An impedance study of an operating direct methanol fuel cell

An electrochemical impedance spectroscopy (EIS) technique was developed to characterize a direct methanol fuel cell (DMFC) under various operating conditions. A silver/silver chloride electrode was used as an external reference electrode to probe the anode and cathode during fuel cell operation and the results were compared to the conventional anode or cathode half-cell performance measurement using a hydrogen electrode as both the counter and reference electrode. The external reference was sensitive to the anode and the cathode as current was passed in a working DMFC. The impedance spectra and DMFC polarization curves were systematically investigated as a function of air and methanol flow rates, methanol concentration, temperature, and current density. Water flooding in the cathode was also examined.     

Three-dimensional CFD modeling of a direct formic acid fuel cell

A three-dimensional (3D) with one straight channel computational fluid dynamics (CFD) model is developed by using the ESI-CFD software to investigate the effect of varying operating parameters on the performance of direct formic acid fuel cell (DFAFC) and formic acid crossover from the anode to the cathode side through the membrane. Formic acid concentration (4 M–10 M), temperature (313 K–353 K), anode stoichiometry (1.5–3.0), and cathode stoichiometry (2.0–3.0) are the selected operating parameters in this study. Validation results of the DFAFC are in reasonable agreement with the typical trends reported in the literature on DFAFC performance. Simulation results indicate that formic acid concentration, temperature, anode, and cathode stoichiometry influenced the DFAFC performance and the formic acid crossover. The increments of formic acid concentration or stoichiometric ratio will improve the cell performance; however, the current densities obtained are declining to the increasing temperature. The increase in temperature of the formic acid concentration is found to lead to the decrease in performance. For the formic acid crossover phenomenon, the formic acid crossover flux increases with the increments of formic acid concentration, DFAFC operating temperature, and anode and cathode stoichiometric ratios.     

Performance improvement in direct formic acid fuel cells (DFAFCs) using metal catalyst prepared by dual mode spraying

In the present study, we investigate performance of direct formic acid fuel cells (DFAFCs) consisting of membrane electrode assembly (MEA) prepared by three different catalyst coating methods - direct painting, air spraying and dual mode spraying. For the DFAFC single cell tests, palladium (Pd) and platinum (Pt) are used as anode and cathode catalyst, respectively, and four different formic acid concentrations are provided as a fuel. In the measurements, dual mode spraying shows the best DFAFC performance. To overhaul how difference in coating method influences DFAFC performance, several characterization techniques are utilized. Zeta potential and TEM are used for evaluating anodic Pd particle distribution and its size. Cyclic voltammogram (CV) is measured to calculate electrochemical active surface (EAS) area in anode electrode of the DFAFCs, while charge transfer resistance (R_ct) is estimated by electrochemical impedance spectroscopy (EIS). As a result of the characterizations, Pd prepared by dual mode spraying induces the most uniform particle distribution and the smallest size, the highest EAS area and the lowest R_ct, which are matched with the DFAFC performance result. Conclusively, by adoption of the dual mode spraying, DFAFC can get the maximum power density as high as 240 mW cm⁻² at 5 M formic acid.     

Numerical analysis of the electrochemical impedance spectra of the cathode of direct methanol fuel cells

A mathematical model is developed to simulate the electrochemical impedance spectra (EIS) of the cathode of a direct methanol fuel cell (DMFC) based on the electrode kinetics and mass transports. Successful simulation of the impedance spectra confirms the usefulness of the model as a diagnostic tool for interpreting the impedance characteristics of the cathode. Numerically, the capacitive semicircle in the impedance pattern is ascribed to the charge transfer process and the inductive semicircle is mainly due to the CO adsorption relaxation. Results show that the impedance pattern is strongly dependent on the electrode potential, which can be used as a criterion for judging the relative effect of the methanol permeation on the cathode. Another capacitive semicircle appears and the charge transfer resistance is changed when the oxygen transport is limited. The effects of the methanol permeation on the impedance pattern are also delineated, indicating that the methanol permeation often leads to larger oxygen transport impedance and the charge transfer resistance of the DMFC cathode depends on the methanol permeation rate.     

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.     

Real contribution of formic acid in direct formic acid fuel cell: Investigation of origin and guiding for micro structure design

We first experimentally verified the real contribution of formic acid (FA) in the direct formic acid fuel cell (DFAFC). By comparing the cell performance of the fuel cell fueled with FA and methanol, we found that FA not only acts as fuel in the fuel cell, but is also of benefit to proton conducting and triple phase boundary (TPB) building in the anode. Considering the real contribution and the special mass transfer behavior of FA in the fuel cell, the anode was reasonably designed and optimized. Carbon cloth was selected as the optimized anode diffusion layer to achieve quick methanol transfer from fuel reservoir to anode catalyst. The decal method was proved to be the better choice for membrane electrode assembly (MEA) fabrication than the traditional hot pressing because it can result in better TPB building and lowering the FA crossover. DFAFC performed approximately 60% better after these anodic micro structure optimizations.     

High performance membrane electrode assemblies by optimization of coating process and catalyst layer structure in direct methanol fuel cells

High performance membrane electrode assemblies (MEAs) for direct methanol fuel cells (DMFCs) are developed by changing the coating process, optimizing the structure of the catalyst layer, adding a pore forming agent to the cathode catalyst layer, and adjusting the hot-pressing conditions, such as pressure and temperature. The effects of these MEA fabrication methods on the DMFC performance are examined using a range of physicochemical and electrochemical analysis tools, such as FE-SEM, electrochemical impedance spectroscopy (EIS), polarization curves, and differential scanning calorimetry (DSC) of the membrane. EIS and polarization curve analysis show that an increase in the thickness and porosity of the cathode catalyst layer plays a key role in improving the cell performance with reduced cathode reaction resistance, whereas the MEA preparation methods have no significant effects on the anode impedance. In addition, the addition of magnesium sulfate as a pore former reduces the cathode reaction transfer resistance by approximately 30 wt%, resulting in improved cell performance.     

Analysis of palladium-based anode electrode using electrochemical impedance spectra in direct formic acid fuel cells

In this study, we used the electrochemical impedance spectra to evaluate the anode performance of direct formic acid fuel cell (DFAFC), and how its anode charge transfer resistance (R_anode,ct) and electrolyte resistance (R_ele) are affected by various cell operating parameters. The parameters investigated in this study include the anode overpotentials, cell operation times, formic acid feed concentrations and cell temperatures. The anode impedance spectra demonstrated that the R_anode,ct and R_ele are low for the DFAFC using 5 M formic acid feed concentration, which leads to its high power density output of 250 mW cm⁻² at 0.35 V and 30 °C. The high performance of the DFAFC demonstrates that it has a great potential for portable power applications. The R_anode,ct increases gradually as either the cell operation time increases or the formic acid feed concentration is raised from 10 to 15 M, which leads to a deactivation of the anode electrode, resulting in reduction of overall cell performance. However, these deactivation processes are reversible and the cell performance can be easily reactivated.     

Characterization of direct methanol fuel cells by ac impedance spectroscopy

The processes taking place in direct methanol fuel cells (DMFC) are characterized by ac impedance spectroscopy under realistic operating conditions. This method allows the separate examination of anode kinetics, anode mass transport, cathode kinetics, cathode mass transport, and membrane conductivity, making it a valuable diagnostic tool for DMFC development.     

Effects of Nafion loading in anode catalyst inks on the miniature direct formic acid fuel cell

Nafion, within the anode and cathode catalyst layers, plays a large role in the performance of fuel cells, especially during the operation of the direct formic acid fuel cell (DFAFC). Nafion affects the proton transfer in the catalyst layers of the fuel cell, and studies presented here show the effects of three different Nafion loadings, 10 wt.%, 30 wt.% and 50 wt.%. Short term voltage-current measurements using the three different loadings show that 30 wt.% Nafion loading in the anode shows the best performance in the miniature, passive DFAFC. Nafion also serves as a binder to help hold the catalyst nanoparticles onto the proton exchange membrane (PEM). The DFAFC anode temporarily needs to be regenerated by raising the anode potential to around 0.8 V vs. RHE to oxidize CO bound to the surface, but the Pourbaix diagram predicts that Pd will corrode at these potentials. We found that an anode loading of 30 wt.% Nafion showed the best stability, of the three Nafion loadings chosen, for reducing the amount of loss of electrochemically active area due to high regeneration potentials. Only 58% of the area was lost after 600 potential cycles in formic acid compared to 96 and 99% for 10 wt.% and 50 wt.% loadings, respectively. Lastly we present cyclic voltammetry data that suggest that the Nafion adds to the production of CO during oxidation of formic acid for 12 h at 0.3 V vs. RHE. The resulting data showed that an increase in CO coverage was observed with increasing Nafion content in the anode catalyst layer.     

Double microporous layer cathode for membrane electrode assembly of passive direct methanol fuel cells

A novel membrane electrode assembly (MEA) is described that utilizes a double microporous layer (MPL) structure in the cathode of a passive direct methanol fuel cell (DMFC). The double MPL cathode uses Ketjen Black carbon as an inner-MPL and Vulcan XC-72R carbon as an outer-MPL. Experimental results indicate that this double MPL structure at the cathode provides not only a higher oxygen transfer rate, but enables more effective back diffusion of water; thus, leading to an improved power density and stability of the passive DMFC. The maximum power density of an MEA with a double MPL cathode was observed to be ca. 33.0 mW cm⁻², which is found to be a substantial improvement over that for a passive DMFC with a conventional MEA. A. C. impedance analysis suggests that the increased performance of a DMFC with the double MPL cathode might be attributable to a decreased charge transfer resistance for the cathode oxygen reduction reaction.     

Basic model for membrane electrode assembly design for direct methanol fuel cells

This research proposes a model that predicts the effect of the anode diffusion layer and membrane properties on the electrochemical performance and methanol crossover of a direct methanol fuel cell (DMFC) membrane electrode assembly (MEA). It is an easily extensible, lumped DMFC model. Parameters used in this design model are experimentally obtainable, and some of the parameters are indicative of material characteristics. The quantification of these material parameters builds up a material database. Model parameters for various membranes and diffusion layers are determined by using various techniques such as polarization, mass balance, electrochemical impedance spectroscopy (EIS), and interpretation of the response of the cell to step changes in current. Since the investigation techniques cover different response times of the DMFC, processes in the cell such as transport, reaction and charge processes can be investigated separately. Properties of single layers of the MEA are systematically varied, and subsequent analysis enables identification of the influence of the layer's properties on the electrochemical performance and methanol crossover. Finally, a case study indicates that the use of a membrane with lower methanol diffusivity and a thicker anode micro-porous layer (MPL) yields MEAs with lower methanol crossover but similar power density.     

Effect of variation of hydrophobicity of anode diffusion media along the through-plane direction in direct methanol fuel cells

Reducing methanol crossover from the anode to cathode in direct methanol fuel cells (DMFCs) is critical for attaining high cell performance and fuel utilization, particularly when highly concentrated methanol fuel is fed into DMFCs. In this study, we present a novel design of anode diffusion media (DM) wherein spatial variation of hydrophobicity along the through-plane direction is realized by special polytetrafluoroethylene (PTFE) coating procedure. According to the capillary transport theory for porous media, the anode DM design can significantly affect both methanol and water transport processes in DMFCs. To examine its influence, three different membrane-electrode assemblies are fabricated and tested for various methanol feed concentrations. Polarization curves show that cell performance at high methanol feed concentration conditions is greatly improved with the anode DM design with increasing hydrophobicity toward the anode catalyst layer. In addition, we investigate the influence of the wettability of the anode microporous layer (MPL) on cell performance and show that for DMFC operation at high methanol feed concentration, the hydrophilic anode MPL fabricated with an ionomer binder is more beneficial than conventional hydrophobic MPLs fabricated with PTFE. This paper highlights that controlling wetting characteristics of the anode DM and MPL is of paramount importance for mitigating methanol crossover in DMFCs.     

Passive direct methanol fuel cells fed with methanol vapor

A vapor fed passive direct methanol fuel cell (DMFC) is proposed to achieve a high energy density by using pure methanol for mobile applications. Vapor is provided from a methanol reservoir to the membrane electrode assembly (MEA) through a vaporizer, barrier and buffer layer. With a composite membrane of lower methanol cross-over and diffusion layers of hydrophilic nanomaterials, the humidity of the MEA was enhanced by water back diffusion from the cathode to the anode through the membrane in these passive DMFCs. The humidity in the MEA due to water back diffusion results in the supply of water for an anodic electrochemical reaction with a low membrane resistance. The vapor fed passive DMFC with humidified MEA maintained 20–25 mW cm⁻² power density for 360 h and performed with a 70% higher fuel efficiency and 1.5 times higher energy density when compared with a liquid fed passive DMFC.     

Two-dimensional two-phase thermal model for passive direct methanol fuel cells

A two-dimensional two-phase thermal model is presented for direct methanol fuel cells (DMFC), in which the fuel and oxidant are fed in a passive manner. The inherently coupled heat and mass transport, along with the electrochemical reactions occurring in the passive DMFC is modeled based on the unsaturated flow theory in porous media. The model is solved numerically using a home-written computer code to investigate the effects of various operating and geometric design parameters, including methanol concentration as well as the open ratio and channel and rib width of the current collectors, on cell performance. The numerical results show that the cell performance increases with increasing methanol concentration from 1.0 to 4.0 M, due primarily to the increased operating temperature resulting from the exothermic reaction between the permeated methanol and oxygen on the cathode and the increased mass transfer rate of methanol. It is also shown that the cell performance upgrades with increasing the open ratio and with decreasing the rib width as the result of the increased mass transfer rate on both the anode and cathode.     

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.     

A three-dimensional mathematical model for liquid-fed direct methanol fuel cells

A three-dimensional, single-phase, multi-component mathematical model has been developed for a liquid-fed direct methanol fuel cell (DMFC). The traditional continuity, momentum, and species conservation equations are coupled with electrochemical kinetics in both the anode and cathode catalyst layer. At the anode side, the liquid phase is considered, and at the cathode side only the gas phase is considered. Methanol crossover due to both diffusion and electro-osmotic drag from the anode to the cathode is taken into consideration and the effect is incorporated into the model using a mixed-potential at the cathode. A finite-volume-based CFD technique is used to develop the in-house numerical code and the code is successfully used to simulate the fuel cell performance as well as the multi-component behavior in a DMFC. The modeling results of polarization curves compare well with our experimental data. Subsequently, the model is used to study the effects of methanol crossover, the effects of porosities of the diffusion layer and the catalyst layer, the effects of methanol flow rates, and the effects of the channel shoulder widths.     

Water management in a passive direct methanol fuel cell

Passive direct methanol fuel cells (DMFCs) are under development for use in portable applications because of their enhanced energy density in comparison with other fuel cell types. The most significant obstacles for DMFC development are methanol and water crossover because methanol diffuses through the membrane generating heat but no power. The presence of a large amount of water floods the cathode and reduces cell performance. The present study was carried out to understand the performance of passive DMFCs, focused on the water crossover through the membrane from the anode to the cathode side. The water crossover behaviour in passive DMFCs was studied analytically with the results of a developed model for passive DMFCs. The model was validated with an in‐house designed passive DMFC. The effect of methanol concentration, membrane thickness, gas diffusion layer material and thickness and catalyst loading on fuel cell performance and water crossover is presented. Water crossover was lowered with reduction on methanol concentration, reduction of membrane thickness and increase on anode diffusion layer thickness and anode and cathode catalyst layer thickness. It was found that these conditions also reduced methanol crossover rate. A membrane electrode assembly was proposed to achieve low methanol and water crossover and high power density, operating at high methanol concentrations. The results presented provide very useful and actual information for future passive DMFC systems using high concentration or pure methanol. Copyright © 2012 John Wiley & Sons, Ltd.     

Analysis of performance losses of direct methanol fuel cell with methanol tolerant PtCoRu/C cathode electrode

The long-term stability of PtCoRu/C to methanol crossover has been evaluated in a direct methanol fuel cell (DMFC) configuration. The DMFC has been subjected to continuous operation under potential step cycles. The degradation of the DMFC with PtCoRu/C has been followed by comparison of the power density curves recorded after 0, 60 and 312 h of continuous operation, and compared to that recorded for a DMFC with Pt/C. Electrochemical Impedance Spectra (EIS) were recorded directly from the DMFCs and used to identify the main degradation phenomena responsible for the loss of performance of the used fuel cell. AC impedance spectra show that the resistance of the anode reaction increases while resistance associated to the cathode reaction decreases after the long-term stability tests; however, the analysis of the power density curves unequivocally show that the performance of the DMFCs goes down during the stability tests. This apparent contradiction can be explained by taking into account the changes between the fresh and used PtCoRu/C observed by X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses. During the potential step cycles Ru dissolves form PtCoRu/C leading to Pt-enriched catalysts which are more active for the oxygen reduction reaction (lower resistance) but less tolerant to methanol (lower power density).     

Investigations of performance degradation and mitigation strategies in direct methanol fuel cells

This paper addresses a gradual performance loss that is encountered in a direct methanol fuel cell (DMFC) when it is subjected to a continuous operation at constant-load conditions for a period of 600 h. To gain insights into the physico-chemical origins of the degradation process, various analytical techniques are employed and characterization of the membrane electrode assembly (MEA) is carried out before and after the lifetime test. The results reveal that the performance degradation of MEA mainly stems from the degradations at the cathode, and this is further confirmed by individual impedance analyses of cathode and anode as well as by the observation on finding increased quantity of methanol exiting from the cathode with increased operational time. Supplement experiments with the cathodes containing either pre-oxidized Pt catalyst or a fractional amount of Ru catalyst offer new clues to understand the deactivation mechanism. The hydrophobicity losses of gas diffusion layers are prominent in the outlet regions compared to the inlet regions of the DMFC assembly. Further, a couple of restoration techniques are employed to evaluate performance recovery. A periodical on–off switching of applied load and an air-break technique are found to be effective to restore the performance loss that occurs during fuel cell operations.