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.     

On the possibility of replacement of Pt by Pd in a hydrogen electrode of PEM fuel cells

Nanostructured Pt- and Pd-based electrocatalysts for hydrogen oxidation in proton exchange membrane (PEM) fuel cells have been synthesized and characterized. Electro-active metallic particles were obtained by chemical reduction of precursor salts on Vulcan XC-72 carbon carrier using ethylene glycol with the addition of formaldehyde. Using the synthesized Pd- and Pt-based catalysts membrane–electrode assemblies (MEAs) have been prepared and successfully tested in single fuel cells. Comparison of MEA performances demonstrates the principal possibility of replacement of the Pt by the Pd on the hydrogen electrode of PEM fuel cells.     

Study of the influence of Nafion/C composition on electrochemical performance of PEM single cells with ultra-low platinum load

The electrochemical performance of membrane electrode assemblies (MEAs) with ultra-low platinum load (0.02 mg_Pt cm^?2) and different compositions of Nafion/C in the catalytic layer have been investigated. The electrodes were fabricated depositing the catalytic ink, prepared with commercial catalyst (HiSPEC 2000), onto the gas diffusion layers by wet powder spraying. The MEAs were electrochemically tested using current-voltage curves and electrochemical impedance spectroscopy measurements. The experiments were carried out at 70 °C in H₂/O₂ and H₂/air as reactant gases at 1 and 2 bar pressure and 100% of relative humidity. For all MEAs tested, power density increases when the gasses pressure is increased from 1 to 2 bar. On the other hand, power density also increased when oxygen is used instead of air as oxidant gas in cathode. The lower power density (34 mW cm^?2) and power per Pt loading (0.86 kW g_Pt^?1) corresponds to the MEA prepared without Nafion in anode and cathode catalytic layers working with hydrogen and air at 1 bar pressure as reactants gas. The MEA with 30% wt Nafion/C reached the highest power density (422 mW cm^?2) and power per Pt loading (10.60 kW g_Pt^?1) using hydrogen and oxygen at 2 bar pressure. Finally, electrode surface microstructure and cross sections of MEAs were analyzed by Scanning Electron Microscopy (SEM). Examination of the electrodes, revealed that the most uniform ionomer network surface corresponds to the electrode with 40 wt% Nafion/C, and MEA ionomer-free catalytic layer shows delamination, it leads to low electrochemical performance.     

The stability of MEA in SPE water electrolysis for hydrogen production

Membrane electrode assemblies (MEAs) for water electrolysis were prepared by decal transferring an Ir black anode and a Pt black cathode on the two sides of a perfluorosulfonate solid polymer electrolyte (SPE) Nafion112 membrane. Performance stability of an MEA with 4 cm² effective electrode area was tested for 208 h in a single cell water electrolysis setup. The catalysts of both electrodes on the MEAs were characterized by means of XPS and XRD. Samples of feed water were analyzed by using conductivity meter, inductance coupling plasma optical emission spectroscopy (ICP-OES), ionic chromatography and total organic carbon (TOC) analyzer. Surface oxidation of the anodic Ir catalyst was evidenced, from the original metal Ir to 71.5% Ir₂O₃ and 28.5% IrO₂ after 208 h of electrolysis. While the metallic state of Pt on the cathode did not change during the same period of operation, the crystallite size of the Pt catalyst increased from 9.1 nm to 9.8 nm. Water analysis shows there is significant accumulation of impurities in the feed water, which can contaminate the MEA. Fortunately, the MEA restored more than 98% of its original performance after a simple treatment with 1 mol/L H₂SO₄ solution. This indicates the short period performance decline of the MEA is mainly caused by a recoverable contamination.     

Performance of carbon-supported PtPd as catalyst for hydrogen oxidation in the anodes of proton exchange membrane fuel cells

In this work, the replacement of platinum by palladium in carbon-supported catalysts as anodes for hydrogen oxidation reaction (HOR), in proton exchange membrane fuel cells (PEMFCs), has been studied. Anodes with carbon-supported Pt, Pd, and equiatomic Pt:Pd, with various Nafion^® contents, were prepared and tested in H₂|O₂ (air) PEMFCs fed with pure or CO-contaminated hydrogen. An electrochemical study of the prepared anodes has been carried out in situ, in membrane electrode assemblies, by cyclic voltammetry and CO electrooxidation voltammetry. The analyses of the corresponding voltammograms indicate that the anode composition influences the cell performance. Single cell experiments have shown that platinum could be replaced, at least partially, saving cost with still good performance, by palladium in the hydrogen diffusion anodes of PEMFCs. The performance of the PtPd catalyst fed with CO-contaminated H₂ used in this work is comparable to Pt, thus justifying further work varying the CO concentration in the H₂ fuel to assert its CO tolerance and to study the effect of the Pt:Pd atomic ratio.     

Improvement of the proton exchange membrane fuel cell (PEMFC) performance at low-humidity conditions by adding hygroscopic γ-Al2O3 particles into the catalyst layer

In this study, hygroscopic γ-alumina particles were added into the catalyst layer of membrane electrode assemblies (MEAs) to improve the wettability and performance of PEMFC at low-humidity conditions. Hygroscopic γ-alumina particles with a BET surface area of 442 m² g⁻¹ and an average pore diameter of 9 nm were synthesized by a three-step sol–gel procedure. Uniform Pt/C/γ-alumina catalyst ink was prepared by utilizing an ultrasonic method, and then sprayed on commercial hydrophobic carbon clothes to serve as the catalyst layer. The water contact angles of the catalyst layer with various amounts of γ-alumina additions 0%, 10%, 20% and 40% were measured to be 136°, 109°, 79° and 0°, respectively. Effect of adding γ-alumina particles into the catalyst layer on the single cell performance was investigated under different temperatures of the electrode humidifier. The increased wettability of the cathode catalyst layer with γ-alumina addition reduced the cell performance due to water flooding, which demonstrates the hygroscopic characteristic of γ-alumina particles. On the other hand, when the γ-alumina particles were added into the anode catalyst layer, it was found that the MEA with 10% γ-alumina addition had the highest current density at anode humidifier temperatures ranging from 25 to 55 °C. Nevertheless, the MEA with 40% γ-alumina addition into the anode catalyst layer showed the lowest current density because of the high electrical resistance of the catalyst layer and the water flooding in the anode caused by excess water absorption. The increased wettability of the anode catalyst layer by an appropriate amount of γ-alumina additions also enhances the water adsorption of the anode due to back diffusion.     

Support effect of anode catalysts using an organic metal complex for fuel cells

The carbon support effect of Pt–Ni(mqph) electrocatalysts on the performance of CO tolerant anode catalysts for polymer electrolyte fuel cells (PEFCs) was investigated using carbon black and multi-walled carbon nanotubes (MWCNTs), with and without defect preparation. 20%Pt–Ni(mqph)/defect-free CNTs showed a very high CO tolerance (75% compared to the CO-free H₂ case) under 100 ppm CO level in the half-cell system of the hydrogen oxidation reaction. On the other hand, the hydrogen oxidation current on Pt–Ni(mqph)/defective CNTs, Pt–Ni(mqph)/VulcanXC-72R and Pt–Ru/VulcanXC-72R significantly decreased with increasing concentration of CO up to 100 ppm (25–47% compared to the CO-free H₂ case). It is thus considered that the carbon support materials strongly affect the CO tolerance of anode catalysts. This is ascribed to a change in the electronic structure of the Pt particles due to the interaction with the graphene surface, leading to a reduction in the adsorption energy of CO. Ni(mqph) also mitigates CO poisoning due to its ability of CO coordination on Ni metal center.     

The effect of functionalised multi-walled carbon nanotubes in the hydrogen electrooxidation reaction in reactive currents impurified with CO

The present article investigates the tolerant effect exerted by a functionalised multi-walled carbon nanotube (MWCNT) support compared with the Vulcan XC-72 support for a nanoparticulate Pt catalyst. The negative effect produced in the hydrogen oxidation reaction (HOR) by the presence of a Pt contaminated with high CO coverage was analysed. This investigation was conducted using a rotating disk electrode (RDE) and a single cell with membrane electrode assemblies (MEAs) with loads of 0.3 mg Pt/cm² for the anode and 0.6 mg Pt/cm² for the cathode at various poisoning times. To this end, polarisation curves were performed, and electrochemical impedance spectroscopy (EIS) measurements were analysed. In addition, the recovery of the poisoning/de-poisoning process was studied. The –OH groups anchored to the MWCNT support exert a protective effect on the Pt nanoparticles, making the catalyst more efficient in a PEMFC fed with H₂ + CO.     

Influence of anion ionomer content and silver cathode catalyst on the performance of alkaline membrane electrode assemblies (MEAs) for direct methanol fuel cells (DMFCs)

Alkaline membrane electrode assemblies (MEAs) were fabricated by a dry spraying method in order to evaluate and improve their performance. I–V tests indicated that the performance of alkaline direct methanol fuel cells (DMFCs) deeply depends on the ionomer contents of MEAs. MEA with 45.4% mass ionomer content showed the highest performance when non-alkaline (MeOH (1 M)) and alkaline (MeOH (1 M), NaOH (0.5 M)) fuels were used. When alkaline fuel was used, the anode and cathode performances of MEAs were also measured. The ionomer content has been shown to contribute ohmic polarization of the anode and diffusion polarization of the cathode. Furthermore, the performance of MEA with an Ag cathode catalyst was characterized. The Ag cathode catalyst was demonstrated to be a promising alternative to a Pt cathode catalyst because of its tolerance for methanol crossover.     

Optimum compositions of membrane electrode assemblies (MEAs) for direct dimethyl ether fuel cell

We investigated the effects of the compositions of catalyst layers and diffusion layers on performances of the membrane electrode assemblies (MEAs) for direct dimethyl ether fuel cell. The performances of the MEAs with different thicknesses of Nafion membranes were compared in this work. The optimal compositions in the anode are: 20 wt% Nafion content and 3.6 mg cm⁻² Pt loading in the catalyst layer, and 30 wt% PTFE content and 1 mg cm⁻² carbon black loading in the diffusion layer. In the cathode, MEA with 20 wt% Nafion content in the catalyst layer and 30 wt% PTFE content in the diffusion layer presented the optimal performance. The MEA with Nafion 115 membrane displayed the highest maximum power density of 46 mW cm⁻² among the three MEAs with different Nafion membranes. Copyright © 2009 John Wiley & Sons, Ltd.     

Self-humidification of a PEM fuel cell using a novel Pt/SiO2/C anode catalyst

In this work, a membrane electrode assembly (MEA) for proton exchange membrane fuel cell (PEMFC) operating under no external humidification has been successfully fabricated by using a composite Pt/SiO₂/C catalyst at the anode. In the composite catalyst, amorphous silica, which originated from the hydrolysis of tetraethyl orthosilicate (TEOS), was immobilized on the surface of carbon powder to enhance the stability of silica and provide a well-humidified surrounding for proton transport in the catalyst layer. The characteristics of silica in the composite catalyst were investigated by XRD, SEM and XPS analysis. The single cell tests showed that the performance of the novel MEA was comparable to MEAs prepared using a standard commercial Pt/C catalyst with 100% external humidification, when both were operated on hydrogen and air. However, in the absence of humidification, the MEA using Pt/SiO₂/C catalyst at the anode continued to show excellent performance, while the performance of the MEA containing only the Pt/C catalyst rapidly decayed. Long-term testing for 80 h further confirmed the high performance of the non-humidified MEA prepared with the composite catalyst. Based on the experimental data, a possible self-humidifying mechanism was proposed.     

Particle size dependence of CO tolerance of anode PtRu catalysts for polymer electrolyte fuel cells

An anode catalyst for a polymer electrolyte fuel cell must be CO-tolerant, that is, it must have the function of hydrogen oxidation in the presence of CO, because hydrogen fuel gas generated by the steam reforming process of natural gas contains a small amount of CO. In the present study, PtRu/C catalysts were prepared with control of the degree of Pt-Ru alloying and the size of PtRu particles. This control has become possible by a new method of heat treatment at the final step in the preparation of catalysts. The CO tolerances of PtRu/C catalysts with the same degree of Pt-Ru alloying and with different average sizes of PtRu particles were thus compared. Polarization curves were obtained with pure H₂ and CO/H₂ (CO concentrations of 500-2040 ppm). It was found that the CO tolerance of highly dispersed PtRu/C (high dispersion (HD)) with small PtRu particles was much higher than that of poorly dispersed PtRu/C (low dispersion (LD)) with large metal particles. The CO tolerance of PtRu/C (HD) was higher than that of any commercial PtRu/C. The high CO tolerance of PtRu/C (HD) is thought to be due to efficient concerted functions of Pt, Ru, and their alloy.     

Nanoimprinted electrodes for micro-fuel cell applications

Nanoimprint lithography (NIL) was used to fabricate electrodes with high specific Pt surface areas for use in micro-fuel cell devices. The Pt catalyst structures were characterized electrochemically using cyclic voltammetry and were found to have electrochemical active surface areas (EAS) ranging from 0.8 to 1.5 m² g⁻¹ Pt. These NIL catalyst structures were tested in fuel cell membrane electrode assemblies (MEA) by directly embossing a Nafion 117 membrane. The features of the mold were successfully transferred to the Nafion and a 7.5 nm thin film of Pt was deposited at a wide angle to form the anode catalyst layer. The resulting MEA yielded a very high Pt utilization of 15,375 mW mg⁻¹ Pt compared to conventionally prepared MEAs (820 mW mg⁻¹ Pt). Embossing pattern transfer was also demonstrated for spin casted Nafion films which could be used for new applications.     

Degradation analysis of dead-ended anode PEM fuel cell at the low and high thermal and pressure conditions

In this study, it is demonstrated that operation of dead-ended anode fuel cell at high temperature and pressure reduce the durability of membrane electrode assembly. In such a way that after 9000 degradation cycles, the maximum power density under H₂/O₂ gas feed mode for the aged MEA at high temperature and pressure is dropped by 38.8%. While the maximum power density drop is 27.1% for the aged MEA at low temperature and pressure. Comparison of the electrochemical impedance spectroscopy responses of MEAs shows that during aging process, the charge transfer resistance increase rate is more at higher temperature and pressure. This suggests the more severe destruction of catalyst layer at higher temperature and pressure and is in agreement with the obtained values of electrochemical surface area from the cyclic voltammetry test. In addition, the transmission electron microscopy and scanning electron microscopy images show the further degradation of cathode catalyst layer and more sever Pt agglomeration at higher temperature and pressure.     

Investigations of a platinum-ruthenium/carbon nanotube catalyst formed by a two-step spontaneous deposition method

Platinum (Pt) is a popular catalyst for hydrogen oxidation on the anode side of solid polymer fuel cells (SPFC). It increases the electrode activity, which catalyzes the reaction of the fuel cell. There are two methods commonly used to produce hydrogen for SPFC: fuel reforming and methanol decomposition. Both of these methods produce carbon monoxide, which is considered to be a poison for SPFC because it deactivates Pt easily. Adding ruthenium (Ru) to a Pt catalyst is an efficient way to improve the inhibition of carbon monoxide (CO) formation and reduce the Pt loading requirement.This study introduces a method to synthesize a bimetal catalyst that is suitable for SPFC. To improve the electrocatalyst activity, a new process with two spontaneous deposition steps is adopted. In the first step, Ru is deposited on the wall of carbon nanotubes (CNTs) to obtain Ru/CNTs. Pt is then added in the second deposition step to form Pt-Ru/CNTs. The morphology and microstructure of catalysts are characterized with microscopes, and the performance of membrane electrode assembly is evaluated by cyclic voltammetry method. Experimental results have proved that even with a lower Pt loading, this home-brewed bimetal catalyst performs a compatible electrocatalytic activity, and is capable of resisting attack from CO when a syngas (H₂ + 20 ppm CO) is provided.     

Durable ultra-low-platinum ionomer-free anode catalyst for hydrogen proton exchange membrane fuel cell

An ultra-low-platinum catalyst based on finely dispersed platinum (Pt) deposited on a highly porous complex microporous layer was investigated as a candidate of durable anode catalyst for hydrogen oxidation reaction (HOR) in proton exchange membrane fuel cells. Etching of teflonated and nitridized base carbon substrate in oxygen plasma and simultaneous deposition of cerium oxide were applied to increase active surface area and electrochemical activity of the platinum nanocatalyst. Ultra-low loadings of Pt (between 0.85 and 8.5 μg cm⁻²) deposited by magnetron sputtering on this substrate were assembled with Nafion 212 membrane and commercially available Pt/C cathodes (300-400 μg cm⁻² Pt). Such membrane electrode assembly (MEA) with extremely low Pt content at anode can deliver high output power densities, reaching 0.95 W cm⁻² or 0.65 W cm⁻² with only 1.7 μg cm⁻² of Pt, using H₂ as fuel and pure O₂ or air as an oxidant, respectively. Although electrocatalysts with highly dispersed active metals are known to often suffer from irreversible degradation, the above MEAs proved to be very stable when the cell was subjected to a durability test under heavy duty conditions of on/off cycling. The system with lower Pt content is more prone to water flooding which can, however, be eliminated by maintaining better control over the fuel humidity. Average decay of the cell voltage less than 50 μV h⁻¹ was obtained in the cycling regime, while excellent stability <10 μV h⁻¹ is achievable under the static load of 0.4 A cm⁻².     

The influence of the membrane thickness on the performance and durability of PEFC during dynamic aging

The influence of the membrane thickness on the performance and durability of 25 cm² membrane electrode assembly (MEA) toward dynamic aging test was investigated. The tested MEAs consist of chemically stabilized membranes (AQUIVION™) with thicknesses of 30 and 50 μm, electrocatalyst – 46 %Pt/C (Tanaka) with Pt loadings of 0.25 (anode), 0.45 mg cm⁻² (cathode) and gas diffusion layers 25 BC (SGL Group). The applied dynamic aging procedure is repetitive current cycling between 0.12 A cm⁻² for 40 s and 0.6 A cm⁻² for 20 s. The testing conditions were 80 °C, fully saturated hydrogen and air, total pressure of 2.5 atm abs. The aging procedure was regularly interrupted for evaluating the MEAs' “health” via electrochemical methods and mass spectrometry. The carbon support degradation as a function of the electrode potential, current cycling and supplied gas was studied. The effects of the Pt particles agglomeration and Pt physical loss in the active layer of the cathode on the MEAs performance degradation were individually assessed. The effect of the membrane thicknesses on the performance and durability of the PEFC was established. The reasons and stages of MEAs performance degradation were analyzed.     

Quantitative analysis of oxygen-containing species adsorbed on the Pt surface of a polymer electrolyte fuel cell membrane electrode assembly electrode using stripping voltammetry

The quantity of oxygen-containing species adsorbed on Pt surface of a single-cell polymer electrolyte fuel cell membrane electrode assembly (PEFC MEA) in the gas-phase system was measured by stripping voltammetry (SV), of which the adsorbed amount is considered in terms of the quantity of electric charge required for stripping. The effect of different experimental parameters on the adsorption quantity was analyzed and an optimum condition for applying SV to a PEFC MEA electrode was then suggested. The electric charge required for stripping was observed to be linearly proportional to the potential and arose from 0.7 V vs. RHE. The adsorption amount of oxygen-containing species for the PEFC MEA at a cell temperature of 60 °C was 384 μC cm⁻²-Pt at a potential of 1.0 V vs. RHE. More importantly, considering the effect of O₂ partial pressure on the adsorption in the gas-phase PEFC MEAs, water is suggested to be the main source of the oxygen in adsorbed oxygen-containing species. The present method is well applicable to quantitative studies of the oxygen-containing species adsorbed on electrodes of PEFC MEAs.     

Structure and electrocatalytic performance of carbon-supported platinum nanoparticles

The structure of Pt nanoparticles and the composition of the catalyst-Nafion films strongly determine the performance of proton exchange membrane fuel cells. The effect of Nafion content in the catalyst ink, prepared with a commercially available carbon-supported Pt, in the kinetics of the hydrogen oxidation reaction (HOR), has been studied by the thin layer rotating disk electrode technique. The kinetic parameters have been related to the catalyst nanoparticles structure, characterized by X-ray diffraction and high-resolution transmission electron microscopy. The size-shape analysis is consistent with the presence of 3D cubo-octahedral Pt nanoparticles with average size of 2.5 nm. The electrochemically active surface area, determined by CO stripping, appears to depend on the composition of the deposited Pt/C-Nafion film, with a maximum value of 73 m² g_Pt⁻¹ for 30 wt.% Nafion. The results of CO stripping indicate that the external Pt faces are mainly (1 0 0) and (1 1 1) terraces, thus confirming the cubo-octahedral structure of nanoparticles. Cyclic voltammetry combined with the RDE technique has been applied to study the kinetic parameters of HOR besides the ionomer resistance effect on the anode kinetic current at different ionomer contents. The kinetic parameters show that H₂ oxidation behaves reversibly with an estimated exchange current density of 0.27 mA cm⁻².     

A novel self-humidifying membrane electrode assembly with water transfer region for proton exchange membrane fuel cells

A novel self-humidifying membrane electrode assembly (MEA) with the active electrode region surrounded by a unactive “water transfer region (WTR)” was proposed to achieve effective water management and high performance for proton exchange membrane fuel cells (PEMFCs). By this configuration, excess water in the cathode was transferred to anode through Nafion membrane to humidify hydrogen. Polarization curves and power curves of conventional and the self-humidifying MEAs were compared. The self-humidifying MEA showed power density of 85 mW cm⁻² at 0.5 V, which is two times higher than that of a conventional MEA with cathode open. The effects of anode hydrogen flow rates on the performance of the self-humidifying MEA were investigated and its best performance was obtained at a flow rate of 40 ml min⁻¹. Its performance was the best when the environmental temperature was 40 °C. The performance of the self-humidifying MEA was slightly affected by environmental humidity. The area of WTR was optimized, and feasible area ratio of the self-humidifying MEA was 28%.