Elucidating Non-aqueous Solvent Stability and Associated Decomposition Mechanisms for Mg Energy Storage Applications From First-Principles
Abstract
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 (Mg2+ → 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.
- Authors:
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1505857
- Alternate Identifier(s):
- OSTI ID: 1507414
- Report Number(s):
- SAND-2019-3254J
Journal ID: ISSN 2296-2646; 175
- Grant/Contract Number:
- AC02-05CH11231; AC04-94AL85000
- Resource Type:
- Published Article
- Journal Name:
- Frontiers in Chemistry
- Additional Journal Information:
- Journal Name: Frontiers in Chemistry Journal Volume: 7; Journal ID: ISSN 2296-2646
- Publisher:
- Frontiers Media SA
- Country of Publication:
- Switzerland
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; multivalent batteries; electrolytes; density functional theory; decomposition mechanism; bifurcation
Citation Formats
Seguin, Trevor J., Hahn, Nathan T., Zavadil, Kevin R., and Persson, Kristin A. Elucidating Non-aqueous Solvent Stability and Associated Decomposition Mechanisms for Mg Energy Storage Applications From First-Principles. Switzerland: N. p., 2019.
Web. doi:10.3389/fchem.2019.00175.
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. Switzerland. https://doi.org/10.3389/fchem.2019.00175
Seguin, Trevor J., Hahn, Nathan T., Zavadil, Kevin R., and Persson, Kristin A. Tue .
"Elucidating Non-aqueous Solvent Stability and Associated Decomposition Mechanisms for Mg Energy Storage Applications From First-Principles". Switzerland. https://doi.org/10.3389/fchem.2019.00175.
@article{osti_1505857,
title = {Elucidating Non-aqueous Solvent Stability and Associated Decomposition Mechanisms for Mg Energy Storage Applications From First-Principles},
author = {Seguin, Trevor J. and Hahn, Nathan T. and Zavadil, Kevin R. and Persson, Kristin A.},
abstractNote = {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 (Mg2+ → 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.},
doi = {10.3389/fchem.2019.00175},
journal = {Frontiers in Chemistry},
number = ,
volume = 7,
place = {Switzerland},
year = {Tue Apr 09 00:00:00 EDT 2019},
month = {Tue Apr 09 00:00:00 EDT 2019}
}
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https://doi.org/10.3389/fchem.2019.00175
https://doi.org/10.3389/fchem.2019.00175
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Cited by: 29 works
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