Preparation and thermoelectric properties of semiconducting Zn4Sb3

Caillat, T.; Fleurial, Jean‐Pierre; Borshchevsky, A.

doi:10.1016/s0022-3697(96)00228-4

Cited by 648 publications

(574 citation statements)

References 14 publications

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“…The complex Zintl phases, especially Sb-based Zintl compounds, have been demonstrated to be promising TE materials for middleto high-temperature applications. Remarkable achievements have been reported with maximal ZT around or more than 1, e.g., β-Zn 4 Sb 3 (20,21), Yb 14 Mn 1−x Al x Sb 11 (22,23), and A y Mo 3 Sb 7-x Te x (24). In particular, Zintl phases AB 2 Sb 2 (A = Ca, Yb, Eu, Sr; B = Zn, Mn, Cd, Mg) (25)(26)(27)(28)(29) crystallizing in CaAl 2 Si 2 structure have been extensively studied with the highest ZT for YbZn 0.4 Cd 1.6 Sb 2 ∼ 1.2 at 700 K. The A sites of these materials have been shown to contain exclusively divalent ions, which are limited to alkalineearth-based and rare-earth-based elements like Eu and Yb, whereas B is a d 0 , d 5 , d 10 transition metal or a main-group element like Mg 2+ (30,31).…”

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confidence: 98%

Higher thermoelectric performance of Zintl phases (Eu _0.5 Yb _0.5 ) _1−x Ca _x Mg ₂ Bi ₂ by band engineering and strain fluctuation

Shuai

Geng

Lan

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

159

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Complex Zintl phases, especially antimony (Sb)-based YbZn 0.4 Cd 1.6 Sb 2 with figure-of-merit (ZT) of ∼1.2 at 700 K, are good candidates as thermoelectric materials because of their intrinsic "electron-crystal, phonon-glass" nature. Here, we report the rarely studied p-type bismuth (Bi)-based Zintl phases (Ca,Yb,Eu)Mg 2 Bi 2 with a record thermoelectric performance. Phase-pure EuMg 2 Bi 2 is successfully prepared with suppressed bipolar effect to reach ZT ∼ 1. Further partial substitution of Eu by Ca and Yb enhanced ZT to ∼1.3 for Eu 0.2 Yb 0.2 Ca 0.6 Mg 2 Bi 2 at 873 K. Density-functional theory (DFT) simulation indicates the alloying has no effect on the valence band, but does affect the conduction band. Such band engineering results in good p-type thermoelectric properties with high carrier mobility. Using transmission electron microscopy, various types of strains are observed and are believed to be due to atomic mass and size fluctuations. Point defects, strain, dislocations, and nanostructures jointly contribute to phonon scattering, confirmed by the semiclassical theoretical calculations based on a modified Debye-Callaway model of lattice thermal conductivity. This work indicates Bi-based (Ca, Yb,Eu)Mg 2 Bi 2 is better than the Sb-based Zintl phases. technology that converts heat into electricity, is currently used in subsea and spacecraft (1), and is foreseen to play an important role in the power industry and automobiles (2-5). Widespread applications are currently limited as a result of the low efficiency of TE materials (6). TE efficiency depends on the Carnot term as well as the TE figure-of-merit, ZT, defined as ZT = (S 2 σ/κ)T, where S, σ, κ, and T are the Seebeck coefficient, electrical conductivity, thermal conductivity, and absolute temperature, respectively. S 2 σ is known as the power factor (PF) (7). Even though PF can be enhanced by electronic structure engineering, and κ can be reduced by an increase in phonon scattering, it is very difficult to independently increase PF and simultaneously decrease κ because they are oppositely related to carrier concentration and effective mass.As an alternative to evaluating the maximum ZT, a dimensionless material parameter B at particular temperature has proven to be useful (8-10).where m*, m 0 , μ, κ Lat , and T are the carrier effective mass, free electron mass, carrier mobility, lattice thermal conductivity, and absolute temperature, respectively. Therefore, heavy effective mass, high carrier mobility, and low lattice thermal conductivity are highly desirable for good TE performance. Practically, some strategies and concepts have been proposed to achieve this goal, e.g., band convergence and resonant states for heavier effective mass (11-13), band alignment and weak electron-phonon and alloy scattering to achieve high carrier mobility (14-16), and alloying or nanostructuring to enhance phonon scattering (17)(18)(19) (22,23), and A y Mo 3 Sb 7-x Te x (24). In particular, Zintl phases AB 2 Sb 2 (A = Ca, Yb, Eu, Sr; B = Zn, Mn, Cd, Mg) (25-29) crystalli...

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mentioning

confidence: 98%

Higher thermoelectric performance of Zintl phases (Eu _0.5 Yb _0.5 ) _1−x Ca _x Mg ₂ Bi ₂ by band engineering and strain fluctuation

Shuai

Geng

Lan

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

159

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“…The one exception in Table I is Bi x Sb 2-x Te 3 , which has equivalent average and peak ZT due to the atypical feature of the maximum being located near the midpoint of the measured temperature range. Although considerable emphasis is placed on achieving high peak or maximum ZT in contemporary thermoelectric materials research literature, 12,13,[16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] it is not as important as achieving high average ZT. Furthermore, the need for high average ZT can place greater expectations on the corresponding requisite value of peak or maximum ZT.…”

Section: Resultsmentioning

confidence: 99%

Estimating Energy Conversion Efficiency of Thermoelectric Materials: Constant Property Versus Average Property Models

Armstrong

Boese

Carmichael

et al. 2016

Journal of Elec Materi

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Maximum thermoelectric energy conversion efficiencies are calculated using the conventional ''constant property'' model and the recently proposed ''cumulative/average property'' model (Kim et al. in Proc Natl Acad Sci USA 112:8205, 2015) for 18 high-performance thermoelectric materials. We find that the constant property model generally predicts higher energy conversion efficiency for nearly all materials and temperature differences studied. Although significant deviations are observed in some cases, on average the constant property model predicts an efficiency that is a factor of 1.16 larger than that predicted by the average property model, with even lower deviations for temperature differences typical of energy harvesting applications. Based on our analysis, we conclude that the conventional dimensionless figure of merit ZT obtained from the constant property model, while not applicable for some materials with strongly temperature-dependent thermoelectric properties, remains a simple yet useful metric for initial evaluation and/or comparison of thermoelectric materials, provided the ZT at the average temperature of projected operation, not the peak ZT, is used.

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“…Новый интерес к материалам на основе антимонида цинка появился после того, как в 1997 г. Лаборатория реактивного движения (НАСА) опубликовала работу, в которой в связи с поиском новых высокоэффективных термоэлектрических материалов была изучена система Zn−Sb [2]. В данной системе были подробно иссле-дованы и описаны свойства фазы β-Zn 4 Sb 3 , а также сообщалось о фазах ZnSb и Zn 3 Sb 2 .…”

Section: Introductionunclassified

Получение и свойства термоэлектрического материала на основе Zn-=SUB=-4-=/SUB=-Sb-=SUB=-3-=/SUB=-

Panchenko¹,

Табачкова²,

Иванов³

et al. 2017

Физика И Техника Полупроводников

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Проведено исследование влияния условий синтеза на структуру и термоэлектрические свойства мате-риалов на основе антимонида цинка. Рассмотрены вопросы влияния избыточного Zn, режимов искрового плазменного спекания и легирования In на фазовый состав и термостабильность свойств полученного материала. Материал получали методом прямого сплавления компонентов и методом искрового плазменного спекания. Показано, что при определенных режимах искрового плазменного спекания введение избыточного количества Zn и легирование In позволяют получить материал β-Zn 4 Sb 3 со значением термоэлектрической эффективности ZT ≈ 1.47 при температуре 720 K, который показал стабильность свойств в рамках проведенных испытаний.

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Preparation and thermoelectric properties of semiconducting Zn4Sb3

Cited by 648 publications

References 14 publications

Higher thermoelectric performance of Zintl phases (Eu _0.5 Yb _0.5 ) _1−x Ca _x Mg ₂ Bi ₂ by band engineering and strain fluctuation

Higher thermoelectric performance of Zintl phases (Eu _0.5 Yb _0.5 ) _1−x Ca _x Mg ₂ Bi ₂ by band engineering and strain fluctuation

Estimating Energy Conversion Efficiency of Thermoelectric Materials: Constant Property Versus Average Property Models

Получение и свойства термоэлектрического материала на основе Zn-=SUB=-4-=/SUB=-Sb-=SUB=-3-=/SUB=-

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Preparation and thermoelectric properties of semiconducting Zn4Sb3

Cited by 648 publications

References 14 publications

Higher thermoelectric performance of Zintl phases (Eu 0.5 Yb 0.5 ) 1−x Ca x Mg 2 Bi 2 by band engineering and strain fluctuation

Higher thermoelectric performance of Zintl phases (Eu 0.5 Yb 0.5 ) 1−x Ca x Mg 2 Bi 2 by band engineering and strain fluctuation

Estimating Energy Conversion Efficiency of Thermoelectric Materials: Constant Property Versus Average Property Models

Получение и свойства термоэлектрического материала на основе Zn-=SUB=-4-=/SUB=-Sb-=SUB=-3-=/SUB=-

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Higher thermoelectric performance of Zintl phases (Eu _0.5 Yb _0.5 ) _1−x Ca _x Mg ₂ Bi ₂ by band engineering and strain fluctuation

Higher thermoelectric performance of Zintl phases (Eu _0.5 Yb _0.5 ) _1−x Ca _x Mg ₂ Bi ₂ by band engineering and strain fluctuation