Electric Double Layer‐Driven Surface Reconstruction Enables Cooperative Zn(002)/(101) Growth for High‐Utilization Zinc Anodes

Aqueous zinc batteries are limited by the mismatch between dynamic interfacial chemistry and anisotropic Zn crystallization. Here, imidazolidinyl urea (IDU) is used to couple electric double layer (EDL) reconstruction with Zn surface reorganization. IDU preferentially enriches at the Zn/electrolyte interface, displaces interfacial water, and interacts strongly with Zn(100). In situ spectroscopic ellipsometry, quartz crystal microbalance, and neutron reflectivity reveal transient removal and reconstruction of surface Zn rather than simple molecular adsorption. The reconstructed interface suppresses Zn(100) and promotes cooperative Zn(002)/(101) evolution, enabling compact deposition with favorable kinetics. Meanwhile, the water‐deficient EDL and hybrid organic‐inorganic interphase inhibit parasitic reactions and stabilize the interfacial environment. Consequently, Zn||Zn cells cycle for over 6000 h at 4 mA cm −2 and 2 mAh cm −2 , while Zn||Cu cells achieve an average Coulombic efficiency of 99.81% over 3000 cycles. Stable operation is further maintained at −10°C and under high Zn utilization. Zn||CVO full cells retain 75% capacity after 650 cycles at an N/P ratio of 2.9, and a 21 mAh pouch cell preserves 84% capacity after 400 cycles. This work links EDL reconstruction with crystallographic evolution to enable highly reversible and practically relevant Zn metal anodes.