MA-SPS制备高热电性能p型(Bi,Sb)2Te3合金块体

机械合金化与放电等离子烧结技术(SPS)相结合制备了p型(Bi,Sb)2Te3合金块体.在300～423K的温度范围内测试了样品的电导率﹑Seebeck系数和热导率.系统研究了球磨时间对合金化与热电性能的影响.球磨2h的样品具有最低的热导率,因此其ZT值最高,在323K时为1.16,在373K达到最大值1.23.     

块体Bi2Te3基热电材料性能优化及最新进展

在分析块体Bi2Te3基热电材料性能优化设计思路的基础上,重点探讨了成分优化、结构优化、合成优化及成型优化中提高块体Bi2Te3基热电材料性能的方法。提出了一套值得探讨的优化设计方案,展望了Bi2Te3基热电材料在温差发电和半导体制冷领域颇具潜力的应用前景。     

快淬和球磨时间对p型(Bi_(0.25)Sb_(0.75))_2Te_3合金热电性能的影响

通过快淬-机械球磨-放电等离子烧结工艺制备了p型(Bi0.25Sb0.75)2Te3块体热电材料.在300~523K温度范围内对其电导率、Seebeck系数和热导率进行了测试,并系统研究了快淬后球磨时间对合金热电性能的影响.研究结果表明,随着球磨时间的延长,样品的电导率呈先降后升的趋势,Seebeck系数变化并不明显,而热导率随球磨时间的延长逐渐下降.球磨20h的样品在室温下具有最高的热电优值,最大值达到0.96,机械抗弯强度达到91MPa.     

高性能Ag-Pb-Sb-Te材料热电性能研究

采用较为经济高效的机械合金化和放电等离子烧结技术制备Ag-Pb-Sb-Te体系材料。系统研究了Pb含量以及Ag含量等变化对材料微观结构和热电性能的影响规律。通过SEM、TEM等材料微观结构表征手段,可以看到材料的晶粒细小,晶粒内部有大量的纳米团簇析出,这种结构可能对降低材料的热导率起了重要作用。研究表明,材料制备方法和工艺显著影响Ag-Pb-Sb-Te材料的热电性能,尤其是电传输特性。材料的热电性能对元素含量,尤其是Pb、Ag等含量变化敏感,适当调整元素含量可优化材料的热电性能。该材料体系优良的热电性能与材料特殊的微观结构有关,如晶粒内部析出的纳米团簇可能引起材料热导率的降低和热电优值的提高。     

机械合金化和放电等离子烧结制备AgPbSbTe热电材料

采用机械合金化和放电等离子烧结方法制备高性能AgPbSbTe热电材料,研究了制备工艺对材料热电性能的影响。结果表明,材料的物相组成和热电性能都受到机械合金化时间的影响;适当地控制放电等离子烧结工艺可以抑制晶粒长大,增加晶界散射,降低热导率。实验中得到AgPbSbTe热电材料的最大功率因子为18μW/K~2cm,最小热导率为1.1 W/m K。机械合金化(球磨4 h、转速350 r/m)并在673 K放电等离子烧结5 min,得到AgPbSbTe材料的最大热电优值ZT为1.2(700 K)。     

Se掺杂量对n型Bi2Te3-xSex微结构及热电性能的影响

通过水热法合成不同Se掺杂量的Bi₂Te_3-xSe_x (0 ≤x ≤0.45)纳米粉体, 采用放电等离子烧结技术, 制备出致密度较高的块体材料。通过X射线衍射、扫描电镜、透射电镜等测试手段对材料的微结构进行了表征, 并重点研究了含有不同Se掺杂量块体材料的显微结构和热电性能。结果表明: Se元素的掺杂使得粉体XRD特征衍射峰向高角度偏移, 并且衍射峰出现宽化, 晶粒尺寸变小。随着Se掺杂量的增加, 块体材料的电导率先增大后减小; Se元素的掺杂有效地降低了材料的热导率, 并提高了材料的Seebeck系数。研究结果表明: 在整个测试温度区间, 所有经过Se掺杂的样品ZT值都高于未掺杂样品。当Se掺杂量为0.3时, 样品具有最大的ZT值, 平均约为0.51, 并在475 K时达到最大值0.57, 相比未经Se掺杂的Bi₂Te₃提高了159%。     

Bi2Te3基热电材料的研究现状及发展

热电材料是能将热能和电能直接相互转化的功能材料,它的出现为解决能源紧缺和环境污染提供了广阔的应用前景.从理论和实验两个方面对Bi2Te3基热电材料近年来国内外的研究现状及发展进行了简要介绍和评述,并指出了今后的发展方向.在理论上主要基于能带理论、半导体超晶格以及密度泛函理论去寻求影响该材料的相关因子,在实验上主要采用分子束外延、激光脉冲沉积、合金化和水热合成法等方法制备该热电材料.     

AgSn18SbTe20无铅中温热电材料的粉末冶金法制备工艺及其对性能的影响

研究了制备p型AgSn₁₈SbTe₂₀无铅热电材料的机械合金化(MA)结合放电等离子烧结(SPS)工艺, 调查了MA过程中球磨时间和SPS温度对材料电热传输性能和热电优值的影响, 分析了样品的物相和显微结构。研究表明, 适当延长球磨时间和降低烧结温度, 可以有效提高材料的热电性能。优化制备条件可以实现59%的性能提升, 最佳条件(球磨12 h、SPS温度743 K)下制备的样品ZT值在723 K达到0.62。     

湿化学法制备纳米Bi2Te3基热电材料的研究进展

Bi2Te3基热电材料是室温下性能最好的热电材料。传统块体Bi2Te。基热电材料的热电性能不高,而纳米Bi2Tes基热电材料可以实现电、声输运特性的协同控制,从而提高材料的热电性能。介绍了几种纳米Bi2Te3。基热电材料不同的湿化学制备方法,比较了各种方法的优缺点,并展望了其发展方向。     

Bi2Te3基热电薄膜材料的制备方法研究

Bi2Te3基热电材料由于在微电子、光电子等高技术领域具有潜在的应用前景,从而得到了人们的广泛关注.低维Bi2Te3基热电材料由于具有特殊的量子限制效应,已成为提高热电性能的有效途径.近年来,研究者非常重视Bi2Te3基热电薄膜的制备及性能研究,并做了大量相关的研究工作,许多制备方法也相继出现,并获得了高质量的Bi2Te3基热电薄膜.     

纳米结构Bi2Te3基热电材料的溶剂热合成

本文评述了近年来溶剂热合成纳米结构Bi2Te3的研究进展，重点讨论了合成过程中的化学反应和晶体生长机制，特别是Bi2Te3纳米管的合成、形成机制和组织结构特征．介绍了含纳米结构Bi2Te3的Bi2Te3基同质纳米复合结构热电材料，其热电优值ZT达到1．25，远高于基体材料，也超过目前的块状先进Bi2Te3基热电材料．     

Radial electric field effect on thermoelectric transport properties of Bi2Te3 cylindrical nanowire coaxial structure

Radial electric field effect (REFE) on the thermoelectric figure of merit and Seebeck coefficient S are studied for a coaxial cylindrical capacitor configuration on the basis of bipolar intrinsic semiconductors. Theoretical analysis of REFE nanowire was done based on Poisson's equation in cylindrical geometry with corresponding boundary conditions. Using Newton's method the radial variation of the local Seebeck coefficient, carrier concentration and others transport characteristics are calculated for the bipolar Bi₂Te₃ nanowires neglecting size quantization. The dependence of the thermoelectric parameters on the gate voltage is studied. It is shown that the existence of the transition bipolar–monopolar semiconductor, electric field, differences in carrier masses and mobility essentially affect the thermoelectric properties. The thermoelectric figure of merit can be significantly increased by REFE.     

Bi_2Te_3/炭黑复合材料的制备及热电性能

采用水热法合成Bi_2Te_3粉体,将炭黑(CB)与其掺杂制备不同比例的碲化铋/炭黑(Bi_2Te_3/CB)复合材料,研究复合材料的热电性能。同时采用TGA、SEM、XRD等分析方法表征Bi_2Te_3/CB复合材料的结构,探究微观结构与热电性能的关系。研究发现:室温下,CB的引入使Bi_2Te_3/CB复合材料的热导率大大降低(0.5957 W/(m·K)降到0.0888 W/(m·K));随着Bi_2Te_3含量的增加,复合材料的电导率、热导率均增大,Seebeck系数先增加后降低;当Bi_2Te_3含量为88.9%时,在558℃烧结10min所得的Bi_2Te_3/CB复合材料室温下热电优值ZT最大(ZT=0.21)。虽然ZT值未能达到应用价值,但是CB的添加为改善Bi_2Te_3材料的热电性能,尤其在降低材料的热导率方面,提供了新方法和新思路。     

n-Type nanostructured thermoelectric materials prepared from chemically synthesized ultrathin Bi2Te3 nanoplates

We herein report on the large-scale synthesis of ultrathin Bi(2)Te(3) nanoplates and subsequent spark plasma sintering to fabricate n-type nanostructured bulk thermoelectric materials. Bi(2)Te(3) nanoplates were synthesized by the reaction between bismuth thiolate and tri-n-octylphosphine telluride in oleylamine. The thickness of the nanoplates was ~1 nm, which corresponds to a single layer in Bi(2)Te(3) crystals. Bi(2)Te(3) nanostructured bulk materials were prepared by sintering of surfactant-removed Bi(2)Te(3) nanoplates using spark plasma sintering. We found that the grain size and density were strongly dependent on the sintering temperature, and we investigated the effect of the sintering temperature on the thermoelectric properties of the Bi(2)Te(3) nanostructured bulk materials. The electrical conductivities increased with an increase in the sintering temperature, owing to the decreased interface density arising from the grain growth and densification. The Seebeck coefficients roughly decreased with an increase in the sintering temperature. Interestingly, the electron concentrations and mobilities strongly depended on the sintering temperature, suggesting the potential barrier scattering at interfaces and the doping effect of defects and organic residues. The thermal conductivities also increased with an increase in the sintering temperature because of grain growth and densification. The maximum thermoelectric figure-of-merit, ZT, is 0.62 at 400 K, which is one of the highest among the reported values of n-type nanostructured materials based on chemically synthesized nanoparticles. This increase in ZT shows the possibility of the preparation of highly efficient thermoelectric materials by chemical synthesis.     

Effects of cation doping on thermoelectric properties of Bi2S3 materials

Bi₂S₃ polycrystals doped with Al, Mn, Ag, and In were fabricated by vacuum melting and plasma activated sintering process, and the phase, microstructure, electrical, and thermal properties were investigated. The electrical conductivity is enhanced via Al and Ag doping. Compared with the Ag dopant, a higher electrical conductivity is achieved in the Al-doped sample, resulting in a peak power factor value of 1.96 μW/cmK² at 423 K. Meanwhile, the thermal conductivity of Bi_1.99Al_0.01S₃ sample is very low in the Bi₂S₃ system due to the high-density defects, and is only 0.39 Wm^?1 K^?1 at 740 K. By combining a power factor and a low thermal conductivity, a peak ZT value of 0.29 at 740 K is achieved in the Bi_1.99Al_0.01S₃ sample, being about two times larger than that of pristine Bi₂S₃.

     

Rational synthesis of ultrathin n-type Bi2Te3 nanowires with enhanced thermoelectric properties

A rational yet scalable solution phase method has been established, for the first time, to obtain n-type Bi(2)Te(3) ultrathin nanowires with an average diameter of 8 nm in high yield (up to 93%). Thermoelectric properties of bulk pellets fabricated by compressing the nanowire powder through spark plasma sintering have been investigated. Compared to the current commercial n-type Bi(2)Te(3)-based bulk materials, our nanowire devices exhibit an enhanced ZT of 0.96 peaked at 380 K due to a significant reduction of thermal conductivity derived from phonon scattering at the nanoscale interfaces in the bulk pellets, which corresponds to a 13% enhancement compared to that of the best n-type commercial Bi(2)Te(2.7)Se(0.3) single crystals (~0.85) and is comparable to the best reported result of n-type Bi(2)Te(2.7)Se(0.3) sample (ZT = 1.04) fabricated by the hot pressing of ball-milled powder. The uniformity and high yield of the nanowires provide a promising route to make significant contributions to the manufacture of nanotechnology-based thermoelectric power generation and solid-state cooling devices with superior performance in a reliable and a reproducible way.     

MOCVD of Bi2Te3 and Sb2Te3 on GaAs substrates for thin-film thermoelectric applications

Metal organic chemical vapour deposition (MOCVD) has been investigated for growth of Bi2Te3 and Sb2Te3 films on (001) GaAs substrates using trimethylbismuth, triethylantimony and diisopropyltelluride as metal organic sources. The surface morphologies of Bi2Te3 and Sb2Te3 films were strongly dependent on the deposition temperatures as it varies from a step-flow growth mode to island coalescence structures depending on deposition temperature. In-plane carrier concentration and electrical Hall mobility were highly dependent on precursor ratio of VI/V and deposition temperature. By optimizing growth parameters, we could clearly observe an electrically intrinsic region of the carrier concentration over the 240 K in Bi2Te3 films. The high Seebeck coefficient (of -160 microVK(-1) for Bi2Te3 and +110 microVK(-1) for Sb2Te3 films, respectively) and good surface morphologies of these materials are promising for the fabrication of a few nm thick periodic Bi2Te3/Sb2Te3 super lattice structures for thin film thermoelectric device applications.     

Structure and properties of thermoelectric materials based on Bi2(SeTe)3 and (BiSb)2Te3 solid solutions prepared by equal-channel angular pressing

Using X-ray diffraction and scanning electron microscopy, we have studied general aspects of defect structure formation in thermoelectric materials in different stages of plastic flow in the equal-channel angular pressing process with three channels. The results demonstrate that materials prepared using this deformation configuration have a fine-grained, homogeneous microstructure with a favorable texture, such that the cleavage planes of the grains are oriented along the extrusion axis. Studies of the structure and properties of the thermoelectric materials allowed us to optimize the equal-channel angular pressing temperature, which should be below the recrystallization onset temperature.     

表面多孔化Bi2 Te3柔性薄膜的制备及热电性能研究

柔性热电器件能够满足复杂环境的热量收集和转化需求,是目前研究的重要方向之一。但受制于材料电/声输运性能的强关联作用,柔性热电器件的能量转化效率仍然较低。以聚酰亚胺为柔性衬底,采用磁控溅射的方式制备Bi₂Te₃柔性热电薄膜,并通过退火对薄膜表面进行改性。结果表明,高温退火能够诱导Bi₂Te₃薄膜表面产生多孔化结构,且孔隙密度和尺寸可通过退火工艺调控;多孔结构对薄膜的电/声输运性能具有协同优化作用,薄膜热导率较退火前降低约50%,Bi₂Te₃柔性薄膜的热电优值显著提升。