The updated Zn–Sb phase diagram. How to make pure Zn13Sb10(“Zn4Sb3”).

Lo, Chun-Wan Timothy; Svitlyk, Volodymyr; Chernyshov, Dmitry; Mozharivskyj, Yurij

doi:10.1039/c8dt02521e

Cited by 25 publications

(13 citation statements)

References 30 publications

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“…Measurements on further samples showed insignificant variations of the composition that lie in the stability range of Zn 13−δ Sb 10 with δ = 0.22−0.38. 26 For the sake of simplicity, the composition of our samples is given as Zn ∼12.8 Sb 10 . SEM images of typical samples (Figure S4) do not show impurity phases.…”

Section: Resultsmentioning

confidence: 99%

“…11 Much work has been devoted to the determination of the exact composition of this phase and showed that the nonstoichiometric description Zn13-δSbx (δ = 0.28 -0.38) is more realistic than the classical formula Zn4Sb3. 19,20,21 At room temperature (RT), β-Zn13-δSb10 crystallizes in space group R 3c with two different atom positions for Sb -III and dumbbells with Sb -II as shown in Fig. S1 (S denotes Figures and Tables in the Supporting Information).…”

Section: Introductionmentioning

confidence: 99%

“…Zn 13−δ Sb 10 is another prominent representative of PLEC materials . Much work has been devoted to the determination of the exact composition of this phase, and these studies showed that the nonstoichiometric description Zn 13−δ Sb x (δ = 0.28–0.38) is more realistic than the classical formula Zn 4 Sb 3 . − At room temperature (RT), β-Zn 13−δ Sb 10 crystallizes in space group R c with two different atom positions for Sb –III and dumbbells with Sb –II as shown in Figure S1 (S denotes figures and tables in the Supporting Information). The Sb –III site forms hexagonal layers that are stacked in such a way that voids form channels in the crystal structure, which are filled with Sb –II dimers.…”

Section: Introductionmentioning

confidence: 99%

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Decomposition Phenomena of Zn_13−δSb₁₀ under Working Conditions of Thermoelectric Generators and Minimum Current Densities for Electromigration

Jakob

Grauer

Ziółkowski

2019

ACS Appl. Energy Mater.

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The mixed ionic-electronic conductor (MIEC) Zn13-δSb10 is a thermoelectric material with high performance at intermediate temperatures and contains only abundant elements. This work evaluates its suitability for thermoelectric applications with respect to thermal instability and decomposition by electromigration of Zn under current flow. In addtion to the formation of Zn whiskers, this migration often leads to cracks. Thermoelectric measurements of bulk Zn13-δSb10 (δ ~ 0.2) prepared by a slow cooling method show zT values of 0.7 at 200 °C. A series of tests under flowing currents with different voltages and current densities on bar-shaped samples was followed by the space-resolved investigation of their composition and its systematical correlation with the Seebeck coefficient. The latter increases upon Zn depletion, especially when ZnSb is formed. At RT, Zn migration starts a voltage of ~0.01 V, which is much lower than for other MIECs like copper chalcogenides. At higher electrical fields, which may be enhanced by the Seebeck voltage, the amount of deposited Zn at the negative pole increases with the current density even if the transported charge is kept constant.ASSOCIATED CONTENT Supporting Information. The supporting information is available free of charge; it contains: illustration of the crystal structure of Zn13-δSb10, photograph of experimental setup, details of selected tests under current flow, details of Rietveld refinements, electron microscopy images, results of thermoelectric meassurements, Zn-concentration profiles of samples after testing under current flow and different thermal gradients, estimated masses of deposited Zn.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Decomposition Phenomena of Zn_13−δSb₁₀ under Working Conditions of Thermoelectric Generators and Minimum Current Densities for Electromigration

Jakob

Grauer

Ziółkowski

2019

ACS Appl. Energy Mater.

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“…[1,26] Despite all the efforts, [113][114][115][116][117][118] the thermal stability of Zn 4 Sb 3 is still the main concern for practical applications. Lo et al [119] provide a comprehensive study regarding the phase relationship and phase transformation for the binary Zn-Sb system. The phase boundary mapping and phase diagram engineering illustrate the relationship between TE performance and phase stability for the doped Zn 4 Sb 3 .…”

Section: Zn 4 Sb 3 -Based Alloysmentioning

confidence: 99%

Eliciting High‐Performance Thermoelectric Materials via Phase Diagram Engineering: A Review

Deng

Yen

Tsai

et al. 2021

Adv Energy and Sustain Res

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Alongside the evolution of technology timeline, environmental protection and energy sustainability significantly guide the research feast toward the high-performance green energy resources and technologies. [1,2] Alternatives to the fossil fuels that emit harmful greenhouse gases become desired, in which the thermoelectric (TE) materials have played an inevitable role since the 1960s. [3] One of TE technology features is the waste heat recovery via the Seebeck effect, [4] which allows the conversion between thermal energy and electricity. Such a TE generator produces precious electrical energy from any arbitrary interfaces where a temperature gradient exists, simultaneously boosting energy usage efficiency while eases global warming.Many TE materials are being explored for power generation applications, such as GeTe, [5] PbTe, [6,7] Bi 2 Te 3 , [8] and silicides. [9] Moreover, the TE cooler, which utilizes the Peltier effect, [4] emerges as a vital spot-cooling device assembled by all-solid-state materials. With the advantages of refrigerant-free and size-minimization, the TE cooler exhibits the advantages of refrigerant-free and size-minimization, which can be used as the next-generation cooling technology. [10] After more than 60 years of development, the practical application and potential coverage of TE technology are comprehensive. Nevertheless, a TE material's thermal-to-electric efficiency is still required to be boosted. In general, the TE figure-of-merit zT ¼ ðS 2 σÞT=κ positively relates to the performance of TE materials, in which the S is the Seebeck coefficient, σ ¼ ρ À1 refers to the electrical conductivity, and κ ¼ κ e þ κ L þ κ b comprises the total thermal conductivity κ, lattice thermal conductivity κ, and bipolar thermal conductivity κ b , respectively. Most importantly, the S, σ, and κ e have the carrier concentration n H as a common factor, which correlates and depends on each other. Therefore, the counterbalance between the thermal and electrical transport properties is essential to attain high zT values, which could be fulfilled by band structure engineering, [11] carrier optimization, [12,13] filtering effect, [14] , and so on. In parallel, the reduction in κ L also paves the way toward highperformance TE materials, mainly accomplished by all-scale defect engineering [15] and alloying effect. [16] Those imperfections introduce multiscale roadblocks, such as the interstitial/ antisite defect, dislocations, nanoprecipitates, and grain boundaries, aiming to impede the phonons with different wavelengths.Countless efforts bring the breakthroughs of zT value in succession. The peak zT grows less than unity in the 1960s to greater than 2.5 after 2015, [17] whose progress is slow yet steadily. Complex TE materials with various dopants are the primary targets, while different approaches can be adopted. [18,19] The

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“…Aside from the interest in the excellent thermoelectric properties, the extreme structural diversity of the zinc-antimony binary phase diagram has also been intensively investigated. Recently, Lo et al (2018) updated the Zn-Sb phase diagram, and White et al (2018) explored the Li-Zn-Sb phase diagram using a solution-phase method. It is now established that there exists a large number of unique Zn-Sb phases within a narrow compositional range (50-60 at% Zn) including ZnSb (Telkes, 1947), Zn 8 Sb 7 (Pomrehn et al, 2011;Wang & Kovnir, 2015), Zn 9 Sb 7 (He et al, 2015), Zn 4 Sb 3 (Caillat et al, 1997) and Zn 3 Sb 2 (Lo et al, 2017;Boströ m & Lidin, 2004).…”

Section: Introductionmentioning

confidence: 99%

Structural evolution in thermoelectric zinc antimonide thin films studied by in situ X-ray scattering techniques

Song

Roelsgaard

Blichfeld

et al. 2021

IUCrJ

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Zinc antimonides have been widely studied owing to their outstanding thermoelectric properties. Unlike in the bulk state, where various structurally unknown phases have been identified through their specific physical properties, a number of intermediate phases in the thin-film state remain largely unexplored. Here, in situ X-ray diffraction and X-ray total scattering are combined with in situ measurement of electrical resistivity to monitor the crystallization process of as-deposited amorphous Zn-Sb films during post-deposition annealing. The as-deposited Zn-Sb films undergo a structural evolution from an amorphous phase to an intermediate crystalline phase and finally the ZnSb phase during heat treatment up to 573 K. An intermediate phase (phase B) is identified to be a modified β-Zn8Sb7 phase by refinement of the X-ray diffraction data. Within a certain range of Sb content (∼42–55 at%) in the films, phase B is accompanied by an emerging Sb impurity phase. Lower Sb content leads to smaller amounts of Sb impurity and the formation of phase B at lower temperatures, and phase B is stable at room temperature if the annealing temperature is controlled. Pair distribution function analysis of the amorphous phase shows local ordered units of distorted ZnSb4 tetrahedra, and annealing leads to long-range ordering of these units to form the intermediate phase. A higher formation energy is required when the intermediate phase evolves into the ZnSb phase with a significantly more regular arrangement of ZnSb4 tetrahedra.

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The updated Zn–Sb phase diagram. How to make pure Zn₁₃Sb₁₀(“Zn₄Sb₃”).

Cited by 25 publications

References 30 publications

Decomposition Phenomena of Zn_13−δSb₁₀ under Working Conditions of Thermoelectric Generators and Minimum Current Densities for Electromigration

Decomposition Phenomena of Zn_13−δSb₁₀ under Working Conditions of Thermoelectric Generators and Minimum Current Densities for Electromigration

Eliciting High‐Performance Thermoelectric Materials via Phase Diagram Engineering: A Review

Structural evolution in thermoelectric zinc antimonide thin films studied by in situ X-ray scattering techniques

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The updated Zn–Sb phase diagram. How to make pure Zn13Sb10(“Zn4Sb3”).

Cited by 25 publications

References 30 publications

Decomposition Phenomena of Zn13−δSb10 under Working Conditions of Thermoelectric Generators and Minimum Current Densities for Electromigration

Decomposition Phenomena of Zn13−δSb10 under Working Conditions of Thermoelectric Generators and Minimum Current Densities for Electromigration

Eliciting High‐Performance Thermoelectric Materials via Phase Diagram Engineering: A Review

Structural evolution in thermoelectric zinc antimonide thin films studied by in situ X-ray scattering techniques

Contact Info

Product

Resources

About

The updated Zn–Sb phase diagram. How to make pure Zn₁₃Sb₁₀(“Zn₄Sb₃”).

Decomposition Phenomena of Zn_13−δSb₁₀ under Working Conditions of Thermoelectric Generators and Minimum Current Densities for Electromigration

Decomposition Phenomena of Zn_13−δSb₁₀ under Working Conditions of Thermoelectric Generators and Minimum Current Densities for Electromigration