Synergistic Modulation of Cationic Preferential Adsorption and Anionic Solvation Structure Reconstruction for Enhanced Stability of Zinc Anode

Abstract Rechargeable aqueous zinc‐ion batteries (AZIBs) with low cost and high safety are promising for energy storage. However, challenges such as the hydrogen evolution reaction, corrosion, and dendrite growth diminish the stability and reversibility of the zinc anode. Herein, zirconium oxychloride is used as an electrolyte additive to address these issues via synergistic modulation. Experimental and theoretical results reveal that the cations (ZrO 2+ ) preferentially anchor to the Zn anode, forming a water‐poor electrical double layer that alters zinc ion migration pathways and restrains side reactions. Meanwhile, the anions (Cl − ) enter the solvation‐sheath structure of zinc ions, reconstruct the hydrogen‐bond network of the electrolyte, and weaken water reactivity, eliminating dendrite growth and promoting anticorrosion behavior. Consequently, the Zn||Zn symmetric cell confers a lifespan of 1800 h at 3 mA cm −2 for 1 mAh cm −2 . Zn||Cu half‐cells maintain a high coulombic efficiency of 99.8% after 1900 cycles. When matched with NaV 3 O 8 ·1.5H 2 O (NVO) cathode, the Zn||NVO full‐cell achieves a capacity retention of 77% at 5.0 A g −1 after 1000 cycles. This work provides a solution for developing high‐performance AZIBs.