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Title: Superhalogen-based lithium superionic conductors

Abstract

The development of cheap, durable, and safe inorganic solid electrolytes with superionic conductivity is the key for the next generation of all-solid metal-ion batteries. The recent discovery of antiperovskites with composition Li 3OA (A = halogen) shows promise in this regard. Here, we demonstrate the potential of a new class of antiperovskites where halogens are replaced by BH 4 superhalogens. In addition to maintaining the high ionic conductivity of Li 3OA, Li 3O(BH 4) is lightweight, mechanically flexible, thermodynamically more stable, and electronically more insulating than Li 3OA. By mixing BH 4 with Cl to make Li 3O(BH 4) 0.5Cl 0.5, we further show that the conductivity will be doubled. The Li +-ion conductivity of the new materials is of the order of 10 -4 to over 10 -3 S cm -1 at room temperature and will be well above 10 -2 S cm -1 at higher temperatures below the melting point. The conduction mechanism of the material is revealed by identifying the relationship between the orientational symmetry of the BH 4- rotors and the potential surface felt by the lithium ions.

Authors:
ORCiD logo [1];  [2];  [2];  [3];  [1]
  1. Virginia Commonwealth Univ., Richmond, VA (United States). Dept. of Physics
  2. Peking Univ., Beijing (China). Department of Materials Science and Engineering
  3. Peking Univ., Beijing (China). Department of Materials Science and Engineering and Center for Applied Physics and Technology
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1493600
DOE Contract Number:  
FG02-96ER45579; AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 26; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Fang, Hong, Wang, Shuo, Liu, Junyi, Sun, Qiang, and Jena, Puru. Superhalogen-based lithium superionic conductors. United States: N. p., 2017. Web. doi:10.1039/c7ta01648d.
Fang, Hong, Wang, Shuo, Liu, Junyi, Sun, Qiang, & Jena, Puru. Superhalogen-based lithium superionic conductors. United States. doi:10.1039/c7ta01648d.
Fang, Hong, Wang, Shuo, Liu, Junyi, Sun, Qiang, and Jena, Puru. Sun . "Superhalogen-based lithium superionic conductors". United States. doi:10.1039/c7ta01648d.
@article{osti_1493600,
title = {Superhalogen-based lithium superionic conductors},
author = {Fang, Hong and Wang, Shuo and Liu, Junyi and Sun, Qiang and Jena, Puru},
abstractNote = {The development of cheap, durable, and safe inorganic solid electrolytes with superionic conductivity is the key for the next generation of all-solid metal-ion batteries. The recent discovery of antiperovskites with composition Li3OA (A = halogen) shows promise in this regard. Here, we demonstrate the potential of a new class of antiperovskites where halogens are replaced by BH4 superhalogens. In addition to maintaining the high ionic conductivity of Li3OA, Li3O(BH4) is lightweight, mechanically flexible, thermodynamically more stable, and electronically more insulating than Li3OA. By mixing BH4 with Cl to make Li3O(BH4)0.5Cl0.5, we further show that the conductivity will be doubled. The Li+-ion conductivity of the new materials is of the order of 10-4 to over 10-3 S cm-1 at room temperature and will be well above 10-2 S cm-1 at higher temperatures below the melting point. The conduction mechanism of the material is revealed by identifying the relationship between the orientational symmetry of the BH4- rotors and the potential surface felt by the lithium ions.},
doi = {10.1039/c7ta01648d},
journal = {Journal of Materials Chemistry. A},
issn = {2050-7488},
number = 26,
volume = 5,
place = {United States},
year = {2017},
month = {1}
}

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