Fernanda F. C. Bazito

Transport Coefficients, Raman Spectroscopy, and Computer Simulation of Lithium Salt Solutions in an Ionic Liquid

Lithium salt solutions of Li(CF3SO2)2N, LiTFSI, in a room-temperature ionic liquid (RTIL), 1-butyl-2,3-dimethyl-imidazolium cation, BMMI, and the (CF3SO2)2N(-), bis(trifluoromethanesulfonyl)imide anion, [BMMI][TFSI], were prepared in different concentrations. Thermal properties, density, viscosity, ionic conductivity, and self-diffusion coefficients were determined at different temperatures for pure [BMMI][TFSI] and the lithium solutions. Raman spectroscopy measurements and computer simulations were also carried out in order to understand the microscopic origin of the observed changes in transport coefficients. Slopes of Walden plots for conductivity and fluidity, and the ratio between the actual conductivity and the Nernst-Einstein estimate for conductivity, decrease with increasing LiTFSI content. All of these studies indicated the formation of aggregates of different chemical nature, as it is corroborated by the Raman spectra. In addition, molecular dynamics (MD) simulations showed that the coordination of Li+ by oxygen atoms of TFSI anions changes with Li+ concentration producing a remarkable change of the RTIL structure with a concomitant reduction of diffusion coefficients of all species in the solutions.

Cathodes for lithium ion batteries: the benefits of using nanostructured materials

Commercially available lithium ion cells, which are the most advanced among rechargeable batteries available so far, employ microcrystalline transition metal oxides as cathodes, which function as Li insertion hosts. In search for better electrochemical performance the use of nanomaterials in place of these conventional ones has emerged as excellent alternative. In this review we present a brief introduction about the motivations to use nanostructured materials as cathodes in lithium ion batteries. To illustrate such advantages we present some examples of research directed toward preparations and electrochemical data of the most used cathodes in nanoscale, such as LiCoO2, LiMn2O4, LiMnO2, LiV2O5 e LiFePO4.

Shielding of Ionic Interactions by Sulfur Dioxide in an Ionic Liquid

The effect of adding SO2 on the structure and dynamics of 1-butyl-3-methylimidazolium bromide (BMIBr) was investigated by low-frequency Raman spectroscopy and molecular dynamics (MD) simulations. The MD simulations indicate that the long-range structure of neat BMIBr is disrupted resulting in a liquid with relatively low viscosity and high conductivity, but strong correlation of ionic motion persists in the BMIBr-SO2 mixture due to ionic pairing. Raman spectra within the 5<omega<200 cm(-1) range at low temperature reveal the short-time dynamics, which is consistent with the vibrational density of states calculated by MD simulations. Several time correlation functions calculated by MD simulations give further insights on the structural relaxation of BMIBr-SO2.

Electrostatic Layer-by-Layer Deposition and Electrochemical Characterization of Thin Films Composed of MnO2 Nanoparticles in a Room-Temperature Ionic Liquid

Thin films of MnO(2) nanoparticles were grown using the layer-by-layer method with poly(diallyldimetylammonium) as the intercalated layer. The film growth was followed by UV-vis, electrochemical quartz crystal microbalance (EQCM), and atomic force microscopy. Linear growth due to electrostatic immobilization of layers was observed up to 30 bilayers, but electrical connectivity was maintained only for 12 MnO(2)/PPDA bilayers. The electrochemical characterization of this film in 1-butyl-2,3-dimethyl-imidazolium (BMMI) bis(trifluoromethanesulfonyl)imide (TFSI) (BMMITFSI) with and without addition of a lithium salt indicated a higher electrochemical response of the nanostructured electrode in the lithium-containing electrolyte. On the basis of EQCM experiments, it was possible to confirm that the charge compensation process is achieved mainly by the TFSI anion at short times (<2 s) and by BMMI and lithium cations at longer times. The fact that large ions like TFSI and BMMI participate in the electroneutrality is attributed to the redox reaction that occurs at the superficial sites and to the high concentration of these species compared to that of lithium cations.