阳极支撑型单气室固体氧化物燃料电池的性能

 使用浆料旋涂法制备了致密氧化钇稳定的氧化锆电解质薄膜,进而组装成阳极支撑型单气室固体氧化物燃料电池. 该电池在CH4, N2和O2混合气氛下运行,可产生很高的输出性能. 在700 ℃时开路电压达到1 V, 最大功率密度达到398 mW/cm2. 在开路状态下,电池的欧姆电阻为0.097 Ω·cm2, 仅为电极阻抗的6.4%, 远小于电极极化电阻. 通过优化电极材料,阳极支撑型单气室固体氧化物燃料电池将具有更优异的输出性能和更广阔的应用前景.     

NiO-YSZ-石墨水系浆料的研制及其在注浆成型制备固体氧化物燃料电池中的应用

Ni-YSZ(钇稳定氧化锆)金属陶瓷普遍被用作固体氧化物燃料电池(SOFC)的阳极材料,其氧化物浆料的性质对湿法制备的SOFC的性能具有重要影响. 通过zeta 电位分析,研究了NiO-YSZ双分散相水系浆料的稳定性. 对六种分散剂作用于NiO、YSZ 表面的zeta 电位进行研究,发现采用的阴离子分散剂和两性分散剂使NiO 和YSZ在水中带有相反电荷而引起迅速絮凝; 采用阳离子分散剂聚二烯二甲基氯化铵(PDAC)时,NiO 和YSZ因带有正电荷相互排斥而稳定分散于水中,在此基础上,加入作为SOFC阳极造孔剂的石墨,采用聚乙烯吡咯烷酮(PVP)作为石墨的分散剂,制备出了NiO-YSZ-石墨的稳定水系浆料. 采用此浆料通过注浆成型制得阳极支撑管,进而组装成SOFC单电池. 该单电池在800℃时最大功率密度达到509 mW·cm^-2; 扫描电镜(SEM)分析表明电极与电解质间接触良好,阳极孔洞分布均匀.     

Efficient Mass Transport and Electrochemistry Coupling Scheme for Reliable Multiphysics Modeling of Planar Solid Oxide Fuel Cell Stack

A multiphysics model for a production scale planar solid oxide fuel cell (SOFC) stack is important for the SOFC technology, but usually requires an unpractical amount of computing resource. The major cause for the huge computing resource requirement is identified as the need to solve the cathode O₂ transport and the associated electrochemistry. To overcome the technical obstacle, an analytical model for solving the O₂ transport and its coupling with the electrochemistry is derived. The analytical model is used to greatly reduce the numerical mesh complexity of a multiphysics model. Numerical test shows that the analytical approximation is highly accurate and stable. A multiphysics numerical modeling tool taking advantage of the analytical solution is then developed through Fluent®. The numerical efficiency and stability of this modeling tool are further demonstrated by simulating a 30-cell stack with a production scale cell size. Detailed information about the stack performance is revealed and brie y discussed. The multiphysics modeling tool can be used to guide the stack design and select the operating parameters.     

氧分压对固体氧化物电解池性能的影响

High-temperature (700–900 ℃) steam electrolysis based on solid oxide electrolysis cells (SOECs) is valuable as an efficient and clean path for large-scale hydrogen production with nearly zero carbon emissions, compared with the traditional paths of steam methane reforming or coal gasification. The operation parameters, in particular the feeding gas composition and pressure, significantly affect the performance of the electrolysis cell. In this study, a computational fluid dynamics model of an SOEC is built to predict the electrochemical performance of the cell with different sweep gases on the oxygen electrode. Sweep gases with different oxygen partial pressures between 1.01 × 10³ and 1.0 × 10⁵ Pa are fed to the oxygen electrode of the cell, and the influence of the oxygen partial pressure on the chemical equilibrium and kinetic reactions of the SOECs is analyzed. It is shown that the rate of increase of the reversible potential is inversely proportional to the oxygen partial pressure. Regarding the overpotentials caused by the ohmic, activation, and concentration polarization, the results vary with the reversible potential. The Ohmic overpotential is constant under different operating conditions. The activation and concentration overpotentials at the hydrogen electrode are also steady over the entire oxygen partial pressure range. The oxygen partial pressure has the largest effect on the activation and concentration overpotentials on the oxygen electrode side, both of which decrease sharply with increasing oxygen partial pressure. Owing to the combined effects of the reversible potential and polarization overpotentials, the total electrolysis voltage is nonlinear. At low current density, the electrolysis cell shows better performance at low oxygen partial pressure, whereas the performance improves with increasing oxygen partial pressure at high current density. Thus, at low current density, the best sweep gas should be an oxygen-deficient gas such as nitrogen, CO₂, or steam. Steam is the most promising because it is easy to separate the steam from the by-product oxygen in the tail gas, provided that the oxygen electrode is humidity-tolerant. However, at high current density, it is best to use pure oxygen as the sweep gas to reduce the electric energy consumption in the steam electrolysis process. The effects of the oxygen partial pressure on the power density and coefficient of performance of the SOEC are also discussed. At low current density, the electrical power demand is constant, and the efficiency decreases with growing oxygen partial pressure, whereas at high current density, the electrical power demand drops, and the efficiency increases.     

中温固体氧化物燃料电池Pr1.2Sr0.8NiO4阴极材料的制备、结构和性能

以相应的氧化物粉末和盐为原料,通过甘氨酸-硝酸盐法合成出了中温固体氧化物燃料电池(IT-SOFC)Pr1.2Sr0.8NiO4(PSNO)阴极原料粉体,并制备出了烧结体试样.采用X射线衍射(XRD)分析对所合成粉体的相组成进行了分析,分别采用热膨胀仪和四端子法对PSNO烧结体试样的热膨胀系数和电导率进行了测定,同时对该阴极材料与Sm0.2Ce0.8O1.9(sco)电解质材料的电化学阻抗谱(EIS)进行了测试分析以SCO作电解质,分别以NiO/SCO和PSNO作阳极和阴极材料,制备出固体氧化物燃料单电池,并对其性能进行测试.实验结果表明,通过甘氨酸-硝酸盐法,在1050℃以上煅烧前驱体,可以获得具有K2NiF4结构的PSNO粉体.所制备的PSNO烧结体试样在200-800℃间的热膨胀系数约为12×10-6 K-1,在450℃下的电导率约为155 S· cm-1,在400-800℃,平均电导活化能为0.034 eV.电化学阻抗谱分析结果表明,在700 ℃下PSNO阴极和SCO电解质间的比表面阻抗(ASR)为0.37Ω·cm2,而Ni-SCO/SCO/PSNO单电池的比表面阻抗为0.61Ω·cm2;所制备的SOFC单电池在800℃下的输出功率为288 mW· cm-2,开路电压为0.75 V.本研究的初步结果表明PSNO 材料是一种综合性能较为优良的新型巾温固体氧化物燃料电池阴极材料.     

真空注浆法制备YSZ电解质膜管及其在固体氧化物燃料电池中的应用

以吡啶为分散剂,采用真空注浆法制备出膜厚为0.2mm、长度为140mm的致密YSZ电解质膜管。研究了烧结温度对样品致密度和离子导电率的影响.用1650℃烧结2h制备的致密YSZ电解质膜管组装成固体氧化物燃料电池,以氢气和煤气为燃料,研究了电池在500～900℃的电化学性能.实验结果表明,用真空注浆法可制备出高质量和高密度的YSZ电解质膜管,在1600℃烧结后,其相对密度已达到理论密度的98.1%,接近理论密度.单电池的开路电压最大值为1.213V,最大输出功率为0.48W.以氢气为燃料的燃料电池性能明显高于以煤气为燃料的电池性能.     

Multi-Physics Modeling of Solid Oxide Fuel Cell Fueled by Methane and Analysis of Carbon Deposition

Internal reformation of low steam methane fuel is important for the high e ciency and low cost operation of solid oxide fuel cell. Understanding and overcoming carbon deposition is crucial for the technology development. Here a multi-physics model is established for the relevant experimental cells. Balance of electrochemical potentials for the electrochemical reactions, generic rate expression for the methane steam reforming, dusty gas model in a form of Fick's model for anode gas transport are used in the model. Excellent agreement between the theoretical and experimental current-voltage relations is obtained, demonstrating the validity of the proposed theoretical model. The steam reaction order in low steam methane reforming reaction is found to be 1. Detailed information about the distributions of physical quantities is obtained by the numerical simulation. Carbon deposition is analyzed in detail and the mechanism for the coking inhibition by operating current is illustrated clearly. Two expressions of carbon activity are analyzed and found to be correct qualitatively, but not quantitatively. The role of anode diffusion layer on reducing the current threshold for carbon removal is also explained. It is noted that the current threshold reduction may be explained quantitatively with the carbon activity models that are only qualitatively correct.     

Multi-Physics Modeling Assisted Design of Non-Coking Anode for Planar Solid Oxide Fuel Cell Fueled by Low Steam Methane

Internal reformation of low steam methane fuel is highly beneficial for improving the energy efficiency and reducing the system complexity and cost of solid oxide fuel cells (SOFCs). However, anode coking for the Ni-based anode should be prevented before the technology becomes a reality. A multi-physics fully coupled model is employed to simulate the operations of SOFCs fueled by low steam methane. The multi-physics model produces I-V relations that are in excellent agreement with the experimental results. The multi-physics model and the experimental non-coking current density deduced kinetic carbon activity criterion are used to examine the effect of operating parameters and the anode diffusion barrier layer on the propensity of carbon deposition. The interplays among the fuel utilization ratio, current generation, thickness of the barrier layer and the cell operating voltage are revealed. It is demonstrated that a barrier layer of 400 μm thickness is an optimal and safe anode design to achieve high power density and non-coking operations. The anode structure design can be very useful for the development of high efficiency and low cost SOFC technology.