Unveiling the Reversibility and Stability Origin of the Aqueous V2O5–Zn Batteries with a ZnCl2 “Water‐in‐Salt” Electrolyte

Abstract Aqueous V 2 O 5 –Zn batteries, an alternative chemistry format that is inherently safer to operate than lithium‐based batteries, illuminates the low‐cost deployment of the stationary energy storage devices. However, the cathode structure collapse caused by H 2 O co‐insertion in aqueous solution dramatically deteriorates the electrochemical performance and hampers the operation reliability of V 2 O 5 –Zn batteries. The real‐time phase tracking and the density functional theory (DFT) calculation prove the high energy barrier that inhibits the Zn 2+ diffusion into the bulk V 2 O 5 , instead the ZnCl 2 “water‐in‐salt electrolyte” (WiSE) can enable the dominant proton insertion with negligible lattice strain or particle fragment. Thus, ZnCl 2 WiSE enables the enhanced reversibility and extended shelf life of the V 2 O 5 –Zn battery upon the high temperature storage. The improved electrochemical performance also benefits by the inhibition of vanadium cation dissolution, enlarged voltage window, as well as the suppression of the Zn dendrite protrusion. This study comprehensively elucidates the pivotal role of a concentrated ZnCl 2 electrolyte to stabilize the aqueous batteries at both the static storage and dynamic operation scenarios.