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Register a new userInfluence of particle size and agglomeration in solid oxide fuel cell cathodes using manganite nanoparticles
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In this work we studied the influence of particle size and agglomeration in the performance of solid oxide fuel cell cathodes made with nanoparticles of La0.8Sr0.2MnO3. We followed two synthesis routes based on the Liquid Mix method. In both procedures we introduced additional reagents in order to separated the manganite particles. We evaluated cathodic performance by Electrochemical Impedance Spectroscopy in symmetrical (CATHODE/ELECTROLYTE/CATHODE) cells. Particle size was tuned by the temperature used for cathode sintering. Our results show that deagglomeration of the particles, serves to improve the cathodes performance. However, the dependence of the performance with the size of the particles is not clear, as different trends were obtained for each synthesis route. As a common feature, the cathodes with the lowest area specific resistance are the ones sintered at the largest temperature. This result indicates that an additional factor related with the quality of the cathode/electrolyte sintering, is superimposed with the influence of particle size, however further work is needed to clarify this issue. The enhancement obtained by deagglomeration suggest that the use of this kind of methods deserved to be considered to develop high performance electrodes for solid oxide fuel cells.
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In this work we outline the mechanisms contributing to the oxygen reduction reaction in nanostructured cathodes of La0.8Sr0.2MnO3 (LSM) for Solid Oxide Fuel Cells (SOFC). These cathodes, developed from LSM nanostructured tubes, can be used at lower temperatures compared to microstructured ones, and this is a crucial fact to avoid the degradation of the fuel cell components. This reduction of the operating temperatures stems mainly from two factors: i) the appearance of significant oxide ion diffusion through the cathode material in which the nanostructure plays a key role and ii) an optimized gas phase diffusion of oxygen through the porous structure of the cathode, which becomes negligible. A detailed analysis of our Electrochemical Impedance Spectroscopy supported by first principles calculations point towards an improved overall cathodic performance driven by a fast transport of oxide ions through the cathode surface.
Critical to the development of improved solid oxide fuel cell (SOFC) technology are novel compounds with high oxygen reduction reaction (ORR) catalytic activity and robust stability under cathode operating conditions. Approximately 2145 distinct perovskite compositions are screened for potential use as high activity, stable SOFC cathodes, and it is verified that the screening methodology qualitatively reproduces the experimental activity, stability, and conduction properties of well-studied cathode materials. The calculated oxygen p-band center is used as a first principle-based descriptor of the surface exchange coefficient (k*), which in turn correlates with cathode ORR activity. Convex hull analysis is used under operating conditions in the presence of oxygen, hydrogen, and water vapor to determine thermodynamic stability. This search has yielded 52 potential cathode materials with good predicted stability in typical SOFC operating conditions and predicted k* on par with leading ORR perovskite catalysts. The established trends in predicted k* and stability are used to suggest methods of improving the performance of known promising compounds. The material design strategies and new materials discovered in the computational search help enable the development of high activity, stable compounds for use in future solid oxide fuel cells and related applications.
We report a study on the pressure response of the anisotropy energy of hollow and solid maghemite nanoparticles. The differences between the maghemite samples are understood in terms of size, magnetic anisotropy and shape of the particles. In particular, the differences between hollow and solid samples are due to the different shape of the nanoparticles and by comparing both pressure responses it is possible to conclude that the shell has a larger pressure response when compared to the core.
We have studied the magnetic and power absorption properties of a series of magnetic nanoparticles (MNPs) of Fe3O4 with average sizes <d> ranging from 3 to 26 nm. Heating experiments as a function of particle size revealed a strong increase in the specific power absorption (SPA) values for particles with <d> = 25-30 nm. On the other side saturation magnetization MS values of these MNPs remain essentially constant for particles with <d> above 10 nm, suggesting that the absorption mechanism is not determined by MS. The largest SPA value obtained was 130 W/g, corresponding to a bimodal particle distribution with average size values of 17 and 26 nm.
In order to better understand the transition from quantum to classical behavior in spin system, electron magnetic resonance (EMR) is studied in suspensions of superparamagnetic magnetite nanoparticles with an average diameter of ~ 9 nm and analyzed in comparison with the results obtained in the maghemite particles of smaller size (~ 5 nm). It is shown that both types of particles demonstrate common EMR behavior, including special features such as the temperature-dependent narrow spectral component and multiple-quantum transitions. These features are common for small quantum systems and not expected in classical case. The relative intensity of these signals rapidly decreases with cooling or increase of particle size, marking gradual transition to the classical FMR behavior.
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