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Title: Studies of Functional Defects for Fast Na-Ion Conduction in Na 3− y PS 4− x Cl x with a Combined Experimental and Computational Approach

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, Na3−yPS4−xClx, 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 Na3.0PS3.8Cl0.2, which is two orders of magnitude higher compared with that of tetragonal Na3PS4 (t‐Na3PS4). The activation energy (Ea) 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/Na3.0PS3.8Cl0.2/Na3V2(PO4)3 with a reversible capacity of ≈100 mAh g‐1 at room temperature.

Authors:
 [1];  [1];  [2];  [2];  [1];  [1];  [1];  [2]; ORCiD logo [3]
  1. Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way Tallahassee FL 32306 USA
  2. Department of NanoEngineering, University of California San Diego, 9500 Gilman Drive La Jolla CA 92093-0448 USA
  3. Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way Tallahassee FL 32306 USA; Center of Interdisciplinary Magnetic Resonance, National High Magnetic Field Laboratory, 1800 East Paul Dirac Drive Tallahassee FL 32310 USA
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1542272
Alternate Identifier(s):
OSTI ID: 1491266
Grant/Contract Number:  
SC0012118; DESC0012118
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 9; Journal ID: ISSN 1616-301X
Country of Publication:
United States
Language:
English

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− y PS 4− x Cl x 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− y PS 4− x Cl x with a Combined Experimental and Computational Approach. United States. 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, and Hu, Yan-Yan. Fri . "Studies of Functional Defects for Fast Na-Ion Conduction in Na 3− y PS 4− x Cl x with a Combined Experimental and Computational Approach". United States. doi:10.1002/adfm.201807951.
@article{osti_1542272,
title = {Studies of Functional Defects for Fast Na-Ion Conduction in Na 3− y PS 4− x Cl x 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 = {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, Na3−yPS4−xClx, 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 Na3.0PS3.8Cl0.2, which is two orders of magnitude higher compared with that of tetragonal Na3PS4 (t‐Na3PS4). The activation energy (Ea) 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/Na3.0PS3.8Cl0.2/Na3V2(PO4)3 with a reversible capacity of ≈100 mAh g‐1 at room temperature.},
doi = {10.1002/adfm.201807951},
journal = {Advanced Functional Materials},
issn = {1616-301X},
number = 9,
volume = 29,
place = {United States},
year = {2019},
month = {1}
}

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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


Projector augmented-wave method
journal, December 1994


Generalized Gradient Approximation Made Simple
journal, October 1996

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