Deciphering the Role of Basic Amino Acids Additives in Boosting Zinc Ions Transfer Kinetics and Interfacial Stability for Ah‐Level Rechargeable Zinc Metal Batteries

ABSTRACT Aqueous zinc metal batteries (AZMBs) have attracted considerable attention due to their inherent safety and low cost. However, their development has been significantly impeded by the sluggish Zn 2+ transport and instable aqueous interface. Here, we introduce basic amino acids as multifunctional electrolyte additives to tackle this issue, with L‐arginine (Arg) selected as a representative case for in‐depth mechanistic investigation. We elucidate that protonated Arg (Arg + ) restricts SO 4 2− anions migration by forming large‐size anion clusters via electrostatic interactions. Concurrently, it constructs a hydrophobic, O‐down oriented, and low‐reactivity water microenvironment at the electrode‐electrolyte interface. This coordinated regulation of the bulk electrolyte and the electrode‐electrolyte interface optimizes Zn 2+ migration kinetics and reduction thermodynamics, effectively suppressing side reactions and eliminating disordered dendrite growth. Consequently, the zinc anode achieves highly reversible stripping/plating efficiency of 99.43% at 0.5 mA cm −2 and 0.5 mAh cm −2 , and demonstrates stable cycling for over 1200 h at 5 mA cm −2 and 5 mAh cm −2 . Furthermore, Zn//VOX full coin cells retain 74.5% capacity after 1200 cycles at 2 A g −1 , and 2.28 Ah‐level pouch cell maintains 80.5% capacity after 160 cycles. This work establishes a multiscale framework for additive‐electrolyte interactions and provides a molecular design strategy for aqueous battery additives.