Cobalt vanadium chalcogenide microspheres decorated with dendrite-like fiber nanostructures for flexible wire-typed energy conversion and storage microdevices

Abstract

The increasing energy demand for next-generation portable and miniaturized electronics has drawn tremendous attention to develop microscale energy storage and conversion devices with light weight and flexible characteristics. Herein, we report the preparation of flower-like cobalt vanadium selenide/nickel copper selenide (CoVSe/NiCuSe) microspheres with three-dimensional hierarchical structure of micropore growth on copper wire for a flexible fiber microsupercapacitor (microSC) and overall water splitting. The CoV-LDH microspheres are anchored on the dendrite-like NiCu nanostructured Cu wire using a hydrothermal method (CoV-LDH/NiCu@CW). The sulfidation and selenization of CoV-LDH/NiCu was carried out through the ion-exchange reaction of OH⁻ with sulfide and selenide ions to obtain CoVS/NiCuS@CW and CoVSe/NiCuSe@CW electrodes, respectively. Benefitting from the unique structure, the flower-like CoVSe/NiCuSe@CW microspheres exhibit better electrochemical performance compared with other as-prepared fiber-shaped electrodes. As an electrode active material for microSC, CoVSe/NiCuSe microspheres exhibit a specific capacitance of 35.40 F cm⁻³ at 4 mA cm⁻², and maintain 281.25 F cm⁻³ even at a high current density of 83 mA cm⁻², indicating outstanding charge storage capacitance and excellent rate capability. Moreover, the assembled flexible solid-state asymmetric microSCs based on flower-like CoVSe/NiCuSe microspheres-coated Cu wire as the positive electrode and polypyrrole/reduced graphene oxide-coated carbon fiber as the negative electrode manifests a maximum energy density of 20.17 mW h cm⁻³ at a power density of 624.32 mW cm⁻³ and remarkable cycling stability (96.7% after 5000 cycles) with good mechanical stability. As an electrocatalyst for oxygen and hydrogen evolution reactions in alkaline medium, the CoVSe/NiCuSe electrode delivers an overpotential of 297 mV and 165 mV at 100 mA cm⁻². Furthermore, the CoVSe/NiCuSe-based electrolysis cell for overall water splitting presents a low cell voltage (1.7 V at 50 mA cm⁻²) as well as high durability.