Preparation and performance of highly-conductive dual-doped Li7La3Zr2O12 solid electrolytes for thermal batteries

Garnet Li7La3Zr2O12 (LLZO) electrolytes have been recognized as a promising candidate to replace liquid/molten-state electrolytes in battery applications due to their exceptional performance, particularly Ga-doped LLZO (LLZGO), which exhibits high ionic conductivity. However, the limited size of the...

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Main Authors: Wei Li, Shu Zhang, Xinya Bu, Jing Luo, Yi Zhang, Mengyu Yan, Ting Quan, Yanli Zhu
Format: Article
Language:English
Published: KeAi Communications Co., Ltd. 2025-02-01
Series:Green Energy & Environment
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Online Access:http://www.sciencedirect.com/science/article/pii/S2468025724001018
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author Wei Li
Shu Zhang
Xinya Bu
Jing Luo
Yi Zhang
Mengyu Yan
Ting Quan
Yanli Zhu
author_facet Wei Li
Shu Zhang
Xinya Bu
Jing Luo
Yi Zhang
Mengyu Yan
Ting Quan
Yanli Zhu
author_sort Wei Li
collection DOAJ
description Garnet Li7La3Zr2O12 (LLZO) electrolytes have been recognized as a promising candidate to replace liquid/molten-state electrolytes in battery applications due to their exceptional performance, particularly Ga-doped LLZO (LLZGO), which exhibits high ionic conductivity. However, the limited size of the Li+ transport bottleneck restricts its high-current discharging performance. The present study focuses on the synthesis of Ga3+ and Ba2+ co-doped LLZO (LLZGBO) and investigates the influence of doping contents on the morphology, crystal structure, Li+ transport bottleneck size, and ionic conductivity. In particular, Ga0.32Ba0.15 exhibits the highest ionic conductivity (6.11E-2 S cm−1 at 550 °C) in comparison with other compositions, which can be attributed to its higher-energy morphology, larger bottleneck and unique Li+ transport channel. In addition to Ba2+, Sr2+ and Ca2+ have been co-doped with Ga3+ into LLZO, respectively, to study the effect of doping ion radius on crystal structures and the properties of electrolytes. The characterization results demonstrate that the easier Li+ transport and higher ionic conductivity can be obtained when the electrolyte is doped with larger-radius ions. As a result, the assembled thermal battery with Ga0.32Ba0.15-LLZO electrolyte exhibits a remarkable voltage platform of 1.81 V and a high specific capacity of 455.65 mA h g−1 at an elevated temperature of 525 °C. The discharge specific capacity of the thermal cell at 500 mA amounts to 63% of that at 100 mA, showcasing exceptional high-current discharging performance. When assembled as prototypes with fourteen single cells connected in series, the thermal batteries deliver an activation time of 38 ms and a discharge time of 32 s with the current density of 100 mA cm−2. These findings suggest that Ga, Ba co-doped LLZO solid-state electrolytes with high ionic conductivities holds great potential for high-capacity, quick-initiating and high-current discharging thermal batteries.
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spelling doaj-art-3f0e293d405b4c2e920f7bd6a31b59e32025-08-20T02:43:43ZengKeAi Communications Co., Ltd.Green Energy & Environment2468-02572025-02-0110239940910.1016/j.gee.2024.04.002Preparation and performance of highly-conductive dual-doped Li7La3Zr2O12 solid electrolytes for thermal batteriesWei Li0Shu Zhang1Xinya Bu2Jing Luo3Yi Zhang4Mengyu Yan5Ting Quan6Yanli Zhu7State Key Laboratory of Explosion Science and Safety Protection, Beijing Institute of Technology, Beijing, 100081, ChinaState Key Laboratory of Explosion Science and Safety Protection, Beijing Institute of Technology, Beijing, 100081, ChinaState Key Laboratory of Explosion Science and Safety Protection, Beijing Institute of Technology, Beijing, 100081, ChinaXi'an North Qinghua Electromechanical Co., Ltd., Xi'an, 710025, ChinaXi'an North Qinghua Electromechanical Co., Ltd., Xi'an, 710025, ChinaXi'an North Qinghua Electromechanical Co., Ltd., Xi'an, 710025, ChinaState Key Laboratory of Explosion Science and Safety Protection, Beijing Institute of Technology, Beijing, 100081, China; Corresponding authors.State Key Laboratory of Explosion Science and Safety Protection, Beijing Institute of Technology, Beijing, 100081, China; Beijing Institute of Technology Chongqing Innovation Center, Chongqing, 401120, China; Corresponding authors.Garnet Li7La3Zr2O12 (LLZO) electrolytes have been recognized as a promising candidate to replace liquid/molten-state electrolytes in battery applications due to their exceptional performance, particularly Ga-doped LLZO (LLZGO), which exhibits high ionic conductivity. However, the limited size of the Li+ transport bottleneck restricts its high-current discharging performance. The present study focuses on the synthesis of Ga3+ and Ba2+ co-doped LLZO (LLZGBO) and investigates the influence of doping contents on the morphology, crystal structure, Li+ transport bottleneck size, and ionic conductivity. In particular, Ga0.32Ba0.15 exhibits the highest ionic conductivity (6.11E-2 S cm−1 at 550 °C) in comparison with other compositions, which can be attributed to its higher-energy morphology, larger bottleneck and unique Li+ transport channel. In addition to Ba2+, Sr2+ and Ca2+ have been co-doped with Ga3+ into LLZO, respectively, to study the effect of doping ion radius on crystal structures and the properties of electrolytes. The characterization results demonstrate that the easier Li+ transport and higher ionic conductivity can be obtained when the electrolyte is doped with larger-radius ions. As a result, the assembled thermal battery with Ga0.32Ba0.15-LLZO electrolyte exhibits a remarkable voltage platform of 1.81 V and a high specific capacity of 455.65 mA h g−1 at an elevated temperature of 525 °C. The discharge specific capacity of the thermal cell at 500 mA amounts to 63% of that at 100 mA, showcasing exceptional high-current discharging performance. When assembled as prototypes with fourteen single cells connected in series, the thermal batteries deliver an activation time of 38 ms and a discharge time of 32 s with the current density of 100 mA cm−2. These findings suggest that Ga, Ba co-doped LLZO solid-state electrolytes with high ionic conductivities holds great potential for high-capacity, quick-initiating and high-current discharging thermal batteries.http://www.sciencedirect.com/science/article/pii/S2468025724001018Element dopingThermal batterySolid electrolyteLLZOIonic conductivity
spellingShingle Wei Li
Shu Zhang
Xinya Bu
Jing Luo
Yi Zhang
Mengyu Yan
Ting Quan
Yanli Zhu
Preparation and performance of highly-conductive dual-doped Li7La3Zr2O12 solid electrolytes for thermal batteries
Green Energy & Environment
Element doping
Thermal battery
Solid electrolyte
LLZO
Ionic conductivity
title Preparation and performance of highly-conductive dual-doped Li7La3Zr2O12 solid electrolytes for thermal batteries
title_full Preparation and performance of highly-conductive dual-doped Li7La3Zr2O12 solid electrolytes for thermal batteries
title_fullStr Preparation and performance of highly-conductive dual-doped Li7La3Zr2O12 solid electrolytes for thermal batteries
title_full_unstemmed Preparation and performance of highly-conductive dual-doped Li7La3Zr2O12 solid electrolytes for thermal batteries
title_short Preparation and performance of highly-conductive dual-doped Li7La3Zr2O12 solid electrolytes for thermal batteries
title_sort preparation and performance of highly conductive dual doped li7la3zr2o12 solid electrolytes for thermal batteries
topic Element doping
Thermal battery
Solid electrolyte
LLZO
Ionic conductivity
url http://www.sciencedirect.com/science/article/pii/S2468025724001018
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