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Title: High damage tolerance of electrochemically lithiated silicon

Abstract

Mechanical degradation and resultant capacity fade in high-capacity electrode materials critically hinder their use in high-performance rechargeable batteries. Despite tremendous efforts devoted to the study of the electro–chemo–mechanical behaviours of high-capacity electrode materials, their fracture properties and mechanisms remain largely unknown. In this paper, we report a nanomechanical study on the damage tolerance of electrochemically lithiated silicon. Our in situ transmission electron microscopy experiments reveal a striking contrast of brittle fracture in pristine silicon versus ductile tensile deformation in fully lithiated silicon. Quantitative fracture toughness measurements by nanoindentation show a rapid brittle-to-ductile transition of fracture as the lithium-to-silicon molar ratio is increased to above 1.5. Molecular dynamics simulations elucidate the mechanistic underpinnings of the brittle-to-ductile transition governed by atomic bonding and lithiation-induced toughening. Finally, our results reveal the high damage tolerance in amorphous lithium-rich silicon alloys and have important implications for the development of durable rechargeable batteries.

Authors:
 [1];  [1];  [2];  [3];  [1];  [1];  [4];  [3];  [2];  [1];  [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States). Woodruff School of Mechanical Engineering
  2. Univ. of Pittsburgh, PA (United States). Dept. of Mechanical Engineering and Materials Science
  3. Univ. of Illinois, Urbana, IL (United States). Dept. of Aerospace Engineering
  4. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Center for Integrated Nanotechnologies
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Georgia Inst. of Technology, Atlanta, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
Contributing Org.:
Univ. of Illinois, Urbana, IL (United States); Univ. of Pittsburgh, PA (United States)
OSTI Identifier:
1347348
Alternate Identifier(s):
OSTI ID: 1261096
Report Number(s):
SAND2015-5484J
Journal ID: ISSN 2041-1723; ncomms9417
Grant/Contract Number:  
AC04-94AL85000; NSF-CMMI-1300458; NSF-CMMI-1300805; NSF-CMMI-1100205; NSF-DMR-1410936; NSF-CMMI-08010934
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 6; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; chemical sciences; materials science; nanotechnology; batteries; mechanical properties

Citation Formats

Wang, Xueju, Fan, Feifei, Wang, Jiangwei, Wang, Haoran, Tao, Siyu, Yang, Avery, Liu, Yang, Beng Chew, Huck, Mao, Scott X., Zhu, Ting, and Xia, Shuman. High damage tolerance of electrochemically lithiated silicon. United States: N. p., 2015. Web. doi:10.1038/ncomms9417.
Wang, Xueju, Fan, Feifei, Wang, Jiangwei, Wang, Haoran, Tao, Siyu, Yang, Avery, Liu, Yang, Beng Chew, Huck, Mao, Scott X., Zhu, Ting, & Xia, Shuman. High damage tolerance of electrochemically lithiated silicon. United States. doi:10.1038/ncomms9417.
Wang, Xueju, Fan, Feifei, Wang, Jiangwei, Wang, Haoran, Tao, Siyu, Yang, Avery, Liu, Yang, Beng Chew, Huck, Mao, Scott X., Zhu, Ting, and Xia, Shuman. Thu . "High damage tolerance of electrochemically lithiated silicon". United States. doi:10.1038/ncomms9417. https://www.osti.gov/servlets/purl/1347348.
@article{osti_1347348,
title = {High damage tolerance of electrochemically lithiated silicon},
author = {Wang, Xueju and Fan, Feifei and Wang, Jiangwei and Wang, Haoran and Tao, Siyu and Yang, Avery and Liu, Yang and Beng Chew, Huck and Mao, Scott X. and Zhu, Ting and Xia, Shuman},
abstractNote = {Mechanical degradation and resultant capacity fade in high-capacity electrode materials critically hinder their use in high-performance rechargeable batteries. Despite tremendous efforts devoted to the study of the electro–chemo–mechanical behaviours of high-capacity electrode materials, their fracture properties and mechanisms remain largely unknown. In this paper, we report a nanomechanical study on the damage tolerance of electrochemically lithiated silicon. Our in situ transmission electron microscopy experiments reveal a striking contrast of brittle fracture in pristine silicon versus ductile tensile deformation in fully lithiated silicon. Quantitative fracture toughness measurements by nanoindentation show a rapid brittle-to-ductile transition of fracture as the lithium-to-silicon molar ratio is increased to above 1.5. Molecular dynamics simulations elucidate the mechanistic underpinnings of the brittle-to-ductile transition governed by atomic bonding and lithiation-induced toughening. Finally, our results reveal the high damage tolerance in amorphous lithium-rich silicon alloys and have important implications for the development of durable rechargeable batteries.},
doi = {10.1038/ncomms9417},
journal = {Nature Communications},
number = ,
volume = 6,
place = {United States},
year = {2015},
month = {9}
}

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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

Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011


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

High-performance lithium-ion anodes using a hierarchical bottom-up approach
journal, March 2010

  • Magasinski, A.; Dixon, P.; Hertzberg, B.
  • Nature Materials, Vol. 9, Issue 4, p. 353-358
  • DOI: 10.1038/nmat2725

Current-induced transition from particle-by-particle to concurrent intercalation in phase-separating battery electrodes
journal, September 2014

  • Li, Yiyang; El Gabaly, Farid; Ferguson, Todd R.
  • Nature Materials, Vol. 13, Issue 12
  • DOI: 10.1038/nmat4084

Decrepitation model for capacity loss during cycling of alloys in rechargeable electrochemical systems
journal, January 2000


Colossal Reversible Volume Changes in Lithium Alloys
journal, January 2001

  • Beaulieu, L. Y.; Eberman, K. W.; Turner, R. L.
  • Electrochemical and Solid-State Letters, Vol. 4, Issue 9
  • DOI: 10.1149/1.1388178

High-performance lithium battery anodes using silicon nanowires
journal, December 2007

  • Chan, Candace K.; Peng, Hailin; Liu, Gao
  • Nature Nanotechnology, Vol. 3, Issue 1, p. 31-35
  • DOI: 10.1038/nnano.2007.411

Evolution of stress within a spherical insertion electrode particle under potentiostatic and galvanostatic operation
journal, May 2009


Fracture of electrodes in lithium-ion batteries caused by fast charging
journal, October 2010

  • Zhao, Kejie; Pharr, Matt; Vlassak, Joost J.
  • Journal of Applied Physics, Vol. 108, Issue 7
  • DOI: 10.1063/1.3492617

In situ measurements of stress evolution in silicon thin films during electrochemical lithiation and delithiation
journal, August 2010


In situ atomic-scale imaging of electrochemical lithiation in silicon
journal, October 2012

  • Liu, Xiao Hua; Wang, Jiang Wei; Huang, Shan
  • Nature Nanotechnology, Vol. 7, Issue 11
  • DOI: 10.1038/nnano.2012.170

A High Capacity Nano-Si Composite Anode Material for Lithium Rechargeable Batteries
journal, January 1999

  • Li, Hong; Huang, Xuejie; Chen, Liquan
  • Electrochemical and Solid-State Letters, Vol. 2, Issue 11, p. 547-549
  • DOI: 10.1149/1.1390899

Anisotropic Swelling and Fracture of Silicon Nanowires during Lithiation
journal, August 2011

  • Liu, Xiao Hua; Zheng, He; Zhong, Li
  • Nano Letters, Vol. 11, Issue 8, p. 3312-3318
  • DOI: 10.1021/nl201684d

Real-Time Measurement of Stress and Damage Evolution during Initial Lithiation of Crystalline Silicon
journal, July 2011


Size-Dependent Fracture of Silicon Nanoparticles During Lithiation
journal, January 2012

  • Liu, Xiao Hua; Zhong, Li; Huang, Shan
  • ACS Nano, Vol. 6, Issue 2
  • DOI: 10.1021/nn204476h

Two-Phase Electrochemical Lithiation in Amorphous Silicon
journal, January 2013

  • Wang, Jiang Wei; He, Yu; Fan, Feifei
  • Nano Letters, Vol. 13, Issue 2
  • DOI: 10.1021/nl304379k

In Situ TEM of Two-Phase Lithiation of Amorphous Silicon Nanospheres
journal, January 2013

  • McDowell, Matthew T.; Lee, Seok Woo; Harris, Justin T.
  • Nano Letters, Vol. 13, Issue 2
  • DOI: 10.1021/nl3044508

25th Anniversary Article: Understanding the Lithiation of Silicon and Other Alloying Anodes for Lithium-Ion Batteries
journal, August 2013

  • McDowell, Matthew T.; Lee, Seok Woo; Nix, William D.
  • Advanced Materials, Vol. 25, Issue 36
  • DOI: 10.1002/adma.201301795

“Electrochemical Shock” of Intercalation Electrodes: A Fracture Mechanics Analysis
journal, January 2010

  • Woodford, William H.; Chiang, Yet-Ming; Carter, W. Craig
  • Journal of The Electrochemical Society, Vol. 157, Issue 10
  • DOI: 10.1149/1.3464773

Atomic-Scale Mechanisms of Sliding along an Interdiffused Li–Si–Cu Interface
journal, February 2015

  • Wang, Haoran; Hou, Binyue; Wang, Xueju
  • Nano Letters, Vol. 15, Issue 3
  • DOI: 10.1021/nl5043837

Mechanical properties of amorphous Li x Si alloys: a reactive force field study
journal, October 2013

  • Fan, Feifei; Huang, Shan; Yang, Hui
  • Modelling and Simulation in Materials Science and Engineering, Vol. 21, Issue 7
  • DOI: 10.1088/0965-0393/21/7/074002

Elastic softening of amorphous and crystalline Li–Si Phases with increasing Li concentration: A first-principles study
journal, October 2010


Ex-situ depth-sensing indentation measurements of electrochemically produced Si–Li alloy films
journal, August 2011


Mechanical behavior of electrochemically lithiated silicon
journal, January 2015


In situ tensile and creep testing of lithiated silicon nanowires
journal, December 2013

  • Boles, Steven T.; Thompson, Carl V.; Kraft, Oliver
  • Applied Physics Letters, Vol. 103, Issue 26
  • DOI: 10.1063/1.4858394

Variation of stress with charging rate due to strain-rate sensitivity of silicon electrodes of Li-ion batteries
journal, December 2014


Quantitative Fracture Strength and Plasticity Measurements of Lithiated Silicon Nanowires by In Situ TEM Tensile Experiments
journal, October 2012

  • Kushima, Akihiro; Huang, Jian Yu; Li, Ju
  • ACS Nano, Vol. 6, Issue 11
  • DOI: 10.1021/nn3037623

Measurements of the Fracture Energy of Lithiated Silicon Electrodes of Li-Ion Batteries
journal, October 2013

  • Pharr, Matt; Suo, Zhigang; Vlassak, Joost J.
  • Nano Letters, Vol. 13, Issue 11
  • DOI: 10.1021/nl403197m

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


Stress generation during lithiation of high-capacity electrode particles in lithium ion batteries
journal, July 2013


Strength and sharp contact fracture of silicon
journal, February 2006


The Tension of Metallic Films Deposited by Electrolysis
journal, May 1909

  • Stoney, G. G.
  • Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 82, Issue 553
  • DOI: 10.1098/rspa.1909.0021

On Plastic Deformation and Fracture in Si Films during Electrochemical Lithiation/Delithiation Cycling
journal, January 2013

  • Nadimpalli, Siva P. V.; Sethuraman, Vijay A.; Bucci, Giovanna
  • Journal of The Electrochemical Society, Vol. 160, Issue 10
  • DOI: 10.1149/2.098310jes

Surface effects on the structure and lithium behavior in lithiated silicon: A first principles study
journal, June 2013


Robustness of amorphous silicon during the initial lithiation/delithiation cycle
journal, July 2014


Studying the Kinetics of Crystalline Silicon Nanoparticle Lithiation with In Situ Transmission Electron Microscopy
journal, September 2012

  • McDowell, Matthew T.; Ryu, Ill; Lee, Seok Woo
  • Advanced Materials, Vol. 24, Issue 45
  • DOI: 10.1002/adma.201202744

Tough Germanium Nanoparticles under Electrochemical Cycling
journal, March 2013

  • Liang, Wentao; Yang, Hui; Fan, Feifei
  • ACS Nano, Vol. 7, Issue 4
  • DOI: 10.1021/nn400330h

Increased cycling efficiency and rate capability of copper-coated silicon anodes in lithium-ion batteries
journal, January 2011


    Works referencing / citing this record:

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


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