Bismuth Telluride Supported Sub-1 nm Polyoxometalate Cluster for High-Efficiency Thermoelectric Energy Conversion.

Size plays a crucial role in chemistry and material science. Subnanometer polyoxometalate (POM) clusters have gained attention in various fields, but their use in thermoelectrics is still limited. To address this issue, we propose the POM clusters as an effective second phase to enhance the thermoelectric properties of Bi0.4Sb1.6Te3. Thanks to their subnanometer size, POM clusters improve electrical transport behavior through the superposition of atomic orbitals and the interfacial scattering effect. Furthermore, their ultrasmall size strongly reduces thermal conductivity. Consequently, the introduction of a mere 0.1 mol % of POM into the Bi0.4Sb1.6Te3 matrix realizes a state-of-the-art zT value of 1.46 at 348 K, a 45% enhancement over Bi0.4Sb1.6Te3 (1.01), along with a maximum thermoelectric-conversion efficiency of the integrated module of 6.0%. The enhancement of carrier mobility and the suppression of thermal conduction achieved by introducing the subnanometer clusters hold promise for various applications, such as electronic devices and thermal management.

Modifying Electronic Structure of Bismuth Telluride Through S Doping and Te Vacancy Engineering for Enhanced Zn-Ion Storage Ability in Aqueous Zn-proton Hybrid Ion Batteries.

Bismuth chalcogenides are used as cathode materials in Zn-proton hybrid ion batteries, which exhibit an ultraflat discharge plateau that is favorable for practical applications. Unfortunately, their capacity is not competitive, and their charge storage mechanisms are ambiguous, both of which hinder their further development. In this study, S-doped Bi2Te3- x (SBT) nanosheets are prepared by tellurizing a Bi2O2S precursor using a hydrothermal process. As revealed by density functional theory analyses, the S dopant and its induced Te vacancies can distinctly manipulate the electronic structure of SBT, resulting in decent electrical conductivity and more negative adsorption energy to Zn2+. These advantages boost the Zn2+ storage ability of SBT materials. Consequently, compared with defect-free Bi2Te3, the SBT cathodes have superior specific capacity, rate capability, and cycling stability.

Ultralow-Overpotential Acidic Oxygen Evolution Reaction Over Bismuth Telluride-Carbon Nanotube Heterostructure with Organic Framework.

The state-of-the-art iridium and ruthenium oxides-based materials are best known for high efficiency and stability in acidic oxygen evolution reaction (OER). However, the development of economically feasible catalysts for water-splitting technologies is challenging by the requirements of low overpotential, high stability, and resistance of catalysts to dissolution during the acidic oxygen evolution reaction . Herein, an organometallic core-shell heterostructure composed of a carbon nanotube core (CNT) and bismuth telluride (Bi2Te3) shell (denoted as nC-Bi2Te3) is designed and use it as a catalyst for the acidic OER. The proposed catalyst achieves an ultralow overpotential of 160 mV at 10 mA cm-2 (geometrical), thereby outperforming most of the state-of-the-art precious-metal-based catalysts. The low Tafel slope of 30 mV dec-1 and charge transfer resistance (RCT) of 1.5 Ω demonstrate its excellent electrocatalytic activity. The morphological and chemical compositions of nC-Bi2Te3 enable the generation of ─OH functional group in the Bi─Te sections formed via a ligand support, which enhances the absorption capacity of H+ ions and increases the intrinsic catalytic activity. The presented insights regarding the material composition-structure relationship can help expand the application scope of high-performance catalysts.

Thermoelectric Cooling-Oriented Large Power Factor Realized in N-Type Bi2Te3 Via Deformation Potential Modulation and Giant Deformation.

Thermoelectric refrigeration, utilizing Peltier effect, has great potential in all-solid-state active cooling field near room temperature. The performance of a thermoelectric cooling device is highly determined by the power factor of consisting materials besides the figure of merit. In this work, it is demonstrated that successive addition of Cu and Nd can realize non-trivial modulation of deformation potential in n-type room temperature thermoelectric material Bi2Te2.7Se0.3 and result in a significant increment of electron mobility and remarkably enhanced power factor. Following giant hot deformation process improves grain texturing and strengthens inter-layer interaction in Bi2Te2.7Se0.3 lattice, further pushing the power factor to ≈47 µW cm-1 K-2 at 300 K and maximal figure of merit ZTmax to ≈1.34 at 423 K with average ZTave of ≈1.27 at 300-473 K. Moreover, robust compressive strength is enhanced to ≈146.6 MPa. The corresponding finite element simulations demonstrate large temperature differences ΔT of ≈70 K and a maximal coefficient of performance COP ≈ 10.6 (hot end temperature at 300 K), which can be achieved in a ten-pair thermoelectric cooling virtual module. The strategies and results as shown in this work can further advance the application of n-type Bi2Te3 for thermoelectric cooling.

Giant Deformation Induced Staggered-Layer Structure Promoting the Thermoelectric and Mechanical Performance in n-Type Bi2(Te, Se)3.

Bismuth telluride has long been recognized as the most promising near-room temperature thermoelectric material for commercial application; however, the thermoelectric performance for n-type Bi2(Te, Se)3-based alloys is far lagging behind that of its p-type counterpart. In this work, a giant hot deformation (GD) process is implemented in an optimized Bi2Te2.694Se0.3I0.006+3 wt%K2Bi8Se13 precursor and generates a unique staggered-layer structure. The staggered-layered structure, which is only observed in severely deformed crystals, exhibits a preferential scattering on heat-carrying phonons rather than charge-carrying electrons, thus resulting in an ultralow lattice thermal conductivity while retaining high-weight carrier mobility. Moreover, the staggered-layer structure is located adjacent to the van der Waals gap in Bi2(Te, Se)3 lattice and is able to strengthen the interaction between anion layers across the gap, leading to obviously improved compressive strength and Vickers hardness. Consequently, a high peak figure of merit ZT of ≈ 1.3 at 423 K, and an average ZT of ≈ 1.2 at 300-473 K can be achieved in GD sample. This study demonstrates that the GD process can successfully decouple the electrical and thermal transports with simultaneously enhanced mechanic performance.

Bismuth Telluride Nanoplates Hierarchically Confined by Graphene and N-Doped C as Conversion-Alloying Anode Materials for Potassium-Ion Batteries.

Potassium-ion batteries (PIBs) have broad application prospects in the field of electric energy storage systems because of its abundant K reserves, and similar "rocking chair" operating principle as lithium-ion batteries (LIBs). Aiming to the large volume expansion and sluggish dynamic behavior of anode materials for storing large sized K-ion, bismuth telluride (Bi2 Te3 ) nanoplates hierarchically encapsulated by reduced graphene oxide (rGO), and nitrogen-doped carbon (NC) are constructed as anodes for PIBs. The resultant Bi2 Te3 @rGO@NC architecture features robust chemical bond of Bi─O─C, tightly physicochemical confinement effect, typical conductor property, and enhanced K-ion adsorption ability, thereby producing superior electrochemical kinetics and outstanding morphological and structural stability. It is visually elucidated via high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) that conversion-alloying dual-mechanism plays a significant role in K-ion storage, allowing 12 K-ion transport per formular unit employing Bi as redox site. Thus, the high first reversible specific capacity of 322.70 mAh g-1 at 50 mA g-1 , great rate capability and cyclic stability can be achieved for Bi2 Te3 @rGO@NC. This work lays the foundation for an in-depth understanding of conversion-alloying mechanism in potassium-ion storage.

Selective sulfidation-vacuum volatilization processes for tellurium and bismuth recovery from bismuth telluride waste thermoelectric material.

Bismuth telluride-based alloy materials are currently the best performing thermoelectric materials at near room temperature; however, their production and use generate waste (e.g., cutting waste and failed grains). There is also lack of efficient recycling strategies for the generated waste. In this study, a selective sulfidation-vacuum volatilization method is proposed for recovering bismuth telluride waste. The Gibbs free energies of the sulfidation reaction of bismuth telluride are calculated, the saturated vapor pressure of each substance is analyzed, and the composition of the products is predicted. Based on the differences among the sulfidation and volatile properties of bismuth and tellurium, by adding sulfur to bismuth telluride waste, the composition of the substances was regulated, and efficient separation of tellurium and bismuth was achieved. We combined theoretical calculations and experimental studies to investigate the effect of process conditions on the separation and recovery of tellurium and bismuth. The results show that bismuth was thoroughly sulfereted and tellurium was a pure metal when the mass ratio of sulfur to bismuth telluride was 0.168, the sulfidation temperature was 573 K, and the holding time was 60 min. After sulfidation of the bismuth telluride waste, the sulfides were telluride and bismuthous sulfide. The sulfides, that resulted from sulfureted bismuth telluride production, were treated via vacuum volatilization. The optimal vacuum volatilization condition was 873 K for 120 min. The purities of tellurium and bismuth sulfide obtained by the selective sulfidation-vacuum volatilization experiment were >99%. The distribution ratios of tellurium and bismuth were 98.46% and 99.59%, respectively. The method thoroughly separated tellurium and bismuth from bismuth telluride waste, considerably reducing the environmental and economic costs compared with those of the conventional processes.

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.

Quantum transport and potential of topological states for thermoelectricity in Bi2Te3thin films.

This paper reviews recent developments in quantum transport and it presents current efforts to explore the contribution of topological insulator boundary states to thermoelectricity in Bi2Te3thin films. Although Bi2Te3has been used as a thermoelectric material for many years, it is only recently that thin films of this material have been synthesized as 3D topological insulators with interesting physics and potential applications related to topologically protected surface states. A major bottleneck in Bi2Te3thin films has been eliminating its bulk conductivity while increasing its crystal quality. The ability to grow epitaxial films with high crystal quality and to fabricate sophisticated Bi2Te3-based devices is attractive for implementing a variety of topological quantum devices and exploring the potential of topological states to improve thermoelectric properties. Special emphasis is laid on preparing low-defect-density Bi2Te3epitaxial films, gate-tuning of normal-state transport and Josephson supercurrent in topological insulator/superconductor hybrid devices. Prospective quantum transport experiments on Bi2Te3thin-film devices are discussed as well. Finally, an overview of current progress on the contribution of topological insulator boundary states to thermoelectricity is presented. Future explorations to reveal the potential of topological states for improving thermoelectric properties of Bi2Te3films and realizing high-performance thermoelectric devices are discussed.

Melting, Crystallization, and Alloying Dynamics in Nanoscale Bismuth Telluride.

It is critical to understand the transformation mechanisms in layered metal chalcogenides to enable controlled synthesis and processing. Here, we develop an alumina encapsulation layer-based in situ transmission electron microscopy (TEM) setup that enables the investigation of melting, crystallization, and alloying of nanoscale bismuth telluride platelets while limiting sublimation in the high-vacuum TEM environment. Heating alumina-encapsulated platelets to 700 °C in situ resulted in melting that initiated at edge planes and proceeded via the movement of a sharp interface. The encapsulated melt was then cooled to induce solidification, with individual nuclei growing to form single crystals with the same basal plane orientation as the original platelet and nonequilibrium crystal shapes imposed by the encapsulation layer. Finally, heating platelets in the presence of antimony caused alloying and lattice strain, along with heterogeneous phase formation. These findings provide new insight into important transformation processes in layered metal chalcogenide materials.

Fine-Tuning Bi2Te3-Copper Selenide Alloys Enables an Efficient n-Type Thermoelectric Conversion.

Bismuth tellurides is one of the most promising thermoelectric (TE) material candidates in low-temperature application circumstances, but the n-type thermoelectric property is relatively low compared to the p-type counterpart and still needs to be improved. Herein, we incorporated different copper selenides (CuSe, Cu3Se2 and Cu2-xSe) into a Bi2Te3 matrix to create the alloy by grinding and successive sintering to enable higher thermoelectric performance. The results demonstrated that all alloys achieved n-type TE characteristics and Bi2Te3-CuSe exhibited the best Seebeck coefficient and power factor among them. Along with the low thermal conductivity, the maximum dimensionless TE figure of merit (ZT) value of 1.64 at 573 K was delivered for Bi2Te3-CuSe alloy, which is among the best reported results in the n-type Bi2Te3-based TE materials to the best of our knowledge. The improved TE properties should be related to the co-doping process of Se and Cu. Our investigation shows a new method to enhance the performance of n-type TE materials by appropriate co-doping or alloying.

Interface-Dominated Topological Transport in Nanograined Bulk Bi2 Te3.

3D topological insulators (TI) host surface carriers with extremely high mobility. However, their transport properties are typically dominated by bulk carriers that outnumber the surface carriers by orders of magnitude. A strategy is herein presented to overcome the problem of bulk carrier domination by using 3D TI nanoparticles, which are compacted by hot pressing to macroscopic nanograined bulk samples. Bi2 Te3 nanoparticles well known for their excellent thermoelectric and 3D TI properties serve as the model system. As key enabler for this approach, a specific synthesis is applied that creates nanoparticles with a low level of impurities and surface contamination. The compacted nanograined bulk contains a high number of interfaces and grain boundaries. Here it is shown that these samples exhibit metallic-like electrical transport properties and a distinct weak antilocalization. A downward trend in the electrical resistivity at temperatures below 5 K is attributed to an increase in the coherence length by applying the Hikami-Larkin-Nagaoka model. THz time-domain spectroscopy reveals a dominance of the surface transport at low frequencies with a mobility of above 103 cm2 V-1 s-1 even at room temperature. These findings clearly demonstrate that nanograined bulk Bi2 Te3 features surface carrier properties that are of importance for technical applications.

Delivery of Platinum(IV) Prodrugs via Bi2Te3 Nanoparticles for Photothermal-Chemotherapy and Photothermal/Photoacoustic Imaging.

Combinational administration of photothermal therapy (PTT) and chemotherapy (CT) shows great potential in improving the efficiency of tumor treatment. Herein, we designed a novel nanocomposite Pt@Bi2Te3 composed of bismuth telluride (Bi2Te3) nanoparticles and platinum(IV) prodrugs (Pt) for PTT-CT combination therapy. The obtained Bi2Te3 was synthesized by a simple solvothermal method and modified by polyethylene glycol, which exhibited excellent photothermal (PT) efficiency and stability and could also serve as a bimodal bioimaging contrast agent in PT and photoacoustic (PA) imaging. In vitro experiment results showed that the nanocomposite Pt@Bi2Te3 could effectively increase the uptake of platinum in cancer cells, which could kill tumor cells through the combined effect of PTT and CT. Furthermore, combination therapy of cancer in vivo was achieved with obvious tumor-growth inhibition without inducing observed side effects. We revealed the great potential of Bi2Te3 nanocomposites in increasing therapeutic efficiency by PTT-CT therapy and PA-PT imaging.

Pulsed current-voltage electrodeposition of stoichiometric Bi2Te3 nanowires and their crystallographic characterization by transmission electron backscatter diffraction.

Bi2Te3 nanowires with diameters ranging from 25 to 270 nm, ultra-high aspect ratio, and uniform growth front were fabricated by electrodeposition, pulsing between zero current density during the off time and constant potential during the on time (pulsed-current-voltage method, p-IV). The use of zero current density during the off time is to ensure no electrodeposition is carried out and the system is totally relaxed. By this procedure, stoichiometric nanowires oriented perpendicular to the c-axis is obtained for the different diameters of porous alumina templates. In addition, the samples show a uniform growth front with ultra-high aspect ratio single crystal nanowires. The high degree of crystallinity was verified by transmission electron backscatter diffraction. This characterization revealed that the nanowires present both large single crystalline areas and areas with alternating twin configurations.

Hierarchical Bi2 Te3 Nanostrings: Green Synthesis and Their Thermoelectric Properties.

Bi2 Te3 hierarchical nanostrings have been synthesized through a solvothermal approach with the assistance of sucrose. The hierarchical Bi2 Te3 was supposed to be fabricated through a self-assembly process. Te nanorods first emerge with the reduction of TeO32- followed by heterogeneous nucleation of Bi2 Te3 nanoplates on the surface and tips of Te nanorods. Te nanorods further transform into Bi2 Te3 nanorods simultaneously with the nanoplates' growth leading to a hierarchical structure. By controlling the reaction kinetics by adding different amount of ethylene glycol, the length of nanorods and the number of nanoplates could be tailored. The use of sucrose is vital to the formation of hierarchical structure because it not only serves as a template for the well-defined growth of Te nanorods but also promotes the heterogeneous nucleation of Bi2 Te3 in the self-assembly process. The Bi2 Te3 nanomaterial shows a moderate thermoelectric performance because of its hierarchical structure. This study shows a promising way to synthesize Bi2 Te3 -based nanostructures through environmental friendly approach.

Solvothermal Synthesis of Lateral Heterojunction Sb2Te3/Bi2Te3 Nanoplates.

A lateral heterojunction of topological insulator Sb2Te3/Bi2Te3 was successfully synthesized using a two-step solvothermal method. The two crystalline components were separated well by a sharp lattice-matched interface when the optimized procedure was used. Inspecting the heterojunction using high-resolution transmission electron microscopy showed that epitaxial growth occurred along the horizontal plane. The semiconducting temperature-resistance curve and crossjunction rectification were observed, which reveal a staggered-gap lateral heterojunction with a small junction voltage. Quantum correction from the weak antilocalization reveals the well-maintained transport of the topological surface state. This is appealing for a platform for spin filters and one-dimensional topological interface states.

Nanoscale Probing of Local Electrical Characteristics on MBE-Grown Bi2Te3 Surfaces under Ambient Conditions.

The local electrical characteristics on the surface of MBE-grown Bi2Te3 are probed under ambient conditions by conductive atomic force microscopy. Nanoscale mapping reveals a 10-100× enhancement in current at step-edges compared to that on terraces. Analysis of the local current-voltage characteristics indicates that the transport mechanism is similar for step-edges and terraces. Comparison of the results with those for control samples shows that the current enhancement is not a measurement artifact but instead is due to local differences in electronic properties. The likelihood of various possible mechanisms is discussed. The absence of enhancement at the step-edges for graphite terraces is consistent with the intriguing possibility that spin-orbit coupling and topological effects play a significant role in the step-edge current enhancement in Bi2Te3.

Thermoelectric bismuth telluride nanostructures fabricated by electrodeposition within flexible templates.

Bismuth telluride, a highly efficient thermoelectric material, stands out for applications around room temperature in wearable devices. By harnessing the thermal gradient established between the human body and ambient temperature, we can generate useable electricity. Notably, bismuth telluride nanostructures exhibit significantly lower thermal conductivities compared to their bulk counterparts. As a result, the thermoelectric efficiency achieved is notably higher. Our research focuses on developing efficient nanostructured materials based on bismuth telluride inside a flexible substrate made of polyester. We employ scalable methods, such as template-assisted electrochemical deposition, to fabricate these nanostructures. In this study, we present an approach to the development of flexible nanostructured thermoelectric materials. Despite using a reduced quantity of active material, our electrochemically deposited nanostructures inside a flexible template demonstrate a remarkable performance. They exhibit 24 % of the Power Factor reported for conventional electrochemically fabricated Bi2Te3 thin films, and notably, they even surpass the Power Factor reported for flexible Bi2Te3-based inks used in the creation of flexible generators. This achievement underscores the potential of our method in the advancement of efficient, flexible thermoelectric devices.

Construct Amorphous Polymer Interface to Enhance the Thermoelectric Performance of Commercial Bi0.5Sb1.5Te3 Materials.

Interfaces, such as grain boundaries and phase boundaries in thermoelectric (TE) materials, play a crucial role in the carrier/phonon transport. Accurate control of the features of interfaces, including composition, crystalline nature, and thickness may give rise to a promising pathway to break the trade-off between phonon and carrier transport properties, which is essential to design high-performance TE materials. In this work, the amorphous polymer interface (API) layer is introduced to the p-type commercial Bi0.5Sb1.5Te3 (BST) TE material by the liquid-phase sintering process. Due to the larger mismatch in the acoustic impedance or phonon spectra between the amorphous polymer layer and the BST phase, the additional interfacial thermal resistance is introduced, which results in a large decrease in lattice thermal conductivity. It is found that the interfacial thermal resistance at the API is much higher than that of normal grain boundary and hetero interface reported in the literature. Conversely, taking advantage of the strong electron and phonon scattering, a large net get of ZT was achieved. A maximum ZT of ∼1.22 at 350 K was obtained in the BST/polyimide-0.5% sample, which is considerably greater than that of the commercial BST matrix (∼0.99 at 350 K). Furthermore, the optimized BST/polymer sample also exhibited almost 20% enhancement in hardness compared with the pure BST sample. This work has opened a new window for designing high-performance TE composites, which may extend to other material systems.

Synergistic Improvement of BiI3 and In on Thermoelectric Properties of Zone-Melted n-Type Bi2Te2.7Se0.3.

Bismuth telluride (Bi2Te3) is the only commercial thermoelectric material so far, and it is also the best thermoelectric material with the best performance at room temperature. However, up to now, the zT value of n-type materials used on a large scale is only about 1.0; this makes the thermoelectric conversion efficiency of thermoelectric devices and thermoelectric applications stagnant. Therefore, under the synergistic action of BiI3 and In, the properties of n-type Bi2Te2.7Se0.3 material are improved. The experiments show that BiI3, which is nontoxic and non-absorbent, can effectively improve the power factor of the material and inhibit the bipolar effect and is an effective dopant. After the inclusion of In, due to the low bond energy of the In-Te bond, it is easy to form the InTe phase in the matrix material and then introduce the second phase, and the presence of the second phase in the material will scatter phonons and reduce the lattice thermal conductivity so that it can reach 0.31 W m-1 K-1 at 350 K. Ultimately, a high maximum zT of 1.20 at 325 K and a remarkable average zT of 1.04 (300-500 K) are attained in the In0.005Bi1.995Te2.7Se0.3 + 0.13 wt % BiI3 sample.