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The vertical TiO2 nanotube arrays constituting the core of 3-D nanoscale electrode architecture were synthesized over Ti sheet by anodization. Such formed TiO2 nanotubes are electrically conducting and amorphous as confirmed by XRD studies. Nanotube morphology is affected by water content and in the present study, close-packed 3-4 μm long TiO2 nanotube arrays of 45-50 nm diameter are formed with 2% water as revealed by the transmission and scanning electron microscopy. The redox active polypyrrole sheath is created by ultra-short pulsed current electropolymerization. Electrochemical properties of the 3-D nanoscaled TiO2 nanotube core-polypyrrole sheath electrodes relevant to the energy storage were investigated using cyclic voltammetry (CV) plots, electrochemical impedance spectroscopy (EIS), Charge discharge (CD) tests. High areal capacitance density of 48 mF cm-2 and low charge transfer resistance 12 Ω cm-2 with least ion diffusion limitation are realized at optimized polypyrrole sheath thickness. The Raman spectra studies reveal anion at specific chain locations involve in the redox process.
Nanocomposites in the 3-D nanoarchitecture using vertically aligned ZnO nanorods template to create conducting polymer Poly(3,4-ethylenedioxythiophene) (Pedot) nanotube and nanofibrous network structures using the facile electrochemical synthesis approach is described. Such electrodes structured at the nanoscale enable many fold enhancement of electroactive surface and interface with electrolyte facilitating absorption, ingress and diffusion of electrolyte ions which lead to increased energy and power density of supercapacitor devices. Electrochemical properties evaluated by electrochemical impedance show specific capacitance of 99 to162.99 mF.cm-2 and extremely low bulk and charge transfer resistance of 5.4 Ω.cm2 in comparison to ZnO and Pedot.
Ordered one dimensional polypyrrole conducting polymer structure as a shell over TiO2 nanotube arrays at the core were formed by pulsed current electropolymerization. TiO2 nanotubes with rippled wall structure are designed by action of water in the anodizing medium. This provides open tube structure supporting short diffusion length and increased accessibility of ions involved in redox transition for energy storage. Electrochemical properties evaluated by cyclic voltammetry and electrochemical impedance spectroscopy show specific capacitance of 34-44 mF.cm-2 and extremely low bulk and charge transfer resistances.
Polypyrrole (pPy) conducting polymer films embedded with MnO2 nanoparticles have been synthesized by electrochemical polymerization and anodic oxidation processes. MnO2 nanoparticles coexist in the hydrated Mn(II) and Mn(IV) states and undergo valence state change along side pPy anion doping-dedoping contributing to the system pseudocapacitance. Increased density of sequestered MnO2 nanoparticles in pPy significantly improves charge storage properties as shown by increased electrodic specific capacitance from 200 to 620 Fg-1 based on cyclic voltammetry studies. MnO2 nanoparticle dispersion in open porous pPy microstructure is affected by current density in excess of 4 mA.cm-2 used in synthesis and results in MnO2 particle agglomeration that excludes open surface access reducing specific capacitance. Charge-discharge studies show stable capacitance retention for ∼1000 cycles. The redox performance of MnO2-pPy composite electrodes is suitable for application in the high energy density supercapacitors.
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