Insights into the Li Intercalation and SEI Formation on LiSi Nanoclusters

doi:10.1149/2.0311711jes

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

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 Li ₁₆Si ₁₆ 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 Li ₁₆Si ₁₆ cluster in contact with two different electrolyte solutions: one with pure ethylene carbonate (EC), and another with a 1 M solution of LiPF ₆ 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 oppositemore »

Authors:

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

Publication Date:: 2017-01-01

Grant/Contract Number:: EE0007766

Type:: Accepted Manuscript

Journal Name:: Journal of the Electrochemical Society

Additional Journal Information:: Journal Volume: 164; Journal Issue: 11; Journal ID: ISSN 0013-4651

Publisher:: The Electrochemical Society

Research Org:: Texas A&M Engineering Experiment Station, College Station, TX (United States)

Sponsoring Org:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

Country of Publication:: United States

Language:: English

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

OSTI Identifier:: 1430637


                    Hankins, Kie, Soto, Fernando A., and Balbuena, Perla B.. Insights into the Li Intercalation and SEI Formation on LiSi Nanoclusters.  United States: N. p.,  
        Web.  doi:10.1149/2.0311711jes.

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                    Hankins, Kie, Soto, Fernando A., & Balbuena, Perla B.. Insights into the Li Intercalation and SEI Formation on LiSi Nanoclusters.  United States.  doi:10.1149/2.0311711jes.

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                    Hankins, Kie, Soto, Fernando A., and Balbuena, Perla B.. 2017.  
        "Insights into the Li Intercalation and SEI Formation on LiSi Nanoclusters".  United States.  
        doi:10.1149/2.0311711jes.  https://www.osti.gov/servlets/purl/1430637.

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@article{osti_1430637,

  title        = {Insights into the Li Intercalation and SEI Formation on LiSi Nanoclusters},

  author       = {Hankins, Kie and Soto, Fernando A. and Balbuena, Perla B.},

  abstractNote = {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 Li2.5Si and Li3.5Si. 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.},

  doi          = {10.1149/2.0311711jes},

  journal      = {Journal of the Electrochemical Society},

  number       = 11,

  volume       = 164,

  place        = {United States},

  year         = {2017},

  month        = {1}

}

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10.1149/2.0311711jes
https://doi.org/10.1149/2.0311711jes

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Works referenced in this record:

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Kresse, G.; Furthmüller, J.
Physical Review B, Vol. 54, Issue 16, p. 11169-11186
DOI: 10.1103/PhysRevB.54.11169

From ultrasoft pseudopotentials to the projector augmented-wave method
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Kresse, G.; Joubert, D.
Physical Review B, Vol. 59, Issue 3, p. 1758-1775
DOI: 10.1103/PhysRevB.59.1758

Nanostructured materials for advanced energy conversion and storage devices
journal, May 2005

Aricò, Antonino Salvatore; Bruce, Peter; Scrosati, Bruno
Nature Materials, Vol. 4, Issue 5, p. 366-377
DOI: 10.1038/nmat1368

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

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