The electrooxidation of ascorbic acid (H2A), which does not occur on a bare Ni electrode, has been shown to take place on a polyaniline (PANI)-coated Ni electrode in aqueous electrolytes of a wide pH range. The characteristic voltammetric peak of PANI in 0.1 M H2SO4 at 0.2 V vs SCE corresponding to the transformation of leucoemeraldine to emeraldine gradually diminishes with an increase in concentration of H2A as a result of adsorption. This peak disappears before the appearance of another peak corresponding to the oxidation of H2A at a concentration of 1 mM. The irreversible oxidation current of H2A exhibits a linear dependence on the concentration. The effect of adsorption of H2A on PANI has been shown to increase the voltammetric peak current. A study on the variation of the PANI thickness and its influence on the voltammetric oxidation of H2A has led to an optimum thickness of 1.6 microm. The oxidation currents on the porous PANI/Ni electrode have been found to be several times higher at lower potentials in comparison with the data of a Pt electrode. The reaction has also been studied by ac impedance spectroscopy. In alkaline electrolytes, the Nyquist impedance plot is characterized by two semicircles instead of a single semicircle in acidic electrolytes. Thus, Ni, which is a non-platinum metal, has been found to be useful, by surface modification with PANI, for electrooxidation of H2A. The data are reproducible in the electrolytes of a wide pH range, thus suggesting a good stability, reusability and a long life for the PANI/Ni electrodes.
In the pursuit to develop practical sodium-ion batteries, safe negative insertion (anode) materials are essential. Recently, Na2Ti6O13 has been unveiled by conventional solid-state synthesis as a 0.85 V anode with 1-dimensional Na+ diffusion pathways. Here, an energy-savvy autocombustion synthesis has been successfully implemented to produce the target compound Na2Ti6O13 by restricting the annealing duration within 2 h. This drastic reduction in heat-treatment time involves minimal grain-growth hence forming homogeneous nanostructured particles (∼100 nm). It benchmarks the shortest synthesis of Ti-based anodes for sodium-ion batteries. The current work describes various aspects of autocombustion route. The as-prepared compound delivers near theoretical capacity (ca. 40 mAh g−1) involving a Ti4+/Ti3+ redox potential centered at 0.83 V (vs. Na/Na+) with excellent reversibility. Using both experiment and bond valence site energy (BVSE) modeling, the electrochemical, Na+ diffusion pathways and corresponding energy barriers have been explained.
Achieving high energy density has been the focus of research in rechargeable batteries. Lithiumsulfur system is attractive due to its high theoretical energy density (2500 Wh kg-1). The major problem in Li-S system is associated with the dissolution of lithium polysulfides formed at the cathode during discharge. Shuttling of polysulfides between the cathode and anode during cycling reduces the efficiency of cycling. In the present study, TiO2 nanotubes are prepared from nanoparticles by hydrothermal route. Titania-sulfur composite has been prepared by infiltrating sulfur solution into the TiO2 nanotubes and studied as a cathode material in a non-aqueous electrolyte. Cycling behavior of Li-S cells fabricated using pristine sulfur and TiO2 nanoparticle-sulfur composite is also studied for comparison. Cells with TiO2 nanotubes exhibit better discharge capacity and coulombic efficiency than the cells with TiO2 nanoparticles and pristine sulfur.
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