ABSTRACT
Sulfur particles with a conductive polymer coating of poly(3,4-ethylene dioxythiophene) "PEDOT" were prepared by dielectric barrier discharge (DBD) plasma technology under atmospheric conditions (low temperature, ambient pressure). We report a solvent-free, low-cost, low-energy-consumption, safe, and low-risk process to make the material development and production compatible for sustainable technologies. Different coating protocols were developed to produce PEDOT-coated sulfur powders with electrical conductivity in the range of 10-8-10-5 S/cm. The raw sulfur powder (used as the reference) and (low-, optimum-, high-) PEDOT-coated sulfur powders were used to assemble lithium-sulfur (Li-S) cells with a high sulfur loading of â¼4.5 mg/cm2. Long-term galvanostatic cycling at C/10 for 100 cycles showed that the capacity fade was mitigated by â¼30% for the cells containing the optimum-PEDOT-coated sulfur in comparison to the reference Li-S cells with raw sulfur. Rate capability, cyclic voltammetry, and electrochemical impedance analyzes confirmed the improved behavior of the PEDOT-coated sulfur as an active material for lithium-sulfur batteries. The Li-S cells containing optimum-PEDOT-coated sulfur showed the highest reproducibility of their electrochemical properties. A wide variety of bulk and surface characterization methods including conductivity analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and NMR spectroscopy were used to explain the chemical features and the superior behavior of Li-S cells using the optimum-PEDOT-coated sulfur material. Moreover, postmortem [SEM and Brunauer-Emmett-Teller (BET)] analyzes of uncoated and coated samples allowed us to exclude any significant effect at the electrode scale even after 70 cycles.
ABSTRACT
Potassium doped titanium oxide (KTiOx) nanowires were prepared by the wet corrosion process (WCP) and their photocatalytic effects were systematically characterized. For the synthesis of KTiOx, the potassium hydroxide concentration of the WCP was varied in order to obtain nanostructures with different surface area and surface charge. Structural and crystalline properties of KTiOx were studied by means of X-ray diffraction, scanning and transmission electron microscopy. Chemical composition was determined by X-ray fluorescence and energy-dispersive X-ray analysis. Photocatalytic performance was investigated as a function of the surface area, pH, and crystalline structures by studying the degradation of methylene blue, cardiogreen, and azorubine red dyes upon UV irradiation. The negatively charged crystalline KTiOx nanostructures with high surface area showed significantly higher photocatalytic degradation compared to their TiOx counterpart. They also showed high efficiency for recovery and re-use. Annealing KTiOx nanostructures improved structural properties leading to well-ordered layered structures and improved photocatalysis. However, annealing at temperatures higher than 600 °C yielded formation of rutile grains at the surface of nanowires, significantly affecting the photocatalytic performance. We believe that KTiOx nanostructures produced by WCP are very promising for photocatalysis, especially due to their high photocatalytic efficiency as well as their potential for re-use and durability.
ABSTRACT
Electrolytes consisting of sodium bis(fluorosulfonyl)imide (NaFSI) dissolved in glymes (monoglyme, diglyme, and triglyme) were characterized by FT-Raman spectroscopy and 13C, 17O, and 23Na NMR spectroscopy. The glyme:NaFSI molar ratio was varied from 50:1 to 1:1, and it was observed that, in the dilute electrolytes, the sodium salt is completely dissociated into solvent separated ion pairs (SSIPs). However, contact ion pairs (CIPs) and aggregates (AGGs) become the predominant species in more concentrated solutions. Some of the electrolytes with the highest concentrations can be classified as solvate ionic liquids (SILs), where all of the solvent molecules are coordinated to sodium cations. Therefore, these electrolytes are fundamentally different from more dilute electrolytes which are typically used in commercially available secondary batteries. The melting point or glass transition temperature, dynamic viscosity, density, sodium concentration, and ionic conductivity of these solvate ionic liquids are reported as well as the crystal structures of [Na(G3)][FSI] and [Na(G3)2][FSI]. Galvanostatic cycling experiments were performed in coin-type cells with a Na2/3[Mn0.55Ni0.30Co0.15]O2 cathode to study the influence of these electrolytes on the electrochemical stability and charge/discharge behavior.
ABSTRACT
We report the vibrational properties of sulfonated poly(ether ether ketone) (SPEEK) membranes, used as electrolytes in proton exchange membrane (PEM) fuel cells, studied by Fourier transform infrared (FTIR) spectroscopy. We discuss the changes in the vibrational modes of the functional groups present in the polymer arising due to the sulfonation process and the subsequent incorporation of silica particles functionalized with sulfonic acid group. From the infrared spectra, we confirm the incorporation of sulfonic acid group in the polymer chain as well as in the functionalized silica particles. We have also measured the variations in the peak area ratio of the characteristic out-of-plane vibrations of the aromatic rings in the PEEK polymer at 1280cm(-1) with respect to a reference peak at 1305cm(-1). These values were correlated to the crystallinity (XC) values experimentally determined by DSC technique, providing a non-destructive means to calculate the crystallinity of polymer membranes. The calculated XC values were in good agreement with the experimental values. The crystallinity was observed to decrease with increasing degree of sulfonation (DS), indicating the crystalline-to-amorphous phase modification of the polymer by sulfonation, which along with the enhanced ion-exchange capacity and water uptake, is responsible for the improved ionic conductivity at higher DS values.
