Membrane electrode assembly with doped polyaniline interlayer for proton exchange membrane fuel cells under low relative humidity conditions

A membrane electrode assembly (MEA) was designed by incorporating an interlayer between the catalyst layer and the gas diffusion layer (GDL) to improve the low relative humidity (RH) performance of proton exchange membrane fuel cells (PEMFCs). On the top of the micro-porous layer of the GDL, a thin layer of doped polyaniline (PANI) was deposited to retain moisture content in order to maintain the electrolyte moist, especially when the fuel cell is working at lower RH conditions, which is typical for automotive applications. The surface morphology and wetting angle characteristics of the GDLs coated with doped PANI samples were examined using FESEM and Goniometer, respectively. The surface modified GDLs fabricated into MEAs were evaluated in single cell PEMFC between 50 and 100% RH conditions using H₂ and O₂ as reactants at ambient pressure. It was observed that the MEA with camphor sulfonic acid doped PANI interlayer showed an excellent fuel cell performance at all RH conditions including that at 50% at 80 °C using H₂ and O_2.     

High performance proton exchange membrane fuel cell electrode assemblies

The conventional 5-layer membrane electrode assembly (MEA) consists of a proton exchange membrane (PEM) locating at its center, two layers of Pt-C-40 (Pt content 40 wt%) locating next on both surfaces of PEM, and two gas diffusion layers (GDL) locating next on the outer surfaces of Pt-C layers (structure-a MEA). In this paper, we report three modified MEAs consisting of Pt-C-40 (Pt content 40 wt%) and Pt-C-80 (Pt content 80 wt%) catalysts. These are: (1) 7-layer structure-b MEA with a thin Pt-C-80 layer locating between Pt-C-40 layer and PEM; (2) 7-layer structure-c MEA with a thin Pt-C-80 layer locating between Pt-C-40 layer and GDL; and (3) 5-layer structure-d MEA with Pt-C-40 and Pt-C-80 mixing homogeneously and locating between PEM and GDL. Under a fixed Pt loading, we find structure-b, -c, and -d MEAs with 20-40 wt% Pt contributed from Pt-C-80 have better fuel cell performance than structure-a MEA consisting only of Pt-C-40. The reasons for the better fuel cell performance of these modified MEAs are attributed to the better feasibility for O₂ gas to reach cathode Pt particles and lower proton transport resistance in catalyst layers of the modified MEAs than structure-a MEA.     

Preparation and operation of gas diffusion electrodes for high-temperature proton exchange membrane fuel cells

Gas diffusion electrodes for high-temperature PEMFC based on acid-doped polybenzimidazole membranes were prepared by a tape-casting method. The overall porosity of the electrodes was tailored in a range from 38% to 59% by introducing porogens into the supporting and/or catalyst layers. The investigated porogens include volatile ammonium oxalate, carbonate and acetate and acid-soluble zinc oxide, among which are ammonium oxalate and ZnO more effective in improving the overall electrode porosity. Effects of the electrode porosity on the fuel cell performance were investigated in terms of the cathodic limiting current density and minimum air stoichiometry, anodic limiting current and hydrogen utilization, as well as operations under different pressures and temperatures.     

A novel method for preparing proton exchange membrane fuel cell electrodes by the ultrasonic-spray technique

A novel ultrasonic-spray method for preparing gas diffusion electrodes (GDEs) for proton exchange membrane fuel cell (PEMFC) is described. Platinum (Pt) loaded on Nafion^®-bonded GDEs were prepared by the ultrasonic-spray method on various commercial woven and non-woven gas diffusion layers (GDLs) at several Pt loadings in the range of 0.40-0.05 mg cm⁻². The ultrasonic-sprayed GDEs were tested and compared to commercial and hand-painted GDEs. It was found that the GDEs prepared by the ultrasonic-spray method exhibited better performances compared to those prepared by the hand-painting technique, especially at low Pt loadings. GDEs fabricated by the ultrasonic-spray method with a platinum loading of 0.05 mg cm⁻² exhibited a peak power rating of 10.9 W mg⁻¹ compared to 9.8 W mg⁻¹ for hand-painted GDEs. For all experiments using various GDLs, Sigracet SGL 10BC exhibited the best performance with a peak power of 0.695 W cm⁻².     

Imaging of membrane electrode assemblies of proton exchange membrane fuel cells by X-ray computed tomography

X-ray computed tomography was applied for the 3D imaging of membrane electrode assemblies (MEAs) together with two attached gas diffusion layers. These samples were investigated as prepared and after voltage cycling. It was possible to achieve sub-μm resolution using a lab-based stand-alone tomography system as well as a tomography add-on for a scanning electron microscope. The carbon fibres of the gas diffusion layers could be clearly resolved and the catalyst layers could be visualized.X-ray computed tomography data were also used for the validation of results from scanning electron microscopy of cross-sections of membrane electrode assemblies where the sample is exposed to significant mechanical loads during sample preparation. More specifically, it was shown that the cracks observed in catalyst layers by scanning electron microscopy already exist in the membrane electrode assembly as prepared and are not a result of sample preparation. Finally it was shown that the crack density in the catalyst layers does not significantly change during voltage cycling which suggests that crack formation is not a principal cause of the observed performance decay of the MEA.     

The effect of materials on proton exchange membrane fuel cell electrode performance

This paper describes the optimisation in the fabrication materials and techniques used in proton exchange membrane fuel cell (PEMFC) electrodes. The effect on the performance of membrane electrode assemblies (MEAs) from the solvents used in producing catalyst inks is reported. Comparison in MEA performances between various gas diffusion layers (GDLs) and the importance of microporous layers (MPLs) in gas diffusion electrodes (GDEs) are also shown. It was found that the best performances were achieved for GDEs using tetrahydrofuran (THF) as the solvent in the catalyst ink formulation and Sigracet 10BC as the GDL. The results also showed that our in-house painted GDEs were comparable to commercial ones (using Johnson Matthey HiSpec™ and E-TEK catalysts).     

Effects of porosity gradient in gas diffusion layers on performance of proton exchange membrane fuel cells

A three-dimensional, two-phase, non-isothermal model has been developed to explore the interaction between heat and water transport in proton exchange membrane fuel cells (PEMFCs). Water condensate produced from the electrochemical reaction may accumulate in the open pores of the gas diffusion layer (GDL) and retard the oxygen transport to the catalyst sites. This study predicts the enhancement of the water transport for linear porosity gradient in the cathode GDL of a PEMFC. An optimal porosity distribution was found based on a parametric study. Results show that a optimal linear porosity gradient with ?₁ = 0.7 and ?₂ = 0.3 for the parallel and z-serpentine channel design leads to a maximum increase in the limiting current density from 10,696 Am⁻² to 13,136 Am⁻² and 14,053 Am⁻² to 16,616 Am⁻² at 0.49 V, respectively. On the other hand, the oxygen usage also increases from 36% to 46% for the parallel channel design and from 55% to 67% for the z-serpentine channel design. The formation of a porosity gradient in the GDL enhances the capillary diffusivity, increases the electrical conductivity, and hence, benefits the oxygen transport throughout the GDL. The present study provides a theoretical support for existing reports that a GDL with a gradient porosity improves cell performance.     

Evaluating breakthrough pressure in gas diffusion layers of proton exchange membrane fuel cells

This paper studied the breakthrough pressure for liquid water to penetrate the gas diffusion layer （GDL） of a pro- ton exchange membrane fuel cell （PEMFC）. An ex-situ testing was conducted on a transparent test cell to visu- alize the water droplet formation and detachment on the surface of different types of GDLs through a CCD cam- era. The breakthrough pressure, at which the liquid water penetrates the GDL and starts to form a droplet, was measured. The breakthrough pressure was found to be different for the GDLs with different porosities and thick- nesses. The equilibrium pressure, which is defined as the minimum pressure required maintaining a constant flow through the GDL, was also recorded. The equilibrium pressure was found to be much lower than the breakthrough pressure for the same type of GDL. A pore network model was modified to further study the relationship between the breakthrough pressure and the GDL properties and thicknesses. The breakthrough pressure increases for the thick GDL with smaller micro-pore size.     

Water permeation through gas diffusion layers of proton exchange membrane fuel cells

Water transport through gas diffusion layer of proton exchange membrane fuels cells is investigated experimentally. A filtration cell is designed and the permeation threshold and the apparent water permeability of several carbon papers are investigated. Similar carbon paper with different thicknesses and different Teflon loadings are tested to study the effects of geometrical and surface properties on the water transport. Permeation threshold increases with both GDL thickness and Teflon loading. In addition, a hysteresis effect exists in GDLs and the permeation threshold reduces as the samples are retested. Moreover, several compressed GDLs are tested and the results show that compression does not affect the breakthrough pressure significantly. The measured values of apparent permeability indicate that the majority of pores in GDLs are not filled with water and the reactant access to the catalyst layer is not hindered.     

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.     

Effect of gas diffusion layer modulus and land-groove geometry on membrane stresses in proton exchange membrane fuel cells

The electrical functionality of PEM fuel cells is facilitated by minimizing the contact resistances between different materials in the fuel cell, which is achieved via compressive clamping. The effect of the gas diffusion layer (GDL) modulus on the in-plane stress in the membrane after clamping is studied via numerical simulations, including both isotropic and anisotropic GDL properties. Furthermore, the effect of cell width and land-groove width ratio on the in-plane stress in the membrane subjected to a single hygro-thermal cycle is investigated for aligned and alternating gas channel geometries. The results from varying the GDL properties suggest that the in-plane stress in the membrane after clamping is due to a non-linear and coupled interaction of GDL and membrane deformation. The results of the geometric studies indicate that when the gas channels are aligned, the cell width and land-groove width ratio affect the in-plane stress distribution, but do not significantly affect the stress magnitudes. However, when the gas channels are alternating, the cell width and land-groove width ratio have significant effect on the membrane in-plane stresses. The effect of land-groove geometry is qualitatively verified by a series of experimental compression tests.     

Pore-network modeling of liquid water flow in gas diffusion layers of proton exchange membrane fuel cells

Fluid flow through the gas diffusion layer (GDL) of fuel cells is numerically studied using a pore network modeling approach. The model is developed based on an experimental visualization technique (fluorescence microscopy). The images obtained from this technique are analyzed to find patterns of flow inside the GDL samples with different hydrophobicity. Three different flow patterns are observed: initial invasion, progression, and pore-filling. The observation shows that liquid water flows into the majority of available pores on the boundary of the untreated GDL and several branches are segregated from the initial pathways. For the treated GDL, however, a handful of boundary pores are invaded and the original pathways extend toward the other side of the medium with minimum branching. The numerical model, developed based on an invasion percolation algorithm, is used to study the effects of GDL hydrophobicity and thickness on the flow configuration and breakthrough time as well as to determine the flow rate and saturation in different GDL samples. During the injection of water into the samples, it is numerically shown that the flow rates are monotonically decreasing for both treated and untreated samples. For the treated sample, however, the injection flow rate is constantly lower than that of the untreated sample, resulting in a lower overall water saturation at breakthrough. The numerical results also suggest that hydrophobic treatment of thick samples has minor effects on water management and overall performance. The developed model can be used to optimize the GDL properties for designing porous medium with effective transport characteristics.     

Optimization of gas diffusion electrode for polybenzimidazole-based high temperature proton exchange membrane fuel cell: Evaluation of polymer binders in catalyst layer

Gas diffusion electrodes (GDEs) prepared with various polymer binders in their catalyst layers (CLs) were investigated to optimize the performance of phosphoric acid doped polybenzimidazole (PBI)-based high temperature proton exchange membrane fuel cells (HT-PEMFCs). The properties of these binders in the CLs were evaluated by structure characterization, electrochemical analysis, single cell polarization and durability test. The results showed that polytetrafluoroethylene (PTFE) and polyvinylidene difluoride (PVDF) are more attractive as CL binders than conventional PBI or Nafion binder. At ambient pressure and 160 °C, the maximum power density can reach ∼ 0.61 W cm⁻² (PTFE GDE), and the current density at 0.6 V is up to ca. 0.52 A cm⁻² (PVDF GDE), with H₂/air and a platinum loading of 0.5 mg cm⁻² on these electrodes. Also, both GDEs showed good stability for fuel cell operation in a short term durability test.     

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.     

Nafion/polyaniline composite membranes specifically designed to allow proton exchange membrane fuel cells operation at low humidity

A Nafion and polyaniline composite membrane (designated Nafion/PANI) was fabricated using an in situ chemical polymerization method. The composite membrane showed a proton conductivity that was superior to that obtained with Nafion^® 112 at low humidity (e.g. RH = 60%). Water uptake measurements revealed similarities between the Nafion^® 112 and Nafion/PANI membranes at different humidities. The high conductivity of the Nafion/PANI membrane at low humidity is hypothesized to be due to the existence of the extended conjugated bonds in the polyaniline; proton transfer is facilitated via the conjugated bonds in lower humidity environments allowing retention of the relatively high conductivity. Correspondingly, the performance of a single cell fuel cell containing the Nafion/PANI composite membrane is improved compared to a Nafion^® 112-containing cell under low humidity conditions. This is important for portable fuel cells, which are required to operate without external humidification.     

Water permeation analysis on gas diffusion layers of proton exchange membrane fuel cells for Teflon-coating annotation

This study presents an analysis of water permeation of a polytetrafluoroethylene (PTFE)-coated gas diffusion layer (GDL) to determine the influence of hydrophobic treatment on the GDL for diagnosis of water flooding. It is found that the behaviour of water drainage is controlled by the pore configuration instead of the hydrophobicity in GDL. Better water drainage is achieved by the action of the Teflon coating in modulating the GDL pore configuration to give both a larger average pore size and a wider distribution of pore size. The results show that water penetration through the GDL must overcome a threshold surface tension defined by the largest pore range. A 30 wt.% PTFE coating of a GDL is shown to generate a satisfactory pore configuration, explaining the improved cell polarization performance with a lower driven pressure (∼1.91 kPa) and a higher rate of water drainage.     

Surface modification of gas diffusion layers by inorganic nanomaterials for performance enhancement of proton exchange membrane fuel cells at low RH conditions

Prompted by our earlier study that fumed silica on gas diffusion layer (GDL) favored a performance improvement of the single fuel cell at lower RH conditions, the present study has been carried out with inorganic oxides in the nanoscale such as TiO₂, Al₂O₃, commercially available mixed oxides, hydrophilic silica and aerosil silica. The structure of each of the oxide coating on the GDL surface has resulted in refinement with graded pore dimension as seen from the Hg porosimetry data. The fuel cell evaluation at various RH conditions (50–100%) revealed that the performance of all the inorganic oxides loaded GDL is very high compared to that of pristine GDL. The results confirm our earlier observation that inorganic oxides on GDL bring about structural refinement favorable for the transport of gases, and their water retaining capacity enable a high performance of the fuel cell even at low RH conditions.     

Fractal model for prediction of effective hydrogen diffusivity of gas diffusion layer in proton exchange membrane fuel cell

This paper presents a novel prediction model of the effective hydrogen diffusivity for the gas diffusion layer (GDL) in proton exchange membrane fuel cell (PEMFC) by using fractal theory to characterize microstructure. With the consideration of pore-size distribution and Knudsen diffusion effect, a relationship between micro-structural parameters and effective hydrogen diffusivity of GDL is deduced. The prediction of effective hydrogen diffusivities of two samples shows that Knudsen diffusion effect makes the effective diffusivity value decrease, and after being treated with polytetrafluoroethylene (PTFE), carbon paper, a basal material of the GDL, exhibits a lower effective diffusivity value due to the decrease in the pore space and porosity. From the parametric effect study, it can be concluded that effective diffusivity has a positive correlation with pore area fractal dimension D_p or porosity ?, whereas it has a negative correlation with tortuosity fractal dimension D_t.     

In-plane gas permeability of proton exchange membrane fuel cell gas diffusion layers

A new analytical approach is proposed for evaluating the in-plane permeability of gas diffusion layers (GDLs) of proton exchange membrane fuel cells. In this approach, the microstructure of carbon papers is modeled as a combination of equally-sized, equally-spaced fibers parallel and perpendicular to the flow direction. The permeability of the carbon paper is then estimated by a blend of the permeability of the two groups. Several blending techniques are investigated to find an optimum blend through comparisons with experimental data for GDLs. The proposed model captures the trends of experimental data over the entire range of GDL porosity. In addition, a compact relationship is reported that predicts the in-plane permeability of GDL as a function of porosity and the fiber diameter. A blending technique is also successfully adopted to report a closed-form relationship for in-plane permeability of three-directional fibrous materials.