Jeff T. Gostick

Impact of Liquid Water on Reactant Mass Transfer in PEM Fuel Cell Electrodes

The breakthrough conditions (capillary pressure and liquid water saturation) in a fibrous gas diffusion medium (GDM) used in polymer electrolyte membrane (PEM) fuel cell electrodes have been studied experimentally by two independent techniques and numerically by pore network modeling. Experiments show that treatment of the GDMs with a hydrophobic polymer coating reduces the water saturation at a breakthrough by 50%. Invasion percolation modeling is employed to simulate the breakthrough process and to determine mass-transfer rates through the partially saturated network. This model shows that the water saturation at breakthrough is drastically reduced when a microporous layer (MPL) is incorporated into the GDM, agreeing with experiments. However, the simulations yield limiting currents significantly higher than those observed in practice whether or not an MPL is present. Further calculations to include the contribution of condensation to water saturation within the GDM also result in unrealistically high limiting currents and suggest that mass-transfer resistance in the catalyst layer that is not included in the model plays an important role. If condensation is the principal mode for water accumulation within the GDM, simulations show that the MPL has only a small impact on liquid water distribution and does not improve performance, contrary to expectation.

OpenPNM: A Pore Network Modeling Package

Pore network modeling is a widely used technique for simulating multiphase transport in porous materials, but there are very few software options available. This work outlines the OpenPNM package that was jointly developed by several porous media research groups to help address this gap. OpenPNM is written in Python using NumPy and SciPy for most mathematical operations, thus combining Pythons ease of use with the performance necessary to perform large simulations. The package assists the user with managing and interacting with all the topological, geometrical, and thermophysical data. It also includes a suite of commonly used algorithms for simulating percolation and performing transport calculations on pore networks. Most importantly, it was designed to be highly flexible to suit any application and be easily customized to include user-specified pore-scale physics models. The framework is fast, powerful, and concise. An illustrative example is included that determines the effective diffusivity through a partially water-saturated porous material with just 29 lines of code.

Electrocatalytic Oxygen Reduction Performance of Silver Nanoparticle Decorated Electrochemically Exfoliated Graphene

We have developed a potentiostatic double-pulse technique for silver nanoparticle (Ag NP) deposition on graphene (GRn) with superior electronic and ionic conductivity. This approach yielded a two-dimensional electrocatalyst with a homogeneous Ag NP spatial distribution having remarkable performance in the oxygen reduction reaction (ORR). GRn sheets were reproducibly prepared by the electrochemical exfoliation of graphite (GRp) at high yield and purity with a low degree of oxidation. Polystyrenesulfonate added during exfoliation enhanced the stability of the GRn solution by preventing the restacking of the graphene sheets and increased its ionic conductivity. The potentiostatic double-pulse technique is generally used to electrodeposit Pt nanoparticles and remains challenging for silver metal that exhibits nucleation and growth potentials relatively close to each other. We judiciously exploited this narrow margin of potential, and for the first time we report Ag NP electrodeposited onto graphene with the subsequent ability to control both the density and the size of metallic nanoparticles. Considering the high activity along with the lower cost of Ag compared to Pt, these findings are highly relevant to the successful commercialization of fuel cells and other electrochemical energy devices.

In-Plane Effective Diffusivity in PEMFC Gas Diffusion Layers

The in-plane effective diffusion coefficients in gas diffusion layers typically used in fuel cell electrodes were measured as a function of compression and hydrophobic polymer loading. This method was based on the transient diffusion of oxygen from air into an initially nitrogen purged porous sample and has proven to be accurate, fast, and straightforward. As anticipated, with higher compressions and higher PTFE loadings, effective diffusivity decreased, as a result of less pore space available for transport and because tortuosity increased. When plotted against compressed porosity, the effective diffusivity of untreated and treated materials for a given type of sample collapsed on top of each other, despite the simultaneous impact of PTFE loading and compression. It was possible to distinguish between the impact of PTFE and compression by plotting the data as tortuosity against compressed thickness. High compressions on the sample lead to irreversible damages to the fiber structure, resulting in decreased or unexpectedly low tortuosity. Finally, a percolation model was fitted through one of the tested materials and a reasonable agreement was observed for lower compression, but a fit to the entire data could not be achieved. This was attributed to fundamental structural changes occurring in the sample upon high compressions, an observation that helps to explain the general inability of theoretical tortuosity models to describe GDLs.

Characterization of the Capillary Properties of Gas Diffusion Media

The present generation of membrane materials used in polymer electrolyte membrane fuel cells (PEMFCs) requires high humidity to maintain sufficient proton conductivity. Mass transport through the porous electrodes, however, is most effective in dry conditions since the presence of liquid water in the pores reduces effective oxygen diffusivity to the catalytic sites. Management of these competing requirements is further complicated by the production of water inside the cell as a by-product of the cathode reaction. Maximizing fuel cell power density therefore requires effective water management techniques to prevent excessive liquid water from accumulating in the porous electrode components. Liquid water distribution and flow in the cathode gas diffusion media (GDM) of an operating PEMFC is critically affected by capillary forces. Perhaps the most widely employed technique for improving water management is to impregnate the fibrous GDM with a polymer, such as poly-tetra-fluoro-ethylene (PTFE), to coat the carbon fibers and thereby render the GDM more hydrophobic. It is thus important to understand the relationship between wettability and capillary properties of native (i.e., untreated) or PTFE-treated GDMs on the one hand and the relationship between GDM capillary properties and fuel cell performance on the other hand. Until recently, however, few experimental techniques were available to measure the capillary properties of GDMs. This chapter discusses the present understanding of the capillary properties of GDM–water–air systems and provides a critical analysis of reported experimental techniques that have recently contributed to this understanding.

Versatile and efficient pore network extraction method using marker-based watershed segmentation

Obtaining structural information from tomographic images of porous materials is a critical component of porous media research. Extracting pore networks is particularly valuable since it enables pore network modeling simulations which can be useful for a host of tasks from predicting transport properties to simulating performance of entire devices. This work reports an efficient algorithm for extracting networks using only standard image analysis techniques. The algorithm was applied to several standard porous materials ranging from sandstone to fibrous mats, and in all cases agreed very well with established or known values for pore and throat sizes, capillary pressure curves, and permeability. In the case of sandstone, the present algorithm was compared to the network obtained using the current state-of-the-art algorithm, and very good agreement was achieved. Most importantly, the network extracted from an image of fibrous media correctly predicted the anisotropic permeability tensor, demonstrating the critical ability to detect key structural features. The highly efficient algorithm allows extraction on fairly large images of 500^{3} voxels in just over 200 s. The ability for one algorithm to match materials as varied as sandstone with 20% porosity and fibrous media with 75% porosity is a significant advancement. The source code for this algorithm is provided.

Water Uptake in PEMFC Catalyst Layers

Water uptake profiles of proton-exchange-membrane fuel-cell catalyst layers are characterized in the form of capillary-pressure saturation (Pc-S) curves. The curves indicate that the catalyst layers tested are highly hydrophilic and require capillary pressures as low as -80 kPa to eject imbibed water. Comparison of materials made with and without Pt indicates a difference in water ejection and uptake phenomena due to the presence of Pt. The addition of Pt increases the tendency of the catalyst layer to retain water. Dynamic vapor sorption (DVS) is used to characterize the water-vapor sorption onto Nafion, Pt/C, and C surfaces. The DVS results align with the trends found from the Pc-S curves and show an increased propensity for water uptake in the presence of Pt. The effect of the ion in Nafion, sodium or protonated form, is also compared and demonstrates that although the protonation of the Nafion in the catalyst layer also increases hydrophilicity, the effect is not as great as that caused by Pt.

Pore network modeling of phase change in PEM fuel cell fibrous cathode

A pore network model has been applied to the cathode side of a fuel cell membrane electrode assembly to investigate the mechanisms leading to liquid water formation in the cell. This model includes mass diffusion, liquid water percolation, thermal and electrical conduction to model phase change which is highly dependent on the local morphology of the cathode side. An iterative algorithm was developed to simulate transport processes within the cathode side of PEMFC applying a pseudo-transient pore network model at constant voltage boundary condition. This algorithm represents a significant improvement over previous pore network models that only considered capillary invasion of water from the catalyst layer and provides useful insights into the mechanism of water transport in the electrodes, especially condensation and evaporation. The electrochemical performance of PEMFCs was simulated under different relative humidity conditions to study the effect of water phase change on the cell performance. This model highlights the ability of pore network models to resolve the discrete water clusters in the electrodes which is essential to the two-phase transport behavior especially the transport of water vapor to and from condensed water clusters.Graphical Abstract

Capillary Hysteresis in Neutrally Wettable Fibrous Media: A Pore Network Study of a Fuel Cell Electrode

Hysteresis in the saturation versus capillary pressure curves of neutrally wettable fibrous media was simulated with a random pore network model using a Voronoi diagram approach. The network was calibrated to fit experimental air-water capillary pressure data collected for carbon fibre paper commonly used as a gas diffusion layer in fuel cells. These materials exhibit unusually strong capillary hysteresis, to the extent that water injection and withdrawal occur at positive and negative capillary pressures, respectively. Without the need to invoke contact angle hysteresis, this capillary behaviour is re-produced when using a pore-scale model based on the curvature of a meniscus passing through the centre of a toroid. The classic Washburn relation was shown to produce erroneous results, and its use is not recommended when modelling fibrous media. The important effect of saturation distribution on the effective diffusivity of the medium was also investigated for both water injection and withdrawal cases. The findings have bearing on the understanding of both capillarity in fibrous media and fuel cell design.

Insights into the Effect of Structural Heterogeneity in Carbonized Electrospun Fibrous Mats for Flow Battery Electrodes by X-Ray Tomography

Electrospun custom made flow battery electrodes are imaged in 3D using X-ray computed tomography. A variety of computational methods and simulations are applied to the images to determine properties including the porosity, fiber size, and pore size distributions as well as the material permeability and flow distributions. The simulations are performed on materials before and after carbonization to determine the effect it has in the internal microstructure and material properties. It is found that the deposited fiber size is constantly changing throughout the electrospinning process. The results also show that the surfaces of the fibrous material are the most severely altered during carbonization and that the rest of the material remained intact. Pressure driven flow is modeled using the lattice Boltzmann method and excellent agreement with experimental results is found. The simulations coupled with the material analysis also demonstrate the highly heterogeneous nature of the flow. Most of the flow is concentrated to regions with high porosity while regions with low porosity shield other pores and starve them of flow. The importance of imaging these materials in 3D is highlighted throughout.