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Title: Origin of Outstanding Phase and Moisture Stability in a Na 3P 1–x As xS 4 Superionic Conductor

Abstract

Sodium ion (Na) solid-state electrolytes (SSEs) are critical to address notorious safety issues associated with liquid electrolytes used in the current Na ion batteries. Fulfilling multiple innovations is a grand challenge but is imperative for advanced Na ion SSEs, such as a combination of high ionic conductivity and excellent chemical stability. Here, our first-principles and phonon calculations reveal that Na 3P 1–xAs xS 4 (0 ≤ x ≤ 1) is a solid-state superionic conductor stabilized at 0 K by zero-point vibrational energy and at finite temperatures by vibrational and configurational entropies. Especially, our integrated first-principles and experimental approach indicates that Na 3P 1–xAs xS 4 is dry-air stable. Additionally, the alloying element arsenic greatly enhances the moisture (i.e., H 2O) stability of Na 3P 1–xAs xS 4 by shifting the reaction products from the easy-forming oxysulfides (such as Na 3POS 3 and Na 3PO 2S 2 with H 2S release) to the difficult-forming hydrates (such as Na 3P 1–xAs xS 4·$n$H 2O with n = 8 and/or 9) due mainly to a weaker As–O affinity compared to that of P–O. The present work demonstrates that alloying is able to achieve multiple innovations for solid-state electrolytes, such as a desirable superionicmore » conductor with not only a high ionic conductivity (for example, 1.46 mS/cm at room temperature achieved in Na 3P 0.62As 0.38S 4) but also an excellent chemical stability with respect to temperature, composition, and moisture.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [3];  [1]
  1. Pennsylvania State Univ., University Park, PA (United States). Dept. of Materials Science and Engineering
  2. Pennsylvania State Univ., University Park, PA (United States). Dept. of Mechanical and Nuclear Engineering
  3. Pennsylvania State Univ., University Park, PA (United States). Dept. of Mechanical and Nuclear Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1484768
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 9; Journal Issue: 19; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

Citation Formats

Shang, Shun-Li, Yu, Zhaoxin, Wang, Yi, Wang, Donghai, and Liu, Zi-Kui. Origin of Outstanding Phase and Moisture Stability in a Na3P1–x AsxS4 Superionic Conductor. United States: N. p., 2017. Web. doi:10.1021/acsami.7b03606.
Shang, Shun-Li, Yu, Zhaoxin, Wang, Yi, Wang, Donghai, & Liu, Zi-Kui. Origin of Outstanding Phase and Moisture Stability in a Na3P1–x AsxS4 Superionic Conductor. United States. doi:10.1021/acsami.7b03606.
Shang, Shun-Li, Yu, Zhaoxin, Wang, Yi, Wang, Donghai, and Liu, Zi-Kui. Thu . "Origin of Outstanding Phase and Moisture Stability in a Na3P1–x AsxS4 Superionic Conductor". United States. doi:10.1021/acsami.7b03606. https://www.osti.gov/servlets/purl/1484768.
@article{osti_1484768,
title = {Origin of Outstanding Phase and Moisture Stability in a Na3P1–x AsxS4 Superionic Conductor},
author = {Shang, Shun-Li and Yu, Zhaoxin and Wang, Yi and Wang, Donghai and Liu, Zi-Kui},
abstractNote = {Sodium ion (Na) solid-state electrolytes (SSEs) are critical to address notorious safety issues associated with liquid electrolytes used in the current Na ion batteries. Fulfilling multiple innovations is a grand challenge but is imperative for advanced Na ion SSEs, such as a combination of high ionic conductivity and excellent chemical stability. Here, our first-principles and phonon calculations reveal that Na3P1–xAsxS4 (0 ≤ x ≤ 1) is a solid-state superionic conductor stabilized at 0 K by zero-point vibrational energy and at finite temperatures by vibrational and configurational entropies. Especially, our integrated first-principles and experimental approach indicates that Na3P1–xAsxS4 is dry-air stable. Additionally, the alloying element arsenic greatly enhances the moisture (i.e., H2O) stability of Na3P1–xAsxS4 by shifting the reaction products from the easy-forming oxysulfides (such as Na3POS3 and Na3PO2S2 with H2S release) to the difficult-forming hydrates (such as Na3P1–xAsxS4·$n$H2O with n = 8 and/or 9) due mainly to a weaker As–O affinity compared to that of P–O. The present work demonstrates that alloying is able to achieve multiple innovations for solid-state electrolytes, such as a desirable superionic conductor with not only a high ionic conductivity (for example, 1.46 mS/cm at room temperature achieved in Na3P0.62As0.38S4) but also an excellent chemical stability with respect to temperature, composition, and moisture.},
doi = {10.1021/acsami.7b03606},
journal = {ACS Applied Materials and Interfaces},
number = 19,
volume = 9,
place = {United States},
year = {2017},
month = {5}
}

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