skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Strong texturing of lithium metal in batteries

Abstract

Lithium, with its high theoretical specific capacity and lowest electrochemical potential, has been recognized as the ultimate negative electrode material for next-generation lithium-based high-energy-density batteries. However, a key challenge that has yet to be overcome is the inferior reversibility of Li plating and stripping, typically thought to be related to the uncontrollable morphology evolution of the Li anode during cycling. Here we show that Li-metal texturing (preferential crystallographic orientation) occurs during electrochemical deposition, which governs the morphological change of the Li anode. X-ray diffraction pole-figure analysis demonstrates that the texture of Li deposits is primarily dependent on the type of additive or cross-over molecule from the cathode side. With adsorbed additives, like LiNO3 and polysulfide, the lithium deposits are strongly textured, with Li (110) planes parallel to the substrate, and thus exhibit uniform, rounded morphology. A growth diagram of lithium deposits is given to connect various texture and morphology scenarios for different battery electrolytes. In conclusion, this understanding of lithium electrocrystallization from the crystallographic point of view provides significant insight for future lithium anode materials design in high-energy-density batteries.

Authors:
 [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [1];  [1];  [2]
  1. Stanford Univ., Stanford, CA (United States)
  2. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1439108
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 114; Journal Issue: 46; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; lithium metal; texture; battery; electrocrystallization; morphology

Citation Formats

Shi, Feifei, Pei, Allen, Vailionis, Arturas, Xie, Jin, Liu, Bofei, Zhao, Jie, Gong, Yongji, and Cui, Yi. Strong texturing of lithium metal in batteries. United States: N. p., 2017. Web. https://doi.org/10.1073/pnas.1708224114.
Shi, Feifei, Pei, Allen, Vailionis, Arturas, Xie, Jin, Liu, Bofei, Zhao, Jie, Gong, Yongji, & Cui, Yi. Strong texturing of lithium metal in batteries. United States. https://doi.org/10.1073/pnas.1708224114
Shi, Feifei, Pei, Allen, Vailionis, Arturas, Xie, Jin, Liu, Bofei, Zhao, Jie, Gong, Yongji, and Cui, Yi. Mon . "Strong texturing of lithium metal in batteries". United States. https://doi.org/10.1073/pnas.1708224114. https://www.osti.gov/servlets/purl/1439108.
@article{osti_1439108,
title = {Strong texturing of lithium metal in batteries},
author = {Shi, Feifei and Pei, Allen and Vailionis, Arturas and Xie, Jin and Liu, Bofei and Zhao, Jie and Gong, Yongji and Cui, Yi},
abstractNote = {Lithium, with its high theoretical specific capacity and lowest electrochemical potential, has been recognized as the ultimate negative electrode material for next-generation lithium-based high-energy-density batteries. However, a key challenge that has yet to be overcome is the inferior reversibility of Li plating and stripping, typically thought to be related to the uncontrollable morphology evolution of the Li anode during cycling. Here we show that Li-metal texturing (preferential crystallographic orientation) occurs during electrochemical deposition, which governs the morphological change of the Li anode. X-ray diffraction pole-figure analysis demonstrates that the texture of Li deposits is primarily dependent on the type of additive or cross-over molecule from the cathode side. With adsorbed additives, like LiNO3 and polysulfide, the lithium deposits are strongly textured, with Li (110) planes parallel to the substrate, and thus exhibit uniform, rounded morphology. A growth diagram of lithium deposits is given to connect various texture and morphology scenarios for different battery electrolytes. In conclusion, this understanding of lithium electrocrystallization from the crystallographic point of view provides significant insight for future lithium anode materials design in high-energy-density batteries.},
doi = {10.1073/pnas.1708224114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 46,
volume = 114,
place = {United States},
year = {2017},
month = {10}
}

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

Citation Metrics:
Cited by: 20 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: Lithium deposition morphology in various electrolyte systems at the current density of 0.1 mA/cm2, 1 mAh/cm2. (A and B) EC/DEC 1 M LiPF6. (C and D) DOL/DME 1 M LiTFSI, 1% LiNO3. (E and F) Sulfur catholyte 5 M S8 dissolved in DOL/DME 1 M LiTFSI, 1% LiNO3.more » (G and H) TEGDME 1 M LiTFSI with Li2O2 as cathode. (Scale bars: A, C, and G, 5 μm; E, 20 μm; D and F, 2 μm; B and H, 1 µm.)« less

Save / Share:

Works referenced in this record:

Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?
journal, December 2008

  • Xia, Younan; Xiong, Yujie; Lim, Byungkwon
  • Angewandte Chemie International Edition, Vol. 48, Issue 1, p. 60-103
  • DOI: 10.1002/anie.200802248

Dendrite-separator interactions in lithium-based batteries
journal, February 2015


Texture of Metals
journal, January 1974


A Reversible and Higher-Rate Li-O2 Battery
journal, July 2012


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


The synergetic effect of lithium polysulfide and lithium nitrate to prevent lithium dendrite growth
journal, June 2015

  • Li, Weiyang; Yao, Hongbin; Yan, Kai
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8436

Corrosion protection of secondary lithium electrodes in organic electrolytes
journal, July 1987


Structure Evolution During Processing of Polycrystalline Films
journal, August 2000


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

Topological defect dynamics in operando battery nanoparticles
journal, June 2015


Electrocrystallization - theory and applications
journal, June 1992


Biologically Closed Electrical Circuits in Plants
conference, January 2010

  • Foster, Justin C.; Volkov, Alexander; Markin, Vladislav S.
  • 216th ECS Meeting, ECS Transactions
  • DOI: 10.1149/1.3300059

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


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

Mussel-Inspired Polydopamine-Treated Polyethylene Separators for High-Power Li-Ion Batteries
journal, May 2011

  • Ryou, Myung-Hyun; Lee, Yong Min; Park, Jung-Ki
  • Advanced Materials, Vol. 23, Issue 27
  • DOI: 10.1002/adma.201100303

Factors Which Limit the Cycle Life of Rechargeable Lithium (Metal) Batteries
journal, January 2000

  • Aurbach, D.; Zinigrad, E.; Teller, H.
  • Journal of The Electrochemical Society, Vol. 147, Issue 4
  • DOI: 10.1149/1.1393349

Some Observations on Rechargeable Lithium Electrodes in a Propylene Carbonate Electrolyte
journal, January 1974

  • Selim, R.; Bro, P.
  • Journal of The Electrochemical Society, Vol. 121, Issue 11
  • DOI: 10.1149/1.2401708

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

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


Visualization and Quantification of Electrochemical and Mechanical Degradation in Li Ion Batteries
journal, October 2013


In Situ Observation of the Electrochemical Lithiation of a Single SnO2 Nanowire Electrode
journal, December 2010


Aprotic and Aqueous Li–O2 Batteries
journal, April 2014

  • Lu, Jun; Li, Li; Park, Jin-Bum
  • Chemical Reviews, Vol. 114, Issue 11, p. 5611-5640
  • DOI: 10.1021/cr400573b

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


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


Study of the Surface Composition of Highly Smooth Lithium Deposited in Various Carbonate Electrolytes Containing HF
journal, June 1997

  • Shiraishi, Soshi; Kanamura, Kiyoshi; Takehara, Zen-ichiro
  • Langmuir, Vol. 13, Issue 13
  • DOI: 10.1021/la960876c

Promises and challenges of nanomaterials for lithium-based rechargeable batteries
journal, June 2016


Study on electrochemically deposited Mg metal
journal, August 2011


Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth
journal, February 2016

  • Yan, Kai; Lu, Zhenda; Lee, Hyun-Wook
  • Nature Energy, Vol. 1, Issue 3, Article No. 16010
  • DOI: 10.1038/nenergy.2016.10

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

Exploring stereographic surface energy maps of cubic metals via an effective pair-potential approach
journal, January 2016


Electrolytes and Interphases in Li-Ion Batteries and Beyond
journal, October 2014


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


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

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

Electron backscatter diffraction applied to lithium sheets prepared by broad ion beam milling: EBSD Applied to Lithium Sheets
journal, October 2014

  • Brodusch, Nicolas; Zaghib, Karim; Gauvin, Raynald
  • Microscopy Research and Technique, Vol. 78, Issue 1
  • DOI: 10.1002/jemt.22441

In Situ Scanning Electron Microscopy Characterization of the Mechanism for Li Dendrite Growth
journal, January 2016

  • Tang, Ching-Yen; Dillon, Shen J.
  • Journal of The Electrochemical Society, Vol. 163, Issue 8
  • DOI: 10.1149/2.0891608jes

Layered reduced graphene oxide with nanoscale interlayer gaps as a stable host for lithium metal anodes
journal, March 2016

  • Lin, Dingchang; Liu, Yayuan; Liang, Zheng
  • Nature Nanotechnology, Vol. 11, Issue 7
  • DOI: 10.1038/nnano.2016.32

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

Investigation of Lithium Electrodeposits Formed in Practical Rechargeable Li-Li[sub x]MnO[sub 2] Batteries Based on LiAsF[sub 6]/1,3-Dioxolane Solutions
journal, January 2004

  • Zinigrad, E.; Levi, E.; Teller, H.
  • Journal of The Electrochemical Society, Vol. 151, Issue 1
  • DOI: 10.1149/1.1630591

Stable lithium electrodeposition in liquid and nanoporous solid electrolytes
journal, August 2014

  • Lu, Yingying; Tu, Zhengyuan; Archer, Lynden A.
  • Nature Materials, Vol. 13, Issue 10
  • DOI: 10.1038/nmat4041

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

    Works referencing / citing this record:

    Marginal Magnesium Doping for High‐Performance Lithium Metal Batteries
    journal, September 2019

    • Choi, Seung Ho; Lee, Seung Jong; Yoo, Dong‐Joo
    • Advanced Energy Materials, Vol. 9, Issue 41
    • DOI: 10.1002/aenm.201902278

    Marginal Magnesium Doping for High‐Performance Lithium Metal Batteries
    journal, September 2019

    • Choi, Seung Ho; Lee, Seung Jong; Yoo, Dong‐Joo
    • Advanced Energy Materials, Vol. 9, Issue 41
    • DOI: 10.1002/aenm.201902278

    Enabling Stable Lithium Metal Anode through Electrochemical Kinetics Manipulation
    journal, September 2019

    • Han, Yehu; Jie, Yulin; Huang, Fanyang
    • Advanced Functional Materials, Vol. 29, Issue 46
    • DOI: 10.1002/adfm.201904629

    Operando Observations and First-Principles Calculations of Reduced Lithium Insertion in Au-Coated LiMn 2 O 4
    journal, January 2019

    • Bassett, Kimberly L.; Warburton, Robert E.; Deshpande, Siddharth
    • Advanced Materials Interfaces, Vol. 6, Issue 4
    • DOI: 10.1002/admi.201801923

    Magnetic Field–Suppressed Lithium Dendrite Growth for Stable Lithium‐Metal Batteries
    journal, April 2019

    • Shen, Kang; Wang, Zeng; Bi, Xuanxuan
    • Advanced Energy Materials, Vol. 9, Issue 20
    • DOI: 10.1002/aenm.201900260

    Uniform High Ionic Conducting Lithium Sulfide Protection Layer for Stable Lithium Metal Anode
    journal, April 2019

    • Chen, Hao; Pei, Allen; Lin, Dingchang
    • Advanced Energy Materials, Vol. 9, Issue 22
    • DOI: 10.1002/aenm.201900858

    Bio‐Inspired Stable Lithium‐Metal Anodes by Co‐depositing Lithium with a 2D Vermiculite Shuttle
    journal, May 2019


    A Sustainable Solid Electrolyte Interphase for High‐Energy‐Density Lithium Metal Batteries Under Practical Conditions
    journal, January 2020


    Bio‐Inspired Stable Lithium‐Metal Anodes by Co‐depositing Lithium with a 2D Vermiculite Shuttle
    journal, May 2019

    • Ma, Qingtao; Sun, Xiaowen; Liu, Ping
    • Angewandte Chemie International Edition, Vol. 58, Issue 19
    • DOI: 10.1002/anie.201900783

    A Sustainable Solid Electrolyte Interphase for High‐Energy‐Density Lithium Metal Batteries Under Practical Conditions
    journal, February 2020

    • Zhang, Xue‐Qiang; Li, Tao; Li, Bo‐Quan
    • Angewandte Chemie International Edition, Vol. 59, Issue 8
    • DOI: 10.1002/anie.201911724

    Additive‐Assisted Novel Dual‐Salt Electrolyte Addresses Wide Temperature Operation of Lithium–Metal Batteries
    journal, March 2019


    The Challenge of Lithium Metal Anodes for Practical Applications
    journal, April 2019


    Fast lithium growth and short circuit induced by localized-temperature hotspots in lithium batteries
    journal, May 2019


    Designing polymers for advanced battery chemistries
    journal, April 2019


    A substrate-influenced three-dimensional unoriented dispersion pathway for dendrite-free lithium metal anodes
    journal, January 2018

    • Hu, Mengfei; Yuan, Yuan; Guo, Man
    • Journal of Materials Chemistry A, Vol. 6, Issue 30
    • DOI: 10.1039/c8ta04343d

    Investigation of the temperature-dependent behaviours of Li metal anode
    journal, January 2019

    • Guo, Yanpeng; Li, Dian; Xiong, Rundi
    • Chemical Communications, Vol. 55, Issue 66
    • DOI: 10.1039/c9cc04897a

    Suppressing lithium dendrite formation by slowing its desolvation kinetics
    journal, January 2019

    • Yang, Huicong; Yin, Lichang; Shi, Huifa
    • Chemical Communications, Vol. 55, Issue 88
    • DOI: 10.1039/c9cc07092c

    Electrochemomechanics of lithium dendrite growth
    journal, January 2019

    • Jana, Aniruddha; Woo, Sang Inn; Vikrant, K. S. N.
    • Energy & Environmental Science, Vol. 12, Issue 12
    • DOI: 10.1039/c9ee01864f

    Stabilizing a sodium-metal battery with the synergy effects of a sodiophilic matrix and fluorine-rich interface
    journal, January 2019

    • Wang, Qidi; Zhao, Chenglong; Lv, Xiaohui
    • Journal of Materials Chemistry A, Vol. 7, Issue 43
    • DOI: 10.1039/c9ta06877e

    Lithium metal stripping beneath the solid electrolyte interphase
    journal, August 2018

    • Shi, Feifei; Pei, Allen; Boyle, David Thomas
    • Proceedings of the National Academy of Sciences, Vol. 115, Issue 34
    • DOI: 10.1073/pnas.1806878115

    Lithium Mechanics: Roles of Strain Rate and Temperature and Implications for Lithium Metal Batteries
    journal, January 2019

    • LePage, William S.; Chen, Yuxin; Kazyak, Eric
    • Journal of The Electrochemical Society, Vol. 166, Issue 2
    • DOI: 10.1149/2.0221902jes

    Combinatorial Methods for Improving Lithium Metal Cycling Efficiency
    journal, January 2018

    • Genovese, Matthew; Louli, A. J.; Weber, Rochelle
    • Journal of The Electrochemical Society, Vol. 165, Issue 13
    • DOI: 10.1149/2.0401813jes

    Measuring the Coulombic Efficiency of Lithium Metal Cycling in Anode-Free Lithium Metal Batteries
    journal, January 2018

    • Genovese, Matthew; Louli, A. J.; Weber, Rochelle
    • Journal of The Electrochemical Society, Vol. 165, Issue 14
    • DOI: 10.1149/2.0641814jes

    Influence of Current Density on Graphite Anode Failure in Lithium-Ion Batteries
    journal, January 2019

    • Zhang, Pengcheng; Yuan, Tao; Pang, Yuepeng
    • Journal of The Electrochemical Society, Vol. 166, Issue 3
    • DOI: 10.1149/2.0701903jes

    Electrochemical Kinetics of Lithium Plating and Stripping in Solid Polymer Electrolytes: Pulsed Voltammetry
    journal, January 2019

    • Berliner, Marc D.; McGill, Brandon C.; Majeed, Muneeb
    • Journal of The Electrochemical Society, Vol. 166, Issue 2
    • DOI: 10.1149/2.0851902jes

    High Capacity Utilization of Li Metal Anodes by Application of Celgard Separator-Reinforced Ternary Polymer Electrolyte
    journal, January 2019

    • Zhang, Mengyi; Gui, Alicia Lei; Sun, Wei
    • Journal of The Electrochemical Society, Vol. 166, Issue 10
    • DOI: 10.1149/2.1131910jes

    On our Limited Understanding of Electrodeposition
    journal, January 2019


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