Reversing Zincophobic/Hydrophilic Nature of Metal‐N‐C via Metal‐Coordination Interaction for Dendrite‐Free Zn Anode with High Depth‐of‐Discharge

Abstract Dendrite‐free Zn metal anodes with high depth‐of‐discharge (DoD) and robust cycle performances are highly desired for the practical application of aqueous Zn‐ion batteries. Herein, the zincophobic/hydrophilic nature of Metal‐N‐C through manipulating the electronic interactions between metal and coordination atoms is successfully reversed, thereby fabricating a zincophilic/hydrophobic asymmetric Zn‐N_3Py+1Pr‐C (consisting of a Zn center coordinated with 3 pyridinic N atoms and 1 pyrrolic N atom) host, which realizes uniformed Zn deposition and a long lifespan with high DoD. The experimental and theoretical investigations demonstrate weakened interaction between pyrrolic N and metal center in the asymmetric Zn‐N_3Py+1Pr‐C triggers downshift of the Zn 3d‐band‐center and a new localization nonbonding state in the N and C 2p‐band, resulting in preferred Zn adsorption to water adsorption. Consequently, the asymmetric Zn‐N_3Py+1Pr‐C host delivers small Zn nucleation overpotential and high Coulombic efficiency of 98.3% over 500 cycles. The symmetric cells with Zn‐N_3Py+1Pr‐C@Zn anode demonstrate 500 h dendrite‐free cycles at DoD up to 50%. The Zn‐N_3Py+1Pr‐C@Zn/S‐PANI full cell also shows a robust long‐term cycle performance of 1000 cycles at 10 A g⁻¹. This strategy of constructing zincophilic/hydrophobic Metal‐N‐C may open up their application for the dendrite‐free metal anode.