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Frontiers of Physics · 2018 ·Vol. 14 ·期 1 ·1-12 · IF 1.892

Enhancing the thermoelectric performance of Bi2S3: A promising earth-abundant thermoelectric material

Chen Ye,Wang Dongyang,Zhou Yuling,Pang Qiantao,Shao Jianwei,Wang Guangtao,Wang Jinfeng,Zhao Li-Dong

Recently, bismuth sulfide (Bi 2 S 3 ) has attracted much attention in the thermoelectric community owing to its abundance, low cost, and advanced properties. However, its poor electrical transport properties have prevented Bi 2 S 3 devices from realizing high thermoelectric performance. In this work, our motivation is to decrease the large electrical resistivity, which is recognized as the origin of the low ZT value in undoped Bi 2 S 3 . We combined melting and spark plasma sintering (SPS) in a continuous fabrication process to produce Bi 2 S 3- x Se x ( x = 0, 0.09, 0.15, 0.21) and Bi 2 S 2.85- y Se 0.15 Cl y ( y = 0.0015, 0.0045, 0.0075, 0.015, 0.03) samples. Our results show that Se alloying at S sites can narrow the band gap and activate intrinsic electron conduction, leading to a high power factor of ~ 2.0 μW·cm -1 ·K -2 cat room temperature in Bi 2 S 2.85 S 0.15 , about 100 times higher than that of undoped Bi 2 S 3 . Moreover, our further introduction of Cl atoms into the S sites resulted in a second-stage optimization of carrier concentration and simultaneously reduced the lattice thermal conductivity, which contributed to a high ZT value of ~ 0.6 at 723 K for Bi 2 S 2.835 Se 0.15 Cl 0.015 . Our results indicate that high thermoelectric performance could be realized in Bi 2 S 3 with earth-abundant and low-cost elements.

研究领域: 材料科学 · 热电学 · 固体物理学
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CERAMICS INTERNATIONAL · 2022 · IF 5.532

S0.05Co4Sb11.6Te0.4 skutterudite introduced into graphene at high pressure and high temperature and its thermoelectric performance enhancement

Xin Fan,Yaqi Chen,Qi Chen,Yao Wang,Dayi Zhou,Lijie Chang,Xinjian Li,Yuewen Zhang,Hongan Ma,Xiaopeng Jia

A series of graphene-S 0.05 Co 4 Sb 11.6 Te 0.4 (C x -S 0.05 Co 4 Sb 11.6 Te 0.4 ) composite polycrystalline skutterudite materials with graphene stoichiometric ratio of x  = 0, 0.05, 0.10, 0.20 have been successfully prepared by high pressure and high temperature (HPHT) technology. Graphene is a two-dimensional material with large carrier mobility and large specific surface area. Through microscopic observation, it is found that graphene is attached to the grains in the sample. At the same time, with the increase of graphene content, grain growth is inhibited. Graphene addition reduces the thermal conductivity of skutterudite by increasing grain boundaries and achieves the purpose of optimizing its thermoelectric properties. At the same time, there are numerous lattice defects and distortions introduced in skutterudite synthesized by HPHT technology. Finally, the samples were synthesized under the conditions of 1.5 GPa and 900 K. The lattice thermal conductivity of the graphene composite sample C x -S 0.05 Co 4 Sb 11.6 Te 0.4 with x  = 0.10 reaches a minimum of 0.99 at 773 K, and the zT value of this sample is 1.25 at 773 K, which is greater than pure S 0. 05 Co 4 Sb 11.6 Te 0.4 , its zT value is 1.00 at 773 K. Compared with the method of synthesizing skutterudite under normal pressure, the HPHT technology can dramatically reduce the reaction time from several days to less than 30 min, while forming a high-pressure airtight reaction environment, which can effectively prevent the volatilization and oxidation of samples during the reaction process, thus providing a convenient method for synthesizing thermoelectric materials quickly and efficiently.

研究领域: 材料科学 · 热电材料研究
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ACS Applied Materials & Interfaces · 2022 · IF 10.383

From Brittle to Ductile: A Scalable and Tailorable All-Inorganic Semiconductor Foil through a Rolling Process toward Flexible Thermoelectric Modules

Jia Liang,Xuefei Zhang,Chunlei Wan

Inorganic thermoelectric (TE) materials with outstanding capacity for energy conversion are expected to be promising eco-friendly and renewable power sources, but they are always intrinsically brittle, restricting their development in flexible TE electronics. Therefore, we have developed a facile manufacturing method of large-scale all-inorganic silver chalcogenide foils and flexible TE generators in this work. A rolling process, as an effective and facile molding technique, is applied in ductile TE materials. The figure-of-merit for flexibility of this free-standing foil is in the range of 0.02–0.13, suggesting the superior flexibility of the all-inorganic TE foils. A high TE figure-of-merit ZT of 0.47 at room temperature is reached for Ag2S0.45Se0.45Te0.1, which is one of the most promising room-temperature ZTs among flexible TE materials. A proof-of-concept flexible TE generator based on silver chalcogenide foils achieves an open-circuit voltage of 1.19 mV and an output power density of 1.8 mW/m2 with a temperature difference of 2.7 °C across the TE leg, showing great potential in heat-to-electricity conversion.

研究领域: 材料科学 · 能源技术
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DALTON TRANSACTIONS · 2017 ·Vol. 46 ·期 8 ·2510-2515 · IF 4.029

Thermoelectric properties of Bi1−xSnxCuSeO solid solutions

Yuqing Yang,Xiaocun Liu,Xin Liang

We report the enhanced thermoelectric properties of p-type BiCuSeO by tin doping on bismuth sites. Powder X-ray diffraction analysis and Hall measurements indicated effective tin doping in all samples. We found that the doping efficiency of Sn is lower than expected, as seen from the measured carrier concentration. First-principles calculations indicate that the Sn lone pair modifies the band structure at the Fermi level, with the consequent effect observed in the electrical transport and Seebeck coefficient measurements. An enhanced thermoelectric power factor of ∼2.5 μW cm−1 K−2 was reached at 773 K. No significant effect of Sn doping on the thermal conductivity was found; a thermoelectric figure of merit value (ZT) of 0.3 at 773 K is achieved for Bi0.9Sn0.1CuSeO, which is more than twice that of the pristine BiCuSeO.

研究领域: 材料科学 · 凝聚态物理 · 无机非金属材料 · 能源材料 · 半导体物理
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ACS Nano · 2024 · IF 15.8

Simultaneously Boosting Thermoelectric and Mechanical Properties of n-Type Mg3Sb1.5Bi0.5-Based Zintls through Energy-Band and Defect Engineering

Lu Yu,Xiao-Lei Shi,Yuanqing Mao,Wei-Di Liu,Zhen Ji,Sitong Wei,Zipei Zhang,Weiyu Song,Shuqi Zheng,Zhi-Gang Chen

Incorporating donor doping into Mg3Sb1.5Bi0.5 to achieve n-type conductivity is one of the crucial strategies for performance enhancement. In pursuit of higher thermoelectric performance, we herein report co-doping with Te and Y to optimize the thermoelectric properties of Mg3Sb1.5Bi0.5, achieving a peak ZT exceeding 1.7 at 703 K in Y0.01Mg3.19Sb1.5Bi0.47Te0.03. Guided by first-principles calculations for compositional design, we find that Te-doping shifts the Fermi level into the conduction band, resulting in n-type semiconductor behavior, while Y-doping further shifts the Fermi level into the conduction band and reduces the bandgap, leading to enhanced thermoelectric performance with a power factor as high as >20 μW cm–1 K–2. Additionally, through detailed micro/nanostructure characterizations, we discover that Te and Y co-doping induces dense crystal and lattice defects, including local lattice distortions and strains caused by point defects, and densely distributed grain boundaries between nanocrystalline domains. These defects efficiently scatter phonons of various wavelengths, resulting in a low thermal conductivity of 0.83 W m–1 K–1 and ultimately achieving a high ZT. Furthermore, the dense lattice defects induced by co-doping can further strengthen the mechanical performance, which is crucial for its service in devices. This work provides guidance for the composition and structure design of thermoelectric materials.

研究领域: 材料科学 · 物理学 · 纳米技术
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Thermoelectric performance of p-type (Bi,Sb)2Te3 incorporating amorphous Sb2S3 nanospheres

Deyu Bao,Qiang Sun,Linsen Huang,Jie Chen,Jun Tang,Dali Zhou,Min Hong,Lei Yang,Zhi-Gang Chen

Tremendous efforts have been focusing on the improvement of p-type (Bi, Sb) 2 Te 3 -based thermoelectric materials for commercial applications. In this study, we achieve versatile interface engineering through a surface decoration of Bi 0.5 Sb 1.5 Te 3 by amorphous Sb 2 S 3 combining with spark plasma sintering, which introduces semi-coherent Sb/Bi 0.5 Sb 1.5 Te 3 interfaces and dopes S into Bi 0.5 Sb 1.5 Te 3 . Semi-coherent Sb/Bi 0.5 Sb 1.5 Te 3 interfaces strongly scatter phonons and lower energy carriers, leading to decreased thermal conductivity and increased Seebeck coefficient, while the electrical conductivity is not sacrificed due to the compromise of the slightly reduced carrier mobility by interfacial scattering and the increased carrier concentration by S doping. Benefited from the decoupled thermoelectric properties, a significantly enhanced power factor of 3345.40 μW m −1 K −2 and a low thermal conductivity of 0.78 W m −1 K −1 is obtained in Bi 0.5 Sb 1.5 Te 3 -0.4%Sb 2 S 3 , leading to a high peak zT of ∼ 1.31 at 330 K, which shows a 54% enhancement compared with pristine Bi 0.5 Sb 1.5 Te 3 . Moreover, a conversion efficiency of ∼ 7.6% can be predicted in a single leg Bi 0.5 Sb 1.5 Te 3 -0.4%Sb 2 S 3 -based module under a cold side temperature of 300 K and hot side temperature of 480 K. This study paves a facile amorphous Sb 2 S 3 induced interface engineering strategy for the development of high performance (Bi,Sb) 2 Te 3 -based thermoelectric materials.

研究领域: 材料科学 · 能源科学
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CHEMICAL ENGINEERING JOURNAL · 2020 · IF 10.652

Texture-dependent thermoelectric properties of nano-structured Bi2Te3

Deyu Bao,Jie Chen,Yuan Yu,Weidi Liu,Linsen Huang,Guang Han,Jun Tang,Dali Zhou,Lei Yang,Zhi-Gang Chen

In this study, Bi 2 Te 3 nanostructures were synthesized with controlled morphologies by using a solvothermal process and then sintered by spark plasma sintering to obtain bulk samples with controllable texture degrees. The sintered nanostructured Bi 2 Te 3 pellets show texture-dependent thermoelectric properties, in which their Seebeck coefficient, electrical conductivity and thermal conductivity can be optimized by the proper texture design to simultaneously secure a high carrier mobility and strong phonon scattering, resulting in a peak ZT value of ~0.69 at 333 K. This study reveals the potential of texture engineering in developing high performance anisotropic thermoelectric materials.

研究领域: 材料科学 · 物理学
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International Journal of Applied Ceramic Technology · 2023 ·Vol. 21 ·期 2 ·1220-1230 · IF 2.1

Filtering low-energy carriers to enhance thermoelectric performance of Cd-doped SnSe via incorporation of MXene sheets

Yi Qin,Mengxue Wang,Xiaohan Li,Yajuan Zhang,Shenglai Tang,Jianfeng Zhu,Ting Zhao

SnSe-based materials have attracted widespread attention in thermoelectrics due to their outstanding thermoelectric performance. However, the pristine and unmodified polycrystalline SnSe reveals poor electrical properties. Doping and constructing nanostructured composite architectures to produce energy filtering effect proved to be an effective method to strengthen thermoelectric performance. In this study, Ti 3 C 2 /Sn 0.98 Cd 0.02 Se composites are successfully fabricated by the solvothermal method combined with the electrostatic self-assembly method and spark plasma sintering. The phase interface introduced by incorporating Ti 3 C 2 into Sn 0.98 Cd 0.02 Se can effectively filter low-energy carriers due to its generation of energy barriers, thereby the Seebeck coefficient of x wt% Ti 3 C 2 /Sn 0.98 Cd 0.02 Se x = (0.05, 0.5, 1) samples is better than that of the pristine Sn 0.98 Cd 0.02 Se over the whole temperature range. Meanwhile, high conductivity was also obtained in 1 wt% Ti 3 C 2 /Sn 0.98 Cd 0.02 Se sample so that the high power factor of 3.31 μWcm −1 K − 2 was acquired at 773 K. Ultimately, a peak ZT value of 0.41 was obtained at 773 K, compared with pristine Sn 0.98 Cd 0.02 Se, and the thermoelectric performance improved by 24%. This study offers an available approach to efficiently enhance the thermoelectric properties of polycrystalline SnSe-based materials.

研究领域: 材料科学 · 热电学 · 纳米技术
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ACS Applied Energy Materials · 2019 · IF 0

Enhancement of Thermoelectric Performance of Layered SnSe2 by Synergistic Modulation of Carrier Concentration and Suppression of Lattice Thermal Conductivity

Shaohai Wu,Hengquan Yang,Zhengsen Wu,Chengyan Liu,Lei Miao,Jie Gao,Xiaoyang Wang,Xiuxia Wang,Chengjin Shen,Jacques G. Noudem,Jun Wang

Eco-friendly and low-cost layered SnSe2-based materials have been attracting great attention in the thermoelectric field for their intrinsically low thermal conductivity. In this work, we applied AgCl as Cl-dopant and formed Ag-rich precipitates in SnSe2 polycrystals, and their thermoelectric properties were investigated. The results demonstrate that Cl was artificially incorporated into SnSe2 by the substitution of Se atoms, playing as donor centers and thus increasing the carrier concentration by 2 orders of magnitude, leading to a tremendous improvement of the electrical conductivity and power factor. However, Ag atoms hardly enter into the Sn lattice sites and brought about the generation of Ag-rich precipitates. The complicated microstructures with multiple types of defects, such as point defects, boundaries, dislocations, and so on, result in a relatively low lattice thermal conductivity in the AgCl-introduced SnSe2 samples. Additionally, the anisotropic electrical and thermal transport properties were investigated, and the results show that higher ZT values were obtained along the pressing direction in these textured samples because of the significantly suppressed lattice thermal conductivity caused by the enhanced phonon scattering via the interior van der Waals layers. Ultimately, a maximum ZT value of 0.35 was realized at 400 °C in the polycrystalline SnSe2 with introduction of 11 mol % AgCl, which is nearly 3 times higher than that value of the pristine counterpart. It demonstrates that the combined effects of Cl-doping, Ag-rich precipitates, and texturing could effectively enhance the ZT value for polycrystalline SnSe2.

研究领域: 材料科学 · 热电学 · 固体物理学
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Materials Science and Engineering B-Advanced Functional Solid-State Materials · 2025 · IF 4.6

Enhancement of the thermoelectric properties of (Ba0.15Pb0.15Ag0.1Na0.2Cu0.2Bi1.2)Sr2Co2Oy ceramics by high-entropy engineering

Senlin Leng,Shibo Guan,Yingying Xu,Hongzhang Song,Mengyao Li,Haoshan Hao

Bi 2 Sr 2 Co 2 O y has good thermoelectric performance, but it still has wide room for further improvement. In this study, the (Ba 0.15 Pb 0.15 Ag 0.1 Na 0.2 Cu 0.2 Bi 1.2 )Sr 2 Co 2 O y high-entropy sample was prepared by the Bi 2 Sr 2 Co 2 O y pristine sample and the multi-element doping in Bi cite. On the one hand, the carrier concentration and carrier mobility of the high-entropy sample increase, so its electrical transport performance is improved greatly. On the other hand, due to the high disorder introduced by the multi- element doping, the phonon scattering is enhanced, and the thermal conductivity of the high-entropy sample is suppressed significantly. Finally, at 923 K, the ZT value (the dimensionless thermoelectric figure of merit) of the high-entropy sample reaches 0.26, which is about 1.9 times higher than that of the pristine sample.

研究领域: 材料科学 · 凝聚态物理 · 无机非金属材料 · 能源材料 · 热电转换
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Materials Today Physics · 2021 · IF 9.298

Magnetoresistance-enhanced electro-thermal conversion performance

C. Li,S. Ma,W. Cui,X. Sang,P. Wei,W. Zhu,X. Nie,W. Zhao,Q. Zhang

Seeking novel and effective approaches to synergistically improve the electrical and thermal transport properties and electro-thermal conversion efficiency of Bi 2 Te 3 -based alloys is essential for commercial applications. Here, GdCo 2 /Bi 0.37 Sb 1.63 Te 3 thermoelectric nanocomposites were designed and synthesized to achieve synergistic improvement of electrical and thermal properties . As confirmed by magnetoresistance measurement, the built-in magnetic field and magnetic scattering generated by magnetic nanoparticles decrease the carrier concentration and mobility, and increase the Seebeck coefficient . Meanwhile, GdCo 2 nanoparticles lead to broad-frequency phonon scattering, which effectively reduces the lattice thermal conductivity of nanocomposites. Eventually, the average ZT of the nanocomposite is increased by 18% in the range of 300–500 K, and the cooling temperature difference is increased by 68% near room temperature. This work proves that the thermoelectromagnetic coupling effects generated by magnetic particles can effectively improve the electro-thermal conversion performance.

研究领域: 材料科学 · 凝聚态物理 · 热电材料 · 纳米科技 · 功能材料
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Small Methods · 2024 ·Vol. 8 ·期 10 ·2301619 · IF 10.7

Boosting Thermoelectric Performance via Weakening Carrier-Phonon Coupling in BiCuSeO-Graphene Composites

Zhifang Zhou,Jinming Guo,Yunpeng Zheng,Yueyang Yang,Bin Yang,Dengfeng Li,Wenyu Zhang,Bin Wei,Chang Liu,Jin-Le Lan,Ce-Wen Nan,Yuan-Hua Lin

BiCuSeO is a promising oxygen-containing thermoelectric material due to its intrinsically low lattice thermal conductivity and excellent service stability. However, the low electrical conductivity limits its thermoelectric performance. Aliovalent element doping can significantly improve their carrier concentration, but it may also impact carrier mobility and thermal transport properties. Considering the influence of graphene on carrier-phonon decoupling, Bi 0.88 Pb 0.06 Ca 0.06 CuSeO (BPCCSO)-graphene composites are designed. For further practical application, a rapid preparation method is employed, taking less than 1 h, which combines self-propagating high-temperature synthesis with spark plasma sintering. The incorporation of graphene simultaneously optimizes the electrical properties and thermal conductivity, yielding a high ratio of weighted mobility to lattice thermal conductivity (144 at 300 K and 95 at 923 K). Ultimately, BPCCSO-graphene composites achieve exceptional thermoelectric performance with a ZT value of 1.6 at 923 K, bringing a ≈40% improvement over BPCCSO without graphene. This work further promotes the practical application of BiCuSeO-based materials and this facile and effective strategy can also be extended to other thermoelectric systems.

研究领域: 材料科学 · 凝聚态物理 · 能源材料 · 热电转换 · 纳米复合材料
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