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Title: A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries

Abstract

Rechargeable solid-state sodium-ion batteries (SSSBs) hold great promise for safer and more energy-dense energy storage. However, the poor electrochemical stability between current sulfide-based solid electrolytes and high-voltage oxide cathodes has limited their long-term cycling performance and practicality. Here, we report the discovery of the ion conductor Na3-xY1-xZrxCl6 (NYZC) that is both electrochemically stable (up to 3.8 V vs. Na/Na+) and chemically compatible with oxide cathodes. Its high ionic conductivity of 6.6 × 10–5 S cm–1 at ambient temperature, several orders of magnitude higher than oxide coatings, is attributed to abundant Na vacancies and cooperative MCl6 rotation, resulting in an extremely low interfacial impedance. A SSSB comprising a NaCrO2 + NYZC composite cathode, Na3PS4 electrolyte, and Na-Sn anode exhibits an exceptional first-cycle Coulombic efficiency of 97.1% at room emperature and can cycle over 1000 cycles with 89.3% capacity retention at 40 °C. These findings highlight the immense potential of halides for SSSB applications.

Authors:
 [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1];  [1]; ORCiD logo [1];  [3];  [1];  [1];  [1];  [2];  [1];  [4];  [5]; ORCiD logo [3];  [2];  [6]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of California San Diego, La Jolla, CA (United States)
  2. Univ. of California, Santa Barbara, CA (United States)
  3. Stony Brook Univ., NY (United States)
  4. Shell International Exploration & Production Inc., Houston, TX (United States)
  5. Shell Global Solutions International BV, The Hague (Netherlands)
  6. Univ. of California San Diego, La Jolla, CA (United States); TCG Centres for Research and Education in Science and Technology (TCG CREST), Kolkata (India)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Science Foundation (NSF)
OSTI Identifier:
1783756
Report Number(s):
BNL-221438-2021-JACI
Journal ID: ISSN 2041-1723
Grant/Contract Number:  
SC0012704; ECCS-1542148
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 12; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
99 GENERAL AND MISCELLANEOUS; Batteries; Engineering

Citation Formats

Wu, Erik A., Banerjee, Swastika, Tang, Hanmei, Richardson, Peter M., Doux, Jean-Marie, Qi, Ji, Zhu, Zhuoying, Grenier, Antonin, Li, Yixuan, Zhao, Enyue, Deysher, Grayson, Sebti, Elias, Nguyen, Han, Stephens, Ryan, Verbist, Guy, Chapman, Karena W., Clément, Raphaële J., Banerjee, Abhik, Meng, Ying Shirley, and Ong, Shyue Ping. A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries. United States: N. p., 2021. Web. doi:10.1038/s41467-021-21488-7.
Wu, Erik A., Banerjee, Swastika, Tang, Hanmei, Richardson, Peter M., Doux, Jean-Marie, Qi, Ji, Zhu, Zhuoying, Grenier, Antonin, Li, Yixuan, Zhao, Enyue, Deysher, Grayson, Sebti, Elias, Nguyen, Han, Stephens, Ryan, Verbist, Guy, Chapman, Karena W., Clément, Raphaële J., Banerjee, Abhik, Meng, Ying Shirley, & Ong, Shyue Ping. A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries. United States. https://doi.org/10.1038/s41467-021-21488-7
Wu, Erik A., Banerjee, Swastika, Tang, Hanmei, Richardson, Peter M., Doux, Jean-Marie, Qi, Ji, Zhu, Zhuoying, Grenier, Antonin, Li, Yixuan, Zhao, Enyue, Deysher, Grayson, Sebti, Elias, Nguyen, Han, Stephens, Ryan, Verbist, Guy, Chapman, Karena W., Clément, Raphaële J., Banerjee, Abhik, Meng, Ying Shirley, and Ong, Shyue Ping. 2021. "A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries". United States. https://doi.org/10.1038/s41467-021-21488-7. https://www.osti.gov/servlets/purl/1783756.
@article{osti_1783756,
title = {A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries},
author = {Wu, Erik A. and Banerjee, Swastika and Tang, Hanmei and Richardson, Peter M. and Doux, Jean-Marie and Qi, Ji and Zhu, Zhuoying and Grenier, Antonin and Li, Yixuan and Zhao, Enyue and Deysher, Grayson and Sebti, Elias and Nguyen, Han and Stephens, Ryan and Verbist, Guy and Chapman, Karena W. and Clément, Raphaële J. and Banerjee, Abhik and Meng, Ying Shirley and Ong, Shyue Ping},
abstractNote = {Rechargeable solid-state sodium-ion batteries (SSSBs) hold great promise for safer and more energy-dense energy storage. However, the poor electrochemical stability between current sulfide-based solid electrolytes and high-voltage oxide cathodes has limited their long-term cycling performance and practicality. Here, we report the discovery of the ion conductor Na3-xY1-xZrxCl6 (NYZC) that is both electrochemically stable (up to 3.8 V vs. Na/Na+) and chemically compatible with oxide cathodes. Its high ionic conductivity of 6.6 × 10–5 S cm–1 at ambient temperature, several orders of magnitude higher than oxide coatings, is attributed to abundant Na vacancies and cooperative MCl6 rotation, resulting in an extremely low interfacial impedance. A SSSB comprising a NaCrO2 + NYZC composite cathode, Na3PS4 electrolyte, and Na-Sn anode exhibits an exceptional first-cycle Coulombic efficiency of 97.1% at room emperature and can cycle over 1000 cycles with 89.3% capacity retention at 40 °C. These findings highlight the immense potential of halides for SSSB applications.},
doi = {10.1038/s41467-021-21488-7},
url = {https://www.osti.gov/biblio/1783756}, journal = {Nature Communications},
issn = {2041-1723},
number = 1,
volume = 12,
place = {United States},
year = {Tue Feb 23 00:00:00 EST 2021},
month = {Tue Feb 23 00:00:00 EST 2021}
}

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