Stoichiometric irreversibility of aged garnet electrolytes

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

doi:10.1016/j.mtener.2021.100669

Stoichiometric irreversibility of aged garnet electrolytes

Journal Article · Mon Feb 08 00:00:00 EST 2021 · Materials Today Energy

DOI:https://doi.org/10.1016/j.mtener.2021.100669· OSTI ID:1773604

Cai, Jiyu ^[1]; Polzin, Bryant ^[2]; Fan, Longlong ^[3]; Yin, Liang ^[3]; ^[2]; Li, Xiang ^[2]; Liu, Qian ^[2]; ^[2]; Liu, Yuzi ^[4]; Ren, Yang ^[3]; Meng, Xiangbo ^[5]; Chen, Zonghai ^[2]

Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division; Univ. of Arkansas, Fayetteville, AR (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
Univ. of Arkansas, Fayetteville, AR (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1773604

Alternate ID(s):: OSTI ID: 1781465

Journal Information:: Materials Today Energy, Journal Name: Materials Today Energy Vol. 20; ISSN 2468-6069

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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