Gas Solubility and Vapor Pressure of Electrolytes Based on Alkylcarbonates Containing Litfsi, Lifap, and LiPF6 Lithium Salt: Measurement and Prediction

Most liquid electrolytes used in commercial lithium-ion batteries are composed by alkylcarbonate mixture containing lithium salt. The decomposition of these solvents by oxidation or reduction during cycling of the cell, induce generation of gases (CO2, CH4, C2H4, CO …) increasing of pressure in the sealed cell, which causes a safety problem [1]. The prior understanding of parameters, such as structure and nature of salt, temperature pressure, concentration, salting effects and solvation parameters, which influence gas solubility and vapor pressure of electrolytes is required to formulate safer and suitable electrolytes especially at high temperature.

We present in this work the CO2, CH4, C2H4, CO solubility in different pure alkyl-carbonate solvents (PC, DMC, EMC, DEC) and their binary or ternary mixtures as well as the effect of temperature and lithium salt LiX (X = LiPF6, LiTFSI or LiFAP) structure and concentration on these properties. Furthermore, in order to understand parameters that influence the choice of the structure of the solvents and their ability to dissolve gas through the addition of a salt, we firstly analyzed experimentally the transport properties (Self diffusion coefficient (D), fluidity (h-1), and conductivity (s) and lithium transport number (tLi) using the Stock-Einstein, and extended Jones-Dole equations [2]. Furthermore, measured data for the of CO2, C2H4, CH4 and CO solubility in pure alkylcarbonates and their mixtures containing LiPF6; LiFAP; LiTFSI salt, are reported as a function of temperature and concentration in salt. Based on experimental solubility data, the Henry’s law constant of gases in these solvents and electrolytes was then deduced and compared with values predicted by using COSMO-RS methodology within COSMOthermX software. From these results, the molar thermodynamic functions of dissolution such as the standard Gibbs energy, the enthalpy, and the entropy, as well as the mixing enthalpy of the solvents and electrolytes with the gases in its hypothetical liquid state were calculated and discussed [3]. Finally, the analysis of the CO2 solubility variations with the salt addition was then evaluated by determining specific ion parameters Hi by using the Setchenov coefficients in solution. This study showed that the gas solubility is entropy driven and can been influenced by the shape, charge density, and size of the anions in lithium salt.

References

[1] S.A. Freunberger, Y. Chen, Z. Peng, J.M. Griffin, L.J. Hardwick, F. Bardé, P. Novák, P.G. Bruce, Journal of the American Chemical Society 133 (2011) 8040-8047.

[2] P. Porion, Y.R. Dougassa, C. Tessier, L. El Ouatani, J. Jacquemin, M. Anouti, Electrochimica Acta 114 (2013) 95-104.

[3] Y.R. Dougassa, C. Tessier, L. El Ouatani, M. Anouti, J. Jacquemin, The Journal of Chemical Thermodynamics 61 (2013) 32-44.

Spectral analysis of four 'hypervariable' AGN: a micro-needle in the haystack?

We analyze four extreme AGN transients to explore the possibility that they are caused by rare, high-amplitude microlensing events. These previously unknown type-I AGN are located in the redshift range 0.6-1.1 and show changes of > 1.5 magnitudes in the g-band on a timescale of ~years. Multi-epoch optical spectroscopy, from the William Herschel Telescope, shows clear differential variability in the broad line fluxes with respect to the continuum changes and also evolution in the line profiles. In two cases a simple point-source, point-lens microlensing model provides an excellent match to the long-term variability seen in these objects. For both models the parameter constraints are consistent with the microlensing being due to an intervening stellar mass object but as yet there is no confirmation of the presence of an intervening galaxy. The models predict a peak amplification of 10.3/13.5 and an Einstein timescale of 7.5/10.8 years respectively. In one case the data also allow constraints on the size of the CIII] emitting region, with some simplifying assumptions, to to be ~1.0-6.5 light-days and a lower limit on the size of the MgII emitting region to be > 9 light-days (half-light radii). This CIII] radius is perhaps surprisingly small. In the remaining two objects there is spectroscopic evidence for an intervening absorber but the extra structure seen in the lightcurves requires a more complex lensing scenario to adequately explain.