Publication Date

10-3-2019

Department

Ames Laboratory; Chemistry; Physics and Astronomy

Campus Units

Ames Laboratory, Chemistry, Physics and Astronomy

OSTI ID+

1572381

Report Number

IS-J 10066

DOI

10.1021/acs.chemmater.9b02239

Journal Title

Chemistry of Materials

Volume Number

31

Issue Number

21

First Page

8695

Last Page

8707

Abstract

Two new sodium zinc antimonides NaZn4Sb3 and HT-Na1–xZn4–ySb3 were synthesized by using reactive sodium hydride, NaH, as a precursor. The hydride route provides uniform mixing and comprehensive control over the composition, facilitating fast reactions and high-purity samples, whereas traditional synthesis using sodium metal results in inhomogeneous samples with a significant fraction of the more stable NaZnSb compound. NaZn4Sb3 crystallizes in the hexagonal P63/mmc space group (No. 194, Z = 2, a = 4.43579(4) Å, c = 23.41553(9) Å) and is stable upon heating in vacuum up to 736 K. The layered crystal structure of NaZn4Sb3 is related to the structure of the well-studied thermoelectric antimonides AeZn2Sb2 (Ae = Ca, Sr, Eu). Upon heating in vacuum, NaZn4Sb3 transforms to HT-Na1–xZn4–ySb3 (x = 0.047(3), y = 0.135(1)) due to partial Na/Zn evaporation/elimination, as was determined from high-temperature in situ synchrotron powder X-ray diffraction. HT-Na1–xZn4–ySb3 has a complex monoclinic structure with considerable degrees of structural disorder (P21/c (No. 14), Z = 32, a = 19.5366(7) Å, b = 14.7410(5) Å, c = 20.7808(7) Å, β = 90.317(2)°) and is stable exclusively in a narrow temperature range of 736–885 K. Further heating of HT-Na1–xZn4–ySb3 leads to a reversible transformation to NaZnSb above 883 K. Both compounds exhibit similarly low thermal conductivity at room temperature (0.9 W m–1 K–1) and positive Seebeck coefficients (38–52 μV/K) indicative of holes as the main charge carriers. However, resistivities of the two phases differ by 2 orders of magnitude.

DOE Contract Number(s)

AC02-07CH11358

Language

en

Department of Energy Subject Categories

36 MATERIALS SCIENCE

Publisher

Iowa State University Digital Repository, Ames IA (United States)

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