High-capacity zinc vanadium oxides with long-term cyclability enabled by in-situ electrochemical oxidation as zinc-ion battery cathode

The rechargeable aqueous zinc ion batteries hold great promise owing to their non-flammability and low cost, but are extremely limited by the lack of suitable cathode materials. Vanadium oxides such as V2O5 center dot nH(2)O, Zn0.25V2O5 center dot nH(2)O, Ca0.24V2O5 center dot 0.83H(2)O, and so on have been exploited owing to their high Zn2+ storage activity. However, due to the structural disintegration because of the impact of Zn2+ transportation and poor conductivity, their low capacity, poor cyclability and rate property hinder further utilization. Herein, we report the stable zinc vanadium oxides Zn0.36V2O5 center dot nH(2)O as cathode material for zinc-ion batteries. The zinc vanadium oxides with different stoichiometry converted from in-situ electrochemical oxidation of VOOH precursors in various space groups. The introduction of zinc atoms improves the conductivity of the materials and stabilizes the host structure by bonding with the host oxygen atoms without hindering the interlayer migration of mobile Zn2+, thus greatly optimizing the comprehensive behaviors of the batteries. Ex-situ XRD spectra collected at various states show no shift during (dis)charging and the electrode morphology under different cycles remains intact, indicating the high reversibility and stability. The as-prepared Zn0.36V2O5 center dot nH(2)O presents a high specific capacity of 508.3 mAh g(-1) and 343 mAh g(-1) at current densities of 0.5 A g(-1) and 5.0 A g(-1), and excellent capacity retention of 95% and 80% after 2000 and 5000 cycles respectively. The role of interlayer intercalated-Zn on the stability of vanadium oxides is revealed via density functional theory simulations. In addition, materials with low crystallinity provide shortcuts for ion transportation. The in-situ conversion mechanism of zinc vanadium oxides and the later dual ion energy storage mechanism of which are illustrated in detail.

Automated summary

Rechargeable aqueous zinc ion batteries are promising due to their non-flammability and low cost, but the lack of suitable cathode materials has been a limitation. This study reports the use of stable zinc vanadium oxides as cathode material, with improved conductivity and stability through the introduction of zinc atoms. The comprehensive performance of the batteries has been greatly optimized.