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Nanocrystalline cathodes for PC-SOFCs

Dos-Santos-Gómez, Lucía

Abstract

Ceramic proton conductors are of great interest for the development of solid oxide fuel cells (PC-SOFC) operating at relatively low temperatures between 400 and 700 ºC. Perovskites based on BaCeO3-δ exhibit the highest proton conductivity among this class of materials, however, they are susceptible to hydra-tion 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 usually 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 tempe-ratures depends significantly on the ohmic resis-tance of the electrolyte, although it can be lowered by reducing the electrolyte thickness. Another im-portant 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 symmet-rically 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 im-pedance spectroscopy. The stability of these elec-trodes at intermediate temperatures was evaluated as a function of time. These nanocrystalline cathodes exhibit a sub-stantial improvement of the electrode polarization resistance with respect to the same materials pre-pared by screen-printing method at high sintering temperatures, e.g. 0.7 and 3.2 cm2 at 600ºC for LSCF cathodes prepared by spray-pyrolysis and screen-printing method respectively (Fig. 1). An anode supported cell with composition LSCF/BCZY/NiO-BCZY was also prepared to test the electrochemical performance.

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V Iberian Symposium on Hydrogen, Fuel Cells and Advanced Batteries. Tenerife, España, July 05-08 2015 Nanocrystalline cathodes for PC-SOFCs Lucía dos Santos-Gómez1*, Jesús D. Zea-García1, 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: BaCe0.6Zr0.2Y0.2O3-δ, fuel cells, proton conductor, microstructure, impedance spectroscopy. 1 Abstract Ceramic proton conductors are of great interest for the development of solid oxide fuel cells (PCSOFC) operating at relatively low temperatures between 400 and 700 ºC. 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 usually 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 Zncontaining 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 Ωcm2 at 600ºC for LSCF cathodes prepared by spray-pyrolysis and screen-printing method respectively (Fig. 1). An anode supported cell with composition LSCF/BCZY/NiO-BCZY was also prepared to test the electrochemical performance. 0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 LSCF deposited by screen-printing LSCF deposited by spray-pyrolysis 10 Hz 1 Hz 0.1 Hz -Z´´(Ωcm2) Z´(Ωcm2) 0.01 Hz Fig. 1. Impedance spectra of LSCF cathodes deposited by spray-pyrolysis and conventional screen-printing on BCZY electrolytes. 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. 3 References [1] Zakowsky, N., Williamson, S., Irvine, J.T.S., Elaboration of tolerance limits of BaCe0.9Y0.1O3–δ electrolytes for fuel cells and other applications, Solid State Ionics, 176, pp. 3019-3026, 2005. [2] Amsif, M., Marrero-López, D., Ruíz-Morales, J.C., Savvin, S.N., Núñez, P., The effect of Zn addition on the structure and transport properties of BaCe0.9−xZrxY0.1O3−δ, J. Eur. Ceram. Soc., 34, pp. 1553-1562, 2014. [3] dos Santos-Gómez, L., R. Losilla, E., Martín, F., Ramos-Barrado, J.R., Marrero-López, D., Novel microstructural strategies to enhance the electrochemical performance of La0.8Sr0.2MnO3-δ cathodes, ACS Appl. Mater. Inter., DOI: 10.1021/acsami.5b00255.