Porous layered ZnV2O4@C synthesized based on a bimetallic MOF as a stable cathode material for aqueous zinc ion batteries

Abstract

Vanadium-based oxides are considered potential cathode materials for aqueous zinc ion batteries (AZIBs) due to their distinctive layered (or tunnel) structure suitable for zinc ion storage. However, the structural instability and sluggish kinetics of vanadium-based oxides have limited their capacity and cycling stability for large-scale applications. To overcome these shortcomings, here a porous vanadium-based oxide doped with zinc ions and carbon with the molecular formula ZnV₂O₄@C (ZVO@C) as the cathode material is synthesized by the pyrolysis of a bimetallic MOF precursor containing Zn/V. This electrode demonstrates a remarkable specific capacity of 425 mA h g⁻¹ at 0.5 A g⁻¹ and excellent cycling stability with about 97% capacity retention after 1000 cycles at 10 A g⁻¹. The excellent electrochemical performance of ZVO@C can be attributed to more reaction active sites and the faster reaction kinetics for zinc ion diffusion and storage brought about by the porous layered spinel-type tunnel structure with high surface area and massive mesoporosity, as well as the enhanced electron transport efficiency and more stable channel structure achieved from the doped conductive carbon. The reaction mechanism and structural evolution of the ZVO@C electrode are analyzed using X-ray diffraction and X-ray photoelectron spectroscopy, revealing the formation of a new phase of ZnxV₂O₅·nH₂O during the first charge, which participates in reversible cycling together with ZVO@C during the charging and discharging processes. Moreover, the energy storage mechanism is revealed, in which zinc ions and hydrogen ions jointly participate in intercalation and extraction. The present study demonstrates that constructing composite vanadium-based oxides based on bimetallic organic frameworks as precursor templates is an effective strategy for the development of high-performance cathode materials for AZIBs.