Enhanced thermoelectric performance of n-type TiCoSb halfHeusler by Ta doping and Hf alloying

The p-type TiCoSb-based half-Heuslers are widely studied due to the good electrical transport properties after hole doping,while the pristine TiCoSb is intrinsically n-type.It is thus desired to obtain a comparable n-type counterpart through optimization of electron concentration.In this work,n-type Ti_(0.9-x)Hf_xTa_(0.1)CoSb half-Heuslers were fabricated by arc melting,ball milling,and spark plasma sintering.An optimized carrier concentration,together with a decreased lattice thermal conductivity,was obtained by Ta doping at the Ti site,leading to a peak figure of merit(ZT) of 0.7 at 973 K in Ti_(0.9)Ta_(0.1)-CoSb.By further alloying Hf at the Ti site,the lattice thermal conductivity was significantly reduced without deteriorating the power factor.As a result,a peak ZT of 0.9 at 973 K and an average ZT of 0.54 in the temperature range of 300-973 K were achieved in Ti_(0.6)Hf_(0.3)Ti_(0.1)CoSb.This work demonstrates that n-type TiCoSb-based halfHeuslers are promising thermoelectric materials.     

B掺杂p型SiGe合金的制备与热电性能表征

以一定化学计量比均匀混合的Si、Ge、B混合粉末为原材料,使用放电等离子烧结(SPS)一步法合金化制备了p型Si₈₀Ge₂₀B_x(x=0.5,1.0,2.0)合金热电材料,并对样品的组成、微观形貌、热电性能进行了表征与分析。结果表明,放电等离子烧结过程实现原位合金化并烧结为块体材料。随着B掺杂量的增加,电导率明显提升,热导率显著下降,当温度为950K时,热导率为1.79W/(m·K)。在1050K时,ZT值达到了0.899。球磨和掺杂的协同作用使得SiGe合金基体内产生不同类型的缺陷特征而散射不同波长的声子,导致硅锗合金热导率的降低。     

Enhanced thermoelectric cooling properties of Bi2Te3−xSex alloys fabricated by combining casting,milling and spark plasma sintering

Bi₂Te_3−xSe_x alloys are extensively used for thermoelectric cooling around room temperature, but, previous studies have reported peak thermoelectric efficiency of the material at higher temperature around 450 K. This study presents the casting followed by high energy ball milling and spark plasma sintering as a thriving methodology to produce efficient and well-built Bi₂Te_3−xSe_x material for the thermoelectric cooling around room temperature. In addition, changes in electrical and thermal transport properties brought up by amount of Se in the Bi₂Te_3−xSe_x material for this methodology are measured and discussed. Although Seebeck coefficient and electrical conductivity showed irregular trend, power factor, thermal conductivity and figure of merit ZT gradually decreased with the increase in amount of Se. A maximum ZT value of 0.875 at 323 K was obtained for x = 0.15 sample owing to its higher power factor. This value is 17% and 38% greater than for x = 0.3 and x = 0.6 samples respectively. At 323 K, herein reported ZT value of 0.875 is higher than the state of art n-type Bi₂Te₃ based thermoelectric materials produced by the time consuming and expensive methodologies.     

镁-镍/石墨烯复合物的储氢性能

分别通过物理法和化学法制备石墨烯载镍催化剂(Ni/Graphene),并采用球磨预处理或超声分散的方式与镁粉混匀,结合氢化燃烧合成和机械球磨复合技术制备镁-镍/石墨烯(Mg-Ni/Graphene)复合物储氢材料。采用X射线衍射仪、扫描电镜及气体反应控制器研究了材料的相组成、微观形貌和吸放氢性能。比较发现,添加化学法制备的Ni/Graphene并采用球磨预处理的Mg-Ni/Graphene复合物具有最佳的吸放氢性能,复合物的起始放氢温度降低,放氢速率加快。其在373 K温度下,100 s内就基本能达到饱和吸氢量6.21%(质量分数);553 K,1800 s内完全放氢,且放氢量达到6.05%。球磨预处理使得Ni/Graphene更均匀的与Mg接触,利于发挥Ni的催化作用和石墨烯优异的导电导热性。化学法制备的Ni/Graphene原位还原出纳米晶Ni,有利于形成纳米级Mg2NiH4晶粒,促进复合物储氢性能的改善。     

Thermoelectric properties of MxMo6Te8 （M=Ag, Cu）

Ag and Cu filled Chevrel phase MxMo6Te8 (x=1.0, 2.0) samples were synthesized by direct solid state reaction and spark plasma sintering. The electrical and thermal properties were investigated in the temperature range of 300-800 K. The results show that both the electrical and thermal properties are affected by filler atoms. Although the electrical conductivity of MxMo6Te8 is slightly higher than that of state-of-the-art thermoelectric material, such as filled skutterudites, the absolute value of Seebeck coefficient is relatively low. Due to the phonon scattering by the filler atoms, the decrease of the thermal conductivity and the lattice thermal conductivity is obvious. As a result, the dimensionless figure of merit(ZT) is improved over the whole temperature region. The highest ZT value is 0.034 at 800 K for the AgMo6Te8 sample.     

多壁碳纳米管复合BiSbTe材料的热电性能

研究了BiSbTe/多壁碳纳米管(MWCNTs)复合材料的球磨法制备及其热电性能(300~500 K)。采用商用BiSbTe块体作为基体材料,利用球磨及压力辅助的感应加热烧结进行致密化得到了不同复合比的BiSbTe/0.5、1.0 vol% MWCNTs复合材料。复合MWCNTs后,引入的纳米复合结构增强了声子散射,大幅降低了热导率,同时由于载流子散射的增强和较低的致密度使电导率恶化。尽管电导率降低但热导率得到抑制,BiSbTe/1.0 vol% MWCNT复合材料的热电优值与BiSbTe基体接近。结果表明,优化加工参数获得更高的致密度可以优化BiSbTe/MWCNTs复合材料的热电性能。     

CaB6的原位反应合成及其热电性能

CaB6作为一种新型的热电材料,原料丰富且环保。以硼粉和氢化钙粉为原料,通过放电等离子烧结原位反应合成成功制备出了CaB6块体材料。第一性原理计算结果表明,CaB6呈现金属输运特性。试验结果表明,CaB6呈现n型金属输运特性。在373~773 K测试温度范围内,功率因子随着温度的升高呈上升趋势,从2.86×10-3 W·m-1 K-2增加到3.6×10-3 W·m-1 K-2,热导率随着温度的升高呈下降趋势,从11.63 W·m-1 K-1减小到9.06 W·m-1 K-1,其中晶格热导率占主导,且晶格热导率随温度的变化趋势与理论计算结果一致。在1 673 K制得的CaB6样品在773 K取得最大ZT值,达到0.34。     

Preparation of pure Higher Manganese Silicides through wet ball milling and reactive sintering with enhanced thermoelectric properties

A simple and effective process is used to synthesize undoped Higher Manganese Silicides (HMS), involving ball milling under soft conditions to obtain homogeneous mixtures of constituting elements, and subsequent spark plasma sintering for a direct solid state reaction. For comparison purpose, the ball milling step is carried out under both dry and wet conditions using n-hexane as the liquid medium, Analysis of the granulometry demonstrates that the wet milling process in n-hexane results in finer particles, thus improving the reaction rate later on. According to X-ray diffraction and scanning microscopy, materials produced via wet milling and spark plasma sintering contain only HMS while dry milled samples contain MnSi impuritties. The Seebeck coefficient of the wet milling sample is 20% higher, while its electrical resistivity is 23% lower than those of the dry milling one over the whole temperature range. Moreover, the thermal conductivity was reduced up to 30% when using n-hexane as milling media. The maximum thermoelectric figure of merit obtained is 0.55 at 850 K, a high value for undoped HMS.     

SPS法制备的三元合金Ag0.405Sb0.532Te的热电性能

采用放电等离子烧结法(SPS)制备了三元合金Ag0.405Sb0.532Te,并研究了它的输运性能,即Seebeck系数、电导率和热导率。结果表明,当温度从316K上升到548K时,电导率从7.6×104S·m-1下降到6.6×104S·m-1。在438K以上,热导率随温度上升逐渐增加,低于438K时,热导率趋于稳定,约为0.86W·(K·m)-1。无量纲热电优值ZT在548K时取得最大值0.65,稍高于Ag0.365Sb0.558Te三元合金的0.61。与掺Ag的AgxBi0.5Sb1.5-xTe3(x=0～0.4)合金相比,热电性能得到了改善。并再次讨论了AgxBi0.5Sb1.5-xTe3合金中析出的第二相Ag-Sb-Te三元合金的作用机制。     

Transport properties on Sn-filled and Te-doped CoSb<Subscript>3</Subscript> skutterudites

Sn-filled and Te-doped CoSb₃ skutterudites (Sn_xCo₈Sb_23.25Te_0.75) were synthesized by the encapsulated induction melting process. Single δ-phase was successfully obtained by subsequent heat treatment at 823 K for 6 days. Structural characterizations were carried out through X-ray diffraction studies. Transport properties such as the Seebeck coefficient, electrical resistivity, thermal conductivity, carrier concentration and mobility were measured and analyzed. The unfilled Co₈Sb_23.25Te_0.75 sample showed n-type conductivity from 300 K to 700K. However, the Sn-filled Sn_xCo₈Sb_23.25Te_0.75 showed n-type conductivity for z=0.25 and 0.5, and p-type conductivity for z=1.0 and 1.5 from 300 K to 700 K. Thermal conductivity was reduced by the impurity-phonon scattering. The dimensionless figure of merit (ZT) was remarkably improved over that of untreated CoSb₃. However, the ZT value decreased when filling with z≥1.0 because the conductivity type was changed from n-type to p-type, thereby allowing bipolar conduction. The details are discussed in terms of the two-band model and the bipolar thermoelectric effect.     

高能球磨掺杂氧化物粉体和压敏陶瓷粉体对氧化锌压敏陶瓷性能的影响(英文)

采用高能球磨掺杂氧化物粉体和压敏陶瓷粉体2种不同制备技术制备ZnO-Bi2O3压敏陶瓷,通过扫描电镜和X-射线衍射对其显微组织和相成分进行分析,探讨不同高能球磨制备技术对氧化锌压敏陶瓷电性能和显微组织的影响。结果表明:压敏陶瓷粉体高能球磨是制备高性能氧化锌压敏陶瓷的一种优异的技术,在1000°C下烧结3h,压敏陶瓷的电位梯度为617V/mm,非线性系数为57;压敏陶瓷的致密度高达95%,显微组织均匀、致密;高能球磨压敏陶瓷粉体可细化晶粒,增强烧结驱动力,加速烧结过程,降低烧结温度。     

Growth and transport properties of oriented bismuth telluride films

Oriented n-type bismuth telluride thin films with various layered nanostructures have been fabricated by radio-frequency (RF) magnetron sputtering. The crystal structures and microstructures of the films were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The transport properties including carrier concentration, mobility, Seebeck coefficient and in-plane electrical conductivity were measured, which showed strong microstructure-dependent behaviors. The relationship between morphologies and transport properties of the films was explored. The optimal morphology and transport properties of films were obtained at the substrate temperature of 350 °C under the pressure of 1.0 Pa with oriented layered structure. Based on these results, a formation mechanism of these nanostructures is proposed and discussed. The interfaces and grain boundaries formed in these layered structures are beneficial to the reduction in thermal conductivity, which could result in potential TE films with high ZT value.     

单晶和多晶SnSe热电性能对比

硒化锡材料因为其优良的ZT性能,有巨大的热发电应用潜力。此文我们详细地对比了单晶和多晶硒化锡在热力学和电性能输运方面的差异。其中,单晶样品是通过布里奇曼法合成的,多晶样品是通过熔融、粉碎和SPS烧结合成的。热电性能的测量则是通过四探针法和激光闪射法完成的。我们发现单晶样品的功率因子是多晶的2倍,而热导率也是多晶样品的3倍左右,这就直接导致了单晶和多晶的最高ZT值差异不大。单晶硒化锡在823 K处取得最高ZT 为0.65,而多晶则是在923K 取得最高ZT为0.5. 这些发现可以为系统地探索硒化锡材料的热电应用提供坚实的基础。     

Thermoelectric Properties of P-Type Ga2Te5 Based Compounds

采用放电等离子烧结技术(SPS)制备P型复相Ga2Te5基化合物,对其进行微观分析和热电性能测试。通过XRD分析观察到主相Ga2Te5和少量的SnTe、单质Te。在整个测试温度(319～549K)范围内,Ga2Te5基化合物的Seebeck系数、电导率和热导率都随温度的升高而降低。由于具有相对较低的热导率和较高的电导率,Ga2SnTe5在549K时取得了最高ZT值0.16。     

放电等离子烧结温度对超细晶W-40Cu复合材料的影响

采用高能球磨法制备了W-40Cu超细晶复合粉体,继而进行了放电等离子烧结(SPS),获得了致密的超细晶W-40Cu块体复合材料,着重研究了烧结温度对复合材料组织和性能的影响.结果表明,随着烧结温度升高,材料的致密度、硬度和电导率也随之升高;在950℃烧结5 min的W-40Cu复合材料,W颗粒尺寸约300～500 nm,相对致密度达98％,显微硬度HV为287,电导率为17.9 MS/m.     

Structure and thermoelectric performance of β-Cu2Se doped with Fe,Ni, Mn,In, Zn or Sm

Cu_1.99A_0.01Se (A = Fe, Ni, Mn, In, Zn or Sm) alloys with high thermoelectric performance were prepared through a conventional melting, ball milling and quenching route, followed by a spark plasma sintering technique. Elemental doping did not change the structure type of Cu₂Se. All the samples showed p-type conduction. All the doping elements except Indium reduced the electric resistivity and modified the carrier concentration, leading to a significant increase in the power factor. The lattice distortion and point defects due to the substitution of Cu became new phonon scattering centers, leading to a significant decrease in thermal conductivity. All the samples except the In-doped sample obtained better thermoelectric properties compared with the undoped Cu₂Se sample. The values of the figure of merit ZT of the samples doped with Zn, Mn, Ni, Fe and Sm were 1.25, 1.28, 1.51, 1.07 and 1.07 at 823 K, respectively. In Cu_2−xNi_xSe system, High ZT value of 1.51 is obtained for the sample of x = 0.0075 and 0.010 at 823 K.     

硅纳米线复合Mg2Si基热电材料的制备与性能研究

利用溶液法混合粉体并通过电场激活压力辅助烧结(FAPAS)方法制备了不同硅纳米线含量的Mg_2Si基复合热电材料,研究了硅纳米线的掺入及含量对基体材料热电性能的影响。结果表明:硅纳米线掺入后材料电导率大幅降低,塞贝克系数基本不变,热导率小幅降低。随着硅纳米线掺量增加,材料电导率降低,塞贝克系数稍有提高,热导率有升高趋势。硅纳米线掺量为0.1at%的样品在800 K时ZT值达到最高值0.5。     

添加Sb的Ga2Te3合金热电性能

本研究采用等摩尔分数的Sb元素替换Ga2Te3中的Ga元素,并利用放电等离子烧结技术制备Ga1.9Sb0.1Te3合金,研究其微观结构和热电性能。结果表明,添加Sb元素后,材料的Seebeck系数为130～240μV/K,明显低于单晶Ga2Te3,电导率为3600～1740??1·m?1,至少是单晶Ga2Te3的17倍,热导率提高近25%。在649K时Ga1.9Sb0.1Te3合金的热电优值(ZT)达到最大值0.1,是同温度下单晶Ga2Te3ZT值的3倍。     

Te掺杂对TiCoSb基Half-Heusler化合物高温热电性能的影响

采用固相反应法制备了Te掺杂的TiCoSb基half-Hcuslcr化合物。X射线衍射分析表明，Te掺杂的TiCoSb化合物是单相。在300～850K的温度范围内测量了材料的电阻率、赛贝克系数和热导率。结果表明：未经掺杂的TiCoSb化合物是n型半导体，在高温下有很高的赛贝克系数。在Sb位掺杂Te后，材料的电阻率和赛贝克系数的绝对值随着掺杂量的增加明显降低。材料的热导率随着掺杂量的增加而呈小幅度减小。Te掺杂后材料ZT值提高，最高的ZT值比基体提高了5倍多。     

Ga、K双掺杂P型Bi_(0.5)Sb_(1.5)Te_3材料的制备及热电性能

采用真空熔炼和热压方法制备了Ga和K双掺杂Bi0.5Sb1.5Te3热电材料。XRD结果表明,Ga0.02Bi0.5Sb1.48-x Kx Te3块体材料的XRD图谱与Bi0.5Sb1.5Te3的XRD图谱对应一致,但双掺杂样品的衍射峰略微向左偏移。热压块体材料中存在明显的(00l)晶面择优取向。SEM形貌表明材料组织致密且有层状结构特征。Ga和K双掺杂可使Bi0.5Sb1.5Te3在室温附近的Seebeck系数有一定的提高,而双掺杂样品的电导率均得到了不同程度的提高,其中Ga0.02Bi0.5Sb1.42K0.06Te3样品的电导率得到较明显的改善。在300~500 K测量温度范围内,所有双掺杂样品的热导率高于Bi0.5Sb1.5Te3的热导率,在300 K附近双掺杂样品的ZT值得到提高,其中Ga0.02Bi0.5Sb1.42K0.06Te3样品在300 K时ZT值达到1.5。