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Title: Stoichiometric irreversibility of aged garnet electrolytes

Abstract

Solid-state lithium batteries (SSLBs) have been regarded as one of the next-generation energy storage systems. With the adoption of solid-state electrolytes (SSEs) and lithium metal anodes, SSLBs enable higher energy density and more reliable safety than the state-of-the-art lithium-ion batteries. Among potential SSEs, the cation-doped Li7La3Zr2O12 (LLZO) is promising for its high ionic conductivity (~10–3 S cm–2) at room temperature and high stability with Li metal anode. However, the storage of doped LLZO in the ambient condition suffers the aging effect, including the structural transition (i.e. low-temperature cubic form) and the stoichiometric changes (i.e. Li2CO3). These changes are detrimental to LLZO ionic conductivity and interfacial stability in SSLBs. To this end, in this study we are motivated to investigate the structural and stoichiometric reversibility of aged LLZO during thermal treatment. With the help of an in-situ synchrotron-based high-energy X-ray diffraction technique, our experiments revealed that the LLZO powders became a low-temperature cubic phase when exposed to the ambient condition for an extended period of time. A high temperature cubic form can be restored after a thermal treatment of the aged LLZO powder, regardless of the type of dopant. However, the restoration of the stoichiometry remained a challenge, and the degreemore » of the restoration showed a clear dependence on the dopant chemistry.« less

Authors:
 [1];  [2];  [3];  [3]; ORCiD logo [2];  [2];  [2]; ORCiD logo [2];  [4];  [3];  [5];  [2]
+ Show Author Affiliations
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division; Univ. of Arkansas, Fayetteville, AR (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
  5. Univ. of Arkansas, Fayetteville, AR (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1773604
Alternate Identifier(s):
OSTI ID: 1781465
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Materials Today Energy
Additional Journal Information:
Journal Volume: 20; Journal ID: ISSN 2468-6069
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; solid-state electrolytes; garnets; thermal treatment; reversibility; dopants

Citation Formats

Cai, Jiyu, Polzin, Bryant, Fan, Longlong, Yin, Liang, Liang, Yujia, Li, Xiang, Liu, Qian, Trask, Steve E., Liu, Yuzi, Ren, Yang, Meng, Xiangbo, and Chen, Zonghai. Stoichiometric irreversibility of aged garnet electrolytes. United States: N. p., 2021. Web. doi:10.1016/j.mtener.2021.100669.
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Cai, Jiyu, Polzin, Bryant, Fan, Longlong, Yin, Liang, Liang, Yujia, Li, Xiang, Liu, Qian, Trask, Steve E., Liu, Yuzi, Ren, Yang, Meng, Xiangbo, & Chen, Zonghai. Stoichiometric irreversibility of aged garnet electrolytes. United States. https://doi.org/10.1016/j.mtener.2021.100669
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Cai, Jiyu, Polzin, Bryant, Fan, Longlong, Yin, Liang, Liang, Yujia, Li, Xiang, Liu, Qian, Trask, Steve E., Liu, Yuzi, Ren, Yang, Meng, Xiangbo, and Chen, Zonghai. Mon . "Stoichiometric irreversibility of aged garnet electrolytes". United States. https://doi.org/10.1016/j.mtener.2021.100669. https://www.osti.gov/servlets/purl/1773604.
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@article{osti_1773604,
title = {Stoichiometric irreversibility of aged garnet electrolytes},
author = {Cai, Jiyu and Polzin, Bryant and Fan, Longlong and Yin, Liang and Liang, Yujia and Li, Xiang and Liu, Qian and Trask, Steve E. and Liu, Yuzi and Ren, Yang and Meng, Xiangbo and Chen, Zonghai},
abstractNote = {Solid-state lithium batteries (SSLBs) have been regarded as one of the next-generation energy storage systems. With the adoption of solid-state electrolytes (SSEs) and lithium metal anodes, SSLBs enable higher energy density and more reliable safety than the state-of-the-art lithium-ion batteries. Among potential SSEs, the cation-doped Li7La3Zr2O12 (LLZO) is promising for its high ionic conductivity (~10–3 S cm–2) at room temperature and high stability with Li metal anode. However, the storage of doped LLZO in the ambient condition suffers the aging effect, including the structural transition (i.e. low-temperature cubic form) and the stoichiometric changes (i.e. Li2CO3). These changes are detrimental to LLZO ionic conductivity and interfacial stability in SSLBs. To this end, in this study we are motivated to investigate the structural and stoichiometric reversibility of aged LLZO during thermal treatment. With the help of an in-situ synchrotron-based high-energy X-ray diffraction technique, our experiments revealed that the LLZO powders became a low-temperature cubic phase when exposed to the ambient condition for an extended period of time. A high temperature cubic form can be restored after a thermal treatment of the aged LLZO powder, regardless of the type of dopant. However, the restoration of the stoichiometry remained a challenge, and the degree of the restoration showed a clear dependence on the dopant chemistry.},
doi = {10.1016/j.mtener.2021.100669},
journal = {Materials Today Energy},
number = ,
volume = 20,
place = {United States},
year = {Mon Feb 08 00:00:00 EST 2021},
month = {Mon Feb 08 00:00:00 EST 2021}
}
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