Al,Bi元素对合成LSCF的影响

将La(NO3)3、Sr(NO3)2、Fe(NO3)3和Co(NO3)2按照La0.8Sr0.2Co0.8Fe0.8O3(LSCF)摩尔比配置硝酸盐混合溶液,并在其中添加Al、Bi硝酸盐,用差示扫描量热法(DSC)、热重-差热分析法(TG-DTA)和X射线衍射光谱法(XRD)结合研究Al,Bi两种元素的添加对在锶掺杂的锰酸镧-氧化钇稳定的氧化锆(LSM-YSZ)阴极现场低温合成LSCF的影响。DSC、TG-DTA的研究结果表明,Al、Bi两种元素的加入,改变了LSCF前驱物的熔融状态和均匀性。XRD的研究结果表明,未添加和添加Al的样品,需要在800℃以上出现明显的LSCF钙钛矿结构特征峰,添加Bi的LSCF样品在650℃有明显的LSCF特征峰,Bi对LSCF钙钛矿结构形成有促进作用。添加Bi的LSCF样品有La稳定的Bi2O3和Sr稳定的Bi2O3峰。     

Electrocatalytic activity of perovskite-based cathodes for solid oxide fuel cells

A very active cathode material for intermediate temperature - solid oxide fuel cells (IT-SOFCs) is obtained by mixing La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF) powders. Three different volume ratios are considered: BSCF-LSCF 50-50 v/v% (BL50), BSCF-LSCF 70-30 v/v% (BL70) and 30–70 v/v% (BL30).The electrodes are slurry coated on Ce_0.8Sm_0.2O_2-δ electrolyte and sintered at 1100 °C. After the sintering step XRD-analyses highlight relevant cation inter-diffusion within the mixed powders. As a result, an enhanced activity of BL30-BL70 electrodes towards oxygen reduction reaction is detected in comparison to LSCF or BSCF pure powders. A polarization resistance of 0.021 Ω cm2 at 650 °C for BL70 is obtained, one of the lowest value reported in literature for SOFC cathodes. Furthermore, all the electrodes show lower activation energy than the two reference materials in the considered temperature range (500–650 °C) and two different kinetic regimes are identified at the extremes of this range. Effect of the applied overpotential (0–0.3 V) on the electrode kinetic is also investigated.After a preliminary ageing, performed at 650 °C for 200 h by applying a current density of 200 mA cm-2, the electrodes preserve a remarkable performance as IT-SOFC cathodes, despite an initial degradation. A stable value of 0.048 Ω cm2 of polarization resistance for the sample richer in BSCF is recorded.     

Mechanisms of synthesis gas production via thermochemical cycles over La0·3Sr0·7Co0·7Fe0·3O3

La_0·3Sr_0·7Co_0·7Fe_0·3O₃ (LSCF3773) was chosen as an oxygen carrier material for synthesis gas production and synthesized using ethylene-diamine-tetra-acetic acid (EDTA) citrate-complexing method. LSCF exhibited a pure cubic structure where 110 and 100 plane diffractions were active for CO₂ splitting, while 111 was more favored by H₂O splitting. Overall oxygen storage capacity (OSC) of LSCF was 4072 μmol/g_cat. During the reduction process, regular cations (Co⁴⁺, Fe⁴⁺), polaron cations (Co³⁺, Fe³⁺) and localized cations (Co²⁺, Fe²⁺) were achieved when the LSCF was reduced at 500, 700 and 900 °C, respectively. The strength of the active sites depended on reduction temperatures. An increase in oxidation temperature enhanced H₂ production at temperature ranging from 500 °C to 700 °C while effected CO production at 900 °C. H₂O and CO₂ was competitively split during the oxidation step, especially at 700 °C. The activation energy of each reaction was ordered as; CO₂ splitting > H₂O splitting > CO₂ adsorption, supporting the above evidence where H₂ and CO production were found to increase when the operating temperature was increased.     

Porous LSCF/dense 3YSZ interface fracture toughness measured by single cantilever beam wedge test

Sandwich specimens were prepared by firing a thin inter-layer of porous La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) to bond a thin tetragonal yttria-stabilised zirconia (3YSZ) beam to a thick 3YSZ substrate. Fracture of the joint was evaluated by introducing a wedge between the two YSZ adherands so that the stored energy in the thin YSZ cantilever beam drives a stable crack in the adhesive bond. It was found that the extent of adhesive fracture increased with firing temperature and decreased with LSCF layer thickness. The adhesive failures were mainly at the interface between the LSCF and the thin YSZ beam and FEM modelling revealed that this is due to asymmetric stresses in the LSCF. The intrinsic adhesive fracture toughness of the LSCF/YSZ interface was estimated to be 11 J m⁻² and was not firing temperature dependent within the temperature range investigated.     

Performance improvement by metal deposition at the cathode active site in solid oxide fuel cells

In this study, the performance improvement of the SOFC single cell and its underlying mechanism was investigated. Furthermore, an application of the identified electrochemical mechanism is proposed and tested experimentally. The deposition of Platinum (Pt) at electrochemically active sites for the oxygen reduction reaction is determined to be responsible for the improved performance. Pt migration from a current collector to the cathode active sites originates from the oxygen partial pressure difference between current collector and triple phase boundary, and the electrochemical reduction reaction. It is supported by the confirmation of Pt particles at the cathode active sites by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and calculations of the thermodynamic equilibrium partial pressure values. In addition, correlation of the initial performance change and the quantities of Pt deposition are investigated. This selective Pt deposition mechanism at the active sites is applied to the LSCF cathode, as well.     

On the role of ultra-thin oxide cathode synthesis on the functionality of micro-solid oxide fuel cells: Structure, stress engineering and in situ observation of fuel cell membranes during operation

Microstructure and stresses in dense La_0.6Sr_0.4Co_0.8Fe_0.2O₃ (LSCF) ultra-thin films have been investigated to increase the physical thickness of crack-free cathodes and active area of thermo-mechanically robust micro-solid oxide fuel cell (μSOFC) membranes. Processing protocols employ low deposition rates to create a highly granular nanocrystalline microstructure in LSCF thin films and high substrate temperatures to produce linear temperature-dependent stress evolution that is dominated by compressive stresses in μSOFC membranes. Insight and trade-off on the synthesis are revealed by probing microstructure evolution and electrical conductivity in LSCF thin films, in addition to in situ monitoring of membrane deformation while measuring μSOFC performance at varying temperatures. From these studies, we were able to successfully fabricate failure-resistant square μSOFC (LSCF/YSZ/Pt) membranes with width of 250 μm and crack-free cathodes with thickness of ∼70 nm. Peak power density of ∼120 mW cm⁻² and open circuit voltage of ∼0.6 V at 560 °C were achieved on a μSOFC array chip containing ten such membranes. Mechanisms affecting fuel cell performance are discussed. Our results provide fundamental insight to pathways of microstructure and stress engineering of ultra-thin, dense oxide cathodes and μSOFC membranes.     

Interlayer-free nanostructured La0.58Sr0.4Co0.2 Fe0.8O3−δ cathode on scandium stabilized zirconia electrolyte for intermediate-temperature solid oxide fuel cells

LSCF powders with a specific surface area of 25.2 m² g⁻¹ and an average particle size of 89 nm are synthesized by the polymerizable complex method. The use of nanocrystalline LSCF powders allows the fabrication of an interlayer-free nanoporous cathode on top of an ScSZ electrolyte at a low temperature at which non-electrocatalytic secondary phases cannot form. The electrochemical performance of the interlayer-free cathode depends largely on the sintering temperature. A cathode sintered at below 750 °C lacks sufficient mechanical adhesion to the electrolyte, while the electrode surfaces are locally densified when sintered at above 800 °C. Impedance spectroscopy combined with microstructural evidence reveals that the optimum sintering temperature for LSCF is 750 °C. This avoids excess densification and grain growth, and results in the lowest polarization resistance (0.048 Ω cm² at 750 °C).     

Preparation and characterization of graded cathode La0.6Sr0.4Co0.2Fe0.8O3−δ

Perovskite oxide La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF6428), a wonderful electronic–ionic conductor could be used as cathode of solid oxide fuel cell (SOFC). Graded cathode with coarse layer and fine layer, could improve the diffusion rate and electrochemical reaction activity of oxidant. The fabrication and properties of graded LSCF6428 cathode were discussed in this paper. First, pure perovskite LSCF6428 powders were prepared by citrate–EDTA method (CEM), citrate method (CM) and solid phase synthesis (SPS). The powders with higher specific surface area and smaller grain size are easier to be sintered and densified. Single LSCF6428 cathode with thickness of 30 μm was prepared by SPS powders, the porosity of cathode was high about 30% and pore size was about 5 μm. Graded LSCF6428 cathode including 30 μm outer layer and 10 μm inner layer was prepared by SPS and CM powders, respectively. Clear double-layer cathode was observed by SEM, which combined tightly and transited gradually. Porosity of outer layer is high about 30% and pore size is about 1–5 μm; inner layer is finer and pore size is about 0.2–1 μm. Based on the above research, 300 μm yttria stabilized zirconia (YSZ) electrolyte supported cell with single LSCF6428 cathode and double-layer LSCF6428 cathode were prepared, and the properties of two type cells were tested in H₂. Power density of graded cell is 197 mW cm⁻² at 950 °C, and improved about 46% comparing that of single layer LSCF6428 cell (135 mW cm⁻²).     

Fabrication of ultrathin La0.6Sr0.4Co0.2Fe0.8O3-δ hollow fibre membranes for oxygen permeation

An ultrathin La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) hollow fibre membrane for enhanced oxygen permeation flux was fabricated using a wet spinning/sintering method. The membrane exhibits a highly asymmetric structure comprising of a very thin dense outer layer supported by finger-like structures that are fully open on the inner surface. Oxygen permeation measurements were conducted using sweep gas as an operating mode. Effects of operating temperatures and flow rates of the sweep gas on the oxygen permeation fluxes were investigated in details. The highest oxygen permeation flux, i.e. 0.096 cm³/cm² s (5.77 cm³/cm² min) was obtained from the ultrathin hollow fibre membrane at 1323 K (1050 °C) and the sweep gas flow rate of 2.42 cm³/s. The results indicate that the oxygen permeation flux obtained is much higher (4.9-11.2 times) than that obtained from conventional LSCF hollow fibre membranes mainly due to the reduced thickness of the membrane as well as the porous surface on the permeate side. In addition, despite a very thin dense layer, the LSCF hollow fibre membrane possessed a reasonable mechanical strength (113.22 MPa).