Functionalizing carbon nanotubes for proton exchange membrane fuel cells electrode

In recent years, carbon nanotubes (CNTs) have been increasingly considered as an advanced metal catalyst support for proton exchange membrane fuel cells (PEMFCs), owing to their outstanding physical and mechanical characteristics. However, the effective attachment of metal catalysts, uniformly dispersed onto the CNT surface, remains a formidable challenge because of the inertness of the CNT walls. Therefore, the surface functionalization of CNTs seems necessary in most cases in order to enable a homogeneous metal deposition. This review presents the different surface functionalization approaches that provide efficient avenues for the deposition of metal nanoparticles on CNTs, for the application of catalyst supports in PEMFCs with improved reactivity.     

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.     

Electrochemical carbon corrosion in high temperature proton exchange membrane fuel cells

Electrochemical carbon corrosion occurring in a high temperature proton exchange membrane fuel cell (HT-PEMFC) operating under non-humidification conditions was investigated by measuring CO₂ generation using on-line mass spectrometry and comparing the results with a low-temperature proton exchange membrane fuel cell (LT-PEMFC) operated under fully humidified conditions. The experimental results showed that more CO₂ was measured for the HT-PEMFC, indicating that more electrochemical carbon corrosion occurs in HT-PEMFCs. This observation is attributed to the enhanced kinetics of electrochemical carbon corrosion due to the elevated operating temperature in HT-PEMFCs. Additionally, electrochemical carbon corrosion in HT-PEMFCs showed a strong dependence on water content. Therefore, it is critical to remove the water content in the supply gases to reduce electrochemical carbon corrosion.     

Crosslinked carbon nanodots with highly sulfonated polyphenylsulfone as proton exchange membrane for fuel cell applications

The crosslinked highly sulfonated polyphenylsulfone (SPPSU) membranes that consists of carbon nanodots (CNDs) was prepared as a proton exchange membrane for fuel cell applications. The crosslinked membranes were developed by annealing at 180 °C, in which the crosslinking occurred between the SPPSU and CNDs. The CNDs potential was explored in detail under various loadings (0 wt %, 1 wt %, 2 wt %, and 3 wt %). Upon annealing at 180 °C, the flexibilities and strength of the SPPSU-CNDs membranes improved. The proton conductivity of the crosslinked membrane was enhanced than that of pristine SPPSU membrane due to the crosslinking effect between SPPSU and CNDs. The highest conductivity, which was at 56.3 mS/cm was obtained when 3 wt % of CNDs was incorporated at 80 °C and 90% relative humidity (RH). The results indicated that the incorporation of CNDs in the SPPSU membrane by annealing at 180 °C, exhibited a proton conductive membrane in combination with superior dimensional stability, and proton conductivity suitable for fuel cell applications.     

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.     

Carbon film coating on gas diffusion layer for proton exchange membrane fuel cells

This study discusses a novel process to increase the performance of proton exchange membrane fuel cells (PEMFC). In order to improve the electrical conductivity and reduce the surface indentation of the carbon fibers, we modified the carbon fibers with pitch-based carbon materials (mesophase pitch and coal tar pitch). Compared with the gas diffusion backing (GDB), GDB-A240 and GDB-MP have 32% and 33% higher current densities at 0.5 V, respectively. Self-made carbon paper with the addition of a micro-porous layer (MPL) (GDL-A240 and GDL-MP) show improved performance compared with GDB-A240 and GDB-MP. The current densities of GDL-A240 and GDL-MP at 0.5 V increased by 37% and 31% compared with GDL, respectively. This study combines these two effects (carbon film and MPL coating) to promote high current density in a PEMFC.     

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.     

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.     

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.     

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.     

Fabrication of a carbon nanofiber sheet as a micro-porous layer for proton exchange membrane fuel cells

A carbon nanofiber sheet (CNFS) has been prepared by electrospinning, stabilisation and subsequent carbonisation processes. Imaging with scanning electron microscope (SEM) indicates that the CNFS is formed by nonwoven nanofibers with diameters between 400 and 700 nm. The CNFS, with its three-dimensional pores, shows excellent electrical conductivity and hydrophobicity. In addition, it is found that the CNFS can be successfully applied as a micro-porous layer (MPL) in the cathode gas diffusion layer (GDL) of a proton exchange membrane fuel cell (PEMFC). The GDL with the CNFS as a MPL has higher gas permeability than a conventional GDL. Moreover, the resultant cathode GDL exhibits excellent fuel cell performance with a higher peak power density than that of a cathode GDL fabricated with a conventional MPL under the same test condition.     

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.     

Artificial ecosystem optimizer for parameters identification of proton exchange membrane fuel cells model

Modeling and optimization of the proton exchange membrane fuel cells (PEMFCs) raise a crucial challenge due to their characteristics of multi-variability and nonlinearity natures. To ensure an accurate and reliable model for PEMFCs, best values of their uncertain parameters should be defined carefully. A conventional artificial ecosystem optimizer (AEO) and an improved and developed AEO (called IAEO) are used to realize the later aim. In the proposed IAEO, a dynamic crossover pattern is presented to enable the algorithm to achieve better solution, and also prevent the stuck in local optima. Sum of squared errors (SSE) defines the fitness function subjected to set of practical constraints. The proposed IAEO-based algorithm is analyzed and demonstrated on different typical benchmarking PEMFCs modules widely used in the literature. Comprehensive simulations and performance assessments are carried out on the PEMFCs models to affirm the efficacy and robustness of the proposed IAEO based on methodology while simulating the commercial PEMFC stacks behavior in regards to the experimental data. In this context, best values of SSE resulted by IAEO are 0.0116, 0.3359, and 2.1459, for BCS 500-W, 250 W stack, and NedStack PS6, respectively that are very competitive values among other challenging methodologies. This noticeably indicates that the developed IAEO-based method gives better efficiency with the highest robustness and convergence speed compared with the other methods. At a later stage, dynamic performance of PEMFCs stacks are carried out. It can be established that the reported outcomes affirm the superiority and reliability of the IAEO algorithm over the conventional AEO and the other competitors.     

Effects of chlorides on the performance of proton exchange membrane fuel cells

This paper investigates the effects of cathode gases containing chloride ions on the proton exchange membrane fuel cell (PEMFC) performance. Chloride solutions are vaporized using an ultrasonic oscillator and mixed with oxygen/air. The salt concentration of the mixed gas in the cathode is set by varying the concentration of the chloride solution. Five-hour tests show that an increase in the concentration of sodium chloride did not significantly affect the cell performance of the PEMFC. It is found that variations in the concentration of chloride do not show significant influence on the cell performance at low current density operating condition. However, for high current density operating conditions and high calcium chloride concentrations, the chloride ion appears to have a considerable effect on cell performance. Experimental results of 108-h tests indicate that the fuel cell operating with air containing calcium chloride has a performance decay rate of 3.446 mV h⁻¹ under the operating condition of current density at 1 A/cm². From the measurements of the I-V polarization curves, it appears that the presence of calcium chloride in the cathode fuel gas affects the cell performance more than sodium chloride does.     

Impedance study of membrane dehydration and compression in proton exchange membrane fuel cells

Electrochemical impedance spectroscopy (EIS) is used to measure drying and rehydration in proton exchange membrane fuel cells running under load. The hysteresis between forward and backward acquisition of polarization curves is shown to be largely due to changes in the membrane resistance. Drying tests are carried out with hydrogen and simulated reformate (hydrogen and carbon dioxide), and quasi-periodic drying and rehydration conditions are studied. The membrane hydration state is clearly linked to the high-frequency arc in the impedance spectrum, which increases in size for dry conditions indicating an increase in membrane resistance. Changes in impedance spectra as external compression is applied to the cell assembly show that EIS can separate membrane and interfacial effects, and that changes in membrane resistance dominate. Reasons for the presence of a capacitance in parallel with the membrane resistance are discussed.     

Thermal and electrochemical durability of carbonaceous composites used as a bipolar plate of proton exchange membrane fuel cell

Thermal and electrochemical durability of carbonaceous composite plates, which are made from graphite powders and a resin for use as bipolar plates of PEMFC (proton exchange membrane fuel cell), were investigated. The thermal durability was investigated by TG (thermal gravimetry) coupled with DTA (differential thermal analysis) technique under air up to 600 °C. A weight loss was significant over 300 °C, but the hydrophobicity was decreased after heated at 80 °C for 192 h.The electrochemical durability was investigated in 10 μmol dm⁻³ of hydrochloric acid solution under nitrogen or oxygen atmosphere by means of potential holding test from 0.8 to 1.5 V against RHE (reversible hydrogen electrode) at 80 °C. During the potential holding tests, CO₂ production due to the corrosion was quantified by a GC (gas-chromatography) and the production was detectable above 1.3 V irrespective with atmosphere; on the other hand, it was clarified from the contact angle measurements that the hydrophobicity was changed below 1.3 V. The results of this study showed that the carbonaceous composite plates were electrochemically degraded under PEMFC condition and were seriously degraded in URFC (unitized regenerative fuel cell) condition.     

Nafion/PTFE/silicate membranes for high-temperature proton exchange membrane fuel cells

Fuel cell performance of membrane electrode assemblies (MEAs) prepared from poly(tetrafluoroethylene)/Nafion/silicate (PNS) membrane and Nafion-112 membrane were investigated. Due to the low conductivity of PTFE and silicate, PNS had a higher proton resistance than Nafion-112. However, in this work we show that PNS performs better than Nafion-112 for a high current density operation with a low inlet gas humidity. As the PEMFCs were operated at with 100% RH, the results showed the maximum power density (PD_max) of PNS was: at with both H₂ and O₂ flow rates of 300 ml/min, and at with H₂ flow rate of 360 ml/min and O₂ flow rate of 600 ml/min, which were much higher than the at of Nafion-112 with both H₂ and O₂ flow rates of 300 ml/min. The PD_max of PNS was: , , and at as the operating temperature and inlet gas humidity were set at with 67.7% RH, with 46.8% RH, and with 33.1% RH, respectively. However, no output power was detected for Nafion-112 MEA when the cell was operated at a temperature higher than and an inlet gas humidity lower than 67.7% RH. The high PEMFC performance of PNS at high current density and low humidity is attributed to the presence of silicate in the PNS membrane, which enhances water uptake and reduces electro-osmosis water loss at a high current density.