Selective Interface Engineering with Large π‐Conjugated Molecules Enables Durable Zn Anodes

Undesirable dendrite growth and side reactions at the electrical double layer (EDL) of Zn/electrolyte interface are critical challenges limiting the performance of aqueous zinc ion batteries. Through density functional theory calculations, we demonstrate that grafting large π‐conjugated molecules (e.g. bilirubin, biliverdin, lumirubin, and hemoglobin) onto Zn surface induces preferential adsorption on non‐(002) facets, leading to interfacial charge redistribution, upshifted Zn d‐band center, and enhanced H+ fixation capability. Among these, bilirubin (BR) is identified as the most effective, preferentially adsorbing onto non‐Zn(002) facets to inhibit hydrogen evolution reaction and promote Zn(002) planar growth during plating. This approach results in average Coulombic efficiency of 99.86% over 4000 cycles in Zn||BR‐1@Cu cells and prolonged lifespan exceeding 1600 h in BR‐1@Zn||BR‐1@Zn cells at 10 mA cm−2 and 1 mAh cm−2. Even under harsh condition of 25 mA cm−2 and 10 mAh cm−2, BR‐1@Zn||BR‐1@Zn cell maintains a lifespan of over 400 h. Furthermore, BR‐1@Zn||MnO2 and BR‐1@Zn||NVO full cells achieve 76.4% and 86.1% capacity retention after 800 and 1400 cycles at 1.0 A g−1, respectively. This study underscores the importance of grafting large π‐conjugated molecules to allow selective Zn(002) exposure, Zn d‐band center upshift, and EDL structure regulation, paving the way towards durable Zn anodes.