Inert substrate-supported microtubular solid oxide fuel cells based on highly porous ceramic by low-temperature co-sintering

Inert substrate-supported microtubular solid oxide fuel cells (MT-SOFCs) are attractive due to their advantages, including high reduction–oxidation (redox) cycling stability and thermal cycling tolerance. A method involving sequential dip-coating, leaching, and co-sintering was developed and applied to fabricate inert substrate-supported MT-SOFCs through acid leaching nickel from the conventional Ni–yttria-stabilized zirconia (YSZ) anode. A thin current collector was deposited onto the support surface to minimize the current collection losses by collecting current from the entire surface area of the anode. A dense electrolyte could be obtained at a co-sintering temperature of 1250?°C. The produced MT-SOFC with the configuration of porous zirconia support/Ni–Scandia-stabilized zirconia (SSZ) anode current collector/Ni-SSZ anode/SSZ electrolyte/strontium-doped lanthanum manganite (LSM)-SSZ cathode/LSM cathode current collector was evaluated by electrochemical characterization tests. The inert substrate-supported MT-SOFC exhibited the maximum power densities of 616, 542, 440, and 300?mW?cm^?2 at 800, 750, 700, and 650?°C, respectively using dry hydrogen and air. In addition, the thermal cycling stability of the MT-SOFC was evaluated. The cell survived from thermal cycling tests and came out intact after 50 thermal cycles between 700?°C and 400?°C during an operation time of 50?h.     

Development of ceramic fiber reinforced glass ceramic sealants for microtubular solid oxide fuel cells

Ceramic fibers in various forms with different fiber sizes are tested to improve the sealing performance of glass ceramic seals for microtubular solid oxide fuel cell applications. In this regard, several sealing pastes are prepared by mixing each ceramic fibers type with glass ceramics at 1.25 wt %. Five layered microtubular anode supported cells are also fabricated by extrusion and dip coating methods to evaluate the sealing performance of the composite sealants. The pastes are applied between the cells and gas manifolds made of Crofer22 APU. The electrochemical and sealing performances at an operating temperature of 800 °C under hydrogen are investigated after the glass forming process. Microstructures of the sealants are also examined by a scanning electron microscope. Experimental investigations reveal that the cells sealed by the pastes with ceramic bulk fiber and ceramic fiber rope gasket show acceptable open circuit potentials close to the theoretical one. These cells can be also pressurized up to around 150 kPa back pressure in the sealing performance tests. On the other hand, the pastes without any filler, with ceramic rope and with ceramic blanket exhibit poor sealing performance due to gas leakage originated from flowing of the main glass ceramic matrix from the joints. Therefore, ceramic bulk fiber and ceramic fiber rope gasket are found to behave as a stopper and can be used to prevent glass ceramics from flowing for microtubular solid oxide fuel cells or similar applications.     

Direct-methane anode-supported solid oxide fuel cells fabricated by aqueous gel-casting

Direct methane Solid Oxide Fuel Cells (SOFCs) operated under catalytic partial oxidation (CPOX) conditions are investigated, focusing on the processing of the anode support and the anode deactivation caused by carbon deposition. Anode-supported SOFCs based on gadolinium-doped ceria (GDC) electrolyte, and NiO-GDC anode support were fabricated by the gel-casting method. Suitable aqueous slurries formulations of NiO–GDC were prepared, starting NiO-GDC nanocomposite powders, agarose as gelling agent and rice starch as pore former. Electrochemical and mechanical tests evidenced that the support of 550 ± 50 µm thickness and 10 wt% pore former is a good candidate for direct-methane SOFCs. The cells operating under stoichiometric conditions of CPOX reached a performance of 0.64 W·cm^?2 at 650 ºC, a very close value to that measured under humidified hydrogen (0.71 W·cm^?2). The best electrochemical stability of the cell is achieved at a CH₄/O₂ ratio of 2.5, showing no evidence of carbon deposition and reducing nickel re-oxidation significantly.     

Mechanical and electrochemical behavior of novel electrolytes based on partially stabilized zirconia for solid oxide fuel cells

In this study, 3 mol% yttria stabilized zirconia (3YSZ) is investigated as a SOFC electrolyte alternative to 8 mol% yttria stabilized zirconia (8YSZ). The mechanical and electrochemical properties of both materials are compared. The mechanical tests indicate that the thickness of 3YSZ can be reduced to half without sacrificing the strength compared to 8YSZ. By reducing the thickness of 3YSZ from 150 µm to 75 µm, the peak power density is shown to increase by around 80%. The performance is further enhanced by around 22% by designing of novel electrode structure with regular cut-off patterns previously optimized. However, the cell with novel designed 3YSZ electrolyte exhibits 30% lower maximum power density than that of the cell with 150 µm-thick standard 8YSZ electrolyte. Nevertheless, the loss in the performance may be tolerated by decreasing the fabrication cost revealing that 3YSZ electrolyte with cut-off patterns can be employed as SOFC electrolyte alternative to 8YSZ.     

Optimum processing parameters to improve sealing performance in solid oxide fuel cells

Glass–ceramic composites are among the favorable candidates as a sealing material for solid oxide fuel cells (SOFC). In order to obtain a reliable, robust and hermetic sealing, the glass–ceramics must chemically bond to both the metallic interconnector and the ceramic electrolyte. A high-bonding strength and good wetting, which strongly depend on the thermal treatment, are always preferred to ensure gas-tight sealing. The thermal treatment involves three stages: binder burnout (stage-I), sintering (stage-II), and cooling (stage-III). This study investigates effects of various parameters on the sealing quality at the sintering stage. The effects of sintering temperature, clamping pressure and sealant thickness are considered. The glass–ceramic laminates are produced employing a tape casting method. The sealing quality is evaluated by measuring leakage and final macro-structure of the sealing region. It is suggested that a 900–930 °C sintering temperature and 1.5–7.6 N cm⁻² clamping pressure ranges are better for successful sealing. The initial thickness of glass–ceramic laminates is also desired to be between 0.25–0.5 mm thickness range for both a cost-effective and reliable sealing.     

Fabrication of glass ceramic sealants with ceramic fiber filler for solid oxide fuel cells

In this study, ceramic fibers are used as a filler material for glass ceramic sealant in solid oxide fuel cells to improve the thermal cycle behavior. Beside the bare glass ceramic sealant for comparison, multilayered sealants with different ceramic fiber contents are fabricated to investigate the effect of ceramic fiber quantity also. The mechanical performances of the samples are measured via tensile tests by placing them between two metallic interconnector plates after the glass formation process as well as after 1, 5 and 10 thermal cycles. The results show that the mechanical strength in general tends to decrease with increasing the ceramic filler content, which can be attributed to poor adhesion due to reduced glass ceramic composition. On the other hand, thermal cycle behavior of the samples with ceramic fibers is found to be improved at some extend. This may be due to the behavior of ceramic filler network and relatively slow crystallization with increasing the amount of the filler as proven by microstructural observations. Especially for the sample including 4 ceramic fiber interlayers each having 0.030 g ceramic fibers, the mechanical strength shows an increasing trend with the number of thermal cycles.     

Effects of solid loading on joining and thermal cycling performance of glass-ceramic sealing pastes for solid oxide fuel cells

The variation of the joining performance of glass-ceramic sealants in the form of a paste as a function of the solid powder content in the sealing paste after the formation and a number of thermal cycles are experimentally studied. Three different sealing pastes having 40, 50 and 60 wt % solid loadings are prepared and tested for this purpose. The pastes are applied between two metallic interconnector plates and subjected to a glass formation step for the joining. The fracture strengths of 24 samples prepared for each case are determined via tensile tests. Similarly, the mechanical performances of the sealants after 3, 6 and 9 thermal cycles are also obtained. The results reveal that the joining strength tends to increase with the amount of solid powder content in the paste. This can be attributed to increased number of crystalline phases in the sealants with increasing the solid loading. The thermal cycles, on the other hand, are shown to have an adverse effect on the joining performance regardless of the solid loading. However, the rate of decrease in the fracture strengths is found to decrease with the solid powder contents in the pastes. This can be elucidated by the amount of glassy phases in the sealants, which can be expected to increase with the solid loading and provide self-healing ability. The microstructures of the fracture surfaces of all samples are also investigated by a scanning electron microscopy. The obtained images confirm the tensile test results.     

Enhancing thermal-stability of metal electrodes with a sputtered gadolinia-doped ceria over-layer for low-temperature solid oxide fuel cells

Cathodic activation loss is the dominant loss mechanism in the operation of low-temperature solid oxide fuel cells (LT-SOFCs). The thermal degradation of metallic cathodes decreases the performance of LT-SOFCs, causing practical issues in long-term operation. In this paper, we investigate the effect of the sputtered gadolinia-doped ceria (GDC) over-layer on the thermal stability of platinum (Pt) cathodes. The thermal stability of Pt cathodes with 23 nm-thick GDC over-layers significantly increased compared to that of the Pt-only cathodes after 2hrs’ operation at 450 °C. (<4% vs. 17% performance degradation, respectively).     

Isothermal models for anode-supported tubular solid oxide fuel cells

Modeling of solid oxide fuel cells (SOFCs) has gained considerable significance in recent years. A detailed phenomenological model for SOFC can be used to understand performance limitations, optimization, in situ diagnostics and control. In this paper, we study the transport and various electrochemical phenomena in an anode-supported tubular SOFC using a steady-state model. In particular, we discuss the importance of modeling different phenomena vis-a-vis their impact on the prediction capability of the model. It is observed that even a reasonably simple model can be sufficiently predictive in a particular operating range. As the operating range of the cell is increased, the predictive capability of a model validated in a narrow range cannot be guarantied. It has also been observed that neglecting momentum conservation in the model for a tubular SOFC can affect the predictive capability of the model at higher overpotentials. An extensively validated model is used to study the percentage conversion of oxygen and oxygen concentration profile within a cell at different operating conditions. All of the simulation studies are supported by experimental data that spans a wide range of operation in terms of the DC polarization, reactant flow rates and operating temperatures.     

High gas tightness ZrO2-added silicate glass sealant with low thermal stress for solid oxide fuel cells

A low leakage rate sealant of 10 wt% ZrO₂-added CaO–K₂O–Na₂O–BaO silicate glass for SOFC has been studied. The structure of the sealant is stable at high temperatures with leakage rates less than 10⁻⁴ sccm∙cm⁻¹, and no crystal except for ZrO₂ is found in XRD analysis after heating at 800 °C for 100 h. ZrO₂ is distributed in the glass matrix and plays a supporting role in avoiding over-softening at operating temperature. Good compatibility in both oxidizing and reducing atmospheres between the sealant and SUS430 interconnect was proved by SEM at 750 °C for 100 h. A fully coupled 3D Multiphysics button SOFC is constructed for mechanical analyses. The results show that the increase of ZrO₂ in the sealant will decrease the stress and displacement in the SOFC. Besides, the width of the sealant also affects the stress value and distribution. The results show that GZ10 is a competitive sealing material compared with other ZrO₂-added sealants.     

Development of La(CrCoFeNi)O3 system perovskites as interconnect and cathode materials for solid oxide fuel cells

The purpose of this research is to develop interconnect and cathode materials for use in solid oxide fuel cells (SOFCs) which demonstrate desired properties of outstanding sintering properties, high electrical conductivity, and excellent chemical stability at high temperatures. Five different perovskite oxides of lanthanum in combination with chromium, iron, cobalt and nickel oxides powders, i.e. LaCr_0.7Co_0.1Fe_0.1Ni_0.1O₃(LCr7CFN), LaCo_0.7Cr_0.1Fe_0.1 Ni_0.1O₃(LCo7CFN), LaFe_0.7Cr_0.1Co_0.1Ni_0.1O₃(LFe7CCN), LaNi_0.7Cr_0.1Co_0.1Fe_0.1O₃(LNi7CCF), and LaCr_0.25Co_0.25Fe_0.25Ni_0.25O₃(LCCFN), were synthesized through the Pechini method. XRD results show that all materials are in single phase, either rhombohedral or orthorhombic crystal structure. The resulting powders were able to be sintered to a high relative density at a temperature of 1400 °C for 2 h in air. The electrical conductivity of the sintered sample was measured and evaluated from 300 °C to 800 °C. The LCCFN sample appears to have the best combination of sintering property (approximate 94% relative density) and electrical conductivity (88.13 Scm⁻¹ at 800 °C).     

Biodiesel formulations as fuel for internally reforming solid oxide fuel cell

Biodiesel (alkyl ester of rapeseed oil) is prepared using various, methyl, ethyl and butyl alcohols through the transesterification process. Sodium hydroxide and sulfuric acid are used as catalyst for methyl alcohol, ethyl alcohol and butyl alcohol respectively. Biodiesel-water formulations are formulated using water and emulsifiers like sodium lauryl sulphate (SLS) and SPAN 80 in a high shear mixer. The formulations are tested at 800 °C as fuel for internal reforming in solid oxide fuel cells (SOFCs). The formulations based on methyl and butyl esters require the use of emulsifiers to prepare stable emulsions, while ethyl esters are able to form stable emulsions without emulsifiers. The decrease in the biodiesel concentration of formulation does not have any effect on the power density of the ethyl ester formulation. Fuel cells fuelled with 20% formulations lasted longer than 50% formulations in all the formulations tested as result of increase in steam carbon ratio resulting in effective removal of carbon deposited on the anode surface. Butyl ester formulations exhibited the worst performance in both types of formulation tests. The best performance was exhibited by 20% ethyl formulation in terms of life of the cell but 50% methyl ester formulations exhibit the highest power density.     

Thermo-mechanical analysis of 3D manufactured electrodes for solid oxide fuel cells

Additive manufacturing has widened the scope for designing more performing microstructures for solid oxide fuel cells (SOFCs). Structural modifications, such as the insertion of ceramic pillars within the electrode, facilitate ion transport and boost the electrochemical performance. However, questions still remain on the related mechanical requirements during operation. This study presents a comprehensive thermal-electrochemical-mechanical model targeted to assess the stress distribution in 3D manufactured electrodes. Simulations show that a dense pillar increases the stress distribution by ca. 10 % compared to a flat electrode benchmark. The stress is generated by the material thermal contraction and intensifies at the pillar-electrolyte junction while external loads have negligible effects. An analysis on manufacturing inaccuracies indicates that sharp edges, surface roughness and tilted pillars intensify the stress; nonetheless, the corresponding stress increase is narrow, suggesting that manufacturing inaccuracies can be easily tolerated. The model points towards robust design criteria for 3D manufactured electrodes.     

Film percolation for composite electrodes of solid oxide fuel cells

A film percolation model is proposed for composite electrodes of solid oxide fuel cells (SOFCs). The model is developed to predict the percolation properties of 2D-infinite structures which represent the structural characteristics of composite electrodes of electrochemical devices such as SOFCs. The model can be used to estimate electrode properties, such as percolation probability, active three-phase boundary length and interfacial polarization resistance. Compared with the classic percolation theory, which is particularly applicable to 3D-infinite bulks, the model can explicitly capture the effects of thinly layered nature of composite electrodes, and describes a cross-over between 2D-infinite films and 3D-infinite bulks. It also permits the prediction within whole electrode composition range, and can be easily applied in SOFC modeling.     

Electrochemical behaviour of propane-fed solid oxide fuel cells based on low Ni content anode catalysts

Two different low Ni content (10 wt.%) anode catalysts were investigated for intermediate temperature (800 °C) operation in solid oxide fuel cells fed with dry propane. Both catalysts were prepared by the impregnation of a Ni-precursor on different oxide supports, i.e. gadolinia doped ceria (CGO) and La_0.6Sr_0.4Fe_0.8Co_0.2O₃ perovskite, and thermal treated at 1100 °C for 2 h. The Ni-modified perovskite catalyst was mixed with a CGO powder and deposited on a CGO electrolyte to form a composite catalytic layer with a proper triple-phase boundary. Anode reduction was carried out in-situ in H₂ at 800 °C for 2 h during cell conditioning. Electrochemical performance was recorded at different times during 100 h operation in dry propane. The Ni-modified perovskite showed significantly better performance than the Ni/CGO anode. A power density of about 300 mW cm⁻² was obtained for the electrolyte supported SOFC in dry propane at 800 °C. Structural investigation of the composite anode layer after SOFC operation indicated a modification of the perovskite structure and the occurrence of a La₂NiO₄ phase. The occurrence of metallic Ni in the Ni/CGO system caused catalyst deactivation due to the formation of carbon deposits.     

Nano-structured composite cathodes for intermediate-temperature solid oxide fuel cells via an infiltration/impregnation technique

Solid oxide fuel cells (SOFCs) are high temperature energy conversion devices working efficiently and environmental friendly. SOFC requires a functional cathode with high electrocatalytic activity for the electrochemical reduction of oxygen. The electrode is often fabricated at high temperature to achieve good bonding between the electrode and electrolyte. The high temperature not only limits material choice but also results in coarse particles with low electrocatalytic activity. Nano-structured electrodes fabricated at low temperature by an infiltration/impregnation technique have shown many advantages including superior activity and wider range of material choices. The impregnation technique involves depositing nanoparticle catalysts into a pre-sintered electrode backbone. Two basic types of nano-structures are developed since the electrode is usually a composite consists of an electrolyte and an electrocatalyst. One is infiltrating electronically conducting nano-catalyst into a single phase ionic conducting backbone, while the other is infiltrating ionically conducting nanoparticles into a single phase electronically conducting backbone. In addition, nanoparticles of the electrocatalyst, electrolyte and other oxides have also been infiltrated into mixed conducting backbones. These nano-structured cathodes are reviewed here regarding the preparation methods, their electrochemical performance, and stability upon thermal cycling.     

Fabrication of one-step co-fired proton-conducting solid oxide fuel cells with the assistance of microwave sintering

A microwave sintering technique is reported for fabricating co-sintered proton-conducting solid oxide fuel cells. With this method, high-quality ceramic electrolyte membranes can be prepared at 1100?°C, thus enabling the fabrication of entire cells in a single step. The microwave sintering method not only enhances electrolyte densification but also improves the cathode/electrolyte interface, which is critical for improving fuel cell performance. The power output of the co-sintered cell prepared under the microwave conditions (up to 449?mW?cm^?2 at 700?°C) was significantly higher than that of the cell fabricated using the traditional co-sintering method (approximately 292?mW?cm^?2 at the same temperature). Electrochemical analysis revealed that the enhanced electrolyte density and the improved cathode/electrolyte interface achieved by using the microwave sintering technique decrease both the ohmic resistance and the polarisation resistance of the cell, leading to good fuel cell performance.     

Electrophoretically deposited thin film electrolyte for solid oxide fuel cell

Abstract

Thin films of 8 mol% yttria stabilised zirconia (YSZ) electrolyte have been deposited on non-conducting porous NiO–YSZ anode substrates using electrophoretic deposition (EPD) technique. Deposition of such oxide particulates on non-conducting substrates is made possible by placing a conducting steel plate on the reverse side of the presintered porous substrates. Thickness of the substrates, onto which the deposition has been carried out, varied in the range 0·5–2·0 mm. Dense and uniform YSZ thin films (thickness: 5–20 μm) are obtained after being cofired at 1400°C for 6 h. The thickness of the deposited films is seemed to be increased with increasing porous substrate thickness. Solid oxide fuel cell (SOFC) performance is measured at 800°C using coupon cells with various anode thicknesses. While a peak power density of 1·41 W cm^?2 for the cells with minimum anode thickness of 0·5 mm is achieved, the cell performance decreases with anode thickness.     

Fabrication of electrolyte materials for solid oxide fuel cells by tape-casting

In this research, solid oxide fuel cell electrolytes were fabricated by aqueous tape-casting technique. The basic compositions for SOFC electrolyte systems were focused on yttria-stabilized zirconia (YSZ) system. The powders used in this study were from different sources. ZrO₂-based system doped with 3, 8, and 10 mol% of Y₂O₃, and 8YSZ electrolyte tape illustrated the desirable properties. The grain size of the sintered electrolyte tapes was in the range of 0.5–1 μm with 98–99% of theoretical density. Phase and crystal structure showed the pure cubic fluorite structure for 8–10 mol% YSZ and tetragonal phase for 3 mol% doped. The electrolyte tapes sintered at 1450 °C for 4 h had the highest ionic conductivity of 30.11 × 10⁻³ S/cm which was measured at 600 °C. The flexural strengths were in the range of 100–180 MPa for 8–10 mol% YSZ, and 400–680 MPa for 3 mol% YSZ.     

Optimization of a ScCeSZ/GDC bi-layer electrolyte fabrication process for intermediate temperature solid oxide fuel cells

Cost-effective wet ceramic coating techniques for fabricating ScCeSZ/GDC bi-layer electrolyte anode-supported button cells were investigated in this study. Aqueous ceramic slurries were prepared by ball milling and then used for Ni/ScCeSZ half cell fabrication by tape casting and spin coating. Prepared cells were tested at operating temperature between 700 and 800°C with a fuel composition of hydrogen:nitrogen 3:1 and air at the cathode. The cell with a spin coated GDC film showed the maximum power density of 1.142, 1.012, 0.813 W?cm^?2 at 800, 750, and 700°C, respectively. It was also able to produce power output around 0.7 W?cm^?2 for 500 h at 750°C, which confirms the cell operational stability. More importantly, the GDC film prepared by spin coating effectively avoided the formation of the (Zr,Ce)O₂^?based solid solution at the ceria/zirconia interface compared with the other cells with the co-casted and sintered GDC film.