Transient analysis of alkaline anion exchange membrane fuel cell anode

Alkaline anion exchange membrane (AAEM) fuel cell has attracted increasing attention in recent years due to its several outstanding advantages over proton exchange membrane (PEM) fuel cell such as fast electrochemical kinetics and friendly alkaline environment for catalysts. In this study, a three-dimensional (3D) half-cell transient model is developed to study the dynamic characteristics of AAEM fuel cell under different step changes of operating conditions. It is found that the current density has significant effects on the distribution of liquid water, while the anode stoichiometric ratio effect is insignificant. More time is needed to reach a steady state when the current density decreases rather than increases, and the similar phenomenon also occurs when the operating temperature decreases rather than increases, however, this effect within a low temperature range becomes insignificant. Moreover, the overshoot and undershoot of water diffusion through membrane can also be observed with the step change of the anode stoichiometric ratio and anode inlet relative humidity. The model prediction also has reasonable agreement with published experimental data. The dynamic behaviors observed in this study are of significant importance to the development of AAEM fuel cells for portable and automotive applications.     

Three-dimensional multiphase modeling of alkaline anion exchange membrane fuel cell

Alkaline anion exchange membrane (AAEM) fuel cell is becoming more attractive because of its outstanding merits, such as fast electrochemical kinetics and low dependence on non-precious catalyst. In this study, a three-dimensional multiphase non-isothermal AAEM fuel cell model is developed. The modeling results show that the performance is improved with more anode humidification, but the improvement becomes less significant at higher humidification levels. The humidification level of anode can change the water removal mechanisms: at partial humidification, water is removed as vapor; and for full humidification, water is removed as liquid. Cathode humidification is even more critical than anode. Liquid water supply in cathode has a positive effect on performance, especially at high current densities. With more liquid water supply in cathode, liquid water starts moving from channel to CL, rather than being removed from CL. Liquid water supply in cathode is needed to balance the water amounts in anode and cathode. Decreasing the membrane thickness generally improves the cell performance, and the improvement is even enhanced with thinner membranes, due to the faster water diffusion between anode and cathode, which reduces the mass transport losses.     

Study of operating conditions and cell design on the performance of alkaline anion exchange membrane based direct methanol fuel cells

Direct methanol fuel cells using an alkaline anion exchange membrane (AAEM) were prepared, studied, and optimized. The effects of fuel composition and electrode materials were investigated. Membrane electrode assemblies fabricated with Tokuyama^® AAEM and commercial noble metal catalysts achieved peak power densities between 25 and 168 mW cm⁻² depending on the operating temperature, fuel composition, and electrode materials used. Good electrode wettability at the anode was found to be very important for achieving high power densities. The performance of the best AAEM cells was comparable to Nafion^®-based cells under similar conditions. Factors limiting the performance of AAEM MEAs were found to be different from those of Nafion^® MEAs. Improved electrode kinetics for methanol oxidation in alkaline electrolyte at Pt-Ru are apparent at low current densities. At high current densities, rapid CO₂ production converts the hydroxide anions, necessary for methanol oxidation, to bicarbonate and carbonate: consequently, the membrane and interfacial conductivity are drastically reduced. These phenomena necessitate the use of aqueous potassium hydroxide and wettable electrode materials for efficient hydroxide supply to the anode. However, aqueous hydroxide is not needed at the cathode. Compared to AAEM-based fuel cells, methanol fuel cells based on proton-conducting Nafion^® retain better performance at high current densities by providing the benefit of carbon dioxide rejection.     

Water management in an alkaline fuel cell

Alkaline fuel cells are low temperature fuel cells for which stationary applications, like cogeneration in buildings, are a promising market. To guarantee a long life, water and thermal management has to be controlled in a careful way. To understand the water, alkali and thermal flows, a model for an alkaline fuel cell module is developed using a control volume approach. Special attention is given to the physical flow of hydrogen, water and air in the system and the diffusion laws are used to gain insight in the water management. The model is validated on the prediction of the electrical performance and thermal behaviour. The positive impact of temperature on fuel cell performance is shown. New in this model is the inclusion of the water management, for which an extra validation is performed. The model shows that a minimum temperature has to be reached to maintain the electrolyte concentration. Increasing temperature for better performance without reducing the electrolyte concentration is possible with humidified hot air.     

A polytetrafluoroethylene-quaternary 1,4-diazabicyclo-[2.2.2]-octane polysulfone composite membrane for alkaline anion exchange membrane fuel cells

The quaternary 1,4-diazabicyclo-[2.2.2]-octane (DABCO) polysulfone (QDPSU) was synthesised. A thin (30 μm) composite membrane based on polytetrafluoroethylene (PTFE) and QDPSU was obtained by impregnation method of QDPSU solution in PTFE support. SEM images revealed a dense and homogenous structure of PTFE-QDPSU membrane. The PTFE-QDPSU composite membrane showed good mechanical strength (a 32 MPa maximum load), and a water uptake of 61 ± 3% and a 17 ± 2% swelling degree. An ionic conductivity of 0.051 S cm⁻¹ was achieved at 50 °C and 100% RH. Preliminary data of a single MEA gave power outputs of 146 and 103 mW cm⁻² with oxygen and air respectively.     

Effect of water distribution in gas diffusion layer on proton exchange membrane fuel cell performance

Water management of proton exchange membrane fuel cells remains a prominent issue in research concerning fuel cells. In this study, the gas diffusion layer (GDL) of a fuel cell is partially treated with a hydrophobic agent, and the effect of GDL hydrophobicity on the water distribution in the fuel cell is examined. First, the effect of the position of the cathode GDL hydrophobic area relative to the channel on the fuel cell performance is investigated. Then, the water distribution in the fuel cell cathode GDL is observed using X-ray imaging. The experimental results indicate that when the hybrid GDL's hydrophobic area lies on the channel, water tends to accumulate under the rib, and the water content in the channel is low; this improves the fuel cell performance. When the hydrophobic area is under the rib, the water distribution is more uniform, but the performance deteriorates.     

Direct ethanol fuel cells using an anion exchange membrane

Direct ethanol fuel cells (DEFCs) with a PtRu anode and a Pt cathode were prepared using an anion exchange membrane (AEM) as an electrolyte instead of a cation exchange membrane (CEM), as in conventional polymer electrolyte fuel cells. The maximum power density of DEFCs significantly increased from 6 mW cm⁻² to 58 mW cm⁻² at room temperature and atmospheric pressure when the electrolyte membrane was changed from CEM to AEM. The anode and cathode polarization curves showed a decrease in the anode potential and an increase in the cathode potential for AEM-type DEFCs compared to CEM-type. This suggests that AEM-type DEFCs have superior catalytic activity toward both ethanol oxidation and oxygen reduction in alkaline medium than in acidic medium. The product species from the exhausted liquid from DEFCs operated at a constant current density were identified by enzymatic analysis. The main product was confirmed to be acetic acid in AEM-type, while both acetaldehyde and acetic acid were detected in 1:1 ratio in CEM-type. The anodic reaction of AEM-type DEFCs can be estimated to be the oxidation of ethanol to acetic acid via a four-electron process under these experimental conditions.     

Water transport characteristics in the gas diffusion media of proton exchange membrane fuel cell - Role of the microporous layer

Water transport through the gas diffusion media of a proton exchange membrane fuel cell (PEMFC) was investigated with a focus on the role of the microporous layer (MPL) coated on the cathode gas diffusion layer (GDL). The capillary pressure of the MPL and GDL, which plays a significant role in water transport, is derived as a function of liquid saturation using a pore size distribution (PSD) model. PSD functions are derived with parameters that are determined by fitting to the measured total PSD data. Computed relations between capillary pressure and liquid saturation for a GDL and a double-layered GDL (GDL + MPL) show good agreement with the experimental data and proposed empirical functions. To investigate the role of the MPL, the relationship between the water withdrawal pressure and liquid saturation are derived for a double-layered GDL. Water transport rates and cell voltages were obtained for various feed gas humidity using a two-dimensional cell model, and are compared with the experimental results. The calculated results for the net drag with application of the capillary pressure derived from the PSD model show good agreement with the experimental values. Furthermore, the results show that the effect of the MPL on the cell output voltage is significant in the range of high humidity operation.     

Nature inspired flow field designs for proton exchange membrane fuel cell

Nature inspired flow field designs for proton exchange membrane fuel cells (PEMFCs) are a relatively recent development in the technology evolution. These novel designs have the potential to show dramatic performance improvements by effective distribution of reactant gases without water flooding. Optimization of a flow field requires balancing gas distribution, water management, electron transport, pressure drop and manufacturing simplicity. Computational fluid dynamics (CFD) simulation studies are a useful tool for evaluating nature inspired flow field designs; however, the predictions should be used with caution until validated by an experimental study. Nature inspired flow field designs can be generated using formal mathematical algorithms or by making heuristic modifications to existing natural structures. This paper reviews the current state of nature inspired PEMFC flow field designs and discusses the challenges in evaluating these designs.     

Review on water management methods for proton exchange membrane fuel cells

Control of water content of proton exchange membrane fuel cells (PEMFCs) within a reasonable rangeis a question worthy of study. This paper addresses questions of water transport, water fault, and water management methods in a PEMFC. Both an excess (overflow) or lack (dehydration) of water in a fuel cell may affect the performance and the service life. Herein, we describe in detail the effects of water content on the cathode, anode, gas diffusion layer (GDL), catalyst layer (CL) and flow channel. Monitoring the flow and accumulation of water directly in the PEMFC is the most effective approach to determine which of the two scenarios, overflow or dehydration, occurs. The water transport can be effectively investigated in a transparent fuel cell, using neutron scanning, nuclear magnetic resonance, and X-ray irradiation. Regarding the PEMFC water management, this paper reviews some current methods, such as improvement of the flow field structure, changing hydrophilic materials, and optimizing control systems.     

Transient behavior of water generation in a proton exchange membrane fuel cell

The effect of water generation on the performance of proton exchange membrane fuel cell (PEMFC) was investigated by using a periodical linear sweep method. Three different kinds of I–V curves were obtained, which reflected different amount of water uptake in the fuel cell. The maximum water uptake that could avoid flooding in the fuel cell and the hysteresis of water diffusion were also discussed. Quantitative analysis of water uptake and water transport phenomena in this study were conducted both experimentally and theoretically. Results showed that the water uptake capacity for the fuel cell under no severe flooding was 27.837 mg cm⁻². The transient response of the internal resistance indicated that the high frequency resistance (HFR) lagged the current with a value of about 20 s. The effect of purging operation on the internal resistance of the fuel cell was also explored. Experimental data showed that the cell experienced a continuous 8-min purging process can maintain at a relatively steady and dry state.     

A novel three-dimensional, two-phase and non-isothermal numerical model for proton exchange membrane fuel cell

A three-dimensional, two-phase and non-isothermal model of a proton exchange membrane fuel cell (PEMFC) based on the previously developed model is established using the two-fluid method. This two-phase model considers the liquid water transport in both cathode and anode sides and accounts for the intrinsic heat transfer between the reactant fluids and the solid matrices. The latent heat of water condensation/evaporation is considered in the present model. The numerical results demonstrate that the lower cathode humidity is beneficial for cell performance. In the anode side, the water vapor can be condensed at high current density because the water vapor transport is less than the hydrogen consumption rate. Near the catalyst layer, the reactant fluid temperature is higher than the solid matrix temperature, and far from the catalyst layer, the temperature difference between the reactant fluid and the solid matrix decreases. Near the channel, the reactant fluid temperature is lower than the solid matrix temperature.     

质子交换膜燃料电池的水热管理

质子交换膜燃料电池电化学反应生成电能、热能和水。质子交换膜燃料电池中水管理与热管理是紧密关联互相耦合的,有效的水热管理对于提高电池的性能和寿命起着关键作用。本文对膜中水的迁移机理及影响水平衡的主要因素进行了分析,对目前较为有效的水管理方法进行了综述。另外,分析了在微重力条件下燃料电池水管理问题的重要性。燃料电池中约有40%~50%的能量耗散为热能,必须采取有效的散热方式及时排除这些热量。本文对质子交换膜燃料电池的温度分布、局部换热系数及散热等燃料电池热管理相关问题进行了分析。     

Investigation of the effect of microporous layers on water management in a proton exchange membrane fuel cell using novel diagnostic methods

Water management remains a significant challenge for the Proton Exchange Membrane Fuel Cell (PEMFC) with respect to performance, lifetime and operational flexibility. In recent years, microporous layers (MPL) have been widely used on the cathode side of the PEMFC in order to improve fuel cell performance and water management capabilities. Many modeling and experimental studies have with limited success attempted to analyze the underlying mechanisms that are responsible for the performance improvement due to the MPL. In this study, porous inserts along with various in-situ experimental techniques are used to investigate the MPLs. It was observed that the anode pressure drop increased when a cathode MPL was present, indicating water cross-over from the cathode towards the anode side. Further testing identified that the MPL improved cell performance due to the reduction of water saturation in the cathode catalyst layer, which resulted in enhanced oxygen diffusion. The influence of the MPL on the anode side was also studied with the aid of porous inserts and other techniques, and it was observed that the anode MPL improves cell voltage stability and reduces water accumulation in the anode catalyst layer. The present investigation provides further important information on the critical role of the MPL in the PEMFC.     

Synthesis and characterization of anion exchange membranes for alkaline direct methanol fuel cells

Alkaline fuel cells suggest solution for the problems of low methanol oxidation kinetics and methanol crossover, which are limiting the development of direct methanol fuel cells. In this work, a novel anion exchange membrane, quaternized poly(aryl ether oxadiazole), was prepared through polycondensation, grafting and quaternization. The ionic conductivity of as-synthesized anion exchange membrane can reach up to 2.79 × 10⁻² S/cm at 70 °C. The physical and chemical stability of the anion exchange membranes could also meet the requirement for alkaline direct methanol fuel cells.     

A review of water flooding issues in the proton exchange membrane fuel cell

We have reviewed more than 100 references that are related to water management in proton exchange membrane (PEM) fuel cells, with a particular focus on the issue of water flooding, its diagnosis and mitigation. It was found that extensive work has been carried out on the issues of flooding during the last two decades, including prediction through numerical modeling, detection by experimental measurements, and mitigation through the design of cell components and manipulating the operating conditions. Two classes of strategies to mitigate flooding have been developed. The first is based on system design and engineering, which is often accompanied by significant parasitic power loss. The second class is based on membrane electrode assembly (MEA) design and engineering, and involves modifying the material and structural properties of the gas diffusion layer (GDL), cathode catalyst layer (CCL) and membrane to function in the presence of liquid water. In this review, several insightful directions are also suggested for future investigation.     

Radiation grafted membranes for superior anion exchange polymer membrane fuel cells performance

A study of radiation grafted polymers on the conductivity and performance of alkaline anion exchange membrane fuel cells (AAEMFCs) is reported. The aminated poly (LDPE-g-VBC), poly (HDPE-g-VBC) and poly (ETFE-g-VBC) membranes were produced by the using the radiation grafting technique. Differences in grafting behaviour are observed between the studied materials caused by differences in the base polymer film properties as molar mass, crystallinity, orientation or grafting technique used. In plane conductivities increased with Degree of Grafting DoG. At a DoG of 68% the LDPE-g-VBC membrane achieved an in-plane ionic conductivity between 0.18 and 0.32 S cm⁻¹ in the temperature range 20–80 °C. Measured through plane conductivities were lower than that of the in plane ones for all studied membranes. Membranes with the highest degree of swelling showed the highest through plane conductivity of 0.07–0.11 S cm⁻¹. The membrane specific resistance (per MEA cm²) of most of the produced membranes was in the range of 0.09–0.18 Ω cm². While membrane conductivity and hence IR loss is a crucial factor in fuel cell performance, membrane water permeability is a similarly crucial key for optimised water transport to the cathode. The main source of performance loss of AAEMFCs is believed to be restricted mass transport of water to the cathode reaction sites. The highly humidified anode stream along with large amount of water produced at the anode at high current densities could lead to flooding if water is not removed quickly to the cathode via the membrane (back diffusion) where it is consumed.     

Demonstration of a residence time distribution method for proton exchange membrane fuel cell evaluation

The volume sensitive residence time distribution method is ideally suited for the study of liquid water and ice formation within operating proton exchange membrane fuel cells. Sensitivity was demonstrated with the use of simulated water drops within the flow field channel (machined obstructions) yielding a linear correlation in the 0–20% volume obstruction range between measured and theoretical hydraulic volumes. The correlation was independent of obstruction spatial distribution but dependent on gas flow rate. Sensitivity was also demonstrated by varying the amount of liquid water within a gas diffusion electrode resulting in a linear correlation in the 7–44% void volume obstruction range between normalized time difference between the points at which the tracer concentration has decayed by 20 and 90% of the steady-state value prior to the tracer injection interruption and measured gas diffusion electrode liquid water content. Sensitivity to liquid water obstructions was maintained using an operating fuel cell and two different gas diffusion media with relatively similar transport properties but further work is needed to separate flow field from gas diffusion electrode contributions. The usefulness of the residence time distribution is also demonstrated for other applications, including gas crossover through the proton exchange membrane, flow distribution uniformity and gas diffusion electrode compressibility/deformation.     

Electrochemical and fuel cell evaluation of Co based catalyst for oxygen reduction in anion exchange polymer membrane fuel cells

Co based catalyst were evaluated for oxygen reduction (ORR) in liquid KOH and alkaline anion exchange membrane fuel cells (AAEMFCs). In liquid KOH solution the catalyst exhibited good performance with an onset potential 120 mV more negative than platinum and a Tafel slope of ca. 120 mV dec⁻¹. The hydrogen peroxide generated, increased from 5 to 50% as the electrode potential decreased from 175 to −300 mV vs. SHE.In an AAEMFC environment, one catalyst (GP2) showed promising performance for ORR, i.e. at 50 mA cm⁻² the differences in cell potential between the stable performance for platinum (more positive) and cobalt cathodes with air and oxygen, were only 45 and 67 mV respectively. The second catalyst (GP4) achieved the same stable power density as with platinum, of 200 and 145 mW cm⁻², with air at 1 bar (gauge) pressure and air (atm) cathode feed (60 °C), respectively. However the efficiency was lower (i.e. cell voltage was lower) i.e. 40% in comparison to platinum 47.5%.     

Numerical analysis of effects of gas crossover through membrane pinholes in high-temperature proton exchange membrane fuel cells

Durability is a major issue in the widespread commercialization of proton exchange membrane fuel cells (PEMFCs). Various failure modes have been identified over their long runtime. These mainly originate from membrane and catalyst layer failures. One of the most common failure modes in PEMFCs is due to pinhole formation in the membrane and resultant reactant gas crossover through the membrane. Gas crossover induces several critical problems in PEMFCs, including severe reactant depletion in the downstream regions, mixed potential at the electrodes, and formation of local hot spots by hydrogen/oxygen catalytic reaction, which indicates that the cell performance decreases with increasing gas crossover. In this study, we numerically investigate the effects of gas crossover on the performance of a high-temperature PEMFC based on a phosphoric-acid-doped polybenzimidazole (PBI) membrane. In contrast to previous gas-crossover studies 1 and 2 in which uniform gas crossover throughout the entire membrane has been simply assumed, our focus is on examining the impacts of localized gas crossover due to membrane pinholes. Numerical simulations are carried out via arbitrarily assuming pinholes in the membrane. The simulation results clearly show that the presence of pinholes in the membrane significantly disrupts the species, current density, and temperature distributions. Our findings may improve the fundamental and detailed understanding of localized gas-crossover phenomena through the membrane pinholes and the influence of these phenomena on high-temperature PEMFC operation.