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Title: Lithium Self-Discharge and Its Prevention: Direct Visualization through In Situ Electrochemical Scanning Transmission Electron Microscopy

Abstract

To understand the mechanism that controls low-aspect-ratio lithium deposition morphologies for Li-metal anodes in batteries, we conducted direct visualization of Li-metal deposition and stripping behavior through nanoscale in situ electrochemical scanning transmission electron microscopy (EC-STEM) and macroscale-cell electrochemistry experiments in a recently developed and promising solvate electrolyte, 4 M lithium bis(fluorosulfonyl)imide in 1,2-dimethoxyethane. In contrast to published coin cell studies in the same electrolyte, our experiments revealed low Coulombic efficiencies and inhomogeneous Li morphology during in situ observation. We conclude that this discrepancy in Coulombic efficiency and morphology of the Li deposits was dependent on the presence of a compressed lithium separator interface, as we have confirmed through macroscale (not in the transmission electron microscope) electrochemical experiments. Our data suggests that cell compression changed how the solid-electrolyte interphase formed, which is likely responsible for improved morphology and Coulombic efficiency with compression. Furthermore, during the in situ EC-STEM experiments, we observed direct evidence of nanoscale self-discharge in the solvate electrolyte (in the state of electrical isolation). This self-discharge was duplicated in the macroscale, but it was less severe with electrode compression, likely due to a more passivating and corrosion-resistant solid-electrolyte interphase formed in the presence of compression. By combining the solvatemore » electrolyte with a protective LiAl0.3S coating, we show that the Li nucleation density increased during deposition, leading to improved morphological uniformity. Furthermore, self-discharge was suppressed during rest periods in the cycling profile with coatings present, as evidenced through EC-STEM and confirmed with coin cell data.« less

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [2];  [3]; ORCiD logo [4];  [5]
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  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Joint Center for Energy Storage Research and Nanoscale Sciences
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Joint Center for Energy Storage Research; Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). MESA Fabrication Operations
  4. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Joint Center for Energy Storage Research; Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy & Environmental Directorate
  5. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Joint Center for Energy Storage Research and Center for Integrated Nanotechnologies
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Energy Frontier Research Centers (EFRC) (United States). Nanostructures for Electrical Energy Storage (NEES); Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1411618
Alternate Identifier(s):
OSTI ID: 1426804; OSTI ID: 1430700; OSTI ID: 1481420
Report Number(s):
SAND-2017-12954J; SAND-2018-1499J; PNNL-SA-128261
Journal ID: ISSN 1936-0851; 659164; TRN: US1800254
Grant/Contract Number:  
AC04-94AL85000; SC0001160; NA0003525; AC05-76RL01830; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 11; Journal Issue: 11; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; artificial solid-electrolyte interphase; electrochemical transmission electron microscopy; lithium-ion batteries; lithium-metal anode; mechanical compression; protective coating; solid-electrolyte interphase

Citation Formats

Harrison, Katharine L., Zavadil, Kevin R., Hahn, Nathan T., Meng, Xiangbo, Elam, Jeffrey W., Leenheer, Andrew, Zhang, Ji-Guang, and Jungjohann, Katherine L. Lithium Self-Discharge and Its Prevention: Direct Visualization through In Situ Electrochemical Scanning Transmission Electron Microscopy. United States: N. p., 2017. Web. doi:10.1021/acsnano.7b05513.
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Harrison, Katharine L., Zavadil, Kevin R., Hahn, Nathan T., Meng, Xiangbo, Elam, Jeffrey W., Leenheer, Andrew, Zhang, Ji-Guang, & Jungjohann, Katherine L. Lithium Self-Discharge and Its Prevention: Direct Visualization through In Situ Electrochemical Scanning Transmission Electron Microscopy. United States. https://doi.org/10.1021/acsnano.7b05513
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Harrison, Katharine L., Zavadil, Kevin R., Hahn, Nathan T., Meng, Xiangbo, Elam, Jeffrey W., Leenheer, Andrew, Zhang, Ji-Guang, and Jungjohann, Katherine L. Tue . "Lithium Self-Discharge and Its Prevention: Direct Visualization through In Situ Electrochemical Scanning Transmission Electron Microscopy". United States. https://doi.org/10.1021/acsnano.7b05513. https://www.osti.gov/servlets/purl/1411618.
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@article{osti_1411618,
title = {Lithium Self-Discharge and Its Prevention: Direct Visualization through In Situ Electrochemical Scanning Transmission Electron Microscopy},
author = {Harrison, Katharine L. and Zavadil, Kevin R. and Hahn, Nathan T. and Meng, Xiangbo and Elam, Jeffrey W. and Leenheer, Andrew and Zhang, Ji-Guang and Jungjohann, Katherine L.},
abstractNote = {To understand the mechanism that controls low-aspect-ratio lithium deposition morphologies for Li-metal anodes in batteries, we conducted direct visualization of Li-metal deposition and stripping behavior through nanoscale in situ electrochemical scanning transmission electron microscopy (EC-STEM) and macroscale-cell electrochemistry experiments in a recently developed and promising solvate electrolyte, 4 M lithium bis(fluorosulfonyl)imide in 1,2-dimethoxyethane. In contrast to published coin cell studies in the same electrolyte, our experiments revealed low Coulombic efficiencies and inhomogeneous Li morphology during in situ observation. We conclude that this discrepancy in Coulombic efficiency and morphology of the Li deposits was dependent on the presence of a compressed lithium separator interface, as we have confirmed through macroscale (not in the transmission electron microscope) electrochemical experiments. Our data suggests that cell compression changed how the solid-electrolyte interphase formed, which is likely responsible for improved morphology and Coulombic efficiency with compression. Furthermore, during the in situ EC-STEM experiments, we observed direct evidence of nanoscale self-discharge in the solvate electrolyte (in the state of electrical isolation). This self-discharge was duplicated in the macroscale, but it was less severe with electrode compression, likely due to a more passivating and corrosion-resistant solid-electrolyte interphase formed in the presence of compression. By combining the solvate electrolyte with a protective LiAl0.3S coating, we show that the Li nucleation density increased during deposition, leading to improved morphological uniformity. Furthermore, self-discharge was suppressed during rest periods in the cycling profile with coatings present, as evidenced through EC-STEM and confirmed with coin cell data.},
doi = {10.1021/acsnano.7b05513},
journal = {ACS Nano},
number = 11,
volume = 11,
place = {United States},
year = {Tue Nov 07 00:00:00 EST 2017},
month = {Tue Nov 07 00:00:00 EST 2017}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acsnano.7b05513
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Cited by: 38 works
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Figures / Tables:

Figure 1 Figure 1: Images depicting CINT-EC platform. (a) 50 nm SiN membrane windows centered in the Si top and base chips were aligned with ruby beads. The top chip contains two ports for filling liquid in the epoxy-sealed chamber. (b) Scanning electron microscopy image of the bottom chip’s SiN window regionmore » showing both the electrochemically inactive (passivated) large tungsten electrodes and the electrochemically active lithographically patterned WEs. (c) Photograph of the top and bottom chips epoxied together during clamping, prior to liquid filling. (d) Photograph of the filled and sealed platform wire-bonded to the chip carrier and inserted into a custom 16-lead TEM holder.« less
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Works referenced in this record:

Issues and challenges facing rechargeable lithium batteries
journal, November 2001

  • Tarascon, J.-M.; Armand, M.
  • Nature, Vol. 414, Issue 6861, p. 359-367
  • DOI: 10.1038/35104644

Quantifying the promise of lithium–air batteries for electric vehicles
journal, January 2014

  • Gallagher, Kevin G.; Goebel, Steven; Greszler, Thomas
  • Energy & Environmental Science, Vol. 7, Issue 5
  • DOI: 10.1039/c3ee43870h

Critical Link between Materials Chemistry and Cell-Level Design for High Energy Density and Low Cost Lithium-Sulfur Transportation Battery
journal, January 2015

  • Eroglu, Damla; Zavadil, Kevin R.; Gallagher, Kevin G.
  • Journal of The Electrochemical Society, Vol. 162, Issue 6
  • DOI: 10.1149/2.0611506jes

High Energy Rechargeable Li-S Cells for EV Application: Status, Remaining Problems and Solutions
conference, January 2010

  • Mikhaylik, Yuriy V.; Kovalev, Igor; Schock, Riley
  • 216th ECS Meeting, ECS Transactions
  • DOI: 10.1149/1.3414001

Electrode–solution interactions in Li-ion batteries: a short summary and new insights
journal, June 2003

A Review of Solid Electrolyte Interphases on Lithium Metal Anode
journal, November 2015

A review of lithium deposition in lithium-ion and lithium metal secondary batteries
journal, May 2014

Metallic anodes for next generation secondary batteries
journal, January 2013

  • Kim, Hansu; Jeong, Goojin; Kim, Young-Ugk
  • Chemical Society Reviews, Vol. 42, Issue 23
  • DOI: 10.1039/c3cs60177c

Reviving the lithium metal anode for high-energy batteries
journal, March 2017

  • Lin, Dingchang; Liu, Yayuan; Cui, Yi
  • Nature Nanotechnology, Vol. 12, Issue 3
  • DOI: 10.1038/nnano.2017.16

Lithium metal anodes for rechargeable batteries
journal, January 2014

  • Xu, Wu; Wang, Jiulin; Ding, Fei
  • Energy Environ. Sci., Vol. 7, Issue 2
  • DOI: 10.1039/C3EE40795K

High rate and stable cycling of lithium metal anode
journal, February 2015

  • Qian, Jiangfeng; Henderson, Wesley A.; Xu, Wu
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7362

Atomic Layer Deposition of Li x Al y S Solid-State Electrolytes for Stabilizing Lithium-Metal Anodes
journal, April 2016

Next-Generation Lithium Metal Anode Engineering via Atomic Layer Deposition
journal, May 2015

Improved Cycle Life and Stability of Lithium Metal Anodes through Ultrathin Atomic Layer Deposition Surface Treatments
journal, September 2015

Lithium metal protected by atomic layer deposition metal oxide for high performance anodes
journal, January 2017

  • Chen, Lin; Connell, Justin G.; Nie, Anmin
  • Journal of Materials Chemistry A, Vol. 5, Issue 24
  • DOI: 10.1039/C7TA03116E

Lithium Electrodeposition Dynamics in Aprotic Electrolyte Observed in Situ via Transmission Electron Microscopy
journal, February 2015

  • Leenheer, Andrew J.; Jungjohann, Katherine L.; Zavadil, Kevin R.
  • ACS Nano, Vol. 9, Issue 4
  • DOI: 10.1021/acsnano.5b00876

Effects of physical constraints on Li cyclability
journal, December 1991

In-situ study of electrode stack growth in rechargeable cells at constant pressure
journal, August 1993

Effect of vinylene carbonate as additive to electrolyte for lithium metal anode
journal, February 2004

Influence of Electrolyte on Lithium Cycling Efficiency with Pressurized Electrode Stack
journal, January 1994

  • Hirai, Toshiro
  • Journal of The Electrochemical Society, Vol. 141, Issue 3
  • DOI: 10.1149/1.2054778

A Sealed Liquid Cell for In Situ Transmission Electron Microscopy of Controlled Electrochemical Processes
journal, August 2015

  • Leenheer, Andrew J.; Sullivan, John P.; Shaw, Michael J.
  • Journal of Microelectromechanical Systems, Vol. 24, Issue 4
  • DOI: 10.1109/JMEMS.2014.2380771

Phase Boundary Propagation in Li-Alloying Battery Electrodes Revealed by Liquid-Cell Transmission Electron Microscopy
journal, May 2016

  • Leenheer, Andrew J.; Jungjohann, Katherine L.; Zavadil, Kevin R.
  • ACS Nano, Vol. 10, Issue 6
  • DOI: 10.1021/acsnano.6b02200

Probing the Degradation Mechanisms in Electrolyte Solutions for Li-Ion Batteries by in Situ Transmission Electron Microscopy
journal, February 2014

  • Abellan, Patricia; Mehdi, B. Layla; Parent, Lucas R.
  • Nano Letters, Vol. 14, Issue 3
  • DOI: 10.1021/nl404271k

Observation and Quantification of Nanoscale Processes in Lithium Batteries by Operando Electrochemical (S)TEM
journal, February 2015

Effect of Additives on Lithium Cycling Efficiency
journal, January 1994

  • Hirai, Toshiro; Yoshimatsu, Isamu; Yamaki, Jun‐ichi
  • Journal of The Electrochemical Society, Vol. 141, Issue 9, p. 2300-2305
  • DOI: 10.1149/1.2055116

Lithium-Iron Fluoride Battery with In Situ Surface Protection
journal, February 2016

  • Gu, Wentian; Borodin, Oleg; Zdyrko, Bogdan
  • Advanced Functional Materials, Vol. 26, Issue 10
  • DOI: 10.1002/adfm.201504848

The effect of a solid electrolyte interphase on the mechanism of operation of lithium–sulfur batteries
journal, January 2015

  • Markevich, E.; Salitra, G.; Rosenman, A.
  • Journal of Materials Chemistry A, Vol. 3, Issue 39
  • DOI: 10.1039/C5TA04613K

In Situ Formation of Protective Coatings on Sulfur Cathodes in Lithium Batteries with LiFSI-Based Organic Electrolytes
journal, December 2014

  • Kim, Hyea; Wu, Feixiang; Lee, Jung Tae
  • Advanced Energy Materials, Vol. 5, Issue 6
  • DOI: 10.1002/aenm.201401792

Direct Visualization of Solid Electrolyte Interphase Formation in Lithium-Ion Batteries with In Situ Electrochemical Transmission Electron Microscopy
journal, July 2014

  • Unocic, Raymond R.; Sun, Xiao-Guang; Sacci, Robert L.
  • Microscopy and Microanalysis, Vol. 20, Issue 4
  • DOI: 10.1017/S1431927614012744

Lithium-Sulfur Cells: The Gap between the State-of-the-Art and the Requirements for High Energy Battery Cells
journal, April 2015

  • Hagen, Markus; Hanselmann, Dominik; Ahlbrecht, Katharina
  • Advanced Energy Materials, Vol. 5, Issue 16, 1401986
  • DOI: 10.1002/aenm.201401986

Nanoscale Imaging of Fundamental Li Battery Chemistry: Solid-Electrolyte Interphase Formation and Preferential Growth of Lithium Metal Nanoclusters
journal, February 2015

  • Sacci, Robert L.; Black, Jennifer M.; Balke, Nina
  • Nano Letters, Vol. 15, Issue 3
  • DOI: 10.1021/nl5048626

Direct visualization of initial SEI morphology and growth kinetics during lithium deposition by in situ electrochemical transmission electron microscopy
journal, January 2014

  • Sacci, Robert L.; Dudney, Nancy J.; More, Karren L.
  • Chemical Communications, Vol. 50, Issue 17
  • DOI: 10.1039/c3cc49029g

Electrochemical in situ investigations of SEI and dendrite formation on the lithium metal anode
journal, January 2015

  • Bieker, Georg; Winter, Martin; Bieker, Peter
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 14
  • DOI: 10.1039/C4CP05865H

In situ TEM electrochemistry of anode materials in lithium ion batteries
journal, January 2011

  • Liu, Xiao Hua; Huang, Jian Yu
  • Energy & Environmental Science, Vol. 4, Issue 10
  • DOI: 10.1039/c1ee01918j

Visualization of Electrode–Electrolyte Interfaces in LiPF 6 /EC/DEC Electrolyte for Lithium Ion Batteries via in Situ TEM
journal, March 2014

  • Zeng, Zhiyuan; Liang, Wen-I; Liao, Hong-Gang
  • Nano Letters, Vol. 14, Issue 4
  • DOI: 10.1021/nl403922u

Perspectives in in situ transmission electron microscopy studies on lithium battery electrodes
journal, May 2016

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    Works referencing / citing this record:

    Origin of lithium whisker formation and growth under stress
    journal, October 2019

    Recent Progress of Metal–Air Batteries—A Mini Review
    journal, July 2019

    • Wang, Chunlian; Yu, Yongchao; Niu, Jiajia
    • Applied Sciences, Vol. 9, Issue 14
    • DOI: 10.3390/app9142787

    Recent Progress of In Situ Transmission Electron Microscopy for Energy Materials
    journal, September 2019

    • Zhang, Chao; Firestein, Konstantin L.; Fernando, Joseph F. S.
    • Advanced Materials, Vol. 32, Issue 18
    • DOI: 10.1002/adma.201904094

    Fast galvanic lithium corrosion involving a Kirkendall-type mechanism
    journal, January 2019

    Rethinking How External Pressure Can Suppress Dendrites in Lithium Metal Batteries
    journal, January 2019

    • Zhang, Xin; Wang, Q. Jane; Harrison, Katharine L.
    • Journal of The Electrochemical Society, Vol. 166, Issue 15
    • DOI: 10.1149/2.0701914jes

    Atomic and Molecular Layer Deposition for Superior Lithium-Sulfur Batteries: Strategies, Performance, and Mechanisms
    journal, May 2018

    • Sun, Qian; Lau, Kah Chun; Geng, Dongsheng
    • Batteries & Supercaps, Vol. 1, Issue 2
    • DOI: 10.1002/batt.201800024

    Cryogenic specimens for nanoscale characterization of solid–liquid interfaces
    journal, December 2019

    • Zachman, Michael J.; de Jonge, Niels; Fischer, Robert
    • MRS Bulletin, Vol. 44, Issue 12
    • DOI: 10.1557/mrs.2019.289

    Atomic and Molecular Layer Deposition for Superior Lithium-Sulfur Batteries: Strategies, Performance, and Mechanisms
    journal, June 2018

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