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.     

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.     

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.     

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.     

Characterization of CO tolerance of PEMFC by ac impedance spectroscopy

The CO tolerance of a proton exchange membrane fuel cell (PEMFC) was investigated by ac impedance spectroscopy. The impedance of the fuel cell could be obtained by feeding oxygen into the cathode side and simulated gas into anode side. Furthermore, the anode impedance could be obtained by feeding hydrogen into the cathode side and simulated gas into anode side. The CO gas had a greater effect on the charge transfer reaction (high frequency arc) and hydrogen dissociative chemisorption (medium frequency arc) but little effect on the low frequency arc. Although the cathode impedance is a main part at high temperature, irrespective of CO concentration (≤100 ppm), the impedance of the full cell depends on anode impedance at low temperature and high CO concentration. It was found that CO gas has little effect on cathode impedance.     

Polarization losses in Gratzel solar cells with a porous anode

Polarization losses under the redox reaction on the anode and cathode in the iodine electrolyte of a Gratzel solar cell are considered. It is shown that the value of the maximum cell current is bounded by the diffusion transfer of ions on the cathode or anode, depending on the electrolyte composition. It is demonstrated that the value of polarization losses for a nonporous anode is determined by a linear Tafel law, whereas for a porous anode it is determined by the obtained nonlinear Tafel law that yields half as much polarization loss, according to Zeldovich theory. Operating conditions of Gratzel cell with a porous anode of finite thickness, under which the nonlinear Tafel law is realized for polarization losses, are considered.     

具有可渗透阳极的自呼吸微流体燃料电池性能特性

微流体燃料电池去除了质子交换膜,避免了膜退化、水管理等问题,是微型燃料电池领域新的研究热点。本文构建了具有可渗透阳极和空气自呼吸阴极的微流体燃料电池,采用甲酸溶液作为燃料对其性能特性进行了实验研究。结果表明:具有可渗透阳极的自呼吸微流体燃料电池性能随燃料浓度或流量的增加先升高后下降,随电解液浓度的增加而升高;阳极侧反应产生的CO₂气泡对自呼吸微流体燃料电池的性能和燃料利用率的影响较大,适当提高燃料流量有利于气泡的排除。     

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.     

Progress in Developments of Inorganic Nanocatalysts for Application in Direct Methanol Fuel Cells

Significant progress has been made in the last few years toward synthesizing highly dispersible inorganic catalysts for application in the electrodes of direct methanol fuel cells. In addition, research toward achieving an efficient catalyst supporting matrix has also attracted much attention in recent years. Carbon black- (Vulcan XC-72) supported Platinum and Platinum-Ruthenium catalysts have for long served as the conventional choice as the cathode and the anode catalyst materials, respectively. Oxygen reduction reaction at the cathode and methanol oxidation reaction at the anode occur simultaneously during the operation of a direct methanol fuel cell. However, inefficiencies in these reactions result in a generation of mixed potential. This, in turn, gives rise to reduced cell voltage, increased oxygen stoichiometric ratio, and generation of additional water that is responsible for water flooding in the cathode chamber. In addition, the lack of long-term stability of Pt-Ru anode catalyst, coupled with the tendency of Ru to cross through the polymer electrolyte membrane and eventually get deposited on the cathode, is also a serious drawback. Another source of potential concern is the fact that the natural resource of Pt and the rare earth metal Ru is very limited, and has been predicted to become exhausted very soon. To overcome these problems, new catalyst systems with high methanol tolerance and higher catalytic activity than Pt need to be developed. In addition, the catalyst-supporting matrix is also witnessing a change from traditionally used carbon powder to transition metal carbides and other high-performance materials. This article surveys the recent literature based on the advancements made in the field of highly dispersible inorganic catalysts for application in direct methanol fuel cells, as well as the progress made in the area of catalyst-supporting matrices.     

Influence of fuel and media on membraneless sodium percarbonate fuel cell

This paper reports the media flexibility of membraneless sodium percarbonate fuel cell (MLSPCFC) using acid/alkaline bipolar electrolyte in which the anode is in acidic media while the cathode is in alkaline media, or vice versa. Investigation of the cell operation is conducted by using formic acid as a fuel and sodium percarbonate as an oxidant for the first time under ‘acid–alkaline media’ configurations. The MLSPCFC architecture enables interchangeable operation with different media combinations. The experimental results indicate that operating under acid–alkaline media conditions significantly improves the fuel cell performance compared with all-acidic and all-alkaline conditions. The effects of flow rates and the concentrations of various species at both the anode and cathode on the cell performance are also investigated. It has been demonstrated that the laminar flow-based microfluidic membraneless fuel cell can reach a maximum power density of 25.62 mW cm^?2 with a fuel mixture flow rate of 0.3 mL min^?1 at room temperature.     

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。     

平板式阳极支撑SOFC多场耦合数值模拟

建立了平板式固体氧化物燃料电池多场耦合数学模型,利用商业CFD软件FLUENT对包括阳极和阴极多孔介质、致密固体氧化物电解质、燃料流道、氧化剂流道、电流收集双极板、外壳的单电池三维整体计算区域进行了数值模拟,得到了流场、温度场、组分浓度场、电流密度场、Nernst电动势、活化过电势和欧姆过电势等重要物理量的详细分布,并分析了影响电池性能的主要因素。模拟结果与SOFC研制单位提供的实验数据基本符合。     

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.     

Operational characteristics of a plasma cathode with a grid stabilization in a two-stage ion source

The discharge characteristics and the parameters of the cathode plasma in a two-stage ion source with a grid plasma cathode and a magnetic trap in the anode region are investigated. It is shown that an increase in the gas pressure and the accompanying increase in the reverse ion current in the bipolar diode between the cathode and anode plasmas lead to an increase in the cathode plasma potential and a transition of the cathode into the regime of electron emission from the open plasma boundary. The dependence of the ion current extracted from the anode plasma on the area of the exit aperture of the hollow cathode and the mesh size of the grid plasma cathode is explained. The conditions at which the ion emission current from the anode plasma is maximum are determined. The potential difference at the bipolar diode is measured by using the probe method. It is shown that, when the gas pressures reaches a critical value determined by the mesh size of the grid plasma cathode, the discharge passes into a contracted operating mode, in which the ion current extracted from the anode plasma decreases severalfold.     

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.     

Fabrication of anode supported thick film ceria electrolytes for IT-SOFCs

Anode supported thick film ceria electrolyte unit cells were fabricated using a colloidal dip coating method for IT-SOFCs. Pre-sintering temperature of the anode substrate and the final sintering temperature were found to be the primary parameters determining the density of the film. With Ni-Ce_0.89Gd_0.11 O_2–δ cermet anode, La_0.6Sr_0.4Co_0.2Fe_0.8O₃ cathode and 15 μm Ce_0.89Gd_0.11 O_2–δ electrolyte, the cells were tested in a fuel cell configuration with air at the cathode and moist H₂ at the anode. At 650 °C, the cell indicated a maximum power density of ∼0.27 W/cm² at a current density of 0.62 A/cm². Cell performance was compared with oxygen at the cathode and the cell indicated a maximum power density of ∼0.50 W/cm² at 1.14 A/cm², 650 °C. Activation energy for the area specific resistance (ASR) of the cell suggests that with air at cathode, the cell performance was limited by gaseous diffusion at cathode and with oxygen at cathode, by oxygen ion transport across the electrolyte.     

An intermediate temperature solid oxide fuel cell utilizing superior oxide ion conducting electrolyte, doubly doped LaGaO3 perovskite

LaGaO₃-based perovskite oxide doped with Sr and Mg exhibits high ionic conduction over a wide oxygen partial pressure. In this study, the stability of the LaGaO₃ based oxide was investigated. It became clear that LaGaO₃ based oxide is very stable for reduction and oxidation. SOFCs utilizing LaGaO₃-based perovskite type oxide for electrolyte were further studied for the decreased temperature solid oxide fuel cells. The power generation characteristics of cells were strongly affected by the electrode, both anode and cathode. It became clear that Ni and LnCoO₃ (Ln: rare earth) are suitable for anode and cathode, respectively. Rare earth cations in the Ln-site of Co-based perovskite cathode also have a great effect on the power generation characteristics. In particular, high power density could be attained in the temperature range from 973 to 1273 K by using doped SmCoO₃ for the cathode. The electrical conductivity of SmCoO₃ increases with increasing Sr amount doped for the Sm site and attained the maximum at Sm_0.5Sr_0.5CoO₃. The cathodic overpotential and the internal cell resistance exhibit almost opposite dependence on the amount of doped Sr. Consequently, the power density of the cell reaches a maximum when Sm_0.5Sr_0.5CoO₃ is used for cathode. On this cell, the maximum power density is as high as 0.58 W/cm² at 1073 K, although a 0.5 mm thick electrolyte is used. Therefore, this study reveals that the LaGaO₃ based oxide for electrolyte and the SmCoO₃ based oxide for cathode are promising for solid oxide fuel cells at intermediate temperature. Paper presented at the 97th Xiangshan Science Conference on New Solid State Fuel Cells, Xiangshan, Beijing, China, June, 14–17, 1998.     

A simplified way of sensing gases based on electrochemical cells

A simple approach for sensing gases is reported by employing an electrochemical cell which is fabricated in the general configuration of sodium as anode and a mixture of MnO₂ + graphite powder (1:1) as cathode and a polymer electrolyte. The interaction of the mobile sodium ions with the gases at the cathode surface is observed. Fluorine and chlorine gases have been detected which were prepared from mixtures of manganese dioxide with hydrofluoric and hydrochloric acid, respectively. The sensing of gases is based on the observation of voltage and current changes of the electrochemical cell. The working conditions of sensor and the limitations are discussed as well as the basic performance, such as sensitivity, response speed and reproducibility.     

Solid hydrocarbon conversion in a fuel cell with molten carbonate electrolyte

A new architecture of a molten carbonate electrolyte fuel cell is considered. The architecture ensures efficient implementing the processes of direct electrochemical solid hydrocarbon oxidation. Experimental results demonstrate the possibility of achieving high specific characteristics of the fuel cell (current density and specific power values) by using graphite, various types of coal, and plastic as the dispersive fuel. The effect of the organic fuel composition on the energy parameters of the electrochemical cell is illustrated. It is shown that the fuel oxidation rate and the achievable maximal values of the specific power increase with the relative amount of hydrogen. It is concluded that application of the proposed ideology is promising for creating real energy devices with direct electrochemical oxidation of solid hydrocarbons.     

Mathematical modeling of the operation of SOFC Nickel-cermet anodes

A surface diffusion–reaction model is developed and solved to describe the steady-state operation of Nickel-cermet anodes in solid oxide fuel cells. The model accounts for the migration (backspillover) and diffusion of oxygen ions from the solid electrolyte onto the nickel surface and the concomitant reaction with the fuel over a finite reaction zone extending from the three-phase boundaries onto the Ni–gas interface. The model is developed for various nickel particle geometries and is compared with existing anode model predictions for flat geometries. The performance of the anode, expressed by an anodic effectiveness factor, is found to depend on two dimensionless numbers, which contain all the operational and structural information of the anode. The model is validated with literature experimental data regarding the dependence of the anode performance on the fuel partial pressure and predicts correctly the observed deviation from linearity of the dependence of cell current on fuel partial pressure.