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Compatibility and performance of SOFCs based on lanthanum tungstates

Dos-Santos-Gómez, Lucía,Porras-Vázquez, José Manuel,Zayas-Rey, María José,Ramírez-Losilla, Enrique,Marrero-López, David

Abstract

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.

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V Iberian Symposium on Hydrogen, Fuel Cells and Advanced Batteries. Tenerife, España, July 05-08 2015 Compatibility and performance of SOFCs based on lanthanum tungstates Lucía dos Santos-Gómez1*, José M. Porras-Vázquez1, María José Zayas-Rey, Enrique R. Losilla1 and David Marrero-López2 1Universidad de Málaga, Dpto. de Química Inorgánica, 29071-Málaga, Spain 2Unversidad de Málaga, Dpto. de Física Aplicada I, Laboratorio de Materiales y Superficies (Unidad Asociada al C.S.I.C.), 29071Málaga, Spain (*) e-mail corresponding author: lucia_2_sant[email protected] ______________________________________________________________________________________ Keywords: La6WO12, fluorite structure, fuel cell, proton conductor 1 Abstract Rare-earth tungstates with general composition “Ln6WO12” have attracted great attention in last few years due to their relatively high mixed protonelectron conductivity [1, 2]. One of the main advantages 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 composition 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 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 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. Fig. 1. Cell voltage and power density as a function of current density at different temperatures using air and 5% H2–Ar as oxidant and fuel respectively. 2 Acknowledgements This work was supported by MINECO through the MAT2013-41836-R research grant (Spain) which is co-funded by FEDER. Lucía dos SantosGómez thanks to the Spanish MECD for her FPU grant. Dr. J.M. Porras-Vázquez thanks Andalucía Tech for the funding. 3 References [1] Magrasó, A., Frontera, C., Marrero-López, D., Núñez, P., New crystal structure and characterization of lanthanum tungstate "La6WO12" prepared by freeze-drying synthesis, Dalton Trans. 46, pp. 10273-10283, 2009. [2] Haugsrud, R., Kjølseth, C., Effects of protons and acceptor substitution on the electrical conductivity of La6WO12, J. Phys. Chem. Solids, 69, pp. 1758-1765, 2008. [3] Zayas-Rey, M.J., dos Santos-Gómez, L., Cabeza, A., Marrero-López, D., R. Losilla, E., Proton conductors based on alkaline-earth substituted La28-xW4+xO54+3x/2, Dalton Trans., 43 (17), pp. 64906499, 2014.