From NaZn4Sb3 to HT-Na1–xZn4–ySb3 : Panoramic Hydride Synthesis, Structural Diversity, and Thermoelectric Properties

Gvozdetskyi, Volodymyr; Owens-Baird, Bryan; Hong, Sangki; Cox, Tori; Bhaskar, Gourab; Harmer, Colin; Sun, Yang; Zhang, Feng; Wang, Cai-Zhuang; Ho, Kai-Ming; Zaikina, Julia V.

doi:10.1021/acs.chemmater.9b02239

Title: From NaZn₄Sb₃ to HT-Na_1–xZn_4–ySb₃ : Panoramic Hydride Synthesis, Structural Diversity, and Thermoelectric Properties

Journal Article · 02 October 2019 · Chemistry of Materials

DOI: https://doi.org/10.1021/acs.chemmater.9b02239 · OSTI ID:1572381

Gvozdetskyi, Volodymyr ^[1];

^[2]; Hong, Sangki ^[1]; Cox, Tori ^[1]; Bhaskar, Gourab ^[1]; Harmer, Colin ^[2];

^[3]; Zhang, Feng ^[3];

^[4]; Ho, Kai-Ming ^[4];

^[1]

Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
Iowa State Univ., Ames, IA (United States). Dept. of Chemistry; Ames Lab., Ames, IA (United States)
Ames Lab., Ames, IA (United States)
Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States). Dept of Physics & Astronomy,

Two new sodium zinc antimonides NaZn₄Sb₃ and $HT$-Na_1-xZn_4-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 crystalizes in the hexagonal $$P$$6₃/$mmc$ 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 $HT$-Na_1-xZn_4-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. $HT$-Na_1-xZn_4-ySb₃ has a complex monoclinic structure with considerable degrees of structural disorder ($$P2_1/c$$ (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-Na_1-xZn_4-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 $$μ$$V/K) indicative of holes as the main charge carriers. However, resistivities of the two phases differ by two orders of magnitude.

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Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1572381

Report Number(s):: IS-J 10066

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 21 Vol. 31; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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CSD 1919785: Experimental Crystal Structure Determination Volodymyr, Gvozdetskyi,; Bryan, Owens-Baird,; Sangki, Hong, https://doi.org/10.25505/fiz.icsd.cc22fpks The current record is supplemented by this dataset	dataset	January 2019
CSD 1919786: Experimental Crystal Structure Determination Volodymyr, Gvozdetskyi,; Bryan, Owens-Baird,; Sangki, Hong, https://doi.org/10.25505/fiz.icsd.cc22fplt The current record is supplemented by this dataset	dataset	January 2019

Title: From NaZn4Sb3 to HT-Na1–xZn4–ySb3 : Panoramic Hydride Synthesis, Structural Diversity, and Thermoelectric Properties

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Title: From NaZn₄Sb₃ to HT-Na_1–xZn_4–ySb₃ : Panoramic Hydride Synthesis, Structural Diversity, and Thermoelectric Properties