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Title: Localized High Concentration Electrolyte Behavior near a Lithium-Metal Anode Surface

Abstract

Wide-scale practical application of rechargeable lithium-metal batteries remains a significant challenge due to dendrite growth. To overcome this challenge, electrolytes must be designed to allow for the formation of protective solid electrolyte interphase (SEI) layers on the highly reactive lithium-metal anode (LMA) surfaces. Recently, novel localized high-concentration electrolytes (LHCEs) were introduced as a potential solution to enable dendrite-free cycling of LMAs, by using an inert solvent to “dilute” the high concentration electrolytes. Ideally, the diluent itself does not dissolve the salt but is miscible with the solvent to form a localized high concentrated salt/solvent cluster surrounded by the diluent. However, detailed structure and potential surface reactions that may take place in LHCE environment are not yet clear. In this work, we investigated the reactivity of a 1M lithium bis(fluorosulfonyl)imide (LiFSI) in a mixture of dimethoxyethane (DME)/Tris(2,2,2-trifluoroethyl)orthoformate (TFEO) (1:3 by mol) electrolyte near a Li metal surface based on density functional theory and ab-initio molecular dynamics (MD) simulations. Selected liquid interfacial configurations were obtained from classical MD simulasults indicate that when salt and TFEO molecules are close to each other and to the surface, fluorine anions resulting from the fast salt anion decomposition can trigger a cascade of reactions that leadmore » to the decomposition of TFEO. However, if the Li cation is initially solvated by DME and the anion forming a complex, the stability of the anion increases significantly. The Li solvated structure is implied in the LHCE concept; however statistically the larger amount of TFEO molecules suggest also the first scenario leading to TFEO decomposition. Therefore, the broader implication of our simulations is that the defluorination of TFEO may contribute, together with the anion decomposition, to the observed rapid formation of a stable SEI on the surface of the lithium metal; consequently, favorably affecting the stability of LMAs during battery operation.« less

Authors:
 [1];  [1];  [1];  [1];  [2]; ORCiD logo [2];  [1]
  1. Texas A & M University
  2. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1574904
Report Number(s):
PNNL-SA-148417
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Materials Chemistry A
Additional Journal Information:
Journal Volume: 7; Journal Issue: 43
Country of Publication:
United States
Language:
English

Citation Formats

Zheng, Yu, Soto, Fernando A., Ponce, Victor, Seminario, Jorge, Cao, Xia, Zhang, Jiguang, and Balbuena, Perla B. Localized High Concentration Electrolyte Behavior near a Lithium-Metal Anode Surface. United States: N. p., 2019. Web. doi:10.1039/C9TA08935G.
Zheng, Yu, Soto, Fernando A., Ponce, Victor, Seminario, Jorge, Cao, Xia, Zhang, Jiguang, & Balbuena, Perla B. Localized High Concentration Electrolyte Behavior near a Lithium-Metal Anode Surface. United States. doi:10.1039/C9TA08935G.
Zheng, Yu, Soto, Fernando A., Ponce, Victor, Seminario, Jorge, Cao, Xia, Zhang, Jiguang, and Balbuena, Perla B. Thu . "Localized High Concentration Electrolyte Behavior near a Lithium-Metal Anode Surface". United States. doi:10.1039/C9TA08935G.
@article{osti_1574904,
title = {Localized High Concentration Electrolyte Behavior near a Lithium-Metal Anode Surface},
author = {Zheng, Yu and Soto, Fernando A. and Ponce, Victor and Seminario, Jorge and Cao, Xia and Zhang, Jiguang and Balbuena, Perla B.},
abstractNote = {Wide-scale practical application of rechargeable lithium-metal batteries remains a significant challenge due to dendrite growth. To overcome this challenge, electrolytes must be designed to allow for the formation of protective solid electrolyte interphase (SEI) layers on the highly reactive lithium-metal anode (LMA) surfaces. Recently, novel localized high-concentration electrolytes (LHCEs) were introduced as a potential solution to enable dendrite-free cycling of LMAs, by using an inert solvent to “dilute” the high concentration electrolytes. Ideally, the diluent itself does not dissolve the salt but is miscible with the solvent to form a localized high concentrated salt/solvent cluster surrounded by the diluent. However, detailed structure and potential surface reactions that may take place in LHCE environment are not yet clear. In this work, we investigated the reactivity of a 1M lithium bis(fluorosulfonyl)imide (LiFSI) in a mixture of dimethoxyethane (DME)/Tris(2,2,2-trifluoroethyl)orthoformate (TFEO) (1:3 by mol) electrolyte near a Li metal surface based on density functional theory and ab-initio molecular dynamics (MD) simulations. Selected liquid interfacial configurations were obtained from classical MD simulasults indicate that when salt and TFEO molecules are close to each other and to the surface, fluorine anions resulting from the fast salt anion decomposition can trigger a cascade of reactions that lead to the decomposition of TFEO. However, if the Li cation is initially solvated by DME and the anion forming a complex, the stability of the anion increases significantly. The Li solvated structure is implied in the LHCE concept; however statistically the larger amount of TFEO molecules suggest also the first scenario leading to TFEO decomposition. Therefore, the broader implication of our simulations is that the defluorination of TFEO may contribute, together with the anion decomposition, to the observed rapid formation of a stable SEI on the surface of the lithium metal; consequently, favorably affecting the stability of LMAs during battery operation.},
doi = {10.1039/C9TA08935G},
journal = {Journal of Materials Chemistry A},
number = 43,
volume = 7,
place = {United States},
year = {2019},
month = {11}
}

Works referenced in this record:

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

Solid State Electrodes for High Energy Batteries
journal, August 1979


A review of advanced and practical lithium battery materials
journal, January 2011

  • Marom, Rotem; Amalraj, S. Francis; Leifer, Nicole
  • Journal of Materials Chemistry, Vol. 21, Issue 27
  • DOI: 10.1039/c0jm04225k

The Application of Atomic Force Microscopy for the Study of Li Deposition Processes
journal, January 1996

  • Aurbach, Doron
  • Journal of The Electrochemical Society, Vol. 143, Issue 11
  • DOI: 10.1149/1.1837248

Stable lithium electrodeposition in liquid and nanoporous solid electrolytes
journal, August 2014

  • Lu, Yingying; Tu, Zhengyuan; Archer, Lynden A.
  • Nature Materials, Vol. 13, Issue 10
  • DOI: 10.1038/nmat4041

Reviving the lithium metal anode for high-energy batteries
journal, March 2017

  • Lin, Dingchang; Liu, Yayuan; Cui, Yi
  • Nature Nanotechnology, Vol. 12, Issue 3
  • DOI: 10.1038/nnano.2017.16

Effects of Carbonate Solvents and Lithium Salts on Morphology and Coulombic Efficiency of Lithium Electrode
journal, January 2013

  • Ding, Fei; Xu, Wu; Chen, Xilin
  • Journal of The Electrochemical Society, Vol. 160, Issue 10
  • DOI: 10.1149/2.100310jes

Lithium metal anodes for rechargeable batteries
journal, January 2014

  • Xu, Wu; Wang, Jiulin; Ding, Fei
  • Energy Environ. Sci., Vol. 7, Issue 2
  • DOI: 10.1039/C3EE40795K

Synergistic Effect of Graphene Oxide for Impeding the Dendritic Plating of Li
journal, February 2018

  • Foroozan, Tara; Soto, Fernando A.; Yurkiv, Vitaliy
  • Advanced Functional Materials, Vol. 28, Issue 15
  • DOI: 10.1002/adfm.201705917

Research Progress towards Understanding the Unique Interfaces between Concentrated Electrolytes and Electrodes for Energy Storage Applications
journal, March 2017

  • Zheng, Jianming; Lochala, Joshua A.; Kwok, Alexander
  • Advanced Science, Vol. 4, Issue 8
  • DOI: 10.1002/advs.201700032

Superconcentrated electrolytes for a high-voltage lithium-ion battery
journal, June 2016

  • Wang, Jianhui; Yamada, Yuki; Sodeyama, Keitaro
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12032

Anode-Free Rechargeable Lithium Metal Batteries
journal, August 2016

  • Qian, Jiangfeng; Adams, Brian D.; Zheng, Jianming
  • Advanced Functional Materials, Vol. 26, Issue 39
  • DOI: 10.1002/adfm.201602353

Extremely Stable Sodium Metal Batteries Enabled by Localized High-Concentration Electrolytes
journal, January 2018


Accurate Determination of Coulombic Efficiency for Lithium Metal Anodes and Lithium Metal Batteries
journal, October 2017

  • Adams, Brian D.; Zheng, Jianming; Ren, Xiaodi
  • Advanced Energy Materials, Vol. 8, Issue 7
  • DOI: 10.1002/aenm.201702097

High-Voltage Lithium-Metal Batteries Enabled by Localized High-Concentration Electrolytes
journal, March 2018

  • Chen, Shuru; Zheng, Jianming; Mei, Donghai
  • Advanced Materials, Vol. 30, Issue 21
  • DOI: 10.1002/adma.201706102

A Highly Reversible Lithium Metal Anode
journal, January 2014

  • Park, Min Sik; Ma, Sang Bok; Lee, Dong Joon
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep03815

High‐Fluorinated Electrolytes for Li–S Batteries
journal, February 2019

  • Zheng, Jing; Ji, Guangbin; Fan, Xiulin
  • Advanced Energy Materials, Vol. 9, Issue 16
  • DOI: 10.1002/aenm.201803774

Locally Concentrated LiPF 6 in a Carbonate-Based Electrolyte with Fluoroethylene Carbonate as a Diluent for Anode-Free Lithium Metal Batteries
journal, February 2019

  • Hagos, Tesfaye Teka; Thirumalraj, Balamurugan; Huang, Chen-Jui
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 10
  • DOI: 10.1021/acsami.8b21052

Multi-scale computation methods: Their applications in lithium-ion battery research and development
journal, January 2016


Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries
journal, March 2018


Review on multi-scale models of solid-electrolyte interphase formation
journal, February 2019


Formation and Growth Mechanisms of Solid-Electrolyte Interphase Layers in Rechargeable Batteries
journal, November 2015


Ab initio molecular dynamics simulations of the initial stages of solid–electrolyte interphase formation on lithium ion battery graphitic anodes
journal, January 2010

  • Leung, Kevin; Budzien, Joanne L.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 25
  • DOI: 10.1039/b925853a

Buildup of the Solid Electrolyte Interphase on Lithium-Metal Anodes: Reactive Molecular Dynamics Study
journal, April 2018

  • Bertolini, Samuel; Balbuena, Perla B.
  • The Journal of Physical Chemistry C, Vol. 122, Issue 20
  • DOI: 10.1021/acs.jpcc.8b03046

Interfacial Structure and Dynamics of the Lithium Alkyl Dicarbonate SEI Components in Contact with the Lithium Battery Electrolyte
journal, July 2014

  • Borodin, Oleg; Bedrov, Dmitry
  • The Journal of Physical Chemistry C, Vol. 118, Issue 32
  • DOI: 10.1021/jp504598n

Molecular dynamics simulations of the first charge of a Li-ion—Si-anode nanobattery
journal, March 2017

  • Galvez-Aranda, Diego E.; Ponce, Victor; Seminario, Jorge M.
  • Journal of Molecular Modeling, Vol. 23, Issue 4
  • DOI: 10.1007/s00894-017-3283-2

Analysis of a Li-Ion Nanobattery with Graphite Anode Using Molecular Dynamics Simulations
journal, June 2017

  • Ponce, Victor; Galvez-Aranda, Diego E.; Seminario, Jorge M.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 23
  • DOI: 10.1021/acs.jpcc.7b04190

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Ab initiomolecular dynamics for liquid metals
journal, January 1993


Projector augmented-wave method
journal, December 1994


A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006


Improved grid-based algorithm for Bader charge allocation
journal, January 2007

  • Sanville, Edward; Kenny, Steven D.; Smith, Roger
  • Journal of Computational Chemistry, Vol. 28, Issue 5
  • DOI: 10.1002/jcc.20575

Reactivity at the Lithium–Metal Anode Surface of Lithium–Sulfur Batteries
journal, November 2015

  • Camacho-Forero, Luis E.; Smith, Taylor W.; Bertolini, Samuel
  • The Journal of Physical Chemistry C, Vol. 119, Issue 48
  • DOI: 10.1021/acs.jpcc.5b08254

Effects of High and Low Salt Concentration in Electrolytes at Lithium–Metal Anode Surfaces
journal, December 2016

  • Camacho-Forero, Luis E.; Smith, Taylor W.; Balbuena, Perla B.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 1
  • DOI: 10.1021/acs.jpcc.6b10774

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

How Accurate Are DFT Treatments of Organic Energies?
journal, May 2007

  • Wodrich, Matthew D.; Corminboeuf, Clémence; Schreiner, Peter R.
  • Organic Letters, Vol. 9, Issue 10
  • DOI: 10.1021/ol070354w

An ab Initio CFF93 All-Atom Force Field for Polycarbonates
journal, April 1994

  • Sun, Huai; Mumby, Stephen J.; Maple, Jon R.
  • Journal of the American Chemical Society, Vol. 116, Issue 7
  • DOI: 10.1021/ja00086a030

Potential Energy Landscape of Bis(fluorosulfonyl)amide
journal, August 2008

  • Canongia Lopes, José N.; Shimizu, Karina; Pádua, Agílio A. H.
  • The Journal of Physical Chemistry B, Vol. 112, Issue 31
  • DOI: 10.1021/jp803309c

Publisher Correction: Advances and issues in developing salt-concentrated battery electrolytes
journal, March 2019


Elucidating electrolyte decomposition under electron-rich environments at the lithium-metal anode
journal, January 2017

  • Camacho-Forero, Luis E.; Balbuena, Perla B.
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 45
  • DOI: 10.1039/C7CP06485C