Optimization of cathode microporous layer materials for proton exchange membrane fuel cell

The microporous layer (MPL) of diffusion medium has an important impact on the water management ability of proton exchange membrane fuel cells. In this study, six kinds of carbon black were used to prepare the cathode MPL. The thickness, conductivity, pore structure, hydrophobicity, and surface microstructure of MPL were characterized. The single cell was prepared and electrochemical tests were performed. The results showed that the single cell prepared by Acetylene black (ACET) and Vulcan XC-72R has a considerable power generation performance. In addition, polyvinylidene fluoride hexafluoropropylene copolymer P(VDF-HFP) was used to replace Polytetrafluoroethylene (PTFE) as hydrophobic binder. MPL with different P(VDF-HFP) contents were prepared, and the single cell performance was investigated. The results showed that all the single cells prepared by P(VDF-HFP) were worse than that of PTFE. This study provides an important reference for further improving the performance of fuel cells from the perspective of material optimization with MPL.     

Preparation of microporous layer for proton exchange membrane fuel cell by using polyvinylpyrrolidone aqueous solution

A new method of preparing microporous layer (MPL) for proton exchange membrane fuel cell (PEMFC) was presented in this paper. Considering the bad dispersion of PTFE aqueous suspension in the carbon slurry based on ethanol, polyvinylpyrrolidone (PVP) aqueous solution was used to prepare carbon slurry for microporous layer. The prepared gas diffusion layers (GDLs) were characterized by scanning electron microscopy, contact angle system and pore size distribution analyzer. It was found that the GDL prepared with PVP aqueous solution had higher gas permeability, as well as more homogeneous hydrophobicity. Moreover, the prepared GDLs were used in the cathode of fuel cell and evaluated with fuel cell performance and EIS analysis, and the GDL prepared with PVP aqueous solution indicated better fuel cell performance and lower ohmic resistance and mass transfer resistance.     

Effect of preparative parameters on the characteristic of poly(vinylidene fluoride)-based microporous layer for proton exchange membrane fuel cells

The effect of preparative parameters on the characteristic of PVDF-based microporous layers (MPL) for proton exchange membrane (PEM) fuel cell was investigated. Physical properties of MPL involving electrical resistance, gas permeability and microstructure were examined. The results show that the characteristics of MPL were affected by preparative parameters, such as PVDF concentration, type of electrically conductive filler and its loading, PVDF/electrically conductive filler ratio, as well as type of PVDF solvent. The PEM fuel cell performance test demonstrates that the obtained MPL has a great potential and interest for further study and development.     

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.     

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.     

Novel single-layer gas diffusion layer based on PTFE/carbon black composite for proton exchange membrane fuel cell

A series of poly(tetrafluoroethylene)/carbon black composite-based single-layer gas diffusion layers (PTFE/CB-GDLs) for proton exchange membrane fuel cell (PEMFC) was successfully prepared from carbon black and un-sintered PTFE, which included powder resin and colloidal dispersion, by a simple inexpensive method. The scanning electron micrographs of PTFE/CB-GDLs indicated that the PTFE resins were homogeneously dispersed in the carbon black matrix and showed a microporous layer (MPL)-like structure. The as-prepared PTFE/CB-GDLs exhibited good mechanical property, high gas permeability, and sufficient water repellency. The best current density obtained from the PEMFC with the single-layer PTFE/CB-GDL was 1.27 and 0.42 A cm⁻² for H₂/O₂ and H₂/air system, respectively.     

Freezing characteristics of supercooled water in gas diffusion layer of proton exchange membrane fuel cells

The freezing characteristics of supercooled water in a gas diffusion layer (GDL), which are the bases for the cold start-up of proton exchange membrane fuel cells (PEMFCs), were investigated. An experimental apparatus for noncontact temperature measurement and observation systems was developed. GDL and GDL with a microporous layer (MPL) were prepared, and freezing experiments using a water-containing GDL under various cooling rates were performed with variations in polytetrafluoroethylene (PTFE) content and water saturation. Furthermore, based on the experimental results, the freezing initiation probability was theoretically investigated to elucidate the freezing characteristics. Results showed that, with increasing supercooling of water in GDL, the freezing probability of water increased abruptly. The effect of saturation showed a different trend depending on PTFE addition. For the GDL without PTFE, the freezing initiations occurred at approximately 6 °C of supercooling degree, and the probability approached 1.0 at approximately 9.5–11.5 °C, with saturation dependency. In contrast, for both GDL and GDL + MPL containing PTFE, the initiation temperature characteristics were relatively similar, which were approximately 8–12 °C, regardless of the saturation and PTFE content. In these cases, the ice-nucleating activity of water in the GDL was possibly stronger than that in the MPL.     

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.     

Enhancement of proton exchange membrane fuel cell performance by titanium-coated anode gas diffusion layer

Titanium was coated onto an anode gas diffusion layer (GDL) by direct current sputtering to improve the performance and durability of a proton exchange membrane fuel cell (PEMFC). Scanning electron microscopy (SEM) images showed that the GDLs were thoroughly coated with titanium, which showed angular protrusion. Single-cell performance of the PEMFCs with titanium-coated GDLs as anodes was investigated at operating temperatures of 25 °C, 45 °C, and 65 °C. Cell performances of all membrane electrode assemblies (MEAs) with titanium-coated GDLs were superior to that of the MEA without titanium coating. The MEA with titanium-coated GDL, with 10 min sputtering time, demonstrated the best performance at 25 °C, 45 °C, and 65 °C with corresponding power densities 58.26%, 32.10%, and 37.45% higher than that of MEA without titanium coating.     

Optimization of polytetrafluoroethylene content in cathode gas diffusion layer by the evaluation of compression effect on the performance of a proton exchange membrane fuel cell

This research investigates the optimal polytetrafluoroethylene (PTFE) content in the cathode gas diffusion layer (GDL) by evaluating the effect of compression on the performance of a proton exchange membrane (PEM) fuel cell. A special test fixture is designed to control the compression ratio, and thus the effect of compression on cell performance can be measured in situ. GDLs with and without a microporous layer (MPL) coating are considered. Electrochemical impedance spectroscopy (EIS) is used to diagnose the variations in ohmic resistance, charge transfer resistance and mass transport resistance with compression ratio. The results show that the optimal PTFE content, at which the maximum peak power density occurs, is about 5 wt% with a compression ratio of 30% for a GDL without an MPL coating. For a GDL with an MPL coating, the optimal PTFE content in the MPL is found to be 30% at a compression ratio of 30%.     

Gas diffusion layer for proton exchange membrane fuel cells—A review

Gas diffusion layer (GDL) is one of the critical components acting both as the functional as well as the support structure for membrane-electrode assembly in the proton exchange membrane fuel cell (PEMFC). The role of the GDL is very significant in the H₂/air PEM fuel cell to make it commercially viable. A bibliometric analysis of the publications on the GDLs since 1992 shows a total of 400+ publications (>140 papers in the Journal of Power Sources alone) and reveals an exponential growth due to reasons that PEMFC promises a lot of potential as the future energy source for varied applications and hence its vital component GDL requires due innovative analysis and research. This paper is an attempt to pool together the published work on the GDLs and also to review the essential properties of the GDLs, the method of achieving each one of them, their characterization and the current status and future directions. The optimization of the functional properties of the GDLs is possible only by understanding the role of its key parameters such as structure, porosity, hydrophobicity, hydrophilicity, gas permeability, transport properties, water management and the surface morphology. This paper discusses them in detail to provide an insight into the structural parts that make the GDLs and also the processes that occur in the GDLs under service conditions and the characteristic properties. The required balance in the properties of the GDLs to facilitate the counter current flow of the gas and water is highlighted through its characteristics.     

Degradations in porous components of a proton exchange membrane fuel cell under freeze-thaw cycles: Morphology and microstructure effects

In this study, porous components of a proton exchange membrane (PEM) fuel cell, i.e., single-layer gas diffusion layer (GDL, carbon paper), double-layer GDL (microporous layer (MPL) deposited carbon papers), and catalyzed electrodes, are subjected to 60 repetitive freeze-thaw cycles between −40 °C and 30 °C under water-submerged conditions; and their morphological and microstructural characteristics are investigated at each 15 cycles and compared with those of virgin materials. The results indicate that consecutive cycling of temperature causes different degradation patterns in different components. The single-layer GDL shows a unique degradation mechanism, in which macro-scale pores volumetrically expand, and relatively small-scale hollows and cracks form on the polymeric binder and carbon fiber interfaces, respectively. For the double-layer GDL, large-scale surface cracks form on the MPL surface after 15 cycles, and the morphology and microstructure degradation gains momentum with the formation of these cracks, and upon completion of 30 cycles, large-scale carbon/hydrophobic agent flakes start to detach from the surface. For the catalyzed electrodes, due to their inherently cracked surface, the catalyst layers (CLs) degrade first through expansion of the cracks in the in- and through-plane directions, and then through swelling and agglomeration of the ionomer; and combination of these two patterns triggers detachment of large CL flakes from the surface, negatively affecting the microstructure.     

Liquid water breakthrough pressure through gas diffusion layer of proton exchange membrane fuel cell

The dynamic behavior of liquid water transport through the gas diffusion layer (GDL) of the proton exchange membrane fuel cell is studied with an ex-situ approach. The liquid water breakthrough pressure is measured in the region between the capillary fingering and the stable displacement on the drainage phase diagram. The variables studied are GDL thickness, PTFE/Nafion content within the GDL, GDL compression, the inclusion of a micro-porous layer (MPL), and different water flow rates through the GDL. The liquid water breakthrough pressure is observed to increase with GDL thickness, GDL compression, and inclusion of the MPL. Furthermore, it has been observed that applying some amount of PTFE to an untreated GDL increases the breakthrough pressure but increasing the amount of PTFE content within the GDL shows minimal impact on the breakthrough pressure. For instance, the mean breakthrough pressures that have been measured for TGP-060 and for untreated (0 wt.% PTFE), 10 wt.% PTFE, and 27 wt.% PTFE were 3589 Pa, 5108 Pa, and 5284 Pa, respectively.     

Electrochemical durability of gas diffusion layer under simulated proton exchange membrane fuel cell conditions

An effective ex-situ method for characterizing electrochemical durability of a gas diffusion layer (GDL) under simulated polymer electrolyte membrane fuel cell (PEMFC) conditions is reported in this article. Electrochemical oxidation of the GDLs are studied following potentiostatic treatments up to 96 h holding at potentials from 1.0 to 1.4 V (vs.SCE) in 0.5 mol L⁻¹ H₂SO₄. From the analysis of morphology, resistance, gas permeability and contact angle, the characteristics of the fresh GDL and the oxidized GDLs are compared. It is found that the maximum power densities of the fuel cells with the oxidized GDLs hold at 1.2 and 1.4 V (vs.SCE) for 96 h decreased 178 and 486 mW cm⁻², respectively. The electrochemical impedance spectra measured at 1500 mA cm⁻² are also presented and they reveal that the ohmic resistance, charge-transfer and mass-transfer resistances of the fuel cell changed significantly due to corrosion at high potential.     

Effects of the carbon black properties in gas diffusion layer on the performance of proton exchange membrane fuel cells

The microporous layer (MPL) as a part of diffusion medium has an important impact on mass transfer of proton exchange membrane fuel cell (PEMFC). In this study, MPLs of gas diffusion layers (GDLs) are prepared with different carbon blacks, and the properties of carbon blacks and their effects as MPLs on cell performance are systematically investigated. The results show that the GDL prepared by Acetylene Black (ACET) exhibits the best performance with a maximum power density up to 2.05 W cm⁻². Moreover, it still maintains extremely high performance with increasing current density even at humidity condition of 100% relative humidity, which means its excellent water/gas transportation capacity. This study contributes to deeply understanding the correlations between the properties of MPL material itself and their corresponding performance exhibited in cell. It also provides an important reference for enhancing cell performance and further advancing the practical applications of MPLs in PEMFC field.     

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.     

Recent progress of the gas diffusion layer in proton exchange membrane fuel cells: Material and structure designs of microporous layer

Proton exchange membrane fuel cells (PEMFCs) have become the most attractive power supply units for stationary and mobile applications. The operation, design characteristics, as well as performance of PEMFCs, are closely related to the multiphase transport of mass, heat, and electricity in the cell, a critical of which is the gas diffusion layer (GDL). It is very important to guarantee the transmission of water and gasses under high current density, and which is the weakness of PEMFCs at present. Microporous layer (MPL) is considered to be the key variable for mass transfer, so varieties of works focus on modification of MPL materials and its structure design. However, there is still a lack of special review to summarize and prospect the progress of MPL in recent years. This review article therefore focuses on the insights and comprehensive understanding of four critical issues of the MPL, the porosity, pore size distribution, wettability, structural design and the durability of MPL. At last, the conclusion and recommendations section summarized the future prospects and recommendations for possible research opportunities.     

Carbon film coating on gas diffusion layer for proton exchange membrane fuel cells

This study discusses a novel process to increase the performance of proton exchange membrane fuel cells (PEMFC). In order to improve the electrical conductivity and reduce the surface indentation of the carbon fibers, we modified the carbon fibers with pitch-based carbon materials (mesophase pitch and coal tar pitch). Compared with the gas diffusion backing (GDB), GDB-A240 and GDB-MP have 32% and 33% higher current densities at 0.5 V, respectively. Self-made carbon paper with the addition of a micro-porous layer (MPL) (GDL-A240 and GDL-MP) show improved performance compared with GDB-A240 and GDB-MP. The current densities of GDL-A240 and GDL-MP at 0.5 V increased by 37% and 31% compared with GDL, respectively. This study combines these two effects (carbon film and MPL coating) to promote high current density in a PEMFC.