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Title: Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)2 in Diglyme: Implications for Multivalent Electrolytes

Abstract

In this paper, we reveal the general mechanisms of partial reduction of multivalent complex cations in conditions specific for the bulk solvent and in the vicinity of the electrified metal electrode surface and disclose the factors affecting the reductive stability of electrolytes for multivalent electrochemistry. Using a combination of ab initio techniques, we clarify the relation between the reductive stability of contact-ion pairs comprising a multivalent cation and a complex anion, their solvation structures, solvent dynamics, and the electrode overpotential. We found that for ion pairs with multiple configurations of the complex anion and the Mg cation whose available orbitals are partially delocalized over the molecular complex and have antibonding character, the primary factor of the reductive stability is the shape factor of the solvation sphere of the metal cation center and the degree of the convexity of a polyhedron formed by the metal cation and its coordinating atoms. We focused specifically on the details of Mg (II) bis(trifluoromethanesulfonyl)imide in diethylene glycol dimethyl ether (Mg(TFSI)2)/diglyme) and its singly charged ion pair, MgTFSI+. In particular, we found that both stable (MgTFSI)+ and (MgTFSI)0 ion pairs have the same TFSI configuration but drastically different solvation structures in the bulk solution. This impliesmore » that the MgTFSI/dyglyme reductive stability is ultimately determined by the relative time scale of the solvent dynamics and electron transfer at the Mg–anode interface. In the vicinity of the anode surface, steric factors and hindered solvent dynamics may increase the reductive stability of (MgTFSI)+ ion pairs at lower overpotential by reducing the metal cation coordination, in stark contrast to the reduction at high overpotential accompanied by TFSI decomposition. By examining other solute/solvent combinations, we conclude that the electrolytes with highly coordinated Mg cation centers are more prone to reductive instability due to the chemical decomposition of the anion or solvent molecules. Finally, the obtained findings disclose critical factors for stable electrolyte design and show the role of interfacial phenomena in reduction of multivalent ions.« less

Authors:
 [1];  [1]
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  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry. Material Science Division
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1379107
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 7; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Baskin, Artem, and Prendergast, David. Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)2 in Diglyme: Implications for Multivalent Electrolytes. United States: N. p., 2016. Web. doi:10.1021/acs.jpcc.5b08999.
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Baskin, Artem, & Prendergast, David. Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)2 in Diglyme: Implications for Multivalent Electrolytes. United States. https://doi.org/10.1021/acs.jpcc.5b08999
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Baskin, Artem, and Prendergast, David. Fri . "Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)2 in Diglyme: Implications for Multivalent Electrolytes". United States. https://doi.org/10.1021/acs.jpcc.5b08999. https://www.osti.gov/servlets/purl/1379107.
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@article{osti_1379107,
title = {Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)2 in Diglyme: Implications for Multivalent Electrolytes},
author = {Baskin, Artem and Prendergast, David},
abstractNote = {In this paper, we reveal the general mechanisms of partial reduction of multivalent complex cations in conditions specific for the bulk solvent and in the vicinity of the electrified metal electrode surface and disclose the factors affecting the reductive stability of electrolytes for multivalent electrochemistry. Using a combination of ab initio techniques, we clarify the relation between the reductive stability of contact-ion pairs comprising a multivalent cation and a complex anion, their solvation structures, solvent dynamics, and the electrode overpotential. We found that for ion pairs with multiple configurations of the complex anion and the Mg cation whose available orbitals are partially delocalized over the molecular complex and have antibonding character, the primary factor of the reductive stability is the shape factor of the solvation sphere of the metal cation center and the degree of the convexity of a polyhedron formed by the metal cation and its coordinating atoms. We focused specifically on the details of Mg (II) bis(trifluoromethanesulfonyl)imide in diethylene glycol dimethyl ether (Mg(TFSI)2)/diglyme) and its singly charged ion pair, MgTFSI+. In particular, we found that both stable (MgTFSI)+ and (MgTFSI)0 ion pairs have the same TFSI configuration but drastically different solvation structures in the bulk solution. This implies that the MgTFSI/dyglyme reductive stability is ultimately determined by the relative time scale of the solvent dynamics and electron transfer at the Mg–anode interface. In the vicinity of the anode surface, steric factors and hindered solvent dynamics may increase the reductive stability of (MgTFSI)+ ion pairs at lower overpotential by reducing the metal cation coordination, in stark contrast to the reduction at high overpotential accompanied by TFSI decomposition. By examining other solute/solvent combinations, we conclude that the electrolytes with highly coordinated Mg cation centers are more prone to reductive instability due to the chemical decomposition of the anion or solvent molecules. Finally, the obtained findings disclose critical factors for stable electrolyte design and show the role of interfacial phenomena in reduction of multivalent ions.},
doi = {10.1021/acs.jpcc.5b08999},
journal = {Journal of Physical Chemistry. C},
number = 7,
volume = 120,
place = {United States},
year = {Fri Feb 05 00:00:00 EST 2016},
month = {Fri Feb 05 00:00:00 EST 2016}
}
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https://doi.org/10.1021/acs.jpcc.5b08999
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