Improvement of carbon dioxide tolerance of PEMFC electrocatalyst by using microwave irradiation technique

The microwave irradiation technique was used to prepare platinum and platinum–ruthenium-based electrocatalysts on Vulcan for PEMFCs. The effects of microwave duration, base concentration and surfactant/precursor ratios on the properties of Pt-based catalysts were investigated. The prepared Pt-based catalysts were characterized by XRD and then PEMFC tests were performed. The particle sizes of the catalysts were ranging between 2 and 6 nm. Platinum–ruthenium-based catalysts were prepared to improve the carbon dioxide tolerance of the PEMFCs. The power losses arising from carbon dioxide in hydrogen feed were decreased by using the prepared PtRu-based catalysts when 30% carbon dioxide including hydrogen was sent to the fuel cell.     

Pt-based electrocatalysts for polymer electrolyte membrane fuel cells prepared by supercritical deposition technique

Pt-based electrocatalysts were prepared on different carbon supports which are multiwall carbon nanotubes (MWCNTs), Vulcan XC 72R (VXR) and black pearl 2000 (BP2000) using a supercritical carbon dioxide (scCO₂) deposition technique. These catalysts were characterized by using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and cyclic voltammetry (CV). XRD and HRTEM results demonstrated that the scCO₂ deposition technique enables a high surface area metal phase to be deposited, with the size of the Pt particles ranging from 1 to 2 nm. The electrochemical surface areas (ESAs) of the prepared electrocatalysts were compared to the surface areas of commercial ETEK Pt/C (10 wt% Pt) and Tanaka Pt/C (46.5 wt% Pt) catalysts. The CV data indicate that the ESAs of the prepared Pt/VXR and Pt/MWCNT catalysts are about three times larger than that of the commercial ETEK catalyst for similar (10 wt% Pt) loadings. Oxygen reduction activity was investigated by hydrodynamic voltammetry. From the slope of Koutecky–Levich plots, the average number of electrons transferred in the oxygen reduction reaction (ORR) was 3.5, 3.6 and 3.7 for Pt/BP2000, Pt/VXR and Pt/MWCNT, correspondingly, which indicated almost complete reduction of oxygen to water.     

Synthesis methods of low-Pt-loading electrocatalysts for proton exchange membrane fuel cell systems

While the use of a high level of platinum (Pt) loading in proton exchange membrane fuel cells (PEMFCs) can amplify the trade off towards higher performance and longer lifespan for these PEMFCs, the development of PEMFC electrocatalysts with low-Pt-loadings and high-Pt-utilization is critical and the limited supply and high cost of the Pt used in PEMFC electrocatalysts necessitate a reduction in the Pt level. In order to make such electrocatalysts commercially feasible, cost-effective and innovative, catalyst synthesis methods are needed for Pt loading reduction and performance optimization. Since a Pt-deposited carbon nanotube (CNT) shows higher performance than a commercial Pt-deposited carbon black (CB) with reducing 60% Pt load per electrode area in PEMFCs, use of CNTs in preparing electrocatalysts becomes considerable. This paper reviews the literature on the synthesis methods of carbon-supported Pt electrocatalysts for PEMFC catalyst loading reduction through the improvement of catalyst utilization and activity. The features of electroless deposition (ED) method, deposition on sonochemically treated CNTs, polyol process, electrodeposition method, sputter-deposition technique, γ-irradiation method, microemulsion method, aerosol assisted deposition (AAD) method, Pechini method, supercritical deposition technique, hydrothermal method and colloid method are discussed and characteristics of each one are considered.     

The influence of the electrochemical stressing (potential step and potential-static holding) on the degradation of polymer electrolyte membrane fuel cell electrocatalysts

The understanding of the degradation mechanisms of electrocatalysts is very important for developing durable electrocatalysts for polymer electrolyte membrane (PEM) fuel cells. The degradation of Pt/C electrocatalysts under potential-static holding conditions (at 1.2 V and 1.4 V vs. RHE) and potential step conditions with the upper potential of 1.4 V for 150 s and lower potential limits (0.85 V and 0.60 V) for 30 s in each period [denoted as Pstep(1.4V_150s–0.85V_30s) and Pstep(1.4V_150s–0.60V_30s), respectively] were investigated. The electrocatalysts and support were characterized with electrochemical voltammetry, transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS). Pt/C degrades much faster under Pstep conditions than that under potential-static holding conditions. Pt/C degrades under the Pstep(1.4V_150s–0.85V_30s) condition mainly through the coalescence process of Pt nanoparticles due to the corrosion of carbon support, which is similar to that under the conditions of 1.2 V- and 1.4 V-potential-static holding; however, Pt/C degrades mainly through the dissolution/loss and dissolution/redeposition process if stressed under Pstep(1.4V_150s–0.60V_30s). The difference in the degradation mechanisms is attributed to the chemical states of Pt nanoparticles: Pt dissolution can be alleviated by the protective oxide layer under the Pstep(1.4V_150s–0.85V_30s) condition and the potential-static holding conditions. These findings are very important for understanding PEM fuel cell electrode degradation and are also useful for developing fast test protocol for screening durable catalyst support materials.     

Preparation of Cu-Ni/YSZ solid oxide fuel cell anodes using microwave irradiation

A microwave irradiation process is used to deposit Cu nanoparticles on the Ni/YSZ anode of an electrolyte-supported solid oxide fuel cell (SOFC). The reaction time in the microwave is only 15 s for the deposition of 6 wt% Cu (with respect to Ni) from a solution of Cu(NO₃)₂·3H₂O and ethylene glycol (HOCH₂CH₂OH). The morphology of the deposited Cu particles is spherical and the average size of the particles is less than 100 nm. The electrochemical performance of the microwave Cu-coated Ni/YSZ anodes is tested in dry H₂ and dry CH₄ at 1073 K, and the anodes are characterized with scanning electron microscopy, electrochemical impedance spectroscopy, and temperature-programmed oxidation. The results indicate that preparation of the anodes by the microwave technique produces similar performance trend as those reported for Cu-Ni/YSZ/CeO₂ anodes prepared by impregnation. Specifically, less carbon is formed on the Cu-Ni/YSZ than on conventional Ni/YSZ anodes when exposed to dry methane and the carbon that does form is more reactive.     

Influence of carbon nanofiber properties as electrocatalyst support on the electrochemical performance for PEM fuel cells

Novel carbonaceous supports for electrocatalysts are being investigated to improve the performance of polymer electrolyte fuel cells. Within several supports, carbon nanofibers blend two properties that rarely coexist in a material: a high mesoporosity and a high electrical conductivity, due to their particular structure. Carbon nanofibers have been obtained by catalytic decomposition of methane, optimizing growth conditions to obtain carbon supports with different properties. Subsequently, the surface chemistry has been modified by an oxidation treatment, in order to create oxygen surface groups of different nature that have been observed to be necessary to obtain a higher performance of the electrocatalyst.     

Investigation of thermal and electrochemical degradation of fuel cell catalysts

A significant problem hindering large-scale implementation of proton exchange membrane (PEM) fuel cell technology is the loss of performance during extended operation and automotive cycling. Recent investigations of the deterioration of cell performance have revealed that a considerable part of the performance loss is due to the degradation of the electrocatalyst. In this study, an attempt is made to experimentally simulate the degradation processes such as carbon corrosion and platinum (Pt) surface area loss using an accelerated thermal sintering protocol. Two types of Tanaka fuel cell catalyst samples were heat-treated at 250 °C in humidified helium (He) gas streams and several oxygen (O₂) concentrations. The catalysts were then cycled electrochemically in pellet electrodes to determine the hydrogen adsorption (HAD) area and its evolution in subsequent electrochemical cycling. Samples that had undergone different degrees of carbon corrosion and Pt sintering were characterized for changes in carbon mass, active Pt surface area, BET (Brunauer, Emmett and Teller) surface area, and Pt crystallite size. Studies of the effect of oxygen and water concentration on two Tanaka catalysts, dispersed on carbon supports with varying BET areas, revealed that carbon oxidation in the presence of Pt follows two pathways: an oxygen pathway that leads to mass loss due to formation of gaseous products, and a water pathway that results in mass gains, especially for high BET area supports. These processes may be assisted by the formation of highly reactive OH and OOH type radicals. Platinum surface area loss, measured at varying oxygen concentrations and as a function of sintering time using X-ray diffraction (XRD), CO chemisorption, and electrochemical hydrogen adsorption, reveal an important role for carbon corrosion rather than an increase in Pt particle size for the surface area loss. Platinum surface area loss during 10 h of thermal degradation was equivalent to electrochemical degradation observed over 500 cycles for a Tanaka Pt/Vulcan electrode cycled between 0 and 1.2 V (normal hydrogen electrode-NHE). Carbon mass loss observed for 5 h of thermal degradation was comparable to that obtained during a potential hold for 86 h at 1.2 V (NHE) and 95 °C for the same catalysts.     

Use of cellulose-based carbon aerogels as catalyst support for PEM fuel cell electrodes: Electrochemical characterization

New nanostructured carbons have been developed through pyrolysis of organic aerogels, based on supercritical drying of cellulose acetate gels. These cellulose acetate-based carbon aerogels (CA) are activated by CO₂ at 800 °C and impregnated by PtCl₆²⁻; the platinum salt is then chemically or electrochemically reduced. The resulting platinized carbon aerogels (Pt/CA) are characterized with transmission electron microscopy (TEM) and electrochemistry. The active area of platinum is estimated from hydrogen adsorption/desorption or CO-stripping voltammetry: it is possible to deposit platinum nanoparticles onto the cellulose acetate-based carbon aerogel surface in significant proportions. The oxygen reduction reaction (ORR) kinetic parameters of the Pt/CA materials, determined from quasi-steady-state voltammetry, are comparable with that of Pt/Vulcan XC72R. These cellulose acetate-based carbon aerogels are thus promising electrocatalyst support for PEM application.     

High performance electrocatalysts supported on graphene based hybrids for polymer electrolyte membrane fuel cells

In this study, new electrocatalysts for PEM fuel cells, based on Pt nanoparticles supported on hybrid carbon support networks comprising reduced graphene oxide (rGO) and carbon black (CB) at varying ratios, were designed and prepared by means of a rapid and efficient microwave-assisted synthesis method. Resultant catalysts were characterized ex-situ for their structure, morphology, electrocatalytic activity. In addition, membrane-electrode assemblies (MEAs) fabricated using resultant electrocatalysts and evaluated in-situ for their fuel cell performance and impedance characteristics. TEM studies showed that Pt nanoparticles were homogeneously decorated on rGO and rGO-CB hybrids while they had bigger size and partially agglomerated distribution on CB. The electrocatalyst, supported on GO-CB hybrid containing 75% GO (HE75), possessed very encouraging results in terms of Pt particle size and dispersion, catalytic activity towards HOR and ORR, and fuel cell performance. The maximum power density of 1090 mW cm^?2 was achieved with MEA (Pt loading of 0.4 mg cm^?2) based on electrocatalyst, HE75. Therefore, the resultant hybrid demonstrated higher Pt utilization with enhanced FC performance output. Our results, revealing excellent attributes of hybrid supported electrocatalysts, can be ascribed to the role of CB preventing rGO sheets from restacking, effectively modifying the array of graphene and providing more available active catalyst sites in the electrocatalyst material.     

Durability improvement at high current density by graphene networks on PEM fuel cell

This study presents a novel structure of catalyst layers of membrane electrode assemblies (MEAs) by adding graphene to platinum on carbon black (Pt/C) to improve the durability at high current density operation (3 A cm⁻²). Graphene displays outstanding low electrical resistance and has the advantage of high electron mobility. It is also used in lithium ion batteries to improve electrical performance such as high rate charge/discharge capability and cycle-life stability. In this study, three MEAs are compared, and graphene is used as an excellent conductive additive in catalyst layers for better electrons transport at high current density operation. The MEA coated Pt/C mixed with 0.1 wt% graphene shows best durability for 0.3 V h⁻¹ which is almost 3.7 times better than that of without graphene additive (1.1 V h⁻¹). The graphene additive effectively extends the durability of the MEA. Furthermore, the MEAs are analyzed by AC impedance. The impedance arc of the MEA coated with Pt/C only is getting worse, but those two coated with graphene show similar and smaller impedance arcs after high current density operation for 80 h.     

Modeling of PEM fuel cell Pt/C catalyst degradation

Pt/C catalyst degradation remains as one of the primary limitations for practical applications of proton exchange membrane (PEM) fuel cells. Pt catalyst degradation mechanisms with the typically observed Pt nanoparticle growth behaviors have not been completely understood and predicted. In this work, a physics-based Pt/C catalyst degradation model is proposed with a simplified bi-modal particle size distribution. The following catalyst degradation processes were considered: (1) dissolution of Pt and subsequent electrochemical deposition on Pt nanoparticles in cathode; (2) diffusion of Pt ions in the membrane electrode assembly (MEA); and (3) Pt ion chemical reduction in membrane by hydrogen permeating through the membrane from the negative electrode. Catalyst coarsening with Pt nanoparticle growth was clearly demonstrated by Pt mass exchange between small and large particles through Pt dissolution and Pt ion deposition. However, the model is not adequate to predict well the catalyst degradation rates including Pt nanoparticle growth, catalyst surface area loss and cathode Pt mass loss. Additional catalyst degradation processes such as new Pt cluster formation on carbon support and neighboring Pt clusters coarsening was proposed for further simulative investigation.     

Synthesis and characterization of polypyrrole/carbon composite as a catalyst support for fuel cell applications

Polypyrrole (PPy)/Carbon composites were synthesized by in situ chemical oxidative polymerization of pyrrole monomer on carbon black. Effects of polymerization temperature (either 0 °C or 25 °C) and different dopants including p-toluenesulfonic acid (p-TSA) and sodium dodecyl sulfate (SDS) on the properties of the composites were investigated. The synthesized composites were characterized by XRD, FTIR and TGA. Electrical conductivities of the composites were determined by using four-point probe technique. Electrochemical oxidation characteristics of the synthesized PPy/Carbon composites were investigated by cyclic voltammetry via potential holding experiments. The PPy/Carbon composites synthesized at 0 °C and with p-TSA as dopant showed the best oxidation resistance than carbon and other composites.     

The influence of ethene impurities in the gas feed of a PEM fuel cell

Hydrogen produced by reforming may contain traces of hydrocarbon contaminants. These traces may affect the performance and lifetime of a fuel cell run on reformate-hydrogen. This study treats the influence of low concentrations of ethene on the adsorption and deactivation chemistry in a polymer electrolyte membrane (PEM) fuel cell. The study employs mainly cyclic voltammetry accompanied with an on-line mass spectrometer to analyse the outlet gas. Results from adsorption and desorption, by either oxidation or reduction, are presented, and the influence of adsorption potential, temperature and humidity and the presence of hydrogen are discussed. The results show that the adsorption of traces of ethene in a fuel cell is highly dependent on adsorption potential and that ethene adsorbs on Pt catalyst in a limited potential window only. Ethene cannot displace adsorbed H and is oxidised already at potentials of 0.6 V versus RHE at 80 °C, where the only detectable product is CO₂. A considerable part of ethene adsorbed at potentials above the hydrogen adsorption/desorption region can be reduced at low potentials and is desorbed as methane or ethene. Overall, the effect of low concentrations of ethene in the hydrogen feed on fuel cell performance is minimal, and no significant loss in cell voltage is found when ethene contaminated hydrogen is fed to a fuel cell running on hydrogen and oxygen at a constant load at 80 °C and at highly humidified conditions.     

Hollow core mesoporous shell carbon supported Pt electrocatalysts with high Pt loading for PEMFCs

The aim of this study is to synthesize mesoporous carbon supports and prepare their corresponding electrocatalysts with microwave irradiation method and also increasing the Pt loading over the carbon support by using some additional reducing agents. Pt loadings on hollow core mesoporous shell (HCMS) and commercial Vulcan XC72 carbon supports up to 34% and 44%, respectively, were achieved via polyol process with microwave irradiation method. When hydrazine or sodium borohydride was used in addition to ethylene glycol, Pt loading over the HCMS carbon support was increased. Characterization of the prepared electrocatalysts was performed by ex situ (BET, XRD, SEM, TGA and Cyclic Voltammetry) and in situ (PEM fuel cell tests) analysis. PEM fuel cell performance tests showed that 44% Pt/Vulcan XC72 and 28% Pt/HCMS electrocatalysts exhibited improved fuel cell performances. The results revealed that as the Pt loading increased PEM fuel cell performance was also increased.     

Commercial vehicle auxiliary loads powered by PEM fuel cell

The commercial vehicles are in leadership in emission production for on-road vehicles. This high rate of emission is released in highly populated areas where diesel driven internal combustion engines are running in inefficient operating ranges. Except the propulsion, the internal combustion engine is powering the auxiliary devices such as refrigerator unit, etc. The auxiliary units are significant contributor to the overall pollutant production. In this paper the auxiliary load power supply for refrigerator unit is shifted from internal combustion engine to PEM fuel cell. The decrease in CO₂ accumulated emissions was estimated by simulation model containing vehicle model (tire, brake, differential, gearbox and driver model), diesel engine model and auxiliary power demand model. Four stroke diesel engine was modeled and investigated. For this investigation the fully filled truck was used for simulating 100% weight load. The gross weight is 7500 kg.The novelty of the approach is the simulation performed on realistic combination of city and urban road cycle. The focus was on modelling the realistic truck driving cycle in order to correctly predict emission and fuel consumption reduction. Since initial investigation are performed on constant load demand of fuel cell, simplified model of PEMFC was applied. PEM fuel cell stack was designed in order to meet the demands of auxiliary consumers. The H₂ consumption and size of hydrogen tank was estimated based on assumed 8-h daily drive. Finally, the migration of power supply for auxiliary units on commercial vehicle from internal combustion engine showed potential of fuel savings and CO₂ reduction of up to 9% for a given case on this specific test cycle.     

Innovative catalyst supports to address fuel cell stack durability

To successfully penetrate the automotive market, cost-efficient and durable fuel cell technologies are necessary to compete with existing mature technologies.     

Carbon support oxidation in PEM fuel cell cathodes

Oxidation of the cathode carbon catalyst support in polymer electrolyte fuel cells (PEMFC) has been examined. For this purpose platinum supported electrodes and pure carbon electrodes were fabricated and tested in membrane-electrode-assemblies (MEAs) in air and nitrogen atmosphere. The in situ experiments account for the fuel cell environment characterized by the presence of a solid electrolyte and water in the gas and liquid phases. Cell potential transients occurring during automotive fuel cell operation were simulated by dynamic measurements. Corrosion rates were calculated from CO₂ and CO concentrations in the cathode exhaust measured by non-dispersive infrared spectroscopy (NDIR). Results from these potentiodynamic measurements indicate that different potential regimes relevant for carbon oxidation can be distinguished. Carbon corrosion rates were found to be higher under dynamic operation and to strongly depend on electrode history. These characteristics make it difficult to predict corrosion rates accurately in an automotive drive cycle.     

Catalytic activity vs. size correlation in platinum catalysts of PEM fuel cells prepared on carbon black by different methods

In this work nanoparticulated platinum catalysts have been prepared on carbon Vulcan XC-72 using three methods starting with chloroplatinic acid as a precursor: (i) formic acid as a reductor agent; (ii) impregnation method followed by reduction in hydrogen atmosphere at moderated temperature; and (iii) microwave-assisted reduction in ethylene glycol. The catalytic and size studies were also performed on a commercial Pt catalyst (E-Tek, De Nora).     

Microstructure changes induced by capillary condensation in catalyst layers of PEM fuel cells

This paper proposes a hypothesis for explaining Pt/C particles’ coarsening inside the catalyst layers of a PEM fuel cell. The hypothesis includes the two parts: (1) due to capillary condensation a water-bridge could be formed between two neighboring nano-scale Pt/C particles at relative humidity under 100% when the surfaces of the Pt/C particles are hydrophilic; (2) the capillary force of the water-bridge tends to pull together the Pt/C particles. The relation is derived in this paper between the capillary force and the factors including the diameter of Pt/C particles, relative humidity, temperature, distance between the two neighboring Pt/C particles and water contact angle. A parametric study is performed showing some details about water-bridge formation. Finally, the stress level induced by the capillary force inside the Nafion thin-film connecting with the Pt/C particles is calculated. The result shows that the capillary force could be large enough to break apart the Nafion thin-film, facilitating the movement of Pt/C particles towards each other.     

Detaching behaviors of catalyst layers applied in PEM fuel cells by off-line accelerated test

The detaching behavior of catalyst layers in membrane electrode assembly (MEA) for PEM fuel cells could affect the lifetime of both catalyst layers and membranes. However, this issue is always neglected. Therefore, the study of detaching behavior of catalyst layer is very conducive to investigate the failure mechanism of fuel cells. The detaching of catalyst layers was simulated by dipping membrane electrode assemblies (MEAs) into H₂O₂ solution with or without Fe²⁺. We observed the presence of detaching of catalyst layers and found the varied detaching behaviors with different accelerated testing solutions: a layered-type detaching behavior is shown for the catalyst layer treated with 30% H₂O₂ solution, whereas a crack-like detaching behavior in the case of 30% H₂O₂ solution with Fe²⁺ species (or Fenton's test). At the same time, the layered-type detaching of catalyst layers has a higher detaching rate than the crack-like detaching. These detaching behaviors should have an inherent link to degradation of recast-ionomer (Nafion) films in catalyst layers. In addition, the effect of detaching behaviors of catalyst layers on the lifetime of fuel cells has been studied by hydrogen crossover measurement, and shows that, for the crack-like detaching, the membrane has a shorter lifetime than that for the layered detaching.