skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Robust high pressure stability and negative thermal expansion in sodium-rich antiperovskites Na{sub 3}OBr and Na{sub 4}OI{sub 2}

Abstract

The structure stability under high pressure and thermal expansion behavior of Na{sub 3}OBr and Na{sub 4}OI{sub 2}, two prototypes of alkali-metal-rich antiperovskites, were investigated by in situ synchrotron X-ray diffraction techniques under high pressure and low temperature. Both are soft materials with bulk modulus of 58.6 GPa and 52.0 GPa for Na{sub 3}OBr and Na{sub 4}OI{sub 2}, respectively. The cubic Na{sub 3}OBr structure and tetragonal Na{sub 4}OI{sub 2} with intergrowth K{sub 2}NiF{sub 4} structure are stable under high pressure up to 23 GPa. Although being a characteristic layered structure, Na{sub 4}OI{sub 2} exhibits nearly isotropic compressibility. Negative thermal expansion was observed at low temperature range (20–80 K) in both transition-metal-free antiperovskites for the first time. The robust high pressure structure stability was examined and confirmed by first-principles calculations among various possible polymorphisms qualitatively. The results provide in-depth understanding of the negative thermal expansion and robust crystal structure stability of these antiperovskite systems and their potential applications.

Authors:
 [1];  [2];  [3];  [4]; ;  [5]; ;  [1];  [6];  [7]
  1. High Pressure Science and Engineering Center, University of Nevada, Las Vegas, Nevada 89154 (United States)
  2. (China)
  3. (HPSynC), Geophysical Laboratory, Carnegie Institution of Washington, Argonne, Illinois 60439 (United States)
  4. Institute of Nanostructured Functional Materials, Huanghe Science and Technology College, Zhengzhou, Henan 450006 (China)
  5. High Pressure Collaborative Access Team (HPCAT), Geophysical Laboratory, Carnegie Institution of Washington, Argonne, Illinois 60439 (United States)
  6. High Pressure Synergetic Consortium (HPSynC), Geophysical Laboratory, Carnegie Institution of Washington, Argonne, Illinois 60439 (United States)
  7. (HPSTAR), Shanghai 201203 (China)
Publication Date:
OSTI Identifier:
22494920
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Applied Physics; Journal Volume: 119; Journal Issue: 2; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; COMPRESSIBILITY; CRYSTAL STRUCTURE; MATERIALS; PRESSURE RANGE GIGA PA; SODIUM; STABILITY; TEMPERATURE RANGE 0065-0273 K; THERMAL EXPANSION; TRANSITION ELEMENTS; X-RAY DIFFRACTION

Citation Formats

Wang, Yonggang, E-mail: yyggwang@gmail.com, E-mail: yangwg@hpstar.ac.cn, E-mail: yusheng.zhao@unlv.edu, Institute of Nanostructured Functional Materials, Huanghe Science and Technology College, Zhengzhou, Henan 450006, High Pressure Synergetic Consortium, Wen, Ting, Park, Changyong, Kenney-Benson, Curtis, Pravica, Michael, Zhao, Yusheng, E-mail: yyggwang@gmail.com, E-mail: yangwg@hpstar.ac.cn, E-mail: yusheng.zhao@unlv.edu, Yang, Wenge, E-mail: yyggwang@gmail.com, E-mail: yangwg@hpstar.ac.cn, E-mail: yusheng.zhao@unlv.edu, and Center for High Pressure Science and Technology Advanced Research. Robust high pressure stability and negative thermal expansion in sodium-rich antiperovskites Na{sub 3}OBr and Na{sub 4}OI{sub 2}. United States: N. p., 2016. Web. doi:10.1063/1.4940020.
Wang, Yonggang, E-mail: yyggwang@gmail.com, E-mail: yangwg@hpstar.ac.cn, E-mail: yusheng.zhao@unlv.edu, Institute of Nanostructured Functional Materials, Huanghe Science and Technology College, Zhengzhou, Henan 450006, High Pressure Synergetic Consortium, Wen, Ting, Park, Changyong, Kenney-Benson, Curtis, Pravica, Michael, Zhao, Yusheng, E-mail: yyggwang@gmail.com, E-mail: yangwg@hpstar.ac.cn, E-mail: yusheng.zhao@unlv.edu, Yang, Wenge, E-mail: yyggwang@gmail.com, E-mail: yangwg@hpstar.ac.cn, E-mail: yusheng.zhao@unlv.edu, & Center for High Pressure Science and Technology Advanced Research. Robust high pressure stability and negative thermal expansion in sodium-rich antiperovskites Na{sub 3}OBr and Na{sub 4}OI{sub 2}. United States. doi:10.1063/1.4940020.
Wang, Yonggang, E-mail: yyggwang@gmail.com, E-mail: yangwg@hpstar.ac.cn, E-mail: yusheng.zhao@unlv.edu, Institute of Nanostructured Functional Materials, Huanghe Science and Technology College, Zhengzhou, Henan 450006, High Pressure Synergetic Consortium, Wen, Ting, Park, Changyong, Kenney-Benson, Curtis, Pravica, Michael, Zhao, Yusheng, E-mail: yyggwang@gmail.com, E-mail: yangwg@hpstar.ac.cn, E-mail: yusheng.zhao@unlv.edu, Yang, Wenge, E-mail: yyggwang@gmail.com, E-mail: yangwg@hpstar.ac.cn, E-mail: yusheng.zhao@unlv.edu, and Center for High Pressure Science and Technology Advanced Research. 2016. "Robust high pressure stability and negative thermal expansion in sodium-rich antiperovskites Na{sub 3}OBr and Na{sub 4}OI{sub 2}". United States. doi:10.1063/1.4940020.
@article{osti_22494920,
title = {Robust high pressure stability and negative thermal expansion in sodium-rich antiperovskites Na{sub 3}OBr and Na{sub 4}OI{sub 2}},
author = {Wang, Yonggang, E-mail: yyggwang@gmail.com, E-mail: yangwg@hpstar.ac.cn, E-mail: yusheng.zhao@unlv.edu and Institute of Nanostructured Functional Materials, Huanghe Science and Technology College, Zhengzhou, Henan 450006 and High Pressure Synergetic Consortium and Wen, Ting and Park, Changyong and Kenney-Benson, Curtis and Pravica, Michael and Zhao, Yusheng, E-mail: yyggwang@gmail.com, E-mail: yangwg@hpstar.ac.cn, E-mail: yusheng.zhao@unlv.edu and Yang, Wenge, E-mail: yyggwang@gmail.com, E-mail: yangwg@hpstar.ac.cn, E-mail: yusheng.zhao@unlv.edu and Center for High Pressure Science and Technology Advanced Research},
abstractNote = {The structure stability under high pressure and thermal expansion behavior of Na{sub 3}OBr and Na{sub 4}OI{sub 2}, two prototypes of alkali-metal-rich antiperovskites, were investigated by in situ synchrotron X-ray diffraction techniques under high pressure and low temperature. Both are soft materials with bulk modulus of 58.6 GPa and 52.0 GPa for Na{sub 3}OBr and Na{sub 4}OI{sub 2}, respectively. The cubic Na{sub 3}OBr structure and tetragonal Na{sub 4}OI{sub 2} with intergrowth K{sub 2}NiF{sub 4} structure are stable under high pressure up to 23 GPa. Although being a characteristic layered structure, Na{sub 4}OI{sub 2} exhibits nearly isotropic compressibility. Negative thermal expansion was observed at low temperature range (20–80 K) in both transition-metal-free antiperovskites for the first time. The robust high pressure structure stability was examined and confirmed by first-principles calculations among various possible polymorphisms qualitatively. The results provide in-depth understanding of the negative thermal expansion and robust crystal structure stability of these antiperovskite systems and their potential applications.},
doi = {10.1063/1.4940020},
journal = {Journal of Applied Physics},
number = 2,
volume = 119,
place = {United States},
year = 2016,
month = 1
}
  • The structure stability under high pressure and thermal expansion behavior of Na 3OBr and Na 4OI 2, two prototypes of alkali-metal-rich antiperovskites, were investigated by in situ synchrotron X-ray diffraction techniques under high pressure and low temp. Both are soft materials with bulk modulus of 58.6 GPa and 52.0 GPa for Na 3OBr and Na 4OI 2, resp. The cubic Na 3OBr structure and tetragonal Na 4OI 2 with intergrowth K 2NiF 4 structure are stable under high pressure up to 23 GPa. Although being a characteristic layered structure, Na 4OI 2 exhibits nearly isotropic compressibility. Neg. thermal expansion wasmore » obsd. at low temp. range (20-80 K) in both transition-metal-free antiperovskites for the first time. The robust high pressure structure stability was examined. and confirmed by first-principles calculations. among various possible polymorphisms qualitatively. The results provide in-depth understanding of the neg. thermal expansion and robust crystal structure stability of these antiperovskite systems and their potential applications.« less
  • High-performance solid electrolytes are critical for realizing all-solid-state batteries with enhance safety and cycling efficiency. However, currently available candidates (sulfides and the NASICON-typ ceramics) still suffer from drawbacks such as inflammability, high-cost and unfavorable machinability Here we present the structural manipulation approaches to improve the sodium ionic conductivity in series of affordable Na-rich antiperovskites. Experimentally, the whole solid solutions of Na 3OX (X ¼ Cl Br, I) are synthesized via a facile and timesaving route from the cheapest raw materials (Na, NaOH an NaX). The materials are nonflammable, suitable for thermoplastic processing due to low melting temperature (<300° C) withoutmore » decomposing. Notably, owing to the flexibility of perovskite-type structure it's feasible to control the local structure features by means of size-mismatch substitution an unequivalent-doping for a favorable sodium ionic diffusion pathway. Enhancement of sodium ioni conductivity by 2 magnitudes is demonstrated by these chemical tuning methods. The optimized sodiu ionic conductivity in Na 2.9Sr 0.05OBr 0.6I 0.4 bulk samples reaches 1.9 10 - 3 S/cm at 200° C and even highe at elevated temperature. Here, we believe further chemical tuning efforts on Na-rich antiperovskites wil promote their performance greatly for practical all-solid state battery applications.« less
  • CaZrF 6 has recently been shown to combine strong negative thermal expansion (NTE) over a very wide temperature range (at least 10–1000 K) with optical transparency from mid-IR into the UV range. Variable-temperature and high-pressure diffraction has been used to determine how the replacement of calcium by magnesium and zirconium by niobium(IV) modifies the phase behavior and physical properties of the compound. Similar to CaZrF 6, CaNbF 6 retains a cubic ReO 3-type structure down to 10 K and displays NTE up until at least 900 K. It undergoes a reconstructive phase transition upon compression to ~400 MPa at room temperature and pressure-induced amorphization above ~4 GPa. Prior to the first transition, it displays very strong pressure-induced softening. MgZrF 6 adopts a cubic ( Fmmore » $$\bar{3}$$m) structure at 300 K and undergoes a symmetry-lowering phase transition involving octahedral tilts at ~100 K. Immediately above this transition, it shows modest NTE. Its’ thermal expansion increases upon heating, crossing through zero at ~500 K. Unlike CaZrF 6 and CaNbF 6, it undergoes an octahedral tilting transition upon compression (~370 MPa) prior to a reconstructive transition at ~1 GPa. Cubic MgZrF 6 displays both pressure-induced softening and stiffening upon heating. MgNbF 6 is cubic ( Fm$$\bar{3}$$m) at room temperature, but it undergoes a symmetry-lowering octahedral tilting transition at ~280 K. It does not display NTE within the investigated temperature range (100–950 K). Furthermore the replacement of Zr(IV) by Nb(IV) leads to minor changes in phase behavior and properties, the replacement of the calcium by the smaller and more polarizing magnesium leads to large changes in both phase behavior and thermal expansion.« less
  • No abstract prepared.