Reshaping Inner Helmholtz Layer and Electrolyte Structure via Multifunctional Organic Molecule Enabling Dendrite‐Free Zn Metal Anode

Abstract The dendrite growth and parasitic reactions that occur on Zn metal anode (ZMA)/electrolyte interface hinder the development of aqueous zinc ion batteries (AZIBs) in next‐generation renewable energy storage systems. Fortunately, reconstructing the inner Helmholtz layer (IHL) by introducing an electrolyte additive, is viewed as one of the most promising strategies to harvest the stable ZMA. Herein, (4‐chloro‐3‐nitrophenyl) (pyridin‐4‐yl) methanone (CNPM) with quadruple functional groups is introduced into the ZnSO 4 electrolyte to reshape the interface between ZMA and electrolyte and change the solvation structure of Zn 2+ . Density functional theory (DFT) calculations manifest that the ─C═O, ─Cl, ─C═N─, and ─NO 2 functional groups of CNPM interact with metallic Zn simultaneously and adsorb on the ZMA surface in a parallel arrangement manner, thus forming a water‐poor IHL and creating well‐arranged ion transportation channels. Furthermore, theoretical calculations and experimental results demonstrate that CNPM absorbed on the Zn anode surface can serve as zincophilic sites for inducing uniform Zn deposition along the (002) plane. Benefiting from the synergistic effect of these functions, the dendrite growth and parasitic reactions are suppressed significantly. As a result, ZMA exhibits a long cycle life (2900 h) and high coulombic efficiency (CE) (500 cycles) in the ZnSO 4 +CNPM electrolyte.