Revealing the Pnma crystal structure and ion-transport mechanism of the Li3YCl6 solid electrolyte

Lv Hu; Jinze Zhu; Chaomin Duan; Jinfeng Zhu; Jinzhu Wang; Kai Wang; Zhenqi Gu; Zhiwei Xi; Jipeng Hao; Yan Chen; Jie Ma; Jin Xun Liu; Cheng Ma

doi:10.1016/j.xcrp.2023.101428

Revealing the Pnma crystal structure and ion-transport mechanism of the Li₃YCl₆ solid electrolyte

Lv Hu, Jinze Zhu, Chaomin Duan, Jinfeng Zhu, Jinzhu Wang, Kai Wang, Zhenqi Gu, Zhiwei Xi, Jipeng Hao, Yan Chen, Jie Ma, Jin Xun Liu, Cheng Ma

Materials Engineering

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

14 Scopus citations

Abstract

Chloride solid electrolytes represented by Li₃YCl₆ excel simultaneously in ionic conductivity, deformability, and oxidative stability; their structure-property relationship would provide guiding principles for designing high-performance solid electrolytes. Here, we report that the prototype system Li₃YCl₆ does not exhibit the P3¯m1 symmetry as commonly believed. This structure occurs only when the material partially decomposes at an overly high annealing temperature of 550°C. With the decomposition being suppressed at 450°C, the material shows a Pnma symmetry instead. Based on this orthorhombic structure, the ion-transport mechanism is clarified through neutron diffraction and first-principles computation. Guided by the established structure-property relationship, the efficient ion transport previously achievable only in the low-crystallinity state is realized in highly crystalline materials. The all-solid-state cells formed by this high-crystallinity material and LiNi_0.8Mn_0.1Co_0.1O₂ deliver performance exceeding most reported Li₃YCl₆-based cells; under 3 C at 25°C, the capacity retention is above 80% for 780 cycles.

Original language	English
Article number	101428
Journal	Cell Reports Physical Science
Volume	4
Issue number	6
DOIs	https://doi.org/10.1016/j.xcrp.2023.101428
State	Published - Jun 21 2023

Funding

C.M. acknowledges financial support from the Strategic Priority Research Program of the Chinese Academy of Sciences ( XDB0450201 ), the National Key R&D Program of China ( 2018YFA0209600 and 2017YFA0208300 ), the National Natural Science Foundation of China ( 51802302 ), the Fundamental Research Funds for the Central Universities ( WK3430000006 ), and the National Synchrotron Radiation Laboratory ( KY2060000199 ). J.-X.L. acknowledges the start-up funds of University of Science and Technology of China ( KY2060000171 ), the National Natural Science Foundation of Anhui province ( 2108085QB62 ), USTC Research Funds of the Double First-Class Initiative ( YD2060002012 ), and K.C. Wong Education ( GJTD-2020-15 ) and high-performance computational resources provided by the University of Science and Technology of China ( http://scc.ustc.edu.cn ) and Hefei advanced computing center. J.M. acknowledges financial support from the National Science Foundation of China ( U2032213 ).

Funders	Funder number
Hefei advanced computing center
K.C. Wong Education	GJTD-2020-15
USTC Research Funds of the Double First-Class Initiative	YD2060002012
National Natural Science Foundation of China	U2032213, 51802302
Chinese Academy of Sciences	XDB0450201
Natural Science Foundation of Anhui Province	2108085QB62
University of Science and Technology of China	KY2060000171
National Key Research and Development Program of China	2017YFA0208300, 2018YFA0209600
Fundamental Research Funds for the Central Universities	WK3430000006
National Synchrotron Radiation Laboratory	KY2060000199

Keywords

chloride solid electrolytes
crystal structure
first-principles computation
ionic conductivity
neutron diffraction

Access to Document

10.1016/j.xcrp.2023.101428

Cite this

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title = "Revealing the Pnma crystal structure and ion-transport mechanism of the Li3YCl6 solid electrolyte",

abstract = "Chloride solid electrolytes represented by Li3YCl6 excel simultaneously in ionic conductivity, deformability, and oxidative stability; their structure-property relationship would provide guiding principles for designing high-performance solid electrolytes. Here, we report that the prototype system Li3YCl6 does not exhibit the P3¯m1 symmetry as commonly believed. This structure occurs only when the material partially decomposes at an overly high annealing temperature of 550°C. With the decomposition being suppressed at 450°C, the material shows a Pnma symmetry instead. Based on this orthorhombic structure, the ion-transport mechanism is clarified through neutron diffraction and first-principles computation. Guided by the established structure-property relationship, the efficient ion transport previously achievable only in the low-crystallinity state is realized in highly crystalline materials. The all-solid-state cells formed by this high-crystallinity material and LiNi0.8Mn0.1Co0.1O2 deliver performance exceeding most reported Li3YCl6-based cells; under 3 C at 25°C, the capacity retention is above 80% for 780 cycles.",

keywords = "chloride solid electrolytes, crystal structure, first-principles computation, ionic conductivity, neutron diffraction",

author = "Lv Hu and Jinze Zhu and Chaomin Duan and Jinfeng Zhu and Jinzhu Wang and Kai Wang and Zhenqi Gu and Zhiwei Xi and Jipeng Hao and Yan Chen and Jie Ma and Liu, {Jin Xun} and Cheng Ma",

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doi = "10.1016/j.xcrp.2023.101428",

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AU - Hu, Lv

AU - Zhu, Jinze

AU - Duan, Chaomin

AU - Zhu, Jinfeng

AU - Wang, Jinzhu

AU - Wang, Kai

AU - Gu, Zhenqi

AU - Xi, Zhiwei

AU - Hao, Jipeng

AU - Chen, Yan

AU - Ma, Jie

AU - Liu, Jin Xun

AU - Ma, Cheng

PY - 2023/6/21

Y1 - 2023/6/21

N2 - Chloride solid electrolytes represented by Li3YCl6 excel simultaneously in ionic conductivity, deformability, and oxidative stability; their structure-property relationship would provide guiding principles for designing high-performance solid electrolytes. Here, we report that the prototype system Li3YCl6 does not exhibit the P3¯m1 symmetry as commonly believed. This structure occurs only when the material partially decomposes at an overly high annealing temperature of 550°C. With the decomposition being suppressed at 450°C, the material shows a Pnma symmetry instead. Based on this orthorhombic structure, the ion-transport mechanism is clarified through neutron diffraction and first-principles computation. Guided by the established structure-property relationship, the efficient ion transport previously achievable only in the low-crystallinity state is realized in highly crystalline materials. The all-solid-state cells formed by this high-crystallinity material and LiNi0.8Mn0.1Co0.1O2 deliver performance exceeding most reported Li3YCl6-based cells; under 3 C at 25°C, the capacity retention is above 80% for 780 cycles.

AB - Chloride solid electrolytes represented by Li3YCl6 excel simultaneously in ionic conductivity, deformability, and oxidative stability; their structure-property relationship would provide guiding principles for designing high-performance solid electrolytes. Here, we report that the prototype system Li3YCl6 does not exhibit the P3¯m1 symmetry as commonly believed. This structure occurs only when the material partially decomposes at an overly high annealing temperature of 550°C. With the decomposition being suppressed at 450°C, the material shows a Pnma symmetry instead. Based on this orthorhombic structure, the ion-transport mechanism is clarified through neutron diffraction and first-principles computation. Guided by the established structure-property relationship, the efficient ion transport previously achievable only in the low-crystallinity state is realized in highly crystalline materials. The all-solid-state cells formed by this high-crystallinity material and LiNi0.8Mn0.1Co0.1O2 deliver performance exceeding most reported Li3YCl6-based cells; under 3 C at 25°C, the capacity retention is above 80% for 780 cycles.

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