SOFC characteristics along the flow path

Solid oxide fuel cells (SOFCs) in metallic housings were integrally and locally characterised. The tests were performed in counter flow operation for hydrogen concentrations from 2% to 100%, to identify concentration limitations and to optimise fuel utilisation. Cell characterisations were performed by spatially resolved electrochemical impedance spectroscopy (EIS), current density/voltage (i–V) and temperature measurements as well as gas chromatography measurements at 16 distinct points across the cell. The results show a substantial variation of current density and voltage distribution along the flow path with varying hydrogen content and fuel utilisation. The fuel utilisation was calculated from the local current densities and compared to the values measured by gas chromatography. Both sets of results showed good agreement. At low hydrogen inlet concentrations the voltage at the fuel outlet drops to values that might be harmful for the stability of the anode since reoxidation of nickel can occur. The impedances obtained by local EIS did not show an overall coherent dependency on the hydrogen concentration. EIS under load revealed two distinct domains: in the range of hydrogen concentrations of 2–10% H₂ the impedance decreased significantly with increasing hydrogen content whereas at higher hydrogen contents the impedance was hardly affected. This indicates significant concentration and diffusion overpotential at low hydrogen concentrations. The local data showed differing behaviour in the middle of the cell compared to the fuel outlet. Leakage at the sealing could be identified as a possible reason. As an additional method of investigation, the voltage drop over the contact resistance of the cathode side was measured. Temperature measurements show that local temperatures differ significantly depending on the load applied to the cell. This observation emphasizes the importance of a thermal management adapted to the characteristics on operation conditions of the cells, particularly when the stack itself has only a low mass.     

Interrelation of anode and cathode processes in electrochemical carbon oxidation in a fuel cell with molten carbonate electrolyte

The object to be investigated is a fuel cell with a free molten carbonate electrolyte, which ensures direct electrochemical oxidation of solid hydrocarbons. The polarization characteristics of anode and cathode fuel cell assemblies, and also composition and gas release rate of gaseous products of anode reactions are studied. It is shown that the maximum voltages in the open cell circuit are obtained when the oxygen-carbon dioxide ratio in the cathode gas mixture corresponds to stoichiometric reaction coefficients that ensure replenishment of ions in electrolyte. However, the maximum current density values were obtained with a low carbon dioxide content. It is found that at high current values, anode potential fluctuations are observed. It is shown that carbon monoxide is the product of anode processes, along with carbon dioxide. The carbon monoxide content grows with temperature. The carbon dioxide content grows with increasing current in the fuel cell and with growing carbon dioxide content in cathode gases. The release rate of carbon oxidation products nonlinearly depends on the current value in the fuel cell. It is concluded that there is interrelation between the mass-exchange processes in the fuel cell, which is determined by the balance between cathode gas incoming into the reaction zone, the number of molecules generated during fuel oxidation, molecule dissolution and diffusion into the cathode region, and also the amount of gas released in the form of bubbles.     

Direct conversion of solid hydrocarbons in a molten carbonate fuel cell

Electrical characteristics of a molten carbonate fuel cell allowing direct electrochemical oxidation of dispersed hydrocarbons have been examined. As the fuel, graphite, anthracite, and cannel coal samples were used. Data illustrating the effect of electrolyte temperature, fuel type and dispersion, and also reactant gas mixture composition on the performance characteristics of the fuel cell, were obtained. Correlation between the specific characteristics of the fuel cell and the hydrogen content of fuel material was established. The maximum current-density values were achieved with hydrogen-rich cannel coal. For dispersed fuel samples, interparticle contact losses were found to have influence on the cell-generated voltage. The maximum cell opencircuit voltage was reached with stoichiometric oxygen-carbon dioxide mixture blown into the cathode. Yet, the largest current-density values were obtained when carbon dioxide lean mixtures were used. Even at zero carbon dioxide concentration the range of cathode polarizations was less than that observed with stoichiometric mixture. The processes proceeding in the cathode and anode packs of the fuel cell are believed to be interrelated processes. In a model fuel cell fueled with dispersed coal, current densities up to 140 mA/cm² and specific powers up to 70 mW/cm² were achieved.     

Vacuum Arc Anode Phenomena

This paper briefly reviews anode phenomena in vacuum arcs, specially experimental work. It discusses, in succession, arc modes at the anode, anode temperature measurements, anode ions, transitions of the arc into various modes (principally the anode spot mode), and theoretical explanations of anode phenomena. The two most common anode modes in a vacuum arc are a low current mode where the anode is basically passive, acting only as a collector of particles emitted from the cathode, and a high current mode with a fully developed anode spot. Characteristically this anode spot has a temperature near the atmospheric boiling point of the anode material and is a copious source of vapor and energetic ions. However, other anode modes can exist. A low current vacuum arc with electrodes of readily sputterable material may emit a flux of sputtered atoms from the anode. Usually this sputtered flux will have little effect upon the vacuum arc, but in certain circumstances it could be significant. A vacuum arc doesn't always transfer directly from a low current mode to the anode spot mode. In appropriate experimental conditions, formation of an anode spot may be preceded by the formation of an anode footpoint. This footpoint is luminous, but much cooler than a true anode spot. Finally, (again in appropriate circumstances) several small anode spots may form instead of one large anode spot. With sufficient increase in arc current or arcing time these will usually combine to form a single large active spot.     

质子交换膜燃料电流道淹没与传质强化

在地面常重力环境下,采用透明电池可视化方法研究了质子交换膜燃料电池阳极和阴极的流道淹没现象。分别研究了阳极和阴极反应物流量对电池内部传质和电池性能的影响。结果表明,电池阴极的淹没区域比阳极大,由电极淹没引起的气体传质受限和电化学反应受限主要发生在阴极。提高反应物流量能够强化气体传质并提高电池性能,并且提高电池阴极侧反应物流量比提高阳极侧反应物流量对提高电池性能更有效。本文工作为进一步开展微重力环境中的燃料电池实验提供了比较依据。     

Measurement of electrode overpotentials for direct hydrocarbon conversion fuel cells

Cathodic and anodic overpotentials were measured using current interruption and AC impedance spectroscopy for two separate solid oxide fuel cells (SOFCs). The fuel cells used yttria-stabilized zirconia (YSZ) as the electrolyte, strontium-doped lanthanum manganite (LSM) as the cathode, and a porous YSZ layer impregnated with copper and ceria as the anode. The Cu/CeO₂/YSZ anode is active for the direct conversion of hydrocarbon fuels. Overpotentials measured using both current interruption and impedance spectroscopy for the fuel cell operating at 700 °C on both hydrogen and n-butane fuels are reported. In addition to providing the first electrode overpotential measurements for direct conversion fuel cells with Cu-based anodes, the results demonstrate that there may be significant uncertainties in measurements of electrode overpotentials for systems where there is a large difference between the characteristic frequencies of the anode and cathode processes and/or complex electrode kinetics.     

Cathode overpotential investigation by means of “Built-in” potential electrode

The objective of the present work is the development of a “built-in” potential electrode method for direct measurements of the cathode and anode overpotentials and the corresponding interface resistances of solid oxide fuel cells (SOFC). The studies were performed on a yttria-stabilised zirconia (YSZ) electrolyte-supported SOFC using La_0.8Sr_0.2MnO₃ as cathode, GDC as protecting layer and Ni-ScSZ cermet as anode. The mesh potential electrode was placed inside the YSZ membrane near the cathode side. Using the combination of the I-U and the impedance measurements with the built-in potential electrode technique, the temperature dependencies of the electrodes and electrolyte contributions to the total cell resistance were determined.     

Influence of methanol impurity in hydrogen on PEMFC performance

Proton exchange membrane fuel cells [PEMFC] have become highly attractive for stationary as well as mobile energy applications due to their good efficiency compact cell design and zero emissions. PEM fuel cells mainly consist of anode and cathode containing platinum/platinum alloy electrocatalysts and Nafion membrane as the electrolyte. They operate on hydrogen fuel, which is generally produced by reforming of hydrocarbons, alcohols such as methanol and may contain large amounts of impurities such as methanol, carbon dioxide, trace amounts of carbon monoxide, etc. The studies on the effect of methanol impurity in hydrogen on fuel cell performance and methods of mitigation of poisoning are very important for the commercialization of fuel cells and are described in a limited number of papers only. In this paper, we present the studies on the influence of methanol impurity in hydrogen for the PEM fuel cells. The effect of various parameters such as methanol concentration, cell voltage, current density, exposure time, reversibility, operating temperature, etc. on the cell performances was investigated using pure hydrogen. Various methods of methanol poisoning mitigation were also investigated.     

Effect of nitrogen and carbon dioxide as fuel impurities on PEM fuel cell performances

Polymer electrolyte membrane (PEM) fuel cells are considered to have the highest power density of all the fuel cells. They operate on hydrogen fuel, which is generally produced by reforming of hydrocarbons, and may contain large amounts of impurities such as carbon dioxide, nitrogen, and trace amounts of carbon monoxide. We studied the effect of dilution of hydrogen gas with carbon dioxide on PEM fuel cells by polarization studies. The polarization curves were different when hydrogen gas was diluted with same quantities of carbon dioxide and with nitrogen. It may be due to carbon monoxide formation by reverse shift reaction and poisoning of anode platinum catalyst. Use of Pt–Ru alloy catalyst was found to suppress the poisoning. The effects of hydrogen gas composition, temperature, current density, and anode catalyst on fuel cell performances were examined in this study.     

A Review of Anode Phenomena in Vacuum Arcs

This paper discusses arc modes at the anode, anode temperature measurments, anode ions, transitions of the arc into various modes (principally the anode-spot mode), and theoretical explanations of anode phenomena. A vacuum arc can exhibit five anode discharge modes: 1) a low-current mode in which the anode is basically passive, acting only as a collector of particles emitted from the cathode; 2) a second low-current mode that can occur if the electrode material is readily sputtered (a flux of sputtered atoms will be emitted by the anode); 3) a footpoint mode, characterized by the appearance of one or more luminous spots on the anode (footpoints are much cooler than the true anode spots present in the last two modes); 4) an anode-spot mode in which one large or several small anode spots are present (such spots are very luminous, have a temperature near the atmospheric boiling point of the anode material, and are a copious source of vapor and ions); and 5) an intense-arc mode where an anode spot is present, but accompanied by severe cathode erosion. The arc voltage is relatively low and quiet in the two low-current modes and the intense-arc mode. It is usually high and noisy in the footpoint mode, and it can be either in the anode-spot mode. Anode erosion is low, indeed negative, in the two low-current modes, and it is low to moderate in the footpoint mode. Severe anode erosion occurs in both the anode-spot and intense-arc modes.     

Study of thermal effects on the performance of micro-tubular solid-oxide fuel cells

Mathematical modeling of methane-fed anode-supported micro-tubular solid-oxide fuel cell (MT-SOFC) is developed. Steam reforming of methane is considered in two cases of: direct internal reforming (DIR) and gradual internal reforming (GIR). The polarization curves and temperature distribution of a cell fed with three variations of fueling (i.e., DIR and GIR of methane and pure hydrogen) are compared with each other. The simulation results are verified through temperature and performance measurements of a MT-SOFC sample operating on above three variations of fueling. In DIR operating condition, a drop in the anode gas temperature at a short distance after entering the cell takes place which results in high temperature gradient. In GIR operating condition, the temperature distribution in axial direction is steadier. The ohmic loss is lower in the case of pure hydrogen fuel than internal reforming of methane, but the concentration loss is lower in methane-fed operating conditions.     

Anode Phenomena in Vacuum and Atmospheric Pressure Arcs

This paper summarizes recent experimental data related to anode phenomena in both vacuum and atmospheric pressure arcs. Currents in the range 10A to 3OkA are discussed, and particular emphasis is placed on the effect of plasma flow from the cathode. For vacuum arcs this plasma flow is the directed motion of metal ions from the cathode spots. These ions reduce the anode voltage drop, and maintain a diffuse anode termination. At atmospheric pressure the ion flow is impeded by gas-atom collisions. However, a plasma flow towards the anode can result from magnetic pinch forces at the constricted cathode termination. In the absence of plasma flow, the anode termination constricts to a vigorously evaporating anode spot. For a typical non-refractory electrode such as copper, the spot operates at a temperature close to the boiling point irrespective of the gas pressure. The spot temperature is dictated by the balance between electrical input power and evaporative losses. These anode phenomena are discussed in relation to vacuum switchgear, arc welding and arc furnaces.     

PEMFC插指型流道阴极中气体扩散特性的数值分析

本文对PEMFC插指型流道阴极扩散层建立了二维单相的多组分物理数学模型,对PEMFC插指型流道的阴极扩散层中气体的扩散特性及反应行为进行了数值研究,采用有限容积法对模型控制方程进行求解,比较了插指型和平直型流道两类电池的性能曲线,以及两种流道中氧气的组分摩尔浓度和局部电流密度的分布,分析了插指型流道结构参数对电池性能的影响。     

PEM燃料电池中的两相传质及其影响

建立了一个新的二维、两相流模型来研究质子交换膜(PEM)燃料电池中的两相传质及其对质子膜阻抗和阴极性能的影响。模型不仅将催化剂层(CL)包含在电极中,还考虑了电池中相变及其对传质的影响。模型可同时使用在电池的阴极和阳极。主要模拟了电池阴极中两相传质、质子膜阻抗、阴极有效孔隙率和电流密度。模拟结果显示,提高加湿温度可以降低质子膜的阻抗,但过高的加湿温度会降低阴极气体扩散层(GDL)的有效孔隙率,降低阴极的性能。     

Studies on modified anode polymer hydrogen sensor

An improved polymer electrolyte membrane (PEM) fuel cell based amperometric hydrogen sensor that operates at room temperature has been developed. The electrolyte used in the sensor is PVA/H₃PO₄ blend, which is a proton conducting solid polymer electrolyte. A blend of palladium and platinum coated on the membrane is used as anode and platinum as cathode. The sensor functions as a fuel cell, H₂/Pd-Pt//PVA-H₃PO₄//Pt/O₂, and the short circuit current is found to be linearly related to the hydrogen concentration. The present study aims at investigating the dependence of sensor behaviour on the anode composition. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

光声光谱技术在多组分气体浓度探测中的应用

CO和CH_4气体作为判断变压器运行状态的故障气体,对其浓度的探测在变压器维护中具有重要意义.为了准确探测变压器运行过程中产生的CH_4和CO气体浓度,本文利用光声光谱技术,设计了一套基于宽带光源的多组分气体探测系统,和共振型光声系统相比,该系统中所用的非共振型光声池体积小,易加工,池内各处信号强度相同,降低了对声学信号探测器的安装要求.系统的性能通过对CO和CH_4气体的探测进行评估.首先,从理论上分析了信号强度与调制频率呈反比,然后根据宽带光声系统在不同调制频率下的响应,确定系统的最佳调制频率为22 Hz.在最佳调制频率下,根据温度与待测气体光声信号的关系,对光声信号进行温度补偿,消除温度变化对光声信号的影响,进一步提高了系统的稳定性.最后,通过不同浓度的CH_4和CO气体对系统进行标定.实验表明,温度补偿前后,光声信号随温度的漂移分别为0.023 23V/℃和8.383 48×10~(-5) V/℃,通过对不同浓度CH_4和CO气体的探测,系统的线性度分别达到0.995和0.998 4.在一个大气压下,积分时间为1s时,宽带光声探测系统对CO和CH_4气体的探测极限浓度能够达到1μL/L.该系统成本低,线性度好,探测灵敏度符合国标对变压器维护过程中CO和CH_4气体的探测要求.     

Fuel quality and operational issues for polymer electrolyte membrane (PEM) fuel cells

Polymer electrolyte membrane (PEM) fuel cells are susceptible to degradation due to the catalyst poisoning caused by CO present in the fuel above certain limits. Although the amount of CO in the fuel may be within the permissible limit, the fuel composition (% CO₂, CH₄, CO and H₂O) and the operating conditions of the cell (level of gas humidification, cell temperature and pressure) can be such that the equilibrium CO content inside the cell may exceed the permissible limit leading to a degradation of the fuel cell performance. In this study, 50 cm² active area PEM fuel cells were operated at 55–60 °C for periods up to 250 hours to study the effect of methane, carbon dioxide and water in the hydrogen fuel mix on the cell performance (stability of voltage and power output). Furthermore, the stability of fuel cells was also studied during operation of cells in a cyclic dead end / flow through configuration, both with and without the presence of carbon dioxide in the hydrogen stream. The presence of methane up to 10% in the hydrogen stream showed a negligible degradation in the cell performance. The presence of carbon dioxide in the hydrogen stream even at 1–2% level was found to degrade the cell performance. However, this degradation was found to disappear by bleeding only about 0.2% oxygen into the fuel stream.     

Growth of buckytubes on the anode at are discharge

It is shown that for an arc discharge between carbon electrodes in an inert gas atmosphere the temperatures at the electrode surfaces play a key role in determining the structure and the electrode on which a deposit can grow. The heat balance equations determine that the anode temperature is higher due to the energy carried by the electrons. This leads to anode sublimation and deposition on the cathode. It is shown that by cathode heating, by anode cooling or by a combination of these, a deposit may be obtained on the anode due to cathode erosion. The deposit grown by the “inverse” method is compared with a deposit obtained on the cathode under the same conditions but at reverse supply voltage polarity. The material from both deposits, studied by TEM, shows that there are graphite crystals within the anode deposit, and that the carbon forms within have a relatively small number of structural defects while the buckytubes are greater in length than those within the cathode deposit. The reasons for these differences are discussed. In the “inverse” method, the constant decrease in cooling of the anode surface leads to an equalization of the anode and cathode temperatures. This creates conditions that favor buckytube growth.     

Two-Temperature Modeling of the Anode Contraction Region of High-Intensity Arcs

In this paper, an analytical model for a two-temperature plasma (Te > Tg) is established which is suitable for dealing with arcflow interactions induced by the arc itself. This model is applied to the anode contraction region of high-intensity argon arcs taking the interaction of anode and cathode jets close to the anode into account. The complete set of conservation equations describing the mass, charge, momentum, and energy transport of a two-temperature plasma with temperature-dependent transport properties is solved numerically by an interative finite-difference method using appropriate boundary conditions. Results for an atmospheric-pressure argon arc indicate that the temperature discrepancy between electrons and heavy particles is very pronounced in the arc fringes and in the regions close to the anode, while the departure from kinetic equilibrium becomes insignificant in regions in which the temperature exceeds 12 000 K (i.e., in the arc core). The computed temperature fields of the heavy particles in the anode contraction region resemble the observed arc appearance which clearly shows the interaction of anode and cathode jets in front of the anode.     

含氢电极真空弧放电等离子体时空分布特性研究

真空弧离子源在真空镀膜、材料表面改性、真空大电流开关、加速器离子注入等领域有广泛应用,目前国内外对真空弧放电等离子体的研究主要针对纯金属或合金电极,对含氢电极的研究和公开报道较少.本文利用高时空分辨的四分幅图像诊断系统,结合氢和钛原子特征线单色器件,研究了含氢钛电极的真空弧微秒级脉冲放电等离子体的轴向和径向时空分布特性.研究表明:在真空击穿阶段,阳极区域发光更为明显,阳极电极解吸附释放的氢原子是引发击穿的主要放电介质;在真空弧阶段,阴极-绝缘-真空三结合点处产生圆锥状阴极斑,喷射出大量的等离子体以维持弧放电,同时电极内壁非阴极斑区域也有少量等离子体产生,等离子体中H原子的轴向和径向空间分布均比Ti原子均匀.