Controlling Electrolyte Properties and Redox Reactions Using Solvation and Implications in Battery Functions: A Mini‐Review

Electrolytes will play a central role in the development of next‐generation batteries with increased energy density and cycle life and reduced cost. While molecular designs can enable electrolytes with favorable properties like increased (electro)chemical stability, such properties can be manipulated additionally through the intermolecular interactions among species within the electrolyte. In this mini‐review, a number of intermolecular interactions in the electrolyte that can give rise to significant enhancement in battery functions are highlighted. The critical role of reactant and product solubility is shown in battery reactions, where increasing solubility can enable a dissolution–precipitation reaction pathway, decrease overpotential, and increase capacity. Through the intermolecular interactions among solvent, additives, and ions, the reactivity of electrolyte species can be altered significantly by either enhancing solvent (electro)chemical stability or facilitating water deprotonation in Li–O2 reactions. It is shown that incorporating redox active species in the electrolyte can reduce the reaction overpotential and enhance cycle life. Moreover, intermolecular interactions that can increase the ionic conductivity and transference number of electrolytes are identified. Finally, future opportunities are highlighted to exploit these intermolecular interactions to gain unprecedented molecular control over the electrolyte and enable next‐generation batteries. Electrolytes will be central to the development of next‐generation batteries. Intermolecular interactions among species within the electrolyte can alter many vital electrolyte properties like (electro)chemical stability and ionic conductivity. Moreover, these interactions control vital reactions in beyond Li‐ion batteries like Li–S and Li–O2 as well as the reactions that form the solid electrolyte interphase.