Unveiling Surface Redox Charge Storage of Interacting Two-Dimensional Heteronanosheets in Hierarchical Architectures

Two-dimensional (2D) heteronanosheets are currently the focus of intense study due to the unique properties that emerge from the interplay between two low-dimensional nanomaterials with different properties. However, the properties and new phenomena based on the two 2D heteronanosheets interacting in a 3D hierarchical architecture have yet to be explored. Here, we unveil the surface redox charge storage mechanism of surface-exposed WS₂ nanosheets assembled in a 3D hierarchical heterostructure using in situ synchrotron X-ray absorption and Raman spectroscopic methods. The surface dominating redox charge storage of WS₂ is manifested in a highly reversible and ultrafast capacitive fashion due to the interaction of heteronanosheets and the 3D connectivity of the hierarchical structure. In contrast, compositionally identical 2D WS₂ structures fail to provide a fast and high capacitance with different modes of lattice vibration. The distinctive surface capacitive behavior of 3D hierarchically structured heteronanosheets is associated with rapid proton accommodation into the in-plane W-S lattice (with the softening of the E_2g bands), the reversible redox transition of the surface-exposed intralayers residing in the electrochemically active 1T phase of WS₂ (with the reversible change in the interatomic distance and peak intensity of W-W bonds), and the change in the oxidation state during the proton insertion/deinsertion process. This proposed mechanism agrees with the dramatic improvement in the capacitive performance of the two heteronanosheets coupled in the hierarchical structure.(Figure Presented).