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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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Results in Physics · 2021 · IF 4.476

Grain size and compositional gradient dependence of thermoelectric performance for Cu3−xNixSbSe4 materials

Lin Bo,Yongpeng Wang,Wenying Wang,Lei Wang,Fujin Li,Min Zuo,Yanzhen Ma,Degang Zhao

The ternary Cu 3 SbSe 4 thermoelectric material with diamond-like structure exhibit good thermoelectric performance in the middle temperature region. In this study, the Cu 3− x Ni x SbSe 4 ( x  = 0–0.03) materials were fabricated by melting-ball milling-hot pressing process. The influences of grain size and compositional gradient on the microstructure and thermoelectric properties of Cu 3− x Ni x SbSe 4 were evaluated. It is found that the electrical conductivity of Cu 2.97 Ni 0.03 SbSe 4 was about 33% higher than that of Cu 3 SbSe 4 sample, and the lattice thermal conductivity was reduced from 3.3 Wm −1 K −1 to 2.4 Wm −1 K −1 at room temperature due to the grain refinement and more V Se defects. The maximum zT value for the Cu 2.97 Ni 0.03 SbSe 4 sample was 0.62 at 650 K.

研究领域: 材料科学 · 凝聚态物理 · 功能材料 · 热电材料 · 半导体材料
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Journal of Materiomics · 2024 ·Vol. 11 ·期 4 ·100995 · IF 8.4

Tuning the bonding environment of Se atom in Cu2MnSnSe4-based alloys for raised thermoelectric performance

Yuqing Sun,Zhihao Li,Yujie Zong,Fulong Liu,Hongxiang Wang,Hui Sun,Chunlei Wang,Hongchao Wang

The intrinsic low lattice thermal conductivities originates from the complex anion bonding environment make quaternary chalcogenides potential thermoelectric materials. Here, the bonding environment of Se atom in Cu 2.1 Mn 0.9 SnSe 4 is further regulated by substituting Mn 2+ with equimolar pairing elements (Ag + and In 3+ ). The increase in both bond length and angle, together with the reduction in bond strength of Ag Se and In Se bonds, cause the doped samples to display strong anharmonicities ( γ  ∼ 1.84–2.04). And the weakened bond strength also lower the sound velocities. Consequently, the κ L of the doped samples is effectively constrained, achieving a minimum value of 0.55 W⸱m −1 ⸱K −1 at 673 K in x  = 0.10 sample. Ultimately, a zT value of 0.53 at 673 K is attained in x  = 0.10 sample. The modification of bonding environment around anion is considered as an effective mean to optimize the thermoelectric performance of quaternary chalcogenides.

研究领域: 材料科学 · 凝聚态物理 · 功能材料 · 热电转换 · 固态化学
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APPLIED PHYSICS A-MATERIALS SCIENCE & PROCESSING · 2024 ·Vol. 130 ·期 3 ·203 · IF 2.5

Enhanced thermoelectric properties of Bi2Sr2Co2Oy ceramics by dispersing B2O3 additive

Xu Yingying,Xia Siyi,Zhang Yingjiu,Song Hongzhang,Liu Shaohui,Hao Haoshan

In this study, ceramic samples of Bi 2 Sr 2 Co 2 O y  +  v wt% B 2 O 3 ( v  = 0.0, 0.1, 0.2, 0.3, 0.4) were synthesized using the solid state reaction method, and the influence of B 2 O 3 additive on their microstructure and thermoelectric properties were investigated. On one hand, the B 2 O 3 additive acted as a sintering aid, enhancing carrier mobility. On the other hand, B 2 O 3 dispersion served as a nano-second-phase, increasing hetero-interfaces and strengthen phonon scattering, thereby effectively suppressing lattice thermal conductivity. By dual optimization of both electric and thermal transport performance, the Bi 2 Sr 2 Co 2 O y  + 0.3 wt% B 2 O 3 sample achieved a high ZT value (thermoelectric figure of merit) of 0.31 at 923 K, which was improved by approximately 33% compared with the pristine Bi 2 Sr 2 Co 2 O y sample.

研究领域: 材料科学 · 凝聚态物理 · 无机非金属材料 · 热电材料
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Journal of Materials Chemistry A · 2023 ·Vol. 11 ·期 43 ·23319-23329 · IF 11.9

Interfacial modulation to achieve low lattice thermal conductivity and enhanced thermoelectric performance in n-type Mg3(Sb, Bi)2-based materials via graphene and MXene

Bang-Zhou Tian,Yi-Yan Liao,Fang Xu,Xiao-Ling Qiu,Fu-Jie Zhang,Ran Ang

Interfacial modulation has been considered an effective strategy to enhance the thermoelectric (TE) performance by decoupling thermal and electrical parameters. However, inappropriate interfacial heterojunctions can significantly deteriorate electrical transport while enhancing phonon scattering, which causes no substantial improvement in TE performance. Herein, we introduce two-dimensional graphene or MXene into the Mg3.2Sb0.5Bi1.49Te0.01 matrix by ball mixing combined with rapid sintering to modify the composition and structure at the interface. The differences in morphology, size and distribution of interfacial graphene and MXene lead to distinct results which show that incorporated graphene flakes with larger size hinder the carrier transport, while the homogeneously dispersed tiny MXene provides improved carrier channels and boosts the mobility. On the other hand, such uniformly diffused heterogeneous MXene structures create stronger scattering on phonons compared to enriched graphene phases, resulting in a low lattice thermal conductivity of ∼0.66 W m−1 K−1 and enhanced zT of ∼1.0 at 513 K in Mg3.2Sb0.5Bi1.49Te0.01-0.6 wt% MXene with good component stability in air. This work highlights the importance of size, concentration, and distribution in the interfacial modulation strategy, demonstrating an effective method for developing high TE performance Mg3(Sb, Bi)2-based near-room-temperature materials.

研究领域: 材料科学 · 凝聚态物理 · 纳米材料 · 能源材料 · 固体化学
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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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Journal of Materials Chemistry A · 2022 ·Vol. 10 ·期 23 ·12429-12437 · IF 14.511

Realization of high thermoelectric performance in solution-synthesized porous Zn and Ga codoped SnSe nanosheets

Shuang Li,Yunxiang Hou,Di Li,Bo Zou,Qingtang Zhang,Yang Cao,Guodong Tang

SnSe is considered one of the most intriguing new thermoelectric materials. Polycrystalline SnSe offers a wide range of thermoelectric applications due to its facile synthetic processing and machinability. Herein, we have achieved a high average ZT of 0.8 as well as a high peak ZT of 1.86 in solution-synthesized porous Zn and Ga codoped SnSe nanosheets, generating a maximum energy conversion efficiency of 13.3%. High-density micro/nanopores are induced in the SnSe matrix, which are more effective for scattering phonons and reducing the thermal conductivity. The high density of micro/nanopores, nanosheet structure and dislocations contribute to an ultralow lattice thermal conductivity (0.157 W m−1 K−1 at 873 K). Meanwhile, Ga incorporation can induce band convergence and create resonance levels, producing a large Seebeck coefficient. Ga and Zn codoping contributes to a sharp increase in carrier concentration and an obviously increased electrical conductivity. The enhanced Seebeck coefficient and increased carrier concentration help in achieving a significant enhancement of the power factor over a wide temperature range in the porous Zn and Ga codoped SnSe nanosheets. Consequently, high thermoelectric performance is realized over a wide temperature range via the decoupling of electron–phonon transport in SnSe. This work opens up a great opportunity for designing prospective materials for thermoelectric applications with the aid of the solution synthesis route.

研究领域: 材料科学 · 凝聚态物理 · 纳米科技 · 能源材料 · 半导体物理 · 热电转换 · 无机功能材料
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JOURNAL OF ALLOYS AND COMPOUNDS · 2019 · IF 4.175

Synergistically optimizing charge and phonon transport properties in n-type PbTe via introducing ternary compound AgSb(Se, Te)2

Siqi Wang,Zhi Yang,Yuejun Sun,Yu Xiao,Li-Dong Zhao

PbTe-based thermoelectric materials are considered to be a medium-temperature thermoelectric candidates and the high-performance n -type PbTe is urgently to be developed to match its p -type counterpart on account of practical application. Herein, we firstly optimized the carrier density of n -type PbTe through Sb doping, and obtained a maximum ZT value of ∼1.0. Then, based on the optimized carrier density, we introduced ternary compounds AgSb(Se, Te) 2 to suppress the lattice thermal conductivity . Minimum lattice thermal conductivity of n -type PbTe was reduced as low as ∼0.53 W m −1 K −1 and ∼0.62 Wm −1 K −1 through introducing AgSbSe 2 and AgSbTe 2 , respectively. Combining the maintained electrical properties with suppressed thermal conductivity , maximum ZT values ∼1.2 and ∼1.3 were obtained in PbTe+2%AgSbSe 2 and PbTe+2%AgSbTe 2 , respectively. This work provides an effective strategy of synergistically balancing charge and phonon transports in n -type PbTe with ternary AgSb(Se, Te) 2 compounds.

研究领域: 材料科学 · 热电转换 · 凝聚态物理 · 半导体物理 · 功能材料 · 能量转换材料
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Enhancement of thermoelectric performance of Cu2MnSnSe4 alloys by regulation of lattice strain

Yuqing Sun,Adeel Abbas,Hongxiang Wang,Chang Tan,Zhihao Li,Yujie Zong,Hui Sun,Chunlei Wang,Hongchao Wang

Quaternary Cu 2 MnSnSe 4 alloys with low intrinsic thermal conductivity are identified as promising middle-temperature thermoelectric materials. However, zT is depressed by the poor electrical performance. To overcome this issue, here, a series of Cu 2.1 Mn 0.9 SnSe 4 samples are prepared by ball-milling method which appears as a time-saving technique and lattice strain variation is observed by changing the annealing time ( x  = 0, 1, 2, 3, 4 days). The vacancy defects concentration of Cu, with lowest vacancy defects formation energy, is changed with the competition between compression and tension-strain state, consistent with the first principles calculations, which optimizes the carrier transport. As a result, about 4 times increment of the carrier mobility is found. Moreover, the lattice strain of several nanometers is observed with TEM analysis, which scatters phonon strongly. A lowest κ L value of 0.57 W m −1 K −1 at 673 K is obtained for  x   = 3 sample, which is close to the amorphous limit. The interactive effect of enhanced mobility and strong scattering of phonons, contributing to a record zT ∼ 0.48 at 673 K for  x   = 3 sample. Lattice strain engineering is an effective tactic to simultaneously optimize the electrical and thermal transport.

研究领域: 材料科学 · 凝聚态物理 · 功能材料 · 能源材料 · 半导体物理
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Small · 2023 ·Vol. 20 ·期 3 ·2306251 · IF 13.3

Mechanism of Thermoelectric Performance Enhancement in CaMg2Bi2-Based Materials with Different Cation Site Doping

Muchun Guo,Ming Liu,Jianbo Zhu,Yuke Zhu,Fengkai Guo,Wei Cai,Yongsheng Zhang,QinYong Zhang,Jiehe Sui

Chemical bonds determine electron and phonon transport in solids. Tailoring chemical bonding in thermoelectric materials causes desirable or compromise thermoelectric transport properties. In this work, taking an example of CaMg 2 Bi 2 with covalent and ionic bonds, density functional theory calculations uncover that element Zn, respectively, replacing Ca and Mg sites cause the weakness of ionic and covalent bonding. Electrically, Zn doping at both Ca and Mg sites increases carrier concentration, while the former leads to higher carrier concentration than that of the latter because of its lower vacancy formation energy. Both doping types increase density-of-state effective mass but their mechanisms are different. The Zn doping Ca site induces resonance level in valence band and Zn doping Mg site promotes orbital alignment. Thermally, point defect and the change of phonon dispersion introduced by doping result in pronounced reduction of lattice thermal conductivity. Finally, combining with the further increase of carrier concentration caused by Na doping and the modulation of band structure and the decrease of lattice thermal conductivity caused by Ba doping, a high figure-of-merit ZT of 1.1 at 823 K in Zn doping Ca sample is realized, which is competitive in 1–2–2 Zintl phase thermoelectric systems.

研究领域: 材料科学 · 凝聚态物理 · 无机化学 · 能源材料 · 热电转换
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Small · 2024 ·Vol. 20 ·期 45 ·2403852 · IF 13

Enhanced Thermoelectric Performance of N-Type PbSe Through Semi-Coherent Nanostructure by AgCuTe Alloying

Xinxin Wang,Chao Wang,Yajing Wang,Min Hao,Shengqiang Cui,Xudong Huang,Chunhui Wang,Jing Chen,Zhenxiang Cheng,Jianli Wang

N-type PbSe thermoelectric materials encounter challenges in improving the power factor due to the single-band structure near the Fermi level, which obstructs typical band convergence. The primary strategy for enhancing the thermoelectric figure of merit (ZT) for n-type PbSe involves reducing lattice thermal conductivity (κ lat ) by introducing various defect structures. However, lattice mismatches resulting from internal defects within the matrix can diminish carrier mobility, thereby affecting electrical transport properties. In this study, n-type AgCuTe-alloyed PbSe systems achieve a peak ZT value of ≈1.5 at 773 K. Transmission electron microscopy reveals nanoprecipitates of Ag 2 Te, the room temperature second phase of AgCuTe, within the PbSe matrix. Meanwhile, a unique semi-coherent phase boundary is observed between the PbSe matrix and the Ag 2 Te nanoprecipitates. This semi-coherent phase interface effectively scatters low-frequency phonons while minimizing damage to carrier mobility. Additionally, the dynamic doping effect of Cu atoms from the decomposition of AgCuTe within the matrix further optimize the high-temperature thermoelectric performance. Overall, these factors significantly enhance the ZT across the whole temperature range. The ZT value of ≈1.5 indicates high competitiveness compared to the latest reported n-type PbSe materials, suggesting that these findings hold promise for advancing the development of efficient thermoelectric systems.

研究领域: 材料科学 · 凝聚态物理 · 能源材料 · 纳米结构工程 · 热电转换
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