Abstract Water's Janus‐faced functionality as both an ion‐transport medium and parasitic‐electrochemistry instigator creates an irreconcilable interfacial dilemma for Zn anodes in aqueous electrolytes. Herein, a hierarchical optimization strategy is proposed, integrating dual collaborative mechanisms: hydrophobic shielding and cationic regulation, achieved by functionalizing Zn anodes with an alkylated silane‐based quaternary ammonium salt (Zn@SiONH + ‐C 18 ). The hydrophobic octadecyl chains suppress H 2 O‐induced corrosion and hydrogen evolution, while ─NH 4 + groups enhance Zn 2+ deposition kinetics via the electrostatic repulsion effect and anchor SO 4 2‐ to mitigate passivation reaction. Simultaneously, the siloxane‐derived Si‐O‐Zn skeleton with cross‐linked Si‐O‐Si networks ensures mechanical robustness of the interface, fundamentally inhibiting dendrite formation. Consequently, the Zn@SiONH + ‐C 18 symmetric cells exhibit exceptional cycling over 3400 h (1 mA cm −2 ) and 2800 h (5 mA cm −2 ) at 1 mAh cm −2 . Notably, the Zn@SiONH + ‐C 18 anode sustains 1000 h under a 55.6% depth of discharge (DOD, 10 mAh cm −2 ) and achieves a high DOD of 92% (16.6 mAh cm −2 ). When paired with a MnO 2 cathode, the full battery retains 63.2% capacity after 10,000 cycles at 10C. This specific molecular‐layer engineering strategy, which simultaneously addresses dendrite suppression and interfacial stabilization, establishes a paradigm for developing sustainable aqueous metal batteries.
Lei et al. (Sun,) studied this question.