Design of N-Type Textured Bi2 Te3 with Robust Mechanical Properties for Thermoelectric Micro-Refrigeration Application.

Thermoelectric refrigeration is one of the mature techniques used for cooling applications, with the great advantage of miniaturization over traditional compression refrigeration. Due to the anisotropic thermoelectric properties of n-type bismuth telluride (Bi2 Te3 ) alloys, these two common methods, including the liquid phase hot deformation (LPHD) and traditional hot forging (HF) methods, are of considerable importance for texture engineering to enhance performance. However, their effects on thermoelectric and mechanical properties are still controversial and not clear yet. Moreover, there has been little documentation of mechanical properties related to micro-refrigeration applications. In this work, the above-mentioned methods are separately employed to control the macroscopic grain orientation for bulk n-type Bi2 Te3 samples. The HF method enabled the stabilization of both composition and carrier concentration, therefore yielding a higher quality factor to compare with that of LPHD samples, supported by DFT calculations. In addition to superior thermoelectric performance, the HF sample also exhibited robust mechanical properties due to the presence of nano-scale distortion and dense dislocation, which is the prerequisite for realizing ultra-precision machining. This work helps to pave the way for the utilization of n-type Bi2 Te3 for commercial micro-refrigeration applications.

Bi0.33(Bi6S9)Br compositing in Bi2S3 bulk materials forwards high thermoelectric properties.

The hexagonal Bi0.33(Bi6S9)Br intermediate was incorporated to enhance the thermoelectric properties of Bi2S3 by a facile synthesis process. As a result of the increase of carrier concentration caused by Br diffusion doping and the enhancement of phonon scattering caused by pores, point defects, and secondary phase interfaces, a maximum ZT value of 0.64 was achieved at 773 K in Bi2S3 + 5% Bi0.33(Bi6S9)Br. This study provides a strategy for achieving Br doping in the Bi2S3 system by adding the Bi0.33(Bi6S9)Br intermediate alloy, while the nanostructure was maintained in the matrix, which may be also suitable for other thermoelectric materials to obtain higher performance.

Tunable Electrical Conductivity and Simultaneously Enhanced Thermoelectric and Mechanical Properties in n-type Bi2 Te3.

The recent growing energy crisis draws considerable attention to high-performance thermoelectric materials. n-type bismuth telluride is still irreplaceable at near room temperature for commercial application, and therefore, is worthy of further investigation. In this work, nanostructured Bi2 Te3 polycrystalline materials with highly enhanced thermoelectric properties are obtained by alkali metal Na solid solution. Na is chosen as the cation site dopant for n-type polycrystalline Bi2 Te3 . Na enters the Bi site, introducing holes in the Bi2 Te3 matrix and rendering the electrical conductivity tunable from 300 to 1800 Scm-1 . The solid solution limit of Na in Bi2 Te3 exceeds 0.3 wt%. Owing to the effective solid solution, the Fermi level of Bi2 Te3 is properly regulated, leading to an improved Seebeck coefficient. In addition, the scattering of both charge carriers and phonons is modulated, which ensured a high-power factor and low lattice thermal conductivity. Benefitting from the synergistic optimization of both electrical and thermal transport properties, a maximum figure of merit (ZT) of 1.03 is achieved at 303 K when the doping content is 0.25 wt%, which is 70% higher than that of the pristine sample. This work disclosed an effective strategy for enhancing the performance of n-type bismuth telluride-based alloy materials.

Mediating Point Defects Endows n-Type Bi2 Te3 with High Thermoelectric Performance and Superior Mechanical Robustness for Power Generation Application.

Bi2 Te3 -related alloys dominate the commercial thermoelectric market, but the layered crystal structure leads to the dissociation and intrinsic brittle fracture, especially for single crystals that may worsen the practical efficiency. In this work, point defect configuration by S/Te/I defects engineering is engaged to boost thermoelectric and mechanical properties of n-type Bi2 Te3 alloy, which, coupled with p-type BiSbTe, shows a competitive conversion efficiency for the fabricated module. First, as S alloying suppresses the intrinsic B i T e , antisite defects and forms a donor-like effect, electronic transport properties are optimized, associated with the decreased thermal conductivity due to the point defect scattering. The periodide compound TeI4 is afterward adopted to further tune carrier concentration for the realization of an optimal ZT. Finally, an advanced average ZT of 1.05 with ultra-high compressive strength of 230 MPa is achieved for Bi2 Te2.9 S0.1 (TeI4 )0.0012 . Based on this optimum composition, a fabricated 17-pair module demonstrates a maximum conversion efficiency of 5.37% under the temperature difference of 250 K, rivaling the current state-of-the-art Bi2 Te3 modules. This work reveals the novel mechanism of point defect reconfiguration in synergistic enhancement of thermoelectric and mechanical properties for durably commercial application, which may be applicable to other thermoelectric systems.

Highly Enhanced Thermoelectric and Mechanical Properties of Bi-Sb-Te Compounds by Carrier Modulation and Microstructure Adjustment.

Bi0.42Sb1.58Te3 + x wt % Cu1.8S (x = 0, 0.03, 0.05, and 0.1) bulk materials with enhanced thermoelectric and mechanical properties were fabricated by a solid-state reaction and spark plasma sintering. The thermoelectric properties, such as electrical transport properties and thermal conductivity, are highly dependent on the Cu1.8S content. The highest value of ZT obtained for Bi0.42Sb1.58Te3 with 0.05 wt % Cu1.8S is 1.23 at 373 K, and an optimistic average ZT of 1.2 is achieved at temperatures in the range of 323-448 K, which is 34% higher than that of the pristine sample. The highly enhanced ZT of the doped sample is attributed to the increased electrical conductivity and reduced lattice thermal conductivity caused by the effective element doping and the multiscale phonon scattering by quantities of point defects, twin boundaries, and nanopores. Further, the hardness obtained for this sample is 1.02 GPa, which is increased by 16% in comparison with that of the pristine sample. The conversion efficiency of the doped sample is also significantly higher than that of the pristine sample. Therefore, Cu1.8S is considered to be a promising dopant for enhancing the thermoelectric and mechanical properties of Bi-Sb-Te-based thermoelectric materials.

Ternary Ag2Se1-xTex: A Near-Room-Temperature Thermoelectric Material with a Potentially High Figure of Merit.

Discovering high-performance near-room-temperature thermoelectric materials is extremely imperative to widen the practical application in thermoelectric power generation and refrigeration. Here, ternary Ag2Se1-xTex (x = 0.1, 0.2, 0.3, 0.4, and 0.5) materials are prepared via the wet-mechanical alloying and spark plasma sintering process to investigate their near-room-temperature thermoelectric properties. From density functional theory calculation and single-parabolic-band modeling study, we found that the reduced contribution of Se 4p orbitals to the total density of states decreases the carrier effective mass with increasing Te content, which should enhance the theoretically maximum zT. These calculation results are also verified by the experimental results. Meanwhile, complex microstructures including dislocations, nanograins, high-density boundaries, TeSe substitution, lattice distortions, and localized strain have been observed in ternary Ag2Se1-xTex. These complex microstructures strengthen phonon scattering and in turn lead to ultralow lattice thermal conductivity in the range of 0.21-0.31 W m-1 K-1 in ternary Ag2Se1-xTex at 300 K. Although the increased deformation potential suppresses the carrier mobility, benefiting from the engineered band structures and ultralow lattice thermal conductivity, a high zT of >1 can be potentially obtained in the ternary Ag2Se1-xTex with appropriate carrier concentration. This study indicates that ternary Ag2Se1-xTex is a promising candidate for near-room-temperature thermoelectric applications.

Excellent thermoelectric performance achieved in Bi2Te3/Bi2S3@Bi nanocomposites.

A Bi2Te3/Bi2S3@Bi nanocomposite with a network microstructure was successfully synthesized via a hydrothermal method and spark plasma sintering. This composite was constructed from Bi2Te3 nanoparticles and Bi2S3@Bi nanowires, and its network structure is beneficial for obtaining excellent thermoelectric performance. A ZT peak of 1.2 at 450 K was realized for the nanocomposite sample.