Electronic Structure and Lattice Vibration Regulating Enables Highly Stable Zn Metal Anode for Zinc Ion Batteries

Abstract Uncontrolled dendrite growth and parasitic side reactions are the primary challenges that hamper the practical viability of Zn‐ion batteries (ZIBs). Here, strongly polar trifluoropropanol (TFP) is introduced as an electrolyte additive to modulate the Zn deposition behavior and enhance anode stability. Beyond modifying the electrolyte microenvironment, TFP inclines to adsorb on the Zn surface and change surface electronic structure through dipole‐metal interactions, raising the d‐band center of the Zn anode, thereby suppressing the hydrogen evolution reaction. Moreover, the adsorption of TFP molecules on the Zn surface locally passivates active sites and suppresses anharmonic lattice vibrations through interfacial stress coupling, thereby facilitating uniform Zn deposition. Consequently, a highly reversible plating/stripping performance of 2800 h is achieved for Zn||Zn symmetric cell using TFP additive. In addition, the Zn||NH ₄ V ₄ O ₁₀ full cell using TFP maintains an impressive capacity retention of 90.66% after 1800 cycles, demonstrating the potential of TFP additive for practical application in high‐performance AZIBs. This work offers a novel perspective on interfacial optimization through electronic structure and lattice vibration modulation for Zn‐based and other metal‐ion battery systems.