Modeling the Effect of Low Pt loading Cathode Catalyst Layer in Polymer Electrolyte Fuel Cells. Part I: Model Formulation and Validation

A model for the cathode catalyst layer (CL) is presented, which is validated with previous experimental data in terms of both performance and oxygen transport resistance. The model includes a 1D macroscopic description of proton, electron and oxygen transport across the CL thickness, which is locally coupled to a 1D microscopic model that describes oxygen transport toward Pt sites. Oxygen transport from the channel to the CL and ionic transport across the membrane are incorporated through integral boundary conditions. The model is complemented with data of effective transport and electrochemical properties extracted from multiple experimental works. The results show that the contribution of the thin ionomer film and Pt/ionomer interface increases with the inverse of the roughness factor. Whereas the contribution of the water film and the water/ionomer interface increases with the ratio between the geometric area and the surface area of active ionomer. Moreover, it is found that CLs diluted with bare carbon provide lower performance than non-diluted samples due to their lower electrochemical surface area and larger local oxygen transport resistance. Optimized design of non-diluted samples with a good distribution of the overall oxygen flux among Pt sites is critical to reduce mass transport losses at low Pt loading.This work was supported by the projects PID2019-106740RB-I00 and EIN2020-112247 (Spanish Agencia Estatal de Investigación) and the project PEM4ENERGY-CM-UC3M funded by the call "Programa de apoyo a la realización de proyectos interdisciplinares de I + D para jóvenes investigadores de la Universidad Carlos III de Madrid 2019–2020" under the frame of the "Convenio Plurianual Comunidad de Madrid-Universidad Carlos III de Madrid".Publicad

Analysis of representative elementary volume and through-plane regional characteristics of carbon-fiber papers: diffusivity, permeability and electrical/thermal conductivity

Understanding the transport processes that occur in carbon-fiber papers (CFPs) used in fuel cells, electrolyzers, and metal-air/redox flow batteries is necessary to help predict cell performance and durability, optimize materials and diagnose problems. The most common technique used to model these thin, heterogeneous, anisotropic porous media is the volume-averaged approximation based on the existence of a representative elementary volume (REV). However, the applicability of the continuum hypothesis to these materials has been questioned many times, and the error incurred in the predictions is yet to be quantified. In this work, the existence of a REV in CFPs is assessed in terms of dry effective transport properties: mass diffusivity, permeability and electrical/thermal conductivity. Multiple sub-samples with different widths and thicknesses are examined by combining the lattice Boltzmann method with X-ray tomography images of four uncompressed CFPs. The results show that a meaningful length scale can be defined in the material plane in the order of 1–2 mm, which is comparable to the rib/channel width used in the aforementioned devices. As for the through-plane direction, no distinctive length scale smaller than the thickness can be identified due to the lack of a well-defined separation between pore and volume-averaged scales in these inherently thin heterogeneous materials. The results also show that the highly porous surface region (amounting up to 20% of the thickness) significantly reduces the through-plane electrical/thermal conductivity. Overall, good agreement is found with previous experimental data of virtually uncompressed CFPs when approximately the full thickness is considered.The authors thank the support team of Calcul Quebec and Compute Canada for their help during the simulation campaign, as well as Dr. Dula Parkinson and Dr. Alastair MacDowell at the Advanced Light Source (ALS) for help in obtaining the tomographic images. This work was funded under the Fuel Cell Performance and Durability Consortium (FC-PAD), by the Fuel Cell Technologies Office (FCTO), Office of Energy Efficiency and Renewable Energy (EERE), of the U.S. Department of Energy under contract number DE-AC02-05CH11231, Project ENE2015-68703-C2-1-R (MINECO/FEDER, UE) and the research grant 'Ayudas a la Investigation en Energia y Medio Ambiente' awarded to the first author by the Spanish lberdrola Foundation. I.V. Zenyuk and A.D. Shum would like to acknowledge support from the National Science Foundation under CBET Award 1605159. X-ray tomography experiments were performed on beamline 8.3.2 at the ALS (Lawrence Berkeley National Laboratory), which is a national user facility funded by the Department of Energy, Office of Basic Energy Sciences under contract DE-ACO2-05CH11231. Numerical calculations were performed on the supercomputing clusters Briaree, Colosse, Guillimin and Mp2, managed by Calcul Quebec and Compute Canada. The operation of these supercomputers is funded by the Canada Foundation for Innovation (CFI), Ministere de l'Economie, de l'Innovation et des Exportations du Quebec (MEIE), RMGA and the Fonds de recherche du Quebec -Nature et technologies (FRQ-NT)

Probing the Structure-Performance Relationship of Lithium-Ion Battery Cathodes Using Pore-Networks Extracted from Three-Phase Tomograms

Pore-scale simulations of Li-ion battery electrodes were conducted using both pore-network modeling and direct numerical simulation. Ternary tomographic images of NMC811 cathodes were obtained and used to create the pore-scale computational domains. A novel network extraction method was developed to manage the extraction of N-phase networks which was used to extract all three phases of NMC-811 electrode along with their interconnections Pore network results compared favorably with direct numerical simulations (DNS) in terms of effective transport properties of each phase but were obtained in significantly less time. Simulations were then conducted with combined diffusion-reaction to simulate the limiting current behavior. It was found that when considering only ion and electron transport, the electrode structure could support current densities about 300 times higher than experimentally observed values. Additional case studies were conducted to illustrate the necessity of ternary images which allow separate consideration of carbon binder domain and active material. The results showed a 24.4% decrease in current density when the carbon binder was treated as a separate phase compared to lumping the CBD and active material into a single phase. The impact of nanoporosity in the carbon binder phase was also explored and found to enhance the reaction rate by 16.8% compared to solid binder. In addition, the developed technique used 58 times larger domain volume than DNS which opens up the possibility of modelling much larger tomographic data sets, enabling representative areas of typically inhomogeneous battery electrodes to be modelled accurately, and proposes a solution to the conflicting needs of high-resolution imaging and large volumes for image-based modelling. For the first time, three-phase pore network modelling of battery electrodes has been demonstrated and evaluated, opening the path towards a new modelling framework for lithium ion batteries.The described here was financially supported by the University of Engineering and Technology Lahore, Pakistan as well as the Natural Science and Engineering Research Council (NSERC) of Canada and in the UK by the Faraday Institution (EP/R042012/1 and EP/R042063/1). Pablo A. García-Salaberri thanks the support from the STFC Early Career Award (ST/R006873/1) during his stay at the Electrochemical Innovation La

Mass transfer in fibrous media with varying anisotropy for flow battery electrodes: Direct numerical simulations with 3D X-ray computed tomography

The final publication is available at Elsevier via https://doi.org/10.1016/j.ces.2018.10.049. © 2018. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/A numerical method for calculating the mass transfer coefficient in fibrous media is presented. First, pressure driven flow was modelled using the Lattice Boltzmann Method. The advection-diffusion equation was solved for convective-reacting porous media flow, and the method is contrasted with experimental methods such as the limiting current diffusion technique, for its ability to determine and simulate mass transfer systems that are operating at low Reynolds number flows. A series of simulations were performed on three materials; specifically, commercially available carbon felts, electrospun carbon fibers and electrospun carbon fibers with anisotropy introduced to the microstructure. Simulations were performed in each principal direction (x,y,z) for each material in order to determine the effects of anisotropy on the mass transfer coefficient. In addition, the simulations spanned multiple Reynolds and Péclet numbers, to fully represent highly advective and highly diffusive systems. The resulting mass transfer coefficients were compared with values predicted by common correlations and a good agreement was found at high Reynolds numbers, but less so at lower Reynolds number typical of cell operation, reinforcing the utility of the numerical approach. Dimensionless mass transfer correlations were determined for each material and each direction in terms of the Sherwood number. These correlations were analyzed with respect to each materials’ permeability tensor. It was found that as the permeability of the system increases, the expected mass transfer coefficient decreases. Two general mass transfer correlations are presented, one correlation for isotropic fibrous media and the other for through-plane flow in planar fibrous materials such as electrospun media and carbon paper. The correlations are Sh = 0.879 Re0.402 Sc0.390 and Sh = 0.906 Re0.432 Sc0.432 respectively.The authors acknowledge support from the EPSRC under grants EP/L014289/1 and EP/N032888/1, as well as the STFC Extended Network in Batteries and Electrochemical Energy Devices (ST/N002385/1) for funding of travel for Rhodri Jervis to Canada. Paul R Shearing acknowledges the support of the Royal Academy of Engineering. This work was supported by the Natural Science and Engineering Research Council (NSERC) of Canada. MDR Kok is grateful to the Eugenie Ulmer Lamothe Endowment as well as the Vadasz Family Doctoral Fellowship for funding his work, as well the McGill University’s Graduate Mobility Award for funding his travel to the UK

Modeling the effect of low Pt loading cathode catalyst layer in polymer electrolyte fuel cells. Part II: Parametric analysis

A parametric analysis is presented using a previously validated 1D model for a cathode catalyst layer (CL). The results show that maximum power density at low Pt loading can be maximized with relatively thin CLs (thickness - 2 micrómetros) featuring a high carbon volume fraction (low ionomer-to-carbon weight ratio, I/C) compared to high Pt loading CLs. The shift of the optimal carbon volume fraction (I/C ratio) is caused by the dominant role of the local oxygen transport resistance at low Pt loading, which is lowered by a reduction of the average ionomer film thickness (better ionomer distribution among carbon particles). In contrast, at high Pt loading, higher porosity and pore radius (lower carbon volume fraction) is beneficial due to an increase of bulk effective diffusivity despite thickening of ionomer films. Moreover, the results show that performance at low Pt loading is significantly improved with increasing mass-specific activity. The effect of average saturation and ionomer permeability on performance at low Pt loading is lower compared to dry CL composition and mass-specific activity.This work was supported by projects EIN2020-112247 and PID2019-106740RB-I00 (Spanish Agencia Estatal de Investigación)

Modeling Single and Two-Phase Transport in Thin Porous Layers Using a Composite Continuum-Pore Network Formulation

In this work, a composite continuum-pore network formulation is presented to model single and two-phase transport thin porous layers, such as gas diffusion layers in polymer electrolyte fuel cells (PEFCs) and active electrodes in redox flow batteries (RFBs). The formulation can be integrated into CFD codes, thus combining the ease of implementation of continuum-based modeling and the computational power of pore-network modeling. The composite model includes a control volume (CV) mesh at the layer scale, which embeds a cubic pore network [1,2]. The pore-network model is used to determine analytically local anisotropic effective transport properties (local effective diffusivity and permeability), which are mapped onto the CV mesh to simulate transport in the porous transport layer [3,4]. Good agreement is found between the predicted global effective transport properties (global effective diffusivity and permeability) under dry and wet conditions and previous experimental data reported in the literature for Toray TGP-H series carbon paper. Water saturation distributions are also compared with results obtained using X-ray computed tomography [4]. [1] P.A. García-Salaberri, I.V. Zenyuk, J.T. Gostick, A.Z. Weber, Modeling Gas Diffusion Layer in Polymer Electrolyte Fuel Cells Using a Continuum-Based Pore-Network Formulation, ECS Trans. 97 (2020) 615. [2] P.A. García-Salaberri, Modeling diffusion and convection in thin porous transport layers using a composite continuum-network model: Application to gas diffusion layers in polymer electrolyte fuel cells, Int J. Heat Mass Transf. (2020), submitted. [3] P.A. García-Salaberri, J.T. Gostick, G. Hwang, A.Z. Weber, M. Vera, Effective diffusivity in partially-saturated carbon-fiber gas diffusion layers: Effect of local saturation and application to macroscopic continuum models, J. Power Sources 296 (2015) 440–453. [4] P.A. García-Salaberri, G. Hwang, M. Vera, A.Z. Weber, J.T. Gostick, Effective diffusivity in partially-saturated carbon-fiber gas diffusion layers: Effect of through-plane saturation distribution, Int. J. Heat Mass Transf. 86 (2015) 319–333

Modeling Gas Diffusion Layers in Polymer Electrolyte Fuel Cells Using a Continuum-based Pore-network Formulation

Multiscale modeling of porous media in polymer electrolyte fuel cells is of paramount importance to improve predictions and assist the design of new materials. In this work, a composite-continuum-network formulation is presented to model species diffusion and convection in gas diffusion layers (GDLs). The model can be incorporated into CFD codes with moderate computational cost. The macroscopic model is based on a structured mesh composed of parallelepiped control volumes (CVs) and differential connectors (with negligible volume). The CV mesh embeds an internal structured pore network, which is used to determine analytically local anisotropic effective transport properties (effective diffusivity and permeability). The global structural parameters and effective transport properties predicted by the model are in good agreement with previous experimental data. Moreover, the results show that heterogeneities in the GDL can have significant influence on the fluxes from/to the catalyst layer, thus affecting local degradation rates.The model was conceived and partially developed during the stay of P.A. García-Salaberri at LBNL, which was supported by the US-Spain Fulbright commission. P.A. GarcíaSalaberri also thanks the support of the project for young researchers PEM4ENERGYCMUC3M (Universidad Carlos III de Madrid)