Ion Association in Aprotic Solvents for Lithium Ion Batteries Requires Discrete–Continuum Approach: Lithium Bis(oxalato)borate in Ethylene Carbonate Based Mixtures
| Autor: | Igor O. Fritsky, Oleg N. Kalugin, Oleksandr M. Korsun, Oleg V. Prezhdo |
|---|---|
| Rok vydání: | 2016 |
| Předmět: |
chemistry.chemical_classification
Inorganic chemistry Solvation Thermodynamics 02 engineering and technology Ion-association 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences 0104 chemical sciences Surfaces Coatings and Films Electronic Optical and Magnetic Materials Ion Gibbs free energy symbols.namesake chemistry.chemical_compound General Energy chemistry symbols Density functional theory Physical and Theoretical Chemistry 0210 nano-technology Alkyl Order of magnitude Ethylene carbonate |
| Zdroj: | The Journal of Physical Chemistry C. 120:16545-16552 |
| ISSN: | 1932-7455 1932-7447 |
| DOI: | 10.1021/acs.jpcc.6b05963 |
| Popis: | Ion association in solutions of lithium salts in mixtures of alkyl carbonates carries significant impact on the performance of lithium ion batteries. Focusing on lithium bis(oxalato)borate, LiBOB, in binary solvents based on ethylene carbonate, EC, we show that neither continuum nor discrete solvation approaches are capable of predicting physically meaningful results. So-called mixed or the discrete–continuum solvation approach, based on explicit consideration of an ion solvatocomplex combined with estimation of the medium polarization effect, is required in order to characterize the ion association at the quantitative level. The calculated changes of the Gibbs free energy are overestimated by nearly an order of magnitude by the purely continuum and purely discrete approaches, with the values having the opposite signs. The physically balanced discrete–continuum description predicts weak ion association. The numerical data obtained with density functional theory are validated using coupled-cluster calculat... |
| Databáze: | OpenAIRE |
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