CoSb_3纳米热电材料的制备及热传输特性

以Sb ,Co为起始原料 ,采用固相反应法合成了CoSb3.通过高能球磨制得CoSb3纳米粉末 ,用放电等离子烧结(SPS)方法制备出最小平均晶粒尺寸为 1 5 0nm的块体材料 .研究了晶粒尺寸与热传输性能之间的关系 :CoSb3化合物结构纳米化对其晶格热导率κL 有显著影响 ,当晶粒尺寸由微米尺度减小到纳米尺度 ,晶格热导率κL 显著降低 ,但对载流子热导率κc 的影响不甚显著 .CoSb3化合物的热导率κ随晶粒尺寸的减小而降低主要是由于晶格热导率κL 随晶粒尺寸的减小而降低所致     

晶粒尺寸对CoSb3化合物热电性能的影响

系统地研究了晶粒尺寸对CoSb3化合物热电性能的影响规律,结果表明晶粒尺寸对CoSb3化合物的晶格热导率κp、电导率σ、能隙宽度Eg和Seebeck系数α有显著影响.当晶粒尺寸由微米尺度减小到纳米尺度时,晶格热导率κp显著降低,Seebeck系数α有较大幅度的增加,能隙宽度Eg变宽,电导率σ有一定程度的下降.平均晶粒尺寸为200nm的CoSb3化合物在温度为700K时,ZT值达到0.43,比平均晶粒尺寸为5000 nm的试样增加了4倍.     

晶粒尺寸对CoSb3化合物热电性能的影响

系统地研究了晶粒尺寸对CoSb₃化合物热电性能的影响规律，结果表明晶粒尺寸对CoSb₃化合物的晶格热导率κ_p、电导率σ、能隙宽度E_g和Seebeck系数α有显著影响.当晶粒尺寸由微米尺度减小到纳米尺度时，晶格热导率κ_p显著降低，Seebeck系数α有较大幅度的增加，能隙宽度E_g变宽，电导率σ有一定程度的下降.平均晶粒尺寸为200nm的CoSb₃化合物在温度为700K时，ZT值达到0.43，比平均晶粒尺寸为5000nm的试样增加了4倍.     

CoSb_3/C_(60)复合材料的固相反应合成和热电性能

用固相反应法和脉冲电流直接通电烧结法制备了CoSb3 C6 0 复合材料 ,其组分通过粉末x射线衍射法确定 ,SEM分析表明C6 0 颗粒是均匀地分布在CoSb3基体中 .在 30 0— 80 0K范围内测量了材料的电导率、赛贝克系数和热导率 ,研究了纳米颗粒的尺寸和分布状态对复合材料热电性能的影响 .外加的C6 0 纳米颗粒在高温时降低了复合材料的晶格热导率 ,而对电传输性能影响较小 ,从而有效地提高了复合材料的热电性能 .与CoSb3相比 ,CoSb3 6 5 4 ? 0复合材料的ZT值提高了 4 0 % .     

致密度对填充skutterudite化合物La0.75Fe3CoSb12热电性能的影响

研究了致密度对填充skutterudite化合物La0.75Fe3CoSb12热电性能的影响.La0.75Fe3CoSb12表现为p型传导,载流子迁移率随着致密度的增加而升高.由于样品中空洞的散射作用,致使电阻率ρ随着致密度的降低而升高,同时造成热导率κ的下降,但塞贝克系数α与致密度关系不大,致密度造成电阻率ρ升高的比率与热导率κ下降的比率相当,致密度不同的样品具有相当的ZT值.致密度对填充式skutterudite化合物La0.75Fe3CoSb12ZT值关系影响不明显.     

纳米镍粉体的晶格膨胀

采用阳极弧放电等离子体技术成功制备了各种不同晶粒尺寸的纳米镍粉体材料，并利用X射线衍射(XRD)、透射电子显微镜(TEM)和相应选区电子衍射(SAED)等测试手段对所制备的样品的晶体结构、晶格参数、形貌、粒度进行性能表征. 实验结果表明：阳极弧等离子体法制备的镍纳米粉的晶体结构与相应的块物质相同，为fcc结构的晶态. 不同晶粒尺寸的纳米镍粉体的晶格常数均大于完整单晶镍的晶格常数，晶格畸变表现为晶格膨胀. 晶格常数和晶胞体积随着晶粒尺寸的减小而增大，晶格畸变量与晶粒尺寸的倒数成正比. 镍纳米粉体的晶格膨胀主要是由于受到表面能和表面张力的作用而引起的，可以利用纳米晶体的热力学理论作定性解释. 关键词： 镍纳米粉体 晶格常数 晶格膨胀 晶胞体积     

Grain Growth Kinetics of BaTiO3 Nanocrystals During Calcining Process

以醋酸钡和钛酸四丁酯为原料，采用溶胶-凝胶法合成了纳米BaTiO3粉体；运用差示/热重、X射线衍射及透射电镜对前驱体凝胶和产物进行了表征，并根据XRD结果，研究了纳米BaTiO3的晶格常数、晶格畸变度和晶粒尺寸随焙烧温度及时间的变化。结果表明，焙烧温度与时间对纳米BaTiO3晶格常数的影响不明显；随焙烧温度或时间的延长，纳米BaTiO3的晶格畸变度减小，晶粒尺寸增大，但晶格畸变度和晶粒尺寸更敏感于焙烧温度. 基于扩散控制机理的传统模型探讨了焙烧过程纳米BaTiO3晶粒生长动力学，得出其晶粒生长指数为7，晶粒生长活化能为75.49 kJ/mol. 将基于扩散与反应共同控制机理的新型等温模型应用于本研究中，结果表明，新型等温模型更能真实地反映纳米BaTiO3焙烧过程中的晶粒生长行为，说明纳米BaTiO3晶粒生长过程同时受溶质扩散和表面反应控制，其藕合晶粒生长活化能为27.23 kJ/mol.     

金属纳米颗粒的热导率

本文使用统计模拟方法对金属纳米颗粒的电子平均自由程进行了计算,并考察了纳米颗粒的晶格比热和声子平均群速度,最后应用动力学理论对纳米颗粒的电子热导率和声子热导率分别进行了求解.研究结果表明:具有相同特征尺寸的方形、球形纳米颗粒的无量纲电子(或声子)平均自由程比较接近.金属纳米颗粒的电子热导率远大于声子热导率;电子、声子热导率随着直径减小呈现降低趋势,而电子热导率的颗粒尺度依赖性比声子热导率更为明显;随着颗粒直径进一步减小,声子热导率与电子热导率趋于同一数量级.当纳米颗粒特征尺寸大于4倍块材电子(或声子)平均自由程,其电子(或声子)热导率的颗粒尺度依赖性将减弱.     

纳米复合永磁材料的有效各向异性与矫顽力

研究了纳米Nd2Fe14B/α-Fe复合永磁材料中晶粒交换耦合相互作用对有效各向异性的影响和变化规律.结果表明：晶粒之间的交换耦合作用使材料的有效各向异性Keff随晶粒尺寸的减小而下降、随软磁性相成分的增加而降低. 当晶粒尺寸 减小到4nm时，Keff值减小为其各自通常各向异性常数值的1/3—1/4.有效各向异性的变化特点与矫顽力的变化规律基本相同.纳米复合永磁材料矫顽力的降低主要由于有效各向异性的减小而引起. 关键词： 纳米复合永磁材料 交换耦合相互作用 有效各向异性 矫顽力     

Ga填充n型方钴矿化合物的结构及热电性能

用熔融退火结合放电等离子烧结(SPS)技术制备了具有不同Ga填充含量的Ga_xCo₄Sb₁₂方钴矿化合物，研究了不同Ga含量对其热电传输特性的影响规律. Rietveld结构解析表明,Ga占据晶体学2a空洞位置，Ga填充上限约为0.22，当Ga的名义组成x≤0.25时，样品的电导率、室温载流子浓度N_p随Ga含量的增加而增加，Seebeck系数随Ga含量的增加而减小. 室温下霍尔测试表明，每一个Ga授予框架0.9个电子，比Ga的氧化价态Ga³⁺小得多. 由于Ga离子半径相对较小，致使Ga填充方钴矿化合物的热导率κ及晶格热导率κ_L较其他元素填充的方钴矿化合物低. 当x＝0.22时对应的样品在300K时的热导率和晶格热导率分别为3.05Wm^-1·K^-1和 2.86Wm^-1·K^-1.在600K下Ga_0.22Co_4.0Sb_12.0样品晶格热导率达到最小，为1.83Wm^-1·K^-1，最大热电优值Z，在560K处达1.31×10^-3K^-1. 关键词： skutterudite化合物 Ga原子填充 结构 热电性能     

Grain-size-dependent thermal conductivity of nanocrystalline materials

In order to study the influence of grain size and lattice strain on the thermal conductivity of nanocrystalline (NC) materials, both experimental and theoretical studies were carried out on NC copper. The NC copper samples were prepared by hot isostatic pressing of nano-sized powder particles with mean grain size of 30 nm. The thermal behaviors of the samples were measured to be 175.63–233.37 W (m K)^?1 by using a laser method at 300 K, which is 45.6 and 60.6 % of the coarse-grained copper, respectively. The average grain size lies in the range of 56–187 nm, and the lattice strain is in the range of ?0.21 to ?0.45 % (in the direction of 111) and ?0.09 to 0.92 % (in the direction of 200). In addition, a modified Kapitza resistance model was developed to study the thermal transport in NC copper. The theoretical calculations based on the presented theoretical model were in good agreement with our experimental results, and it demonstrated that the thermal conductivity of NC materials show obvious size effect. It is also evident that the decrease in the thermal conductivity of NC material can be mainly attributed to the nano-size effect rather than the lattice strain effect.     

Titanium Doping to Enhance Thermoelectric Performance of 19-Electron VCoSb Half-Heusler Compounds with Vanadium Vacancies

The 19-electron VCoSb compounds are actually composites of an off-stoichiometric half-Heusler phase and impurities. Here the compositional adjustment is systematically studied in V_1−xCoSb to obtain single-phase V_0.955CoSb. Hall measurements suggest that such a V vacancy, as well as Ti doping, can optimize the carrier concentration, which decreases from ≈11.3 × 10²¹ cm⁻³ for VCoSb to ≈6.3 × 10²¹ cm⁻³ for V_0.755Ti_0.2CoSb. Low sound velocity contributes to the intrinsically low lattice thermal conductivity for VCoSb-based materials. The high Ti-dopant content results in enhanced point-defect scattering, which further decreases the lattice thermal conductivity. Finally, the optimized n-type V_0.855Ti_0.1CoSb is found to reach a peak ZT of ≈0.7 at 973 K. The work demonstrates that the VCoSb-based half-Heuslers are promising thermoelectric materials.     

Effect of phonon scattering mechanisms on the lattice thermal conductivity of skutterudite-related compound

We have prepared the skutterudite-related compounds FeCo_3Sb_{12} and La_{0.75}Fe_3CoSb_{12} with different average grain sizes (about 0.8 and 3.9μm) by hot pressing. Samples were characterized by XRD, EPMA and SEM. The lattice thermal conductivity was investigated in the temperature range from room temperature to 200℃. Based on the Debye model, we analyse the change in lattice thermal conductivity due to various phonon scattering mechanisms by examining the relationship between the weighted phonon relaxation time τ(ω/ω_D)^2 and the reduced phonon frequency ω/ω_D. The effect of grain boundary scattering to phonon is negligible within the range of grain sizes considered in this study. The large reduction in lattice thermal conductivity of FeCo_3Sb_{12} compound contributes to the electron－phonon scattering. As for La_{0.75}Fe_3CoSb_{12} compound, the atoms of La filled into the large voids in the structure of the skutterudite produce more significant electron－phonon scattering as well as more substitute of Fe at Co site at the same time. Moreover, the point-defect scattering appears due to the difference between the atoms of La and the void. In addition, the scattering by the rattling of the rare-earth atoms in the void is another major contribution to the reduced lattice thermal conductivity. Introducing the coupling of the electron－phonon scattering with the point-defect scattering and the scattering by the rattling of the rare-earth atom is an effective method to reduce the lattice thermal conductivity of the skutterudite-related compounds by substitution of Fe for Co and the atoms of La filled in the large voids in the skutterudite structure.     

Role of lone-pair electrons in producing minimum thermal conductivity in nitrogen-group chalcogenide compounds

Fully dense crystalline solids with extremely low lattice thermal conductivity (κ(L)) are of practical importance for applications including thermoelectric energy conversion and thermal barrier coatings. Here we show that lone-pair electrons can give rise to minimum κ(L) in chalcogenide compounds that contain a nominally trivalent group VA element. Electrostatic repulsion between the lone-pair electrons and neighboring chalcogen ions creates anharmonicity in the lattice, the strength of which is determined by the morphology of the lone-pair orbital and the coordination number of the group VA atom.     

纳晶铜晶粒尺寸对热导率的影响

用热压烧结法制备得到纳晶铜块体. 用激光法测定了不同温度下制备得到的纳晶铜块体的热导率, 并建立卡皮查热阻模型对样品热导率进行模拟. 通过对比, 模拟结果与实验数据基本一致. 随着热压烧结温度的升高, 纳晶铜晶粒尺寸也随之增大. 在900和700 ℃其热导率分别达到了最大和最小值且所对应的热导率分别为200.63和233.37 W·m^-1·K^-1, 各占粗晶铜块体热导率的53.4%和60.6%. 验证了纳晶铜热导率在一定的晶粒尺寸范围内具有尺寸效应, 随着晶粒尺寸的减小, 热导率逐渐减小.     

考虑界面散射的金属纳米线热导率修正

理论分析了声子和电子输运对Cu, Ag金属纳米线热导率的贡献. 采用镶嵌原子作用势模型描述纳米尺寸下金属原子间的相互作用, 应用平衡分子动力学方法和Green-Kubo函数模拟了金属纳米线的声子热导率; 采用玻尔兹曼输运理论和Wiedemann-Franz定律计算电子热导率; 并通过散射失配模型和Mayadas-Shatzkes模型引入晶界散射的影响. 在此基础上, 考察分析了纳米线尺度和温度的影响. 研究结果表明: Cu, Ag纳米线热导率的变化规律相似; 电子输运对金属纳米线的导热占主导地位, 而声子热导率的贡献也不容忽视; 晶界散射导致热导率减小, 尤其对电子热导率作用显著; 纳米线总热导率随着温度的升高而降低; 随着截面尺寸减小而减小, 但声子热导率所占份额有所增加. 关键词： 纳米线 热导率 表面散射 晶界散射     

Influence of grain size distribution on the lattice thermal conductivity of Bi2Te3-Sb2Te3-based nanostructured materials

The change of the lattice thermal conductivity of bulk nanostructured materials based on Bi₂Te₃-Sb₂Te₃ solid solutions with grain size distribution has been studied. These materials have a polycrystalline structure with grain sizes ranging from a few tens of a nanometer to a few micrometers. Large grains may contain inclusions or consist of several smaller parts which can be identified with coherent scattering regions seen in X-ray diffraction. The change of the lattice thermal conductivity mediated by additional scattering by inclusions and grain boundaries has been calculated. This calculation allows for the effect of nanoparticle size distribution. The calculated estimates are compared with the available experimental data.     

Lattice thermal conductivity of compounds with inhomogeneous intermediate rare-earth ion valence

The thermal conductivity κ (within the range 4–300 K) and electrical conductivity σ (from 80 to 300 K) of polycrystalline Sm₃S₄ with the lattice parameter a=8.505 Å (with a slight off-stoichiometry toward Sm₂S₃) are measured. For T>95 K, charge transfer is shown to occur, as in stoichiometric Sm₃S₄ samples, by the hopping mechanism (σ ～ exp(?ΔE/kT) with ΔE ～ 0.13 eV). At low temperatures [up to the maximum in the lattice thermal conductivity κ_ph(T)], κ_ph ～ T ^2.6; in the range 20–50 K, κ_ph ～ T ^?1.2; and for T>95 K, where the hopping charge-transfer mechanism sets in, κ_ph ～ T ^?0.3 and a noticeable residual thermal resistivity is observed. It is concluded that in compounds with inhomogeneous intermediate rare-earthion valence, to which Sm₃S₄ belongs, electron hopping from Sm²⁺ (ion with a larger radius) to Sm³⁺ (ion with a smaller radius) and back generates local stresses in the crystal lattice which bring about a change in the thermal conductivity scaling of κ_ph from T ^?1.2 to T ^?0.3 and the formation of an appreciable residual thermal resistivity.