Positioning the reference electrode in proton exchange membrane fuel cells: calculations of primary and secondary current distribution

The primary and secondary current distribution study indicates the geometry of a thin electrolyte in a proton exchange membrane (PEM) fuel cell has a direct relation to the measured electrode polarization, thus making the positioning of the reference electrode and ohmic compensation critical. The different kinetic overpotentials on the electrodes can also affect the potential distribution and therefore affect the measurement accuracy. The measurement error can be significant for the fuel cell system with different kinetic overpotentials and with electrode misalignment. The measurement error for both hydrogen and direct methanol fuel cells (DMFC) has been analyzed over the current density region with no mass transfer effects. By using two reference electrodes, the measurement error can be substantially decreased for both anode and cathode measurement in a direct methanol fuel cell, and for the cathode measurement in a hydrogen/air fuel cell.     

Design of a reference electrode for high-temperature PEM fuel cells

In this work, we present the design of an external reference electrode for high-temperature PEM fuel cells. The connection between the reference electrode with one of the fuel cell electrodes is realized by an ionic connector. Using the same material for the ionic connection as for the fuel cell membrane gives us the advantage to reach temperatures above 100 °C without destroying the reference electrode. This configuration allows for the separation of the anode and cathode overpotential in a working fuel cell system. In addition to the electrode overpotentials in normal hydrogen/air operation, the influence of CO and CO + H₂O in the anode feed on the fuel cell potentials was investigated. When CO poisons the anode catalyst, not only the anode potential increased, but also the cathode overpotential, due to fewer protons reaching the cathode. By the use of synthetic reformate containing hydrogen, carbon monoxide and water on the anode, fuel cell voltage oscillations were observed at high constant current densities. The reference electrode measurements showed that the fuel cell oscillations were only related to reactions on the anode side influencing the anode overpotential. The cathode potential, in contrast, was only negligibly affected by the oscillations under the applied conditions.     

Study of direct type ethanol fuel cells: Analysis of anode products and effect of acetaldehyde

The anode products are observed when ethanol fuel is circulated in the direct ethanol fuel cell system using Nafion^® as an electrolyte. The main products are CO₂ and acetaldehyde. I-V characteristics of a direct type fuel cell using ethanol and acetaldehyde as fuels are investigated. Anode and cathode overpotentials are also measured to analyze the characters of the polarization curves obtained for both fuels. The MEA consisted of PtRu anode catalyst. The voltage drops as the concentration of acetaldehyde solution increases. In the case of ethanol solution, the voltage increases as the concentration increases. The anode overpotential increases as the concentration of acetaldehyde increases although the increase of cathode overpotential is smaller than that of anode overpotential. The opposite result is observed for ethanol solutions, i.e., the anode overpotential increases as the concentration of ethanol decreases. This result shows that the voltage drop observed for acetaldehyde solution results from the anode overpotential. Rotating disc electrode (RDE) measurements and polarization curve measurements were also performed to confirm the relation between acetaldehyde concentration and overpotentials. It is supposed that the electrocatalytic oxidation mechanism of acetaldehyde on PtRu catalyst is different from that of ethanol.     

An experimental study on the placement of reference electrodes in alkaline polymer electrolyte membrane fuel cells

The ability to accurately measure separate in situ anode and cathode overpotentials and impedance responses is still a source of debate when investigating fuel cells of planar configuration containing <100 μm thickness solid electrolytes and when using the common three-electrode arrangement. The results obtained in this study indicate that the overpotentials and impedances of the anode and cathode can be successfully measured when using two spatially separated reference electrodes and when the cathode and anode of alkaline membrane electrode assemblies (for alkaline polymer electrolyte membrane fuel cells) are precisely and optimally misaligned. The frequency dependent response between the two reference electrodes is attributed to the membrane response and the “crosstalk” between anode and cathode.     

Effects of anode orientation and flow channel design on performance of refuelable zinc-air fuel cells

The effects of anode orientation (whether an anode is located above or under a cathode) and flow channel design (parallel or serpentine flow channel) on the performance of refuelable zinc-air fuel cells (RZAFC) continuously fed with KOH electrolyte were investigated. The performance test was conducted at different electrolyte flow rates of 2, 4, and 6 ml h^?1. A polarization test of the cell was conducted at the initial stage of operation, followed by a long-term current discharge test in potentiostatic mode. The spent zinc powders were characterized by a scanning electron microscope and X-ray diffraction. The experimental results revealed that the anode-bottom orientation in the cell performed much better than the anode-top orientation with 11.4 times higher zinc utilization. The performance reduction of the anode-top orientation cell was caused by the cathode overpotential, due to the flooding of the cathode by water crossover from the anode, which was induced by the gravity force. For the flow channel design effects, there was an optimum electrolyte flow rate, to yield a maximum current discharge capacity, of 4 ml h^?1 in this study. At this optimum flow rate, the total charge per gram of zinc delivered from the anode serpentine cell was 1.75 times higher than that from the anode-parallel one.     

Development and electrochemical studies of gas diffusion electrodes for polymer electrolyte fuel cells

Electrochemical studies on low catalyst loading gas diffusion electrodes for polymer electrolyte fuel cells are reported. The best performance is obtained with an electrode formed from 20 wt% Pt/C, 0.4 mg Pt cm^–2 and 1.1 mg Nafion^® cm^–2 in the catalyst layer and 15% PTFE in a diffusion layer of 50 µm thickness, for both the cathode and the anode. However, it is also observed that the platinum requirement can be diminished to values close to 0.2 mg Pt cm^–2 in the cathode and 0.1 mg pt cm^–2 in the anode, without appreciably affecting the good characteristics of the fuel cell response. The experimental fuel cell data were analysed using theoretical models of the electrode structure and of the fuel cell system. It is seen that most of the electrode systems present limiting currents and some also show linear diffusion components arising from diffusion limitations in the gas channels and/or in the thin film of electrolyte covering the catalyst particles.     

Quasi Three–Dimensional Modelling of the PEM Fuel Cell: Comparison of the Catalyst Layers Performance

The results of the first quasi three dimensional modelling of a polymer electrolyte membrane fuel cell with meander–like gas channels are reported. The model resolves the catalyst layers and takes into account feed gas consumption in the channels. The results show that in both catalyst layers the rate of electrochemical reaction in front of the channels is higher, than in front of the current collectors. The overpotential is almost constant across the cathode catalyst layer and varies rapidly (exponentially) across the anode catalyst layer. A current on the anode side is produced in a thin sub–layer adjacent to the membrane, where the overpotential is close to its maximum value. A simple formula for optimal thickness of the anode catalyst layer is derived and compared with numerical results.     

Cell Configurations for Performance Evaluation in Planar Solid Oxide Fuel Cells

Cell configurations with asymmetric and symmetric electrode geometries and different reference electrode positions were investigated on 50 mm×50 mm planar solid oxide fuel cells (SOFC). The reliability and accuracy of the polarization performance of individual electrodes were studied with respect to the electrode geometry and the reference electrode position. The results indicate that a centrally located reference electrode creates inactive electrolyte regions in the center of the cell, pushing the equipotential lines close to the electrode–electrolyte interface region and thus introducing error in the measurement of polarization performance. The potential of reference electrodes located at the corner of the electrode coating was not stable due to the steam build-up in the reference electrode region. Cells with a symmetric electrode geometry arrangement and reference electrodes located at the side of the working electrodes, away from the receiving end of the fuel and oxidant gases, were found to be suitable for performance evaluation in planar SOFC.     

Effects of Microstructural Functional Layers on Flat‐Tubular Solid Oxide Fuel Cells

The functional layer of a flat‐tubular solid oxide fuel cell (SOFC) is examined using a three‐dimensional microscale electrode model. SOFC electrodes essentially include two types of layers: a structural layer and a functional layer. The structural layers, which are the anode support layer and the cathode current collector layer, are composed of large particles with a high porosity that facilitates gas diffusion. The functional layers consist of small particles with a low porosity that increases the triple phase boundary (TPB) reaction area and reduces the activation overpotential. In the model, the particle diameter and functional layer thickness are adjusted and analyzed. The effects of the two parameters on the performance of the functional layer are monitored in the contexts of several multilateral approaches. Most reactions occurred near the electrode–electrolyte interface; however, an electrode design that included additional TPB areas improved the electrode performance. The role of the functional layer in a flat‐tubular SOFC is examined as a function of the functional layer particle size and thickness. The performance of a cell could be enhanced by preparing a functional layer using particles of optimal size and thickness, and by operating the device under conditions optimized for these parameters.     

Modeling and Optimization of Anode‐Supported Solid Oxide Fuel Cells on Cell Parameters via Artificial Neural Network and Genetic Algorithm

An artificial neural network (ANN) and a genetic algorithm (GA) are employed to model and optimize cell parameters to improve the performance of singular, intermediate‐temperature, solid oxide fuel cells (IT‐SOFCs). The ANN model uses a feed‐forward neural network with an error back‐propagation algorithm. The ANN is trained using experimental data as a black‐box without using physical models. The developed model is able to predict the performance of the SOFC. An optimization algorithm is utilized to select the optimal SOFC parameters. The optimal values of four cell parameters (anode support thickness, anode support porosity, electrolyte thickness, and functional layer cathode thickness) are determined by using the GA under different conditions. The results show that these optimum cell parameters deliver the highest maximum power density under different constraints on the anode support thickness, porosity, and electrolyte thickness.     

Mathematical model for a direct propane phosphoric acid fuel cell

A mathematical model was developed and used to predict the performance of direct propane phosphoric acid (PPAFC) fuel cells, utilizing both Pt/C state-of the-art electrodes and older Pt black electrodes. It was found that the overpotential caused by surface processes on the platinum catalyst in the anode is much greater than the potential losses caused by either ohmic resistance or propane diffusion in gas-filled and liquid-filled pores. In one comparison, the anode overpotential (0.5 V) was larger than the cathode overpotential (0.3 V) at a current density of 0.4 A cm⁻² for Pt loadings 4 mg Pt cm⁻². The need for sufficient water concentration at the anode, where water is a reactant, was indicated by the large effect of H₃PO₄ concentration. In another comparison, the model predicted that at 0.2 A cm⁻², modern carbon supported Pt catalysts would produce 0.35 V compared to 0.1 V for unsupported Pt black catalysts that were used several decades ago, when the majority of the research on direct hydrocarbon fuel cells was performed. The propane anode and oxygen cathode catalyst layers were modeled as agglomerates of spherical catalyst particles having their interior spaces filled with liquid electrolyte and being surrounded by gas-filled pores. The Tafel equation was used to describe the electrochemical reactions. The model incorporated gas and liquid-phase diffusion equations for the reactants in the anode and cathode and ionic transport in the electrolyte. Experimental data were used for propane and oxygen diffusivities, and for their solubilities in the electrolyte. The accuracy of the predicted electrical potentials and polarization curves were normally within ±0.02 V of values reported in experimental investigations of temperature and electrolyte concentration. Polarization curves were predicted as a function of temperature, pressure, electrolyte concentration, and Pt loading. A performance of 0.45 V at 0.5 A cm⁻² was predicted at some conditions.     

Numerical analysis of thermal and electrochemical phenomena for anode supported microtubular SOFC

A 2D model considering momentum, heat/species transport and electrochemical phenomena, has been proposed for tubular solid oxide fuel cell. The model was validated using experimental polarization curves and the good agreement with the experimental data was attained. The temperature distributions show that temperature varies severely at the tube inlet than at the tube outlet. The heat generation and transfer mechanisms in electrodes, electrolyte and electrochemical reaction interface were investigated. The results show that the overall electrochemical reaction heat is produced at cathode/electrolyte interface, and a small portion of the heat is consumed at anode/electrolyte interface. The heat produced at cathode/electrolyte interface is about five times as much as that consumed at anode/electrolyte interface. Overwhelming part of the heat transfer between cell and outside occurs at cathode external surface. Most current flow goes into anode from a very small area where the current collectors locates. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Nafion degradation in PEFCs from end plate iron contamination

Nafion degradation in polymer electrolyte fuel cells from SS316L end plate iron contamination was tested in a single cell configuration. Water collected at the cathode and anode exhausts was analysed by means of pH measurements, conductivity, fluoride and metal concentration. The investigations revealed that stainless steel is unsuitable as material for end plates in PEM fuel cells. In fact, iron contamination of membrane electrode assemblies led to polymer degradation, revealed by a massive fluoride loss. In contrast, iron-free plates (aluminium alloy) showed higher stability in the cell environment.     

Comparative studies of configurations and preparation methods for direct methanol fuel cell electrodes

Catalyst-coated membrane (CCM) and catalyzed diffusion medium (CDM) prepared either by brush painting method or by spraying method were compared for direct methanol fuel cell (DMFC) anode and cathode. The pore structure and the morphology of the electrodes were characterized by mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). Internal resistance corrected polarization curves were employed to separate the contribution of each compartment of the membrane electrode assembly (MEA) to the overall polarization. It was shown that the increased mass transport resistance in the anode diffusion layer made the anode in CDM form act as the methanol barrier. The CCM configuration and the increased pores in micron scales in the catalyst layer were in favor of improving the performance of both anode and cathode. Accounting for the effect of methanol permeation, the combination of the anode in CDM form prepared by brush painting method and the cathode in CCM form prepared by spraying method was finally selected as the optimized configuration for MEA, which had the highest DMFC performance under near-ambient conditions.     

A primary, secondary and pseudo-tertiary mathematical model of a chlor-alkali membrane cell

A theoretical study of current density and potential at the anode, membrane and cathode, of a chlor-alkali membrane cell where the electrode blades are placed vertically, is presented. A representative unit cell is modelled in primary, secondary and pseudo-tertiary current distribution models. It is shown that electrolyte and membrane resistance has the greatest effect on current distribution. Furthermore, it is shown that there is a surprisingly small influence of mass transport on current distribution, on the assumption that the diffusion layer is of constant thickness. In converse to this, it is shown that mass transport affects the anode overpotential distribution to the extent that conclusions can be made about the occurrence of side-reactions and where they occur. Finally, it is shown that it is possible to estimate tertiary behaviour with a secondary current distribution model, by using an analytic expression at the anode surface.     

表面修饰对镧锶钴铁阴极材料电化学性能的影响

通过柠檬酸-EDTA络合法制备固体氧化物燃料电池阴极材料La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ(LSCF)粉体。以Sm_0.2Ce_0.8O_1.9(SDC)为电解质,制备了LSCF/SDC/LSCF对称电极。采用浸渍法在LSCF/SDC/LSCF两侧浸渍La(NO₃)₃、Ni(NO₃)₂、Fe(NO₃)₃混合溶液,850℃烧结后得到表面修饰后的阴极材料。研究了浸渍烧结后表面修饰阴极材料的物相结构特征、电化学交流阻抗、电化学催化活性及单电池输出性能。结果表明:通过浸渍法在LSCF阴极表面形成了与LSCF结构相似的La_0.62Sr_0.38Ni_0.03Co_0.19Fe_0.78O_3-δ(LSNCF)固溶体,在表面产生的纳米颗粒提升了阴极材料对O2的吸附解离能力,并表现出较低的极化阻抗,在800℃时LSNCF阴极材料的极化面电阻为0.083Ω·cm²,在800℃连续工作7 200 min后,LSNCF阴极材料对称电池极化阻抗为0.117Ω·cm²。以Ni-SDC为阳极,SDC为电解质,LSNCF为阴极组装阳极支撑单电池,在750℃时最大功率密度为693 m W/cm²。     

pH值对高锰酸钾作阴极的微生物燃料电池阴极电位的影响

构建了一个以葡萄糖水溶液为阳极原料,高锰酸钾为阴极氧化剂的双室微生物燃料电池。考察了MnO_4溶液的pH值对MFC产电性能的影响。结果表明,在pH值不同时,其对MFC的还原电位和MnO_4的还原产物有显著影响。当pH>3时,阴极E°=+1.51V,当pH>11时,E°=+0.56V。研究表明:(1)二氧化锰沉淀是导致阴极极化的主要原因,当阴极电解液流动时可有效抑制二氧化锰的沉淀。(2)根据电池电压曲线图判断,pH值对电池的阴极电位有较大影响,电池电压的变化与阴极电位变化具有很好的一致性,但不会对阳极电位造成影响。(3)pH值对阴极电势的影响符合Nernst方程。     

Multi-layer configuration for the cathode electrode of polymer electrolyte fuel cell

This paper conducts a one-dimensional theoretical study on the electrochemical phenomenon in the dual-layer cathode electrode of polymer electrolyte fuel cells (PEFCs) with varying sub-layer thicknesses, and further extends the analysis to a triple-layer configuration. We obtain the explicit solution for a general dual-layer configuration with different layer thicknesses. Distributions of the key quantities such as the local reaction current and electrolyte overpotential are exhibited at different ratios of the ionic conductivities, electrochemical kinetics, and layer thicknesses. Based on the dual-layer approach, we further derive the explicit solutions for a triple-layer electrode. Sub-layer performances are plotted and compared. The results indicate that the layer adjacent to the electrolyte membrane may contribute a major part of the electrode faradic current production. The theoretical analysis presented in this paper can be applied to assist electrode development through complicated multi-layer configuration for cost-effective high performance electrodes.     

Novel approach to membraneless direct methanol fuel cells using advanced 3D anodes

A conventional membrane electrode assembly (MEA) for a direct methanol fuel cell (DMFC) consists of a polymer electrolyte membrane (PEM) compressed between an anode and cathode electrode. Limitations with this conventional design include: cost, fuel crossover, membrane degradation or contamination, ohmic losses and reduced active triple phase boundary (TPB) sites for catalyst located away from the electrode/membrane interface. In this work, ex situ and in situ characterization of a novel electrode assembly based on a membraneless architecture and advanced 3D anodes was investigated. The approach was shown to be fuel independent and scaleable to a conventional bi-polar fuel cell arrangement. The membraneless configuration exhibits comparable performance to a conventional ambient (25 °C, 1 atm) air-breathing DMFC. However, it has the additional advantages of a simplified design, the elimination of the membrane (a significant component expense) and enhanced fuel and catalyst utilization through the extension of the active catalyst zone.