Hydrophobic Organic‐Electrolyte‐Protected Zinc Anodes for Aqueous Zinc Batteries

Aqueous Zn batteries are promising energy-storage devices. However, their lifespan is limited by irreversible Zn anodes owing to water decomposition and Zn dendrite growth. Here, we separate aqueous electrolyte from Zn anode by coating a thin MOF layer on anode and filling the pores of MOF with hydrophobic Zn(TFSI)2 -tris(2,2,2-trifluoroethyl)phosphate (TFEP) organic electrolyte that is immiscible with aqueous Zn(TFSI)2 -H2 O bulk electrolyte. The MOF encapsulated Zn(TFSI)2 -TFEP forms a ZnF2 -Zn3 (PO4 )2 solid electrolyte interphase (SEI) preventing Zn dendrite and water decomposition. The Zn(TFSI)2 -TFEP@MOF electrolyte protected Zn anode enables a Zn||Ti cell to achieve a high average Coulombic efficiency of 99.1 % for 350 cycles. The highly reversible Zn anode brings a high energy density of 210 Wh kg-1 (of cathode and anode mass) and a low capacity decay rate of 0.0047 % per cycle over 600 cycles in a Zn||MnO2 full cell with a low capacity ratio of Zn:MnO2 at 2:1.