Effect of Nafion gradient in dual catalyst layer on proton exchange membrane fuel cell performance

The role of Nafion^® binder in the electrodes was evaluated by changing its content for the membrane electrode assembly (MEA) fabrication. In the study, we prepared MEAs that have two different compositions of catalyst layers in electrodes. One layer which is close to the electrolyte membrane has the higher Nafion^® content. The other which is near the gas diffusion media (GDM) has the lower one. Also, we changed the thickness of two layers to find the ideal composition of the binder and Pt/C in the electrode. The dual catalyst layer coated MEA showed higher cell performance at high current density region than the pristine MEA.     

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.     

Effect of platinum amount in carbon supported platinum catalyst on performance of polymer electrolyte membrane fuel cell

The performance of polymer electrolyte membrane fuel cells fabricated with different catalyst loadings (20, 40 and 60 wt.% on a carbon support) was examined. The membrane electrode assembly (MEA) of the catalyst coated membrane (CCM) type was fabricated without a hot-pressing process using a spray coating method with a Pt loading of 0.2 mg cm⁻². The surface was examined using scanning electron microscopy. The catalysts with different loadings were characterized by X-ray diffraction and cyclic voltammetry. The single cell performance with the fabricated MEAs was evaluated and electrochemical impedance spectroscopy was used to characterize the fuel cell. The best performance of 742 mA cm⁻² at a cell voltage of 0.6 V was obtained using 40 wt.% Pt/C in both the anode and cathode.     

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.     

Tunable aggregation of short-side-chain perfluorinated sulfonic acid ionomers for the catalyst layer in polymer electrolyte membrane fuel cells

We control the aggregation of short-side-chain (SSC) perfluorinated sulfonic acid (PFSA) ionomers for catalyst-layer (CL) inks by using a dispersion solvent of dipropylene glycol (DPG) and water. By increasing the fraction of PFSA backbone preferable DPG content in a dispersion solvent, the size of SSC-PFSA aggregates decreases exponentially from microscale to nanoscale, affecting the catalyst-ionomer agglomerates’ size and distribution in the CL inks. The surface morphology and porosity properties of the resulting CL are investigated, and the fuel cell performances are studied at two different humidity conditions (50 and 100% RH). Compared to the previous study with long-side-chain (LSC) PFSA ionomers, the SSC-PFSA ionomers show the optimized performance at higher DPG content, where the solvating power is intermediate for SSC-PFSA ionomers having shorter hydrophilic side chain than LSC-PFSA ionomers.     

Ultra-low Pt loading for proton exchange membrane fuel cells by catalyst coating technique with ultrasonic spray coating machine

This paper reports use of an ultrasonic spray for producing ultra-low Pt load membrane electrode assemblies (MEAs) with the catalyst coated membrane (CCM) fabrication technique. Anode Pt loading optimization and rough cathode Pt loading were investigated in the first stage of this research. Accurate cathode Pt coating with catalyst ink using the ultrasonic spray method was investigated in the second stage. It was found that 0.272 mg_Pt/cm² showed the best observed performance for a 33 wt% Nafion CCM when it was ultrasonically spray coated with SGL 24BC, a Sigracet manufactured gas diffusion layer (GDL). Two different loadings (0.232 and 0.155 mg_Pt/cm²) exposed to 600 mA/cm² showed cathode power mass densities of 1.69 and 2.36 W/mg_Pt, respectively. This paper presents impressive cathode mass power density and high fuel cell performance using air as the oxidant and operated at ambient pressure.     

Prediction of the effective conductivity of Nafion in the catalyst layer of a proton exchange membrane fuel cell

In a previous study, a simple acid catalyzed reaction (esterification) was found to predict excellently conductivity of a membrane contaminated with NH₄⁺ or Na⁺. Since measurement of the conductivity of Nafion in a catalyst layer is problematic, being able to predict this conductivity for various formulations and fuel cell conditions would be advantageous. In this study, the same methodology as before was used to examine the proton availabilities of supported Nafion (Nafion on carbon and on Pt/C), as exists in the catalyst layer used in a PEMFC, during impurity exposure (e.g., NH₃) as a means for prediction of its conductivity. It was found that the effect of NH₃ exposure on the proton composition (yH+) of supported Nafion was similar to that of N-211 under the same conditions. Determined values of yH+ were then used to estimate the effective conductivity of an ammonium-poisoned cathode layer using the correlation developed and the agglomerate model. The predicted conductivities were matched with the results available in the literature. This technique would be useful for the optimization of catalyst design and for fuel cell simulation, since it provides many benefits over conventional performance test procedures.     

Influence of catalyst layer polybenzimidazole molecular weight on the polybenzimidazole-based proton exchange membrane fuel cell performance

The catalyst layer (CL) of a polybenzimidazole (PBI) membrane electrode assembly (MEA) consists of Pt–C (Pt on a carbon support), PBI, and H₃PO₄. Two series of catalyst ink solutions each containing Pt–C, N,N′-dimethyl acetamide, and PBIs comprising four different molecular weights (MWs) (i.e., M_w = 1.1 × 10⁴, 4.4 × 10⁴, 9.0 × 10⁴, and 17.4 × 10⁴ g mol⁻¹) are used to fabricate CLs. One catalyst ink solution series is mixed with LiCl, while the other solution series lacks LiCl. We demonstrate that the CL prepared using a lower MW PBI has a higher electrochemical surface area, lower charge transfer resistance, and higher fuel cell performance. The addition of LiCl enhances the dispersion of the high MW PBIs in the catalyst ink solution and acts as a foaming agent in CL, thus improving fuel cell performance. However, LiCl exerts small influence on the fuel cell performance of the MEAs fabricated using low MW PBIs.     

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).     

Impact of catalyst layer morphology on the performance of PEM fuel cell cathode via lattice Boltzmann simulation

Lattice Boltzmann method is an effective tool for depicting all transport phenomena governed by advection-diffusion-reaction mechanisms. In the present study, five different cathode catalyst layers of PEM fuel cells with dissimilar morphologies are stochastically reconstructed. The agglomerates of carbon black particles are considered as ellipsoids which can have different level of stretching. The reactive air flow through the reconstructed catalyst layers is simulated by 3D lattice Boltzmann agglomerate modeling for the first time. Species distributions in the pore region, electrical potential distribution in the electrolyte film, and current density distribution at the interface of catalyst layer and membrane are depicted and analyzed. The results of this study show that oxygen and water vapor mole fraction variation is unsmooth and disturbed; and by increasing of ellipsoid stretching, this unsmooth and disturbed manner becomes more severe. Besides, the water content of the electrolyte film remains at its initial value mostly at the top of upper agglomerates while higher water content is observed where the agglomerates are closer to each other. Moreover, the catalyst layer in which ellipsoidal agglomerates have the highest level of stretching provides the maximum average current density.     

Effect of catalyst layer with zeolite on the performance of a proton exchange membrane fuel cell operated under low-humidity conditions

Proton exchange membrane fuel cells (PEMFCs) employ a proton conductive membrane as the separator to transport a hydrogen proton from the anode to the cathode. The membrane's proton conductivity depends on the water content in the membrane, which is affected by the operating conditions. A membrane electrode assembly (MEA) that can self-sustain water is the key component for developing a light-weight and compact PEMFC system without humidifiers. Hence, zeolite is employed to the anode catalyst layer in this study. The effect of the gas diffusion layer (GDL) materials, catalyst loading, binder loading, and zeolite loading on the MEA performance is investigated. The MEA durability is also investigated through the electrochemical impedance spectroscopy (EIS) method. The results suggest that the MEA with the SGL28BCE carbon paper, Pt loadings of 0.1 and 0.7 mg cm^?2 in the anode and cathode, respectively, Nafion-to-carbon weight ratio of 0.5, and zeolite-to-carbon weight ratio of 0.3 showed the best performance when the cell temperature is 60 °C and supplies with dry hydrogen and air from the environment. According to the impedance variation measured by EIS, the MEA with zeolite in the anode catalyst layer shows higher and more stable performance than those without zeolite.     

Low temperature decal transfer method for hydrocarbon membrane based membrane electrode assemblies in polymer electrolyte membrane fuel cells

Decal transfer is an effective membrane electrode assembly (MEA) fabrication method known for its low interfacial resistance and suitability for mass processing. Previously decal transfer for hydrocarbon membranes was performed at temperatures above 200 °C. Here a novel low temperature decal transfer (LTD) method for hydrocarbon membranes is introduced. The new method applies a small amount (2.2 mg cm⁻²) of liquid (1-pentanol) onto the membrane separator before decal transfer to lower the T_g of the membrane and achieves complete decal transfer at 110 °C and 6 MPa. Nafion binder amount in the catalyst layer and catalyst layer annealing temperature is controlled to optimize the fuel cell performance. Compared to conventional decal transfer (CDT), the novel LTD method shows enhancement in energy efficiency, simplicity in the process scheme, and improvement in fuel cell performance.     

Controlling the microscopic morphology and permeability of catalyst layers in proton exchange membrane fuel cells by adjusting catalyst ink agglomerates

Since agglomerates in catalyst inks affect the catalyst layers (CL) and membrane electrode assemblies (MEA) of proton exchange membrane fuel cell (PEMFC), it is important to study the connection among catalyst agglomerates, CL structure, and MEA performance. This study investigates the effect of Pt/GC catalyst agglomerates on the morphology and permeability of the CL by modulating the properties of the catalyst ink in two different ways. Additionally, MEA was further electrochemically tested to understand the relationship between the catalyst agglomerates and MEA performance. The result shows that High-pressure homogenization is more effective than mechanical shear mixing in dispersing the agglomerates in catalyst inks. However, the excessive homogenization pressure produced larger agglomerated particles, probably because more effective dispersion caused by higher homogenization pressure supplies new chain carriers for polymerization and higher temperature caused by higher homogenization pressure. Moreover, the surface of the CL fabricated in inks prepared by a homogenizer is more uniform, neat, and hydrophilic. But the number of secondary pores in the catalyst layer decreases at excessive homogeneous pressure, and the water permeability becomes poor, which in turn result in lower performance and higher mass transfer resistance. The electrochemical performance test results showed that the MEA with a relatively hydrophobic CL had a performance of 0.707 V at 1000 mA cm⁻², which was 30 mV higher than that with a relatively hydrophilic CL. This study provides insights for better tuning the properties of catalyst ink, CL morphology, and permeability to obtain better performance of MEA.     

Study on the membrane electrode assembly fabrication with carbon supported cobalt triethylenetetramine as cathode catalyst for proton exchange membrane fuel cell

An improved fabrication technique for conventional hot-pressed membrane electrode assemblies (MEAs) with carbon supported cobalt triethylenetetramine (CoTETA/C) as the cathode catalyst is investigated. The V-I results of PEM single cell tests show that addition of glycol to the cathode catalyst ink leads to significantly higher electrochemical performance and power density than the single cell prepared by the traditional method. SEM analysis shows that the MEAs prepared by the conventional hot-pressed method have cracks between the cathode catalyst layer and Nafion membrane, and the contact problem between cathode catalyst layer and Nafion membrane is greatly suppressed by addition of glycol to the cathode catalyst ink. Current density-voltage curve and impedance studies illuminate that the MEAs prepared by adding glycol to the cathode catalyst ink have a higher electrochemical surface area, lower cell ohmic resistance, and lower charge transfer resistance. The effects of CoTETA/C loading, Nafion content, and Pt loading are also studied. By optimizing the preparation parameters of the MEA, the as-fabricated cell with a Pt loading of 0.15 mg cm⁻² delivers a maximum power density of 181.1 mW cm⁻², and a power density of 126.2 mW cm⁻² at a voltage of 0.4 V.     

Enhanced low-humidity performance of proton exchange membrane fuel cell by incorporating phosphoric acid-loaded covalent organic framework in anode catalyst layer

Developing self-humidifying membrane electrode assembly (MEA) is of great significance for the practical use of proton exchange membrane fuel cell (PEMFC). In this work, a phosphoric acid (PA)-loaded Schiff base networks (SNW)-type covalent organic framework (COF) is proposed as the anode catalyst layer (CL) additive to enhance the PEMFC performance under low humidity conditions. The unique polymer structure and immobilized PA endow the proposed COF network with not only excellent water retention capacity but also proton transfer ability, thus leading to the superior low humidity performance of the PEMFC. The optimization of the additive content, the effect of relative humidity (RH) and PEMFC operating temperature are investigated by means of electrochemical characterization and single cell test. At a normal operation temperature of 60 °C and 38% RH, the MEA with optimized COF content (10 wt%) showes the maximum power density of 582 mW cm^?2, which is almost 7 times higher than that of the routine MEA (85 mW cm^?2). Furthermore, a preliminary durability test demonstrates the potential of the proposed PEMFC for practice operation under low humidity environment.     

Performance prediction of PEM fuel cell cathode catalyst layer using agglomerate model

Computation of Proton Exchange Membrane (PEM) fuel cell's cathode Catalyst Layer (CL) is performed using agglomerate models in this paper, and the results are compared with homogenous one. Following our earlier homogenous model for cathode CL (see Khajeh-Hosseini et al., 2010), the focus of the present study is on agglomerate model. In this study, the derivation of agglomerate model is performed in such a way that in the simplified case when agglomerate sizes shrink to zero, the homogeneous model condition is retrieved. Validations versus two sets of experimental data are performed. For example, in one of the validation cases, Case (II), it is observed that in I_tot = 3000 [A m⁻²] the homogeneous model overestimates the performance by 80%. But the agglomerate model agrees well with the validating test cases. A set of parametric studies are performed using the agglomerate model, in which the influences of some CL structural- and cell operating-parameters are studied. A sensitivity study on the cell performance is performed to rank the influence of the parameters, with rank 1 for the most influential parameter. It is observed the agglomerate sizes possess rank 1. These results give useful guidelines for manufactures of PEMFC catalyst layers.     

Self-humidifying membrane electrode assembly prepared by adding PVA as hygroscopic agent in anode catalyst layer

In this work, a novel self-humidifying membrane electrode assembly (MEA) with addition of polyvinyl alcohol (PVA) as the hygroscopic agent into anode catalyst layer was developed for proton exchange membrane fuel cell (PEMFC). The MEA shows good self humidification performance, for the sample with PVA addition of 5 wt.% (MEA PVA5), the maximum power density can reach up to 623.3 mW·cm⁻², with current densities of 1000 mA·cm⁻² at 0.6 V and 600 mA·cm⁻² at 0.7 V respectively, at 50 °C and 34% of relative humidity (RH). It is interesting that the performance of MEA PVA5 hardly changes even if the relative humidity of both the anode and cathode decreased from 100% to 34%. The MEA PVA5 also shows good stability at low humidity operating conditions: keeping the MEA discharged at constant voltage of 0.6 V for 60 h at 34% of RH, the attenuation of the current density is less than 10%, whilst for the MEA without addition of PVA, the attenuation is high up to 80% within 5 h.     

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.     

Copolymer synergistic coupling for chemical stability and improved gas barrier properties of a polymer electrolyte membrane for fuel cell applications

A novel radiation grafted ETFE based proton conducting membrane was prepared by double irradiation grafting of two different monomers. The intrinsic oxidative stability of the ETFE-g-poly(styrene sulfonic acid-co-divinylbenzene) membrane was improved by reducing the gas crossover through incorporation of polymethacrylonitrile (PMAN) containing the strong polar nitrile group. A fuel cell test was carried out at 80 °C under constant current density of 500 mA cm⁻² for a time exceeding 1′900 h. The incorporation of PMAN considerably improves the interfacial properties of the membrane-electrode assembly. No significant change in the membrane hydrogen crossover and performance over the testing time was observed, except for a measured decrease in the membrane ohmic resistance after 1′000 h. The combination of the double irradiation induced grafting with the use of the PMAN as gas barrier in addition to its chelating abilities (e. g. Ce³⁺) offers a promising strategy to develop more durable membranes for fuel cells.