Multicomponent hierarchical NiCo2O4@CoMoO4@Co3O4 arrayed structures for high areal energy density aqueous NiCo//Zn batteries

Abstract Directly growing nickel/cobalt-based cathode materials on current collectors as binder-free electrodes for rechargeable aqueous nickel/cobalt-Zn-based (NiCo//Zn) batteries have attracted tremendous attentions. However, most of the present binder-free cathodes suffer from low areal capacity and energy density, which severely restrict their practical applications. Herein, we demonstrate an efficient metal-organic framework (MOF)-involved strategy to rationally integration of the active NiCo2O4, CoMoO4 and Co3O4 cathode materials into one hierarchical arrayed structure that uniformly grown on nickel foam (NF) substrate (denoted as NF–NCO@CMO@CO) with a high mass loading of 9.6 ​mg ​cm−2. Such electrode design possesses favorable merits in the aspects of high electrical conductivity, robust arrayed architectures, abundant electrochemical active sites, rich redox reactions, facile ion diffusion and components’ synergetic effect. As a result, the aqueous NiCo//Zn battery based on NF–NCO@CMO@CO binder-free cathode exhibits an ultrahigh areal capacity of 2.51 ​mAh cm−2 at a current density of 2 ​mA ​cm−2, as well as good rate capability and long-term cycling stability. Impressively, the aqueous NF–NCO@CMO@CO//Zn battery shows a maximum areal energy density of 4.09 ​mWh cm−2 (corresponding to 424.5 ​Wh kg−1), which is superior to most of the previously reported aqueous NiCo//Zn batteries. Electrode reaction kinetics analysis reveals that both capacitive and diffusion-controlled behaviors are involved during the charge storage processes. Moreover, a quasi-solid-state NF–NCO@CMO@CO//Zn battery is also assembled by replacing the liquid electrolyte with gel electrolyte, suggesting the potential for practical applications. This work might shed light on the rational construction of advanced binder-free cathodes for high-performance aqueous NiCo//Zn batteries.