Synthesis and characterization of carbon nanotubes supported platinum nanocatalyst for proton exchange membrane fuel cells

Multi-walled carbon nanotubes (MWCNTs) were used as catalyst support for depositing platinum nanoparticles by a wet chemistry route. MWCNTs were initially surface modified by citric acid to introduce functional groups which act as anchors for metallic clusters. A two-phase (water-toluene) method was used to transfer PtCl₆²⁻ from aqueous to organic phase and the subsequent sodium formate solution reduction step yielded Pt nanoparticles on MWCNTs. High-resolution TEM images showed that the platinum particles in the size range of 1-3 nm are homogeneously distributed on the surface of MWCNTs. The Pt/MWCNTs nanocatalyst was evaluated in the proton exchange membrane (PEM) single cell using H₂/O₂ at 80 °C with Nafion-212 electrolyte. The single PEM fuel cell exhibited a peak power density of about 1100 mW cm⁻² with a total catalyst loading of 0.6 mg Pt cm⁻² (anode: 0.2 mg Pt cm⁻² and cathode: 0.4 mg Pt cm⁻²). The durability of Pt/MWCNTs nanocatalyst was evaluated for 100 h at 80 °C at ambient pressure and the performance (current density at 0.4 V) remained stable throughout. The electrochemically active surface area (64 m² g⁻¹) as estimated by cyclic voltammetry (CV) was also similar before and after the durability test.     

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.     

Synthesis and characterization of platinum nanoparticles on in situ grown carbon nanotubes based carbon paper for proton exchange membrane fuel cell cathode

Multi-walled carbon nanotubes (MWCNTs) based micro-porous layer on the carbon paper substrates was prepared by in situ growth in a chemical vapor deposition setup. Platinum nanoparticles were deposited on in situ grown MWCNTs/carbon paper by a wet chemistry route at <100 °C. The in situ MWCNTs/carbon paper was initially surface modified by silane derivative to incorporate sulfonic acid–silicate intermediate groups which act as anchors for metal ions. Platinum nanoparticles deposition on the in situ MWCNTs/carbon paper was carried out by reducing platinum (II) acetylacetonate precursor using glacial acetic acid. High resolution TEM images showed that the platinum particles are homogeneously distributed on the outer surface of MWCNTs with a size range of 1–2 nm. The Pt/MWCNTs/carbon paper electrode with a loading of 0.3 and 0.5 mg Pt cm⁻² was evaluated in proton exchange membrane single cell fuel cell using H₂/O₂. The single cells exhibited a peak power density of 600 and 800 mW cm⁻² with catalyst loadings of 0.3 and 0.5 mg Pt cm⁻², respectively with H₂/O₂ at 80 °C, using Nafion-212 electrolyte. In order to understand the intrinsically higher fuel cell performance, the electrochemically active surface area was estimated by the cyclic voltammetry of the Pt/MWCNTs/carbon paper.     

Cathode catalyst layer using supported Pt catalyst on ordered mesoporous carbon for direct methanol fuel cell

The development of a cathode catalyst layer based on a supported Pt catalyst using an ordered mesoporous carbon (OMC) for direct methanol fuel cell is reported. An OMC with a mesopore structure between hexagonally arranged carbon nanorods is prepared using a template method. Platinum nanoparticles are supported on the OMC (Pt/OMC) with high metal loading of 60 wt.%. Compositional and morphological variations are made by varying the ionomer content and by compressing the catalyst layer to detect a parameter that determines the power performance. Increase in power density with decrease in the volume fraction of ionomer in the agglomerate comprising the Pt/OMC and the ionomer indicates that mass transport through the ionomer phase governs the kinetics of oxygen reduction. Impedance spectroscopic analysis suggests that a significant mass-transport limitation occurs at high ionomer content and in the compressed cathode. The power density of the optimum cathode layer, which employs a Pt/OMC catalyst with a Pt loading of 2 mg cm⁻², is greater than that of a catalyst layer with 6 mg cm⁻² Pt-black catalyst at a voltage higher than 0.4 V. This would lead to a significant reduction in the cost of the membrane electrode assembly.     

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.     

Synthesis and performance of platinum supported on ordered mesoporous carbons as catalyst for PEM fuel cells: Effect of the surface chemistry of the support

Platinum electrocatalysts supported on ordered mesoporous carbon (CMK-3) have been prepared as alternative catalysts for PEM fuel cells. Their performance has been compared with that of a commercial Pt-carbon black on carbon cloth electrode (E-TEK) for the hydrogen oxidation in a PEM single cell. Ordered mesoporous carbon was synthesized using nanocasting method and then platinum was deposited by incipient wetness impregnation. Before the platinum deposition, carbon support was functionalized using HNO₃ as oxidizing agent to modify its surface chemistry. The characterization study of the electrocatalysts demonstrated that the surface chemistry of the support has an important effect on both the physicochemical and electrochemical properties of electrocatalysts. For this catalyst synthesis method, functionalization did not improve the preparation of the catalyst, since the presence of surface oxygen groups facilitated the aggregation of metal particles. However, the Pt/CMK-3 based electrodes showed a better performance than the commercial one, which could be attributed to the porous structure of the support.     

Pt incorporated hollow core mesoporous shell carbon nanocomposite catalyst for proton exchange membrane fuel cells

In the present study, various commercial carbon black materials like Vulcan XC72, Black Pearl 2000, and Regal 330 were used as supporting material for polymer electrolyte membrane fuel cell (PEMFC) electrocatalysts. A promising carbon material exhibiting hollow core mesoporous shell (HCMS) structure was synthesized by the template replication of the silica spheres with solid core and mesoporous shell structure. Two carbon supports with similar pore texture were prepared by the injection of two different carbon precursors. 20 wt% Pt/C electrocatalysts were synthesized by microwave irradiation method as the cathode electrode for PEMFC. Ex situ characterization of the electrocatalysts was performed by N₂ adsorption analysis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). Electrochemical characterization of the electrocatalysts was conducted by cyclic voltammetry (CV) analysis. Effect of different carbon supports on the cathode performance was investigated in a single cell H₂/O₂ PEMFC. Fuel cell performance tests and additional ex situ characterizations showed that HCMS carbons exhibit good support characteristics with improved single cell performance. For the cathode electrode kinetics, promising fuel cell performance results were obtained as compared to the commercial carbon blacks.     

The dependence of performance degradation of membrane electrode assembly on platinum loading in polymer electrolyte membrane fuel cell

The durability of membrane electrode assemblies (MEAs) with varying amounts of Pt loading on the cathode of polymer electrolyte membrane fuel cells was investigated using load cycling as an accelerated degradation test (ADT). The single-cell performance of the MEA as determined by the ADT declined by approximately 34, 48, and 78%, when cathode Pt loading in the MEA was reduced to 0.3, 0.2, and 0.1 mg cm⁻², respectively. The increase in MEA performance declined at higher cathode Pt loading conditions, and the degradation rate of MEA performance was also diminished. To characterize the electrochemical and structural properties of the MEAs, cyclic voltammograms, electrochemical impedance spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and field-emission scanning electron microscopy were utilized before and after ADT.     

Effect of carbon black support corrosion on the durability of Pt/C catalyst

The work intends to clarify the effect of carbon black support corrosion on the stability of Pt/C catalyst. The corrosion investigations of carbon blacks with similar structures and characteristics were analyzed by cyclic voltammograms (CV) and X-ray photoelectron spectroscopy (XPS). The results indicate that a higher oxidation degree appears on the Black Pearl 2000 (BP-2000) support, i.e. BP-2000 has a lower corrosion resistance than Vulcan XC-72 (XC-72). The durability investigation of Pt supported on the two carbon blacks was evaluated by a potential cycling test between 0.6 and 1.2 V versus reversible hydrogen electrode (RHE). A higher performance loss was observed on the Pt/BP-2000 gas diffusion electrode (GDE), compared with that of Pt/XC-72. XPS analysis suggests that higher Pt amount loss appeared in the Pt/BP-2000 GDE after durability test. X-ray diffraction (XRD) analysis also shows that Pt/BP-2000 catalyst presents a higher Pt size growth. The higher performance degradation of Pt/BP-2000 is attributed significantly to the less support corrosion resistance of BP-2000.     

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

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

Pore structure and effective diffusion coefficient of catalyzed electrodes in polymer electrolyte membrane fuel cells

For polymer electrolyte membrane (PEM) fuel cells, the pore structure and small effective diffusion coefficient (EDC) of the catalyst layers have significant impact on the cell performance. In this study, both the pore structure and EDC of the catalyst layers are investigated experimentally; the pore structure of the catalyst layer is characterized by the method of standard porosimetry, and the EDC is measured by a modified Loschmidt cell for oxygen-nitrogen mixture through the catalyzed electrodes. It is found that Pt loading has a direct impact on the pore structure and consequently the EDC of the catalyzed electrodes. As the Pt loading is increased, the porosity and mean pore size of the catalyzed electrode decrease, and the EDC decreases accordingly, however, it is increased by 15–25% by increasing the temperature from 25 °C to 75 °C. The EDC of the catalyst layer is about 4.6 × 10^?7 m² s^?1 at 75 °C, compared with 25.0 × 10^?7 m² s^?1 for the uncatalyzed electrode at the same temperature.     

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

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

Engineered catalyst layer design with graphene-carbon black hybrid supports for enhanced platinum utilization in PEM fuel cell

In this study, a new approach was applied to prepare platinum/reduced graphene oxide/carbon black (Pt/rGO/CB) hybrid electrocatalysts. Unlike literature firstly GO and CB in varying ratios are homogeneously mixed with a high shear mixer and then Pt was impregnated onto the hybrid support structure according to the polyol method. According to our approach CB was used as a spacer and intercalating agent in both Pt impregnation and electrode preparation to avoid restacking and increase the Pt utilization. Thus rGO/CB based hybrid support can ease the diffusion while it is promoting to the use of high electrical connectivity and surface area of graphene. The maximum power density of 645 mW cm^?2 with Pt utilization efficiency of 2.58 kW/gPt was achieved with the hybrid containing the smallest amount of CB. It seems that this small amount of CB effectively modifies the electrode structure. The enhanced fuel cell performance can be attributed to synergistic effects from graphene and CB providing better mass transport and Pt utilization in the catalyst layer.     

Numerical investigation of delamination onset and propagation in catalyst layers of PEM fuel cells under hygrothermal cycles

Durability is one of the main obstacles that inhibits the commercialization of polymer electrolyte membrane (PEM) fuel cells for transport applications, in which the microstructure of the catalyst layers (CLs) deteriorates under dynamic loading operation. In this study, CLs’ naturally random porous structure is simplified to be a random three-phase microstructure consisting of ionomers, catalyst agglomerates and pores, and the onset and growth of delamination process between the ionomer and catalyst agglomerate is investigated numerically by considering the catalyst agglomerate as elastic while the ionomer is elasto-viscoplastic, influenced by the cell assembly force arising from the cell clamping and variations in temperature and relative humidity. It is found that increasing clamping stress delays the delamination onset but has marginal effect on delamination propagation. The amplitude of hygrothermal cycles is the dominating factor in delamination and more frequent startup/shutdown of PEM fuel cells alleviates the delamination. Correlation between the rate of plastic strain accumulation in the ionomer and the interface delamination has been observed.     

A novel catalyst layer with carbon matrix for Pt nanowire growth in proton exchange membrane fuel cells (PEMFCs)

Novel catalyst layers for proton exchange membrane fuel cells (PEMFCs) were investigated by in-situ growing of Pt nanowires (Pt-NWs) on carbon matrix. The Pt-NWs grew on the matrix along the thickness direction with a length of 10–20 nm and a diameter of 4 nm. In-situ cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and polarization experiments were employed to characterize the electrochemical performance of the Pt-NWs electrodes. The results showed that the predominantly {111}-oriented facets and oxygen access of the Pt-NWs structure contribute to the higher performance in comparison with that of the conventional catalyst layers. This work is advantageous for fuel cell catalyst layer design by allowing the controlled modification of both Pt distribution and pore size.     

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).     

Sulfonation of carbon-nanotube supported platinum catalysts for polymer electrolyte fuel cells

Sulfonic acid groups were grafted onto the surface of carbon-nanotube supported platinum (Pt/CNT) catalysts to increase platinum utilization in polymer electrolyte fuel cells (PEFCs) by both thermal decomposition of ammonium sulfate and in situ radical polymerization of 4-styrenesulfonate. The resultant sulfonated Pt/CNT catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectrometry, thermal gravimetric analysis (TGA) and electrochemical methods. The electrodes with the Pt/CNT catalysts sulfonated by the in situ radical polymerization of 4-styrenesulfonate exhibited better performance than did those with the unsulfonated counterparts, mainly because of the easier access with protons and well dispersed distribution of the sulfonated Pt/CNT catalysts, indicating that sulfonation is an efficient approach to improve performance and reduce cost for the Pt/CNT-based PEFCs. The electrodes with the Pt/CNT catalysts sulfonated by the thermal decomposition of ammonium sulfate, however, did not yield the expected performance as in the case of carbon black supported platinum (Pt/C) catalysts, probably due to the significant agglomeration of platinum particles on the CNT surface at high temperatures, indicating that the Pt/CNT catalysts are more sensitive to temperature than the Pt/C catalysts.     

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.     

Self-assembled mesoporous carbon sensitized with ceria nanoparticles as durable catalyst support for PEM fuel cell

Mesocarbon-ceria nanocomposite is proposed for developing highly durable catalyst for the application in fuel cells. Ordered arrays of the mesoporous channels with d spacing of ∼8 nm and wall thickness of ∼3 nm are fabricated through a self-assembly route between the phenolic oligomers and PEO-containing P123 block polymer combined with self-assembly of CeOH₂⁺ and the surfactant. As a result, the Pt-mesocarbon-ceria presents a high electrochemically active surface of 105 m²/g_Pt. It is also found that ceria has an appreciable influence on the performance of the fuel cell at low humidity due to the water retention of ceria nanoparticles. At 75 RH% humidity of 65 °C, single cell assembled with Pt-mesocarbon-ceria has performance better than that of the conventional Pt/C catalyst. The Pt-mesocarbon-ceria displays high resistance to corrosion because of radical scavenges of ceria. Under long period operation at open circuit voltage (OCV), the voltage of the fuel cell assembled with Pt-mesocarbon-ceria has a slight decay rate of 9.5 μV/min, in comparison to 28.5 μV/min of conventional Pt/C. After an OCV accelerated degradation of 2000 min, the electrochemically active surface of Pt-mesocarbon-ceria is 45%, much lower than 70% of Pt/C catalyst.     

Hierarchy carbon paper for the gas diffusion layer of proton exchange membrane fuel cells

This communication described the fabrication of a hierarchy carbon paper, and its application to the gas diffusion layer (GDL) of proton exchange membrane (PEM) fuel cells. The carbon paper was fabricated by growing carbon nanotubes (CNTs) on carbon fibers via covalently assembling metal nanocatalysts. Surface morphology observation revealed a highly uniform distribution of hydrophobic materials within the carbon paper. The contact angle to water of this carbon paper was not only very large but also particularly even. Polarization measurements verified that the hierarchy carbon paper facilitated the self-humidifying of PEM fuel cells, which could be mainly attributed to its higher hydrophobic property as diagnosed by electrochemical impedance spectroscopy (EIS).