Comparative Study of On‐Line Membrane Electrode Assembly Activation Procedures in Proton Exchange Membrane Fuel Cell

The major objectives of this study are to identify the best activation procedure between commonly used procedures that can significantly reduce the conditioning duration and to understand the change in interfacial properties during conditioning. In order to do that, three on‐line activation procedures were employed for activating of identical MEAs in PEMFC and studied by polarization curve and electrochemical impedance spectroscopy (EIS). These methods are constant current (0.25 A cm^–2) for 19 h, constant voltage (0.6 V) for 9 h, and USFCC protocol. The best performance was achieved by USFCC protocol within 15 h, but by constant voltage procedure, 96% of mentioned protocol was obtained during 6 h. So constant voltage activation proceeded remarkably fast, and most of the activation process was achieved in the first few hours. Obtained results from Nyquist plots during/after MEA conditioning indicate mentioned process are irreversible and interfacial structures of MEAs are different even after finishing of MEA break‐in. It could be affected the MEA performance and even its durability. These results are consistence with the obtained performance of activated MEAs either in H₂/air or H₂/O₂ PEMFC. We found the mentioned constant current procedure consume long time without reaching to expectable performance even after 19 h.     

Proton Exchange Membrane Fuel Cell Operation and Degradation in Short‐Circuit

Hybridization of proton exchange membrane fuel cells (PEMFC) and ultra capacitors (UC) are considered as an alternative way to implement high autonomy, high dynamic, and reversible energy sources. PEMFC allow high efficiency and high autonomy, however their dynamic response is limited and this source does not allow recovering energy. UC appears to be a complementary source to fuel cell systems (FCS) due to their high power density, fast dynamics, and reversibility. A direct hybridization of these sources could allow reducing the number of power converters and then the total cost of the hybridized system. Simulations show the behavior of the hybrid source when the fuel cell and ultra capacitors are interconnected and the natural energy management when a charge is connected. The results show that the magnitude of the transient current supplied by the fuel cell to charge the UC can be much higher than its nominal value. An experimental setup is implemented to study the effects of these high currents in a PEMFC. This is done by imposing a controlled short‐circuit between the electrodes. The PEMFC degradation is quantified by using electrochemical impedance spectroscopy.     

Energy Dispersive X‐ray Diffraction Applied to Laboratory Investigation on Proton Exchange Membrane Water Content in Working Fuel Cells

An original method, based on the energy‐dispersive X‐ray diffraction, has been recently proposed as a possible laboratory tool to accomplish long time resolved investigation of the water content in a proton exchange membrane fuel cell. However, this method has never been applied to a real working fuel cell. Therefore, a clear comprehension of its effectiveness in terms of relevant parameters such as time and space resolution, sensitivity, and reproducibility has not yet been achieved. In this paper, all these aspects are discussed and clarified. In order to focus on the method overall effectiveness and on the extent of possible improvements, a basic experimental configuration for both the electrochemical station and the X‐ray equipment has been set. The method is described with particular attention to its operating principle and to the evaluation of the errors introduced in data assessment. Finally, applications to some model experiments, in particular working states of the device, are provided and the obtained results are discussed.     

直接甲醇燃料电池质子交换膜的发展现状

直接甲醇燃料电池(DMFC)是20世纪90年代兴起的第六代燃料电池,以其诸多的优点引起人们的广泛关注和研究。其中聚合物电解质膜是DMFC的关键技术,起着隔离阴阳极、质子传输、绝缘电子的作用。它的作用决定着DMFC的输出功率、电池效率、成本及应用前景。本文介绍了已商品化的全氟磺酸膜(Nafion膜)的结构及性能、以及替代膜的国内外发展现状,指出DMFC用膜的研究是21世纪能源研究的重点。     

Preparation and Characterization of Perfluorosulfonate‐Free Phosphosilicate Glass‐Based Composite Proton‐Exchange Membrane

Based on hydrothermally treated phosphosilicate (SiO₂–P₂O₅) glass and sulfonated poly(ether ether ketone) (SPEEK) polymer, perfluorosulfonate‐free SiO₂–P₂O₅/SPEEK composite membranes are prepared. The morphology, thermal and mechanical properties, pore structure, proton conductivity, water uptake, as well as the fuel cell performances of the SiO₂–P₂O₅/SPEEK composite membranes are investigated. The SiO₂–P₂O₅/SPEEK composite membranes with proton conductive SiO₂–P₂O₅ glass powders of more than 50 wt.% were determined to be flexible due to the incorporation of the SPEEK polymer component, and it showed proton conductivities of above 10^–2 S cm^–1. A single H₂/O₂ fuel cell was assembled based on the SiO₂–P₂O₅/SPEEK composite membrane, and was found to release a peak power density of 355.6 mW cm^–2 at 68 °C.     

An Algorithm for On‐line Measurement of the Internal Resistance of Proton Exchange Membrane Fuel Cell

The internal resistance of proton exchange membrane fuel cell (PEMFC) system is difficult to measure on‐line due to its variation with time. The traditional electrochemical impedance spectroscopy (EIS) and its variants such as high frequency resistance (HFR) can be used to measure the resistance when the system is in steady state, but they fail in automotive applications where a change in speed or inclination modifications could lead to a sharp fluctuation in demand on power. In order to resolve this problem, a novel algorithm is proposed in this paper to estimate the resistance based on the alternating current (AC) impedance spectroscopy technique by adding an extra term to eliminate the errors caused by voltage variation or when the system is under unsteady state. Numerical simulations show that the proposed algorithm can not only accurately track the variation of the internal resistance, but is also robust against the noises caused by uncertainty and measurements.     

燃料电池用的含氟质子交换膜的研发现状

质子交换膜是燃料电池中的关键部件。本文介绍了有关用于燃料电池的质子交换膜的研发现状。     

Mathematical Model of Proton Exchange Membrane Fuel Cell with Consideration of Water Management

One‐dimensional model on the membrane electrode assembly (MEA) of proton exchange membrane fuel cell is proposed, where the membrane hydration/dehydration and the possible water flooding of the respective cathode and anode gas diffusion layers are considered. A novel approach of phase‐equilibrium approximation is proposed to trace the water front and the detailed saturation profile once water emerges in either anode or cathode gas diffusion layer. The approach is validated by a semi‐analytical method published earlier. The novel approach is applicable to the polarization regime from open circuit voltage to the limiting current density under practical operation conditions. Oxygen diffusion is limited by water accumulation in the cathode gas diffusion layer as current increases, caused by excessive water generation at the cathode catalyst layer and the electro‐osmotic drag across the membrane. The existence of liquid water in the anode gas diffusion layer is predicted at low current densities if high degrees of humidification in both anode and cathode feeds are employed. The influences of inlet relative humidity, imposed pressure drop, and cell temperature are correlated well with the cell performance. In addition, the overpotentials attributed from individual components of the MEA are delineated against the cell current densities.     

Enhanced Proton Conductivity of Sulfonated Poly(ether ether ketone) Membrane Embedded by Dopamine‐Modified Nanotubes for Proton Exchange Membrane Fuel Cell

Design and fabrication of alternative proton exchange membrane (PEM) with high proton conductivity is crucial to the commercial application of PEM fuel cell. Inspired by the bioadhesion principle, dopamine‐modified halloysite nanotubes (DHNTs) bearing –NH₂ and –NH– groups are facilely synthesized by directly immersing natural halloysite nanotubes (HNTs) into dopamine aqueous solution under mild conditions. DHNTs are then embedded into sulfonated poly(ether ether ketone) (SPEEK) matrix to prepare hybrid membranes. HNTs‐filled hybrid membranes are prepared for comparison. The microstructure and physicochemical properties of the membranes are extensively investigated. Fourier transform infrared analysis implies that ordered acid–base pairs (e.g., –S–O^–…⁺H–HN–, –S–O^–…⁺H–N–) are formed at SPEEK–DHNT interface through strong electrostatic interaction. In such a way, continuous surface‐induced ion‐channels emerge along DHNTs. Although the incorporation of DHNTs reduces the channel size, water uptake, and area swelling of the hybrid membranes, which in turn would reduce the vehicle‐type proton transfer, the acid–base pairs create continuous pathways for fast proton transfer with low energy barrier via Grotthuss mechanism. Consequently, DHNT‐filled hybrid membrane with 15% DHNTs achieves a 30% increase in proton conductivity and a 52% increase in peak power density of single cell when compared with SPEEK control membrane, particularly.     

Simulation and Validation of Thermo‐mechanical Stresses in Planar SOFCs

To study possible failure modes of the Hexis Galileo solid oxide fuel cell stack, various stack components such as nickel/yttria stabilised zirconia anodes, lanthanum strontium manganese cathodes, 3 mol%‐yttria stabilised zirconia electrolytes and chromium alloy metallic interconnectors have been characterised with respect to their thermo‐mechanical properties. Specifically, coefficients of thermal expansion, Young's moduli, bending strengths, Poisson's ratios and fracture toughnesses have been measured. Furthermore, the temperature‐dependent warpage of complete cells has been investigated by video analysis. All experimental data were taken as input parameters for a set of finite element models to analyse various thermo‐mechanical phenomena on different length scales. The simulations offer an explanation for the often observed ‘saddle‐like‘ deformations of cells at room temperature. They also show that cracks that first develop within the anode induce local tensile stresses within the electrolyte and hence represent a weakening mechanism for the cells. It is shown that the induced electrolyte stresses depend on the anode crack density. The electrolyte stresses decrease as the distances between the anode cracks become smaller.     

Fabrication of Function‐Graded Proton Exchange Membranes for Direct Methanol Fuel Cells Using Electron Beam‐Grafting

Function‐graded proton exchange membranes (G‐PEMs) based on poly(tetrafluoroethylene‐co‐hexafluoropropylene) were fabricated for direct methanol fuel cells (DMFCs) via electron beam‐grafting using the heterogeneous energy deposition technique. The G‐PEMs had a water uptake gradient in the proton transfer direction, originating from the sulfonic acid group gradient. The distribution of sulfonic acid groups in the various G‐PEMs was evaluated using X‐ray photoelectron spectroscopy. Four types of PEMs (flat‐type, strong‐gradient, meso‐gradient, and weak‐gradient types) were fabricated. By varying the direction of the G‐PEMs, the methanol permeation test and DMFC operation were performed with two orientations of the sulfonic acid group gradient, decreasing from the methanol injection (anode) side (decrease‐type) or the other (cathode) side (increase‐type). The methanol permeability of the strong‐gradient, meso‐gradient, and weak‐gradient G‐PEMs was lower than that of Nafion®117 and the flat‐type PEM. The “increase‐type” orientation of the strong‐gradient G‐PEM resulted in the lowest methanol permeability. The DMFC performance of the G‐PEMs was influenced by the thickness direction, such as “decrease‐type” and “increase‐type.” The performance of the “decrease‐type” assembly was higher than that of the “increase‐type.” The “decrease‐type” assembly with P‐200 k (weak‐gradient G‐PEM) exhibited the highest performance of the fabricated PEMs, comparable to that of Nafion®117.     

A Three‐Dimensional Non‐isothermal Model of High Temperature Proton Exchange Membrane Fuel Cells with Phosphoric Acid Doped Polybenzimidazole Membranes

High temperature proton exchange membrane fuel cells (HT‐PEMFCs) with phosphoric acid doped polybenzimidazole (PBI) membranes have gained tremendous attentions due to its attractive advantages over conventional PEMFCs such as faster electrochemical kinetics, simpler water management, higher carbon monoxide (CO) tolerance and easier cell cooling and waste heat recovery. In this study, a three‐dimensional non‐isothermal model is developed for HT‐PEMFCs with phosphoric acid doped PBI membranes. A good agreement is obtained by comparing the numerical results with the published experimental data. Numerical simulations have been carried out to investigate the effects of operating temperature, phosphoric acid doping level of the PBI membrane, inlet relative humidity (RH), stoichiometry ratios of the feed gases, operating pressure and air/oxygen on the cell performance. Numerical results indicate that increasing both the operating temperature and phosphoric acid doping level are favourable for improving the cell performance. Humidifying the feed gases at room temperature has negligible improvement on the cell performance, and further humidification is needed for a meaningful performance enhancement. Pressurising the cell and using oxygen instead of air all have significant improvements on the cell performance, and increasing the stoichiometry ratios only helps prevent the concentration loss at high current densities.     

Gas Diffusion Layers for Proton Exchange Membrane Fuel Cells Using In situ Modified Carbon Papers with Multi‐walled Carbon Nanotubes Nanoforest

Gas diffusion layers (GDLs) in the proton exchange membrane fuel cells (PEMFCs) enable the distribution of reactant gases to the reaction zone in the catalyst layers by controlling the water in the pore channels apart from providing electrical and mechanical support to the membrane electrode assembly (MEA). In the present work, we report the in situ growth of carbon nanotubes nanoforest (CNN) directly onto macro‐porous carbon paper substrates. The surface property as analysed by a Goniometer showed that the CNN/carbon paper surface is highly hydrophobic. CNN/carbon paper was employed as a GDL in an MEA using Nafion‐212 membrane as an electrolyte and evaluated in single cell PEMFCs. While the GDLs prepared by wire‐rod coating process have major performance losses at lower humidities, the in situ CNN/carbon paper, developed in this work, shows very stable performance at all humidity conditions demonstrating a significant improvement for fuel cell performance. The CNN/carbon‐based MEAs showed very stable performance with power density values of ∼1,100 and 550 mW cm^–2, respectively, both using O₂ and air as oxidants at ambient pressure.     

Improvement of the Ohmic Loss Process Model of the Proton Exchange Membrane Fuel Cell

The impedance characteristics of the ohmic overpotential of the proton exchange membrane (PEM) fuel cells are studied analytically using the process modeling approach. The water transport in the membrane, the cathode catalyst layer, and gas diffusion layer are analyzed. The analytical relation of the impedance of the ohmic loss is determined and is converted to an equivalent circuit. Then, the impedance of a PEM fuel cell is measured experimentally in different current densities, operating temperatures and the anode and cathode relative humidities. The measured impedances are compared with the predicted ones from the analytical model. It is shown that the predicted impedance characteristics are in great agreement with the measured ones in all different operating conditions.     

Simulation and Experiment of a Cogeneration System Based on Proton Exchange Membrane Fuel Cell

This project designs and simulates a cogeneration system of proton exchange membrane fuel cell using Matlab/Simulink software and Thermolib heat module components. The system not only satisfies the need for electric power, but also provides heat recovery for future uses, thus increasing energy transfer efficiency. PEM fuel cell‐based cogeneration system is introduced, including the hydrogen supply subsystem, air supply subsystem, load control subsystem, real‐time monitoring block, and heat recovery subsystem. The complete fuel cell‐based cogeneration system is constructed by assembling the fuel cell stack, fuel, coolant flow rate control system, and all the subsystems. In addition to the fuel cell experiment, influencing factors on the fuel cell‐based system, such as the fuel inhale rate, coolant flow rate, system temperature, fuel humidification, thermal efficiency, electrical efficiency, and combined heat and power (CHP) system efficiency, are analyzed and charted regarding different loads. In this system, with the power at 3 kW, the CHP efficiency reaches 64%. The CHP efficiency is 76.6% with the load power at 4 kW. When the power is at 5 kW, the thermal efficiency reaches 36.9% and the CHP efficiency reaches 82.9%.     

Water Free Operated Phosphoric Acid Doped Radiation‐Grafted Proton Conducting Membranes for High Temperature Polymer Electrolyte Membrane Fuel Cells

The present study uses the radiation‐induced grafting method and applies it onto poly(ethylene‐alt‐tetrafluoroethylene) (ETFE) for the synthesis of proton‐exchange membranes by using monomers 4‐vinyl pyridine (4VP), 2‐vinyl pyridine (2VP), N‐vinyl‐2‐pyrrolidone (NVP) followed by phosphoric acid doping. Phosphoric acid that provides Grotthuss mechanism in proton mobilization is used to transform the graft copolymers to a high temperature membrane state. Resultant proton‐exchange membranes are verified with their proton conductivity, water uptake, mechanical and thermal properties, and phosphorous distribution as ex situ characterization. Our most important finding as a novelty in literature is that ETFE‐g‐P4VP phosphoric acid doped proton‐exchange membranes exhibit proton conductivities as 66 mS cm^–1 at 130 °C, 53 mS cm^–1 at 120 °C, 45 mS cm^–1 at 80 °C at RH 100% and 55 mS cm^–1 at 130 °C, 40 mS cm^–1 at 120 °C, 35 mS cm^–1 at 80 °C at dry conditions. Moreover, ETFE‐g‐P4VP membranes still conserves the mechanical properties, i.e., tensile strength up to 48 MPa. ETFE‐g‐P4VP membranes were tested in PEMFC at 80, 100, and 120 °C and RH <2% and exhibit promising performance as an alternative to commercial Nafion® membranes. The single cell testing performance of ETFE‐g‐P4VP membranes is presented for the first time in literature in our study.     

Performance and Durability of Membrane Electrode Assemblies Based on Radiation‐Grafted FEP‐g‐Polystyrene Membranes

Membrane electrode assemblies (MEAs) based on radiation‐grafted proton exchange membranes developed at PSI have shown encouraging performance in the past in hydrogen and methanol fuelled polymer electrolyte fuel cells. In this study, the effect of the pre‐treatment of crosslinked radiation‐grafted FEP membranes prior to lamination with the electrodes on the performance of the MEAs was investigated. Two approaches were assessed separately and in combination: (1) the impregnation of the radiation‐grafted membranes with solubilised Nafion®, and (2) the use of a swollen vs. dry membrane. It is found that the combination of coating the membrane with Nafion® ionomer and hot‐pressing the MEA with the membrane in the wet state produce the best single cell performance. In the second part of the study, the durability of an MEA, based on a radiation‐grafted FEP membrane, was investigated. The performance was stable for 4,000 h at a cell temperature of 80 °C. Then, a notable degradation of the membrane, as well as the electrode material, started to occur as a consequence of either controlled or uncontrolled start‐stop cycles of the cell. It is assumed that particular conditions, to which the cell is subjected during such an event, strongly accelerate materials degradation, which leads to the premature failure of the MEA.     

Experimental Evaluation of Effective Parameters for the Synthesis of Polysulfone‐Based Anion Exchange Membrane

Experimental evaluation using screening design is employed to determine the significant parameters in preparation of anion exchange membranes applicable in solid alkaline fuel cell. Anion exchange membranes are prepared based on quaternized polysulfone using trimethylamine and N,N,N′,N′‐tetramethyl‐1,6‐hexanediamine as amination agents. Plackett Burman and Fractional Factorial designs are used to model variable factors and responses. Chloromethylation time and temperature, amination time and temperature and molar ratio of amines to chloromethylated sites on the polymer chain are studied as the model variables. Moreover, ex situ ionic conductivity (at 25 and 60 °C) and swelling ratio (at 25 °C) of the prepared anion exchange membranes are considered as the responses. Finally, based on analysis of variance using statistical software, the chloromethylation time, the amination temperature and the molar ratio of amines are defined as the dominant parameters which significantly affect the performance of the anion exchange membranes.     

Matrix Material Study for in situ Grown Pt Nanowire Electrocatalyst Layer in Proton Exchange Membrane Fuel Cells (PEMFCs)

The cathode electrocatalyst layers were prepared by in situ growing Pt nanowires (Pt‐NWs) in two kinds of matrixes with various Pt loadings for proton exchange membrane fuel cells (PEMFCs). Commercial carbon powder and 20 wt.% Pt/C electrocatalyst were used as the matrix material for the comparison. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD), polarization curves tests, and electrochemical impedance spectroscopy (EIS) were carried out to examine the effects of the matrix materials on the Pt‐NW growing and the electrode performance. The optimum Pt‐NW loadings of 0.30 mg cm⁻² in the carbon matrix (CM) and 0.20 mg cm⁻² for the Pt/C matrix (PM) were obtained. The results indicated that the Pt‐NWs grown in the CM had a better crystalline, longer size length and better catalyst activity than those in the PM. The mechanism of the matrix affection is further discussed in this paper.     

Synthesis and Characterization of Sulfonated Cardo Poly(Arylene Ether Sulfone)s for Fuel Cell Proton Exchange Membrane Application

Sulfonated cardo poly(arylene ether sulfone)s ( SPPA ‐ PES ) with various degrees of sulfonation (DS) were prepared by post‐sulfonation of synthesized phenolphthalein anilide ( PPA ; N‐phenyl‐3,3′‐bis(4‐hydroxyphenyl)‐1‐isobenzopyrolidone) poly(arylene ether sulfone)s ( PPA ‐ PES ) by using concentrated sulfuric acid. PPA ‐ PES copolymers were synthesized by direct polycondensation of PPA with bis‐(4‐fluorophenyl)‐sulfone and 4,4′‐sulfonyldiphenol. The DS was varied with different mole ratios of PPA (24, 30, 40, 50 mol.%) in the polymer. The structure of the resulting SPPA ‐ PES copolymers and the different contents of the sulfonated unit were studied by Fourier transform infrared (FT‐IR) spectroscopy, ¹H NMR spectroscopy, and thermogravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymer with water. The ion exchange capacity (IEC) and proton conductivity of SPPA ‐ PES were evaluated according to the increase of DS. The water uptake (WU) of the resulting SPPA ‐ PES membranes was in the range of 20–72%, compared with 28% for Nafion 211®. The SPPA ‐ PES membranes showed proton conductivities of 23–82 mS cm^–1, compared with 194 mS cm^–1 for Nafion 211®, under 100% relative humidity (RH) at 80 °C.