Molecule‐Directed Close Packing of All Zinc Crystal Facets Enables Surface Energy Homogenization for Stable Zn Metal Anodes

ABSTRACT Controlling zinc grain growth during electrodeposition is crucial for suppressing dendrite formation and enhancing the cycling stability of zinc metal anodes in aqueous electrolytes. In conventional ZnSO ₄ electrolytes, zinc deposition typically forms hexagonal platelets with sharp edges and tips, which promote dendrite nucleation due to localized tip‐enhanced electric fields. In this work, a thermodynamic strategy to manipulate zinc deposition geometry by employing adenosine‐5'‐triphosphate disodium (ATPDS) as an electrolyte additive is presented, which minimizes surface energy anisotropy across different crystallographic facets. First‐principles calculations demonstrate that ATPDS adsorption induces structural reorganization of non‐(002) zinc facets, driving the outermost atomic layers into close‐packed configurations and thereby homogenizing surface energies. This ATPDS‐mediated surface energy equalization shifts zinc growth kinetics from orientation‐dominated to isotropic deposition. Experimentally, ATPDS‐modified electrolytes produce zinc grains with rounded edges, effectively mitigating the tip effect. As a result, symmetric Zn||Zn cells achieve an exceptional cycling lifespan exceeding 4000 h, a tenfold improvement over the 370 h baseline in additive‐free electrolytes.