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Title: Lithium Acetylide: A Spectroscopic Marker for Lithium Deposition During Fast Charging of Li-Ion Cells

Abstract

Rapid charging of lithium-ion batteries being developed for electric vehicles is a formidable challenge. Electrochemical polarization of cells during fast charging favors deposition of metallic Li onto the surface of the graphite electrode, and this Li plating compromises safety and accelerates performance degradation. Observing the onset of Li nucleation is essential for elucidation of mechanisms and defining conditions favoring this Li plating, but presently available methods are not sufficiently sensitive and selective while also allowing satisfactory spatial resolution. We demonstrate the use of Raman spectroscopy as a sensitive means to identify Li nucleation and map Li deposition. Metallic Li is detected indirectly by probing the vibrations in an acetylide species (represented as Li—C≡C—X) that is formed on the exposed surface of Li nuclei in contact with the solid electrolyte interphase on graphite. Surface-enhanced Raman scattering (SERS) involving this species on Li nuclei appears to dramatically increase sensitivity and selectivity of this detection, making our method an excellent complement to the existing spectroscopy and microscopy approaches for determining Li deposition.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Nanoscience and Technology Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1493919
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Energy Materials
Additional Journal Information:
Journal Volume: 2; Journal Issue: 1; Journal ID: ISSN 2574-0962
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; fast charge; graphite; lithium plating; Raman spectroscopy; SERS

Citation Formats

Fonseca Rodrigues, Marco-Tulio, Maroni, Victor A., Gosztola, David J., Yao, Koffi P. C., Kalaga, Kaushik, Shkrob, Ilya A., and Abraham, Daniel P. Lithium Acetylide: A Spectroscopic Marker for Lithium Deposition During Fast Charging of Li-Ion Cells. United States: N. p., 2018. Web. doi:10.1021/acsaem.8b01975.
Fonseca Rodrigues, Marco-Tulio, Maroni, Victor A., Gosztola, David J., Yao, Koffi P. C., Kalaga, Kaushik, Shkrob, Ilya A., & Abraham, Daniel P. Lithium Acetylide: A Spectroscopic Marker for Lithium Deposition During Fast Charging of Li-Ion Cells. United States. https://doi.org/10.1021/acsaem.8b01975
Fonseca Rodrigues, Marco-Tulio, Maroni, Victor A., Gosztola, David J., Yao, Koffi P. C., Kalaga, Kaushik, Shkrob, Ilya A., and Abraham, Daniel P. Mon . "Lithium Acetylide: A Spectroscopic Marker for Lithium Deposition During Fast Charging of Li-Ion Cells". United States. https://doi.org/10.1021/acsaem.8b01975. https://www.osti.gov/servlets/purl/1493919.
@article{osti_1493919,
title = {Lithium Acetylide: A Spectroscopic Marker for Lithium Deposition During Fast Charging of Li-Ion Cells},
author = {Fonseca Rodrigues, Marco-Tulio and Maroni, Victor A. and Gosztola, David J. and Yao, Koffi P. C. and Kalaga, Kaushik and Shkrob, Ilya A. and Abraham, Daniel P.},
abstractNote = {Rapid charging of lithium-ion batteries being developed for electric vehicles is a formidable challenge. Electrochemical polarization of cells during fast charging favors deposition of metallic Li onto the surface of the graphite electrode, and this Li plating compromises safety and accelerates performance degradation. Observing the onset of Li nucleation is essential for elucidation of mechanisms and defining conditions favoring this Li plating, but presently available methods are not sufficiently sensitive and selective while also allowing satisfactory spatial resolution. We demonstrate the use of Raman spectroscopy as a sensitive means to identify Li nucleation and map Li deposition. Metallic Li is detected indirectly by probing the vibrations in an acetylide species (represented as Li—C≡C—X) that is formed on the exposed surface of Li nuclei in contact with the solid electrolyte interphase on graphite. Surface-enhanced Raman scattering (SERS) involving this species on Li nuclei appears to dramatically increase sensitivity and selectivity of this detection, making our method an excellent complement to the existing spectroscopy and microscopy approaches for determining Li deposition.},
doi = {10.1021/acsaem.8b01975},
journal = {ACS Applied Energy Materials},
number = 1,
volume = 2,
place = {United States},
year = {2018},
month = {12}
}

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Works referencing / citing this record:

Challenges of Fast Charging for Electric Vehicles and the Role of Red Phosphorous as Anode Material: Review
journal, October 2019