Ultrafast Metal Electrodeposition Revealed by In Situ Optical Imaging and Theoretical Modeling towards Fast‐Charging Zn Battery Chemistry

Abstract Metallic Zn is a preferred anode material for rechargeable aqueous batteries towards a smart grid and renewable energy storage. Understanding how the metal nucleates and grows at the aqueous Zn anode is a critical and challenging step to achieve full reversibility of Zn battery chemistry, especially under fast‐charging conditions. Here, by combining in situ optical imaging and theoretical modeling, we uncover the critical parameters governing the electrodeposition stability of the metallic Zn electrode, that is, the competition among crystallographic thermodynamics, kinetics, and Zn 2+ ‐ion diffusion. Moreover, steady‐state Zn metal plating/stripping with Coulombic efficiency above 99 % is achieved at 10–100 mA cm −2 in a reasonably high concentration (3 M) ZnSO 4 electrolyte. Significantly, a long‐term cycling‐stable Zn metal electrode is realized with a depth of discharge of 66.7 % under 50 mA cm −2 in both Zn||Zn symmetrical cells and MnO 2 ||Zn full cells.