Effect of optimal GDC loading on long-term stability of La0.8Sr0.2Co0.2Fe0.8O3-δ/Gd0.2Ce0.8O1.9 composite cathodes

Three types of La_0.8Sr_0.2Co_0.2Fe_0.8O_3-δ/Gd_0.2Ce_0.8O_1.9 (LSCF/GDC) composite cathodes with different optimal GDC loading are fabricated through electrospinning, screen printing and solution infiltration method. Constant current polarization with current density of 100 mA cm^?2 at 750°C is applied to test the stability of LSCF/GDC composite cathodes. After constant current polarization for 144 h, the polarization resistance (R_p) of 280 nm-nanofiber skeletal LSCF/GDC composite cathode after pore-forming exhibits the minimum increase, from 0.062 Ω cm² to 0.098 Ω cm². Scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS) results show that the microstructure and surface chemical composition of the cathode maintain stable during the constant current polarization. Combined with the X-ray diffraction (XRD) result, a relationship among GDC loading, stress, Sr surface segregation and long-term stability is established.     

The Effect of Plasma Spraying Power on La0.58Sr0.4Co0.2Fe0.8O3–δ–La0.8Sr0.2Ga0.8Mg0.2O3–δ Composite Cathode Interlayer Microstructure and Cell Performance

The metal‐supported intermediate temperature solid oxide fuel cells with a porous nickel substrate, a nano‐structured LDC (Ce_0.55La_0.45O_2–δ)–Ni composite anode, an LDC diffusion barrier layer, an LSGM (La_0.8Sr_0.2Ga_0.8Mg_0.2O_3–δ) electrolyte, an LSCF (La_0.58Sr_0.4Co_0.2Fe_0.8O_3–δ)–LSGM composite cathode interlayer and an LSCF cathode current collector are fabricated by atmospheric plasma spraying. Four different plasma spraying powers of 26, 28, 30, and 34 kW are used to fabricate the LSCF–LSGM composite cathode interlayers. Each cell with a prepared LSCF–LSGM composite cathode interlayer has been post‐heat treated at 960 °C for 2 h in air with an applied pressure of 450 g cm^–2. The current‐voltage‐power and AC impedance measurements indicate that the LSCF–LSGM composite cathode interlayer formed at 28 kW plasma spraying power has the best power performance and the smallest polarization resistance at temperatures from 600 to 800 °C. The microstructure of the LSCF–LSGM composite cathode interlayer shows to be less dense and composed of smaller dense regions as the plasma spraying power decreases to 28 kW. The durability test of the cell with an optimized LSCF–LSGM composite cathode interlayer gives a degradation rate of 1.1% kh^–1 at the 0.3 A cm^–2 constant current density and 750 °C test temperature.     

Suppression of Sr surface segregation in La0.8Sr0.2Co0.2Fe0.8O3-δ via Nb doping in B-site

Sr surface segregation has been one of the main reasons for the cathode performance degradation during the long-term operation of solid oxide fuel cells (SOFC). Investigation on Sr segregation mechanism and proposing strategies on suppressing the Sr surface segregation are significant for SOFC development. In this paper, La_0.8Sr_0.2Co_0.2Fe_0.8-xNb_xO_3-δ (LSCFNb, x = 0, 0.02, 0.04, 0.06, 0.08 and 0.1) are prepared via sol-gel method. The electrochemical performance and long-term stability are tested through electrochemical impedance spectroscopy (EIS) and constant current polarization. The results show that the long-term stability of LSCFNb cathodes are strongly affected by Nb content. Combining the results of ICP and XPS, it's revealed that the Sr surface segregation can be effectively suppressed with the increase of Nb content. The LSCFNb cathodes gain the optimal electrochemical performance when x = 0.04, with minimum polarization resistance of 0.27 Ω cm² at 750 °C and oxygen reduction reaction activation energy of 1.54 eV. After cathodic polarization for 144 h, the polarization resistance and activation energy of LSCFNb4 cathode increase slightly, revealing it a promising cathode material for SOFC research.     

Characterization of La0.58Sr0.4Co0.2Fe0.8O3−δ–Ce0.8Gd0.2O2 composite cathode for intermediate temperature solid oxide fuel cells

La_0.58Sr_0.4Co_0.2Fe_0.8O_3?δ–Ce_0.8Gd_0.2O₂ (LSCF–GDC) composite cathodes with various weight ratios 90%, 70% and 50% of LSCF were prepared. Mechanical properties, thermal expansion properties and electrical properties were measured for potential applications in solid oxide fuel cells (SOFCs) with graded cathodes. LSCF and GDC as pure cathode and electrolyte materials were characterized as reference. The absence of new phases as confirmed by X-ray diffraction (XRD) analysis demonstrated the excellent compatibility between the cathode and electrolyte materials. Mechanical properties such as hardness and fracture toughness were measured by the micro-indentation technique, while hardness and elastic modulus were measured by the nano-indentation technique. Thermal expansion behavior was recorded by a dilatometer. Electrical conductivity was measured by the four probe DC method. The 50% LSCF–GDC composite has the lowest relative density among all the samples. Thermal expansion coefficients (TECs) and electrical conductivity increased with addition of LSCF contents in the composite, while mechanical properties depended more on the density than the LSCF content.     

Degradation behaviours of Fe-doped La0.8Sr0.2CoO3-δ by thermal stress

ABSTRACT

The improvement in durability by Fe doping to La_0.8Sr_0.2CoO_3-δ (LSC) and its degradation mechanism were investigated in terms of structural and morphological analyses. Polarisation resistance of LSC was increased approximately by 65.7% after exposure to thermal stress at 900°C for 100?h because the oxygen reduction reaction was declined by particle coarsening and aggregation of LSC powders. The polarisation resistance of La_0.8Sr_0.2Co_0.8Fe_0.2O_3-δ (LSCF) was increased from 0.269 to 0.328?Ωcm² after the heat treatment. Increasing rate of polarisation resistance of LSCF was 21.9%, which was three times lower than that of LSC due to reduced particle coarsening and aggregation by Fe doping. Particle size of LSCF powders was maintained about 0.5–3?μm, and morphologies were also similar before and after the heat treatment. Chemical reaction between the LSCF and Sm-doped Ceria electrolyte powders did not occur despite the thermal stress, indicating the interface between the cathode and electrolyte is chemically stable.     

Characterization of La0.6Sr0.4Co0.2Fe0.8O3–δ + La2NiO4+δ Composite Cathode Materials for Solid Oxide Fuel Cells

The structure, electrical conduction, thermal expansion and electrochemical properties of the La_0.6Sr_0.4Co_0.2Fe_0.8O_3–δ + La₂NiO_4+δ (LSCF‐LNO) composite cathodes were investigated with regard to the volume fraction of the LNO composition. No chemical reaction product between the two constituent phases was found for the composite cathodes sintered at 1,400 °C for 10 h within the sensitivity of the XRD. Compared to the performance of the LSCF cathode, the LNO composition in the composite cathode plays a role in deteriorating both electrical conductivity and electrochemical properties, however, improving the thermal expansion properties. The trade‐off between electrical conducting and thermal expansion classifies the composite cathode containing 30 volume percent (vol.%) LNO as the optimum composition. For characterizing cathode performance in a single cell, a slurry spin coating technique was employed to prepare a porous cathode layer as well as a YSZ/Ce_0.8Sm_0.2O_3–δ (SDC) electrolyte. The optimum conditions for fabricating the YSZ/SDC electrolyte were investigated. The resulting single cell with 70 vol.% LSCF‐30 vol.%LNO (LSCF‐LNO30) cathode shows a power density of 497 mW cm^–2 at 800 °C, which is lower than that of the cell with a LSCF cathode, but still within the limits acceptable for practical applications.     

Microstructure and Polarization Studies on Interlayer Free La0.65Sr0.3Co0.2Fe0.8O3–δ Cathodes Fabricated on Yttria Stabilized Zirconia by Solution Precursor Plasma Spraying

Nano‐structured cathodes of La_0.65Sr_0.3Co_0.2Fe_0.8O_3–δ (LSCF) are fabricated by solution precursor plasma spraying (SPPS) on yttria stabilized zirconia (YSZ) electrolytes (LSCF‐SPPS‐YSZ). Phase pure LSCF is obtained at all plasma power. Performances of LSCF‐SPPS‐YSZ cathodes are compared with conventionally prepared LSCF cathodes on YSZ (LSCF‐C‐YSZ) and gadolinium doped ceria (GDC) (LSCF‐C‐GDC) electrolytes. High R_p is observed in the LSCF‐C‐YSZ (∼42 Ohm cm² at 700 °C) followed by LSCF‐C‐GDC (R_p ∼ 1.5 Ohm cm² at 700 °C) cathodes. Performance of the LSCF‐SPPS‐YSZ cathodes (R_p ∼ 0.1 Ohm cm² at 700 °C) is found to be even superior to the performance of LSCF‐C‐GDC cathodes. High performance in LSCF‐SPPS‐YSZ cathodes is attributed to its nano‐structure and absence of any interfacial insulating phase which may be attributed to the low temperature at the interaction point of LSCF and YSZ and low interaction time between LSCF and YSZ during SPPS process. In the time scale of 100 h, no change in the polarization resistances is observed at 750 °C. Based on the literature and from the present studies it can be stated that SOFC with YSZ electrolyte and LSCF‐SPPS‐YSZ cathode can be operated at 750 °C for a longer duration of time and good performance can probably be achieved.     

Fatigue improvement in modified lead zirconate titanate ceramics through employment of La0.8Sr0.2MnO3 buffer layers

The dielectric, ferroelectric and fatigue properties of modified lead zirconate titanate (PZT) ceramics were investigated in terms of the effect of La_0.8Sr_0.2MnO₃ (LSM) buffer layers. The double sided LSM buffer layers resulted in a lower dielectric loss, a weaker frequency dependence of dielectric constant, a lower leakage current density, and an increase in the saturation polarization. Moreover, it was found that up to 1.4×10⁷ cycle numbers, the Ag||LSM/PZT/LSM||Ag capacitor, with remanent polarization decreased by 55%, was superior to the Ag||PZT||Ag capacitor by 85%. The results indicate that the LSM buffer layers can improve the fatigue endurance of the PZT ceramics with Ag electrodes, mainly because the accumulated charges were compensated at the interface junctions between the LSM buffer layers and the Ag electrodes. We fit the polarization fatigue data using a modified model and calculated the characteristic decay time of oxygen vacancy migration in the Ag||LSM/PZT/LSM||Ag and the Ag||PZT||Ag capacitors, respectively.     

La0.6Sr0.4Co0.2Fe0.8O3-δ nanofiber cathode for intermediate-temperature solid oxide fuel cells by water-based sol-gel electrospinning: Synthesis and electrochemical behaviour

Water-based sol-gel electrospinning is employed to manufacture perovskite oxide La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) nanofiber cathodes for intermediate-temperature solid oxide fuel cells. LSCF fibrous scaffolds are synthesized through electrospinning of a sol-gel solution employing water as the only solvent. Morphological characterizations demonstrate that the LSCF fibers have highly crystalline structure with uniform elemental distribution. After heat treatment, the average fiber diameter is 250 nm and the porosity of the nanofiber tissue is 37.5 %. The heat treated LSCF nanofibers are applied directly onto a Ce_0.9Gd_0.1O_1.95 (CGO) electrolyte disk to form a symmetrical cell. Electrochemical characterization is carried out through electrochemical impedance spectroscopy (EIS) in the temperature range 550?°C–950?°C, and reproducibility of the electrochemical performance for a series of cells is demonstrated. At 650?°C, the average measured polarization resistance R_p is 1.0 Ω cm². Measured performance decay is 1 % during the first 33?h of operation at 750?°C, followed by an additional 0.7 % over the subsequent 70?h.     

La0.6Sr0.4Co0.2Fe0.8O3 as the anode and cathode for intermediate temperature solid oxide fuel cells

The perovskite material La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF-6428) has been considered as both the anode and cathode in solid oxide fuel cells (SOFCs) operating at intermediate temperatures (550–700°C). Solid electrolyte coulometry (SEC) has been used to measure the oxygen non-stoichiometry as a function of temperature and ambient oxygen partial pressure, thus enabling kinetic data relating to oxygen transport in cathodes to be correlated with the material oxygen vacancy concentration. The catalytic activity towards methane oxidation, and susceptibility to deactivation through carbon deposition have both been investigated by temperature programmed methods, and compared with data for the conventional Ni/YSZ anode material.     

Improved electrochemical performance of Bi doped La0.8Sr0.2FeO3-δ nanofiber cathode for IT-SOFCs via electrospinning

In this study, perovskite La_0.8-xBi_xSr_0.2FeO_3-δ (LBSF, x = 0.0–0.5) nanofibers with great crystallinity were prepared by electrospinning method and used as cathodes for intermediate temperature solid oxide fuel cells (IT-SOFCs). The symmetric cells of nanofiber-based LBSF electrode on Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte show excellent electrochemical performance. The La_0.4Bi_0.4Sr_0.2FeO_3-δ (LBSF4) cathode has the best performance with a polarization resistance (R_P) of 0.126 Ω cm² at 650 °C. The anode-supported single cell with LBSF4 as the cathode film and Ni-SDC as the anode has a maximum power density of 448 mW cm^-2 at 650 °C using wet H₂ as the fuel. In addition, the LBSF4 cathode with fibrous structure exhibits outstanding electrochemical behavior. The catalytic activity of the cathode was improved due to the incorporation of the Bi element, indicating that LBSF4 is promising as a cathode material in the field of IT-SOFCs.     

Degradation of La0.6Sr0.4Co0.2Fe0.8O3–δ–Ce0.8Sm0.2O1.9 Cathodes on Coated and Uncoated Porous Metal Supports

The degradation of composite LSCF‐SDC cathodes on porous 430 stainless steel supports was investigated. Two degradation mechanisms were observed: a multi‐layer oxide scale, believed to consist of Cr₂O₃ and SrCrO₄, formed at the support‐cathode interface, and small amounts of chromium were detected within the cathodes. To reduce degradation, La₂O₃ and Y₂O₃ reactive element oxide coatings were deposited on the internal pore surfaces of the metal supports. The reactive element oxide coatings reduced the amount of volatile chromium that deposited in the cathodes. As a result, the degradation rates of the cathodes on coated supports were significantly lower than the degradation rates of cathodes made on uncoated metal supports. In cathode symmetrical cells, polarization resistance degradation rates as low as 2.56 × 10⁻⁶ Ω cm² h⁻¹ were observed over 100 hours on coated metal supports, compared to an average of 1.23 × 10⁻⁴ Ω cm² h⁻¹ on uncoated supports.     

Enhancement of grain growth and electrical conductivity of La0.8Sr0.2MnO3 ceramics by microwave irradiation

We studied crystallization, grain growth and electric properties of La_0.8Sr_0.2MnO₃ (LSM) ceramics which were produced using the microwave-treatment. While co-precipitated nanoparticles remain mainly amorphous, the microwave irradiated particles are crystallized into LSM and La₂Mn₂O₇ at 550 °C, due to higher dielectric polarizability of La. This, in turn, decreases the amount of the second phase La₂O₃ in calcined powder and promotes the growth of perovskite grains during sintering at 1400 °C. Larger grains of LSM ceramics lower the activation energy of small polaron hopping from 0.35 eV to 0.24 eV and increases high-temperature electric conductivity. In addition, high crystallinity of LSM ceramics from the microwave-treatment suppresses a chemical reaction with ZrO₂ and NiO in a temperature range of 900 – 1100 °C under oxidizing and reducing ambiances. These results show that LSM ceramics from the microwave-assisted reaction meet requirements for an interconnect layer for solid oxide electrolysis cells.     

Microstructure anisotropy of La0.6Sr0.4Co0.2Fe0.8O3-δ film on rigid Gd0.1Ce0.9O1.95 substrate during constrained sintering

La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) cathodes on rigid Gd_0.1Ce_0.9O_1.95 (GDC) substrate were sintered to different densities, and their three dimensional (3D) microstructures were characterized using focused ion beam-scanning electronic microscopy (FIB-SEM) tomography. The microstructure anisotropies of the green and constrainedly sintered cathodes were studied using 3D mean intercept length (MIL) method and the two dimensional (2D) best-fit ellipse method and 3D best-fit ellipsoid method. It shows that in the constrained sintering of LSCF films, the microstructures were transversely isotropic in the plane parallel to the substrate, while the microstructures in the thickness direction were anisotropic. Density and grain size gradients were observed and quantified along the cathode thickness direction during constrained sintering. The pores were preferentially oriented and elongated in the thickness direction. The anisotropy factor increased as increasing the sintering time or sintering temperature in the current density range. Cross-sectional 2D measurements underestimated the pore anisotropy, but showed qualitative agreement with 3D measurements.     

Creep behavior of porous La0.6Sr0.4Co0.2Fe0.8O3-δ substrate material for oxygen separation application

Advanced oxygen transport membrane designs consist of a thin functional layer supported by a porous substrate material that carries mechanical loads. Creep deformation behavior is to be assessed to warrant a long-term reliable operation at elevated temperatures. Aiming towards an asymmetric composite, the current study reports and compares the creep behavior of La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) perovskite porous substrate material with different porosity and pore structures in air for a temperature range of 800–1000?°C. A porosity and pore structure independent average stress exponent and activation energy are derived from the deformation data, both being representative for the LSCF material. To investigate the structural stability of the dense layer in an asymmetric membrane, sandwich samples of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF) and La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) with porous substrate and dense layers on both side were tested by three-point bending with respect to creep rupture behavior of the dense layer. Creep rupture cracks were observed in the tensile surface of BSCF, but not in the case of LSCF.     

Disappearance of Fatigue Heterogeneity Due to an Introduction of La0.8Sr0.2MnO3 Buffer Layers in Modified Lead Zirconate Titanate Ceramics

A disappearance of fatigue heterogeneity has been observed with an introduction of La_0.8Sr_0.2MnO₃ (LSM) buffer layers in modified lead zirconate titanate ceramics. This disappearance provides clear evidence for the presence of trapped charge defects near the ferroelectric‐electrode interface. The time‐dependent polarization switching curves reveal that the modified lead zirconate titanate ceramics with LSM buffer layers displayed much less retardation after fatigue cycles. These results point to the essential role of oxygen vacancy during fatigue.     

Synthesis and characterization of fibrous La0.8Sr0.2Fe1-xCuxO3-δ cathode for intermediate-temperature solid oxide fuel cells

Aiming to offer a high-performance Co-free cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs), a series of La_0.8Sr_0.2Fe_1-xCu_xO_3-δ (LSFCux, x = 0.0–0.3) nanofiber cathodes were synthesized by the electrospinning method. The effects of various Cu doping amounts on the crystal structure, fiber morphology, and electrochemical performance of LSF nanofiber cathode materials were investigated. The results indicate that after being calcined at 800 °C for 2 h, the perovskite structure samples with a high degree of crystallinity are obtained. The morphology of electrospun nanofibers is continuous, and the average diameter of nanofibers is about 110 nm. In addition, the La_0.8Sr_0.2Fe_0.8Cu_0.2O_3-δ (LSFCu2) fiber cathode displays the optimal electrochemical performance, and the polarization resistance (R_p) is 0.674 Ω cm² at 650 °C. The doping of Cu transforms the main control step of the low-frequency band from dissociation of oxygen molecules to charge transfer on the electrode, and the maximum power density (P_m) of the Ni-SDC/SDC/LSFCu2 single cell reaches 362 mW cm^-2 at 650 °C.     

Determination of the rate-determining step of the oxygen reduction reaction of La0.8Sr0.2MnO3(LSM)- 8mol% yttria-stabilized zirconia(YSZ): Composition and microstructure

In this study, LSM-YSZ composite cathodes were analyzed by changing the firing temperature, composition, and operating temperature to determine the contribution of each step of the oxygen reduction reaction (ORR). The overall resistance of the cathode reaction was characterized by fitting the AC impedance spectra with an equivalent circuit model. It was found that initial reactions of ORR (dissociative adsorption) are the main rate-determining step (RDS) regardless of operating or sintering temperature, while reactions on LSM surface become the main RDS when the ratio of LSM catalysts has a relatively small proportion. The [LSM-YSZ]_5:5 cathode fired at 1100 °C showed the best microstructure and lowest resistance in the ORR at an operating temperature of 700 °C (R_HF: 0.18 Ωcm², R_MF: 0.20 Ω cm², R_LF: 0.25 Ωcm², R_cathode: 1.14 Ωcm²). This demonstrates the potential use of LSM-YSZ cathodes for IT/LT-SOFC without the use of expensive materials, such as LSCF and BSCF.     

A bi-layered composite cathode of La0.8Sr0.2MnO3-YSZ and La0.8Sr0.2MnO3-La0.4Ce0.6O1.8 for IT-SOFCs

A bi-layered composite cathode of La_0.8Sr_0.2MnO₃ (LSM)-YSZ and LSM-La_0.4Ce_0.6O_1.8 (LDC) was fabricated for anode-supported solid oxide fuel cells with a thin YSZ electrolyte film. The cell with the bi-layered composite cathode displayed better performance than the cell with the corresponding single-layered composite cathode of LSM-LDC or LSM-YSZ. At 650 °C, the cell with the bi-layered composite cathode gave a higher maximum power density than the cells with the single-layered LSM-LDC and LSM-YSZ composite cathodes, by 52% and 175%, respectively. The impedance spectra results show that the thin LSM-YSZ interlayer not only improves the cathode/electrolyte interface but also reduces the polarization resistance of the cathode. The activation energy for oxygen reduction on the bi-layered composite cathode is much smaller than that on LSM-YSZ composite cathode, and it is suggested that the special redox property of Ce⁴⁺/Ce³⁺ in LDC facilitates the oxygen reduction process on the bi-layered composite cathode. The cell with the bi-layered composite cathode operated quite stably during a 100 h run.     

In Situ Foaming of Porous (La0.6Sr0.4)0.98 (Co0.2 Fe0.8) O3−δ (LSCF) Cathodes for Solid Oxide Fuel Cell Applications

A binder system containing polyurethane precursors was used to in situ foam (direct foam) a (La_0.6Sr_0.4)_0.98 (Co_0.2 Fe_0.8) O_3?δ (LSCF) composition for solid oxide fuel cell (SOFC) cathode applications. The relation between in situ foaming parameters on the final microstructure and electrochemical properties was characterized by microscopy and electrochemical impedance spectroscopy (EIS), respectively. The optimal porous cathode architecture was formed with a 70 vol% solids loading within a polymer precursor composition with a volume ratio of 8:4:1 (isocyanate: PEG: surfactant) in a terpineol‐based ink vehicle. The resultant microstructure displayed a broad pore size distribution with highly elongated pore structure.