skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Molecular Level Structure and Dynamics of Electrolytes Using 17O Nuclear Magnetic Resonance Spectroscopy

Abstract

Electrolytes help harness the energy from electrochemical processes by serving as solvents and transport media for redox-active ions. Molecular-level interactions between ionic solutes and solvent molecules – commonly referred to as solvation phenomena – give rise to many functional properties of electrolytes such as ionic conductivity, viscosity, and stability. It is critical to understand the evolution of solvation phenomena as a function of competing counterions and solvent mixtures to predict and design the optimal electrolyte for a target application. Probing oxygen environments is of great interest as oxygens are located at strategic molecular sites in battery solvents and are directly involved in inter- and intramolecular solvation interactions. NMR signals from 17O nuclei in battery electrolytes offer nondestructive bulk measurements of isotropic shielding, electric field gradient tensors, and transverse and longitudinal relaxation rates, which are excellent means for probing structure, bonding, and dynamics of both solute and solvent molecules. This article describes the use of 17O NMR spectroscopy in probing the solvation structures of various electrolyte systems ranging from transition metal ions in aqueous solution to lithium cations in organic solvent mixtures.

Authors:
; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1390436
Report Number(s):
PNNL-SA-128311
Journal ID: ISBN 9780470034590; 49376; KC0208010
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
eMagRes
Additional Journal Information:
Journal Volume: 6; Journal Issue: 1
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Murugesan, Vijayakumar, Han, Kee Sung, Hu, Jianzhi, and Mueller, Karl T. Molecular Level Structure and Dynamics of Electrolytes Using 17O Nuclear Magnetic Resonance Spectroscopy. United States: N. p., 2017. Web. doi:10.1002/9780470034590.emrstm1529.
Murugesan, Vijayakumar, Han, Kee Sung, Hu, Jianzhi, & Mueller, Karl T. Molecular Level Structure and Dynamics of Electrolytes Using 17O Nuclear Magnetic Resonance Spectroscopy. United States. doi:10.1002/9780470034590.emrstm1529.
Murugesan, Vijayakumar, Han, Kee Sung, Hu, Jianzhi, and Mueller, Karl T. Sun . "Molecular Level Structure and Dynamics of Electrolytes Using 17O Nuclear Magnetic Resonance Spectroscopy". United States. doi:10.1002/9780470034590.emrstm1529.
@article{osti_1390436,
title = {Molecular Level Structure and Dynamics of Electrolytes Using 17O Nuclear Magnetic Resonance Spectroscopy},
author = {Murugesan, Vijayakumar and Han, Kee Sung and Hu, Jianzhi and Mueller, Karl T.},
abstractNote = {Electrolytes help harness the energy from electrochemical processes by serving as solvents and transport media for redox-active ions. Molecular-level interactions between ionic solutes and solvent molecules – commonly referred to as solvation phenomena – give rise to many functional properties of electrolytes such as ionic conductivity, viscosity, and stability. It is critical to understand the evolution of solvation phenomena as a function of competing counterions and solvent mixtures to predict and design the optimal electrolyte for a target application. Probing oxygen environments is of great interest as oxygens are located at strategic molecular sites in battery solvents and are directly involved in inter- and intramolecular solvation interactions. NMR signals from 17O nuclei in battery electrolytes offer nondestructive bulk measurements of isotropic shielding, electric field gradient tensors, and transverse and longitudinal relaxation rates, which are excellent means for probing structure, bonding, and dynamics of both solute and solvent molecules. This article describes the use of 17O NMR spectroscopy in probing the solvation structures of various electrolyte systems ranging from transition metal ions in aqueous solution to lithium cations in organic solvent mixtures.},
doi = {10.1002/9780470034590.emrstm1529},
journal = {eMagRes},
number = 1,
volume = 6,
place = {United States},
year = {2017},
month = {3}
}

Works referenced in this record:

Nuclear Magnetic Resonance Studies of Ions in Pure and Mixed Solvents
journal, August 1967

  • Hinton, James F.; Amis, Edward S.
  • Chemical Reviews, Vol. 67, Issue 4
  • DOI: 10.1021/cr60248a002

Effects of Electrolyte Salts on the Performance of Li–O 2 Batteries
journal, February 2013

  • Nasybulin, Eduard; Xu, Wu; Engelhard, Mark H.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 6
  • DOI: 10.1021/jp311114u

Molecular structure and stability of dissolved lithium polysulfide species
journal, January 2014

  • Vijayakumar, M.; Govind, Niranjan; Walter, Eric
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 22
  • DOI: 10.1039/C4CP00889H

Variable-Temperature and Variable-Pressure17O-NMR Study of Water Exchange of Hexaaquaaluminium(III)
journal, May 1985

  • Hugi-Cleary, Deirdre; Helm, Lothar; Merbach, Andr� E.
  • Helvetica Chimica Acta, Vol. 68, Issue 3
  • DOI: 10.1002/hlca.19850680302

Challenges for Rechargeable Li Batteries
journal, February 2010

  • Goodenough, John B.; Kim, Youngsik
  • Chemistry of Materials, Vol. 22, Issue 3, p. 587-603
  • DOI: 10.1021/cm901452z

Solvate Structures and Computational/Spectroscopic Characterization of LiPF 6 Electrolytes
journal, April 2015

  • Han, Sang-Don; Yun, Sung-Hyun; Borodin, Oleg
  • The Journal of Physical Chemistry C, Vol. 119, Issue 16
  • DOI: 10.1021/acs.jpcc.5b00826

Proton NMR evidence for π-bonding in oxovanadium(IV) complexes
journal, August 1968


Issues and challenges facing rechargeable lithium batteries
journal, November 2001

  • Tarascon, J.-M.; Armand, M.
  • Nature, Vol. 414, Issue 6861, p. 359-367
  • DOI: 10.1038/35104644

DMSO exchange on [Gd(DMSO) 8 ] 3+ —a variable pressure 17 O NMR study
journal, March 2004

  • Dessapt, Rémi; Helm, Lothar; Merbach, André E.
  • Journal of Physics: Condensed Matter, Vol. 16, Issue 14
  • DOI: 10.1088/0953-8984/16/14/012

Li + Cation Environment, Transport, and Mechanical Properties of the LiTFSI Doped N -Methyl- N -alkylpyrrolidinium + TFSI - Ionic Liquids
journal, August 2006

  • Borodin, Oleg; Smith, Grant D.; Henderson, Wesley
  • The Journal of Physical Chemistry B, Vol. 110, Issue 34
  • DOI: 10.1021/jp061930t

Oxygen-17 NMR spectroscopy: Basic principles and applications (part II)
journal, July 2010


Protonation Equilibria of Mononuclear Vanadate:  Thermodynamic Evidence for the Expansion of the Coordination Number in VO 2 +
journal, January 1996

  • Cruywagen, Johannes J.; Heyns, J. Bernard B.; Westra, Arjan N.
  • Inorganic Chemistry, Vol. 35, Issue 6
  • DOI: 10.1021/ic950832b

Contact Shift Studies of Some Paramagnetic Hexaaquo Metal Ion Complexes
journal, January 1966

  • Wayland, Bradford B.; Rice, William L.
  • Inorganic Chemistry, Vol. 5, Issue 1
  • DOI: 10.1021/ic50035a013

LiTFSI Structure and Transport in Ethylene Carbonate from Molecular Dynamics Simulations
journal, March 2006

  • Borodin, Oleg; Smith, Grant D.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 10
  • DOI: 10.1021/jp056249q

Role of Mixed Solvation and Ion Pairing in the Solution Structure of Lithium Ion Battery Electrolytes
journal, June 2015

  • Seo, Daniel M.; Reininger, Stefanie; Kutcher, Mary
  • The Journal of Physical Chemistry C, Vol. 119, Issue 25
  • DOI: 10.1021/acs.jpcc.5b03694

Design of electrolyte solutions for Li and Li-ion batteries: a review
journal, November 2004


Non-Aqueous Li-Based Redox Flow Batteries
journal, January 2012

  • Hamelet, S.; Tzedakis, T.; Leriche, J. -B.
  • Journal of The Electrochemical Society, Vol. 159, Issue 8
  • DOI: 10.1149/2.071208jes

Ligand nuclear hyperfine coupling constants in the vanadyl(IV)-aquo complex. Evidence for metal-ligand .pi. bonding
journal, September 1969


The polarized absorption spectra of three crystalline polymorphs of VOSO4.5H2O
journal, June 1968

  • Ballhausen, C. J.; Djurinskij, B. F.; Watson, K. J.
  • Journal of the American Chemical Society, Vol. 90, Issue 13
  • DOI: 10.1021/ja01015a001

Towards understanding the poor thermal stability of V5+ electrolyte solution in Vanadium Redox Flow Batteries
journal, April 2011


Electronic Structure of the Aqueous Vanadyl Ion Probed by 9 and 94 GHz EPR and Pulsed ENDOR Spectroscopies and Density Functional Theory Calculations
journal, December 1999

  • Grant, Christopher V.; Cope, William; Ball, James A.
  • The Journal of Physical Chemistry B, Vol. 103, Issue 48
  • DOI: 10.1021/jp992186y

Molecular Dynamics Simulation of LiTFSI−Acetamide Electrolytes: Structural Properties
journal, May 2008

  • Li, Shu; Cao, Zhen; Peng, Yuxing
  • The Journal of Physical Chemistry B, Vol. 112, Issue 20
  • DOI: 10.1021/jp710898h

"Water-in-salt" electrolyte enables high-voltage aqueous lithium-ion chemistries
journal, November 2015


Structure and Stability of VO 2 + in Aqueous Solution:  A Car−Parrinello and Static ab Initio Study
journal, June 2007

  • Sadoc, Aymeric; Messaoudi, Sabri; Furet, Eric
  • Inorganic Chemistry, Vol. 46, Issue 12
  • DOI: 10.1021/ic0614519

Vanadium redox cell electrolyte optimization studies
journal, May 1990

  • Kazacos, M.; Cheng, M.; Skyllas-Kazacos, M.
  • Journal of Applied Electrochemistry, Vol. 20, Issue 3
  • DOI: 10.1007/BF01076057

High-pressure 17O NMR studies on some aqueous polyoxoions in water
journal, November 2008

  • Balogh, Edina; Casey, William H.
  • Progress in Nuclear Magnetic Resonance Spectroscopy, Vol. 53, Issue 4
  • DOI: 10.1016/j.pnmrs.2008.01.001

Electrolytes and Interphases in Li-Ion Batteries and Beyond
journal, October 2014


Natural abundance 17O nuclear magnetic resonance and computational modeling studies of lithium based liquid electrolytes
journal, July 2015


A Stable Vanadium Redox-Flow Battery with High Energy Density for Large-Scale Energy Storage
journal, March 2011

  • Li, Liyu; Kim, Soowhan; Wang, Wei
  • Advanced Energy Materials, Vol. 1, Issue 3, p. 394-400
  • DOI: 10.1002/aenm.201100008

Structure and stability of hexa-aqua V(iii) cations in vanadium redox flow battery electrolytes
journal, January 2012

  • Vijayakumar, M.; Li, Liyu; Nie, Zimin
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 29
  • DOI: 10.1039/c2cp40707h

Medium Effects on51V NMR Chemical Shifts: A Density Functional Study
journal, October 2001


Vanadium redox battery: Positive half-cell electrolyte studies
journal, April 2009


Glyme−Lithium Bis(trifluoromethanesulfonyl)imide and Glyme−Lithium Bis(perfluoroethanesulfonyl)imide Phase Behavior and Solvate Structures
journal, April 2005

  • Henderson, Wesley A.; McKenna, Fred; Khan, Masood A.
  • Chemistry of Materials, Vol. 17, Issue 9
  • DOI: 10.1021/cm047881j

The COSMO and COSMO-RS solvation models: The COSMO and COSMO-RS solvation models
journal, April 2011

  • Klamt, Andreas
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 1, Issue 5
  • DOI: 10.1002/wcms.56

Prototropic charge migration in water. Part 1.—Rate constants in light and heavy water and in salt solution from oxygen-17 spin relaxation
journal, January 1983

  • Halle, Bertil; Karlström, Gunnar
  • J. Chem. Soc., Faraday Trans. 2, Vol. 79, Issue 7
  • DOI: 10.1039/F29837901031

Oxygen‐17 NMR Linewidths as Influenced by Proton Exchange in Water
journal, July 1967

  • Rabideau, Sherman W.; Hecht, Harry G.
  • The Journal of Chemical Physics, Vol. 47, Issue 2
  • DOI: 10.1063/1.1711928

Effect of the Anion Activity on the Stability of Li Metal Anodes in Lithium-Sulfur Batteries
journal, March 2016

  • Cao, Ruiguo; Chen, Junzheng; Han, Kee Sung
  • Advanced Functional Materials, Vol. 26, Issue 18
  • DOI: 10.1002/adfm.201505074

High pressure NMR studies on ligand exchange reactions in the equatorial sites of [VO(L)5]2+ (L=acetonitrile, N,N-dimethylformamide, and N,N-dimethylacetamide)
journal, November 1999


Isotropic Nuclear Resonance Shifts
journal, December 1958

  • McConnell, Harden M.; Robertson, Richard E.
  • The Journal of Chemical Physics, Vol. 29, Issue 6
  • DOI: 10.1063/1.1744723

Speciation and NMR relaxation studies of VO(IV) complexes with several O-donor containing ligands: oxalate, malonate, maltolate and kojate
journal, August 2000


The Chemistry of Oxovanadium(IV)
journal, April 1965


Formation equilibria of vanadium(V) species in different ionic media: Salt effect and protonation constant
journal, February 2008


QM/MM–MD simulation of hydrated vanadium(II) ion
journal, September 2002


Oxygen-17 NMR spectroscopy: Basic principles and applications (Part I)
journal, March 2010


Density functional theory calculations for ethylene carbonate-based binary electrolyte mixtures in lithium ion batteries
journal, March 2014


Challenges in the development of advanced Li-ion batteries: a review
journal, January 2011

  • Etacheri, Vinodkumar; Marom, Rotem; Elazari, Ran
  • Energy & Environmental Science, Vol. 4, Issue 9
  • DOI: 10.1039/c1ee01598b

Electrostriction in Electrolyte Solutions
journal, February 2011


NMR‐Relaxation Mechanisms of O 17 in Aqueous Solutions of Paramagnetic Cations and the Lifetime of Water Molecules in the First Coordination Sphere
journal, July 1962

  • Swift, T. J.; Connick, Robert E.
  • The Journal of Chemical Physics, Vol. 37, Issue 2
  • DOI: 10.1063/1.1701321

Li + solvation in glyme–Li salt solvate ionic liquids
journal, January 2015

  • Ueno, Kazuhide; Tatara, Ryoichi; Tsuzuki, Seiji
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 12
  • DOI: 10.1039/C4CP05943C

Oxovanadium(IV) complexes
journal, August 1966


The Electronic Structure of the Vanadyl Ion
journal, February 1962

  • Ballhausen, C. J.; Gray, Harry B.
  • Inorganic Chemistry, Vol. 1, Issue 1
  • DOI: 10.1021/ic50001a022

Inorganic and Bioinorganic Solvent Exchange Mechanisms
journal, June 2005

  • Helm, Lothar; Merbach, André E.
  • Chemical Reviews, Vol. 105, Issue 6
  • DOI: 10.1021/cr030726o

Spectroscopic study of vanadium(V) precipitation in the vanadium redox cell electrolyte
journal, August 2001


Nuclear magnetic resonance studies on vanadium(IV) electrolyte solutions for vanadium redox flow battery
journal, November 2010


Magnetic resonance studies of ion solvation. The hydration of the vanadyl(IV) ion
journal, March 1967


Nuclear and Electronic Relaxation of Eu 2+ ( a q) :  An Extremely Labile Aqua Ion 1
journal, November 1999

  • Caravan, Peter; Tóth, Éva; Rockenbauer, Antal
  • Journal of the American Chemical Society, Vol. 121, Issue 44
  • DOI: 10.1021/ja992264v

High pressure oxygen-17 NMR study on the kinetics of water exchange reaction in pentaquaoxovanadium(IV)
journal, June 1988


Understanding Li + –Solvent Interaction in Nonaqueous Carbonate Electrolytes with 17 O NMR
journal, May 2013

  • Bogle, Xavier; Vazquez, Rafael; Greenbaum, Steven
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 10
  • DOI: 10.1021/jz400661k

Water exchange on metal ions: experiments and simulations
journal, June 1999