Co‐Solvent Electrolyte Design to Inhibit Phase Transition toward High Performance K+/Zn2+ Hybrid Battery

Abstract Manganese hexacyanoferrate (MnHCF) is one of the most promising cathode materials for aqueous battery because of its non‐toxicity, high energy density, and low cost. But the phase transition from MnHCF to Zinc hexacyanoferrate (ZnHCF) and the larger Stokes radius of Zn 2+ cause rapid capacity decay and poor rate performance in aqueous Zn battery. Hence, to overcome this challenge, a solvation structure of propylene carbonate (PC)‐trifluoromethanesulfonate (Otf)‐H 2 O is designed and constructed. A K + /Zn 2+ hybrid battery is prepared using MnHCF as cathode, zinc metal as anode, KOTf/Zn(OTf) 2 as the electrolyte, and PC as the co‐solvent. It is revealed that the addition of PC inhabits the phase transition from MnHCF to ZnHCF, broaden the electrochemical stability window, and inhibits the dendrite growth of zinc metal. Hence, the MnHCF/Zn hybrid co‐solvent battery exhibits a reversible capacity of 118 mAh g −1 and high cycling performance, with a capacity retention of 65.6% after 1000 cycles with condition of 1 A g −1 . This work highlights the significance of rationally designing the solvation structure of the electrolyte and promotes the development of high‐energy‐density of aqueous hybrid ion batteries.