A Theoretical Model for Computing Freezing Point Depression of Lithium-Ion Battery Electrolytes

Reliable prediction of freezing point depression in liquid electrolytes will accelerate the development of improved Li-ion batteries which can operate in low temperature environments. In this work we establish a computational methodology to calculate activity coefficients and liquidus lines for battery-relevant liquid electrolytes. Electronic structure methods are used in conjunction with classical molecular dynamics simulations and theoretical expressions for Born solvation energy, ion-atmosphere effects from Debye-Hückel theory and solvent entropic effects. The framework uses no a priori knowledge beyond neat solvent properties and the concentration of salt. LiPF 6 in propylene carbonate (PC), LiPF 6 in dimethyl carbonate (DMC) and LiClO4 in DMC are investigated up to 1 molal with accuracy better than 3◦C when compared to experimental freezing point measurements. We find that the difference in freezing point depression between the propylene carbonate-based electrolyte and the dimethyl cabonate electrolytes originates from the difference in the solvent dielectric constant.

Solid-liquid Equilibrium in the System 2-Keto-L-gulonic Acid + Sodium-2-keto-L-gulonate + Water

The solid-liquid equilibrium (SLE) in the ternary system 2-keto-L-gulonic acid (HKGA) + sodium-2-keto-L-gulonate (NaKGA) + water was studied experimentally at temperatures between 275 and 313 K and ambient pressure. At these conditions, HKGA and NaKGA precipitate as monohydrates: HKGA H2O and NaKGA H2O, respectively. Phase diagrams with one eutonic point are found for all temperatures. A thermodynamic model of the SLE that is based on an extended version of the Debye-Hückel theory was developed and the dissociation constant of HKGA as well as the solubility products of HKGA H2O and NaKGA H2O were determined. The agreement between the experimental data and the results from the model is excellent.

DOPANT EFFECT ON PHENALENE BANDGAP CONTROL: A HÜCKEL MOLECULAR ORBITAL PERSPECTIVE

In this study, we investigate the effects of nitrogen and boron dopants on the properties of phenalene/phenalenyl systems based on the Hückel theory by using the Hueckel Molecular Orbital software. The dopants configurations are graphitic, pyridinic, and pyrrolic. The electronic configuration of bare phenalene confirms the delocalization of π electrons and the radical properties of the molecule, which is in good agreement with the results of previous studies. Dopant types and positions strongly affect the number of π electrons in the system, molecular orbital energy, total energy, average π-electron energy, and gap energy. The molecular energy level degeneracy strongly depends on the rotational symmetry of the system, in the order of graphitic, pyridinic, and pyrrolic. A preserved radical behavior and the number of π electrons are found for the pyridinic dopant type, while closed electronic configuration is observed for graphitic and pyrrolic types. A lower gap energy is typically found for B-doped phenalene compared to that for N-doped phenalene; this opens the possibility for the enhancement of photoluminescence intensity. This study, although qualitative, confirms the effects of dopants on the chemical and physical properties of phenalene/phenalenyl systems.