Rocking‐Chair Aqueous Fluoride‐Ion Batteries Enabled by Hydrogen Bonding Competition

Aqueous fluoride ion batteries (FIBs) have garnered attention for their high theoretical energy density, yet they are challenged by sluggish fluorination kinetics, active material dissolution, and electrolyte instability. Here, we present a room temperature rocking‐chair aqueous FIBs featuring KOAc‐KF binary salt electrolytes, enabling concurrent fluorination and defluorination reactions at both cathode and anode electrodes. Experimental and theoretical results reveal that acetate ions in the electrolyte compete with fluoride ions in hydrogen bonding formation, weakening the excessively strong solvation between H2O and F− ions. This results in the suppression of detrimental HF formation and a reduced desolvation energy of F− ions, enhancing the electrochemical reaction kinetics. The bismuth‐based cathode exhibits direct conversion in the optimized electrolyte, effectively suppressing the detrimental disproportionation reactions from Bi2+ intermediates. Additionally, zinc anode undergoes a typical fluorination process, forming solid KZnF3 as the electrode product, minimizing the risks of hydrogen evolution. The proposed aqueous FIBs with the optimized electrolyte demonstrate high discharge capacity, long‐term cycling stability and excellent rate capabilities. A room temperature rocking‐chair aqueous fluoride ion battery with the development of electrolytes with KOAc‐KF binary salts is constructed, which exhibits concurrent fluorination or defluorination reactions occurring at both cathode and anode electrodes. Weakening of the F−−H2O hydrogen bonding by OAc− anion in the electrolyte is responsible for the optimized electrochemical process.