Skutterudite系热电材料制备及性能研究
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摘要
Skutterudite 材料具有优良的电性能,包括很高的载流子迁移率和中等的Seebeck系数,虽然热导率比目前常用的热电材料偏高,但它具有特殊的晶体结构,可以通过合金化、置入填充原子等途径使晶格热导率得到显著降低,因而是当前热电材料家族中最具发展前途的热电材料之一。
本文对Skutterudite 系热电材料的制备工艺、组织结构、热电性能及其内在机理展开了系统深入的研究。首次将机械合金化应用于Skutterudite 系材料制备中,研究了Co-Sb、Co-Fe-Sb 系的机械合金化,发展了两种制备置换及填充Skutterudite 材料的新工艺:高能球磨-无压烧结与高能球磨-热压成型-等温退火,其中后者可得到较致密、晶粒大小较均匀的块体材料。对Fe 置换Skutterudite 化合物Co_(4-x)Fe_xSb_(12)中Fe 的置换固溶度进行了研究,表明Fe 的最大置换固溶度近似为x=0.68。研究了Fe 置换对热电性能的影响,随Fe 置换量增加,P 型载流子浓度增大,电导率上升,Seebeck 系数下降,功率因子在x=0.5 时达到最大。同时,Fe 置换使热导率显著降低。对其热传导机制的分析表明,Fe 置换引入的点缺陷散射并不是导致晶格热导率降低的主要原因,载流子对声子的散射不容忽视,此外,可能有其它尚未知晓的机制存在。随Fe 置换量增加,ZT 值增大,Co_(3.35)Fe_(0.65)Sb_(12)在773K 时达到0.32 的ZT 值。置换量继续增大,Co_3FeSb_(12)成分在550K 以后ZT 值反而开始降低。在置换化合物中加入稀土La 填充元素,制备了部分填充Skutterudite 化合物La_yCo_(4-x)FexSb_(12) (x≤1,y≤1)。对比研究了Fe 置换和La 部分填充对晶体拉曼谱的影响,Fe 置换对拉曼谱影响不大,而La 部分填充则使拉曼谱产生明显变化,峰位有红移,部分峰位明显展宽。对La 填充化合物的Rietveld 结构精修表明,稀土原子具有异常大的热振动参数,证明了填充原子在晶格空隙中处于“扰动”状态。这种特殊的结构使热导率显著下降。此外,对Skutterudite/Bi_2Te_3系梯度复合热电材料的制备进行了初步尝试,结果表明,以低熔点Bi_2Te_3系组元作为中间介质可以获得界面结合紧密的梯度材料。
Skutterudite compound has perfect electrical properties, including high carrier mobility and appropriate Seebeck coefficient. Though its thermal conductivity is higher than that of state-of-the-art thermoelectric materials such as Bi_2Te_3, fortunately, there are two large voids in a unit call of the crystal structure and undersized atoms can be filled into them to yield a remarkable reduction to the lattice thermal conductivity. Therefore it is of great importance for promising thermoelectric applications.
A wide and deep investigation has been carried out on the synthesis process, microstructure, thermoelectric properties and transport mechanism of the Skutterudite compound. Mechanical alloying of Co-Sb and Co-Fe-Sb has been studied and applied to its preparation. Two new approaches, mechanical grinding-sintering and mechanical grinding-hot pressing-annealing, have been developed for synthesizing the substituted as well as the filled Skutterudite compounds. Structure analysis on the Fe substituted Skutterudite compounds Co_(4-x)Fe_xSb_(12) shows that there is a maximal solubility of Fe and is found at about x=0.68. Thermoelectric property measurement between 300~773K shows that both the electrical resistivity and Seebeck coefficient decrease with increasing Fe content due to an increase of the carrier concentration, and thermal conductivity is lowered considerably when Fe is substituted. Mass fluctuation and strain fluctuation scattering due to Fe substitution has been calculated in an effort to qualify the effect of Fe substitution on the lattice thermal conductivity, and it reveals that disorder scattering is not the main reason for decrease of the lattice thermal conductivity, while carrier scattering could not be ignored in these heavily-doped semiconductors, and some unknown mechanism may exist. The overall figure of metir (ZT) is improved with increasing Fe content except the Co_3FeSb_(12) sample, therefore the maximal ZT value of 0.32 is achieved for Co~(3.35)Fe_(0.65)Sb_(12)
in 773K. Subsequently, La partially filled Skutterudite compounds LayCo4-xFexSb12 (x≤1,y≤1) have been prepared and their structure, optical and thermoelectric properties been studied. Investigation on Raman spectra of the Skutterudite compounds shows that, only Fe substitution makes little change, whereas La filling produces a shift and apparent broadening of the vibrational modes. Also abnormally large thermal parameter of the filling atom is observed from Rietveld refinement of the partially filled compound, revealing that the filling atom is rattling in the oversized voids. These local rattlers could scatter large numbers of phonons and decrease lattice thermal conductivity dramatically, which then is verified by the thermal conductivity measurement. Finally, preparation and interface analysis of a segmented Skutterudite/Bi2Te3 material have been performed. Strong bonding is acquired in sample with Bi2Te3-type powders as interface layer.
本文对Skutterudite 系热电材料的制备工艺、组织结构、热电性能及其内在机理展开了系统深入的研究。首次将机械合金化应用于Skutterudite 系材料制备中,研究了Co-Sb、Co-Fe-Sb 系的机械合金化,发展了两种制备置换及填充Skutterudite 材料的新工艺:高能球磨-无压烧结与高能球磨-热压成型-等温退火,其中后者可得到较致密、晶粒大小较均匀的块体材料。对Fe 置换Skutterudite 化合物Co_(4-x)Fe_xSb_(12)中Fe 的置换固溶度进行了研究,表明Fe 的最大置换固溶度近似为x=0.68。研究了Fe 置换对热电性能的影响,随Fe 置换量增加,P 型载流子浓度增大,电导率上升,Seebeck 系数下降,功率因子在x=0.5 时达到最大。同时,Fe 置换使热导率显著降低。对其热传导机制的分析表明,Fe 置换引入的点缺陷散射并不是导致晶格热导率降低的主要原因,载流子对声子的散射不容忽视,此外,可能有其它尚未知晓的机制存在。随Fe 置换量增加,ZT 值增大,Co_(3.35)Fe_(0.65)Sb_(12)在773K 时达到0.32 的ZT 值。置换量继续增大,Co_3FeSb_(12)成分在550K 以后ZT 值反而开始降低。在置换化合物中加入稀土La 填充元素,制备了部分填充Skutterudite 化合物La_yCo_(4-x)FexSb_(12) (x≤1,y≤1)。对比研究了Fe 置换和La 部分填充对晶体拉曼谱的影响,Fe 置换对拉曼谱影响不大,而La 部分填充则使拉曼谱产生明显变化,峰位有红移,部分峰位明显展宽。对La 填充化合物的Rietveld 结构精修表明,稀土原子具有异常大的热振动参数,证明了填充原子在晶格空隙中处于“扰动”状态。这种特殊的结构使热导率显著下降。此外,对Skutterudite/Bi_2Te_3系梯度复合热电材料的制备进行了初步尝试,结果表明,以低熔点Bi_2Te_3系组元作为中间介质可以获得界面结合紧密的梯度材料。
Skutterudite compound has perfect electrical properties, including high carrier mobility and appropriate Seebeck coefficient. Though its thermal conductivity is higher than that of state-of-the-art thermoelectric materials such as Bi_2Te_3, fortunately, there are two large voids in a unit call of the crystal structure and undersized atoms can be filled into them to yield a remarkable reduction to the lattice thermal conductivity. Therefore it is of great importance for promising thermoelectric applications.
A wide and deep investigation has been carried out on the synthesis process, microstructure, thermoelectric properties and transport mechanism of the Skutterudite compound. Mechanical alloying of Co-Sb and Co-Fe-Sb has been studied and applied to its preparation. Two new approaches, mechanical grinding-sintering and mechanical grinding-hot pressing-annealing, have been developed for synthesizing the substituted as well as the filled Skutterudite compounds. Structure analysis on the Fe substituted Skutterudite compounds Co_(4-x)Fe_xSb_(12) shows that there is a maximal solubility of Fe and is found at about x=0.68. Thermoelectric property measurement between 300~773K shows that both the electrical resistivity and Seebeck coefficient decrease with increasing Fe content due to an increase of the carrier concentration, and thermal conductivity is lowered considerably when Fe is substituted. Mass fluctuation and strain fluctuation scattering due to Fe substitution has been calculated in an effort to qualify the effect of Fe substitution on the lattice thermal conductivity, and it reveals that disorder scattering is not the main reason for decrease of the lattice thermal conductivity, while carrier scattering could not be ignored in these heavily-doped semiconductors, and some unknown mechanism may exist. The overall figure of metir (ZT) is improved with increasing Fe content except the Co_3FeSb_(12) sample, therefore the maximal ZT value of 0.32 is achieved for Co~(3.35)Fe_(0.65)Sb_(12)
in 773K. Subsequently, La partially filled Skutterudite compounds LayCo4-xFexSb12 (x≤1,y≤1) have been prepared and their structure, optical and thermoelectric properties been studied. Investigation on Raman spectra of the Skutterudite compounds shows that, only Fe substitution makes little change, whereas La filling produces a shift and apparent broadening of the vibrational modes. Also abnormally large thermal parameter of the filling atom is observed from Rietveld refinement of the partially filled compound, revealing that the filling atom is rattling in the oversized voids. These local rattlers could scatter large numbers of phonons and decrease lattice thermal conductivity dramatically, which then is verified by the thermal conductivity measurement. Finally, preparation and interface analysis of a segmented Skutterudite/Bi2Te3 material have been performed. Strong bonding is acquired in sample with Bi2Te3-type powders as interface layer.
引文
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