Development of co-sintering process for anode-supported solid oxide fuel cells with gadolinia-doped ceria/lanthanum silicate bi-layer electrolyte

Gadolinia-doped ceria (GDC) and lanthanum silicate (LS) are expected to be promising materials for electrolytes of solid oxide fuel cells (SOFCs) because of their high ionic conductivities at intermediate temperatures. However, performance degradation of SOFCs is caused by current leakage through GDC and poor densification of LS. In the present study, LS was used as a blocking layer for preventing the current leakage of GDC electrolyte. Thermal shrinkage measurements and scanning electron microscopy (SEM) observation suggested that the addition of Bi₂O₃ in LS electrolyte (LSB) contributed to the decrease in the sintering temperature of the LS and improved densification of the GDC/LS bi-layer electrolyte. Consequently, the open-circuit voltage for the cell with GDC/LS and GDC/LSB bi-layer electrolytes increased effectively in comparison with that of the cell with GDC single-layer electrolyte. The electrical conductivity and fuel cell characteristics were compared among the cells with GDC, GDC/LS, and GDC/LSB electrolytes.     

Direct ceramic inkjet printing of yttria-stabilized zirconia electrolyte layers for anode-supported solid oxide fuel cells

Electromagnetic drop-on-demand direct ceramic inkjet printing (EM/DCIJP) was employed to fabricate dense yttria-stabilized zirconia (YSZ) electrolyte layers on a porous NiO-YSZ anode support from ceramic suspensions. Printing parameters including pressure, nozzle opening time and droplet overlapping were studied in order to optimize the surface quality of the YSZ coating. It was found that moderate overlapping and multiple coatings produce the desired membrane quality. A single fuel cell with a NiO-YSZ/YSZ (∼6 μm)/LSM + YSZ/LSM architecture was successfully prepared. The cell was tested using humidified hydrogen as the fuel and ambient air as the oxidant. The cell provided a power density of 170 mW cm⁻² at 800 °C. Scanning electron microscopy (SEM) revealed a highly coherent dense YSZ electrolyte layer with no open porosity. These results suggest that the EM/DCIJP inkjet printing technique can be successfully implemented to fabricate electrolyte coatings for SOFC thinner than 10 μm and comparable in quality to those fabricated by more conventional ceramic processing methods.     

Solid oxide fuel cell bi-layer anode with gadolinia-doped ceria for utilization of solid carbon fuel

Pyrolytic carbon was used as fuel in a solid oxide fuel cell (SOFC) with a yttria-stabilized zirconia (YSZ) electrolyte and a bi-layer anode composed of nickel oxide gadolinia-doped ceria (NiO-GDC) and NiO-YSZ. The common problems of bulk shrinkage and emergent porosity in the YSZ layer adjacent to the GDC/YSZ interface were avoided by using an interlayer of porous NiO-YSZ as a buffer anode layer between the electrolyte and the NiO-GDC primary anode. Cells were fabricated from commercially available component powders so that unconventional production methods suggested in the literature were avoided, that is, the necessity of glycine-nitrate combustion synthesis, specialty multicomponent oxide powders, sputtering, or chemical vapor deposition. The easily-fabricated cell was successfully utilized with hydrogen and propane fuels as well as carbon deposited on the anode during the cyclic operation with the propane. A cell of similar construction could be used in the exhaust stream of a diesel engine to capture and utilize soot for secondary power generation and decreased particulate pollution without the need for filter regeneration.     

Anode-supported solid oxide fuel cell based on dense electrolyte membrane fabricated by filter-coating

A simple and cost-effective technique, filter-coating, has been developed to fabricate dense electrolyte membranes. Eight mole percent yttria-stabilized zirconia (YSZ) electrolyte membrane as thin as 7 μm was prepared by filter-coating on a porous substrate. The thickness of the YSZ film was uniform, and could be readily controlled by the concentration of the YSZ suspension and the rate of the suspension deposition. The YSZ electrolyte film was dense and was well bonded to the Ni-YSZ anode substrate. An anode-supported solid oxide fuel cell (SOFC) with a YSZ electrolyte film and a La_0.85Sr_0.15MnO₃ (LSM) + YSZ cathode was fabricated and its performance was evaluated between 700 and 850 °C with humidified hydrogen as the fuel and ambient air as the oxidant. An open circuit voltage (OCV) of 1.09 V was observed at 800 °C, which was close to the theoretical value, and the maximum power density measured was 1050 mW cm⁻². The results demonstrate that the dense YSZ film fabricated by filter-coating is suitable for application to SOFCs.     

Solid oxide fuel cells with dense yttria-stabilized zirconia electrolyte membranes fabricated by a dry pressing process

Dense yttria-stabilized zirconia (YSZ) electrolyte films were successfully fabricated onto anode substrates using a modified dry pressing process. The film thickness was uniform, and could be readily controlled by the mass of the nanocrystalline YSZ powders. The electrolyte films adhered well to the anode substrates by controlling the anode composition. An anode-supported solid oxide fuel cell (SOFC) with a dense YSZ electrolyte film of 8 μm in thickness was operated at temperatures from 700 to 800 °C using humidified (3 vol% H₂O) hydrogen as fuel and air as oxidant. An open circuit voltage of 1.06 V and a maximum power density of 791 mW cm⁻² were achieved at 800 °C. The results indicate that the gas permeation through the electrolyte film was negligible, and that good performance can be obtained by this simple and cost-effective technique which can significantly reduce the fabrication cost of SOFCs.     

Performance of anode-supported solid oxide fuel cell using novel ceria electrolyte

The potential of a novel co-doped ceria material Sm_0.075Nd_0.075Ce_0.85O_2−δ as an electrolyte was investigated under fuel cell operating conditions. Conventional colloidal processing was used to deposit a dense layer of Sm_0.075Nd_0.075Ce_0.85O_2−δ (thickness 10 μm) over a porous Ni-gadolinia doped ceria anode. The current-voltage performance of the cell was measured at intermediate temperatures with 90 cm³ min⁻¹ of air and wet hydrogen flowing on cathode and anode sides, respectively. At 650 °C, the maximum power density of the cell reached an exceptionally high value of 1.43 W cm⁻², with an area specific resistance of 0.105 Ω cm². Impedance measurements show that the power density decrease with decrease in temperature is mainly due to the increase in electrode resistance. The results confirm that Sm_0.075Nd_0.075Ce_0.85O_2−δ is a promising alternative electrolyte for intermediate temperature solid oxide fuel cells.     

Properties of bias-assisted sputtered gadolinia-doped ceria interlayers for solid oxide fuel cells

The growth and electrochemical properties of gadolinia-doped ceria (GDC) interlayers deposited by bias-assisted magnetron sputtering in solid oxide fuel cells have been investigated. Such interlayers act as diffusion barriers to protect the yttria-stabilized zirconia electrolyte, preventing possible degradation when mixed ionic-electronic conductor (La,Sr)(Co,Fe)O_3−δ is used as the cathode. The dependence of the applied bias during the sputtering deposition on both the interlayer microstructure and fuel cell performance has been studied in anode-supported single cells. The main experimental results showed that bias-assisted sputtering of GDC interlayers produced microstructures denser than those of unbiased depositions, which resulted in increased electrochemical properties of fuel cells.     

Electrospun yttria-stabilized zirconia nanofibers for low-temperature solid oxide fuel cells

We report a 3.5-fold improvement in the performance of solid oxide fuel cells (SOFCs) operating at 450 °C with the introduction of electrospun yttria-stabilized zirconia (YSZ) nanofiber interlayers between the electrolyte and cathode. YSZ nanofibers with diameters of 150–200 nm were uniformly deposited with various thicknesses on a single-crystal YSZ substrate. Electrochemical impedance spectroscopy analyses revealed a drastically reduced polarization resistance, which was mainly attributed to the high specific surface area and high porosity of the YSZ nanofiber interlayers. Our results demonstrate the possibility of using YSZ nanofibers for the development of high-performance SOFCs at low temperature.     

High performance solid oxide fuel cells based on tri-layer yttria-stabilized zirconia by low temperature sintering process

Performance of solid oxide fuel cells (SOFCs) depends critically on the composition and microstructure of the electrodes. It is fabricated a dense yttria-stabilized zirconia (YSZ) electrolyte layer sandwiched between two porous YSZ layers at low temperature. The advantages of this structure include excellent structural stability and unique flexibility for evaluation of new electrode materials for SOFC applications, which would be difficult or impossible to be evaluated using conventional cell fabrication techniques because of incompatibility with YSZ under processing conditions. The porosity of porous YSZ increases from 65.8% to 68.6% as the firing temperature decreased from 1350 to 1200 °C. The open cell voltages of the cells based on the tri-layers of YSZ, co-fired using a two-step sintering at 1200 °C, are above 1.0 V at 700-800 °C, and the peak power densities of cells infiltrated LSCF and Pd-SDC electrodes are about 525, 733, and 935 mW cm⁻² at 700, 750, and 800 °C, respectively.     

A study of the process parameters for yttria-stabilized zirconia electrolyte films prepared by screen-printing

Screen-printing technology was developed to fabricate gas-tight yttria-stabilized zirconia (YSZ) electrolyte films on porous NiO–YSZ anode substrates for use in solid oxide fuel cells (SOFCs). Several key process parameters such as the starting YSZ powder, printing ink composition, printing time and sintering temperature were studied and reported in detail. SEM results revealed that the selected process parameters exerted obvious influences on the microstructure of the screen-printed YSZ films. Open-circuit voltages (OCVs) were used to evaluate the usage feasibility of screen-printed YSZ films in SOFCs. Cell performance test results showed that the above-mentioned parameters had crucial effects on the OCVs and power density of the prepared cells. Based on appropriate parameters, an OCV value of 1.081 V and a power density of 0.96 Wcm⁻² were obtained at 800 °C using hydrogen as fuel and ambient air as oxidant.     

Novel copper-based anodes for solid oxide fuel cells with samaria-doped ceria electrolyte

A novel copper-based anode for low-temperature solid oxide fuel cells was prepared through the conventional ceramic technology and using CuO and SDC (Ce_0.8Sm_0.2O_1.9) powders with controlled particle size. The new Cu–SDC anode also contained highly dispersed CeO₂ and Ni particles to increase its surface area and fuel cell performance. The specific surface area of the Cu–SDC bare anode, CeO₂ and Ni-dispersed phases were estimated to be 1.53, 39.4 and 86.4 m² g⁻¹, respectively. Solid oxide fuel cells having the new anode were tested for both humid hydrogen and methane. Power densities of ca. 250 mW cm⁻² were achieved in H₂ at 600 °C and in CH₄ 700 °C, even if the SDC–electrolyte supporting membrane was 250-μm thick. Short term stability tests (maximum 64 h) showed an initial impairment, but not dramatic, of the new anode performance and the formation of carbon deposits. The addition of MoO_x to the new anode did not prevent the formation of carbon deposits.     

Influence of through-lamella grain growth on ionic conductivity of plasma-sprayed yttria-stabilized zirconia as an electrolyte in solid oxide fuel cells

The development of a cost-effective fabrication method for stabilized zirconia electrolyte for the most advanced tubular solid oxide fuel cell (SOFC) remains the most important challenge for the commercialization of an SOFC power generation system. Atmospheric plasma spraying is expected to be a promising alternative to other costly electrolyte processing methods. The problem with the plasma-sprayed ceramic coating is the limited interface bonding of the lamellar structure, which reduces the ionic conductivity of stabilized zirconia deposits to one-fifth of the comparable bulk. Continuous growth of columnar grains across splat–splat interfaces has been achieved through control of the substrate surface temperature which affects spreading of molten droplets. These cross-splats columnar grains lead to improved bonding between lamellae. Measurements over the temperature range of 600–1000 °C have shown that the microstructural changes result in a significant increase of ionic conductivity of the yttria-stabilized zirconia deposit (by a factor of about 3). A change in activation energy at about 750 °C was observed for coatings deposited with two different sets of spray conditions. This change is associated with a switch of the predominant ion conduction path from grain boundary to intragrain with increasing temperature.     

Nickel/gadolinium-doped ceria anode for direct ethanol solid oxide fuel cell

This report investigates the properties of nickel/gadolinium-doped ceria (Ni/GDC) as anode material for bio-ethanol fueled SOFC. The Ni/GDC cermets with 18 and 44 wt.% Ni were prepared by a hydrothermal method. Ethanol decomposition, steam reforming, and partial oxidation of ethanol were studied using a fixed-bed reactor at 1123 K. Carbon was formed only under dry ethanol for both catalysts. The addition of water or oxygen to the feed inhibited the formation of carbon. Ni/GDC was used as the anode current collector layer and as a catalytic layer in single cells tests. No deposits of carbon were detected in single cells with Ni/GDC catalytic layer after 50 h of continuous operation under direct (dry) ethanol. This result was attributed to the catalytic properties of the Ni/GDC layer and the operation mechanism of gradual internal reforming, in which the oxidation of hydrogen provides the steam for ethanol reforming, thus avoiding carbon deposition.     

Synthesis and characterization of scandia ceria stabilized zirconia powders prepared by polymeric precursor method for integration into anode-supported solid oxide fuel cells

Scandia ceria stabilized zirconia (10Sc1CeSZ) powders are synthesized by polymeric precursor method for use as the electrolyte of anode-supported solid oxide fuel cell (SOFC). The synthesized powders are characterized in terms of crystalline structure, particle shape and size distribution by X-ray diffraction (XRD), transmission electron microscopy (TEM) and photon correlation spectroscopy (PCS). 10Sc1CeSZ electrolyte films are deposited on green anode substrate by screen-printing method. Effects of 10Sc1CeSZ powder characteristics on sintered films are investigated regarding the integration process for application as the electrolytes in anode-supported SOFCs. It is found that the 10Sc1CeSZ films made from nano-sized powders with average size of 655 nm are very porous with many open pores. In comparison, the 10Sc1CeSZ films made from micron-sized powders with average size of 2.5 μm, which are obtained by calcination of nano-sized powders at higher temperatures, are much denser with a few closed pinholes. The cell performances are 911 mW cm⁻² at the current density of 1.25 A cm⁻² and 800 °C by application of Ce_0.8Gd_0.2O₂ (CGO) barrier layer and La_0.6Sr_0.4CoO₃ (LSC) cathode.     

Bismuth oxide doped scandia-stabilized zirconia electrolyte for the intermediate temperature solid oxide fuel cells

Electrical and structural properties of bismuth oxide doped scandia-stabilized zirconia (ScSZ) electrolyte for solid oxide fuel cells (SOFCs) have been evaluated by means of XRD, TGA, DTA, and impedance spectroscopy. The amount of Bi₂O₃ in the ScSZ was varied in the range of 0.25–2.0 mol%. The original ScSZ samples indicated a rhombohedral crystalline structure that in general has lower conductivity than the cubic phase. However, the addition of Bi₂O₃ to ScSZ electrolyte was found to stabilize the cubic crystalline phase as detected by XRD. Impedance spectroscopy measurements in the temperature range between 350 and 900 °C indicated a sharp increase in conductivity for the system containing 2 mol% of Bi₂O₃ that is attributed to the presence of the cubic phase. In addition, impedance spectroscopy measurements revealed significant decrease of both the grain bulk and grain boundary resistances with respect to the temperature change from 600 to 900 °C and concentration of Bi₂O₃ from 0.5 to 2 mol%. The electrical conductivity at 600 °C obtained for 2 mol% Bi₂O₃ doped ScSZ was 0.18 S cm⁻¹.     

Fabrication of micro-tubular solid oxide fuel cells with a single-grain-thick yttria stabilized zirconia electrolyte

This study discusses the fabrication and electrochemical performance of micro-tubular solid oxide fuel cells (SOFCs) with an electrolyte consisting a single-grain-thick yttria stabilized zirconia (YSZ) layer. It is found that a uniform coating of an electrolyte slurry and controlled shrinkage of the supported tube leads to a dense, crack-free, single-grain-thick (less than 1 μm) electrolyte on a porous anode tube. The SOFC has a power density of 0.39 W cm⁻² at an operating temperature as low as 600 °C, with YSZ and nickel/YSZ for the electrolyte and anode, respectively. An examination is made of the effect of hydrogen fuel flow rate and shown that a higher flow rate leads to better cell performance. Hence a YSZ cell can be used for low-temperature SOFC systems below 600 °C, simply by optimizing the cell structure and operating conditions.     

Fabrication and characterization of anode support low-temperature solid oxide fuel cell based on the samaria-doped ceria electrolyte

In this paper anode support was fabricated by tape casting method using SDC-50 wt.% NiO slurry, then printed the Ce_0.8Sm_0.2O_1.9 (SDC) electrolyte on the green piece which is cut out from the dried slurry piece. After at 90 °C drying for 14 h and co-sintered at 1350 °C for 10 h, get the Φ70 mm anode support and electrolyte planar bilayer. Based on the observation of photos and scanning electron microscopy (SEM) indicated that bilayer owns the flat anode support substrate, and the highly dense, crack free electrolyte film which is 12 μm in thickness. Small disks which were cut out from the Φ70 mm bilayer structure electrochemically were examined in a single button-cell mode incorporating a SDC-60 wt.% La_0.5Sr_0.5Co_0.8Fe_0.2O₃ composite cathode. The single cell was tested at 450 °C∼600 °C, an open-circuit voltage (OCV) of 0.94 V and the maximum power density of 797 mV cm⁻² achieved with dry hydrogen as fuel gas and air as oxidant gas at 600 °C.     

High performance yttria-stabilized zirconia based intermediate temperature solid oxide fuel cells with double nano layer composite cathode

A composite double layer cathode of La_0.6Sr_0.4Co_0.8Fe_0.2O_3?δ/La_0.8Sr_0.2FeO_3?δ (LSCF/LSF) was successfully fabricated by infiltration method to accelerate the sluggish oxygen reduction reaction (ORR) processes. In this composite cathode, both LSF and LSCF layers are uniformly distributed on Yttria-stabilized Zirconia (YSZ) scaffold by optimizing the infiltrating solution components. LSF serves as a protective layer between LSCF and YSZ. The introduction of the LSCF exterior layer has greatly improved cell performance compared with the cell with sole LSF cathode. At 600 °C, the maximum power density of the cell with LSCF/LSF/YSZ composite cathode reaches up to 0.559 W cm^?2. The evolution of the cathode polarization resistance verifies that the ORR activity has been greatly enhanced. Therefore, the results indicate that the high cell performance at intermediate temperatures can be obtained by adopting the LSCF cathode into YSZ-based SOFCs using protective layer and that the infiltration method is a practical way for constructing electrode.     

A phase inversion/sintering process to fabricate nickel/yttria-stabilized zirconia hollow fibers as the anode support for micro-tubular solid oxide fuel cells

NiO/YSZ hollow fibers were fabricated via a combined phase inversion and sintering technique, where polyethersulfone (PESf) was employed as the polymeric binder, N-methyl-2-pyrrolidone (NMP) as the solvent and polyvinylpyrrolidone (PVP) as the additive, respectively. After reduction with hydrogen at 750 °C for 5 h, the porous Ni/YSZ hollow fibers with an asymmetric structure comprising of a microporous layer integrated with a finger-like porous layer were obtained, which can be served as the anode support of micro-tubular solid oxide fuel cells (SOFCs). As the sintering temperature was increased from 1200 to 1400 °C, the mechanical strength and the electrical conductivity of the Ni/YSZ hollow fibers increased from 35 to 178 MPa and from 30 to 772 S cm⁻¹, respectively but the porosity decreased from 64.2% to 37.0%. The optimum sintering temperature was found to be between 1350 and 1400 °C for Ni/YSZ hollow fibers applied as the anode support for micro-tubular SOFCs.     

Reactivity between La(Sr)FeO3 cathode,doped CeO2 interlayer and yttria-stabilized zirconia electrolyte for solid oxide fuel cell applications

Detailed X-ray diffraction (XRD) analysis of two different Sr-doped LaFeO₃ cathodes, YSZ electrolyte and two Sm/Gd-doped CeO₂ interlayer and their mixtures were used to evaluate the formation of undesired secondary reaction compounds. The analysis of room temperature X-ray diffraction data of the mixtures indicates the crystallization of strontium and/or lanthanum zirconates between the cathode and the electrolyte materials and no detected reaction between the cathode and the interlayer materials.