Desolvation and Self‐Assembled Molecular Engineering Synergistically Reshape the Electric Double Layer toward Highly Stable Zinc Metal Anodes

Aqueous zinc‐ion batteries (AZIBs) offer significant advantages and wide applications. However, Zn dendrite growth and water‐induced side reactions still hinder their commercialization. Here, bis ( 2 ‐carboxyethyl) disulfide (BD), a centrosymmetric molecule featuring a dynamic covalent disulfide bond and highly electronegative carboxyl groups, serves as a multifunctional electrolyte additive. It is discovered that BD optimizes the Zn 2+ solvation structure and restructures the hydrogen‐bond network. In particular, the adsorbed layer of BD molecules at the electrode/electrolyte interface undergoes S─S bond cleavage, forming a self‐assembled molecular layer of β ‐mercaptopropionic acid. This unique self‐assembled molecular layer not only provides numerous uniform and stable deposition sites for Zn 2+ , but also constructs an H 2 O‐poor and SO 4 2− ‐repellent electric double layer (EDL), effectively suppressing H 2 O‐induced side reactions and corrosion while guiding uniform and orderly Zn 2+ deposition on the (002) plane. Consequently, Zn||Zn symmetric cells based on BD‐containing electrolyte exhibit stable stripping/plating behavior for over 4700 h at 1 mA cm −2 and 3000 h at 5 mA cm −2 . Furthermore, Zn||VO 2 full cells maintain a capacity retention of 79.5% after 5000 cycles at 5 A g −1 . This self‐assembled molecular engineering of reshaping the EDL offers a novel strategy for constructing stable and reversible Zn anodes in AZIBs.