Unexpected High-Temperature Stability of β-Zn<sub>4</sub>Sb<sub>3</sub> Opens the Door to Enhanced Thermoelectric Performance

Lin, Jianping; Li, Xudong; Qiao, Guanjun; Wang, Zhao; Carrete, Jesús; Ren, Yang; Ma, Lingzhi; Fei, Youjian; Yang, Baishun; Lei, Lei; Li, Ju

doi:10.1021/ja410605f

Cited by 118 publications

(77 citation statements)

References 38 publications

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“…It should be noted that the formation of a nanostructured secondary phase during heating in the β-Zn4Sb3 alloys has been previously suggested due to the decomposition [21][22][23][24][25][26]38] . However, our in-situ TEM observation and structural analysis revealed that there is no decomposition process occurring over the whole investigated temperature region from 300 K to 718 K. On the other hand, by looking closer to the secondary phase shown in magnified BF TEM images in Fig.…”

Section: Discussionmentioning

confidence: 99%

In Operando Study of High‐Performance Thermoelectric Materials for Power Generation: A Case Study of β‐Zn₄sb₃

Hưng

Ngo

Han

et al. 2017

Adv Elect Materials

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To date, many high-performance thermoelectric (TE) materials for power generation have been studied and reported. However, so far they have not been implemented in reliable commercial devices. To bring current achievements into a device for power generation, a full understanding the dynamic behavior of thermoelectric materials under operating conditions is needed. In this work, an in operando study is conducted on the high-performance TE material β-Zn4Sb3 under large temperature gradient and thermal cycling by a new approach using in-situ transmission electron microscopy combined with characterization of the TE properties. We found that after 30 thermal cycles in a low-pressure helium atmosphere the TE performance of β-Zn4Sb3 is maintained with the zT value of 1.4 at 718 K. Nevertheless, under a temperature gradient of 380 K (Thot = 673 K and Tcold = 293 K) operating for only 30 hours, zinc whiskers gradually precipitate on the cold side of the β-Zn4Sb3 leg. The dynamical evolution of Zn in the matrix of β-Zn4Sb3 was found to be the source that leads to a high zT value by lowering of the thermal conductivity and electrical resistivity, but it is also the failure mechanism for the leg under these conditions. The in operando study brings deep insight into the dynamic behavior of Advanced Electronic Materials 2 nanostructured TE materials for tailoring future TE materials and devices with higher efficiency and longer durability.

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Section: Discussionmentioning

confidence: 99%

In Operando Study of High‐Performance Thermoelectric Materials for Power Generation: A Case Study of β‐Zn₄sb₃

Hưng

Ngo

Han

et al. 2017

Adv Elect Materials

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“…[29][30][31][32][33][34][35] A computationally derived convex hull of formation enthalpies for various binary zinc antimonides predicts ZnSb to have the most negative formation enthalpy. 36 Low-temperature, soft chemistry techniques may provide a reproducible means to observe and isolate many of these compounds.…”

Section: Introductionmentioning

confidence: 99%

Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides

et al. 2018

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Soft chemistry methods offer the possibility of synthesizing metastable and kinetic products that are unobtainable through thermodynamically-controlled, high-temperature reactions. A recent solution-phase exploration of Li-Zn-Sb phase space revealed a previously unknown cubic half-Heusler MgAgAs-type LiZnSb polytype. Interestingly, this new cubic phase was calculated to be the most thermodynamically stable, despite prior literature reporting only two other ternary phases (the hexagonal half-Heusler LiGaGe-type LiZnSb, and the full-Heusler Li2ZnSb). This surprising discovery, coupled with the intriguing optoelectronic and transport properties of many antimony containing Zintl phases, required a thorough exploration of syn-thetic parameters. Here, we systematically study the effects that different precursor concentrations, injection order, nucleation and growth temperatures, and reaction time have on the solution-phase synthesis of these materials. By doing so, we identify conditions that selectively yield several unique ternary (c-LiZnSb vs. h*-LiZnSb), binary (ZnSb vs. Zn8Sb7), and metallic (Zn, Sb) products. Further, we find one of the ternary phases adopts a variant of the previously observed hexagonal LiZnSb struc-ture. Our results demonstrate the utility of low temperature solution phase-soft synthesis-methods in accessing and mining a rich phase space. We anticipate that this work will motivate further exploration of multinary I-II-V compounds, as well as encourage similarly thorough investigations of related Zintl systems by solution phase methods. Disciplines Materials ChemistryComments "This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in Chemistry of Materials, copyright © American Chemical Society after peer review. To access the final edited and published work see http://dx.doi.org/10.1021/acs.chemmater.8b02910. ABSTRACT: Soft chemistry methods offer the possibility of synthesizing metastable and kinetic products that are unobtainable through thermodynamically-controlled, high-temperature reactions. A recent solution-phase exploration of Li-Zn-Sb phase space revealed a previously unknown cubic half-Heusler MgAgAs-type LiZnSb polytype. Interestingly, this new cubic phase was calculated to be the most thermodynamically stable, despite prior literature reporting only two other ternary phases (the hexagonal half-Heusler LiGaGe-type LiZnSb, and the full-Heusler Li2ZnSb). This surprising discovery, coupled with the intriguing optoelectronic and transport properties of many antimony containing Zintl phases, required a thorough exploration of synthetic parameters. Here, we systematically study the effects that different precursor concentrations, injection order, nucleation and growth temperatures, and reaction time have on the solution-phase synthesis of these materials. By doing so, we identify conditions that selectively yield several unique ternary (c-LiZnSb vs. h*-LiZnSb), binary (ZnSb vs. Zn8Sb7), and metallic (Zn, Sb) products. Furt...

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“…However, the discovery of Cd 13-x In y Zn 10 (x ≈ 2.7, y ≈ 1.5), which crystallizes in a disorder-free variant of the β-Zn 4 Sb 3 structure and shows a comparable low thermal conductivity, casted doubts into the significance of structural disorder to low thermal conductivity [10]. Recently, peculiarities in the dynamic behavior -notably Einstein rattling of dumbbell units build from Sb atoms [11] and/or loosely bonded Zn atoms as evidenced from the superionic behavior of β-Zn 4 Sb 3 [12,13] have been put forward as possible reasons. It is not clear if these aspects would also apply to ZnSb.…”

Section: Introductionmentioning

confidence: 99%

Thermal and vibrational properties of thermoelectric ZnSb: Exploring the origin of low thermal conductivity

et al. 2015

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The intermetallic compound ZnSb is an interesting thermoelectric material, largely due to its low lattice thermal conductivity. The origin of the low thermal conductivity has so far been speculative. Using multi-temperature single crystal X-ray diffraction (9 -400 K) and powder X-ray diffraction (300 -725 K) measurements we characterized the volume expansion and the evolution of structural properties with temperature and identify an increasingly anharmonic behavior of the Zn atoms. From a combination of Raman spectroscopy and first principles calculations of phonons we consolidate the presence of low-energy optic modes with wavenumbers below 60 cm -1 . Heat capacity measurements between 2 and 400 K can be well described by a Debye-Einstein model containing one Debye and two Einstein contributions with temperatures Θ D = 195K, Θ E1 = 78 K and Θ E2 = 277 K as well as a significant contribution due to anharmonicity above 150 K. The presence of a multitude of weakly dispersed low-energy optical modes (which couple with the acoustic, heat carrying phonons) combined with anharmonic thermal behavior provides an effective mechanism for low lattice thermal conductivity. The peculiar vibrational properties of ZnSb are attributed to its chemical bonding properties which are characterized by multicenter bonded structural entities. We argue that the proposed mechanism to explain the low lattice thermal conductivity of ZnSb might also control the thermoelectric properties of other electron poor semiconductors, such as Zn 4 Sb 3 , CdSb, Cd 4 Sb 3 , Cd 13-x In y Zn 10 , and Zn 5 Sb 4 In 2-δ .2

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Unexpected High-Temperature Stability of β-Zn₄Sb₃ Opens the Door to Enhanced Thermoelectric Performance

Cited by 118 publications

References 38 publications

In Operando Study of High‐Performance Thermoelectric Materials for Power Generation: A Case Study of β‐Zn₄sb₃

In Operando Study of High‐Performance Thermoelectric Materials for Power Generation: A Case Study of β‐Zn₄sb₃

Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides

Thermal and vibrational properties of thermoelectric ZnSb: Exploring the origin of low thermal conductivity

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Unexpected High-Temperature Stability of β-Zn4Sb3 Opens the Door to Enhanced Thermoelectric Performance

Cited by 118 publications

References 38 publications

In Operando Study of High‐Performance Thermoelectric Materials for Power Generation: A Case Study of β‐Zn4sb3

In Operando Study of High‐Performance Thermoelectric Materials for Power Generation: A Case Study of β‐Zn4sb3

Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides

Thermal and vibrational properties of thermoelectric ZnSb: Exploring the origin of low thermal conductivity

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Unexpected High-Temperature Stability of β-Zn₄Sb₃ Opens the Door to Enhanced Thermoelectric Performance

In Operando Study of High‐Performance Thermoelectric Materials for Power Generation: A Case Study of β‐Zn₄sb₃

In Operando Study of High‐Performance Thermoelectric Materials for Power Generation: A Case Study of β‐Zn₄sb₃