Influence of Deposition Temperature of GDC Interlayer Deposited by RF Magnetron Sputtering on Anode‐Supported SOFC

Gadolinia‐doped ceria (GDC) film, as a barrier layer to prevent chemical reaction between yttria‐stabilized zirconia (YSZ) electrolyte and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3–δ (BSCF)–GDC cathode, is deposited by radio frequency (RF) magnetron sputtering on YSZ electrolyte, and the influence of deposition temperature on Ni–YSZ/YSZ/GDC/BSCF–GDC single cell performance is investigated. The SEM results show that the GDC film deposited at 30 °C exhibits a porous structure, whereas the GDC film deposited at 400 °C has a dense structure. The single cells show excellent performance when the deposition temperature is above 250 °C, whereas the single cells show poor performance when the deposition temperature is below 200 °C. The large difference in cell performance occurs from their large difference in polarization resistance. The porous structure of GDC interlayer, which cannot well prevent the reaction between BSCF and YSZ, is responsible for the poor performance of the cells with GDC interlayer deposited at a temperature below 200 °C.     

Performance and Evaluation of Cu‐based Nano‐composite Anodes for Direct Utilisation of Hydrocarbon Fuels in SOFCs

The anodes for direct utilisation of hydrocarbon fuels have been developed by using Cu/Ceria‐based nano‐composite powders. The CuO/GDC/YSZ–YSZ or CuO/GDC‐GDC nano‐composite powders were synthesised by coating nano‐sized CuO and CeO₂ particles on the YSZ or GDC core particles selectively by the Pechini process. Their microstructures and electrical properties have been investigated with long‐term stability in reactive gases of dry methane and air. The anodes fabricated using Cu‐based nano‐composite anodes showed almost no carbon deposition until 500 h in dry CH₄ atmosphere. The type of an electrolyte‐supported single cell in conjunction with the Cu/Ceria‐based anode must be selected together for the low melting temperature of Cu/CuO. The GDC electrolyte supported unit cell with the Cu/GDC–GDC anode showed the maximum power density of 0.1 Wcm^–2 and long‐term stability for more than 500 h under electronic load of 0.05 Acm^–2 at 650 °C in dry methane atmosphere.     

Compilation of mechanical properties for the structural analysis of solid oxide fuel cell stacks. Constitutive materials of anode-supported cells

The mechanical failure of one cell is sufficient to lead to the end of service of a solid oxide fuel cell (SOFC) stack. Therefore, there is growing interest in gaining knowledge on the mechanical properties of the cell materials for stress analysis.This study compiles available data from the literature on the mechanical properties of the most common materials used in intermediate-temperature anode-supported cells: nickel and yttria-stabilized zirconia (Ni–YSZ) anodes, YSZ electrolytes, yttria (YDC) or gadolinia-doped ceria (GDC) compatibility layers and lanthanum strontium manganite (LSM) or lanthanum strontium cobalt ferrite (LSCF) cathodes. The properties for the simulation of stresses, i.e. coefficient of thermal expansion (CTE), Young's modulus, Poisson's ratio, creep behaviour and strength are reported, with an emphasis on temperature and porosity dependence and the evolution upon aging or cycling when available. Measurements of our Ni(O)–YSZ anode material includes the CTE (oxidised and reduced state), Young's modulus and strength at room temperature (oxidised and reduced) and 1073 K (oxidised).     

Electrochemical performance and microstructure characterization of nickel yttrium‐stabilized zirconia anode

A nickel and yttrium‐stabilized zirconia (Ni‐YSZ) composite is one of the most commonly used anode materials in solid oxide fuel cells (SOFCs). One of the drawbacks of the Ni‐YSZ anode is its susceptibility to deactivation due to the formation of carbonaceous species when hydrocarbons are used as fuel supplies. We therefore initiated an electrochemical study of the influence of methane (CH₄) on the performance of Ni‐YSZ anodes by examining the kinetics of the oxidation of CH₄ and H₂ over operating temperatures of 600–800°C. Anode performance deterioration was then correlated with the degree of carbonization observed on the anode using ex‐situ X‐ray powder diffraction and scanning electron microscopy techniques. Results showed that carbonaceous species led to a significant deactivation of Ni‐YSZ anode toward methane oxidation. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Performance of mix‐impregnated CeO2‐Ni/YSZ Anodes for Direct Oxidation of Methane in Solid Oxide Fuel Cells

CeO₂‐Ni/YSZ anodes for methane direct oxidation were prepared by the vacuum mix‐impregnation method. By this method, NiO and CeO₂ are obtained from nitrate decomposition and high temperature sintering is avoided, which is different from the preparation of conventional Ni‐yttria‐stabilised zirconia(YSZ) anodes. Impregnating CeO₂ into the anode can improve the cell performance, especially, when CH₄ is used as fuel_. The investigation indicated that CeO₂‐Ni/YSZ anodes calcined at higher temperature exhibited better stability than those calcined at lower temperature. Under the testing temperature of 1,073 K, the anode calcined at 1,073 K exhibited the best performance. The maximum power density of a cell with a 10 wt.‐%CeO₂‐25 wt.‐%Ni anode calcined at 1,073 K reached 480 mW cm^–2 after running on CH₄ for 5 h. At the same time, high discharge current favoured cell operation on CH₄ when using these anodes. No obvious carbon was found on the CeO₂‐Ni anode after testing in CH₄ as revealed from SEM and corresponding linear EDS analysis. In addition, cell performance decreased at the beginning of discharge testing which was attributed to the anode microstructure change observed with SEM.     

Catalytic Influence of Oxide Component in Ni‐Based Cermet Anodes for Ammonia‐Fueled Solid Oxide Fuel Cells

Recently, the promising prospect of ammonia as a hydrogen carrier for solid oxide fuel cells (SOFCs) has attracted significant interests. In this work, the effects of temperature, fuel content, and total flow rate of anode gas on the performance of Ni/yttria‐stabilized zirconia (Ni/YSZ) anode for ammonia‐fueled SOFCs were investigated. Based on obtained results, the utilization route of ammonia on Ni/YSZ anode was discussed; the results of electrochemical experiments were related with the catalytic decomposition bahavior of ammonia over Ni/YSZ. Moreover, the catalytic activity for ammonia decomposition and anode performance of Ni/samarium‐doped ceria (Ni/SDC) and Ni/yttrium‐doped barium cerate (Ni/BCY) were also investigated. Among these anode materials, Ni/BCY exhibited the highest ammonia decomposition activity and anode performance for ammonia‐fueled SOFCs at intermediate temperatures.     

Effect of Ethane and Propane in Simulated Natural Gas on the Operation of Ni–YSZ Anode Supported Solid Oxide Fuel Cells

Solid oxide fuel cells with Ni–yittria‐stabilised zirconia (YSZ) anode supports were tested on surrogate natural gas fuels (methane containing 2.5–10% ethane and 1.25–5% propane) and compared with results for pure methane. Inert anode‐side diffusion barriers were found to help suppress coking on the Ni–YSZ anodes. However, carbonaceous deposits were observed on anode compartment surfaces and the barrier layers for all of the natural gas compositions tested. The addition of air to the natural gas was shown to suppress this coking. For natural gas with 5% ethane and 2.5% propane, the addition of 33% air yielded stable, coke‐free operation at 750 °C and 800 mA cm^–2. Cell performance on this fuel was only slightly worse than for the same cell operated with dry hydrogen.     

Planar Metal‐Supported SOFC with Novel Cermet Anode

Metal‐supported solid oxide fuel cells are expected to offer several potential advantages over conventional anode (Ni‐YSZ) supported cells. For example, increased resistance against mechanical and thermal stresses and a reduction in material costs. When Ni‐YSZ based anodes are used in metal supported SOFC, elements from the active anode layer may inter‐diffuse with the metallic support during sintering. This work illustrates how the inter‐diffusion problem can be circumvented by using an alternative anode design based on porous and electronically conducting layers, into which electrocatalytically active materials are infiltrated after sintering. The paper presents the electrochemical performance and durability of the novel planar metal‐supported SOFC design. The electrode performance on symmetrical cells has also been evaluated. The novel cell and anode design shows a promising performance and durability at a broad range of temperatures and is especially suitable for intermediate temperature operation at around 650 °C.     

Applications of heterogeneous catalysis in the direct oxidation of hydrocarbons in a solid-oxide fuel cell

This review article provides an overview of our recent studies of the direct oxidation of hydrocarbons in solid-oxide fuel cells. The use of a thermally stable, highly porous, yttria-stabilized zirconia (YSZ) matrix, which allows for the optimization of the anode composition and catalytic properties, is described. Studies of the direct oxidation of hydrocarbons using anodes composed of mixtures of YSZ, copper, ceria and samaria-doped ceria are also presented. The results of these studies demonstrate that copper-ceria based anodes are active for the direct electrocatalytic oxidation of a wide range of hydrocarbons including alkanes, alkenes, and aromatics.     

Modeling of complex interfaces: Gadolinium‐doped ceria in contact with yttria‐stabilized zirconia

Gadolinium‐doped ceria (GDC) and yttria‐stabilized zirconia (YSZ) are well‐known electrolyte materials in solid oxide fuel cells (SOFCs). Although they can be used independently, it is common to find them in combination in SOFCs, where they are used as protective layers against the formation of secondary phases or electron conduction blockers. Despite their different optimum operating temperatures, it appears that oxygen conduction is not affected by their interface. However, the intrinsic mechanisms of oxygen diffusion at these interfaces still remain unclear. One of the main difficulties when modeling the contact between different materials, or indeed different particles of the same material, is caused by the structural complexity of these systems. If we wish to evaluate the properties of the materials, we first need to obtain a model that includes the main features of the GDC/YSZ interface, such as large‐scale defects or cation interdiffusion in the contiguous phase. Since the generation of such a mixed system is complicated, we show here how the “amorphization and recrystallization” strategy can help us to obtain realistic systems. In this, the first of our papers on the structure and properties of layered GDC/YSZ materials, we discuss the structural features of the grain boundary between GDC and YSZ obtained by molecular dynamics simulations.     

Effect of grain boundary diffusion on electrolyte stability in direct carbon fuel cells with antimony anodes

Direct carbon fuel cells (DCFC) that employ solid oxide electrolytes and molten Sb anodes are promising for the efficient generation of electricity using a range of carbonaceous fuels. The present study examined the etching of yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (GDC) electrolytes by Sb₂O₃ produced during fuel-cell operation. Migration of Sb along grain boundaries and electrolyte corrosion were observed for both polycrystalline YSZ and GDC electrolytes; however, corrosion and electrolyte thinning were not observed for a single-crystal YSZ electrolyte, even after long-term operation. These results indicate that Sb migration along grain boundaries plays a significant role in electrolyte corrosion in DCFCs with molten Sb anodes. Several strategies for avoiding this problem are also discussed.     

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.     

Carbon-tolerance effects of Sm0.2Ce0.8O2−δ modified Ni/YSZ anode for solid oxide fuel cells under methane fuel conditions

Samarium-doped ceria (SDC) is coated onto a Ni/yttria-stabilized zirconia (Ni/YSZ) anode for the direct use of methane in solid-oxide fuel cells. Porous SDC thin layer is applied to the anode using the sol–gel coating method. The experiment was performed in H₂ and CH₄ conditions at 800 °C. The cell performance was improved by approximately 20 % in H₂ conditions by the SDC coating, due to the high ionic conductivity, the mixed ionic and electronic conductive property of the SDC, and the increased triple phase boundary area by the SDC coating in the anode. Carbon was hardly deposited in the SDC-coated Ni/YSZ anode. The cell performance of the SDC-coated Ni/YSZ anode did not show any significant degradation for up to 90 h under 0.1 A cm^?2 at 800 °C. The porous thin SDC coating on the Ni/YSZ anode provided the electrochemical oxidation of CH₄ over the whole anode, and minimized the carbon deposition by electrochemical carbon oxidation.     

Effect of nanostructured grains in co-sputtered Ni-GDC thin-film anode on methane conversion kinetics for low temperature solid oxide fuel cells operating on nearly dry methane

Direct-methane solid oxide fuel cells (DMSOFCs) have recently attracted substantial attention due to their simplified system, reduced cost, and the direct availability of methane fuel obtained from natural gas. Among oxygen-ion conductive materials, doped-ceria such as gadolinium-doped ceria (GDC) or samarium-doped ceria can be incorporated into Ni-based anodes to reinforce their coking resistance, enlarge their electrochemical reaction area, and improve the kinetics of the internal reforming/electrochemical oxidation of methane. To reduce the range of operating temperatures of DMSOFCs while maintaining their performance, the thin film deposition technique of magnetron sputtering was adopted in this work. An Ni-GDC thin-film anode and a Pt thin-film cathode were deposited on scandia-stabilized zirconia (ScSZ) electrolyte supports. This fuel cell was tested with directly supplied methane fuel (3% H₂O) at 500 °C. The results demonstrated the effects of the GDC volume fraction in the anode—which was controlled by co-sputtering power—on open circuit voltage and electrochemical performance. The co-sputtered Ni-GDC anode was able to survive through 36-h operation, although there was some performance degradation. Field-emission scanning electron microscopy results revealed no formation of filamentous carbon on the Ni catalysts, despite the fact that both X-ray photoelectron spectroscopy and Raman spectroscopy analyses detected carbon coking. The relatively high performance and resistance to carbon coking of co-sputtered thin-film anode were attributed to its intrinsic small grain size.     

Redox Tolerance of Thin and Thick Ni/YSZ Anodes of Electrolyte‐Supported Single‐Chamber Solid Oxide Fuel Cells under Methane Oxidation Conditions

Redox tolerance of 50 and 500 μm thick Ni/YSZ (yttria‐stabilized zirconia) anodes supported on YSZ electrolytes were studied under single‐chamber solid oxide fuel cell conditions. Open circuit voltage, electrochemical impedance spectra, and discharge curves of the cells were measured under different methane/oxygen ratios at 700 °C. For the cell with the thin anode, a significant degradation accompanying oscillatory behaviors was observed, whereas the cell based on the thick anode was much more stable under the same conditions. In situ local anode resistance (R_s) results indicated that the Ni/NiO redox cycling was responsible for the oscillatory behaviors, and the cell degradation was primarily caused by the Ni reoxidation. Reoxidation of the thick anode took place at a low methane/oxygen ratio, but the anode can be recovered to its original state by switching to a methane‐rich environment. On the contrary, the thin anode was unable to be regenerated after the oxidation. Microstructure damage of the anode was attributed to its irreversible degradation.     

Development and Characterization of Porous Composites for Solid Oxide Fuel Cell Anode Conduction Layers Using Ceramic-Filled Highly Porous Ni Foam

Porous Ni-yttria stabilized zirconia (YSZ) composites are the most common materials used for solid oxide fuel cell anodes. In conventional anodes, percolation of the Ni phase for acceptable conductivity requires relatively high Ni contents (i.e., >35 vol% of solids) which can reduce cell reliability due to increased coefficient of thermal expansion (CTE) mismatch with the YSZ electrolyte and damage produced by redox cycling. In this study, the incorporation of highly porous Ni foam into an anode structure was investigated in order to produce an anode conduction layer with high conductivity values at lower Ni volumes. This was done by developing techniques for pasting various YSZ based slurries into a Ni foam structure followed by sintering. The electrical conductivity, dimensional stability, and CTE of these structures were measured as a function of Ni, YSZ, and porous volume. Sintered anodes made with Ni-foam exhibited a superior combination of conductivity and CTE compared with conventional anode structures. For example, a Ni foam–YSZ composite with a nickel loading of 13 vol% has a CTE of 10.7 × 10⁻⁶ K⁻¹, but with a similar electrical conductivity to a conventional anode (∼3000 S/cm) which requires at least 30 vol% Ni resulting in a CTE >13 × 10⁻⁶ K⁻¹. Alteration of the paste composition produced a porous composite with engineered porosity and good dimensional stability.     

Electrochemical Performance of a Ni and YSZ Composite Synthesised by Ultrasonic Spray Pyrolysis as an Anode for SOFCs

The electrochemical performance of an anode material for a solid oxide fuel cell (SOFC) depends highly on microstructure in addition to composition. In this study, a NiO–yttria‐stabilised zirconia (NiO–YSZ) composite with a highly dispersed microstructure and large pore volume/surface area has been synthesised by ultrasonic spray pyrolysis (USP) and its electrochemical characteristics has been investigated. For comparison, the electrochemical performance of a conventional NiO–YSZ is also evaluated. The power density of the zirconia electrolyte‐supported SOFC with the synthesised anode is ∼392 mW cm^–2 at 900 °C and that of the SOFC with the conventional NiO–YSZ anode is ∼315 mW cm^–2. The improvement is ∼24%. This result demonstrates that the synthesised NiO–YSZ is a potential alternative anode material for SOFCs fabricated with a zirconia solid electrolyte.     

Pore orientation of the gadolinia‐doped ceria cathode interlayer for a tubular SOFC using dip‐coating

An active region of cathode interlayer in a tubular solid oxide fuel cell (SOFC) is structurally analyzed using a dual‐beam focused ion beam/scanning electron microscope (FIB/SEM). The GDC (10 mol% gadolinia‐doped ceria) cathode interlayer (about 1 μm in thickness) is dip‐coated, and then sintered on YSZ (8 mol% yttria‐stabilized zirconia) electrolyte. At 1150°C sintering temperature, the pores oriented more along the axial direction than the radial direction. The anisotropy of pore shape is accounted for the withdrawal force during the dip‐coating of the GDC interlayer.     

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.     

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.