Cubic Iodide LixYI3+x Superionic Conductors through Defect Manipulation for All-Solid-State Li Batteries

Shumin Zhang; Feipeng Zhao; Han Su; Yu Zhong; Jianwen Liang; Jiatang Chen; Matthew Liu Zheng; Jue Liu; Lo Yueh Chang; Jiamin Fu; Sandamini H. Alahakoon; Yang Hu; Yu Liu; Yining Huang; Jiangping Tu; Tsun Kong Sham; Xueliang Sun

doi:10.1002/anie.202316360

Cubic Iodide Li_xYI_3+x Superionic Conductors through Defect Manipulation for All-Solid-State Li Batteries

Shumin Zhang, Feipeng Zhao, Han Su, Yu Zhong, Jianwen Liang, Jiatang Chen, Matthew Liu Zheng, Jue Liu, Lo Yueh Chang, Jiamin Fu, Sandamini H. Alahakoon, Yang Hu, Yu Liu, Yining Huang, Jiangping Tu, Tsun Kong Sham, Xueliang Sun

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Abstract

Halide solid electrolytes (SEs) have attracted significant attention due to their competitive ionic conductivity and good electrochemical stability. Among typical halide SEs (chlorides, bromides, and iodides), substantial efforts have been dedicated to chlorides or bromides, with iodide SEs receiving less attention. Nevertheless, compared with chlorides or bromides, iodides have both a softer Li sublattice and lower reduction limit, which enable iodides to possess potentially high ionic conductivity and intrinsic anti-reduction stability, respectively. Herein, we report a new series of iodide SEs: Li_xYI_3+x (x=2, 3, 4, or 9). Through synchrotron X-ray/neutron diffraction characterizations and theoretical calculations, we revealed that the Li_xYI_3+x SEs belong to the high-symmetry cubic structure, and can accommodate abundant vacancies. By manipulating the defects in the iodide structure, balanced Li-ion concentration and generated vacancies enables an optimized ionic conductivity of 1.04 × 10⁻³ S cm⁻¹ at 25 °C for Li₄YI₇. Additionally, the promising Li-metal compatibility of Li₄YI₇ is demonstrated via electrochemical characterizations (particularly all-solid-state Li-S batteries) combined with interface molecular dynamics simulations. Our study on iodide SEs provides deep insights into the relation between high-symmetry halide structures and ionic conduction, which can inspire future efforts to revitalize halide SEs.

Original language	English
Article number	e202316360
Journal	Angewandte Chemie - International Edition
Volume	63
Issue number	12
DOIs	https://doi.org/10.1002/anie.202316360
State	Published - Mar 18 2024

Funding

This research was supported by the Natural Sciences and Engineering Research Council of Canada (NSERC), the Canada Research Chair Program (CRC), the Canada Foundation for Innovation (CFI), Ontario Research Foundation (ORF), and the University of Western Ontario (UWO). The synchrotron research was performed at the Canadian Light Source, a national research facility of the University of Saskatchewan, which was supported by the CFI, NSERC, the National Research Council (NRC), the Canadian Institutes of Health Research (CIHR), the Government of Saskatchewan, and the University of Saskatchewan. A portion of this research used resources (NOMAD) at the Spallation Neutron Source, a DOE Office of Science User Facility Operated by the Oak Ridge National Laboratory. We thank Prof. Hong Zhu from Shanghai Jiao Tong University for providing the crystallographic information files of non-cubic Li3YI6. This research was supported by the Natural Sciences and Engineering Research Council of Canada (NSERC), the Canada Research Chair Program (CRC), the Canada Foundation for Innovation (CFI), Ontario Research Foundation (ORF), and the University of Western Ontario (UWO). The synchrotron research was performed at the Canadian Light Source, a national research facility of the University of Saskatchewan, which was supported by the CFI, NSERC, the National Research Council (NRC), the Canadian Institutes of Health Research (CIHR), the Government of Saskatchewan, and the University of Saskatchewan. A portion of this research used resources (NOMAD) at the Spallation Neutron Source, a DOE Office of Science User Facility Operated by the Oak Ridge National Laboratory. We thank Prof. Hong Zhu from Shanghai Jiao Tong University for providing the crystallographic information files of non‐cubic LiYI. 3 6

Funders	Funder number
Office of Science
University of Saskatchewan
Ontario Research Foundation
National Research Council
Government of Saskatchewan
Canadian Institutes of Health Research
Natural Sciences and Engineering Research Council of Canada
Canada Foundation for Innovation
Canada Research Chairs
Western University
Shanghai Jiao Tong University

Keywords

cubic crystal structures
iodides
ionic conductivity
reduction stability
solid electrolytes

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1002/anie.202316360

Cite this

Zhang, S., Zhao, F., Su, H., Zhong, Y., Liang, J., Chen, J., Zheng, M. L., Liu, J., Chang, L. Y., Fu, J., Alahakoon, S. H., Hu, Y., Liu, Y., Huang, Y., Tu, J., Sham, T. K., & Sun, X. (2024). Cubic Iodide Li_xYI_3+x Superionic Conductors through Defect Manipulation for All-Solid-State Li Batteries. Angewandte Chemie - International Edition, 63(12), Article e202316360. https://doi.org/10.1002/anie.202316360

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title = "Cubic Iodide LixYI3+x Superionic Conductors through Defect Manipulation for All-Solid-State Li Batteries",

abstract = "Halide solid electrolytes (SEs) have attracted significant attention due to their competitive ionic conductivity and good electrochemical stability. Among typical halide SEs (chlorides, bromides, and iodides), substantial efforts have been dedicated to chlorides or bromides, with iodide SEs receiving less attention. Nevertheless, compared with chlorides or bromides, iodides have both a softer Li sublattice and lower reduction limit, which enable iodides to possess potentially high ionic conductivity and intrinsic anti-reduction stability, respectively. Herein, we report a new series of iodide SEs: LixYI3+x (x=2, 3, 4, or 9). Through synchrotron X-ray/neutron diffraction characterizations and theoretical calculations, we revealed that the LixYI3+x SEs belong to the high-symmetry cubic structure, and can accommodate abundant vacancies. By manipulating the defects in the iodide structure, balanced Li-ion concentration and generated vacancies enables an optimized ionic conductivity of 1.04 × 10−3 S cm−1 at 25 °C for Li4YI7. Additionally, the promising Li-metal compatibility of Li4YI7 is demonstrated via electrochemical characterizations (particularly all-solid-state Li-S batteries) combined with interface molecular dynamics simulations. Our study on iodide SEs provides deep insights into the relation between high-symmetry halide structures and ionic conduction, which can inspire future efforts to revitalize halide SEs.",

keywords = "cubic crystal structures, iodides, ionic conductivity, reduction stability, solid electrolytes",

author = "Shumin Zhang and Feipeng Zhao and Han Su and Yu Zhong and Jianwen Liang and Jiatang Chen and Zheng, {Matthew Liu} and Jue Liu and Chang, {Lo Yueh} and Jiamin Fu and Alahakoon, {Sandamini H.} and Yang Hu and Yu Liu and Yining Huang and Jiangping Tu and Sham, {Tsun Kong} and Xueliang Sun",

note = "Publisher Copyright: {\textcopyright} 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

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Zhang, S, Zhao, F, Su, H, Zhong, Y, Liang, J, Chen, J, Zheng, ML, Liu, J, Chang, LY, Fu, J, Alahakoon, SH, Hu, Y, Liu, Y, Huang, Y, Tu, J, Sham, TK & Sun, X 2024, 'Cubic Iodide Li_xYI_3+x Superionic Conductors through Defect Manipulation for All-Solid-State Li Batteries', Angewandte Chemie - International Edition, vol. 63, no. 12, e202316360. https://doi.org/10.1002/anie.202316360

TY - JOUR

T1 - Cubic Iodide LixYI3+x Superionic Conductors through Defect Manipulation for All-Solid-State Li Batteries

AU - Zhang, Shumin

AU - Zhao, Feipeng

AU - Su, Han

AU - Zhong, Yu

AU - Liang, Jianwen

AU - Chen, Jiatang

AU - Zheng, Matthew Liu

AU - Liu, Jue

AU - Chang, Lo Yueh

AU - Fu, Jiamin

AU - Alahakoon, Sandamini H.

AU - Hu, Yang

AU - Liu, Yu

AU - Huang, Yining

AU - Tu, Jiangping

AU - Sham, Tsun Kong

AU - Sun, Xueliang

PY - 2024/3/18

Y1 - 2024/3/18

N2 - Halide solid electrolytes (SEs) have attracted significant attention due to their competitive ionic conductivity and good electrochemical stability. Among typical halide SEs (chlorides, bromides, and iodides), substantial efforts have been dedicated to chlorides or bromides, with iodide SEs receiving less attention. Nevertheless, compared with chlorides or bromides, iodides have both a softer Li sublattice and lower reduction limit, which enable iodides to possess potentially high ionic conductivity and intrinsic anti-reduction stability, respectively. Herein, we report a new series of iodide SEs: LixYI3+x (x=2, 3, 4, or 9). Through synchrotron X-ray/neutron diffraction characterizations and theoretical calculations, we revealed that the LixYI3+x SEs belong to the high-symmetry cubic structure, and can accommodate abundant vacancies. By manipulating the defects in the iodide structure, balanced Li-ion concentration and generated vacancies enables an optimized ionic conductivity of 1.04 × 10−3 S cm−1 at 25 °C for Li4YI7. Additionally, the promising Li-metal compatibility of Li4YI7 is demonstrated via electrochemical characterizations (particularly all-solid-state Li-S batteries) combined with interface molecular dynamics simulations. Our study on iodide SEs provides deep insights into the relation between high-symmetry halide structures and ionic conduction, which can inspire future efforts to revitalize halide SEs.

AB - Halide solid electrolytes (SEs) have attracted significant attention due to their competitive ionic conductivity and good electrochemical stability. Among typical halide SEs (chlorides, bromides, and iodides), substantial efforts have been dedicated to chlorides or bromides, with iodide SEs receiving less attention. Nevertheless, compared with chlorides or bromides, iodides have both a softer Li sublattice and lower reduction limit, which enable iodides to possess potentially high ionic conductivity and intrinsic anti-reduction stability, respectively. Herein, we report a new series of iodide SEs: LixYI3+x (x=2, 3, 4, or 9). Through synchrotron X-ray/neutron diffraction characterizations and theoretical calculations, we revealed that the LixYI3+x SEs belong to the high-symmetry cubic structure, and can accommodate abundant vacancies. By manipulating the defects in the iodide structure, balanced Li-ion concentration and generated vacancies enables an optimized ionic conductivity of 1.04 × 10−3 S cm−1 at 25 °C for Li4YI7. Additionally, the promising Li-metal compatibility of Li4YI7 is demonstrated via electrochemical characterizations (particularly all-solid-state Li-S batteries) combined with interface molecular dynamics simulations. Our study on iodide SEs provides deep insights into the relation between high-symmetry halide structures and ionic conduction, which can inspire future efforts to revitalize halide SEs.

KW - cubic crystal structures

KW - iodides

KW - ionic conductivity

KW - reduction stability

KW - solid electrolytes

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