Inorganic thermoelectric materials: A review

Thermoelectric generator, which converts heat into electrical energy, has great potential to power portable devices. Nevertheless, the efficiency of a thermoelectric generator suffers due to inefficient thermoelectric material performance. In the last two decades, the performance of inorganic thermoelectric materials has been significantly advanced through rigorous efforts and novel techniques. In this review, major issues and recent advancements that are associated with the efficiency of inorganic thermoelectric materials are encapsulated. In addition, miscellaneous optimization strategies, such as band engineering, energy filtering, modulation doping, and low dimensional materials to improve the performance of inorganic thermoelectric materials are reported. The methodological reviews and analyses showed that all these techniques have significantly enhanced the Seebeck coefficient, electrical conductivity, and reduced the thermal conductivity, consequently, improved ZT value to 2.42, 2.6, and 1.85 for near-room, medium, and high temperature inorganic thermoelectric material, respectively. Moreover, this review also focuses on the performance of silicon nanowires and their common fabrication techniques, which have the potential for thermoelectric power generation. Finally, the key outcomes along with future directions from this review are discussed at the end of this article.     

Modeling and optimization of hybrid solar thermoelectric systems with thermosyphons

We present the modeling and optimization of a new hybrid solar thermoelectric (HSTE) system which uses a thermosyphon to passively transfer heat to a bottoming cycle for various applications. A parabolic trough mirror concentrates solar energy onto a selective surface coated thermoelectric to produce electrical power. Meanwhile, a thermosyphon adjacent to the back side of the thermoelectric maintains the temperature of the cold junction and carries the remaining thermal energy to a bottoming cycle. Bismuth telluride, lead telluride, and silicon germanium thermoelectrics were studied with copper–water, stainless steel–mercury, and nickel–liquid potassium thermosyphon-working fluid combinations. An energy-based model of the HSTE system with a thermal resistance network was developed to determine overall performance. In addition, the HSTE system efficiency was investigated for temperatures of 300–1200 K, solar concentrations of 1–100 suns, and different thermosyphon and thermoelectric materials with a geometry resembling an evacuated tube solar collector. Optimizations of the HSTE show ideal system efficiencies as high as 52.6% can be achieved at solar concentrations of 100 suns and bottoming cycle temperatures of 776 K. For solar concentrations less than 4 suns, systems with thermosyphon wall thermal conductivities as low as 1.2 W/mK have comparable efficiencies to that of high conductivity material thermosyphons, i.e. copper, which suggests that lower cost materials including glass can be used. This work provides guidelines for the design, as well as the optimization and selection of thermoelectric and thermosyphon components for future high performance HSTE systems.     

纳米硅锗热电材料和纳米器件的研究进展

近年来,纳米技术逐渐被用来设计和制备硅锗（Si−Ge）热电材料和新型器件。为了提高Si−Ge热电材料的热电性能,研究学者利用各种纳米结构对Si−Ge热电材料进行了理论研究。其中,利用纳米线、超晶格和量子点等结构中的能带机理与散射机理,从理论上设计了降低Si−Ge纳米结构热导率和提高其功率因子的途径。同时,高效的Si−Ge纳米热电材料被制备出来,包括纳米块体材料的热电性能得到大幅度提高,室温下薄膜和纳米线的热电性能实现了重大突破。在高性能材料的基础上,新型Si−Ge纳米热电器件的研发除了关注于制备工艺优化外,还包括传热结构和原型器件的设计。     

氧化钛基半导体热电材料的研究进展

热电材料—即实现热能和电能之间直接相互转换的一类功能材料,提供了一种制冷或发电的新方法—在解决能源和环境危机问题上正在扮演越来越重要的角色。传统的三维材料中,由于几个决定热电性能的关键物理参数相互关联,使得现有热电材料很难获得较高热电优值（ZT）。金属氧化物热电材料由于其良好的耐高温性能,是中高温区使用的理想候选者。如果能提高氧化钛基化合物的热电优值,那么氧化钛基化合物将是一类非常优秀的热电材料,因为其不仅具有优良的化学稳定性和热稳定性,而且原材料丰富、不含有毒元素以及制备工艺简单。纳米化能显著降低材料的热导率,是最近二十年提高热电性能的一条主要途径。同时,通过界面和化学组成调控增加与电学性能相关的功率因子也是一种继续提高热电性能的重要方法。本文综述了我们近期对氧化钛基热电材料的研究成果,包括对钛酸盐纳米管较大赛贝克（Seebeck）系数的实验发现,提出利用一维纳米材料独特的空心结构和纳米管层状特殊构造,将两个相关联的物理参数（热导率和电导率）分别调控;通过合成氧化钛基纳米复合材料,研究界面对载流子和声子散射的作用,提出通过载流子能量过滤效应提高其热电性能;采用尿素燃烧法和高温烧结等方法合成具有纳米结构和化学组成调控的氧化钛基化合物,认识化学组成以及界面对声电输运的作用规律;最后介绍能显著提高热电材料功率因子的载流子非对称迁移的理论。     

Impacts of cone-structured interface and aperiodicity on nanoscale thermal transport in Si/Ge superlattices

Si/Ge superlattices are promising thermoelectric materials to convert thermal energy into electric power. The nanoscale thermal transport in Si/Ge superlattices is investigated via molecular dynamics (MD) simulation in this short communication. The impact of Si and Ge interface on the cross-plane thermal conductivity reduction in the Si/Ge superlattices is studied by designing cone-structured interface and aperiodicity between the Si and Ge layers. The temperature difference between the left and right sides of the Si/Ge superlattices is set up for nonequilibrium MD simulation. The spatial distribution of temperature is recorded to examine whether the steady-state has been reached. As a crucial factor to quantify thermal transport, the temporal evolution of heat flux flowing through Si/Ge superlattices is calculated. Compared with the even interface, the cone-structured interface contributes remarkable resistance to the thermal transport, whereas the aperiodic arrangement of Si and Ge layers with unequal thicknesses has a marginal influence on the reduction of effective thermal conductivity. The interface with divergent cone-structure shows the most excellent performance of all the simulated cases, which brings a 33% reduction of the average thermal conductivity to the other Si/Ge superlattices with even, convergent cone-structured interfaces and aperiodic arrangements. The design of divergent cone-structured interface sheds promising light on enhancing the thermoelectric efficiency of Si/Ge based materials.     

A review on the performance of photovoltaic/thermoelectric hybrid generators

Utilization of a broad range of solar spectrum has the potential for high power output from solar cells. However, solar photovoltaics (PVs) can convert only part of the solar electromagnetic spectrum into electricity efficiently. The remaining of the solar radiation is often dissipated in the form of heat, which causes performance reduction and reduces the life expectancy of the solar PV cell. Thermoelectric generators (TEGs) are devices that operate like a heat engine by converting thermal energy into electricity through thermoelectric effect. Integrating a TEG into a PV converter will enhance its efficiency and reduce the amount of heat dissipated. Different studies have been carried out and are still taking place to increase the total efficiency of a coupled photovoltaic thermoelectric generator (PV-TEG) system. This review discusses the concept of PV converters and thermoelectric devices and presents the various models and numerical and experimental investigations on performance enhancement of integrated PV-TEGs. The influence of key parameters on the performance of PV-TEG were also discussed. The review is expected to serve as a reference to recent work on research and development of integrated PV-TEG systems.     

温差发电技术及其在节能领域的应用

温差发电技术是利用热电转换材料直接将热能转化为电能的发电技术,具有无运动部件、体积小、重量轻、移动方便和可靠性高等特点,是绿色环保的发电方式。随着能源与环境问题的日益突出,温差发电技术在节能领域的应用日新月异,它是合理利用太阳能、地热能、海洋温差、余热和废热等热能转换为电能的有效方式。     

基于单层MNCl(M=Zr,Hf)的温差发电模型仿真分析

在研究单层ZrNCl和HfNCl材料热电性能的基础上,搭建温差发电模型,研究不同规格温差发电模块的输出性能,然后与其他学者研究的温差发电模型及热电材料的热电转换效率进行对比分析.结果表明:在低温区和中温区,单层ZrNCl的热电转换效率更高.温差发电模块的输出功率随温差发电模块横截面积和热电单元对数的增大而增大.单层Zr...     

Nanostructural thermoelectric materials and their performance

In this review, an attempt was made to introduce the traditional concepts and materials in thermoelectric application and the recent development in searching high-performance thermoelectric materials. Due to the use of nanostructural engineering, thermoelectric materials with a high figure of merit are designed, leading to their blooming application in the energy field. One dimensional nanotubes and nanoribbons, two-dimensional planner structures, nanocomposites, and heterostructures were summarized. In addition, the state-of-the-art theoretical calculation in the prediction of thermoelectric materials was also reviewed, including the molecular dynamics (MD), Boltzmann transport equation, and non-equilibrium Green’s function. The combination of experimental fabrication and first-principles prediction significantly promotes the discovery of new promising candidates in the thermoelectric field.     

新型发动机排气温差发电器结构探索

根据汽车发动机排气可利用能量的形式,提出了一种新型的置于排气通道内的热电转换系统,使热电偶与热气流直接进行对流/辐射换热,将强化热流密度和转换电流密度、提高系统的温差。在使用现有热电材料的条件下,提高温差发电器的功率密度。     

Experimental investigation of a novel heat pipe thermoelectric generator for waste heat recovery and electricity generation

Waste heat recovery helps reduce energy consumption, decreases carbon emissions, and enhances sustainable energy development. In China, energy-intensive industries dominate the industrial sector and have significant potential for waste heat recovery. We propose a novel waste heat recovery system assisted by a heat pipe and thermoelectric generator (TEG) namely, heat pipe TEG (HPTEG)，to simultaneously recover waste heat and achieve electricity generation. Moreover, the HPTEG provides a good approach to bridging the mismatch between energy supply and demand. Based on the technical reserve on high-temperature heat pipe manufacturing and TEG device integration, a laboratory-scale HPTEG prototype was established to investigate the coupling performances of the heat pipes and TEGs. Static energy conversion and passive thermal transport were achieved with the assistance of skutterudite TEGs and potassium heat pipes. Based on the HPTEG prototype, the heat transfer and the thermoelectric conversion performances were investigated. Potassium heat pipes exhibited excellent heat transfer performance with 95% thermal efficiency. The isothermality of such a heat pipe was excellent, and the heat pipe temperature gradient was within 15°C. The TEG's thermoelectric conversion efficiency of 7.5% and HPTEG's prototype system thermoelectric conversion efficiency of 6.2% were achieved. When the TEG hot surface temperature reached 625°C, the maximum electrical output power of the TEG peaked at 183.2 W, and the open-circuit voltage reached 42.2 V. The high performances of the HPTEG prototype demonstrated the potential of the HPTEG for use in engineering applications.     

A comprehensive review of solar thermoelectric cooling systems

The negative environmental impacts of burning fossil fuels have forced the energy research community seriously to consider renewable sources, such as naturally available solar energy. This paper provides an overview of solar thermoelectric (TE) cooling systems. Thus, this review presents the details referring to TE cooling parameters and formulations of the performance indicators and focuses on the development of TE cooling systems in recent decade with particular attention on advances in materials and modeling and design approaches. Additionally, the TE cooling applications have been also reviewed in aspects of electronic cooling, domestic refrigeration, air conditioning, and power generation. Finally, the possibility of solar TE cooling technologies application in “nearly zero” energy buildings is briefly discussed, and some future research directions are included. This research shows that TE cooling systems have advantages over conventional cooling devices, including compact in size, light in weight, high reliability, no mechanical moving parts, no working fluid, being powered by direct current, and easily switching between cooling and heating modes.     

Performance analysis on a novel micro‐channel heat pipe evacuated tube solar collector‐incorporated thermoelectric generation

In China, because of the emergence of a large number of high‐rise buildings, the solar hot water heater system often uses the balcony wall‐mounted method for installation. The thermoelectric energy converter is proposed as one of the possible technologies to incorporate solar water heater to produce electricity for building application. In this paper, the conceptual development and theoretical analysis of a novel micro‐channel heat pipe evacuated tube solar collector‐incorporated thermoelectric generation are all proposed. The new system takes into account many advantages, including the high heat transfer, low convective heat loss, and low contact thermal resistance. The exergy analysis method based on the second law of thermodynamics is also introduced to evaluate the performance of this system. The results show that a novel micro‐channel heat pipe evacuated tube solar collector‐incorporated thermoelectric generation has a high thermal performance with addition of electricity production. Copyright © 2016 John Wiley & Sons, Ltd.     

Recent developments in thermoelectric materials

The increased activity in attempts to develop improved thermoelectric semiconductors for use in the direct conversion of heat into electrical energy results mostly from research sponsorship by the US Military and NASA. Thermoelectric generators have no moving parts and are difficult to detect by visual, aural or thermal infrared means. Fossil multifuelled thermoelectric generators are the leading candidates for replacing standard US Military engine generator sets up to 1·5 kW under the SLEEP programme (Signature Suppressed Lightweight Electric Energy Plants). When coupled to an isotopic heat source, thermoelectric generators are able to operate reliably and unattended for long periods of time and have a proven performance record in supplying electrical power to the Lunar Experimental Package (Apollo Program) and in providing onboard electrical power to the Voyager spacecrafts.In both military and space applications any improvement in the thermoelectric generators' conversion efficiency would result in a saving in fuel—an important consideration. One way of improving the conversion efficiency is by increasing the so called ‘Figure of merit’ of the semiconductor material employed in the fabrication of the generators' thermocouples. In this paper an assessment is made of current thermoelectric materials; recent attempts to improve the figure of merit of existing materials are discussed and a number of new thermoelectric materials described.Significant headway has been made in reducing the lattice thermal conductivity of thermoelectric materials through the use of additives, small grain sizes or combinations of both. This development will result in substantial improvements in the thermoelectric figure of merit, provided the electrical properties can be maintained close to single crystal values. It is concluded that, because in the past the development of new thermoelectric materials has occupied long periods of time, even during periods of intense research activity, it is likely that established or ‘modified’ established materials will remain the mainstay of military and space applications at least for the forseeable future.     

Properties of Ag-doped Bi-Sb alloys as thermoelectric conversion materials for solid state refrigeration

The energy conversion properties of Bi-Sb system thermoelectric materials doped by Ag was investigated. Bi₈₅Sb_{15 − x} Ag _x (x = 0, 1, 2, 3, 4) alloys with Ag substitution for Sb were synthesized by mechanical alloying and then pressed under 5 GPa at 523 K for 30 min. The phase structure of the alloys was characterized by Xray diffraction. The electric conductivities and the Seebeck coefficients were measured at the temperature range of 80–300 K. The results reveal that the electric conductivities of the Ag-doped Bi-Sb alloys are highly improved. The power factor of Bi₈₅Sb₁₄Ag₁ reaches a maximum value of 2.98×10⁻³ W/(K²·m) at 255 K, which is about three times that of the un-doped sample Bi₈₅Sb₁₅ at the same temperature.     

High-temperature thermoelectric energy conversion—II. Materials survey

The current status of materials research for high-temperature thermoelectric energy conversion is reviewed. Two general classes of materials show promise for high temperature figure of merit (Z) values, viz, the rare-earth chalcogenides and the boron-rich borides. The electronic transport properties of the rare-earth chalcogenides are explicable on the basis of degenerate or partially degenerate n-type semiconductors. Boron and boron-rich borides exhibit p-type hopping conductivity, with detailed explanations proposed for the transport differing from compound to compound. Some discussion is presented on the reasons for the low thermal conductivities in these materials. Also, ZTs greater than one appear to have been realized at high temperature in many of these compounds.     

Sensitivity analysis of the effects of the thermal parameters of exhaust gases on the output of a thermoelectric generator

Recovering the dissipated heat from exhaust is a useful means of reducing the energy consumption level as well as cutting down on environmental pollution. An efficient technique for recovering this lost heat is the use of thermoelectric generators, which directly convert the dissipated heat into useful electrical energy. In this paper, a whole thermoelectric generator system installed on the exhaust pipe of a vehicle has been modeled, and the effects of thermal parameters on the output of this thermoelectric generator have been measured and evaluated by means of sensitivity analysis. The E‐Fast sensitivity analysis method has been used in this study. The sensitivity analysis results indicate that, among the thermal parameters examined, the temperature of gases entering the heat sink installed at exhaust pipe outlet () has the greatest influence (37%) and the flow rate of fluid entering the heatsink installed on the cold side of thermoelectric modules () has the second greatest influence (17%) on the output power of the considered thermoelectric generator. By using these results, the best cases of hot exhaust gases from various industries and vehicles with the highest potential of recovering the dissipated energy and heat from them by thermoelectric generators can be identified.     

Effect of material anisotropy on the transverse thermoelectricity of layered composites

Thermoelectric devices can achieve conversion between thermal and electrical energies. In contrast to longitudinal thermoelectrics, transverse thermoelectrics can decouple the directions of heat flux and electric current, which in turn offers more flexibility in device design. While many studies have focused on composite structures constructed using materials with isotropic properties, this work investigated the effect of material anisotropy on the transverse thermoelectricity of layered composite materials. A simplified analytical model was derived based on the equivalent circuit principle to correlate the effective thermoelectric properties of the composite structure and the properties of the constituting phases. The effects of the geometrical design parameters of the composite structure and the material anisotropy were investigated. The transverse thermoelectric figure of merit increases with the increase in material anisotropy. The analytical model was then compared with the finite element analysis model with respect to the cooling capacity of transverse thermoelectric devices. The good agreement achieved between the two approaches indicated the effectiveness of the simplified analytical model in predicting the transverse thermoelectric performance of layered structures with anisotropic material properties.     

Largely reduced cross-plane thermal conductivity of nanoporous In0.1Ga0.9N thin films directly grown by metal organic chemical vapor deposition

In recent year, nanoporous Si thin films have been widely studied for their potential applications in thermoelectrics, in which high thermoelectric performance can be obtained by combining both the dramatically reduced lattice thermal conductivity and bulk-like electrical properties. Along this line, a high thermoelectric figure of merit (ZT) is also anticipated for other nanoporous thin films, whose bulk counterparts possess superior electrical properties but also high lattice thermal conductivities. Numerous thermoelectric studies have been carried out on Si-based nanoporous thin films, whereas cost-effective nitrides and oxides are not systematically studied for similar thermoelectric benefits. In this work, the cross-plane thermal conductivities of nanoporous In_0.1Ga_0.9N thin films with varied porous patterns were measured with the time-domain thermoreflectance technique. These alloys are suggested to have better electrical properties than conventional Si_xGe_1−x alloys; however, a high ZT is hindered by their intrinsically high lattice thermal conductivity, which can be addressed by introducing nanopores to scatter phonons. In contrast to previous studies using dry-etched nanopores with amorphous pore edges, the measured nanoporous thin films of this work are directly grown on a patterned sapphire substrate to minimize the structural damage by dry etching. This removes the uncertainty in the phonon transport analysis due to amorphous pore edges. Based on the measurement results, remarkable phonon size effects can be found for a thin film with periodic 300-nm-diameter pores of different patterns. This indicates that a significant amount of heat inside these alloys is still carried by phonons with ~300 nm or longer mean free paths. Our studies provide important guidance for ZT enhancement in alloys of nitrides and similar oxides.     

热电机组最小电出力计算方法及在节能调度中的应用

北方地区电网的热电机组比重大,在冬季采暖季节,系统低谷调峰非常困难,风电弃风现象时有发生。本文首先基于热电机组工况图建立了机组最小电出力与抽汽量之间的函数关系式,然后在此基础上构建了含热电、火电和风电机组的节能调度模型,并提出了一种改进的粒子群算法。实例计算表明:本文调度模型能充分挖掘热电机组调峰潜力、提高风电利用率,具有较好的节能效果。