Document Type

Article

Journal/Book Title

Batteries & Supercaps

Publication Date

9-1-2019

Publisher

Wiley - VCH Verlag GmbH & Co. KGaA

Volume

2

Issue

9

First Page

1

Last Page

20

Abstract

DFT calculations were conducted to provide insightful and unprecedented thermodynamic insights on tetrahydrofuran (THF) solvation, isomerization, chlorination, and complexation of possible Mg-Cl coordination species for the popular Mg-Cl electrolytes. Computational results using the M06-2x functional with the 6-31+G(d) basis set indicate trigonal bipyramidal e, e-cis-tbp-MgCl2(THF)3 dichloride species and octahedral [MgCl(THF)5]+ monochloride species are the dominant mononuclear species. These two can combine to form the active dinuclear species, [(μ-Cl)3Mg2(THF)6]+ with a free energy -6.30 kcal/mol, which is calculated to be the dominant Mg-Cl species in solution. Two mono-cation species, [(μ-Cl)3Mg2(THF)6]+ and [MgCl(THF)5]+ have comparable LUMO energies, thus both of them can act as active species for Mg deposition. However, the significant dominance of the dinuclear species in the electrolyte indicates that it is the primary species involved in reversible Mg deposition.

Comments

This is the peer reviewed version of the following article: Moss, J. B., Zhang, L., Nielson, K. V., Bi, Y., Wu, C., Scheiner, S. I., Liu, T. L. (2019). Computational Insights into Mg-Cl Complex Electrolytes for Rechargeable Magnesium Batteries. Batteries \& Supercaps, 2(9), 792-800. https://onlinelibrary.wiley.com/doi/abs/10.1002/batt.201900029, which has been published in final form at https://doi.org/10.1002/batt.201900029. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.

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