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Title: Composition and Impedance Heterogeneity in Oxide Electrode Cross-Sections Detected by Raman Spectroscopy

Abstract

Abstract Lithium‐bearing layered transition metal oxides are the materials of choice for positive electrodes in high energy lithium‐ion cells being developed for electric vehicle applications. During electrochemical cycling, the loss of mobile lithium‐ions due to undesirable side reactions and an increase in cell resistance leads to a decline in the energy and power performance of the cells. This performance loss is often nonuniform across multiple cells, especially for those cycled at high voltages or high C‐rates. This nonuniformity results from inhomogeneous behavior in the battery electrodes, which can lead to localized areas that deteriorate faster than the neighboring regions. Raman spectroscopy is among the many techniques that are used to probe inhomogeneity in electrode behavior. Typically, Raman spectroscopy measurements on lithium‐ion cell electrodes are conducted in the top‐down mode, and at‐best produce an incomplete, surface biased account of electrode behavior. In contrast, micro‐Raman measurements conducted on ion‐milled electrode cross‐sections provide information from regions that span the full thickness of the electrode. Here, Raman spectroscopy data from pristine, aged, and relithiated/aged positive electrodes are reported. The spectral differences between oxide particles near the top‐surface and particles deeper into the aged electrodes clearly indicate compositional heterogeneities that arise during cell aging.

Authors:
 [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]
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  1. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1461430
Alternate Identifier(s):
OSTI ID: 1419894
Grant/Contract Number:  
AC02-06CH11357; DE‐AC02‐06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials Interfaces
Additional Journal Information:
Journal Volume: 5; Journal Issue: 9; Journal ID: ISSN 2196-7350
Publisher:
Wiley-VCH
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; NCM523; aging; inhomogeneity; ion milling; lithium battery

Citation Formats

Gilbert, James A., Maroni, Victor A., Cui, Yanjie, Gosztola, David J., Miller, Dean J., and Abraham, Daniel P. Composition and Impedance Heterogeneity in Oxide Electrode Cross-Sections Detected by Raman Spectroscopy. United States: N. p., 2018. Web. doi:10.1002/admi.201701447.
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Gilbert, James A., Maroni, Victor A., Cui, Yanjie, Gosztola, David J., Miller, Dean J., & Abraham, Daniel P. Composition and Impedance Heterogeneity in Oxide Electrode Cross-Sections Detected by Raman Spectroscopy. United States. https://doi.org/10.1002/admi.201701447
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Gilbert, James A., Maroni, Victor A., Cui, Yanjie, Gosztola, David J., Miller, Dean J., and Abraham, Daniel P. Thu . "Composition and Impedance Heterogeneity in Oxide Electrode Cross-Sections Detected by Raman Spectroscopy". United States. https://doi.org/10.1002/admi.201701447. https://www.osti.gov/servlets/purl/1461430.
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@article{osti_1461430,
title = {Composition and Impedance Heterogeneity in Oxide Electrode Cross-Sections Detected by Raman Spectroscopy},
author = {Gilbert, James A. and Maroni, Victor A. and Cui, Yanjie and Gosztola, David J. and Miller, Dean J. and Abraham, Daniel P.},
abstractNote = {Abstract Lithium‐bearing layered transition metal oxides are the materials of choice for positive electrodes in high energy lithium‐ion cells being developed for electric vehicle applications. During electrochemical cycling, the loss of mobile lithium‐ions due to undesirable side reactions and an increase in cell resistance leads to a decline in the energy and power performance of the cells. This performance loss is often nonuniform across multiple cells, especially for those cycled at high voltages or high C‐rates. This nonuniformity results from inhomogeneous behavior in the battery electrodes, which can lead to localized areas that deteriorate faster than the neighboring regions. Raman spectroscopy is among the many techniques that are used to probe inhomogeneity in electrode behavior. Typically, Raman spectroscopy measurements on lithium‐ion cell electrodes are conducted in the top‐down mode, and at‐best produce an incomplete, surface biased account of electrode behavior. In contrast, micro‐Raman measurements conducted on ion‐milled electrode cross‐sections provide information from regions that span the full thickness of the electrode. Here, Raman spectroscopy data from pristine, aged, and relithiated/aged positive electrodes are reported. The spectral differences between oxide particles near the top‐surface and particles deeper into the aged electrodes clearly indicate compositional heterogeneities that arise during cell aging.},
doi = {10.1002/admi.201701447},
journal = {Advanced Materials Interfaces},
number = 9,
volume = 5,
place = {United States},
year = {Thu Feb 08 00:00:00 EST 2018},
month = {Thu Feb 08 00:00:00 EST 2018}
}
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https://doi.org/10.1002/admi.201701447
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Cited by: 16 works
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Figures / Tables:

Figure 1 Figure 1: (a) Cell voltage vs. discharge capacity plot for a NCM523/Gr cell after formation (initial) and aging (400, 3-4.4 V cycles). (b) XRD plots showing the (003) peak for pristine (black), 400 cycle (red), and 400 cycle-relithiated (blue) electrodes; the plots are offset in the vertical direction for clarity.more » (c and d) EIS data (100 kHz – 5 mHz, 30 °C) for the full cell and for the positive electrode after formation (black) and after 400 aging cycles (red), respectively; the EIS data are from a NCM523/Gr cell containing a LixSn reference electrode. (e, f, and g) SEM images showing the exterior of a pristine NCM523 oxide (e), and cross sections of secondary particles from a pristine (f) and aged (g) electrode; the separation between primary particles is clearly evident in (g).« less
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