Synthesis, structure, and transport properties of Ba8Cu16 – xAuxP30 clathrate solid solution

Wang, Jian; Voyles, Jackson; Grzybowski, Scott; Kovnir, Kirill

doi:10.1063/1.5134080

Title: Synthesis, structure, and transport properties of Ba₈Cu_{16 – x}Au_xP₃₀ clathrate solid solution

Abstract

In this work, a new clathrate solid solution Ba₈Cu_{16 –}_xAu_xP₃₀ (x = 4, 8, 12) was synthesized by a high-temperature solid-state annealing method. The crystal structures of Ba₈Cu_{16 –}_xAu_xP₃₀ were determined by single crystal x-ray diffraction. This clathrate solid solution crystallizes in the orthorhombic superstructure of clathrate-I type with 23 crystallographically independent framework sites, eight of them are occupied by Au/Cu and 15 are exclusively occupied by P atoms. The distribution of Au and Cu atoms over these eight framework sites is not random with a clear preference for Au to occupy the largest (Au/Cu)P₄ tetrahedra in the framework. The thermal stability and thermoelectric properties of the Ba₈Cu_{16 –}_xAu_xP₃₀ solid solution were evaluated. Low thermal conductivity was achieved for Ba₈Cu_{16 –}_xAu_xP₃₀ due to the combination of the host–guest crystal structure with rattling Ba atoms with the presence of heavy Au atoms and substitutional Cu/Au disorder in the clathrate framework.

Authors:

^[1]; Voyles, Jackson ^[2]; Grzybowski, Scott ^[2];

^[1]

Iowa State Univ., Ames, IA (United States); Ames Lab., Ames, IA (United States)
Iowa State Univ., Ames, IA (United States)

Publication Date:: 2020-02-03

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

OSTI Identifier:: 1599456

Alternate Identifier(s):: OSTI ID: 1596889

Grant/Contract Number:: SC0008931; AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Applied Physics

Additional Journal Information:: Journal Volume: 127; Journal Issue: 5; Journal ID: ISSN 0021-8979

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: ENGLISH

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    Wang, Jian, Voyles, Jackson, Grzybowski, Scott, and Kovnir, Kirill. Synthesis, structure, and transport properties of Ba8Cu16 – xAuxP30 clathrate solid solution.  United States: N. p., 2020. 
Web.  doi:10.1063/1.5134080.

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                    Wang, Jian, Voyles, Jackson, Grzybowski, Scott, & Kovnir, Kirill. Synthesis, structure, and transport properties of Ba8Cu16 – xAuxP30 clathrate solid solution.  United States.  https://doi.org/10.1063/1.5134080

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                    Wang, Jian, Voyles, Jackson, Grzybowski, Scott, and Kovnir, Kirill. Mon .  
"Synthesis, structure, and transport properties of Ba8Cu16 – xAuxP30 clathrate solid solution".  United States.  https://doi.org/10.1063/1.5134080.  https://www.osti.gov/servlets/purl/1599456.

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@article{osti_1599456,

  title        = {Synthesis, structure, and transport properties of Ba8Cu16 – xAuxP30 clathrate solid solution},

  author       = {Wang, Jian and Voyles, Jackson and Grzybowski, Scott and Kovnir, Kirill},

  abstractNote = {In this work, a new clathrate solid solution Ba8Cu16 – xAuxP30 (x = 4, 8, 12) was synthesized by a high-temperature solid-state annealing method. The crystal structures of Ba8Cu16 – xAuxP30 were determined by single crystal x-ray diffraction. This clathrate solid solution crystallizes in the orthorhombic superstructure of clathrate-I type with 23 crystallographically independent framework sites, eight of them are occupied by Au/Cu and 15 are exclusively occupied by P atoms. The distribution of Au and Cu atoms over these eight framework sites is not random with a clear preference for Au to occupy the largest (Au/Cu)P4 tetrahedra in the framework. The thermal stability and thermoelectric properties of the Ba8Cu16 – xAuxP30 solid solution were evaluated. Low thermal conductivity was achieved for Ba8Cu16 – xAuxP30 due to the combination of the host–guest crystal structure with rattling Ba atoms with the presence of heavy Au atoms and substitutional Cu/Au disorder in the clathrate framework.},

  doi          = {10.1063/1.5134080},

  journal      = {Journal of Applied Physics},

  number       = 5,

  volume       = 127,

  place        = {United States},

  year         = {2020},

  month        = {2}

}

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Cooling, Heating, Generating Power, and Recovering Waste Heat with Thermoelectric Systems journal, September 2008

Intrinsically Minimal Thermal Conductivity in Cubic I−V−VI2 Semiconductors journal, July 2008

Strained endotaxial nanostructures with high thermoelectric figure of merit journal, January 2011

Intricate Short-Range Ordering and Strongly Anisotropic Transport Properties of Li 1– x Sn 2+ x As 2 journal, March 2015

Thermoelectrics Run Hot and Cold journal, May 1996

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

Clathrate thermoelectrics journal, October 2016

High Thermoelectric Figure of Merit and Nanostructuring in Bulk p-type Na1−xPbmSbyTem+2 journal, June 2006

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

Geometric tuning of thermal conductivity in three-dimensional anisotropic phononic crystals journal, January 2016

Phonon-glass electron-crystal thermoelectric clathrates: Experiments and theory journal, June 2014

Guest–Framework Interaction in Type I Inorganic Clathrates with Promising Thermoelectric Properties: On the Ionic versus Neutral Nature of the Alkaline-Earth Metal Guest A in A8Ga16Ge30 (A=Sr, Ba) journal, September 2003

Thermal Barrier Coatings for Gas-Turbine Engine Applications journal, April 2002

Thermoelectric enhancement in PbTe with K, Na co-doping from tuning the interaction of the light and heavy hole valence bands text, January 2010

Phonon-glass electron-crystal thermoelectric clathrates: Experiments and theory text, January 2014

Title: Synthesis, structure, and transport properties of Ba₈Cu_{16 – x}Au_xP₃₀ clathrate solid solution

Elusive β-Zn ₈ Sb ₇ : A New Zinc Antimonide Thermoelectric
journal, September 2015

Chemical trends of the rattling phonon modes in alloyed germanium clathrates
journal, June 2000

Twisted Kelvin Cells and Truncated Octahedral Cages in the Crystal Structures of Unconventional Clathrates, AM ₂ P ₄ (A = Sr, Ba; M = Cu, Ni)
journal, June 2015

Guest—Framework Interaction in Type I Inorganic Clathrates with Promising Thermoelectric Properties: On the Ionic versus Neutral Nature of the Alkaline-Earth Metal Guest A in A8Ga16Ge30 (A: Sr, Ba)
journal, December 2003

High Thermoelectric Figure of Merit and Nanostructuring in Bulk p-type Na1−xPbmSbyTem+2
journal, June 2006

Complex thermoelectric materials
journal, February 2008

Thermoelectric properties of a clathrate compound Ba8Cu16P30
journal, April 2003

High-efficiency thermoelectric Ba ₈ Cu ₁₄ Ge ₆ P ₂₆ : bridging the gap between tetrel-based and tetrel-free clathrates
journal, January 2017

Convergence of electronic bands for high performance bulk thermoelectrics
journal, May 2011

Enhancement of Thermoelectric Efficiency in PbTe by Distortion of the Electronic Density of States
journal, July 2008

Ultra-low thermal conductivity of two-dimensional phononic crystals in the incoherent regime
journal, April 2018

Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba ₈ M ₂₄ P _{28+ δ} ( M =Cu/Zn)
journal, January 2017

High Thermoelectric Performance in PbTe Due to Large Nanoscale Ag2Te Precipitates and La Doping
journal, November 2010

A practical field guide to thermoelectrics: Fundamentals, synthesis, and characterization
journal, June 2018

Ba8Cu16P30 - eine neue tern�re Variante des Clathrat I-Strukturtyps
journal, February 1995

Thermoelectric Cooling and Power Generation
journal, July 1999

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

Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals
journal, April 2014

Ag9TlTe5: A high-performance thermoelectric bulk material with extremely low thermal conductivity
journal, August 2005

Better thermoelectrics through glass-like crystals
journal, November 2015

Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba ₈ M ₂₄ P _{28+ δ} ( M =Cu/Zn)
journal, January 2017

Thermoelectric enhancement in PbTe with K or Na codoping from tuning the interaction of the light- and heavy-hole valence bands
journal, September 2010

Neutron Diffraction Study of the Type I Clathrate Ba ₈ Al _x Si _{46– x} : Site Occupancies, Cage Volumes, and the Interaction between the Guest and the Host Framework
journal, December 2011

Inhomogeneity and anisotropy of chemical bonding and thermoelectric properties of materials
journal, June 2019

A short history of SHELX
journal, December 2007

Unconventional Clathrates with Transition Metal–Phosphorus Frameworks
journal, December 2017

Controlling superstructural ordering in the clathrate-I Ba ₈ M ₁₆ P ₃₀ (M = Cu, Zn) through the formation of metal–metal bonds
journal, January 2017

Spinodal Decomposition and Nucleation and Growth as a Means to Bulk Nanostructured Thermoelectrics: Enhanced Performance in Pb _1- _x Sn _x Te−PbS
journal, August 2007

The Smaller the Better: Hosting Trivalent Rare-Earth Guests in Cu–P Clathrate Cages
journal, June 2018

Introducing a Magnetic Guest to a Tetrel-Free Clathrate: Synthesis, Structure, and Properties of Eu _x Ba _{8– x} Cu ₁₆ P ₃₀ (0 ≤ x ≤ 1.5)
journal, October 2011

Chemical Bonding and Transport Properties in Clathrates-I with Cu–Zn–P Frameworks
journal, April 2018

Ca _{1– x} RE _x Ag _{1– y} Sb (RE = La, Ce, Pr, Nd, Sm; 0 ≤ x ≤1; 0 ≤ y ≤1): Interesting Structural Transformation and Enhanced High-Temperature Thermoelectric Performance
journal, July 2013

Theoretical chemistry of gold. III
journal, January 2008

Cooling, Heating, Generating Power, and Recovering Waste Heat with Thermoelectric Systems
journal, September 2008

Intrinsically Minimal Thermal Conductivity in Cubic $I − V − {VI}_{2}$ Semiconductors
journal, July 2008

Strained endotaxial nanostructures with high thermoelectric figure of merit
journal, January 2011

Intricate Short-Range Ordering and Strongly Anisotropic Transport Properties of Li _{1– x} Sn _{2+ x} As ₂
journal, March 2015

Thermoelectrics Run Hot and Cold
journal, May 1996

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

Clathrate thermoelectrics
journal, October 2016

High Thermoelectric Figure of Merit and Nanostructuring in Bulk p-type Na_1−xPb_mSb_yTe_m+2
journal, June 2006

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

Geometric tuning of thermal conductivity in three-dimensional anisotropic phononic crystals
journal, January 2016

Phonon-glass electron-crystal thermoelectric clathrates: Experiments and theory
journal, June 2014

Guest–Framework Interaction in Type I Inorganic Clathrates with Promising Thermoelectric Properties: On the Ionic versus Neutral Nature of the Alkaline-Earth Metal Guest A in A8Ga16Ge30 (A=Sr, Ba)
journal, September 2003

Thermal Barrier Coatings for Gas-Turbine Engine Applications
journal, April 2002

Thermoelectric enhancement in PbTe with K, Na co-doping from tuning the interaction of the light and heavy hole valence bands
text, January 2010

Phonon-glass electron-crystal thermoelectric clathrates: Experiments and theory
text, January 2014