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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Performance of solid oxide electrolysis cells based on composite La0.8Sr0.2MnO3−δ – yttria stabilized zirconia and Ba0.5Sr0.5Co0.8Fe0.2O3−δ oxygen electrodes

The electrochemical performance of solid oxide electrolysis cells (SOECs) having barium strontium cobalt ferrite (Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ) and composite lanthanum strontium manganite–yttria stabilized zirconia (La_0.8Sr_0.2MnO_3−δ–YSZ) oxygen electrodes has been studied over a range of operating conditions. Increasing the operating temperature (973 K to 1173 K) significantly increased electrochemical performance and hydrogen generation efficiency for both systems. The presence of water in the hydrogen electrode was found to have a marked positive effect on the EIS response of solid oxide cell (SOC) under open circuit voltage (OCV). The difference in operation between electrolytic and galvanic modes was investigated. Cells having BSCF oxygen electrodes (Ni–YSZ/YSZ/BSCF) showed greater performance than LSM-YSZ-based cells (Ni–YSZ/YSZ/LSM-YSZ) over the range of temperatures, in both galvanic and electrolytic regimes of operation. The area specific resistance (ASR) of the LSM-YSZ-based cells remained unchanged when transitioning between electrolyser and fuel cell modes; however, the BSCF cells exhibited an overall increase in cell ASR of ∼2.5 times when entering electrolysis mode.     

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.     

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).     

Electrochemical impedance spectroscopic characterization of impregnated La0.6Sr0.4Co0.2Fe0.8O3−δ cathode for intermediate-temperature SOFCs

The electrochemical performance of the impregnated La_0.6Sr_0.4Co_0.2Fe_0.8O_3?δ-Y₂O₃ stabilized ZrO₂ cathode (LSCF-YSZ) was studied with different amount of LSCF. Function as P_O2, electrode resistance revealed that the rate-determining steps for oxygen reduction were changed with amount of LSCF loading. The rate-determining step is the charge transfer process for 12 wt% LSCF loading cathode. With the increasing amount of LSCF particles on the YSZ scaffold, the rate determining steps are the dissociation of oxygen molecules and adsorption-diffusion of oxygen atom for 20 wt% LSCF loading cathode. Accumulation of a great many LSCF particles on the YSZ scaffold makes the Knudsen diffusion of oxygen molecular of great importance for ORR. The rate-determining step is the Knudsen diffusion for 32 wt% LSCF loading cathode. The mean free path of oxygen molecules is about 0.22–0.27 μm at 1 atm and the temperature is between 600 and 800 °C. The appearance of inductive loop in the EIS for the cathode with high LSCF loading was possible influenced by the Knudsen diffusion process.     

Ultra-thin nanocrystalline lanthanum strontium cobalt ferrite (La0.6Sr0.4Co0.8Fe0.2O3−δ) films synthesis by RF-sputtering and temperature-dependent conductivity studies

Nanocrystalline lanthanum strontium cobalt ferrite (LSCF) ultra-thin films with high in-plane electrical conductivity have been deposited by RF sputtering from composite targets. The films, with nominal thickness of 54 nm, are crystalline when annealed or deposited at temperatures above 450 °C. Effects of annealing temperature, annealing time, and substrate temperature on crystallization, microstructure, and room temperature lateral electrical conductivity have been systematically studied. No interfacial reaction products between the LSCF and single crystalline yttria-stabilized zirconia (YSZ) were observed from X-ray diffraction studies upon annealing until 750 °C. In-plane electrical conductivity as high as 580 S cm⁻¹ at 650 °C has been observed for LSCF thin films deposited on single crystalline YSZ substrates and sputtered nanocrystalline YSZ thin films; while activation energy for conductivity were determined to be 0.15 eV and 0.10 eV for the former and latter films, respectively, in 650–400 °C range. The high in-plane electrical conductivity for the nanocrystalline LSCF ultra-thin films is likely attributed to their low level of porosity. Micro-solid oxide fuels cells using 15 nm thick LSCF films as cathodes and sub-100 nm yttria-doped zirconia thin film electrolytes have been fabricated successfully and demonstrated to achieve peak power density of 60 mW cm⁻² at 500 °C. Our results demonstrate that RF sputtering provides a low-temperature synthesis route for realizing ultra-thin nanocrystalline LSCF films as cathodes for intermediate- or low-temperature solid oxide fuel cells.     

Performance stability of impregnated La0.6Sr0.4Co0.2Fe0.8O3−δ–Y2O3 stabilized ZrO2 cathodes of intermediate temperature solid oxide fuel cells

The stability of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ impregnated Y₂O₃ stabilized ZrO₂ (LSCF–YSZ) cathodes was investigated under the condition of open circuit or current polarization at 750 °C in air. The electrochemical measurement and the microstructure characteristic show that the flattening of LSCF particles has great contribution to the increase of resistance of LSCF–YSZ cathodes after 500 h heat treatment at 750 °C. Microstructure coarsening and the damage of well-connected porous structure are main reasons of the performance degradation for LSCF–YSZ cathodes testing at 200 mA cm⁻² and 750 °C in air. Higher current density of 500 mA cm⁻² applying on cathodes accelerates degradation processes. X-ray photoelectron spectroscopy (XPS) shows that Sr concentration on the cathode surface decreases after current polarization, which plays a main role in performance activation processes observed at the beginning stage. The enhancement of cobalt activity in LSCF lattice by current polarization increases the conductivity and decreases the stability of LSCF–YSZ cathodes.     

Co-precipitation in aqueous medium of La0.8Sr0.2Ga0.8Mg0.2O3−δ via inorganic precursors

A simple and inexpensive co-precipitation route in aqueous medium is proposed to prepare La_0.8Sr_0.2Ga_0.8Mg₀₂O_3−δ ionic conductor (LSGM). Different synthetic procedures and operating parameters (i.e. nature and amount of the precipitating agents, HNO₃ addition and temperature) have been evaluated in order to underline their influence on the composition and microstructure of the final phase. Intermediate and final products were characterized by Thermal-Gravimetry, IR-spectroscopy, X-ray Powder Diffraction, Rietveld analysis and Scanning Electron Microscopy. The electrical properties were measured by Impedance Spectroscopy in the temperature range 250-800 °C. Slight variations of the synthetic procedure (such as precipitating agent amount or no HNO₃ addition) have a considerable and detrimental effect on the ions losses and the subsequent achievement of the final phase. The use NH₄OH as an alternative precipitating agent is dramatically disadvantageous. Ions losses during precipitation must be controlled (i) to avoid understoichiometry in the LSGM phase and (ii) to prevent the formation of large amounts of secondary phases. In fact, both affect the total electrical conductivity.The use of large excess of (NH₄)₂CO₃ precipitating agent and the addition of HNO₃ lead to the best material characterized by a rhombohedral structure, small amount of side phases, a relative density of 98% and a total conductivity of 6.44 × 10⁻² S cm⁻¹ at 800 °C and 1.13 × 10⁻² S cm⁻¹ at 600 °C.     

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.