High pressure-high temperature synthesis of lithium-rich Li3O(Cl, Br) and Li3 - XCax/2OCl anti-perovskite halides

Jianzhong Zhang; Jiantao Han; Jinlong Zhu; Zhijun Lin; Maria H. Braga; Luke L. Daemen; Liping Wang; Yusheng Zhao

doi:10.1016/j.inoche.2014.08.036

High pressure-high temperature synthesis of lithium-rich Li₃O(Cl, Br) and Li_{3 - X}Ca_x/2OCl anti-perovskite halides

Jianzhong Zhang, Jiantao Han, Jinlong Zhu, Zhijun Lin, Maria H. Braga, Luke L. Daemen, Liping Wang, Yusheng Zhao

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

32 Scopus citations

Abstract

In this work, we investigated the systems of (Li, Ca)-O-(Cl, Br) under high pressure and temperature for the synthesis of lithium-rich anti-perovskite (LiRAP) halides. We successfully synthesized Li_{3 - x}Ca_x/2OCl anti-perovskite with x = 0.0, 0.1, 0.2 near 0.5 GPa and temperatures of 400-425 K and Li₃OBr anti-perovskite at 3.0 GPa and 450 K. Different from the synthetic route previously reported at ambient pressure, LiA + 2LiOH → Li₃OA + H₂O, the LiRAP halides under high P-T conditions are formed by dehydration of end-member and Ca-doped halide hydrates with a general formula of Li_{2x + 1}A(OH)_2y, where A can be Cl or Br and x must be equal to y. This proposed formula predicts several new halide hydrates including Li₃Cl(OH)₂, Li₅Cl(OH)₄, Li₃Br(OH)₂, and Li₅Br(OH)₄, indicating that halide hydrates are structurally flexible to accommodate a range of lithium and hydroxide occupancies in the puckered layers of [Li_{2x + 1}(OH)_2y⁺].

Original language	English
Pages (from-to)	140-143
Number of pages	4
Journal	Inorganic Chemistry Communications
Volume	48
DOIs	https://doi.org/10.1016/j.inoche.2014.08.036
State	Published - Oct 2014
Externally published	Yes

Funding

This research is supported by the Laboratory-Directed Research and Development program of Los Alamos National Laboratory, which is operated by Los Alamos National Security LLC under DOE Contract DE-AC52-06NA25396. The use of the National Synchrotron Light Source (NSLS), Brookhaven National Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences , under contract no. DE-AC02-98CH10886 . The use of the X17B2 beamline at NSLS was supported by COMPRES, the Consortium for Materials Properties Research in Earth Sciences under NSF Cooperative Agreement EAR 01–35554 . This research was also sponsored in part by the National Nuclear Security Administration under the Stewardship Science Academic Alliances program through DOE Cooperative Agreement # DE-NA0001982 .

Funders	Funder number
COMPRES
Laboratory-Directed Research and Development
Office of Basic Energy Sciences
National Science Foundation	EAR 01–35554
U.S. Department of Energy	DE-AC52-06NA25396
Office of Science
National Nuclear Security Administration	DE-NA0001982
Brookhaven National Laboratory
Los Alamos National Laboratory

Keywords

High-pressure/high-temperature synthesis
Lithium hydrate halides
Lithium-rich anti-perovskite

Access to Document

10.1016/j.inoche.2014.08.036

Cite this

@article{aa91ff0fd81e4892b09c0630f09621be,

title = "High pressure-high temperature synthesis of lithium-rich Li3O(Cl, Br) and Li3 - XCax/2OCl anti-perovskite halides",

abstract = "In this work, we investigated the systems of (Li, Ca)-O-(Cl, Br) under high pressure and temperature for the synthesis of lithium-rich anti-perovskite (LiRAP) halides. We successfully synthesized Li3 - xCax/2OCl anti-perovskite with x = 0.0, 0.1, 0.2 near 0.5 GPa and temperatures of 400-425 K and Li3OBr anti-perovskite at 3.0 GPa and 450 K. Different from the synthetic route previously reported at ambient pressure, LiA + 2LiOH → Li3OA + H2O, the LiRAP halides under high P-T conditions are formed by dehydration of end-member and Ca-doped halide hydrates with a general formula of Li2x + 1A(OH)2y, where A can be Cl or Br and x must be equal to y. This proposed formula predicts several new halide hydrates including Li3Cl(OH)2, Li5Cl(OH)4, Li3Br(OH)2, and Li5Br(OH)4, indicating that halide hydrates are structurally flexible to accommodate a range of lithium and hydroxide occupancies in the puckered layers of [Li2x + 1(OH)2y+].",

keywords = "High-pressure/high-temperature synthesis, Lithium hydrate halides, Lithium-rich anti-perovskite",

author = "Jianzhong Zhang and Jiantao Han and Jinlong Zhu and Zhijun Lin and Braga, {Maria H.} and Daemen, {Luke L.} and Liping Wang and Yusheng Zhao",

year = "2014",

month = oct,

doi = "10.1016/j.inoche.2014.08.036",

language = "English",

volume = "48",

pages = "140--143",

journal = "Inorganic Chemistry Communications",

issn = "1387-7003",

publisher = "Elsevier",

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TY - JOUR

T1 - High pressure-high temperature synthesis of lithium-rich Li3O(Cl, Br) and Li3 - XCax/2OCl anti-perovskite halides

AU - Zhang, Jianzhong

AU - Han, Jiantao

AU - Zhu, Jinlong

AU - Lin, Zhijun

AU - Braga, Maria H.

AU - Daemen, Luke L.

AU - Wang, Liping

AU - Zhao, Yusheng

PY - 2014/10

Y1 - 2014/10

N2 - In this work, we investigated the systems of (Li, Ca)-O-(Cl, Br) under high pressure and temperature for the synthesis of lithium-rich anti-perovskite (LiRAP) halides. We successfully synthesized Li3 - xCax/2OCl anti-perovskite with x = 0.0, 0.1, 0.2 near 0.5 GPa and temperatures of 400-425 K and Li3OBr anti-perovskite at 3.0 GPa and 450 K. Different from the synthetic route previously reported at ambient pressure, LiA + 2LiOH → Li3OA + H2O, the LiRAP halides under high P-T conditions are formed by dehydration of end-member and Ca-doped halide hydrates with a general formula of Li2x + 1A(OH)2y, where A can be Cl or Br and x must be equal to y. This proposed formula predicts several new halide hydrates including Li3Cl(OH)2, Li5Cl(OH)4, Li3Br(OH)2, and Li5Br(OH)4, indicating that halide hydrates are structurally flexible to accommodate a range of lithium and hydroxide occupancies in the puckered layers of [Li2x + 1(OH)2y+].

AB - In this work, we investigated the systems of (Li, Ca)-O-(Cl, Br) under high pressure and temperature for the synthesis of lithium-rich anti-perovskite (LiRAP) halides. We successfully synthesized Li3 - xCax/2OCl anti-perovskite with x = 0.0, 0.1, 0.2 near 0.5 GPa and temperatures of 400-425 K and Li3OBr anti-perovskite at 3.0 GPa and 450 K. Different from the synthetic route previously reported at ambient pressure, LiA + 2LiOH → Li3OA + H2O, the LiRAP halides under high P-T conditions are formed by dehydration of end-member and Ca-doped halide hydrates with a general formula of Li2x + 1A(OH)2y, where A can be Cl or Br and x must be equal to y. This proposed formula predicts several new halide hydrates including Li3Cl(OH)2, Li5Cl(OH)4, Li3Br(OH)2, and Li5Br(OH)4, indicating that halide hydrates are structurally flexible to accommodate a range of lithium and hydroxide occupancies in the puckered layers of [Li2x + 1(OH)2y+].

KW - High-pressure/high-temperature synthesis

KW - Lithium hydrate halides

KW - Lithium-rich anti-perovskite

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