Thermodynamic Interactions as a Descriptor of Cross-Over in Nonaqueous Redox Flow Battery Membranes

Grid-scale energy storage is increasingly needed as wind, solar, and other intermittent renewable energy sources become more prevalent. Redox flow batteries (RFBs) are well suited to this application because of the advantages in scalability and modularity over competing technologies. Commercial aqueous flow batteries often have low energy density, but nonaqueous RFBs can offer higher energy density. Nonaqueous RFBs have not been studied as extensively as aqueous RFBs, and the use of organic solvents and organic active materials in nonaqueous RFBs presents unique membrane separator challenges compared to aqueous systems. Specifically, organic active material cross-over, which degrades battery performance, may be affected by membrane/active material thermodynamic interactions in a fundamentally different way than ionic active material cross-over in aqueous RFB membranes. Hansen solubility parameters (HSPs) were used to quantify these interactions and explain differences in organic active material permeability properties. Probe molecules with a more unfavorable HSP-determined enthalpy of mixing with the membrane polymer exhibited lower permeability or cross-over properties. The HSP approach, which accounts for the uncharged polymer backbone and the charged side chain, revealed that interactions between the uncharged organic probe molecule and the hydrophobic polymer backbone were more important for determining permeability or cross-over properties than interactions between the probe molecule and the hydrophilic side chain. This result is significant for nonaqueous RFBs because it suggests a decoupling of ionic conduction expected to predominantly occur in charged polymer regions and cross-over of organic molecules via hydrophobic or uncharged polymer regions. Such decoupling is not expected in aqueous systems where active materials are often polar or ionic and both cross-over and conduction occur predominantly in charged polymer regions. For nonaqueous RFBs, or other membrane applications where selective organic molecule transport is important, HSP analysis can guide the co-design of the polymer separator materials and soluble organic molecules.