Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Intricate Short-Range Ordering and Strongly Anisotropic Transport Properties of Li1–x Sn 2+x As2

Abstract

A new ternary compound, Li1-xSn2+xAs2, 0.2 < x < 0.4, was synthesized via solid-state reaction of elements. The compound crystallizes in a layered structure in the R$$\overline{3}m$$ space group (No. 166) with Sn-As layers separated by layers of jointly occupied Li/Sn. The Sn-As layers are comprised of Sn3As3 puckered hexagons in a chair conformation that share all edges. Li/Sn atoms in the interlayer space are surrounded by a regular As6 octahedron. Thorough investigations by synchrotron x-ray and neutron powder diffraction indicate no long-range Li/Sn ordering. In contrast, local Sn/Li ordering was revealed by synergistic investigations via solid-state 6,7Li NMR spectroscopy, HR-TEM, and neutron and X-ray pair distribution function analyses. Due to their different chemical natures, Li and Sn atoms tend to segregate into Li-rich and Sn-rich regions creating substantial inhomogeneity on the nanoscale. Inhomogeneous local structure has high impact on the physical properties of the synthesized compounds: local Li/Sn ordering and multiple nanoscale interfaces result in unexpectedly low thermal conductivity and highly anisotropic resistivity in Li1-xSn2+xAs2.

Authors:
 [1];  [2];  [2];  [3];  [3];  [4];  [4];  [5];  [5];  [6];  [1]
+ Show Author Affiliations
  1. Univ. of California, Davis, CA (United States). Dept. of Chemistry
  2. Univ. of California, Davis, CA (United States). Dept. of of Chemical Engineering and Materials Science
  3. Florida State Univ., Tallahassee, FL (United States). Center of Interdisciplinary Magnetic Resonance, National High Magnetic Field Lab. (MagLab)
  4. Univ. of Munster, Munster (Germany). Inst. of Inorganic and Analytical Chemistry
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division
  6. Univ. of Caen, Caen (France). CRISMAT Lab.
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1334418
Grant/Contract Number:  
AC05-00OR22725; SC0008931; AC02-06CH11357; DMR-0084173
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 137; Journal Issue: 10; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Lee, Kathleen, Kaseman, Derrick, Sen, Sabyasachi, Hung, Ivan, Gan, Zhehong, Gerke, Birgit, Pöttgen, Rainer, Feygenson, Mikhail, Neuefeind, Jörg, Lebedev, Oleg I., and Kovnir, Kirill. Intricate Short-Range Ordering and Strongly Anisotropic Transport Properties of Li1–x Sn 2+x As2. United States: N. p., 2015. Web. doi:10.1021/jacs.5b00237.
Copy to clipboard
Lee, Kathleen, Kaseman, Derrick, Sen, Sabyasachi, Hung, Ivan, Gan, Zhehong, Gerke, Birgit, Pöttgen, Rainer, Feygenson, Mikhail, Neuefeind, Jörg, Lebedev, Oleg I., & Kovnir, Kirill. Intricate Short-Range Ordering and Strongly Anisotropic Transport Properties of Li1–x Sn 2+x As2. United States. https://doi.org/10.1021/jacs.5b00237
Copy to clipboard
Lee, Kathleen, Kaseman, Derrick, Sen, Sabyasachi, Hung, Ivan, Gan, Zhehong, Gerke, Birgit, Pöttgen, Rainer, Feygenson, Mikhail, Neuefeind, Jörg, Lebedev, Oleg I., and Kovnir, Kirill. Sun . "Intricate Short-Range Ordering and Strongly Anisotropic Transport Properties of Li1–x Sn 2+x As2". United States. https://doi.org/10.1021/jacs.5b00237. https://www.osti.gov/servlets/purl/1334418.
Copy to clipboard
@article{osti_1334418,
title = {Intricate Short-Range Ordering and Strongly Anisotropic Transport Properties of Li1–x Sn 2+x As2},
author = {Lee, Kathleen and Kaseman, Derrick and Sen, Sabyasachi and Hung, Ivan and Gan, Zhehong and Gerke, Birgit and Pöttgen, Rainer and Feygenson, Mikhail and Neuefeind, Jörg and Lebedev, Oleg I. and Kovnir, Kirill},
abstractNote = {A new ternary compound, Li1-xSn2+xAs2, 0.2 < x < 0.4, was synthesized via solid-state reaction of elements. The compound crystallizes in a layered structure in the R$\overline{3}m$ space group (No. 166) with Sn-As layers separated by layers of jointly occupied Li/Sn. The Sn-As layers are comprised of Sn3As3 puckered hexagons in a chair conformation that share all edges. Li/Sn atoms in the interlayer space are surrounded by a regular As6 octahedron. Thorough investigations by synchrotron x-ray and neutron powder diffraction indicate no long-range Li/Sn ordering. In contrast, local Sn/Li ordering was revealed by synergistic investigations via solid-state 6,7Li NMR spectroscopy, HR-TEM, and neutron and X-ray pair distribution function analyses. Due to their different chemical natures, Li and Sn atoms tend to segregate into Li-rich and Sn-rich regions creating substantial inhomogeneity on the nanoscale. Inhomogeneous local structure has high impact on the physical properties of the synthesized compounds: local Li/Sn ordering and multiple nanoscale interfaces result in unexpectedly low thermal conductivity and highly anisotropic resistivity in Li1-xSn2+xAs2.},
doi = {10.1021/jacs.5b00237},
journal = {Journal of the American Chemical Society},
number = 10,
volume = 137,
place = {United States},
year = {Sun Feb 22 00:00:00 EST 2015},
month = {Sun Feb 22 00:00:00 EST 2015}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/jacs.5b00237
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 31 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

A lithium superionic conductor
journal, July 2011

  • Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro
  • Nature Materials, Vol. 10, Issue 9, p. 682-686
  • DOI: 10.1038/nmat3066

The Li-Ion Rechargeable Battery: A Perspective
journal, January 2013

  • Goodenough, John B.; Park, Kyu-Sung
  • Journal of the American Chemical Society, Vol. 135, Issue 4
  • DOI: 10.1021/ja3091438

First Principles Study of the Li10GeP2S12 Lithium Super Ionic Conductor Material
journal, December 2011

  • Mo, Yifei; Ong, Shyue Ping; Ceder, Gerbrand
  • Chemistry of Materials, Vol. 24, Issue 1, p. 15-17
  • DOI: 10.1021/cm203303y

Pair Distribution Function Analysis and Solid State NMR Studies of Silicon Electrodes for Lithium Ion Batteries: Understanding the (De)lithiation Mechanisms
journal, January 2011

  • Key, Baris; Morcrette, Mathieu; Tarascon, Jean-Marie
  • Journal of the American Chemical Society, Vol. 133, Issue 3
  • DOI: 10.1021/ja108085d

Revision of the Li–Si Phase Diagram: Discovery and Single-Crystal X-ray Structure Determination of the High-Temperature Phase Li 4.11 Si
journal, November 2013

  • Zeilinger, Michael; Kurylyshyn, Iryna M.; Häussermann, Ulrich
  • Chemistry of Materials, Vol. 25, Issue 22
  • DOI: 10.1021/cm4029885

In Situ Three-Dimensional Synchrotron X-Ray Nanotomography of the (De)lithiation Processes in Tin Anodes
journal, March 2014

  • Wang, Jiajun; Chen-Wiegart, Yu-chen Karen; Wang, Jun
  • Angewandte Chemie International Edition, Vol. 53, Issue 17
  • DOI: 10.1002/anie.201310402

A systematic solid state NMR spectroscopic study of the equiatomic lithium half-Heusler phases LiTX (T = Mg, Zn, Cd; X = P, As, Sb, Bi)
journal, December 2014

Lithium-Transition Metal-Tetrelides – Structure and Lithium Mobility
journal, November 2010

  • Pöttgen, Rainer; Dinges, Tim; Eckert, Hellmut
  • Zeitschrift für Physikalische Chemie, Vol. 224, Issue 10-12
  • DOI: 10.1524/zpch.2010.0011

A Promising Thermoelectric Material:  Zn 4 Sb 3 or Zn 6 - δ Sb 5 . Its Composition, Structure, Stability, and Polymorphs. Structure and Stability of Zn 1 - δ Sb
journal, April 2004

  • Mozharivskyj, Yurij; Pecharsky, Alexandra O.; Bud'ko, Sergey
  • Chemistry of Materials, Vol. 16, Issue 8
  • DOI: 10.1021/cm035274a

The Structure of α-Zn 4 Sb 3 :  Ordering of the Phonon-Glass Thermoelectric Material β-Zn 4 Sb 3
journal, December 2004

  • Nylén, Johanna; Andersson, Magnus; Lidin, Sven
  • Journal of the American Chemical Society, Vol. 126, Issue 50
  • DOI: 10.1021/ja044980p

Disordered zinc in Zn4Sb3 with phonon-glass and electron-crystal thermoelectric properties
journal, June 2004

  • Snyder, G. Jeffrey; Christensen, Mogens; Nishibori, Eiji
  • Nature Materials, Vol. 3, Issue 7
  • DOI: 10.1038/nmat1154

Fulfilling thermoelectric promises: β-Zn4Sb3 from materials research to power generation
journal, January 2010

  • Iversen, Bo Brummerstedt
  • Journal of Materials Chemistry, Vol. 20, Issue 48
  • DOI: 10.1039/c0jm02000a

Clathrate Ba 8 Au 16 P 30 : The “Gold Standard” for Lattice Thermal Conductivity
journal, August 2013

  • Fulmer, James; Lebedev, Oleg I.; Roddatis, Vladimir V.
  • Journal of the American Chemical Society, Vol. 135, Issue 33
  • DOI: 10.1021/ja4052679

LiPbSb 3 S 6 : A Semiconducting Sulfosalt with Very Low Thermal Conductivity
journal, December 2013

  • Agha, Eva C.; Malliakas, Christos D.; Im, Jino
  • Inorganic Chemistry, Vol. 53, Issue 2
  • DOI: 10.1021/ic402262z

Arsenidostannate mit Arsen-analogen [SnAs]-Schichten: Darstellung und Struktur von Na[Sn2As2], Na0,3Ca0,7[Sn2As2], Na0,6Sr0,6[Sn2As2], Na0,6Ba0,4[Sn2As2] und K0,3Sr0,7[Sn2As2]
journal, April 1995

  • Asbrand, M.; Eisenmann, B.; Klein, J.
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 621, Issue 4
  • DOI: 10.1002/zaac.19956210415

Puckered hexagonal nets in and
journal, April 1987

Sn4As3 revisited: Solvothermal synthesis and crystal and electronic structure
journal, March 2009

  • Kovnir, Kirill; Kolen’ko, Yury V.; Baranov, Alexey I.
  • Journal of Solid State Chemistry, Vol. 182, Issue 3
  • DOI: 10.1016/j.jssc.2008.12.007

Response of Superconductivity and Crystal Structure of LiFeAs to Hydrostatic Pressure
journal, February 2009

  • Mito, Masaki; Pitcher, Michael J.; Crichton, Wilson
  • Journal of the American Chemical Society, Vol. 131, Issue 8
  • DOI: 10.1021/ja808914a

Tern�re Phosphide und Arsenide des Lithiums mit Eisen, Kobalt oder Chrom im Cu2Sb-Typ
journal, August 1968

  • Juza, R.; Langer, K.
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 361, Issue 1-2
  • DOI: 10.1002/zaac.19683610107

�ber tern�re Phasen im System Lithium-Kupfer-Arsen
journal, December 1969

  • v. Benda, K.; Juza, R.
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 371, Issue 3-4
  • DOI: 10.1002/zaac.19693710308

Notizen: Single-Crystal Structure Refinement of LiZnAs
journal, May 1993

arachno-[Sn8]6− orcloso-[Li2Sn8]4−? Synthesis and Characterization of A4Li2Sn8 (A=Rb, K)
journal, March 2001

Synthesis, characterization and bonding of Ba3Li4Sn8
journal, May 2002

Structure and Lithium Dynamics of Li2AuSn2—A Ternary Stannide with Condensed AuSn4/2 Tetrahedra
journal, March 2004

  • Wu, Zhiyun; Mosel, Bernd D.; Eckert, Hellmut
  • Chemistry - A European Journal, Vol. 10, Issue 6
  • DOI: 10.1002/chem.200305479

The stannides LiAuSn and LiAu3Sn4: synthesis, structure and chemical bonding
journal, February 2002

  • Hoffmann, Rolf-Dieter; Johrendt, Dirk; Wu, Zhiyun
  • Journal of Materials Chemistry, Vol. 12, Issue 3
  • DOI: 10.1039/b109381a

Ternary Stannides Li T Sn 4 ( T = Ru, Rh, Ir)Chemical Bonding and Physical Properties
journal, February 2003

  • Wu, Zhiyun; Eckert, Hellmut; Senker, Jürgen
  • The Journal of Physical Chemistry B, Vol. 107, Issue 9
  • DOI: 10.1021/jp0220635

Structure and Bonding of Li 1.42(5) Pd 2 Sn 5.58(5) :  A Lithium Intercalated Palladium Stannide
journal, January 2005

  • Sreeraj, Puravankara; Hoffmann, Rolf-Dieter; Wu, Zhiyun
  • Chemistry of Materials, Vol. 17, Issue 4
  • DOI: 10.1021/cm0401995

Ternary lithium stannides LixT3Sn7−x (T=Rh, Ir)
journal, November 2005

  • Sreeraj, Puravankara; Kurowski, Daniel; Hoffmann, Rolf-Dieter
  • Journal of Solid State Chemistry, Vol. 178, Issue 11
  • DOI: 10.1016/j.jssc.2005.08.021

Zintl-Phasen mit Schichtanionen: Darstellung und Kristallstrukturen der isotypen Verbindungen SrSn2As2 und Sr0,87Ba0,13Sn2As2 sowie eine Einkristallstrukturbestimmung von KSnSb
journal, June 1991

  • Eisenmann, Brigitte; Klein, J�rgen
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 598, Issue 1
  • DOI: 10.1002/zaac.19915980109

Interpretation of the 119 Sn Mössbauer isomer shifts in complex tin chalcogenides
journal, August 1999

Mössbauer spectra as a “fingerprint” in tin–lithium compounds: Applications to Li-ion batteries
journal, January 2007

  • Robert, F.; Lippens, P. E.; Olivier-Fourcade, J.
  • Journal of Solid State Chemistry, Vol. 180, Issue 1
  • DOI: 10.1016/j.jssc.2006.10.026

Stannides and Intermetallic Tin Compounds – Fundamentals and Applications
journal, June 2006

7 Li NMR Knight Shifts in Li−Sn Compounds: MAS NMR Measurements and Correlation with DFT Calculations
journal, March 2010

  • Bekaert, Emilie; Robert, Florent; Lippens, Pierre Emmanuel
  • The Journal of Physical Chemistry C, Vol. 114, Issue 14
  • DOI: 10.1021/jp100365u

6 Li NMR Studies of Cation Disorder and Transition Metal Ordering in Li[Ni 1/3 Mn 1/3 Co 1/3 ]O 2 Using Ultrafast Magic Angle Spinning
journal, November 2005

  • Cahill, L. S.; Yin, S. -C.; Samoson, A.
  • Chemistry of Materials, Vol. 17, Issue 26
  • DOI: 10.1021/cm0508773

Spatial distribution of lithium ions in glasses studied by 7Li{6Li} spin echo double resonance
journal, January 2007

  • Peter Puls, Stefan; Eckert, Hellmut
  • Physical Chemistry Chemical Physics, Vol. 9, Issue 30
  • DOI: 10.1039/b705338j

Contribution to the system tin-arsenic
journal, March 1969

Nanoscale Ordering in Oxygen Deficient Quintuple Perovskite Sm 2-ε Ba 3+ε Fe 5 O 15-δ : Implication for Magnetism and Oxygen Stoichiometry
journal, October 2014

  • Volkova, Nadezhda E.; Lebedev, Oleg I.; Gavrilova, Ludmila Ya.
  • Chemistry of Materials, Vol. 26, Issue 21
  • DOI: 10.1021/cm503276p

Electrochemical Study and Material Characterization of x SiO · (1- x )Sn 30 Co 30 C 40 Composite Anode Material for Lithium-Ion Batteries
journal, January 2013

  • Liu, Bo; Abouimrane, Ali; Ren, Yang
  • Journal of The Electrochemical Society, Vol. 160, Issue 6
  • DOI: 10.1149/2.100306jes

Atomic pair distribution functions analysis of disordered low-Z materials
journal, January 2013

  • Petkov, V.; Ren, Y.; Kabekkodu, S.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 22
  • DOI: 10.1039/c2cp43378h

SnAs with the NaCl-type Structure: Type-I Superconductivity and Single Valence State of Sn
journal, December 2014

  • Wang, Yue; Sato, Hikaru; Toda, Yoshitake
  • Chemistry of Materials, Vol. 26, Issue 24
  • DOI: 10.1021/cm503992d

Bond-valence parameters for solids
journal, April 1991

  • Brese, N. E.; O'Keeffe, M.
  • Acta Crystallographica Section B Structural Science, Vol. 47, Issue 2
  • DOI: 10.1107/S0108768190011041

Roles of cations, electronegativity difference, and anionic interlayer interactions in the metallic versus nonmetallic character of Zintl phases related to arsenic
journal, October 2008

  • Alemany, Pere; Llunell, Miquel; Canadell, Enric
  • Journal of Computational Chemistry, Vol. 29, Issue 13
  • DOI: 10.1002/jcc.20989

Probing the Lower Limit of Lattice Thermal Conductivity in an Ordered Extended Solid: Gd 117 Co 56 Sn 112 , a Phonon Glass–Electron Crystal System
journal, March 2012

  • Schmitt, Devin C.; Haldolaarachchige, Neel; Xiong, Yimin
  • Journal of the American Chemical Society, Vol. 134, Issue 13
  • DOI: 10.1021/ja300240g

Phonon engineering through crystal chemistry
journal, January 2011

  • Toberer, Eric S.; Zevalkink, Alex; Snyder, G. Jeffrey
  • Journal of Materials Chemistry, Vol. 21, Issue 40
  • DOI: 10.1039/c1jm11754h

Reduction of thermal conductivity of bulk nanostructured bismuth telluride composites embedded with silicon nano-inclusions
journal, January 2014

  • Satyala, Nikhil; Tahmasbi Rad, Armin; Zamanipour, Zahra
  • Journal of Applied Physics, Vol. 115, Issue 4
  • DOI: 10.1063/1.4861727

Thermal conductivity of bulk nanostructured lead telluride
journal, January 2014

  • Hori, Takuma; Chen, Gang; Shiomi, Junichiro
  • Applied Physics Letters, Vol. 104, Issue 2
  • DOI: 10.1063/1.4862323

Large Enhancements in the Thermoelectric Power Factor of Bulk PbTe at High Temperature by Synergistic Nanostructuring
journal, October 2008

  • Sootsman, Joseph R.; Kong, Huijun; Uher, Ctirad
  • Angewandte Chemie International Edition, Vol. 47, Issue 45, p. 8618-8622
  • DOI: 10.1002/anie.200803934

High-performance bulk thermoelectrics with all-scale hierarchical architectures
journal, September 2012

  • Biswas, Kanishka; He, Jiaqing; Blum, Ivan D.
  • Nature, Vol. 489, Issue 7416, p. 414-418
  • DOI: 10.1038/nature11439

Nanostructures versus Solid Solutions:  Low Lattice Thermal Conductivity and Enhanced Thermoelectric Figure of Merit in Pb 9.6 Sb 0.2 Te 10 - x Se x Bulk Materials
journal, November 2006

  • Poudeu, Pierre F. P.; D'Angelo, Jonathan; Kong, Huijun
  • Journal of the American Chemical Society, Vol. 128, Issue 44
  • DOI: 10.1021/ja0647811
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Synthesis, structure, and transport properties of Ba 8 Cu 16 –  x Au x P 30 clathrate solid solution
    journal, February 2020

    • Wang, Jian; Voyles, Jackson; Grzybowski, Scott
    • Journal of Applied Physics, Vol. 127, Issue 5
    • DOI: 10.1063/1.5134080

    Chemical and Electrochemical Lithiation of van der Waals Tetrel‐Arsenides
    journal, April 2019

    • Mark, Justin; Hanrahan, Michael P.; Woo, Katherine E.
    • Chemistry – A European Journal, Vol. 25, Issue 25
    • DOI: 10.1002/chem.201900339

    Crystal and Electronic Structure and Optical Properties of AE 2 SiP 4 ( AE = Sr, Eu, Ba) and Ba 4 Si 3 P 8 : Crystal and Electronic Structure and Optical Properties of
    journal, November 2018

    • Mark, Justin; Dolyniuk, Juli-Anna; Tran, Nhon
    • Zeitschrift für anorganische und allgemeine Chemie, Vol. 645, Issue 3
    • DOI: 10.1002/zaac.201800430

    Temperature dependent local atomic displacements in NaSn 2 As 2 system
    journal, July 2019

    • Pugliese, G. M.; Stramaglia, F.; Goto, Y.
    • Journal of Physics: Condensed Matter, Vol. 31, Issue 42
    • DOI: 10.1088/1361-648x/ab2bd4
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: