Aqueous Zn-ion battery development is challenged by H₂O-induced side reactions and dendrite growth. Interface protective engineering and electrolyte additive including high-concentration salts or organic co-solvents can reduce H₂O molecules, but often at the expense of cost, ionic conductivity, and safety. An approach that mitigates H₂O damage without compromising the merits of aqueous electrolytes is highly desired. Herein, we propose an intrinsic tuning strategy to strengthen the intramolecular O–H bond and elongate the Zn²⁺–O (H₂O) bond length by utilizing electronic and steric hindrance effects, thereby inherently reducing the H₂O reactivity and constructing a relaxed solvation shell. Using ascorbic acid (AA) as a proof-of-concept additive, this bond-length engineering is verified to facilitate Zn²⁺ desolvation and raise the H₂O reduction barrier, leading to even Zn electrodeposition together with inhibition of detrimental side reactions. Therefore, the Zn anode achieves stable cycling for over 380 h under ultrahigh depth of discharge (DOD) of 86.1% together with high current density and areal capacity (100 mA/mAh cm⁻²). Full Zn/NaV₃O₈·1.5H₂O cell also presents remarkably enhanced cycling stability, demonstrating the practicality of this approach for high-performance AZIB.

Here, the structural transformations of H₄ETTC induced by coronene (COR) and selective adsorption behaviors of COR in different templates were investigated by scanning tunnelling microscope (STM). It was discovered that the assembled architecture of H₄ETTC at the HOPG/ heptanoic acid interface depended on the concentration of COR, and the clusters of COR were obtained in the kagomé nanoporous network of H₄ETTC molecules at a high concentration of COR solution. In addition, COR clusters can also be formed in the hexagonal porous structure of hexaphenylbenzene (HPB) molecules modified by alkyl chains at the HOPG/heptanoic acid interface. When both H₄ETTC and HPB assembly structures, based on hydrogen bonding and van der Waals force respectively, were selected as the host templates, COR showed selectivity for HPB template to form HPB/COR hexagonal host–guest architecture. Density functional theory (DFT) calculations were also performed to disclose the mechanisms involved.