Areum Jun

Layered oxygen-deficient double perovskite as an efficient and stable anode for direct hydrocarbon solid oxide fuel cells

Different layered perovskite-related oxides are known to exhibit important electronic, magnetic and electrochemical properties. Owing to their excellent mixed-ionic and electronic conductivity and fast oxygen kinetics, cation layered double perovskite oxides such as PrBaCo2O5 in particular have exhibited excellent properties as solid oxide fuel cell oxygen electrodes. Here, we show for the first time that related layered materials can be used as high-performance fuel electrodes. Good redox stability with tolerance to coking and sulphur contamination from hydrocarbon fuels is demonstrated for the layered perovskite anode PrBaMn2O5+δ (PBMO). The PBMO anode is fabricated by in situ annealing of Pr0.5Ba0.5MnO3-δ in fuel conditions and actual fuel cell operation is demonstrated. At 800 °C, layered PBMO shows high electrical conductivity of 8.16 S cm(-1) in 5% H2 and demonstrates peak power densities of 1.7 and 1.3 W cm(-2) at 850 °C using humidified hydrogen and propane fuels, respectively.

Highly efficient and robust cathode materials for low-temperature solid oxide fuel cells: PrBa0.5Sr0.5Co2−xFexO5+δ

Solid oxide fuel cells (SOFC) are the cleanest, most efficient, and cost-effective option for direct conversion to electricity of a wide variety of fuels. While significant progress has been made in anode materials with enhanced tolerance to coking and contaminant poisoning, cathodic polarization still contributes considerably to energy loss, more so at lower operating temperatures. Here we report a synergistic effect of co-doping in a cation-ordered double-perovskite material, PrBa0.5Sr0.5Co2−xFexO5+δ, which has created pore channels that dramatically enhance oxygen ion diffusion and surface oxygen exchange while maintaining excellent compatibility and stability under operating conditions. Test cells based on these cathode materials demonstrate peak power densities ~2.2 W cm−2 at 600°C, representing an important step toward commercially viable SOFC technologies.

Development of Double-Perovskite Compounds as Cathode Materials for Low-Temperature Solid Oxide Fuel Cells

A class of double-perovskite compounds display fast oxygen ion diffusion and high catalytic activity toward oxygen reduction while maintaining excellent compatibility with the electrolyte. The astoundingly extended stability of NdBa(1-x)Ca(x)Co2O(5+δ) (NBCaCO) under both air and CO2-containing atmosphere is reported along with excellent electrochemical performance by only Ca doping into the A site of NdBaCo2O(5+δ) (NBCO). The enhanced stability can be ascribed to both the increased electron affinity of mobile oxygen species with Ca, determined through density functional theory calculations and the increased redox stability from the coulometric titration.

Chemically Stable Perovskites as Cathode Materials for Solid Oxide Fuel Cells: La‐Doped Ba0.5Sr0.5Co0.8Fe0.2O3−δ

Ba0.5Sr0.5Co0.8Fe0.2O(3-δ) (BSCF) has won tremendous attention as a cathode material for intermediate-temperature solid-oxide fuel cells (IT-SOFC) on the basis of its fast oxygen-ion transport properties. Nevertheless, wide application of BSCF is impeded by its phase instabilities at intermediate temperature. Here we report on a chemically stable SOFC cathode material, La0.5Ba0.25Sr0.25Co0.8Fe0.2O(3-δ) (LBSCF), prepared by strategic approaches using the Goldschmidt tolerance factor. The tolerance factors of LBSCF and BSCF indicate that the structure of the former has a smaller deformation of cubic symmetry than that of the latter. The electrical property and electrochemical performance of LBSCF are improved compared with those of BSCF. LBSCF also shows excellent chemical stability under air, a CO2-containg atmosphere, and low oxygen partial pressure while BSCF decomposed under the same conditions. Together with this excellent stability, LBSCF shows a power density of 0.81 W cm(-2) after 100 h, whereas 25 % degradation for BSCF is observed after 100 h.

Correlation between fast oxygen kinetics and enhanced performance in Fe doped layered perovskite cathodes for solid oxide fuel cells

Many researchers have recently focused on layered perovskite oxides as cathode materials for solid oxide fuel cells because of their much higher chemical diffusion and surface exchange coefficients relative to those of ABO3-type perovskite oxides. Herein, we study the catalytic effect of Fe doping into SmBa0.5Sr0.5Co2O5+δ on the oxygen reduction reaction (ORR) and investigate the optimal Fe substitution through an analysis of the structural characteristics, electrical properties, redox properties, oxygen kinetics, and electrochemical performance of SmBa0.5Sr0.5Co2−xFexO5+δ (x = 0, 0.25, 0.5, 0.75, and 1.0). The optimal Fe substitution, SmBa0.5Sr0.5Co1.5Fe0.5O5+δ, enhanced the performance and redox stability remarkably and also led to satisfactory electrical properties and electrochemical performance due to its fast oxygen bulk diffusion and high surface kinetics under typical fuel cell operating conditions. The results suggest that SmBa0.5Sr0.5Co1.5Fe0.5O5+δ is a promising cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs).

Nanostructured Double Perovskite Cathode With Low Sintering Temperature For Intermediate Temperature Solid Oxide Fuel Cells

This study focuses on reducing the cathode polarization resistance through the use of mixed ionic electronic conductors and the optimization of cathode microstructure to increase the number of electrochemically active sites. Among the available mixed ionic electronic conductors (MIECs), the layered perovskite GdBa0.5 Sr0.5 CoFeO5+δ (GBSCF) was chosen as a cathode material for intermediate temperature solid oxide fuel cells owing to its excellent electrochemical performance and structural stability. The optimized microstructure of a GBSCF-yttria-stabilized zirconia (YSZ) composite cathode was prepared through an infiltration method with careful control of the sintering temperature to achieve high surface area, adequate porosity, and well-organized connection between nanosized particles to transfer electrons. A symmetric cell shows outstanding results, with the cathode exhibiting an area-specific resistance of 0.006 Ω cm(2) at 700 °C. The maximum power density of a single cell using Ce-Pd anode with a thickness of ∼80 μm electrolyte was ∼0.6 W cm(-2) at 700 °C.

Influence of Ca-doping in layered perovskite PrBaCo2O5+δ on the phase transition and cathodic performance of a solid oxide fuel cell

Layered perovskite oxides with the formula LnBaCo2O5+δ (Ln = Pr, Nd, Sm and Gd) have received attention as promising cathode materials for solid oxide fuel cells (SOFCs) because of their high oxygen diffusion and surface exchange coefficients. Recently, many researchers have reported that substituting barium with strontium or calcium can increase the structural stability, electrical conductivity, and catalytic activity of LnBaCo2O5+δ. In this study, we investigated the effect of Ca doping on the structural, electrical, and electrochemical properties of PrBa1−xCaxCo2O5+δ (x = 0, 0.1, 0.2, 0.3 and 0.4). Increasing the amount of Ca dopant changed the structure of PrBa1−xCaxCo2O5+δ from a layered perovskite to a simple perovskite. At x = 0.3, co-existence of the simple and the layered perovskite structure is observed. Electrical conductivity and electro-chemical performance were improved with increasing amount of Ca in the layered perovskite structure and declined with increasing amount of the simple perovskite phase.

Achieving High Efficiency and Eliminating Degradation in Solid Oxide Electrochemical Cells Using High Oxygen-Capacity Perovskite

Recently, there have been efforts to use clean and renewable energy because of finite fossil fuels and environmental problems. Owing to the site-specific and weather-dependent characteristics of the renewable energy supply, solid oxide electrolysis cells (SOECs) have received considerable attention to store energy as hydrogen. Conventional SOECs use Ni-YSZ (yttria-stabilized zirconia) and LSM (strontium-doped lanthanum manganites)-YSZ as electrodes. These electrodes, however, suffer from redox-instability and coarsening of the Ni electrode along with delamination of the LSM electrode during steam electrolysis. In this study, we successfully design and fabricate highly efficient SOECs using layered perovskites, PrBaMn2 O5+δ (PBM) and PrBa0.5 Sr0.5 Co1.5 Fe0.5 O5+δ (PBSCF50), as both electrodes for the first time. The SOEC with layered perovskites as both-side electrodes shows outstanding performance, reversible cycling, and remarkable stability over 600 hours.

Catalytic Dynamics and Oxygen Diffusion in Doped PrBaCo2O5.5+δ Thin Films

The Sr and Fe codoped double perovskites PrBaCo2O5.5+δ (PrBCO) thin films of Pr(Ba0.5Sr0.5)(Co1.5Fe0.5)O5.5+δ (PBSCFO) were epitaxially grown for chemical catalytic studies. The resistance behavior of PBSCFO epitaxial films was monitored under the switching flow of reducing and oxidizing gases as a function of the gas flow time, t, using an electrical conductivity relaxation (ECR) experimental setup. The R(t) vs t relationships determined at various temperatures show the occurrence of two oxidation processes, Co(2+)/Co(3+) ↔ Co(3+) and Co(3+) ↔ Co(3+)/Co(4+). Mathematical fitting of the observed R(t) vs t relationships was carried out using Ficks second law for one-dimensional diffusion of charge carriers to derive the diffusivity D(T) and τ(T) for the two processes at various temperatures, T. The D(T) vs T relationships were analyzed in terms of the Arrhenius relationship to find the activation energies Ea for each process. Oscillations in the dR(t)/dt plots, observed under oxidation reactions, were discussed in terms of a layer-by-layer oxygen vacancy exchange diffusion mechanism. Our work suggests that thin films of LnBCO (Ln = lanthanide) with their A and B sites doped as in PBSCFO are excellent candidates for the development of low or intermediate temperature energy conversion devices and gas sensor applications.