Electrode Imbibition and Surfactant Interactions with Vanadium Flow Battery Electrolytes

Abstract

Redox flow batteries (RFB) are a critical technology for stationary grid-scale energy storage, with potential usage with intermittent power sources, such as wind and solar. RFBs are attractive for long-duration energy storage because the anolyte and catholyte are stored separately external to the electrochemical reactor. Separating the electrolytes and the electrochemical cell decouples energy and power densities, unlike batteries that store charge in the solid-state, such as Li-ion, Pb-acid, or Ni-Cd. A standard RFB chemistry is the all-vanadium redox flow battery (VRFB), which utilizes the four oxidation states of vanadium, with V2+, V3+, V4+, and V5+. Recently our group found that adding small amounts of sodium dodecyl sulfate (SDS) to a VFRB increased the kinetics of the V2+ to V3+oxidation.Furthermore, surfactants play essential roles in battery manufacturing and operation. Surfactants can change metal oxide crystal structure, inhibit dendrite growth, limit corrosion, and prevent nanoparticle agglomeration. Surfactants are never wholly removed during manufacturing and can be present during battery operation. Therefore, it is crucial to understand how surfactants impact battery performance and their effect on the materials.This talk describes SDS's equilibrium surface properties and adsorption characteristics at the liquid−air and liquid-solid interfaces, thus providing insights into the interactions of SDS with a VFRB electrolyte. Experiments focusing on the effects of sulfuric acid and vanadium ions on SDS's equilibrium surface tension and critical micelle concentration (CMC) were completed. The Szyszkowski equation is used to calculate SDS's adsorption parameters, such as interfacial surface excess, Γsz [mol/m2], the surface excess at the saturated interface, Γ∞ [mol/m2], the minimum molecular area in the adsorption layer at the saturated interface, Amin [nm2], and the Gibbs free energy of adsorption, ΔGads [kJ/mol]. Furthermore, an examination of the spontaneous imbibition of the VFRB electrolyte with SDS into a porous carbon electrode is presented. The microstructure of porous systems, interfacial tension, and fluid−solid interactions controls the capillary-driven flow and is vital in multiphase flow in porous media. Therefore, understanding SDS's effects on the VFRB electrolyte in an electrode is critical to understanding the electrochemical reactions and molecular interactions occurring.This work was supported as part of the Breakthrough Electrolytes for Energy Storage and Systems (BEES2), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0019409.