Regulating Single‐Plane Growth by Selective Self‐Assembly Shielding Molecule for Ultra‐High Areal Capacity Zn‐Metal Batteries

ABSTRACT The dendrite‐free Zn anode is crucial for the commercialization of aqueous Zn‐metal batteries (ZMBs), but dendrite growth and thermodynamic instability are two major obstacles. Regulating the specific crystal plane growth of Zn can effectively address these issues. Here, we propose an in situ construction of a selective self‐assembled monolayer (S‐SAM) strategy to induce the growth of the (002) crystal plane (85%) and improve the interface properties. Specifically, 2,2'‐dithiobis(ethylamine) generated unsaturated ─S groups through the cleavage of S─S bonds, which selectively self‐assemble on the (100) and (101) planes to shield the nucleation process of these planes, leading to the single growth of (002) plane finally. Therefore, compared to the blank electrolyte, the S‐SAM anode with preferential exposure of the (002) crystal plane significantly improved cycling lifetime under conditions of high current density and large plating capacity, with a cumulative plating capacity exceeding 2.875 Ah cm −2 . Furthermore, a Zn//V 2 O 5 full battery with an areal capacity of over 11 mAh cm −2 achieved more than 128 stable cycles at 0.4 A g −1 . This study enhances the understanding of SAM in crystal plane regulation and has universal value for constructing metal batteries with ultra‐high areal capacities.