Document Type

Article

Publication Date

7-25-2016

Abstract

Graphene nanosheets and graphene nanoribbons, G combined with vanadium pentoxide (VO) nanobelts (VNBs) and VNBs forming GVNB composites with varying compositions were synthesized via a one-step low temperature facile hydrothermal decomposition method as high-performance electrochemical pseudocapacitive electrodes. VNBs from vanadium pentoxides (VO) are formed in the presence of graphene oxide (GO), a mild oxidant, which transforms into reduced GO (rGOHT), assisting in enhancing the electronic conductivity coupled with the mechanical robustness of VNBs. From electron microscopy, surface sensitive spectroscopy and other complementary structural characterization, hydrothermally-produced rGO nanosheets/nanoribbons are decorated with and inserted within the VNBs' layered crystal structure, which further confirmed the enhanced electronic conductivity of VNBs. Following the electrochemical properties of GVNBs being investigated, the specific capacitance Csp is determined from cyclic voltammetry (CV) with a varying scan rate and galvanostatic charging-discharging (V-t) profiles with varying current density. The rGO-rich composite V1G3 (i.e., VO/GO = 1:3) showed superior specific capacitance followed by VO-rich composite V3G1 (VO/GO = 3:1), as compared to V1G1 (VO/GO = 1:1) composite, besides the constituents, i.e., rGO, rGOHT and VNBs. Composites V1G3 and V3G1 also showed excellent cyclic stability and a capacitance retention of >80% after 500 cycles at the highest specific current density. Furthermore, by performing extensive simulations and modeling of electrochemical impedance spectroscopy data, we determined various circuit parameters, including charge transfer and solution resistance, double layer and low frequency capacitance, Warburg impedance and the constant phase element. The detailed analyses provided greater insights into physical-chemical processes occurring at the electrode-electrolyte interface and highlighted the comparative performance of thin heterogeneous composite electrodes. We attribute the superior performance to the open graphene topological network being beneficial to available ion diffusion sites and the faster transport kinetics having a larger accessible geometric surface area and synergistic integration with optimal nanostructured VO loading. Computational simulations via periodic density functional theory (DFT) with and without V2O5 adatoms on graphene sheets are also performed. These calculations determine the total and partial electronic density of state (DOS) in the vicinity of the Fermi level (i.e., higher electroactive sites), in turn complementing the experimental results toward surface/interfacial charge transfer on heterogeneous electrodes.

Comments

© Materials. Original version available at: http://doi.org/10.3390/ma9080615

Publication Title

Materials

DOI

10.3390/ma9080615

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