Insights into the Li Intercalation and SEI Formation on LiSi Nanoclusters

Hankins, Kie; Soto, Fernando A.; Balbuena, Perla B.

doi:10.1149/2.0311711jes

Title: Insights into the Li Intercalation and SEI Formation on LiSi Nanoclusters

Journal Article · Wed Jun 21 00:00:00 EDT 2017 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/2.0311711jes· OSTI ID:1430637

Hankins, Kie ^[1]; Soto, Fernando A. ^[1]; Balbuena, Perla B. ^[2]

Texas A & M Univ., College Station, TX (United States). Department of Chemical Engineering
Texas A & M Univ., College Station, TX (United States). Department of Chemical Engineering, Department of Materials Science and Engineering, and Department of Chemistry

We report a first-principles atomic level assessment of the lithiation and reactivity of pre-lithiated Si clusters. Density functional theory formation energy calculations reveal that the pre-lithiated Li₁₆Si₁₆ cluster exposed to two different Li fluxes can store Li between the concentrations of Li_2.5Si and Li_3.5Si. This increase in storage capacity is attributed to the start of an amorphization process in the cluster, and more importantly these results show that the intercalation reaction can be controlled by the flux of the Li-ions. However, in a real battery, the lithiation of the anode occurs simultaneously to the electrode-electrolyte reactions. Here we simulate the solid-electrolyte interphase (SEI) formation and simultaneous lithiation of a Li₁₆Si₁₆ cluster in contact with two different electrolyte solutions: one with pure ethylene carbonate (EC), and another with a 1 M solution of LiPF₆ in EC. Our ab initio molecular dynamics simulations show that the solvent and salt are decomposed leading to the initial stages of the SEI layer formation and large part of the added Li becomes part of the SEI. Interestingly, the pure EC solution results in lower storage capacity and higher reactivity, whereas the presence of the salt causes the opposite effect: higher lithiation and reduced reactivity.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Texas A & M Univ., College Station, TX (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office

Grant/Contract Number:: EE0007766

OSTI ID:: 1430637

Alternate ID(s):: OSTI ID: 1868489

Journal Information:: Journal of the Electrochemical Society, Vol. 164, Issue 11; ISSN 0013-4651

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 9 works

Citation information provided by
Web of Science

References (47)

Solid Electrolyte Interphase Growth and Capacity Loss in Silicon Electrodes Michan, Alison L.; Divitini, Giorgio; Pell, Andrew J. Journal of the American Chemical Society, Vol. 138, Issue 25 https://doi.org/10.1021/jacs.6b02882	journal	June 2016
Kinetics and fracture resistance of lithiated silicon nanostructure pairs controlled by their mechanical interaction Lee, Seok Woo; Lee, Hyun-Wook; Ryu, Ill Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8533	journal	June 2015
Advanced electrolyte/additive for lithium-ion batteries with silicon anode Zhang, Shuo; He, Meinan; Su, Chi-Cheung Current Opinion in Chemical Engineering, Vol. 13 https://doi.org/10.1016/j.coche.2016.08.003	journal	August 2016
Yolk-shell silicon-mesoporous carbon anode with compact solid electrolyte interphase film for superior lithium-ion batteries Yang, Jianping; Wang, Yun-Xiao; Chou, Shu-Lei Nano Energy, Vol. 18 https://doi.org/10.1016/j.nanoen.2015.09.016	journal	November 2015
Ab-initio simulations of materials using VASP: Density-functional theory and beyond Hafner, Jürgen Journal of Computational Chemistry, Vol. 29, Issue 13 https://doi.org/10.1002/jcc.21057	journal	October 2008
Silicon Solid Electrolyte Interphase (SEI) of Lithium Ion Battery Characterized by Microscopy and Spectroscopy Nie, Mengyun; Abraham, Daniel P.; Chen, Yanjing The Journal of Physical Chemistry C, Vol. 117, Issue 26 https://doi.org/10.1021/jp404155y	journal	June 2013
Anisotropic Lithium Insertion Behavior in Silicon Nanowires: Binding Energy, Diffusion Barrier, and Strain Effect Zhang, Qianfan; Cui, Yi; Wang, Enge The Journal of Physical Chemistry C, Vol. 115, Issue 19 https://doi.org/10.1021/jp1115977	journal	April 2011
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Si-Based Anode Materials for Li-Ion Batteries: A Mini Review Ma, Delong; Cao, Zhanyi; Hu, Anming Nano-Micro Letters, Vol. 6, Issue 4 https://doi.org/10.1007/s40820-014-0008-2	journal	September 2014
RETRACTED ARTICLE: Theoretical Limits of Energy Density in Silicon-Carbon Composite Anode Based Lithium Ion Batteries Dash, Ranjan; Pannala, Sreekanth Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep27449	journal	June 2016
Breathing silicon anodes for durable high-power operations Hwang, Chihyun; Joo, Sehun; Kang, Na-Ri Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep14433	journal	September 2015
A room temperature study of the binary lithium–silicon and the ternary lithium–chromium–silicon system for use in rechargeable lithium batteries Weydanz, W. J.; Wohlfahrt-Mehrens, M.; Huggins, R. A. Journal of Power Sources, Vol. 81-82 https://doi.org/10.1016/S0378-7753(99)00139-1	journal	September 1999
DFT Study of Reduction Mechanisms of Ethylene Carbonate and Fluoroethylene Carbonate on Li ⁺ -Adsorbed Si Clusters Ma, Yuguang; Balbuena, Perla B. Journal of The Electrochemical Society, Vol. 161, Issue 8 https://doi.org/10.1149/2.014408jes	journal	January 2014
Electrolytes and Interphases in Li-Ion Batteries and Beyond Xu, Kang Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500003w	journal	October 2014
Theoretical Studies To Understand Surface Chemistry on Carbon Anodes for Lithium-Ion Batteries: Reduction Mechanisms of Ethylene Carbonate Wang, Yixuan; Nakamura, Shinichiro; Ue, Makoto Journal of the American Chemical Society, Vol. 123, Issue 47 https://doi.org/10.1021/ja0164529	journal	November 2001
Pomegranate-Like Silicon/Nitrogen-doped Graphene Microspheres as Superior-Capacity Anode for Lithium-Ion Batteries Lin, Jie; He, Jiarui; Chen, Yuanfu Electrochimica Acta, Vol. 215 https://doi.org/10.1016/j.electacta.2016.08.147	journal	October 2016
Computational Studies of Interfacial Reactions at Anode Materials: Initial Stages of the Solid-Electrolyte-Interphase Layer Formation Ramos-Sanchez, G.; Soto, F. A.; Martinez de la Hoz, J. M. Journal of Electrochemical Energy Conversion and Storage, Vol. 13, Issue 3 https://doi.org/10.1115/1.4034412	journal	August 2016
Reduction mechanisms of additives on Si anodes of Li-ion batteries Martínez de la Hoz, Julibeth M.; Balbuena, Perla B. Phys. Chem. Chem. Phys., Vol. 16, Issue 32 https://doi.org/10.1039/C4CP01948B	journal	January 2014
Analysis of Vinylene Carbonate Derived SEI Layers on Graphite Anode Ota, Hitoshi; Sakata, Yuuichi; Inoue, Atsuyoshi Journal of The Electrochemical Society, Vol. 151, Issue 10 https://doi.org/10.1149/1.1785795	journal	January 2004
Structure and electronic properties of lithium–silicon clusters González, Sebastián I.; Oña, Ofelia B.; Ferraro, Marta B. Computational and Theoretical Chemistry, Vol. 1024 https://doi.org/10.1016/j.comptc.2013.09.019	journal	November 2013
A Highly Cross-Linked Polymeric Binder for High-Performance Silicon Negative Electrodes in Lithium Ion Batteries Koo, Bonjae; Kim, Hyunjung; Cho, Younghyun Angewandte Chemie International Edition, Vol. 51, Issue 35 https://doi.org/10.1002/anie.201201568	journal	July 2012
Formation and Growth Mechanisms of Solid-Electrolyte Interphase Layers in Rechargeable Batteries Soto, Fernando A.; Ma, Yuguang; Martinez de la Hoz, Julibeth M. Chemistry of Materials, Vol. 27, Issue 23 https://doi.org/10.1021/acs.chemmater.5b03358	journal	November 2015
Generalized gradient approximation for the exchange-correlation hole of a many-electron system Perdew, John P.; Burke, Kieron; Wang, Yue Physical Review B, Vol. 54, Issue 23 https://doi.org/10.1103/PhysRevB.54.16533	journal	December 1996
Reduction Mechanisms of Ethylene Carbonate on Si Anodes of Lithium-Ion Batteries: Effects of Degree of Lithiation and Nature of Exposed Surface Martinez de la Hoz, Julibeth M.; Leung, Kevin; Balbuena, Perla B. ACS Applied Materials & Interfaces, Vol. 5, Issue 24 https://doi.org/10.1021/am404365r	journal	November 2013
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
Open Framework Allotropes of Silicon: Potential Anode Materials for Na and Li-ion Batteries Marzouk, Asma; Balbuena, Perla B.; El-Mellouhi, Fedwa Electrochimica Acta, Vol. 207 https://doi.org/10.1016/j.electacta.2016.04.118	journal	July 2016
Lithium Insertion In Silicon Nanowires: An ab Initio Study Zhang, Qianfan; Zhang, Wenxing; Wan, Wenhui Nano Letters, Vol. 10, Issue 9 https://doi.org/10.1021/nl904132v	journal	September 2010
Synthesis of Single-Phase LiSi by Ball-Milling: Electrochemical Behavior and Hydrogenation Properties Tang, Wan Si; Chotard, Jean-Noël; Janot, Raphaël Journal of The Electrochemical Society, Vol. 160, Issue 8 https://doi.org/10.1149/2.089308jes	journal	January 2013
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Li-Rich Li-Si Alloy As A Lithium-Containing Negative Electrode Material Towards High Energy Lithium-Ion Batteries Iwamura, Shinichiroh; Nishihara, Hirotomo; Ono, Yoshitaka Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep08085	journal	January 2015
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
Review on recent progress of nanostructured anode materials for Li-ion batteries Goriparti, Subrahmanyam; Miele, Ermanno; De Angelis, Francesco Journal of Power Sources, Vol. 257 https://doi.org/10.1016/j.jpowsour.2013.11.103	journal	July 2014
Scaling Atomic Partial Charges of Carbonate Solvents for Lithium Ion Solvation and Diffusion Chaudhari, Mangesh I.; Nair, Jijeesh R.; Pratt, Lawrence R. Journal of Chemical Theory and Computation, Vol. 12, Issue 12 https://doi.org/10.1021/acs.jctc.6b00824	journal	November 2016
Challenges in Accommodating Volume Change of Si Anodes for Li-Ion Batteries Ko, Minseong; Chae, Sujong; Cho, Jaephil ChemElectroChem, Vol. 2, Issue 11 https://doi.org/10.1002/celc.201500254	journal	August 2015
Designing nanostructured Si anodes for high energy lithium ion batteries Wu, Hui; Cui, Yi Nano Today, Vol. 7, Issue 5 https://doi.org/10.1016/j.nantod.2012.08.004	journal	October 2012
Nanostructured Si/TiB[sub 2] Composite Anodes for Li-Ion Batteries Kim, Il-seok; Blomgren, G. E.; Kumta, P. N. Electrochemical and Solid-State Letters, Vol. 6, Issue 8 https://doi.org/10.1149/1.1584212	journal	January 2003
Nanostructured materials for advanced energy conversion and storage devices Aricò, Antonino Salvatore; Bruce, Peter; Scrosati, Bruno Nature Materials, Vol. 4, Issue 5, p. 366-377 https://doi.org/10.1038/nmat1368	journal	May 2005
Effect of the Electrolyte Composition on SEI Reactions at Si Anodes of Li-Ion Batteries Martinez de la Hoz, Julibeth M.; Soto, Fernando A.; Balbuena, Perla B. The Journal of Physical Chemistry C, Vol. 119, Issue 13 https://doi.org/10.1021/acs.jpcc.5b01228	journal	March 2015
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
Effect of Vinylene Carbonate Additive in Li-Ion Batteries: Comparison of LiCoO[sub 2]∕C, LiFePO[sub 4]∕C, and LiCoO[sub 2]∕Li[sub 4]Ti[sub 5]O[sub 12] Systems El Ouatani, L.; Dedryvère, R.; Siret, C. Journal of The Electrochemical Society, Vol. 156, Issue 6 https://doi.org/10.1149/1.3111891	journal	January 2009
Modeling solid-electrolyte interfacial phenomena in silicon anodes Soto, Fa; Martinez de la Hoz, Jm; Seminario, Jm Current Opinion in Chemical Engineering, Vol. 13 https://doi.org/10.1016/j.coche.2016.08.017	journal	August 2016
Lithium ion solvation by ethylene carbonates in lithium-ion battery electrolytes, revisited by density functional theory with the hybrid solvation model and free energy correction in solution Cui, Wei; Lansac, Yves; Lee, Hochun Physical Chemistry Chemical Physics, Vol. 18, Issue 34 https://doi.org/10.1039/C6CP01667G	journal	January 2016
Hybrid DFT Functional-Based Static and Molecular Dynamics Studies of Excess Electron in Liquid Ethylene Carbonate Yu, Jiamei; Balbuena, Perla B.; Budzien, Joanne Journal of The Electrochemical Society, Vol. 158, Issue 4 https://doi.org/10.1149/1.3545977	journal	January 2011
First-Principles Calculations of Lithiation of a Hydroxylated Surface of Amorphous Silicon Dioxide Perez-Beltran, Saul; Ramírez-Caballero, Gustavo E.; Balbuena, Perla B. The Journal of Physical Chemistry C, Vol. 119, Issue 29 https://doi.org/10.1021/acs.jpcc.5b02992	journal	July 2015
Structural Changes in Silicon Anodes during Lithium Insertion/Extraction Obrovac, M. N.; Christensen, Leif Electrochemical and Solid-State Letters, Vol. 7, Issue 5 https://doi.org/10.1149/1.1652421	journal	January 2004
Revision of the Li ₁₃ Si ₄ structure Zeilinger, Michael; Fässler, Thomas F. Acta Crystallographica Section E Structure Reports Online, Vol. 69, Issue 12 https://doi.org/10.1107/S1600536813029759	journal	November 2013
VMD: Visual molecular dynamics Humphrey, William; Dalke, Andrew; Schulten, Klaus Journal of Molecular Graphics, Vol. 14, Issue 1 https://doi.org/10.1016/0263-7855(96)00018-5	journal	February 1996

Cited By (2)

Ab Initio-Based Structural and Thermodynamic Aspects of the Electrochemical Lithiation of Silicon Nanoparticles Lee, Seung-Eun; Lim, Hyung-Kyu; Lee, Sangheon Catalysts, Vol. 10, Issue 1 https://doi.org/10.3390/catal10010008	journal	December 2019
Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries Wang, Aiping; Kadam, Sanket; Li, Hong npj Computational Materials, Vol. 4, Issue 1 https://doi.org/10.1038/s41524-018-0064-0	journal	March 2018

Similar Records

Investigating the Chemical Reactivity of Lithium Silicate Model SEI Layers

Journal Article · Thu Mar 19 00:00:00 EDT 2020 · Journal of Physical Chemistry. C · OSTI ID:1430637

Coyle, Jaclyn E.; Brumbach, Michael T.; Veith, Gabriel M.; +1 more

Electrolyte Role in SEI Evolution at Si in the Pre-lithiation Stage vs the Post-lithiation Stage

Journal Article · Tue Feb 07 00:00:00 EST 2023 · Journal of the Electrochemical Society · OSTI ID:1430637

Cora, Saida; Key, Baris; Vaughey, John; +1 more

Investigating the Chemical Reactivity of Lithium Silicate Model SEI Layers

Journal Article · Thu Mar 19 00:00:00 EDT 2020 · Journal of Physical Chemistry C · OSTI ID:1430637

Coyle, Jaclyn E.; Brumbach, Michael T.; Veith, Gabriel M.; +1 more

Related Subjects

25 ENERGY STORAGE
36 MATERIALS SCIENCE
ab initio molecular dynamics
density functional theory
irreversible capacity
lithiation
SEI
silicon anodes

Title: Insights into the Li Intercalation and SEI Formation on LiSi Nanoclusters

Citation Formats

References (47)

Cited By (2)

Similar Records

Related Subjects