Crystal Growth Engineering for Dendrite‐Free Zinc Metal Plating

The practical implementation of aqueous zinc-ion batteries (AZIBs) is limited by uncontrolled zinc (Zn) dendrite growth during anode plating, compromising both safety and cycle life. Typically, Zn plating proceeds via 2D growth along the six equivalent prismatic [ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics><mml:mrow><mml:mn>10</mml:mn> <mml:mover><mml:mn>1</mml:mn> <mml:mo>¯</mml:mo></mml:mover> <mml:mrow><mml:mn>0</mml:mn> <mml:mo>]</mml:mo></mml:mrow> </mml:mrow> <mml:annotation>$10\bar 10]$</mml:annotation></mml:semantics> </mml:math> directions of the hexagonal close-packed (HCP) Zn lattice, forming hexagonal platelets that promote dendrite formation. Here, an effective electrolyte engineering strategy is presented using rare-earth ions to regulate Zn plating. Combined multiscale experimental analyses and computational modeling reveal that these ions preferentially adsorb onto the prismatic { <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics><mml:mrow><mml:mn>10</mml:mn> <mml:mover><mml:mn>1</mml:mn> <mml:mo>¯</mml:mo></mml:mover> <mml:mn>0</mml:mn></mml:mrow> <mml:annotation>$10\bar 10$</mml:annotation></mml:semantics> </mml:math> } facets, suppressing lateral epitaxial growth of the basal (0002) planes. This redirects Zn plating toward an apparent screw dislocation-driven growth along the [0001] axis. The resulting growth pathway, together with randomly oriented Zn nucleation, yields dense, uniform, and dendrite-free Zn layers with markedly improved cycling stability and high depth-of-discharge operation, thereby challenging the prevailing assumption that dendrite suppression requires (0002)-oriented growth parallel to the substrate. This work provides new mechanistic insights into Zn plating dynamics and establishes a scalable strategy for stable, dendrite-free Zn anodes in next-generation AZIBs.