High performance anode-supported tubular solid oxide fuel cells fabricated by a novel slurry-casting method.
ABSTRACT: Tubular solid oxide fuel cells were fabricated and evaluated for their microstructure and electrochemical performance. The tubular substrate was prepared by casting NiO-Y2O3 stabilized ZrO2 (YSZ) slurry on the inner wall of a plastic mold (tube). The wall thickness and uniformity were controlled by slurry viscosity and rotation speed of the tube. The cells consisted of Ni-YSZ functional anode, YSZ electrolyte and (La0.8Sr0.2)0.95MnO(3-?) (LSM)-YSZ cathode prepared in sequence on the substrate by dip-coating and sintering. Their dimension was 50?mm in length, 0.8?mm in thickness and 10.5?mm in outside diameter. The peak power density of the cell at temperatures between 650 and 850°C was in the range from 85 to 522?mW cm(-2) and was greatly enhanced to the range from 308 to 1220?mW cm(-2) by impregnating PdO into LSM-YSZ cathode. During a cell testing at 0.7?A cm(-2) and 750°C for 282?h, the impregnated PdO particles grew by coalescence, which increased the cathode polarization resistance and so that decreased the cell performance. According to the degradation tendency, the cell performance will be stabilized in a longer run.
Project description:Solid oxide fuel cells (SOFCs) are promising electrochemical energy conversion devices owing to their high power generation efficiency and environmentally benign operation. Micro-tubular SOFCs, which have diameters ranging from a few millimeters to the sub-millimeter scale, offer several advantages over competing SOFCs such as high volumetric power density, good endurance against thermal cycling, and flexible sealing between fuel and oxidant streams. Herein, we successfully realized a novel micro-tubular SOFC design based on a porous yttria-stabilized zirconia (YSZ) support using multi-step dip coating and co-sintering methods. The micro-tubular SOFC consisted of Ni-YSZ, YSZ, and strontium-doped lanthanum manganite (LSM)-YSZ as the anode, electrolyte, and cathode, respectively. In addition, to facilitate current collection from the anode and cathode, Ni and LSM were applied as an anode current collector and cathode current collector, respectively. Micro-crystalline cellulose was selected as a pore former to achieve better shrinkage behavior of the YSZ support so that the electrolyte layer could be densified at a co-sintering temperature of 1300 °C. The developed micro-tubular design showed a promising electrochemical performance with maximum power densities of 525, 442, and 354 mW cm(-2) at 850, 800, and 750 °C, respectively.
Project description:Abstract All?solid?sate Al?air batteries with features of high theoretical energy density, low cost, and environmental?friendliness are promising as power sources for next?generation flexible and wearable electronics. However, the sluggish oxygen reduction reaction (ORR) and poor interfacial contact in air cathodes cause unsatisfied performance. Herein, a free?standing Co3Fe7 nanoalloy and Co5.47N encapsulated in 3D nitrogen?doped carbon foam (Co3Fe7@Co5.47N/NCF) is prepared as an additive?free and integrated air cathode for flexible Al?air batteries in both alkaline and neutral electrolytes. The Co3Fe7@Co5.47N/NCF outperforms commercial platinum/carbon (Pt/C) toward ORR with an onset potential of 1.02 V and a positive half?wave potential of 0.92 V in an alkaline electrolyte (0.59 V in sodium chloride solution), which is ascribed to the unique interfacial structure between Co3Fe7 and Co5.47N supported by 3D N?doped carbon foam to facilitate fast electron and mass transfer. The high ORR performance is also supported by in?situ electrochemical Raman spectra and density functional theory calculation. Furthermore, the fabricated Al?air battery displays good flexibility and delivers a power density of 199.6 mW cm?2, and the binder?free and integrated cathode shows better discharge performance than the traditionally slurry casting cathode. This work demonstrates a facile and efficient approach to develop integrated air cathode for metal?air batteries. A free?standing Co3Fe7 and Co5.47N encapsulated in 3D N?doped carbon foam (Co3Fe7@Co5.47N/NCF) is fabricated and served as an additive?free and integrated air cathode for flexible Al?air batteries in both alkaline and neutral electrolytes. The designed air cathode with faster mass and electron transfer demonstrates better battery performance than the traditional slurry casting cathode or commercial Pt/C cathode.
Project description:In this study, the effects of calcination and milling of 8YSZ (8 mol% yttria stabilized zirconia) used in the nickel-YSZ anode on the performance of anode supported tubular fuel cells were investigated. For this purpose, two different types of cells were prepared based on a Ni-YSZ/YSZ/Nd2NiO4+δ-YSZ configuration. For the anode preparation, a suspension was prepared by mixing NiO and YSZ in a ratio of 65:35 wt% (Ni:YSZ 50:50 vol.%) with 30 vol.% graphite as the pore former. As received Tosoh YSZ or its calcined form (heated at 1500 °C for 3 hours) was used in the anode support as the YSZ source. Electrochemical results showed that optimization of the fuel electrode microstructure is essential for the optimal distribution of gas within the support of the cell, especially under electrolysis operation where the performance for an optimized cell (calcined YSZ) was enhanced by a factor of two. In comparison with a standard cell (containing as received YSZ), at 1.5 V and 800 °C the measured current density was -1380 mA cm(-2) and -690 mA cm(-2) for the cells containing calcined and as received YSZ, respectively. The present study suggests that the anode porosity for improved cell performance under SOEC is more critical than SOFC mode due to more complex gas diffusion under electrolysis mode where large amount of steam needs to be transfered into the cell.
Project description:Thermal stability of composite cathodes for solid oxide fuel cells, the mixtures of (La0.8Sr0.2)0.95MnO(3-?) (LSM) and (Y2O3)(x)(ZrO2)(1-x) (xYSZ, x = 3, 6, 8 and 10), is determined using in-situ neutron diffraction. Thanks to the most advanced high flux neutron source, our work highlights the visualization of the phase evolutions in heterogeneous material systems at high temperatures, along with the analysis of the diffusion activities of transition metal ions that reveal the reaction mechanism and kinetics. It is found that the tetragonal-to-cubic phase transition in YSZ at T > 900°C leads to a heterogeneous redistribution of Mn ions. The subsequent reaction of LSM and YSZ occurring at T > 1100°C is revealed as a three-stage kinetic process, yielding La2Zr2O7, SrZrO3 and MnO. The diffusion activities of Y, Mn and La ions in the heterogeneous systems at elevated temperatures are derived by the structural analysis, and the three-stage reaction of YSZ and LSM is found strongly correlated to ions' behaviors as functions of temperature.
Project description:Due to the high cost of polymer electrolyte fuel cells (PEFCs), replacing platinum (Pt) with some inexpensive metal was carried out. Here, we deposited palladium nanoparticles (Pd-NPs) on nanoporous carbon (NC) after wrapping by poly[2,2'-(2,6-pyridine)-5,5'-bibenzimidazole] (PyPBI) doped with phosphoric acid (PA) and the Pd-NPs size was successfully controlled by varying the weight ratio between Pd precursor and carbon support doped with PA. The membrane electrode assembly (MEA) fabricated from the optimized electrocatalyst with 0.05?mgPd cm(-2) for both anode and cathode sides showed a power density of 76?mW cm(-2) under 120?°C without any humidification, which was comparable to the commercial CB/Pt, 89?mW cm(-2) with 0.45?mgPt cm(-2) loaded in both anode and cathode. Meanwhile, the power density of hybrid MEA with 0.45?mgPt cm(-2) in cathode and 0.05?mgPd cm(-2) in anode reached 188?mW cm(-2). The high performance of the Pt-free electrocatalyst was attributed to the porous structure enhancing the gas diffusion and the PyPBI-PA facilitating the proton conductivity in catalyst layer. Meanwhile, the durability of Pd electrocatalyst was enhanced by coating with acidic polymer. The newly fabricated Pt-free electrocatalyst is extremely promising for reducing the cost in the high-temperature PEFCs.
Project description:Graphene oxide (GO) was deposited on the surface of a MnO2 air cathode by thermal evaporation at 50°C from a GO colloidal suspension. Fourier transformed infrared spectroscopy and field emission scanning electron microscopy confirmed the presence of GO on the MnO2 air cathode (GO-MnO2). Voltammetry and chrono-amperometry showed increased currents for the oxygen reduction reaction (ORR) in 6?M KOH solution for GO-MnO2 compared to the MnO2 cathode. The GO-MnO2 was used as an air cathode in an alkaline tin-air cell and produced a maximum power density of 13?mW cm(-2), in contrast to MnO2, which produced a maximum power density of 9.2?mW cm(-2). The electrochemical impedance spectroscopy results suggest that the chemical step for the ORR is the rate determining step, as proposed earlier by different researchers. It is suggested that the presence of GO and electrochemically reduced graphene oxide (ERGO) on the MnO2 surface are responsible for the increased rate of this step, whereby GO and ERGO accelerate the process of electron donation to the MnO2 and to adsorbed oxygen atoms.
Project description:A Plant Microbial Fuel Cell (Plant-MFCs) has been studied both in the lab and in a field. So far, field studies were limited to a more conventional Plant-MFC design, which submerges the anode in the soil and places the cathode above the soil surface. However, for a large scale application a tubular Plant-MFC is considered more practical since it needs no topsoil excavation. In this study, 1 m length tubular design Plant-MFC was installed in triplicate in a paddy field located in West Kalimantan, Indonesia. The Plant-MFC reactors were operated for four growing seasons. The rice paddy was grown in a standard cultivation process without any additional treatment due to the reactor instalation. An online data acquisition using LoRa technology was developed to investigate the performance of the tubular Plant-MFC over the final whole rice paddy growing season. Overall, the four crop seasons, the Plant-MFC installation did not show a complete detrimental negative effect on rice paddy growth. Based on continuous data analysis during the fourth crop season, a continuous electricity generation was achieved during a wet period in the crop season. Electricity generation dynamics were observed before, during and after the wet periods that were explained by paddy field management. A maximum daily average density from the triplicate Plant-MFCs reached 9.6 mW/m2 plant growth area. In one crop season, 9.5-15 Wh/m2 electricity can be continuously generated at an average of 0.4 ± 0.1 mW per meter tube. The Plant-MFC also shows a potential to be used as a bio sensor, e.g., rain event indicator, during a dry period between the crop seasons.
Project description:Iron single atom catalysts (Fe SACs) are the best-known nonprecious metal (NPM) catalysts for the oxygen reduction reaction (ORR) of polymer electrolyte membrane fuel cells (PEMFCs), but their practical application has been constrained by the low Fe SACs loading (<2 wt%). Here, a one-pot pyrolysis method is reported for the synthesis of iron single atoms on graphene (FeSA-G) with a high Fe SAC loading of ≈7.7 ± 1.3 wt%. The as-synthesized FeSA-G shows an onset potential of 0.950 V and a half-wave potential of 0.804 V in acid electrolyte for the ORR, similar to that of Pt/C catalysts but with a much higher stability and higher phosphate anion tolerance. High temperature SiO2 nanoparticle-doped phosphoric acid/polybenzimidazole (PA/PBI/SiO2) composite membrane cells utilizing a FeSA-G cathode with Fe SAC loading of 0.3 mg cm-2 delivers a peak power density of 325 mW cm-2 at 230 °C, better than 313 mW cm-2 obtained on the cell with a Pt/C cathode at a Pt loading of 1 mg cm-2. The cell with FeSA-G cathode exhibits superior stability at 230 °C, as compared to that with Pt/C cathode. Our results provide a new approach to developing practical NPM catalysts to replace Pt-based catalysts for fuel cells.
Project description:Nanoionics has become increasingly important in devices and systems related to energy conversion and storage. Nevertheless, nanoionics and nanostructured electrodes development has been challenging for solid oxide fuel cells (SOFCs) owing to many reasons including poor stability of the nanocrystals during fabrication of SOFCs at elevated temperatures. In this study, a conformal mesoporous ZrO2 nanoionic network was formed on the surface of La1-xSrxMnO3/yttria-stabilized zirconia (LSM/YSZ) cathode backbone using Atomic Layer Deposition (ALD) and thermal treatment. The surface layer nanoionic network possesses open mesopores for gas penetration, and features a high density of grain boundaries for enhanced ion-transport. The mesoporous nanoionic network is remarkably stable and retains the same morphology after electrochemical operation at high temperatures of 650-800?°C for 400?hours. The stable mesoporous ZrO2 nanoionic network is further utilized to anchor catalytic Pt nanocrystals and create a nanocomposite that is stable at elevated temperatures. The power density of the ALD modified and inherently functional commercial cells exhibited enhancement by a factor of 1.5-1.7 operated at 0.8?V at 750?°C.
Project description:The inner surface of a metallic tube (i.d. 0.5 mm) was coated with a palladium (Pd)-based thin metallic layer by flow electroless plating. Simultaneous plating of Pd and silver (Ag) from their electroless-plating solution produced a mixed distributed bimetallic layer. Preferential acid leaching of Ag from the Pd-Ag layer produced a porous Pd surface. Hydrogenation of p-nitrophenol was examined in the presence of formic acid simply by passing the reaction solution through the catalytic tubular reactors. p-Aminophenol was the sole product of hydrogenation. No side reaction occurred. Reaction conversion with respect to p-nitrophenol was dependent on the catalyst layer type, the temperature, pH, amount of formic acid, and the residence time. A porous and oxidized Pd (PdO) surface gave the best reaction conversion among the catalytic reactors examined. p-Nitrophenol was converted quantitatively to p-aminophenol within 15 s of residence time in the porous PdO reactor at 40 °C. Evolution of carbon dioxide (CO2) was observed during the reaction, although hydrogen (H2) was not found in the gas phase. Dehydrogenation of formic acid did not occur to any practical degree in the absence of p-nitrophenol. Consequently, the nitro group was reduced via hydrogen transfer from formic acid to p-nitrophenol and not by hydrogen generated by dehydrogenation of formic acid.