Superior electronic/ionic transport dynamics of Zn-Co-OH/MnO2 heterointerface containing oxygen vacancies for pseudocapacitive storage

•The hierarchical M-ZCOH/NPG/NF heterostructures were successfully constructed.•The BIEF in the heterointerface enhanced electronic/ionic transport dynamics.•A high capacity reaching ∼1247.1C g−1 (∼2771.3 F g−1) at 1 A g−1 was obtained.•The HSC displayed ultrahigh energy density of ∼78.3 Wh kg−1 at ∼800 W kg−1. The superior electronic/ionic transport dynamics of electrode materials have been crucial to achieve appealing high performance for supercapacitors. Herein, a fascinating one-dimensional (1D) zinc cobalt hydroxide nanobelts/0D irregular manganese dioxide nanoparticles (M-ZCOH) have been vertically loaded into the 3D Ni foam (NF) substrate wrapped by nitrogen-doped graphene (NPG) (M-ZCOH/NPG/NF) for supercapacitors. The ingeniously designed M-ZCOH/NPG/NF composites feature powerful built-in electric field (BIEF) introduced by well-defined heterointerface with abundant oxygen vacancies defects. The formed electron accumulation triggering strong interfacial interaction verified by the differential charge density analysis may endow M-ZCOH/NPG/NF with the extra driving force to increase the diffusion/adsorption of electrolyte ions, thereby facilitating electron/ion transfer kinetics. Also, the qualitative negative shift of the d band center for M-ZCOH composites further evidences a lower electron/ion transfer barrier compared with the monomers. Obviously, the penetrating understanding of heterointerface on the improved properties is manifestly interpreted by combining theoretical and experimental analysis. Moreover, the ingenious strategy of engineering the heterointerfaces in unique heterostructure with rich defects may provide a new prospect for optimizing other advanced materials in sustainable energy storage systems.