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.     

SrO‐Containing Diopside Glass–Ceramic Sealants for Solid Oxide Fuel Cells: Mechanical Reliability and Thermal Shock Resistance

A series of glasses and glass–ceramics (GCs) aiming at applications as sealants for solid oxide fuel cells (SOFCs) were synthesized by partial substitution of Ca for Sr in the diopside‐Ba disilicate composition. X‐ray diffraction in conjunction with the Rietveld‐RIR technique were employed to quantify the crystalline (diopside and Sr‐diopside) and amorphous phases in the glasses sintered/heat treated at 850 °C in humidified 10%H₂–90%N₂ gas mixture for 250 h. Weibull modulus varied in the range 11.6–34.4 implying toward good mechanical reliability of synthesized GCs. Thermal shock resistance of model electrochemical cells made of yttria‐stabilized zirconia, gadolinia‐doped ceria, and lanthanum gallate based solid electrolytes, hermetically sealed by one diopside‐based composition, was evaluated employing quenching from 800 °C in air and water. Suitable thermal expansion coefficient, mechanical reliability, and strong adhesion to stabilized zirconia and metallic interconnects, are all suggesting a good suitability of the sealants for SOFC applications.     

Oxygen vacancy levels on gadolinia-doped ceria interlayer deposited by atmospheric pressure plasma jet for solid oxide fuel cells

The oxygen vacancy levels as a factor on different gadolinia-doped ceria interlayer (GDCi) films deposited on yttria stabilized zirconia (YSZ) electrolyte substrates by an atmospheric pressure plasma jet (APPJ) via precursor solution of nitrate salts are investigated. Focusing on the effect of carrier gases, scanning electron microscopy (SEM), Raman, and X-ray diffraction (XRD) are implemented for the materials characterization of the as-deposited GDCi films and sintered-GDCi films at various temperatures. The higher level of oxygen vacancies in GDCi films adhered on 8YSZ electrolyte are evidently analyzed using Ar as the carrier gas during the deposition, of which the interdiffusion resulted in the formation of (GDC + YSZ) solid solution for sintering over 1300?°C degraded the total conductivity. The deposition of GDCi films on 8YSZ by APPJ method using O₂ carrier gas significantly improved the total conductivities of the whole electrolyte layers. Moreover, this study provides the useful insight into the oxygen vacancy levels on GDC films as interlayer (GDCi) to improve the values of open circuit voltage in LSM/GDCi/YSZ/Pt full-cell, as well as offering the efficiency of APPJ as one step deposition process.     

Effect of annealing on grain growth and Y segregation behavior in tetragonal ZrO2 thin film

In order to fabricate tetragonal yttria stabilized zirconia samples with large grain size, 3 mol% Y₂O₃ doped zirconia thin films were grown on (0001) α-Al₂O₃ substrate by pulsed laser deposition (PLD) followed by subsequent high temperature annealing. The thin film samples were annealed at 1200°C, 1250°C, 1300°C, and 1350°C in order to obtain larger grain size without Y segregation. The microstructure and chemical composition of these annealed films were analyzed using atomic force microscopy, scanning transmission electron microscopy, and energy-dispersive X-ray spectroscopy. The as-grown thin film was found to be composed of [111]-oriented grains of ∼100 nm connected with small-angle tilt boundaries. Based on analysis of annealed thin films, it was revealed that grain growth of tetragonal zirconia occurred anisotropically. Cross section scanning transmission electron microscopy observations revealed that such grain growth behavior is affected by the step-terrace structures of the sapphire substrate. Energy-dispersive X-ray spectroscopy showed that Y was found to distribute almost uniformly below 1300°C but to segregate at the grain boundaries at 1350°C. As a conclusion, the 1300°C-annealed sample shows the largest grain size with homogeneous Y distributions.     

Direct Applicability of La0.6Sr0.4CoO3 – δ Thin Film Cathode to Yttria Stabilised Zirconia Electrolytes at T ≤ 650 °C

For investigating the direct applicability of highly active cobalt containing cathodes on YSZ electrolytes at a lower processing and operating temperature range (T ≤ 650 °C), we fabricated a thin film lanthanum strontium cobalt oxide (LSC) cathode on an yttria stabilised zirconia (YSZ)‐based solid oxide fuel cell (SOFC) via pulsed laser deposition (PLD). Its electrochemical performance (5.9 mW cm^–2 at 0.7 V, 650 °C) was significantly inferior to that (595 mW cm^–2 at 0.7 V, 650 °C) of an SOFC with a thin (t ∼ 200 nm) gadolinium doped ceria (GDC) buffer layer in between the LSC thin film cathode and the YSZ electrolyte. It implies that even though the cathode processing and cell operating temperatures were strictly controlled not to exceed 650 °C, the direct application of LSC on YSZ should be avoided. The origin of the cell performance deterioration is thoroughly studied by glancing angle X‐ray diffraction (GAXRD) and transmission electron microscopy (TEM), and the decomposition of the cathode and diffusion of La and Sr into YSZ were observed when LSC directly contacted YSZ.     

Electrostatic Spray Deposition of Doped Ceria Films

Dense and thin electrolyte films are desirable for solid oxide fuel cells (SOFCs) because of their low gas leakage and low ohmic resistances. This work aims at the preparation of thin dense Gd‐doped ceria (CGO) electrolyte films using a cost‐effective deposition method in ambient atmosphere–electrostatic spray deposition (ESD). The deposition parameters such as deposition temperature, concentration and flow rate of precursor solution were changed systematically to examine their effects on film morphology and hence electrochemical performance. While the film morphology was examined by a scanning electron microscope, the electrochemical performance was revealed by measuring open circuit voltages (OCVs) of NiO‐CGO/CGO/Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3‐δ (BSCF) cells in 500–700 °C with humidified hydrogen as fuel and air as oxidant. The results show that a CGO film of 25 μm thick obtained at a deposition temperature of 400 °C, a precursor solution flow rate of 6 ml h^–1 and a precursor concentration of 0.3 M was dense with very few isolated pores and the OCV of the associated cell was 0.915 V at 500 °C. This implies that the CGO film has negligible gas leakage and ESD is a promising method for preparing thin dense electrolyte films for SOFCs.     

Low Thermal Conductivity of SnO2‐Doped Y2O3‐Stabilized ZrO2: Effect of the Lattice Tetragonal Distortion

Considering the phonon scattering effect and the stability of t′ zirconia, Sn⁴⁺ ion is recognized as an appropriate dopant to achieve the best combination of thermal insulating capability and durability of yttria‐stabilized zirconia thermal barrier coatings (TBCs). In this research, unusual lattice expansion and strong structural disordering were observed in a series of SnO₂‐doped Y₂O₃‐stabilized ZrO₂ compounds, which are caused by the tetragonal distortion of oxygen coordination. Phonon scattering due to the structural disordering rather than point defects of Sn⁴⁺ substitutions predominates in reducing the thermal conductivity. However, deterioration of the thermal properties was observed at high doping content, which may be attributed to the t‐m phase transformation during the measurements. Considering the structure stability and thermal properties, SnO₂‐doped Y₂O₃‐stabilized ZrO₂ compounds can be promising candidates for TBCs.     

Synthesis of monodisperse nanocrystalline 8 mol-% yttria doped ceria powder by oleate complex route

Abstract

Preparation of monodisperse nanocrystalline yttria doped ceria powder by the oleate complex route has been reported. Y(III) and Ce(III) oleate complexes have been prepared by the reaction between YCl₃, Ce(NO₃)₃ and sodium oleate at the interface of hexane rich and water rich conjugate layers of water-ethanol-hexane ternary liquid system. Cubic yttria doped ceria crystallises when the waxy solid containing Y(III) oleate and Ce(III) oleate complexes was heat treated at 400°C. The powder after planetary ball milling contains monodisperse near spherical particles of 0·2?μm. These particles contain monodisperse nanocrystallites of size <10?nm. The yttria doped ceria powder pellets were sintered to >98% theoretical density at 1450°C. The sintered ceramic showed an ionic conductivity of 0·0623?S?cm^?1 at 800°C and activation energy of 1·0?eV.     

Integration of Spin‐Coated Nanoparticulate‐Based La0.6Sr0.4CoO3–δ Cathodes into Micro‐Solid Oxide Fuel Cell Membranes

Thin cathodes for micro‐solid oxide fuel cells (micro‐SOFCs) are fabricated by spin‐coating a suspension of La_0.6Sr_0.4CoO_3–δ (LSC) nanoparticulates obtained by salt‐assisted spray pyrolysis. The resulting 250 nm thin LSC layers exhibit a three‐dimensional porous microstructure with a grain size of around 45 nm and can be integrated onto free‐standing 3 mol.% yttria‐stabilized‐zirconia (3YSZ) electrolyte membranes with high survival rates. Weakly buckled micro‐SOFC membranes enable a homogeneous distribution of the LSC dispersion on the electrolyte, whereas the steep slopes of strongly buckled membranes do not allow for a perfect LSC coverage. A micro‐SOFC membrane consisting of an LSC cathode on a weakly buckled 3YSZ electrolyte and a sputtered Pt anode has an open‐circuit voltage of 1.05 V and delivers a maximum power density of 12 mW cm^–2 at 500 °C.     

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.     

Microstructure and Microfabrication Considerations for Self‐Supported On‐Chip Ultra‐Thin Micro‐Solid Oxide Fuel Cell Membranes

La_0.6Sr_0.4Co_0.8Fe_0.2O_{3 – δ} (LSCF) has been sputtered on bare Si and Si₃N₄ and yttria‐stabilised zirconia (YSZ) thin films to investigate annealing temperature‐ and thickness‐dependent microstructure and functional properties, as well as their implications for designing failure‐resistant micro‐solid oxide fuel cell (μSOFC) membranes. The LSCF thin films crystallise in the 400–450 °C range; however, after annealing in the 600–700 °C range, cracks are observed. The formation of cracks is also thickness‐dependent. High electrical conductivity, ∼520 Scm^–1 at 600 °C, and low activation energy, ∼0.13 eV, in the 400–600 °C range, are still maintained for LSCF films as thin as 27 nm. Based on these studies, a strong correlation between microstructure and electrical conductivity has been observed and an annealing temperature‐thickness design space that is complementary to temperature‐stress design space has been proposed for designing reliable membranes using sputtered LSCF thin films. Microfabrication approaches that maintain the highest possible surface and interface quality of heterostructured membranes have been carefully examined. By taking advantage of the microstructure, microfabrication and geometrical structural considerations, we were able to successfully fabricate large‐area, self‐supported membranes. These results are also relevant to conventional or grid‐supported SOFC membranes using ultrathin nanocrystalline cathodes and μSOFCs using cathode thin films other than LSCF.     

Investigation of Annealing Induced Yttria Segregation in Sputtered Yttria‐Stabilized Zirconia Thin Films

8 mol% yttria‐stabilized zirconia (8YSZ) is an extensively studied solid electrolyte. But there is no consistency in the reported ionic conductivity values of 8YSZ thin films. Interfacial segregation in YSZ thin films can affect its ionic conductivity by locally altering the surface chemistry. This article presents the effects of annealing temperature and film thickness on free surface yttria segregation behavior in 8YSZ thin film by Angle Resolved XPS and its influence on the ionic conductivity of sputtered 8YSZ thin films. Surface yttria concentration of about 32, 20, and 9 mol% have been found in 40 nm 8YSZ films annealed at 1273, 1173, and 1073 K, respectively. Yttria segregation is found to increase with increase in annealing temperature and film thickness. Ionic conductivities of 0.23, 0.16, and 0.08 Scm^?1 are observed at 923 K for 40 nm 8YSZ films annealed at 1073, 1173, and 1273 K, respectively. The decrease in conductivity with increase in annealing temperature is attributed to the increased yttria segregation with annealing. Neither segregation nor film thickness is found to affect the activation energy of oxygen ion conduction. Target purity is found to play a key role in determining free surface yttria segregation in 8YSZ thin films.     

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.     

Electrospinning and characterisation of ceria doped yttria fibres

Abstract

Homogeneous inorganic-organic composite fibres were produced using electrospinning technique from alcoholic solutions containing polyvinyl butyral and precursors of yttrium and cerium ions. Upon heat treatment, ceria and yttria doped ceria fibres retaining the original morphological features observed in the as spun composition were obtained. X-ray diffraction was used to identify the crystalline phases of the final products. Scanning electron microscopy, thermogravimetric analysis, differential thermal analysis and Brunauer-Emmett-Teller analysis were used to study the ceramic phase formation and the evolution of morphological features of the fibres. Thus, several micrometres long, uniform ceria and yttria doped ceria fibres of high phase purity were produced. The CeO₂ and the CeO₂ with Y₂O₃ fibres presented average diameter that ranged from 19 to 25?μm, and the distribution of specific surface ranged from 33 to 43?m²?g^?1.     

Processing and characterisation of fine crystalline ceria gadolinia–yttria stabilized zirconia powders

For low temperature SOFCs the yttria stabilized zirconia (YSZ)-coated ceria is a promising candidate for replacing YSZ-electrolyte. An important requirement for the co-firing feasibility of such a configuration is the densification of ceria at low temperatures (<1400°C). Fine crystalline gadolinia doped ceria (CGO)-powder readily sinterable at 1250°C was synthesized by co-precipitation with oxalic acid of 0·05 M and crystallization in methanol at 200°C for 6 h. The fabrication and characterisation of solid solution phases with a graded composition (CGO)_x(YSZ)_1−x, to be used as an interlayer between YSZ and CGO, in order to avoid delamination, were also studied and discussed. CGO_xYSZ_1−x powders, prepared by the glycine combustion method, required higher sintering temperatures (1500°C) to densify, while they showed significantly lower ionic conductivity than YSZ and CGO, attributed to the large lattice deformation and scattering of oxygen ions.     

Experimental investigation of Al2O3/8YSZ and CeO2/8YSZ plasma sprayed thermal barrier coating on diesel engine

In this research work, aluminium oxide/yttria stabilized zirconia (20%Al₂O₃/80%8YSZ) and ceria/yttria stabilized zirconia (20%CeO₂/80%8YSZ) were coated through atmospheric plasma spray technique (APS) as thermal barrier coating (TBC) over CoNiCrAlY bond coat on aluminium alloy (Al-13%Si) substrate piston crown material and their thermal cycling behavior were studied experimentally. Thermal cycle test of both samples were conducted at 800?°C. Microstructural, phase and elemental analysis of the TBC coatings were experimentally investigated. The performance, combustion and emission characteristics of Al₂O₃/8YSZ, CeO₂/8YSZ TBC coated and uncoated standard diesel engine were experimentally investigated. The test results revealed that CeO₂/8YSZ based TBC has an excellent thermal cycling behavior in comparison to the Al₂O₃/8YSZ based TBC. The spallation of the Al₂O₃/8YSZ TBC occurred mainly due to the formation of thermally grown oxide (TGO), and growth of residual stresses at top coating and bond coating interface. The experimental results also revealed that the increase of brake thermal efficiency and reduction of specific fuel consumption for both TBC coated engine. Further reduction of HC, CO and smoke and increase of NOx emission were recorded for both TBC coated engine compared to the standard diesel engine.     

Electron hole conductivity of gadolinia doped ceria

The electron hole conductivity of gadolinia doped ceria (GCO) was estimated from electrochemical permeability measurements, at temperatures in the range of 800 to 1000°C. The transient behaviour of the cell (while recovering from reducing to oxidising conditions) was used to assess the accuracy of the experimental procedure, and some of these results still suggested the presence of leaks in the sealings. However, the temperature dependence of steady state results indicates that electrochemical permeability prevails, and these results were thus used to estimate the hole conductivity. These results showed that the hole conductivity of GCO at 1000°C is about two orders of magnitude higher than reported for yttria stabilized zirconia, and the activation energy (129 kJmol⁻¹) is slightly lower.     

Defect induced magnetic transition in Co doped CeO2 sputtered thin films

Cobalt-doped cerium dioxide thin films exhibit room temperature ferromagnetism due to high oxygen mobility in doped CeO₂ lattice. CeO₂ is an excellent doping matrix as there is a possibility of it losing oxygen while retaining its structure. This leads to increased oxygen mobility within the fluorite CeO₂ lattice, leading to formation of Ce³⁺ and Ce⁴⁺ species. Magnetic ceria materials are important in several applications from magnetic data storage devices to magnetically recoverable catalysts. In this paper, the room temperature ferromagnetism of rf sputtered Co doped CeO₂ thin films is reported whereas undoped CeO₂ thin films exhibit paramagnetic behavior. The ferromagnetic properties of the Co doped films were explained based on oxygen vacancies created by Co ions in Ce sites. This is further supported by X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and Raman. Change in surface morphology due to Co doping of the samples were analyzed using atomic force microscopy (AFM).     

Electrical conductivity and oxygen semipermeability of terbia and yttria stabilized zirconia

This paper reports an electrochemical study on terbia and yttria stabilized zirconia. (Tb, Y)-ZrO₂ solid solutions with a fluorite type structure were prepared by using citrate synthesis and sintered at 1500°C. They are mixed electronic and oxygen ionic conductive, as well as oxygen semipermeable materials at elevated temperatures. The total electrical conductivity reaches 3.8 S m^–1 at 900°C and the oxygen permeation is about 6.5 × 10^–6 mol m^–2 s^–1 at 1100°C. The electrical conductivity of zirconia doped with a total of 30 mol % of terbia and yttria increases with oxygen partial pressure when P _{O 2} is below 10^–2 atm, and decreases as the oxygen partial pressure rises above 10^–2 atm. This is ascribed to the defect association and the predomination of oxygen ionic conductivity. The oxygen semipermeation is proportional to the square root of the oxygen partial pressure, and is not influenced by the variation of oxygen ionic or electronic conduction. The results indicate that the surface exchange reaction is most probably the rate limiting step for the oxygen semipermeation.     

Investigation of the Mechanical Stability of Micro‐Solid Oxide Fuel Cell Membranes Using Scanning Laser Vibrometry

Scanning laser vibrometry was used to investigate the mechanical stability of free‐standing micro‐solid oxide fuel cell (micro‐SOFC) membranes. Arrays of square‐shaped 460 nm thin micro‐SOFC membranes were fabricated on silicon substrates using pulsed laser deposition for the yttria‐stabilized zirconia electrolyte and magnetron sputtering for the platinum electrodes. Resonance frequency, displacement and acceleration measurements were carried out using interferometry analysis of the membrane reflection. The resonance frequencies scale with the reciprocal of the membrane length. At the resonance, the 390 × 390 μm² micro‐SOFC membranes exhibit an out‐of‐plane displacement of ca. 1.2 μm only. All free‐standing micro‐SOFC membranes survive the resonant vibration without rupturing. These results are promising for the failure‐free implementation of micro‐SOFC in portable electronic devices.