In Situ Constructing Hybrid Solid Electrolyte Interphase and Regulating D‐Band Center on Zn Substrate to Enable High‐Rate and High‐Capacity Zn Metal Anodes

Abstract Constructing stable Zn electrode‐electrolyte interface in water‐based media remains a critical challenge for developing high‐performance aqueous zinc metal batteries (AZMBs). In this work, acetylurea (ACE) is identified from two molecular structure analogues as an effective electrolyte additive for in situ constructing a hybrid solid electrolyte interphase and regulating the D‐band center on Zn substrate. Theoretical calculations and experimental analysis reveal ACE additive reshapes the electrolyte microenvironment by participating in Zn 2+ solvation structure and reconstructing the H‐bond network, thereby suppressing the water activity and enhancing the zinc deposition kinetics. More importantly, preferential adsorption of ACE molecules alters the zinc surface chemistry with a modulated D‐band center of Zn electrode and in situ creates an organic–inorganic hybrid solid electrolyte interphase, to further safeguard Zn anode and induce homogeneous zinc deposition. As a result, Zn||Zn symmetric cells exhibit exceptional cycling stability over 2700 h at a high rate of 10 mA cm −2 . Furthermore, a 564.5 mAh‐level single‐layer soft‐pack cell incorporating ACE additive achieves notable capacity retention of 86.36% after 100 cycles at 0.2 A g −1 under a high‐capacity cathode of 33.6 mg cm −2 . This study offers mechanistic insights for the ACE additive in dictating the AZMBs performance and is expected to stimulate future research into advanced electrode‐electrolyte interface design.