Microscopic interactions in nanocomposite electrolytes

Nanocomposite electrolytes of a fully amorphous trifunctional polyether (3PEG) and poly- (methylene ethylene oxide) (PMEO) have been complexed with two lithium salts and nanoparticulate (~20 nm) fillers of TiO2 and Al2O3. Addition of the fillers to the polymer salt complexes shows a significant change in the conformational modes of both polymers, especially the D-LAM region between 200 and 400 cm-1, indicating a reduced segmental flexibility of the chain. These changes are more pronounced with the use of TiO2 than Al2O3. Incorporation of the nanoparticulate fillers to the electrolytes fails to influence the degree of ion association, suggesting that the number of charge carriers available for conduction in both polymers using both LiClO4 and LiCF3SO3 is not the source of any conductivity increase. Addition of the fillers, which was seen to increase the conductivity in PEO-based systems, generally lowers the conductivity in the present PMEO systems, while the addition of TiO2 has little or no effect except in the cases of 3PEG 1.5 and 1.25 mol/kg LiClO4. In this case, 10 wt % TiO2 provides a conductivity increase of half an order of magnitude at approximately 60 °C. We also report for the first time a Raman spectroscopy investigation into the PEO-based nanocomposite electrolytes. The present results are discussed in terms of the electrostatic interactions involving dielectric properties of the fillers, of special interest being the interactions between the polymer and the fillers and between the ionic species and the fillers, when the effect of crystallization can be ignored.

Conductivity in amorphous polyether nanocomposite materials

Using a completely amorphous polyether we have investigated the effect of the inclusion of a nano-particulate filler on a polymer electrolyte. Nano-sized TiO₂ is shown not to significantly affect the conductivity of composite electrolytes containing 1.0 or 1.25 mol/kg LiClO₄ or 1.5 or 2.0 mol/kg LiTFSI. At 1.5 mol/kg LiClO₄ a significant increase in conductivity is observed. Raman spectroscopy experiments have been used to investigate the effect of filler on ion-aggregation. Only one new vibrational mode can be assigned to the composite which is not due to the polymer electrolyte or the filler. From this work, we believe the increased conductivity observed by previous researchers as a result of filler addition may be largely attributed to the effect on the degree of crystallinity along with some disruption of ion-aggregation by the fillers in PEO based electrolytes.

Ionic conductivity studies of polymeric electrolytes containing lithium salt with plasticizer

New plasticized polymer electrolytes were synthesized based on poly ethylene oxide (PEO), Poly (N,N-dimethylamino-ethyl-methacrylate) (PDMAEMA), LiN(CF₃SO₂)₂ (LITFSI) as the salt and tetraethylene glycol dimethyl ether(tetraglyme) and EC + PC as plasticizers. The preparation and characterization of the polymer electrolytes were investigated as a function of temperature and various concentrations of LITFSI. Impedance spectroscopy and differential scanning calorimeter (DSC) were used to characterize the effects of various temperature, lithium salt concentration and two plasticizers on conductivity. The complex of PDMAEMA/PEO/LiTFSI/tetraglyme (S2) exhibits higher conductivity (4.74 × 10⁻⁴ S cm⁻¹at 25 °C) than PDMAEMA/PEO/LiTFSI/EC + PC (S1).

Visible transparent, UV-blocking polymer nanocomposite films containing nano-sized organic-LDH (Layered Double Hydroxide) hybrid

A nano-sized Mg2Al layered double hydroxide (LDH) was used for encapsulating an organic UV absorber, 2-hydroxy-4- methoxybenzeophenone-5-sulfonic acid (HMBS), to produce HMBS@LDH hybrid nano-platelets. Upon dispersing this organic-inorganic hybrid LDH into ethylene-vinyl alcohol copolymer (EVOH) for film casting, a thin polymer
nanocomposite film that is UV opaque but highly transparent to visible light (higher than 90%) was formed. Thermogravimetry (TG) analysis confirmed that the intercalation of HMBS into LDH considerably increased the thermal stability of HMBS. Such an improvement was attributed to the strong guest-host interaction between the HMBS anions and the LDH layers. Also, the nanocomposite films were flexible and had good mechanical properties.

Synthesis of silica-coated ZnO nanocomposite : the resonance structure of polyvinyl pyrrolidone (PVP) as a coupling agent

Abstract The preparation of silica-coated ZnO nanocomposite using polyvinyl pyrrolidone (PVP) as a coupling agent was investigated. Transmission electron microscopy analysis revealed that silica has been deposited on the surface of PVP-capped ZnO nanoparticles as a continuous thin layer. Two-dimensional correlation analysis based on the time-dependent UV–vis spectra was introduced to study the interaction governing the deposition of silica on to PVP-capped ZnO. Strong hydrogen bonds formed between the amphiphilic PVP molecules and silica in the silicacoated PVP-capped ZnO composites. The reduced photocatalytic activity of silica-coated ZnO nanoparticles will enhance their performance as durable, safe, and nonreactive UV blockers in plastics, paints, and coating for outdoor textile and timber products.

Ionic liquid-assisted synthesis of polyaniline/gold nanocomposite and its biocatalytic application

In this report, a novel chemical synthesis of polyaniline/gold nanocomposite is explored using ionic liquid (IL) 1-Butyl-3-methylimidazolium hexafluorophosphate. The direct chemical synthesis of polyaniline/gold nanocomposite was initiated via the spontaneous oxidation of aniline by AuCl4 − in IL. A nearly uniform dispersion of polyaniline/Au particles with a diameter of 450 ± 80 nm was produced by this method, which indicates that this method is more suitable for controlling particle dimensions. It was also found that the electrical conductivity of the polyaniline/gold nanocomposite was more than 100 times higher than that of the pure polyaniline nanoparticles. The polyaniline/gold nanocomposite displays superior function in the biocatalytic activation of microperoxidase-11 because of the high surface area of the assembly and the enhanced charge transport properties of the composite material. We also report the possible application of polyaniline/gold nanocomposite as a H2O2 biosensor.

Shear-enhanced solution precipitation : a simple process to produce short polymeric nanofibers

The growing interest in polymeric nanofibers has been increasing the push for the development of simple and efficient nanofiber-preparation techniques. We herein describe how a conventional solution process is readapted to suit the needs for fast and efficient production of short polymeric nanofibers. Poly(ethylene-co-acrylic acid) (PEAA), a semi-crystalline polymer, was used as model. When a PEAA solution was injected into an alcoholic non-solvent while simultaneously applying high shear to the non-solvent system, PEAA nanofibers were obtained with average diameter as thin as 113 nm and length as short as 4.5 _m. The fiber diameter and length were also adjustable by varying the operating parameters. This one-step technique advances the currently available nanofabrication tools by adjusting a widely accepted concept to the nano-scale. It may constitute a viable method for large-scale production of short polymeric nanofibers.

One-dimensional polyelectrolyte/polymeric semiconductor core/shell structure : sulfonated poly(arylene ether ketone)/polyaniline nanofibers for organic field-effect transistors

A polyelectrolyte/polymeric semiconductor core/shell structure is developed for organic field-effect transistors (OFETs) based on sulfonated poly(arylene ether ketone)/polyaniline core/shell nanofibers via electrospinning and solution-phase selective polymerization. The polyelectrolyte does not work as a gate dielectric, but can provide an internal modulation from the nanointerface of the 1D core/shell nanostructure. The transistor devices display very high mobilities.

Polymeric materials with ordered nanostructures templated from hexagonal lyotropic liquid crystals

In this study, successful methods have been established to retain the ordered nanostructures in polymer materials templated from hexagonal lyotropic liquid crystals, which potentially renders broad applications as biomedical and membrane materials.