Measurement of oxygen chemical potential in Gd2O3-doped ceria-Y2O3-stabilized zirconia bi-layer electrolyte, anode-supported solid oxide fuel cells

Solid oxide fuel cells (SOFC) were fabricated with gadolinia-doped ceria (GDC)-yttria stabilized zirconia (YSZ), thin bi-layer electrolytes supported on Ni + YSZ anodes. The GDC and YSZ layer thicknesses were 45 μm, and ∼5 μm, respectively. Two types of cells were made; YSZ layer between anode and GDC (GDC/YSZ) and YSZ layer between cathode and GDC (YSZ/GDC). Two platinum reference electrodes were embedded within the GDC layer. Cells were tested at 650 °C with hydrogen as fuel and air as oxidant. Electric potentials between embedded reference electrodes and anode and between cathode and anode were measured at open circuit, short circuit and under load. The electric potential was nearly constant through GDC in the cathode/YSZ/GDC/anode cells. By contrast, it varied monotonically through GDC in the cathode/GDC/YSZ/anode cells. Estimates of oxygen chemical potential, μO₂, variation through GDC were made. μO₂ within the GDC layer in the cathode/GDC/YSZ/anode cell decreased as the current was increased. By contrast, μO₂ within the GDC layer in the cathode/YSZ/GDC/anode cell increased as the current was increased. The cathode/YSZ/GDC/anode cell exhibited maximum power density of ∼0.52 W cm⁻² at 650 °C while the cathode/GDC/YSZ/anode cell exhibited maximum power density of ∼0.14 W cm⁻² for the same total electrolyte thickness.     

A non-sealed solid oxide fuel cell micro-stack with two gas channels

Non-sealed solid oxide fuel cell (NS-SOFC) micro-stacks with two gas channels were fabricated and operated successfully under various CH₄/O₂ gas mixtures in a box-like stainless-steel chamber. The cells with an anode-facing-cathode configuration were connected in serial by zigzag sliver sheets. Each cell consisted of the Ni/yttria-stabilized zirconia (YSZ) anode, the YSZ electrolyte, and the Sm_0.2Ce_0.8O_1.9-impregnated (La_0.75Sr_0.25)_0.95MnO₃ cathode. In this configuration, to ensure the identical gas distribution over the electrode surfaces, two gas channels with small vents flanking the stacks were used as gas channels of methane and oxygen for anodes and cathodes, respectively. The selectivity requirement of both the anode and cathode for the oxidation and reduction of CH₄ and O₂ was lowered and the sheets could extend the residence time of gas flow over the electrode surface. By the direct flame heat with a liquefied petroleum gas burner, the stacks presented a rapid start-up and full utilization of the exhaust gas. Eventually, an open-circuit voltage (OCV) of 1.8 V and maximum power output of 276 mW was produced by a two-cell stack. For a four-cell stack, a maximum power output of 373 mW was obtained.     

NiO/YSZ,anode-supported,thin-electrolyte,solid oxide fuel cells fabricated by gel casting

A simple and cost-effective gel-casting technique is developed and optimized to fabricate NiO/stabilized yttria–zirconia (YSZ) anode-supported solid oxide fuel cells (SOFCs). The effect of ammonium poly-(methacrylate) (PMAA) dispersant and pH on the zeta potential of YSZ and NiO particles and the viscosity of the NiO/YSZ slurries is studied in detail. The results show that the absolute zeta potential of YSZ and NiO particles reaches a maximum value at pH value ∼10 and the viscosity of the NiO/YSZ slurry is lowest when the PMAA dispersant content is 1.5 wt.%. A gel-cast NiO/YSZ anode-supported button cell with a spin-coated, thin, YSZ electrolyte film (∼9 μm) and a La_0.72Sr_0.18MnO_3−δ (LSM)/YSZ composite cathode gives a peak power output of 1.07 and 0.65 W cm⁻² at 900 and 800 °C under humidified hydrogen and air. The effect of a graphite pore-former in the gelation and microstructure of NiO/YSZ anode substrates is investigated.     

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.     

Scale-up of a high temperature polymer electrolyte membrane fuel cell based on polybenzimidazole

A high temperature PEM fuel cell stack with a total active area 150 cm² has been studied. The PEM technology is based on a polybenzimidazole (PBI) membrane. Cast from a PBI polymer synthesised in our lab, the performance of a three-cell stack was analysed in static and dynamic modes. In static mode, operating at high constant oxygen flow rate (QO₂>1105 ml O₂/min) produces a small decrease on the stack performance. High constant oxygen stoichiometry (λO₂>3) does not produce a decrease on the performance of the stack. There are not differences between operating at constant flow rate of oxygen and constant stoichiometry of oxygen in the stack performance. The effect of operating at high temperature with a pressurization system and operating at higher temperatures are beneficial since the performance of the fuel cell is enhanced. A large shut-down stage produces important performance losses due to the loss of catalyst activity and the loss of membrane conductivity. After 150 h of operation at 0.2 A cm⁻², it is observed a very high voltage drop. The phosphoric acid leached from the stack was also evaluated and did not exceed 2% (w/w). This fact suggests that the main degradation mechanism of a fuel cell stack based on polybenzimidazole is not the electrolyte loss. In dynamic test mode, it was observed a rapid response of power and current output even at the lower step-time (10 s). In the static mode at 125 °C and 1 atm, the stack reached a power density peak of 0.29 W cm⁻² (43.5 W) at 1 V.     

Fabrication and performance of membrane solid oxide fuel cells with La0.75Sr0.25Cr0.5Mn0.5O3−δ impregnated anodes

La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ (LSCrM)-impregnated anodes have been fabricated by infiltrating 70% porous yttria-stabilized zirconia (YSZ) matrixes with an LSCrM solution. In these anodes, LSCrM is a primary electronic conducive phase while the well-sintered YSZ provides an ionic-conducting pathway throughout the electrode. The maximum power densities of a single cell with YSZ + 35 wt.% LSCrM composite anode reach 567 and 561 mW cm⁻² at 850 °C in dry H₂ and CH₄, respectively. Further, Ag and Ni are added via nitrate impregnating method for improving electronic conductivity and catalytic activity. With the addition of 6 wt.% Ni and 2 wt.% Ag to the YSZ + 32 wt.% LSCrM composite anode, the maximum power densities at 850 °C increase to 1302 mW cm⁻² in dry H₂ and 769 mW cm⁻² in dry CH₄. No carbon deposition is detected in the tested anodes, even with the presence of Ni.     

Assessment of perovskite-type La0.8Sr0.2ScxMn1−xO3-δ oxides as anodes for intermediate-temperature solid oxide fuel cells using hydrocarbon fuels

Composites formed by the infiltration of 40 wt% La_0.8Sr_0.2Sc_xMn_1−xO_3-δ (LSSM) oxides (x = 0.1, 0.2, 0.3) into 65% porous yttria-stabilized zirconia (YSZ) are investigated as anode materials for intermediate-temperature solid oxide fuel cells for hydrocarbon oxidation. The oxygen non-stoichiometry and electrical conductivity of each LSSM-YSZ composite are determined by coulometric titration. As the concentration of Sc increases, the composites show higher phase stability and the electrical conductivity of LSSM is significantly affected by the Sc doping, the non-stoichiometric oxygen content, and oxygen partial pressure (p(O₂)). To achieve better electrochemical performance, it is necessary to add ceria-supported palladium catalyst for operation with humidified CH₄. Anode polarization resistance increases with Sc doping due to a decrease in electrical conductivity. An electrolyte-supported cell with a LSSM-YSZ composite anode delivers peak power densities of 395 and 340 mW cm⁻² at 923 K in humidified (3% H₂O) H₂ and CH₄, respectively, at a flow rate of 20 mL min⁻¹.     

Fabrication of bilayered YSZ/SDC electrolyte film by electrophoretic deposition for reduced-temperature operating anode-supported SOFC

Bilayered Y₂O₃-stabilized ZrO₂ (YSZ)/Sm₂O₃-doped CeO₂ (SDC) electrolyte films were successfully fabricated on porous NiO–YSZ composite substrates by electrophoretic deposition (EPD) based on electrophoretic filtration followed by co-firing with the substrates. In EPD, positively charged YSZ and SDC powders were deposited directly on the substrates, layer by layer from ethanol-based suspensions. Delamination between YSZ and SDC films was avoided by reducing the SDC films’ thickness to ca. 1 μm. A single cell was constructed on the bilayered electrolyte films composed of ca. 4 μm-thick YSZ and ca. 1 μm-thick SDC films. As a cathode in the cell, La_0.6Sr_0.4Co_0.2Fe_0.8O_3−x (LSCF) was used. Maximum output power densities greater than 0.6 W cm⁻² were obtained at 700 °C for the bilayered YSZ/SDC electrolyte cells thus constructed.     

Enhanced performance of a single-chamber solid oxide fuel cell with an SDC-impregnated cathode

The electrochemical performance of anode-supported single-chamber solid oxide fuel cells (SC-SOFCs) with and without SDC-impregnated cathodes was compared in a diluted methane–oxygen mixture. These cells were made of conventional materials including yttrium-stabilized zirconia (YSZ) thin film, a Ni + YSZ anode and a La_0.7Sr_0.3MnO₃ (LSM) cathode. Our results showed that the cell performance was greatly enhanced with the SDC-impregnated LSM cathode. At a furnace temperature of 750 °C, the maximum power density was as high as 404 mW cm⁻² for a CH₄ to O₂ ratio of 2:1, which was 4.0 times higher than the cell with a pure LSM cathode (100 mW cm⁻²). The overall polarization resistance of the impregnated cell was 1.6 Ω cm², which was much smaller than that of the non-impregnated one (4.2 Ω cm²). The impregnation introduced SDC nanoparticles greatly extended the electrochemical active zone and hence greatly improved the cell performance.     

Development of LSM-based cathodes for solid oxide fuel cells based on YSZ films

In an attempt to achieve desirable cell performance, the effects of La_0.7Sr_0.3MnO₃ (LSM)-based cathodes on the anode-supported solid oxide fuel cells (SOFCs) were investigated in the present study. Three types of cathodes were fabricated on the anode-supported yttria-stabilized zirconia (YSZ) thin films to constitute several single cells, i.e., pure LSM cathode, LSM/YSZ composite by solid mixing, LSM/Sm_0.2Ce_0.8O_1.9 (SDC) composite by the ion-impregnation process. Among the three single cells, the highest cell output performance 1.25 W cm⁻² at 800 °C, was achieved by the cell using LSM/SDC cathode when the cathode was exposed to the stationary air. Whereas, the most considerable cell performance of 2.32 W cm⁻² was derived from the cell with LSM/YSZ cathode, using 100 ml min⁻¹ oxygen flow as the oxidant. At reduced temperatures down to 700 °C, the LSM/SDC cathode was the most suitable cathode for zirconia-based electrolyte SOFC in the present study. The variation in the cell performances was attributed to the mutual effects between the gas diffusing rate and three-phase boundary length of the cathode.     

On the role of ultra-thin oxide cathode synthesis on the functionality of micro-solid oxide fuel cells: Structure, stress engineering and in situ observation of fuel cell membranes during operation

Microstructure and stresses in dense La_0.6Sr_0.4Co_0.8Fe_0.2O₃ (LSCF) ultra-thin films have been investigated to increase the physical thickness of crack-free cathodes and active area of thermo-mechanically robust micro-solid oxide fuel cell (μSOFC) membranes. Processing protocols employ low deposition rates to create a highly granular nanocrystalline microstructure in LSCF thin films and high substrate temperatures to produce linear temperature-dependent stress evolution that is dominated by compressive stresses in μSOFC membranes. Insight and trade-off on the synthesis are revealed by probing microstructure evolution and electrical conductivity in LSCF thin films, in addition to in situ monitoring of membrane deformation while measuring μSOFC performance at varying temperatures. From these studies, we were able to successfully fabricate failure-resistant square μSOFC (LSCF/YSZ/Pt) membranes with width of 250 μm and crack-free cathodes with thickness of ∼70 nm. Peak power density of ∼120 mW cm⁻² and open circuit voltage of ∼0.6 V at 560 °C were achieved on a μSOFC array chip containing ten such membranes. Mechanisms affecting fuel cell performance are discussed. Our results provide fundamental insight to pathways of microstructure and stress engineering of ultra-thin, dense oxide cathodes and μSOFC membranes.     

A symmetrical solid oxide fuel cell prepared by dry-pressing and impregnating methods

In this study, a simple and cost-effective dry-pressing method has been used to fabricate a symmetrical solid oxide fuel cell (SOFC) where the dense yttria-stabilized zirconia (YSZ) electrolyte film is sandwiched between two symmetrical porous YSZ layers in which La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ (LSCM) based anode and cathode are incorporated using wet impregnation techniques. The maximum power densities (P_max) of a single cell with 32 wt.% LSCM impregnated YSZ anode and cathode reach 333 and 265 mW cm⁻² at 900 °C in dry H₂ and CH₄, respectively. The cell performance is further improved with additional impregnation of a small amount of Sm-doped CeO₂ (SDC) or Ni. When 6 wt.% Ni as catalyst is added to both the anode and cathode, P_max values of 559 and 547 mW cm⁻² can be achieved, which are better than with SDC. The effect of Ni on the cathode performance is also investigated by impedance spectra analysis.     

A direct flame solid oxide fuel cell for potential combined heat and power generation

A sealant-free solid oxide fuel cell (SOFC) micro-stack was successfully operated inside a liquefied petroleum gas (LPG) flame during cooking. This micro-stack consisted of 4 single cells with infiltrated La_0.75Sr_0.25Cr_0.5Mn_0.5O_3-δ (LSCM) based composite anodes, achieving an open circuit voltage of 0.92 V and a peak power density of 348 mW cm⁻². This performance is significantly better than that of stack with its cathode operation outside flame. The results confirmed that the perovskite oxide anode showed good properties of carbon-free, redox-stability, quick-start (less than 1 min) and successful operation under a wide range of oxygen partial pressure. For comparison, the conventional Ni/yttria-stabilized zirconia (Ni/YSZ) anode was prepared and tested under the same conditions, showing an open circuit voltage of 0.915 V and a peak power density of 366 mW cm⁻², but obvious carbon deposition, poor stability and slow/difficult-start. The direct flame SOFC (DFFC) with a new configuration and design has a potential for combined heat and power generation for many applications.     

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.     

Dual-pump CARS temperature and major species concentration measurements in counter-flow methane flames using narrowband pump and broadband Stokes lasers

Dual-pump coherent anti-Stokes Raman scattering (CARS) is used to measure temperature and species profiles in representative non-premixed and partially-premixed CH₄/O₂/N₂ flames. A new laser system has been developed to generate a tunable single-frequency beam for the second pump beam in the dual-pump N₂-CO₂ CARS process. The second harmonic output (∼532 nm) from an injection-seeded Nd:YAG laser is used as one of the narrowband pump beams. The second single-longitudinal-mode pump beam centered near 561 nm is generated using an injection-seeded optical parametric oscillator, consisting of two non-linear β-BBO crystals, pumped using the third harmonic output (∼355 nm) of the same Nd:YAG laser. A broadband dye laser (BBDL), pumped using the second harmonic output of an unseeded Nd:YAG laser, is employed to produce the Stokes beam centered near 607 nm with full-width-at-half-maximum of ∼250 cm⁻¹. The three beams are focused between two opposing nozzles of a counter-flow burner facility to measure temperature and major species concentrations in a variety of CH₄/O₂/N₂ non-premixed and partially-premixed flames stabilized at a global strain rate of 20 s⁻¹ at atmospheric-pressure. For the non-premixed flames, excellent agreement is observed between the measured profiles of temperature and CO₂/N₂ concentration ratios with those calculated using an opposed-flow flame code with detailed chemistry and molecular transport submodels. For partially-premixed flames, with the rich side premixing level beyond the stable premixed flame limit, the calculations overestimate the distance between the premixed and the non-premixed flamefronts. Consequently, the calculated temperatures near the rich, premixed flame are higher than those measured. Accurate prediction of the distance between the premixed and the non-premixed flames provides an interesting challenge for future computations.     

Bimetallic (Ni–Fe) anode-supported solid oxide fuel cells with gadolinia-doped ceria electrolyte

Anode-supported solid oxide fuel cells (SOFC) comprising nickel + iron anode support and gadolinia-doped ceria (GDC) of composition Gd_0.1Ce_0.9O_2−δ thin film electrolyte were fabricated, and their performance was evaluated. The ratio of Fe₂O₃ to NiO in the anode support was 3 to 7 on a molar basis. Fe₂O₃ and NiO powders were mixed in the desired proportions and discs were die-pressed. All other layers were sequentially applied on the anode support. The cell structure consisted of five distinct layers: anode support – Ni + Fe; anode functional layer – Ni + GDC; electrolyte – GDC; cathode functional layer – LSC (La_0.6Sr_0.4CoO_3−δ) + GDC; and cathode current collector – LSC. Cells with three different variations of the electrolyte were made: (1) thin GDC electrolyte (∼15 μm); (2) thick GDC electrolyte (∼25 μm); and (3) tri-layer GDC/thin yttria-stabilized zirconia (YSZ)/GDC electrolyte (∼25 μm). Cells were tested with hydrogen as fuel and air as oxidant up to 650 °C. The maximum open circuit voltage measured at 650 °C was ∼0.83 V and maximum power density measured was ∼0.68 W cm⁻². The present work shows that cells with Fe + Ni containing anode support can be successfully made.     

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.     

Thick-film electrolyte (thickness <20 μm)-supported solid oxide fuel cells

A novel design of solid oxide fuel cell (SOFC) which utilizes a thick film (<20 μm) as an electrolyte support is developed and tested. The sintered 16 μm-thick yttria-stabilized zirconia (YSZ) electrolyte film is mounted on a 1-mm thick YSZ ring by sintering the two pieces together. With this new configuration, it is possible to fabricate a thick (<20 μm) electrolyte-supported SOFC and measure the power density of the unit cell. With LSCF (La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ) as a cathode and Ni–YSZ as a composite anode, the cell with a 16 μm-thick YSZ electrolyte achieves a high performance, i.e., a maximum power density of 590 mW cm⁻² at 800 °C. This value is comparable with that of most anode-supported SOFCs using YSZ electrolytes.     

Fabrication and evaluation of a Ni/La0.75Sr0.25Cr0.5Fe0.5O3−δ co-impregnated yttria-stabilized zirconia anode for single-chamber solid oxide fuel cells

In this study, an anode-supported solid oxide fuel cell (SOFC) has been prepared using a porous yttria-stabilized zirconia (YSZ) anode matrix. The anode was prepared by impregnating the sintered porous YSZ matrix with a nitrate aqueous containing La³⁺, Sr²⁺, Cr³⁺, Fe³⁺, Ni²⁺ and urea. The formed anode exhibited high surface area and porosity, and had fast path for the transportation of oxygen ion and electron, as well as resulting in high three-phase boundaries (TPBs). Single-chamber fuel cell test was conducted in a methane-oxygen gas mixture using an YSZ membrane as the electrolyte and La_0.8Sr_0.2MnO_3−δ (LSM) as the cathode. The influences of environmental temperature and gas composition on the cell performance were also investigated. Under the optimized gas composition (CH₄/O₂ = 2/1) and furnace temperature (800 °C) conditions, a maximum power density of 214 mW cm⁻² was achieved. The test results demonstrated good cell stability and indicated that the perovskite oxide-based anodes were quite robust with redox cycling.     

Effect of substitution with Cr and addition of Ni on the physical and electrochemical properties of Ce0.9Sr0.1VO3 as a H2S-active anode for solid oxide fuel cells

Whereas Ce_0.9Sr_0.1Cr_0.5V_0.5O₃ is an active fuel cell anode catalyst for conversion of only the H₂S content of 0.5% H₂S-CH₄ at 850 °C, inclusion of 5 wt% NiO to form a composite catalyst enabled concurrent electrochemical conversion of CH₄. A fuel cell with a 0.3 mm thick YSZ membrane and Ce_0.9Sr_0.1Cr_0.5V_0.5O₃ as anode catalyst had a maximum power density of 85 mW cm⁻² in 0.5% H₂S-CH₄ at 850 °C, arising only from the electro-oxidation of H₂S. Using a same thick membrane, promotion of the anode with 5 wt% NiO increased the total anode electro-oxidation activity to afford maximum power density of 100 mW cm⁻² in 0.5% H₂S-CH₄. The same membrane provided 30 mW cm⁻² in pure CH₄, showing that the incremental improvement arose substantially from CH₄ conversion. Performance of each anode was stable for over 12 h at maximum power output. XPS and XRD analyses showed that an increase in conductivity of Ce_0.9Sr_0.1Cr_0.5V_0.5O₃ in H₂S-containing environments resulted from a change in composition and structure from the tetragonal oxide to monoclinic Ce_0.9Sr_0.1Cr_0.5V_0.5(O,S)₃.