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

Title: Heat capacity of Mg3Sb2, Mg3Bi2, and their alloys at high temperature

Abstract

The thermoelectric figure of merit reported for n-type Mg3(Sb,Bi)2 compounds has made these materials of great engineering significance, increasing the need for accurate evaluations of their thermal conductivity. Thermal conductivity is typically derived from measurements of thermal diffusivity and determination of the specific heat capacity. The uncertainty in this method (often 10% or more) is frequently attributed to measurement of heat capacity such that estimated values are often more accurate. Inconsistencies between reported thermal conductivity of Mg3(Sb,Bi)2 compounds may be attributed to the different values of heat capacity measured or used to calculate thermal conductivity. The high anharmonicity of these materials can lead to significant deviations at high temperatures from the Dulong-Petit heat capacity, which is often a reasonable substitute for measurements at high temperatures. Herein, a physics-based model is used to assess the magnitude of the heat capacity over the entire temperature range up to 800 K. The model agrees in magnitude with experimental low-temperature values and reproduces the linear slope observed in high-temperature data. Owing to the large scatter in experimental values of high-temperature heat capacity, the model is likely more accurate (within ±3%) than a measurement of a new sample even for doped or alloyed materials. Itmore » is found that heat capacity for the solid solution series can be simply described (for temperatures: 200K≤T≤800K ) by the polynomial equation: cp[Jg–1K–1]=3NR/MW(1 + 1.3 × 10–4 T – 4 × 103 T–2), where 3NR = 124.71 J mol–1K–1, MW is the molecular weight [gmol–1] of the formula unit being considered, and T is temperature in K. This heat capacity is recommended to be a standard value for reporting and comparing the thermal conductivity of Mg3(Sb,Bi)2 including doped or alloyed derivatives. Furthermore, a general form of the equation is given which can be used for other material systems« less

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [2];  [2];  [3];  [4];  [4];  [5];  [1]
+ Show Author Affiliations
  1. Northwestern Univ., Evanston, IL (United States)
  2. Jet Propulsion Lab./California Inst. of Technology (CalTech), Pasadena, CA (United States)
  3. Michigan State Univ., East Lansing, MI (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1489260
Alternate Identifier(s):
OSTI ID: 1637232
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Materials Today Physics
Additional Journal Information:
Journal Volume: 6; Journal Issue: C; Journal ID: ISSN 2542-5293
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Heat capacity; Mg3Bi2; Mg3Sb2; Thermal conductivity; Thermoelectric

Citation Formats

Agne, Matthias T., Imasato, Kazuki, Anand, Shashwat, Lee, Kathleen, Bux, Sabah K., Zevalkink, Alex, Rettie, Alexander J. E., Chung, Duck Young, Kanatzidis, Mercouri G., and Snyder, G. Jeffrey. Heat capacity of Mg3Sb2, Mg3Bi2, and their alloys at high temperature. United States: N. p., 2018. Web. doi:10.1016/j.mtphys.2018.10.001.
Copy to clipboard
Agne, Matthias T., Imasato, Kazuki, Anand, Shashwat, Lee, Kathleen, Bux, Sabah K., Zevalkink, Alex, Rettie, Alexander J. E., Chung, Duck Young, Kanatzidis, Mercouri G., & Snyder, G. Jeffrey. Heat capacity of Mg3Sb2, Mg3Bi2, and their alloys at high temperature. United States. https://doi.org/10.1016/j.mtphys.2018.10.001
Copy to clipboard
Agne, Matthias T., Imasato, Kazuki, Anand, Shashwat, Lee, Kathleen, Bux, Sabah K., Zevalkink, Alex, Rettie, Alexander J. E., Chung, Duck Young, Kanatzidis, Mercouri G., and Snyder, G. Jeffrey. 2018. "Heat capacity of Mg3Sb2, Mg3Bi2, and their alloys at high temperature". United States. https://doi.org/10.1016/j.mtphys.2018.10.001. https://www.osti.gov/servlets/purl/1489260.
Copy to clipboard
@article{osti_1489260,
title = {Heat capacity of Mg3Sb2, Mg3Bi2, and their alloys at high temperature},
author = {Agne, Matthias T. and Imasato, Kazuki and Anand, Shashwat and Lee, Kathleen and Bux, Sabah K. and Zevalkink, Alex and Rettie, Alexander J. E. and Chung, Duck Young and Kanatzidis, Mercouri G. and Snyder, G. Jeffrey},
abstractNote = {The thermoelectric figure of merit reported for n-type Mg3(Sb,Bi)2 compounds has made these materials of great engineering significance, increasing the need for accurate evaluations of their thermal conductivity. Thermal conductivity is typically derived from measurements of thermal diffusivity and determination of the specific heat capacity. The uncertainty in this method (often 10% or more) is frequently attributed to measurement of heat capacity such that estimated values are often more accurate. Inconsistencies between reported thermal conductivity of Mg3(Sb,Bi)2 compounds may be attributed to the different values of heat capacity measured or used to calculate thermal conductivity. The high anharmonicity of these materials can lead to significant deviations at high temperatures from the Dulong-Petit heat capacity, which is often a reasonable substitute for measurements at high temperatures. Herein, a physics-based model is used to assess the magnitude of the heat capacity over the entire temperature range up to 800 K. The model agrees in magnitude with experimental low-temperature values and reproduces the linear slope observed in high-temperature data. Owing to the large scatter in experimental values of high-temperature heat capacity, the model is likely more accurate (within ±3%) than a measurement of a new sample even for doped or alloyed materials. It is found that heat capacity for the solid solution series can be simply described (for temperatures: 200K≤T≤800K ) by the polynomial equation: cp[Jg–1K–1]=3NR/MW(1 + 1.3 × 10–4 T – 4 × 103 T–2), where 3NR = 124.71 J mol–1K–1, MW is the molecular weight [gmol–1] of the formula unit being considered, and T is temperature in K. This heat capacity is recommended to be a standard value for reporting and comparing the thermal conductivity of Mg3(Sb,Bi)2 including doped or alloyed derivatives. Furthermore, a general form of the equation is given which can be used for other material systems},
doi = {10.1016/j.mtphys.2018.10.001},
url = {https://www.osti.gov/biblio/1489260}, journal = {Materials Today Physics},
issn = {2542-5293},
number = C,
volume = 6,
place = {United States},
year = {Sat Nov 03 00:00:00 EDT 2018},
month = {Sat Nov 03 00:00:00 EDT 2018}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1016/j.mtphys.2018.10.001
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 55 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:

Isotropic Conduction Network and Defect Chemistry in Mg 3+ δ Sb 2 -Based Layered Zintl Compounds with High Thermoelectric Performance
journal, September 2016

Recent progress and future challenges on thermoelectric Zintl materials
journal, June 2017

Phase Boundary Mapping to Obtain n-type Mg3Sb2-Based Thermoelectrics
journal, January 2018

Discovery of high-performance low-cost n-type Mg3Sb2-based thermoelectric materials with multi-valley conduction bands
journal, January 2017

An Unlikely Route to Low Lattice Thermal Conductivity: Small Atoms in a Simple Layered Structure
journal, September 2018

Enhancement of average thermoelectric figure of merit by increasing the grain-size of Mg 3.2 Sb 1.5 Bi 0.49 Te 0.01
journal, January 2018

Grain boundary dominated charge transport in Mg 3 Sb 2 -based compounds
journal, January 2018

Tuning the carrier scattering mechanism to effectively improve the thermoelectric properties
journal, January 2017

Improving the thermoelectric performance in Mg 3+ x Sb 1.5 Bi 0.49 Te 0.01 by reducing excess Mg
journal, January 2018

Anomalous electrical conductivity of n-type Te-doped Mg3.2Sb1.5Bi0.5
journal, December 2017

Defect Engineering for Realizing High Thermoelectric Performance in n-Type Mg 3 Sb 2 -Based Materials
journal, September 2017

Crystal chemistry and thermoelectric transport of layered AM 2 X 2 compounds
journal, January 2018

Thermoelectric properties of Na-doped Zintl compound: Mg3−Na Sb2
journal, July 2015

Measuring thermoelectric transport properties of materials
journal, January 2015

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

High thermoelectric figure of merit in heavy hole dominated PbTe
journal, January 2011

A simplified method for calculating the debye temperature from elastic constants
journal, July 1963

Density Functional Theory of Electronic Structure
journal, January 1996

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Generalized Gradient Approximation Made Simple
journal, October 1996

First principles phonon calculations in materials science
journal, November 2015

Solving the Christoffel equation: Phase and group velocities
journal, October 2016

Observation of valence band crossing: the thermoelectric properties of CaZn 2 Sb 2 –CaMg 2 Sb 2 solid solution
journal, January 2018

AN EQUATION FOR THE REPRESENTATION OF HIGH-TEMPERATURE HEAT CONTENT DATA 1
journal, August 1932

Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
journal, July 2013

Enhanced thermoelectric performance of p-type Mg3Sb2 by lithium doping and its tunability in an anionic framework
journal, August 2018

    Sort options
    [ × clear filter / sort ]

    Works referencing / citing this record:

    The manipulation of substitutional defects for realizing high thermoelectric performance in Mg 3 Sb 2 -based Zintl compounds
    journal, January 2019

    Improvement of Low‐Temperature zT in a Mg 3 Sb 2 –Mg 3 Bi 2 Solid Solution via Mg‐Vapor Annealing
    journal, July 2019

    Phase Transformation Contributions to Heat Capacity and Impact on Thermal Diffusivity, Thermal Conductivity, and Thermoelectric Performance
    journal, July 2019

    Extraordinary n‐Type Mg 3 SbBi Thermoelectrics Enabled by Yttrium Doping
    journal, June 2019

    Enhanced Thermoelectric Performance in N‐Type Mg 3.2 Sb 1.5 Bi 0.5 by La or Ce Doping into Mg
    journal, January 2020

    Improved stability and high thermoelectric performance through cation site doping in n-type La-doped Mg 3 Sb 1.5 Bi 0.5
    journal, January 2018

      Sort options
      [ × clear filter / sort ]

      Similar records in OSTI.GOV collections: