LAPSE:2023.13563v1
Published Article
LAPSE:2023.13563v1
Comparative Study of Stability against Moisture for Solid Garnet Electrolytes with Different Dopants
March 1, 2023
Abstract
The cubic garnet Li7La3Zr2O12 (c-LLZO) is one of the most promising solid electrolytes due to its high ionic conductivity and large electrochemical window. However, the critical issue of Li2CO3 formation on the c-LLZO surface when exposed to air is problematic, which is detrimental to the ionic conductivity and storage. Herein, comparative studies were carried out on the air stability of Al-doped Li7La3Zr2O12 (Al-LLZO), Al-Ta-doped Li7La3Zr2O12 (Al-LLZTO), and Al-Nb-doped Li7La3Zr2O12 (Al-LLZNO). It was found that Al-LLZTO and Al-LLZNO are less reactive with air than Al-LLZO. The morphology of Li2CO3 on Al-LLZTO micro-sized powders after air exposure was island-like with ~1.5 μm in thickness. The interfacial resistance of Li/Al-LLZTO was also a factor of ~3 smaller than that of Li/Al-LLZO, leading to the improved cycle stability of Li/Al-LLZTO/Li symmetric cells. The first-principles calculations based on density functional theory (DFT) verified that the decomposition energy of Al-LLZTO was larger than that of Al-LLZO, inhibiting the reaction product of Li2O and, thus, the next step product of Li2CO3 following the reactions of Li2O + H2O → LiOH and LiOH + CO2 → Li2CO3.
The cubic garnet Li7La3Zr2O12 (c-LLZO) is one of the most promising solid electrolytes due to its high ionic conductivity and large electrochemical window. However, the critical issue of Li2CO3 formation on the c-LLZO surface when exposed to air is problematic, which is detrimental to the ionic conductivity and storage. Herein, comparative studies were carried out on the air stability of Al-doped Li7La3Zr2O12 (Al-LLZO), Al-Ta-doped Li7La3Zr2O12 (Al-LLZTO), and Al-Nb-doped Li7La3Zr2O12 (Al-LLZNO). It was found that Al-LLZTO and Al-LLZNO are less reactive with air than Al-LLZO. The morphology of Li2CO3 on Al-LLZTO micro-sized powders after air exposure was island-like with ~1.5 μm in thickness. The interfacial resistance of Li/Al-LLZTO was also a factor of ~3 smaller than that of Li/Al-LLZO, leading to the improved cycle stability of Li/Al-LLZTO/Li symmetric cells. The first-principles calculations based on density functional theory (DFT) verified that the decomposition energy of Al-LLZTO was larger than that of Al-LLZO, inhibiting the reaction product of Li2O and, thus, the next step product of Li2CO3 following the reactions of Li2O + H2O → LiOH and LiOH + CO2 → Li2CO3.
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Keywords
air stability, doped electrolytes, Li2CO3, solid garnet electrolytes
Subject
Suggested Citation
Huang L, Gao J, Bi Z, Zhao N, Wu J, Fang Q, Wang X, Wan Y, Guo X. Comparative Study of Stability against Moisture for Solid Garnet Electrolytes with Different Dopants. (2023). LAPSE:2023.13563v1
Author Affiliations
Huang L: College of Physics, Qingdao University, Qingdao 266071, China
Gao J: Beijing Advanced Innovation Center for Soft Matter Science and Engineering, State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China
Bi Z: College of Physics, Qingdao University, Qingdao 266071, China
Zhao N: College of Physics, Qingdao University, Qingdao 266071, China [ORCID]
Wu J: Laboratory for Advanced Materials & Electron Microscopy, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China; College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, Chin
Fang Q: Laboratory for Advanced Materials & Electron Microscopy, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China; College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, Chin
Wang X: Laboratory for Advanced Materials & Electron Microscopy, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China; College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, Chin
Wan Y: College of Physics, Qingdao University, Qingdao 266071, China
Guo X: College of Physics, Qingdao University, Qingdao 266071, China [ORCID]
Gao J: Beijing Advanced Innovation Center for Soft Matter Science and Engineering, State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China
Bi Z: College of Physics, Qingdao University, Qingdao 266071, China
Zhao N: College of Physics, Qingdao University, Qingdao 266071, China [ORCID]
Wu J: Laboratory for Advanced Materials & Electron Microscopy, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China; College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, Chin
Fang Q: Laboratory for Advanced Materials & Electron Microscopy, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China; College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, Chin
Wang X: Laboratory for Advanced Materials & Electron Microscopy, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China; College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, Chin
Wan Y: College of Physics, Qingdao University, Qingdao 266071, China
Guo X: College of Physics, Qingdao University, Qingdao 266071, China [ORCID]
Journal Name
Energies
Volume
15
Issue
9
First Page
3206
Year
2022
Publication Date
2022-04-27
ISSN
1996-1073
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PII: en15093206, Publication Type: Journal Article
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LAPSE:2023.13563v1
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