热电材料发电的商业化进展与前景展望

综述了热电材料作为绿色环保能源转换材料的商业化进展与应用前景. 阐述了商业化的热电材料热电性能指标要求，分析了提高热电性能的条件和理论上的局限性. 通过分析近20年提高热电性能的研究，总结了一些突破上述局限性的有效手段，提出了将来提高热电性能的一些有效方法. 预测了热电性能商业化的前景.     

热电材料断裂力学及热电转换效率研究的若干进展

热电材料作为一种新型功能材料可以将热能与电能相互转换,其断裂力学问题以及热电转换效率受到越来越广泛的关注,国内外许多学者开展了大量的研究工作.基于作者近几年在热电材料断裂力学和热电转换效率方面开展的研究工作,从理论分析、数值模拟和实验研究3个方面,综述了热电材料断裂力学问题的最新研究进展以及提高热电转换效率的研究成果.最后对未来热电材料断裂力学及热电转换效率的研究进行了展望.     

In和Pr双填充方钴矿的电子结构及电传输性能研究

利用基于密度泛函理论的第一性原理方法,计算了未填充型、In单填充型、In和Pr双填充型CoSb_3方钴矿热电材料的电子结构.结果表明:In和Pr双填充CoSb_3方钴矿热电材料可以较In单填充的材料进一步提升费米能级从而有更高的电导率σ,In和Pr双填充CoSb_3方钴矿热电材料导带底有In的5p和Pr的6s轨道产生的局部共振态叠加,进而使得其Seebeck系数更高.由于电导率和Seebeck系数的提升,使得In和Pr双填充能有效提高CoSb_3的功率因子.计算结果很好地解释了实验现象,阐述了双填充方式优化CoSb_3基方钴矿材料的热电性能内在物理机制.     

Bi_2Te_3热电材料的研究现状与发展趋势

随着人类科学技术的进步,各种热电材料不断被开发利用。Bi_2Te_3作为室温条件下性能最好的热电材料,多年来一直是热电领域的研究热点。本文将在简要介绍热电材料研究背景的基础上,概述Bi_2Te_3材料的结构和性质,综述Bi_2Te_3基热电材料的最新研究进展以及提高其热电性能的研究方法,主要包括提高载流子迁移率、增大材料Seebeck系数以提高功率因子,增加不同波长声子散射以降低晶格热导率两方面。最后对Bi_2Te_3基材料目前的研究热点以及未来可能的重点研究方向做简单讨论,同时展望了Bi_2Te_3基热电材料未来的发展趋势。     

NaxCoO2热电性质的第一性原理研究

热电材料能够进行热能与电能的直接转化,对其进行理论研究对实际应用具有指导意义.NaxCoO2是一种新型的热电功能材料,近年来逐渐成为研究的热点.本文在基于密度泛函理论的第一性原理电子结构研究的基础上,利用恒定弛豫时间近似条件下的线性波尔兹曼方程研究了这种材料体系的热电性质,得出了其热电功率在确定温度下作为Na原子含量的函数.     

Mg_3Sb_2基热电材料的研究进展

首次实现n型传导以来,无毒低成本Mg_3Sb_2基热电材料的研究便得到快速发展,有望能成为目前唯一大规模商业化的Bi_2Te_3热电化合物的替代材料。介绍了热电转化原理、Mg_3Sb_2基材料的晶体结构、电子结构及其p型、n型热电性能的研究现状。同时,简要分析了Mg_3Sb_2基材料性能优化的主要策略及其作用机制,如掺杂、固溶、晶粒尺寸调控和能带结构设计等对载流子浓度、载流子散射、迁移率和Seebeck系数等热电性能的影响机制。最后,讨论了Mg_3Sb_2基热电材料应用于发电和制冷的初步研究结果和后期热电模块应用的相关问题。     

β-Zn4Sb3热电材料的研究进展

本文介绍了热电材料的基本理论,叙述了β-Zn4Sb3热电材料的物理学的基本性质,综述了β-Zn4Sb3的热电性能的研究进展,并指出了存在的问题和未来的研究重点。     

热电行业低碳经济评价指标体系研究

基于热电行业低碳经济评价指标体系的研究,运用模糊数学综合评价理论,构建了热电行业低碳经济评价模型和评价方法,综合评价热电行业低碳经济的发展水平,以便系统地反映热电行业低碳经济发展的差距,及时修正战略途径,切实推进低碳经济发展.     

N型碳纳米管基热电材料研究进展

科技的不断发展对于能源供给方式提出了新的要求和挑战。在人体与外界环境温度差的驱动下,热电材料可以实现持续稳定的电能输出,能有效缓解能源危机。其中,碳纳米管(CNT)独特的结构使其具有优异的电学和力学性能以及较大的表面积,在热电材料中具有明显的优势,n型CNT在热电材料领域的应用也越来越广泛。围绕CNT基热电材料,首先介绍了热电材料的基本概念,接着概述了CNT的分类及其结构,重点介绍了n型CNT基热电材料的制备策略：掺杂和复合,指出了增强n型CNT的稳定性仍是未来的研究方向。     

瞬态热冲击下热电材料梁的温度场及热应力分析

基于热电材料特性,通过热电平衡方程和本构方程,得出热电材料梁瞬态模型的控制方程.采用分离变量法结合模型的初始条件和边界条件求出热电材料梁的非线性瞬态温度场,根据热应力理论分析求出瞬态热应力场,利用数学软件MATLAB给出了热电材料梁的呈抛物线分布的瞬态温度场和瞬态热应力场的特性曲线,研究了热冲击载荷下的热电材料梁在热电耦合环境中的热应力分析.讨论了不同时刻温度场和应力场随厚度的变化,以及对比p型和n型Bi₂Te₃热电材料梁热应力特性曲线.结果表明:瞬态温度场受其瞬态项的影响随厚度增加有增有减;瞬态温度场和瞬态热应力场随时间的增加最终趋于稳态不再随时间变化;趋于稳态后的Bi₂Te₃热电材料梁的热应力最值大于瞬态下的热应力最值;p型Bi₂Te₃热电材料梁的热应力总是大于n型Bi₂Te₃热电材料梁的热应力.     

有机无机复合温差电材料的无机掺杂剂

有机导电高分子因其低的热导率在温差电方面受到广泛的关注,但低电导率限制了其发展.掺杂无机半导体或CNT等纳米材料可有效改善有机导电高分子的热电性能.以PEDOT/PSS有机高分子为代表介绍有机无机复合温差电材料的无机掺杂剂的最新进展,并展望有机无机复合温差电材料未来的发展与应用.     

Enhanced thermoelectric performance of rough silicon nanowires

Approximately 90 per cent of the world's power is generated by heat engines that use fossil fuel combustion as a heat source and typically operate at 30-40 per cent efficiency, such that roughly 15 terawatts of heat is lost to the environment. Thermoelectric modules could potentially convert part of this low-grade waste heat to electricity. Their efficiency depends on the thermoelectric figure of merit ZT of their material components, which is a function of the Seebeck coefficient, electrical resistivity, thermal conductivity and absolute temperature. Over the past five decades it has been challenging to increase ZT > 1, since the parameters of ZT are generally interdependent. While nanostructured thermoelectric materials can increase ZT > 1 (refs 2-4), the materials (Bi, Te, Pb, Sb, and Ag) and processes used are not often easy to scale to practically useful dimensions. Here we report the electrochemical synthesis of large-area, wafer-scale arrays of rough Si nanowires that are 20-300 nm in diameter. These nanowires have Seebeck coefficient and electrical resistivity values that are the same as doped bulk Si, but those with diameters of about 50 nm exhibit 100-fold reduction in thermal conductivity, yielding ZT = 0.6 at room temperature. For such nanowires, the lattice contribution to thermal conductivity approaches the amorphous limit for Si, which cannot be explained by current theories. Although bulk Si is a poor thermoelectric material, by greatly reducing thermal conductivity without much affecting the Seebeck coefficient and electrical resistivity, Si nanowire arrays show promise as high-performance, scalable thermoelectric materials.     

成型压力和掺杂对Na1.4Co2O4基材料性能的影响

采用溶胶-凝胶法制备了Na位掺杂Sr和Li(掺杂量分别为0.1,0.2,0.3和0.4)的Nal.4Co2O4基热电材料,研究了成型压力和掺杂对Nal.4Co2O4基材料电导率、Seebeck系数和功率因子等热电性能的影响.采用XRD分析了NaxCo2O4基热电材料的相组成.研究结果表明:掺杂Sr和Li制备的Nal.4...     

Convergence of electronic bands for high performance bulk thermoelectrics

Thermoelectric generators, which directly convert heat into electricity, have long been relegated to use in space-based or other niche applications, but are now being actively considered for a variety of practical waste heat recovery systems-such as the conversion of car exhaust heat into electricity. Although these devices can be very reliable and compact, the thermoelectric materials themselves are relatively inefficient: to facilitate widespread application, it will be desirable to identify or develop materials that have an intensive thermoelectric materials figure of merit, zT, above 1.5 (ref. 1). Many different concepts have been used in the search for new materials with high thermoelectric efficiency, such as the use of nanostructuring to reduce phonon thermal conductivity, which has led to the investigation of a variety of complex material systems. In this vein, it is well known that a high valley degeneracy (typically ≤6 for known thermoelectrics) in the electronic bands is conducive to high zT, and this in turn has stimulated attempts to engineer such degeneracy by adopting low-dimensional nanostructures. Here we demonstrate that it is possible to direct the convergence of many valleys in a bulk material by tuning the doping and composition. By this route, we achieve a convergence of at least 12 valleys in doped PbTe(1-x)Se(x) alloys, leading to an extraordinary zT value of 1.8 at about 850 kelvin. Band engineering to converge the valence (or conduction) bands to achieve high valley degeneracy should be a general strategy in the search for and improvement of bulk thermoelectric materials, because it simultaneously leads to a high Seebeck coefficient and high electrical conductivity.     

Mg2Si热电材料力学性能的分子动力学模拟研究:纳孔效应

在热电材料里引入纳孔能有效降低材料的热导率从而提高其热电性能,但纳米孔洞的引入也可能影响材料的力学性能。以圆柱孔理想单晶Mg_2Si块体热电材料为研究对象,建立不同孔径、孔隙率以及分布形式的纳孔Mg_2Si材料的原子模型,采用分子动力学模拟方法研究不同模型下材料的拉伸力学性能。结果表明:①纳孔的引入造成Mg_2Si热电材料的极限应力和弹性模量的降低,而纳孔孔隙率、分布形式都会影响到材料的极限应力,而材料的弹性模量主要与孔隙率有关,孔隙率越大,材料的弹性模量越低;②纳孔的引入不仅减小材料的有效荷载面积,更重要的是造成材料内部应力分布不均匀,而材料所能承受的拉伸方向的应力极限是一定的,因而当纳孔Mg_2Si热电材料平均应力远小于完整块体的极限应力时,材料内部最薄弱的地方的应力就已达到其极限应力,造成材料的破坏。     

Enhancing thermoelectric performance of Cu-modified Bi0.5Sb1.5Te3 by electroless plating and annealing

With the capacity of energy conversion from heat to electricity directly, thermoelectric materials have been considered as an alternative solution to global energy crisis. In this work, Cu modified Bi_(0.5)Sb_(1.5)Te_3(BST)composites are prepared by a facile electroless plating Cu method, spark plasma sintering, and annealing. The annealed 0.22 wt.%Cu/BST has an enhanced peak Figure of Merit(z T) of ~ 0.71 at 573 K with high average z T of0.65 in the wide temperature range between 300 and 573 K. Due to the significant increase of electrical conductivity and low lattice thermal conductivity, the annealed 0.22 wt.%Cu/BST shifts peak z T to high temperature, and shows 492% enhancement than that of pristine BST with z T of 0.12 at 573 K. Through detailed structural characterization of the annealed 0.22 wt.%Cu/BST, we found that Cu can dope into BST matrix and further form Cu2 Te nanoprecipitates, dislocations, and massive grain boundaries, leading to a low lattice thermal conductivity of 0.30 Wm-1 K-1 in the annealed 0.22 wt.%Cu/BST. Such enhanced peak z T in high-temperature and high average z T in the wide temperature range shows that the electroless plating Cu method and annealing can improve the thermoelectric performance of commercial BST and expand the applicability of Bi_2Te_3 thermoelectric materials in the power generations.     

Bi掺杂的Ca3Co4O9的微结构和电输运性能

采用固相反应法制备了Bi掺杂的Ca3Co4O9热电材料。利用XRD和SEM等方法表征了样品的物相和微观组织,利用四线法测量了所有样品的电导率。研究结果表明：Bi掺杂的样品具有Ca3Co4O9单相,晶粒呈片状结构;随着Bi掺杂浓度的增加,样品的平均晶粒大小和致密度增加,电导率增大;电导率增加与样品的致密度,择优生长,晶粒大小密切相关。     

Improving thermoelectric properties of p-type Bi_2Te_3-based alloys by spark plasma sintering

High-performance(Bi_2Te_3)_x(Sb_1Te_3)_(1-x) bulk materials were prepared by combining fusion technique with spark plasma sintering,and their thermoelectric properties were investigated.The electrical resistivity and Seebeck coefficient increase greatly and the thermal conductivity decreases significantly with the increase of Bi_2Te_3 content,which leads to a great improvement in the thermoelectric figure of merit ZT.The maximum ZT value reaches 1.33 at 398 K for the composition of 20%Bi_2Te_3-80%Sb_2Te_...     

Ag,Er,Cu双掺杂对Ca3Co2O6热电性能的影响

采用溶胶 凝胶法和常压烧结技术, 制备一系列钴基氧化物热电材料Ca₃Co₂O₆和Ca_2.85M_0.15Co_2-yCu_yO₆(M=Ag,Er; y=0,0.1,0.2), 并通过X射线衍射(XRD)和扫描电子显微镜(SEM)考察样品的物相组成和微观形貌, 在300~1 000 K测定样品的电导率和Seebeck系数, 分析掺杂不同元素对复合物热电性能的影响. 结果表明: 制备的所有材料均为单一物相, 结构致密; 不同双掺杂元素对材料的热电性能均有提升作用; 当Ag⁺和Cu²⁺的掺杂量分别为0.15,0.2时, 可获得最优的热电性能, Ca_2.85Ag_0.15Co_1.8Cu_0.2O₆在965 K时的功率因子为71 μW/(K₂·m).