Tunable Lithium-Ion Transport in Mixed-Halide Argyrodites Li6- xPS5- xClBrx: An Unusual Compositional Space

Sawankumar V. Patel; Swastika Banerjee; Haoyu Liu; Pengbo Wang; Po Hsiu Chien; Xuyong Feng; Jue Liu; Shyue Ping Ong; Yan Yan Hu

doi:10.1021/acs.chemmater.0c04650

Tunable Lithium-Ion Transport in Mixed-Halide Argyrodites Li_{6- x}PS_{5- x}ClBr_x: An Unusual Compositional Space

Sawankumar V. Patel, Swastika Banerjee, Haoyu Liu, Pengbo Wang, Po Hsiu Chien, Xuyong Feng, Jue Liu, Shyue Ping Ong, Yan Yan Hu

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Abstract

Argyrodites, with fast lithium-ion conduction, are promising for applications in rechargeable solid-state lithium-ion batteries. We report a new compositional space of argyrodite superionic conductors, Li6-xPS5-xClBrx [0 ≤ x ≤ 0.8], with a remarkably high ionic conductivity of 24 mS/cm at 25 °C for Li5.3PS4.3ClBr0.7. In addition, the extremely low lithium migration barrier of 0.155 eV makes Li5.3PS4.3ClBr0.7 highly promising for low-temperature operation. Average and local structure analyses reveal that bromination (x > 0) leads to (i) retention of the parent Li6PS5Cl structure for a wide range of x in Li6-xPS5-xClBrx (0 ≤ x ≤ 0.7), (ii) co-occupancy of Cl-, Br-, and S2- at 4a/4d sites, and (iii) gradually increased Li+-ion dynamics, eventually yielding a "liquid-like"Li-sublattice with a flattened energy landscape when x approaches 0.7. In addition, the diversity of anion species and Li-deficiency in halogen-rich Li6-xPS5-xClBrx induce hypercoordination and coordination entropy for the Li-sublattice, also leading to enhanced Li+-ion transport in Li6-xPS5-xClBrx. This study demonstrates that mixed-anion framework can help stabilize highly conductive structures in a compositional space otherwise unstable with lower anion diversity.

Original language	English
Pages (from-to)	1435-1443
Number of pages	9
Journal	Chemistry of Materials
Volume	33
Issue number	4
DOIs	https://doi.org/10.1021/acs.chemmater.0c04650
State	Published - Feb 23 2021

Funding

The authors acknowledge the support from the National Science Foundation under grant no. DMR-1847038. The collaboration was facilitated by the Scialog Award #26319 from Research Corporation for Science Advancement. All solid-state NMR experiments were performed at the National High Magnetic Field Laboratory. The National High Magnetic Field Laboratory is supported by National Science Foundation through NSF/DMR-1644779 and the State of Florida. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The computational studies were supported by the UCI MRSEC program, Prime Sponsor (NSF) award number DMR-2011967. Computing resources were performed using the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the National Science Foundation grant ACI-1053575. Software development and data resources were provided by the Materials Project, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under contract no. DE-AC02-05-CH11231: Materials Project program KC23MP.

Funders	Funder number
State of Florida
UCI MRSEC	DMR-2011967, ACI-1053575
National Science Foundation	NSF/DMR-1644779, DMR-1847038, 1847038
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Division of Materials Sciences and Engineering	DE-AC02-05-CH11231

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10.1021/acs.chemmater.0c04650

Cite this

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title = "Tunable Lithium-Ion Transport in Mixed-Halide Argyrodites Li6- xPS5- xClBrx: An Unusual Compositional Space",

abstract = "Argyrodites, with fast lithium-ion conduction, are promising for applications in rechargeable solid-state lithium-ion batteries. We report a new compositional space of argyrodite superionic conductors, Li6-xPS5-xClBrx [0 ≤ x ≤ 0.8], with a remarkably high ionic conductivity of 24 mS/cm at 25 °C for Li5.3PS4.3ClBr0.7. In addition, the extremely low lithium migration barrier of 0.155 eV makes Li5.3PS4.3ClBr0.7 highly promising for low-temperature operation. Average and local structure analyses reveal that bromination (x > 0) leads to (i) retention of the parent Li6PS5Cl structure for a wide range of x in Li6-xPS5-xClBrx (0 ≤ x ≤ 0.7), (ii) co-occupancy of Cl-, Br-, and S2- at 4a/4d sites, and (iii) gradually increased Li+-ion dynamics, eventually yielding a {"}liquid-like{"}Li-sublattice with a flattened energy landscape when x approaches 0.7. In addition, the diversity of anion species and Li-deficiency in halogen-rich Li6-xPS5-xClBrx induce hypercoordination and coordination entropy for the Li-sublattice, also leading to enhanced Li+-ion transport in Li6-xPS5-xClBrx. This study demonstrates that mixed-anion framework can help stabilize highly conductive structures in a compositional space otherwise unstable with lower anion diversity.",

author = "Patel, {Sawankumar V.} and Swastika Banerjee and Haoyu Liu and Pengbo Wang and Chien, {Po Hsiu} and Xuyong Feng and Jue Liu and Ong, {Shyue Ping} and Hu, {Yan Yan}",

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T1 - Tunable Lithium-Ion Transport in Mixed-Halide Argyrodites Li6- xPS5- xClBrx

T2 - An Unusual Compositional Space

AU - Patel, Sawankumar V.

AU - Banerjee, Swastika

AU - Liu, Haoyu

AU - Wang, Pengbo

AU - Chien, Po Hsiu

AU - Feng, Xuyong

AU - Liu, Jue

AU - Ong, Shyue Ping

AU - Hu, Yan Yan

PY - 2021/2/23

Y1 - 2021/2/23

N2 - Argyrodites, with fast lithium-ion conduction, are promising for applications in rechargeable solid-state lithium-ion batteries. We report a new compositional space of argyrodite superionic conductors, Li6-xPS5-xClBrx [0 ≤ x ≤ 0.8], with a remarkably high ionic conductivity of 24 mS/cm at 25 °C for Li5.3PS4.3ClBr0.7. In addition, the extremely low lithium migration barrier of 0.155 eV makes Li5.3PS4.3ClBr0.7 highly promising for low-temperature operation. Average and local structure analyses reveal that bromination (x > 0) leads to (i) retention of the parent Li6PS5Cl structure for a wide range of x in Li6-xPS5-xClBrx (0 ≤ x ≤ 0.7), (ii) co-occupancy of Cl-, Br-, and S2- at 4a/4d sites, and (iii) gradually increased Li+-ion dynamics, eventually yielding a "liquid-like"Li-sublattice with a flattened energy landscape when x approaches 0.7. In addition, the diversity of anion species and Li-deficiency in halogen-rich Li6-xPS5-xClBrx induce hypercoordination and coordination entropy for the Li-sublattice, also leading to enhanced Li+-ion transport in Li6-xPS5-xClBrx. This study demonstrates that mixed-anion framework can help stabilize highly conductive structures in a compositional space otherwise unstable with lower anion diversity.

AB - Argyrodites, with fast lithium-ion conduction, are promising for applications in rechargeable solid-state lithium-ion batteries. We report a new compositional space of argyrodite superionic conductors, Li6-xPS5-xClBrx [0 ≤ x ≤ 0.8], with a remarkably high ionic conductivity of 24 mS/cm at 25 °C for Li5.3PS4.3ClBr0.7. In addition, the extremely low lithium migration barrier of 0.155 eV makes Li5.3PS4.3ClBr0.7 highly promising for low-temperature operation. Average and local structure analyses reveal that bromination (x > 0) leads to (i) retention of the parent Li6PS5Cl structure for a wide range of x in Li6-xPS5-xClBrx (0 ≤ x ≤ 0.7), (ii) co-occupancy of Cl-, Br-, and S2- at 4a/4d sites, and (iii) gradually increased Li+-ion dynamics, eventually yielding a "liquid-like"Li-sublattice with a flattened energy landscape when x approaches 0.7. In addition, the diversity of anion species and Li-deficiency in halogen-rich Li6-xPS5-xClBrx induce hypercoordination and coordination entropy for the Li-sublattice, also leading to enhanced Li+-ion transport in Li6-xPS5-xClBrx. This study demonstrates that mixed-anion framework can help stabilize highly conductive structures in a compositional space otherwise unstable with lower anion diversity.

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