The water-dominated inner Helmholtz plane (IHP) at the electrode/electrolyte interface is a critical factor responsible for notorious parasitic reactions and Zn dendrite growth, which severely limit the development of aqueous zinc-metal batteries (AZMBs). In this work, we report a universal competitive adsorption strategy to reconstruct the interfacial molecular distribution and induce orderly Zn2+ deposition behavior by introducing DL-malic acid additive (denoted as DL). Specifically, the DL molecules preferentially adsorb on the Zn anode surface, forming a water-shielding IHP layer that effectively excludes water molecules. The zincophilic groups within DL provide abundant active sites and homogenize Zn2+ flux, achieving uniform Zn2+ deposition. Moreover, the original hydrogen-bond network is reset, thereby efficiently suppressing active water-induced parasitic reactions. As a result, symmetric cells with DL additive exhibit remarkable cycling stability over 8600 cycles at 5 mA cm-2 and 1 mAh cm-2, while Zn||Cu asymmetric cells achieve a coulombic efficiency of 99.9% over 3600 cycles. The advanced Zn||I2 full cell delivers stable operation for 4000 cycles with 82.7% capacity retention at 1 A g-1. Moreover, the Zn||I2 pouch cell with limited N/P (1.82) reserves 78.2% capacity after 860 cycles. Surprisingly, an Ah-level Zn||I2 pouch cell maintains marvel stability and reversibility over 220 cycles.
Li et al. (Tue,) studied this question.