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

Title: Nanoscale in situ detection of nucleation and growth of Li electrodeposition at various current densities

Abstract

Li metal batteries can store at least ten times more energy than currently existing Li-ion batteries. However, during routine charging and discharging, Li dendrites grow on the Li metal electrode, which can lead to capacity loss by the consumption of Li salt at the surface of the Li dendrites, and be a safety hazard resulting from the potential for short-circuits. Although past efforts have provided useful information about the morphology and surface area of Li dendrite formation at the microscale, a nanoscale understanding of nucleation and growth of Li nanoparticle electrodeposition is still elusive. In this study, using a new electrochemical cell for transmission mode grazing incidence small angle X-ray scattering, we obtained, for the first time, the primary nucleus size of Li nanoparticles, their size evolution and their fractal structures at various current densities and in real-time. The measured average radius of gyration, Rg, at current densities of 0.1, 0.5, and 2.0 mA cm-2 is 5.4 ± 0.4, 4.5 ± 0.3, and 3.5 ± 0.3 nm, respectively. This variation in size with current density is noteworthy when recognizing that the surface area-to-volume ratio of the Li nanoparticles is 3.7 times higher at 2.0 mA cm-2 than at 0.1 mAmore » cm-2. We also compared a hierarchical fractal structure of Li particles from the nanometer to micrometer scale. Our findings illuminate the role of overpotential in the reactive surface area of Li dendrites at the nanoscale, and provide a novel research platform for suppressing Li dendrite formation in Li metal battery systems.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1];  [1];  [3]; ORCiD logo [3]; ORCiD logo [1]
  1. Washington Univ., St. Louis, MO (United States). Dept. of Energy, Environmental and Chemical Engineering
  2. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
  3. Seoul National Univ. (Korea, Republic of). Program in Nano Science and Technology, Graduate School of Convergence Science and Technology
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1460946
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 6; Journal Issue: 11; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; MRI; cells; dendrite growth; deposition; interface; ionic-liquid; lithium metal anodes; sulfur batteries

Citation Formats

Jung, Haesung, Lee, Byeongdu, Lengyel, Miklos, Axelbaum, Richard, Yoo, Jeeyoung, Kim, Youn Sang, and Jun, Young-Shin. Nanoscale in situ detection of nucleation and growth of Li electrodeposition at various current densities. United States: N. p., 2018. Web. doi:10.1039/C8TA00343B.
Jung, Haesung, Lee, Byeongdu, Lengyel, Miklos, Axelbaum, Richard, Yoo, Jeeyoung, Kim, Youn Sang, & Jun, Young-Shin. Nanoscale in situ detection of nucleation and growth of Li electrodeposition at various current densities. United States. https://doi.org/10.1039/C8TA00343B
Jung, Haesung, Lee, Byeongdu, Lengyel, Miklos, Axelbaum, Richard, Yoo, Jeeyoung, Kim, Youn Sang, and Jun, Young-Shin. Fri . "Nanoscale in situ detection of nucleation and growth of Li electrodeposition at various current densities". United States. https://doi.org/10.1039/C8TA00343B. https://www.osti.gov/servlets/purl/1460946.
@article{osti_1460946,
title = {Nanoscale in situ detection of nucleation and growth of Li electrodeposition at various current densities},
author = {Jung, Haesung and Lee, Byeongdu and Lengyel, Miklos and Axelbaum, Richard and Yoo, Jeeyoung and Kim, Youn Sang and Jun, Young-Shin},
abstractNote = {Li metal batteries can store at least ten times more energy than currently existing Li-ion batteries. However, during routine charging and discharging, Li dendrites grow on the Li metal electrode, which can lead to capacity loss by the consumption of Li salt at the surface of the Li dendrites, and be a safety hazard resulting from the potential for short-circuits. Although past efforts have provided useful information about the morphology and surface area of Li dendrite formation at the microscale, a nanoscale understanding of nucleation and growth of Li nanoparticle electrodeposition is still elusive. In this study, using a new electrochemical cell for transmission mode grazing incidence small angle X-ray scattering, we obtained, for the first time, the primary nucleus size of Li nanoparticles, their size evolution and their fractal structures at various current densities and in real-time. The measured average radius of gyration, Rg, at current densities of 0.1, 0.5, and 2.0 mA cm-2 is 5.4 ± 0.4, 4.5 ± 0.3, and 3.5 ± 0.3 nm, respectively. This variation in size with current density is noteworthy when recognizing that the surface area-to-volume ratio of the Li nanoparticles is 3.7 times higher at 2.0 mA cm-2 than at 0.1 mA cm-2. We also compared a hierarchical fractal structure of Li particles from the nanometer to micrometer scale. Our findings illuminate the role of overpotential in the reactive surface area of Li dendrites at the nanoscale, and provide a novel research platform for suppressing Li dendrite formation in Li metal battery systems.},
doi = {10.1039/C8TA00343B},
journal = {Journal of Materials Chemistry. A},
number = 11,
volume = 6,
place = {United States},
year = {Fri Feb 02 00:00:00 EST 2018},
month = {Fri Feb 02 00:00:00 EST 2018}
}

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

Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: Experimental setup for in situ transmission GISAXS. (a) Newly developed Li electrodeposition cell operated in beamline 12-ID-B, Advanced Photon Sources (APS), Argonne National Laboratory (ANL), IL. (b) Schematic cell design for Li electrodeposition. (c) The measurement of Li electrodeposition at an electrolyte-electrode interface using in situ time resolvedmore » transmission GISAXS. The transmitted beam through the edge of the substrate gives the scattered patterns from the primary Li nanoparticles and aggregated particles.« less

Save / Share:

Works referenced in this record:

In situ NMR observation of the formation of metallic lithium microstructures in lithium batteries
journal, May 2010

  • Bhattacharyya, Rangeet; Key, Baris; Chen, Hailong
  • Nature Materials, Vol. 9, Issue 6
  • DOI: 10.1038/nmat2764

Direct In Situ Observation and Numerical Simulations of Non-Shrinking-Core Behavior in an MCMB Graphite Composite Electrode
journal, January 2012

  • Harris, Stephen J.; Rahani, Ehsan Kabiri; Shenoy, Vivek B.
  • Journal of The Electrochemical Society, Vol. 159, Issue 9
  • DOI: 10.1149/2.055209jes

Prospects for Dendrite-Free Cycling of Li Metal Batteries
journal, January 2015

  • Chen, Qing; Geng, Ke; Sieradzki, K.
  • Journal of The Electrochemical Society, Vol. 162, Issue 10
  • DOI: 10.1149/2.0261510jes

Ionic-Liquid-Nanoparticle Hybrid Electrolytes: Applications in Lithium Metal Batteries
journal, November 2013

  • Lu, Yingying; Korf, Kevin; Kambe, Yu
  • Angewandte Chemie International Edition, Vol. 53, Issue 2
  • DOI: 10.1002/anie.201307137

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

Controlled Lithium Dendrite Growth by a Synergistic Effect of Multilayered Graphene Coating and an Electrolyte Additive
journal, April 2015

  • Kim, Joo-Seong; Kim, Dae Woo; Jung, Hee Tae
  • Chemistry of Materials, Vol. 27, Issue 8
  • DOI: 10.1021/cm503447u

Anode-Free Rechargeable Lithium Metal Batteries
journal, August 2016

  • Qian, Jiangfeng; Adams, Brian D.; Zheng, Jianming
  • Advanced Functional Materials, Vol. 26, Issue 39
  • DOI: 10.1002/adfm.201602353

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode
journal, March 2016

  • Liu, Yayuan; Lin, Dingchang; Liang, Zheng
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms10992

Optical observation of Li dendrite growth in ionic liquid
journal, June 2013


Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal
journal, January 2017


Designing Safe Electrolyte Systems for a High-Stability Lithium-Sulfur Battery
journal, January 2018

  • Chen, Wei; Lei, Tianyu; Wu, Chunyang
  • Advanced Energy Materials, Vol. 8, Issue 10
  • DOI: 10.1002/aenm.201702348

Electrochemical aspects of the generation of ramified metallic electrodeposits
journal, December 1990


Lithiophilic Sites in Doped Graphene Guide Uniform Lithium Nucleation for Dendrite-Free Lithium Metal Anodes
journal, May 2017

  • Zhang, Rui; Chen, Xiao-Ru; Chen, Xiang
  • Angewandte Chemie International Edition, Vol. 56, Issue 27
  • DOI: 10.1002/anie.201702099

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

Magnetosome-like ferrimagnetic iron oxide nanocubes for highly sensitive MRI of single cells and transplanted pancreatic islets
journal, January 2011

  • Lee, N.; Kim, H.; Choi, S. H.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 7
  • DOI: 10.1073/pnas.1016409108

In Situ Observations of Nanoparticle Early Development Kinetics at Mineral−Water Interfaces
journal, November 2010

  • Jun, Young-Shin; Lee, Byeongdu; Waychunas, Glenn A.
  • Environmental Science & Technology, Vol. 44, Issue 21
  • DOI: 10.1021/es101491e

Columnar Lithium Metal Anodes
journal, September 2017

  • Zhang, Xue-Qiang; Chen, Xiang; Xu, Rui
  • Angewandte Chemie International Edition, Vol. 56, Issue 45
  • DOI: 10.1002/anie.201707093

Dendrite-Free Lithium Deposition via Self-Healing Electrostatic Shield Mechanism
journal, March 2013

  • Ding, Fei; Xu, Wu; Graff, Gordon L.
  • Journal of the American Chemical Society, Vol. 135, Issue 11, p. 4450-4456
  • DOI: 10.1021/ja312241y

Three-dimensional characterization of electrodeposited lithium microstructures using synchrotron X-ray phase contrast imaging
journal, January 2015

  • Eastwood, David S.; Bayley, Paul M.; Chang, Hee Jung
  • Chemical Communications, Vol. 51, Issue 2
  • DOI: 10.1039/C4CC03187C

7Li MRI of Li batteries reveals location of microstructural lithium
journal, February 2012

  • Chandrashekar, S.; Trease, Nicole M.; Chang, Hee Jung
  • Nature Materials, Vol. 11, Issue 4
  • DOI: 10.1038/nmat3246

Design principles for electrolytes and interfaces for stable lithium-metal batteries
journal, September 2016


The critical role of lithium nitrate in the gas evolution of lithium–sulfur batteries
journal, January 2016

  • Jozwiuk, Anna; Berkes, Balázs B.; Weiß, Thomas
  • Energy & Environmental Science, Vol. 9, Issue 8
  • DOI: 10.1039/C6EE00789A

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

Grazing-incidence transmission small angle X-ray scattering from thin films of block copolymers
journal, February 2013

  • Mahadevapuram, Nikhila; Strzalka, Joseph; Stein, Gila E.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 51, Issue 7
  • DOI: 10.1002/polb.23261

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

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


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

Dendritic growth mechanisms in lithium/polymer cells
journal, September 1999


Transition of lithium growth mechanisms in liquid electrolytes
journal, January 2016

  • Bai, Peng; Li, Ju; Brushett, Fikile R.
  • Energy & Environmental Science, Vol. 9, Issue 10
  • DOI: 10.1039/C6EE01674J

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


Electroless Formation of Hybrid Lithium Anodes for Fast Interfacial Ion Transport
journal, September 2017

  • Choudhury, Snehashis; Tu, Zhengyuan; Stalin, Sanjuna
  • Angewandte Chemie International Edition, Vol. 56, Issue 42
  • DOI: 10.1002/anie.201707754

A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries
journal, May 2009

  • Ji, Xiulei; Lee, Kyu Tae; Nazar, Linda F.
  • Nature Materials, Vol. 8, Issue 6, p. 500-506
  • DOI: 10.1038/nmat2460

Detection of subsurface structures underneath dendrites formed on cycled lithium metal electrodes
journal, November 2013

  • Harry, Katherine J.; Hallinan, Daniel T.; Parkinson, Dilworth Y.
  • Nature Materials, Vol. 13, Issue 1
  • DOI: 10.1038/nmat3793

Interconnected hollow carbon nanospheres for stable lithium metal anodes
journal, July 2014

  • Zheng, Guangyuan; Lee, Seok Woo; Liang, Zheng
  • Nature Nanotechnology, Vol. 9, Issue 8
  • DOI: 10.1038/nnano.2014.152

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

The interplay between solid electrolyte interface (SEI) and dendritic lithium growth
journal, October 2017


Lithiophilic Sites in Doped Graphene Guide Uniform Lithium Nucleation for Dendrite-Free Lithium Metal Anodes
journal, May 2017


Electroless Formation of Hybrid Lithium Anodes for Fast Interfacial Ion Transport
journal, September 2017

  • Choudhury, Snehashis; Tu, Zhengyuan; Stalin, Sanjuna
  • Angewandte Chemie, Vol. 129, Issue 42
  • DOI: 10.1002/ange.201707754

Columnar Lithium Metal Anodes
journal, September 2017


The critical role of lithium nitrate in the gas evolution of lithium–sulfur batteries
text, January 2016


Works referencing / citing this record:

Favorable lithium deposition behaviors on flexible carbon microtube skeleton enable a high-performance lithium metal anode
journal, January 2018

  • Sun, Changzhi; Wu, Tian; Wang, Jianing
  • Journal of Materials Chemistry A, Vol. 6, Issue 39
  • DOI: 10.1039/c8ta06828c

An acetylene black modified gel polymer electrolyte for high-performance lithium–sulfur batteries
journal, January 2019

  • Yang, Dezhi; He, Liang; Liu, Yu
  • Journal of Materials Chemistry A, Vol. 7, Issue 22
  • DOI: 10.1039/c9ta03123e

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.