Density Functional Theory (DFT) Study on the Ternary Interaction System of the Fluorinated Ethylene Carbonate, Li+ and Graphene Model

Abstract

Abstract:The ternary interaction system composed of fluorinated ethylene carbonate, denoted by EC(F), lithium ion (Li + ) and a model of nano-structured graphene has been investigated by means of the density functional theory (DFT) method. For comparison, fluorinated vinylene carbonate, denoted by VC(F), was also used. The model of graphene consisting of 14 benzene rings was examined as a nano-structured graphene. The effects of fluorine substitution on the electronic state and binding energy were investigated from a theoretical point of view. It was found that both EC(F) and VC(F) bind to a hexagonal site corresponding to the central benzene ring of the model of the graphene surface. The binding energies of Li + EC(F) and Li + VC(F) to the model of graphene decreased with increasing number of fluorine atoms (n).

Understanding the Role of Fluorination on the Interaction of Electrolytic Carbonates with Li+ through an Electronic Structure Approach

“…The HOMO and LUMO energy levels for both pristine and fluorinated carbonates have been summarised in Table S2 (see supporting information), and depicted in Figure for better understanding. Our results agree well with the earlier reports which have correlated the lowering of both the HOMO‐LUMO levels to substitution of hydrogen with fluorine ,,. In the fluorinated carbonates, both HOMO and LUMO are delocalised over the whole molecule with major localisation taking place on C=O and partial localisation on C−O bond, which is similar to that observed in the case of pristine carbonates.…”

“…We have extended our study towards the calculation of the electronic properties of pristine and fluorinated carbonates. Table lists the calculated values of their dipole moments and HOMO‐LUMO energy gap, which are in good agreement with earlier reports ,,. Detailed analysis of Table reveals that the cyclic pristine carbonates (EC, PC, BC, and VC) exhibit much higher dipole moment in comparison to acyclic pristine carbonates (DEC and EMC).…”

“…The propylene carbonate can also be directly fluorinated to form Trifluoropropylene carbonate (TFPC) . Several additional cyclic fluorinated carbonates such as Trifluorobutylene carbonate (TFBC) and Difluorovinyl carbonate (DFVC) have also been considered on the basis of their stability and ease of synthesis ,. The linear carbonates (EMC and DEC) provide stable fluorinated linear carbonates, namely, trifluoroethyl methyl carbonate (TFEMC), di‐trifluoroethyl carbonate (HFDEC), respectively .…”

“…The effect of the fluorine substituent on both the dipole moment and HOMO‐LUMO gap of fluorinated ethylene carbonate, vinylene carbonate and their interaction with Li + and Graphene model is studied by Shigeaki et. al . Recently, Andrzej et.al have studied the binding of Li + with fluorinated ethylene and diethyl carbonate solvent through change in vibrational spectra .…”

Reactions of Graphene Nano-Flakes in Materials Chemistry and Astrophysics

“…Hence, the interaction of GNFs with atomic hydrogen plays an important role in the initial reactions of chemical evolution in the universe. In the field of materials science, GNF is used as a model compound of graphene [14][15][16][17]. In this chapter, the mechanism of hydrogen addition to GNFs is introduced using the results from density functional theory (DFT) calculations.…”