GdBaCo2O5+x layered perovskite as an intermediate temperature solid oxide fuel cell cathode

GdBaCo₂O_5+x (GBCO) was evaluated as a cathode for intermediate-temperature solid oxide fuel cells. A porous layer of GBCO was deposited on an anode-supported fuel cell consisting of a 15 μm thick electrolyte of yttria-stabilized zirconia (YSZ) prepared by dense screen-printing and a Ni–YSZ cermet as an anode (Ni–YSZ/YSZ/GBCO). Values of power density of 150 mW cm⁻² at 700 °C and ca. 250 mW cm⁻² at 800 °C are reported for this standard configuration using 5% of H₂ in nitrogen as fuel. An intermediate porous layer of YSZ was introduced between the electrolyte and the cathode improving the performance of the cell. Values for power density of 300 mW cm⁻² at 700 °C and ca. 500 mW cm⁻² at 800 °C in this configuration were achieved.     

Performance of metal-supported SOFCs with infiltrated electrodes

Metal-supported solid oxide fuel cells (SOFCs) with thin YSZ electrolyte films and infiltrated Ni and LSM catalysts are operated in the temperature range 650–750 °C. A five-layer structure consisting of porous metal-support/porous YSZ interlayer/dense YSZ electrolyte film/porous YSZ interlayer/porous metal current collector is prepared at 1300 °C in reducing atmosphere. This cell structure is then sealed and joined to a cell housing/gas manifold using a commercially available braze. Finally, the porous YSZ interlayers are infiltrated with Ni and LSM catalyst precursor solutions at low temperature prior to cell testing. Infiltrating the catalysts after the high temperature sintering and brazing steps avoids undesirable decomposition of LSM, Ni coarsening, and interdiffusion between Ni catalyst and FeCr in the support. Maximum power densities of 233 and 332 mW cm⁻² were achieved at 650 and 700 °C, respectively, with air as oxidant. With pure oxygen as oxidant, power densities of 726, 993, and >1300 mW cm⁻² were achieved at 0.7 V at 650, 700, and 750 °C, respectively.     

Stability and robustness of metal-supported SOFCs

Tubular metal-supported SOFCs with YSZ electrolyte and electrodes comprising porous YSZ backbone and infiltrated Ni and LSM catalysts are operated at 700 °C. Tolerance to five complete anode redox cycles and five very rapid thermal cycles is demonstrated. The power output of a cell with as-infiltrated Ni anode degrades rapidly over 15 h operation. This degradation can be attributed primarily to coarsening of the fine infiltrated Ni particles. A cell in which the infiltrated Ni anode is precoarsened at 800 °C before operation at 700 °C shows dramatically improved stability. Stable operation over 350 h is demonstrated.     

High temperature solid oxide electrolysis cell employing porous structured (La0.75Sr0.25)0.95MnO3 with enhanced oxygen electrode performance

An efficient steam electrolysis process for hydrogen production via a solid oxide electrolysis cell using porous network-like strontium doped lanthanum manganite (LSM)-yttria stabilized zirconia (YSZ) as the oxygen electrode material has been demonstrated. The porous network-like LSM powder was prepared by a nitrate–glycine combustion method. Impedance spectra and voltage-current density curves were measured as a function of cell current density and absolute humidity at 800 °C and 900 °C to characterize the cell performance. The cell area specific resistance (ASR) was 0.26 Ω cm² at 900 °C with 0.5 A/cm² current density and 50% absolute humidity (AH). The hydrogen production rate calculated from the Faraday's law was 362 ml/cm² h at 900 °C with 80 vol.% AH. The cell performance results indicate that the porous network-like LSM–YSZ is a promising oxygen electrode for high temperature electrolysis cells.     

Behavior of 3 mol% yttria-stabilized tetragonal zirconia polycrystal film prepared by slurry spin coating

A dense and uniform 3 mol% yttria-stabilized tetragonal zirconia polycrystal (3YSZ) electrolyte film of 6 μm in thickness was fabricated by slurry spin coating on a porous NiO/3YSZ anode substrate. Composite cathodes of La_0.7Sr_0.3MnO₃ impregnated with Sm_0.2Ce_0.8O_1.9 were fabricated on the 3YSZ films. A single cell produced in this way was tested at 700, 750 and 800 °C with hydrogen as fuel and stationary air as oxidant. Test results revealed an open-circuit voltage of 1.04 V at 800 °C, and maximum power density of 551, 895 and 1143 mW cm⁻² at 700, 750 and 800 °C, respectively. Impedance spectra results demonstrated that the cell performance was determined by the polarization resistance of the cathode.     

Fabrication and characterization of Sm0.2Ce0.8O2−δ-Sm0.5Sr0.5CoO3−δ composite cathode for anode supported solid oxide fuel cell

The Sm_0.5Sr_0.5CoO_3−δ (SSC) with perovskite structure is synthesized by the glycine nitrate process (GNP). The phase evolution of SSC powder with different calcination temperatures is investigated by X-ray diffraction and thermogravimetric analyses. The XRD results show that the single perovskite phase of the SSC is completely formed above 1100 °C. The anode-supported single cell is constructed with a porous Ni-yttria-stabilized zirconia (YSZ) anode substrate, an airtight YSZ electrolyte, a Sm_0.2Ce_0.8O_2−δ (SDC) barrier layer, and a screen-printed SSC-SDC composite cathode. The SEM results show that the dense YSZ electrolyte layer exhibits the good interfacial contact with both the Ni-YSZ and the SDC barrier layer. The porous SSC-SDC cathode shows an excellent adhesion with the SDC barrier layer. For the performance test, the maximum power densities are 464, 351 and 243 mW cm⁻² at 800, 750 and 700 °C, respectively. According to the results of the electrochemical impedance spectroscopy (EIS), the charge-transfer resistances of the electrodes are 0.49 and 1.24 Ω cm², and the non charge-transfer resistances are 0.48 and 0.51 Ω cm² at 800 and 700 °C, respectively. The cathode material of SSC is compatible with the YSZ electrolyte via a delicate scheme employed in the fabrication process of unit cell.     

Study of slurry spin coating technique parameters for the fabrication of anode-supported YSZ Films for SOFCs

A slurry spin coating method was developed to fabricate gas-tight anode-supported YSZ films for solid oxide fuel cells (SOFCs). Several technique parameters for slurry spin coating, such as the slurry viscosity, spinning speed, number of coating cycles, film thickness and their effects on YSZ electrolyte film were investigated. SEM results, open-circuit voltage (OCV) values and cell performance indicated that these parameters had crucial and obvious influences on YSZ film quality and fuel cell performance. Based on the optimized parameters, anode-supported YSZ films and several single fuel cells were successfully fabricated and tested. An OCV as high as 1.06 V was obtained at 800 °C and maximum power densities of 900, 1567, 2005 mW cm⁻² were achieved at 700, 750, 800 °C, respectively, using hydrogen as fuel and ambient air as oxidant.     

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.     

Solid oxide fuel cell cathodes prepared by infiltration of LaNi0.6Fe0.4O3 and La0.91Sr0.09Ni0.6Fe0.4O3 in porous yttria-stabilized zirconia

SOFC composite electrodes of yttria-stabilized zirconia (YSZ) and either LaNi_0.6Fe_0.4O₃ (LNF) or La_0.91Sr_0.09Ni_0.6Fe_0.4O₃ (LSNF) were prepared by infiltration to a loading of 40 wt% of the perovskite into porous YSZ using aqueous solutions of the nitrate salts. XRD measurements indicated that the perovskite structures were formed following calcination at 850 °C, at which temperature the LNF and LSNF form small particles that coat the YSZ pores. Heating to 1100 °C causes the particles to form a dense film over the YSZ but caused no solid-state reaction. Calcination of an LNF-YSZ composite to 1200 °C led to an expansion of the LNF lattice, suggesting introduction of Zr(IV) into the perovskite; further heating to 1300 °C caused the formation of La₂Zr₂O₇. For 850 °C calcination, the electrode performance of both LNF-YSZ and LSNF-YSZ composites was similar to that reported for composites of YSZ and La_0.8Sr_0.2FeO₃ (LSF), with a current-independent impedance of approximately 0.1 Ω cm² at 700 °C in air. For 1100 °C calcination, both LNF-YSZ and LSNF-YSZ composites exhibited impedances that decreased strongly under both anodic and cathodic polarization. The implications of these results for preparing electrodes based on LNF and LSNF are discussed.     

Polarization measurements on single-step co-fired solid oxide fuel cells (SOFCs)

Anode-supported planar solid oxide fuel cells (SOFC) were successfully fabricated by a single step co-firing process. The cells comprised of a Ni + yttria-stabilized zirconia (YSZ) anode, a YSZ or scandia-stabilized zirconia (ScSZ) electrolyte, a (La_0.85Ca_0.15)_0.97MnO₃ (LCM) + YSZ cathode active layer, and an LCM cathode current collector layer. The fabrication process involved tape casting of the anode, screen printing of the electrolyte and the cathode, and single step co-firing of the green-state cells in the temperature range of 1300–1330 °C for 2 h. Cells were tested in the temperature range of 700–800 °C with humidified hydrogen as fuel and air as oxidant. Cell test results and polarization modeling showed that the polarization losses were dominated by the ohmic loss associated with the electrodes and the activation polarization of the cathode, and that the ohmic loss due to the ionic resistance of the electrolyte and the activation polarization of the anode were relatively insignificant. Ohmic resistance associated with the electrode was lowered by improving the electrical contact between the electrode and the current collector. Activation polarization of the cathode was reduced by the improvement of the microstructure of the cathode active layer and lowering the cell sintering temperature. The cell performance was further improved by increasing the porosity in the anode. As a result, the maximum power density of 1.5 W cm⁻² was achieved at 800 °C with humidified hydrogen and air.     

A study of process parameters of LSM and LSM–YSZ composite cathode films prepared by screen-printing

A screen-printing technique was developed to fabricate porous cathode film for solid oxide fuel cells. Several key process parameters such as the selection of binders, the mesh of screen, sintering temperature and sintering time were investigated and reported. SEM results showed that the selected process parameters exerted obvious influences on the structure of the screen-printed cathode film. Impedance spectra data were used to evaluate the performance of cathode films made by different process parameters. The optimized process parameters were as follows: ethyl cellulose used as a binder, 120 mesh screen-printing sintering at 1200 °C for 2 h. Based on the optimized parameters, the polarization resistance of pure LSM cathode was 0.396 Ω cm² at 800 °C; the LSM–YSZ composite cathode displayed R_p value of 0.2027 Ω cm² at 850 °C, 0.2463 Ω cm² at 800 °C and 0.5168 Ω cm² at 750 °C, respectively. The performance of the LSM–YSZ composite cathode improved significantly after being polarized at 300 mA cm⁻² and 800 °C for 150 h. After 150 h, the over-potential of the composite cathode was stable.     

YSZ films fabricated by a spin smoothing technique and its application in solid oxide fuel cell

A dense single-layer YSZ film has been successfully fabricated by a spin smoothing method. Followed by a simplified slurry coating, an additional spin smoothing process was conducted to obtain a thinner and smoother film. By employment of high-viscosity slurry including high YSZ content, the film has a suitable thickness by a single coating cycle. With Sm_0.2Ce_0.8O_1.9 (SDC)-impregnated La_0.7Sr_0.3MnO₃ (LSM) cathode and porous NiO–YSZ anode, single solid oxide fuel cell (SOFC) based on an 8-μm-thick YSZ film was obtained. Open-circuit voltage (OCV) of the cell was 1.04 V at 800 °C, and maximum power densities were 676, 965 and 1420 mW cm⁻² at 700, 750 and 800 °C, respectively, using H₂ at a flow rate of 40 mL min⁻¹ as fuel and ambient air as oxidant. The power density could be increased to 1648 mW cm⁻² at 800 °C when the flow rate of H₂ was enhanced to 200 mL min⁻¹.     

Plasma sprayed metal supported YSZ/Ni–LSGM–LSCF ITSOFC with nanostructured anode

Intermediate temperature solid oxide fuel cells (ITSOFCs) supported by a porous Ni-substrate and based on Sr and Mg doped lanthanum gallate (LSGM) electrolyte, lanthanum strontium cobalt ferrite (LSCF) cathode and nanostructured yttria stabilized zirconia–nickel (YSZ/Ni) cermet anode have been fabricated successfully by atmospheric plasma spraying (APS). From ac impedance analysis, the sprayed YSZ/Ni cermet anode with a novel nanostructure and advantageous triple phase boundaries after hydrogen reduction has a low resistance. It shows a good electrocatalytic activity for hydrogen oxidation reactions. The sprayed LSGM electrolyte with ∼60 μm in thickness and ∼0.054 S cm⁻¹ conductivity at 800 °C shows a good gas tightness and gives an open circuit voltage (OCV) larger than 1 V. The sprayed LSCF cathode with ∼30 μm in thickness and ∼30% porosity has a minimum resistance after being heated at 1000 °C for 2 h. This cathode keeps right phase structure and good porous network microstructure for conducting electrons and negative oxygen ions. The APS sprayed cell after being heated at 1000 °C for 2 h has a minimum inherent resistance and achieves output power densities of ∼440 mW cm⁻² at 800 °C, ∼275 mW cm⁻² at 750 °C and ∼170 mW cm⁻² at 700 °C. Results from SEM, XRD, ac impedance analysis and I–V–P measurements are presented here.     

High performance metal-supported solid oxide fuel cells fabricated by thermal spray

Metal-supported solid oxide fuel cells (SOFCs) have been fabricated and characterized in this work. The cells consist of porous NiO-SDC as anode, thin SDC as electrolyte, and SSCo as cathode on porous stainless steel substrate. The anode and electrolyte layers were consecutively deposited onto porous metal substrate by thermal spray, using standard industrial thermal spray equipment, operated in an open-air atmosphere. The cathode materials were applied to the as-sprayed half-cells by screen-printing and heat-treated at 800 °C for 2 h. The cell components and performance were examined by scanning electron microscopy (SEM), X-ray diffraction, leakage test, ac impedance and electrochemical polarization at temperatures between 500 and 700 °C. The half-inch button cells exhibit a maximum power density in excess of 0.50 W cm⁻² at 600 °C and 0.92 W cm⁻² at 700 °C operated with humidified hydrogen fuel, respectively. The half-inch button cell was run at 0.5 A cm⁻² at 603 °C for 100 h. The cell voltage decreased from 0.701 to 0.698 V, giving a cell degradation rate of 4.3% kh⁻¹. Impedance analysis indicated that the cell degradation included 4.5% contribution from ohmic loss and 1.4% contribution from electrode polarization. The 5 cm × 5 cm cells were also fabricated under the same conditions and showed a maximum power density of 0.26 W cm⁻² at 600 °C and 0.56 W cm⁻² at 700 °C with dry hydrogen as fuel, respectively. The impedance analysis showed that the ohmic resistance of the cells was the major polarization loss for all the cells, while both ohmic and electrode polarizations were significantly increased when the operating temperature decreased from 700 to 500 °C. This work demonstrated the feasibility for the fabrication of metal-supported SOFCs with relatively high performance using industrially available deposition techniques. Further optimization of the metal support, electrode materials and microstructure, and deposition process is ongoing.     

A symmetrical,planar SOFC design for NASA's high specific power density requirements

Solid oxide fuel cell (SOFC) systems for aircraft applications require an order of magnitude increase in specific power density (1.0 kW kg⁻¹) and long life. While significant research is underway to develop anode supported cells which operate at temperatures in the range of 650–800 °C, concerns about Cr-contamination from the metal interconnect may drive the operating temperature down further, to 750 °C and lower. Higher temperatures, 850–1000 °C, are more favorable in order to achieve specific power densities of 1.0 kW kg⁻¹. Since metal interconnects are not practical at these high temperatures and can account for up to 75% of the weight of the stack, NASA is pursuing a design that uses a thin, LaCrO₃-based ceramic interconnect that incorporates gas channels into the electrodes. The bi-electrode supported cell (BSC) uses porous YSZ scaffolds, on either side of a 10–20 μm electrolyte. The porous support regions are fabricated with graded porosity using the freeze-tape casting process which can be tailored for fuel and air flow. Removing gas channels from the interconnect simplifies the stack design and allows the ceramic interconnect to be kept thin, on the order of 50–100 μm. The YSZ electrode scaffolds are infiltrated with active electrode materials following the high-temperature sintering step. The NASA-BSC is symmetrical and CTE matched, providing balanced stresses and favorable mechanical properties for vibration and thermal cycling.     

Silver infiltrated La0.6Sr0.4Co0.2Fe0.8O3 cathodes for intermediate temperature solid oxide fuel cells

Porous La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) electrodes on anode support cells were infiltrated with AgNO₃ solutions in citric acid and ethylene glycol. Two types of solid oxide fuel cells with the LSCF–Ag cathode, Ni–YSZ/YSZ/LSCF–Ag and Ni–Ce_0.9Gd_0.1O_1.95(GDC)/GDC/LSCF–Ag, were examined in a temperature range 530–730 °C under air oxidant and moist hydrogen fuel. The infiltration of about 18 wt.% Ag fine particles into LSCF resulted in the enhancement of the power density of about 50%. The maximum power density of Ni–YSZ/YSZ/LSCF was enhanced from 0.16 W cm⁻² to 0.25 W cm⁻² at 630 °C by infiltration of AgNO₃. No significant degradation of out-put power was observed for 150 h at 0.7 V and 700 °C. The Ni–GDC/GDC/LSCF–Ag cell showed the maximum power density of 0.415 W cm⁻² at 530 °C.     

Performance and durability of nanostructured (La0.85Sr0.15)0.98MnO3/yttria-stabilized zirconia cathodes for intermediate-temperature solid oxide fuel cells

In this communication we report the fabrication of nanostructured (La_0.85Sr_0.15)_0.98MnO₃ (LSM)/yttria-stabilized zirconia (YSZ) composite cathodes consisting of homogeneously distributed and connected LSM and YSZ grains approximately 100 nm large. We also investigate for the first time the role of the cathode nanostructure on the performance and the durability of intermediate-temperature solid oxide fuel cells. The cathodes were fabricated using homogenous LSM/YSZ nanocomposite particles synthesized by co-precipitation, using YSZ nanoparticles of 3 nm as seed crystals. Detailed microstructural characterization by transmission electron microscopy with energy-dispersive X-ray spectroscopy revealed that many of the LSM/YSZ junctions in the cathode faced the homogeneously connected pore channels, indicating the formation of a considerable number of triple phase boundaries. The nanostructure served to reduce cathodic polarization. As a result, these anode-supported solid oxide fuel cells showed high power densities of 0.18, 0.40, 0.70 and 0.86 W cm⁻² at 650, 700, 750 and 800 °C, respectively, under the cell voltage of 0.7 V. Furthermore, no significant performance degradation of the cathode was observed during operation at 700 °C for 1000 h under a constant current density of 0.2 A cm⁻².     

High-performance cathode-supported SOFCs prepared by a single-step co-firing process

Cathode-supported solid oxide fuel cells (SOFCs), comprising porous Pr_0.35Nd_0.35Sr_0.3MnO_3−δ (PNSM)/Sm_0.2Ce_0.8O_1.95 (SDC) cathode supports, SDC function layers, YSZ electrolyte membranes and NiO/SDC anode layers, were successfully fabricated via suspensions coating and single-step co-firing process. The microstructures of electrolyte membranes were observed with scanning electron microscope (SEM). The assembled single cell was electrochemically characterized with humidified hydrogen as fuel and ambient air as oxidant. The open circuit voltage (OCV) of the cell was 1.036 V at 650 °C, and the peak power densities were 657, 472, 290 and 166 mW cm⁻² at 800, 750, 700 and 650 °C, respectively. Impedance analysis indicated that the performance of cathode-supported cell was determined essentially by electrode polarization resistance, which suggested that optimizing electrodes was especially important for improving the cell performance.     

Fabrication and characterization of Cu–Ni–YSZ SOFC anodes for direct use of methane via Cu-electroplating

The Cu–Ni–YSZ cermet anodes for direct use of methane in solid oxide fuel cells have been fabricated by electroplating Cu into a porous Ni–YSZ cermet anode. The uniform distribution of Cu in the Ni–YSZ anode was obtained by electroplating in an aqueous solution mixture of CuSO₄·5H₂O and H₂SO₄ for 30 min with 0.1 A of applied current. When the Cu–Ni–YSZ anode was exposed to methane at 700 °C, the amount of carbon deposited on the anode decreased as the amount of Cu in the Cu–Ni solid solution increased. The power density (0.24 W/cm²) of a single cell with a Cu–Ni–YSZ anode was slightly lower in methane at 700 °C than the power density (0.28 W/cm²) of a single cell with a Ni–YSZ anode. However, the performance of the Ni–YSZ anode-supported single cell degraded steeply over 21 h because of carbon deposition, whereas the Cu–Ni–YSZ anode-supported single cell showed enhanced durability up to 200 h.     

Fabrication and evaluation of the electrochemical performance of the anode-supported solid oxide fuel cell with the composite cathode of La0.8Sr0.2MnO3−δ-Gadolinia-doped ceria oxide/La0.8Sr0.2MnO3−δ

The anode-supported single cell was constructed with porous Ni-Yittria-stabilized zirconia (YSZ) as the anode substrate, an airtight YSZ as the electrolyte, and a screen-printed La_0.8Sr_0.2MnO_3−δ (LSM)-Gadolinia-doped ceria (GDC)/LSM double-layer cathode. The SEM results show that the YSZ thin film is highly integrated, fully dense with a thickness of 13 μm, and exhibits excellent compatibility between cathode and electrolyte layers. The effects of feed rates of the reactants, temperature, and contact pressure between the current collector and the unit cell were systematically investigated. The results are based on the assumption that the anode contribution to the polarization resistance is negligible. Our analysis showed that the electrochemical reaction is limited by mass transfer control when the airflow rate is decreased to 500 ml min⁻¹. The maximum power density is 204.6 mW cm⁻² at 800 °C with H₂ and air at flow rates of 800 and 2000 ml min⁻¹, respectively. According to the AC-impedance data, the resistances of charge transfer at the electrode/electrolyte interface are 3.79 and 1.90 Ω cm². The resistances of oxygen-reduction processes are 3.63 and 1.01 Ω cm² at 700 and 800 °C, respectively. The results from the sensitivity analysis of the variation of contact pressure between current collectors and membrane electrode assembly (MEA) show that the influence is enhanced at the regions of the high current density.