Dynamically Adaptive Interfacial Chemistry <i>via</i> Molecular Programming for Sustainable Zn Batteries

Artificial interfacial layers represent a promising strategy for enhancing reversible Zn redox through spatial regulation of mass-electron transport. However, intrinsic dynamic degradation of the interface, coupled with parasitic side reactions, continues to compromise long-term electrochemical stability. Herein, we engineered a mechanically adaptive ionic liquid interphase that simultaneously suppresses dendrite growth and corrosion. Crucially, this interphase dynamically self-reconfigures during cycling to maintain structural and functional integrity <i>via</i> zincophilic coordination and hydrophobic shielding. The engineered Zn anode achieves exceptional cyclability, operating for 200 h at 30 mAh cm^-2 and delivering 5400 mAh cumulative capacity at 20 mA cm^-2. Superior thermodynamic stability enables record-long 4400 h operation at 1 mA cm^-2 with minimal polarization (30 mV). The deformation-adaptive architecture sustains >500% capacity retention enhancement in 30 cm² pouch cells under multiaxial stress. Paired with an I₂ cathode, the full battery retains 86% capacity after 30000 high-rate cycles at 10 A g^-1. <i>Operando</i> spectroscopy and theoretical simulations uncover that bis(trifluoromethanesulfonyl)imide anions establish ordered nucleation templates, while 1-ethyl-3-methylimidazolium cations form dynamic hydrophobic barriers blocking water. This work integrates zincophilic-hydrophobic coordination with self-adaptive interfacial layers for practical Zn batteries.