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Title: Lithium electrodeposition dynamics in aprotic electrolyte observed in situ via transmission electron microscopy

Abstract

Electrodeposited metallic lithium is an ideal negative battery electrode, but nonuniform microstructure evolution during cycling leads to degradation and safety issues. A better understanding of the Li plating and stripping processes is needed to enable practical Li-metal batteries. Here we use a custom microfabricated, sealed liquid cell for in situ scanning transmission electron microscopy (STEM) to image the first few cycles of lithium electrodeposition/dissolution in liquid aprotic electrolyte at submicron resolution. Cycling at current densities from 1 to 25 mA/cm2 leads to variations in grain structure, with higher current densities giving a more needle-like, higher surface area deposit. The effect of the electron beam was explored, and it was found that, even with minimal beam exposure, beam-induced surface film formation could alter the Li microstructure. The electrochemical dissolution was seen to initiate from isolated points on grains rather than uniformly across the Li surface, due to the stabilizing solid electrolyte interphase surface film. As a result, we discuss the implications for operando STEM liquid-cell imaging and Li-battery applications.

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1235316
Report Number(s):
SAND-2015-2431J
Journal ID: ISSN 1936-0851; 579677
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 9; Journal Issue: 4; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; lithium electrodeposition; liquid-cell electron microscopy; electron beam radiolysis; lithium-ion battery; solid electrolyte interphase; in situ TEM

Citation Formats

Leenheer, Andrew Jay, Jungjohann, Katherine Leigh, Zavadil, Kevin Robert, Sullivan, John P., and Harris, Charles Thomas. Lithium electrodeposition dynamics in aprotic electrolyte observed in situ via transmission electron microscopy. United States: N. p., 2015. Web. doi:10.1021/acsnano.5b00876.
Leenheer, Andrew Jay, Jungjohann, Katherine Leigh, Zavadil, Kevin Robert, Sullivan, John P., & Harris, Charles Thomas. Lithium electrodeposition dynamics in aprotic electrolyte observed in situ via transmission electron microscopy. United States. https://doi.org/10.1021/acsnano.5b00876
Leenheer, Andrew Jay, Jungjohann, Katherine Leigh, Zavadil, Kevin Robert, Sullivan, John P., and Harris, Charles Thomas. Wed . "Lithium electrodeposition dynamics in aprotic electrolyte observed in situ via transmission electron microscopy". United States. https://doi.org/10.1021/acsnano.5b00876. https://www.osti.gov/servlets/purl/1235316.
@article{osti_1235316,
title = {Lithium electrodeposition dynamics in aprotic electrolyte observed in situ via transmission electron microscopy},
author = {Leenheer, Andrew Jay and Jungjohann, Katherine Leigh and Zavadil, Kevin Robert and Sullivan, John P. and Harris, Charles Thomas},
abstractNote = {Electrodeposited metallic lithium is an ideal negative battery electrode, but nonuniform microstructure evolution during cycling leads to degradation and safety issues. A better understanding of the Li plating and stripping processes is needed to enable practical Li-metal batteries. Here we use a custom microfabricated, sealed liquid cell for in situ scanning transmission electron microscopy (STEM) to image the first few cycles of lithium electrodeposition/dissolution in liquid aprotic electrolyte at submicron resolution. Cycling at current densities from 1 to 25 mA/cm2 leads to variations in grain structure, with higher current densities giving a more needle-like, higher surface area deposit. The effect of the electron beam was explored, and it was found that, even with minimal beam exposure, beam-induced surface film formation could alter the Li microstructure. The electrochemical dissolution was seen to initiate from isolated points on grains rather than uniformly across the Li surface, due to the stabilizing solid electrolyte interphase surface film. As a result, we discuss the implications for operando STEM liquid-cell imaging and Li-battery applications.},
doi = {10.1021/acsnano.5b00876},
journal = {ACS Nano},
number = 4,
volume = 9,
place = {United States},
year = {Wed Mar 18 00:00:00 EDT 2015},
month = {Wed Mar 18 00:00:00 EDT 2015}
}

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Works referenced in this record:

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

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


Advanced Model for Solid Electrolyte Interphase Electrodes in Liquid and Polymer Electrolytes
journal, January 1997

  • Peled, E.
  • Journal of The Electrochemical Society, Vol. 144, Issue 8
  • DOI: 10.1149/1.1837858

Mechanisms of dendritic growth investigated by in situ light microscopy during electrodeposition and dissolution of lithium
journal, September 2014


Nucleation of Electrodeposited Lithium Metal: Dendritic Growth and the Effect of Co-Deposited Sodium
journal, January 2013

  • Stark, Johanna K.; Ding, Yi; Kohl, Paul A.
  • Journal of The Electrochemical Society, Vol. 160, Issue 9
  • DOI: 10.1149/2.028309jes

In Situ Observation of Dendrite Growth of Electrodeposited Li Metal
journal, January 2010

  • Nishikawa, Kei; Mori, Takeshi; Nishida, Tetsuo
  • Journal of The Electrochemical Society, Vol. 157, Issue 11
  • DOI: 10.1149/1.3486468

Effect of Electrolyte Composition on Lithium Dendrite Growth
journal, January 2008

  • Crowther, Owen; West, Alan C.
  • Journal of The Electrochemical Society, Vol. 155, Issue 11
  • DOI: 10.1149/1.2969424

Live Scanning Electron Microscope Observations of Dendritic Growth in Lithium/Polymer Cells
journal, January 2002

  • Dollé, Mickaël; Sannier, Lucas; Beaudoin, Bernard
  • Electrochemical and Solid-State Letters, Vol. 5, Issue 12
  • DOI: 10.1149/1.1519970

In situ scanning electron microscopy on lithium-ion battery electrodes using an ionic liquid
journal, August 2011


In Situ TEM Experiments of Electrochemical Lithiation and Delithiation of Individual Nanostructures
journal, May 2012

  • Liu, Xiao Hua; Liu, Yang; Kushima, Akihiro
  • Advanced Energy Materials, Vol. 2, Issue 7
  • DOI: 10.1002/aenm.201200024

Morphological changes in and around Sn electrodes during Li ion cycling characterized by in situ environmental TEM
journal, November 2013


Nanoscale Imaging of Lithium Ion Distribution During In Situ Operation of Battery Electrode and Electrolyte
journal, February 2014

  • Holtz, Megan E.; Yu, Yingchao; Gunceler, Deniz
  • Nano Letters, Vol. 14, Issue 3
  • DOI: 10.1021/nl404577c

Observation of Single Colloidal Platinum Nanocrystal Growth Trajectories
journal, June 2009


Controlled Growth of Nanoparticles from Solution with In Situ Liquid Transmission Electron Microscopy
journal, July 2011

  • Evans, James E.; Jungjohann, Katherine L.; Browning, Nigel D.
  • Nano Letters, Vol. 11, Issue 7
  • DOI: 10.1021/nl201166k

Facet development during platinum nanocube growth
journal, August 2014


Direction-Specific Interactions Control Crystal Growth by Oriented Attachment
journal, May 2012


In Situ Liquid Cell Electron Microscopy of the Solution Growth of Au–Pd Core–Shell Nanostructures
journal, May 2013

  • Jungjohann, K. L.; Bliznakov, S.; Sutter, P. W.
  • Nano Letters, Vol. 13, Issue 6
  • DOI: 10.1021/nl4014277

Bubble and Pattern Formation in Liquid Induced by an Electron Beam
journal, December 2013

  • Grogan, Joseph M.; Schneider, Nicholas M.; Ross, Frances M.
  • Nano Letters, Vol. 14, Issue 1
  • DOI: 10.1021/nl404169a

Real-time imaging and local elemental analysis of nanostructures in liquids
journal, January 2014

  • Lewis, Edward A.; Haigh, Sarah J.; Slater, Thomas J. A.
  • Chem. Commun., Vol. 50, Issue 70
  • DOI: 10.1039/C4CC02743D

Anisotropic Lithiation Onset in Silicon Nanoparticle Anode Revealed by in Situ Graphene Liquid Cell Electron Microscopy
journal, June 2014

  • Yuk, Jong Min; Seo, Hyeon Kook; Choi, Jang Wook
  • ACS Nano, Vol. 8, Issue 7
  • DOI: 10.1021/nn502779n

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

In Situ Transmission Electron Microscopy of Lead Dendrites and Lead Ions in Aqueous Solution
journal, June 2012

  • White, Edward R.; Singer, Scott B.; Augustyn, Veronica
  • ACS Nano, Vol. 6, Issue 7
  • DOI: 10.1021/nn3017469

In Situ Study of the Growth Kinetics of Individual Island Electrodeposition of Copper
journal, April 2006

  • Radisic, A.; Ross, F. M.; Searson, P. C.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 15
  • DOI: 10.1021/jp057549a

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

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

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

Electron–Water Interactions and Implications for Liquid Cell Electron Microscopy
journal, September 2014

  • Schneider, Nicholas M.; Norton, Michael M.; Mendel, Brian J.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 38
  • DOI: 10.1021/jp507400n

In situ TEM observation of lithium nanoparticle growth and morphological cycling
journal, January 2012

  • Ghatak, Jay; Guan, Wei; Möbus, Günter
  • Nanoscale, Vol. 4, Issue 5
  • DOI: 10.1039/c2nr11546h

Chemistry, Impedance, and Morphology Evolution in Solid Electrolyte Interphase Films during Formation in Lithium Ion Batteries
journal, December 2013

  • Lu, Peng; Li, Chen; Schneider, Eric W.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 2
  • DOI: 10.1021/jp4111019

Electrochemically lithiated graphite characterised by photoelectron spectroscopy
journal, June 2003


In Situ Electrochemical Atomic Force Microscope Study on Graphite Electrodes
journal, April 1997

  • Hirasawa, Karen A.; Sato, Tomohiro; Asahina, Hitoshi
  • Journal of The Electrochemical Society, Vol. 144, Issue 4
  • DOI: 10.1149/1.1837560

In Situ Micromorphological Studies of Li Electrodes by Atomic Force Microscopy in a Glove Box System
journal, January 1999

  • Aurbach, Doron
  • Electrochemical and Solid-State Letters, Vol. 2, Issue 1
  • DOI: 10.1149/1.1390719

Lithium metal stripping/plating mechanisms studies: A metallurgical approach
journal, October 2006


The Mechanism of the Dendritic Electrocrystallization of Zinc
journal, January 1969

  • Diggle, J. W.; Despic, A. R.; Bockris, J. O'M.
  • Journal of The Electrochemical Society, Vol. 116, Issue 11
  • DOI: 10.1149/1.2411588

Dendrite Growth in Lithium/Polymer Systems
journal, January 2003

  • Monroe, Charles; Newman, John
  • Journal of The Electrochemical Society, Vol. 150, Issue 10
  • DOI: 10.1149/1.1606686

Stability Analysis of Electrodeposition across a Structured Electrolyte with Immobilized Anions
journal, January 2014

  • Tikekar, Mukul D.; Archer, Lynden A.; Koch, Donald L.
  • Journal of The Electrochemical Society, Vol. 161, Issue 6
  • DOI: 10.1149/2.085405jes

Insights into the Role of Interphasial Morphology on the Electrochemical Performance of Lithium Electrodes
journal, January 2012

  • López, Carmen M.; Vaughey, John T.; Dees, Dennis W.
  • Journal of The Electrochemical Society, Vol. 159, Issue 6
  • DOI: 10.1149/2.100206jes

Onset of dendritic growth in lithium/polymer cells
journal, July 2001


Heterogeneous Nucleation and Growth of Lithium Electrodeposits on Negative Electrodes
journal, January 2013

  • Ely, David R.; García, R. Edwin
  • Journal of The Electrochemical Society, Vol. 160, Issue 4
  • DOI: 10.1149/1.057304jes

Comparison of the growth of lithium filaments and dendrites under different conditions
journal, January 2015


A consideration of the morphology of electrochemically deposited lithium in an organic electrolyte
journal, August 1998


Attempts to Improve the Behavior of Li Electrodes in Rechargeable Lithium Batteries
journal, January 2002

  • Aurbach, D.; Zinigrad, E.; Teller, H.
  • Journal of The Electrochemical Society, Vol. 149, Issue 10
  • DOI: 10.1149/1.1502684

Ultrathin Two-Dimensional Atomic Crystals as Stable Interfacial Layer for Improvement of Lithium Metal Anode
journal, September 2014

  • Yan, Kai; Lee, Hyun-Wook; Gao, Teng
  • Nano Letters, Vol. 14, Issue 10
  • DOI: 10.1021/nl503125u

The Nanoaquarium: A Platform for In Situ Transmission Electron Microscopy in Liquid Media
journal, August 2010


Works referencing / citing this record:

Liquid-Phase Transmission Electron Microscopy for Studying Colloidal Inorganic Nanoparticles
journal, November 2017

  • Kim, Byung Hyo; Yang, Jiwoong; Lee, Donghoon
  • Advanced Materials, Vol. 30, Issue 4
  • DOI: 10.1002/adma.201703316

Morphological stability during electrodeposition
journal, June 2017

  • Enrique, Raúl A.; DeWitt, Stephen; Thornton, Katsuyo
  • MRS Communications, Vol. 7, Issue 3
  • DOI: 10.1557/mrc.2017.38

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

Review—Promises and Challenges of In Situ Transmission Electron Microscopy Electrochemical Techniques in the Studies of Lithium Ion Batteries
journal, January 2017

  • Xie, Zhi-Hui; Jiang, Zimin; Zhang, Xueyuan
  • Journal of The Electrochemical Society, Vol. 164, Issue 9
  • DOI: 10.1149/2.1451709jes

Understanding materials challenges for rechargeable ion batteries with in situ transmission electron microscopy
journal, August 2017

  • Yuan, Yifei; Amine, Khalil; Lu, Jun
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15806

In Situ Transmission Electron Microscopy Studies of Electrochemical Reaction Mechanisms in Rechargeable Batteries
journal, June 2019


Safe Lithium‐Metal Anodes for Li−O 2 Batteries: From Fundamental Chemistry to Advanced Characterization and Effective Protection
journal, May 2019

  • Hong, Yan‐Shuai; Zhao, Chen‐Zi; Xiao, Ye
  • Batteries & Supercaps, Vol. 2, Issue 7
  • DOI: 10.1002/batt.201900031

In situ plasmonic optical fiber detection of the state of charge of supercapacitors for renewable energy storage
journal, July 2018


The formation of cerium( iii ) hydroxide nanoparticles by a radiation mediated increase in local pH
journal, January 2017

  • Abellan, P.; Moser, T. H.; Lucas, I. T.
  • RSC Advances, Vol. 7, Issue 7
  • DOI: 10.1039/c6ra27066b

In Situ Transmission Electron Microscopy on Energy‐Related Catalysis
journal, December 2019


Real-time mass spectrometric characterization of the solid–electrolyte interphase of a lithium-ion battery
journal, January 2020


Reviving Lithium-Metal Anodes for Next-Generation High-Energy Batteries
journal, June 2017


Review of Recent Development of In Situ/Operando Characterization Techniques for Lithium Battery Research
journal, May 2019

  • Liu, Dongqing; Shadike, Zulipiya; Lin, Ruoqian
  • Advanced Materials, Vol. 31, Issue 28
  • DOI: 10.1002/adma.201806620

Operando monitoring the lithium spatial distribution of lithium metal anodes
journal, June 2018


Using in situ and operando methods to characterize phase changes in charged lithium nickel cobalt aluminum oxide cathode materials
journal, January 2020


In Situ Transmission Electron Microscopy
book, January 2019


Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy
journal, October 2017


Degradation of Si/Ge core/shell nanowire heterostructures during lithiation and delithiation at 0.8 and 20 A g −1
journal, January 2018

  • Kim, Dongheun; Li, Nan; Sheehan, Chris J.
  • Nanoscale, Vol. 10, Issue 16
  • DOI: 10.1039/c8nr00865e

Automated analysis of evolving interfaces during in situ electron microscopy
journal, February 2016

  • Schneider, Nicholas M.; Park, Jeung Hun; Norton, Michael M.
  • Advanced Structural and Chemical Imaging, Vol. 2, Issue 1
  • DOI: 10.1186/s40679-016-0016-z

Liquid-Phase Electrochemical Scanning Electron Microscopy for In Situ Investigation of Lithium Dendrite Growth and Dissolution
journal, January 2017


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

Morphological Stability during Electrodeposition
journal, January 2003

  • Haataja, Mikko; Srolovitz, David J.; Bocarsly, Andrew B.
  • Journal of The Electrochemical Society, Vol. 150, Issue 10
  • DOI: 10.1149/1.1602456

Understanding materials challenges for rechargeable ion batteries with in situ transmission electron microscopy
journal, August 2017

  • Yuan, Yifei; Amine, Khalil; Lu, Jun
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15806

In situ plasmonic optical fiber detection of the state of charge of supercapacitors for renewable energy storage
journal, July 2018


Nanoscale evolution of interface morphology during electrodeposition
journal, December 2017

  • Schneider, Nicholas M.; Park, Jeung Hun; Grogan, Joseph M.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/s41467-017-02364-9

Phase evolution and structural modulation during in situ lithiation of MoS2, WS2 and graphite in TEM
journal, April 2021