Search

Bi6Cu2Se4O6 is considered as an ideal n‐type thermoelectric material to pair with p‐type BiCuSeO for preparing oxyselenide‐based thermoelectric devices, but its thermoelectric performance is limited by poor electrical conductivity. In this research, the reduced graphene oxide (rGO) nanosheets are introduced into Bi6Cu2Se3.6Cl0.4O6 matrix through liquid‐phase shear exfoliation to modify the microstructure. rGO can insert into matrix grains as intercalations, or embed into grain boundaries as wetting phase, and prompt grain alignment, which contributes to the significantly enhanced carrier mobility, thus leading to an improvement in electrical conductivity from ≈15 S cm−1 to ≈230 S cm−1 at 303 K. Whereafter, the effective donor dopant Nb is chosen to substitute Bi. The carrier concentration is increased without damaging the carrier mobility, resulting in a further improved electrical conductivity of ≈840 S cm−1 at 303 K. Lattice thermal conductivity is also suppressed owing to the intensive phonon scattering by point defects and grain boundaries. Ultimately, a record‐breaking peak ZT ≈0.5 (873 K) and average ZT ≈0.3 (303–873 K) can be achieved in Bi5.91Nb0.09Cu2Se3.6Cl0.4O6 + 0.5% rGO. The microstructure optimization method in this research effectively improves thermoelectric performance, and is anticipated to be applied in other thermoelectrics. [ABSTRACT FROM AUTHOR]

The main bottleneck in obtaining high‐performance thermoelectric (TE) materials is identified as how to decouple the strong interrelationship between electrical and thermal parameters. Herein, a precise interface modification approach based on the powder atomic layer deposition (ALD) technology is presented to enhance the performance of CuNi alloys. ZnO and Al2O3 layers as well as their combinations are deposited on the surface of powders, typically in 10–100 ALD cycles, and their effects on the TE performance of bulks is thoroughly investigated. The enhancement of the Seebeck coefficient, caused by the energy filtering effect, compensates for the electrical conductivity deterioration due to the low electrical conductivity of oxide layers. Furthermore, the oxide layers may significantly increase the phonon scattering. Therefore, to reduce the resistivity of coating layer, a multilayer structure is deposited on the surface of powders by inserting Al2O3 into ZnO. The accurate microstructure characterization shows that the Al atoms diffused into ZnO and realized the doping effect after pressing. Al diffusion has the potential to increase the electrical conductivity and complexity of coating layers. Compared to pure CuNi, zT increases by 128% due to the decrease in resistivity and stronger phonon scattering in phase boundaries. [ABSTRACT FROM AUTHOR]

Bismuth sulfide (Bi2S3) is a promising thermoelectric material with earth‐abundant, low‐cost, and environment‐friendly constituents. However, it shows poor thermoelectric performance due to its extremely low electrical conductivity derived from the low electron concentration. Here, a high‐performance Bi2S3‐based material is reported to benefit from the Fermi level tuning by Ag and Cl co‐doping and defect engineering by introducing dense low‐angle grain boundaries. Both Ag and Cl act as donors in Bi2S3, upshifting the Fermi level. This increases the electron concentration without degrading the electron mobility, thereby obtaining improved electrical conductivity. The electron localization function (ELF) contour map indicates that interstitial Ag causes electron delocalization, showing higher electron mobility in Bi2S3. More importantly, dense low‐angle grain boundaries block phonon propagation, yielding an ultralow lattice thermal conductivity of 0.30 W m−1 K−1. Consequently, a record ZT value of ≈0.9 at 676 K is achieved in the Bi2Ag0.01S3‐0.5%BiCl3 sample. [ABSTRACT FROM AUTHOR]

Bismuth sulfide (Bi2S3) is a promising thermoelectric material with earth‐abundant, low‐cost, and environment‐friendly constituents. However, it shows poor thermoelectric performance due to its extremely low electrical conductivity derived from the low electron concentration. Here, a high‐performance Bi2S3‐based material is reported to benefit from the Fermi level tuning by Ag and Cl co‐doping and defect engineering by introducing dense low‐angle grain boundaries. Both Ag and Cl act as donors in Bi2S3, upshifting the Fermi level. This increases the electron concentration without degrading the electron mobility, thereby obtaining improved electrical conductivity. The electron localization function (ELF) contour map indicates that interstitial Ag causes electron delocalization, showing higher electron mobility in Bi2S3. More importantly, dense low‐angle grain boundaries block phonon propagation, yielding an ultralow lattice thermal conductivity of 0.30 W m−1 K−1. Consequently, a record ZT value of ≈0.9 at 676 K is achieved in the Bi2Ag0.01S3‐0.5%BiCl3 sample. [ABSTRACT FROM AUTHOR]

ZnO is a promising high‐temperature thermoelectric (TE) material due to its superior stability and earth abundance. However, the coupling relation between Seebeck coefficient and electrical conductivity on carrier concentration limits the optimum TE performance for most TE materials, especially ZnO. Herein, enhancement of TE performance is achieved via a stepwise optimization strategy composed of carrier concentration optimization and carrier filtering effect for fabricating robust ZnO‐based composite ceramics through a self‐developed specific high‐pressure synthesis followed by spark plasma sintering. Specifically, doping SnO2 provide substantial electrons to surge the carrier concentration. The subsequent compositing Si3N4 nanoparticles results in the unique reaction‐generated Zn2SiO4 nanoprecipitates with a larger bandgap and intrinsically low thermal conductivity, which introduce an excellent carrier filtering effect to increase the Seebeck coefficient by 57.7% at 300 K without compromising electrical conductivity much and enhance phonon scattering to cause an ultralow lattice thermal conductivity of 1.39 W m−1 K−1 achieving amorphous limits of ZnO (1.4±0.1 W m−1 K−1). Consequently, a high peak ZT (figure of merit) of 0.691 at 873 K is obtained, which is higher than that of previously reported ZnO‐based TE materials. This work demonstrates a feasible and effective strategy to fabricate high‐performance TE materials, especially those with inferior electrical conductivity. [ABSTRACT FROM AUTHOR]

Temperature variation‐induced thermoelectric catalytic efficiency of thermoelectric material is simultaneously restricted by its electrical conductivity, Seebeck coefficient, and thermal conductivity. Herein, Bi2Te3 nanosheets are in situ grown on reduced graphene oxides (rGO) to generate an efficient photo‐thermoelectric catalyst (rGO‐Bi2Te3). This system exhibits phonon scattering effect and extra carrier transport channels induced by the formed heterointerface between rGO and Bi2Te3, which improves the power factor value and reduces thermal conductivity, thus enhancing the thermoelectric performance of 2.13 times than single Bi2Te3. The photo‐thermoelectric catalysis of rGO‐Bi2Te3 significantly improves the reactive oxygen species yields, resulting from the effective electron–hole separation caused by the unique thermoelectric field and heterointerfaces of rGO‐Bi2Te3. Correspondingly, the electrospinning membranes containing rGO‐Bi2Te3 nanosheets exhibit high antibacterial efficiency in vivo (99.35 ± 0.29%), accelerated tissue repair ability, and excellent biosafety. This study provides an insight into heterointerface design in photo‐thermoelectric catalysis. [ABSTRACT FROM AUTHOR]

The Seebeck coefficient and electrical conductivity are two central quantities to be optimized simultaneously in designing thermoelectric materials, and they are determined by the dynamics of carrier scattering. Here a new regime is uncovered where the presence of multiple electron bands with different effective masses, crossing near the Fermi level, leads to strong energy‐dependent carrier lifetimes due to intrinsic electron–phonon scattering. In this anomalous regime, electrical conductivity decreases with carrier concentration, Seebeck coefficient reverses sign even at high doping, and power factor exhibits an unusual second peak. The origin and magnitude of this effect is explained using a general simplified model as well as first‐principles Boltzmann transport calculations in recently discovered half‐Heusler alloys. General design rules for using this paradigm to engineer enhanced performance in thermoelectric materials are identified. [ABSTRACT FROM AUTHOR]

As an eco‐friendly oxide‐based thermoelectric material, Bi2O2Se exhibits considerable potential for practical device application, but its low electrical conductivity needs to be further improved to achieve higher thermoelectric performance. Here, a record‐high figure of merit, ZT of >0.7 at 773 K in the shear‐exfoliated nanostructured Bi2O2Se with graphite nanosheets as multifunctional secondary nanoinclusions, is achieved. The introduced graphite nanosheets regularize the arrangement of Bi2O2Se nanograins, strengthen the anisotropy, and act as the "expressway" to improve the electrical conductivity by simultaneously enhancing the electron carrier concentration and mobility of the hybrid materials, leading to a high power factor of ≈6.0 µW cm–1 K–2 at 773 K. Also, the liquid‐phase shear exfoliation refines both graphite and Bi2O2Se into nanosheets. Moreover, the as‐sintered hybrid bulk materials composed of these nanosheets possess dense grain and phase boundaries, as well as various lattice imperfections, such as lattice distortions and stacking faults formed by physical shearing, which can significantly scatter the phonons with different wavelengths and in turn contribute to a low thermal conductivity of only 0.63 W m–1 K–1 at 773 K, both contributing to a competitive ZT of ≈0.73 at this temperature, indicating the great potential for practical applications. [ABSTRACT FROM AUTHOR]

Bi2S3‐based thermoelectric materials without toxic and expensive elements have a high Seebeck coefficient and intrinsic low thermal conductivity. However, Bi2S3 suffers from low electrical conductivity, which makes it a less‐than‐perfect thermoelectric material. In this work, halogen elements F, Cl, and Br from halogen acid are successfully introduced into the Bi2S3 lattice using a hydrothermal procedure to efficiently improve the carrier concentration. Compared with the pure sample, the electron concentration of the Bi2S3 sample treated with HCl is increased by two orders of magnitude. An optimal power factor of 470 µW m−1 K−2 for the Bi2S2.96Cl0.04 sample at 673 K is obtained. Density functional theory calculations reveal that an effective delocalized electron conductive network forms after Cl doping, which raises the Fermi level into the conduction bands, thus generating more free electrons and improving the conductivity of the Bi2S3‐based materials. Ultimately, an excellent ZT of ≈0.8 is achieved at 673 K for the Bi2S2.96Cl0.04 sample, which is one of the highest values reported for a state‐of‐the‐art Bi2S3 system. The energy conversion efficiency of the module reaches 2.3% at 673 K with a temperature difference of 373 K. This study offers a new method for enhancing the thermoelectric properties of Bi2S3 by adding halogen acid in the hydrothermal process for powder synthesis. [ABSTRACT FROM AUTHOR]

Despite the same crystal structure and homologous constituent elements, the chalcopyrite compounds ABTe2 (A = Cu, Ag; B = Ga, In) exhibit distinct electronic and thermal transport properties. The aim of this work is to understand the origin of such discrepancy employing experiments and theoretical calculations. The results of Hall coefficient measurements, absorption spectroscopy, and electronic transport studies suggest the deep‐level in‐gap states induced by the native A‐site vacancies play a key role in the observed intrinsic semiconductor to degenerate semiconductor transition and are the origins of the distinct electrical conductivity among ABTe2 compounds. In addition, the cryogenic heat capacity measurements and calculated phonon dispersion relations show that the acoustic and low‐frequency optical modes of AgGaTe2 and AgInTe2 are governed by the vibrations of AgTe clusters while the counterparts of CuGaTe2 and CuInTe2 compounds are dominated by the vibrations of Te atoms, and the coupling between the acoustic and low‐frequency optical modes is notably different among ABTe2 compounds. Specifically, lower avoided‐crossing frequencies, lower sound velocity together with stronger Umklapp process yield lower thermal conductivities of AgGaTe2 and AgInTe2 than CuGaTe2 and CuInTe2. This work provides new insights into the understanding and improvement of electrical and thermal properties toward higher thermoelectric performance of chalcopyrite compounds. [ABSTRACT FROM AUTHOR]

Se‐doped Mg3.2Sb1.5Bi0.5‐based thermoelectric materials are revisited in this study. An increased ZT value ≈1.4 at about 723 K is obtained in Mg3.2Sb1.5Bi0.49Se0.01 with optimized carrier concentration ≈1.9 × 1019 cm−3. Based on this composition, Co and Mn are incorporated for the manipulation of the carrier scattering mechanism, which are beneficial to the dramatically enhanced electrical conductivity and power factor around room temperature range. Combined with the lowered lattice thermal conductivity due to the introduction of effective phonon scattering centers in Se&Mn‐codoped sample, a highest room temperature ZT value ≈0.63 and a peak ZT value ≈1.70 at 623 K are achieved for Mg3.15Mn0.05Sb1.5Bi0.49Se0.01, leading to a high average ZT≈1.33 from 323 to 673 K. In particular, a remarkable average ZT≈1.18 between the temperature of 323 and 523 K is achieved, suggesting the competitive substitution for the commercialized n‐type Bi2Te3‐based thermoelectric materials. [ABSTRACT FROM AUTHOR]