Dynamic Behavior of a PEM Fuel Cell During Electrochemical CO Oxidation on a PtRu Anode

The dynamic behaviour of a single PEM fuel cell (PEMFC) with a PtRu/C anode catalyst using CO containing H₂ as anode feed was investigated at ambient temperature. The autonomous oscillations of the cell potential were observed during the galvanostatic operation with hydrogen anode feed containing CO up to 1000 ppm. The oscillations were ascribed to the coupling of the adsorption of CO (the poisoning step) and the subsequent electrochemical oxidation of CO (the regeneration step) on the anode catalyst. The oscillations were dependent on the CO concentration of the feed gas and the applied current density. Furthermore, it was found that with CO containing feed gas, the time average power output was remarkably higher under potential oscillatory conditions in the galvanostatic mode than during potentiostatic operation. Accompanying these self-sustained potential oscillations, oscillation patterns of the anode outlet CO concentration were also detected at low current density (<100 mA/cm²). The online measurements of the anode outlet CO concentrations revealed that CO in the anode CO/H₂ feed was partially electrochemically removed during galvanostatic operation. More than 90% CO conversion was obtained at the current densities above 125 mA/cm² with low feed flow rates (100–200 mL/min).     

Transient carbon monoxide poisoning of a polymer electrolyte fuel cell operating on diluted hydrogen feed

The transient behavior of a 50 cm² PEM fuel cell fed on simulated reformate containing diluted hydrogen and trace quantities of carbon monoxide (CO) was experimentally investigated. It was found that the overall cell performance throughout the CO poisoning process can be described with a lumped model of hydrogen and CO adsorption, desorption, and electro-oxidation coupled with a current-voltage relationship for fuel cell performance. It was shown that while hydrogen dilution alone does not have an appreciable effect on cell polarization, in the presence of trace amounts of CO, hydrogen dilution amplifies the problem of CO poisoning. This is a result of the diluent reducing the partial pressure of reactants in the anode fed stream, thus retarding the already CO-impaired hydrogen adsorption onto the catalyst surface. In a diluted hydrogen stream, even low CO concentrations (i.e. 10 ppm), which are traditionally considered safe for PEM fuel cell operation, were found to be harmful to cell performance.     

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.     

PEM fuel cell Pt anode inhibition by carbon monoxide: Non-uniform behaviour of the cell caused by the finite hydrogen excess

Inhibition of platinum surfaces by carbon monoxide, in particular in polymer membrane electrolyte fuel cells (PEMFC) has been observed for decades by electrochemists. Significant effects have been observed in the hydrogen stream fed to the anode of the fuel cell with concentrations ranging from 1 to 100 ppm depending on the operating conditions e.g. temperature, pressure and excess in reacting gases. As a matter of fact, the gas composition and the surface coverage by CO and H₂ vary in the cell, because of the hydrogen consumption at the anode: this is to result to non-uniform distributions of electrode poisoning, current density, and overvoltage, from the inlet to the outlet of the cell. A simple 1D-model has been developed for prediction of the profiles of the above variables in the fuel cells, with the support of experimental data obtained with a 25 cm² PEMFC: interpretation of polarization curves and impedance spectra yielded the kinetic laws of the two electrode reactions, with both neat hydrogen and CO-containing hydrogen at ppm levels. Simulations show that for low excess in hydrogen – as for practical use of fuel cells – the coverage fractions of the various species can greatly vary in the cell, resulting in non-uniform distributions of current density in the cell and enhanced electrode poisoning near the cell outlet. In contrast working with very high hydrogen excess, as can be done at bench scale, leads to uniform behaviour of the cell, and far less visibility of the anode poisoning by carbon monoxide.     

Influence of temperature and relative humidity on performance and CO tolerance of PEM fuel cells with Nafion-Teflon-Zr(HPO4)2 higher temperature composite membranes

The carbon monoxide (CO) poisoning effect on carbon supported catalysts (Pt-Ru/C and Pt/C) in polymer electrolyte membrane (PEM) fuel cells has been investigated at higher temperatures (T > 100 °C) under different relative humidity (RH) conditions. To reduce the IR losses in higher temperature/lower relative humidity, Nafion^®-Teflon^®-Zr(HPO₄)₂ composite membranes were applied as the cell electrolytes. Fuel cell polarization investigation as well as CO stripping voltammetry measurements was carried out at three cell temperatures (80, 105 and 120 °C), with various inlet anode relative humidity (35%, 58% and 100%). CO concentrations in hydrogen varied from 10 ppm to 2%. The fuel cell performance loss due to CO poisoning was significantly alleviated at higher temperature/lower RH due to the lower CO adsorption coverage on the catalytic sites, in spite that the anode catalyst utilization was lower at such conditions due to higher ionic resistance in the electrode. Increasing the anode inlet relative humidity at the higher temperature also alleviated the fuel cell performance losses, which could be attributed to the combination effects of suppressing CO adsorption, increasing anode catalyst utilization and favoring OH_ads group generation for easier CO oxidation.     

Improved electrochemical CO removal via potential oscillations in serially connected PEM fuel cells with PtRu anodes

The polarization performance of two PEM fuel cells (with anode PtRu/C catalyst) connected either in parallel or serial, was compared to the performance of a single PEM fuel cell in galvanostatic operation using CO-free H₂ or 200 ppm CO-containing H₂ stream as anode feed at ambient temperature. Spontaneous potential oscillations were observed experimentally for the coupled configuration with two cells connected in serial or parallel using CO-containing H₂ feed at various current densities applied. The potential oscillations are ascribed by the dynamic CO adsorption and subsequent electrochemical CO oxidation on the anode. The measured anode outlet CO concentration was found to decrease with the order: single cell > parallel cells > serial cells at various current densities and anodic flow rates. The low anode outlet CO concentration (<10 ppm) at high current densities applied showed that CO in the anode feed was removed efficiently by the electrochemical CO oxidation occurring on the PtRu anode. The anode outlet CO concentration decreased as follows: a single cell > the parallel cells > the serial cells at broad range of current densities and anodic flow rates. The highest CO conversion and the highest average power output at equal hydrogen recovery degree were obtained with serially coupled fuel cells.     

操作条件对固体氧化物燃料电池阳极反应转变的影响

研究了不同电流密度下,甲烷浓度、反应温度对甲烷在SOFC中反应由部分氧化到完全氧化转变的规律;测量了不同电流密度下,阳极出口气体产生速率;确定了甲烷浓度和电池反应温度变化时甲烷电化学反应由部分氧化转变为完全氧化的电流密度门槛值,及该门槛值与甲烷浓度、电池操作温度的变化关系.结果说明甲烷开始发生完全氧化的电流密度门槛值与甲烷浓度成正比;甲烷浓度一定,温度升高,甲烷开始发生完全氧化的电流密度的门槛值也随之提高.     

SOFC中低浓度干甲烷在Ni/YSZ阳极上的反应

固体氧化物燃料电池(SOFC)趋向于直接使用甲烷天然气为燃料,确定甲烷在固体氧化物燃料电池阳极发生的化学与电化学反应非常重要.以Ni/YSZ为阳极、YSZ板做电解质、LSM为阴极,用涂浆法制作电解质支撑的电池,研究低浓度干甲烷在固体氧化物燃料电池中的反应.改变甲烷浓度、电池工作温度、电解质厚度,用在线色谱测量不同电流密度下,阳极出口气体产生速率.根据阳极出口气体产生速率变化,分析干甲烷在阳极的反应变化.通过氧消耗计算和转移电子数的分析,说明甲烷在电池阳极发生不同类型的反应.电流密度小时,甲烷发生部分氧化反应.电流密度大时,发生氢氧化和CO氧化,部分甲烷发生总反应为完全氧化的反应.部分甲烷发生完全氧化反应的同时,部分甲烷仍发生部分氧化反应,但其反应速率随电流密度增加逐渐降低.甲烷浓度和试验温度增加,甲烷开始发生完全氧化的电流密度增加.     

The effect of current density and temperature on the degradation of nickel cermet electrodes by carbon monoxide in solid oxide fuel cells

The oxidation of dry carbon monoxide (CO) in intermediate temperature solid oxide fuel cells (IT-SOFCs) has been studied using a three electrode assembly. Ni/CGO:CGO:LSCF/CGO three electrode pellet cells at 500, 550 and 600 °C were exposed to dry carbon monoxide for fixed periods of time, at open circuit and under load at 50 and 100 mA cm⁻², in an aggressive test designed to accelerate electrode degradation. It is shown that if the anode is kept under load during exposure to dry CO, degradation in anode performance can be minimised, and that under most conditions the anode showed significant irreversible degradation in performance after subsequent load cycling on dry H₂. Only at 500 °C and at 100 mA cm⁻² was the degradation in performance after operation on dry CO and subsequent load cycling on dry H₂ within the background degradation rates measured. Where anode performance was compromised, this appeared to be caused by a reduction in the exchange current density for hydrogen oxidation, and the relatively large degradation after load cycling on dry H₂ was primarily caused by an increase in the series resistance of the anode. It is suggested that this increase in series resistance is associated with the removal of carbon deposited in the non-electrochemically active region of the electrode during operation on dry CO, and that operation under load inhibits carbon deposition in the active region.     

Three-dimensional non-isothermal modeling of carbon monoxide poisoning in high temperature proton exchange membrane fuel cells with phosphoric acid doped polybenzimidazole membranes

The performance of proton exchange membrane fuel cell (PEMFC) degrades when carbon monoxide (CO) is present in the supplied fuel, which is referred to as CO poisoning. Even though the high temperature PEMFC (HT-PEMFC) with a typical operating temperature range from 100 °C to 200 °C features higher CO tolerance than the conventional PEMFC operating at lower than 100 °C, the performance degradation of HT-PEMFC is still significant with high CO concentrations (e.g. ?0.5% CO by volume at 130 °C) in the supplied fuel. In this study, a CO poisoning model is developed for HT-PEMFCs with phosphoric acid doped polybenzimidazole (PBI) membranes. The present three-dimensional non-isothermal model compares well with published experimental data at various operating temperatures and CO concentrations in the supplied fuel. It is found that the CO adsorption/desorption processes follow Langmuir kinetics in HT-PEMFCs instead of the well-known Temkin kinetics in conventional PEMFCs. The results indicate that a HT-PEMFC can operate with sufficiently good performance at 130 °C or higher with hydrogen gas produced by methanol reforming with selective oxidation process, and at 160 °C or higher even without the selective oxidation process. At high current densities, it is also observed that severe performance degradation due to CO poisoning only occurs if the volume averaged hydrogen coverage is lower than 0.1 in the anode catalyst layer (CL).     

The inclusion of Mo, Nb and Ta in Pt and PtRu carbon supported electrocatalysts in the quest for improved CO tolerant PEMFC anodes

The effect of the inclusion of Mo, Nb and Ta in Pt and PtRu carbon supported anode electrocatalysts on CO tolerance in proton exchange membrane fuel cells (PEMFC) has been investigated by cyclic voltammetry and fuel cell tests. CO stripping voltammetry on binary Pt_xM/C (M: Mo, Nb, Ta) reveals partial oxidation of the CO adlayer at low potential, with PtMo (4:1)/C exhibiting the lowest value. At 80 °C, the operating temperature of the fuel cell, CO oxidation was observed at potentials close to 0 V versus the reversible hydrogen electrode (RHE). No significant difference for CO electro-oxidation at the lower potential limit, compared to PtRu/C, was observed for PtRuM_y/C (M: Mo, Nb). Fuel cell tests demonstrated that while all the prepared catalysts exhibited enhanced performance compared to Pt/C, only the addition of a relatively small amount of Mo to PtRu results in an electrocatalyst with a higher activity, in the presence of carbon monoxide, to PtRu/C, the current catalyst of choice for PEM fuel cell applications.     

A mathematical model of polymer electrolyte fuel cell with anode CO kinetics

We develop a mathematical model of solid polymer electrolyte fuel cell with anode CO kinetics, which is essentially a model that marrying the work of Bernardi and Verbrugge (J. Electrochem. Soc. 139 (1992) 2477) with that of Springer et al. (J. Electrochem. Soc. 148 (2001) A11). Two cases of study were carried out. First, the water self-sufficiency of fuel cell operation was conducted under different current density, temperature, pressure differential across the membrane-electrode-assembly (MEA), hydraulic permeability and electro-kinetic permeability. Comparison of superficial water velocities in the MEA under the effect of different current density with those from Bernardi and Verbrugge was conducted. Results showed that, treating the catalyst layers as interfaces instead of regions as simplified by Bernardi and Verbrugge, would significantly underestimate the water velocities in the MEA and the error is particularly large at high current density operations. Second, the effect of CO poisoning of fuel cell was presented in terms on cell polarization. The prediction covered 0, 25, 50, 100 and 250 ppm of CO concentration in hydrogen feedstock and results were validated by experimental data obtained from Springer et al. The trends of anode polarization curve due to CO poisoning were explained.     

SOFC中不同浓度干甲烷在Ni-YSZ阳极上的反应

引言 天然气是适于固体氧化物燃料电池(SOFC)应用的燃料之一,天然气中主要成分是甲烷.甲烷通过全氧化或部分氧化[1-4]反应,在发电的同时,生成适于发电或其他用途的富含H2、CO的气体.     

Adsorption kinetics for carbon monoxide on platinum in hot phosphoric acid

The availability and activity of platinum electrocatalyst sites for oxidation of the hydrogen in reformed natural gas has been one of the problems associated with efficient utilization of the platinum-anode catalyst. The major anode catalyst poison is carbon monoxide and the mechanism of poisoning of the hydrogen reaction by carbon monoxide has been reported.The equilibrium adsorptions and the rates of adsorption of CO on platinum surfaces were studied at a series of p_co values between 0·01 and 0·10 atm in 96 per cent H₃PO₄ between 105 and 148°C. This range of partial pressures of CO is expected within an operating fuel cell.The adsorption isotherms are explicable in terms of single-site adsorption of the carbon monoxide molecule on the platinum surface atoms, causing a slow anion adsorption at the unpoisoned platinum sites. The equilibrium coverages for carbon monoxide on the platinum surfaces are independent of temperature in the range studied. Adsorption equations are used to describe the coverages of the platinum surface by carbon monoxide so that extrapolation of the data to both higher and lower carbon monoxide partial pressures gives reliable estimates of the resultant surface coverages.     

Effect of hydrogen partial pressure on a polymer electrolyte fuel cell performance

We first investigated the effect of partial pressure of hydrogen (H₂) on the performance of polymer electrolyte fuel cells (PEFCs) by controlling the ratio of hydrogen and nitrogen (N₂). The cell performance with Pt/C anode was significantly decreased with reduction of the partial pressure of H₂ in the presence of carbon monoxide (CO), while the performance variation was negligible in the absence of CO. Severe CO poisoning on Pt/C electrode at low partial pressure of H₂ might be attributed to the hindering effect by N₂ and CO. On the other hand, PtRu/C anode showed consistent power performance even at low partial pressure of H₂.     

Steam reforming of liquid hydrocarbon fuels for micro-fuel cells. Pre-reforming of model jet fuels over supported metal catalysts

The present work deals with pre-reforming of logistic hydrocarbon fuel (jet fuel) as a part of an integrated approach to developing an on-board fuel reformer for use in a micro-solid-oxide fuel cell system. The purpose of doing pre-reforming is to ensure carbon-free reformulation of JP-8 jet fuel into hydrogen and carbon monoxide for use in a micro-solid-oxide fuel cell. Several model jet fuels have been tested for the pre-reforming at low temperature (450–550 °C) in a lab-scale reforming reactor. Proper temperature control and pre-mixing of feed fuels and steam have been found to be important for the prevention of coke formation prior to pre-reforming. Both noble metal and base-metal catalysts have been prepared and tested. As compared with an Al₂O₃-supported Ni catalyst, supported Rh catalysts show not only high activity but also high resistance to deactivation due to carbon formation. Removal of residual Cl⁻ from Rh/CeO₂–Al₂O₃ improves the metal dispersion and the pre-reforming activity. The reformates from the current pre-reformer contain mainly CH₄, CO, H₂, in which CH₄ can be further converted to H₂ and CO by subsequent main-reforming.     

Components for PEM fuel cell systems using hydrogen and CO containing fuels

Proton exchange membrane fuel cells (PEMFC) show a significant performance drop in CO containing hydrogen as fuel gas in comparison to pure hydrogen. The lower performance is due to CO adsorption at the anode thus poisoning the hydrogen oxidation reaction. Two approaches to improve the cell performance are discussed. First, the use of improved electrocatalysts for the anode, such as PtRu alloys, can significantly enhance the CO tolerance. On the other hand, CO poisoning of the anode could be avoided by the use of non-electrochemical methods. For example, the addition of liquid hydrogen peroxide to the humidification water of the cell leads to the formation of active oxygen by decomposition of H₂O₂ and the oxidation of CO. In such a way a complete recovery of the CO free cell performance is achieved for H₂/100 ppm CO.     

Impact of carbon monoxide on PEFC catalyst carbon support degradation under current-cycled operating conditions

It is well known that, even at ppm levels, the presence of CO in a PEFC anode feed stream has a significant impact on the MEA performance. Numerous work on short-term CO impact on PEFC performance under steady-state current demands has been carried out. However, to the best of our knowledge, the impact of long-term (i.e., >600 h) CO contamination on intrinsic Pt and C support aging (Pt oxidation/dissolution/ripening, C oxidation, …) under current-cycled operating conditions has never been explored. In this paper, on the basis of a combined theoretical and experimental approach, we investigate the long-term CO effect on PEFC performance and degradation. Firstly, on the basis of our previously published PEFC materials degradation models, we suggest that anodic CO poisoning could be used to mitigate the cathodic carbon catalyst-support corrosion phenomena and thus to enhance the MEA durability. Secondly, endurance experiments are performed on single fuel cells with current-cycled protocols representative of transport applications. The impact of CO on electrochemical transient response shows a reasonable agreement with simulated behaviors, and it is experimentally demonstrated that the impact of CO on the cell potential degradation rate is strongly dependent on the current-cycle mode.     

Electrochemical impedance spectra of solid-oxide fuel cells and polymer membrane fuel cells

Electrochemical impedance spectroscopy (EIS) is a very useful method for the characterization of fuel cells. The anode and cathode transfer functions have been determined independently without a reference electrode using symmetric gas supply of hydrogen or oxygen on both electrodes of the fuel cell at open circuit potential (OCP). EIS are given for both polymer electrolyte fuel cells (PEFC) and solid oxide fuel cells (SOFC) at current densities up to 0.76 A cm⁻² (PEFC) and 0.22 A cm⁻² (SOFC). With increasing current density the PEFC-impedance decreases significantly in the low frequency range reaching a minimum at 0.4 A cm⁻². At even higher current densities an increasing contribution of water diffusion is observed: the cell impedance increases again. From EIS of SOFC a finite diffusion behavior is observed even at OCP, depending on water partial pressure of the anodic gas supply. This additional element reflects the influence of water partial pressure on the cell potential. The simulation of the measured EIS with an equivalent circuit enables the calculation of the individual voltage losses in the fuel cell.     

Overpotential Behavior of Carbon Monoxide Fuel in a Molten Carbonate Fuel Cell

The overpotential of carbon monoxide (CO) fuel was analyzed with a 100‐cm² class molten carbonate fuel cell. The overpotential at the anode was measured using the steady state polarization, inert gas step addition, and reactant gas addition methods. Then, the overpotential was compared between normal hydrogen fuel (H₂:CO₂:H₂O = 0.69:0.17:0.14 atm, inlet composition) and CO fuels (CO:CO₂:H₂O = 0.5:0.5:0 atm and 0.43:0.43:0.14 atm, inlet compositions). The CO fuel without H₂O showed a much greater overpotential at 150 mA cm^–2 than the CO fuel with H₂O. This implies that the water‐gas‐shift reaction prevails at the anode and humidification of CO fuel is an efficient way to reduce anodic overpotential. The anodic overpotential with CO:CO₂:H₂O = 0.43:0.43:0.14 atm was about 73% of that of the H₂ fuel at 150 mA cm^–2. The anode showed gas‐phase mass‐transfer limitations with CO fuels.