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Title: Operando and three-dimensional visualization of anion depletion and lithium growth by stimulated Raman scattering microscopy

Abstract

Visualization of ion transport in electrolytes provides fundamental understandings of electrolyte dynamics and electrolyte-electrode interactions. However, this is challenging because existing techniques are hard to capture low ionic concentrations and fast electrolyte dynamics. Here we show that stimulated Raman scattering microscopy offers required resolutions to address a long-lasting question: how does the lithium-ion concentration correlate to uneven lithium deposition? In this study, anions are used to represent lithium ions since their concentrations should not deviate for more than 0.1 mM, even near nanoelectrodes. A three-stage lithium deposition process is uncovered, corresponding to no depletion, partial depletion, and full depletion of lithium ions. Further analysis reveals a feedback mechanism between the lithium dendrite growth and heterogeneity of local ionic concentration, which can be suppressed by artificial solid electrolyte interphase. This report shows that stimulated Raman scattering microscopy is a powerful tool for the materials and energy field.

Authors:
ORCiD logo [1];  [1];  [2];  [1];  [1];  [1];  [1];  [1];  [1];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Columbia Univ., New York, NY (United States)
  2. Pennsylvania State Univ., University Park, PA (United States)
Publication Date:
Research Org.:
Michigan State Univ., East Lansing, MI (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1513262
Grant/Contract Number:  
[EE0007803]
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
[ Journal Volume: 9; Journal Issue: 1]; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Cheng, Qian, Wei, Lu, Liu, Zhe, Ni, Nan, Sang, Zhe, Zhu, Bin, Xu, Weiheng, Chen, Meijie, Miao, Yupeng, Chen, Long-Qing, Min, Wei, and Yang, Yuan. Operando and three-dimensional visualization of anion depletion and lithium growth by stimulated Raman scattering microscopy. United States: N. p., 2018. Web. doi:10.1038/s41467-018-05289-z.
Cheng, Qian, Wei, Lu, Liu, Zhe, Ni, Nan, Sang, Zhe, Zhu, Bin, Xu, Weiheng, Chen, Meijie, Miao, Yupeng, Chen, Long-Qing, Min, Wei, & Yang, Yuan. Operando and three-dimensional visualization of anion depletion and lithium growth by stimulated Raman scattering microscopy. United States. doi:10.1038/s41467-018-05289-z.
Cheng, Qian, Wei, Lu, Liu, Zhe, Ni, Nan, Sang, Zhe, Zhu, Bin, Xu, Weiheng, Chen, Meijie, Miao, Yupeng, Chen, Long-Qing, Min, Wei, and Yang, Yuan. Mon . "Operando and three-dimensional visualization of anion depletion and lithium growth by stimulated Raman scattering microscopy". United States. doi:10.1038/s41467-018-05289-z. https://www.osti.gov/servlets/purl/1513262.
@article{osti_1513262,
title = {Operando and three-dimensional visualization of anion depletion and lithium growth by stimulated Raman scattering microscopy},
author = {Cheng, Qian and Wei, Lu and Liu, Zhe and Ni, Nan and Sang, Zhe and Zhu, Bin and Xu, Weiheng and Chen, Meijie and Miao, Yupeng and Chen, Long-Qing and Min, Wei and Yang, Yuan},
abstractNote = {Visualization of ion transport in electrolytes provides fundamental understandings of electrolyte dynamics and electrolyte-electrode interactions. However, this is challenging because existing techniques are hard to capture low ionic concentrations and fast electrolyte dynamics. Here we show that stimulated Raman scattering microscopy offers required resolutions to address a long-lasting question: how does the lithium-ion concentration correlate to uneven lithium deposition? In this study, anions are used to represent lithium ions since their concentrations should not deviate for more than 0.1 mM, even near nanoelectrodes. A three-stage lithium deposition process is uncovered, corresponding to no depletion, partial depletion, and full depletion of lithium ions. Further analysis reveals a feedback mechanism between the lithium dendrite growth and heterogeneity of local ionic concentration, which can be suppressed by artificial solid electrolyte interphase. This report shows that stimulated Raman scattering microscopy is a powerful tool for the materials and energy field.},
doi = {10.1038/s41467-018-05289-z},
journal = {Nature Communications},
number = [1],
volume = [9],
place = {United States},
year = {2018},
month = {7}
}

Journal Article:
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Cited by: 23 works
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Figures / Tables:

Fig. 1 Fig. 1: Experimental principle and design. a Energy diagrams of spontaneous Raman scattering and stimulated Raman scattering (SRS). In spontaneous Raman, only one laser (green, solid line) is used, and the scattered photons (red, dashed line) will have an energy loss of Ω, corresponding to the vibrational energy of themore » targeted bond. In SRS, two different lasers (green/red, solid line) with energy gaps matching Ω are simultaneously used and yield up to 108 times faster vibrational transitions. b A schematic illustration of a Li–Li symmetric cell under SRS imaging. The two lasers are the pump laser and Stokes laser. c A camera image of a Li–Li symmetric cell (top) and zoom-in microscope image (bottom). Scale bar is 100 μm. The red, dashed rectangle indicates the imaging area. The molecular structure is of the LiBOB salt used in our study. Scale bar is 100 μm. d The SRS spectrum of 0.5M LiBOB in TEGDME/PVdF-HFP gel electrolyte. The inset shows the linear concentration dependence between the Raman intensity at 1830 cm-1 (dashed circle) and the LiBOB concentration from 0 M to 0.5 M« less

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