热电材料的热输运调控及其在微型器件中的应用

热电能量转换技术是一种利用材料实现热能和电能直接相互转换的清洁能源技术。热电材料的性能是决定热电转换效率的关键因素,而热电材料的性能优化涉及电输运和热输运性能的协同优化。文章介绍了近期热电材料中热输运的调控机制和方法,其中重点论述了基于原子分子层次调控热传导的宽频声子散射效应和横波阻尼效应,以及低维结构和复合材料中的基于纳米微米尺度的微结构调控。最后介绍了室温附近热传导的调控机制及其在高效微型热电器件研发中的应用和进展。     

Performance of thermoelectric generator with graphene nanofluid cooling

Improvement of the heat transfer of the cold side is one of the approaches to enhance the performance of TEG systems.As a new type of heat transfer media, nanofluids can enhance the heat transfer performance of working liquid significantly.Based on a three-dimensional and steady-state numerical model,the heat transfer and thermoelectric conversion properties of TEG systems were studied. Graphene anoplatelet aqueous nanofluids were used as the coolants for the cold side of the TEG system to improve the heat transfer capacity of the cold side. The results showed that the heat absorbed by the hot side, voltage, output power, and conversion efficiency of the TEG system were increased greatly by the nanofluid coolants.The output power and the conversion efficiency using 0.1-wt% graphene nanoplatelet aqueous nanofluid as the coolant are enhanced by 26.39% and 14.74%, respectively.     

能源效率、热电效应和纳米技术

文章介绍了能源效率、热电效应以及纳米技术这三者之间的关系。文章首先讨论了能源效率的重要性以及余热浪费对能源效率的影响,然后介绍了材料的热电效应以及利用热电效应使余热发电的可能性和实际应用中的主要障碍。最后阐明了近年来纳米技术的发展使得这一技术有可能取得突破性进展的主要原因。     

能源效率、热电效应和纳米技术

文章介绍了能源效率、热电效应以及纳米技术这三者之间的关系。文章首先讨论了能源效率的重要性以及余热浪费对能源效率的影响,然后介绍了材料的热电效应以及利用热电效应使余热发电的可能性和实际应用中的主要障碍。最后阐明了近年来纳米技术的发展使得这一技术有可能取得突破性进展的主要原因。     

稳态平板法在热电器件热电转换效率测试中的应用

将稳态平板法测导热系数的实验应用于热电器件热电转换效率的测试,通过测量输入器件的传热速率和负载的输出电功获得热电器件的热电转换效率。研究发现,稳态平板法可以测量工作温度在室温到100℃范围内热电器件的热电转换效率。     

磁各向异性热电效应对自旋相关器件的影响

在纳米点接触热电效应的实验中检测到"T"形Ni线两端的温差电压在外磁场作用下有较大变化,确认了这是由Ni线的磁各向异性热电效应引起的,外磁场的作用总是在逆温度梯度的方向产生一个额外的电动势,它与磁场以及Ni线两端温度差之间有清晰的对应关系.实验结果提示,自旋相关效应器件的研究需要留意器件样品的磁性材料构形设计和测试方法,以避免混入额外的电磁信号,给实验结果带来误判.     

Sb_2Te_3热电薄膜的离子束溅射制备与表征

采用离子束溅射技术交替沉积Sb-Te-Sb多层薄膜后进行高真空热处理,直接制备Sb2Te3薄膜.利用X射线衍射(XRD)仪、霍尔系数测试仪、薄膜Seebeck系数测量系统对所制备的薄膜特性进行表征.XRD测量结果显示,薄膜的主要衍射峰与Sb2Te3标准衍射峰相同,在[101]/[012]晶向取向明显,存在较多的Te杂质峰;霍尔系数测试结果表明,薄膜为p型半导体薄膜,薄膜电阻率较低,其电导率接近于金属电导率,载流子浓度量级为1023cm-3,具有良好的电学性能;Seebeck系数测量结果显示,薄膜具有良好的热电性能,在不同条件下制备的薄膜的Seebeck系数在7.8—62μV/K范围;在所制备的薄膜中,退火时间为6h、退火温度为200℃的薄膜其Seebeck系数达到最大,约为62μV/K,且电阻率最小.     

Tunable thermoelectric properties in bended graphene nanoribbons

The ballistic thermoelectric properties in bended graphene nanoribbons(GNRs) are systematically investigated by using atomistic simulation of electron and phonon transport. We find that the electron resonant tunneling effect occurs in the metallic–semiconducting linked ZZ-GNRs(the bended GNRs with zigzag edge leads). The electron-wave quantum interference effect occurs in the metallic–metallic linked AA-GNRs(the bended GNRs with armchair edge leads).These different physical mechanisms lead to the large Seebeck coefficient S and high electron conductance in bended ZZGNRs/AA-GNRs. Combined with the reduced lattice thermal conduction, the significant enhancement of the figure of merit ZT is predicted. Moreover, we find that the ZTmax(the maximum peak of ZT) is sensitive to the structural parameters. It can be conveniently tuned by changing the interbend length of bended GNRs. The magnitude of ZT ranges from the 0.15 to 0.72. Geometry-controlled ballistic thermoelectric effect offers an effective way to design thermoelectric devices such as thermocouples based on graphene.     

半导体温差发电过程的模型分析与数值仿真

本文提出一种新型的半导体温差发电模型,在温差发电过程的数值模拟中考虑了热电单元之间封闭腔体内空气传热的影响.同时进一步运用有限元的数值计算方法对不同电臂对数和不同型号温差发电模型的温度场、电压场进行了数值仿真计算,并对仿真结果进行分析.结果表明:采用127对热电单元模型计算的能量转换效率随冷热端温差增大而迅速提高,与采用1对热电单元模型计算的能量转换效率之差从冷热端温差为20℃的0.39%提高到冷热端温差为220℃时的5.16%,能量转换效率比1对热电单元平均高出3.02%.冷端温度恒定在30℃时,温差发电芯片的输出电压、功率以及能量转换效率均随着电偶臂的横截面积的增大而提高,且电偶臂冷热两端的温差越大提高幅度也越大,而温差发电芯片内阻则与电偶臂横截面积成反比关系,当温差为220℃时对应的输出功率最高达28.9 W.     

Progress of microscopic thermoelectric effects studied by micro- and nano-thermometric techniques

Heat dissipation is one of the most serious problems in modern integrated electronics with the continuously decreasing devices size. Large portion of the consumed power is inevitably dissipated in the form of waste heat which not only restricts the device energy-efficiency performance itself, but also leads to severe environment problems and energy crisis. Thermoelectric Seebeck effect is a green energy-recycling method, while thermoelectric Peltier effect can be employed for heat management by actively cooling overheated devices, where passive cooling by heat conduction is not sufficiently enough. However, the technological applications of thermoelectricity are limited so far by their very low conversion efficiencies and lack of deep understanding of thermoelectricity in microscopic levels. Probing and managing the thermoelectricity is therefore fundamentally important particularly in nanoscale. In this short review, we will first briefly introduce the microscopic techniques for studying nanoscale thermoelectricity, focusing mainly on scanning thermal microscopy (SThM). SThM is a powerful tool for mapping the lattice heat with nanometer spatial resolution and hence detecting the nanoscale thermal transport and dissipation processes. Then we will review recent experiments utilizing these techniques to investigate thermoelectricity in various nanomaterial systems including both (two-material) heterojunctions and (single-material) homojunctions with tailored Seebeck coefficients, and also spin Seebeck and Peltier effects in magnetic materials. Next, we will provide a perspective on the promising applications of our recently developed Scanning Noise Microscope (SNoiM) for directly probing the non-equilibrium transporting hot charges (instead of lattice heat) in thermoelectric devices. SNoiM together with SThM are expected to be able to provide more complete and comprehensive understanding to the microscopic mechanisms in thermoelectrics. Finally, we make a conclusion and outlook on the future development of microscopic studies in thermoelectrics.     

电偶极子在磁各向异性介质中的辐射功率

在经典电动力学框架下对磁各向异性介质中的电磁辐射问题进行研究, 得到了电偶极子在磁各向异性介质中的辐射功率表达式. 当介质为磁各向同性时其结果与文献报道的结果相符合, 验证了推导结果的正确性. 利用本文结果可对电偶极子在磁各向异性介质中的辐射效果做出判断, 而且对于进一步研究磁各向异性介质的电磁特性、更有效地开发利用磁各向异性介质具有实际意义.     

电子-声子相互作用对平行双量子点体系热电效应的影响

量子点体系是一种典型的低维体系, 该体系的独特物理特性有利于提高热电转换效率. 本文采用非平衡态格林函数方法, 选择平行双量子点结构, 详细讨论了电子-声子相互作用对该体系的电导、热电功率、热电优值以及热导等热电效应相关参数的影响, 全面描述了电子-声子相互作用对该结构中热电效应的影响. 理论计算结果表明, 在低温情况下, 该体系中的法诺干涉能够有效增强热电效应, 而电子-声子相互作用通过破坏法诺干涉而在一定程度上抑制电导以及热导过程. 然而, 电子-声子相互作用不会显著地影响热电功率的幅值, 并且热电优值的极值几乎不会改变, 因此在低温条件下电子-声子相互作用并不是破坏量子点体系热电效应的必要条件. 本文的结果将有利于澄清电子-声子相互作用对量子点体系热电效应的影响.     

块体热电材料的研究进展

文章重点介绍了现役热电材料（Bi2Te3,PbTe,SiGe）、常见结构类型（方钴矿型,笼合物型,Half-Heusler合金型,钠钴氧型和Zn4Sb3型）热电材料及新颖晶体结构类型的热电材料的晶体结构、热电性能、热电性能优化等方面的最新研究进展.     

Micro thermoelectric devices: From principles to innovative applications

Thermoelectric devices (TEDs), including thermoelectric generators (TEGs) and thermoelectric coolers (TECs) based on the Seebeck and Peltier effects, respectively, are capable of converting heat directly into electricity and vice versa. Tough suffering from low energy conversion efficiency and relatively high capital cost, TEDs have found niche applications, such as the remote power source for spacecraft, solid-state refrigerators, waste heat recycling, and so on. In particular, on-chip integrable micro thermoelectric devices (μ-TEDs), which can realize local thermal management, on-site temperature sensing, and energy harvesting under minor temperature gradient, could play an important role in biological sensing and cell cultivation, self-powered Internet of Things (IoT), and wearable electronics. In this review, starting from the basic principles of thermoelectric devices, we summarize the most critical parameters for μ-TEDs, design guidelines, and most recent advances in the fabrication process. In addition, some innovative applications of μ-TEDs, such as in combination with microfluidics and photonics, are demonstrated in detail.     

平板集热太阳热电器件建模及结构优化

太阳能热电转换是光伏效应外另一种直接将太阳辐射转变为电能的途径, 近年来已经成为太阳能利用的热点之一. 本文以Bi₂Te₃材料为基础构建平板集热太阳热电器件模型, 采用有限元法分析AM1.5辐射条件下器件温度分布情况, 并结合基于温度的物性参数计算集热比、热臂截面积与长度变化等因素对器件的开路电压、 最大输出功率及转化效率的影响. 研究发现: 集热比与热臂长度的变化对器件性能有显著影响, 热臂截面积的变化对器件转化效率影响相对较弱; 在这一模型中, 平板集热太阳热电器件的转化效率达到1.56%.     

Recent progress in design of conductive polymers to improve the thermoelectric performance

Organic semiconductors,especially polymer semiconductors,have attracted extensive attention as organic thermoelectric materials due to their capabilities for flexibility,low-cost fabrication,solution processability and low thermal conductivity.However,it is challenging to obtain high-performance organic thermoelectric materials because of the low intrinsic carrier concentration of organic semiconductors.The main method to control the carrier concentration of polymers is the chemical doping process by charge transfer between polymer and dopant.Therefore,the deep understanding of doping mechanisms from the point view of chemical structure has been highly desired to overcome the bottlenecks in polymeric thermoelectrics.In this contribution,we will briefly review the recently emerging progress for discovering the structure–property relationship of organic thermoelectric materials with high performance.Highlights include some achievements about doping strategies to effectively modulate the carrier concentration,the design rules of building blocks and side chains to enhance charge transport and improve the doping efficiency.Finally,we will give our viewpoints on the challenges and opportunities in the field of polymer thermoelectric materials.     

纳米陶瓷中限域效应与界面效应对热电性能影响的理论研究

采用玻尓兹曼输运方程与密度泛函计算相结合的方法, 理论研究了限域效应与界面效应对SrTiO₃纳米陶瓷热电性能的影响. 理论计算的结果表明, 室温下纳米陶瓷的热电优值较单晶有了大幅度提高, 可达到0.8. 热电优值的提高主要来源于晶粒内的声子限域效应与电子在晶界处的界面能量过滤效应, 电子的限域效应与声子的界面散射效应起到了辅助作用. 本文结论也可推广至其他材料, 因此对高性能热电纳米陶瓷的设计将起到积极的作用.     

纳米结构碲化铋合金的制备及电热输运特性

采用惰性气体保护蒸发-冷凝法制备了纳米Bi及Te粉末, 结合机械合金化和放电等离子烧结技术, 在不同烧结温度下制备出了单一物相且具有纳米层状结构及孪晶亚结构的n型Bi₂Te₃块体材料, 并系统研究了块体材料的晶粒尺度、微结构及其对电热传输特性的影响. SEM, TEM分析结果表明, 以纳米粉末为原料, 通过有效控制工艺条件, 可以制备出具有纳米层状结构Bi₂Te₃合金块体材料, 同时纳米层状结构中存在孪晶亚结构; 热电性能测试结果表明, 具有纳米层状结构及孪晶亚结构的块体试样与粗晶材料相比, 热导率大幅度降低, 在423 K附近, 热导率由粗晶材料的1.80 W/mK降至1.19 W/mK, 晶格热导率从1.16 W/mK降至0.61 W/mK, 表明纳米层状结构与孪晶亚结构共存, 有利于进一步提高声子散射, 降低晶格热导率. 其中在693 K放电等离子烧结后的试样于423K附近取得最大值的无量纲热电优值(ZT), 达到0.74.     

Thermodynamic performance characteristics of a three-terminal quantum dot hybrid thermoelectric heat engine

We propose a new model of the three-terminal quantum dot hybrid thermoelectric heat engine in which the electrons transfer between two electronic terminals at different temperatures and chemical potentials through two coupled single-level quantum dots. Based on master equation we derive the expressions for the output power and the efficiency. The working region of the hybrid heat engine is determined according to the first and second law of thermodynamics. The performance characteristic curves are plotted and the optimal performance parameters are obtained. Finally, the influence of the non-radiative effect on the optimal performance parameters is discussed in detail.