Stabilities and defect-mediated lithium-ion conduction in a ground state cubic Li3 N structure

Nguyen, Manh Cuong; Hoang, Khang; Wang, Cai-Zhuang; Ho, Kai-Ming

doi:10.1039/C5CP06946G

Title: Stabilities and defect-mediated lithium-ion conduction in a ground state cubic Li₃ N structure

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Abstract

A stable ground state structure with cubic symmetry of Li₃N (c-Li₃N) is found by ab initio initially symmetric random-generated crystal structure search method. Gibbs free energy, calculated within quasi-harmonic approximation, shows that c-Li₃N is the ground state structure for a wide range of temperature. The c-Li₃N structure has a negative thermal expansion coefficient at temperatures lower than room temperature, due mainly to two transverse acoustic phonon modes. This c-Li₃N phase is a semiconductor with an indirect band gap of 1.90 eV within hybrid density functional calculation. We also investigate the migration and energetics of native point defects in c-Li₃N, including lithium and nitrogen vacancies, interstitials, and anti-site defects. Lithium interstitials are found to have a very low migration barrier (~0.12 eV) and the lowest formation energy among all possible defects. Thus, the ionic conduction in c-Li₃N is expected to occur via an interstitial mechanism, in contrast to that in the well-known α-Li₃N phase which occurs via a vacancy mechanism.

Authors:

Nguyen, Manh Cuong ^[1]; Hoang, Khang ^[2]; Wang, Cai-Zhuang ^[3]; Ho, Kai-Ming ^[3]

Ames Lab. and Iowa State Univ., Ames, IA (United States). Dept. of Physics and Astronomy
North Dakota State Univ., Fargo, ND (United States). Center for Computationally Assisted Science and Technology
Ames Lab. and Iowa State Univ., Ames, IA (United States). Dept. of Physics and Astronom

Publication Date:: Thu Jan 07 00:00:00 EST 2016

Research Org.:: Ames Lab., Ames, IA (United States)

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

OSTI Identifier:: 1249339

Report Number(s):: IS-J-8948
Journal ID: ISSN 1463-9076; PPCPFQ

Grant/Contract Number:: AC02-07CH11358; SC0001717

Resource Type:: Accepted Manuscript

Journal Name:: Physical Chemistry Chemical Physics. PCCP (Print)

Additional Journal Information:: Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 18; Journal Issue: 5; Journal ID: ISSN 1463-9076

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

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                    Nguyen, Manh Cuong, Hoang, Khang, Wang, Cai-Zhuang, and Ho, Kai-Ming. Stabilities and defect-mediated lithium-ion conduction in a ground state cubic Li3 N structure.  United States: N. p., 2016. 
Web.  doi:10.1039/C5CP06946G.

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                    Nguyen, Manh Cuong, Hoang, Khang, Wang, Cai-Zhuang, & Ho, Kai-Ming. Stabilities and defect-mediated lithium-ion conduction in a ground state cubic Li3 N structure.  United States.  https://doi.org/10.1039/C5CP06946G

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                    Nguyen, Manh Cuong, Hoang, Khang, Wang, Cai-Zhuang, and Ho, Kai-Ming. Thu .  
"Stabilities and defect-mediated lithium-ion conduction in a ground state cubic Li3 N structure".  United States.  https://doi.org/10.1039/C5CP06946G.  https://www.osti.gov/servlets/purl/1249339.

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@article{osti_1249339,

  title        = {Stabilities and defect-mediated lithium-ion conduction in a ground state cubic Li3 N structure},

  author       = {Nguyen, Manh Cuong and Hoang, Khang and Wang, Cai-Zhuang and Ho, Kai-Ming},

  abstractNote = {A stable ground state structure with cubic symmetry of Li3N (c-Li3N) is found by ab initio initially symmetric random-generated crystal structure search method. Gibbs free energy, calculated within quasi-harmonic approximation, shows that c-Li3N is the ground state structure for a wide range of temperature. The c-Li3N structure has a negative thermal expansion coefficient at temperatures lower than room temperature, due mainly to two transverse acoustic phonon modes. This c-Li3N phase is a semiconductor with an indirect band gap of 1.90 eV within hybrid density functional calculation. We also investigate the migration and energetics of native point defects in c-Li3N, including lithium and nitrogen vacancies, interstitials, and anti-site defects. Lithium interstitials are found to have a very low migration barrier (~0.12 eV) and the lowest formation energy among all possible defects. Thus, the ionic conduction in c-Li3N is expected to occur via an interstitial mechanism, in contrast to that in the well-known α-Li3N phase which occurs via a vacancy mechanism.},

  doi          = {10.1039/C5CP06946G},

  journal      = {Physical Chemistry Chemical Physics. PCCP (Print)},

  number       = 5,

  volume       = 18,

  place        = {United States},

  year         = {Thu Jan 07 00:00:00 EST 2016},

  month        = {Thu Jan 07 00:00:00 EST 2016}

}

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Title: Stabilities and defect-mediated lithium-ion conduction in a ground state cubic Li3 N structure

Abstract

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Title: Stabilities and defect-mediated lithium-ion conduction in a ground state cubic Li₃ N structure