Spectroscopic Characterization of the SEI Layer Formed on Lithium Metal Electrodes in Phosphonium Bis(fluorosulfonyl)imide Ionic Liquid Electrolytes

Gaetan M.A. Girard, Matthias Hilder, Nicolas Dupre, Dominique Guyomard, Donato Nucciarone, Kristina Whitbread, Serguei Zavorine, Michael Moser, Maria Forsyth, Douglas R. MacFarlane, Patrick C. Howlett

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The chemical composition of the solid electrolyte interphase (SEI) layer formed on the surface of lithium metal electrodes cycled in phosphonium bis(fluorosulfonyl)imide ionic liquid (IL) electrolytes are characterized by magic angle spinning nuclear magnetic resonance (MAS NMR), X-ray photoelectron spectroscopy (XPS), fourier transformed infrared spectroscopy, and electrochemical impedance spectroscopy. A multiphase layered structure is revealed, which is shown to remain relatively unchanged during extended cycling (up to 250 cycles at 1.5 mA·cm-2, 3 mA h·cm-2, 50 °C). The main components detected by MAS NMR and XPS after several hundreds of cycles are LiF and breakdown products from the bis(fluorosulfonyl)imide anion including Li2S. Similarities in chemical composition are observed in the case of the dilute (0.5 mol·kg-1 of Li salt in IL) and the highly concentrated (3.8 mol·kg-1 of Li salt in IL) electrolyte during cycling. The concentrated system is found to promote the formation of a thicker and more uniform SEI with larger amounts of reduced species from the anion. These SEI features are thought to facilitate more stable and efficient Li cycling and a reduced tendency for dendrite formation.

Original languageEnglish
Pages (from-to)6719-6729
Number of pages11
JournalACS Applied Materials and Interfaces
Volume10
Issue number7
DOIs
Publication statusPublished - 21 Feb 2018

Keywords

  • FSI
  • ionic liquids
  • lithium
  • SEI layer
  • X-ray photoelectron spectroscopy

Cite this

Girard, Gaetan M.A. ; Hilder, Matthias ; Dupre, Nicolas ; Guyomard, Dominique ; Nucciarone, Donato ; Whitbread, Kristina ; Zavorine, Serguei ; Moser, Michael ; Forsyth, Maria ; MacFarlane, Douglas R. ; Howlett, Patrick C. / Spectroscopic Characterization of the SEI Layer Formed on Lithium Metal Electrodes in Phosphonium Bis(fluorosulfonyl)imide Ionic Liquid Electrolytes. In: ACS Applied Materials and Interfaces. 2018 ; Vol. 10, No. 7. pp. 6719-6729.
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title = "Spectroscopic Characterization of the SEI Layer Formed on Lithium Metal Electrodes in Phosphonium Bis(fluorosulfonyl)imide Ionic Liquid Electrolytes",
abstract = "The chemical composition of the solid electrolyte interphase (SEI) layer formed on the surface of lithium metal electrodes cycled in phosphonium bis(fluorosulfonyl)imide ionic liquid (IL) electrolytes are characterized by magic angle spinning nuclear magnetic resonance (MAS NMR), X-ray photoelectron spectroscopy (XPS), fourier transformed infrared spectroscopy, and electrochemical impedance spectroscopy. A multiphase layered structure is revealed, which is shown to remain relatively unchanged during extended cycling (up to 250 cycles at 1.5 mA·cm-2, 3 mA h·cm-2, 50 °C). The main components detected by MAS NMR and XPS after several hundreds of cycles are LiF and breakdown products from the bis(fluorosulfonyl)imide anion including Li2S. Similarities in chemical composition are observed in the case of the dilute (0.5 mol·kg-1 of Li salt in IL) and the highly concentrated (3.8 mol·kg-1 of Li salt in IL) electrolyte during cycling. The concentrated system is found to promote the formation of a thicker and more uniform SEI with larger amounts of reduced species from the anion. These SEI features are thought to facilitate more stable and efficient Li cycling and a reduced tendency for dendrite formation.",
keywords = "FSI, ionic liquids, lithium, SEI layer, X-ray photoelectron spectroscopy",
author = "Girard, {Gaetan M.A.} and Matthias Hilder and Nicolas Dupre and Dominique Guyomard and Donato Nucciarone and Kristina Whitbread and Serguei Zavorine and Michael Moser and Maria Forsyth and MacFarlane, {Douglas R.} and Howlett, {Patrick C.}",
year = "2018",
month = "2",
day = "21",
doi = "10.1021/acsami.7b18183",
language = "English",
volume = "10",
pages = "6719--6729",
journal = "ACS Applied Materials and Interfaces",
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Girard, GMA, Hilder, M, Dupre, N, Guyomard, D, Nucciarone, D, Whitbread, K, Zavorine, S, Moser, M, Forsyth, M, MacFarlane, DR & Howlett, PC 2018, 'Spectroscopic Characterization of the SEI Layer Formed on Lithium Metal Electrodes in Phosphonium Bis(fluorosulfonyl)imide Ionic Liquid Electrolytes' ACS Applied Materials and Interfaces, vol. 10, no. 7, pp. 6719-6729. https://doi.org/10.1021/acsami.7b18183

Spectroscopic Characterization of the SEI Layer Formed on Lithium Metal Electrodes in Phosphonium Bis(fluorosulfonyl)imide Ionic Liquid Electrolytes. / Girard, Gaetan M.A.; Hilder, Matthias; Dupre, Nicolas; Guyomard, Dominique; Nucciarone, Donato; Whitbread, Kristina; Zavorine, Serguei; Moser, Michael; Forsyth, Maria; MacFarlane, Douglas R.; Howlett, Patrick C.

In: ACS Applied Materials and Interfaces, Vol. 10, No. 7, 21.02.2018, p. 6719-6729.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Spectroscopic Characterization of the SEI Layer Formed on Lithium Metal Electrodes in Phosphonium Bis(fluorosulfonyl)imide Ionic Liquid Electrolytes

AU - Girard, Gaetan M.A.

AU - Hilder, Matthias

AU - Dupre, Nicolas

AU - Guyomard, Dominique

AU - Nucciarone, Donato

AU - Whitbread, Kristina

AU - Zavorine, Serguei

AU - Moser, Michael

AU - Forsyth, Maria

AU - MacFarlane, Douglas R.

AU - Howlett, Patrick C.

PY - 2018/2/21

Y1 - 2018/2/21

N2 - The chemical composition of the solid electrolyte interphase (SEI) layer formed on the surface of lithium metal electrodes cycled in phosphonium bis(fluorosulfonyl)imide ionic liquid (IL) electrolytes are characterized by magic angle spinning nuclear magnetic resonance (MAS NMR), X-ray photoelectron spectroscopy (XPS), fourier transformed infrared spectroscopy, and electrochemical impedance spectroscopy. A multiphase layered structure is revealed, which is shown to remain relatively unchanged during extended cycling (up to 250 cycles at 1.5 mA·cm-2, 3 mA h·cm-2, 50 °C). The main components detected by MAS NMR and XPS after several hundreds of cycles are LiF and breakdown products from the bis(fluorosulfonyl)imide anion including Li2S. Similarities in chemical composition are observed in the case of the dilute (0.5 mol·kg-1 of Li salt in IL) and the highly concentrated (3.8 mol·kg-1 of Li salt in IL) electrolyte during cycling. The concentrated system is found to promote the formation of a thicker and more uniform SEI with larger amounts of reduced species from the anion. These SEI features are thought to facilitate more stable and efficient Li cycling and a reduced tendency for dendrite formation.

AB - The chemical composition of the solid electrolyte interphase (SEI) layer formed on the surface of lithium metal electrodes cycled in phosphonium bis(fluorosulfonyl)imide ionic liquid (IL) electrolytes are characterized by magic angle spinning nuclear magnetic resonance (MAS NMR), X-ray photoelectron spectroscopy (XPS), fourier transformed infrared spectroscopy, and electrochemical impedance spectroscopy. A multiphase layered structure is revealed, which is shown to remain relatively unchanged during extended cycling (up to 250 cycles at 1.5 mA·cm-2, 3 mA h·cm-2, 50 °C). The main components detected by MAS NMR and XPS after several hundreds of cycles are LiF and breakdown products from the bis(fluorosulfonyl)imide anion including Li2S. Similarities in chemical composition are observed in the case of the dilute (0.5 mol·kg-1 of Li salt in IL) and the highly concentrated (3.8 mol·kg-1 of Li salt in IL) electrolyte during cycling. The concentrated system is found to promote the formation of a thicker and more uniform SEI with larger amounts of reduced species from the anion. These SEI features are thought to facilitate more stable and efficient Li cycling and a reduced tendency for dendrite formation.

KW - FSI

KW - ionic liquids

KW - lithium

KW - SEI layer

KW - X-ray photoelectron spectroscopy

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U2 - 10.1021/acsami.7b18183

DO - 10.1021/acsami.7b18183

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JF - ACS Applied Materials and Interfaces

SN - 1944-8244

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