Stress effects on the initial lithiation of crystalline silicon nanowires: Reactive molecular dynamics simulations using ReaxFF

Ostadhossein, Alireza; Cubuk, Ekin D.; Tritsaris, Georgios A.; Kaxiras, Efthimios; Zhang, Sulin

doi:10.1039/C4CP05198J

Title: Stress effects on the initial lithiation of crystalline silicon nanowires: Reactive molecular dynamics simulations using ReaxFF

Journal Article · Thu Dec 18 00:00:00 EST 2014 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/C4CP05198J· OSTI ID:1265270

Ostadhossein, Alireza ^[1]; Cubuk, Ekin D. ^[2]; Tritsaris, Georgios A. ^[2]; Kaxiras, Efthimios ^[2]; Zhang, Sulin ^[1]

Pennsylvania State Univ., University Park, PA (United States)
Harvard Univ., Cambridge, MA (United States)

Silicon (Si) has been recognized as a promising anode material for the next-generation high-capacity lithium (Li)-ion batteries because of its high theoretical energy density. Recent in situ transmission electron microscopy (TEM) revealed that the electrochemical lithiation of crystalline Si nanowires (c-SiNWs) proceeds by the migration of the interface between the lithiated Si (LixSi) shell and the pristine unlithiated core, accompanied by solid-state amorphization. The underlying atomic mechanisms of Li insertion into c-Si remain poorly understood. In this research, we perform molecular dynamics (MD) simulations using the reactive force field (ReaxFF) to characterize the lithiation process of c-SiNWs. Our calculations show that ReaxFF can accurately reproduce the energy barriers of Li migration from DFT calculations in both crystalline (c-Si) and amorphous Si (a-Si). The ReaxFF-based MD simulations reveal that Li insertion into interlayer spacing between two adjacent (111) planes results in the peeling-off of the (111) facets and subsequent amorphization, in agreement with experimental observations. We find that breaking of the Si–Si bonds between (111)-bilayers requires a rather high local Li concentration, which explains the atomically sharp amorphous–crystalline interface (ACI). Our stress analysis shows that lithiation induces compressive stress at the ACI layer, causing retardation or even the stagnation of the reaction front, also in good agreement with TEM observations. Lithiation at high temperatures (e.g. 1200 K) shows that Li insertion into c-SiNW results in an amorphous to crystalline phase transformation at Li : Si composition of ~4.2:1. In conclusion, our modeling results provide a comprehensive picture of the effects of reaction and diffusion-induced stress on the interfacial dynamics and mechanical degradation of SiNW anodes under chemo-mechanical lithiation.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1265270

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 17, Issue 5; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 81 works

Citation information provided by
Web of Science

References (56)

Kinetics of Initial Lithiation of Crystalline Silicon Electrodes of Lithium-Ion Batteries Pharr, Matt; Zhao, Kejie; Wang, Xinwei Nano Letters, Vol. 12, Issue 9 https://doi.org/10.1021/nl302841y	journal	January 2012
Thermo-Chemo-Mechanics of ASR Expansion in Concrete Structures Ulm, Franz-Josef; Coussy, Olivier; Kefei, Li Journal of Engineering Mechanics, Vol. 126, Issue 3 https://doi.org/10.1061/(ASCE)0733-9399(2000)126:3(233)	journal	March 2000
First Principles Simulations of the Electrochemical Lithiation and Delithiation of Faceted Crystalline Silicon Chan, Maria K. Y.; Wolverton, C.; Greeley, Jeffrey P. Journal of the American Chemical Society, Vol. 134, Issue 35 https://doi.org/10.1021/ja301766z	journal	August 2012
Lithiation induced corrosive fracture in defective carbon nanotubes Huang, Xu; Yang, Hui; Liang, Wentao Applied Physics Letters, Vol. 103, Issue 15 https://doi.org/10.1063/1.4824418	journal	October 2013
On the Nature and Behavior of Li Atoms in Si: A First Principles Study Kim, Hyunwoo; Kweon, Kyoung Eun; Chou, Chia-Yun The Journal of Physical Chemistry C, Vol. 114, Issue 41 https://doi.org/10.1021/jp104289x	journal	September 2010
High-performance lithium battery anodes using silicon nanowires Chan, Candace K.; Peng, Hailin; Liu, Gao Nature Nanotechnology, Vol. 3, Issue 1, p. 31-35 https://doi.org/10.1038/nnano.2007.411	journal	December 2007
In situ atomic-scale imaging of electrochemical lithiation in silicon Liu, Xiao Hua; Wang, Jiang Wei; Huang, Shan Nature Nanotechnology, Vol. 7, Issue 11 https://doi.org/10.1038/nnano.2012.170	journal	October 2012
Empirical chemical pseudopotential theory of molecular and metallic bonding Abell, G. C. Physical Review B, Vol. 31, Issue 10 https://doi.org/10.1103/PhysRevB.31.6184	journal	May 1985
Analysis of stresses generated during hydrogen extraction from and injection into Ni(OH)2/NiOOH film electrode Pyun, Su-Il; Kim, Kwang-Hoon; Han, Jeong-Nam Journal of Power Sources, Vol. 91, Issue 2 https://doi.org/10.1016/S0378-7753(00)00464-X	journal	December 2000
ReaxFF Reactive Force Field for Molecular Dynamics Simulations of Hydrocarbon Oxidation Chenoweth, Kimberly; van Duin, Adri C. T.; Goddard, William A. The Journal of Physical Chemistry A, Vol. 112, Issue 5 https://doi.org/10.1021/jp709896w	journal	February 2008
Real-time stress measurements in lithium-ion battery negative-electrodes Sethuraman, V. A.; Van Winkle, N.; Abraham, D. P. Journal of Power Sources, Vol. 206, p. 334-342 https://doi.org/10.1016/j.jpowsour.2012.01.036	journal	May 2012
Self-Limiting Oxidation in Small-Diameter Si Nanowires Khalilov, U.; Pourtois, G.; Duin, A. C. T. van Chemistry of Materials, Vol. 24, Issue 11 https://doi.org/10.1021/cm300707x	journal	May 2012
Structure and Properties of Li−Si Alloys: A First-Principles Study Kim, Hyunwoo; Chou, Chia-Yun; Ekerdt, John G. The Journal of Physical Chemistry C, Vol. 115, Issue 5 https://doi.org/10.1021/jp1083899	journal	December 2010
First Principles Model of Amorphous Silicon Lithiation Chevrier, V. L.; Dahn, J. R. Journal of The Electrochemical Society, Vol. 156, Issue 6 https://doi.org/10.1149/1.3111037	journal	January 2009
First-Principles Calculation of Stress Nielsen, O. H.; Martin, Richard M. Physical Review Letters, Vol. 50, Issue 9 https://doi.org/10.1103/PhysRevLett.50.697	journal	February 1983
Bending-Induced Symmetry Breaking of Lithiation in Germanium Nanowires Gu, Meng; Yang, Hui; Perea, Daniel E. Nano Letters, Vol. 14, Issue 8 https://doi.org/10.1021/nl501680w	journal	July 2014
Chemical diffusion in intermediate phases in the lithium-silicon system Wen, C. John; Huggins, Robert A. Journal of Solid State Chemistry, Vol. 37, Issue 3, p. 271-278 https://doi.org/10.1016/0022-4596(81)90487-4	journal	May 1981
A chemo-mechanical model of lithiation in silicon Yang, Hui; Fan, Feifei; Liang, Wentao Journal of the Mechanics and Physics of Solids, Vol. 70 https://doi.org/10.1016/j.jmps.2014.06.004	journal	October 2014
Orientation-Dependent Interfacial Mobility Governs the Anisotropic Swelling in Lithiated Silicon Nanowires Yang, Hui; Huang, Shan; Huang, Xu Nano Letters, Vol. 12, Issue 4 https://doi.org/10.1021/nl204437t	journal	January 2012
Diffusion of Lithium in Bulk Amorphous Silicon: A Theoretical Study Tritsaris, Georgios A.; Zhao, Kejie; Okeke, Onyekwelu U. The Journal of Physical Chemistry C, Vol. 116, Issue 42 https://doi.org/10.1021/jp307221q	journal	October 2012
Thermodynamic Properties of the Lithium-Silicon System Sharma, Ram A.; Seefurth, Randall N. Journal of The Electrochemical Society, Vol. 123, Issue 12, p. 1763-1768 https://doi.org/10.1149/1.2132692	journal	January 1976
Investigation of Stresses Generated during Lithium Transport through the RF Sputter-Deposited Li[sub 1−δ]CoO[sub 2] Film by a DQCR Technique Go, Joo-Young; Pyun, Su-Il Journal of The Electrochemical Society, Vol. 150, Issue 8 https://doi.org/10.1149/1.1584438	journal	January 2003
Real-Time Measurement of Stress and Damage Evolution during Initial Lithiation of Crystalline Silicon Chon, M. J.; Sethuraman, V. A.; McCormick, A. Physical Review Letters, Vol. 107, Issue 4 https://doi.org/10.1103/PhysRevLett.107.045503	journal	July 2011
Morphological Evolution of Si Nanowires upon Lithiation: A First-Principles Multiscale Model Cubuk, Ekin D.; Wang, Wei L.; Zhao, Kejie Nano Letters, Vol. 13, Issue 5 https://doi.org/10.1021/nl400132q	journal	April 2013
Theory of Structural Transformation in Lithiated Amorphous Silicon Cubuk, Ekin D.; Kaxiras, Efthimios Nano Letters, Vol. 14, Issue 7 https://doi.org/10.1021/nl5015525	journal	June 2014
Reactive Potentials for Advanced Atomistic Simulations Liang, Tao; Shin, Yun Kyung; Cheng, Yu-Ting Annual Review of Materials Research, Vol. 43, Issue 1 https://doi.org/10.1146/annurev-matsci-071312-121610	journal	July 2013
Nano- and bulk-silicon-based insertion anodes for lithium-ion secondary cells Kasavajjula, Uday; Wang, Chunsheng; Appleby, A. John Journal of Power Sources, Vol. 163, Issue 2, p. 1003-1039 https://doi.org/10.1016/j.jpowsour.2006.09.084	journal	January 2007
Studying the Kinetics of Crystalline Silicon Nanoparticle Lithiation with In Situ Transmission Electron Microscopy McDowell, Matthew T.; Ryu, Ill; Lee, Seok Woo Advanced Materials, Vol. 24, Issue 45 https://doi.org/10.1002/adma.201202744	journal	September 2012
Anisotropic Swelling and Fracture of Silicon Nanowires during Lithiation Liu, Xiao Hua; Zheng, He; Zhong, Li Nano Letters, Vol. 11, Issue 8, p. 3312-3318 https://doi.org/10.1021/nl201684d	journal	August 2011
All-Solid Lithium Electrodes with Mixed-Conductor Matrix Boukamp, B. A. Journal of The Electrochemical Society, Vol. 128, Issue 4 https://doi.org/10.1149/1.2127495	journal	January 1981
Concurrent Reaction and Plasticity during Initial Lithiation of Crystalline Silicon in Lithium-Ion Batteries Zhao, Kejie; Pharr, Matt; Wan, Qiang Journal of The Electrochemical Society, Vol. 159, Issue 3 https://doi.org/10.1149/2.020203jes	journal	January 2012
Colossal Reversible Volume Changes in Lithium Alloys Beaulieu, L. Y.; Eberman, K. W.; Turner, R. L. Electrochemical and Solid-State Letters, Vol. 4, Issue 9 https://doi.org/10.1149/1.1388178	journal	January 2001
The phase diagram of the system lithium-silicon van der Marel, C.; Vinke, G. J. B.; van der Lugt, W. Solid State Communications, Vol. 54, Issue 11 https://doi.org/10.1016/0038-1098(85)90155-3	journal	June 1985
Self-Limiting Lithiation in Silicon Nanowires Liu, Xiao Hua; Fan, Feifei; Yang, Hui ACS Nano, Vol. 7, Issue 2 https://doi.org/10.1021/nn305282d	journal	January 2013
A High Capacity Nano-Si Composite Anode Material for Lithium Rechargeable Batteries Li, Hong; Huang, Xuejie; Chen, Liquan Electrochemical and Solid-State Letters, Vol. 2, Issue 11, p. 547-549 https://doi.org/10.1149/1.1390899	journal	January 1999
Reactive Flow in Silicon Electrodes Assisted by the Insertion of Lithium Zhao, Kejie; Tritsaris, Georgios A.; Pharr, Matt Nano Letters, Vol. 12, Issue 8 https://doi.org/10.1021/nl302261w	journal	July 2012
Computation of ring statistics for network models of solids Franzblau, D. S. Physical Review B, Vol. 44, Issue 10 https://doi.org/10.1103/PhysRevB.44.4925	journal	September 1991
The Mixing Mechanism during Lithiation of Si Negative Electrode in Li-Ion Batteries: An Ab Initio Molecular Dynamics Study Johari, Priya; Qi, Yue; Shenoy, Vivek B. Nano Letters, Vol. 11, Issue 12 https://doi.org/10.1021/nl203302d	journal	December 2011
Stresses of a Titanium Thin-Film Electrode Generated during Anodic Oxidation by a Beam-Bending Method Ueno, K.; Pyun, S. -I.; Seo, M. Journal of The Electrochemical Society, Vol. 147, Issue 12 https://doi.org/10.1149/1.1394095	journal	January 2000
Mechanical properties of amorphous Li _x Si alloys: a reactive force field study Fan, Feifei; Huang, Shan; Yang, Hui Modelling and Simulation in Materials Science and Engineering, Vol. 21, Issue 7 https://doi.org/10.1088/0965-0393/21/7/074002	journal	October 2013
Deformations in Si−Li Anodes Upon Electrochemical Alloying in Nano-Confined Space Hertzberg, Benjamin; Alexeev, Alexander; Yushin, Gleb Journal of the American Chemical Society, Vol. 132, Issue 25, p. 8548-8549 https://doi.org/10.1021/ja1031997	journal	June 2010
ReaxFF: A Reactive Force Field for Hydrocarbons van Duin, Adri C. T.; Dasgupta, Siddharth; Lorant, Francois The Journal of Physical Chemistry A, Vol. 105, Issue 41 https://doi.org/10.1021/jp004368u	journal	October 2001
Insights into Degradation of Si Anodes from First-Principle Calculations Rohrer, Jochen; Albe, Karsten The Journal of Physical Chemistry C, Vol. 117, Issue 37 https://doi.org/10.1021/jp401379d	journal	September 2013
Size-Dependent Fracture of Silicon Nanoparticles During Lithiation Liu, Xiao Hua; Zhong, Li; Huang, Shan ACS Nano, Vol. 6, Issue 2 https://doi.org/10.1021/nn204476h	journal	January 2012
Pair Distribution Function Analysis and Solid State NMR Studies of Silicon Electrodes for Lithium Ion Batteries: Understanding the (De)lithiation Mechanisms Key, Baris; Morcrette, Mathieu; Tarascon, Jean-Marie Journal of the American Chemical Society, Vol. 133, Issue 3 https://doi.org/10.1021/ja108085d	journal	January 2011
Small-Diameter Silicon Nanowire Surfaces Ma, D. D. D.; Lee, C. S.; Au, F. C. K. Science, Vol. 299, Issue 5614, p. 1874-1877 https://doi.org/10.1126/science.1080313	journal	February 2003
Self-weakening in lithiated graphene electrodes Yang, Hui; Huang, Xu; Liang, Wentao Chemical Physics Letters, Vol. 563 https://doi.org/10.1016/j.cplett.2013.01.048	journal	March 2013
Anisotropic Volume Expansion of Crystalline Silicon during Electrochemical Lithium Insertion: An Atomic Level Rationale Jung, Sung Chul; Choi, Jang Wook; Han, Young-Kyu Nano Letters, Vol. 12, Issue 10 https://doi.org/10.1021/nl3027197	journal	September 2012
Fracture of crystalline silicon nanopillars during electrochemical lithium insertion Lee, S. W.; McDowell, M. T.; Berla, L. A. Proceedings of the National Academy of Sciences, Vol. 109, Issue 11 https://doi.org/10.1073/pnas.1201088109	journal	February 2012
Roles of nanosize in lithium reactive nanomaterials for lithium ion batteries Lee, Kyu Tae; Cho, Jaephil Nano Today, Vol. 6, Issue 1 https://doi.org/10.1016/j.nantod.2010.11.002	journal	February 2011
Tough Germanium Nanoparticles under Electrochemical Cycling Liang, Wentao; Yang, Hui; Fan, Feifei ACS Nano, Vol. 7, Issue 4 https://doi.org/10.1021/nn400330h	journal	March 2013
Lithium-Assisted Plastic Deformation of Silicon Electrodes in Lithium-Ion Batteries: A First-Principles Theoretical Study Zhao, Kejie; Wang, Wei L.; Gregoire, John Nano Letters, Vol. 11, Issue 7 https://doi.org/10.1021/nl201501s	journal	July 2011
In situ measurements of stress evolution in silicon thin films during electrochemical lithiation and delithiation Sethuraman, Vijay A.; Chon, Michael J.; Shimshak, Maxwell Journal of Power Sources, Vol. 195, Issue 15 https://doi.org/10.1016/j.jpowsour.2010.02.013	journal	August 2010
Silicon-Based Negative Electrode for High-Capacity Lithium-Ion Batteries: “SiO”-Carbon Composite Yamada, Masayuki; Ueda, Atsushi; Matsumoto, Kazunobu Journal of The Electrochemical Society, Vol. 158, Issue 4 https://doi.org/10.1149/1.3551539	journal	January 2011
Anomalous Shape Changes of Silicon Nanopillars by Electrochemical Lithiation Lee, Seok Woo; McDowell, Matthew T.; Choi, Jang Wook Nano Letters, Vol. 11, Issue 7 https://doi.org/10.1021/nl201787r	journal	July 2011
Crystalline-Amorphous Core−Shell Silicon Nanowires for High Capacity and High Current Battery Electrodes Cui, Li-Feng; Ruffo, Riccardo; Chan, Candace K. Nano Letters, Vol. 9, Issue 1, p. 491-495 https://doi.org/10.1021/nl8036323	journal	January 2009

Cited By (13)

Failure modes and mechanisms for rechargeable Lithium-based batteries: a state-of-the-art review Lyu, Dandan; Ren, Bo; Li, Shaofan Acta Mechanica, Vol. 230, Issue 3 https://doi.org/10.1007/s00707-018-2327-8	journal	November 2018
Evolving affinity between Coulombic reversibility and hysteretic phase transformations in nano-structured silicon-based lithium-ion batteries Ogata, K.; Jeon, S.; Ko, D. -S. Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-02824-w	journal	February 2018
Chemomechanical modeling of lithiation-induced failure in high-volume-change electrode materials for lithium ion batteries Zhang, Sulin npj Computational Materials, Vol. 3, Issue 1 https://doi.org/10.1038/s41524-017-0009-z	journal	February 2017
Mechanical response of all-MoS ₂ single-layer heterostructures: a ReaxFF investigation Mortazavi, Bohayra; Ostadhossein, Alireza; Rabczuk, Timon Physical Chemistry Chemical Physics, Vol. 18, Issue 34 https://doi.org/10.1039/c6cp03612k	journal	January 2016
Rare event simulations reveal subtle key steps in aqueous silicate condensation Moqadam, Mahmoud; Riccardi, Enrico; Trinh, Thuat T. Physical Chemistry Chemical Physics, Vol. 19, Issue 20 https://doi.org/10.1039/c7cp01268c	journal	January 2017
Two-dimensional porous silicon nanosheets as anode materials for high performance lithium-ion batteries Tang, Jingjing; Yin, Qifang; Wang, Qian Nanoscale, Vol. 11, Issue 22 https://doi.org/10.1039/c9nr01440c	journal	January 2019
New insights into Li diffusion in Li–Si alloys for Si anode materials: role of Si microstructures Wang, Guoqing; Xu, Bo; Shi, Jing Nanoscale, Vol. 11, Issue 29 https://doi.org/10.1039/c9nr03986d	journal	January 2019
Estimating Arrhenius parameters using temperature programmed molecular dynamics Imandi, Venkataramana; Chatterjee, Abhijit The Journal of Chemical Physics, Vol. 145, Issue 3 https://doi.org/10.1063/1.4958834	journal	July 2016
Constructing first-principles phase diagrams of amorphous Li _x Si using machine-learning-assisted sampling with an evolutionary algorithm Artrith, Nongnuch; Urban, Alexander; Ceder, Gerbrand The Journal of Chemical Physics, Vol. 148, Issue 24 https://doi.org/10.1063/1.5017661	journal	June 2018
A simple local expression for the prefactor in transition state theory Kadkhodaei, S.; van de Walle, A. The Journal of Chemical Physics, Vol. 150, Issue 14 https://doi.org/10.1063/1.5086746	journal	April 2019
Energy landscape and diffusion kinetics of lithiated silicon: A kinetic activation-relaxation technique study Trochet, Mickaël; Mousseau, Normand Physical Review B, Vol. 96, Issue 13 https://doi.org/10.1103/physrevb.96.134118	journal	October 2017
Structural Damage of Few-Layer Silicene in Vertical and Parallel Lithiations Yao, Mingze; Ai, Liqiang; Zhou, Yusi Journal of The Electrochemical Society, Vol. 166, Issue 14 https://doi.org/10.1149/2.1051914jes	journal	January 2019
A simple local expression for the prefactor in transition state theory Kadkhodaei, Sara; van de Walle, Axel arXiv https://doi.org/10.48550/arxiv.1812.09599	text	January 2018

Similar Records

Surface-Coating Regulated Lithiation Kinetics and Degradation in Silicon Nanowires for Lithium Ion Battery

Journal Article · Tue May 26 00:00:00 EDT 2015 · ACS Nano, 9(5):5559-5566 · OSTI ID:1265270

Luo, Langli; Yang, Hui; Yan, Pengfei; +12 more

In Situ TEM Investigation of Congruent Phase Transition and Structural Evolution of Nanostructured Silicon/Carbon Anode for Lithium Ion Batteries

Journal Article · Fri Mar 02 00:00:00 EST 2012 · Nano Letters, 12(3):1624–1632 · OSTI ID:1265270

Wang, Chong M; Li, Xiaolin; Wang, Zhiguo; +11 more

Self-Assembled Framework Formed During Lithiation of SnS₂ Nanoplates Revealed by in Situ Electron Microscopy

Journal Article · Thu Jul 06 00:00:00 EDT 2017 · Accounts of Chemical Research · OSTI ID:1265270

Yin, Kuibo; Zhang, Minghao; Hood, Zachary D.; +3 more

Related Subjects

36 MATERIALS SCIENCE
25 ENERGY STORAGE

Title: Stress effects on the initial lithiation of crystalline silicon nanowires: Reactive molecular dynamics simulations using ReaxFF

Citation Formats

References (56)

Cited By (13)

Similar Records

Related Subjects