La0.6Sr0.4Fe0.8Cu0.2O3−δ perovskite oxide as cathode for IT-SOFC

A La_0.6Sr_0.4Fe_0.8Cu_0.2O_3−δ (LSFCu) perovskite was investigated as a cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFC). The LSFCu material exhibited chemical compatibility with the Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte up to a temperature of 1100 °C. The electrical conductivity of the sintered sample was measured as a function of temperature from 100 to 800 °C. The highest conductivity of about 238 S cm⁻¹ was observed for LSFCu. The average thermal-expansion coefficient (TEC) of LSFCu was 14.6 × 10⁻⁶ K⁻¹, close to that of typical CeO₂ electrolyte material. The investigation of electrical properties indicated that the LSFCu cathode had lower interfacial polarization resistance of 0.070 Ω cm² at 800 °C and 0.138 Ω cm² at 750 °C in air. An electrolyte-supported single cell with 300 μm thick SDC electrolyte and LSFCu as cathode shows peak power densities of 530 mW cm⁻² at 800 °C.     

Characteristics of nano La0.6Sr0.4Co0.2Fe0.8O3−δ-infiltrated La0.8Sr0.2Ga0.8Mg0.2O3−δ scaffold cathode for enhanced oxygen reduction

The chemical compatibility and electrochemical properties of nanoLa_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF)-infiltrated La_0.8Sr_0.2Ga_0.8Mg_0.2O_3−δ (LSGM) scaffold were manufactured and assessed for the application as a solid oxide fuel cell cathode with an LSGM electrolyte. When the LSCF and LSGM powder mixture was fired above 950 °C, the characteristic peaks of the two materials merged and an insulation peak (derived from LaSrGaO₄) was observed. To prevent reactions between LSCF and LSGM, an infiltration technique was utilized with the LSGM as a scaffold. Using this infiltration technique, nano LSCF particles (approximately 100 nm) can be uniformly coated on the LSGM scaffold surface. Good nano particle adhesion was observed at the LSGM/LSCF interface, even at relatively low firing temperatures (850 °C). The cathode polarization resistance (R_p) of the nano LSCF infiltrated LSGM scaffold cathode was lower than that of a conventional LSCF cathode. The improvement in performance of the nano LSCF-infiltrated cathode was attributed to an increase in the number of triple phase boundaries (TPB) as a result of the nano LSCF coating. In addition, the oxygen reduction reaction (ORR) paths were extended from the TPBs to the LSCF surface because LSCF particles are considerably smaller than the LSCF oxygen ion penetration depth (3–4 μm) over the temperature range of 700 °C–800 °C.     

Development of La0.6Sr0.4Co0.2Fe0.8O3−δ cathode with an improved stability via La0.8Sr0.2MnO3-film impregnation

Uniform, dense and continuous coatings of La_0.8Sr_0.2MnO_3−δ (LSM) have been successfully deposited on dense/porous La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) substrates via a one-step drop-coating process using a water-based solution in order to improve the operating stability of solid oxide fuel cell cathode. The processing conditions were optimized by precise control of the composition of infiltrating solution, including chelating agents (glycine, citric acid and ethylene glycol), surfactants (polyvinyl alcohol (PVA), polyethylene glycol (PEG) and polyvinyl pyrrolidone (PVP)) and pH values (5.25, 4.29, 3.01 and 2.09). Ethanol was found to improve the wetting ability of the water-based solution significantly, but unfortunately causing precipitation. The symmetrical and full cells tests demonstrated that both performance and stability of LSCF cathode can be enhanced by surface modification with an optimized LSM film coating, leading to ∼31% reduction in cathodic polarization resistance and ∼45% improvement in power density (without observable degradation) for almost 350 h operation at 750 °C under a constant voltage of 0.7 V.     

In situ sinterable cathode with nanocrystalline La0.6Sr0.4Co0.2Fe0.8O3−δ for solid oxide fuel cells

A nanocrystalline powder with a lanthanum based iron- and cobalt-containing perovskite, La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF), is investigated for solid oxide fuel cell (SOFC) applications at a relatively low operating temperature (600-800 °C). A LSCF powder with a high surface area of 88 m² g⁻¹, which is synthesized via a complex method with using inorganic nano dispersants, is printed onto an anode supported cell as a cathode electrode. A LSCF cathode without a sintering process (in situ sintered cathode) is characterized and compared with that of a sintering process at 780 °C (ex situ sintered cathode). The in situ sintered SOFC shows 0.51 A cm⁻² at 0.9 V and 730 °C, which is comparable with that of the ex situ sintered SOFC. The conventional process for SOFCs, the ex situ sintered SOFC, including a heat treatment process after printing the cathodes, is time consuming and costly. The in situ sinterable nanocrystalline LSCF cathode may be effective for making the process simple and cost effective.     

Photo-excitation enhanced high temperature conductivity and crystallization kinetics in ultra-thin La0.6Sr0.4Co0.8Fe0.2O3−δ films

The synthesis of high performance nanostructured oxide electrodes is critical to advancement of energy technologies such as intermediate temperature solid oxide fuel cells. In this communication, we demonstrate that photo-excitation during crystallization of nanostructured 60-nm-thick La_0.6Sr_0.4Co_0.8Fe_0.2O_3−δ films leads to a significant improvement in electrical conductivity. Crystallization kinetics is also enhanced by photo-excitation while the crystallization onset temperature remains similar.     

Nano-structured cathodes based on La0.6Sr0.4Co0.2Fe0.8O3−δ for solid oxide fuel cells

Lanthanum-based iron- and cobalt-containing perovskite is a promising cathode material because of its electrocatalytic activity at a relatively low operating temperature in solid oxide fuel cells (SOFCs), i.e., 700-800 °C. To enhance the electrocatalytic reduction of oxidants on La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF), nanocrystalline LSCF materials are successfully fabricated using a complexing method with chelants and inorganic nano dispersants. When inorganic dispersants are added to the synthesis process, the surface area of the LSCF powder increases from 18 to 88 m² g⁻¹, which results in higher electrocatalytic activity of the cathode. The performance of a unit cell of a SOFC with nanocrystalline LSCF powders synthesized with nano dispersants is increased by 60%, from 0.7 to 1.2 W cm⁻².     

Synthesis and properties of La0.6Sr0.4CoO3−δ nanopowder

Uniform nanopowders of La_0.6Sr_0.4CoO_3−δ (LSC) were synthesized by the combined citrate–EDTA method. The precursor solution was prepared from nitrates of the constituent metal ion, citric acid and EDTA with a pH value controlled by ammonia. The obtained product was characterized by TG/DTA, XRD, SEM, and BET measurements. The single perovskite phase could form completely after sintering at the temperature of 900 °C. There was no significant effect of the precursor solution pH value on the perovskite phase formation temperature; however, LSC powders prepared from the precursors with different pH values showed specific shapes. The morphology of La_0.6Sr_0.4CoO_3−δ powder was also optimized with proper surfactant addition. The sintered La_0.6Sr_0.4CoO_3−δ bulk samples exhibited an electrical conductivity of 1867 S cm⁻¹ in air at 800 °C. The impedance spectra of a symmetric LSC cathode on a GDC electrolyte substrate were measured and polarization resistance (R_p) values of 0.17 Ω cm² at 700 °C and 0.07 Ω cm² at 750 °C in air were obtained.     

Electrical conductivity of epitaxial La0.6Sr0.4Co0.2Fe0.8O3−δ thin films grown by pulsed laser deposition

Epitaxial La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) thin films have been grown successfully on single crystal LaAlO₃ substrate by pulsed laser deposition (PLD). AFM micrographs have shown a rms roughness of 5Å for the 550 °C deposited films. The films further exhibited electrical conductivities of as high as 2.3 × 10³ S cm⁻¹ at 600 °C, with an activation energy of 0.09 eV. The surface exchange coefficient (k_chem$k_{chem}$) of the epitaxial LSCF thin film, determined by electrical conductivity relaxation (ECR) technique, increased with the increasing temperature, and reached a value of ∼5.1 × 10⁻⁶ S cm⁻¹ at temperatures above 620 °C.     

Electrochemical stability of La0.6Sr0.4Co0.2Fe0.8O3−δ-infiltrated YSZ oxygen electrode for reversible solid oxide fuel cells

La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF)-YSZ (yttria stabilized zirconia) oxygen electrodes were developed by an infiltration process for reversible solid oxide fuel cells (RSOFCs). Electrochemical performance of the LSCF-YSZ composite oxygen electrode was investigated in both fuel cell and steam electrolysis modes. Galvanostatic polarization operated at ±600 mA cm⁻² and 750 °C showed that the cell has a voltage degradation rate of 3.4% and 4.9% for fuel cell mode and steam electrolysis mode, respectively. Post-test SEM (scanning electronic microscopy) analysis of the electrodes indicates that the agglomeration of infiltrated LSCF particles is possibly responsible for the performance degradation of the cell.     

Interface reactivity study between La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) cathode material and metallic interconnect for fuel cell

Interface reactivity between La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) cathode material and metallic interconnect (Crofer22APU) was investigated in laboratory air at 700 °C. Due to the interconnect geometry, two interfaces have been analysed: (i) interconnect rib/cathode interface (physically in contact); (ii) the interface under the channel of interconnect. In both cases, formation of a parasite phase was observed after various ageing treatments (20 h, 100 h and 200 h). However, the growth of the determined SrCrO₄ parasite phase depends on interface type and on ageing time. Two different mechanisms have been established in function of interface type: (i) SrCrO₄ phase was formed after solid state diffusion of Cr from metallic interconnect to the cathode; (ii) gas phase reaction induced formation of SrCrO₄ under the channel of interconnect. Finally, the influence of a chemical etching on cathode/interconnect reactivity was evaluated.     

La0.6Sr0.4Co0.2Fe0.8O3−δ cathodes infiltrated with samarium-doped cerium oxide for solid oxide fuel cells

Porous La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) cathodes are coated with a thin film of Sm_0.2Ce_0.8O_1.95−δ (SDC) using a one-step infiltration process. Examination of the microstructures reveals that small SDC particles are formed on the surface of LSCF grains with a relatively narrow size distribution. Impedance analysis indicates that the SDC infiltration has dramatically reduced the polarization of LSCF cathode, reaching interfacial resistances of 0.074 and 0.44 Ω cm² at 750 °C and 650 °C, respectively, which are about half of those for LSCF cathode without infiltration of SDC. The activation energies of the SDC infiltrated LSCF cathodes are in the range of 1.42-1.55 eV, slightly lower than those for a blank LSCF cathode. The SDC infiltrated LSCF cathodes have also shown improved stability under typical SOFC operating conditions, suggesting that SDC infiltration improves not only power output but also performance stability and operational life.     

Enhanced electrochemical performance of solution impregnated La0.8Sr0.2Co0.8Ni0.2O3−δ cathode for intermediate temperature solid oxide fuel cells

Solution impregnated La_0.8Sr_0.2Co_0.8Ni_0.2O₃ + Gd-doped CeO₂ (LSCN + GDC) cathodes for intermediate temperature solid oxide fuel cells (IT-SOFC) are prepared and their electrochemical properties are evaluated and compared with the conventional LSCN cathodes. The results indicate that the cathode performance can be enhanced by the presence of the nanosized microstructure produced with the solution impregnation method. It is determined that the amount of LSCN loading in the LSCN + GDC composite cathode needs to be higher than 35 wt% in order to achieve a performance superior to that of the conventional LSCN cathode. The optimum amount of LSCN loading is in the range of 45-55 wt% with an activation energy near 1.32 eV for oxygen reduction. At temperatures between 600 and 750 °C, the polarization resistance of the 55 wt% LSCN loaded LSCN + GDC cathode is in the range of 1.07 and 0.08 Ω cm², which is only about one half of that for the conventional cathode.     

Effects of bi-layer La0.6Sr0.4Co0.2Fe0.8O3−δ-based cathodes on characteristics of intermediate temperature solid oxide fuel cells

In this study, anode-supported planar IT-SOFCs, with a thin Sm_0.2Ce_0.8O_2−δ (SDC) electrolyte film and a bi-layer cathode, are fabricated using tape-casting and screen-printing processes. The bi-layer cathode consists of a current collector La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) layer and a functional LSCF-SDC composite layer in various thicknesses. Microstructure studies reveal that the interfaces among various layers show good adhesion, except for Cell A equipped with a cathode of pure LSCF. Cell A reports the lowest ohmic (R₀) and polarization (R_P) resistances. R_P, which increases with the thickness of the LSCF-SDC composite layer in the cathode, rises rapidly as the temperature drops, particularly at temperatures ≤550 °C. This indicates the high electrical conductivity of the cathode as a major contribution to the decrease of R_P at 500 °C. The best cell performances are observed at 650 °C for all cases, in which Cell A shows a maximum power density of 1.51 W cm⁻² and an open circuit voltage of 0.80 V. Considering both of the electrical and the mechanical integrity of the single cell, insertion of the composite layer is required to guarantee a good adhesion of cathode layer to electrolyte layer. However, the thickness of the composite layer should be retained as thin as possible to minimize the R₀ and R_P and maximize the cell performance.     

Electrospinning La0.8Sr0.2Co0.2Fe0.8O3−δ tubes impregnated with Ce0.8Gd0.2O1.9 nanoparticles for an intermediate temperature solid oxide fuel cell cathode

In order to reduce the polarization resistance of the cathode, we have developed one-dimensional (1D) nanostructured La_0.8Sr_0.2Co_0.2Fe_0.8O_3−δ (LSCF) tubes/Ce_0.8Gd_0.2O_1.9 (GDC) nanoparticles composite cathodes for solid oxide fuel cell. Uniform LSCF/PVP composite nanofibers have been firstly synthesized by a single-nozzle electrospinning technique, followed by firing at 800 °C for 2 h to form one-dimensional LSCF tubes. Subsequently, the GDC phases were introduced into tube structured LSCF scaffold pre-sintered on a GDC pellet by a multi-impregnation process. Electrochemical Impedance spectra reveal that nanostructured LSCF tubes/GDC nanoparticles composite cathodes have a better electrochemical performance, achieving area-specific resistances of 4.70, 1.12, 0.27 and 0.07 Ω cm² at 500, 550, 600 and 650 °C for the composite of GDC and LSCF in a weight ratio of 0.52:1. The low ASR values are mainly related to its optimal microstructure with larger triple-phase boundaries and higher porosity. These results suggest that LSCF tube/GDC nanoparticle composite can be an alternative cathode material for intermediate temperature solid oxide fuel cell (IT-SOFC).     

Performance stability and degradation mechanism of La0.6Sr0.4Co0.2Fe0.8O3−δ cathodes under solid oxide fuel cells operation conditions

The performance stability and degradation mechanism of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) cathodes and LSCF impregnated Gd_0.1Ce_0.9O_2−δ (LSCF-GDC) cathodes are investigated under solid oxide fuel cell operation conditions. LSCF and LSCF-GDC cathodes show initially performance improvement but degrade under cathodic polarization treatment at 750 °C for 120 h. The results confirm the grain growth and agglomeration of LSCF and in particular GDC-LSCF cathodes as well as the formation of SrCoO_x particles on the surface of LSCF under cathodic polarization conditions. The direct observation of SrCoO_x formation has been made possible on the surface of dense LSCF electrode plate on GDC electrolyte. The formation of SrCoO_x is most likely due to the interaction between the segregated Sr and Co from LSCF lattice under polarization conditions. The formation of SrCoO_x would contribute to the deterioration of the electrocatalytic activity of the LSCF-based electrodes for the O₂ reduction in addition to the agglomeration and microstructure coarsening.     

Low-temperature solid oxide fuel cells with novel La0.6Sr0.4Co0.8Cu0.2O3−δ perovskite cathode and functional graded anode

The perovskite La_0.6Sr_0.4Co_0.8Cu_0.2O_3−δ (LSCCu) oxide is synthesized by a modified Pechini method and examined as a novel cathode material for low-temperature solid oxide fuel cells (LT-SOFCs) based upon functional graded anode. The perovskite LSCCu exhibits excellent ionic and electronic conductivities in the intermediate-to-low-temperature range (400-800 °C). Thin Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte and NiO-SDC anode functional layer are prepared over macroporous anode substrates composed of NiO-SDC by a one-step dry-pressing/co-firing process. A single cell with 20 μm thick SDC electrolyte on a porous anode support and LSCCu-SDC cathode shows peak power densities of only 583.2 mW cm⁻² at 650 °C and 309.4 mW cm⁻² for 550 °C. While a cell with 20 μm thick SDC electrolyte and an anode functional layer on the macroporous anode substrate shows peak power densities of 867.3 and 490.3 mW cm⁻² at 650 and 550 °C, respectively. The dramatic improvement of cell performance is attributed to the much improved anode microstructure that is confirmed by both SEM observation and impedance spectroscopy. The results indicate that LSCCu is a very promising cathode material for LT-SOFCs and the one-step dry-pressing/co-firing process is a suitable technique to fabricate high performance SOFCs.     

Thermochemical compatibility and polarization behaviors of La0.8Sr0.2Co0.8Ni0.2O3−δ as a cathode material for solid oxide fuel cell

Thermochemical compatibilities with Ce_0.8Gd_0.2O_2−δ (GDC) electrolyte and electrochemical behaviors under the condition of anodic or cathodic current treatment are investigated for La_0.8Sr_0.2Co_0.8Ni_0.2O_3−δ (LSCN) cathode of solid oxide fuel cell (SOFC). X-ray diffractometer (XRD) shows that cation exchange at 1150 °C leads to the formation of solid state solution between the cathode and electrolyte. Considering thermal expansion coefficient (TEC) and conductivity, La_1−xSr_xCo_1−yNi_yO_3−δ with the composition of La_0.8Sr_0.2Co_0.8Ni_0.2O_3−δ is indicated as a promising cathode for intermediate temperature SOFC. Electrochemical measurement reveals that the performance of LSCN cathode shows reversibility under anodic with subsequent cathodic current treatment. Further, the low frequency electrode process is strongly affected by anodic current. While the high frequency arc shows independent relationship with current polarization.     

Characteristics of Ba0.5Sr0.5Co0.8Fe0.2O3−δ–La0.9Sr0.1Ga0.8Mg0.2O3−δ composite cathode for solid oxide fuel cell

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ–La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ composite cathodes are prepared successfully using combustion synthesis method. Microstructure, chemical compatibility and electrochemical performance have been investigated and analyzed in detail. SEM micrographs show that a structure with porosity and well-necked particles forms after sintering at 1000 °C in the composites. Grain growth is suppressed by addition of La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ phase and grain sizes decrease with increasing weight percent of La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ phase in the composites. Phase analysis demonstrates that chemical compatibility between Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ and La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ is excellent when the weight percent of La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ in the composite is not more than 40%. Through fitting ac impedance spectra, it is found that the ohmic resistance and polarization resistance decrease with increasing La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ content. The polarization resistance reaches a minimum at about 30 and 40 wt.% La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ in the composite.