自燃法制备Na掺杂Ca_3Co_4O_9及其热电性能的研究

采用简单的自燃法, 以去离子水为溶剂, 柠檬酸为螯合剂, 硝酸盐为原料制备了金属钠掺杂的(Na_xCa_(1-x))_3Co_4O_9热电材料前驱粉.前驱粉经煅烧、球磨、冷压、烧结等工艺获得块体材料.通过X射线衍射, 扫描电镜观察等方法对样品的结构与形貌进行了分析表征.在573～1073K温度区间内, 测试了材料的电阻率和Seebeck系数.研究表明,试样(x=0.15)在973K时的电阻率可达ρ=5.899mΩ·cm,Seebeck系数S=185μV/K,热电转换功率因子值p=5.802×10~(-6)W/(m·K2).     

Ag、La双掺杂对Ca3Co4O9热电性能的影响

采用固相反应法,在常压空气中烧结制备出了(Ca1-x-yAgxLay)3Co4O9(x=0、0.1,y=0;x=0.1,y=0.02、0.04、0.06)系列块体样品;通过X射线衍射和扫描电镜对样品的物相组成和微观结构进行了表征;研究了Ag、La双掺杂对样品热电性能参数Seebeck系数、电阻率和热导率的影响。结果表明,双掺杂可以进一步提高材料热电性能,且掺杂浓度的选择对热电性能有较大的影响;在873K时,x=0.1,y=0.02样品的ZT值最大。     

N型La0.9NixCo4-xSb12化合物的制备及热电性能研究

采用放电等离子烧结(SPS)方法制备了N型La0.9NixCo4-xSb12(x=0.05-1.0)化合物热电材料.借助于先进的结构和性能表征手段,系统研究了Ni含量对化合物热电性能的影响规律.实验结果表明,随着Ni含量增加,La0.9NixCo4-xSb12化合物的电阻率和Seebeck系数减小.当Ni含量x＜0.6时,化合物的热导率随Ni含量增大而降低,说明加入一定量的Ni能很好地降低材料的热导率.N型La0.9Ni0.4Co3.6Sb12化合物在温度773K时具有最大的热电性能优值(ZT)0.4558.     

Sm掺杂对Ca3Co4O9+δ基化合物高温热电性能的影响

用溶胶-凝胶法合成了Ca3-xSmxCo4O9+5(x=0,0.15,0.3和0.45)化合物粉体,并用SPS(Spark Plasma Sintering)烧结方法制备出相对密度＞95%的块体材料.研究了Sm掺杂对其高温热电性能的影响.结果表明在Ca位用Sm替代后材料的Seebeck系数和电阻率都增大,热导率降低.当Sm的掺杂量为10%(即x=0.3)时可获得最佳的热电性能,1000K时它的ZT值可达0.3.     

Sm~(3+)掺杂CaMnO_3的制备与热电性能

以硝酸盐为原料,采用溶胶-凝胶法结合常压烧结在1000℃制备出CaMnO3和掺杂Sm3+的(Ca1-xSmxMnO3)热电材料。利用TG-DTA、XRD、SEM研究了材料的物相和微观形貌,重点考察了Sm3+掺杂对CaMnO3的高温热电性能参数Seebeck系数、电阻率和功率因子的影响。结果表明,制备出的Sm3+掺杂的热电材料为单一的物相,具有致密的内部结构,Sm3+掺杂可以有效地改变其热电性能,当Sm3+的掺杂量为0.05时可获得最佳的热电性能,600℃它的功率因子为2.3×10-4W/(m·K2)。     

Ag_2Te掺杂对p型Bi_(0.5)Sb_(1.5)Te_3块状合金热电性能的影响

采用真空熔炼、机械球磨及放电等离子烧结技术(SPS)制备得到了(Ag2Te)x(Bi0.5Sb1.5Te3)1-x(x=0,0.025,0.05,0.1)系列样品,性能测试表明,Ag2Te的掺入可以显著改变材料的热电性能变化趋势,掺杂样品在温度为450~550K范围内具有较未掺杂样品更优的热电性能.适当量的Ag2Te掺入能够有效地提高材料的声子散射,降低材料的热导率.在测试温度范围内,(Ag2Te)0.05(Bi0.5Sb1.5Te3)0.95具有最低的晶格热导,室温至575K范围内保持在0.2~0.3W/(m·K)之间,在575K时,(Ag2Te)0.05(Bi0.5Sb1.5Te3)0.95试样具有最大热电优值ZT=0.84,相较于未掺杂样品提高了约20%.     

熔炼-退火法制备La_(0.3)Co_(4-x)Ni_xSb_(12)材料及其热电性能

采用熔炼-退火方法制备了La、Ni共掺方钴矿热电材料La0.3Co4-xNixSb12(x=0,0.1,0.5,0.75,1)。研究发现,x≥0.75时,出现NiSb2杂相,这说明当La的填充量为0.3时,Ni的固溶度在0.5到0.75之间。经电学性能测试发现,La0.3Co4-xNixSb12呈n型。随着x值的增大,Seebeck系数绝对值总体呈下降趋势,而电导率和热导率则随着Ni的掺杂量的增加而增加。La0.3Co3.9Ni0.1Sb12功率因子和ZT值分别达到最佳:功率因子σ.α2max=3.97×10-3Wm-1K-2(520K),ZTmax=0.64(773K)。     

稀土Gd对热压烧结Bi_2Te_3基材料热电性能的影响

稀土元素对Bi2Te3基材料热电性能的影响一直是Bi2Te3基热电材料研究的热点。本文研究了不同Gd掺杂量Bi2Te3基热电材料的热压烧结工艺参数,运用XRD,SEM方法对材料的物相成分和形貌进行了表征,研究了20MPa下不同Gd掺杂对Bi2Te3基材料的载流子浓度、电导率、Seebeck系数的影响。研究结果表明,Gd掺杂没有明显改变Bi2Te3基材料的晶体结构,适量的Gd掺杂有利于减小载流子浓度、提高Bi2Te3基材料的热电性能。     

Bi-Te基热电材料的研究进展

阐述了Bi2Te3热电材料的基本特性,评述了Se,TeL,SiC,RE(La,Ce等)的掺杂对BiTe材料热电性能的影响,以及国内外掺杂Bi-Te基热电材料的研究进展.介绍了Bi-Te基合金的制备技术的发展.最后指出通过材料的结构优化、组分调整及制备技术的改进,可以进一步提高材料的热电性能,得到理想的热电优值.     

Ce掺杂Ca3Co4O9的高温热电性能

利用二次固相反应方法制备了Ce掺杂的Ca3Co4O9热电材料(CexCa3-xCo4O9,x=0、0.1、0.3),并测试了样品的微观结构和高温热电性能。测试结果表明,Ce替代Ca可有效调制Ca3Co4O9的热电参数;随着温度的升高,样品的电阻率和热导率降低,See-beck系数增大。在973K的温度下,Ce0.1Ca2.9Co4O9具有最高的热电性能(ZT=0.23)。     

Microstructure and Thermoelectric Properties of Bi- and Cu-Substituted Ca3Co4O9 Oxides

Bi- and Cu-substituted Ca3Co4O9 samples were prepared by conventional solid-state reaction method and the effect of element substitution on the microstructures and thermoelectric properties was investigated. Partial substitution of Cu for Co leads to an increase in electrical conductivity and a decrease in Seebeck coefficient due to the rise of hole concentration. The microstructure of Cu-substituted sample is almost unchanged compared with undoped Ca3Co4O9. On the other hand, partial substitution of Bi for Ca gives rise to a significant increase in the grain size, and c-axis-oriented structure can be formed in Ca2.7Bi0.3Co4O9, resulting in an obvious increase in electrical conductivity. Cu and Bi co-substitution further increases the grain growth and the electrical conductivity of Ca2.7Bi0.3Co3.7Cu0.3O9. Thus, Cu and Bi co-substitution samples possess the optimal thermoelectric performance at high temperature and the highest value of power factor can reach 3.1×10-4 Wm-1·K-2 at 1000 K.     

溅射沉积掺Ag的SnSe薄膜的微结构和热电性能

使用粉末烧结SnSe合金靶高真空磁控溅射制备掺杂Ag的SnSe热电薄膜,利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和能谱仪(EDS)等手段分析薄膜的相组成、表面形貌、截面形貌、微区元素含量和元素分布,利用塞贝克系数/电阻分析系统LSR-3测量沉积薄膜的电阻率和Seebeck系数,研究了不同Ag含量SnSe薄膜的热电性能。结果表明,采用溅射技术可制备出正交晶系Pnma结构的SnSe相薄膜,掺杂的Ag在薄膜中生成了纳米Ag₃Sn。与未掺杂Ag相比,掺杂Ag的SnSe薄膜其电阻率和Seebeck系数(绝对值,下同)明显减小。并且在一定掺杂范围内,掺杂Ag越多的薄膜电阻率和Seebeck系数越小。未掺杂Ag的SnSe薄膜样品,其Seebeck系数较大但是电阻率也大,因此功率因子较小。Ag掺杂量(原子分数)为7.97%的样品,因其Seebeck系数绝对值较大而电阻率适当,280℃时的功率因子最大(约为0.93 mW·m^-1·K^-2),比未掺杂Ag的样品(PF=0.61 mW·m^-1·K^-2)高52%。掺杂适量的Ag能提高溅射沉积的SnSe薄膜的热电性能(功率因子)。     

(GeTe)nBi2Te3的结构与热电性能研究

在GeTe-Bi₂Te₃赝二元系统中, (GeTe)_n(Bi₂Te₃)_m化合物往往具有较低的晶格热导率, 但其中很多组分的热电性能尚未得到系统研究。本研究通过熔融、淬火、退火结合放电等离子烧结工艺制备了一系列(GeTe)_nBi₂Te₃(n=10, 11, 12, 13, 14)单相多晶样品, 并对其相组成和热电性能进行表征和研究。掺杂Bi₂Te₃可以显著增强点缺陷声子散射, 大幅度降低材料的晶格热导率, 在723 K时, (GeTe)₁₃Bi₂Te₃样品的总热导率低至1.63 W?m ^-1?K ^-1。此外, 掺杂Bi₂Te₃和调控GeTe的相对含量, 提高了材料的载流子有效质量, 即使在较高的载流子浓度下, 样品依然保持较高的塞贝克系数和功率因子, 在723 K, (GeTe)₁₃Bi₂Te₃样品获得最大的功率因子为2.88×10 ^-3 W?m ^-1?K ^-2, 最终(GeTe)₁₃Bi₂Te₃样品在723 K获得的最大ZT值达到1.27, 较未掺杂的GeTe样品提高了16%。     

Thermoelectric properties of Sb2Te3 thin films by electron beam evaporation

This study applies the thermoelectric grains of Sb2Te3 on conductive glass to evaporate Sb2Te3 thin films by the electron beam evaporation method. Through experimental tests with different evaporation process parameters and film annealing conditions, thin films with better Seebeck coefficient, resistivity (p) and power fact (PF) can be obtained. Experimental results show that when thin films are annealed, their defects can be decreased accordingly, and carrier mobility can be enhanced to further elevate the conductivity of thin films. When the substrate temperature is set at 200 degrees C to fabricate Sb2Te3 thin films by the evaporation process and by annealing at 220 degrees C for 60 minutes, the Seebeck coefficient of Sb2Te3 thin films increase from 87.6 microV/K to 177.7 microV/K; resistivity falls from 6.21 m ohms-cm to 2.53 m ohms-cm and PF can achieve the maximum value of 1.24 10(-3) W/K2 m. Finally, this study attempts to add indium (In) to Sb2Te3 thin films. Indium has been successfully fabricated In3SbTe, thin films. This study also analyzes the effects of In on the thermoelectric properties of In3SbTe2 thin films.     

Thermoelectric performance of SPS sintered [(Ca0.95M0.05)2CoO3][CoO2]1.61

The doped [(Ca_0.95M_0.05)₂CoO₃][CoO₂]_1.61 ceramics were sintered by the spark plasma sintering (SPS). The electrical conductivity, Seebeck coefficient and thermal conductivity of all samples were measured from 373 K to 973 K. The doped ions improve thermoelectric performance due to increase of Seebeck coefficient and decrease of thermal conductivity. Since the electrical resistivity of the Y-doped sample has no enhancement, the thermoelectric performance of the Y-doped sample is superior to that of the Gd-doped sample. The reason of the different effects on the thermoelectric performance comes from magnetic action.     

苯二甲酸铽与1,10-邻菲哕啉三元配合物的合成及性质

以邻(间、对)苯二甲酸[o(m、p)-PA]和1,10_邻菲啰啉(phen)为配体,合成了5种Tb(Ⅲ)的三元配合物.各配合物的组成分别为:Tb_2(m-PA)_3(phen)_2·6H_2O、Tb_2(p-PA)_3(phen)_2·2H_2O、Tb_2(o-PA)_3phen·4H_2O、Tb_2(m-PA).phen·4H_2O和Tb_2(p-PA)_3phen·4H_2O.红外光谱分析表明,在各配合物中羧基氧原子和1,10-邻菲啰啉中的氮原子均参与了配住.5种配合物均有较好的热稳定性,它们的热稳定性顺序为:Tb_2(m-PA)_3(phen)_2·6H_2O>Tb_2(p-PA)_3(phen)_2·2H_2O>Tb_2(m-PA)_3phen·4H_2O>Tb_2(o-PA)_3phen·4H_2O>Tb_2(p-PA)_3phen·4H_2O.在室温条件下,5种铽的三元固体配合物均发出绿色荧光,它们在最佳发射峰~5D_4→~7F_5(545nm)时的荧光强度顺序为:Tb_2(p-PA)_3phen·4H_2O>Tb_2(rn-PA)_3(phen)_2·6H_2O>Tb_2(p-PA)_3(phen)_2·2H_2O>Tb_2(m-PA)_3phen·4H_2O>Tb_2(o-PA)_3phen·4H_2O.     

Thermoelectric properties of p-type PbSe nanowires

The thermoelectric properties of individual solution-phase synthesized p-type PbSe nanowires have been examined. The nanowires showed near degenerately doped charge carrier concentrations. Compared to the bulk, the PbSe nanowires exhibited a similar Seebeck coefficient and a significant reduction in thermal conductivity in the temperature range 20 K to 300 K. Thermal annealing of the PbSe nanowires allowed their thermoelectric properties to be controllably tuned by increasing their carrier concentration or hole mobility. After optimal annealing, single PbSe nanowires exhibited a thermoelectric figure of merit (ZT) of 0.12 at room temperature.      

Thermoelectric properties of a Pb0.2Sn0.8Te solid solution prepared through thermal decomposition of salts

We have studied the thermoelectric properties of microcrystalline samples of the Pb_0.2Sn_0.8Te solid solution prepared by hot-pressing fine powders obtained through the thermal decomposition of lead acetate trihydrate and tin oxalate in the presence of tellurium powder. The electrical conductivity, Seebeck coefficient, and thermal conductivity of the samples have been measured at room temperature and in the temperature range 300–700 K and correlated with the particle size of the powders and heat-treatment conditions. We have compared the thermoelectric properties of hot-pressed samples from powders prepared through the thermal decomposition of salts and by mechanical grinding of ingots.     

原位溶剂热和热压制备微纳复合n型CoSb3及热电性能

在块体材料中引入纳米组元构建微纳复合材料是热电材料研究的一个新方向. 采用原位溶剂热和热压方法制备了由纳米晶粒和微米晶粒组成的n 型CoSb₃复合材料. 以CoCl₂、SbCl₃为原料, NaBH₄为还原剂, 乙醇为溶剂, 与熔炼制备的n型CoSb₃微米级别的粉末一起放入高压反应釜中, 在250℃下反应72h得到微纳复合的粉末材料, 热压后得到微纳复合的块体材料. 性能测试结果表明, 该材料表现为典型掺杂半导体的导电特征, 具有较好的电学性能. 微纳复合结构引入大量晶界增强了声子散射, 能有效降低材料的热导率, 并且由纳米组元引起的量子效应能提高材料的Seebeck系数, 使材料的热电性能得到改善. 本工作所制备的微纳复合n型CoSb3具有较低的热导率, 在测试温度范围内, 热导率为2.0～2.3W·m^-1·K^-1. 材料的最大无量纲热电优值在600K时达到0.5.