Synergistic Engineering of Amorphous Cathode and Hybrid Electrolyte Toward Stable High‐Voltage Aqueous Zn‐Ion Batteries

ABSTRACT The development of high‐voltage aqueous zinc‐ion batteries (AZIBs) is primarily hindered by the lack of suitable cathode materials and electrolytes that can work in broad voltage windows. Herein, we propose a synergistic strategy that concurrently addresses these challenges through the integration of an amorphous vanadium oxyphosphate/graphene (A‐VOP/G) cathode with a propylene carbonate (PC)‐based hybrid electrolyte. Notably, the amorphous framework of A‐VOP provides abundant ion transfer pathways and enhanced structural flexibility, whereas the graphene scaffold ensures high electronic conductivity and suppresses material agglomeration. Moreover, mechanistic studies reveal that the PC co‐solvent participates in the Zn 2+ solvation sheath, which significantly mitigates water‐induced side reactions. Simultaneously, the introduction of PC components effectively disrupts the hydrogen‐bond network of water, thereby suppressing parasitic reactions and broadening the electrochemical stability window. As a result, the A‐VOP/G cathode in the optimized hybrid electrolyte delivers a high discharge capacity of 159.6 mAh g −1 at 1 A g −1 , an elevated operating voltage of 1.43 V, and remarkable cycling stability. This work demonstrates the profound potential of integrated cathode and electrolyte design in developing stable high‐voltage AZIBs.