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 self-humidifying membrane electrode assembly with water transfer region for proton exchange membrane fuel cells

A novel self-humidifying membrane electrode assembly (MEA) with the active electrode region surrounded by a unactive “water transfer region (WTR)” was proposed to achieve effective water management and high performance for proton exchange membrane fuel cells (PEMFCs). By this configuration, excess water in the cathode was transferred to anode through Nafion membrane to humidify hydrogen. Polarization curves and power curves of conventional and the self-humidifying MEAs were compared. The self-humidifying MEA showed power density of 85 mW cm⁻² at 0.5 V, which is two times higher than that of a conventional MEA with cathode open. The effects of anode hydrogen flow rates on the performance of the self-humidifying MEA were investigated and its best performance was obtained at a flow rate of 40 ml min⁻¹. Its performance was the best when the environmental temperature was 40 °C. The performance of the self-humidifying MEA was slightly affected by environmental humidity. The area of WTR was optimized, and feasible area ratio of the self-humidifying MEA was 28%.     

Investigating the effect of operating temperature on dynamic behavior of droplets for proton exchange membrane fuel cells

The present work depicts advanced understanding of dynamic behavior of droplets in serpentine channels for proton exchange membrane (PEM) fuel cells using a synchrotron-based X-ray radiographic technique at the Canadian Light Source (CLS). Due to high photon flux, the synchrotron-imaging technique provides high temporal and spatial resolution of images of water droplets in gas flow channels for PEMFCs. The whole cell and in particular, the gas diffusion layer (GDL) were operated under elevated temperatures through a self-designed heating channel around the GDL area (25–75 °C). In the experiments, a Sigracet 35 BC GDL was employed, and droplet height, chord and cycle time were measured over a series of images collected. Experimental results show that the droplet cycle time had been significantly reduced to less than 0.5 s from 14 s with an increase in the operating temperature from 25 °C to 75 °C. In addition, it is also found that increasing the operating temperature decreases the critical dimension of water droplets upon detachment i.e. from 0.46 mm for 25 °C to 0.33 mm for 75 °C. at a superficial gas velocity of 5.98 m/s.     

Hydrocarbon-based electrode ionomer for proton exchange membrane fuel cells

The electrode ionomer is a key factor that significantly affects the catalyst layer morphology and fuel cell performance. Herein, sulfonated poly(arylene ether sulfone)-based electrode ionomers with polymers of various molecular weights and alcohol/water mixtures were prepared, and those comprising the alcohol/water mixture showed a higher performance than the ones prepared using higher boiling solvents, such as dimethylacetamide; this is owing to the formation of the uniformly dispersed ionomer catalyst layer. The relation between ionomer molecular weight for the same polymer structure and the sulfonation degree was investigated. Because the chain length of polymer varies with molecular weight and chain entanglement degree, its molecular weight affects the electrode morphology. As the ionomer covered the catalyst, the agglomerates formed were of different morphologies according to their molecular weight, which could be deduced indirectly through dynamic light scattering and scanning electron microscopy. Additionally, the fuel cell performance was confirmed in the current-voltage curve.     

Microstructured membranes for improving transport resistances in proton exchange membrane fuel cells

Proton exchange membrane fuel cells (PEMFCs) have been identified as one of the most promising renewable energy system for use in automotive applications. However, due to the wide range of weather conditions around the world, the PEMFCs must be stable for operating under these variable conditions. One of the inefficiencies of PEMFCs in automotive applications is during vehicle warm-up, where the low hydration level within the PEMFC can lead to a low performance of the fuel cell. In this study, a proton exchange membrane (PEM) was prepared with regular, microstructured features tuned over a range of aspect ratios. These microstructured membranes were incorporated into MEAs and analyzed for their membrane, proton, and oxygen transport resistances. These fuel cells were tested under different conditions to simulate vehicle start-up, normal operating conditions, and hot operating conditions. It was determined that microstructured PEMs improved performance over planar PEMs under both the start-up and hot conditions. Despite the improved performance of the microstructured PEMs, a high hydrogen cross-over and short-circuit current were also observed for these samples. Adjusting the preparation techniques and tuning the dimensions of the microstructures may provide avenues for further optimization of PEMFC performance.     

Matching of water and temperature fields in proton exchange membrane fuel cells with non-uniform distributions

In this work, a three-dimensional multiphase non-isothermal model incorporated with a capillary-extended sub-model in gas channels is used to investigate the coupled phenomena of water and thermal transport in proton exchange membrane fuel cells. Distributions of water and temperature along the flow path in the channel are highlighted and the pros and cons of various operating temperatures are elaborated. In addition, this work also sheds light on the impacts of temperature variations of bipolar plates induced by non-uniform cooling conditions, which have been overlooked by most previous works. An important phenomenon of water distribution, dry-out at inlets and flooding at outlets (DIFO), is observed and this non-uniform distribution is revealed to be greatly influenced by the operating temperature, inlet relative humidity and gas flow stoichiometry. Moreover, temperature variations of bipolar plates are shown to exert remarkable impacts on water distribution. Consequently, optimum matching between water and temperature fields is proposed to be of vital importance in fuel cell design, e.g., strong cooling at the inlet and weak cooling at the outlet are demonstrated to be a feasible way of mitigating the problem of DIFO.     

Parallel serpentine-baffle flow field design for water management in a proton exchange membrane fuel cell

In a proton exchange membrane fuel cell (PEMFC) water management is one of the critical issues to be addressed. Although the membrane requires humidification for high proton conductivity, water in excess decreases the cell performance by flooding. In this paper an improved strategy for water management in a fuel cell operating with low water content is proposed using a parallel serpentine-baffle flow field plate (PSBFFP) design compared to the parallel serpentine flow field plate (PSFFP). The water management in a fuel cell is closely connected to the temperature control in the fuel cell and gases humidifier. The PSBFFP and the PSFFP were evaluated comparatively under three different humidity conditions and their influence on the PEMFC prototype performance was monitored by determining the current density–voltage and current density–power curves. Under low humidification conditions the PEMFC prototype presented better performance when fitted with the PSBFFP since it retains water in the flow field channels.     

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.     

Development of shut-down process for a proton exchange membrane fuel cell

Several different shut-down procedures were carried out to reduce the degradation of membrane electrode assembly (MEA) in a proton exchange membrane fuel cell (PEMFC). The effects of close/open state of outlets of a single cell and application of a dummy load during the shut-down on the degradation of the MEA were investigated. Also, we elucidated the relationship between the thickness of the electrolyte membrane and the degradation of the MEA for different shut-down procedures. When a thin electrolyte membrane was used, the closer of outlets mitigated the degradation during on/off operation. For the thicker electrolyte membrane, the dummy load which eliminates residual hydrogen and oxygen in the electrodes should be applied to lower the degradation.     

Liquid water flooding process in proton exchange membrane fuel cell cathode with straight parallel channels and porous layer

Liquid water management plays a significant role in proton exchange membrane fuel cell (PEMFC) performance, especially when the PEMFC is operating with high current density. Therefore, understanding of liquid water behavior and flooding process is a critical challenge that must be addressed. To overcome PEMFC durability problems, a liquid water flooding process is studied in the cathode side of a PEMFC with straight parallel channels and a porous layer using FLUENT^® v6.3.26 software with a volume-of-fluid (VOF) algorithm and user-defined-function (UDF). The general process of liquid water flooding within this type of PEMFC cathode is investigated by analyzing the behavior of liquid water in porous layer and gas flow channels. Two important phenomena, the “first channel phenomenon” and the “last channel phenomenon”, and their effects on the flow distribution along different parallel channels are discussed.     

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.     

Nafion/PTFE/silicate membranes for high-temperature proton exchange membrane fuel cells

Fuel cell performance of membrane electrode assemblies (MEAs) prepared from poly(tetrafluoroethylene)/Nafion/silicate (PNS) membrane and Nafion-112 membrane were investigated. Due to the low conductivity of PTFE and silicate, PNS had a higher proton resistance than Nafion-112. However, in this work we show that PNS performs better than Nafion-112 for a high current density operation with a low inlet gas humidity. As the PEMFCs were operated at with 100% RH, the results showed the maximum power density (PD_max) of PNS was: at with both H₂ and O₂ flow rates of 300 ml/min, and at with H₂ flow rate of 360 ml/min and O₂ flow rate of 600 ml/min, which were much higher than the at of Nafion-112 with both H₂ and O₂ flow rates of 300 ml/min. The PD_max of PNS was: , , and at as the operating temperature and inlet gas humidity were set at with 67.7% RH, with 46.8% RH, and with 33.1% RH, respectively. However, no output power was detected for Nafion-112 MEA when the cell was operated at a temperature higher than and an inlet gas humidity lower than 67.7% RH. The high PEMFC performance of PNS at high current density and low humidity is attributed to the presence of silicate in the PNS membrane, which enhances water uptake and reduces electro-osmosis water loss at a high current density.     

Poly(ethylene glycol) modified activated carbon for high performance proton exchange membrane fuel cells

A high water retention membrane is developed by co-assembling poly(ethylene glycol) (PEG) grafted activated carbon (AC-PEG) with Nafion. The AC-PEG is prepared via a sol–gel process. The use of PEG as a transporting medium in AC-PEG shows a largely improved water retention ability, a higher proton conductivity and a reduced swelling ratio, making it well suited for proton exchange membrane fuel cells (PEMFCs). Further, the composite membranes show improved mechanical properties at high temperature, thus ensuring the structural stability of membranes during the fuel cell operation. Compositional optimized AC-PEG/Nafion composite membrane (15 wt% compared to Nafion) demonstrates a better performance than the commercially available counterpart, Nafion 212, in fuel cell measurements. To identify the key factor of the improved performance, current interrupt technique is used to quantitatively verify the changes of resistance under different relative humidity environment.     

Effect of surface dynamic wettability in proton exchange membrane fuel cells

It is known that the static contact angle reflecting the “contact area” between liquid and solid is insufficient to represent the dynamic wettability of a solid surface, and another parameter called the sliding angle is needed to describe the relative easiness of liquid moving on a solid surface. However, sliding angle has been largely neglected in the previous studies for proton exchange membrane fuel cell (PEMFC). In this study, three-dimensional multiphase simulations are carried out for a PEMFC with single straight flow channels considering both the static contact angles and sliding angles of gas diffusion layer (GDL) and catalyst layer (CL). The results show that the liquid water volume fraction in cathode CL (CCL) and GDL (CGDL) can be increased by several times when the sliding angle is increased while the static contact angle is kept constant. This could have significant implication on the water management strategy due to the considerable changes in the water transport and removal processes. Since GDL is much thicker than CL, changing the surface dynamic wettability of GDL has more significant effect on liquid water transport than changing the surface dynamic wettability of CL.     

Effects of chlorides on the performance of proton exchange membrane fuel cells

This paper investigates the effects of cathode gases containing chloride ions on the proton exchange membrane fuel cell (PEMFC) performance. Chloride solutions are vaporized using an ultrasonic oscillator and mixed with oxygen/air. The salt concentration of the mixed gas in the cathode is set by varying the concentration of the chloride solution. Five-hour tests show that an increase in the concentration of sodium chloride did not significantly affect the cell performance of the PEMFC. It is found that variations in the concentration of chloride do not show significant influence on the cell performance at low current density operating condition. However, for high current density operating conditions and high calcium chloride concentrations, the chloride ion appears to have a considerable effect on cell performance. Experimental results of 108-h tests indicate that the fuel cell operating with air containing calcium chloride has a performance decay rate of 3.446 mV h⁻¹ under the operating condition of current density at 1 A/cm². From the measurements of the I-V polarization curves, it appears that the presence of calcium chloride in the cathode fuel gas affects the cell performance more than sodium chloride does.     

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.     

Covalent-ionically cross-linked polyetheretherketone proton exchange membrane for direct methanol fuel cell

In this paper, the proton exchange membrane prepared by covalent-ionically cross-linking water soluble sulfonated-sulfinated poly(oxa-p-phenylene-3,3-phthalido-p-phenylene-oxa-p-phenylene-oxy-phenylene) (SsPEEK-WC) is reported. Compared with covalent cross-linked PEEK-WC membrane, this covalent-ionically cross-linked PEEK-WC membrane exhibits extremely reduced water uptake and methanol permeability, but just slightly sacrificed proton conductivity. The proton conductivity of the covalent-ionically cross-linked PEEK-WC membrane reaches to 2.1 × 10⁻² S cm⁻¹ at room temperature and 4.1 × 10⁻² S cm⁻¹ at 80 °C. The methanol permeability is 1.3 × 10⁻⁷ cm² s⁻¹, 10 times lower than that of Nafion^® 117 membrane. The results suggest that the covalent-ionically cross-linked PEEK-WC membrane is a promising candidate for direct methanol fuel cell because of low methanol permeability and adequate proton conductivity.     

Water and proton transport properties of hexafluorinated sulfonated poly(arylenethioethersulfone) copolymers for applications to proton exchange membrane fuel cells

In the present study, we examine the water and proton transport properties of hexafluorinated sulfonated poly(arylenethioethersulfone) (6F-SPTES) copolymer membranes for applications to proton exchange membrane fuel cells (PEMFCs). The 6F-SPTES copolymer membranes build upon the structures of previously studied sulfonated poly(arylenethioethersulfone) (SPTES) copolymer membranes to include CF₃ functional groups in efforts to strengthen water retention and extend membrane performance at elevated temperatures (above 120 °C). The 6F-SPTES copolymer membranes sustain higher water self-diffusion and greater proton conductivities than the commercial Nafion^® membrane. Water diffusion studies of the 6F-SPTES copolymer membranes using the pulsed-field gradient spin-echo NMR technique reveal, however, the fluorinated membranes to be somewhat unfavorable over their non-fluorinated counterparts as high temperature membranes. In addition, proton conductivity measurements of the fluorinated membranes up to 85 °C show comparable results with the non-fluorinated SPTES membranes.     

Effect of wettability on water removal from the gas diffusion layer surface in a novel proton exchange membrane fuel cell flow channel

Effective water removal from the proton exchange membrane fuel cell (PEMFC) surface exposed to the flow channel is critical to the operation and water management in PEMFCs. In this study, the water removal process is investigated numerically for a novel flow channel formed by inserting a hydrophilic needle in the conventional PEMFC flow channel, and the effect of the surface wettability of the membrane electrode assembly (MEA) and the inserted needle on the water removal process is studied. The results show that the liquid water can be more effectively removed from the MEA surface for larger MEA surface contact angles and smaller needle surface contact angles. The pressure drop for the flow in the channel is also examined and it is seen to be indicative of the liquid water flow and transport in the flow channel, suggesting that pressure drop is a useful parameter for the investigation of water transport and dynamics in the flow channel.