Crystallographic Manipulation Strategies toward Reversible Zn Anode with Orientational Deposition

Abstract The reversibility and sustainability of Zn anode are greatly hampered by the dendrite growth and side reactions. Orientational deposition, which allows the assembly of Zn deposits in a highly ordered and compact manner, offers a solution to these issues by enabling dendrite‐free Zn anodes. Moreover, Zn orientational deposition can effectively inhibit side reaction by reducing the exposed surface area of the electrode. Despite significant progress in the field of Zn orientational deposition, there is still a lack of clear guidelines for regulating the orientation, and the underlying mechanisms remain rather elusive. Therefore, a comprehensive review is urgently needed to provide a mechanistic insight into Zn orientational deposition. This review summarizes the burgeoning strategies for steering Zn orientational deposition, categorizing the corresponding mechanisms into five aspects: heteroepitaxial deposition, homoepitaxial deposition, interfacial cultivation, crystal facet anchoring, and current density regulation. The distinct advantages and limitations of each mechanism in controlling the growth orientation are discussed in detail. Finally, the challenges and future trends pertaining to Zn orientational deposition are envisaged, aiming in essence to realize highly reversible Zn anodes and ultimately bridge the gap between reality and ideal in aqueous Zn‐ion batteries.