skip to main content

DOE PAGESDOE PAGES

Title: 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 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.
Authors:
 [1] ;  [2] ;  [2] ;  [3]
  1. Joint Center for Energy Storage Research, Argonne, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Joint Center for Energy Storage Research, Argonne, IL (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  3. Joint Center for Energy Storage Research, Argonne, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Report Number(s):
SAND-2019-3254J
Journal ID: ISSN 2296-2646; 673711
Grant/Contract Number:
AC04-94AL85000; AC02-05CH11231
Type:
Published Article
Journal Name:
Frontiers in Chemistry
Additional Journal Information:
Journal Volume: 7; Journal ID: ISSN 2296-2646
Publisher:
Frontiers Research Foundation
Research Org:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
multivalent batteries; electrolytes; density functional theory; decomposition mechanism; bifurcation
OSTI Identifier:
1505857
Alternate Identifier(s):
OSTI ID: 1507414

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. United States: N. p., 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. United States. doi:10.3389/fchem.2019.00175.
Seguin, Trevor J., Hahn, Nathan T., Zavadil, Kevin R., and Persson, Kristin A.. 2019. "Elucidating Non-aqueous Solvent Stability and Associated Decomposition Mechanisms for Mg Energy Storage Applications From First-Principles". United States. doi: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 = {United States},
year = {2019},
month = {4}
}

Works referenced in this record:

Raman Study of Aluminum Chloride?Dimethylsulfone Solutions
journal, January 1996
  • Legrand, L.; Tranchant, A.; Messina, R.
  • Inorganic Chemistry, Vol. 35, Issue 5, p. 1310-1312
  • DOI: 10.1021/ic941455q

Sulfone-Based Electrolyte Solutions for Rechargeable Magnesium Batteries Using 2,5-Dimethoxy-1,4-benzoquinone Positive Electrode
journal, January 2014
  • Senoh, H.; Sakaebe, H.; Sano, H.
  • Journal of the Electrochemical Society, Vol. 161, Issue 9, p. A1315-A1320
  • DOI: 10.1149/2.0531409jes

The Coupling between Stability and Ion Pair Formation in Magnesium Electrolytes from First-Principles Quantum Mechanics and Classical Molecular Dynamics
journal, February 2015
  • Rajput, Nav Nidhi; Qu, Xiaohui; Sa, Niya
  • Journal of the American Chemical Society, Vol. 137, Issue 9, p. 3411-3420
  • DOI: 10.1021/jacs.5b01004

On the electrochemical behavior of magnesium electrodes in polar aprotic electrolyte solutions
journal, May 1999

Electrolyte roadblocks to a magnesium rechargeable battery
journal, January 2012
  • Muldoon, John; Bucur, Claudiu B.; Oliver, Allen G.
  • Energy & Environmental Science, Vol. 5, Issue 3, p. 5941-5950
  • DOI: 10.1039/c2ee03029b