Pickering emulsion polymerization of polyaniline/LiCoO2 nanoparticles used as cathode materials for lithium batteries

The oil in water (o/w) emulsions were prepared using aniline dissolved in toluene and LiCoO₂ particles as stabilizers (Pickering emulsions). Pickering emulsions are stabilized by adsorbed solid particles instead of emulsifier molecules. The mean droplet diameter of emulsions was controlled by the mass ratio M (oil)/M (solid particles). The emulsions showed great stability during 3 days. The composite materials containing LiCoO₂ and the conductive polymer polyaniline (PANI) have been prepared by means of polymerization of aniline emulsion stabilized by LiCoO₂ particles. The composite materials were characterized by nanosphere and nanofiber-like structures. The nanofiber-like morphology of the powdered material was distinctly different of the morphologies of the parent materials. The electrochemical reactivity of PANI/LiCoO₂ composites as positive electrode in a lithium battery was examined during lithium ion deinsertion and insertion by galvanostatic charge–discharge testing; PANI/LiCoO₂ (1:4) composite materials exhibited the best electrochemical performance by increasing the reaction reversibility and capacity compared to that of the pristine LiCoO₂ cathode. The first discharge capacity of PANI/LiCoO₂ (1:4) was 167 mAh/g, while that of LiCoO₂ was136 mAh/g.     

Monolith Passive Adsorbers Prepared with Hydrophobic Porous Silica Rods Coated with Hydrogel

This work focuses on the synthesis and characterization of porous silica monolith-based adsorbent materials. Materials with bimodal porosity (macro and meso) were prepared through a sol–gel process. The capacity of adsorption of organic molecules was ensured by grafting of hydrophobic organic coating on the silica surface. Alkylsilane chains or lauryl acrylate polymer were used for this purpose. The adsorption kinetic behavior of the produced materials was assessed through benzophenone adsorption studies in aqueous media. The results have shown that the macropore size of the monoliths had no effect on the adsorption capacity. The thicker organic layer prepared by polymerization of lauryl acrylate has decreased the adsorption kinetics without affecting the total adsorption capacity. The over-coating with additional external layer of hydrogel further slowed the diffusion of benzophenone thus better matches the passive-sampler requirements.     

Structural and electrochemical characterization of polyaniline/LiCoO2 nanocomposites prepared via a Pickering emulsion

Polyaniline (PANI)/LiCoO₂ nanocomposite materials are successfully ready through a solid-stabilized emulsion (Pickering emulsion) route. The properties of nanocomposite materials have been put to the test because of their possible relevance to electrodes of lithium batteries. Such nanocomposite materials appear thanks to the polymerization of aniline in Pickering emulsion stabilized with LiCoO₂ particles. PANI has been produced through oxidative polymerization of aniline and ammonium persulfate in HCl solution. The nanocomposite materials of PANI/LiCoO₂ could be formed with low amounts of PANI. The morphology of PANI/LiCoO₂ nanocomposite materials shows nanofibers and round-shape-like morphology. It was found that the morphology of the resulting nanocomposites depended on the amount of LiCoO₂ used in the reaction system. Ammonium persulfate caused the loss of lithium from LiCoO₂ when it was used at high concentration in the polymerization recipe. Highly resolved splitting of 006/102 and 108/110 peaks in the XRD pattern provide evidence to well-ordered layered structure of the PANI/LiCoO₂ nanocomposite materials with high LiCoO₂ content. The ratios of the intensities of 003 and 104 peaks were found to be higher than 1.2 indicating no pronounced mixing of the lithium and cobalt cations. The electrochemical reactivity of PANI/LiCoO₂ nanocomposites as positive electrode in a lithium battery was examined during lithium ion deinsertion and insertion by galvanostatic charge–discharge testing; PANI/LiCoO₂ nanocomposite materials exhibited better electrochemical performance by increasing the reaction reversibility and capacity compared to that of the pristine LiCoO₂ cathode. The best advancement has been observed for the PANI/LiCoO₂ nanocomposite 5 wt.% of aniline.     

Molecular Imprints Frozen by Strong Intermolecular Interactions in Place of Cross-Linking

A new way to freeze molecular imprints in a polymer material is reported. So far, molecular imprinted polymers (MIP) involve copolymerization of a functional monomer and large amounts of cross-linking agent, which keeps the template shape memory in rigid molecular imprints. MIP materials are prepared herein without cross-linking agent. Stiff chains of polyaniline grafted on a solid support as a brush-like material achieve the necessary rigidity. Differential adsorption to imprinted and non-imprinted materials provides evidence of molecular imprints. A correct adsorption isotherm for mobile adsorbed layers (Volmer isotherm) is introduced instead of the popular but inadequate Langmuir isotherm. Non-selective adsorption is entropic, whereas adsorption to molecular imprints has an enthalpic contribution coming from specific interactions. Fast adsorption kinetics are a definite benefit with regards to applications such as chromatographic separations and chemical sensors.     

Application of R.O.P. in polymerization of furanic oligoesters with cyclic esters: Synthesis,characterization and degradation

Furano-Aliphatic copolyesters, such as poly(propylene furanic)-co-(polycaprolactone) (PPF-co-PCL), Poly(propylene furanic)-co-(polylactide) (PPF-co-PLA) and Poly(propylene furanic)-co-(polyglycolide) (PPF-co-PGA) were prepared by ring opening polymerization (R.O.P.) using monomers derived from renewable resources. These copolyesters were characterized by ¹H-NMR, DSC and TGA. The degree of randomness determined by ¹H-NMR is close to 1, reflecting a random distribution, sometimes less than one. This indicates that these polyesters have a character to block. The hydrolytic degradation of polymers was performed at pH 4.35 at 37°C over a period of four weeks. The oxidative degradation proved a mass loss of about 50%.