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Title: Effect of electrolyte on the nanostructure of the solid electrolyte interphase (SEI) and performance of lithium metal anodes

Abstract

Developing electrolytes that enable commercially viable lithium metal anodes for rechargeable lithium batteries remains challenging, despite recent exhaustive efforts. Electrolytes of similar composition, yet different structure, have been investigated to understand key mechanisms for improving the cycling performance of lithium metal anodes. Specifically, the electrolytes investigated include LiPF6, LiBF4, lithium bis(oxalato)borate (LiBOB), and lithium difluoro(oxalato)borate (LiDFOB) dissolved in a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC). There is a remarkable difference in the cycling performance of 1.2 M LiDFOB in EC:EMC (3:7) compared to 0.6 M LiBF4 + 0.6 M LiBOB in EC:EMC (3:7), despite the effectively equivalent chemical composition. The LiDFOB electrolyte has significantly better cycling performance. Furthermore, the chemical compositions of the SEI generated on the lithium metal electrode from the two electrolytes are very similar, especially after the 1st plating, suggesting that the chemical composition of the SEI may not be the primary source for the difference in cycling performance. Ex-situ transmission electron microscopy (TEM) reveals that the difference in cycling performance can be traced to the presence of nanostructured LiF particles in the SEI from the LiDFOB electrolyte. It is proposed that the capping ability of the oxalate moiety from LiDFOB, in combinationmore » with simultaneous generation of LiF, leads to generation of uniform and evenly distributed nanostructured LiF particles. The presence of nanostructured LiF in the SEI results in uniform diffusion field gradients on the lithium electrode which leads to improved cycling performance. The proposed mechanism not only provides insight for improving lithium metal anodes for batteries, but also expands upon the understanding of the role of LiF in the SEI on graphite electrodes in commercial lithium ion batteries. A superior understanding of the structure and function of the SEI will facilitate the development of next-generation energy storage systems.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
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  1. Univ. of Rhode Island, Kingston, RI (United States)
Publication Date:
Research Org.:
Brown Univ., Providence, RI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1512926
Alternate Identifier(s):
OSTI ID: 1459686
Grant/Contract Number:  
SC0007074
Resource Type:
Accepted Manuscript
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Volume: 11; Journal Issue: 9; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Jurng, Sunhyung, Brown, Zachary L., Kim, Jiyeon, and Lucht, Brett L. Effect of electrolyte on the nanostructure of the solid electrolyte interphase (SEI) and performance of lithium metal anodes. United States: N. p., 2018. Web. doi:10.1039/c8ee00364e.
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Jurng, Sunhyung, Brown, Zachary L., Kim, Jiyeon, & Lucht, Brett L. Effect of electrolyte on the nanostructure of the solid electrolyte interphase (SEI) and performance of lithium metal anodes. United States. https://doi.org/10.1039/c8ee00364e
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Jurng, Sunhyung, Brown, Zachary L., Kim, Jiyeon, and Lucht, Brett L. Tue . "Effect of electrolyte on the nanostructure of the solid electrolyte interphase (SEI) and performance of lithium metal anodes". United States. https://doi.org/10.1039/c8ee00364e. https://www.osti.gov/servlets/purl/1512926.
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@article{osti_1512926,
title = {Effect of electrolyte on the nanostructure of the solid electrolyte interphase (SEI) and performance of lithium metal anodes},
author = {Jurng, Sunhyung and Brown, Zachary L. and Kim, Jiyeon and Lucht, Brett L.},
abstractNote = {Developing electrolytes that enable commercially viable lithium metal anodes for rechargeable lithium batteries remains challenging, despite recent exhaustive efforts. Electrolytes of similar composition, yet different structure, have been investigated to understand key mechanisms for improving the cycling performance of lithium metal anodes. Specifically, the electrolytes investigated include LiPF6, LiBF4, lithium bis(oxalato)borate (LiBOB), and lithium difluoro(oxalato)borate (LiDFOB) dissolved in a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC). There is a remarkable difference in the cycling performance of 1.2 M LiDFOB in EC:EMC (3:7) compared to 0.6 M LiBF4 + 0.6 M LiBOB in EC:EMC (3:7), despite the effectively equivalent chemical composition. The LiDFOB electrolyte has significantly better cycling performance. Furthermore, the chemical compositions of the SEI generated on the lithium metal electrode from the two electrolytes are very similar, especially after the 1st plating, suggesting that the chemical composition of the SEI may not be the primary source for the difference in cycling performance. Ex-situ transmission electron microscopy (TEM) reveals that the difference in cycling performance can be traced to the presence of nanostructured LiF particles in the SEI from the LiDFOB electrolyte. It is proposed that the capping ability of the oxalate moiety from LiDFOB, in combination with simultaneous generation of LiF, leads to generation of uniform and evenly distributed nanostructured LiF particles. The presence of nanostructured LiF in the SEI results in uniform diffusion field gradients on the lithium electrode which leads to improved cycling performance. The proposed mechanism not only provides insight for improving lithium metal anodes for batteries, but also expands upon the understanding of the role of LiF in the SEI on graphite electrodes in commercial lithium ion batteries. A superior understanding of the structure and function of the SEI will facilitate the development of next-generation energy storage systems.},
doi = {10.1039/c8ee00364e},
journal = {Energy & Environmental Science},
number = 9,
volume = 11,
place = {United States},
year = {2018},
month = {7}
}
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Works referenced in this record:

Nanostructured Electrolytes for Stable Lithium Electrodeposition in Secondary Batteries
journal, October 2015

On Electrolyte-Dependent Formation of Solid Electrolyte Interphase Film in Lithium-Ion Batteries: Strong Sensitivity to Small Structural Difference of Electrolyte Molecules
journal, May 2014

  • Takenaka, Norio; Suzuki, Yuichi; Sakai, Hirofumi
  • The Journal of Physical Chemistry C, Vol. 118, Issue 20
  • DOI: 10.1021/jp5018696

Electrolyte additive enabled fast charging and stable cycling lithium metal batteries
journal, March 2017

Ultrathin Two-Dimensional Atomic Crystals as Stable Interfacial Layer for Improvement of Lithium Metal Anode
journal, September 2014

  • Yan, Kai; Lee, Hyun-Wook; Gao, Teng
  • Nano Letters, Vol. 14, Issue 10
  • DOI: 10.1021/nl503125u

Theory of ultramicroelectrodes
journal, September 1993

Silicon Solid Electrolyte Interphase (SEI) of Lithium Ion Battery Characterized by Microscopy and Spectroscopy
journal, June 2013

  • Nie, Mengyun; Abraham, Daniel P.; Chen, Yanjing
  • The Journal of Physical Chemistry C, Vol. 117, Issue 26
  • DOI: 10.1021/jp404155y

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

An Artificial Solid Electrolyte Interphase Layer for Stable Lithium Metal Anodes
journal, December 2015

Regulating Li deposition at artificial solid electrolyte interphases
journal, January 2017

  • Fan, Lei; Zhuang, Houlong L.; Gao, Lina
  • Journal of Materials Chemistry A, Vol. 5, Issue 7
  • DOI: 10.1039/C6TA10204B

Modified carbons for improved anodes in lithium ion cells
journal, July 2001

Ion Diffusivity through the Solid Electrolyte Interphase in Lithium-Ion Batteries
journal, January 2017

  • Benitez, Laura; Seminario, Jorge M.
  • Journal of The Electrochemical Society, Vol. 164, Issue 11
  • DOI: 10.1149/2.0181711jes

Synthesis and characterization of LiBOB as electrolyte for lithium-ion battery
journal, September 2015

Status of the secondary lithium electrode
journal, January 1981

Lithium Fluoride Additives for Stable Cycling of Lithium Batteries at High Current Densities
journal, January 2016

  • Choudhury, Snehashis; Archer, Lynden A.
  • Advanced Electronic Materials, Vol. 2, Issue 2
  • DOI: 10.1002/aelm.201500246

The Origin of Stress in the Solid Electrolyte Interphase on Carbon Electrodes for Li Ion Batteries
journal, October 2013

  • Tokranov, A.; Sheldon, B. W.; Lu, P.
  • Journal of The Electrochemical Society, Vol. 161, Issue 1
  • DOI: 10.1149/2.009401jes

Study of SEI Layer Formed on Graphite Anodes in PC/LiBOB Electrolyte Using IR Spectroscopy
journal, January 2004

  • Zhuang, G. V.; Xu, K.; Jow, T. R.
  • Electrochemical and Solid-State Letters, Vol. 7, Issue 8
  • DOI: 10.1149/1.1756855

Ultramicroelectrodes: Design, Fabrication, and Characterization
journal, August 2002

Untangling the Role of the Capping Agent in Nanocatalysis: Recent Advances and Perspectives
journal, November 2016

  • Campisi, Sebastiano; Schiavoni, Marco; Chan-Thaw, Carine
  • Catalysts, Vol. 6, Issue 12
  • DOI: 10.3390/catal6120185

Role of Capping Agent in Wet Synthesis of Nanoparticles
journal, April 2017

Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, October 2004

The nanoscale structure of the electrolyte–metal oxide interface
journal, January 2018

  • Steinrück, Hans-Georg; Cao, Chuntian; Tsao, Yuchi
  • Energy & Environmental Science, Vol. 11, Issue 3
  • DOI: 10.1039/C7EE02724A

Investigation of the Lithium Solid Electrolyte Interphase in Vinylene Carbonate Electrolytes Using Cu||LiFePO 4 Cells
journal, January 2017

  • Brown, Zachary L.; Jurng, Sunhyung; Lucht, Brett L.
  • Journal of The Electrochemical Society, Vol. 164, Issue 9
  • DOI: 10.1149/2.0021712jes

Dendrite-free Li deposition using trace-amounts of water as an electrolyte additive
journal, July 2015

K + Reduces Lithium Dendrite Growth by Forming a Thin, Less-Resistive Solid Electrolyte Interphase
journal, July 2016

Nanodiamonds suppress the growth of lithium dendrites
journal, August 2017

Compatibility of lithium oxalyldifluoroborate with lithium metal anode in rechargeable batteries
journal, January 2018

Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?
journal, December 2008

  • Xia, Younan; Xiong, Yujie; Lim, Byungkwon
  • Angewandte Chemie International Edition, Vol. 48, Issue 1, p. 60-103
  • DOI: 10.1002/anie.200802248

Improved Cycle Life and Stability of Lithium Metal Anodes through Ultrathin Atomic Layer Deposition Surface Treatments
journal, September 2015

A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries
journal, September 2010

Oxalate capped iron nanomaterial: from methylene blue degradation to bis(indolyl)methane synthesis
journal, January 2014

  • Pegu, Rupa; Majumdar, Krishna Joyti; Talukdar, Dhruba Joyti
  • RSC Adv., Vol. 4, Issue 63
  • DOI: 10.1039/C4RA04214J

A Secondary, Nonaqueous Solvent Battery
journal, January 1971

  • Dunning, John S.; Tiedemann, William H.; Hsueh, Limin
  • Journal of The Electrochemical Society, Vol. 118, Issue 12
  • DOI: 10.1149/1.2407861

Surface film formation on electrodes in a LiCoO2/graphite cell: A step by step XPS study
journal, December 2007

XPS Identification of the Organic and Inorganic Components of the Electrode/Electrolyte Interface Formed on a Metallic Cathode
journal, January 2005

  • Dedryvère, R.; Laruelle, S.; Grugeon, S.
  • Journal of The Electrochemical Society, Vol. 152, Issue 4
  • DOI: 10.1149/1.1861994

Hybrid Hairy Nanoparticle Electrolytes Stabilizing Lithium Metal Batteries
journal, March 2016

Role of Lithium Salt on Solid Electrolyte Interface (SEI) Formation and Structure in Lithium Ion Batteries
journal, January 2014

  • Nie, Mengyun; Lucht, Brett L.
  • Journal of The Electrochemical Society, Vol. 161, Issue 6
  • DOI: 10.1149/2.054406jes

An Effective Approach To Protect Lithium Anode and Improve Cycle Performance for Li–S Batteries
journal, August 2014

  • Wu, Feng; Qian, Ji; Chen, Renjie
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 17
  • DOI: 10.1021/am504345s

Fluoroethylene Carbonate Additives to Render Uniform Li Deposits in Lithium Metal Batteries
journal, January 2017

  • Zhang, Xue-Qiang; Cheng, Xin-Bing; Chen, Xiang
  • Advanced Functional Materials, Vol. 27, Issue 10
  • DOI: 10.1002/adfm.201605989

Very Stable Lithium Metal Stripping–Plating at a High Rate and High Areal Capacity in Fluoroethylene Carbonate-Based Organic Electrolyte Solution
journal, May 2017

New Insights on the Structure of Electrochemically Deposited Lithium Metal and Its Solid Electrolyte Interphases via Cryogenic TEM
journal, November 2017

Ionic liquid-based electrolyte with dual-functional LiDFOB additive toward high-performance LiMn2O4 batteries
journal, January 2017

X-ray photoelectron spectroscopy of boron compounds
journal, May 2005

  • Il’inchik, E. A.; Volkov, V. V.; Mazalov, L. N.
  • Journal of Structural Chemistry, Vol. 46, Issue 3
  • DOI: 10.1007/s10947-006-0133-y

Chemical Analysis of Graphite/Electrolyte Interface Formed in LiBOB-Based Electrolytes
journal, January 2003

  • Xu, Kang; Lee, Unchul; Zhang, Shengshui
  • Electrochemical and Solid-State Letters, Vol. 6, Issue 7
  • DOI: 10.1149/1.1576049

The influence of lithium salt on the interfacial reactions controlling the thermal stability of graphite anodes
journal, May 2002

Chemical Composition and Morphology of the Elevated Temperature SEI on Graphite
journal, January 2001

  • Andersson, A. M.; Edström, K.
  • Journal of The Electrochemical Society, Vol. 148, Issue 10
  • DOI: 10.1149/1.1397771

Nanocrystalline Oxalate/Carbonate Precursors of Ce and Zr and Their Decompositions to CeO 2 and ZrO 2 Nanoparticles
journal, March 2007

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

High rate and stable cycling of lithium metal anode
journal, February 2015

  • Qian, Jiangfeng; Henderson, Wesley A.; Xu, Wu
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7362

Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, December 2004

Decoupling the origins of irreversible coulombic efficiency in anode-free lithium metal batteries
journal, March 2021

  • Huang, Chen-Jui; Thirumalraj, Balamurugan; Tao, Hsien-Chu
  • Nature Communications, Vol. 12, Issue 1
  • DOI: 10.1038/s41467-021-21683-6

Stable Lithium Electrodeposition in Liquid and Nanoporous Solid Electrolytes
text, January 2014

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    • DOI: 10.1002/adfm.201808756

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    journal, May 2019

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    • Advanced Materials, Vol. 31, Issue 29
    • DOI: 10.1002/adma.201901645

    Tuning the Electron Density of Aromatic Solvent for Stable Solid-Electrolyte-Interphase Layer in Carbonate-Based Lithium Metal Batteries
    journal, October 2018

    • Yoo, Dong-Joo; Yang, Sungyun; Yun, Yang Sik
    • Advanced Energy Materials, Vol. 8, Issue 33
    • DOI: 10.1002/aenm.201802365

    A New Electrolyte Formulation for Securing High Temperature Cycling and Storage Performances of Na‐Ion Batteries
    journal, September 2019

    • Yan, Guochun; Reeves, Kyle; Foix, Dominique
    • Advanced Energy Materials, Vol. 9, Issue 41
    • DOI: 10.1002/aenm.201901431

    Marginal Magnesium Doping for High‐Performance Lithium Metal Batteries
    journal, September 2019

    • Choi, Seung Ho; Lee, Seung Jong; Yoo, Dong‐Joo
    • Advanced Energy Materials, Vol. 9, Issue 41
    • DOI: 10.1002/aenm.201902278

    Boosting Superior Lithium Storage Performance of Alloy‐Based Anode Materials via Ultraconformal Sb Coating–Derived Favorable Solid‐Electrolyte Interphase
    journal, December 2019

    • Xiong, Bing‐Qing; Zhou, Xinwei; Xu, Gui‐Liang
    • Advanced Energy Materials, Vol. 10, Issue 4
    • DOI: 10.1002/aenm.201903186

    Surface Properties of Battery Materials Elucidated Using Scanning Electrochemical Microscopy: The Case of Type I Silicon Clathrate
    journal, December 2019

    • Tarnev, Tsvetan; Wilde, Patrick; Dopilka, Andrew
    • ChemElectroChem, Vol. 7, Issue 3
    • DOI: 10.1002/celc.201901688

    An Interfacial Layer Based on Polymers of Intrinsic Microporosity to Suppress Dendrite Growth on Li Metal Anodes
    journal, August 2019

    • Qi, Liya; Shang, Luoran; Wu, Kai
    • Chemistry – A European Journal, Vol. 25, Issue 52
    • DOI: 10.1002/chem.201902124

    Degradation Mechanisms and Mitigation Strategies of Nickel-Rich NMC-Based Lithium-Ion Batteries
    journal, October 2019

    Anode interfacial layer formation via reductive ethyl detaching of organic iodide in lithium–oxygen batteries
    journal, August 2019

    Long cycle life and dendrite-free lithium morphology in anode-free lithium pouch cells enabled by a dual-salt liquid electrolyte
    journal, July 2019

    A 3D free-standing lithiophilic silver nanowire aerogel for lithium metal batteries without lithium dendrites and volume expansion: in operando X-ray diffraction
    journal, January 2019

    • Phattharasupakun, Nutthaphon; Wutthiprom, Juthaporn; Duangdangchote, Salatan
    • Chemical Communications, Vol. 55, Issue 40
    • DOI: 10.1039/c9cc01528k

    A self-healing interface on lithium metal with lithium difluoro (bisoxalato) phosphate for enhanced lithium electrochemistry
    journal, January 2019

    • Zhuang, Jingchun; Wang, Xianshu; Xu, Mengqing
    • Journal of Materials Chemistry A, Vol. 7, Issue 45
    • DOI: 10.1039/c9ta09539j

    Li-diffusion at the interface between Li-metal and [Pyr 14 ][TFSI]-ionic liquid: Ab initio molecular dynamics simulations
    journal, January 2020

    • Merinov, Boris V.; Naserifar, Saber; Zybin, Sergey V.
    • The Journal of Chemical Physics, Vol. 152, Issue 3
    • DOI: 10.1063/1.5132566

    The intrinsic behavior of lithium fluoride in solid electrolyte interphases on lithium
    journal, December 2019

    • He, Mingfu; Guo, Rui; Hobold, Gustavo M.
    • Proceedings of the National Academy of Sciences, Vol. 117, Issue 1
    • DOI: 10.1073/pnas.1911017116

    Synergistic Performance of Lithium Difluoro(oxalato)borate and Fluoroethylene Carbonate in Carbonate Electrolytes for Lithium Metal Anodes
    journal, December 2018

    • Brown, Zachary L.; Lucht, Brett L.
    • Journal of The Electrochemical Society, Vol. 166, Issue 3
    • DOI: 10.1149/2.0181903jes

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    • Journal of The Electrochemical Society, Vol. 166, Issue 3
    • DOI: 10.1149/2.0281903jes

    Using Triethyl Phosphate to Increase the Solubility of LiNO 3 in Carbonate Electrolytes for Improving the Performance of the Lithium Metal Anode
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    • Journal of The Electrochemical Society, Vol. 166, Issue 12
    • DOI: 10.1149/2.0991912jes

    Deterioration Analysis of Lithium Metal Anode in Full Cell during Long-Term Cycles
    journal, January 2019

    • Nagasaki, Motoko; Nishikawa, Kei; Kanamura, Kiyoshi
    • Journal of The Electrochemical Society, Vol. 166, Issue 12
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