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Solid Oxide Fuel Cells (SOFCs) have proven to be highly efficient and one of the cleanest electrochemical energy conversion devices. However, the commercialization of this technology is hampered by issues related to electrode performance degradation. This article provides a comprehensive review of the various degradation mechanisms that affect the performance and long-term stability of the SOFC anode caused by the interplay of physical, chemical, and electrochemical processes. In SOFCs, the most used anode material is nickel-yttria stabilized zirconia (Ni-YSZ) due to its advantages of high electronic conductivity and high catalytic activity for H2 fuel. However, various factors affecting the long-term stability of the Ni-YSZ anode, such as redox cycling, carbon coking, sulfur poisoning, and the reduction of the triple phase boundary length due to Ni particle coarsening, are thoroughly investigated. In response, the article summarizes the state-of-the-art diagnostic tools and mitigation strategies aimed at improving the long-term stability of the Ni-YSZ anode.
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In the original publication [...].
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The progressive research trends in the development of low-cost, commercially competitive solid oxide fuel cells with reduced operating temperatures are closely linked to the search for new functional materials as well as technologies to improve the properties of established materials traditionally used in high-temperature devices. Significant efforts are being made to improve air electrodes, which significantly contribute to the degradation of cell performance due to low oxygen reduction reaction kinetics at reduced temperatures. The present review summarizes the basic information on the methods to improve the electrochemical performance of conventional air electrodes with perovskite structure, such as lanthanum strontium manganite (LSM) and lanthanum strontium cobaltite ferrite (LSCF), to make them suitable for application in second generation electrochemical cells operating at medium and low temperatures. In addition, the information presented in this review may serve as a background for further implementation of developed electrode modification technologies involving novel, recently investigated electrode materials.
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Oxygen and hydrogen mobility are among the important characteristics for the operation of solid oxide fuel cells, permselective membranes and many other electrochemical devices. This, along with other characteristics, enables a high-power density in solid oxide fuel cells due to reducing the electrolyte resistance and enabling the electrode processes to not be limited by the electrode-electrolyte-gas phase triple-phase boundary, as well as providing high oxygen or hydrogen permeation fluxes for membranes due to a high ambipolar conductivity. This work focuses on the oxygen and hydrogen diffusion of mixed ionic (oxide ionic or/and protonic)-electronic conducting materials for these devices, and its role in their performance. The main laws of bulk diffusion and surface exchange are highlighted. Isotope exchange techniques allow us to study these processes in detail. Ionic transport properties of conventional and state-of-the-art materials including perovskites, Ruddlesden-Popper phases, fluorites, pyrochlores, composites, etc., are reviewed.
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In this study, BaZr0.87Y0.1M0.03O3-δ perovskite electrolytes with sintering aids (M = Mn, Co, and Fe) were synthesized by a sustainable approach using spinach powder as a chelating agent and then compared with chemically synthesized BaZr0.87Y0.1M0.03O3-δ (M = Mn, Co, and Fe) electrolytes for intermediate temperature SOFCs. This is the first example of such a sustainable synthesis of perovskite materials with sintering aids. Structural analysis revealed the presence of a cubic perovskite structure in BaZr0.87Y0.1M0.03O3-δ (M = Mn, Co, and Fe) samples synthesized by both green and conventional chemical methods. No significant secondary phases were observed in the samples synthesized by a sustainable approach. The observed phenomena of plane shift were because of the disparities between ionic radii of the dopants, impurities, and host materials. The surface morphology analysis revealed a denser microstructure for the electrolytes synthesized via green routes due to metallic impurities in the organic chelating agent. The absence of significant impurities was also observed by compositional analysis, while functional groups were identified through Fourier-transform infrared spectroscopy. Conductivity measurements showed that BaZr0.87Y0.1M0.03O3-δ (M = Mn, Co, and Fe) electrolytes synthesized by oxalic acid have higher conductivities compared to BaZr0.87Y0.1M0.03O3-δ (M = Mn, Co, and Fe) electrolytes synthesized by the green approach. The button cells employing BaZr0.87Y0.1Co0.03O3-δ electrolytes synthesized by the chemical and green routes achieved peak power densities 344 and 271 mW·cm-2 respectively, suggesting that the novel green route can be applied to synthesize SOFC perovskite materials with minimal environmental impact and without significantly compromising cell performance.
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Solid oxide fuel cells (SOFCs) are efficient electrochemical devices that allow for the direct conversion of fuels (their chemical energy) into electricity. Although conventional SOFCs based on YSZ electrolytes are widely used from laboratory to commercial scales, the development of alternative ion-conducting electrolytes is of great importance for improving SOFC performance at reduced operation temperatures. The review summarizes the basic information on two representative families of oxygen-conducting electrolytes: doped lanthanum aluminates (LaAlO3) and lanthanum gallates (LaGaO3). Their preparation features, chemical stability, thermal behaviour and transport properties are thoroughly analyzed in terms of their connection with the target functional parameters of related SOFCs. The data presented here will serve as a starting point for further studies of La-based perovskites, including in the fields of solid state ionics, electrochemistry and applied energy.
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In this review, recent achievements in the application of high-entropy alloys (HEAs) and high-entropy oxides (HEOs) in the technology of solid oxide fuel cells (SOFC) are discussed for the first time. The mechanisms of the stabilization of a high-entropy state in such materials, as well as the effect of structural and charge factors on the stability of the resulting homogeneous solid solution are performed. An introduction to the synthesis methods for HEAs and HEOs is given. The review highlights such advantages of high-entropy materials as high strength and the sluggish diffusion of components, which are promising for the use at the elevated temperatures, which are characteristic of SOFCs. Application of the medium- and high-entropy materials in the hydrocarbon-fueled SOFCs as protective layers for interconnectors and as anode components, caused by their high stability, are covered. High-entropy solid electrolytes are discussed in comparison with traditional electrolyte materials in terms of conductivity. High-entropy oxides are considered as prospective cathodes for SOFCs due to their superior electrochemical activity and long-term stability compared with the conventional perovskites. The present review also determines the prioritizing directions in the future development of high-entropy materials as electrolytes and electrodes for SOFCs operating in the intermediate and low temperature ranges.
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The La1.7Ca0.3Ni1-yCuyO4+δ (y = 0.0-0.4) nickelates, synthesized via a solid-state reaction method, are investigated as prospective materials for oxygen permeation membranes and IT-SOFC cathodes. The obtained oxides are single-phase and possess a tetragonal structure (I4/mmm sp. gr.). The unit cell parameter c and the cell volume increase with Cu-substitution. The interstitial oxygen content and total conductivity decrease with Cu-substitution. The low concentration of mobile interstitial oxygen ions results in a limited oxygen permeability of Cu-substituted La1.7Ca0.3NiO4+δ ceramic membranes. However, increasing the Cu content over y = 0.2 induces two beneficial effects: enhancement of the electrochemical activity of the La1.7Ca0.3Ni1-yCuyO4+δ (y = 0.0; 0.2; 0.4) electrodes and decreasing the sintering temperature from 1200 °C to 900 °C. Enhanced electrode activity is due to better sintering properties of the developed materials ensuring excellent adhesion and facilitating the charge transfer at the electrode/electrolyte interface and, probably, faster oxygen exchange in Cu-rich materials. The polarization resistance of the La1.7Ca0.3Ni1.6Cu0.4O4+δ electrode on the Ce0.8Sm0.2O1.9 electrolyte is as low as 0.15 Ω cm2 and 1.95 Ω cm2 at 850 °C and 700 °C in air, respectively. The results of the present work demonstrate that the developed La1.7Ca0.3Ni0.6Cu0.4O4+δ-based electrode can be considered as a potential cathode for intermediate-temperature solid oxide fuel cells.
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The chemical design of new functional materials for solid oxide fuel cells (SOFCs) is of great interest as a means for overcoming the disadvantages of traditional materials. Redox stability, carbon deposition and sulfur poisoning of the anodes are positioned as the main processes that result in the degradation of SOFC performance. In this regard, double perovskite molybdates are possible alternatives to conventional Ni-based cermets. The present review provides the fundamental properties of four members: Sr2NiMoO6-δ, Sr2MgMoO6-δ, Sr2FeMoO6-δ and Sr2Fe1.5Mo0.5O6-δ. These properties vary greatly depending on the type and concentration of the 3d-element occupying the B-position of A2BB'O6. The main emphasis is devoted to: (i) the synthesis features of undoped double molybdates, (ii) their electrical conductivity and thermal behaviors in both oxidizing and reducing atmospheres, as well as (iii) their chemical compatibility with respect to other functional SOFC materials and components of gas atmospheres. The information provided can serve as the basis for the design of efficient fuel electrodes prepared from complex oxides with layered structures.