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JOURNAL OF THE EUROPEAN CERAMIC SOCIETY · 2023 · IF 5.7

p-type Sn0.98Ag0.02Se with low thermal conductivity synthesized by hydrothermal method

Zi-Chen Wang,Xiao-Di Jiang,Yu-Xian Duan,Xu Wang,Zhen-Hua Ge,Jin-Ming Cai,Xiao-Ming Cai,Hong-Lin Tan

Tin selenide exhibits outstanding thermoelectric properties. Among its various forms, multicrystalline SnSe stands out as a more practical choice compared to single-crystal SnSe, owing to its straightforward chemical synthesis process, enhanced processability, and scalability. Herein, we synthesized p-type polycrystalline Sn 1−x Ag X Se bulk materials (x = 0, 0.01, 0.015, 0.02, 0.025, 0.03) using a simple hydrothermal and hot pressing method. Characterization methods such as XRD , Raman and XPS were used to demonstrate the successful doping of Ag + into the SnSe matrix. When the doping concentration reached Sn 0.98 Ag 0.02 Se (x = 0.02), Ag + reached the optimal concentration in the SnSe matrix, causing significant lattice distortion which increased phonon scattering and lowered the thermal conductivity , resulting in Sn 0.98 Ag 0.02 Se achieving ZT max = 1.14. However, when the doping concentration exceeded Sn 0.98 Ag 0.02 Se (x > 0.02), excess silver ions precipitated, partially acting as charge carriers, leading to a significant increase in electrical conductivity , resulting in Sn 0.97 Ag 0.03 Se having an electrical conductivity of 6860 s/m at 773 K. Compared to the pure phase, the electrical conductivity of Sn 0.97 Ag 0.03 Se increased by 259 %, and the ZT value of Sn 0.98 Ag 0.02 Se increased by 178%. This work demonstrates that Ag + is an effective p-type dopant in the SnSe system and indicates that high ZT values in SnSe can be achieved through a simple, low-cost, and environmentally friendly method.

CAS / MDL: 7782-49-2
研究领域: 材料科学 · 能源材料 · 物理化学
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CRYSTENGCOMM · 2022 ·Vol. 24 ·期 26 ·4772-4786 · IF 3.756

The effect of annealing in carbon powders on the anisotropy of the thermoelectric properties of SrTiO3−δ single crystals on the (001) crystal plane

Zhixin Ma,Yang Qi,Xiaoguo Bi,Xu-dong Liu,Xiaodong Li,Ji-guang Li,Xudong Sun

SrTiO3 has high thermoelectric properties and excellent high-temperature stability, which makes it a promising thermoelectric material for use in harsh environments. Hence, it has potential applications in power generation and sensors through direct conversion between heat and electricity. In this study, we investigated the crystal orientations on the crystal growth plane to seek the crystal orientation that is suitable for higher thermoelectric (TE) properties. The [510], [12 5 0] and [320] directions were selected which are on the (001) crystal plane and quarterly divide the angle between the [100] and [110] directions. Two common directions [100] and [110] were selected for comparison purposes. The SrTiO3 single crystals are annealed in carbon powders at 1573 K and 1673 K to form SrTiO3−δ. With the increase in annealing temperature, the electrical conductivity of SrTiO3−δ in the [510], [12 5 0] and [320] directions decreases, which is attributed to the decreasing carrier concentrations. This agrees well with the results calculated using the first-principles calculation. After annealing at 1573 K, the SrTiO3−δ single crystal exhibits the highest ZT value of 0.19 at 873 K in the [510] direction. However, the two common directions, [100] and [110], are not suitable for high thermoelectric properties. In particular, the SrTiO3−δ single crystal in the [12 5 0] direction can always exhibit higher PF and ZT values, regardless of the variation of the annealing temperature in carbon powders. The results of this study are imperative for the design and development of perovskite TE materials.

研究领域: 材料科学 · 热电材料
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RARE METALS · 2021 ·Vol. 41 ·期 3 ·931-941 · IF 4.003

Synergistically enhanced thermoelectric properties of Bi2S3 bulk materials via Cu interstitial doping and BiCl3 alloying

Guo Jun,Wang Zi-Yuan,Zhu Yu-Ke,Chen Lin,Feng Jing,Ge Zhen-Hua

Bi 2 S 3 is composed of inexpensive and environmental friendliness elements, which has received extensive interests and been investigated as a promising mid-temperature thermoelectric material for years. Even pure Bi 2 S 3 possesses a high Seebeck coefficient and low thermal conductivity, its low electrical conductivity leads to a low figure of merit (ZT) value. In this work, Bi 2 S 3 fabricated by solid-state melting combined with spark plasma sintering can significantly enhance the thermoelectric performance via introducing small amounts of Cu and BiCl 3 . Cu interstitial doping and Cl substitution on S site result in a large increase in electrical conductivity. Additionally, the enhanced phonon scattering is derived from the point defects caused by element doping, the grain boundaries, and the small amount of secondary phase, which leads to the low thermal conductivity. Finally, a high ZT value of 0.7 is obtained at 773 K and reaches a large average ZT of 0.36 in the temperature range from room temperature (RT) to 773 K for the Cu-interstitial-doped and BiCl 3 -alloyed (Cu 0.01 Bi 2 S 3  + 0.175 mol% BiCl 3 ) sample. Furthermore, the mechanical properties of the Cu 0.01 Bi 2 S 3  + 0.175 mol% BiCl 3 sample are lower than those of other Bi 2 S 3 samples, which stem from the weak chemical bonding strength. Graphic abstract

研究领域: 材料科学 · 能源材料 · 热电材料
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JOURNAL OF ELECTRONIC MATERIALS · 2022 ·Vol. 51 ·期 2 ·522-531 · IF 2.047

Improved Thermoelectric Performance for β-Zn4Sb3 by Na/Zn Co-doping

Zheng Jie,Chen Jiali,Tang Yu,Shen Kaiyuan,Xiang Yujie,Shen Lanxian,Ge Wen,Yang Peizhi,Deng Shukang

In this study, β -Zn 4 Sb 3 was prepared using the Zn-NaCl mixed-flux method based on the stoichiometric ratio of Zn/Sb/NaCl = (4− x ):3:(7+ x ) ( x = 0, 0.1, 0.2, 0.3). X-ray diffraction results showed that all samples were hexagonal rhombic crystal structures with the space group \(R\overline{3}c\) . A second phase of ZnSb was detected in the samples with x = 0.2 and x = 0.3. In addition, the crystal-cell volume and lattice parameter of all samples increased for the larger ion radius of Na + than Zn 2+ . The transmission electron microscopy image and corresponding area electron diffraction pattern demonstrated that the prepared samples had a complete crystal structure. All samples had hole conduction and exhibited p-type conduction behavior. The carrier concentration of the material increased with increased Na content and decreased Zn, ranging from 8.89 × 10 19 cm −3 to 17.82 × 10 19 cm −3 . Moreover, the thermal conductivity ( κ ) of x = 0–0.2 samples decreased with increased Na content; however, the sample with x = 0.3 had a higher κ owing to the appearance of a ZnSb phase. Thermogravimetric differential thermal analysis showed that no weight loss occurred below the melting point. Eventually, the sample with the nominal composition of β- Zn 3.8 Sb 3 NaCl 7.2 achieved a ZT value of 1.43 at 690 K.

研究领域: 材料科学 · 物理学
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Materials Horizons · 2022 ·Vol. 10 ·期 2 ·454-465 · IF 15.717

Emerging homogeneous superlattices in CaTiO3 bulk thermoelectric materials

Jianbo Li,Yanxia Wang,Xue Jiang,Zhen Tian,Huijun Kang,Zongning Chen,Enyu Guo,Zhiqiang Cao,Tongmin Wang

The thermal conductivity of superlattices is strongly reduced as compared to that of the parent materials due to phonon-scattering and thermal boundary resistances at the superlattice period interfaces. Herein, homogenous superlattices consisting of homogenous structural CeδCa1−δTiO3 and CaTi1−δCeδO3 alternate layers were obtained through a variable-valence Ce doping, providing multi-quantum well interfaces between the alternate layers due to Ce-substitution at Ca and Ti sites, respectively. This material comprising these homogenous superlattices displayed a significantly reduced lattice thermal conductivity of 1.82 W m−1 K−1 and a record high zT value of 0.405 at 1031 K in CaTiO3-based thermoelectric materials. This strategy of synthesizing homogeneous superlattices provides a cost advantage over heterogeneous superlattices prepared by the molecular beam epitaxy method and paves a route for preparing bulk superlattices with unique thermoelectric properties rooting in the quantum domain limiting effect.

研究领域: 材料科学 · 热电学
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APPLIED PHYSICS LETTERS · 2022 ·Vol. 120 ·期 19 · IF 3.971

Enhancing the thermoelectric performance of Ag2Se by non-stoichiometric defects

Wang Ping,Chen Jun-Liang,Zhou Qi,Liao Yun Tiao,Peng Ying,Liang Ji Sheng,Miao Lei

Ag 2 Se is an attractive candidate for room temperature thermoelectric applications because of its extremely low thermal conductivity, large power factor, and excellent mechanical properties. However, its performance is difficult to be improved effectively by doping other atoms. The traditional synthesis processes have the disadvantages of low yield, complex steps, and long period. In this study, the Ag 2 Se 1+ x samples were rapidly synthesized by the melting method via changing the ratio of Ag and Se. The carrier concentration and mobility of Ag 2 Se are optimized by adding excess Se, which could regulate non-stoichiometric defects in the process of synthesis. A high Seebeck coefficient of ∼136.0  μ V K −1 , a large power factor of ∼3000.0  μ W m −1  K −2 , and the maximum figure of merit ( ZT ) of ∼1.02 of the Ag 2 Se 1.015 sample have been achieved at 375 K. The ZT value is 2.3 times than that of the pristine sample (Ag 2 Se). The mechanical properties of the molting sample are comparable to state-of-the-art thermoelectric materials. Finally, the highest ZT value of the material is predicted by factor B . This work provides an idea for further optimizing Ag 2 Se-based and other non-stoichiometric thermoelectric semiconductors by a slight excess of Se. Moreover, the fast synthesis technology can significantly save time and energy, which manifests great advantages to the wholesale manufacturing industry.

研究领域: 材料科学 · 能源工程
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JOURNAL OF MOLECULAR LIQUIDS · 2019 · IF 4.561

Selective recovery of gold ions in aqueous solutions by a novel trithiocyanuric-Zr based MOFs adsorbent

Zhen Huang,Minghu Zhao,Shixing Wang,Linqing Dai,Libo Zhang,Chen Wang

A trithiocyanuric-Zr based MOFs adsorbent (ZT-MOFs) was synthesized by using trithiocyanuric acid as a linker and zirconium chloride as a metal matrix and used to recover Au(III). ZT-MOFs was characterized by FT-IR, BET, Raman and FE-SEM. ZT-MOFs are porous material and have good stability in the range of pH 1–9. ZT-MOFs showed a higher adsorption capacity for Au(III) (333.34 mg/g) at 480 min and pH = 7. The experimental data fitted to Freundlich and pseudo second-order models, indicating a heterogeneous multi-layer chemadsorption is the dominated step. ZT-MOFs separated selectively Au(III) from laboratory wastewater containing various interfering ions. The removal rate of Au(III) decreased only from 94.5% to 87.5% after 4 adsorption and desorption cycles. This shows that ZT-MOFs have good repeatability. FT-IR, XPS and Zeta potential data shows that the adsorption mechanism of Au(III) on ZT-MOFs is coordination. Therefore, ZT-MOFs have great potential in extracting Au(III) from wastewater.

CAS / MDL: 68-12-2 638-16-4
研究领域: 材料科学 · 环境科学
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JOURNAL OF ALLOYS AND COMPOUNDS · 2017 · IF 3.133

Enhancing thermoelectric performance of SnTe via nanostructuring particle size

Xiao Zhang,Yiming Zhou,Yanling Pei,Yuexing Chen,Bifei Yuan,Shuangmei Zhang,Yuan Deng,Shengkai Gong,Jiaqing He,Li-Dong Zhao

SnTe, one lead-free analogue of PbTe, has been paid attention in thermoelectric community because it has the similar rock-salt crystal structure and electronic band structure . However, SnTe possesses a very high total thermal conductivity (∼10.0 W m −1  K −1  at room temperature) and a mediocre ZT (∼0.2 at 723 K). In this study, to reduce its thermal conductivity, we prepare SnTe samples by melting reaction followed by mechanical alloying and spark plasma sintering . We demonstrate that both total thermal conductivity and lattice thermal conductivity can be considerably reduced through reducing particle size from micro-scale to nano-scale via facially mechanical alloying method. Experimental results show that the total thermal conductivity at room temperature can be reduced from ∼10 W m −1  K −1 for SnTe ingot to ∼3Wm −1  K −1 for SnTe with mechanical alloying 25 h. Correspondingly, the lattice thermal conductivity at room temperature was reduced from ∼5Wm −1  K −1 to ∼2Wm −1  K −1 . Combination of reduced thermal conductivity and moderate power factor, average ZT ave can be increased by 33.3%, from 0.09 for SnTe ingot to 0.12 for SnTe with nano-grain size.

CAS / MDL: 7440-31-5 13494-80-9
研究领域: 材料科学 · 热电学
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INORGANIC CHEMISTRY · 2018 · IF 4.7

Thermoelectric Material SnPb2Bi2S6: The 4,4L Member of Lillianite Homologous Series with Low Lattice Thermal Conductivity

Jingpeng Li,Yiming Zhou,Shiqiang Hao,Tianyan Zhang,Chris Wolverton,Jing Zhao,Li-Dong Zhao

Although the binary sulfides Bi2S3, PbS, and SnS have attracted extensive interest as thermoelectric materials, no quaternary sulfides containing Sn/Pb/Bi/S elements have been reported. Herein, we report the synthesis of a new quaternary sulfide, SnPb2Bi2S6, which crystallizes in the orthorhombic space group Pnma with unit cell parameters of a = 20.5458(12) Å, b = 4.0925(4) Å, c = 13.3219(10) Å. SnPb2Bi2S6 has a lillianite-type crystal structure consisting of two alternately aligned NaCl-type structural motifs separated by a mirror plane of PbS7 monocapped trigonal prisms. In the lillianite homologous series, SnPb2Bi2S6 can be classified as 4,4L, where the superscripted numbers indicate the maximum numbers of edge-sharing octahedra in the two adjacent NaCl-shaped slabs along the diagonal direction. The obtained SnPb2Bi2S6 phase exhibited good thermal stability up to 1000 K and n-type degenerate semiconducting behavior, with a power factor of 3.7 μW cm–1 K–2 at 773 K. Notably, this compound exhibited a very low lattice thermal conductivity of 0.69–0.92 W m–1 K–1 at 300–1000 K. Theoretical calculations revealed that the low thermal conductivity is caused by the complex crystal structure and the related elastic properties of a low Debye temperature, low phonon velocity, and large Grüneisen parameters. A reasonable figure of merit (ZT) of ∼0.3 was obtained at 770 K.

研究领域: 材料科学 · 物理学
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CERAMICS INTERNATIONAL · 2019 · IF 3.45

Enhancing the thermoelectric properties of Bi2Ba2Co2Oy by dispersing SiC nanoparticles based on Na element doping

Chuangchuang Ruan,Mengmeng Fan,Yuewen Zhang,Hongzhang Song,Xin-Jian Li,Haoshan Hao

In this work, Bi 2 Ba 2 Co 2 O y  +  v wt% SiC ( v  = 0.00, 0.025, 0.05, 0.1, 0.2) and Bi 1.975 Na 0.025 Ba 2 Co 2 O y  +  w wt% SiC ( w  = 0.00, 0.025, 0.05, 0.1, 0.2) ceramic samples were synthesised. The increase in the carrier concentration caused by a small amount of Na element doping leads to a decrease in the resistivity and Seebeck coefficients. The lattice distortion caused by Na element doping decrease the sample thermal conductivity . After adding SiC nanoparticles , the resistivity can be reduced further. Especially more phonons are scattered by more grain boundaries, which leads to reduced thermal conductivity. The Seebeck coefficients increase slightly due to the low energy carrier scattering effect. Considering the influence of these two factors, dispersing SiC particles on the basis of Na element doping can effectively improve the thermoelectric performance of Bi 2 Ba 2 Co 2 O y -based samples. The ZT value of the Bi 1.975 Na 0.025 Ba 2 Co 2 O y + 0.1 wt% SiC sample reaches a maximum value of 0.21 at 923 K, 26.6% higher than the Bi 1.975 Na 0.025 Ba 2 Co 2 O y sample and 93% higher than the pure Bi 2 Ba 2 Co 2 O y sample.

研究领域: 材料科学 · 物理学
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Physica Status Solidi-Rapid Research Letters · 2020 ·Vol. 14 ·期 4 ·1900679 · IF 2.291

Enhanced Thermoelectric Performance of Bi2Te2.7Se0.3/Bi2S3 Synthesized by Anion Exchange Method

Xi Chen,Fanggong Cai,Chuanrong Liu,Rong Dong,Lanxin Qiu,Lili Jiang,Guocai Yuan,Qinyong Zhang

Decoupling the electric conductivity, Seebeck coefficient, and thermal conductivity is a core issue to improve the properties of thermoelectric materials by tuning the electron and phonon transport properties. Herein, Bi 2 Te 2.7 Se 0.3 /Bi 2 S 3 heterostructure is successfully synthesized by a simple anion exchange method with Bi 2 Te 2.7 Se 0.3 as the starting material. The Bi 2 Te 2.7 Se 0.3 /Bi 2 S 3 heterointerfaces can achieve an effective phonon scattering and significant decrease in thermal conductivity, while maintaining a high power factor, resulting in an enhanced figure of merit ( ZT ). By controlling the concentration of Bi 2 Te 2.7 Se 0.3 /Bi 2 S 3 heterointerfaces, the carrier-transporting and phonon-scattering behaviors can be simultaneously optimized. A maximum ZT of 0.7 is obtained at 473 K, which is 23% higher than that of pure Bi 2 Te 2.7 Se 0.3 . In addition, the average ZT at 300–548 K increases from 0.49 to 0.61, which is 25% higher than that of pure Bi 2 Te 2.7 Se 0.3 .

研究领域: 材料科学 · 物理学
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Materials · 2024 ·Vol. 17 ·期 7 ·1509 · IF 3.1

Optimizing Thermoelectric Performance of Hybrid Crystals Bi2O2Se1−xTex in the Bi2O2X System

Fan Xie,Zhiyao Ma,Jian Zhou

In addressing the global need for sustainable energy conversion, this study presents a breakthrough in thermoelectric materials research by optimizing the Bi2O2Se1–xTexsystem in the Bi2O2Se/Bi2O2Te pseudobinary series. Leveraging the principles of innovative transport mechanisms and defect engineering, we introduce tellurium (Te) doping into Bi2O2Se to enhance its thermoelectric properties synergistically. With the help of various advanced characterization tools such as XRD, SEM, TEM, XPS, FTIR, TGA, LFA, and DSC, combined with relevant resistance and density measurement techniques, we conducted an in-depth exploration of the complex interactions between various factors within thermoelectric materials. We recognize that the balance and synergy of these factors in the thermoelectric conversion process are crucial to achieving efficient energy conversion. Through systematic research, we are committed to revealing the mechanisms of these interactions and providing a solid scientific foundation for the optimal design and performance enhancement of thermoelectric materials. Finally, the advantage coefficient (ZT) of the thermoelectric material has been significantly improved. The crystallographic analysis confirms the formation of a continuous series of mixed crystals with varying Te concentrations, adhering to Vegard’s law and exhibiting significant improvements in electrical and thermal conductivities. The Bi2O2Se1–xTexcrystals, particularly the Bi2O2Se0.6Te0.4composition, demonstrate a peak ZT of 0.86 at 373 K. This achievement aligns with recent advancements in defect-enabled mechanisms and band convergence and sets a new standard for high-performance thermoelectrics. The study’s findings contribute significantly to the ongoing quest for efficient thermal-to-electrical energy conversion, offering a promising avenue for future sustainable energy technologies.

CAS / MDL: 7440-69-9 7782-49-2
研究领域: 材料科学 · 能源转换技术
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