High loading and monodispersed Pt nanoparticles on multiwalled carbon nanotubes for high performance proton exchange membrane fuel cells

Composite electrodes consisting of Pt nanoparticles-supported on multiwalled carbon nanotubes grown directly on carbon paper (Pt/CNTs/carbon paper) have been synthesized by a new method using glacial acetic acid as a reducing agent. Transmission electron microscopy (TEM) images show that the Pt nanoparticles with high density and relative small in size (2–4 nm) were monodispersed on the surface of CNTs. X-ray photoelectron spectroscopy (XPS) analysis indicates that the glacial acetic acid acts as a reducing agent and has the capability of producing a high density of oxygen-containing functional groups on the surface of CNTs that leads to high density and monodispersion of Pt nanoparticles. Compared with standard Pt/C electrode, the Pt/CNT/carbon paper composite electrodes exhibit higher electrocatalytic activity for methanol oxidation reaction and higher single-cell performance in a H₂/O₂ fuel cell.     

Dodecylamine-modified carbon supports for cathode in proton exchange membrane fuel cells

In this investigation, hydrophobic dodecylamine-modified carbon supports are prepared for proton exchange membrane fuel cells by organic synthesis. Well-dispersed Pt-Ru nanoparticles, with a narrow size distribution, are then deposited on the dodecylamine-modified carbon supports by methanol reduction to serve as cathodic catalysts. These dodecylamine-modified catalysts are separately mixed with either a commercial catalyst or unmodified catalyst to provide hydrophobic channels to convey the reaction gas to the active sites in the catalyst layer. The best cathode composite catalyst, containing 20-40 wt% of modified-catalyst, gives approximate 30% increase in the maximum power density, comparing to E-TEK catalyst (125 mW cm⁻²). The increase in the maximum power density is attributed to higher activity and lower resistance. This result is discussed in the context of AC-impedance and proton conductivity analysis.     

Stable support based on highly graphitic carbon xerogel for proton exchange membrane fuel cells

Highly graphitic carbon xerogel (GCX) is prepared by the modified sol-gel polymerization process using cobalt nitrate as the catalyst, followed by high temperature treatment at 1800 °C. The as-prepared GCX is explored as a stable support for Pt in proton exchange membrane fuel cells. The results of N₂ sorption measurement and X-ray diffraction analysis (XRD) reveal that GCX has a better mesoporous structure and a preferably higher degree of graphitization, compared with the commercial XC-72 carbon black. The transmission electron microscopy (TEM) image indicates that Pt nanoparticles are well dispersed on GCX and exhibit relatively narrow size distribution. Accelerated aging test (AAT) based on potential cycling is used to investigate the durability of the as-prepared Pt/GCX in comparison with the commercial Pt/C. Electrochemical analysis demonstrates that the catalyst with GCX as a support exhibits an alleviated degradation rate of electrochemical active surface area (39% for Pt/GCX and 53% for Pt/C). The results of single cell durability tests indicate that the voltage loss of Pt/GCX at 100 mA cm⁻² is about 50% lower than that of Pt/C. GCX is expected to be a corrosion resistant electrocatalyst support.     

Platinum decorated aligned carbon nanotubes: Electrocatalyst for improved performance of proton exchange membrane fuel cells

This study aims to improve the performance of proton exchange membrane fuel cells (PEMFCs) using carbon nanotubes as scaffolds to support nanocatalyst for power generation over prolonged time periods, compared to the current designs. The carbon nanotubes are prepared using chemical vapor deposition and decorated by platinum nanoparticles (Pt-NPs) using an amphiphilic approach. The PEMFC devices are then constructed using these aligned carbon nanotubes (ACNTs) decorated with Pt-NPs as the cathode. The electrochemical analyses of the PEMFC devices indicate the maximum power density reaches to 860 mW cm⁻² and current density reaches 3200 mA cm⁻² at 0.2 V, respectively, when O₂ is introduced into cathode. Importantly, the Pt usage was decreased to less than 0.2 mg cm⁻², determined by X-ray energy dispersive spectroscopy and X-ray photoelectron spectroscopy as complimentary tools. Electron microscopic analyses are employed to understand the morphology of Pt-ACNT catalyst (with diameter of 4-15 nm and length from 8 to 20 μm), which affects PEMFC performance and durability. The Pt-ACNT arrays exhibit unique alignment, which allows for rapid gas diffusion and chemisorption on the catalyst surfaces.     

Effects of surface chemical states of carbon nanotubes supported Pt nanoparticles on performance of proton exchange membrane fuel cells

This study synthesized platinum (Pt) nanoparticles supported on carbon nanotubes (CNTs) using a microwave-assisted polyol method. The oxidation treatment of CNTs introduced primarily -OH and -COOH groups to the CNTs, thereby enhancing the reduction of Pt ionic species, resulting in smaller Pt particles with improved dispersion and attachment properties. The Pt particles supported on oxidized CNTs displayed superior durability to those on pristine CNTs or commercially available Pt/C. These improvements are most likely associated with the percentage of metallic Pt in the particles. After 400 cycles, the losses of electrochemical surface area in Pt nanoparticle supported on oxidized CNTs and pristine CNTs catalysts were 66 and 84%, respectively, of that associated with commercial Pt/C. A single proton exchange membrane fuel cell using Pt supported on oxidized CNTs at the cathode with a total catalytic loading of 0.6 Pt mg cm⁻² exhibited the highest power density of 890 mW cm⁻² and displayed a lower mass transfer loss, compared to Pt/C.     

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.     

On the mesoporous TiN catalyst support for proton exchange membrane fuel cell

A mesoporous TiN structure with high surface area and excellent electrical conductivity was fabricated for application as a catalyst support in proton exchange membrane fuel cell (PEMFC). Pt nanoparticles were then uniformly deposited on the TiN porous support by wet chemical reduction. The performances of PEMFC using Pt@TiN electrodes were evaluated by a single cell test station. The membrane electrode assembly using Pt@TiN for both anode and cathode exhibited 70%–120% higher specific power densities than that of commercial E-Tek due to higher electrical conductivity and porosity of the catalyst support and higher Pt utilization efficiency.     

Sputtered Pt loadings of membrane electrode assemblies in proton exchange membrane fuel cells

The fabrication of electrodes use in proton exchange membrane fuel cells (PEMFCs) by Pt sputter deposition has great potential to increase Pt utilization and reduce Pt loading without loss of cell performance. A radio frequency (RF) magnetron sputter deposition process (RF power = 100 W and argon pressure = 10^?3 Torr) was adopted to prepare Pt catalyst layers of PEMFC electrodes. The effects of cathode Pt and Nafion loadings on membrane electrode assembly (MEA)/cell performance were investigated using cell polarization, cyclic voltammetry, AC impedance, and microstructure analysis. Among the tested MEAs with various cathode Pt loadings (0.02–0.4 mg cm^?2), the one with 0.1 mg‐Pt cm^?2 (grain size = 3.90 nm, mainly Pt(111)) exhibited the best cell performance (320 and 285 mW cm^?2 at 0.44 and 0.60 V, respectively), which was similar to or better than those of some commercial nonsputtered/sputtered electrodes with the same or higher Pt loadings. The electrode Pt utilization efficiency increased as the Pt loading decreased. A Pt loading of greater than or lower than 0.1 mg cm^?2 yielded a lower electrode electrochemical active surface (EAS) area but a higher charge transfer and diffusion resistance. Nafion impregnation (0.1 to 0.3 mg cm^?2) into the sputtered Pt layer (Pt = 0.1 mg cm^?2) noticeably increased the EAS area, consistent with the decrease of the capacitance of the electrode double layer, but did not improve MEA/cell performance, mainly because of the increase in the kinetic and mass transfer resistances associated with oxygen reduction on the cathode. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of sulfonated carbon nanofiber-supported Pt on performance of Nafion-based self-humidifying composite membrane for proton exchange membrane fuel cell

In the present study, the Nafion^®-based self-humidifying composite membrane (N-SHCM) with sulfonated carbon nanofiber-supported Pt (s-Pt/CNF) catalyst, N-s-Pt/CNF, is successfully prepared using the solution-casting method. The scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) images of N-s-Pt/CNF indicate that s-Pt/CNF is well dispersed in the Nafion^® matrix due to the good compatibility between Nafion^® and s-Pt/CNF. Compared with those of the non-sulfonated Pt/CNF-containing N-SHCM, N-Pt/CNF, the properties of N-s-Pt/CNF, including electronic resistivity, ion-exchange capacity (IEC), water uptake, dimensional stability, and catalytic activity, significantly increase. The maximum power density of the proton exchange membrane fuel cell (PEMFC) fabricated with N-s-Pt/CNF operated at 50 °C under dry H₂/O₂ condition is about 921 mW cm⁻², which is approximately 34% higher than that with N-Pt/CNF.     

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.     

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.     

High surface area synthesis,electrochemical activity,and stability of tungsten carbide supported Pt during oxygen reduction in proton exchange membrane fuel cells

The oxidation of carbon catalyst supports to carbon dioxide gas leads to degradation in catalyst performance over time in proton exchange membrane fuel cells (PEMFCs). The electrochemical stability of Pt supported on tungsten carbide has been evaluated on a carbon-based gas diffusion layer (GDL) at 80 °C and compared to that of HiSpec 4000™ Pt/Vulcan XC-72R in 0.5 M H₂SO₄. Due to other electrochemical processes occurring on the GDL, detailed studies were also performed on a gold mesh substrate. The oxygen reduction reaction (ORR) activity was measured both before and after accelerated oxidation cycles between +0.6 V and +1.8 V vs. RHE. Tafel plots show that the ORR activity remained high even after accelerated oxidation tests for Pt/tungsten carbide, while the ORR activity was extremely poor after accelerated oxidation tests for HiSpec 4000™. In order to make high surface area tungsten carbide, three synthesis routes were investigated. Magnetron sputtering of tungsten on carbon was found to be the most promising route, but needs further optimization.     

Enhanced hydrogen generation by hydrolysis of LiBH4 doped with multiwalled carbon nanotubes for micro proton exchange membrane fuel cell application

LiBH₄ has a high hydrogen storage capacity and could potentially serve as a superior hydrogen storage material. However, during the hydrolysis process for hydrogen generation, the agglomeration of the hydrolysis product of LiBH₄ limits its full utilization. In order to completely release the stoichiometric amount of H₂ from LiBH₄ hydrolysis, multiwalled carbon nanotubes (MWCNTs) were doped with LiBH₄ by mechanical milling. The results show that MWCNT carried LiBH₄ can slowly react with water vapor at room temperature which is 25 °C lower than the reaction temperature of neat LiBH₄. Agglomeration can be avoided when the addition of MWCNTs exceeds 7 wt.%, which results in a complete hydrolysis process. The total hydrogen capacity is 7.5 wt.%. The enhanced hydrolysis of LiBH₄ can be attributed to the MWCNTs which increased the contact areas between LiBH₄ and water and created gas channels for hydrogen diffusion. The performance of a micro proton exchange membrane fuel cell connected to MWCNT-doped LiBH₄ powder packed-bed reactor was examined. The result demonstrates that doping with MWCNTs enhanced the hydrogen generation of LiBH₄ hydrolysis. MWCNT-doped LiBH₄ can be applied as hydrogen source of fuel cells.     

Hydrocarbon-based electrode ionomer for proton exchange membrane fuel cells

The electrode ionomer is a key factor that significantly affects the catalyst layer morphology and fuel cell performance. Herein, sulfonated poly(arylene ether sulfone)-based electrode ionomers with polymers of various molecular weights and alcohol/water mixtures were prepared, and those comprising the alcohol/water mixture showed a higher performance than the ones prepared using higher boiling solvents, such as dimethylacetamide; this is owing to the formation of the uniformly dispersed ionomer catalyst layer. The relation between ionomer molecular weight for the same polymer structure and the sulfonation degree was investigated. Because the chain length of polymer varies with molecular weight and chain entanglement degree, its molecular weight affects the electrode morphology. As the ionomer covered the catalyst, the agglomerates formed were of different morphologies according to their molecular weight, which could be deduced indirectly through dynamic light scattering and scanning electron microscopy. Additionally, the fuel cell performance was confirmed in the current-voltage curve.     

Model-based decoupling control for the thermal management system of proton exchange membrane fuel cells

As one of the most promising sustainable energy technologies available today, proton exchange membrane fuel cell (PEMFC) engines are becoming more and more popular in various applications, especially in transportation vehicles. However, the complexity and the severity of the vehicle operating conditions present challenges to control the temperature distribution in single cells and stack, which is an important factor influencing the performance and durability of PEMFC engines. It has been found that regulating the input and output coolant water temperature can improve the temperature distribution. Therefore, the control objective in this paper is regulating the input and output temperature of coolant water at the same time. Firstly, a coupled model of the thermal management system is established based on the physical structure of PEMFC engines. Then, in order to realize the simultaneous control of the inlet and outlet cooling water temperature of the PEMFC stack, a decoupling controller is proposed and its closed-loop stability is proved. Finally, based on the actual PEMFC engine platform, the effectiveness, accuracy and reliability of the proposed decoupling controller are tested. The experimental results show that with the proposed decoupling controller, the inlet and outlet temperatures of the PEMFC stack cooling water can be accurately controlled on-line. The temperature error range is less than 0.2 °C even under the dynamic current load conditions.     

Carbon-supported Pd-Pt cathode electrocatalysts for proton exchange membrane fuel cells

A series of carbon-supported Pd-Pt alloy (Pd-Pt/C) catalysts for oxygen reduction reaction (ORR) with low-platinum content are synthesized via a modified sodium borohydride reduction method. The structure of as-prepared catalysts is characterized by powder X-ray diffraction (XRD) and transmission electron microscope (TEM) measurements. The prepared Pd-Pt/C catalysts with alloy form show face-centered-cubic (FCC) structure. The metal particles of Pd-Pt/C catalysts with mean size of around 4-5 nm are uniformly dispersed on the carbon support. The electrocatalytic activities for ORR of these catalysts are investigated by rotating disk electrode (RDE), cyclic voltammetry (CV), single cell measurements and electrochemical impedance spectra (EIS) measurements. The results suggest that the electrocatalytic activities of Pd-Pt/C catalysts with low platinum are comparable to that of the commercial Pt/C with the same metal loading. The maximum power density of MEA with a Pd-Pt/C catalyst, the Pd/Pt mass ratio of which is 7:3, is about 1040 mW cm⁻².     

Study of sulfur dioxide crossover in proton exchange membrane fuel cells

As one of the most deleterious impurities to proton exchange membrane fuel cells (PEMFCs), sulfur dioxide (SO₂) in air can pass through the membrane from the cathode to the anode and poison the catalyst of the two electrodes. The phenomenon of SO₂ crossover is investigated electrochemically in this paper. The influences of SO₂ concentration, relative humidity, gas pressure and current density on SO₂ crossover are discussed. Experimental results reveal that the anode tends to be poisoned heavily with the increasing concentration of SO₂ in the cathode. The coverage of the anode catalyst by SO₂ permeating from the cathode enlarges with the decreasing relative humidity in the anode. The rate of SO₂ crossover from the anode to the cathode is promoted at high current density when SO₂ is directly introduced into the anode side instead of the cathode side, which can be ascribed to the electro-osmotic drag effect. Gas pressures show no obvious effects on SO₂ crossover. A co-permeation mechanism of SO₂ with water is deduced based on the overall analysis.     

Data-based short-term prognostics for proton exchange membrane fuel cells

Prognostics is an important tool in the life and cost management of the proton exchange membrane fuel cells (PEMFCs). In this paper, we propose a data-based short-term prognostics method based on the group method of data handling and the wavelet analysis. In particular, this method first decomposes the original voltage sequence of PEMFCs into multiple sub-waveforms. Then, prognostics are made for the sub-waveforms and are combined for the overall prognostics of PEMFCs. Moreover, the proposed method is validated by the experimental datasets from real aging tests. Simulation results demonstrate that, compared with the existing approaches, this proposed method not only can achieve accurate short-term prognostics for PEMFCs in different load conditions, but also can directly use the original experimental data with large disturbances.     

The effect of materials on proton exchange membrane fuel cell electrode performance

This paper describes the optimisation in the fabrication materials and techniques used in proton exchange membrane fuel cell (PEMFC) electrodes. The effect on the performance of membrane electrode assemblies (MEAs) from the solvents used in producing catalyst inks is reported. Comparison in MEA performances between various gas diffusion layers (GDLs) and the importance of microporous layers (MPLs) in gas diffusion electrodes (GDEs) are also shown. It was found that the best performances were achieved for GDEs using tetrahydrofuran (THF) as the solvent in the catalyst ink formulation and Sigracet 10BC as the GDL. The results also showed that our in-house painted GDEs were comparable to commercial ones (using Johnson Matthey HiSpec™ and E-TEK catalysts).