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Title: 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) (SC-22)
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. doi: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. 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 = {Switzerland},
year = {2019},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.3389/fchem.2019.00175

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Works referenced in this record:

Magnesium batteries: Current state of the art, issues and future perspectives
journal, January 2014

  • Mohtadi, Rana; Mizuno, Fuminori
  • Beilstein Journal of Nanotechnology, Vol. 5
  • DOI: 10.3762/bjnano.5.143

Systematic optimization of long-range corrected hybrid density functionals
journal, February 2008

  • Chai, Jeng-Da; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 128, Issue 8
  • DOI: 10.1063/1.2834918

Natural population analysis
journal, July 1985

  • Reed, Alan E.; Weinstock, Robert B.; Weinhold, Frank
  • The Journal of Chemical Physics, Vol. 83, Issue 2
  • DOI: 10.1063/1.449486

Non-Grignard and Lewis Acid-Free Sulfone Electrolytes for Rechargeable Magnesium Batteries
journal, March 2017


Conditioning-Free Electrolytes for Magnesium Batteries Using Sufone–Ether Mixtures with Increased Thermal Stability
journal, May 2018


Zinc Blende Magnesium Sulfide in Rechargeable Magnesium-Sulfur Batteries
journal, September 2018


Homoleptic octahedral coordination of CH 3 CN to Mg 2+ in the Mg[N(SO 2 CF 3 ) 2 ] 2 –CH 3 CN system
journal, January 2016

  • Veryasov, Gleb; Matsumoto, Kazuhiko; Hagiwara, Rika
  • Dalton Transactions, Vol. 45, Issue 7
  • DOI: 10.1039/C5DT04821D

Enhanced Stability of the Carba- closo -dodecaborate Anion for High-Voltage Battery Electrolytes through Rational Design
journal, July 2018

  • Hahn, Nathan T.; Seguin, Trevor J.; Lau, Ka-Cheong
  • Journal of the American Chemical Society, Vol. 140, Issue 35
  • DOI: 10.1021/jacs.8b05967

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

Bifurcations on Potential Energy Surfaces of Organic Reactions
journal, September 2008

  • Ess, Daniel H.; Wheeler, Steven E.; Iafe, Robert G.
  • Angewandte Chemie International Edition, Vol. 47, Issue 40
  • DOI: 10.1002/anie.200800918

Elucidating Solvation Structures for Rational Design of Multivalent Electrolytes—A Review
journal, April 2018

  • Rajput, Nav Nidhi; Seguin, Trevor J.; Wood, Brandon M.
  • Topics in Current Chemistry, Vol. 376, Issue 3
  • DOI: 10.1007/s41061-018-0195-2

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

Mapping the Challenges of Magnesium Battery
journal, April 2016

  • Song, Jaehee; Sahadeo, Emily; Noked, Malachi
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 9
  • DOI: 10.1021/acs.jpclett.6b00384

Post-transition state bifurcations gain momentum – current state of the field
journal, June 2017

  • Hare, Stephanie R.; Tantillo, Dean J.
  • Pure and Applied Chemistry, Vol. 89, Issue 6
  • DOI: 10.1515/pac-2017-0104

The Electrolyte Genome project: A big data approach in battery materials discovery
journal, June 2015


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

Evaluation of (CF 3 SO 2 ) 2 N (TFSI) Based Electrolyte Solutions for Mg Batteries
journal, January 2015

  • Shterenberg, Ivgeni; Salama, Michael; Yoo, Hyun Deog
  • Journal of The Electrochemical Society, Vol. 162, Issue 13
  • DOI: 10.1149/2.0161513jes

An Efficient Halogen-Free Electrolyte for Use in Rechargeable Magnesium Batteries
journal, May 2015

  • Tutusaus, Oscar; Mohtadi, Rana; Arthur, Timothy S.
  • Angewandte Chemie International Edition, Vol. 54, Issue 27
  • DOI: 10.1002/anie.201412202

A new class of non-corrosive, highly efficient electrolytes for rechargeable magnesium batteries
journal, January 2017

  • Zhao-Karger, Zhirong; Gil Bardaji, Maria Elisa; Fuhr, Olaf
  • Journal of Materials Chemistry A, Vol. 5, Issue 22
  • DOI: 10.1039/C7TA02237A

Mg(PF 6 ) 2 -Based Electrolyte Systems: Understanding Electrolyte–Electrode Interactions for the Development of Mg-Ion Batteries
journal, July 2016

  • Keyzer, Evan N.; Glass, Hugh F. J.; Liu, Zigeng
  • Journal of the American Chemical Society, Vol. 138, Issue 28
  • DOI: 10.1021/jacs.6b04319

Determination of Mg 2+ Speciation in a TFSI -Based Ionic Liquid With and Without Chelating Ethers Using Raman Spectroscopy
journal, June 2015

  • Watkins, Tylan; Buttry, Daniel A.
  • The Journal of Physical Chemistry B, Vol. 119, Issue 23
  • DOI: 10.1021/acs.jpcb.5b00339

Quest for Nonaqueous Multivalent Secondary Batteries: Magnesium and Beyond
journal, October 2014

  • Muldoon, John; Bucur, Claudiu B.; Gregory, Thomas
  • Chemical Reviews, Vol. 114, Issue 23
  • DOI: 10.1021/cr500049y

Evaluation of Mg[N(SO 2 CF 3 ) 2 ] 2 /Acetonitrile Electrolyte for Use in Mg-Ion Cells
journal, January 2012

  • Tran, Tuan T.; Lamanna, W. M.; Obrovac, M. N.
  • Journal of The Electrochemical Society, Vol. 159, Issue 12
  • DOI: 10.1149/2.012301jes

Hexafluorophosphate-Based Solutions for Mg Batteries and the Importance of Chlorides
journal, July 2017


Distortion/Interaction Energy Control of 1,3-Dipolar Cycloaddition Reactivity
journal, September 2007

  • Ess, Daniel H.; Houk, K. N.
  • Journal of the American Chemical Society, Vol. 129, Issue 35
  • DOI: 10.1021/ja0734086

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


UCSF Chimera?A visualization system for exploratory research and analysis
journal, January 2004

  • Pettersen, Eric F.; Goddard, Thomas D.; Huang, Conrad C.
  • Journal of Computational Chemistry, Vol. 25, Issue 13
  • DOI: 10.1002/jcc.20084

Quantum Mechanical Continuum Solvation Models
journal, August 2005

  • Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto
  • Chemical Reviews, Vol. 105, Issue 8
  • DOI: 10.1021/cr9904009

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

Complex Nature of Ionic Coordination in Magnesium Ionic Liquid-Based Electrolytes: Solvates with Mobile Mg 2+ Cations
journal, May 2014

  • Giffin, Guinevere A.; Moretti, Arianna; Jeong, Sangsik
  • The Journal of Physical Chemistry C, Vol. 118, Issue 19
  • DOI: 10.1021/jp502354h