Molecular Integration of a Fused Building‐Block Architecture for Ultra‐Stable Aqueous Zinc‐Ion Batteries

ABSTRACT Aqueous zinc ion batteries (AZIBs) hold great promise for grid‐scale energy storage, yet their performance is hampered by persistent dendrite growth and detrimental parasitic reactions arising from an unstable electrode/electrolyte interface. Here, the relationship between additive molecular structure and Zn anode interfacial stability is established via a molecular integration strategy based on the prototype additive of diazolidinyl urea (DU). Experimental and computational results demonstrate that DU possesses a strong capability to modulate the H‐bond network in the bulk electrolyte, thereby reducing water activity and broadening the working temperature. Concurrently, the adsorbed DU additives on the Zn anode create a water‐starved inner Helmholtz plane, which not only shields adverse reactions induced by active water but also facilitates Zn electrodeposition along the (101) plane. Furthermore, DU reconstructs the Zn 2 + solvation environment in the inner Helmholtz plane, accelerating Zn 2 + desolvation dynamics. Thus, the Zn//Zn cell with 50 DU/BE achieves a breakthrough cycling lifespan of 1788 h (5 mA cm − 2 /5 mAh cm − 2 ) with 17.1% depth of discharge and can maintain stable operation over a temperature range from −10°C to 50°C. The Zn–I 2 and Zn–NVO full batteries with 50 DU/BE also achieve excellent performance.