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Title: Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)2 in Diglyme: Implications for Multivalent Electrolytes

Abstract

In this paper, we reveal the general mechanisms of partial reduction of multivalent complex cations in conditions specific for the bulk solvent and in the vicinity of the electrified metal electrode surface and disclose the factors affecting the reductive stability of electrolytes for multivalent electrochemistry. Using a combination of ab initio techniques, we clarify the relation between the reductive stability of contact-ion pairs comprising a multivalent cation and a complex anion, their solvation structures, solvent dynamics, and the electrode overpotential. We found that for ion pairs with multiple configurations of the complex anion and the Mg cation whose available orbitals are partially delocalized over the molecular complex and have antibonding character, the primary factor of the reductive stability is the shape factor of the solvation sphere of the metal cation center and the degree of the convexity of a polyhedron formed by the metal cation and its coordinating atoms. We focused specifically on the details of Mg (II) bis(trifluoromethanesulfonyl)imide in diethylene glycol dimethyl ether (Mg(TFSI)2)/diglyme) and its singly charged ion pair, MgTFSI+. In particular, we found that both stable (MgTFSI)+ and (MgTFSI)0 ion pairs have the same TFSI configuration but drastically different solvation structures in the bulk solution. This impliesmore » that the MgTFSI/dyglyme reductive stability is ultimately determined by the relative time scale of the solvent dynamics and electron transfer at the Mg–anode interface. In the vicinity of the anode surface, steric factors and hindered solvent dynamics may increase the reductive stability of (MgTFSI)+ ion pairs at lower overpotential by reducing the metal cation coordination, in stark contrast to the reduction at high overpotential accompanied by TFSI decomposition. By examining other solute/solvent combinations, we conclude that the electrolytes with highly coordinated Mg cation centers are more prone to reductive instability due to the chemical decomposition of the anion or solvent molecules. Finally, the obtained findings disclose critical factors for stable electrolyte design and show the role of interfacial phenomena in reduction of multivalent ions.« less

Authors:
 [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry. Material Science Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1379107
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 7; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Baskin, Artem, and Prendergast, David. Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)2 in Diglyme: Implications for Multivalent Electrolytes. United States: N. p., 2016. Web. doi:10.1021/acs.jpcc.5b08999.
Baskin, Artem, & Prendergast, David. Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)2 in Diglyme: Implications for Multivalent Electrolytes. United States. https://doi.org/10.1021/acs.jpcc.5b08999
Baskin, Artem, and Prendergast, David. Fri . "Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)2 in Diglyme: Implications for Multivalent Electrolytes". United States. https://doi.org/10.1021/acs.jpcc.5b08999. https://www.osti.gov/servlets/purl/1379107.
@article{osti_1379107,
title = {Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)2 in Diglyme: Implications for Multivalent Electrolytes},
author = {Baskin, Artem and Prendergast, David},
abstractNote = {In this paper, we reveal the general mechanisms of partial reduction of multivalent complex cations in conditions specific for the bulk solvent and in the vicinity of the electrified metal electrode surface and disclose the factors affecting the reductive stability of electrolytes for multivalent electrochemistry. Using a combination of ab initio techniques, we clarify the relation between the reductive stability of contact-ion pairs comprising a multivalent cation and a complex anion, their solvation structures, solvent dynamics, and the electrode overpotential. We found that for ion pairs with multiple configurations of the complex anion and the Mg cation whose available orbitals are partially delocalized over the molecular complex and have antibonding character, the primary factor of the reductive stability is the shape factor of the solvation sphere of the metal cation center and the degree of the convexity of a polyhedron formed by the metal cation and its coordinating atoms. We focused specifically on the details of Mg (II) bis(trifluoromethanesulfonyl)imide in diethylene glycol dimethyl ether (Mg(TFSI)2)/diglyme) and its singly charged ion pair, MgTFSI+. In particular, we found that both stable (MgTFSI)+ and (MgTFSI)0 ion pairs have the same TFSI configuration but drastically different solvation structures in the bulk solution. This implies that the MgTFSI/dyglyme reductive stability is ultimately determined by the relative time scale of the solvent dynamics and electron transfer at the Mg–anode interface. In the vicinity of the anode surface, steric factors and hindered solvent dynamics may increase the reductive stability of (MgTFSI)+ ion pairs at lower overpotential by reducing the metal cation coordination, in stark contrast to the reduction at high overpotential accompanied by TFSI decomposition. By examining other solute/solvent combinations, we conclude that the electrolytes with highly coordinated Mg cation centers are more prone to reductive instability due to the chemical decomposition of the anion or solvent molecules. Finally, the obtained findings disclose critical factors for stable electrolyte design and show the role of interfacial phenomena in reduction of multivalent ions.},
doi = {10.1021/acs.jpcc.5b08999},
journal = {Journal of Physical Chemistry. C},
number = 7,
volume = 120,
place = {United States},
year = {2016},
month = {2}
}

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Works referenced in this record:

Prototype systems for rechargeable magnesium batteries
journal, October 2000

  • Aurbach, D.; Lu, Z.; Schechter, A.
  • Nature, Vol. 407, Issue 6805, p. 724-727
  • DOI: 10.1038/35037553

Mg rechargeable batteries: an on-going challenge
journal, January 2013

  • Yoo, Hyun Deog; Shterenberg, Ivgeni; Gofer, Yosef
  • Energy & Environmental Science, Vol. 6, Issue 8, p. 2265-2279
  • DOI: 10.1039/c3ee40871j

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

Effect of Electrolytic Properties of a Magnesium Organohaloaluminate Electrolyte on Magnesium Deposition
journal, December 2013

  • Benmayza, Aadil; Ramanathan, Mayandi; Arthur, Timothy S.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 51, p. 26881-26888
  • DOI: 10.1021/jp4077068

Accelerating Electrolyte Discovery for Energy Storage with High-Throughput Screening
journal, January 2015

  • Cheng, Lei; Assary, Rajeev S.; Qu, Xiaohui
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 2
  • DOI: 10.1021/jz502319n

Operating mechanisms of electrolytes in magnesium ion batteries: chemical equilibrium, magnesium deposition, and electrolyte oxidation
journal, January 2014

  • Kim, Dong Young; Lim, Younhee; Roy, Basab
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 47
  • DOI: 10.1039/C4CP01259C

Structural Analysis of Electrolyte Solutions for Rechargeable Mg Batteries by Stereoscopic Means and DFT Calculations
journal, April 2011

  • Pour, Nir; Gofer, Yossi; Major, Dan T.
  • Journal of the American Chemical Society, Vol. 133, Issue 16
  • DOI: 10.1021/ja1098512

Towards first principles modeling of electrochemical electrode–electrolyte interfaces
journal, January 2015


Modeling the electrified solid–liquid interface
journal, November 2008


Avoiding pitfalls in the modeling of electrochemical interfaces
journal, January 2013


First-principles calculations of charged surfaces and interfaces: A plane-wave nonrepeated slab approach
journal, March 2006


Electrochemical interface between an ionic liquid and a model metallic electrode
journal, February 2007

  • Reed, Stewart K.; Lanning, Oliver J.; Madden, Paul A.
  • The Journal of Chemical Physics, Vol. 126, Issue 8
  • DOI: 10.1063/1.2464084

Finite-bias electronic transport of molecules in a water solution
journal, June 2010


Standard hydrogen electrode and potential of zero charge in density functional calculations
journal, September 2011

  • Tripkovic, Vladimir; Björketun, Mårten E.; Skúlason, Egill
  • Physical Review B, Vol. 84, Issue 11
  • DOI: 10.1103/PhysRevB.84.115452

Alignment of electronic energy levels at electrochemical interfaces
journal, January 2012

  • Cheng, Jun; Sprik, Michiel
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 32
  • DOI: 10.1039/c2cp41652b

Interfacial Effects on the Band Edges of Functionalized Si Surfaces in Liquid Water
journal, November 2014

  • Pham, Tuan Anh; Lee, Donghwa; Schwegler, Eric
  • Journal of the American Chemical Society, Vol. 136, Issue 49
  • DOI: 10.1021/ja5079865

First-Principles Approach to Calculating Energy Level Alignment at Aqueous Semiconductor Interfaces
journal, October 2014


Predicting the voltage dependence of interfacial electrochemical processes at lithium-intercalated graphite edge planes
journal, January 2015

  • Leung, Kevin
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 3
  • DOI: 10.1039/C4CP04494K

Renormalization of Molecular Electronic Levels at Metal-Molecule Interfaces
journal, November 2006


Electronic Energy Levels of Weakly Coupled Nanostructures: C 60 -Metal Interfaces
journal, July 2008


Constrained-DFT method for accurate energy-level alignment of metal/molecule interfaces
journal, October 2013


First-Principles Molecular Dynamics at a Constant Electrode Potential
journal, December 2012


Chemisorbed Molecules under Potential Bias: Detailed Insights from First-Principles Vibrational Spectroscopies
journal, March 2014


Magnesium Borohydride: From Hydrogen Storage to Magnesium Battery
journal, August 2012

  • Mohtadi, Rana; Matsui, Masaki; Arthur, Timothy S.
  • Angewandte Chemie International Edition, Vol. 51, Issue 39, p. 9780-9783
  • DOI: 10.1002/anie.201204913

Solvation structure and energetics of electrolytes for multivalent energy storage
journal, January 2014

  • Lapidus, Saul H.; Rajput, Nav Nidhi; Qu, Xiaohui
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 40
  • DOI: 10.1039/C4CP03015J

Magnesium(II) Bis(trifluoromethane sulfonyl) Imide-Based Electrolytes with Wide Electrochemical Windows for Rechargeable Magnesium Batteries
journal, March 2014

  • Ha, Se-Young; Lee, Yong-Won; Woo, Sang Won
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 6, p. 4063-4073
  • DOI: 10.1021/am405619v

Paving the Way towards Highly Stable and Practical Electrolytes for Rechargeable Magnesium Batteries
journal, October 2014


Nanocomposite polymer electrolyte for rechargeable magnesium batteries
journal, March 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

Li + -solvation/desolvation dictates interphasial processes on graphitic anode in Li ion cells
journal, August 2012

  • Xu, Kang; von Wald Cresce, Arthur
  • Journal of Materials Research, Vol. 27, Issue 18
  • DOI: 10.1557/jmr.2012.104

Electrochemical Windows of Room-Temperature Ionic Liquids from Molecular Dynamics and Density Functional Theory Calculations
journal, June 2011

  • Ong, Shyue Ping; Andreussi, Oliviero; Wu, Yabi
  • Chemistry of Materials, Vol. 23, Issue 11
  • DOI: 10.1021/cm200679y

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

On the Electrochemical Deposition and Dissolution of Divalent Metal Ions
journal, December 2013

  • Pinto, Leandro M. C.; Quaino, Paola; Santos, Elizabeth
  • ChemPhysChem, Vol. 15, Issue 1
  • DOI: 10.1002/cphc.201300856

Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Nonaqueous Electrolytes
journal, April 2015


Ion-pairing effects in intramolecular electron transfer
journal, September 2002


Partial charge transfer during anion adsorptionMethodological aspects
journal, March 2005


Classical solvent dynamics and electron transfer. 1. Continuum theory
journal, September 1983

  • Calef, Daniel F.; Wolynes, Peter G.
  • The Journal of Physical Chemistry, Vol. 87, Issue 18
  • DOI: 10.1021/j100241a008

Nonadiabatic Electron Transfer at Metal Surfaces
journal, March 2000

  • Gosavi, Shachi; Marcus, R. A.
  • The Journal of Physical Chemistry B, Vol. 104, Issue 9
  • DOI: 10.1021/jp9933673

Direct Calculation of Electron Transfer Parameters through Constrained Density Functional Theory
journal, July 2006

  • Wu, Qin; Van Voorhis, Troy
  • The Journal of Physical Chemistry A, Vol. 110, Issue 29
  • DOI: 10.1021/jp061848y

Extracting electron transfer coupling elements from constrained density functional theory
journal, October 2006

  • Wu, Qin; Van Voorhis, Troy
  • The Journal of Chemical Physics, Vol. 125, Issue 16
  • DOI: 10.1063/1.2360263

Constrained Density Functional Theory and Its Application in Long-Range Electron Transfer
journal, May 2006

  • Wu, Qin; Van Voorhis, Troy
  • Journal of Chemical Theory and Computation, Vol. 2, Issue 3
  • DOI: 10.1021/ct0503163

The PYXAID Program for Non-Adiabatic Molecular Dynamics in Condensed Matter Systems
journal, October 2013

  • Akimov, Alexey V.; Prezhdo, Oleg V.
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 11
  • DOI: 10.1021/ct400641n

Theoretical Insights into Photoinduced Charge Transfer and Catalysis at Oxide Interfaces
journal, December 2012

  • Akimov, Alexey V.; Neukirch, Amanda J.; Prezhdo, Oleg V.
  • Chemical Reviews, Vol. 113, Issue 6
  • DOI: 10.1021/cr3004899

Nonadiabatic Dynamics of Charge Transfer and Singlet Fission at the Pentacene/C 60 Interface
journal, January 2014

  • Akimov, Alexey V.; Prezhdo, Oleg V.
  • Journal of the American Chemical Society, Vol. 136, Issue 4
  • DOI: 10.1021/ja411800n

Electrodeposited Bi, Sb and Bi1-xSbx alloys as anodes for Mg-ion batteries
journal, March 2012

  • Arthur, Timothy S.; Singh, Nikhilendra; Matsui, Masaki
  • Electrochemistry Communications, Vol. 16, Issue 1
  • DOI: 10.1016/j.elecom.2011.12.010

Highly Reversible Mg Insertion in Nanostructured Bi for Mg Ion Batteries
journal, December 2013

  • Shao, Yuyan; Gu, Meng; Li, Xiaolin
  • Nano Letters, Vol. 14, Issue 1
  • DOI: 10.1021/nl403874y

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

Plating of magnesium from organic solvents
journal, February 1996


Aqueous Solvation Free Energies of Ions and Ion−Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton
journal, August 2006

  • Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 32
  • DOI: 10.1021/jp063552y

The Solvation Structure of Mg Ions in Dichloro Complex Solutions from First-Principles Molecular Dynamics and Simulated X-ray Absorption Spectra
journal, October 2014

  • Wan, Liwen F.; Prendergast, David
  • Journal of the American Chemical Society, Vol. 136, Issue 41
  • DOI: 10.1021/ja505967u

Quantum Chemistry on Graphical Processing Units. 3. Analytical Energy Gradients, Geometry Optimization, and First Principles Molecular Dynamics
journal, August 2009

  • Ufimtsev, Ivan S.; Martinez, Todd J.
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 10
  • DOI: 10.1021/ct9003004

Assessment of Kohn–Sham density functional theory and Møller–Plesset perturbation theory for ionic liquids
journal, January 2013

  • Zahn, Stefan; MacFarlane, Douglas R.; Izgorodina, Ekaterina I.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 32
  • DOI: 10.1039/c3cp51682b

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

DL-FIND: An Open-Source Geometry Optimizer for Atomistic Simulations
journal, October 2009

  • Kästner, Johannes; Carr, Joanne M.; Keal, Thomas W.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 43
  • DOI: 10.1021/jp9028968

Improved modeling of electrified interfaces using the effective screening medium method
journal, October 2013


Density-functional method for very large systems with LCAO basis sets
journal, January 1997


Self-interaction correction to density-functional approximations for many-electron systems
journal, May 1981


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases
journal, September 2007

  • VandeVondele, Joost; Hutter, Jürg
  • The Journal of Chemical Physics, Vol. 127, Issue 11
  • DOI: 10.1063/1.2770708

cp2k: atomistic simulations of condensed matter systems
journal, June 2013

  • Hutter, Jürg; Iannuzzi, Marcella; Schiffmann, Florian
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 1
  • DOI: 10.1002/wcms.1159

A unified formulation of the constant temperature molecular dynamics methods
journal, July 1984

  • Nosé, Shuichi
  • The Journal of Chemical Physics, Vol. 81, Issue 1
  • DOI: 10.1063/1.447334

Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985


Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


The two-phase model for calculating thermodynamic properties of liquids from molecular dynamics: Validation for the phase diagram of Lennard-Jones fluids
journal, December 2003

  • Lin, Shiang-Tai; Blanco, Mario; Goddard, William A.
  • The Journal of Chemical Physics, Vol. 119, Issue 22
  • DOI: 10.1063/1.1624057

Two-Phase Thermodynamic Model for Efficient and Accurate Absolute Entropy of Water from Molecular Dynamics Simulations
journal, June 2010

  • Lin, Shiang-Tai; Maiti, Prabal K.; Goddard, William A.
  • The Journal of Physical Chemistry B, Vol. 114, Issue 24
  • DOI: 10.1021/jp103120q

Thermodynamics of liquids: standard molar entropies and heat capacities of common solvents from 2PT molecular dynamics
journal, January 2011

  • Pascal, Tod A.; Lin, Shiang-Tai; Goddard III, William A.
  • Phys. Chem. Chem. Phys., Vol. 13, Issue 1
  • DOI: 10.1039/C0CP01549K

Li + −Diglyme Complexes:  Barriers to Lithium Cation Migration
journal, February 1998

  • Sutjianto, Amin; Curtiss, Larry A.
  • The Journal of Physical Chemistry A, Vol. 102, Issue 6
  • DOI: 10.1021/jp972164g

Probing Adsorption Interactions in Metal–Organic Frameworks using X-ray Spectroscopy
journal, November 2013

  • Drisdell, Walter S.; Poloni, Roberta; McDonald, Thomas M.
  • Journal of the American Chemical Society, Vol. 135, Issue 48
  • DOI: 10.1021/ja408972f

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  • Advanced Energy Materials, Vol. 7, Issue 11
  • DOI: 10.1002/aenm.201602055

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journal, February 2018


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journal, November 2018


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journal, January 2019

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  • Journal of Materials Chemistry A, Vol. 7, Issue 14
  • DOI: 10.1039/c9ta00987f

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journal, January 2019

  • Ma, Zheng; MacFarlane, Douglas R.; Kar, Mega
  • Batteries & Supercaps, Vol. 2, Issue 2
  • DOI: 10.1002/batt.201800102

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journal, September 2017

  • Gao, Tao; Hou, Singyuk; Wang, Fei
  • Angewandte Chemie International Edition, Vol. 56, Issue 43
  • DOI: 10.1002/anie.201708241