Next-generation redox flow batteries will benefit from the progress of macroscopic continuum models that enable the optimization of new architectures without the need of expensive fabrication and experimentation. Despite previous attempts, there is still need for robust and thoroughly validated models. Here, a steady-state two-dimensional unit-cell model of an all-vanadium redox flow battery is presented. The model integrates state-of-the-art descriptions of the fundamental physical phenomena, along with new features such as local mass transfer coefficients for each active species, precise sulfuric acid dissociation kinetics, and experimental data of the electrochemical parameters and electrolyte properties. The model is validated at different states of charge and flow rates using polarization, conductivity and open circuit voltage measurements. Then, the contribution of operating conditions on battery performance is studied by analyzing its separate effect on the various phenomena that affect cell performance, such as local pore mass transfer limitations, parasitic hydrogen evolution reactions, crossover and self-discharge fluxes. The resulting model is a reliable tool that can be used to assess the relevance of these coupled phenomena that take place simultaneously within the reaction cell. This important information is critical to optimize cell components, reactor design and to select optimal operating conditions.

At the core of redox flow reactors, the design of the flow field geometry –which distributes the liquid electrolyte through the porous electrodes– and the porous electrode microstructure –which provides surfaces for electrochemical reactions– determines the performance of the system. To date, these two components have been engineered in isolation and their interdependence, although critical, is largely overlooked. Here, we systematically investigate the interaction between state-of-the-art electrode microstructures (a paper and a cloth) and prevailing flow field geometries (flow through, serpentine and four variations of interdigitated). We employ a suite of microscopic, fluid dynamics, and electrochemical diagnostics to elucidate structure-property-performance relationships. We find that interdigitated flow fields in combination with paper electrodes –which features a uniform microstructure with unimodal pore size distribution– and flow-through configurations combined with cloth electrodes –which have a hierarchical microstructure with bimodal pore size distribution– provide the most favorable trade-off between hydraulic and electrochemical performance. Our analysis evidences the importance of carrying out the co-design of flow fields and electrode microstructures in tandem. We hope these results can help researchers and technology practitioners in the design of electrochemical cell for convection-enhanced electrochemical technologies.

Electrochemical flow reactors are increasingly relevant platforms in emerging sustainable energy conversion and storage technologies. As a prominent example, redox flow batteries, a well-suited technology for large energy storage if the costs can be significantly reduced, leverage electrochemical reactors as power converting units. Within the reactor, the flow field geometry determines the electrolyte pumping power required, mass transport rates, and overall cell performance. However, current designs are inspired by fuel cell technologies but have not been engineered for redox flow battery applications, where liquid-phase electrochemistry is sustained. Here, we leverage stereolithography 3D printing to manufacture lung-inspired flow field geometries and compare their performance to conventional flow field designs. A versatile two-step process based on stereolithography 3D printing followed by a coating procedure to form a conductive structure is developed to manufacture lung-inspired flow field geometries. We employ a suite of fluid dynamics, electrochemical diagnostics, and finite element simulations to correlate the flow field geometry with performance in symmetric flow cells. The lung-inspired structural pattern is demonstrated to homogenize the reactant distribution in the porous electrode and to improve the electrolyte accessibility to the electrode reaction area. In addition, the results reveal that these novel flow field geometries can outperform conventional interdigitated flow field designs, as these patterns exhibit a more favorable electrical and pumping power balance, achieving superior current densities at lower pressure loss. Although at its nascent stage, additive manufacturing offers a versatile design space for manufacturing engineered flow field geometries for advanced flow reactors in emerging electrochemical energy storage technologies.

Redox flow batteries are a promising technological option to integrate the growing supply of renewable energies into the electricity grid, however their deployment is hampered by high costs. To increase cost competitiveness, research efforts have targeted design of new electrolytes, high performance materials, and alternative electrochemical reactor concepts [1]. One powerful strategy is to increase the overall efficiency of the electrochemical stack, which can be achieved by improving the electrochemical performance and reducing the pumping power requirements. Selecting and optimizing the flow field design and electrode microstructure is crucial to accomplish an optimum trade-off. Drawing inspiration from polymer electrolyte fuel cells, current flow battery technologies leverage flow-through, interdigitated and serpentine flow field designs [2]. However, while functional, these designs have not been tailored for the specific requirements of redox flow batteries where single-phase reactive flows are sustained. Recent studies have investigated the influence of the channels and ribs dimensions [3], branched channel geometries [4], as well as the electrode microstructure on the reactor performance [5]. However, the interaction between the flow field geometries and the electrode microstructure determines the accessible surface area, mass transfer phenomena, and pressure drop; but remains poorly understood. With this in mind, we are poised to answer the following scientific question: What is the optimal combination of flow field and electrodes in redox flow batteries? In this work, we evaluate the interaction between geometrically diverse flow field geometries and porous electrode microstructures. We study seven different flow field designs in combination with two commonly used fibrous electrode structures – a carbon paper and a cloth (Figure 1). Flow-through, serpentine, and multiple variations of interdigitated flow fields were designed and fabricated by graphite milling. We employ a suite of polarization, electrochemical impedance spectroscopy, capacitance, and pressure drop measurements to elucidate structure-property-performance relationships. We find that the interdigitated designs perform better with high density of channels (i.e. shorter rib-channel width), even though this leads to higher pressure losses. Interestingly, pressure drop measurements show a similar relative contribution of the flow field and the electrode to the pumping losses, which motivates engineering of flow field geometries and electrode structures in tandem. Mass transfer overpotentials and pressure losses in cloth electrodes are reduced when using flow field geometries that force electrolyte flow into an in-plane direction in the electrode (i.e. parallel to the membrane plane), such as flow-through and interdigitated designs with wider ribs between channels. On the contrary, carbon paper electrodes perform better with interdigitated designs that force electrolyte flow into the through-plane direction (i.e. perpendicular to the membrane plane). Based on these findings, we have undertaken the engineering of innovative flow fields designs by combining interdigitated and branched patterns using 3D-printing, obtaining promising results that will be discussed in the final part of my talk. Figure 1. Polarization results for the combination of cloth and paper electrodes with three different flow field designs, at 5 cm·s-1 in the electrode. References Sánchez-Díez, E. Ventosa, M. Guarnieri, A. Trovò, C. Flox, R. Marcilla, F. Soavi, P. Mazur, E. Aranzabe, R. Ferret, Journal of Power Sources, 481, 228804 (2021). D.Milshtein, K.M.Tenny, J.L.Barton, J.Drake, R.M.Darling and F.R.Brushett, J. Electrohcem. Soc., 164, E3265-E3275 (2017). R.Gerhardt, A.A. Wong, M.J. Aziz, J. Electrohcem. Soc., 165, A2625-A2643 (2018). Zeng, F. Li, F. Lu, X. Zhou, Y. Yuan, X. Cao, B. Xiang, Applied Energy, 238, 435-441 (2019). Forner-Cuenca, E.E. Penn, A.M. Oliveira, F.R.Brushett, J. Electrohcem. Soc., 166, A2230-A2241 (2019). Acknowledgments This work has been partially funded by the Agencia Estatal de Investigación (PID2019-106740RB-I00 and RTC-2017-5955-3/AEI/10.13039/501100011033). Figure 1

Redox Flow Batteries (RFBs) are an evolved electrochemical energy storage technology crucial for the transition into a renewable energy future. Mainstream adoption of RFBs is subject to reduction of the capital and operation costs. In that sense, of particular importance is the optimization of the electrochemical stack, which affects the overall efficiency of the battery. Several studies have investigated the importance of thermal effects on the performance of vanadium redox flow batteries through transient non-isothermal models [1-2]. However, due to the simplified assumptions made by these authors some important temperature-dependent features are not included. Therefore, reliable and validated continuum models are also crucial to study the impact of the system temperature on all the fundamental physics in the electrochemical cells as well as to find the key aspects to optimize the stack. In this work, we present a 2D stationary model of a vanadium redox flow battery cell with a comprehensive and updated multiphysics description. The model was validated at a constant temperature of 25 ºC by polarization, conductivity, and open circuit voltage measurements. In a second step, the temperature was also included as a key operating variable in the model. Electrolyte properties, electrochemical rate constants, and H2SO4 dissociation equilibrium were described as a function of temperature as well as the state of charge (SoC) and the total vanadium concentration. The model is currently being validated through a second experimental campaign (see Fig. 1) conducted inside a climatic chamber imitating different environmental scenarios. The model can be used to explore the relevance of each phenomenon or element in the electrochemical stack and the influence of the operating conditions on them, e.g. temperature, state of charge and volumetric flow rate. By using the proposed model, we can elucidate the best temperature strategy to increase the performance of vanadium redox flow batteries in diverse operating scenarios. Figure 1. Open circuit voltage – SoC relation at different operating temperatures. References Al-Fetlawi, A.A. Shah, F.C. Walsh, Electrochimica Acta, 55, 78-89 (2009). Tang, S. Ting, J. Bao, M. Skyllas-Kazacos, Journal of Power Sources, 203, 165-176 (2012). Acknowledgments This work has been partially funded by the Agencia Estatal de Investigación (PID2019-106740RB-I00 and RTC-2017-5955-3/AEI/10.13039/501100011033). Figure 1