Synergistic Ternary Heterostructures Cathode With “Electron‐Complementation” Bridging Interfaces Enable High‐Performance Zinc‐Ion Batteries

ABSTRACT Constructing multiphase heterostructures by interweaving characteristically complementary oxides, sulfides, and metals is promising for advancing aqueous battery electrodes, yet versatile synthesis and heterointerface insight pose significant challenges. Traditional methods often suffer from specificity optimization and non‐redox‐active substrate dependency, compromising performance. Herein, we overcome these limitations with a versatile overpotential‐driven synthetic strategy that enables precisely engineering ternary all‐component‐active heterostructures for compromise‐free high‐performance aqueous zinc batteries. Analysis of localized structure and first‐principles calculations in the model integrated V 2 O 5 @Cu 2 S@Cu heterostructure strongly suggest the formation of amorphous/crystalline bridging interfaces with electronic complementarity, which facilitates deep charge transfer and superior kinetics. In situ synchrotron X‐ray diffraction and ex situ X‐ray absorption spectra reveal the synergistic multi‐electron redox merging anion coordination, collectively enabling the all‐component redox activity and preferred rate capability. As results, V 2 O 5 @Cu 2 S@Cu delivers a high reversible capacity of 492 mAh g −1 , enabling 9000 cycles at 5 A g −1 with 90% capacity retention, greatly surpassing those of any single component. Such synthesis method has been further extended to other accessible vanadium‐based, manganese‐based and bismuth‐based ternary heterostructures, representing an important yet unexplored path to the fabrication of high‐performance aqueous battery cathodes featuring elaborate heterointerface manipulation.