Skip to main content
SpringerLink
Log in

Solvation of the fluorine containing anions and their lithium salts in propylene carbonate and dimethoxyethane

  • Original Paper
  • Published:
Journal of Molecular Modeling Aims and scope Submit manuscript

Abstract

Electrolyte solutions based on the propylene carbonate (PC)-dimethoxyethane (DME) mixtures are of significant importance and urgency due to emergence of lithium-ion batteries. Solvation and coordination of the lithium cation in these systems have been recently attended in detail. However, analogous information concerning anions (tetrafluoroborate, hexafluorophosphate) is still missed. This work reports PM7-MD simulations (electronic-structure level of description) to include finite-temperature effects on the anion solvation regularities in the PC-DME mixture. The reported result evidences that the anions appear weakly solvated. This observation is linked to the absence of suitable coordination sites in the solvent molecules. In the concentrated electrolyte solutions, both BF4 − and PF6 − prefer to exist as neutral ion pairs (LiBF4, LiPF6).

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Barthel J, Gores HJ, Neueder R, Schmid A (1999) Electrolyte solutions for technology — new aspects and approaches. Pure Appl Chem 71:1705–1715

  2. Ganesh P, Jiang DE, Kent PRC (2011) Accurate static and dynamic properties of liquid electrolytes for li-ion batteries from ab initio molecular dynamics. J Phys Chem B 115:3085–3090

  3. Borodin O, Smith GD (2009) Quantum chemistry and molecular dynamics simulation study of dimethyl carbonate: ethylene carbonate electrolytes doped with Lipf6. J Phys Chem B 113:1763–1776

  4. Singh HJ, Mukherjee U (2013) A computational approach to design energetic ionic liquids. J Mol Model 19:2317–2327

  5. Zhang Q, Zhang X, Zhao DX (2013) Ion disturbance and clustering in the NaCl water solutions. J Mol Model 19:661–672

  6. Lai WP, Lian P, Liu YZ, Yu T, Zhu WL, Ge ZX, Lv J (2014) Design and theoretical study of 15 novel high energy density compounds. J Mol Model 20:2479

  7. Zhu XY, Sun H, Zhang DJ, Liu CB (2011) Theoretical study on the interactions between methanol and imidazolium-based ionic liquids. J Mol Model 17:1997–2004

  8. Darvas M, Jorge M, Cordeiro MNDS, Jedlovszky P (2011) Solvation free energy profile of the Scn- ion across the water-1,2-dichloroethane liquid/liquid interface. A computer simulation study. J Phys Chem C 115:11140–11146

  9. Gulaboski R, Pereira CM, Cordeiro MNDS, Bogeski I, Ferreira E, Ribeiro D, Chirea M, Silva AF (2005) Electrochemical study of ion transfer of acetylcholine across the interface of water and a lipid-modified 1,2-dichloroethane. J Phys Chem B 109:12549–12559

  10. Videa M, Xu W, Geil B, Marzke R, Angell CA (2001) High Li+ self-diffusivity and transport number in novel electrolyte solutions. J Electrochem Soc 148:A1352–A1356

  11. Sun X, Lee HS, Yang XQ, McBreen J (2002) A New Additive for Lithium Battery Electrolytes Based on an Alkyl Borate Compound. J Electrochem Soc 149:A355–A359

  12. Soetens JC, Millot C, Maigret B (1998) Molecular new additive for lithium battery electrolytes based on an alkyl borate compound. J Phys Chem A 102:1055–1061

  13. Azeez F, Fedkiw PS (2010) Conductivity of Libob-Based Electrolyte for Lithium-Ion Batteries. J Power Sources 195:7627–7633

  14. Postupna OO, Kolesnik YV, Kalugin ON, Prezhdo OV (2011) Microscopic structure and dynamics of Libf4 solutions in cyclic and linear carbonates. J Phys Chem B 115:14563–14571

  15. Barthel J, Neueder R, Roch H (2000) Density, relative permittivity, and viscosity of propylene carbonate plus dimethoxyethane mixtures from 25 degrees C to 125 degrees C. J Chem Eng Data 45:1007–1011

  16. Kameda Y, Umebayashi Y, Takeuchi M, Wahab MA, Fukuda S, Ishiguro SI, Sasaki M, Amo Y, Usuki T (2007) Solvation structure of Li+ in concentrated Lipf6-propylene carbonate solutions. J Phys Chem B 111:6104–6109

  17. Chaban V (2014) Competitive solvation of (bis)(trifluoromethanesulfonyl)imide anion by acetonitrile and water. Chem Phys Lett 613:90–94

  18. Chaban V (2015) The thiocyanate anion is a primary driver of carbon dioxide capture by ionic liquids. Chem Phys Lett 618:89–93

  19. Chaban V (2015) Annealing relaxation of ultrasmall gold nanostructures. Chem Phys Lett 618:46–50

  20. Andreeva NA, Chaban VV (2015) Global minimum search via annealing: nanoscale gold clusters. Chem Phys Lett 622:75–79

  21. Stewart JJP (2007) Optimization of parameters for semiempirical methods v: modification of Nddo approximations and application to 70 elements. J Mol Model 13:1173–1213

  22. Stewart JJP (2008) Application of the Pm6 method to modeling the solid state. J Mol Model 14:499–535

  23. Stewart JJP (2009) Application of the Pm6 method to modeling proteins. J Mol Model 15:765–805

  24. Stewart JJP (2013) Optimization of parameters for semiempirical methods Vi: more modifications to the Nddo approximations and re-optimization of parameters. J Mol Model 19:1–32

  25. Berendsen HJC, Postma JPM, Vangunsteren WF, Dinola A, Haak JR (1984) Molecular-dynamics with coupling to an external bath. J Chem Phys 81:3684–3690

  26. Nielson KD, van Duin ACT, Oxgaard J, Deng WQ, Goddard WA (2005) Development of the reaxff reactive force field for describing transition metal catalyzed reactions, with application to the initial stages of the catalytic formation of carbon nanotubes. J Phys Chem A 109:493–499

  27. van Duin ACT, Strachan A, Stewman S, Zhang QS, Xu X, Goddard WA (2003) Reaxff(Sio) Reactive force field for silicon and silicon oxide systems. J Phys Chem A 107:3803–3811

  28. van Duin ACT, Dasgupta S, Lorant F, Goddard WA (2001) Reaxff: a reactive force field for hydrocarbons. J Phys Chem A 105:9396–9409

  29. Zhang, Qing and Çağin, Tahir and van Duin, Adri and Goddard, William A, III and Qi, Yue and Hector, Louis G, Jr (2004) Adhesion and nonwetting-wetting transition in the Al/alpha-Al2O3 interface. Phys Rev B 69(4). doi:10.1103/PhysRevB.69.045423

  30. Allouche AR (2011) Gabedit-a graphical user interface for computational chemistry softwares. J Comput Chem 32:174–182

Download references

Acknowledgments

V.V.C. is a CAPES fellow in Brazil under the “Science Without Borders” program.

Author information

Authors and Affiliations

  1. Instituto de Ciência e Tecnologia, Universidade Federal de São Paulo, 12231-280, São José dos Campos, SP, Brazil

    Vitaly Chaban

  2. Department of Chemistry, University of Southern California, Los Angeles, CA, 90089, USA

    Vitaly Chaban

Authors
  1. Vitaly Chaban
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Vitaly Chaban.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chaban, V. Solvation of the fluorine containing anions and their lithium salts in propylene carbonate and dimethoxyethane. J Mol Model 21, 172 (2015). https://doi.org/10.1007/s00894-015-2717-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00894-015-2717-y

Keywords

Search

Navigation