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High damage tolerance of electrochemically lithiated silicon

Journal Article · · Nature Communications
DOI:https://doi.org/10.1038/ncomms9417· OSTI ID:1261096
 [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

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.

Research Organization:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Georgia Inst. of Technology, Atlanta, GA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF) (United States)
Contributing Organization:
Univ. of Illinois, Urbana, IL (United States); Univ. of Pittsburgh, PA (United States)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1261096
Alternate ID(s):
OSTI ID: 1347348
Journal Information:
Nature Communications, Journal Name: Nature Communications Vol. 6; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

References (45)

25th Anniversary Article: Understanding the Lithiation of Silicon and Other Alloying Anodes for Lithium-Ion Batteries journal August 2013
Variation of stress with charging rate due to strain-rate sensitivity of silicon electrodes of Li-ion batteries journal December 2014
Anisotropic Swelling and Fracture of Silicon Nanowires during Lithiation journal August 2011
Two-Phase Electrochemical Lithiation in Amorphous Silicon journal January 2013
In Situ TEM of Two-Phase Lithiation of Amorphous Silicon Nanospheres journal January 2013
Atomic-Scale Mechanisms of Sliding along an Interdiffused Li–Si–Cu Interface journal February 2015
Quantitative Fracture Strength and Plasticity Measurements of Lithiated Silicon Nanowires by In Situ TEM Tensile Experiments journal October 2012
Tough Germanium Nanoparticles under Electrochemical Cycling journal March 2013
The Tension of Metallic Films Deposited by Electrolysis journal May 1909
Real-Time Measurement of Stress and Damage Evolution during Initial Lithiation of Crystalline Silicon journal July 2011
Electrical Energy Storage for the Grid: A Battery of Choices journal November 2011
Increased Cycling Efficiency and Rate Capability of Copper-coated Silicon Anodes in Lithium-ion Batteries text January 2011
Studying the Kinetics of Crystalline Silicon Nanoparticle Lithiation with In Situ Transmission Electron Microscopy journal September 2012
Decrepitation model for capacity loss during cycling of alloys in rechargeable electrochemical systems journal January 2000
Strength and sharp contact fracture of silicon journal February 2006
Stress generation during lithiation of high-capacity electrode particles in lithium ion batteries journal July 2013
Ex-situ depth-sensing indentation measurements of electrochemically produced Si–Li alloy films journal August 2011
Evolution of stress within a spherical insertion electrode particle under potentiostatic and galvanostatic operation journal May 2009
In situ measurements of stress evolution in silicon thin films during electrochemical lithiation and delithiation journal August 2010
Elastic softening of amorphous and crystalline Li–Si Phases with increasing Li concentration: A first-principles study journal October 2010
Increased cycling efficiency and rate capability of copper-coated silicon anodes in lithium-ion batteries journal January 2011
Method to deduce the critical size for interfacial delamination of patterned electrode structures and application to lithiation of thin-film silicon islands journal May 2012
Robustness of amorphous silicon during the initial lithiation/delithiation cycle journal July 2014
Mechanical behavior of electrochemically lithiated silicon journal January 2015
Surface effects on the structure and lithium behavior in lithiated silicon: A first principles study journal June 2013
Challenges for Rechargeable Li Batteries journal February 2010
Measurements of the Fracture Energy of Lithiated Silicon Electrodes of Li-Ion Batteries journal October 2013
Size-Dependent Fracture of Silicon Nanoparticles During Lithiation journal January 2012
Issues and challenges facing rechargeable lithium batteries journal November 2001
High-performance lithium-ion anodes using a hierarchical bottom-up approach journal March 2010
Current-induced transition from particle-by-particle to concurrent intercalation in phase-separating battery electrodes journal September 2014
High-performance lithium battery anodes using silicon nanowires journal December 2007
In situ atomic-scale imaging of electrochemical lithiation in silicon journal October 2012
Fracture of electrodes in lithium-ion batteries caused by fast charging journal October 2010
In situ tensile and creep testing of lithiated silicon nanowires journal December 2013
Mechanical properties of amorphous Li x Si alloys: a reactive force field study journal October 2013
Real-Time Measurement of Stress and Damage Evolution during Initial Lithiation of Crystalline Silicon journal July 2011
In Situ Observation of the Electrochemical Lithiation of a Single SnO2 Nanowire Electrode journal December 2010
Issues and challenges facing rechargeable lithium batteries book October 2010
High-performance lithium battery anodes using silicon nanowires
  • Chan, Candace K.; Peng, Hailin; Liu, Gao
  • Materials for Sustainable Energy: A Collection of Peer-Reviewed Research and Review Articles from Nature Publishing Group, p. 187-191 https://doi.org/10.1142/9789814317665_0026
book October 2010
Colossal Reversible Volume Changes in Lithium Alloys journal January 2001
A High Capacity Nano-Si Composite Anode Material for Lithium Rechargeable Batteries journal January 1999
“Electrochemical Shock” of Intercalation Electrodes: A Fracture Mechanics Analysis journal January 2010
On Plastic Deformation and Fracture in Si Films during Electrochemical Lithiation/Delithiation Cycling journal January 2013
In Situ Measurements of Stress Evolution in Silicon Thin Films During Electrochemical Lithiation and Delithiation text January 2011

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