Studies of Functional Defects for Fast Na-Ion Conduction in Na 3-yPS4-xClx with a Combined Experimental and Computational Approach
Abstract
Abstract All‐solid‐state rechargeable sodium (Na)‐ion batteries are promising for inexpensive and high‐energy‐density large‐scale energy storage. In this contribution, new Na solid electrolytes, Na 3− y PS 4− x Cl x , are synthesized with a strategic approach, which allows maximum substitution of Cl for S ( x = 0.2) without significant compromise of structural integrity or Na deficiency. A maximum conductivity of 1.96 mS cm −1 at 25 °C is achieved for Na 3.0 PS 3.8 Cl 0.2 , which is two orders of magnitude higher compared with that of tetragonal Na 3 PS 4 (t‐Na 3 PS 4 ). The activation energy ( E a ) is determined to be 0.19 eV. Ab initio molecular dynamics simulations shed light on the merit of maximizing Cl‐doping while maintaining low Na deficiency in enhanced Na‐ion conduction. Solid‐state nuclear magnetic resonance (NMR) characterizations confirm the successful substitution of Cl for S and the resulting change of P oxidation state from 5+ to 4+, which is also verified by spin moment analysis. Ion transport pathways are determined with a tracer‐exchange NMR method. The functional detects that promote Na ‐ion transport are maximized for further improvement in ionic conductivity. Full‐cell performance is demonstrated usingmore »
- Authors:
-
[3]
- Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry
- Univ. of California, San Diego, CA (United States). Dept. of NanoEngineering
- Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry; National High Magnetic Field Lab., Tallahassee, FL (United States). Center for Interdisciplinary Magnetic Resonance
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1542272
- Alternate Identifier(s):
- OSTI ID: 1491266
- Grant/Contract Number:
- SC0012118
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Functional Materials
- Additional Journal Information:
- Journal Volume: 29; Journal Issue: 9; Journal ID: ISSN 1616-301X
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; all-solid-state sodium ion batteries; functional defects; NMR; sodium solid electrolyte; thiophosphate
Citation Formats
Feng, Xuyong, Chien, Po-Hsiu, Zhu, Zhuoying, Chu, Iek-Heng, Wang, Pengbo, Immediato-Scuotto, Marcello, Arabzadeh, Hesam, Ong, Shyue Ping, and Hu, Yan-Yan. Studies of Functional Defects for Fast Na-Ion Conduction in Na 3-yPS4-xClx with a Combined Experimental and Computational Approach. United States: N. p., 2019.
Web. doi:10.1002/adfm.201807951.
Feng, Xuyong, Chien, Po-Hsiu, Zhu, Zhuoying, Chu, Iek-Heng, Wang, Pengbo, Immediato-Scuotto, Marcello, Arabzadeh, Hesam, Ong, Shyue Ping, & Hu, Yan-Yan. Studies of Functional Defects for Fast Na-Ion Conduction in Na 3-yPS4-xClx with a Combined Experimental and Computational Approach. United States. https://doi.org/10.1002/adfm.201807951
Feng, Xuyong, Chien, Po-Hsiu, Zhu, Zhuoying, Chu, Iek-Heng, Wang, Pengbo, Immediato-Scuotto, Marcello, Arabzadeh, Hesam, Ong, Shyue Ping, and Hu, Yan-Yan. Fri .
"Studies of Functional Defects for Fast Na-Ion Conduction in Na 3-yPS4-xClx with a Combined Experimental and Computational Approach". United States. https://doi.org/10.1002/adfm.201807951. https://www.osti.gov/servlets/purl/1542272.
@article{osti_1542272,
title = {Studies of Functional Defects for Fast Na-Ion Conduction in Na 3-yPS4-xClx with a Combined Experimental and Computational Approach},
author = {Feng, Xuyong and Chien, Po-Hsiu and Zhu, Zhuoying and Chu, Iek-Heng and Wang, Pengbo and Immediato-Scuotto, Marcello and Arabzadeh, Hesam and Ong, Shyue Ping and Hu, Yan-Yan},
abstractNote = {Abstract All‐solid‐state rechargeable sodium (Na)‐ion batteries are promising for inexpensive and high‐energy‐density large‐scale energy storage. In this contribution, new Na solid electrolytes, Na 3− y PS 4− x Cl x , are synthesized with a strategic approach, which allows maximum substitution of Cl for S ( x = 0.2) without significant compromise of structural integrity or Na deficiency. A maximum conductivity of 1.96 mS cm −1 at 25 °C is achieved for Na 3.0 PS 3.8 Cl 0.2 , which is two orders of magnitude higher compared with that of tetragonal Na 3 PS 4 (t‐Na 3 PS 4 ). The activation energy ( E a ) is determined to be 0.19 eV. Ab initio molecular dynamics simulations shed light on the merit of maximizing Cl‐doping while maintaining low Na deficiency in enhanced Na‐ion conduction. Solid‐state nuclear magnetic resonance (NMR) characterizations confirm the successful substitution of Cl for S and the resulting change of P oxidation state from 5+ to 4+, which is also verified by spin moment analysis. Ion transport pathways are determined with a tracer‐exchange NMR method. The functional detects that promote Na ‐ion transport are maximized for further improvement in ionic conductivity. Full‐cell performance is demonstrated using Na/Na 3.0 PS 3.8 Cl 0.2 /Na 3 V 2 (PO 4 ) 3 with a reversible capacity of ≈100 mAh g ‐1 at room temperature.},
doi = {10.1002/adfm.201807951},
journal = {Advanced Functional Materials},
number = 9,
volume = 29,
place = {United States},
year = {Fri Jan 18 00:00:00 EST 2019},
month = {Fri Jan 18 00:00:00 EST 2019}
}
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Works referencing / citing this record:
Enhanced sodium ion conductivity in Na 3 VS 4 by P-doping
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