Copper Vanadium Oxide Yolk–Shell Microspheres with Excellent Capacitance and Cycling Performance for Electrochromic Supercapacitor

Vanadium pentoxide (V₂O₅) is considered a promising material for electrochromic supercapacitors due to its rich color transitions and excellent electrochemical capacity. However, V₂O₅ exhibits low electrical conductivity, and its volume changes dramatically during charge-discharge cycles, leading to structural collapse and poor long-term cyclability. These issues have hindered the development and application of V₂O₅. In this study, copper vanadium oxide yolk-shell microspheres (CVO) were synthesized through a one-step solvent heat treatment with an annealing process. With the doping of copper element, the capacitance, conductivity, and cyclic stability of CVO microspheres were significantly enhanced. Subsequently, the sphere-wire network structure was formed by blending Na₂V₆O₁₆·3H₂O nanowires (NVO), resulting in the formation of CVO/NVO composites. The three-dimensional sphere-wire network efficiently facilitates the acquisition of additional redox sites and strengthens the material-to-substrate bonding. Under the combined influence of these favorable factors, CVO/NVO achieved a high specific capacitance of 39.2 mF cm^-2, with a capacitance retention of 84% after 7500 cycles at a current density of 0.7 mA cm^-2. The fully inorganic solid-state electrochromic supercapacitor (ECSC), assembled on the basis of CVO/NVO, demonstrates a vivid and clearly distinguishable color change (ΔE* = 37). Even more impressive is the energy storage capacity (18.4 mF·cm^-2) and the cycling stability (up to 89% retention after 10,000 cycles) exhibited by the devices. These key performances are superior to those of most of the previously reported V₂O₅-based ECSCs, opening a promising avenue for the development of V₂O₅-based electrochromic energy storage devices.