A review of PEM hydrogen fuel cell contamination: Impacts,mechanisms, and mitigation

This paper reviewed over 150 articles on the subject of the effect of contamination on PEM fuel cell. The contaminants included were fuel impurities (CO, CO₂, H₂S, and NH₃); air pollutants (NO_x, SO_x, CO, and CO₂); and cationic ions Fe³⁺ and Cu²⁺ resulting from the corrosion of fuel cell stack system components. It was found that even trace amounts of impurities present in either fuel or air streams or fuel cell system components could severely poison the anode, membrane, and cathode, particularly at low-temperature operation, which resulted in dramatic performance drop. Significant progress has been made in identifying fuel cell contamination sources and understanding the effect of contaminants on performance through experimental, theoretical/modeling, and methodological approaches. Contamination affects three major elements of fuel cell performance: electrode kinetics, conductivity, and mass transfer.     

Effect of ammonium ion distribution on Nafion conductivity

Nafion^® conductivity in a proton exchange membrane fuel cell (PEMFC) with the fuel stream containing ammonia is mainly affected by the ammonium ion composition and operating conditions. In this study, the effect of ammonium ion distribution on Nafion conductivity was investigated for the first time. The conductivities of two kinds of contaminated membranes having uniform and non-uniform ammonium ion distributions were studied. To simulate a membrane with a well-defined ammonium ion concentration profile, three individual Nafion membranes containing known amounts of ammonium ions were physically stacked together. The uniform and non-uniform cases represented membranes having three layers with the same yN⁺H₄ or step changes in concentration, respectively. Under fuel cell operations, the conductivities of non-uniformly poisoned membranes were ca. 1.07-1.86 times larger than those of uniformly poisoned membranes, depending on humidity, contamination level, and ammonium ion distribution. Consequently, the performance prediction of a cationic-poisoned PEMFC needs to consider any concentration gradients that may exist in MEA. The liquid-phase conductivities of composite membranes were also studied and the results show that conductivity measurements performed in deionized water are not representative of what exists under fuel cell conditions due to rapid redistribution of ions in the Nafion via the liquid phase.     

Influence of ammonia on the conductivity of Nafion membranes

The effect of NH₃ and NH₄⁺ poisoning on the conductivity of Nafion membranes was investigated via electrochemical impedance spectroscopy. The conductivities of membranes prepared with different NH₄⁺ compositions were measured in deionized water at room temperature and compared to those at 80 °C in a gas phase for various relative humidities. The liquid-phase conductivity decreased linearly with an increase in the NH₄⁺ composition in the membrane (y_NH4⁺), with that of the NH₄⁺-form having a conductivity 25% that of the H⁺-form. The gas-phase conductivity of the NH₄⁺-form, on the other hand, declined by 66–98% relative to the H⁺-form depending on humidity. The conductivities of fresh membranes in the presence of gas-phase NH₃ at different humidities were also studied. The conductivity decreased with time-on-stream and reached the same conductivity at a given humidity regardless of the NH₃ concentration, but the time to reach steady-state varied with NH₃ concentration. The y_NH4⁺ at steady-state conductivity was equivalent for all the NH₃ concentrations studied. The kinetics of conductivity decrease was slower at higher humidities. The humidity and y_NH4⁺ appear to have a concerted effect on the conductivity. The quantitative conductivity data under practical fuel cell conditions should be useful for future fuel cell modeling.     

Steady state and dynamic performance of proton exchange membrane fuel cells (PEMFCs) under various operating conditions and load changes

The steady-state performance and transient response for H₂/air polymer electrolyte membrane (PEM) fuel cells are investigated in both single fuel cell and stack configurations under a variety of loading cycles and operating conditions. Detailed experimental parameters are controlled and measured under widely varying operating conditions. In addition to polarization curves, feed gas flow rates, temperatures, pressure drop, and relative humidity are measured. Performance of fuel cells was studied using steady-state polarization curves, transient I–V response and electrochemical impedance spectroscopy (EIS) techniques. Different feed gas humidity, operating temperature, feed gas stoichiometry, air pressure, fuel cell size and gas flow patterns were found to affect both the steady state and dynamic response of the fuel cells. It was found that the humidity of cathode inlet gas had a significant effect on fuel cell performance. The experimental results showed that a decrease in the cathode humidity has a detrimental effect on fuel cell steady state and dynamic performance. Temperature was also found to have a significant effect on the fuel cell performance through its effect on membrane conductivity and water transport in the gas diffusion layer (GDL) and catalyst layer. The polarization curves of the fuel cell at different operating temperatures showed that fuel cell performance was improved with increasing temperature from 65 to 75 °C. The air stoichiometric flow rate also influenced the performance of the fuel cell directly by supplying oxygen and indirectly by influencing the humidity of the membrane and water flooding in cathode side. The fuel cell steady state and dynamic performance also improved as the operating pressure was increased from 1 to 4 atm. Based on the experimental results, both the steady state and dynamic response of the fuel cells (stack) were analyzed. These experimental data will provide a baseline for validation of fuel cell models.     

Proton-conducting fuel cells operating on hydrogen,ammonia and hydrazine at intermediate temperatures

Anode-supported proton-conducting fuel cell with BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY) electrolyte and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) cathode was fabricated. Peak power densities of ∼420 and 135 mW/cm² were achieved, respectively, at 700 and 450 °C for a cell with 35 μm thick electrolyte operating on hydrogen fuel. The endothermic nature of the ammonia decomposition reaction, however, resulted in cell temperature 30–65 °C lower than the furnace when operating on ammonia. Accounting the cooling effect, comparable power density was achieved for the cell operating on ammonia and hydrogen at high temperature. At reduced temperature, the cell demonstrated worse performance when operating on ammonia than on hydrogen due to the poor activity of the anode towards NH₃ catalytic decomposition. By applying on-line catalytic decomposition products of N₂H₄ as the fuel, similar cell performance to that with NH₃ fuel was also observed.     

Characteristic studies of a PBI/H3PO4 high temperature membrane PEMFC under simulated reformate gases

A high temperature proton exchange membrane fuel cell is considered a solution to improve the cell performance under CO-contained hydrogen and to simplify the gas purification process of a reformate fuel cell system. In this study, polybenzimidazole-based phosphoric acid-doped fuel cells are studied under simulated reformate gases of different H₂, N₂ and CO concentrations. The experimental results show that the dilution effect of N₂ has a minor impact on the cell performance in absence of CO. However, the CO poisoning increases the charge transfer resistance and leads to a substantial performance drop. This work also reveals that increasing the operating temperature can effectively improve the CO tolerance by suppressing the Pt–CO binding reaction. In addition, the CO poisoning effect becomes more significant in diluted H₂. As a result, the CO concentration should be maintained lower than a critical level to prevent a high CO coverage on the catalyst which leads to a noteworthy voltage shut-down, especially in highly diluted H₂.     

Influence of ammonia on membrane-electrode assemblies in polymer electrolyte fuel cells

An experimental investigation of contamination of polymer electrolyte fuel cell (PEFC) membranes and catalyst layers with ammonia (NH₃) is reported. Cyclic voltammetry (CV) scans and electrochemical impedance spectroscopy (EIS) analyses show that trace amounts of ammonia can significantly contaminate both the polymer electrolyte membrane (PEM) and the catalyst layers. The results show that the catalyst layer contamination can be reversed under certain conditions, while the membrane recovery tends to be much slower, and permanent effects of ammonia contamination is observed. Mechanisms of contamination of the polymer electrolyte and catalyst layers, and performance degradation of the PEFC are also postulated.     

Numerical modelling and comparative analysis of direct ammonia fuelled protonic and oxygen- ion conducting tubular solid oxide fuel cell

The main emphasis of this work is developing a 3D numerical model and investigating the performance characteristic of a direct ammonia fuelled protonic-conducting tubular solid oxide fuel cell (NH₃-T–SOFC–H) in comparison with the corresponding hydrogen-fuelled one and direct ammonia feed oxygen -ion conducting tubular solid oxide fuel cell (NH₃-T–SOFC–O) under the same operating parameters and geometrical shape. The findings revealed that NH₃-T–SOFC–H has outstanding performance over T–SOFC–O counterparts at intermediate temperature (973 K) when operated under similar working conditions and geometrical designs. On the other hand the NH₃-T–SOFC–O is promising for higher operating temperatures. The outcomes of the study are also confirmed that the power performance of NH₃-AS-T–SOFC–O is better than the other supports of both electrolytes when the anode electrode is constructed at the outside portion of the tubular cell. Yet, the other remarkable result found in this study is that NH₃– CS- T–SOFC–O has outstanding performance compared to all supports of both electrolytes when the fuel electrode is built in the inner portion of the tube. In addition, the finding indicates that the power performance of ammonia-fuelled tubular cells is strongly influenced by the anode position, operating temperatures, and pressures in both electrolytes yet the effect of cell temperature is more influential in the protonic-conducting cell. It is also observed that the performance of ES-T-SOFC is lower than AS- and CS-T-SOFC in both electrolytes and anode positions.     

Performance of a poly(2,5-benzimidazole)-based polymer electrolyte membrane fuel cell

The performance of an ABPBI-based High Temperature H₂/O₂ PEMFC system was studied under different experimental conditions. Increasing the temperature from 130 to 170 °C improved the cell performance, even though further increase was not beneficial for the system. Humidification of the H₂ stream ameliorated this behaviour, even though operating above 170 °C is not advisable in terms of cell performance. A significant electrolyte dehydration seems to negatively affect the fuel cell performance, especially in the case of the anode. In the presence of 2% vol. CO in the H₂ stream, the temperature exerted a positive effect on the cell performance, reducing the strong adsorption of this poison on the platinum sites. Moreover, humidification of the H₂ + CO stream increased the maximum power densities of the cell, further alleviating the CO poisoning effects. Actual CO–O₂ fuel cell results confirmed the significant beneficial effect of the relative humidity on the kinetics of the CO oxidation process.     

The poisoning level of Pt/C catalysts used in PEM fuel cells by the hydrogen feed gas impurities: The bonding strength

Proton exchange membrane fuel cells (PEMFCs) most likely will use reformed fuel as the primary source for the anode feed despite it nearly always contains carbon monoxide or ammonia. In this paper, the microcalorimetry technique was employed to study and compare the poisoning effect of pollutants such as CO and NH₃ on three commercial carbon-supported platinum catalysts with high Pt loading, aimed to be used in PEMFCs applications. Microcalorimetric measurements were performed at 80 °C and the results were compared with those obtained from hydrogen adsorption in similar conditions. All the catalysts exhibited significantly higher differential heats of CO adsorption in comparison with NH₃ and hydrogen adsorption, indicating that carbon monoxide will be primarily adsorbed in case of co-adsorption, while ammonia and hydrogen will compete in the adsorption process on the same type of active sites. The irreversibly (chemically) amount of adsorbed molecules on Pt/C surfaces decreases in the order: CO >> NH₃ > H₂.     

Experimental investigation of CO tolerance in high temperature PEM fuel cells

In the present work, the effect of operating a high temperature proton exchange membrane fuel cell (HT-PEMFC) with different reactant gases has been investigated throughout performance tests. Also, the effects of temperature on the performance of a HT-PEMFC were analyzed at varying temperatures, ranging from 140 °C to 200 °C. Increasing the operating temperature of the cell increases the performance of the HT-PEMFC. The optimum operating temperature was determined to be 160 °C due to the deformations occurring in the cell components at high working temperatures. To investigate the effects of CO on the performance of HT-PEMFC, the CO concentration ranged from 1 to 5 vol %. The current density at 0.6 V decreases from 0.33 A/cm² for H₂ to 0.31 A/cm² for H₂ containing 1 vol % CO, to 0.29 A/cm² for 3 vol % CO, and 0.25 A/cm² for 5 vol % CO, respectively. The experimental results show that the presence of 25 vol % CO₂ or N₂ has only a dilution effect and therefore, there is a minor impact on the HT-PEMFC performance. However, the addition of CO to H₂/N₂ or H₂/CO₂ mixtures increased the performance loss. After long-term performance test for 500 h, the observed voltage drop at constant current density was obtained as ～14.8% for H₂/CO₂/CO (75/22/3) mixture. The overall results suggest that the anode side gas mixture with up to 5 vol % CO can be supplied to the HT-PEMFC stack directly from the reformer.     

Effect of cations (Na, Ca, Fe) on the conductivity of a Nafion membrane

It is known that trace amounts of cations have a detrimental effect on the liquid-phase conductivity of perfluorosulfonated membranes at room temperature. However, the conditions used were very different from typical fuel cell conditions. Recent research has shown the impact of conductivity measurement conditions on NH₄⁺ contaminated membranes. In this study, the impact of nonproton-containing cations (Mⁿ⁺ = Na⁺, Ca²⁺, and Fe³⁺) on Nafion membrane (N-211) conductivity was investigated both in deionized (DI) water at room temperature (∼25 °C) and in the gas phase at 80 °C under conditions similar to in a PEMFC. These conductivities were compared with those of Nafion membranes contaminated with NH₄⁺ ions. Under the same conditions, the conductivity of a metal cationic-contaminated membrane having the same proton composition (yH⁺m) was similar, but slightly lower than that of an NH₄⁺-contaminated membrane. The conductivity in the purely H⁺-form of N-211 was more than 12 times greater than the Mⁿ⁺-form form at 25 °C in DI water. At 80 °C, the gas-phase conductivity was 6 times and 125 times greater at 100%RH and 30%RH, respectively. The quantitative results for conductivity and activation energy of contaminated membranes under typical fuel cell conditions are reported here for the first time.     

Recalibration of carbon-free NH3/H2 fuel blend process: Qatar's roadmap for blue ammonia

Due to growing concerns about carbon emissions, using zero-carbon fuels has become an interesting alternative to overcome this problem. The NH₃(70%)-H₂(30%) fuel blend is an innovative fuel example that has the potential to replace conventional hydrocarbon fuels. Studies on the NH₃(70%)-H₂(30%) fuel blend have shown its superior combustion performance and its effect on enhancing cycle efficiency compared to other compositions of the NH₃–H₂ blends. However, without calibrating ammonia plants and simply mixing portions of the produced pure ammonia to hydrogen at the desired molar fraction essentially requires coupling ammonia plants with other hydrogen-producing plants, leading to potential difficulties in commercializing the unused (as fuel in the NH₃–H₂/air gas turbines) hydrogen portions from the hydrogen-producing plan. Therefore, in this paper, as an attempt to utilize the existing ammonia production infrastructure and facility without acquiring major changes that could lead to resisting the adoption of the NH₃(70%)-H₂(30%) fuel blend, the independent parameters of a conventional ammonia plant have been calibrated, and the reactors have been sized to provide a continuous supply of the NH₃(70%)-H₂(30%) fuel blend with the exact molar fraction to run a power plant. Calibrating of the ammonia plant has been performed using an ASPEN PLUS model.     

An improved electrochemical model for the NH3 fed proton conducting solid oxide fuel cells at intermediate temperatures

An improved electrochemical model is developed to study the ammonia fed solid oxide fuel cell based on proton conducting electrolyte (SOFC-H). Including the chemical reaction kinetics of NH₃ catalytic thermal decomposition, the present model can be used to predict the performance of the NH₃ fed SOFC-H at an intermediate temperature (i.e. 773 K). Comparison between the simulation results using the present model and experimental data from literature validates the accuracy of this model. Parametrical analyses reveal that at a high operating temperature (i.e. 1073 K), the NH₃ fuel is completely decomposed to H₂ and N₂ within a very thin layer (30 μm) near the anode surface of an SOFC-H. It is also found that operating the NH₃ fed SOFC-H at an intermediate temperature of 773 K is feasible due to sufficiently high rate of NH₃ decomposition. However, further decreasing the temperature to 673 K is not recommended as less than 10% NH₃ fuel can be decomposed to H₂ and N₂ in the SOFC-H. The effects of current density and electrode microstructure on the performance of the NH₃ fed SOFC-H are also studied. It is found that increasing electrode porosity and pore size is beneficial to increase the partial pressure of H₂ at the anode–electrolyte interface. The model developed in this paper can be extended to 2D or 3D models to study practical tubular or planar SOFCs.     

Effects of temperature and humidity on the cell performance and resistance of a phosphoric acid doped polybenzimidazole fuel cell

Performance and electrochemical impedance spectroscopy (EIS) tests were performed at different temperatures and humidity levels to understand the effects of temperature and humidity on the performance and resistance of a PBI/H₃PO₄ fuel cell.The results of the performance tests indicated that increasing the temperature significantly improved the cell performance. In contrast, no improvement was observed when the gas humidity was increased. On the other hand, the EIS results showed that the membrane resistance was reduced for elevated temperatures. This development can be interpreted by the increase in membrane conductivity, as reflected by the Arrhenius equation. As the formation of H₄P₂O₇ and the self-dehydration of H₃PO₄ start around 130-140 °C, in PBI, they increase the membrane resistance at temperatures that are higher than 130 °C. In addition, the membrane resistance was reduced for elevated gas humidity levels. This is because an increase in humidity leads to an increase of the membrane hydration level.The resistance of the catalyst kinetics mainly contributes to the charge transfer resistance. However, under certain conditions, the interfacial charge transfer resistance is also important. It was concluded that the gas diffusion is the main contributor to the mass transfer resistance under dry conditions while it is the gas concentration under humid conditions.     

Comparison of the combustion and emission characteristics of NH3/NH4NO2 and NH3/H2 in a two-stroke low speed marine engine

As a marine engine fuel of great concern, ammonia needs to be mixed with another high reactive fuel to improve its combustion performance. In this work, the combustion performance of NH₃/NH₄NO₂ and NH₃/H₂ was compared under different boundary conditions (excess air coefficient, initial temperature, pressure and mixing ratio). The numerical simulation of compression combustion is carried out under different power loads. The addition of ammonium nitrite decreases the ignition requirement of ammonia and shortens the ignition delay time of the mixture fuel. The boundary conditions of compression ignition can be reduced by mixing hydrogen and mixing ammonium nitrite, but it is not enough to achieve compression ignition under NH₃/H₂ mode. The addition of 30% ammonium nitrite can reduce the intake temperature to 300–360 K, which makes the compression ignition of the mixed fuel feasible. Meanwhile, in order to reduce the high in-cylinder combustion pressure and improve the combustion performance of the mixed fuel, the fuel injection strategy was proposed to achieve constant combustion pressure of 30 MPa under the premise of less power loss, which is a potential solution for the combustion of ammonia fuel.     

PEMFC contamination model: Foreign cation exchange with ionomer protons

A generic, transient fuel cell ohmic loss mathematical model was developed for the case of contaminants that ion exchange with ionomer protons. The model was derived using step changes in contaminant concentration, constant operating conditions and foreign cation transport via liquid water droplets. In addition, the effect of ionomer cations redistribution within the ionomer on thermodynamic, kinetic and mass transport losses and migration were neglected. Thus, a simpler, ideal, ohmic loss case is defined and is applicable to uncharged contaminant species and gas phase contaminants. The closed form solutions were validated using contamination data from a membrane exposed to NH₃. The model needs to be validated against contamination and recovery data sets including an NH₄⁺ contaminated membrane exposed to a water stream. A method is proposed to determine model parameters and relies on the prior knowledge of the initial ionomer resistivity. The model expands the number of previously derived cases. Most models in this inventory, derived with the assumption that the reactant is absent, lead to different dimensionless current vs. time behaviors similar to a fingerprint. These model characteristics facilitate contaminant mechanism identification. Separation between membrane and catalyst (electroinactive contaminant) contamination is conceivably possible using additional indicative cell resistance measurements. Contamination is predicted to be significantly more severe under low relative humidity conditions.     

Investigation of the temperature‐related performance of proton exchange membrane fuel cell stacks in the presence of CO

H₂ is generally used as the fuel in proton exchange membrane fuel cells (PEMFCs). However, H₂ produced from reformate gas usually contains a trace of CO, which may severely affect the fuel cell performance. With the adoption of domestic short side chain, low equivalent weight perfluorosulphonic acid (PFSA) membrane, a 100 W stack is built and evaluated at elevated temperature of 95 °C for the purpose of improving its CO tolerance. The stack is operated with 5 ppm, 10 ppm and 20 ppm CO/H₂, respectively; better performance is obtained as expected. Furthermore, a 5 kW PEMFC stack is prepared with home‐made Ir–V/C and Pt/C as anode catalysts for the membrane electrode assemblies to compare their CO tolerance. Physical and electrochemical characterizations, such as transmission electron microscope and linear scan voltammogram are employed for catalyst investigation. The results demonstrate that the employment of domestic PFSA membrane enables the stack to be operated at 95 °C, which can improve the CO tolerance of all the anode catalysts. In addition, the effect of CO on cell polarization is insignificant at lower current densities. Under the same operating conditions, cells with Ir–V/C catalyst show better CO tolerance. Copyright © 2013 John Wiley & Sons, Ltd.     

Pore-scale simulation of coupled multiple physicochemical thermal processes in micro reactor for hydrogen production using lattice Boltzmann method

A general numerical scheme based on the lattice Boltzmann method (LBM) is established to investigate coupled multiple physicochemical thermal processes at the pore-scale, in which several sets of distribution functions are introduced to simulate fluid flow, mass transport, heat transfer and chemical reaction. Interactions among these processes are also considered. The scheme is then employed to study the reactive transport in a posted micro reactor. Specially, ammonia (NH₃) decomposition, which can generate hydrogen (H₂) for fuel of proton exchange membrane fuel cells (PEMFCs), is considered where the endothermic decomposition reaction takes place at the surface of posts covered with catalysts. Simulation results show that pore-scale phenomena are well captured and the coupled processes are clearly predicted. Effects of several operating and geometrical conditions including NH₃ flow rate, operating temperature, post size, post insert position, post orientation, post arrangement and post orientation on the coupled physicochemical thermal processes are assessed in terms of NH₃ conversion, temperature uniformity, H₂ flow rate and subsequent current density generated in PEMFC.     

Performance of a poly(2,5-benzimidazole) membrane based high temperature PEM fuel cell in the presence of carbon monoxide

The performance of a poly(2,5-benzimidazole) (ABPBI) membrane based high temperature PEM fuel cell in presence of carbon monoxide, at various temperatures is reported here. The ABPBI was synthesized by polymerization of 3,4-diaminobenzoic acid in a polymerization medium containing methanesulfonic acid (CH₃SO₃H) and phosphorous pentoxide (P₂O₅). The ABPBI membranes were characterized by fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). A maximum conductivity of 0.026 S cm⁻¹ at 180 °C was obtained for the membrane doped with 1.2 molecules of phosphoric acid (H₃PO₄) per polymer repeat unit. Fuel cell performance was evaluated using dry hydrogen/oxygen gases and was comparable with that reported in the literature. Performance of a single cell at different temperatures was studied with 0.48 and 1.0 vol.% of CO in the hydrogen fuel. The studies lead to the conclusion that CO poisoning is not a serious problem above 170 °C. Performance of the fuel cell operating at 210 °C is not at all affected by 1.0 vol.% of CO in the hydrogen feed.