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Elucidating Non-aqueous Solvent Stability and Associated Decomposition Mechanisms for Mg Energy Storage Applications From First-Principles
Rational design of novel electrolytes with enhanced functionality requires fundamental molecular-level understanding of structure-property relationships. Here we examine the suitability of a range of organic solvents for non-aqueous electrolytes in secondary magnesium batteries using density functio...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Frontiers Media S.A.
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6465547/ https://www.ncbi.nlm.nih.gov/pubmed/31024883 http://dx.doi.org/10.3389/fchem.2019.00175 |
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author | Seguin, Trevor J. Hahn, Nathan T. Zavadil, Kevin R. Persson, Kristin A. |
author_facet | Seguin, Trevor J. Hahn, Nathan T. Zavadil, Kevin R. Persson, Kristin A. |
author_sort | Seguin, Trevor J. |
collection | PubMed |
description | Rational design of novel electrolytes with enhanced functionality requires fundamental molecular-level understanding of structure-property relationships. Here we examine the suitability of a range of organic solvents for non-aqueous electrolytes in secondary magnesium batteries using density functional theory (DFT) calculations as well as experimental probes such as cyclic voltammetry and Raman spectroscopy. The solvents considered include ethereal solvents (e.g., glymes) sulfones (e.g., tetramethylene sulfone), and acetonitrile. Computed reduction potentials show that all solvents considered are stable against reduction by Mg metal. Additional computations were carried out to assess the stability of solvents in contact with partially reduced Mg cations (Mg(2+) → Mg(+)) formed during cycling (e.g., deposition) by identifying reaction profiles of decomposition pathways. Most solvents, including some proposed for secondary Mg energy storage applications, exhibit decomposition pathways that are surprisingly exergonic. Interestingly, the stability of these solvents is largely dictated by magnitude of the kinetic barrier to decomposition. This insight should be valuable toward rational design of improved Mg electrolytes. |
format | Online Article Text |
id | pubmed-6465547 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | Frontiers Media S.A. |
record_format | MEDLINE/PubMed |
spelling | pubmed-64655472019-04-25 Elucidating Non-aqueous Solvent Stability and Associated Decomposition Mechanisms for Mg Energy Storage Applications From First-Principles Seguin, Trevor J. Hahn, Nathan T. Zavadil, Kevin R. Persson, Kristin A. Front Chem Chemistry Rational design of novel electrolytes with enhanced functionality requires fundamental molecular-level understanding of structure-property relationships. Here we examine the suitability of a range of organic solvents for non-aqueous electrolytes in secondary magnesium batteries using density functional theory (DFT) calculations as well as experimental probes such as cyclic voltammetry and Raman spectroscopy. The solvents considered include ethereal solvents (e.g., glymes) sulfones (e.g., tetramethylene sulfone), and acetonitrile. Computed reduction potentials show that all solvents considered are stable against reduction by Mg metal. Additional computations were carried out to assess the stability of solvents in contact with partially reduced Mg cations (Mg(2+) → Mg(+)) formed during cycling (e.g., deposition) by identifying reaction profiles of decomposition pathways. Most solvents, including some proposed for secondary Mg energy storage applications, exhibit decomposition pathways that are surprisingly exergonic. Interestingly, the stability of these solvents is largely dictated by magnitude of the kinetic barrier to decomposition. This insight should be valuable toward rational design of improved Mg electrolytes. Frontiers Media S.A. 2019-04-09 /pmc/articles/PMC6465547/ /pubmed/31024883 http://dx.doi.org/10.3389/fchem.2019.00175 Text en Copyright © 2019 Seguin, Hahn, Zavadil and Persson. http://creativecommons.org/licenses/by/4.0/ This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms. |
spellingShingle | Chemistry Seguin, Trevor J. Hahn, Nathan T. Zavadil, Kevin R. Persson, Kristin A. Elucidating Non-aqueous Solvent Stability and Associated Decomposition Mechanisms for Mg Energy Storage Applications From First-Principles |
title | Elucidating Non-aqueous Solvent Stability and Associated Decomposition Mechanisms for Mg Energy Storage Applications From First-Principles |
title_full | Elucidating Non-aqueous Solvent Stability and Associated Decomposition Mechanisms for Mg Energy Storage Applications From First-Principles |
title_fullStr | Elucidating Non-aqueous Solvent Stability and Associated Decomposition Mechanisms for Mg Energy Storage Applications From First-Principles |
title_full_unstemmed | Elucidating Non-aqueous Solvent Stability and Associated Decomposition Mechanisms for Mg Energy Storage Applications From First-Principles |
title_short | Elucidating Non-aqueous Solvent Stability and Associated Decomposition Mechanisms for Mg Energy Storage Applications From First-Principles |
title_sort | elucidating non-aqueous solvent stability and associated decomposition mechanisms for mg energy storage applications from first-principles |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6465547/ https://www.ncbi.nlm.nih.gov/pubmed/31024883 http://dx.doi.org/10.3389/fchem.2019.00175 |
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