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First principles study of Li-Si crystalline phases: Charge transfer, electronic structure, and lattice vibrations

Abstract

The crystalline Li-Si phases: LiSi, Li{sub 12}Si{sub 7}, Li{sub 7}Si{sub 3}, Li{sub 13}Si{sub 4}, Li{sub 15}Si{sub 4}, Li{sub 21}Si{sub 5}, and Li{sub 22}Si{sub 5} are studied using density functional theory. Charge transfer is evaluated using the Atoms in Molecules method (Bader charge analysis), showing that the Li atoms donate approximately 0.73 electrons to Si atoms in all crystalline Li-Si phases. The electronic structures of the Li-Si phases are studied using both total and projected densities of states. Results confirm the understanding of Li-Si structures as Zintl-like phases. Phonon density of states are calculated for all structures and thermodynamic properties are calculated in the context of the harmonic approximation. Phonon contributions to the free energy of formation cause a loss of stability with increasing temperature which is more pronounced in the LiSi and Li{sub 15}Si{sub 4} phases compared to their neighboring phases.
Publication Date:
Apr 30, 2010
Product Type:
Journal Article
Resource Relation:
Journal Name: Journal of Alloys and Compounds; Journal Volume: 496; Journal Issue: 1-2; Other Information: DOI: 10.1016/j.jallcom.2010.01.142; PII: S0925-8388(10)00196-9; Copyright (c) 2010 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.
Subject:
36 MATERIALS SCIENCE; COMPUTERIZED SIMULATION; CRYSTAL STRUCTURE; DENSITY FUNCTIONAL METHOD; ELECTRONIC STRUCTURE; ENERGY STORAGE; FREE ENERGY; LATTICE VIBRATIONS; LITHIUM ALLOYS; PHASE DIAGRAMS; SILICON ALLOYS; STABILITY; ALLOYS; CALCULATION METHODS; DIAGRAMS; ENERGY; INFORMATION; PHYSICAL PROPERTIES; SIMULATION; STORAGE; THERMODYNAMIC PROPERTIES; VARIATIONAL METHODS
OSTI ID:
21435756
Country of Origin:
Netherlands
Language:
English
Other Identifying Numbers:
Journal ID: ISSN 0925-8388; JALCEU; TRN: NL10R2281031261
Availability:
Available from http://dx.doi.org/10.1016/j.jallcom.2010.01.142
Submitting Site:
NLN
Size:
page(s) 25-36
Announcement Date:
Jun 06, 2011

Citation Formats

Chevrier, V L, Institute for Research in Materials, Dalhousie University, Halifax, NS, B3H 1W5 (Canada)], Zwanziger, J W, Dahn, J.R., E-mail: jeff.dahn@dal.c [Department of Physics and Atmospheric Science, Dalhousie University, Halifax, NS, B3H 3J5 (Canada), Department of Chemistry, Dalhousie University, Halifax, NS, B3H 4J3 (Canada), and Institute for Research in Materials, Dalhousie University, Halifax, NS, B3H 1W5 (Canada)]. First principles study of Li-Si crystalline phases: Charge transfer, electronic structure, and lattice vibrations. Netherlands: N. p., 2010. Web. doi:10.1016/j.jallcom.2010.01.142.
Chevrier, V L, Institute for Research in Materials, Dalhousie University, Halifax, NS, B3H 1W5 (Canada)], Zwanziger, J W, Dahn, J.R., E-mail: jeff.dahn@dal.c [Department of Physics and Atmospheric Science, Dalhousie University, Halifax, NS, B3H 3J5 (Canada), Department of Chemistry, Dalhousie University, Halifax, NS, B3H 4J3 (Canada), & Institute for Research in Materials, Dalhousie University, Halifax, NS, B3H 1W5 (Canada)]. First principles study of Li-Si crystalline phases: Charge transfer, electronic structure, and lattice vibrations. Netherlands. https://doi.org/10.1016/j.jallcom.2010.01.142
Chevrier, V L, Institute for Research in Materials, Dalhousie University, Halifax, NS, B3H 1W5 (Canada)], Zwanziger, J W, Dahn, J.R., E-mail: jeff.dahn@dal.c [Department of Physics and Atmospheric Science, Dalhousie University, Halifax, NS, B3H 3J5 (Canada), Department of Chemistry, Dalhousie University, Halifax, NS, B3H 4J3 (Canada), and Institute for Research in Materials, Dalhousie University, Halifax, NS, B3H 1W5 (Canada)]. 2010. "First principles study of Li-Si crystalline phases: Charge transfer, electronic structure, and lattice vibrations." Netherlands. https://doi.org/10.1016/j.jallcom.2010.01.142.
@misc{etde_21435756,
title = {First principles study of Li-Si crystalline phases: Charge transfer, electronic structure, and lattice vibrations}
author = {Chevrier, V L, Institute for Research in Materials, Dalhousie University, Halifax, NS, B3H 1W5 (Canada)], Zwanziger, J W, Dahn, J.R., E-mail: jeff.dahn@dal.c [Department of Physics and Atmospheric Science, Dalhousie University, Halifax, NS, B3H 3J5 (Canada), Department of Chemistry, Dalhousie University, Halifax, NS, B3H 4J3 (Canada), and Institute for Research in Materials, Dalhousie University, Halifax, NS, B3H 1W5 (Canada)]}
abstractNote = {The crystalline Li-Si phases: LiSi, Li{sub 12}Si{sub 7}, Li{sub 7}Si{sub 3}, Li{sub 13}Si{sub 4}, Li{sub 15}Si{sub 4}, Li{sub 21}Si{sub 5}, and Li{sub 22}Si{sub 5} are studied using density functional theory. Charge transfer is evaluated using the Atoms in Molecules method (Bader charge analysis), showing that the Li atoms donate approximately 0.73 electrons to Si atoms in all crystalline Li-Si phases. The electronic structures of the Li-Si phases are studied using both total and projected densities of states. Results confirm the understanding of Li-Si structures as Zintl-like phases. Phonon density of states are calculated for all structures and thermodynamic properties are calculated in the context of the harmonic approximation. Phonon contributions to the free energy of formation cause a loss of stability with increasing temperature which is more pronounced in the LiSi and Li{sub 15}Si{sub 4} phases compared to their neighboring phases.}
doi = {10.1016/j.jallcom.2010.01.142}
journal = []
issue = {1-2}
volume = {496}
place = {Netherlands}
year = {2010}
month = {Apr}
}