Electrolyte Engineering Strategy with Catecholate Type Additive Enabled Ultradurable Zn Anode

Abstract Rechargeable aqueous zinc‐ion batteries (RAZBs), considered for grid‐level energy storage, have drawn intensive attention due to their intrinsic safety, earth abundance, and low cost of electrode materials. However, the practical application of RAZBs is severely impeded by the uncontrollable hydrogen evolution reaction, serious self‐corrosion, and uneven zinc deposition. Herein, the study proposes a multifunctional electrolyte additive to form in situ a protective layer on zinc surface, providing a buffering ability of maintaining the stable pH around anode/electrolyte interface and thus inhibiting hydrogen evolution reaction. Additionally, the modified Zn anode shows the preferred orientation growth of (101) plane, inheriting the merits of dense deposition morphology and superior stability. Consequently, the Zn||Zn symmetric cell demonstrates a remarkable life span up to 4000 h (1 mA cm −2 , 1 mA h cm −2 ) and 1300 h (5 mA cm −2 ,1 mA h cm −2 ). After cycling over 1500 h, the Zn||Cu half cell shows a high coulombic efficiency for nearly 100%, verifying the extraordinary Zn stripping/plating reversibility. The as‐assembled Zn||MnO 2 full battery shows good electrochemical characteristics, surpassing the bare cell without the additive. This investigation features a facile yet effective strategy for ultradurable Zn anode design and sheds the light on designing practical rechargeable metal batteries.