Dinesh K. Patel, Yimei Chen, Ashwini Kumar Sharma, Xiaolei Wang
ABSTRACT Aqueous rechargeable zinc‐ion batteries (ARZBs) are an emerging energy storage technology that offers enhanced safety, environmental sustainability, and strong potential for grid‐scale applications. However, the inherent thermodynamic instability of the Zn anode in aqueous electrolytes presents significant challenges, including corrosion, hydrogen evolution reaction (HER), and dendrite formation. These issues drastically reduce the cycle life and coulombic efficiency (CE) of the zinc anode. In this work, trace amounts of perfluoro‐1‐butanesulfonyl fluoride (PFB) is introduced into the electrolyte to regulate the Zn/electrolyte interface (ZEI). PFB hydrolyzes to generate zincophilic ─SO 3 H groups with long hydrophobic ─CF 2 tails, which adsorb strongly onto the Zn surface, displace water molecules from the inner Helmholtz plane (IHP), and reconstruct the electrical double‐layer (EDL) structure. The reconstructed EDL promotes the preferential exposure of the Zn (101) plane, enabling dense and uniform Zn deposition, while simultaneously inducing the in situ formation of a robust ZnS‐rich SEI layer. Benefiting from these interfacial modifications, the Zn anode exhibits suppressed corrosion, mitigated HER, and symmetrical cell performance up to 2500 h. The Zn||NVO full cell operated nearly 5000 stable cycles at 5 A g − 1 in modified electrolyte, highlighting the importance of regulation of EDL structure near the ZMA.