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.

Mass Production of Pt Single-Atom-Decorated Bismuth Sulfide for n-Type Environmentally Friendly Thermoelectrics.

Single-atom materials are widely explored in catalysis, batteries, sensors, etc. However, limited by mass production and centimeter-scale assembly, they are rarely studied in thermoelectrics. Herein, we demonstrate a solvothermal synthesis assisted by a syringe-pump method to yield Bi2S3-supported Pt single-atom materials (Bi2S3-Pt1) at a 10 g scale. Different from Ptn clusters, Pt1 single atoms can increase carrier concentration at a high doping efficiency and provide a unique atomic environment to enhance carrier mobility, and an enlarged effective mass leads to an enhanced Seebeck coefficient. As a result, a high power factor (348 µW m-1 K-2) is achieved at 823 K. Benefiting from the scattering of phonons by Pt1 atomic sites, a minimum thermal conductivity of 0.37 W m-1 K-1 is achieved. Consequently, the Bi2S3-0.5 wt % Pt1 realizes a record-high zT of ∼0.75 at 823 K, being among the best in the state-of-the-art n-type environmentally friendly metal sulfides. The enhancement of the carrier mobility and suppression of the thermal conduction by the unique Pt1 single atoms will inspire various fields, as exemplified by electronic devices and thermal management.

Realizing zT>2 in Environment-Friendly Monoclinic Cu2 S-Tetragonal Cu1.96 S Nano-Phase Junctions for Thermoelectrics.

Phase-junction nanocomposites, made of nanograins with the same composition but different phases, offer a platform to optimize the physiochemical performance of materials. Herein, we demonstrate a straightforward strategy to synthesize Cu2-x S phase-junction nanocomposites by retaining surface 1-dodecanethiol (DDT) ligands, in contrast to the traditional method that strips the ligands. As a result, phase junctions between a conventional monoclinic (m) phase and an unconventional metastable tetragonal (t) phase are obtained. The significantly improved power factor is obtained due to the doping of the t-phase. The phase-junction interfaces reduce thermal conductivity. Finally, surface regulation of phase junctions pushes the peak zT to 2.1 at 932 K, being the highest reported for environment-friendly metal sulfides. This work provides a paradigm to optimize thermoelectric performance by controlling phase junctions through surface-ligand tuning.

Remarkable Roles of Cu To Synergistically Optimize Phonon and Carrier Transport in n-Type PbTe-Cu2Te.

High thermoelectric performance of n-type PbTe is urgently needed to match its p-type counterpart. Here, we show a peak ZT ∼ 1.5 at 723 K and a record high average ZT > 1.0 at 300-873 K realized in n-type PbTe by synergistically suppressing lattice thermal conductivity and enhancing carrier mobility by introducing Cu2Te inclusions. Cu performs several outstanding roles: Cu atoms fill the Pb vacancies and improve carrier mobility, contributing to an unexpectedly high power factor of ∼37 µW cm-1 K-2 at 423 K; Cu atoms filling Pb vacancies and Cu interstitials both induce local disorder and, together with nano- and microscale Cu-rich precipitates and their related strain fields, lead to a very low lattice thermal conductivity of ∼0.38 Wm-1 K-1 in PbTe-5.5%Cu2Te, approaching the theoretical minimum value of ∼0.36 Wm-1 K-1. This work provides an effective strategy to enhance thermoelectric performance by simultaneously improving electrical and thermal transport properties.

All-Inorganic Halide Perovskites Boost High-Ranged Figure-of-Merit in Bi0.4Sb1.6Te3 for Thermoelectric Cooling and Low-Grade Heat Recovery.

The all-inorganic halide perovskite CsPbX3 (X = Cl, Br, or I) offers various advantages, such as tunable electronic structure and high carrier mobility. However, its potential application in thermoelectric materials remains underexplored. In this study, we propose a simple yet effective method to synthesize a CsPbX3/Bi0.4Sb1.6Te3 (BST) nanocomposite by sintering a uniformly mixed raw powder. The intrinsic excitation of the BST system is suppressed by exploiting the rich phase structure and tunable electrical transport properties of CsPbX3, and the thermoelectric properties were synergistically optimized. Notably, for CsPbI3, its phase-transition-induced dislocation arrays together with low group velocities drastically reduce thermal conductivity. As a result, the composite achieves an ultrahigh average figure-of-merit (ZT) of 1.4 from 298 to 523 K. The two-pair TE module demonstrates a superior conversion efficiency of 7.3%. This study expands the potential applications of inorganic halide perovskites, into thermoelectrics.

Dramatic Enhancement of Thermoelectric Performance in PbTe by Unconventional Grain Shrinking in the Sintering Process.

Nanostructure engineering is a key strategy for tailoring properties in the fields of batteries, solar cells, thermoelectrics, and so on. Limited by grain coarsening, however, the nanostructure effect gradually degrades during the materials' manufacturing and in-service period. Herein, a strategy of cleavage-fracture for grain shrinking is developed in a Pb0.98 Sb0.02 Te sample during sintering, and the grain size remains stable after repeated tests. Moreover, the initial grain boundary is filled by fractured slender grains and enriched by dislocations, evolving into a hierarchical grain-boundary structure. The lattice thermal conductivity (klat ) is greatly reduced to approach the amorphous limit. As a result, a record-high ZT value of ≈1.9 is obtained at 815 K in the n-type Pb0.98 Sb0.02 Te sample and a decent efficiency of 6.7% in thermoelectric device. This strategy for grain shrinking will shed light on the application of nanostructure engineering under high temperature and extreme conditions in other material systems.

Enhanced Thermoelectric Performance Achieved in SnTe via the Synergy of Valence Band Regulation and Fermi Level Modulation.

SnTe is deemed a promising mid-temperature thermoelectric material for low toxicity, low cost, and decent performance. Sole doping/alloying on Sn sites was reported to result in either modified band alignment or reduced lattice thermal conductivity, thus contributing to an enhanced overall thermoelectric figure of merit. However, this strategy alone is always unable to take full use of the material's advantage, especially considering that it simultaneously pushes the hole concentration off the optimal range. In this work, we adopted a two-step approach to optimize the thermoelectric performance of SnTe in order to overcome the limitation. First, Mn was alloyed into Sn sites to increase the density of state effective mass of SnTe by regulating the valence bands; the Fermi level was further regulated by iodine doping, guided by a refined two-band model. Additionally, the lattice thermal conductivity was also suppressed by the microstructure optimizing via Mn doping and additional phonon scattering at ITe mass/strain fluctuation. As a result, a high ZT of 1.4 at 873 K was achieved for Sn0.91Mn0.09Te0.99I0.01. This study provides a way to refine the single doping stratagem used in other thermoelectric materials.

Improvement in the thermoelectric performance of highly reproducible n-type (Bi,Sb)2Se3 alloys by Cl-doping.

(Bi,Sb)2Se3 alloys are promising alternatives to commercial n-type Bi2(Te,Se)3 ingots for low-mid temperature thermoelectric power generation due to their high thermoelectric conversion efficiency at elevated temperatures. Herein, we report the enhanced high-temperature thermoelectric performance of the polycrystalline Cl-doped Bi2-x Sb x Se3 (x = 0.8, 1.0) bulks and their sustainable thermal stability. Significant role of Cl substitution, characterized to enhance the power factor and reduce the thermal conductivity synergetically, is clearly elucidated. Cl-doping at Se-site of both Bi1.2Sb0.8Se3 and BiSbSe3 results in a high power factor by carrier generation and Hall mobility improvement while maintaining converged electronic band valleys. Furthermore, point defect phonon scattering originated from mass fluctuations formed at Cl-substituted Se-sites reduces the lattice thermal conductivity. Most importantly, spark plasma sintered Cl-doped Bi2-x Sb x Se3 bulks are thermally stable up to 700 K, and show a reproducible maximum thermoelectric figure of merit, zT, of 0.68 at 700 K.

Dimer rattling mode induced low thermal conductivity in an excellent acoustic conductor.

A solid with larger sound speeds usually exhibits higher lattice thermal conductivity. Here, we report an exception that CuP2 has a quite large mean sound speed of 4155 m s-1, comparable to GaAs, but single crystals show very low lattice thermal conductivity of about 4 W m-1 K-1 at room temperature, one order of magnitude smaller than GaAs. To understand such a puzzling thermal transport behavior, we have thoroughly investigated the atomic structures and lattice dynamics by combining neutron scattering techniques with first-principles simulations. This compound crystallizes in a layered structure where Cu atoms forming dimers are sandwiched in between P atomic networks. In this work, we reveal that Cu atomic dimers vibrate as a rattling mode with frequency around 11 meV, which is manifested to be remarkably anharmonic and strongly scatters acoustic phonons to achieve the low lattice thermal conductivity.

Thermoelectric Performance of Sb2Te3-Based Alloys is Improved by Introducing PN Junctions.

Interface engineering has been demonstrated to be an effective strategy for enhancing the thermoelectric (TE) performance of materials. However, a very typical interface in semiconductors, that is, the PN junction (PNJ), is scarcely adopted by the thermoelectrical community because of the coexistence of holes and electrons. Interestingly, our explorative results provide a definitively positive case that appropriate PNJs are able to enhance the TE performance of p-type Sb2Te3-based alloys. Specifically, owing to the formation of the charge-depletion layer and built-in electric field, the carrier concentration and transport can be optimized and thus the power factor is improved and the electronic thermal conductivity is decreased. Meanwhile, PNJs provide scattering centers for phonons, leading to a reduced lattice thermal conductivity. Consequently, the p-type (Bi2Te3)0.15-(Sb2Te3)0.85 composites comprising PNJs achieve a ∼131% improvement of the ZT value compared with the pure Sb2Te3. The increased ZT demonstrates the feasibility of improving the TE properties by introducing PNJs, which will open a new and effective avenue for designing TE alloys with high performance.