Oxygen Vacancy-Induced Directional Ordering of Li-Ion Pathways for Enhanced Ion-Conducting Solid Electrolytes

Hyeon Ah Ju; Eun Byeol Park; Jaejin Hwang; Young Hoon Kim; Min Hyoung Jung; Min Ji Yang; Seon Je Kim; Jaehan Lee; In Kim; Yoo Shin Kim; Songhun Yoon; Jae Hyuck Jang; Hu Young Jeong; Jaekwang Lee; Jae Hyun Shim; Young Min Kim

doi:10.1021/acsenergylett.4c02078

Oxygen Vacancy-Induced Directional Ordering of Li-Ion Pathways for Enhanced Ion-Conducting Solid Electrolytes

Hyeon Ah Ju
, Eun Byeol Park
, Jaejin Hwang
, Young Hoon Kim
, Min Hyoung Jung
, Min Ji Yang
, Seon Je Kim
, Jaehan Lee
, In Kim
, Yoo Shin Kim
, Songhun Yoon
, Jae Hyuck Jang
, Hu Young Jeong
, Jaekwang Lee
, Jae Hyun Shim
, Young Min Kim

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

Defects in perovskite oxide solid electrolytes (SEs) impact Li-ion conductivity. However, the role of oxygen vacancies (V_o) in transport behavior has been less explored. Herein, our study elucidates the microscopic origin of the role of V_o in enhancing the total ionic conductivity of a prototype lithium lanthanum titanate while maintaining its insulating properties. Scanning transmission electron microscopy and theoretical calculations reveal that the presence of V_o significantly lowers the activation energy of Li-ion migration. The V_o is revealed to be preferentially aligned parallel to c-planes and causes modulated lattice expansion in an alternating manner, resulting in easy directional Li-ion transport. The effect of V_o-assisted Li-ion transport is optimized through the hierarchical rearrangement of structural features at multiple length scales close to the direction of the V_o arrays. Our results offer novel insights into the microscopic origins of superior ion conductivity facilitated by V_o, contributing to the design of high-performance SEs.

Original language	English
Pages (from-to)	5606-5615
Number of pages	10
Journal	ACS Energy Letters
Volume	9
Issue number	11
DOIs	https://doi.org/10.1021/acsenergylett.4c02078
State	Published - Nov 8 2024
Externally published	Yes

Funding

This study was supported by the National Research Foundation of Korea (NRF) grant (No. NRF-2023R1A2C2002403 and NRF-2022M3H4A3046292) funded by the Korean Government. J.-H.S. acknowledges the support of the Gwangju Jeonnam Local Energy Cluster Human Resources Development of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korean government Ministry of Trade, Industry and Energy (No. 20214000000560) and Jeonnam Techno Park, funded by the Jeollanam-do (Special Accounts) in 2023 (J0123009). Y.-M.K. acknowledges the support of the Institute for Basic Science (IBS-R036-D1) and the support of the Nano & Material Technology Development Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (RS-2024-00444986) (50%).

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10.1021/acsenergylett.4c02078

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Ju, H. A., Park, E. B., Hwang, J., Kim, Y. H., Jung, M. H., Yang, M. J., Kim, S. J., Lee, J., Kim, I., Kim, Y. S., Yoon, S., Jang, J. H., Jeong, H. Y., Lee, J., Shim, J. H., & Kim, Y. M. (2024). Oxygen Vacancy-Induced Directional Ordering of Li-Ion Pathways for Enhanced Ion-Conducting Solid Electrolytes. ACS Energy Letters, 9(11), 5606-5615. https://doi.org/10.1021/acsenergylett.4c02078

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title = "Oxygen Vacancy-Induced Directional Ordering of Li-Ion Pathways for Enhanced Ion-Conducting Solid Electrolytes",

abstract = "Defects in perovskite oxide solid electrolytes (SEs) impact Li-ion conductivity. However, the role of oxygen vacancies (Vo) in transport behavior has been less explored. Herein, our study elucidates the microscopic origin of the role of Vo in enhancing the total ionic conductivity of a prototype lithium lanthanum titanate while maintaining its insulating properties. Scanning transmission electron microscopy and theoretical calculations reveal that the presence of Vo significantly lowers the activation energy of Li-ion migration. The Vo is revealed to be preferentially aligned parallel to c-planes and causes modulated lattice expansion in an alternating manner, resulting in easy directional Li-ion transport. The effect of Vo-assisted Li-ion transport is optimized through the hierarchical rearrangement of structural features at multiple length scales close to the direction of the Vo arrays. Our results offer novel insights into the microscopic origins of superior ion conductivity facilitated by Vo, contributing to the design of high-performance SEs.",

author = "Ju, \{Hyeon Ah\} and Park, \{Eun Byeol\} and Jaejin Hwang and Kim, \{Young Hoon\} and Jung, \{Min Hyoung\} and Yang, \{Min Ji\} and Kim, \{Seon Je\} and Jaehan Lee and In Kim and Kim, \{Yoo Shin\} and Songhun Yoon and Jang, \{Jae Hyuck\} and Jeong, \{Hu Young\} and Jaekwang Lee and Shim, \{Jae Hyun\} and Kim, \{Young Min\}",

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doi = "10.1021/acsenergylett.4c02078",

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T1 - Oxygen Vacancy-Induced Directional Ordering of Li-Ion Pathways for Enhanced Ion-Conducting Solid Electrolytes

AU - Ju, Hyeon Ah

AU - Park, Eun Byeol

AU - Hwang, Jaejin

AU - Kim, Young Hoon

AU - Jung, Min Hyoung

AU - Yang, Min Ji

AU - Kim, Seon Je

AU - Lee, Jaehan

AU - Kim, In

AU - Kim, Yoo Shin

AU - Yoon, Songhun

AU - Jang, Jae Hyuck

AU - Jeong, Hu Young

AU - Lee, Jaekwang

AU - Shim, Jae Hyun

AU - Kim, Young Min

PY - 2024/11/8

Y1 - 2024/11/8

N2 - Defects in perovskite oxide solid electrolytes (SEs) impact Li-ion conductivity. However, the role of oxygen vacancies (Vo) in transport behavior has been less explored. Herein, our study elucidates the microscopic origin of the role of Vo in enhancing the total ionic conductivity of a prototype lithium lanthanum titanate while maintaining its insulating properties. Scanning transmission electron microscopy and theoretical calculations reveal that the presence of Vo significantly lowers the activation energy of Li-ion migration. The Vo is revealed to be preferentially aligned parallel to c-planes and causes modulated lattice expansion in an alternating manner, resulting in easy directional Li-ion transport. The effect of Vo-assisted Li-ion transport is optimized through the hierarchical rearrangement of structural features at multiple length scales close to the direction of the Vo arrays. Our results offer novel insights into the microscopic origins of superior ion conductivity facilitated by Vo, contributing to the design of high-performance SEs.

AB - Defects in perovskite oxide solid electrolytes (SEs) impact Li-ion conductivity. However, the role of oxygen vacancies (Vo) in transport behavior has been less explored. Herein, our study elucidates the microscopic origin of the role of Vo in enhancing the total ionic conductivity of a prototype lithium lanthanum titanate while maintaining its insulating properties. Scanning transmission electron microscopy and theoretical calculations reveal that the presence of Vo significantly lowers the activation energy of Li-ion migration. The Vo is revealed to be preferentially aligned parallel to c-planes and causes modulated lattice expansion in an alternating manner, resulting in easy directional Li-ion transport. The effect of Vo-assisted Li-ion transport is optimized through the hierarchical rearrangement of structural features at multiple length scales close to the direction of the Vo arrays. Our results offer novel insights into the microscopic origins of superior ion conductivity facilitated by Vo, contributing to the design of high-performance SEs.

UR - https://www.scopus.com/pages/publications/85208245581

U2 - 10.1021/acsenergylett.4c02078

DO - 10.1021/acsenergylett.4c02078

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SN - 2380-8195

VL - 9

SP - 5606

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JO - ACS Energy Letters

JF - ACS Energy Letters

IS - 11

ER -

Oxygen Vacancy-Induced Directional Ordering of Li-Ion Pathways for Enhanced Ion-Conducting Solid Electrolytes

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