Integrating Micro-Patterned Flow Fields into Electrode Architecture Via Non-Solvent Induced Phase Separation for High Performance Redox Flow Batteries
Authors: Liu Baichen , Jacquemond Rémy , Hjelm Johan , Forner-Cuenca Antoni 
Published: February 2024

To facilitate increasing penetration of intermittent renewables in the energy mix, there is a growing need for energy storage technologies. Redox flow batteries (RFBs) have attracted significant attention in recent years due to their suitable characteristics for long-duration stationary energy storage applications. However, the wider adoption of RFB systems is still limited by the capital cost, to which the reactor stack is a large contributor[1]. Further cost reduction can be achieved by reducing kinetic, mass-transfer, and ohmic losses to improve the stack performance. Porous electrodes are key components within the battery stack, providing active sites for electrochemical reactions, and transport pathways for active species. Commercially available carbon-fiber electrode architectures include carbon paper, carbon felt, and carbon cloth. They have a highly porous structure, but their relatively low surface area and low hierarchical fiber orientation increase both electrochemical and pumping losses[2]. There is still a need to develop a low-cost porous electrode that meets the requirements of high active surface area and facile electrolyte transport to enhance battery performance and system efficiency.
Non-solvent induced phase separation (NIPS) is a manufacturing route in the field of membrane technology, which is widely used to fabricate asymmetric membranes[3]. Recently this route has also been used to fabricate non-fibrous porous electrodes[4]. The microstructure of NIPS electrodes is largely influenced and controlled by the solvent/non-solvent exchange rate at the interface between a polymer solution and a coagulation bath. When the phase exchange process is slow, segregation is delayed. This type of segregation generally results in a sponge-like, relatively dense structure[5]. This sponge-like structure has the advantage of small pore size and high surface area, but also has poor hydraulic permeability and high mass-transfer losses. The trade-off between surface area and permeability needs to be further optimized.
In the present study, inspired by the flow field designs widely used in RFBs to guide the electrolyte flow paths for low pressure drop, uniform electrolyte distribution, and high electrochemical performance[6], we propose a strategy to imprint micro-patterned flow fields directly into the electrode architecture during NIPS processing to improve mass transfer properties. NIPS polymer films were cast onto molds with specific micro-patterns, and the resulting micro-channels can be preserved in the electrodes after carbonization. To verify the effectiveness of the micro-patterned electrodes, here, we investigate two selected micro-patterned designs. The groove-patterned electrodes were combined with flow-through flow fields (FT-FFs) for in-plane mass transport optimization, and the pillar-patterned electrodes were combined with interdigitated flow fields (IDFFs) for through-plane flow optimizations[7]. Two geometric sizes of the micro-patterns were considered in each design. The pore sizes and distributions of the micro-patterned electrodes were determined by mercury intrusion porosimetry. The hydraulic permeability of the electrodes was evaluated by half-cell pressure drop measurements, and the electrochemical specific surface area was determined through electrochemical impedance spectroscopy under non-faradaic conditions. In addition, we performed electrochemical battery tests with symmetric iron RFB (0.5 M Fe2+/Fe3+, 2 M HCl) cells and vanadium full-cells (1.6 M V active species at 50% state-of-charge). It was found that due to the small pore size (e.g., ~1 μm) and narrow pore size distribution of the sponge-like NIPS structure, the main contribution to the total losses in electrodes without micro-patterns in electrochemical performance comes from mass-transfer. Electrodes with groove and pillar patterns can help reduce the pressure drop and improve mass transfer properties. Pillar-patterned electrodes with the combination of IDFF show high overall electrochemical performance with greatly reduced mass transport resistances. At an electrolyte velocity of 10 cm/s, the total resistances for kinetic and mass transfer are less than 0.1 Ω·cm2 in symmetric iron cell tests. Compared to the activated commercial electrode (e.g., 2-layer Freudenberg H23 carbon paper, thermally treated at 450 oC for 12 h), the total resistances for kinetic and mass transfer are reduced by ~60%, which shows great potential for adoption in next generation high-performance RFB systems.

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