4.8 Article

Tuning [VO6] Octahedron of Ammonium Vanadates via F Incorporation for High-Performance Aqueous Zinc Ion Batteries

Journal

SMALL
Volume -, Issue -, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/smll.202306561

Keywords

[VO6] octahedron; ammonium vanadate; aqueous zinc ion batteries; F doping

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The electrochemical properties of vanadium-based materials as cathode materials for aqueous zinc ion batteries can be improved by incorporating F atoms into the vanadium-oxide layer of ammonium vanadates. This improves the electronic conductivity and diffusion kinetics of the battery, resulting in higher discharge capacity, rate capability, and long-term cycling stability.
The electrochemical properties of vanadium-based materials as cathode materials for aqueous zinc ion batteries are still restricted by low conductivity, sluggish reaction kinetics, and poor structural stability. Herein, the [VO6] octahedron, as the basic unit of vanadium-oxide layer of ammonium vanadates (NH4V4O10, denoted as NVO), is incorporated by F atoms to regulate the coordinated environment of vanadium. Density functional theory (DFT) calculations and experimental results show that both physicochemical and electrochemical properties of NVO are improved by F-doping. The enhanced electronic conductivity accelerates the electron transfer and the expanded interlayer spacing expedites the diffusion kinetics of zinc ions. As a result, the F-doped NVO (F-NVO) electrode shows a high discharge capacity (465 mAh g(-1) at 0.1 A g(-1)), good rate capability (260 mAh g(-1) at 5 A g(-1)), and long-term cycling stability (88% capacity retention over 2000 cycles at 4 A g(-1)). The reaction kinetics and energy storage mechanism of F-NVO are further validated by in situ and ex situ characterizations.

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