Inhibiting Dendrite Formation and Electrode Corrosion via a Scalable Self‐Assembled Mercaptan Layer for Stable Aqueous Zinc Batteries

The practical use of Zn metal anodes in aqueous zinc batteries is impeded by the growth of dendrites, anode corrosion, and hydrogen evolution reaction in aqueous electrolytes. In this study, a simple, energy‐efficient, and scalable approach is reported to mitigate these detrimental issues effectively. Using 1‐hexanethiol (HT), a hydrophobic self‐assembled mercaptan layer (SAML) with a highly ordered structure is in situ created on the surface of the Zn anode. This ultrathin interfacial structure guides uniform Zn deposition and shields the Zn anode from water and oxygen‐induced corrosion, thus effectively inhibiting dendrite formation and side reactions. Consequently, the HT‐Zn electrode showcases impressive electrochemical stability and reversibility, and the as‐assembled HT‐Zn||I2 full cell delivers increased specific capacity (from 112 to 155 mAh g−1 at 1 A g−1) and ultra‐stable cyclability (zero capacity decay during the extended 1500 cycles at 4 A g−1). To validate the effectiveness of this simple and scalable method, a large‐sized pouch cell is prepared, which can be stably operated for 1000 cycles with a capacity decay of merely 0.0098% per cycle and Coulombic efficiency exceeding 99.1%. The presented SAML strategy highlights the potential of molecular engineering in improving the performance of aqueous zinc batteries. This study introduces a facile and scalable solution approach for the in situ construction of a self‐assembled mercaptan layer (SAML), which is designed to stabilize the zinc anode. The well‐ordered hydrophobic SAML not only facilitates uniform zinc deposition but also protects the zinc anode from corrosion, resulting in exceptional stability and reversibility.