Determination of oxygen transport resistance in gas diffusion layer for polymer electrolyte fuel cells

Gas diffusion layer (GDL) plays an important role in the performance of membrane electrode assembly (MEA) in polymer electrolyte fuel cells. In this work, 2‐type MEAs were prepared by 2 different GDLs of 29 BC and 29‐WUT, and the performance were investigated using polarization curve methods. The performance of MEA with 29‐WUT was 120 mV higher than 29 BC at 1600 mA/cm². Electrochemical impedance spectroscopy (EIS) was applied to measure the mass transport resistance of 2‐type MEAs under normal running condition. The results of EIS showed that the mass transport resistance of 29 BC was 3.15 times higher than that of 29‐WUT at 1600 mA/cm². To clarify this phenomenon, limiting current methods were applied under diluting oxygen concentration, low humidity, and high flow rate conditions. The results of limiting current methods showed that both the total oxygen transport resistance and the molecular diffusion resistance in the GDL of 29 BC were larger than that of 29‐WUT due to the lower porosity of gas diffusion substrate in 29 BC . As a result, EIS can be well combined with limiting current methods to analyze oxygen transport resistance in GDLs of fuel cells.     

Characteristics of a fluidized bed electrode for a direct carbon fuel cell anode

The characteristics of a fluidized bed electrode applied as a direct carbon fuel cell anode, which has an inner diameter of 35 mm and height of 520 mm and employed bamboo-based activated carbon (BB-AC) as a feedstock, are vigorously studied under various experimental conditions. The optimal performance of the fluidized bed electrode direct carbon fuel cell (FEBDCFC) anode with the BB-AC as a fuel is obtained under the following conditions with a limiting current density of 95.9 mA cm⁻²: reaction temperature, 923 K; N₂ flow rate, 385 ml min⁻¹; O₂/CO₂ flow rate, 10/20 ml min⁻¹; nickel particle content, 30 g; and a cylindrically curved nickel plate as a current collector. Under the same optimal conditions, the limiting current density of the FEBDCFC anode with oak wood-based activated carbon and activated carbon fiber as the fuel is determined to be 94.5 and 88.4 mA cm⁻², which is lower than that determined for BB-AC as the fuel. Comparatively, the limiting current density for graphite, which is utilized as the carbon fuel for this fuel cell system, could not be unequivocally determined because no plateau of the limiting current density against the overpotential is observed.     

Self-humidifying membrane electrode assembly prepared by adding PVA as hygroscopic agent in anode catalyst layer

In this work, a novel self-humidifying membrane electrode assembly (MEA) with addition of polyvinyl alcohol (PVA) as the hygroscopic agent into anode catalyst layer was developed for proton exchange membrane fuel cell (PEMFC). The MEA shows good self humidification performance, for the sample with PVA addition of 5 wt.% (MEA PVA5), the maximum power density can reach up to 623.3 mW·cm⁻², with current densities of 1000 mA·cm⁻² at 0.6 V and 600 mA·cm⁻² at 0.7 V respectively, at 50 °C and 34% of relative humidity (RH). It is interesting that the performance of MEA PVA5 hardly changes even if the relative humidity of both the anode and cathode decreased from 100% to 34%. The MEA PVA5 also shows good stability at low humidity operating conditions: keeping the MEA discharged at constant voltage of 0.6 V for 60 h at 34% of RH, the attenuation of the current density is less than 10%, whilst for the MEA without addition of PVA, the attenuation is high up to 80% within 5 h.     

Electrochemical characterization of polymer electrolyte membrane fuel cells and polarization curve analysis

This paper presents the diagnostic results of single polymer electrolyte membrane fuel cell assemblies characterized by polarization curves. Single PEM fuel cell assemblies were investigated through accelerated voltage cycling test at different values of relative humidity. The fuel cells are tested at different humidity level. The cells are discussed in this paper with analysis results at different relative humidity at atmospheric pressure. This represents a nearly fully humidified, a moderately humidified, and a low humidified condition, respectively. This technique is useful for diagnosing the main sources of loss in MEA development work, especially for high temperature/low relative humidity operation where several sources of loss are present simultaneously. All the fuel cells showed better performance in terms of limiting current density value through polarization curves when oxygen was fed to the cathode side of each cell instead of air. The results indicate that the performance of the fuel cell could be depressed significantly by decreasing RH from 100 to 33%. Decrease in RH can result in slower electrode kinetics, including electrode reaction and mass diffusion rates, and higher membrane resistance.     

Study of catalyst sprayed membrane under irradiation method to prepare high performance membrane electrode assemblies for solid polymer electrolyte water electrolysis

In this work, a catalyst sprayed membrane under irradiation (CSMUI) method was investigated to develop high performance membrane electrode assembly (MEA) for solid polymer electrolyte (SPE) water electrolysis. The water electrolysis performance and properties of the prepared MEA were evaluated and analyzed by polarization curves, electrochemistry impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The characterizations revealed that the CSMUI method is very effective for preparing high performance MEA for SPE water electrolysis: the cell voltage can be as low as 1.564 V at 1 A cm⁻² and the terminal voltage is only 1.669 V at 2 A cm⁻², which are among the best results yet reported for SPE water electrolysis with IrO₂ catalyst. Also, it is found that the noble metal catalysts loadings of the MEA prepared by this method can be greatly decreased without significant performance degradation. At a current density of 1 A cm⁻², the MEA showed good stability for water electrolysis operating: the cell voltage remained at 1.60 V without obvious deterioration after 105 h operation under atmosphere pressure and 80 °C.     

Numerical analyses on oxygen transport resistances in polymer electrolyte membrane fuel cells using a novel agglomerate model

Characterizing oxygen transport resistances in different components of a polymer electrolyte membrane fuel cell (PEMFC) is essential to achieve better cell performance at high current under low Pt loading. In this work, a macroscopic three-dimensional model, together with a novel agglomerate model was proposed to analyze impacts of operating conditions on these resistances via limiting current strategy. By introducing a focusing factor obtained with lattice Boltzmann method at mesoscopic level, the structure-dependent local transport resistance in ionomer thin-film of the electrode was comprehensively captured and validated by existing experimental studies. Contributions of the cell components to the total transport resistance were dissected. Results show that the present agglomerate model could well reproduce the local transport behaviors of oxygen in catalyst layer by fully considering the detailed nanoscale diffusion and adsorption processes. A small mass fraction of oxygen was favored to minimize the relative deviation of the local transport resistance from its intrinsic one due to the water production and heat generation, which can reach 7% for the mass fraction of oxygen of 1%. Contribution of the in-plane diffusion of oxygen in the inactive electrode is around 1%. The total transport resistance increased with the absolute pressure, mainly due to the dominated molecular diffusion mechanism in gas channel and gas diffusion layer. Gas convection accounted for 26% of the oxygen transport resistance originated from gas channel. The transport resistance of catalyst layer increased significantly with the reduction of Pt loading, and decreased with relative humidity and operating temperature, particularly at high Pt loading.     

Voltage jump during polarization of a PEM fuel cell operated at low relative humidities

A PEM fuel cell with a Nafion 211 membrane-based membrane electrode assembly (MEA) was tested with an H₂/air stoichiometry of 2/4 at 25%, 50%, 75%, and 100% relative humidities. A voltage jump on the polarization curve was observed when the cell was operated at a lower humidity. This phenomenon may be explained by the water back-diffusion from the cathode into the membrane resulting in both a non-uniform water distribution in the membrane and a liquid-equilibrated interface between the membrane and the anode catalyst layer. Experimental results obtained by AC impedance spectroscopy measuring the MEA resistance (membrane+catalyst ionomer layers) at different current densities as well as collected polarization data at high feed-gas flow rates (or at low backpressures) and high temperatures all confirmed the validity of the proposed water back-diffusion hypothesis.     

Effect of operating conditions on current density distribution and high frequency resistance in a segmented PEM fuel cell

Understanding losses in polymer electrolyte membrane fuel cells, in the form of ohmic and mass transport, is of great importance to their commercialization. In this study, we use a spatially resolved cell consisting of 49 segments to measure the local current density distribution and high frequency resistance (HFR). A parametric study is used to investigate the effects of cell voltage, inlet relative humidity and flow rate and configuration using a three-channel serpentine flow field. We found that as the cell voltage decreased, the current density increased, while the HFR decreased. However, at a low cell voltage of 200 mV, we found the HFR to be higher than that at 500 mV. This increase is attributed to the increased electro-osmotic drag. This trend is independent of the flow configuration. Further, we found that the effect of the inlet relative humidity on the HFR highly depends on the flow configurations. Finally, a sharp decrease in the current density at some specific bend segments was observed, which correlates with lower OCV values and higher HFR values at this position.     

Degradation analysis of dead-ended anode PEM fuel cell at the low and high thermal and pressure conditions

In this study, it is demonstrated that operation of dead-ended anode fuel cell at high temperature and pressure reduce the durability of membrane electrode assembly. In such a way that after 9000 degradation cycles, the maximum power density under H₂/O₂ gas feed mode for the aged MEA at high temperature and pressure is dropped by 38.8%. While the maximum power density drop is 27.1% for the aged MEA at low temperature and pressure. Comparison of the electrochemical impedance spectroscopy responses of MEAs shows that during aging process, the charge transfer resistance increase rate is more at higher temperature and pressure. This suggests the more severe destruction of catalyst layer at higher temperature and pressure and is in agreement with the obtained values of electrochemical surface area from the cyclic voltammetry test. In addition, the transmission electron microscopy and scanning electron microscopy images show the further degradation of cathode catalyst layer and more sever Pt agglomeration at higher temperature and pressure.     

Proton exchange membrane water electrolysis at high current densities: Investigation of thermal limitations

In this work the thermal limitations of high current density proton exchange membrane water electrolysis are investigated by the use of a one dimensional model. The model encompasses in-cell heat transport from the membrane electrode assembly to the flow field channels. It is validated by in-situ temperature measurements using thin bare wire thermocouples integrated into the membrane electrode assemblies based on Nafion® 117 membranes in a 5 cm² cell setup. Heat conductivities of the porous transport layers, titanium sinter metal and carbon paper, between membrane electrode assembly and flow fields are measured in the relevant operating temperature range of 40 °C – 90 °C for application in the model. Additionally, high current density experiments up to 25 A/cm² are conducted with Nafion® 117, Nafion® 212 and Nafion® XL based membrane electrode assemblies. Experimental results are in agreement with the heat transport model. It is shown that for anode-only water circulation, water flows around 25 ml/(min cm²) are necessary for an effective heat removal in steady state operation at 10 A/cm², 80 °C water inlet temperature and 90 °C maximum membrane electrode assembly temperature. The measured cell voltage at this current density is 2,05 V which corresponds to a cell efficiency of 61 % based on lower heating value. Operation at these high current densities results in three to ten-fold higher power density compared to current state of the art proton exchange membrane water electrolysers. This would drastically lower the material usage and the capital expenditures for the electrolysis cell stack.     

The effect of relative humidity of the cathode on the performance and the uniformity of PEM fuel cells

The effect of relative humidity of the cathode (RHC) on proton exchange membrane (PEM) fuel cells has been studied focusing on automotive operation. Computational fluid dynamics (CFD) simulations were performed on a 300-cm² serpentine flow-field configuration at various RHC levels. The dependency of current density, membrane water contents, net water flux on the performance and the uniformity was investigated. The uniformity of current density and temperature was evaluated by employing standard deviation. The water balance inside a fuel cell was examined by describing electro-osmotic drag and back diffusion. It was concluded that the RHC has strong effect on the cell performance and uniformity. The dry RHC showed low cell voltage and non-uniform distributions of current density and temperature, whereas high RHC presented increased cell performance and uniform distributions of current density and temperature with well-hydrated membrane electrode assembly (MEA). Also the local current density distribution was strongly dependent on the local membrane water contents distribution that has complex phenomena of water transport. The elimination of external humidifier is desirable for the automotive operation, but it could degrade cell performance and durability due to dehydration of the MEA. Therefore a proper humidification of the reactant is necessary.     

Fabrication of electrocatalyst layers for direct methanol fuel cells

To optimize the performance of the membrane electrode assembly (MEA), a manufacturing process for electrocatalyst layers is systematically studied by controlling physical parameters such as electrocatalyst loadings at each electrode, electrocatalyst compositions, and layer thickness. The MEA is evaluated in an air-breathing direct methanol fuel cell (DMFC) with various methanol concentrations. The investigation focuses on finding the best compromise between electrocatalyst loadings and utilization of methanol concentration. Surprisingly, the power density is influenced more by the Pt loading than by the Pt–Ru loading, and can be increased further by using a methanol concentration above 3 wt.% for a certain level of electrocatalyst loading. Current–voltage characteristics indicate that increasing Pt and Pt–Ru loadings at each electrode can reduce the activation overpotentials, but the respective variation of current density with cell voltage differs in the voltage range (0.3–0.8 V). Although MEA performance can be improved by increasing the Pt (and Pt–Ru) concentration, a penalty is paid due to the tendency towards increased nanoparticle aggregation. The MEAs are also applied to a small pack of air-breathing DMFCs to assess their operability in mobile phones.     

Effects of supplied gas humidity change on PEFC transient power generation

Polymer electrolyte fuel cells (PEFCs, PEMFCs) are gaining increasingly more attention as clean and efficient energy‐conversion devices. Vapor and liquid transport has a strong impact on the power generation characteristics and efficiency of PEFCs, and so proper water management is needed for efficiency and durability. However, water transport factors are not well understood, particularly during unsteady operation—often the case in vehicles and distributed stationary power generators. In this study, to understand and generalize the effects of local water transport on PEFC performance, transient mass transport characteristics inside a PEFC were investigated experimentally and numerically. For this purpose, we developed an unsteady two‐dimensional numerical model based on mass‐ and charge‐conservation equations in the channel, gas diffusion layer (GDL), and membrane electrode assembly (MEA). As necessary parameters for model development, we measured the water content of the MEA, the membrane resistivity, the activation overvoltage, overall mass transfer coefficient, and so on. The membrane resistivity greatly increases as the relative humidity decreases. The activation overvoltage is also affected by the relative humidity, and not only by the current density and oxygen activity. Current load and voltage changes are frequently used as PEFC transient inputs, but lead to very complicated and intractable phenomena such as changes in the amount of generated water and electro‐osmosis, state of the electrical double layer, and so on. Hence, stepwise changes in the relative humidity of the supplied gas were adopted in this study. The experimental and numerical transient responses were in good agreement under most operating conditions, and the reliability of our measurement methods for the water transport properties and our numerical model were confirmed. Here we discuss the dominant factor in the transient responses, and conclude that the transport resistance at the PEM–GDL interface is the largest and most dominant factor in a relatively dry state under unsteady operating conditions. © 2011 Wiley Periodicals, Inc. Heat Trans Asian Res; Published online in Wiley Online Library ( wileyonlinelibrary.com/journal/htj ). DOI 10.1002/htj.20371     

Investigation of a cost-effective strategy for polymer electrolyte membrane fuel cells: High power density operation

Polymer electrolyte membrane (PEM) fuel cell technology needs to overcome the cost barrier in order to compete with the internal combustion engines (ICEs) for transportation application. A viable approach is to raise fuel cell's power output without increasing its size and Pt loading in the catalyst layers (CLs). In this strategy, the cost per kW power output can be proportionally reduced due to the increased power density. This paper examines this strategy by exploring several important aspects that influence fuel cell performance under high power or current density using a three-dimensional (3-D) fuel cell model. It is shown that local CLs may be subject to low oxygen concentration under a high current density of 2 A/cm², causing low reaction rate near the outlet, especially under the land. Additionally, the oxygen reduction reaction (ORR) rate may be subject to a large through-plane variation under 2 A/cm², raising ohmic voltage loss in the CL. Two additional cases are investigated to improve fuel cell performance under 2 A/cm²: one has a 5 times thinner CL with the same ORR kinetics per membrane electrode assembly (MEA) area and the other has a 5 times thinner CL with 5 times higher ORR kinetics. The results show the output voltage is raised approximately from 0.5 V to 0.554 V in the former CL case and further to 0.606 V for the latter CL. To enable high-efficiency operation (e.g. >50%), thinner CLs with high ORR kinetics and GDLs with better transport properties are one research and development (R&D) direction.     

Experimental measurements of fuel and water crossover in an active DMFC

This study measured polarization curves as well as the high-frequency resistance of active direct methanol fuel cell (DMFC) operates at around 80 °C with active controls of temperature, methanol concentration, airflow rate, and relative humidity. The relative humidity of the air did not have noticeable impacts on the fuel cell unless the operating temperature was near the evaporation temperature of water (100 °C). The hydrophobic water management layer (WML) between the membrane electrode assembly (MEA) and cathode air channel increases the mass transfer resistance and improves the water retention in MEA. Adding a WML increased the peak power density, decreased the ohmic resistance, and improved the fuel efficiency of the fuel cell, especially when it operated near 100 °C. This study also quantitatively measured methanol and water crossover as well as the fuel efficiency at different operating currents. The fuel efficiency increased significantly with the increase of the current density. Using a hydrophobic fuel management layer (FML) between the anode fuel channel and MEA reduced the fuel and water crossover rates and increased the ohmic resistance due to the decrease of the water content of the Nafion membrane. The FML improved fuel efficiency by reducing the methanol crossover. The combination of the FML and WML enabled the steady operation of DMFC using highly concentrated methanol solutions (up to 75 wt%).     

Single-walled carbon nanotube interlayer modified gas diffusion layers to boost the cell performance of self-humidifying proton exchange membrane fuel cells

A tradeoff between the low humidity and the high performance remains a key challenge for the proton exchange membrane fuel cell (PEMFC). In this work, a novel self-humidifying gas diffusion layer (GDL) with a single-walled carbon nanotube (SWCNT) nonwoven layer between the gas diffusion substrate and the hydrophobic microporous layer is controllably prepared to elevate the cell performance under dry conditions. The membrane electrode assembly (MEA) with 0.25 mg cm⁻² SWCNT loading exhibits a current density of 0.69 A cm⁻² at 0.6 V, which is 392.8% higher than that of the counterpart without the SWCNT interlayer at the same relative humidity. Moreover, the SWCNT interlayer with rational pore structure and proper wettability dramatically improves the water retention capacity of MEA, thus enhancing the low-humidity performance of MEA. The structure design of GDL provides an effective strategy for self-humidifying PEMFC control optimization.     

Effects of property variation and ideal solution assumption on the calculation of the limiting current density condition of alkaline fuel cells

A computational study of the electrochemical hydrodynamic process in an alkaline fuel cell was conducted. The computation relaxed the ideal solution assumption, accounted for thermodynamic solubility of the reactants, and allowed for property variations due to temperature and concentration effects. The results showed that the ideal solution assumption is not adequate for calculation of the transport process of the concentrated electrolyte considered, 7 M. The ideal solution formulation resulted in a lower limiting current density condition by about 50% than that predicted by the non-ideal solution formulation. The study also showed that the thermal condition is important to the calculation of the limiting current density condition. The calculated limiting current density increased by about 30% when the boundary condition was changed from isothermal to adiabatic. The computational results suggest that maintaining a uniform KOH concentration in the electrolyte (for example, at design point of 7 M) be an effective measure to increase the limiting current density condition.     

Clay as a dispersant in the catalyst layer for zinc–air fuel cells

This study proposes a four-layer membrane electrode assembly (MEA) consisting of air-electrode, proton exchange membrane, Zn-electrode with KOH or NaCl aqueous electrolyte and a steel supporter, for use in Zn–air fuel cells. Montmorillonite clay was used to disperse carbon black (CB) and MnO₂ catalyst to improve the performance of the air-electrode. The microstructures of the air-electrode and cell characteristics were investigated by field emission scanning electron microscopy (FE-SEM), optical microscopy (OM) and an electrochemical analyzer. The experimental results indicate that the four-layer MEA for Zn–air fuel cells reached a power density of 6 mW cm⁻² (at 10 mA cm⁻²) without electrolyte leakage from the cells. The open circuit voltage (OCV) and current density were improved by adding clay to the air-electrode as clay can minimize CB aggregation. In the polarization test, the OCV value (1.40 V) reached approximately 90% of the standard potential (1.65 V) and remained steadily over 48 h. These experimental results demonstrate the four-layer MEA can replace conventional Zn–air fuel cells that utilize aqueous electrolyte.     

Adaptive neuro‐fuzzy inference system and artificial neural network modeling of proton exchange membrane fuel cells based on nanocomposite and recast Nafion membranes

In this study, a proton exchange membrane fuel cell (PEMFC) is modeled by multilayer perceptron neural network (MLPNN), RBF neural network (RBFNN), and adaptive neuro‐fuzzy inference system (ANFIS). Experimental data are obtained on the basis of the fabricated membrane‐electrode assembly (MEA) responses using prepared nanocomposite and recast Nafion membranes in the PEMFC. Four parameters including cell temperature, inlet gas temperature, current density, and inorganic additive percent are used as inputs, and the cell voltage is considered as the output. The results show that there is no considerable discrepancy between the RBFNN accuracy (R = 0.99554) and the MLPNN accuracy (R = 0.99609) for the performance prediction. The required time for developing the RBFNN model is significantly lower than the MLPNN model. A variety of ANFIS structure is explored to approximate the behavior of the system. The effect of cell and inlet gas temperatures on the PEMFC performance is investigated by the ANFIS developed model. Predicted polarization and power–current behavior by the ANFIS for the MEA prepared by the recast Nafion and the nanocomposite membranes at the cell temperatures 50 °C to110°C are in high agreement with the experimental data. Predicted data by the ANFIS show that because of the property of Cs_2.5H_0.5PW₁₂O₄₀ additive for retaining water, much higher current density and power density at the same voltage are achieved for the nanocomposite membrane compared with the recast Nafion membrane in the PEMFC. Copyright © 2011 John Wiley & Sons, Ltd.     

The diffusion overpotential increase and appearance of overlapping arcs on the Nyquist plots in the low humidity temperature test conditions of polymer electrolyte fuel cell

We have investigated cell voltage characteristics and AC impedance characteristics of polymer electrolyte fuel cells (PEFCs) at various humidity temperatures for H₂/O₂ and H₂/air test conditions (current density: 200, 400, and 600 mA cm⁻², cell temperature: 80 °C, humidity temperature at respective electrodes: 40, 50, 60, and 70 °C). The diffusion overpotential increases with decreasing humidity in the low humidity temperature region such as 40 and 50 °C and the Nyquist plots obtained from AC impedance measurements show a small arc superposed on an elliptic arc in the low frequency region. The diameter of this small arc increases with decreasing humidity temperature from 50 to 40 °C or with increasing current density. These results suggest that oxygen transport across the ionomer film in the catalyst layer is significantly reduced in the low humidity condition, which causes a decrease in cell voltage, increase in diffusion overpotential, the appearance of overlapping arcs (two separate arcs) in the lower frequency region on the Nyquist plots, and the increase of mass transport resistance from Nyquist plots.