Lattice Boltzmann model for multi-component mass transfer in a solid oxide fuel cell anode with heterogeneous internal reformation and electrochemistry

We have deposited SiC thin films using two different deposition techniques, Pulsed Electron Deposition (PED) and Pulsed Laser Deposition (PLD). The PED technique is a relatively new technique where a pulsed electron flux with high energy directly hits the target surface producing a plasma in a very similar way to PLD, where, instead, a pulsed laser beam is used. These two techniques can give very dense thin films with stoichiometry much closer to the target one’s compared to others physical vapour deposition techniques (sputtering, e-beam). The major drawback of PED is that the thin film surface is affected by the presence of particulate, due to the impact of the high energy electron beam with the target. In the PLD system we used a magnetic field to curve the plasma path in the vacuum and we placed the substrate at 90^○ with respect to the target allowing the deposition of particulate-free samples. The characterization of the films has been made by measuring the optical reflectance vs angle of incidence in the EUV region (from 121.6 nm down to 40.7 nm), taking measurements at different time from deposition. X-ray photoemission measurements have been also carried out to show stoichiometry and the presence of contaminants. Other measurements such as X-ray diffraction, atomic force microscopy and profiling were also carried out to check crystalline domains and surface roughness.     

Synthesis,forming and characterization of ceramic materials for the planar solid oxide fuel cell (SOFC)

Chemically-homogeneous and well-characterized ceramic powders have been used for the preparation and investigation of the SOFC components. The powders were synthesized by spray drying and subsequent calcination. The resulting powders were characterized with regard to the crystalline phases, chemical analysis, specific surface area, particle size and particle size distribution, morphology and particle agglomerates. These parameters are very important for forming thin, flat ceramic sheets and components by tape-casting and screen-printing technology. Forming process, sintering, electrical conductivity and compatibility are discussed. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11 – 18 Sept. 1994     

Oxide anode materials for solid oxide fuel cells

A major advantage of solid oxide fuel cells (SOFCs) over polymer electrolyte membrane (PEM) fuel cells is their tolerance for the type and purity of fuel. This fuel flexibility is due in large part to the high operating temperature of SOFCs, but also relies on the selection and development of appropriate materials — particularly for the anode where the fuel reaction occurs. This paper reviews the oxide materials being investigated as alternatives to the most commonly used nickel–YSZ cermet anodes for SOFCs. The majority of these oxides form the perovskite structure, which provides good flexibility in doping for control of the transport properties. However, oxides that form other crystal structures, such as the cubic fluorite structure, have also shown promise for use as SOFC anodes. In this paper, oxides are compared primarily in terms of their transport properties, but other properties relative to SOFC anode performance are also discussed.     

Applications of the technique of solution aerosol thermolysis (SAT) in solid oxide fuel cell (SOFC) component fabrication

The technique of solution aerosol thermolysis (SAT) for the production of components suitable for operation of solid oxide fuel cells (SOFC) is reviewed. Major advantages of the technique include its versatility, low cost, and control of the product stoichiometry at droplet level. Progress in understanding the major physicochemical parameters that play a role in final film morphology is emphasized.     

Lanthanum chromite as an anode material for solid oxide fuel cells

The electrochemical behavior of pure lanthanum chromite and strontium dopedlanthanum chromite was studied by impedance spectroscopy under H₂/H₂O, CO/CO₂ and CH₄/H₂O. Results show that the electrochemical oxidation of H₂ is faster than that of CO or CH₄. Strontium doping enhances the anodic activity of the material. The impedance diagrams are composed of two semi-circles. The high frequency one does not appear to be related to a chemical or electrochemical reaction. The low frequency one is linked to the nature and concentration of the electroactive species. Paper presented at the 4th Euroconference on Solid State Ionics in Renvyle, Galway, Ireland, Sept. 13–19, 1997     

NiO+YSZ anode substrate for screen-printing fabrication of YSZ electrolyte film in solid oxide fuel cell

Anode substrate has a great effect on screen-printing fabrication of yttria-stabilized zirconia (YSZ) electrolyte film and cell performance. In this work, NiO+YSZ anode substrate was prepared by a conventional ceramic sintering method, on which dense YSZ electrolyte film was successfully fabricated by screen-printing method. Microstructure of the anode substrate and cell performance were investigated. The optimal amount of addition of starch to the anode substrate was 20 wt%. The optimal temperature for pre-sintering of NiO powder was 800 °C. A single cell with the NiO powder pre-sintered at 800 °C exhibited the highest power density of 0.95 W cm⁻² at 700 °C.     

高温固体氧化物燃料电池实验演示

介绍一种高效低污染的新型能源－高温固体氧化物燃料电池的工作原理及其演示实验装置。     

Fabrication of ceramic electrolytic films by the method of solution aerosol thermolysis (SAT) for solid oxide fuel cells (SOFC)

The technique of solution aerosol thermolysis (SAT) for the production of ceramic electrolytic films suitable for solid oxide fuels cells was investigated. The research has focused on the optimization of process parameters and characterization of the obtained films by means of X-ray diffractometry and scanning electron microscopy/energy-dispersive spectroscopy. Dense films of gadolinia-stabilized ceria of uniform thickness have been successfully produced on substrates consisting of dense disks of yttria-stabilized zirconia by SAT using nitrate salts of the precursors dissolved in an ethanol–water solvent. Substrate temperature is an important parameter and in this system the best initial values identified were of the order of 400–420 °C. The interplay between initial substrate temperature, solution flow rate, and postdeposition temperature is important for a good-quality film.     

固体氧化物燃料电池模式阳极内传输与电化学反应耦合机理

模式电极因其结构可控、电化学/化学反应活性位和物质传输路径明确等优势,被广泛应用于固体氧化物燃料电池新型电极研究.现有研究多采用模式电极研究新材料电化学特性、表界面催化反应机理等,尚未涉及几何结构对其内部传输与电化学反应耦合机理的影响,限制了模式电极的应用.本文建立了固体氧化物燃料电池阳极内电荷传输与电化学反应过程的格子玻尔兹曼模拟方法,明确了控制电极过程的关键无量纲参数及其对电极性能的影响规律,研究了模式阳极几何结构的影响机理.根据电极性能对无量纲参数的敏感程度,绘制了指导模式阳极设计与运行的相图,指出相图过渡区(电极性能随操作参数显著变化区域)为进行反应机理研究的最佳操作参数取值范围.同时,研究发现模式阳极电子导体内电子的快速迁移虽不限制阳极性能,其几何结构显著影响过渡区范围;离子导体内离子迁移为影响阳极性能的限速步骤,但其几何结构几乎不影响过渡区范围.本文的数值方法与机理研究结果可为固体氧化物燃料电池模式电极的设计提供重要理论依据.     

Microstructure and performance of novel Ni anode for hollow fibre solid oxide fuel cells

Nickel anodes were deposited on hollow fibre yttria-stabilised zirconia (YSZ) electrolyte substrates for use in solid oxide fuel cells (SOFCs). The hollow fibres are characterised by porous external and internal surfaces supported by a central gas-tight layer (300 μm total wall thickness and 1.6 mm external diameter). The YSZ hollow fibres were prepared by a phase inversion technique followed by high temperature sintering in the range 1200 to 1400 °C. Ni anodes were deposited on the internal surface by electroless plating involving an initial catalyst deposition step with PdCl₂ followed by Ni plating (with a NiSO₄, NaH₂PO₂ and sodium succinate based solution at 70 °C). Fabrication and nickel deposition parameters (nature of solvents, air gap, temperature, electroless bath composition) and heat treatments in oxidising/reducing environments were investigated in order to improve anode and electrolyte microstructure and fuel cell performance. A parallel study of the effect of YSZ sintering temperature, which influences electrolyte porosity, on electrolyte/anode microstructure was performed on mainly dense discs (2.3 mm thick and 15 mm diameter). Complete cells were tested with both disc and hollow fibre design after a La_0.2Sr_0.8Co_0.8Fe_0.2O_3?δ (LSCF) cathode was deposited by slurry coating and co-fired at 1200 °C. Anodes prepared by Ni electroless plating on YSZ electrolytes (discs and hollow fibres) sintered at lower temperature (1000–1200 °C) benefited from a greater Ni penetration compared to electrolytes sintered at 1400 °C. Further increases in anode porosity and performance were achieved by anode oxidation in air at 1200–1400 °C, followed by reduction in H₂ at 800 °C.     

Energy integration strategies for solid oxide fuel cell systems

Solid oxide fuel cells (SOFCs) have operating temperatures ranging from as low as 600 °C for intermediate temperature operation to above 900 °C for higher temperature operation. These high temperatures are often viewed as a considerable disadvantage from a materials point of view because of the occurrence of unwanted interfacial reactions, stresses as a result of thermal expansivity mismatches, etc. However, higher temperatures are also an advantage of SOFC systems. Fuel pretreatment that may involve such processes as reforming is very often highly endothermic in nature. The high operating temperature of an SOFC allows for efficient system energy integration with the waste heat from the fuel cell being used to drive fuel pretreatment processes. Here, we demonstrate this propensity for energy integration by looking at the use of a novel hydrogen-carrier system working with an SOFC.     

Reaction between solid oxide fuel cell materials

In fabrication processes of solid oxide fuel cells, high-temperature heat treatments cannot be avoided. It will give rise to mutual reaction and interdiffusion of the cell component materials: yttria-stabilized zirconia (YSZ, electrolyte), (La, Sr)MnO₃ (cathode), Ni-YSZ cermet (anode) and (La, Ca)CrO₃ (separator). Reactivity of LaMnO₃ and YSZ was estimated by thermodynamic calculations, and it was found that the nonstoichiometry at La site in LaMnO₃ plays an important role on the reaction. Diffusion of Mn into YSZ leads to increase of La activity at the interface and promotes the reaction. Electrical conductivity of YSZ decreases when Mn dissolves in the cubic phase of YSZ. Oxidation state of the dissolving Mn varies with partial pressure of oxygen and affects the electrical properties of YSZ. Migration of Ca from (La, Ca)CrO₃ separator to other cell components is one of the largest problems in the co-firing cell fabrication process because it prohibits the sintering of the separator.     

Spectroelectrochemical cell for in situ studies of solid oxide fuel cells

Solid oxide fuel cells (SOFCs) are able to produce electricity and heat from hydrogen‐ or carbon‐containing fuels with high efficiencies and are considered important cornerstones for future sustainable energy systems. Performance, activation and degradation processes are crucial parameters to control before the technology can achieve breakthrough. They have been widely studied, predominately by electrochemical testing with subsequent micro‐structural analysis. In order to be able to develop better SOFCs, it is important to understand how the measured electrochemical performance depends on materials and structural properties, preferably at the atomic level. A characterization of these properties under operation is desired. As SOFCs operate at temperatures around 1073 K, this is a challenge. A spectroelectrochemical cell was designed that is able to study SOFCs at operating temperatures and in the presence of relevant gases. Simultaneous spectroscopic and electrochemical evaluation by using X‐ray absorption spectroscopy and electrochemical impedance spectroscopy is possible.     

Fabrication and characterization of Ni-supported solid oxide fuel cell

Metal-supported solid oxide fuel cells (SOFCs) are promising due to their good mechanical and thermal properties. Stainless steels are often used as a supporting metal. In this study, the possible use of Ni as a supporting metal was tested. Ni is also a good model of supporting metal due to its lack of Cr which poisons Ni anode.YSZ electrolyte and Ni-YSZ anode were coated on a porous Ni support to fabricate Ni-supported SOFC. A porous Ni support in thick-film form (t ~ 150 µm) was prepared by the mold casting of Ni powders. An anode and an electrolyte layer were sequentially coated on the Ni support using screen printing and tape casting methods, respectively. The Ni-supported cell (t ~ 200 µm) was sintered at 1400 °C in a reducing atmosphere and the performance was evaluated at 800 °C with a La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) cathode. The unit cell showed an open circuit voltage (OCV) of 0.96 V and a peak power density of 470 mW/cm² at 800 °C.     

中温固体氧化物燃料电池的基本性质测量

介绍了固体氧化物燃料电池的工作原理,测量了中温薄膜固体氧化物燃料电池的开路电压、放电曲线及功率曲线,并分析了电池内阻随电流密度的变化.     

Overview on grain-boundary and transport problems in solid oxide fuel cell

An overview is given on the present state of development of fuel cells based on solid oxygen ion conductors. The performance is compared to other types of fuel cells. The employed electrolyte and electrode materials and current problems are described. The possibilities of reduced temperature and the reduction of internal resistances is discussed. Paper presented at the 97th Xiangshan Science Conference on New Solid State Fuel Cells, Xiangshan, Beijing, China, June 14–17, 1998.     

Oxy-combustion of coal in liquid-antimony-anode solid oxide fuel cell system

A novel system based on the indirect oxy-combustion of coal in a liquid Sb anode solid oxide fuel cell (SOFC) has been used to produce electricity for over 48?h. Pulverized anthracite was fed to the liquid-antimony-anode of the fuel cell, and a peak power density of 47?mW cm^?2 was reached at 1023?K and 35?mW cm^?2 at 973?K. The fuel cell was prepared using a porous stainless-steel tube as a support for an LSM cathode, antimony oxide (Sb₂O₃)/yittria stabilized zirconia (YSZ, Y_0.08Z_0.92O_1.96) composite electrolyte (membrane), while liquid antimony acted as the anode. Liquid antimony/antimony oxide served as the intermediate medium for coal oxidation producing mainly carbon dioxide, which evolved as a separate gas stream. The fuel cell will facilitate carbon capture process, and simultaneously convert the chemical energy of coal directly to electricity. The experiment showed that while the fabricated electrolyte was porous, it became dense during the actual operation, preventing nitrogen leakage into the Sb/C side and producing reasonable open circuit voltage. Analysis of the experimental EIS data illustrates that the Ohmic resistance was the primary loss mechanism in the system. It further suggests approaches to improve the design. Continuous operation of this coal fueled oxy-combustion/fuel cell system achieved an overall efficiency of 28.2% despite of its tiny scale. Simple technologies can be employed to scale up this system at relatively low cost of fabrication and materials.     

A practice of single layer solid oxide fuel cell

It has been found that the electrical conduction behavior of La_0.9Sr_0.1InO_3−δ varies with oxygen partial pressure. P-type and n-type conduction at high and low oxygen partial pressure have been observed respectively. While at intermediate oxygen partial pressures, the electrical conductivity changes slightly with the oxygen partial pressure. Thus, La_0.9Sr_0.1InO_3−δ may be a possible material for making single layer solid oxide fuel cell (SLFC). The concept of SLFC has been tested using a piece of thick ceramic pellet of La_0.9Sr_0.1InO_3−δ. The maximum current density and power density is 12 mA/cm² and 3 mW/cm² at 800 °C when dilute H₂ and air were used as fuel and oxidizing agent, respectively. The phase stability of La_0.9Sr_0.1InO_3−δ has been studied by Raman spectra and XRD. It is confirmed that secondary phase may appear in La_0.9Sr_0.1InO_3−δ after long term testing in low oxygen partial pressure, and finally it may be decomposed into La₂O₃ and metal Indium. Much attention should be paid to stabilize La_0.9Sr_0.1InO_3−δ and to improve the performance of SLFC.     

Interaction of samaria-doped ceria anode with highly dispersed Ni catalysts in a medium-temperature solid oxide fuel cell during long-term operation

Mixed conducting samaria-doped ceria (SDC) anode with highly dispersed Ni catalysts exhibited a stable high performance over 1100 h in solid oxide fuel cell (SOFC) operated at constant current density of 0.6 A cm^− 2 at 800 °C. While the apparent average size of Ni particles was found to be increased, both the IR-free polarization performance (reflecting an effective reaction area) and the ohmic resistance (reflecting an electronic network) were not changed noticeably during the long-term operation. It was found by scanning electron microscope (SEM) and scanning transmission electron microscope (STEM) that Ni particles were rather stabilized by changing the morphology at the portion contacting with SDC surface presumably due to a strong interaction.