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Title: Kerr gated Raman spectroscopy of LiPF 6 salt and LiPF 6 -based organic carbonate electrolyte for Li-ion batteries

Abstract

Fluorescent species are formed during cycling of lithium ion batteries as a result of electrolyte decomposition due to the instability of the non-aqueous electrolytes and side reactions that occur at the electrode surface. The increase in the background fluorescence due to the presence of these components makes it harder to analyse data due to the spectroscopic overlap of Raman scattering and fluorescence. Herein, Kerr gated Raman spectroscopy was shown to be an effective technique for the isolation of the scattering effect from the fluorescence enabling the collection of the Raman spectra of LiPF6 salt and LiPF6-based organic carbonate electrolyte, without the interference of the fluorescence component. Kerr gated Raman was able to identify POF3 on the LiPF6 particle surface, after the addition of trace water.

Authors:
 [1]; ORCiD logo [1];  [1];  [2];  [3]; ORCiD logo [1]
  1. Stephenson Institute for Renewable Energy, Department of Chemistry, University of Liverpool, Liverpool, UK
  2. Central Laser Facility, Research Complex at Harwell, STFC Rutherford Appleton Laboratory, Didcot, UK
  3. Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, USA
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1562988
Alternate Identifier(s):
OSTI ID: 1572059
Grant/Contract Number:  
AC02-05CH11231f; AC02-05CH11231
Resource Type:
Published Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print) Journal Volume: 21 Journal Issue: 43; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Cabo-Fernandez, Laura, Neale, Alex R., Braga, Filipe, Sazanovich, Igor V., Kostecki, Robert, and Hardwick, Laurence J. Kerr gated Raman spectroscopy of LiPF 6 salt and LiPF 6 -based organic carbonate electrolyte for Li-ion batteries. United Kingdom: N. p., 2019. Web. doi:10.1039/C9CP02430A.
Cabo-Fernandez, Laura, Neale, Alex R., Braga, Filipe, Sazanovich, Igor V., Kostecki, Robert, & Hardwick, Laurence J. Kerr gated Raman spectroscopy of LiPF 6 salt and LiPF 6 -based organic carbonate electrolyte for Li-ion batteries. United Kingdom. doi:10.1039/C9CP02430A.
Cabo-Fernandez, Laura, Neale, Alex R., Braga, Filipe, Sazanovich, Igor V., Kostecki, Robert, and Hardwick, Laurence J. Thu . "Kerr gated Raman spectroscopy of LiPF 6 salt and LiPF 6 -based organic carbonate electrolyte for Li-ion batteries". United Kingdom. doi:10.1039/C9CP02430A.
@article{osti_1562988,
title = {Kerr gated Raman spectroscopy of LiPF 6 salt and LiPF 6 -based organic carbonate electrolyte for Li-ion batteries},
author = {Cabo-Fernandez, Laura and Neale, Alex R. and Braga, Filipe and Sazanovich, Igor V. and Kostecki, Robert and Hardwick, Laurence J.},
abstractNote = {Fluorescent species are formed during cycling of lithium ion batteries as a result of electrolyte decomposition due to the instability of the non-aqueous electrolytes and side reactions that occur at the electrode surface. The increase in the background fluorescence due to the presence of these components makes it harder to analyse data due to the spectroscopic overlap of Raman scattering and fluorescence. Herein, Kerr gated Raman spectroscopy was shown to be an effective technique for the isolation of the scattering effect from the fluorescence enabling the collection of the Raman spectra of LiPF6 salt and LiPF6-based organic carbonate electrolyte, without the interference of the fluorescence component. Kerr gated Raman was able to identify POF3 on the LiPF6 particle surface, after the addition of trace water.},
doi = {10.1039/C9CP02430A},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 43,
volume = 21,
place = {United Kingdom},
year = {2019},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C9CP02430A

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Cited by: 1 work
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Works referenced in this record:

Efficient Rejection of Fluorescence from Raman Spectra Using Picosecond Kerr Gating
journal, December 1999


Reduction Reactions of Electrolyte Salts for Lithium Ion Batteries: LiPF 6 , LiBF 4 , LiDFOB, LiBOB, and LiTFSI
journal, January 2018

  • Parimalam, Bharathy S.; Lucht, Brett L.
  • Journal of The Electrochemical Society, Vol. 165, Issue 2
  • DOI: 10.1149/2.0901802jes

Breakdown of Kasha’s Rule in a Ubiquitous, Naturally Occurring, Wide Bandgap Aluminosilicate (Feldspar)
journal, January 2018


Review of Fluorescence Suppression Techniques in Raman Spectroscopy
journal, January 2015


Ageing mechanisms in lithium-ion batteries
journal, September 2005


Time-resolved SERS study of the oxygen reduction reaction in ionic liquid electrolytes for non-aqueous lithium–oxygen cells
journal, January 2018

  • Radjenovic, Petar M.; Hardwick, Laurence J.
  • Faraday Discussions, Vol. 206
  • DOI: 10.1039/C7FD00170C

Initial stages of thermal decomposition of LiPF6-based lithium ion battery electrolytes by detailed Raman and NMR spectroscopy
journal, January 2013

  • Wilken, Susanne; Treskow, Marcel; Scheers, Johan
  • RSC Advances, Vol. 3, Issue 37
  • DOI: 10.1039/c3ra42611d

Dual Fluorescence through Kasha’s Rule Breaking: An Unconventional Photomechanism for Intracellular Probe Design
journal, May 2015

  • Brancato, Giuseppe; Signore, Giovanni; Neyroz, Paolo
  • The Journal of Physical Chemistry B, Vol. 119, Issue 20
  • DOI: 10.1021/acs.jpcb.5b01119

Quantitative investigation of the decomposition of organic lithium ion battery electrolytes with LC-MS/MS
journal, January 2017

  • Schultz, Carola; Vedder, Sven; Streipert, Benjamin
  • RSC Advances, Vol. 7, Issue 45
  • DOI: 10.1039/C7RA03839A

Infrared spectroscopy of instantaneous decomposition products of LiPF6-based lithium battery electrolytes
journal, October 2012


Hydrolysis of LiPF 6 in Carbonate-Based Electrolytes for Lithium-Ion Batteries and in Aqueous Media
journal, April 2018

  • Stich, Michael; Göttlinger, Mara; Kurniawan, Mario
  • The Journal of Physical Chemistry C, Vol. 122, Issue 16
  • DOI: 10.1021/acs.jpcc.8b02080

Crystal Structure and Spectroscopic Investigations of POF 3 : Crystal Structure and Spectroscopic Investigations of POF
journal, November 2013

  • Feller, Michael; Lux, Karin; Kornath, Andreas
  • Zeitschrift für anorganische und allgemeine Chemie, Vol. 640, Issue 1
  • DOI: 10.1002/zaac.201300460

Mechanistic insights into lithium ion battery electrolyte degradation – a quantitative NMR study
journal, January 2016

  • Wiemers-Meyer, S.; Winter, M.; Nowak, S.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 38
  • DOI: 10.1039/C6CP05276B

Ultra: A Unique Instrument for Time-Resolved Spectroscopy
journal, December 2010


On the correlation between surface chemistry and performance of graphite negative electrodes for Li ion batteries
journal, September 1999


Fluorescence background suppression in Raman spectroscopy using combined Kerr gated and shifted excitation Raman difference techniques
journal, January 2002

  • Matousek, P.; Towrie, M.; Parker, A. W.
  • Journal of Raman Spectroscopy, Vol. 33, Issue 4
  • DOI: 10.1002/jrs.840

Fluorescence suppression in resonance Raman spectroscopy using a high-performance picosecond Kerr gate
journal, January 2001

  • Matousek, P.; Towrie, M.; Ma, C.
  • Journal of Raman Spectroscopy, Vol. 32, Issue 12
  • DOI: 10.1002/jrs.784

Coupled LiPF 6 Decomposition and Carbonate Dehydrogenation Enhanced by Highly Covalent Metal Oxides in High-Energy Li-Ion Batteries
journal, October 2018

  • Yu, Yang; Karayaylali, Pinar; Katayama, Yu
  • The Journal of Physical Chemistry C, Vol. 122, Issue 48
  • DOI: 10.1021/acs.jpcc.8b07848

Diagnostic Studies of Polyolefin Separators in High-Power Li-Ion Cells
journal, January 2004

  • Kostecki, Robert; Norin, Laura; Song, Xiangyun
  • Journal of The Electrochemical Society, Vol. 151, Issue 4
  • DOI: 10.1149/1.1649233

Quantifying Changes to the Electrolyte and Negative Electrode in Aged NMC532/Graphite Lithium-Ion Cells
journal, January 2018

  • Thompson, L. M.; Stone, W.; Eldesoky, A.
  • Journal of The Electrochemical Society, Vol. 165, Issue 11
  • DOI: 10.1149/2.0721811jes

In situ quantitative analysis of individual H2O–CO2 fluid inclusions by laser Raman spectroscopy
journal, March 2007


Raman spectroscopy of street samples of cocaine obtained using Kerr gated fluorescence rejection
journal, January 2004

  • Littleford, Rachael E.; Matousek, Pavel; Towrie, Michael
  • The Analyst, Vol. 129, Issue 6
  • DOI: 10.1039/b401091d

The Formation Mechanism of Fluorescent Metal Complexes at the Li x Ni 0.5 Mn 1.5 O 4−δ /Carbonate Ester Electrolyte Interface
journal, March 2015

  • Jarry, Angélique; Gottis, Sébastien; Yu, Young-Sang
  • Journal of the American Chemical Society, Vol. 137, Issue 10
  • DOI: 10.1021/ja5116698

In situ Raman spectroscopy of carbon-coated ZnFe 2 O 4 anode material in Li-ion batteries – investigation of SEI growth
journal, January 2016

  • Cabo-Fernandez, Laura; Mueller, Franziska; Passerini, Stefano
  • Chemical Communications, Vol. 52, Issue 20
  • DOI: 10.1039/C5CC09350C

An Investigation of the Effect of Graphite Degradation on Irreversible Capacity in Lithium-ion Cells
journal, January 2008

  • Hardwick, Laurence J.; Marcinek, Marek; Beer, Leanne
  • Journal of The Electrochemical Society, Vol. 155, Issue 6
  • DOI: 10.1149/1.2903882

UV gated Raman spectroscopy for standoff detection of explosives
journal, July 2008


Quantifying capacity loss due to solid-electrolyte-interphase layer formation on silicon negative electrodes in lithium-ion batteries
journal, October 2012


Effects of Solute–Solvent Hydrogen Bonding on Nonaqueous Electrolyte Structure
journal, July 2015

  • Schroder, Kjell W.; Dylla, Anthony G.; Bishop, Logan D. C.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 15
  • DOI: 10.1021/acs.jpclett.5b01216

Solid state vibrational spectroscopy of anhydrous lithium hexafluorophosphate (LiPF6)
journal, October 2012


Decomposition of LiPF 6 in High Energy Lithium-Ion Batteries Studied with Online Electrochemical Mass Spectrometry
journal, January 2016

  • Guéguen, Aurélie; Streich, Daniel; He, Minglong
  • Journal of The Electrochemical Society, Vol. 163, Issue 6
  • DOI: 10.1149/2.0981606jes

Characterization, purification, and stability of gold nanoparticles
journal, December 2010


Hydrolysis of Ethylene Carbonate with Water and Hydroxide under Battery Operating Conditions
journal, January 2016

  • Metzger, Michael; Strehle, Benjamin; Solchenbach, Sophie
  • Journal of The Electrochemical Society, Vol. 163, Issue 7
  • DOI: 10.1149/2.0411607jes