3 resultados para Carbonates
Resumo:
We present in this work a comparative study on density and transport properties, such as the conductivity (sigma), viscosity (eta) and self-diffusion coefficients (D), for electrolytes based on the lithium hexafluorophosphate, LiPF6; or on the lithium tris(pentafluoroethane)-trifluorophosphate, LiFAP dissolved in a binary mixture of ethylene carbonate (EC) and dimethylcarbonate (DMC) (50:50 wt%). For each electrolyte, the temperature dependence on transport properties over a temperature range from 10 to 80 degrees C and 20 to 70 degrees C for viscosity and conductivity, respectively, exhibits a non-Arrhenius behavior. However, this dependence is correctly correlated by using the Vogel-Tamman-Fulcher (VTF) type fitting equation. In each case, the best-fit parameters, such as the pseudo activation energy and ideal glass transition temperature were then extracted. The self-diffusion coefficients (D) of the Li+ cation and PF6- or FAP(-) anions species, in each studied electrolyte, were then independently determined by observing Li-3, F-19 and P-31 nuclei with the pulsed-gradient spin-echo (PGSE) NMR technique over the same temperature range from 20 to 80 degrees C. Results show that even if the diffusion of the lithium cation is quite similar in both electrolytes, the anions diffusion differs notably. In the case of the LiPF6-based electrolyte, for example at T approximate to 75 degrees C (high temperature), the self-diffusion coefficients of Li+ cations in solution (D (Li+)approximate to 5 x 10(-19) m(2) s(-1)) is 1.6 times smaller than that of PF6- anions (D (PF6-) = 8.5 x 10(-19) m(2) s(-1)), whereas in the case of the LiFAP-based electrolyte, FAP(-) anions diffuse at same rate as the Li+ cations (D (FAP(-)) = 5 x 10(-1) m(2) s(-1)). Based on these experimental results, the transport mobility of ions were then investigated through Stokes-Einstein and Nernst-Einstein equations to determine the transport number of lithium t(Li)(+), effective radius of solvated Li+ and of PF6- and FAP(-) anions, and the degree of dissociation of these lithium salts in the selected EC/DMC (50:50 wt%) mixture over a the temperature range from 20 to 80 degrees C. This study demonstrates the conflicting nature of the requirements and the advantage of the well-balanced properties as ionic mobility and dissociation constant of the selected electrolytes. (C) 2013 Elsevier Ltd. All rights reserved.
Resumo:
In this paper, we have reported the CO2 solubility in different pure alkyl carbonate solvents (EC, DMC, EMC, DEC) and their binary mixtures as EC/DMC, EC/EMC, and EC/DEC and for electrolytes [solvent + lithium salt] LiX (X = LiPF6, LiTFSI, or LiFAP) as a function of the temperature and salt concentration. To understand the parameters that influence the structure of the solvents and their ability to dissolve CO2, through the addition of a salt, we first analyzed the viscosities of EC/DMC + LiX mixtures by means of a modified Jones–Dole equation. The results were discussed considering the order or disorder introduced by the salt into the solvent organization and ion solvation sphere by calculating the effective solute ion radius, rs. On the basis of these results, the analysis of the CO2 solubility variations with the salt addition was then evaluated and discussed by determining specific ion parameters Hi by using the Setchenov coefficients in solution. This study showed that the CO2 solubility has been affected by the shape, charge density, and size of the ions, which influence the structuring of the solvents through the addition of a salt and the type of solvation of the ions.
