Constructing a Super‐Saturated Electrolyte Front Surface for Stable Rechargeable Aqueous Zinc Batteries

Rechargeable aqueous zinc batteries (RAZB) have been re‐evaluated because of the superiority in addressing safety and cost concerns. Nonetheless, the limited lifespan arising from dendritic electrodeposition of metallic Zn hinders their further development. Herein, a metal–organic framework (MOF) was constructed as front surface layer to maintain a super‐saturated electrolyte layer on the Zn anode. Raman spectroscopy indicated that the highly coordinated ion complexes migrating through the MOF channels were different from the solvation structure in bulk electrolyte. Benefiting from the unique super‐saturated front surface, symmetric Zn cells survived up to 3000 hours at 0.5 mA cm−2, near 55‐times that of bare Zn anodes. Moreover, aqueous MnO2–Zn batteries delivered a reversible capacity of 180.3 mAh g−1 and maintained a high capacity retention of 88.9 % after 600 cycles with MnO2 mass loading up to 4.2 mg cm−2. Up front: A metal–organic framework (MOF) was constructed as a front surface layer to maintain a super‐saturated electrolyte layer on the Zn anode. Benefiting from the highly coordinated ion complexes in the MOF channels, the Zn anode underwent homogeneous zinc electrode‐position, had a lifespan of up to 3000 hours at 0.5 mA cm−2, and gave stable aqueous MnO2–Zn batteries.