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.     

Quantifying water transport in anion exchange membrane fuel cells

Sufficient water transport through the membrane is necessary for a well-performing anion exchange membrane fuel cell (AEMFC). In this study, the water flux through a membrane electrode assembly (MEA), using a Tokuyama A201 membrane, is quantified using humidity sensors at the in- and outlet on both sides of the MEA. Experiments performed in humidified inert gas at both sides of the MEA or with liquid water at one side shows that the aggregation state of water has a large impact on the transport properties. The water fluxes are shown to be approximately three times larger for a membrane in contact with liquid water compared to vaporous. Further, the flux during fuel cell operation is investigated and shows that the transport rate of water in the membrane is affected by an applied current. The water vapor content increases on both the anode and cathode side of the AEMFC for all investigated current densities. Through modeling, an apparent water drag coefficient is determined to −0.64, indicating that the current-induced transport of water occurs in the opposite direction to the transport of hydroxide ions. These results implicate that flooding, on one or both electrodes, is a larger concern than dry-out in an AEMFC.     

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.     

Numerical analysis of improved water management of open-cathode proton exchange membrane fuel cells with a dead-ended anode by pulsating flow

Anode water management is critical for the efficient operation of proton exchange membrane fuel cells with a dead-ended anode. To clarify the mass transfer phenomenon in the anode flow channel under the dead-ended anode mode, and reveal the influence mechanism of pulsating flow on water management, a three-dimensional, two-phase, non-isothermal transient model is established in this study. The water content and species distribution in different layers are analyzed, and the internal relationship between water transport behavior and output performance of the proton exchange membrane fuel cell under different operating conditions is explored. The simulation results show that the output performance of the proton exchange membrane fuel cell in dead-ended anode mode is directly related to the gas diffusion layer's water saturation and the hydrogen mass transfer. Furthermore, pulsating flow can effectively suppress the back diffusion of water, and improve the mass transfer rate of hydrogen. Consequently, the water management and the operational stability of the proton exchange membrane fuel cell are significantly improved. The research results of this paper have important guiding significance for improving the water and gas management of fuel cells.     

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.     

Water management in a novel proton exchange membrane fuel cell stack with moisture coil cooling

Water flooding causes severe degradation of the performance and lifetime of proton exchange membrane fuel cell (PEMFC). In this study, a novel PEMFC stack with in-built moisture coil cooling was designed and the effects of moisture coil cooling on water management in the new PEMFC stack under various operating conditions were investigated. The result showed that the performance of the PEMFC stack was significantly improved due to the moisture condensation under high current density, high operating temperature, high relative humidity and high operating pressure. The output power was increases by 21.62% (525.71 W) at 1600·mA cm⁻² while the increased parasitic power was no more than 35W. Moreover, degradation of the cathode catalyst layer after 100 h operation was also reduced by using moisture coil cooling. Compared with the situation without moisture condensation, the maximum decay rate of the cathode catalyst layer thickness after 100 h operation was reduced by 13.01%. Accordingly, the novel design is valuable and can be widely used in the future design of PEMFC.     

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.     

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.     

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.     

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。     

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.     

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.     

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.     

ZrO2 incorporated polysulfone anion exchange membranes for fuel cell applications

Novel imidazolium functionalized polysulfone (ImPS) membranes modified with zirconia (ZrO₂) were synthesized through solution casting technique. Structural, morphological, thermal and mechanical analysis of the composite membranes confirmed adhesion and property enhancement caused by ZrO₂. Water absorption investigations revealed better water absorption of the ImPS/ZrO₂ membranes with intact morphology. Maximum ion exchange capacity and ionic conductivity for the composite membranes were obtained as 2.84 mmol/g and 80.2 mS/cm (50 ^°C) which was 21% and 47% higher as compared to pure ImPS membrane. Alkaline stability of the blend membranes was increased due to strong interaction between ZrO₂ and ImPS molecules. Fuel cell performance using Pt/C catalysts exhibited OCP and power density elevation with incremental amounts of ZrO₂ in the composite membrane composition. ImPS membrane with 10% ZrO₂ recorded a highest OCP and power density of 1.04 V and 270 mW/cm² which was 35% and 39% higher than the pure ImPS. Thus, the anion exchange membranes developed by ImPS/ZrO₂ blending could be suiting well for alkaline fuel cells applications.