Jing Shuai

Tuning the carrier scattering mechanism to effectively improve the thermoelectric properties

A high thermoelectric power factor not only enables a potentially high figure of merit ZT but also leads to a large output power density, and hence it is pivotal to find an effective route to improve the power factor. Previous reports on the manipulation of carrier scattering mechanisms (e.g. ionization scattering) were mainly focused on enhancing the Seebeck coefficient. In contrast, here we demonstrate that by tuning the carrier scattering mechanism in n-type Mg3Sb2-based materials, it is possible to noticeably improve the Hall mobility, from ∼19 to ∼77 cm2 V−1 s−1, and hence substantially increase the power factor by a factor of 3, from ∼5 to ∼15 μW cm−1 K−2. The enhancement in mobility is mainly due to the reason that ionization scattering has been converted into mixed scattering between ionization and acoustic phonon scattering, which less effectively scatters the carriers. The strategy of tuning the carrier scattering mechanism to improve the mobility should be widely applicable to various material systems for achieving better thermoelectric performance.

Achieving high power factor and output power density in p-type half-Heuslers Nb1-xTixFeSb.

Significance Thermoelectric technology can boost energy consumption efficiency by converting some of the waste heat into useful electricity. Heat-to-power conversion efficiency optimization is mainly achieved by decreasing the thermal conductivity in many materials. In comparison, there has been much less success in increasing the power factor. We report successful power factor enhancement by improving the carrier mobility. Our successful approach could suggest methods to improve the power factor in other materials. Using our approach, the highest power factor reaches ∼106 μW⋅cm−1⋅K−2 at room temperature. Such a high power factor further yields a record output power density in a single-leg device tested between 293 K and 868 K, thus demonstrating the importance of high power factor for power generation applications. Improvements in thermoelectric material performance over the past two decades have largely been based on decreasing the phonon thermal conductivity. Enhancing the power factor has been less successful in comparison. In this work, a peak power factor of ∼106 μW⋅cm−1⋅K−2 is achieved by increasing the hot pressing temperature up to 1,373 K in the p-type half-Heusler Nb0.95Ti0.05FeSb. The high power factor subsequently yields a record output power density of ∼22 W⋅cm−2 based on a single-leg device operating at between 293 K and 868 K. Such a high-output power density can be beneficial for large-scale power generation applications.

Manipulation of ionized impurity scattering for achieving high thermoelectric performance in n-type Mg3Sb2-based materials

Significance Higher carrier mobility can contribute to a larger power factor, so it is important to identify effective means for achieving higher carrier mobility. Since carrier mobility is governed by the band structure and the carrier scattering mechanism, its possible enhancement could be obtained by manipulating either or both of these. Here, we report a substantial enhancement in carrier mobility by tuning the carrier scattering mechanism in n-type Mg3Sb2-based materials. The ionized impurity scattering in these materials has been shifted into mixed scattering by acoustic phonons and ionized impurities. Our results clearly demonstrate that the strategy of tuning the carrier scattering mechanism is quite effective for improving the mobility and should also be applicable to other material systems. Achieving higher carrier mobility plays a pivotal role for obtaining potentially high thermoelectric performance. In principle, the carrier mobility is governed by the band structure as well as by the carrier scattering mechanism. Here, we demonstrate that by manipulating the carrier scattering mechanism in n-type Mg3Sb2-based materials, a substantial improvement in carrier mobility, and hence the power factor, can be achieved. In this work, Fe, Co, Hf, and Ta are doped on the Mg site of Mg3.2Sb1.5Bi0.49Te0.01, where the ionized impurity scattering crosses over to mixed ionized impurity and acoustic phonon scattering. A significant improvement in Hall mobility from ∼16 to ∼81 cm2⋅V−1⋅s−1 is obtained, thus leading to a notably enhanced power factor of ∼13 μW⋅cm−1⋅K−2 from ∼5 μW⋅cm−1⋅K−2. A simultaneous reduction in thermal conductivity is also achieved. Collectively, a figure of merit (ZT) of ∼1.7 is obtained at 773 K in Mg3.1Co0.1Sb1.5Bi0.49Te0.01. The concept of manipulating the carrier scattering mechanism to improve the mobility should also be applicable to other material systems.

The effect of nickel doping on electron and phonon transport in the n-type nanostructured thermoelectric material CoSbS

The effect of Ni doping on both electron and phonon transport properties of nanostructured CoSbS has been investigated in this study. We found a more than 2 times increase on figure-of-merit (ZT). The noticeable enhancement is mainly attributed to the optimized carrier concentration, high effective mass and strong electron–phonon scattering upon Ni doping. A ZT of 0.5 was achieved at 873 K together with a power factor of 20 μW cm−1 K−2 for the Ni doped CoSbS samples. The reduced lattice thermal conductivity via the strong electron–phonon scattering for Ni doped CoSbS samples is confirmed by the quantitative calculation of the various phonon scattering mechanisms according to the Callaway model.

Thermoelectric properties of Bi-based Zintl compounds Ca1−xYbxMg2Bi2

Bi-based Zintl compounds, Ca1−xYbxMg2Bi2 with the structure of CaAl2Si2, have been successfully prepared by mechanical alloying followed by hot pressing. We found that the electrical conductivity, Seebeck coefficient, carrier concentration, and thermal conductivity can be adjusted by changing the Yb concentration. All Ca1−xYbxMg2Bi2 samples have low carrier concentrations (∼2.4 to 7.2 × 1018 cm−3) and high Hall mobility (∼119 to 153 cm2 V−1 s−1) near room temperature. The partial substitution of Ca with Yb causes structural disorders, which lowers the thermal conductivity. The highest figure of merit of ∼1.0 is observed in Ca0.5Yb0.5Mg2Bi2, and ∼0.8 in the unsubstituted CaMg2Bi2 and YbMg2Bi2. A small amount of free Bi was found in all the samples except YbMg2Bi2. By reducing the initial Bi concentration, we succeeded in obtaining phase pure samples in all compositions, which resulted in a much better thermoelectric performance, especially much higher (ZT)eng and a conversion efficiency near 11%. Such a high efficiency makes this material competitive with half-Heuslers and skutterudites.

Understanding and manipulating the intrinsic point defect in α-MgAgSb for higher thermoelectric performance

Nanostructured α-MgAgSb has been demonstrated as a good p-type thermoelectric material candidate for low temperature power generation. Nevertheless, the intrinsic defect physics that impedes further enhancement of its thermoelectric performance is still unknown. Here we first unveil that an Ag vacancy is a dominant intrinsic point defect in α-MgAgSb and has a low defect formation energy, shown by first-principles calculations. In addition, the formation of an Ag vacancy could increase the crystal stability. More importantly, intrinsic point defects, namely an Ag vacancy, can be rationally engineered via simply controlling the hot press temperature, due to the recovery effect. Collectively, a high peak ZT of ∼1.3 and average ZT of ∼1.1 are achieved when hot pressed at 533 K. These results elucidate the pivotal role of intrinsic point defects in α-MgAgSb and further highlight that point defect engineering is an effective approach to optimize the thermoelectric properties.

Thermal conductivity reduction by isoelectronic elements V and Ta for partial substitution of Nb in half-Heusler Nb(1−x)/2V(1−x)/2TaxCoSb

Recently, we found a new n-type thermoelectric half-Heusler NbCoSb with a valence electron count of 19, different from the usual 18. In this paper, we focus on the effect of partial substitution of Nb by isoelectronic elements V and Ta on the reduction of the thermal conductivity of Nb(1−x)/2V(1−x)/2TaxCoSb. We found that the isoelectronic elements V and Ta for partial substitution of Nb can dramatically decrease the thermal conductivity from 7.0 W m−1 K−1 to 3.3 W m−1 K−1 at room temperature for Nb0.44V0.44Ta0.12CoSb, but unfortunately a large power factor decrease also occurred. Consequently, a peak ZT of ∼0.5 is achieved at 700 °C for Nb0.44V0.44Ta0.12CoSb, which is about 25% higher than the ∼0.4 reported earlier for NbCoSb.

The significant role of Mg stoichiometry in designing high thermoelectric performance for Mg3(Sb,Bi)2-based n-type Zintls

Complex structures with versatile chemistry provide considerable chemical tunability of the transport properties. Good thermoelectric materials are generally extrinsically doped semiconductors with optimal carrier concentrations, while charged intrinsic defects (e.g., vacancies, interstitials) can also adjust the carriers, even in the compounds with no apparent deviation from a stoichiometric nominal composition. Here we report that in Zintl compounds Mg3+xSb1.5Bi0.5, the carrier concentration can be tuned from p-type to n-type by simply altering the initial Mg concentration. The spherical-aberration-corrected (CS-corrected) high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and energy-dispersive X-ray spectroscopy (EDX) mapping analysis show that the excess Mg would form a separate Mg-rich phase after Mg vacancies have been essentially compensated. Additionally, a slight Te doping at Bi site on Mg3.025Sb1.5Bi0.5 has enabled good n-type thermoelectric properties, which is comparable to the Te-doped Mg-rich sample. The actual final composition of Mg3.025Sb1.5Bi0.5 analyzed by EPMA is also close to the stoichiometry Mg3Sb1.5Bi0.5, answering the open question whether excess Mg is prerequisite to realize exceptionally high n-type thermoelectric performance by different sample preparation methods. The motivation for this work is first to understand the important role of vacancy and then to guide for discovering more promising n-type Zintl thermoelectric materials.

Contrasting the Role of Mg and Ba Doping on the Microstructure and Thermoelectric Properties of p-Type AgSbSe2

Microstructure has a critical influence on the mechanical and functional properties. For thermoelectric materials, deep understanding of the relationship of microstructure and thermoelectric properties will enable the rational optimization of the ZT value and efficiency. Herein, taking AgSbSe2 as an example, we first report a different role of alkaline-earth metal ions (Mg(2+) and Ba(2+)) doping in the microstructure and thermoelectric properties of p-type AgSbSe2. For Mg doping, it monotonously increases the carrier concentration and then reduces the electrical resistivity, leading to a substantially enhanced power factor in comparison to those of other dopant elements (Bi(3+), Pb(2+), Zn(2+), Na(+), and Cd(2+)) in the AgSbSe2 system. Meanwhile, the lattice thermal conductivity is gradually suppressed by point defects scattering. In contrast, the electrical resistivity first decreases and then slightly rises with the increased Ba-doping concentrations due to the presence of BaSe3 nanoprecipitates, exhibiting a different variation tendency compared with the corresponding Mg-doped samples. More significantly, the total thermal conductivity is obviously reduced with the increased Ba-doping concentrations partially because of the strong scattering of medium and long wavelength phonons via the nanoprecipitates, consistent with the theoretical calculation and analysis. Collectively, ZT value ∼1 at 673 K and calculated leg efficiency ∼8.5% with Tc = 300 K and Th = 673 K are obtained for both AgSb0.98Mg0.02Se2 and AgSb0.98Ba0.02Se2 samples.

Thermoelectric properties of Zintl compound Ca1−xNaxMg2Bi1.98

Motivated by good thermoelectric performance of Bi-based Zintl compounds Ca1−xYbxMg2Biy, we further studied the thermoelectric properties of Zintl compound CaMg2Bi1.98 by doping Na into Ca as Ca1−xNaxMg2Bi1.98 via mechanical alloying and hot pressing. We found that the electrical conductivity, Seebeck coefficient, power factor, and carrier concentration can be effectively adjusted by tuning the Na concentration. Transport measurement and calculations revealed that an optimal doping of 0.5 at. % Na achieved better average ZT and efficiency. The enhancement in thermoelectric performance is attributed to the increased carrier concentration and power factor. The low cost and nontoxicity of Ca1−xNaxMg2Bi1.98 makes it a potentially promising thermoelectric material for power generation in the mid-temperature range.