Thermodynamics Research Center / ThermoML | Journal of Chemical Thermodynamics

Low pressure carbon dioxide solubility in lithium-ion batteries based electrolytes as a function of temperature. Measurement and prediction

Dougassa, Y. R.[Yvon Rodrigue], Tessier, C.[Cecile], Ouatani, L. E.[Loubna El], Anouti, M.[Meriem], Jacquemin, J.[Johan]
J. Chem. Thermodyn. 2013, 61, 32-44
ABSTRACT
We present in this study the effect of nature and concentration of lithium salt, such as the lithium hexafluorophosphate, LiPF6; lithium tris(pentafluoroethane)-trifluorurophosphate LiFAP; lithium bis(trifluoromethylsulfonyl) imide, LiTFSI, on the CO2 solubility in four electrolytes for lithium ion batteries based on pure solvent that include ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), as well as, in the EC:DMC, EC:EMC and EC:DEC (50:50) wt.% binary mixtures as a function of temperature from (283 to 353) K and atmospheric pressure. Based on experimental solubility values, the Henry s law constant of the carbon dioxide in these solutions with the presence or absence of lithium salt was then deduced and compared with reported values from the literature, as well as with those predicted by using COSMO-RS methodology within COSMOThermX software. From this study, it appears that the addition of 1 mol dm 3 LiPF6 salt in alkylcarbonate solvents decreases their CO2 capture capacity. By using the same experimental conditions, an opposite CO2 solubility trend was generally observed in the case of the addition of LiFAP or LiTFSI salts in these solutions. Additionally, in all solutions investigated during this work, the CO2 solubility is greater in electrolytes containing the LiFAP salt, followed by those based on the LiTFSI case. The precision and accuracy of the experimental data reported therein, which are close to (1 and 15)%, respectively. From the variation of the Henry s law constant with temperature, the partial molar thermodynamic functions of dissolution such as the standard Gibbs energy, the enthalpy, and the entropy, as well as the mixing enthalpy of the solvent with CO2 in its hypothetical liquid state were calculated. Finally, a quantitative analysis of the CO2 solubility evolution was carried out in the EC:DMC (50:50) wt.% binary mixture as the function of the LiPF6 or LiTFSI concentration in solution to elucidate how ionic species modify the CO2 solubility in alkylcarbonatesbased Li-ion electrolytes by investigating the salting effects at T = 298.15 K and atmospheric pressure.
Compounds
# Formula Name
1 C3H4O3 ethylene carbonate
2 C3H6O3 dimethyl carbonate
3 C4H8O3 ethyl methyl carbonate
4 C5H10O3 diethyl carbonate
5 F6LiP lithium hexafluorophosphate
6 C2F6LiNO4S2 lithium bis((trifluoromethyl)sulfonyl)amide
7 C6F18LiP lithium trifluorotris(perfluoroethyl)phosphate
8 CO2 carbon dioxide
Datasets
The table above is generated from the ThermoML associated json file (link above). POMD and RXND refer to PureOrMixture and Reaction Datasets. The compound numbers are included in properties, variables, and phases, if specificied; the numbers refer to the table of compounds on the left.
Type Compound-# Property Variable Constraint Phase Method #Points
  • POMD
  • 1
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 2
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 3
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 4
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 1
  • 8
  • 5
  • Mole fraction - 8 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Solvent: Amount concentration (molarity), mol/dm3 - 5; Liquid
  • Liquid
  • Gas
  • Titration method
  • 4
  • POMD
  • 1
  • 8
  • 6
  • Mole fraction - 8 ; Liquid
  • Temperature, K; Liquid
  • Solvent: Amount concentration (molarity), mol/dm3 - 6; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Gas
  • Titration method
  • 4
  • POMD
  • 8
  • 2
  • 5
  • Mole fraction - 8 ; Liquid
  • Temperature, K; Liquid
  • Solvent: Amount concentration (molarity), mol/dm3 - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Gas
  • Titration method
  • 5
  • POMD
  • 8
  • 2
  • 6
  • Mole fraction - 8 ; Liquid
  • Temperature, K; Liquid
  • Solvent: Amount concentration (molarity), mol/dm3 - 6; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Gas
  • Titration method
  • 5
  • POMD
  • 8
  • 5
  • 3
  • Mole fraction - 8 ; Liquid
  • Temperature, K; Liquid
  • Solvent: Amount concentration (molarity), mol/dm3 - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Gas
  • Titration method
  • 5
  • POMD
  • 8
  • 6
  • 3
  • Mole fraction - 8 ; Liquid
  • Temperature, K; Liquid
  • Solvent: Amount concentration (molarity), mol/dm3 - 6; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Gas
  • Titration method
  • 5
  • POMD
  • 4
  • 8
  • 5
  • Mole fraction - 8 ; Liquid
  • Temperature, K; Liquid
  • Solvent: Amount concentration (molarity), mol/dm3 - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Gas
  • Titration method
  • 5
  • POMD
  • 4
  • 8
  • 6
  • Mole fraction - 8 ; Liquid
  • Temperature, K; Liquid
  • Solvent: Amount concentration (molarity), mol/dm3 - 6; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Gas
  • Titration method
  • 5
  • POMD
  • 1
  • 2
  • Mass density, kg/m3 ; Liquid
  • Mass fraction - 1; Liquid
  • Pressure, kPa; Liquid
  • Temperature, K; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 1
  • 3
  • Mass density, kg/m3 ; Liquid
  • Mass fraction - 1; Liquid
  • Pressure, kPa; Liquid
  • Temperature, K; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 1
  • 4
  • Mass density, kg/m3 ; Liquid
  • Mass fraction - 1; Liquid
  • Pressure, kPa; Liquid
  • Temperature, K; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 1
  • 5
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Amount concentration (molarity), mol/dm3 - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 1
  • 6
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Amount concentration (molarity), mol/dm3 - 6; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 2
  • 5
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Amount concentration (molarity), mol/dm3 - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 2
  • 6
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Amount concentration (molarity), mol/dm3 - 6; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 5
  • 3
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Amount concentration (molarity), mol/dm3 - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 6
  • 3
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Amount concentration (molarity), mol/dm3 - 6; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 4
  • 5
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Amount concentration (molarity), mol/dm3 - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 4
  • 6
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Amount concentration (molarity), mol/dm3 - 6; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 1
  • 2
  • 7
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Amount concentration (molarity), mol/dm3 - 7; Liquid
  • Solvent: Mass fraction - 1; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 1
  • 2
  • 5
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Amount concentration (molarity), mol/dm3 - 5; Liquid
  • Solvent: Mass fraction - 1; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 1
  • 2
  • 6
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Amount concentration (molarity), mol/dm3 - 6; Liquid
  • Solvent: Mass fraction - 1; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 1
  • 7
  • 3
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Amount concentration (molarity), mol/dm3 - 7; Liquid
  • Solvent: Mass fraction - 1; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 1
  • 5
  • 3
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Amount concentration (molarity), mol/dm3 - 5; Liquid
  • Solvent: Mass fraction - 1; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 1
  • 6
  • 3
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Amount concentration (molarity), mol/dm3 - 6; Liquid
  • Solvent: Mass fraction - 1; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 1
  • 4
  • 7
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Amount concentration (molarity), mol/dm3 - 7; Liquid
  • Solvent: Mass fraction - 1; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 1
  • 4
  • 5
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Amount concentration (molarity), mol/dm3 - 5; Liquid
  • Solvent: Mass fraction - 1; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 1
  • 4
  • 6
  • Mass density, kg/m3 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Amount concentration (molarity), mol/dm3 - 6; Liquid
  • Solvent: Mass fraction - 1; Liquid
  • Liquid
  • Pycnometric method
  • 1
  • POMD
  • 1
  • 8
  • 2
  • Mole fraction - 8 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Solvent: Mass fraction - 1; Liquid
  • Liquid
  • Gas
  • Titration method
  • 5
  • POMD
  • 1
  • 8
  • 3
  • Mole fraction - 8 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Solvent: Mass fraction - 1; Liquid
  • Liquid
  • Gas
  • Titration method
  • 5
  • POMD
  • 1
  • 4
  • 8
  • Mole fraction - 8 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Solvent: Mass fraction - 1; Liquid
  • Liquid
  • Gas
  • Titration method
  • 5