviolet-PD (UV-PD) with a metal–semiconductor-metal (MSM) configuration which exhibits a remarkable performance compared to the other CGO-based UV-PDs and have also investigated the effect of metal contacts on the device performance. We demonstrate that UV-PD with the employment of Cu as the electrical contact shows a Schottky behavior with a responsivity of 29 mA/W with a short response time of 1.8 and 5.9 s for rise and decay times, respectively. In contrast, the UV-PD with Ag electrode has shown an improved responsivity of about 85 mA/W with a slower rise/decay time of 12.2/12.8 s. Our work sheds light on the development of p-type delafossite semiconductor for possible optoelectronics application of the future.

Dense ceramic oxygen separation membranes can pass oxygen perm-selectively at elevated temperature and have potential for improving the performance and reducing the cost of several industrial processes: such as the conversion of natural gas to syngas, or to separate oxygen from air for oxy-fuel combustion in electricity generation (to reduce NOx emissions and facilitate CO2 sequestration). These pressure-driven solid state membranes are based on fast oxygen-ion conducting ceramics, but also need a compensating flow of electrons. Dual-phase composites are attractive since they provide an extra degree of freedom, compared with single phase membranes, for optimising the overall membrane performance. In this study, composites containing gadolinia doped ceria (CGO, Ce0.9Gd0.1O2- ) and either strontium-doped lanthanum cobaltite (LSC, La0.9Sr0.1CoO3- or La0.6Sr0.4CoO3- ) or silver (Ag) were investigated for possible application as oxygen separation membranes in oxy-fuel combustion system. These should combine the high oxygen ion conductivity of CGO with the high electronic conductivity and fast oxygen surface exchange of LSC or silver. Dense mixed-conducting composite materials of LSC/CGO (prepared by powder mixing and sintering) and Ag/CGO composites (prepared by silver plus copper oxide infiltration method) showed high relative density (above 95%), low background gas leakage and also good electrical conduction. The percolation threshold of the electronic conducting component was determined to be approximately 20 vol.% for both LSC compositions and 14 vol.% for Ag. Isotopic exchange and depth profiling by secondary ion mass spectrometry was used to investigated the oxygen tracer diffusion (D*) and surface exchange coefficient (k*) of the composites. Composites just above the electronic percolation threshold exhibited high solid state oxygen diffusivity, fast surface exchange activity moderate thermal expansion and sufficient mechanical strength thus combining the benefits of their constituent materials. The preliminary work on oxygen permeation measurement showed that the reasonable magnitude of oxygen fluxes is possible to be achieved. This indicates that the composites of LSC/CGO and Ag/CGO are promising for further development as passive oxygen separation membranes.

Dense ceramic oxygen separation membranes can pass oxygen perm-selectively at elevated temperature and have potential for improving the performance and reducing the cost of several industrial processes: such as the conversion of natural gas to syngas, or to separate oxygen from air for oxy-fuel combustion in electricity generation (to reduce NOx emissions and facilitate CO2 sequestration). These pressure-driven solid state membranes are based on fast oxygen-ion conducting ceramics, but also need a compensating flow of electrons. Dual-phase composites are attractive since they provide an extra degree of freedom, compared with single phase membranes, for optimising the overall membrane performance. In this study, composites containing gadolinia doped ceria (CGO, Ce0.9Gd0.1O2- ) and either strontium-doped lanthanum cobaltite (LSC, La0.9Sr0.1CoO3- or La0.6Sr0.4CoO3- ) or silver (Ag) were investigated for possible application as oxygen separation membranes in oxy-fuel combustion system. These should combine the high oxygen ion conductivity of CGO with the high electronic conductivity and fast oxygen surface exchange of LSC or silver. Dense mixed-conducting composite materials of LSC/CGO (prepared by powder mixing and sintering) and Ag/CGO composites (prepared by silver plus copper oxide infiltration method) showed high relative density (above 95%), low background gas leakage and also good electrical conduction. The percolation threshold of the electronic conducting component was determined to be approximately 20 vol.% for both LSC compositions and 14 vol.% for Ag. Isotopic exchange and depth profiling by secondary ion mass spectrometry was used to investigated the oxygen tracer diffusion (D*) and surface exchange coefficient (k*) of the composites. Composites just above the electronic percolation threshold exhibited high solid state oxygen diffusivity, fast surface exchange activity moderate thermal expansion and sufficient mechanical strength thus combining the benefits of their constituent materials. The preliminary work on oxygen permeation measurement showed that the reasonable magnitude of oxygen fluxes is possible to be achieved. This indicates that the composites of LSC/CGO and Ag/CGO are promising for further development as passive oxygen separation membranes.

L’oxyde d’éthylène (OE) est un précurseur de nombreuses réactions de chimie fine. Il est produit par la réaction d’époxydation de l’éthylène sur un catalyseur à base d’argent. Néanmoins, afin d’atteindre des sélectivités élevées, le procédé industriel utilise des additifs chlorés dans la phase gaz peu écologiques et des modérateurs alcalins sur le catalyseur. L’objectif de cette étude est d’augmenter la sélectivité vers OE sans utilisation de promoteurs chlorés grâce à des électrocatalyseurs Ag/oxydes à structure fluorite synthétisés en couche mince par pulvérisation cathodique magnétron en atmosphère réactive à haute pression. Durant les tests de catalyse les électrocatalyseurs ont été polarisés dans des cellules en configuration 3 électrodes dédiées à la promotion électrochimique de la catalyse, EPOC. Trois systèmes poreux (Ag/YSZ, Ag/CGO & Ag(Cu)/CGO) ont été développés par pulvérisation cathodique magnétron. Le film Ag/YSZ 4 Pa 25 mA présente une microstructure botryoïde caractéristiques d’une séparation des charges d’argent et de la matrice YSZ. Le film nanocomposite Ag/CGO 4 Pa 70 mA présente une morphologie ouverte de type cerveau avec des nano porosités débouchantes. Enfin, le film Ag(Cu)/CGO 4 Pa 70 mA est constitué de nanofils hydrophobes multiphasés entropique. Durant les tests en conditions d’époxydation de l’éthylène en milieu réducteur, le film Ag/CGO 4 Pa 70 mA a présenté un maximum de sélectivité vers OE de 16,55 % à 220 °C et, sous polarisation, la sélectivité a pu être augmentée de 2,78 % sans modification de la vitesse de réaction par effet NEMCA
Ethylene oxide (EO) is an essential building block for the chemical industry. It is produced by the ethylene epoxidation reaction over a silver-based catalyst. Nevertheless, to achieve high selectivity, industrial processes use chloride additives in the gas phase and alkaline moderators on the catalyst. The aim of this study is to increase EO selectivity without chloride additives thanks to Ag/fluorite oxides electrocatalysts synthesized by reactive magnetron sputtering and incorporated in a 3-electrodes configuration cell designed for electrochemical promotion of catalysis, EPOC. Three porous systems (Ag/YSZ, Ag/GDC, Ag(Cu)/GDC) have been synthesized by reactive magnetron sputtering. Ag/YSZ 4 Pa 25 mA nanocomposite thin film exhibits a botryoidal microstructure characteristic of silver segregation inside the YSZ matrix. Ag/GDC 4 Pa 70 mA nanocomposite thin film exhibits a brain like-morphology with open nanoporosities. Ag(Cu)/GDC 4 Pa 70 mA nanocomposite thin film consists of multi-phase hydrophobic entropic nanowires. During catalytic tests under ethylene epoxidation conditions in reducing medium, Ag/GDC 4 Pa 70 mA showed the maximum EO selectivity of 16.55 % at 220 °C and, under polarization, selectivity boost of 2.78 % occur without the appearance of NEMCA effect