Oxygen Dissociation and Interfacial Transfer Rate on Performance of SOFCs with Metal‐Added (LaSr)(CoFe)O3‐(Ce,Gd)O2 – δ Cathodes

A solid oxide fuel cell (SOFC) unit is constructed with Ni‐Ce_0.9Gd_0.1O_{2 – δ} (GDC) as the anode, yttria‐stabilised zirconia (YSZ) as the electrolyte and Pt, Ag or Cu‐added La_0.58Sr_0.4Co_0.2Fe_0.8O_{3 – δ} (LSCF)–GDC as the cathode. The current–voltage measurements are performed at 800 °C. Cu addition leads to best SOFC performance. LSCF–GDC–Cu is better than LSCF–GDC and much better than GDC as the material of the cathode interlayer. Cu content of 2 wt.‐% leads to best SOFC performance. A cathode functional layer calcined at 800 °C is better than that calcined at higher temperature. Metal addition increases the O₂ dissociation reactivity but results in an interfacial resistance for O transfer. A balance between the rates of O₂ dissociation and interfacial O transfer is needed for best SOFC performance.     

Flash Sintering of (La,Sr)(Co,Fe)O3–Gd‐Doped CeO2 Composite

Sintering of composites constituted by two nonstoichiometric phases (La_0.6Sr_0.4)(Co_0.2Fe_0.8)O₃ (LSCF) and Gd_0.1Ce_0.9O₂ (GDC) under constant electric field in constant heating rate experiment is studied in this work. The requirements of field and temperature for composite systematically increase with GDC amounts this indicating the importance of material conductivity. Sintering/grain growth rate is higher in the composite compared to pure LSCF phase. Flash‐sintering phenomenon in the composite is explained on the basis of three factors: (1) large and continuous increase in conductivity of LSCF acts as source of defects, (2) maintenance of sufficient local temperature because of GDC during continuous conductivity increase facilitates the cationic diffusion, and (3) reduction reactions of LSCF, during polaron hopping conduction, and of GDC phase at higher temperature activate the sintering process.     

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.     

Application of dispenser printing for the preparation of a SOFC cathode with controlled microstructure

The fabrication of a cathode layer of solid oxide fuel cells by the dispenser printing was investigated and found to be useful in the creation of a thicker ceramic layer using viscous ceramic slurries. The cathode layer prepared from a mixture of La_0.6Sr_0.4Co_0.2Fe_0.8O_3?δ (LSCF) and Ce_0.9Gd_0.1O_1.95 (GDC) slurry clearly shows an inhomogeneous microstructure which leads to poor cell performance. In order to solve this problem, the size of the LSCF particles was controlled through a milling process. Better cell performance was observed for the cells with controlled microstructure by adjusting the pore former content, the LSCF/GDC ratio, in addition to the particle size control. This process might be useful in the deposition of a thick ceramic layer on a curved substrate such as micro-tubular cell.     

Performance of IT‐SOFC with Ce0.9Gd0.1O1.95 Functional Layer at the Interface of Ce0.9Gd0.1O1.95 Electrolyte and Ni‐Ce0.9Gd0.1O1.95 Anode

In this paper we present results for a high power density IT‐SOFC and a method for dispersing nanosized Ce_0.9Gd_0.1O_1.95 (GDC) particles at the GDC electrolyte and Ni‐GDC anode interface. Dispersed nanosized particles were deposited to form an anode functional layer (AFL). Anode supports were prepared by tape casting of large micron‐sized NiO powder and sub micron‐sized GDC powder without pore former. For the cathode a La_0.6Sr_0.4Co_0.2Fe_0.8O_{3 – δ} (LSCF)‐GDC composite was used. Without an AFL the open circuit potential (OCP) and the maximum power density were 0.677 V and 407 mW cm^–2, respectively, at 650 °C using 30 sccm of hydrogen and air flow‐rate. With an AFL the OCP and the maximum power density increased to 0.796 V and 994 mW cm^–2, respectively, at the same temperature. Two point probe impedance measurements revealed that the AFL fabricated by the proposed method not only increased the OCP but also reduced the electrode polarisation by 68%. The effect of gas flow‐rate is also present in this paper. When hydrogen and air flow‐rate is increased to 90 sccm, the sample with AFL obtained 1.57 W cm^–2 at 650 °C.     

Five-layer reverse tape casting of IT-SOFC

Tape casting is a well-established method for manufacturing thin ceramic layers with controllable thickness and porosity. This study investigates the potential of 10Sc1CeSZ material for the electrolyte and anode layers for intermediate-temperature solid oxide fuel cells (IT-SOFC) in an anode-supported cell (ASC) geometry. In order to use La_0.6Sr_0.4Co_0.2Fe_0.8 Oxide (LSCF) cathode material, a Gd_0.2Ce_0.8 Oxide (GDC) barrier layer is needed; however, thermal expansion coefficient mismatch results in delamination of the GDC from the electrolyte during high temperature sintering when fabricated by conventional tape casting procedures. For the first time, ASCs have been manufactured by a five-layer tape casting technique; barrier layer, novel composite layer, electrolyte, anode functional layer, and anode substrate. Ni-ScCeSZ composite cells were tested between 650 and 800°C in H₂:N₂ fuel (85% H₂) on the anode and air on the cathode to yield a maximum power density of .46 W/cm². These results demonstrate the feasibility of this new five-layer tape casting technique to produce IT-SOFC.     

Electrochemical performance of intermediate temperature micro-tubular solid oxide fuel cells using porous ceria barrier layers

We describe the manufacture and electrochemical characterization of micro-tubular anode supported solid oxide fuel cells (mT-SOFC) operating at intermediate temperatures (IT) using porous gadolinium-doped ceria (GDC: Ce_0.9Gd_0.1O_2−δ) barrier layers. Rheological studies were performed to determine the deposition conditions by dip coating of the GDC and cathode layers. Two cell configurations (anode/electrolyte/barrier layer/cathode): single-layer cathode (Ni–YSZ/YSZ/GDC/LSCF) and double-layer cathode (Ni–YSZ/YSZ/GDC/LSCF–GDC/LSCF) were fabricated (YSZ: Zr_0.92Y_0.16O_2.08; LSCF: La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ). Effect of sintering conditions and microstructure features for the GDC layer and cathode layer in cell performance was studied. Current density–voltage (j–V) curves and impedance spectroscopy measurements were performed between 650–800 °C, using wet H₂ as fuel and air as oxidant. The double-cathode cells using a GDC layer sintered at 1400 °C with porosity about 50% and pores and grain sizes about 1 μm, showed the best electrochemical response, achieving maximum power densities of up to 160 mW cm⁻² at 650 °C and about 700 mW cm⁻² at 800 °C. In this case GDC electrical bridges between cathode and electrolyte are preserved free of insulating phases. A preliminary test under operation at 800 °C shows no degradation at least during the first 100 h. These results demonstrated that these cells could compete with standard IT-SOFC, and the presented fabrication method is applicable for industrial-scale.     

Application of a thin intermediate cathode layer prepared by inkjet printing for SOFCs

The application of an inkjet printing process for fabricating solid oxide fuel cell (SOFC) cathodes was investigated. Stably-dispersed LSCF–GDC inks were prepared by ball milling, and the composition was easily controlled by the preparation process. Fabrication of an LSCF–GDC layer was successfully carried out by depositing dots and the thickness was easily controlled by repeating printing process. A planar SOFC single cell with a double-layered cathode (comprised of a paste painted cathode layer and an inkjet printed interlayer) achieved a maximum power density of 0.71 W/cm² at 600 °C. This is the preliminary work for fabricating the cathode layer of a SOFC single cell via inkjet printing.     

Rietveld refinement and estimation of residual stress in GDC–LSCF oxygen transport membrane ceramic composites

The phase purity and crystal structure of dual-phase Ce_.9Gd_.1O_2–δ–La_.6Sr_.4Co_.2Fe_.8O_3–δ (GDC–LSCF) composites were refined using data obtained from X-ray diffraction (XRD) by employing the Rietveld method. Rietveld analysis indicated that the structures of GDC and LSCF phases are well crystallized as cubic Fm$\stackrel{?}{3}$m and rhombohedral R$\stackrel{?}{3}$c space groups, respectively. Scanning electron microscopy images showed smooth and dense structures, depicting a homogeneous crystalline structure of the samples. When the composites were cooled from their sintering temperature (1250?°C), compressive stresses were generated in the GDC and corresponding tensile stresses were generated in the LSCF due to differences in thermal expansion coefficients. The compressive residual stresses of the composites were investigated by high-angle XRD measurements using the well-known sin²ψ method. The average compressive residual stresses in GDC phase are estimated to be ??312 and ??290?MPa for 80 GDC–20 LSCF and 50 GDC–50 LSCF, respectively. The aim of this study is to provide a better understanding of the crystal structures and residual stresses in GDC–LSCF composites through XRD and the suitability of these composites for oxygen transport membranes.     

Ferritic Cathodes Degradation by Potassium/Chromium Poisoning and Air Humidification

Degradation mechanisms inherent to ferritic LSF‐SDC and LSCF‐GDC cathodes are studied by post‐mortem analysis of cells which suffered the most significant performance deterioration in a set of 18 500 h tests carried out under a specific experimental design. Three cathode processing parameters (composition, thickness, and sintering temperature) were combined with five operation conditions (chromium presence, current density, operating temperature, air flow, and humidification) through this design of experiments based in a L₁₈ Taguchi matrix. In the case of cells exposed to chromium vapors from Crofer 22 APU pieces, those cells which exhibited K₂Cr₂O₇ deposition in the cathode/GDC barrier interface underwent the most aggressive ASR degradation. Similar deposits were also observed on the surface of LSC current collectors. Two cells exposed to highly humidified air (20%) exhibited cathode delamination and GDC barrier deterioration by crack propagation though no foreign elements diffusion to the interface could be detected.     

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.     

A feasible strategy for tailoring stable spray-coated electrolyte layer in micro-tubular solid oxide fuel cells

By this work, the viability of the spray coating as a cost-effective and reliable technique for the coating of Ce_0.9Gd_0.1O_1.95 (GDC) electrolyte layer on the mini-tubular NiO–GDC anodes based a solid oxide fuel cell (SOFC) fabrication was assessed. The compatibility of the anode and electrolyte was analyzed by using XRD. The variation in thickness and morphology of the electrolyte film as a function of the coating cycles was discussed with optical and scanning electron microscopes. By similar formulation, the coating of La_0.6Sr_0.4Fe_0.8Co_0.2O₃ –Ce_0.9Gd_0.1O_2–δ (LSCF–GDC) was performed to achieve porous cathode. An individual micro-tubular anode supported cell with configuration NiO–GDC/GDC/LSCF–GDC as anode/electrolyte/cathode was tested in the SOFC mode with humidified hydrogen as fuel and stationary air as oxidant. The fabricated mini-SOFC prototype that generated a maximum power density of 0.510 W/cm² at 600°C signifies the potential of this industrially scalable low-cost coating technique.     

Effect of GDC interlayer thickness on durability of solid oxide fuel cell cathode

Long-term performance degradation of solid oxide fuel cell (SOFC) cathode as a function of gadolinium doped ceria (GDC) interlayer thickness has been studied under accelerated operating conditions. For this purpose, SOFC half-cells with GDC interlayer thicknesses of 2.4, 3.4 and 6.0 µm were fabricated and tested for 1000 h at 900 °C under constant current density of 1 A/cm². The half-cells consisted of lanthanum strontium cobalt ferrite (LSCF)/GDC composite cathode, GDC interlayer, scandia-ceria stabilized zirconia electrolyte and platinum anode as a counter electrode. Area specific resistance (ASR) of the half-cells was continuously measured over time. Higher increase in ASR was observed for the half-cells with GDC interlayer thickness of 2.4 and 6.0 µm, which is attributed to higher strontium (Sr) diffusion towards electrolyte and to cathode/GDC interface delamination coupled with small Sr diffusion, respectively. However, half-cell with GDC interlayer thickness of 3.4 µm showed smaller degradation rate due to highly dense GDC interlayer which had less interfacial resistance and suppressed Sr diffusion towards electrolyte.     

Fabrication and Characterization of Anode‐Supported Low‐Temperature SOFC Based on Gd‐Doped Ceria Electrolyte

Large‐size, 9.5 cm × 9.5 cm, Ni‐Gd_0.1Ce_0.9O_1.95 (Ni‐GDC) anode‐supported solid oxide fuel cell (SOFC) has been successfully fabricated with NiO‐GDC anode substrate prepared by tape casting method and thin‐film GDC electrolyte fabricated by screen‐printing method. Influence of the sintering shrinkage behavior of NiO‐GDC anode substrate on the densification of thin GDC electrolyte film and on the flatness of the co‐sintered electrolyte/anode bi‐layer was studied. The increase in the pore‐former content in the anode substrate improved the densification of GDC electrolyte film. Pre‐sintering temperature of the anode substrate was optimized to obtain a homogeneous electrolyte film, significantly reducing the mismatch between the electrolyte and anode substrate and improving the electrolyte quality. Dense GDC electrolyte film and flat electrolyte/anode bi‐layer can be fabricated by adding 10 wt.% of pore‐former into the composite anode and pre‐sintering it at 1,100 °C for 2 h. Composite cathode, La_0.6Sr_0.4Fe_0.8Co_0.2O₃, and GDC (LSCF‐GDC), was screen‐printed on the as‐prepared electrolyte surface and sintered to form a complete single cell. The maximum power density of the single cell reached 497 mW cm^–2 at 600 °C and 953 mW cm^–2 at 650 °C with hydrogen as fuel and air as oxidant.     

Characterizations of composite cathodes with La0.6Sr0.4Co0.2Fe0.8O3?δ and Ce0.9Gd0.1O1.95 for solid oxide fuel cells

Composite cathodes with La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) and Ce_0.9Gd_0.1O_1.95 (GDC) are investigated to assess for solid oxide fuel cell (SOFC) applications at relatively low operating temperatures (650–800 °C). LSCF with a high surface area of 55 m²g⁻¹ is synthesized via a complex method involving inorganic nano-dispersants. The fuel cell performances of anode-supported SOFCs are characterized as a function of compositions of GDC with a surface area of 5 m²g⁻¹. The SOFCs consist of the following: LSCF-GDC composites as a cathode, GDC as an interlayer, yttrium stabilized zirconia (YSZ) as an electrolyte, Ni-YSZ (50: 50 wt%) as an anode functional layer, and Ni-YSZ (50: 50 wt%) for support. The cathodes are prepared for 6LSCF-4GDC (60: 40 wt%), 5LSCF-5GDC (50: 50 wt%), and 4LSCF-6GDC (40: 60 wt%). The 5LSCF-5GDC cathode shows 1.29 Wcm⁻², 0.97 Wcm⁻², and 0.47 Wcm⁻² at 780 °C, 730 °C, and 680 °C, respectively. The 6LSCF-4GDC shows 0.92 Wcm⁻², 0.71 Wcm⁻², and 0.54 Wcm⁻² at 780 °C, 730 °C, and 680 °C, respectively. At 780 °C, the highest fuel cell performance is achieved by the 5LSCF-5GDC, while at 680 °C the 6LSCF-4GDC shows the highest performance. The best composition of the porous composite cathodes with LSCF (55 m²g⁻¹) and GDC (5 m²g⁻¹) needs to be considered with a function of temperature.     

Preliminary Study on Direct Operation of LT‐SOFCs Based on GDC Electrolyte Film With DME Fuel

Direct operation of anode‐supported cone‐shaped tubular low temperature solid oxide fuel cells (LT‐SOFCs) based on gadolinia‐doped ceria (GDC) electrolyte film with dimethyl ether (DME) fuel was preliminarily investigated in this study. The single cell exhibited maximum power densities of 500 and 350 mW cm^–2 at 600 °C using moist hydrogen and DME as fuel, respectively. A durability test of the single NiO‐GDC/GDC/LSCF‐GDC cell was performed at a constant current of 0.1 A directly fuelled with DME for about 200 min at 600 °C. The results indicate that the single cell coking easily directly operated in DME fuel. EDX result shows a clear evidence of carbon deposition in the anode. Further studies are needed to develop the novel anti‐carbon anode materials, relate the carbon deposition with anode microstructure and cell‐operating condition.     

Low Temperature Electrode Materials Synthesized by Citrate Precursor Method for Solid Oxide Fuel Cells

Homogeneous nanocrystalline NiO–Ce_0.9Ln_0.1O_2–δ (Ln = La, Sm, Gd, and Pr) composite anode and nanocrystalline Ce_0.9Gd_0.1O_2–δ electrolyte material have been successfully synthesized by citrate precursor method. LSCF has been synthesized by conventional solid state method and used as cathode material in our studies. The synthesized powders have been characterized by powder X‐ray diffraction, microscopy, and surface area studies. The average crystallite size of the anode materials has been found to be in the range of 5–15 nm by HRTEM. Highly dense electrolyte and porous electrode materials have been observed by FESEM and confirmed by BET surface area studies. Three cells have been fabricated successfully. Based on the performance of the three cells containing three different anode materials we have achieved better electrochemical characteristics in Ni–GDC with maximum power density of 302 mW cm^–2 and open circuit voltage of 1.012 V at 500 °C. The difference in the performance of the cells containing Ni–GDC as compared to Ni–LDC and Ni–SDC anode is due to changes in the microstructure and crystallite size of anode which affects the electrochemical performance of the cells. The performances of all the cells containing nanocomposite powders are suitable anode materials for low temperature SOFCs.     

Electrochemical behaviour of the surface treated composite-electrolyte/electrode interface

The effect of surface treatment of the solid electrolyte 50 wt% (4.7 mol% Sc₂O₃+95.3 mol % ZrO₂)+ 50 wt % Al₂O₃ (used in the SIRO₂ low temperature oxygen sensor) on its electrochemical behaviour has been studied by complex impedance spectroscopy. Two techniques, namely, preferential etching of alumina from the surface by a suitable etchant and cosintering of a thin layer of an alumina free electrolyte composition were used. The electrode/electrolyte interfaces prepared by using surface treated electrolyte samples had much lower electrode resistance (by a factor of 3–6) compared with the untreated surfaces. The decrease in the interfacial impedance is attributed mainly to the absence of alumina at the interface (an insulator phase) at which no oxygen exchange reactions could take place.     

Mechanical properties of LSCF (La0.6Sr0.4Co0.2Fe0.8O3−δ)–GDC (Ce0.9Gd0.1O2−δ) for oxygen transport membranes

In this study, for application in oxygen transport membranes, an LSCF (La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ)–GDC (Ce_0.9Gd_0.1O_2−δ) composite was manufactured, and its mechanical properties were studied. Generally, it is known that LSCF has a nonlinear modulus due to changes in its microstructure when a critical stress is loaded. To improve the mechanical properties of this material, which has a perovskite structure, a study was conducted to evaluate whether its properties change according to the rule of mixtures when it is formed into a composite with GDC. The results showed that the nonlinearity of the modulus of the composite for each specimen composition was largely reduced and stable under fatigue loading. The fracture toughness was superior to that of the LSCF (1.05 MPa m^1/2) or GDC (1.28 MPa m^1/2) monolithic materials when the composites (1.63 MPa m^1/2) was manufactured. The mechanisms for these were explained by finite element analysis and the observation of crack propagation. It was also confirmed that when these composite materials are used for oxygen transport membranes, they show stable properties.     

Development of solid oxide cells by co-sintering of GDC diffusion barriers with LSCF air electrode

The effects of a Cu-based additive and nano-Gd-doped ceria (GDC) sol on the sintering temperature for the construction of solid oxide cells (SOCs) were investigated. A GDC buffer layer with 0.25–2 mol% CuO as a sintering aid was prepared by reacting GDC powder and a CuN₂O₆ solution, followed by heating at 600 °C. The sintering of the CuO-added GDC powder was optimized by investigating linear shrinkage, microstructure, grain size, ionic conductivity, and activation energy at temperatures ranging from 1000 to 1400 °C. The sintering temperature of the CuO–GDC buffer layer was decreased from 1400 °C to 1100 °C by adding the CuO sintering aid at levels exceeding 0.25 mol%. The ionic conductivity of the CuO–GDC electrolyte was maximized at 0.5 mol% CuO. However, the addition of CuO did not significantly affect the activation energy of the GDC buffer layer. Buffer layers with CuO-added GDC or nano-GDC sol-infiltrated GDC were fabricated and tested in co-sintering (1050 °C, air) with La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF). In addition, SOC tests were performed using button cells (active area: 1 cm²) and five-cell (active area: 30 cm²/cell) stacks. The button cell exhibited the maximum power density of 0.89 W cm⁻² in solid oxide fuel cell (SOFC) mode. The stack demonstrated more than 1000 h of operation stability in solid oxide electrolysis cell (SOEC) mode (decay rate: 0.004%/kh).