Pore-Water and Proton Transport in Polymer Electrolyte Membrane Fuel Cell: Molecular Dynamics and Mono- and Bimodal Wetting Treatments of Mesopore Hydrated Nafion (original) (raw)

Dry and Wet Molecular Dynamics Simulations of Nafion® Polymer Electrolyte Fuel Cell Membrane

Journal of Solid Mechanics and Materials Engineering, 2007

The interactions between the hydronium ions and the waters in Nafion® polyelectrolyte membrane are relevant in the proton transfer process of fuel cell. To investigate a role of water in the proton transfer mechanism, molecular dynamic simulations have been performed for models of Nafion® side chains cluster with the water molecules and the hydronium ions comparing with dry system. After simulations, the trajectories were analyzed in term of intermolecular distances, potential energy, and radial distribution function.

Cross-sectional insight in the water evolution and transport in polymer electrolyte fuel cells

Applied Physics Letters, 2008

The evolution of liquid water and its transport through the porous gas diffusion media in an operating fuel cell were investigated applying an experimental setup for high spatial resolution of 3 m. Fundamental aspects of cluster formation in hydrophobic/hydrophilic porous materials as well as processes of multiphase flow are addressed. The obtained water distributions provide a detailed insight in the membrane electrode assembly and the porous electrode with regard on the existence and transport of liquid water. In addition, the results approve transport theories used within the framework of percolation theory and demonstrate the need for adapted modeling approaches.

Modeling the Liquid Water Transport in the Gas Diffusion Layer for Polymer Electrolyte Membrane Fuel Cells Using a Water Path Network

Energies, 2013

In order to model the liquid water transport in the porous materials used in polymer electrolyte membrane (PEM) fuel cells, the pore network models are often applied. The presented model is a novel approach to further develop these models towards a percolation model that is based on the fiber structure rather than the pore structure. The developed algorithm determines the stable liquid water paths in the gas diffusion layer (GDL) structure and the transitions from the paths to the subsequent paths. The obtained water path network represents the basis for the calculation of the percolation process with low calculation efforts. A good agreement with experimental capillary pressure-saturation curves and synchrotron liquid water visualization data from other literature sources is found. The oxygen diffusivity for the GDL with liquid water saturation at breakthrough reveals that the porosity is not a crucial factor for the limiting current density. An algorithm for condensation is included into the model, which shows that condensing water is redirecting the water path in the GDL, leading to an improved oxygen diffusion by a decreased breakthrough pressure and changed saturation distribution at breakthrough.

A macroscopic model of proton transport through the membrane-ionomer interface of a polymer electrolyte membrane fuel cell

The Journal of Chemical Physics, 2013

The membrane-ionomer interface is the critical interlink of the electrodes and catalyst to the polymer electrolyte membrane (PEM); together forming the membrane electrode assembly in current stateof-the-art PEM fuel cells. In this paper, proton conduction through the interface is investigated to understand its effect on the performance of a PEM fuel cell. The water containing domains at this interface were modeled as cylindrical pores/channels with the anionic groups (i.e., -SO 3 − ) assumed to be fixed on the pore wall. The interactions of each species with all other species and an applied external field were examined. Molecular-based interaction potential energies were computed in a small test element of the pore and were scaled up in terms of macroscopic variables. Evolution equations of the density and momentum of the species (water molecules and hydronium ions) were derived within a framework of nonequilibrium thermodynamics. The resulting evolution equations for the species were solved analytically using an order-of-magnitude analysis to obtain an expression for the proton conductivity. Results show that the conductivity increases with increasing water content and pore radius, and strongly depends on the separation distance between the sulfonate groups and their distribution on the pore wall. It was also determined that the conductivity of two similar pores of different radii in series is limited by the pore with the smaller radius.

Pore-network analysis of two-phase water transport in gas diffusion layers of polymer electrolyte membrane fuel cells

Electrochimica Acta, 2009

A pore-network model was developed to study the water transport in hydrophobic gas diffusion layers (GDLs) of polymer electrolyte membrane fuel cells (PEMFCs). The pore structure of GDL materials was modeled as a regular cubic network of pores connected by throats. The governing equations for the twophase flow in the pore-network were obtained by considering the capillary pressure in the pores, and the entry pressure and viscous pressure drop through the throats. Numerical results showed that the saturation distribution in GDLs maintained a concave shape, indicating the water transport in GDLs was strongly influenced by capillary processes. Parametric studies were also conducted to examine the effects of several geometrical and capillary properties of GDLs on the water transport behavior and the saturation distribution. The proper inlet boundary condition for the liquid water entering GDLs was discussed along with its effects on the saturation distribution.

Pore network modeling of fibrous gas diffusion layers for polymer electrolyte membrane fuel cells

Journal of Power Sources, 2007

A pore network model of the gas diffusion layer (GDL) in a polymer electrolyte membrane fuel cell is developed and validated. The model idealizes the GDL as a regular cubic network of pore bodies and pore throats following respective size distributions. Geometric parameters of the pore network model are calibrated with respect to porosimetry and gas permeability measurements for two common GDL materials and the model is subsequently used to compute the pore-scale distribution of water and gas under drainage conditions using an invasion percolation algorithm. From this information, the relative permeability of water and gas and the effective gas diffusivity are computed as functions of water saturation using resistor-network theory. Comparison of the model predictions with those obtained from constitutive relationships commonly used in current PEMFC models indicates that the latter may significantly overestimate the gas phase transport properties. Alternative relationships are suggested that better match the pore network model results. The pore network model is also used to calculate the limiting current in a PEMFC under operating conditions for which transport through the GDL dominates mass transfer resistance. The results suggest that a dry GDL does not limit the performance of a PEMFC, but it may become a significant source of concentration polarization as the GDL becomes increasingly saturated with water.

Influence of Wettability on Liquid Water Transport in Gas Diffusion Layer of Proton Exchange Membrane Fuel Cells (Pemfc)

2009

Water management is a key factor that limits PEFC's performance. We show how insights into this problem can be gained from pore-scale simulations of water invasion in a model fibrous medium. We explore the influence of contact angle on the water invasion pattern and water saturation at breakthrough and show that a dramatic change in the invasion pattern, from fractal to compact, occurs as the system changes from hydrophobic to hydrophilic. Then, we explore the case of a system of mixed wettability, i.e. containing both hydrophilic and hydrophobic pores. The saturation at breakthrough is studied as a function of the fraction of hydrophilic pores. The results are discussed in relation with the water management problem, the optimal design of a GDL and the fuel cell performance degradation mechanisms. We outline how the study could be extended to 3D systems, notably from binarised images of GDLs obtained by X ray microtomography.

Coupled Proton and Water Transport in Polymer Electrolyte Membranes

Device and Materials Modeling in Pem Fuel Cells, 2009

This Chapter presents a critical examination and analysis of classical and recently proposed models for transport phenomena in polymer electrolyte membranes, and proposes a new macroscopic model based on the generalized Stefan-Maxwell relations.

Water transport in polymer electrolyte membrane fuel cells

2011

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.

Pore-network modeling of liquid water transport in gas diffusion layer of a polymer electrolyte fuel cell

Electrochimica Acta, 2007

A pore-network model is developed to study the liquid water movement and flooding in a gas diffusion layer (GDL), with the GDL morphology taken into account. The dynamics of liquid water transport at the pore-scale and evolution of saturation profile in a GDL under realistic fuel cell operating conditions is examined for the first time. It is found that capillary forces control liquid water transport in the GDL and that liquid water moves in connected clusters with finger-like liquid waterfronts, rendering concave-shaped saturation profiles characteristic of fractal capillary fingering. The effect of liquid coverage at the GDL-channel interface on the liquid water transport inside GDL is also studied, and it is found that liquid coverage at the GDL-channel interface results in pressure buildup inside the GDL causing the liquid water to break out from preferential locations.