Resolving the Zincophilicity‐Desolvation Dilemma of Electrolyte Additives via Molecular Engineering for Achieving High‐Rate Zinc Anodes with Minimized Polarization

Abstract Zincophilic additives have been widely applied to stabilize Zn metal anodes owing to their efficacy in regulating Zn²⁺ diffusion. However, their high zincophilicity causes elevated desolvation barriers, contributing to increased polarization and reduced stability, particularly under high‐current conditions. Herein, a novel molecular engineering approach is proposed that integrates steric hindrance and H‐bond interactions to promote the desolvation of zincophilic additives, thereby achieving high‐rate Zn anodes with minimized polarization. As a proof‐of‐concept, N,N‐di‐(2‐picolyl)ethylenediamine (NDPA), a zincophilic additive comprising potent Zn²⁺ chelating sites and a polar amino tail group is designed. NDPA boasts four solvation sites, which not only contribute exceptional zincophilicity, effectively regulating Zn²⁺ diffusion but also exhibit significant steric hindrance, reducing the number of solvation H₂O molecules, and lowering dehydration energy. Additionally, NDPA's free amino groups form H‐bonds with H₂O molecules, facilitating the dissociation of coordinated additives. Consequently, at a high current density of 20 mA cm⁻², the addition of NDPA to Zn||Zn symmetric cell improves their lifespan from 37 h to over 2000 h and reduces polarization voltage from 137 to 82 mV. This work presents a novel strategy to overcome the zincophilicity‐desolvation dilemma of electrolyte additives for developing durable and high‐rate zinc anodes.