Hydrophilic and Insulative Interface Strategy Against Side Reactions for Dendrite‐Free Zinc Metal Anodes

Abstract The zinc dendrite growth and the parasitic hydrogen evolution reactions (HER) hinder the commercialization of zinc batteries. To address this, a hydroxyl‐rich Boehmite coating (HR‐BC) strategy is developed that combines excellent electrical insulation and high zinc ion conductivity. The hydrophilic hydroxyl groups facilitate hydrogen bond formation with the hydrated zinc ions, accelerating the de‐solvation process and suppressing the HER. Additionally, the electrically insulative nature of Boehmite prevents the reduction of zinc ions within HR‐BC and results in preferential Zn deposition underneath it, leading to a dendrite‐free “sandwich structure” of HR‐BC//Zn deposition//Zn foil. Symmetric cells using HR‐BC‐Zn electrodes obtain an ultralong and stable cycling lifetime of 1700 h at 5 mA cm⁻², along with a high cumulative plating capacity of 4250 mAh cm⁻². When paired with a V₂O₅ cathode, the HR‐BC‐Zn anode demonstrates a high capacitance retention of 90% and an average Coulombic efficiency (CE) of 99.8% after 4000 cycles. Furthermore, when combined with a heteroatoms‐doped carbon (HDC) cathode, the HR–BC–Zn//HDC pouch‐type cell exhibits superior lifetime performance with nearly 100% average CE after 15000 cycles at 3.0 A g⁻¹. This work highlights the effectiveness of hydrophilic and insulative coating strategies in fostering the progression of long‐lasting zinc‐based energy storage systems.