Influence of the dispersion state of ionomer on the dispersion of catalyst ink and the construction of catalyst layer

The ionomer state in the catalyst ink of a proton exchange membrane fuel cell (PEMFC) plays a critical role in the formation of the catalyst/ionomer interface on the catalyst layer (CL). In this study, the effect of ionomer dispersion state on catalyst ink dispersion and the construction of a reasonable CL was investigated. The study of catalyst inks revealed that the dispersion of n-propanol (NPA) -ionomer dispersion or sonication could effectively reduce the catalyst particle size in inks. For shear-dispersion and homogenizer-dispersion inks, the catalyst particle size was reduced from 6.17 nm to 5.12 nm and from 5.12 nm to 4.67 nm, respectively. The ionomer dispersion was capable of significantly reducing the size of agglomerates in the ink, which resulted in a reduction in the particle size of agglomerates on the surface of the cathode CL and an improvement in its flatness. The pore size distributions of the MEA cathode catalyst layers showed that water bath ultrasonic treatment of the ionomer could result in a more reasonable pore structure for the catalyst layer. The single-cell test revealed that changing the ionomer's dispersion state could significantly increase the fuel cell's output voltage to 0.707 V at 1000 mA cm⁻², and the cell's power density to 1028 mW cm⁻² at 2000 mA cm⁻².     

The impact of the thermal treatment during ink preparation on the ionomer-supported catalyst interactions in the catalyst layers

Catalyst slurries (inks) were prepared with and without thermal treatment to determine the support/ionomer structures and interactions in the catalyst layer (CL) which impact on membrane electrode performance and durability. The thermal treatment of the ink has a nominal effect on the ionomer/support structure in which the carbon support is non-graphitised. The agglomerate/aggregate structures have a high degree of support/ionomer interface and sufficient macroporosity for water movement in the CL. This improves the membrane electrode assembly (MEA) performance, but also accelerates electrochemical carbon degradation. Thermal treatment of graphitised support-containing inks resulted in increased performance facilitated by a larger support/ionomer interface. Without thermal treatment, the more hydrophobic support would form aggregate structures in which water contact was restricted, limiting proton transfer, isolating catalyst, decreasing performance. The water limited access, would however, prolong stability during accelerates carbon degradation. The electrochemical properties were studied using full and half MEA cells.     

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.     

Effect of rheological properties of catalyst slurry on the structure of catalyst layer in PEMFC

The dispersion process significantly influences the dispersion of catalyst slurry in proton exchange membrane fuel cells (PEMFCs). The particle size distribution and rheological properties of clusters in slurry directly affect the catalyst layer's coating state, surface morphology, and structure. This paper prepared four different catalyst slurries by high shear emulsification, homogenization, ball milling, and ultrasonic methods. The average particle sizes of clusters in slurry were 725, 337, 452, and 1098 nm, respectively. The rheological properties of catalyst slurry prepared by several dispersion processes are different. Amplitude scanning test demonstrates that yield stresses of slurries prepared by shear, homogenization, ball milling, and ultrasonic methods are 0.047, 0.185, 0.133, and 0.136 Pa, respectively. The viscosity of catalyst slurry is the lowest when prepared by the shear method and is the highest when prepared by the ultrasonic method, and the slurry prepared by homogenization and ball milling methods has the best thixotropy. By observing the catalyst layer, the slurry cluster prepared by the homogenization method has small particles, a strong network structure, and good thixotropy, producing a flat catalyst layer and fewer cracks. Electrochemical tests demonstrate that the catalyst layer with the smoothest surface morphology, the smallest cluster particles, and fewer cracks leads to higher polarization performance. The output voltage of the ink prepared by the homogenization method can reach 0.726 V under the condition of 1000 mA cm^?2.     

Optimal catalyst layer structure of polymer electrolyte membrane fuel cell

In a membrane electrode assembly (MEA) of polymer electrolyte membrane fuel cells, the structure and morphology of catalyst layers are important to reduce electrochemical resistance and thus obtain high single cell performance. In this study, the catalyst layers fabricated by two catalyst coating methods, spraying method and screen printing method, were characterized by the microscopic images of catalyst layer surface, pore distributions, and electrochemical performances to study the effective MEA fabrication process. For this purpose, a micro-porous layer (MPL) was applied to two different coating methods intending to increase single cell performances by enhancing mass transport. Here, the morphology and structure of catalyst layers were controlled by different catalyst coating methods without varying the ionomer ratio. In particular, MEA fabricated by a screen printing method in a catalyst coated substrate showed uniformly dispersed pores for maximum mass transport. This catalyst layer on micro porous layer resulted in lower ohmic resistance of 0.087 Ω cm² and low mass transport resistance because of enhanced adhesion between catalyst layers and a membrane and improved mass transport of fuel and vapors. Consequently, higher electrochemical performance of current density of 1000 mA cm^-2 at 0.6 V and 1600 mAcm⁻² under 0.5 V came from these low electrochemical resistances comparing the catalyst layer fabricated by a spraying method on membranes because adhesion between catalyst layers and a membrane was much enhanced by screen printing method.     

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.     

Influence of carbon support microstructure on the polarization behavior of a polymer electrolyte membrane fuel cell membrane electrode assemblies

The influence of carbon support morphology on the polarization behavior of a PEM fuel cell membrane electrode assembly has been investigated in this communication. Nanometer sized platinum electrocatalyst particles were deposited on lower surface area fibrous (carbon nanofibers) and particulate carbon supports (carbon blacks) by the well-documented ethylene glycol route for supported electrocatalyst synthesis. These supported catalyst systems were subsequently utilized to prepare catalyst inks and membrane electrode assemblies (MEA) in conjunction with a perflurosulfonated ionomeric membrane-Nafion^®. Level of liquid Nafion binder in the supported catalyst inks was varied and the ramifications of such a variation on polarization behavior of the MEA determined. The trend in polarization performance was found to be independent of the carbon support morphology in the various ink compositions. The two varieties of carbon supports were also mixed together in various weight ratios and platinum was deposited by the glycol method. Key parameters such as the platinum content on carbon and platinum particle size were determined to be independent of the nature of the supports on which the particles had been deposited. The results indicate that lower surface area carbon supports of vastly contrasting morphologies can be interchangeably employed as catalyst support materials in a PEM fuel cell MEA.     

To improve the high temperature polymer electrolyte membrane fuel cells performance by altering the properties of catalyst layer

The structure of electrochemical reaction zone and the catalyst layer (CL) thickness affect the performance of high temperature polymer electrolyte membrane fuel cells. In this study, the physical structures and compositions of CL are investigated by electron microscopy and polarization curve techniques. The Pt concentration of Pt/C decides the thickness of CL when the Pt loading is fixed. A higher weight percentage Pt/C contains a lower amount of carbon powder results in a thin CL and limited space for electrochemical reaction. On the other hand, the lower weight percent Pt/C provides larger space and smaller size of platinum catalyst which engenders the electrochemical reaction in CL more easily. The ionomer binds electrocatalysts Pt/C particles together and offers the ion conducting phase. Two different ionomers, Polytetrafluoroethylene (PTFE) and Polyvinylidene difluoride (PVDF), were tested. SEM results showed that PTFE forms a better uniform CL structure than PVDF. With 10 wt% Pt/C, PTFE ionomer possesses a higher gas permeability property which induces a higher reactant flow rate in CL, and consequently results in a 42.9% higher cell potential than the PVDF at 0.4 A/cm² current density output. A proper combination of 10 wt% Pt/C with PTFE ionomer is able to gain 0.62 A/cm² output at 0.3067 V for the HT-PEMFC.     

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.     

Water-alcohol dispersible and self-cross-linkable sulfonated poly(ether ether ketone): Application as ionomer for direct methanol fuel cell catalyst layer

A sulfonated poly(ether ether ketone) containing hydroxyl groups (HO-SPEEK) has been synthesized for investigation as the ionomer in cathode of direct methanol fuel cells. Na salt-formed HO-SPEEK shows excellent solubility in some aqueous solutions of monohydric alcohol and can be successfully self-cross-linked in-situ during the hot-pressing process of membrane-electrode assembly (MEA) fabrication. The resulted cross-linked HO-SPEEK displays improved stability and mechanical strength. MEA incorporating the HO-SPEEK as both membrane and ionomer shows excellent peak power density of 29.0 mW cm⁻² at 25 °C with 4 M methanol, which is comparable to the Nafion reference MEA (31.8 mW cm⁻²) and 2.9-fold higher than that of the MEA prepared from catalyst ink that contained dimethyl sulfoxide (10.3 mW cm⁻²). Thanks to the avoidance of high-boiling point solvent, the resulted HO-SPEEK-based cathode is loosened with many large pores for reactant gas and product transportation. These results demonstrate that water-alcohol dispersible and cross-linkable sulfonated hydrocarbons hold technological promise as ionomer for electrode.     

Numerical analysis on transport properties of self-humidifying dual catalyst layer via 3-D reconstruction technique

Developing a fuel cell model with fundamental structural properties such as distribution of pore size, geometrical network of individual phase, and volume-specific interfacial area are critical in evaluating the accurate cell performance. Therefore, herein, by Focused Ion Beam Scanning Electron Microscopy (FIB-SEM) tomography, three-dimensional (3-D) microstructure of CLs is reconstructed from two real-time samples: (i) High tortuosity humidifying catalyst layer (HTH CL) and (ii) standard catalyst layer. From the reconstructed microstructure, water imbibition behavior at different levels of capillary pressure is simulated and the effective transport properties such as gas permeability, gas diffusivity, surface area and water permeability are derived as well. By coupling the effective structural and transport properties, a 2D model is developed to predict the performances of the two CLs, at relative humidity (RH) levels of 20% and 100%. Since the effective transport properties are derived from real-time samples, this 2D model is expected to have a greater accuracy in predicting the fuel cell performance. Finally, the mechanism of self-humidifying MEA at lower and higher RH conditions (20% RH and 100% RH) is demonstrated as a function of liquid water saturation in the cathode CL and water dry-out in the anode CL.     

Reduced mass transport resistance in polymer electrolyte membrane fuel cell by polyethylene glycol addition to catalyst ink

Effects of Polyethylene glycol (PEG) addition to cathode catalyst ink were investigated by changing the addition amount of PEG. Performance of the polymer electrolyte membrane fuel cells (PEMFCs) increased and then decreased at the higher current density than 1.5 A/cm² as the amount of PEG addition increased. However, durability was not changed by the addition of PEG to the catalyst ink. Three different molecular weights of PEG were compared for PEG additives to cathode catalyst ink. Performance at high current density region increased and then decreased as PEG molecular weight increases from 200 to 10000. Increased performance by addition of PEG was attributed from reduced mass transport resistance. However, addition of large molecular weight PEG to catalyst ink reduced the performance because it lowered ionomer conductivity in the catalyst layer and then reduced proton transport resistance. Increased pore size in the catalyst layer and increased hydrophilicity on the electrode were also analyzed by addition of PEG to catalyst ink.     

High performance membrane electrode assemblies by optimization of coating process and catalyst layer structure in direct methanol fuel cells

High performance membrane electrode assemblies (MEAs) for direct methanol fuel cells (DMFCs) are developed by changing the coating process, optimizing the structure of the catalyst layer, adding a pore forming agent to the cathode catalyst layer, and adjusting the hot-pressing conditions, such as pressure and temperature. The effects of these MEA fabrication methods on the DMFC performance are examined using a range of physicochemical and electrochemical analysis tools, such as FE-SEM, electrochemical impedance spectroscopy (EIS), polarization curves, and differential scanning calorimetry (DSC) of the membrane. EIS and polarization curve analysis show that an increase in the thickness and porosity of the cathode catalyst layer plays a key role in improving the cell performance with reduced cathode reaction resistance, whereas the MEA preparation methods have no significant effects on the anode impedance. In addition, the addition of magnesium sulfate as a pore former reduces the cathode reaction transfer resistance by approximately 30 wt%, resulting in improved cell performance.     

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.     

Improving cell performance and alleviating performance degradation by constructing a novel structure of membrane electrode assembly (MEA) of DMFCs

The conventional electrodes of direct methanol fuel cells (DMFCs) usually encounter a problem that the catalysts sink into the diffusion layer after a period of operation, causing a lowered catalyst utilization and degraded cell performance. Aiming to alleviate this problem, in this work a novel anode electrode structure is proposed, in which a microporous layer containing Nafion polymer is added between the catalyst layer and the microporous layer with PTFE. The presence of the Nafion-contained layer can expand the three-phase interface region of the electrochemical reactions and improve the utilization of the catalyst. The single cell test showed that the peak power densities of the novel membrane electrode assembly (MEA) fed with 0.5 M and 2 M methanol solutions reached 38.35 mW cm⁻² and 101.82 mW cm⁻², which increased by 100.42% and 15.27% compared with those of conventional single microporous layer. Electrochemical impedance spectroscopy (EIS) measurements indicated the charge transfer resistance of the conventional MEA structure was increased by 303.78%, while the new one was decreased by 47.91% after continuously operating for 48 h. The anode electrochemical active surface area (ECSA) values of the novel MEA and the conventional MEA were 52.6 m² g^-1 and 44.3 m² g^-1. These experimental results showed that the performance of the double microporous layer MEA was higher than that of the conventional MEA. This new microporous layer structure is promising to be used in fuel cells to improve cell performance and alleviate performance degradation after long-term operating.     

Study of catalyst sprayed membrane under irradiation method to prepare high performance membrane electrode assemblies for solid polymer electrolyte water electrolysis

In this work, a catalyst sprayed membrane under irradiation (CSMUI) method was investigated to develop high performance membrane electrode assembly (MEA) for solid polymer electrolyte (SPE) water electrolysis. The water electrolysis performance and properties of the prepared MEA were evaluated and analyzed by polarization curves, electrochemistry impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The characterizations revealed that the CSMUI method is very effective for preparing high performance MEA for SPE water electrolysis: the cell voltage can be as low as 1.564 V at 1 A cm⁻² and the terminal voltage is only 1.669 V at 2 A cm⁻², which are among the best results yet reported for SPE water electrolysis with IrO₂ catalyst. Also, it is found that the noble metal catalysts loadings of the MEA prepared by this method can be greatly decreased without significant performance degradation. At a current density of 1 A cm⁻², the MEA showed good stability for water electrolysis operating: the cell voltage remained at 1.60 V without obvious deterioration after 105 h operation under atmosphere pressure and 80 °C.     

Highly efficient,cell reversal resistant PEMFC based on PtNi/C octahedral and OER composite catalyst

In order to obtain a fuel cell with both enhanced power generation performance and cell reversal resistance, the composite catalyst consisting of the self-made PtNi/C octahedral and the oxygen evolution reaction (OER) catalyst IrO₂ and RuO₂ is mixed and applied in the anode, and the only octahedral catalyst is employed as the cathode to prepare the membrane electrode assembly (MEA). The electrochemical activity of the composite catalyst decreases slightly, but its performance retention after the accelerated durability test (ADT) is higher. In the single cell test, the MEA fabricated using the composite catalyst maintains good single cell power generation performance. Compared with the control fabricated with Pt/C (JM), the cell voltage at 1 A cm⁻² and the maximum power density are increased by 23 mV and 119 mW cm⁻², respectively. Especially, its durability under continuous cell reversal condition is also improved significantly, and the holding time is prolonged by 1 h. This work realizes the transformation of the octahedral catalyst from the laboratory research to the actual application, and solves the difficulties in fuel cell application, and promotes its commercialization.     

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.     

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.     

Optimization of graded catalyst layer to enhance uniformity of current density and performance of high temperature-polymer electrolyte membrane fuel cell

The optimal use of catalyst materials is essential to improve the performance, durability and reduce the overall cost of the fuel cell. The present study is related to spatial distributions of current and overpotential for various graded catalyst structures in a high temperature-polymer electrolyte membrane fuel cell (HT-PEMFC). The effect of catalyst gradient across the catalytic layer (CL) thickness and along the channel and their combination on cell performance and catalyst utilization is investigated. The graded catalytic structure comprises two, three, or multiple layers of catalyst distribution. For a total cathode catalyst loading of 0.35 mg/cm², higher loading near the membrane presents improved cell performance and catalyst utilization due to reduced limitations caused by oxygen and ion diffusions. However, non-uniformity in the current distribution is significantly increased. The increase in the catalyst loading along the reactant flow provides a substantially uniform current density but lower cell performance. The synergy of varying catalytic profiles across the CL thickness and along the cathode flow direction is investigated. The results emphasize the importance of a rational design of cathode structure and mathematical functions as a strategic tool for functional grading of a CL towards improved uniform current distribution and catalyst utilization.