Unveiling the X‐Ray Absorption Chemistry of H3.78V6O13 Cathode for Aqueous Zinc‐Ion Batteries

Abstract The low cost and intrinsic safety of rechargeable aqueous zinc‐ion batteries (ZIBs) contribute to their significant potential in grid‐level energy storage systems. However, the limited cathode options still hinder the development of ZIBs, which always delivers poor rate capacities and cycling stability. Herein, Monoclinic phase H 3.78 V 6 O 13 microspheres with a stable internal framework and intrinsic metallic properties as a high‐performance cathode for ZIBs are proposed and utilized. The reversible Zn 2+ insertion/de‐insertion mechanism in H 3.78 V 6 O 13 through ex situ X‐ray diffraction, X‐ray absorption near‐edge structure, and in situ Raman involves the enlargement/shrink of interplanar distance, the decrease/increase of the V valance, and the open/recombine of V─O/V─V bonds. Further, experiments and theoretical calculations elucidate the superior electrochemical performance and extraordinary reaction kinetics in H 3.78 V 6 O 13 . The as‐prepared H 3.78 V 6 O 13 cathode delivers high specific capacity of 406 mAh g –1 at 0.1 A g –1 , excellent structure stability with 100% manifested after 120 cycles at 0.5 A g –1 , 72.9% retained after 15 000 cycles at 10 A g –1 . This research offers distinctive perspectives on the development of high‐performance cathode materials for ZIBs and enhances the understanding of the electrochemical reaction mechanisms of vanadium oxides.