Noncovalent Interaction Restructuring for Efficient Active Water Exclusion at the Anode Interface in Reversible Zinc Metal Batteries

ABSTRACT The active water molecules trigger interfacial side reactions (HER, corrosion passivation) at the anode‐electrolyte interface (AEI), significantly influencing the electrochemical performance of aqueous zinc‐metal batteries (AZMBs). Noncovalent interactions (at the AEI or in the solution) determine the arrangement of water molecules and Zn 2+ ‐solvent coordination, which is the key to achieving efficient active water exclusion. Herein, targeted noncovalent interaction restructuring is achieved by a rational combination of anions and cations, and its positive impacts on ZMB performance are comprehensively investigated. It is found that Dnn + (a large ammonium cation with benzene ring and amide groups) behaves well in improving Coulombic efficiency (CE), anti‐corrosion and enlarging electrochemical windows due to its strong restructuring role in contrast to Na + and H + , while Na + achieves to balance ion‐transfer kinetics and cycling stability which contributes to the best cycling life (over 2500/4000 h at 1/10 mAh cm −2 ). Specifically, both Dnn + and Na + boost the Zn//MnO 2 full cells to exhibit excellent performance (>120 mAh g −1 over 1600 cycles). In summary, cations with electrostatic shielding effect and/or affinity ability are preferable and highly effective in reshaping noncovalent interactions. This work renders valuable insight into noncovalent interaction restructuring for high‐performance AZMBs.