Direct water balance analysis on a polymer electrolyte fuel cell (PEFC): Effects of hydrophobic treatment and micro-porous layer addition to the gas diffusion layer of a PEFC on its performance during a simulated start-up operation

Effects of hydrophobic treatment and micro-porous layer (MPL) addition to a gas diffusion layer (GDL) in a polymer electrolyte fuel cell (PEFC) have been investigated from water balance analysis at the electrode (catalyst layer), GDL and flow channel in the cathode after a simulated start-up operation. The water balance is directly analyzed by measuring the weight of the adherent water wiped away from each the component. As a result, we find that hydrophobic treatment without MPL leads to the increase in liquid water accumulation at the electrode which limits the oxygen transport to the catalyst and then lowers the cell voltage rapidly during start-up, whereas the treatment decreases the water at the GDL. The water accumulation at the electrode also decreases the cumulative current that represents the power generation and calorific power indispensable for warming up at a temperature below freezing point. On the other hand, we directly find that the hydrophobic treatment with MPL addition suppresses the water accumulation at the electrode, which increases the cumulative current. In addition, it is found that increase in air permeability of a GDL substrate by its coarser structure increases the cumulative current, which is explained by enhancing the exhaust of the product water vapor and liquid as well as by enhancing the oxygen transport directly. Thus, the hydrophobic treatment with MPL addition and larger air permeability of a GDL substrate improve the start-up performance of a PEFC.     

Effects of basic gas diffusion layer components on PEMFC performance with capillary pressure gradient

The gas diffusion layer (GDL) is composed of a substrate and a micro-porous layer (MPL), and is treated with polytetrafluoroethylene (PTFE) to promote water discharge. Additionally, the MPL mainly consists of carbon black and PTFE. In other words, the optimal design of these elements has a dominant effect on the polymer electrolyte membrane fuel cell (PEMFC) performance. For the GDL, it is crucial to prevent water flooding, and the water flux within the GDL is strongly affected by the capillary pressure gradient. In this study, the PEMFC performance was systematically investigated by varying the substrate PTFE content, MPL PTFE content, and MPL carbon loading per unit area. The effects of each experimental variable on the PEMFC performance and especially on the capillary pressure gradient were quantitatively analyzed when the GDLs were manufactured by the doctor blade manufacturing method. The experimental results indicated that as the PTFE content of the anode and cathode GDL increased, the PEMFC performance deteriorated due to the deformation of the porosity and tortuosity of the GDL. Additionally, the PEMFC performance improved as the MPL PTFE content of the cathode GDL increased at low relative humidity (RH), but the PEMFC performance tendency was reversed at high RH. Further, the MPL carbon loading of 2 mg/${\text{cm}}^2$ demonstrated the best performance, and the advantages and disadvantages of the MPL carbon loading were identified. In addition, the effects of each experimental variable on liquid water, water vapor, and gas permeability were investigated.     

Determination of the pore size distribution of micro porous layer in PEMFC using pore forming agents under various drying conditions

In this paper, the effect of the pore size distribution of a micro-porous layer (MPL) on the performance of polymer electrolyte membrane fuel cells (PEMFC) was investigated using self-made gas diffusion layers (GDLs) with different MPLs for which the pore size distribution was modified using pore forming agents under different drying conditions. When MPL dried at high temperature, more macro pores, approximately 1,000–20,000 nm in diameter, and less micro pores, below 100 nm, were observed relative to when MPL was dried at low temperature. Self-made GDLs were characterized by a field-emission scanning electron microscope (FE-SEM), mercury porosimetry and self-made gas permeability measurement equipment. The performance of the single cells was measured under two different humidification conditions. The results demonstrate that the optimum pore size distribution of MPL depended on the cell operating humidification condition. The MPL dried at high temperature performed better than the MPL dried at low temperature under a low humidification condition; however, MPL dried at low temperature performed better under a high humidification condition.     

Effect of wettability heterogeneity and compression on liquid water transport in gas diffusion layer coated with microporous layer of PEMFC

This study applied the pseudo-potential Lattice Boltzmann method (LBM) for investigating liquid water transport in the microporous layer (MPL) and gas diffusion layer (GDL) of polymer electrolyte fuel cell. The MPL and GDL reconstruction is performed by using a stochastic method. Unlike previous studies that examined the GDL as two distinct layers of hydrophilic and hydrophobic, this study considered the wettability heterogeneity. In the present study, some of the carbon fibers in the GDL are randomly considered hydrophilic. Moreover, liquid water transport in the compressed and uncompressed GDL with different hydrophilic fibers percentage are compared. The effect of hydrophilic fibers percentage and the compression ratio of the GDL on the liquid water saturation level, the steady-state time, and the formation and growth of droplets in the gas channel (GC) are investigated. The results indicated that more than 10% of hydrophilicity of the fibers lead to the formation of discontinuous water clusters. This phenomenon increased the steady-state time and water saturation level significantly. The simulation showed that compression increased the number of discontinuous water clusters in the GDL. The obtained results demonstrated that the hydrophilic fibers may have positive or negative effects on water transport in the GDL due to their location. In addition, this study indicated that for 10% of hydrophilic fibers with 10% compression, water saturation level and time required to reach steady-state decreased by 5.2% and 22% respectively compared to purely hydrophobic GDL.     

Application of hyperdispersant to the cathode diffusion layer for direct methanol fuel cell

In this study, Nafion ionomer, as a kind of hyperdispersant, was added to polytetrafluoroethylene (PTFE) water dispersion system to suppress the size of PTFE particles in the ink of microporous layer (MPL). The agglomeration behavior of PTFE in ethanol and MPL were investigated by laser diffraction, dynamic light scattering (DLS) and metallurgical microscopes. The electronic resistance, pore size distribution, gas permeability and surface hydrophobic/hydrophilic properties were also characterized for prepared gas diffusion layers (GDLs). It was shown that PTFE water dispersion system suffered flocculating when dispersed in ethanol and this agglomeration behavior was reduced by employing Nafion ionomer. With the increase in the Nafion ionomer adopted in the MPL, not only the decreased hydrophobic property was shown in the MPL, but the decreased PTFE particle size was also achieved, which results in improved crosslink of carbon and pores themselves as well as the volume loss of pores in micron scale. The increased gas permeability and electronic conductivity of the GDL made the one employing the PTFE dispersion system with 1% Nafion content own its advantages as the cathode diffusion layer for a direct methanol fuel cell (DMFC) under near-ambient conditions.     

Effects of ratio variation in substrate and micro porous layer penetration on polymer exchange membrane fuel cell performance

A gas diffusion layer (GDL) facilitates the diffusion of reactant gas and the discharge of the generated water. The GDL performs various functions, such as conducting heat and electrons generated by electrochemical reactions and providing mechanical support for the catalyst layer. In this study, the effects of ratio variation in the substrate and microporous layer (MPL) penetration region on the proton exchange membrane fuel cell (PEMFC) performance were investigated. Furthermore, the reasons for these performance tendencies are explained based on the thermogravimetric analysis, contact angle, scanning electron microscopy, mercury porosimetry, electrical resistance, electrochemical impedance spectroscopy, and capillary pressure gradient. The experimental results indicate that the MPL penetration ratio within 15–20% of the total GDL thickness and the combined ratio of the MPL and MPL penetration within 35–40% is the best for the overall PEMFC performance. In addition, when the substrate ratio is excessively low, water flooding substantially occurs in the substrate, and this accumulated water functions as a back pressure, causing severe capillary condensation in the MPL penetration region and thus depriving the supply of the reactant gas.     

Numerical modeling and experimental study of the influence of GDL properties on performance in a PEMFC

This work is to study the effect of properties of gas diffusion layer (GDL) on performance in a polymer electrolyte membrane fuel cell (PEMFC) by both numerical simulation and experiments. The 1-dimension numerical simulation using the mixture-phase model is developed to calculate polarization curve. We are able to estimate optimum GDL properties for cell performance from numerical simulation results. Various GDLs which have different properties are prepared to verify accuracy of the simulation results. The contact angle and gas permeability of GDLs are controlled by polytetrafluoroethylene (PTFE) content in micro-porous layers (MPLs). MPL slurry is prepared by homogeneous blending of carbon powder, PTFE suspension, isopropyl alcohol and glycerol. Then the slurry is coated on gas diffusion mediums (GDMs) surface with controlled thickness by blade coating method. Non-woven carbon papers which have different thicknesses of 200 μm and 380 μm are used as GDMs. The prepared GDLs are measured by surface morphology, contact angle, gas permeability and through-plane electrical resistance. Moreover, the GDLs are tested in a 25 cm² single cell at 70 °C in humidified H₂/air condition. The contact angle of GDL increases with increasing PTFE content in MPL. However, the gas permeability and through-plane electrical conductivity decrease with increasing PTFE content and thickness of GDM. These changes in properties of GDL greatly influence the cell performance. As a result, the best performance is obtained by GDL consists of 200 μm thick non-woven carbon paper as GDM and MPL contained 20 wt.% PTFE content.     

A pore network study on the role of micro-porous layer in control of liquid water distribution in gas diffusion layer

In proton exchange membrane fuel cell (PEMFC), a hydrophobic micro-porous layer (MPL) is usually placed between catalyst layer (CL) and gas diffusion layer (GDL) to reduce flooding. Recent experimental studies have demonstrated that liquid water saturation in GDL is drastically decreased in the presence of MPL. However, theoretical studies based on traditional continuum two-phase flow models suggest that MPL has no effect on liquid water distribution in GDL. In the present study, a pore network model with invasion percolation algorithm is developed and used to investigate the impacts of the presence of MPL on liquid water distribution in GDL from the viewpoint at the pore level. A uniform pressure and uniform flux boundary conditions are considered for liquid water entering the porous layer in PEMFC. The simulation results reveal that liquid water saturation in GDL is reduced in the presence of MPL, but the reduction depends on the condition of liquid water entering the porous layer in PEMFC.     

Fabrication of a carbon nanofiber sheet as a micro-porous layer for proton exchange membrane fuel cells

A carbon nanofiber sheet (CNFS) has been prepared by electrospinning, stabilisation and subsequent carbonisation processes. Imaging with scanning electron microscope (SEM) indicates that the CNFS is formed by nonwoven nanofibers with diameters between 400 and 700 nm. The CNFS, with its three-dimensional pores, shows excellent electrical conductivity and hydrophobicity. In addition, it is found that the CNFS can be successfully applied as a micro-porous layer (MPL) in the cathode gas diffusion layer (GDL) of a proton exchange membrane fuel cell (PEMFC). The GDL with the CNFS as a MPL has higher gas permeability than a conventional GDL. Moreover, the resultant cathode GDL exhibits excellent fuel cell performance with a higher peak power density than that of a cathode GDL fabricated with a conventional MPL under the same test condition.     

Effect of PTFE content in microporous layer on water management in PEM fuel cells

The effect of hydrophobic agent (PTFE) concentration in the microporous layer on the PEM fuel cell performance was investigated using mercury porosimetry, water permeation experiment, and electrochemical polarization technique. The mercury porosimetry and water permeation experiments indicated that PTFE increases the resistance of the water flow through the GDL due to a decrease of the MPL porosity and an increase of the volume fraction of hydrophobic pores. When air was used as an oxidant, a maximum fuel cell performance was obtained for a PTFE loading of 20 wt.%. The experimental polarization curves were quantitatively analyzed to determine the polarization resistances resulting from different physical and electrochemical processes in the PEM fuel cell. The polarization analysis indicated that the optimized PTFE content results in an effective water management (i.e., a balancing of water saturations in the catalyst layer and the gas diffusion layer), thereby improving the oxygen diffusion kinetics in the membrane-electrode assembly.     

Effects of gas diffusion layer (GDL) and micro porous layer (MPL) on cathode performance in microbial fuel cells (MFCs)

This study focused on novel cathode structures to increase power generation and organic substrate removal in microbial fuel cells (MFCs). Three types of cathode structures, including two-layer (gas diffusion layer (GDL) and catalyst layer (CL)), three-layer (GDL, micro porous layer (MPL) and CL), and multi-layer (GDL, CL, carbon based layer (CBL) and hydrophobic layers) structures were examined and compared in single-chamber MFCs (SCMFCs). The results showed that the three-layer (3L) cathode structures had lower water loss than other cathodes and had a high power density (501 mW/m²). The MPL in the 3L cathode structure prevented biofilm penetration into the cathode structure, which facilitated the oxygen reduction reaction (ORR) at the cathode. The SCMFCs with the 3L cathodes had a low ohmic resistance (R_ohmic: 26-34 Ω) and a high cathode open circuit potential (OCP: 191 mV). The organic substrate removal efficiency (71-78%) in the SCMFCs with 3L cathodes was higher than the SCMFCs with two-layer and multi-layer cathodes (49-68%). This study demonstrated that inserting the MPL between CL and GDL substantially enhanced the overall electrical conduction, power generation and organic substrate removal in MFCs by reducing water loss and preventing biofilm infiltration into the cathode structure.     

Enhanced low-humidity performance in a proton exchange membrane fuel cell by developing a novel hydrophilic gas diffusion layer

An ultrathin layer of hydrophilic titanium dioxide (TiO₂) is coated on the gas diffusion layer (GDL) to enhance the performance of a proton exchange membrane fuel cell (PEMFC) at low relative humidity (RH) and high cell temperature. Both of the modified and unmodified GDLs are characterized using contact angles, and the cell performance is evaluated at various RHs and cell temperatures. It is found that the modified GDL, which contains a hydrophilic TiO₂ layer between the microporous layer (MPL) and the gas diffusion-backing layer (GDBL), exhibits better self-humidification performance than a conventional GDL without the TiO₂ layer. At 12% RH and 65 °C cell temperature, the current density is 1190 mA cm⁻² at 0.6 V, and it maintains 95.8% of its initial performance after 50 h of continuous testing. The conventional GDL, however, exhibits 55.7% (580 mA cm⁻²) of its initial performance (1040 mA cm⁻²) within 12 h of testing. The coated hydrophilic TiO₂ layer acts as a mini humidifier retaining sufficient moisture for a PEMFC to function at low humidity conditions.     

Measurement of water transport rates across the gas diffusion layer in a proton exchange membrane fuel cell,and the influence of polytetrafluoroethylene content and micro-porous layer

Water management in a proton exchange membrane (PEM) fuel cell is one of the critical issues for improving fuel cell performance and durability, and water transport across the gas diffusion layer plays a key role in PEM fuel cell water management. In this work, we investigated the effects of polytetrafluoroethylene (PTFE) content and the application of a micro-porous layer (MPL) in the gas diffusion layer (GDL) on the water transport rate across the GDL. The results show that both PTFE and the MPL play a similar role of restraining water transport. The effects of different carbon loadings in the MPL on water transport were also investigated. The results demonstrate that the higher the carbon loading in the MPL, the more it reduces the water transport rate. Using the given cell hardware and components, the optimized operation conditions can be obtained based on a water balance analysis.     

Effects of an MPL on water and thermal management in a PEMFC

In this study, the effects of adding a microporous layer (MPL) as well as the impact of its physical properties on polymer electrolyte fuel cell (PEMFC) performance with serpentine flow channels were investigated. In addition, numerical simulations were performed to reveal the effect of relative humidity and operating temperature. It is indicated that adding an extra between the gas diffusion layer (GDL) and catalyst layer (CL), a discontinuity in the liquid saturation shows up at their interface because of differences in the wetting properties of the layers. In addition, results show that a higher MPL porosity causes the liquid water saturation to decrease and the cell performance is improved. A larger MPL thickness reduces the cell performance. The effects of MPL on temperature distribution and thermal transport of the membrane prove that the MPL in addition to being a water management layer also improves the thermal management of the PEMFC.     

Effect of the micro porous layer design on the dynamic performance of a proton exchange membrane fuel cell

The mass transport characteristics of a gas diffusion layer (GDL) predominantly affect the performance of a proton exchange membrane (PEM) fuel cell. However, studies examining the transient response related to the GDL are insufficient, although the dynamic behavior of a PEM fuel cell is an important issue. In this study, the effects of the design of a micro porous layer (MPL) on the transient response of a PEM fuel cell are investigated. The MPL slurry density and multiple functional layers are treated as the variable design parameter. The results show that the transient response is determined by the capillary pressure gradient through the GDL. The trade-off relation for the PEM fuel cell performance under low and high humidity conditions due to the hydrophobic GDL is mitigated by designing a reverse capillary pressure gradient in the MPL.     

Liquid transport in gas diffusion layer of proton exchange membrane fuel cells: Effects of micro-porous layer cracks

Micro porous layer (MPL) is a carbon layer (～15 μm) that coated on the gas diffusion layer (GDL) to enhance the electrical conduction and membrane hydration of proton exchange membrane fuel cell (PEMFC). However, the liquid transport behavior from MPL to GDL and its impact on water management remain unclear. Thus, a three-dimensional volume of fluid (VOF) model is developed to investigate the effects of MPL crack properties on liquid water saturation, liquid pathway formation, and the two-phase mass transport mechanism in GDL. Firstly, a stochastic orientation method is used to reconstruct the fibrous structure of the GDL. After that, the liquid water saturation calculated from the numerical results agrees well with the experimental data. With considering the full morphology of the overlap between MPL and GDL, it's found that this overlap determines the preferred liquid emerging port of both MPL and GDL. Three crack design shapes in MPL are proposed on the base of the similarity crack formation processes of soil mud. In addition, the effects of crack shape, distance between cracks, and crack number on liquid water transport from MPL to GDL are investigated. It is found that the liquid water saturation of GDL increases with crack number and the distance between cracks, while presents little correlation to the crack shape. Hopefully, these results can help the development of PEMFC models without reconstructing full MPL morphology.     

Through-plane thermal conductivity of the microporous layer in a polymer electrolyte membrane fuel cell

Understanding the thermal properties of the microporous layer (MPL) is critical for accurate thermal analysis and improving the performance of proton exchange membrane (PEM) fuel cells operating at high current densities. In this study, the effective through-plane thermal conductivity and contact resistance of the MPL have been investigated. Gas diffusion layer (GDL) samples, coated with 5%-wt. PTFE, with and without an MPL are measured using the guarded steady-state heat flow technique described in the ASTM standard E 1225-04. Thermal contact resistance of the MPL with the iron clamping surface was found to be negligible, owing to the high surface contact area. Effective thermal conductivity and thickness of the MPL remained constant for compression pressures up to 15 bar at 0.30 W/m°K and 55 μm, respectively. The effective thermal conductivity of the GDL substrate containing 5%-wt. PTFE varied from 0.30 to 0.56 W/m°K as compression was increased from 4 to 15 bar. As a result, GDL containing MPL had a lower effective thermal conductivity at high compression than the GDL without MPL. At low compression, differences were negligible. The constant thickness of the MPL suggests that the porosity, as well as heat and mass transport properties, remain independent of the inhomogeneous compression by the bipolar plate. Despite the low effective thermal conductivity of the MPL, thermal performance of the GDL can be improved by exploiting the excellent surface contact resistance of the MPL.     

Effects of a microporous layer on the performance degradation of proton exchange membrane fuel cells through repetitive freezing

The gas diffusion layer (GDL) covered with a microporous layer (MPL) is being widely used in proton exchange membrane fuel cells (PEMFCs). However, the effect of MPL on water transport is not so clear as yet; hence, many studies are still being carried out. In this study, the effect of MPL on the performance degradation of PEMFCs is investigated in repetitive freezing conditions. Two kinds of GDL differentiated by the existence of MPL are used in this experiment. Damage on the catalyst layer due to freezing takes place earlier when GDL with MPL is used. More water in the membrane and catalyst layer captured by MPL causes permanent damage on the catalyst layer faster. More detailed information about the degradation is obtained by electrochemical impedance spectroscopy (EIS). From the point of view that MPL reduces the ohmic resistance, it is effective until 40 freezing cycles, but has no more effect thereafter. On the other hand, from the point of view that MPL enhances mass transport, it delays the increase in the mass transport resistance.     

Non-uniform agglomerate cathode catalyst layer model on the performance of PEMFC with consideration of water effect

We focus on the effect of cathode catalyst layer physical structure on the cell performance of proton exchange membrane fuel cell (PEMFC). At low polarization, high inlet humidification predicts better cell performance because of the more active surface in the CL. As polarization is extended near the mass transfer limited regime, high humidification only renders a flooded electrode and inferior cell performance. Catalyst layer with better capillary water transport parameters performs better than that with inferior water repulsion capability. Permeation in the gas diffusion layer (GDL) is important for efficient oxygen diffusion in mass transfer influenced regime. On the other hand, the permeability in catalyst layer only has secondary effect.The distribution of material properties in the CL is studied for the MEA fabrication strategy. The CL is divided into three sub-layers with changing material properties. With water effect considered, better performance is obtained for higher porosity near the GDL, higher electrolyte fraction in the agglomerate near the membrane. The effect of agglomerate particle size differs in the ohmic and mass transfer controlled regimes. Larger agglomerate size near GDL is preferred in the ohmic limited regime, while smaller size near GDL performs better if operated at mass transfer controlled regime.