DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The Impact of Li Grain Size on Coulombic Efficiency in Li Batteries

Abstract

One of the most promising means to increase the energy density of state-of-the-art lithium (Li)-ion batteries is to replace the graphite anode with a Li metal anode1, 2, 3. While the direct use of Li metal may be highly advantageous4,5, at present its practical application is limited by issues related to dendrite growth and low Coulombic efficiency (CE)6. Here operando electrochemical scanning transmission electron microscopy (STEM) is used to directly image the deposition/stripping of Li at the anode-electrolyte interface in a Li-based battery. A non-aqueous electrolyte containing small amounts of H2O as an additive results in remarkably different deposition/stripping properties as compared to the "dry" electrolyte when operated under identical electrochemical conditions. The electrolyte with the additive deposits more Li during the first cycle, with the grain sizes of the Li deposits being significantly larger and more variable. Here, the stripping of the Li upon discharge is also more complete, i.e., there is a higher cycling CE. This suggests that larger grain sizes are indicative of better performance by leading to more uniform Li deposition and an overall decrease in the formation of Li dendrites and side reactions with electrolyte components, thus potentially paving the way for the direct usemore » of Li metal in battery technologies.« less

Authors:
 [1];  [1];  [1];  [2];  [1];  [1];  [1];  [3];  [4]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Florida State Univ., Tallahassee, FL (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Pennsylvania State Univ., University Park, PA (United States)
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1340836
Report Number(s):
PNNL-SA-120401
Journal ID: ISSN 2045-2322; 48681; KC0208010
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 6; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Environmental Molecular Sciences Laboratory

Citation Formats

Mehdi, B. Layla, Stevens, Andrew, Qian, Jiangfeng, Park, Chiwoo, Xu, Wu, Henderson, Wesley A., Zhang, Ji -Guang, Mueller, Karl T., and Browning, Nigel D. The Impact of Li Grain Size on Coulombic Efficiency in Li Batteries. United States: N. p., 2016. Web. doi:10.1038/srep34267.
Mehdi, B. Layla, Stevens, Andrew, Qian, Jiangfeng, Park, Chiwoo, Xu, Wu, Henderson, Wesley A., Zhang, Ji -Guang, Mueller, Karl T., & Browning, Nigel D. The Impact of Li Grain Size on Coulombic Efficiency in Li Batteries. United States. https://doi.org/10.1038/srep34267
Mehdi, B. Layla, Stevens, Andrew, Qian, Jiangfeng, Park, Chiwoo, Xu, Wu, Henderson, Wesley A., Zhang, Ji -Guang, Mueller, Karl T., and Browning, Nigel D. Wed . "The Impact of Li Grain Size on Coulombic Efficiency in Li Batteries". United States. https://doi.org/10.1038/srep34267. https://www.osti.gov/servlets/purl/1340836.
@article{osti_1340836,
title = {The Impact of Li Grain Size on Coulombic Efficiency in Li Batteries},
author = {Mehdi, B. Layla and Stevens, Andrew and Qian, Jiangfeng and Park, Chiwoo and Xu, Wu and Henderson, Wesley A. and Zhang, Ji -Guang and Mueller, Karl T. and Browning, Nigel D.},
abstractNote = {One of the most promising means to increase the energy density of state-of-the-art lithium (Li)-ion batteries is to replace the graphite anode with a Li metal anode1, 2, 3. While the direct use of Li metal may be highly advantageous4,5, at present its practical application is limited by issues related to dendrite growth and low Coulombic efficiency (CE)6. Here operando electrochemical scanning transmission electron microscopy (STEM) is used to directly image the deposition/stripping of Li at the anode-electrolyte interface in a Li-based battery. A non-aqueous electrolyte containing small amounts of H2O as an additive results in remarkably different deposition/stripping properties as compared to the "dry" electrolyte when operated under identical electrochemical conditions. The electrolyte with the additive deposits more Li during the first cycle, with the grain sizes of the Li deposits being significantly larger and more variable. Here, the stripping of the Li upon discharge is also more complete, i.e., there is a higher cycling CE. This suggests that larger grain sizes are indicative of better performance by leading to more uniform Li deposition and an overall decrease in the formation of Li dendrites and side reactions with electrolyte components, thus potentially paving the way for the direct use of Li metal in battery technologies.},
doi = {10.1038/srep34267},
journal = {Scientific Reports},
number = ,
volume = 6,
place = {United States},
year = {Wed Oct 05 00:00:00 EDT 2016},
month = {Wed Oct 05 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 49 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

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


A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries
journal, September 2010


Characterization of Lithium Electrode in Lithium Imides/Ethylene Carbonate, and Cyclic Ether Electrolytes
journal, January 2004

  • Ota, Hitoshi; Wang, Xianming; Yasukawa, Eiki
  • Journal of The Electrochemical Society, Vol. 151, Issue 3
  • DOI: 10.1149/1.1644136

Electron microscopy of specimens in liquid
journal, October 2011

  • de Jonge, Niels; Ross, Frances M.
  • Nature Nanotechnology, Vol. 6, Issue 11, p. 695-704
  • DOI: 10.1038/nnano.2011.161

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

Challenges for Rechargeable Li Batteries
journal, February 2010

  • Goodenough, John B.; Kim, Youngsik
  • Chemistry of Materials, Vol. 22, Issue 3, p. 587-603
  • DOI: 10.1021/cm901452z

Effects of Some Organic Additives on Lithium Deposition in Propylene Carbonate
journal, January 2002

  • Mogi, Ryo; Inaba, Minoru; Jeong, Soon-Ki
  • Journal of The Electrochemical Society, Vol. 149, Issue 12
  • DOI: 10.1149/1.1516770

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

Dendrite-Free Lithium Deposition with Self-Aligned Nanorod Structure
journal, November 2014

  • Zhang, Yaohui; Qian, Jiangfeng; Xu, Wu
  • Nano Letters, Vol. 14, Issue 12
  • DOI: 10.1021/nl5039117

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

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


Direct Observation of Aggregative Nanoparticle Growth: Kinetic Modeling of the Size Distribution and Growth Rate
journal, December 2013

  • Woehl, Taylor J.; Park, Chiwoo; Evans, James E.
  • Nano Letters, Vol. 14, Issue 1
  • DOI: 10.1021/nl4043328

Electron microscopy of whole cells in liquid with nanometer resolution
journal, January 2009

  • Jonge, N. d.; Peckys, D. B.; Kremers, G. J.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 7
  • DOI: 10.1073/pnas.0809567106

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

Advances in Li–S batteries
journal, January 2010

  • Ji, Xiulei; Nazar, Linda F.
  • Journal of Materials Chemistry, Vol. 20, Issue 44, p. 9821-9826
  • DOI: 10.1039/b925751a

Failure Mechanism for Fast-Charged Lithium Metal Batteries with Liquid Electrolytes
journal, September 2014

  • Lu, Dongping; Shao, Yuyan; Lozano, Terence
  • Advanced Energy Materials, Vol. 5, Issue 3
  • DOI: 10.1002/aenm.201400993

In situ scanning vibrating electrode technique for lithium metal anodes
journal, October 1997


New class of nonaqueous electrolytes for long-life and safe lithium-ion batteries
journal, February 2013

  • Chen, Zonghai; Ren, Yang; Jansen, Andrew N.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2518

In situ liquid-cell electron microscopy of silver–palladium galvanic replacement reactions on silver nanoparticles
journal, September 2014

  • Sutter, E.; Jungjohann, K.; Bliznakov, S.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5946

Li–O2 and Li–S batteries with high energy storage
journal, January 2012

  • Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J.
  • Nature Materials, Vol. 11, Issue 1, p. 19-29
  • DOI: 10.1038/nmat3191

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

Dendrite-free Li deposition using trace-amounts of water as an electrolyte additive
journal, July 2015


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


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

Behavior of lithium/electrolyte interface in organic solutions
journal, March 1993


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

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

Direct Observation of Aggregative Nanoparticle Growth: Kinetic Modeling of the Size Distribution and Growth Rate
journal, August 2014

  • Woehl, Taylor J.; Park, Chiwoo; Evans, James E.
  • Microscopy and Microanalysis, Vol. 20, Issue S3
  • DOI: 10.1017/s1431927614009799

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


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

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

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

Direct Observation of Aggregative Nanoparticle Growth: Kinetic Modeling of the Size Distribution and Growth Rate
journal, December 2013

  • Woehl, Taylor J.; Park, Chiwoo; Evans, James E.
  • Nano Letters, Vol. 14, Issue 1
  • DOI: 10.1021/nl4043328

Dendrite-Free Lithium Deposition with Self-Aligned Nanorod Structure
journal, November 2014

  • Zhang, Yaohui; Qian, Jiangfeng; Xu, Wu
  • Nano Letters, Vol. 14, Issue 12
  • DOI: 10.1021/nl5039117

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

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

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

New class of nonaqueous electrolytes for long-life and safe lithium-ion batteries
journal, February 2013

  • Chen, Zonghai; Ren, Yang; Jansen, Andrew N.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2518

Li–O2 and Li–S batteries with high energy storage
journal, January 2012

  • Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J.
  • Nature Materials, Vol. 11, Issue 1, p. 19-29
  • DOI: 10.1038/nmat3191

Electron microscopy of specimens in liquid
journal, October 2011

  • de Jonge, Niels; Ross, Frances M.
  • Nature Nanotechnology, Vol. 6, Issue 11, p. 695-704
  • DOI: 10.1038/nnano.2011.161

Electron microscopy of whole cells in liquid with nanometer resolution
journal, January 2009

  • Jonge, N. d.; Peckys, D. B.; Kremers, G. J.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 7
  • DOI: 10.1073/pnas.0809567106

Minimum Cost Multi-Way Data Association for Optimizing Multitarget Tracking of Interacting Objects
journal, March 2015

  • Park, Chiwoo; Woehl, Taylor J.; Evans, James E.
  • IEEE Transactions on Pattern Analysis and Machine Intelligence, Vol. 37, Issue 3
  • DOI: 10.1109/tpami.2014.2346202

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


Works referencing / citing this record:

Elektrolytadditive für Lithiummetallanoden und wiederaufladbare Lithiummetallbatterien: Fortschritte und Perspektiven
journal, October 2018

  • Zhang, Heng; Eshetu, Gebrekidan Gebresilassie; Judez, Xabier
  • Angewandte Chemie, Vol. 130, Issue 46
  • DOI: 10.1002/ange.201712702

Electrolyte Additives for Lithium Metal Anodes and Rechargeable Lithium Metal Batteries: Progress and Perspectives
journal, October 2018

  • Zhang, Heng; Eshetu, Gebrekidan Gebresilassie; Judez, Xabier
  • Angewandte Chemie International Edition, Vol. 57, Issue 46
  • DOI: 10.1002/anie.201712702

Monitoring chemical reactions in liquid media using electron microscopy
journal, September 2019


Dead lithium: mass transport effects on voltage, capacity, and failure of lithium metal anodes
journal, January 2017

  • Chen, Kuan-Hung; Wood, Kevin N.; Kazyak, Eric
  • Journal of Materials Chemistry A, Vol. 5, Issue 23
  • DOI: 10.1039/c7ta00371d

Using polyoxometalates to enhance the capacity of lithium–oxygen batteries
journal, January 2018

  • Homewood, Tom; Frith, James T.; Vivek, J. Padmanabhan
  • Chemical Communications, Vol. 54, Issue 69
  • DOI: 10.1039/c8cc03832e

Fluorine-donating electrolytes enable highly reversible 5-V-class Li metal batteries
journal, January 2018

  • Suo, Liumin; Xue, Weijiang; Gobet, Mallory
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 6
  • DOI: 10.1073/pnas.1712895115

Liquid cell transmission electron microscopy and its applications
journal, January 2020

  • Pu, Shengda; Gong, Chen; Robertson, Alex W.
  • Royal Society Open Science, Vol. 7, Issue 1
  • DOI: 10.1098/rsos.191204

Applying shot boundary detection for automated crystal growth analysis during in situ transmission electron microscope experiments
journal, January 2017

  • Moeglein, W. A.; Griswold, R.; Mehdi, B. L.
  • Advanced Structural and Chemical Imaging, Vol. 3, Issue 1
  • DOI: 10.1186/s40679-016-0034-x

Liquid cell transmission electron microscopy and its applications
journal, January 2020

  • Pu, Shengda; Gong, Chen; Robertson, Alex W.
  • Royal Society Open Science, Vol. 7, Issue 1
  • DOI: 10.1098/rsos.191204