Synthesis and thermoelectric properties of Mn-doped AgSbTe2 compounds

Polycrystalline p-type Ag 0.9 Sb 1.1 x Mn x Te 2.05（x = 0.05,0.10,and 0.20） compounds have been prepared by a combined process of melt-quenching and spark plasma sintering.The sample composition of Ag 0.9 Sb 1.1 x Mn x Te 2.05 has been specially designed in order to achieve the doping effect by replacing part of Sb with Mn and to present the uniformly dispersed Ag 2 Te phase in the matrix by adding insufficient Te,which is beneficial for optimizing the electrical transport properties and enhancing the phonon scattering effect.All the samples have the NaCl-type structure according to our X-ray powder diffraction analysis.After the treatment of spark plasma sintering,only the sample with x = 0.20 has a small amount of MnTe 2 impurities.The thermal analysis indicates that a tiny amount of Ag 2 Te phase exists in all these samples.The presence of the MnTe 2 impurity with high resistance and high thermal conductivity leads to the deteriorative thermoelectric performance of the sample with x = 0.20 due to the decreased electrical transport properties and the increased thermal conductivity.In contrast,the sample with x = 0.10 exhibits enhanced thermoeletric properties due to the Mn-doping effect.A dimensionless thermoelectric figure of merit of 1.2 is attained for the sample with x = 0.10 at 573 K,showing promising thermoelectric properties in the medium temperature range.     

Enhanced thermoelectric performance through homogenously dispersed MnTe nanoparticles in p-type Bi_(0.52)Sb_(1.48)Te_3 nanocomposites

In this work,we report that the thermoelectric properties of Bi_(0.52)Sb_(1.48)Te_3alloy can be enhanced by being composited with Mn Te nano particles(NPs)through a combined ball milling and spark plasma sintering(SPS)process.The addition of Mn Te into the host can synergistically reduce the lattice thermal conductivity by increasing the interface phononscattering between Bi_(0.52)Sb_(1.48)Te_3 and MnTe NPs,and enhance the electrical transport properties by optimizing the hole concentration through partial Mn~(2+)acceptor doping on the Bi~(3+)sites of the host lattice.It is observed that the lattice thermal conductivity decreases with increasing the percentage of Mn Te and milling time in a temperature range from 300 Kto 500 K,which is consistent with the increasing of interfaces.Meanwhile,the bipolar effect is constrained to high temperatures,which results in the figure of merit z T peak shifting toward higher temperature and broadening the z T curves.The engineering z T is obtained to be 20%higher than that of the pristine sample for the 2-mol%Mn Te-added composite at a temperature gradient of 200 K when the cold end temperature is set to be 300 K.This result indicates that the thermoelectric performance of Bi_(0.52)Sb_(1.48)Te_3 can be considerably enhanced by being composited with Mn Te NPs.     

I型锗基笼合物Ba8Ga16-xSbxGe30的合成及热电性能

用高温熔融结合放电等离子烧结（SPS）方法合成了Sb掺杂的单相n型Ba8Ga16-xSbxGe30化合物，探索了Sb对Ga的取代对其热电性能的影响规律．研究结果表明：随着Sb取代分数x的增加，Seebeck系数逐渐降低，Seebeck系数峰值对应的温度向低温方向偏移．电导率随着x的增加先增大后减小，当x=2时达到最大值．Sb取代Ga后对化合物的热性能有较大影响，其热导率和晶格热导率都有不同程度的降低．在所有n型Ba8Ga16-xSbxGe30化合物中，Ba8Ga14Sb2Ge30化合物的ZT值最大，在950K左右其最大ZY值达1．1．     

Ⅰ型锗基笼合物Ba8Ga16-xSbxGe30的合成及热电性能

用高温熔融结合放电等离子烧结(SPS)方法合成了Sb掺杂的单相n型Ba8Ga16-xSbxGe30化合物,探索了Sb对Ga的取代对其热电性能的影响规律.研究结果表明随着Sb取代分数x的增加,Seebeck系数逐渐降低,Seebeck系数峰值对应的温度向低温方向偏移.电导率随着x的增加先增大后减小,当x=2时达到最大值.Sb取代Ga后对化合物的热性能有较大影响,其热导率和晶格热导率都有不同程度的降低.在所有n型Ba8Ga16-xSbxGe30化合物中,Ba8Ga14Sb2Ge30化合物的ZT值最大,在950 K左右其最大ZT值达1.1.     

Cu掺杂AgSbTe2化合物的相稳定、晶体结构及热电性能

利用熔融快淬结合放电等离子烧结(SPS), 制备了Cu_xAg_1-xSbTe₂(x= 0---0.3)样品. 粉末X射线衍射(XRD)分析结果显示, SPS处理以前, 含Cu样品形成NaCl型结构的固溶体, 而未加入Cu的样品析出Ag₂Te第二相. 根据热分析和XRD测量结果, Cu的加入能够有效抑制Ag₂Te的析出, 但同时会在快淬样品中产生少量非晶相. 在温度升高到540 K左右时, 非晶相发生晶化, 形成Sb₇Te亚稳相, 并最终转变成Sb₂Te₃稳定相. 对快淬样品进行低温SPS快速处理后, x =0.1样品为面心立方结构的单相化合物, 但是x =0.2, 0.3的样品分别析出第二相Sb₇Te和Sb₂Te₃. 由于析出第二相, x=0.2, 0.3样品的电导率增大, Seebeck系数减小, 热导率相应升高, 综合热电性能降低. x=0.1单相样品的功率因子与文献报道的AgSbTe₂化合物相当. 元素替代的合金化效应 增强了Cu_0.1Ag_0.9SbTe₂化合物的声子散射, 有效降低了样品的热导率. 因此, 单相样品Cu_0.1Ag_0.9SbTe₂表现出较佳的热电性能, 在620 K时热电优值达到1.     

Sm和Ce复合掺杂Skutterudite化合物的制备及热电性能

用熔融法结合放电等离子快速烧结(SPS)制备出了单相的Sm和Ce复合掺杂的Skutterudite化合物Sm_mCe_nFe_1.5Co_2.5Sb₁₂，研究了Sm和Ce复合掺杂总量对其热电性能的影响规律.结果表明：随着Sm和Ce复合掺杂总量的增加，p型Sm_mCe_nFe_1.5Co_2.5Sb₁₂化合物的Seebeck系数增加、电导率和热导率降低.当掺杂总量相近时，和Sm、Ce单原子掺杂相比，Sm和Ce复合掺杂使Skutterudite化合物的热导率低10%—40%.Sm_0.22Ce_0.20Fe_1.54Co_2.46Sb_11.89化合物的最大热电性能指数ZT_max值在775K时为0.84. 关键词： 复合掺杂 方钴矿 热电性能     

非化学计量比AgSbTe2+x化合物制备及热电性能

采用高纯元素直接熔融、淬火并结合放电等离子烧结方法制备了非化学计量比AgSbTe_2+x(x=0—0.05)系列样品,研究了不同Te含量在300—600 K范围内对样品热电性能的影响规律.结果表明:随着Te含量的增加,Ag⁺离子空位浓度增加,空穴浓度和电导率大幅度提高,Seebeck系数减小.热导率随Te过量程度的增加略有增加,但所有Te过量样品的晶格热导率均介于0.32—0.49 W/mK之间,低于化学计量比样品的值,接近理论最低晶格热导率.AgS 关键词： 2')" href="#">AgSbTe₂ 非化学计量比 热电性能 热导率     

高压烧结制备Tb掺杂n型(Bi1–xTbx)2(Te0.9Se0.1)3合金及其微结构和热电性能

采用高压烧结技术制备了稀土元素Tb掺杂的n型Bi2Te2.7Se0.3基纳米晶块体热电材料.将高压烧结成型的样品于633 K真空退火36 h.研究了Tb掺杂量对样品的晶体结构和热电性能的影响.结果表明,高压烧结制备的样品为纳米结构, Tb掺杂使样品的晶胞体积变大,功率因子增大,热导率降低,从而使ZT值提高.Tb掺杂量为x=0.004是最优的掺杂量,该掺杂量的高压烧结样品经退火处理后,于373 K时ZT值达到最大为0.99,并且在323-473 K范围内, ZT值均大于0.8,这对用于温差发电领域具有重要意义.     

热压制备(AgSbTe2)100-x-(GeTe)x合金的热电性能

以Pb粉、Te粉、Ag粉、Ge粉为原材料,在真空气氛下合成(AgSbTe₂)_100-x-(GeTe)_x (x=80---90) (TAGS)合金热电材料, X射线衍射(XRD)分析表明,热压烧结后合金具有低温菱形结构. 通过热压烧结法将TAGS粉末制备成块体材料,运用XRD和扫描电子显微镜对材料的物相成分、 晶体结构和形貌进行了表征.采用直流四探针法测定样品的电导率,当样品两端的温差为1---4℃ 的情况下测量Seebeck系数.通过材料热电性能测试,研究了30---500℃温度范围内不同组分 样品性能参数的变化.结果表明,所制备的TAGS热电材料具有纳米结构, 其性能随着组分的变化而变化, TAGS-80具有较好的热电性能,在530℃时具有最高热电优值(ZT=1.80).     

多壁碳纳米管对p型Ba0.3FeCo3Sb12化合物热电性能的影响

用两步固相反应法合成了P型Ba填充方钴矿化合物Ba0.3FeCo3Sb12，并采用放电等离子烧结法(SPS)制备了Ba0.3FeCo3Sb12／多壁碳纳米管复合材料．研究了Ba0.3FeCo3Sb12／多壁碳纳米管复合材料的结构及多壁碳纳米管对其热电性能的影响规律：SEM分析表明多壁碳纳米管比较均匀地分布在Ba0.3FeCo3Sb12基体中；随着碳纳米管添加量的增加，Ba0.3FeCo3Sb12／多壁碳纳米管复合材料的电导率下降、塞贝克系数略微下降、晶格热导率大幅度降低，当碳纳米管含量为5％时其晶格热导率最小；当碳纳米管的含量为3％时，本研究得到的Ba0.3FeCo3Sb12／碳纳米管复合材料的最大ZT值达0．78．     

Se替代Te对BiCuTeO电热输运性能的影响

层状氧硫族化合物由于其本征的低晶格热导率和可观的热电性能吸引了广泛关注,其中以BiCuSeO化合物的热电性能最为优异.但是,其同晶型化合物BiCuTeO,由于带隙较小且存在大量本征Cu空位,导致载流子浓度较高,热电性能较差,从而研究较少.针对BiCuTeO存在的上述问题,本文利用Se替代部分Te,以期能够展宽带隙并减少Cu空位,提高其热电性能.采用固相反应结合快速热压烧结制备了BiCuTe_(1-x)Se_xO(x=0, 0.1, 0.2, 0.3和0.4)块体热电材料,并系统地研究了该体系的电热输运性能.研究结果表明,利用Se替代Te,可以使BiCuTeO导电层化学键强度增加、带隙增大、载流子有效质量增加以及载流子散射增强,从而导致载流子浓度和迁移率同时降低,进而电导率随着Se含量增加而剧烈降低, Seebeck系数则显著增大.由于综合电输运性能恶化,功率因子随着Se含量增加而减小,导致热电优值zT随着Se含量增加而降低.最终,Se含量为x=0.1的样品,在室温和723 K时的zT值分别达到约0.3和0.7,仍然在较宽温区内保持较高的zT值.由于Se替代Te改变了BiCuTeO的能带结构,通过载流子浓度优化,有望进一步提高其热电性能.     

利用晶体结构工程提升GeSe化合物热电性能的研究

在热电研究领域, Ge Se是一种二维层状结构具有较大带隙的半导体,本征载流子浓度低,热电性能差.在本工作中,采用熔融淬火结合放电等离子活化烧结工艺制备了一系列的Ge Se_1–x Te_x (x=0, 0.05, 0.15, 0.25,0.35, 0.45)多晶样品,研究了Te含量对Ge Se化合物物相结构和热电输运性能的影响规律.结果表明:随着Te含量的增加, Ge Se的晶体结构逐渐由正交相向菱方相转变,使得材料的带隙降低,载流子浓度和迁移率同步增加;同时,晶体对称性的提高增加了化合物的能带简并度,有效提高了载流子有效质量.在这些因素的共同作用下,菱方相Ge Se的功率因子比正交相Ge Se提高约2—3个数量级.此外,菱方相Ge Se具有丰富的阳离子空位缺陷以及铁电特性所导致的声子软化现象,这导致其晶格热导率比正交相Ge Se降低近60%.当Te含量为0.45时,样品在573 K取得最大热电优值ZT为0.75,是本征Ge Se样品的19倍.晶体结构工程是提升Ge Se化合物热电性能的有效途径.     

Enhanced thermoelectric performance of TiO_2-based hybrid materials by incorporating conducting polymer

In order to study the thermoelectric properties of TiO2-based hybrid materials, TiO2/polyparaphenylene(PPP)nanocomposites are fabricated by spark plasma sintering(SPS). The results show that the electrical conductivity follow percolation theory is enhanced due to the electron transfer highway provided by the conducting PPP phase. Furthermore,the thermal conductivity is reduced due to the drastic difference of vibrational spectra between organic and inorganic components. As a result, the greatest ZT= 0.24 is obtained for Ti O2/0.75 wt% PPP sample, which is 15-fold higher than pure Ti O2(ZT= 0.016).     

Effect of thermal treatment on the thermoelectric properties of Sb<Subscript>0.9</Subscript>Bi<Subscript>1.1</Subscript>Te<Subscript>2.9</Subscript>Se<Subscript>0.1</Subscript> solid solution thin films

The effect thermal treatment in a vacuum has on the thermoelectric properties of Sb_0.9Bi_1.1Te_2.9Se_0.1 solid solution thin films obtained via ion-beam sputtering in an argon atmosphere is considered. It is established that the specific resistance and thermopower are determined by the type and concentration of intrinsic point defects of the Sb_0.9Bi_1.1Te_2.9Se_0.1 solid solution. The power factor values are found to be comparable to those of nanostructured materials based on (Bi,Sb)₂(Te,Se)₃ solid solutions.     

聚对苯撑/LiNi0.5Fe2O4纳米复合热电材料的制备及其性能研究

本文以流变相反应法原位合成了聚对苯撑/LiNi_0.5Fe₂O₄纳米复合热电材料,并对其热电性能进行表征,研究了放电等离子烧结时保温时间对其热电性能的影响.结果发现,复合材料铁氧体颗粒粒径为100---300nm,其外部被一层聚对苯撑膜包覆.电子在Fe²⁺和Fe³⁺之间的跳跃机理在铁氧体电导中占主导作用,因此聚对苯撑/LiNi_0.5Fe₂O₄复合材料具有n型导电特性.随着保温时间增加,复合材料电导率基本不变,但热导率逐渐增大且Seebeck系数逐渐减小,导致热电优值系数降低.由于结合了有机物高电导率和低热导率以及无机材料高赛贝克系数的优点,所制备的复合材料热电性能较单一材料有较大提高.     

First-principles theory of competing order types, phase separation, and phonon spectra in thermoelectric AgPbmSbTe(m+2) alloys

Using a first-principles cluster expansion, we shed light on the solid-state phase diagram and structure of the recently discovered high-performance Pb-Ag-Sb-Te thermoelectrics. The calculated bulk thermodynamics favors the formation of coherent precipitates of ordered Ag(m)Sb(n)Te(m+n) phases immiscible with rocksalt PbTe, such as AgSbTe2. The solubility is high for Pb in AgSbTe2 and low for (Ag,Sb) in PbTe (8% vs 0.6% at 850 K). The differences in the phonon spectra of PbTe and AgSbTe2 suggest that these precipitates enhance the thermoelectric performance by lowering thermal conductivity.     

高压烧结对n型PbTe基材料热电性能的影响

 采用高压烧结技术制备了按偏离化学计量比配制的PbTe基热电材料（Pb_0.55Te_0.45），重点研究了烧结压力对材料热电性能的影响。研究结果表明：高压烧结过程能有效降低材料中的晶格缺陷，从而显著改变样品中的载流子浓度及其迁移率。与未经烧结的常压熔融样品相比，高压烧结样品的Seebeck系数得到大幅提高，电导率略有降低，室温热导率降低了50%，所以高压烧结样品的品质因子得到较大提高。当烧结压力为2 GPa时，所得样品在700 K时其品质因子达到0.59，相比未经烧结的常压熔融样品提高了150%。     

(Bi1-x Agx)2(Te1-ySey)3粉体的机械合金化制备及其放电等离子烧结体的热电输运特性

采用机械合金化制备了n型(Bi_1-xAg_x)₂(Te_1-ySe_y)₃合金粉体,对其进行XRD分析表明Bi,Te,Ag,Se单质粉末,经2h球磨后实现了合金化;SEM分析表明随着机械合金化时间延长粉体颗粒变得均匀、细小,颗粒尺寸在微米至亚微米数量级.采用放电等离子烧结制备了块体样品,研究了合金成分和球磨时间对热电性能的影响.结果表明材料的热电性能与掺杂元素有密切关系,Ag有利于提高功率因子和降低晶格热导率,球磨10h的(Bi_0.99Ag_0.01)₂(Te_0.96Se_0.04)₃合金粉末的烧结块体具有最大的功率因子和最低的晶格热导率,并在323K取得最高ZT值0.52. 关键词： 1-xAg_x)₂(Te_1-ySe_y)₃合金')" href="#">(Bi_1-xAg_x)₂(Te_1-ySe_y)₃合金 机械合金化 放电等离子烧结 热电性能     

High thermoelectric performance and low thermal conductivity in K-doped SnSe polycrystalline compounds

SnSe single crystal showed a high thermoelectric zT of 2.6 at 923 K mainly due to an extremely low thermal conductivity 0.23 W m⁻¹ K⁻¹. It has anisotropic crystal structure resulting in deterioration of thermoelectric performance in polycrystalline SnSe, providing a low zT of 0.6 and 0.8 for Ag and Na-doped SnSe, respectively. Here, we presented the thermoelectric properties on the K-doped K_xSn_1−xSe (x = 0, 0.1, 0.3, 0.5, 1.5, and 2.0%) polycrystals, synthesized by a high-temperature melting and hot-press sintering with annealing process. The K-doping in SnSe efficiently enhances the hole carrier concentration without significant degradation of carrier mobility. We find that there exist widespread Se-rich precipitates, inducing strong phonon scattering and thus resulting in a very low thermal conductivity. Due to low thermal conductivity and moderate power factor, the K_0.001Sn_0.999Se sample shows an exceptionally high zT of 1.11 at 823 K which is significantly enhanced value in polycrystalline compounds.     

Effect of heat treatment on the structure and the thermoelectric properties of Sb<Subscript>0.9</Subscript>Bi<Subscript>1.1</Subscript>Te<Subscript>2.9</Subscript>Se<Subscript>0.1</Subscript> thin films and composites based on them

This work considers the effect of vacuum annealing on the thermoelectric properties of Sb_0.9Bi_1.1Te_2.9Se_0.1 thin film and Sb_0.9Bi_1.1Te_2.9Se_0.1–C composites with various carbon contents produced by ion-beam deposition in an argon atmosphere. The electrical resistivity and the thermopower of Sb_0.9Bi_1.1Te_2.9Se_0.1–C nanocomposites are found to be dependent on not only the carbon concentration but also the type and the concentration of intrinsic point defects of the Sb_0.9Bi_1.1Te_2.9Se_0.1 solid solution, which determine the type of conductivity of Sb_0.9Bi_1.1Te_2.9Se_0.1 granules. The power factors are estimated for films of Sb_0.9Bi_1.1Te_2.9Se_0.1 solid solution and films of Sb_0.9Bi_1.1Te_2.9Se_0.1–C composites and found to have values comparable with the values for nanostructured materials on the basis of (Bi,Sb)₂(Te,Se)₃ solid solutions.