A review of high-temperature proton exchange membrane fuel cell (HT-PEMFC) system

This paper provides information encompassing the recent discovery of the High Temperature Proton Exchange Membrane Fuel Cell (HT-PEMFC) focusing on systems requirement. To have a reliable power production and higher durability level, a proper system must be applied in both normal and especially in transient operations. To date many issues of HT-PEMFC especially in durability and performance still unsolved. This article is written to provide clear information about the research undergo and must be the focus in order to produce an efficient performance. Information about the advantages towards Low Temperature Proton Exchange Membrane Fuel Cell (LT-PEMFC), the main components, and the mode of operation also discussed. In-depth research needs to be conducted into the innovative design and development of HT-PEMFC components and its system since these are the key factors for optimum performance.     

Numerical study of thermal stresses in high-temperature proton exchange membrane fuel cell (HT-PEMFC)

The purpose of this work is to numerically examine the thermal stress distributions in a high-temperature proton exchange membrane fuel cell (HT-PEMFC) based on a phosphoric acid doped polybenzimidazole (PBI) membrane. A fluid structure interaction (FSI) method is adopted to simulate the expansion/compression that arises in various components of a membrane electrode assembly (MEA) during the HT-PEMFC assembly processes, as well as during cell operations. First, three-dimensional (3-D) finite element method (FEM) simulations are conducted to predict the cell deformation during cell clamping. Then, a nonisothermal computational fluid dynamic (CFD)-based HT-PEMFC model developed in a previous study [1] is applied to the deformed cell geometry to estimate the key species and temperature distributions inside the cell. Finally, the temperature distributions obtained from these CFD simulations are employed as the input load for 3-D FEM simulations. The present numerical study provides a fundamental understanding of the stress–temperature interaction during HT-PEMFC operations and demonstrates that the coupled FEM/CFD HT-PEMFC model presented in this paper can be used as a useful tool for optimizing HT-PEMFC clamping and operating conditions.     

Feasibility of using thin polybenzimidazole electrolytes in high-temperature proton exchange membrane fuel cells

The use of thin polybenzimidazole membranes in high-temperature polymer electrolyte membrane fuel cells is explored. Membranes in thickness of 10–40 μm are prepared, doped and characterized, including fuel cell test. High molecular weight polymers enable fabrication of membranes as thin as 10 μm with sufficient mechanical strength. The thin membranes, upon acid doping, exhibit comparable conductivity and hence decreased ohmic resistance. Membrane electrode assemblies with thin membranes down to 10 μm show slightly lower open-circuit voltages than that for reference 40 μm but all above 0.97 V. This is in good agreement with the hydrogen permeability measurements, which show a value around 10^?12 mol cm^?1 s^?1 bar^?1, corresponding to a crossover current density of <1 mA cm^?2. The acid transferred from the membrane to the catalyst layer seems constant, as the iR-free polarization plots are nearly the same for membranes of varied thicknesses. The acid remaining in the membrane after the break-in period is estimated, showing an acid inventory issue when thin membranes are used. This is verified by using the membranes of higher acid doping levels.     

Numerical analysis of effects of gas crossover through membrane pinholes in high-temperature proton exchange membrane fuel cells

Durability is a major issue in the widespread commercialization of proton exchange membrane fuel cells (PEMFCs). Various failure modes have been identified over their long runtime. These mainly originate from membrane and catalyst layer failures. One of the most common failure modes in PEMFCs is due to pinhole formation in the membrane and resultant reactant gas crossover through the membrane. Gas crossover induces several critical problems in PEMFCs, including severe reactant depletion in the downstream regions, mixed potential at the electrodes, and formation of local hot spots by hydrogen/oxygen catalytic reaction, which indicates that the cell performance decreases with increasing gas crossover. In this study, we numerically investigate the effects of gas crossover on the performance of a high-temperature PEMFC based on a phosphoric-acid-doped polybenzimidazole (PBI) membrane. In contrast to previous gas-crossover studies 1 and 2 in which uniform gas crossover throughout the entire membrane has been simply assumed, our focus is on examining the impacts of localized gas crossover due to membrane pinholes. Numerical simulations are carried out via arbitrarily assuming pinholes in the membrane. The simulation results clearly show that the presence of pinholes in the membrane significantly disrupts the species, current density, and temperature distributions. Our findings may improve the fundamental and detailed understanding of localized gas-crossover phenomena through the membrane pinholes and the influence of these phenomena on high-temperature PEMFC operation.     

Influence of the phosphoric acid-doping level in a polybenzimidazole membrane on the cell performance of high-temperature proton exchange membrane fuel cells

The acid migration in phosphoric acid-doped polybenzimidazole (PBI) membrane high-temperature proton exchange membrane fuel cells (HT-PEMFC) during operation is experimentally evaluated to clarify the influence of the acid balance between the membrane and electrodes on cell performance. A method for controlling the amount of phosphoric acid doped in PBI membranes is investigated, and PBI membranes with various amounts of phosphoric acid are prepared. Cell operation tests and AC impedance spectroscopy of cells fabricated with these membranes are conducted. It was found that the amount of phosphoric acid doped in the membranes can be controlled by changing the solution temperature and the immersion time in phosphoric acid solution. It was also found that the HT-PEMFC performance can be improved by optimizing the amount of phosphoric acid doped in the membrane and by diffusion of phosphoric acid into the catalyst layer during the initial stage of cell operation.     

The effects of excess phosphoric acid in a Polybenzimidazole-based high temperature proton exchange membrane fuel cell

A series of experiments are conducted in order to investigate the performance of a proton exchange membrane (PEM) fuel cell using a commercially available polybenzimidazole (PBI)-based high temperature membrane. During the study a drastic degradation in performance is observed over time and a significant amount of solid material built-up is found in the flow field plate and the membrane-electrode assembly (MEA). The built-up material is examined by the use of a Scanning Electron Microscope (SEM). Further elemental analysis using Energy Dispersive X-ray Spectroscopy (EDS) finds that the built-up material contains large amount of phosphorus, thus relating it with the excess phosphoric acid found in the MEA. Additional experimental studies show that the built-up material is caused by the excess acid solution in the MEA, and when the excess phosphoric acid is removed from the MEA the fuel cell performance improves significantly and becomes very stable.     

Additives in proton exchange membranes for low- and high-temperature fuel cell applications: A review

Polymer electrolyte membranes, also known as proton exchange membranes (PEMs), are a type of semipermeable membrane that exhibits the property of conducting ions while impeding the mixing of reactant materials across the membrane. Due to the large potential and substantial number of applications of these materials, the development of proton exchange membranes (PEMs) has been in progress for the last few decades to successfully replace the commercial Nafion^® membranes. In the course of this research, an alternate perspective of PEMs has been initiated with a desire to attain successful operations at higher working temperatures (120–200 °C) while retaining the physical properties, stability and high proton conductivity. Both low- and high-temperature PEMs have been fabricated by various processes, such as grafting, cross-linking, or combining polymer electrolytes with nanoparticles, additives and acid-base complexes by electrostatic interactions, or by employing layer-by-layer technologies. The current review suggests that the incorporation of additives such as plasticisers and fillers has proven potential to modify the physical and chemical properties of pristine and/or composite membranes. In many studies, additives have demonstrated a substantial role in ameliorating both the mechanical and electrical properties of PEMs to make them effective for fuel cell applications. It is notable that plasticiser additives are less desirable for the development of high-temperature PEMs, as their inherent highly hydrophilic properties may stiffen the membrane. Conversely, filler additives form an inorganic-organic composite with increased surface area to retain more bound water within the polymer matrices to overcome the drawbacks of ohmic losses at high operating temperatures.     

Sulfonated MWNT and imidazole functionalized MWNT/polybenzimidazole composite membranes for high-temperature proton exchange membrane fuel cells

Composite membranes used for proton exchange membrane fuel cells comprising of polybenzimidazole (PBI) and carbon nanotubes with certain functional groups were studied, because they could enhance both the mechanical property and fuel cell performance at the same time. In this study, sodium poly(4-styrene sulfonate) functionalized multiwalled carbon nanotubes (MWNT-poly(NaSS))/PBI and imidazole functionalized multiwalled carbon nanotubes (MWNT-imidazole)/PBI composite membranes were prepared. The functionalization of carbon nanotubes involving non-covalent modification and covalent modification were confirmed by FITR, XPS, Raman spectroscopy, and TGA. Compared to unmodified MWNTs and MWNT-poly(NaSS), MWNT-imidazole provided more significant mechanical reinforcement due to its better compatibility with PBI. For MWNT-poly(NaSS)/PBI and MWNT-imidazole/PBI composite membranes at their saturated doping levels, the proton conductivities were up to 5.1 × 10⁻² and 4.3 × 10⁻² S/cm at 160 °C under anhydrous condition respectively, which were slightly higher than pristine PBI (2.8 × 10⁻² S/cm). Also, MWNT-poly(NaSS)/PBI and MWNT-imidazole/PBI composite membranes showed relatively improved fuel cell performance at 170 °C compared to pristine PBI.     

Effects of anodic gas conditions on performance and resistance of a PBI/H3PO4 proton exchange membrane fuel cell with metallic bipolar plates

In this study, polybenzimidazole (PBI) is used as membrane material of the high-temperature membrane electrode assembly which has the features of high-performance stability and high CO tolerance. Moreover, compared to graphite bipolar plates, metallic bipolar plates have better mechanical properties and seismic capacity, as well as lighter weight. We thus use metallic bipolar plates and a PBI-based membrane electrode assembly to setup a single cell and examine its performance. The experimental results show that the cell temperature has a significant effect on the cell performance. When the temperature increases from 120 °C to 180 °C, the performance is significantly enhanced. Moreover, the CO tolerance of the fuel cell increases along with the temperature. At the same time, methane is fed in the anode stream to assess the performance of the cell under different simulated methane reformate gases. The test of various CH₄/H₂ mixtures reveals the residual methane in the reformate gases only decreases fuel cell performance slightly due to the dilution effect. We also examined H₂/CO/N₂/CH₄ mixtures in this study, and these had only a small effect on the fuel cell performance at cell temperatures higher than 160 °C. As such, it is recommended that the cell temperature should be kept higher than 160 °C.     

Alkali doped polybenzimidazole membrane for alkaline direct methanol fuel cell

An anion exchange membrane for alkaline direct methanol fuel cell (ADMFC) was prepared by doping polybenzimidazole(PBI) membrane with KOH. The obtained membrane was characterized by means of XRD, TGA–DTA, AC and so on. The results suggested that it possessed satisfying thermal stability and comparable mechanical strength with acid doped PBI. At room temperature, methanol permeability through this membrane was one order of magnitude lower than that of Nafion^® membrane, while its ionic conductivity was comparable with that of other anion exchange membranes in literatures. For ADMFC at 90 °C based on this PBI/KOH membrane electrolyte, the peak power density was about 31 mW/cm², which was significantly improved mainly due to this membrane's high thermal stability, fast kinetics of electrochemical reactions and lower methanol permeability.     

Synthesis and characterization of carbon nanotubes supported platinum nanocatalyst for proton exchange membrane fuel cells

Multi-walled carbon nanotubes (MWCNTs) were used as catalyst support for depositing platinum nanoparticles by a wet chemistry route. MWCNTs were initially surface modified by citric acid to introduce functional groups which act as anchors for metallic clusters. A two-phase (water-toluene) method was used to transfer PtCl₆²⁻ from aqueous to organic phase and the subsequent sodium formate solution reduction step yielded Pt nanoparticles on MWCNTs. High-resolution TEM images showed that the platinum particles in the size range of 1-3 nm are homogeneously distributed on the surface of MWCNTs. The Pt/MWCNTs nanocatalyst was evaluated in the proton exchange membrane (PEM) single cell using H₂/O₂ at 80 °C with Nafion-212 electrolyte. The single PEM fuel cell exhibited a peak power density of about 1100 mW cm⁻² with a total catalyst loading of 0.6 mg Pt cm⁻² (anode: 0.2 mg Pt cm⁻² and cathode: 0.4 mg Pt cm⁻²). The durability of Pt/MWCNTs nanocatalyst was evaluated for 100 h at 80 °C at ambient pressure and the performance (current density at 0.4 V) remained stable throughout. The electrochemically active surface area (64 m² g⁻¹) as estimated by cyclic voltammetry (CV) was also similar before and after the durability test.     

Conducting carbon/polymer composites as a catalyst support for proton exchange membrane fuel cells

Carbon/poly(3,4‐ethylene dioxythiophene) (C/PEDOT) composites are synthesized by in situ chemical oxidative polymerization of EDOT monomer on carbon black in order to decrease carbon corrosion that occurred in carbon‐supported catalysts used in proton exchange membrane fuel cell. The effects of different dopants including polystyrene sulfonic acid, p‐toluenesulfonic acid and camphorsulfonic acid with the addition of ethylene glycol or dimethyl sulfoxide on the properties of the composites are investigated. The synthesized composites are characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, surface area analysis and scanning electron microscope. Electrical conductivity is determined by using the four‐point probe technique. Electrochemical oxidation characteristics of the synthesized C/PEDOT composites are investigated by cyclic voltammetry by applying 1.2 V for 24 h. The composite prepared at 25 °C with p‐toluenesulfonic acid and ethylene glycol shows the best carbon corrosion resistance. Platinum‐supported catalyst by using this composite was prepared using microwave irradiation technique, and it was seen that the prepared catalyst did not significantly lose its hydrogen oxidation and oxygen reduction reaction activities after electrochemical oxidation. Copyright © 2013 John Wiley & Sons, Ltd.     

A simple electric circuit model for proton exchange membrane fuel cells

A simple and novel dynamic circuit model for a proton exchange membrane (PEM) fuel cell suitable for the analysis and design of power systems is presented. The model takes into account phenomena like activation polarization, ohmic polarization, and mass transport effect present in a PEM fuel cell. The proposed circuit model includes three resistors to approach adequately these phenomena; however, since for the PEM dynamic performance connection or disconnection of an additional load is of crucial importance, the proposed model uses two saturable inductors accompanied by an ideal transformer to simulate the double layer charging effect during load step changes. To evaluate the effectiveness of the proposed model its dynamic performance under load step changes is simulated. Experimental results coming from a commercial PEM fuel cell module that uses hydrogen from a pressurized cylinder at the anode and atmospheric oxygen at the cathode, clearly verify the simulation results.     

Dynamic modeling of a high-temperature proton exchange membrane fuel cell with a fuel processor

A dynamic model of a high-temperature proton exchange membrane fuel cell with a fuel processor is developed in this study. In the model, a fuel processing system, a fuel cell stack, and an exhaust gas burner are modeled and integrated. The model can predict the characteristics of the overall system and each component at the steady and transient states. Specifically, a unit fuel cell model is discretized in a simplified quasi-three-dimensional geometry; therefore, the model can rapidly predict the distribution of fuel cell characteristics. Various operating conditions such as the steam-to-carbon ratio, oxygen-to-carbon ratio, and autothermal reforming inlet temperature are varied and investigated in this study. In addition, the dynamic characteristics exhibited during the transient state are investigated, and an efficiency controller is developed and implemented in the model to maintain the electrical efficiency. The simulation results demonstrate that the steam-to-carbon ratio and the oxygen-to-carbon ratio affect the electrical and system efficiency and that controlling the fuel flow rate maintains the electrical efficiency in the transient state. The model may be a useful tool for investigating the characteristics of the overall system as well as for developing optimal control strategies for enhancing the system performance.     

The effect of electrode parameters on performance of a phosphoric acid-doped PBI membrane fuel cell

A study of the effect of electrode parameters in a phosphoric acid-doped polybenzimidazole (PBI) membrane fuel cell is reported. The influence of phosphoric acid and PBI content are described. High levels of PBI in the catalyst layer did not enhance electrode layer performance for both hydrogen oxidation or oxygen reduction. High levels of doping with phosphoric acid in the anode catalyst layer were beneficial to fuel cell performance. Anode polarisation data confirmed that PBI fuel cells could operate at 175 °C with carbon monoxide contents in the feed gas of 10% in volume. There was an optimum amount of acid doping that gave good performance for oxygen reduction in the cathode layer. The effect of a perfluorinated surfactant improved the oxygen reduction behaviour in the catalyst layer. The carbon in catalyst support and it's interaction with the electrolyte have a large influence on cell performance.     

Coupled mechanical stress and multi-dimensional CFD analysis for high temperature proton exchange membrane fuel cells (HT-PEMFCs)

We use a combined finite element method (FEM)/computational fluid dynamics (CFD) methodology to numerically investigate the effects of gas diffusion layer (GDL) compression/intrusion on the performance of a phosphoric acid-doped polybenzimidazole (PBI) membrane-based high temperature proton exchange membrane fuel cell (HT-PEMFC). Three-dimensional (3-D) FEM simulations are conducted under various displacement clamping conditions to analyze cell deformation characteristics. Then, a multi-dimensional HT-PEMFC CFD model is applied to the deformed cell geometries to study transport and electrochemical processes during HT-PEMFC operations. Our numerical simulation results reveal that the maximum stresses in the deformed GDLs always occur near the edge of the ribs. The combined effects of GDL compression/intrusion considerably increase spatial non-uniformity in the species and current density distributions, and reduce cell performance.     

Improving proton exchange membrane fuel cell performance with carbon nanotubes as the material of cathode microporous layer

The cathode microporous layer (MPL) is fabricated by various multiwall carbon nanotubes (CNTs), and its influence on the performance of a proton exchange membrane fuel cell (PEMFC) is evaluated. Three types of CNT with different dimensions are employed in the experiments, and the conventional MPL made by acetylene black (AB) is also considered for the purpose of comparison. The results show that the employment of CNT as MPL composition indeed may improve fuel cell performance significantly in comparison with the case of AB. The type of CNT with the largest tube diameter and straight cylinder in shape exhibits the highest cell performance. The corresponding optimal CNT loading and polytetrafluoroethylene (PTFE) content in the MPL are also evaluated. Results show that the case of cathode MPL composed of 1.5 mg cm^?2 CNT and 20 wt% PTFE exhibits the best performance in all the experimental cases. The present data reveal that the application of CNT for MPL fabrication is beneficial to promote PEMFC performance. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of conductive carbon material content and structure in carbon fiber paper made from carbon felt on the performance of a proton exchange membrane fuel cell

This study concerns the use of conductive carbon material with different content and structure to produce carbon fiber paper for use in proton exchange membrane fuel cells, and investigates how changes in the content and structure of the conductive carbon material influence fuel cell performance.In this study, phenolic resin is used as a conductive carbon material, and is subjected to heat treatment at temperatures of 700 °C, 1000 °C, and 1400 °C, which changes its structure. Before carbon fiber paper is prepared from carbon felt, the felt is treated with phenolic resin solutions with resin content of 5, 10, 15, 20, 25, and 30 wt%. During fuel cell testing, torsion of 40, 60, 80, 100, and 120 kgf-cm is applied. The study found that when the phenolic resin content is 15 wt%, the heat treatment temperature 1400 °C, the test area 25 cm², and the test temperature 65 °C, a fuel cell can achieve a current density of 2020 mA cm⁻² at 0.5 V and torque of 120 kgf-cm.     

Analysis of the water and thermal management in proton exchange membrane fuel cell systems

Water and thermal management is essential to the performance of proton exchange membrane (PEM) fuel cell system. The key components in water and thermal management system, namely the fuel cell stack, radiator, condenser and membrane humidifier are all modeled analytically in this paper. Combined with a steady-state, one-dimensional, isothermal fuel cell model, a simple channel-groove pressure drop model is included in the stack analysis. Two compact heat exchangers, radiator and condenser are sized and rated to maintain the heat and material balance. The influence of non-condensable gas is also considered in the calculation of the condenser. Based on the proposed methodology, the effects of two important operating parameters, namely the air stoichiometric ratio and the cathode outlet pressure, and three kinds of anode humidification, namely recycling humidification, membrane humidification and recycling combining membrane humidification are analyzed. The methodology in this article is helpful to the design of water and thermal management system in fuel cell systems.     

Effects of branching structures on the properties of phosphoric acid-doped polybenzimidazole as a membrane material for high-temperature proton exchange membrane fuel cells

Highly branched copolymers have gained widespread attention due to their outstanding properties as proton exchange membranes (PEMs). However, the utilization of phosphoric acid-doped branched polybenzimidazole (PBI) as a PEM is rarely reported, and thus, the effects of branched structures on the properties of branched PBI membranes are not clear. In this work, three kinds of branched PBIs were prepared as high-temperature PEMs (HT-PEMs), and the branched polymer with the highest degree of branching was synthesized by introducing a branching agent with a large volume and rigid structure. In addition, the properties of the branched polymer membranes, such as the phosphoric acid doping content, proton conductivity, and oxidative stability, were characterized. The branched PBI membrane with the highest branching degree (9%) exhibited the highest proton conductivity (0.053 S cm^?1) and resistance to oxidation (only 6.9% reduction in weight following immersion in Fenton's reagent for 180 h). Furthermore, the proton conductivity and oxidative stability of the branched PBI membranes improved with increasing degree of branching. From these results, we infer that highly branched PBI is a promising material for application in the HT-PEMs of fuel cells.