Planar Deposition via In Situ Conversion Engineering for Dendrite‐Free Zinc Batteries

Abstract Owing to the considerable capacity, high safety, and abundant zinc resources, zinc‐ion batteries (ZIBs) have been garnering much attention. Nonetheless, the unsatisfactory cyclic lifespan and poor reversibility originate from side reactions and dendrite obstacles to their practical applications. In addition to inhibiting the corrosion of aqueous electrolytes, regulating planar deposition is a key strategy to enhance their long‐term stability. Herein, an in situ conversion strategy is reported to construct a protective “dual‐layer” structure (VZSe/V@Zn) on zinc metal, consisting of the VSe ₂ ‐ZnSe outer layer with low lattice mismatch to Zn (002) plane, and corrosion‐resistant nanometallic V inner layer. Such design integrates superior interfacial ionic/electronic transfer, corrosion resistance, and unique planar deposition regulation capability. The as‐prepared VZSe/V@Zn demonstrates remarkable durability of 238 h at 50 mA cm ⁻² with a high depth of discharge (68.3% DOD) in the Zn||Zn symmetric cell. Even in the anode‐free system, the as‐prepared protective layer can extend the cycle life up to 2000 cycles, with an outstanding capacity retention of 93.1% and ultra‐high average coulombic efficiency of 99.998%. This work delineates an effective strategy for fabricating lattice‐matching protective layers, with profound implications for elucidating zinc deposition mechanisms and paving the way for the development of high‐performance zinc batteries.