Effect of anode and cathode flow field depths on the performance of liquid feed direct methanol fuel cells (DMFCs)

The effect of the anode and cathode flow field depths on the performance of a single cell Direct methanol fuel cell (DMFC) of 45 cm² active area were experimentally investigated. Double serpentine flow fields (DSFFs) with varying channel depth namely, 0.2, 0.4, 0.6, 0.8, and 1 mm but with fixed channel and rib width each of 1 mm on both anode and cathode were designed, fabricated, and tested. The experimental study involved measurement of pressure drops across anode and cathode flow field plates, polarization, and carbon dioxide concentration measurements at various current densities. The mass transport at both anode and cathode were found to increase with increase in pressure drop across the flow field on account of reduced channel depth from 1.0 to 0.4 mm at all current densities. However, further decrease to a channel depth of 0.2 mm was found to be counter-productive with different phenomena operating on either side viz., increased CO₂ slug length on the anode flow channel and increased methanol crossover on the cathode side. Hence, the maximum performance for DMFCs was observed for a channel depth of 0.4 mm on anode and cathode flow fields. A decrease in flow field channel depth at cathode was found to increase the methanol crossover due to convective mass transfer effect.     

Preparation of platinum-ruthenium onto solid polymer electrolyte membrane and the application to a DMFC anode

The ‘impregnation-reduction method’ has been investigated as a tool for the preparation of a direct methanol fuel cell (DMFC) anode. In this method, PtRu electrocatalysts were directly bonded onto a polymer electrolyte membrane by the chemical reduction of a mixture of Pt and Ru complexes impregnated in the membrane. The deposited PtRu particles were embedded in the 3-4 μm region of the membrane surface to form a porous and hydrophilic layer. The PtRu layers turned out to be applicable to the DMFC anode, despite their small active surface areas compared to PtRu nanoparticles used in the conventional method. Approximately, 3 mg cm⁻² of the PtRu layer exhibited better catalyst utilization and facilitated the release of evolving CO₂. This preparation technique is attractive for the application of various solid polymer electrolyte materials with low heat-resistance or various shapes, etc.     

Enhancing mass transport in direct methanol fuel cell by optimizing the microstructure of anode microporous layer

The microstructural characteristics of the anode microporous layer (MPL) can significantly affect the mass transport in direct methanol fuel cells by influencing the methanol delivery and CO₂ removal processes. The hydrophilic‐hydrophobic balance and pore structure of the flow path were established by optimizing the content of polytetrafluoroethylene (PTFE) in the anode MPL. An empirical model was developed to design and optimize the anode MPL to achieve better mass transport and cell performance. From the simulated and experimental results, increasing the content of PTFE enhanced the CO₂ removal ability in the anode MPL, thereby alleviating CO₂ blockage in the anode catalyst layer, whereas the narrowed flow path hindered methanol delivery in the anode MPL. A good balance between methanol delivery and CO₂ removal in terms of mass transport was achieved when the PTFE content was adjusted to 15 wt %, leading to the best cell performance. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3519–3528, 2018     

Experimental and Numerical Study of Serpentine Flow Fields for Improving Direct Methanol Fuel Cell Performance

Methanol crossover is an important issue as it affects direct methanol fuel cell (DMFC) performance. But it may be controlled by selecting a proper flow field design. Experiments were carried out to investigate the effect of single, double and triple serpentine flow field configurations on a DMFC with a 25 cm² membrane electrode assembly (MEA) with a constant open ratio. A three dimensional model was also developed for the anode of the DMFC to predict methanol concentration and cell current density distributions. Experimental and model results show that at lower methanol concentrations (0.25–0.5M), single serpentine flow field (SSFF) provides high peak power density, while a double serpentine flow field (DSFF) gives high peak power density at a high methanol concentration (1–2M). Single and double serpentine flow fields exhibit the same peak power density (33 mW cm⁻²) at 1M. But the cell efficiency of double serpentine flow field is 12.5% which is 3.5% point greater than single serpentine flow field. This is attributed to reduced mixed potential. triple serpentine flow field (TSFF) shows the lowest peak power density and cell efficiency, which is attributed to high mass transfer resistance.     

Methanol oxidation at carbon supported Pt and Pt-Ru electrodes: an on line MS study using technical electrodes

Methanol oxidation at technical carbon based electrodes in 0.05 M H₂SO₄ has been investigated by cyclic voltammetry using online MS under the conditions of an acid methanol fuel cell (DMFC). 5% Pt on Norit BRX and 30% Pt/Ru (40/60) on Norit BRX were used as catalysts. It is shown that methanol oxidation at technical electrodes can be characterized by a combination of cyclic voltammetry and mass spectroscopy. The onset potentials and potential dependences of the methanol oxidation rate can be determined directly by monitoring the formation of CO₂. Onset potentials of 0.5V and 0.25 V/RHE have been measured for Pt and Pt-Ru catalysts, respectively. The onset of methanol oxidation can be shifted to even more cathodic potentials (0.2V) if the Pt-Ru electrode reduces oxygen simultaneously. Carbon monoxide gas was also purged into the methanol containing electroyte during measurement in order to investigate the catalyst performance under more adverse conditions. C¹³-labelled methanol was used to distinguish between CO₂. formed from methanol (m/e = 45) and CO-oxidation (m/e = 44). Without CO the use of C¹³-labelled methanol enabled a distinction between methanol oxidation and carbon corrosion. The methanol oxidation at the platinum catalyst is severely inhibited by the presence of CO, shifting its onset to 0.65 V/RHE. In contrast the performance of the Pt-Ru electrode is not seriously affected under these conditions. It is concluded that Pt-Ru is an excellent catalyst for a methanol anode in an acid methanol fuel cell (DMFC).     

微型直接甲醇燃料电池阳极传质分析

针对微型直接甲醇燃料电池,将阳极流场板简化为规则结构的多孔介质,运用多孔介质理论建立了包括流场板在内的阳极传输模型。模型考虑了阳极流道内液体饱和度沿流动方向的变化、催化层的厚度以及甲醇渗透,计算并讨论了阳极流道内液体饱和度的分布和流量对电池电流密度的影响,分析了阳极过电位对甲醇浓度分布和电池性能的影响以及质子交换膜内的传质特性。     

CO_2气泡脱离扩散层孔口过程的数值模拟

在直接甲醇燃料电池(DMFC)中,阳极催化层表面反应生成的CO2气体通过扩散层,及时排出阳极通道,对提高DMFC电流密度具有重要意义,因此研究气泡脱离孔口的过程很有益。今采用Fluent6.2.16对CO2气泡脱离扩散层孔口过程、两孔时气泡形成及聚并过程进行了数值模拟,考察了阳极通道内液体流速、扩散层孔道直径等因素对气泡脱离的影响。结果表明,阳极通道内液体流速越大,气泡脱离扩散层孔口所需的时间越短;扩散层孔道直径越大,气泡脱离扩散层孔口所需的时间越长,且生成的气泡越大;由于从相邻两扩散层孔道出来的气泡的阻挡和挤压作用,使得两气泡周围的压力分布与单气泡不同,气泡脱离过程与从单个扩散层孔口的脱离过程有所不同,脱离时间更早。     

Development and characterization of a silicon-based micro direct methanol fuel cell

A silicon-based micro direct methanol fuel cell (μDMFC) for portable applications has been developed and its electrochemical characterization carried out in this study. Anode and cathode flowfields with channel and rib width of 750 μm and channel depth of 400 μm were fabricated on Si wafers using the microelectromechanical system (MEMS) technology. A membrane-electrode assembly (MEA) was specially fabricated to mitigate methanol crossover. This MEA features a modified anode backing structure in which a compact microporous layer is added to create an additional barrier to methanol transport thereby reducing the rate of methanol crossing over the polymer membrane. The cell with the active area of 1.625 cm² was assembled by sandwiching the MEA between two micro-fabricated Si wafers. Extensive cell polarization testing demonstrated a maximum power density of 50 mW/cm² using 2 M methanol feed at 60 °C. When the cell was operated at room temperature, the maximum power density was shown to be about 16 mW/cm² with both 2 and 4 M methanol feed. It was further found that the present μDMFC still produced reasonable performance under 8 M methanol solution at room temperature.     

Development of a Self‐Adaptive Direct Methanol Fuel Cell Fed with 20 M Methanol

A passive and self‐adaptive direct methanol fuel cell (DMFC) directly fed with 20 M of methanol is developed for a high energy density of the cell. By using a polypropylene based pervaporation film, methanol is supplied into the DMFC's anode in vapor form. The mass transport of methanol from the cartridge to the anodic catalyst layer can be controlled by varying the open ratio of the anodic bipolar plate and by tuning the hydrophobicity of anodic diffusion layer. An effective back diffusion of water from the cathode to the anode through Nafion film is carried out by using an additive microporous layer in the cathode that consists of 50 wt.% Teflon and KB‐600 carbon. Accordingly, the water back diffusion not only ensures the water requirement for the methanol oxidation reaction but also reduces water accumulation in the cathode and then avoids serious water flooding, thus improving the adaptability of the passive DMFC. Based on the optimized DMFC structure, a passive DMFC fed with 20 M methanol exhibits a peak power density of 42 mW cm^–2 at 25 °C, and no obvious performance degradation after over 90 h continuous operation at a constant current density of 40 mA cm^–2.     

Supercritical fluid processing of Nafion® membranes: Methanol permeability and proton conductivity

Nafion® membranes commonly used in direct methanol fuel cells (DMFC) are typically limited by high methanol permeability. These membranes have phase‐segregated sulfonated ionic domains in a perfluorinated backbone, which make processing difficult and limited by phase equilibria considerations. This study used supercritical fluids (SCFs) as a processing alternative, since the gas‐like mass transport properties of SCFs allow for better penetration into the membranes and the use of polar cosolvents could also influence their morphology, thus fine‐tuning their physical and transport properties. The SCF processing was performed at 40°C and 200 bars using pure CO₂ and CO₂ with several polar cosolvents of different size and chemical functionalities like: acetic acid, acetone, acetonitrile, cyclohexanone, dichloromethane, ethanol, isopropanol, methanol, and tetrahydrofuran. Methanol permeability measurements revealed that the SCF processed membranes reduced the permeation of methanol by several orders of magnitude, especially with the use of some small polar cosolvents. Proton conductivity measurements, using AC electrochemical impedance spectroscopy, were on the order of 0.03–0.09 S/cm, which indicates that processing with SCF CO₂ plus some cosolvents maintained the high proton conductivity while reducing the methanol permeability. The results are explained using XRD and SAXS. XRD analysis of the SCF processed samples revealed an increasing pattern in the crystallinity, which influenced the transport properties of the membrane. SAXS measurements confirmed the morphological differences that led to the changes in transport properties of the SCF processed membranes. Finally, processing flow direction (parallel versus perpendicular flow) played a major role in the morphological changes of this anisotropic membrane. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Nano-composite of PtRu alloy electrocatalyst and electronically conducting polymer for use as the anode in a direct methanol fuel cell

Nano-composites comprised of PtRu alloy nanoparticles and an electronically conducting polymer for the anode electrode in direct methanol fuel cell (DMFC) were prepared. Two conducting polymers of poly(N-vinyl carbazole) and poly(9-(4-vinyl-phenyl)carbazole) were used for the nano-composite electrodes. Structural analyses were carried out using Fourier transform nuclear magnetic resonance spectroscopy, AC impedance spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM). Electrocatalytic activities were investigated by voltammetry and chronoamperometry in a 2 M CH₃OH/0.5 M H₂SO₄ solution and the data compared with a carbon-supported PtRu electrode. XRD patterns indicated good alloy formation and nano-composite formation was confirmed by TEM. Electrochemical measurements and DMFC unit-cell tests indicate that the nano-composites could be useful in a DMFC, but its performance would be slightly lower than that of a carbon-supported electrode. The interfacial property between the PtRu-polymer nano-composite anode and the polymer electrolyte was good, as evidenced by scanning electron microscopy. For better performance in a DMFC, a higher electric conductivity of the polymer and a lower catalyst loss are needed in nano-composite electrodes.     

Non-Fluorinated Membranes Thickness Effect on the DMFC Performance

Abstract

In order to study the influence of the proton exchange membrane thickness on the direct methanol fuel cell (DMFC) performance, sulfonated poly (ether ether ketone) (sPEEK) membranes with a sulfonation degree (SD) of 42% and thicknesses of 25, 40, and 55 µm were prepared, characterized, and tested in a DMFC. These polymeric membranes were tested in a DMFC at several temperatures by evaluating the current-voltage polarization curve, the open circuit voltage (OCV) and the constant voltage current (CV, 35 mV). The CO₂ concentration at the cathode outlet was also measured. The thinnest sPEEK membrane proved to have the best DMFC performance, although having lower Faraday efficiency (lower ohmic losses but higher methanol permeation). In contrast, the thickest membrane presented improved properties in terms of methanol permeation (lower methanol crossover). DMFC tests results for this membrane showed 30% global efficiency, obtained with pure oxygen at the cathode feed.     

Facile Preparation of an Excellent Pt/RuO2‐MnO2/CNTs Nanocatalyst for Anodes of Direct Methanol Fuel Cells

RuO₂‐MnO₂ complex supported by multi‐wall carbon nanotubes (CNTs) was firstly synthesised by the oxidation–reduction precipitation of RuCl₃ and KMnO₄ in one step. Then Pt was loaded onto the obtained RuO₂‐MnO₂/CNTs to fabricate a novel anodic catalyst Pt/RuO₂‐MnO₂/CNTs for direct methanol fuel cells (DMFCs). The catalyst was characterised by transmission electron microscopy (TEM), X‐ray diffraction (XRD), temperature programmed reduction (TPR), X‐ray photoelectron spectroscopy (XPS) and BET specific surface areas (BET). Pt nanoparticles were found uniformly dispersed on the surface of CNTs, with the average diameter of about 2.0 nm. The activities of methanol and CO electrocatalytic oxidation were analysed, and the reaction mechanism of methanol electro‐oxidation on Pt/RuO₂‐MnO₂/CNTs catalyst was discussed. The MnO₂ in the catalysts improves the proton conductivity and electrochemical active surface area (EAS) for the catalysts. RuO₂ improves the CO oxidation activity and Pt dispersion. CNTs provide effectively electron channels. Thus, the Pt/RuO₂‐MnO₂/CNTs catalyst has high utilisation of the noble metal Pt, high CO oxidation ability and excellent methanol electro‐oxidation activity, being an outstanding anode catalyst for DMFC.     

Two-dimensional numerical modelling of a direct methanol fuel cell

The results of a numerical simulation of a direct methanol fuel cell (DMFC) with liquid methanol feed are presented. A two-dimensional numerical model of a DMFC is developed based on mass and current conservation equations. The velocity of the liquid is governed by gradients of membrane phase potential (electroosmotic effect) and pressure. The results show that, near the fuel channel, transport of methanol is determined mainly by the pressure gradient, whereas in the active layers, and in the membrane, diffusion transport dominates. Shaded zones, where there is a lack of methanol, are formed in front of the current collectors. The results reveal a strong influence of the hydraulic permeability of the backing layer K _p ^BL on methanol crossover through the membrane. If the value of K _p ^BL is comparable to that of the membrane and active layers, electroosmotic effects lead to the formation of an inverse pressure gradient. The flux of liquid driven by this pressure gradient is directed towards the anode and reduces methanol crossover.     

Methanol crossover effect on the cathode potential of a direct PEM fuel cell

The potential of the oxygen cathode in a direct methanol fuel cell is strongly influenced by the crossover of methanol through the poly-electrolyte membrane. In the presence of methanol, oxygen is reduced at the cathode already at open circuit and the equivalent amount of methanol is oxidized. This results in the formation of a mixed potential, up to 200 mV negative to the original oxygen potential. In this work, the anode and cathode potentials of a DMFC are monitored in situ, using a dynamic hydrogen electrode (DHE). For the first time, the effect of crossover on the cathode potential as function of time is presented. Methanol and ethanol as fuels are compared. Changing from methanol to hydrogen, the influence of methanol crossover on the cathode potential can also be followed as function of current density. It is already known that, in addition to the consumption of fuel and oxygen with the formation of a mixed potential, a purely chemical reaction takes place at the platinum surface. A quantitative determination of the respective CO₂ formation is presented here.     

Nafion-TiO2 composite DMFC membranes: physico-chemical properties of the filler versus electrochemical performance

TiO₂ nanometric powders were prepared via a sol-gel procedure and calcined at various temperatures to obtain different surface and bulk properties. The calcined powders were used as fillers in composite Nafion membranes for application in high temperature direct methanol fuel cells (DMFCs). The powder physico-chemical properties were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and pH measurements. The observed characteristics were correlated to the DMFC electrochemical behaviour. Analysis of the high temperature conductivity and DMFC performance reveals a significant influence of the surface characteristics of the ceramic oxide, such as oxygen functional groups and surface area, on the membrane electrochemical behaviour. A maximum DMFC power density of 350 mW cm⁻² was achieved under oxygen feed at 145 °C in a pressurized DMFC (2.5 bar, anode and cathode) equipped with TiO₂ nano-particles based composite membranes.     

Model‐based design and optimization of the microscale mass transfer structure in the anode catalyst layer for direct methanol fuel cell

Microscale mass transfer structure in the anode catalyst layer (CL) can significantly alter the performance of a direct methanol fuel cell (DMFC) because it changes both the oxidation rate and crossover flux of methanol. The microscale mass transfer structure can be modified by changing the loading of the pore former (PF). An empirical model was developed for the microstructural design and optimization of anode CL by incorporating the PF into the anode CL. The optimal loading of PF is 100 g/m² according to the calculated results. Experimental results confirmed the accuracy of the calculations, and the passive DMFC performs 37% better by incorporating the optimal loading of PF into the anode CL as compared to the conventional anode CL. The validity of the proposed empirical model can also be proven by comparing the calculated polarization results with the previously reported experimental data. © 2012 American Institute of Chemical Engineers AIChE J, 59: 780–786, 2013     

The role of under-rib convection in mass transport of methanol through the serpentine flow field and its neighboring porous layer in a DMFC

Numerical simulation of a direct methanol fuel cell (DMFC) operating under discharging conditions is challenged by the difficulties in modeling of complicated liquid-gas two-phase flows and coupled electrochemical kinetics. Under open-circuit conditions, the net electrochemical reactions in the DMFC anode cease, but, owing to the methanol concentration difference between the anode and cathode, the mass transport of methanol remains, creating a mass transport process of methanol in a single-phase liquid flow with no electrochemical reactions in the DMFC anode. Consequently, an accurate simulation of mass transport of methanol under such open-circuit conditions becomes possible. In this work, we performed a 3D numerical simulation of mass transport of methanol in the DMFC anode under open-circuit conditions and obtained the mass flux of methanol through the porous layer for different values of permeability. We also measured the mass flux of methanol permeation from the anode flow field to the cathode under open-circuit conditions. The comparison between the numerical and measured mass flux of methanol made it possible to in situ determine the permeability of the typical commercial porous layer. Using this in situ determined permeability, we then investigated numerically the effect of methanol feed rates on mass transport and found that the in-plane under-rib convection plays an important role, even at low methanol feed rate, to make the reactant evenly distributed over the entire catalyst layer.     

The influence of sodium ion as a potential fuel impurity on the direct methanol fuel cells

Na⁺ is a likely intrinsic impurity in water and is a sort of common cation impurity in the direct methanol fuel cells (DMFCs). In this paper, the effect of Na⁺ on the DMFC electrochemical response is studied by adding Na⁺ into the methanol water solution fed in the anode of DMFC. The dynamic variation of cell voltage results shows that the DMFC performance degraded by the presence of Na⁺ impurity, and the higher concentration of Na⁺ impurity, the higher poisoning rate is observed. In the meantime, an external reference electrode is used to measure the potential and impedance of the cathode and anode. It is found that the dramatic decrease of the cell voltage is mainly ascribed to the increase of the cathode overpotential which is caused by Na⁺ exchange with protons in the cathode catalyst layer. The electrochemical impedance measurements suggest that the lack of available protons and low oxygen concentration at the cathode catalytic sites contributed to this degradation. Furthermore, the recovery strategy is introduced and it is found that the poisoned MEA could be partly recovered by immersing in 0.5 M H₂SO₄ solution for 4 h.     

Niobium Dioxide Facilitating Methanol Electrooxidation on Pt/C Catalyst by Synergistic Effect

In this work, Pt nanoparticles are deposited on NbO₂‐modified carbon composites and evaluated as promising direct methanol fuel cell (DMFC) electrocatalysts. Transmission electron microscopy (TEM) and X‐ray diffraction (XRD) indicate that Pt nanoparticles (about 2.5 nm) are uniformly dispersed on NbO₂‐modified carbon composites. Electrochemical measurements show that the mass activity toward methanol electrooxidation on Pt/NbO₂‐C is as high as 3.0 times that of conventional Pt/C. Meanwhile, the onset potential of CO oxidation is negatively shifted by about 46 mV as compared with that of Pt/C, which means that the synergistic effect between NbO₂ and Pt facilitates the feasible removal of poisoning intermediate CO during methanol electrooxidation. X‐ray photoelectron spectroscopy (XPS) characterizations reveal the electron transfer from Nb to Pt, which suppress the poisoning CO adsorption on Pt nanoparticles and facilitate methanol electrooxidation. NbO₂ nanoparticles facilitate methanol electrooxidation on Pt/C catalyst by synergistic effect and electronic effect, which represents a step in the right direction for the development of excellent fuel cell anode electrocatalysts.