Electrochemically Finely Regulated NiCo‐LDH/NiCoOOH Nanostructured Films for Supercapacitors with Record High Mass Loading, Areal Capacity, and Energy Density

Abstract The design of supercapacitor materials with both high mass loading and high areal capacity is a major strategy to overcome relatively low energy density of supercapacitors. Herein, NiCo‐layered double hydroxide (NiCo‐LDH)/NiCoOOH composite films with both ultrahigh mass loading and high areal capacity are prepared by a two‐step cyclic voltammetry method. The films consist of NiCo‐LDH/NiCoOOH microspheres assembled with ultrafine nanosheets with highly ordered pore distribution from macropores to micropores and abundant defect active sites, which are conducive to the transport of electrolyte ions, increasing the reaction kinetics, and greatly improving the utilization of active material. The optimal film with hierarchical microstructure featuring an ultrahigh mass loading of 80 mg cm −2 not only exhibits a state‐of‐the‐art high areal capacity of 14.7 mAh cm −2 , but also shows a record‐high energy density of 10.7 mWh cm −2 , as well as presents remarkable mechanical stabilityand superior capacity retention of 99% after 20000 galvanostatic charge‐discharge cycles. Moreover, by combining the experimental analysis and theoretical calculations, the mechanism of preferential conversion of the NiCo‐LDH in the subtle defect region to NiCoOOH by electrochemistry and the synergistic effect in electrochemical energy storage of the NiCo‐LDH and NiCoOOH phases is proposed.