Iron (Fe) metal batteries, such as Fe-ion batteries and all Fe flow batteries, are promising energy storage technologies for grid applications due to the extremely low cost of Fe and Fe salts. Nonetheless, the cycle life of Fe metal batteries is poor primarily due to the low Coulombic efficiency of the Fe deposition/stripping reaction. Current aqueous electrolytes based on Fe chloride or sulfate salts can only operate at a Coulombic efficiency of <91% under mild operation conditions (<5 mA/cm2), largely due to undesired hydrogen evolution reaction (HER). This work reports a series of novel Fe electrolytes, Fe electrolytes reinforced with Mg ions (FERMI) and Ca ions (FERCI), which have remarkably better Coulombic efficiency, higher conductivity, and faster deposition/stripping kinetics. By the addition of 4.5 M MgCl2 or CaCl2 into the baseline FeCl2 electrolyte, the Fe deposition/stripping efficiency can be significantly improved to 99.1%, which greatly boosts the cycling performance of Fe metal batteries in both half-cells and full-cells. Mechanistic studies reveal that the remarkably improved efficiency is due to a reduced amount of "dead Fe" as well as suppressed HER. By the combination of experiments and molecular dynamics and density functional theory computation, the electrolyte structure is revealed, and the mechanism for enhanced water reduction resistance is elucidated. These novel electrolytes not only enable a highly reversible Fe metal anode for low-cost energy storage technologies but also have the potential to address the HER side reaction problem in other electrochemical technologies based on aqueous electrolytes, such as CO2 reduction, NH3 synthesis, etc.
© 2022 The Authors. Published by American Chemical Society.