Redox Flow Batteries: Electrolyte Chemistries Unlock the Thermodynamic Limits

Redox flow batteries (RFBs) represent a promising approach to enabling the widespread integration of intermittent renewable energy. Rapid developments in RFB materials and electrolyte chemistries are needed to meet the cost and performance targets. In this review, special emphasis is given to the recent advances how electrolyte design could circumvent the main thermodynamic restrictions of aqueous electrolytes. The recent success of aqueous electrolyte chemistries has been demonstrated by extending the electrochemical stability window of water beyond the thermodynamic limit, the operating temperature window beyond the thermodynamic freezing temperature of water and crystallization of redox-active materials, and the aqueous solubility beyond the thermodynamic solubility limit. They would open new avenues towards enhanced energy storage and all-climate adaptability. Depending on the constituent, concentration and condition of electrolytes, the performance gain has been correlated to the specific solvation environment, interactions among species and ion association at a molecular level.