Unlatching the Additional Zinc Storage Ability of Vanadium Nitride Nanocrystallites

Abstract Vanadium‐based materials, due to their diverse valence states and open‐framework lattice, are promising cathodes for aqueous zinc ion batteries (AZIBs), but encounters the major challenges of in situ electrochemical activation process, potent polarity of the aqueous electrolyte and periodic expansion/contraction for efficient Zn 2+ storage. Herein, architecting vanadium nitride (VN) nanosheets over titanium‐based hollow nanoarrays skeletal host (denoted VNTONC) can simultaneously modulate address those challenges by creating multiple interfaces and maintaining the (1 1 1) phase of VN, which optimizes the Zn 2+ storage and the stability of VN. Benefiting from the modulated crystalline thermodynamics during the electrochemical activation of VN, two outcomes are achieved; I) the cathode transforms into a nanocrystalline structure with increased active sites and higher conductivity and; II) a significant portion of the (1 1 1) crystal facets is retained in the process leading to the additional Zn 2+ storage capacity. As a result, the as‐prepared VNTONC electrode demonstrates remarkable discharge capacities of 802.5 and 331.8 mAh g −1 @ 0.5 and 6.0 A g −1 , respectively, due to the enhanced kinetics as validated by theoretical calculations. The assembled VNTONC||Zn flexible ZIB demonstrates excellent Zn storage properties up to 405.6 mAh g −1 , and remarkable robustness against extreme operating conditions.