Water transport in polymer electrolyte membrane fuel cells

Polymer electrolyte membrane fuel cell (PEMFC) has been recognized as a promising zero-emission power source for portable, mobile and stationary applications. To simultaneously ensure high membrane proton conductivity and sufficient reactant delivery to reaction sites, water management has become one of the most important issues for PEMFC commercialization, and proper water management requires good understanding of water transport in different components of PEMFC. In this paper, previous researches related to water transport in PEMFC are comprehensively reviewed. The state and transport mechanism of water in different components are elaborated in detail. Based on the literature review, it is found that experimental techniques have been developed to predict distributions of water, gas species, temperature and other parameters in PEMFC. However, difficulties still remain for simultaneous measurements of multiple parameters, and the cell and system design modifications required by measurements need to be minimized. Previous modeling work on water transport in PEMFC involves developing rule-based and first-principle-based models, and first-principle-based models involve multi-scale methods from atomistic to full cell levels. Different models have been adopted for different purposes and they all together can provide a comprehensive view of water transport in PEMFC. With the development of computational power, application of lower length scale methods to higher length scales for more accurate and comprehensive results is feasible in the future. Researches related to cold start (startup from subzero temperatures) and high temperature PEMFC (HT-PEMFC) (operating at the temperatures higher than 100 °C) are also reviewed. Ice formation that hinders reactant delivery and damages cell materials is the major issue for PEMFC cold start, and enhancing water absorption by membrane electrolyte and external heating have been identified as the most effective ways to reduce ice formation and accelerate temperature increment. HT-PEMFC that can operate without liquid water formation and membrane hydration greatly simplifies water management strategy, and promising performance of HT-PEMFC has been demonstrated.     

A novel membrane transport model for polymer electrolyte fuel cell simulations

This work presents the development of a 1D model describing water and charge transport through the polymer electrolyte membrane (PEM) in the fuel cell. The considered driving forces are electrical potential, concentration and pressure gradients. The membrane properties such as water diffusion and electro-osmotic coefficients, water sorption and ionic conductivity are treated as temperature dependent functions. The dependencies of diffusion and electro-osmotic coefficients on the membrane water concentration are described by linear functions. The membrane conductivity is computed in the framework of the percolation theory under consideration that the conducting phase in the PEM is formed by a hydrated functional groups and absorbed water. This developed membrane model was implemented in the CFD code AVL FIRE using 1D/3D coupling. The simulated polarization curves at various humidification of the cathode are found in good agreement with the experiments thus confirming the validity of the model.     

Water transport during startup and shutdown of polymer electrolyte fuel cell stacks

A dynamic three-phase transport model is developed to analyze water uptake and transport in the membrane and catalyst layers of polymer electrolyte fuel cells during startup from subfreezing temperatures and subsequent shutdown. The initial membrane water content (λ, the number of water molecules per sulfonic acid site) is found to be an important parameter that determines whether a successful unassisted self-start is possible. For a given initial subfreezing temperature at startup, there is a critical λ (λ_h), above which self-start is not possible because the product water completely engulfs the catalyst layers with ice before the stack can warm-up to 0 °C. There is a second value of λ (λ_l), below which the stack can be self-started without forming ice. Between λ_l and λ_h, the stack can be self-started, but with intermediate formation of ice that melts as the stack warms up to 0 °C. Both λ_l and λ_h are functions of the initial stack temperature, cell voltage at startup, membrane thickness, catalyst loading, and stack heat capacity. If the stack is purged during the previous shutdown by flowing air in the cathode passages, then depending on the initial amount of water in the membrane and gas diffusion layers and the initial stack temperature, it may not be possible to dry the membrane to the critical λ for a subsequent successful startup. There is an optimum λ for robust and rapid startup and shutdown. Startup and shutdown time and energy may be unacceptable if the λ is much less than the optimum. Conversely, a robust startup from subfreezing temperatures cannot be assured if the λ is much higher than this optimum.     

Development of polymer electrolyte membrane fuel cell stack

The proton exchange membrane fuel cell (PEMFC) is one of the strongest contenders as a power source for space, electric vehicle and domestic applications. Since 1988 intensive research is being carried out at our centre to develop PEMFCs. The main RandD activities are: (i) to develop a method for the electrode preparation (ii) to enhance platinum utilisation using low platinum loading and (iii) to design multicell stacks. The results of RandD development of the above activities are discussed in this paper.     

Humidification studies on polymer electrolyte membrane fuel cell

Two methods of humidifying the anode gas, namely, external and membrane humidification, for a polymer electrolyte membrane fuel (PEMFC) cell are explained. It is found that the water of solvation of protons decreases with increase in the current density and the electrode area. This is due to insufficient external humidification. In a membrane-based humidification, an optimum set of parameters, such as gas flow rate, area and type of the membrane, must be chosen to achieve effective humidification. The present study examines the dependence of water pick-up by hydrogen on the temperature, area and thickness of the membrane in membrane humidification. Since the performance of the fuel cell is dependent more on hydrogen humidification than on oxygen humidification, the scope of the work is restricted to the humidification of hydrogen using Nafion^® membrane. An examination is made on the dependence of water pick-up by hydrogen in membrane humidification on the temperature, area and thickness of the membrane. The dependence of fuel cell performance on membrane humidification and external humidification in the anode gas is also considered.     

Calculations of transport phenomena and reaction distribution in a polymer electrolyte membrane fuel cell

The performance of Polymer Electrolyte Membrane fuel cells depends on the design of the cell as well as the operating conditions. The design of the cell influences the complex interaction of activation effects, ohmic losses, and transport limitations, which in turn determines the local current density. Detailed models of the electrochemical reactions and transport phenomena in Polymer Electrolyte Membrane fuel cells can be used to determine the current density distribution for a given fuel cell design and operating conditions. In this work, three-dimensional, multicomponent and multiphase transport calculations are performed using a computational fluid dynamics code. The computational results for a full-scale fuel cell design show that ohmic effects due to drying of polymer electrolyte in the anode catalyst layer and membrane, and transport limitations of air and flooding in the cathode cause the current density to be a maximum near the gas channel inlets where ohmic losses and transport limitations are a minimum. Elsewhere in the cell, increased ohmic losses and transport limitations cause a decrease in current density, and the performance of the fuel cell is significantly lower than that which could be attained if the ohmic losses and transport limitations throughout the cell were the same as those near the gas channel inlets. Thus overall fuel cell design is critical in maximizing unit performance.     

X-ray computed tomography reconstruction and analysis of polymer electrolyte membrane fuel cell porous transport layers

A commercially available porous transport layer (SGL carbon group Sigracet^® GDL 30BA), is investigated using X-ray computed tomography reconstruction. A novel aspect of this study is an investigation of the effects of non-homogeneous compression of the GDL 30BA sample including effective transport properties. Non-homogeneous compression is typical in polymer electrolyte fuel cells as the flow field plates consist of a series of lands and channels which apply an uneven loading to the porous transport layers. The X-ray computed tomography technique provides input data for the computer reconstruction procedures integrating image post-processing and iso-surface reconstruction. The resulting tomographic and surface reconstruction is converted into the computational volume/grid for microstructural and computational fluid dynamics (CFD) analysis. The heterogeneous compression effects on effective geometric and transport properties are investigated for various compression levels and effective transport properties are compared to theoretical studies such as Bruggeman [1] and Tomadakis and Sotirchos [2]. The effects of non-homogeneous compression are significant, with the transport properties differing by a factor of about 2 between the land and the channel regions. It is found that the effective transport properties are significantly lower than predicted by commonly used relations, with the lowest values representing only 15% of the predictions from the Bruggeman relation.     

Proton transport of porous triazole-grafted polysulfone membranes for high temperature polymer electrolyte membrane fuel cell

Introduction of porous structure to high temperature polymer electrolyte membranes is one of effective pathways to increase their proton conductivity under elevated temperature. However, the effect of the porous structure on the proton diffusion mechanism of these membranes is still unclear. In this work, the proton transport behaviour of a series of porous triazole-polysulfone (PSf) membranes under elevated temperature is comprehensively investigated. The functional triazole ring in the framework of porous triazole-PSf acts a proton acceptor to form acid-base pair with phosphoric acid (PA). In addition, the proton diffusion coefficient and proton conductivity of PA-doped porous triazole-PSf is an order of magnitude higher than that of the PA-doped dense triazole-PSf membrane. Percolation theory calculation convinces that the high proton conductivity of PA-doped porous triazole-PSf is due to the formation of continuous long-range proton diffusion channels under high pore connectivity and porosity. On the contrary, excessive pore connectivity also results in high gas permeability, leading to decrease of the open circuit voltage and cell performance of the single cell. Consequently, the optimum porosity for the PA-doped porous triazole-PSf membrane is 75% for fuel cell operating with the maximum peak power density of 550 mW·cm^?2 and great durability for 120 h under 140 °C.     

Water quality and yield from polymer electrolyte membrane fuel cells

Water and energy production and demand are interconnected. Polymer electrolyte membrane fuel cells (PEMFCs) are devices that produce water while they generate power using hydrogen as a fuel. Herein, a lab-scale PEMFC was operated under variable experimental conditions, such as membrane chemical composition, operating temperature, operating current density, external humidification water quality, and fuel cell materials, to investigate the quality and quantity of the water produced. At each experimental condition the quantity and quality of the recovered product water was evaluated in the context of its suitability for use as drinking water. The results indicate that water produced by PEMFCs needs some treatment to comply with the US Environmental Protection Agency (US EPA) drinking water standards and World Health Organization (WHO) guidelines for drinking water quality. The measurements show a correlation between the fluoride concentration and the total organic matter (TOC) in the water samples when the fuel cell is operated with self-humidified membranes. A water collection efficiency up to 70% was obtained.     

Optimal catalyst layer structure of polymer electrolyte membrane fuel cell

In a membrane electrode assembly (MEA) of polymer electrolyte membrane fuel cells, the structure and morphology of catalyst layers are important to reduce electrochemical resistance and thus obtain high single cell performance. In this study, the catalyst layers fabricated by two catalyst coating methods, spraying method and screen printing method, were characterized by the microscopic images of catalyst layer surface, pore distributions, and electrochemical performances to study the effective MEA fabrication process. For this purpose, a micro-porous layer (MPL) was applied to two different coating methods intending to increase single cell performances by enhancing mass transport. Here, the morphology and structure of catalyst layers were controlled by different catalyst coating methods without varying the ionomer ratio. In particular, MEA fabricated by a screen printing method in a catalyst coated substrate showed uniformly dispersed pores for maximum mass transport. This catalyst layer on micro porous layer resulted in lower ohmic resistance of 0.087 Ω cm² and low mass transport resistance because of enhanced adhesion between catalyst layers and a membrane and improved mass transport of fuel and vapors. Consequently, higher electrochemical performance of current density of 1000 mA cm^-2 at 0.6 V and 1600 mAcm⁻² under 0.5 V came from these low electrochemical resistances comparing the catalyst layer fabricated by a spraying method on membranes because adhesion between catalyst layers and a membrane was much enhanced by screen printing method.     

Modeling of flow field in polymer electrolyte membrane fuel cell

Isothermal two- and three-dimensional polymer electrolyte membrane (PEM) fuel cell cathode flow field models were implemented to study the behavior of reactant and reaction product gas flow in a parallel channel flow field. The focus was on the flow distribution across the channels and the total pressure drop across the flow field. The effect of the density and viscosity variation in the gas resulting from the composition change due to cell reactions was studied and the models were solved with governing equations based on three different approximations. The focus was on showing how a uniform flow profile can be achieved by improving an existing channel design. The modeling results were verified experimentally. A close to uniform flow distribution was achieved in a parallel channel system.     

Free vibration analysis of a polymer electrolyte membrane fuel cell

A free vibration analysis of a polymer electrolyte membrane fuel cell (PEMFC) is performed by modelling the PEMFC as a 20 cm × 20 cm composite plate structure. The membrane, gas diffusion electrodes, and bi-polar plates are modelled as composite material plies. Energy equations are derived based on Mindlin's plate theory, and natural frequencies and mode shapes of the PEMFC are calculated using finite element modelling. A parametric study is conducted to investigate how the natural frequency varies as a function of thickness, Young's modulus, and density for each component layer. It is observed that increasing the thickness of the bi-polar plates has the most significant effect on the lowest natural frequency, with a 25% increase in thickness resulting in a 17% increase in the natural frequency. The mode shapes of the PEMFC provide insight into the maximum displacement exhibited as well as the stresses experienced by the single cell under vibration conditions that should be considered for transportation and stationary applications. This work provides insight into how the natural frequencies of the PEMFC should be tuned to avoid high amplitude oscillations by modifying the material and geometric properties of individual components.     

Development of porous carbon foam polymer electrolyte membrane fuel cell

In order to prove the feasibility of using porous carbon foam material in a polymer electrolyte membrane fuel cell (PEMFC), a single PEMFC is constructed with a piece of 80PPI (pores per linear inch) Reticulated Vitreous Carbon (RVC) foam at a thickness of 3.5 mm employed in the cathode flow-field. The cell performance of such design is compared with that of a conventional fuel cell with serpentine channel design in the cathode and anode flow-fields. Experimental results show that the RVC foam fuel cell not only produces comparative power density to, but also offers interesting benefits over the conventional fuel cell. A 250 h long term test conducted on a RVC foam fuel cell shows that the durability and performance stability of the material is deemed to be acceptable. Furthermore, a parametric study is conducted on single RVC foam fuel cells. Effect of geometrical and material parameters of the RVC foam such as PPI and thickness and operating conditions such as pressure, temperature, and stoichiometric ratio of the reactant gases on the cell performance is experimentally investigated in detail. The single cell with the 80PPI RVC foam exhibits the best performance, especially if the thinnest foam (3.5 mm) is used. The cell performance improves with increasing the operating gauge pressure from 0 kPa to 80 kPa and the operating temperature from 40 °C to 60 °C, but deteriorates as it further increases to 80 °C. The cell performance improves as the stoichiometric ratio of air increases from 1.5 to 4.5; however, the improvement becomes marginal when it is raised above 3.0. On the other hand, changing the stoichiometric ratio of hydrogen does not have a significant impact on the cell performance.     

A review of polymer electrolyte membrane fuel cell stack testing

This paper presents an overview of polymer electrolyte membrane fuel cell (PEMFC) stack testing. Stack testing is critical for evaluating and demonstrating the viability and durability required for commercial applications. Single cell performance cannot be employed alone to fully derive the expected performance of PEMFC stacks, due to the non-uniformity in potential, temperature, and reactant and product flow distributions observed in stacks. In this paper, we provide a comprehensive review of the state-of-the art in PEMFC testing. We discuss the main topics of investigation, including single cell vs. stack-level performance, cell voltage uniformity, influence of operating conditions, durability and degradation, dynamic operation, and stack demonstrations. We also present opportunities for future work, including the need to verify the impact of stack size and cell voltage uniformity on performance, determine operating conditions for achieving a balance between electrical efficiency and flooding/dry-out, meet lifetime requirements through endurance testing, and develop a stronger understanding of degradation.     

Detailed thermodynamic analysis of polymer electrolyte membrane fuel cell efficiency

It is common knowledge that efficiency of fuel cells is highest when no electric current is produced while when the fuel cell is really working, the efficiency is reduced by dissipation. In this paper the relation between efficiency and dissipation inside the fuel cell is formulated within the framework of classical irreversible thermodynamics of mixtures. It is shown that not only dissipation influences the efficiency but that there are also some other terms which become important if there are steep temperature gradients inside the fuel cell. Indeed, we show that the new terms are negligible in polymer-electrolyte membrane fuel cells while they become important in solid oxide fuel cells. In summary, this paper presents a formulation of non-equilibrium thermodynamics of fuel cells and provides analysis of efficiency in terms of processes inside the fuel cells, revealing some new terms affecting the efficiency.     

Water balance in a polymer electrolyte fuel cell system

Polymer electrolyte fuel cell (PEFC) systems operating on carbonaceous fuels require water for fuel processing. Such systems can find wider applications if they do not require a supply of water in addition to the supply of fuel, that is, if they can be self-sustaining based on the water produced at the fuel cell stack. This paper considers a generic PEFC system and identifies the parameters that affect, and the extent of their contribution to, the net water balance in the system. These parameters include the steam-to-carbon and the oxygen-to-carbon ratios in the fuel processor, the electrochemical fuel and oxygen utilizations in the fuel cell stack, the ambient pressure and temperature, and the composition of the fuel used. The analysis shows that the amount of water lost from the system as water vapor in the exhaust is very sensitive to the system pressure and ambient temperature, while the amount of water produced in the system is a function of the composition of the fuel. Fuels with a high H/C (hydrogen to carbon atomic ratio) allow the system to be operated as a net water producer under a wider range of operating conditions.     

Externally cooled high temperature polymer electrolyte membrane fuel cell stack

One key issue in high temperature polymer electrolyte membrane fuel cell (HT-PEMFC) stack development is heat removal at the operating temperature of 140–180 °C. Conventionally, this process is done using coolants such as thermooil, steam or pressurized water. In this contribution, external liquid cooling designs are described, which are avoiding two constraints. First, in the cell active area, no liquid coolant is present avoiding any sealing problems with respect to the electrode. Secondly, the external positioning allows high temperature gradients between the heat removal zone and the active area resulting in a good adjustability of appropriate reformate conversion temperatures (e.g. 160 °C) and a more compact cell design. Different design concepts were investigated using modeling techniques and a selection of them has also been investigated experimentally. The experiments proved the feasibility of the external cooling design and showed that the temperature gradients within the active area are below 15 K under typical operating conditions.     

New materials for polymer electrolyte membrane fuel cell current collectors

Polymer Electrolyte Membrane Fuel cells for automotive applications need to have high power density, and be inexpensive and robust to compete effectively with the internal combustion engine. Development of membranes and new electrodes and catalysts have increased power significantly, but further improvements may be achieved by the use of new materials and construction techniques in the manufacture of the bipolar plates. To show this, a variety of materials have been fabricated into flow field plates, both metallic and graphitic, and single fuel cell tests were conducted to determine the performance of each material. Maximum power was obtained with materials which had lowest contact resistance and good electrical conductivity. The performance of the best material was characterised as a function of cell compression and flow field geometry.     

Analysis of microporous layer characteristics of the anode for high-temperature polymer electrolyte membrane fuel cell

Four commercial gas diffusion layers (GDLs) are applied to high-temperature polymer electrolyte fuel cell anodes to investigate the relationship between microporous layer (MPL) properties and the performance of membrane electrode assembly. Subsequently, the physical properties such as the crack area and porosity of the MPL are analyzed via various methods. It is found that the capillary pressure of phosphoric acid (PA) from several theories is inversely related to the mass transfer capability (MTC) of the MPL. Finally, a new transport property named PA MTC of the MPL is proposed using the PA capillary pressure and MTC in MPL. The results indicate that the voltage at both low and high current densities increases separately as the PA MTC in the MPL adjusts to 0.5 MPa mm^-1. Subsequently, the voltage beyond 0.5 MPa mm^-1 increases in low current density contrary to the voltage at a high current density.