Enhancement of proton exchange membrane fuel cell performance by titanium-coated anode gas diffusion layer

Titanium was coated onto an anode gas diffusion layer (GDL) by direct current sputtering to improve the performance and durability of a proton exchange membrane fuel cell (PEMFC). Scanning electron microscopy (SEM) images showed that the GDLs were thoroughly coated with titanium, which showed angular protrusion. Single-cell performance of the PEMFCs with titanium-coated GDLs as anodes was investigated at operating temperatures of 25 °C, 45 °C, and 65 °C. Cell performances of all membrane electrode assemblies (MEAs) with titanium-coated GDLs were superior to that of the MEA without titanium coating. The MEA with titanium-coated GDL, with 10 min sputtering time, demonstrated the best performance at 25 °C, 45 °C, and 65 °C with corresponding power densities 58.26%, 32.10%, and 37.45% higher than that of MEA without titanium coating.     

Effect of catalyst layer with zeolite on the performance of a proton exchange membrane fuel cell operated under low-humidity conditions

Proton exchange membrane fuel cells (PEMFCs) employ a proton conductive membrane as the separator to transport a hydrogen proton from the anode to the cathode. The membrane's proton conductivity depends on the water content in the membrane, which is affected by the operating conditions. A membrane electrode assembly (MEA) that can self-sustain water is the key component for developing a light-weight and compact PEMFC system without humidifiers. Hence, zeolite is employed to the anode catalyst layer in this study. The effect of the gas diffusion layer (GDL) materials, catalyst loading, binder loading, and zeolite loading on the MEA performance is investigated. The MEA durability is also investigated through the electrochemical impedance spectroscopy (EIS) method. The results suggest that the MEA with the SGL28BCE carbon paper, Pt loadings of 0.1 and 0.7 mg cm^?2 in the anode and cathode, respectively, Nafion-to-carbon weight ratio of 0.5, and zeolite-to-carbon weight ratio of 0.3 showed the best performance when the cell temperature is 60 °C and supplies with dry hydrogen and air from the environment. According to the impedance variation measured by EIS, the MEA with zeolite in the anode catalyst layer shows higher and more stable performance than those without zeolite.     

Facile microwave-assisted synthesized reduced graphene oxide/tin oxide nanocomposite and using as anode material of microbial fuel cell to improve power generation

A new nanocomposite material was fabricated by a facile and reliable method for microbial fuel cell (MFC) anode. Tin oxide (SnO₂) nanoparticles were anchored on the surface of reduced graphene oxide (RGO/SnO₂) in two steps. The hydrothermal method was used for the modification of GO and then microwave-assisted method was used for coating of SnO₂ on the modified GO. Nanohybrids of RGO/SnO₂ achieved a maximum power density of 1624 mW m⁻², when used as the MFC anode. The obtained power density was 2.8 and 4.8 times larger than that of RGO coated and bare anodes, respectively. The electrodes were characterized by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). The electrochemical characteristics were also studied by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). The high conductivity and large specific surface of the nanocomposite were greatly improved the bacterial biofilm formation and increased the electron transfer. The results demonstrate that the RGO/SnO₂ nanocomposite was advantageous material for the modification of anode and enhanced electricity generation of MFC.     

Investigation of sintered stainless steel fiber felt as gas diffusion layer in proton exchange membrane fuel cells

The feasibility of using sintered stainless steel fiber felt (SSSFF) as gas diffusion layer (GDL) in proton exchange membrane fuel cells (PEMFCs) is evaluated in this study. The SSSFF is coated with an amorphous carbon (a-C) film by closed field unbalanced magnetron sputter ion plating (CFUBMSIP) to enhance the corrosion resistance and reduce the contact resistance. The characteristics of treated SSSFF, including microscopic morphology, mechanical properties, electrical conductivity, electrochemical behavior and wettablity characterization, are systematically investigated and summarized according to the requirements of GDL in PEMFC. A membrane electrode assembly (MEA) with a-C coated SSSFF-15 GDL is fabricated and assembled with a-C coated stainless steel bipolar plates in a single cell. The initial peak power density of the single cell is 877.8 mW cm⁻² at a current density of 2324.9 mA cm⁻². Lifetime test of the single cell over 200 h indicates that the a-C coating protects the SSSFF-15 GDL from corrosion and decreases the performance degradation from 30.6% to 6.3%. The results show that the SSSFF GDL, enjoying higher compressive modulus and ductility, is a promising solution to improve fluid permeability of GDL under compression and PEMFC durability.     

Investigations of direct methanol fuel cell (DMFC) fading mechanisms

In this report, we present the microscopic investigations on various fading mechanisms of a direct methanol fuel cell (DMFC). High energy X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), energy dispersive X-ray spectroscopy (EDX), and Raman spectroscopic analysis were applied to a membrane-electrode-assembly (MEA) before and after fuel cell operation to figure out the various factors causing its fading. High energy XRD analysis of the fresh and faded MEA revealed that the agglomeration of the catalyst particles in the cathode layer of the faded MEA was more significant than in the anode layer of the faded MEA. The XAS analysis demonstrated that the alloying extent of Pt (J_Pt) and Ru (J_Ru) in the anode catalyst was increased and decreased, respectively, from the fresh to the faded MEA, indicating that the Ru environment in the anode catalyst was significantly changed after the fuel cell operation. Based on the X-ray absorption edge jump measurements at the Ru K-edge on the anode catalyst of the fresh and the faded MEA it was found that Ru was dissolved from the Pt-Ru catalyst after the fuel cell operation. Both the Ru K-edge XAS and EDX analysis on the cathode catalyst layer of the faded MEA confirms the presence of Ru environment in the cathode catalyst due to the Ru crossover from the anode to the cathode side. The changes in the membrane and the gas diffusion layer (GDL) after the fuel cell operation were observed from the Raman spectroscopy analysis.     

An impedance study for the anode micro-porous layer in an operating direct methanol fuel cell

This study presents the benefit to an operating direct methanol fuel cell (DMFC) by coating a micro-porous layer (MPL) on the surface of anode gas diffusion layer (GDL). Taking the membrane electrode assembly (MEA) with and without the anodic MPL structure into account, the performances of the two types of MEA are evaluated by measuring the polarization curves together with the specific power density at a constant current density. Regarding the cell performances, the comparisons between the average power performances of the two different MEAs at low and high current density, various methanol concentrations and air flow rates are carried out by using the electrochemical impedance spectroscopy (EIS) technique. In contrast to conventional half cell EIS measurements, both the anode and cathode impedance spectra are measured in real-time during the discharge regime of the DMFC. As comparing each anode and cathode EIS between the two different MEAs, the influences of the anodic MPL on the anode and cathode reactions are systematically discussed and analyzed. Furthermore, the results are used to infer complete and reasonable interpretations of the combined effects caused by the anodic MPL on the full cell impedance, which correspond with the practical cell performance.     

Membrane electrode assembly with additives for proton-exchange membrane water electrolysis in high-voltage operation

In a proton-exchange membrane water-electrolysis system, performance is greatly affected by the anode materials and operation modes. Moreover, high voltages allow greater hydrogen production as well as the potential of creating ozone for green disinfection. However, after switching off power and restarting, a big decrease in performance drop as well as hydrogen/ozone generation. In this study, different additives—multi-wall carbon nanotubes, surface-modification graphene, reduction graphene oxide, and graphene oxide—are adopted and mixed with PbO₂ and to create anode catalyst ink. The characteristics of the anode catalysts are investigated with voltage-current test, interruptive power supply, electrochemical impedance spectroscopy and high voltage accelerating tests. The results show that the anode of MEA with additive, multi-wall carbon nanotubes or multi-wall carbon nanotubes plus surface-modification graphene, lead to twice higher performance. Further, anode of MEA with additive, multi-wall carbon nanotubes, multi-wall carbon nanotubes plus graphene oxide, and multi-wall carbon nanotubes plus reduction graphene oxide, displays better restoration (34–36%↓).     

A novel anode catalyst layer with multilayer and pore structure for improving the performance of a direct methanol fuel cell

A novel anode catalyst layer (CL) has been prepared by ultrasonic‐spray process which combines directly spraying method and catalyst‐coated membrane switchover method, and heated‐stereoscopic process has been used to enhance bond force between CLs and proton exchange membrane in this paper. The scanning electron microscopy, electrochemical impedance spectra and polarization curves show that: the anode outer CL with pores and meshwork structure has increased the electrochemical active surface area and retained the transfer of protons and electrons, and the anode inner CL with compact structure has prevented methanol crossover. And the gradient catalysis for methanol electrochemical catalytic oxidation reaction has been achieved. The open circuit voltage has reached 0.697 V, and the performance has increased from 116.8 mW cm^?2 of traditional membrane electrode assembly (MEA) to 202.6 mWcm^?2 of novel MEA at 80°C. Copyright © 2012 John Wiley & Sons, Ltd.     

The hydrophilicity of carbon for the performance enhancement of direct ascorbic acid fuel cells

As a representative of low-temperature direct biomass fuel cells, direct ascorbic acid fuel cells (DAAFCs) carry many advantages, including renewable fuel, easy transportation and storage, and high safety. However, a major challenge of DAAFCs confronting us is relatively low power density. Herein, to deal with this challenge, we treat carbon black (BP 2000) with nitric acid at an optimal concentration (4 M), which is further employed as anodic electrocatalyst for AA oxidation with improved hydrophilicity. Consequently, hydrophilic AA molecules can more readily access the surface of the carbon electrocatalyst and donate electrons. Furthermore, the electrocatalytic effect of acid-treated carbon for AA oxidation reaction is quantitatively evaluated by the determination of activation energy, which has not been assessed prior to this study. In a similar way, nitric acid treatment is also applied to gas diffusion layer (GDL) at the anode side. In addition, Nafion content in anodic electrocatalyst layer, single cell operating temperature, and hot pressing conditions for the fabrication of membrane electrode assembly (MEA) as well as membrane thickness are also optimized. A maximum power density of 31 mW cm^?2 is eventually attained at 80 °C with anode ionomer content of 9.2% and hot pressing at 130 °C and 6 MPa for 2 min. This power density is 1.72 times of that reported previously with carbon black as the anode electrocatalyst.     

A study of the effect of compression on the performance of polymer electrolyte fuel cells using electrochemical impedance spectroscopy and dimensional change analysis

Compression plays an important role in the performance of polymer electrolyte fuel cells (PEFCs). In this study, dynamic compression is applied using a cell compression unit (CCU) to study the effect on performance of a membrane electrode assembly (MEA) with dimension change. The stress/strain characteristics of the MEA are observed to be dominated by the gas diffusion layer (GDL), with the GDL exhibiting a degree of plasticity. Electrochemical impedance spectroscopy (EIS) is used to delineate the effect of compression on contact resistance and mass transfer losses.     

The influence of anode gas diffusion layer on the performance of low-temperature DMFC

The influence of the anode gas diffusion layers (GDLs) on the performances of low-temperature DMFCs, and the properties of mass transport and CO₂ removal on these anode GDLs were investigated. The membrane electrode assembly (MEA) based on the hydrophilic anode GDL, which consisted of the untreated carbon paper and hydrophilic anode micro-porous layer (comprised carbon black and 10 wt.% Nafion), showed the highest power density of 13.4 mW cm⁻² at 30 °C and ambient pressure. The performances of the MEAs tended to decline with the increase of the PTFE content in the anode GDLs due to the difficulty of methanol transport. The contact angle measurements revealed that the wettabilities of the anode GDLs decreased as the increase of PTFE content. The wettabilities of the GDLs were improved by addition of hydrophilic Nafion ionomer to the GDLs. From the visualizations of CO₂ gas bubbles dynamics on the anodes using a transparent cell, it was observed that uniform CO₂ gas bubbles with smaller size formed on hydrophilic anode GDLs. And bubbles with larger size were not uniform over the hydrophobic anode GDLs. It was believed that adding PTFE to the anode GDL was not helpful for improving the CO₂ gas transport in the anode GDL of the low-temperature DMFC.     

Characteristics of water transport through the membrane in direct methanol fuel cells operating with neat methanol

The water required for the methanol oxidation reaction in a direct methanol fuel cell (DMFC) operating with neat methanol can be supplied by diffusion from the cathode to the anode through the membrane. In this work, we present a method that allows the water transport rate through the membrane to be in-situ determined. With this method, the effects of the design parameters of the membrane electrode assembly (MEA) and operating conditions on the water transport through the membrane are investigated. The experimental data show that the water flux by diffusion from the cathode to the anode is higher than the opposite flow flux of water due to electro-osmotic drag (EOD) at a given current density, resulting in a net water transport from the cathode to the anode. The results also show that thinning the anode gas diffusion layer (GDL) and the membrane as well as thickening the cathode GDL can enhance the water transport flux from the cathode to the anode. However, a too thin anode GDL or a too thick cathode GDL will lower the cell performance due to the increases in the water concentration loss at the anode catalyst layer (CL) and the oxygen concentration loss at the cathode CL, respectively.     

Electrochemical performance of reduced graphene oxide in Spiro‐(1, 1')‐bipyrrolidinium tetrafluoroborate electrolyte

This paper investigates the relationship between structure and electrochemical performance of reduced graphene oxide (RGO) prepared via heat treatment and chemical reduction method. Structure and morphology of RGO was characterized by means of Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction and Brunauer–Emmett–Teller. Electrochemical performance of RGO electrode supercapacitor was investigated in the organic electrolyte by cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance. The results show heat treatment RGO has high graphitization degree, less surface oxygen‐containing groups, good charge–discharge efficiency and stable life cycle. The chemical reduced RGO has single‐graphene structure, high specific surface area, high specific capacitance and low internal resistance. The ascorbic acid reduction RGO exhibits good comprehensive electrochemical performance: Its specific capacitance was 220.7 F g^?1, internal resistance was 3.0 Ω and charge–discharge efficiency was 97.0% after 2000 cycles of charging/discharging tests. Copyright © 2016 John Wiley & Sons, Ltd.     

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.     

Durability and characterization studies of polymer electrolyte membrane fuel cell’s coated aluminum bipolar plates and membrane electrode assembly

Coated aluminum bipolar plates demonstrate better mechanical strength, ease of manufacturability, and lower interfacial contact resistance (ICR) than graphite composite plates in polymer electrolyte membrane (PEM) fuel cell applications. In this study, coated aluminum and graphite composite bipolar plates were installed in separate single PEM fuel cells and tested under normal operating conditions and cyclic loading. After 1000 h of operation, samples of both the bipolar plates and the membrane electrode assembly (MEA) were collected from both the cathode and the anode sides of the cell and characterized to examine the stability and integrity of the plate coating and evaluate possible changes of the ionic conductivity of the membrane due any electrochemical reaction with the coating material. Scanning electron microscope (SEM) and energy dispersive X-ray (EDX) analysis were performed on the land and valley surfaces of the reactant flow fields at both the anode and the cathode sides of the bipolar plates. The measurements were superimposed on the reference to identify possible zones of anomalies for the purpose of conducting focused studies in these locations. The X-ray diffraction (XRD) analysis of samples scraped from the anode and cathode electrodes of the MEA showed the tendency for catalyst growth that could result in power degradation. Samples of the by-product water produced during the single fuel cell operation were also collected and tested for the existence of chromium, nickel, carbon, iron, sulfur and aluminum using mass spectroscopy techniques. The EDX measurements indicated the possibility of dissociation and dissolution of nickel chrome that was used as the binder for the carbide-based corrosion-resistant coating with the aluminum substrate.     

High‐performance and robust operation of anode‐supported solid oxide fuel cells in mixed‐gas atmosphere

We demonstrate the high‐performance and robust operation of anode‐supported solid oxide fuel cells under a mixed‐gas atmosphere applying a novel cell structure and characterization method, useful for minimizing the conventional problems of mixed‐gas operation with anode‐supported solid oxide fuel cells. To achieve the exothermic methane (CH₄) partial oxidation and sufficient difference in oxygen partial pressure even in mixed‐gas mode, a composite of metallic rhodium and cerium dioxide (CeO₂) was chosen as the optimized reforming and oxygen barrier layer after the comprehensive catalytic experiment. We also obtained increased cell operation reliability through the combination of anode pre‐reduction, an optimized material system, and a customized characterization jig (including cathode‐ahead layout and impinging jet flow). According to the cell test at 600°C under a feeding gas of CH₄ and O₂, an open‐circuit voltage and maximum power density of 0.916 V and 0.422 W/cm², respectively, were successfully achieved. Copyright © 2015 John Wiley & Sons, Ltd.     

Pool Boiling Enhancement through Graphene and Graphene Oxide Coatings

ABSTRACT

Boiling has served as an effective means to dissipate large quantities of heat over small areas. Graphene, a two-dimensional material, has garnered significant attention of researchers due to its excellent thermal properties. In this study, copper test chips are dip coated with a solution consisting of graphene oxide and graphene and its pool boiling performance with distilled water at atmospheric pressure was investigated. The surfaces were characterized using X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy which confirmed the presence of graphene and graphene oxide. The contact angles measured on the coated surfaces indicated hydrophobic wetting behavior. Four heat transfer surfaces were prepared with dip coating durations of 120 s, 300 s, 600 s, and 1200 s, respectively. A Critical Heat Flux (CHF) of 182 W/cm² and a heat transfer coefficient (HTC) of 96 kW/m²°C was obtained with the shortest coating duration which translated to an enhancement of 42% in CHF and 47% in HTC when compared to a plain uncoated surface under similar conditions. Contact angle changes were not seen to be responsible, although roughness was seen as an influencing factor contributing to the enhancement. Further studies are needed to explain the enhancement mechanism.     

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.     

Optimization of GDLs for high-performance PEMFC employing stainless steel bipolar plates

The effects of polytetraflouroethylene (PTFE) content in the gas diffusion layer (GDL) on the performance of PEMFCs with stainless-steel bipolar plates are studied under various operation conditions, including relative humidity, cell temperature, and gas pressure. The optimal PTFE content in the GDL strongly depends on the cell temperature and gas pressure. Under unpressurized conditions, the best cell performance was obtained by the GDL without PTFE, at a cell temperature of 65 °C and relative humidity (RH) of 100%. However, under the conditions of high cell temperature (80 °C), low RH (25%) and no applied gas pressure, which is more desirable for fuel cell vehicle (FCV) applications, the GDL with 30 wt.% PTFE shows the best performance. The GDL with 30 wt.% PTFE impedes the removal of produced water and increases the actual humidity within the membrane electrode assembly (MEA). A gas pressure of 1 bar in the cell using the GDL with 30 wt.% PTFE greatly improves the performance, especially at low RH, resulting in performance that exceeds that of the cell under no gas pressure and high RH of 100%.     

Noble-free oxygen reduction reaction catalyst supported on Sengon wood (Paraserianthes falcataria L.) derived reduced graphene oxide for fuel cell application

Reduced graphene oxide (RGO) has progressed as one of key emerging carbon for catalyst support material. As an alternative to the conventional RGO precursor, biomass Sengon wood was converted into RGO for use as a noble metal free catalyst support in oxygen reduction reaction (ORR). This work intends to reveal the applicability of Sengon wood-derived RGO in anchoring/doping iron and nitrogen particles onto its surface and to study its ORR performance in a half-cell environment. Thin-sheet layer and highly defective (I_D/I_G) was gradually obtained at elevated pyrolysis temperature of Sengon wood graphene oxide (GO) at range 700°C to 900°C. As prepared RGO was further doped into catalyst (Fe/N/RGO) through the same pyrolysis procedure at a selected temperature after mixing the GO powder with iron chloride and different nitrogen precursors (urea, choline chloride, and polyaniline) at a fixed ratio. The ORR activity reached a current density up to 2.43 mA/cm², which in conjunction with smooth multilayer sheet morphology and high graphitic-N content as the active sites. Stability analysis indicated an 85% current efficiency and only 0.03 V reduction in onset potential on methanol resistant test for Fe/ChoCl/RGO catalyst. This study revealed that Sengon wood-derived RGO successfully supported Fe-N-C catalyst which showed comparable oxygen reduction activity to Pt/C.