Thermal Conductivity and ZT in Disordered Organic Thermoelectrics

For decades, continuous attempts have been made to improve the figure of merit (ZT) of thermoelectrics. The theory behind the Seebeck effect itself is well researched, but the problem with ZT is related to materials properties that offset one another. This work analyzed the link between the site energy distributions and thermal conductivity of oxidized poly(3,4-ethylenedioxythiophene-tosylate) (PEDOT:Tos), which was reported to be a good organic thermoelectric. To understand how heat flow was affected by “disorder” in PEDOT:Tos and the associated electron–phonon interactions, we computed the values of the thermal conductivity κ and ZT using materials parameters extracted from the open literature. By varying the values of the parameters separately, we were able to identify their individual influence on κ and ZT. Our results suggest that ZT is most sensitive to changes in σ, the bandwidth of the density of states (DOS) of the transport sites, and less so to changes in n _eff, the effective carrier density. Our simulations also suggested that ZT could become exceptionally large (approaching a value of ~20) if σ were lowered to 1 meV to 2 meV. This would be a tremendous approach to increase ZT in oxidized PEDOT:Tos.     

Thermal Cycling, Mechanical Degradation, and the Effective Figure of Merit of a Thermoelectric Module

Thermoelectric modules experience performance reduction and mechanical failure due to thermomechanical stresses induced by thermal cycling. The present study subjects a thermoelectric module to thermal cycling and evaluates the evolution of its thermoelectric performance through measurements of the thermoelectric figure of merit, ZT, and its individual components. The Seebeck coefficient and thermal conductivity are measured using steady-state infrared microscopy, and the electrical conductivity and ZT are evaluated using the Harman technique. These properties are tracked over many cycles until device failure after 45,000 thermal cycles. The mechanical failure of the TE module is analyzed using high-resolution infrared microscopy and scanning electron microscopy. A reduction in electrical conductivity is the primary mechanism of performance reduction and is likely associated with defects observed during cycling. The effective figure of merit is reduced by 20% through 40,000 cycles and drops by 97% at 45,000 cycles. These results quantify the effect of thermal cycling on a commercial TE module and provide insight into the packaging of a complete TE module for reliable operation.     

Transport Properties of Bulk Thermoelectrics—An International Round-Robin Study, Part I: Seebeck Coefficient and Electrical Resistivity

Recent research and development of high-temperature thermoelectric materials has demonstrated great potential for converting automobile exhaust heat directly into electricity. Thermoelectrics based on classic bismuth telluride have also started to impact the automotive industry by enhancing air-conditioning efficiency and integrated cabin climate control. In addition to engineering challenges of making reliable and efficient devices to withstand thermal and mechanical cycling, the remaining issues in thermoelectric power generation and refrigeration are mostly materials related. The dimensionless figure of merit, ZT, still needs to be improved from the current value of 1.0 to 1.5 to above 2.0 to be competitive with other alternative technologies. In the meantime, the thermoelectric community could greatly benefit from the development of international test standards, improved test methods, and better characterization tools. Internationally, thermoelectrics have been recognized by many countries as a key component for improving energy efficiency. The International Energy Agency (IEA) group under the Implementing Agreement for Advanced Materials for Transportation (AMT) identified thermoelectric materials as an important area in 2009. This paper is part I of the international round-robin testing of transport properties of bulk thermoelectrics. The main foci in part I are the measurement of two electronic transport properties: Seebeck coefficient and electrical resistivity.     

Experimental and theoretical study of the thermoelectric properties of copper selenide

The temperature dependences of the specific heat, thermal conductivity, coefficient of thermal expansion (CTE), and transport coefficients (electrical conductivity and thermoelectric power) of copper selenide are experimentally and theoretically investigated in the temperature range of 300–873 K. The calculation results correlate with the experimental data up to a temperature of ~773 K. The maximum thermoelectric figure of merit of nanostructured copper selenide is ZT ~ 1.8. The correlation dependence between ZT and the thermal conductivity within the entire temperature range under consideration is shown.     

Enhancement of Thermoelectric Figure‐of‐Merit by a Bulk Nanostructuring Approach

Recently a significant figure‐of‐merit (ZT) improvement in the most‐studied existing thermoelectric materials has been achieved by creating nanograins and nanostructures in the grains using the combination of high‐energy ball milling and a direct‐current‐induced hot‐press process. Thermoelectric transport measurements, coupled with microstructure studies and theoretical modeling, show that the ZT improvement is the result of low lattice thermal conductivity due to the increased phonon scattering by grain boundaries and structural defects. In this article, the synthesis process and the relationship between the microstructures and the thermoelectric properties of the nanostructured thermoelectric bulk materials with an enhanced ZT value are reviewed. It is expected that the nanostructured materials described here will be useful for a variety of applications such as waste heat recovery, solar energy conversion, and environmentally friendly refrigeration.     

Spatially Resolved Thermal Conductivity Measurements Using a Thermoreflectance Microprobe

A transient thermoreflectance technique capable of creating maps of the out-of-plane thermal conductivity of materials with spatial resolution of 5 μm is presented. The applied noncontact optical microprobe uses a thin reflective metal film as temperature transducer and heat reservoir. The parameters of the experimental setup guarantee that the heat flow is one dimensional. Thus, relatively simple mathematical relations can be used to extract the thermal conductivity from the recorded signal shape, which is important for thermal conductivity maps with high pixel count. For reference materials (soda-lime glass and PbTe), the determined thermal conductivities were in good agreement with bulk values, indicating a typical measurement uncertainty of 10%. For low-conductivity substrates, the measuring scheme is relatively insensitive to thermal interface resistance. Thermal conductivity maps of lead-antimony-silver-tellurium surfaces showed distinct features which could be correlated with optical surface micrographs. The local conductivity fluctuations can possibly be attributed to local changes in chemical composition and secondary phase formation.     

Low Frequency Impedance Spectroscopy Analysis of Thermoelectric Modules

Impedance spectroscopy is a well-established technique for the study of semiconductors and energy-related devices. However, in the area of thermoelectrics (TEs), this technique is not frequently used and there is a lack of a physical background for a proper interpretation of the results. Usually, in the low frequency regime, the impedance spectrum of TE modules working in cooling mode is characterized by a semicircle which can be modelled as a parallel connection of a resistor and a capacitor. Here, we present a theoretical analysis to understand the origin of both parameters in bulk TE modules working as Peltier coolers. The analysis introduces a thermoelectric capacitance and a thermoelectric resistance that are defined by the temperature, the Seebeck coefficient and the thermal properties of the module (specific heat and thermal conductivity, respectively). The product of both provides a time constant that directly relates to the thermal diffusivity. Our analysis provides a theoretical model able to interpret the low frequency results and obtain relevant thermal parameters from a single impedance measurement.     

Thermal-lens and photo-acoustic methods for the determination of SiC thermal properties

In this paper we report the use of photothermal techniques such as Thermal lens (TL) spectrometry, Photoacoustic and heat capacity, ρc_p, to determine the thermo-optical parameters, such as thermal conductivity (K), thermal diffusivity (D), specific heat (c_p) and the optical path dependence with temperature (ds/dT), of an undoped polycrystalline 3C-SiC. To our knowledge, this is the first time that Thermal lens technique is used for wide band-gap systems. Results obtained for the polycrystalline sample with TL technique indicates that ds/dT is negative at room temperature. Moreover, the obtained values of thermal diffusivity and thermal conductivity are in good agreement with that found in the literature, indicating that the phototermal techniques can be used to obtain the referred parameters in circumstances where other techniques cannot be used, for example, in harsh environments.     

Thermoelectric Properties of Magnesium Silicide Deposited by Use of an Atmospheric Plasma Thermal Spray

The thermoelectric properties of magnesium silicide (Mg₂Si) samples prepared by use of an atmospheric plasma spray (APS) were compared with those of samples prepared from the same feedstock powder by use of the conventional hot-pressing method. The characterization performed included measurement of thermal conductivity, electrical conductivity, Seebeck coefficient, and figure of merit, ZT. X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive x-ray spectroscopy (EDX) were used to assess how phase and microstructure affected the thermoelectric properties of the samples. Hall effect measurements furnished carrier concentration, and measurement of Hall mobility provided further insight into electrical conductivity and Seebeck coefficient. Low temperature and high velocity APS using an internal-powder distribution system achieved a phase of composition similar to that of the feedstock powder. Thermal spraying was demonstrated in this work to be an effective means of reducing the thermal conductivity of Mg₂Si; this may be because of pores and cracks in the sprayed sample. Vacuum-annealed APS samples were found to have very high Seebeck coefficients. To further improve the figure of merit, carrier concentration must be adjusted and carrier mobility must be enhanced.     

Understanding Thermal Insulation in Porous,Particulate Materials

Silica hollow nanosphere colloidal crystals feature a uniquely well‐defined structure across multiple length scales. This contribution elucidates the intricate interplay between structure and atmosphere on the effective thermal diffusivity as well as the effective thermal conductivity. Using silica hollow sphere assemblies, one can independently alter the particle geometry, the density, the packing symmetry, and the interparticle bonding strength to fabricate materials with an ultralow thermal conductivity. Whereas the thermal diffusivity decreases with increasing shell thickness, the thermal conductivity behaves inversely. However, the geometry of the colloidal particles is not the only decisive parameter for thermal insulation. By a combination of reduced packing symmetry and interparticle bonding strength, the thermal conductivity is lowered by additionally 70% down to only 8 mW m^?1 K^?1 in vacuum. The contribution of gaseous transport, even in these tiny pores (<200 nm), leads to minimum thermal conductivities of ≈35 and ≈45 mW m^?1 K^?1 for air and helium atmosphere, respectively. The influence of the individual contributions of the solid and (open‐ and closed‐pore) gaseous conductions is further clarified by using finite element modeling. Consequently, these particulate materials can be considered as a non‐flammable and dispersion‐processable alternative to commercial polymer foams.     

Self-Assembled Germanium Quantum-Dot Supercrystals in Silicon with Extremely Low Thermal Conductivities for Thermoelectrics

Superlattices with one-dimensional (1D) phonon confinement were studied to obtain a low thermal conductivity for thermoelectrics. Since they are composed of materials with a lattice mismatch, they often show dislocations. Like 1D nanowires, they also decrease heat transport in only one main propagation direction. It is therefore challenging to design superlattices with a thermoelectric figure of merit ZT higher than unity. Epitaxial self-assembly is a major technology to fabricate three-dimensional (3D) Ge quantum-dot (QD) arrays in Si. They have been used for quantum and solar-energy devices. Using the atomic-scale phononic crystal model, 3D Ge QD supercrystals in Si also present an extreme reduction of the thermal conductivity to a value that can be under 0.04 W/m/K. Owing to incoherent phonon scattering, the same conclusion holds for 3D supercrystals with moderate QD disordering. As a result, they might be considered for the design of highly efficient complementary metal–oxide–semiconductor (CMOS)-compatible thermoelectric devices with ZT possibly much higher than unity. Such a small thermal conductivity was only obtained for two-dimensional layered WSe₂ crystals in an experimental study. However, electronic conduction in the Si/Ge compounds is significantly enhanced. The 0.04 W/m/K value can be computed for different Ge QD filling ratios of the Si/Ge supercrystal with size parameters in the range of current fabrication technologies.     

Determination of Thermoelectric Module Efficiency: A Survey

The development of thermoelectrics (TE) for energy conversion is in the transition phase from laboratory research to device development. There is an increasing demand to accurately determine the module efficiency, especially for the power generation mode. For many TE, the figure of merit, ZT, of the material sometimes cannot be fully realized at the device level. Reliable efficiency testing of thermoelectric modules is important to assess the device ZT and provide end-users with realistic values for how much power can be generated under specific conditions. We conducted a general survey of efficiency testing devices and their performance. The results indicated a lack of industry standards and test procedures. This study included a commercial test system and several laboratory systems. Most systems are based on the heat flow meter method, and some are based on the Harman method. They are usually reproducible in evaluating thermoelectric modules. However, different systems often showed large differences that are likely caused by uncertain heat loss and thermal resistance. Efficiency testing is an important capability for the thermoelectric community to improve. A follow-up international standardization effort is planned.     

Lower Thermal Conductivity and Higher Thermoelectric Performance of Fe-Substituted and Ce, Yb Double-Filled p-Type Skutterudites

Substituting Fe on Co sites is an effective way to produce p-type skutterudite compounds as well as to reduce the thermal conductivity of skutterudites. In this work, we investigated thermoelectric properties of Fe-substituted and Ce + Yb double-filled Ce _x Yb _y Fe _z Co_4?z Sb₁₂ (x = y = 0.5, z = 2.0 to 3.25 nominal) skutterudite compounds by studying the Seebeck coefficient, electrical conductivity, thermal conductivity, and Hall coefficient over a broad range of temperatures. All samples were prepared by using the traditional method of melting–annealing and spark plasma sintering. The signs of the Hall coefficient and Seebeck coefficient indicate that all samples are p-type conductors. Electrical conductivity increases with increasing Fe content. The temperature dependence of electrical conductivity indicates that a transition from the extrinsic to the intrinsic regime of conduction depends on the amount of Fe substituted for Co. The temperature dependence of mobility reflects the dominance of acoustic phonon scattering at temperatures above ambient. Except for Ce_0.5Yb_0.5Fe_3.25Co_0.75Sb₁₂, the thermal conductivity increases with increasing Fe content, reaching the maximum value of 2.23 W/m K at room temperature for Ce_0.5Yb_0.5Fe₃CoSb₁₂. A high power factor (27 μW/K² cm) combined with a rather low thermal conductivity for Ce_0.5Yb_0.5Fe_3.25Co_0.75Sb₁₂ (nominal) lead to a dimensionless figure of merit ZT = 1.0 at 750 K for this compound, one of the highest ZT values achieved in p-type skutterudite compounds prepared by the traditional method of melting–annealing and spark plasma sintering.     

Engineering Thermal Conductivity for Balancing Between Reliability and Performance of Bulk Thermoelectric Generators

The nanostructuring approach has significantly contributed to the improving of thermoelectric figure‐of‐merit (ZT) by reducing lattice thermal conductivity. Even though it is an effective method to enhance ZT, the drastically lowered thermal conductivity in some cases can cause thermomechanical issues leading to decreased reliability of thermoelectric generators. Here, an engineering thermal conductivity (κ_eng) is defined as a minimum allowable thermal conductivity of a thermoelectric material in a module, and is evaluated to avoid thermomechanical failure and thermoelectric degradation of a device. Additionally, there is dilemma of determining thermoelectric leg length: a shorter leg is desired for higher W kg^?1, W cm^?3, and W The nanostructuring approach has significantly contributed to the improving of thermoelectric figure‐of‐merit (ZT) by reducing lattice thermal conductivity. Even though it is an effective method to enhance ZT, the drastically lowered thermal conductivity in some cases can cause thermomechanical issues leading to decreased reliability of thermoelectric generators. Here, an engineering thermal conductivity (κ_eng) is defined as a minimum allowable thermal conductivity of a thermoelectric material in a module, and is evaluated to avoid thermomechanical failure and thermoelectric degradation of a device. Additionally, there is dilemma of determining thermoelectric leg length: a shorter leg is desired for higher W kg^?1, W cm^?3, and W $^?1, but it raises the thermomechanical vulnerability issue. By considering a balance between the thermoelectric performance and thermomechanical reliability issues, it is discussed how to improve device reliability of thermoelectric generators and the engineering thermal conductivity of thermoelectric materials.     

Thermoelectric Properties of Nano/microstructured p-Type Bi0.4Sb1.6Te3 Powders Fabricated by Mechanical Alloying and Vacuum Hot Pressing

Two kinds of Bi_0.4Sb_1.6Te₃ powder with different particle and grain sizes were fabricated by high-energy ball milling. Powder mixtures with varied weight ratios were consolidated by vacuum hot pressing (HP) to produce nano/ microstructured composites of identical chemical composition. From measurements of the Seebeck coefficient, electrical resistivity, and thermal conductivity of these composites, a figure of merit (ZT) value of up to 1.19 was achieved at 373 K for the sample containing 40% nanograin powder. This ZT value is higher than that of monolithic nanostructured Bi_0.4Sb_1.6Te₃. It is further noted that the ZT value of this sample in the temperature range of 450 K to 575 K is in the range of 0.7 to 1.1. Such ZT characteristics are suitable for power generation applications as no other material with a similar high ZT value in this temperature range has been observed until now. The achieved high ZT value can probably be attributed to the unique nano/microstructure, in which the dispersed nanograin powder increases the number of phonon scattering sites, which in turn results in a decrease of the thermal conductivity while simultaneously increasing the electrical conductivity, owing to the existence of the microsized powder that can provide a fast carrier transportation network. These results indicate that the nano/microstructured Bi_0.4Sb_1.6Te₃ alloy can serve as a high-performance material for application in thermoelectric devices.     

一种用于薄膜热容测量的微热量计的设计与制作

目前已发现并证实薄膜的热导率和热扩散率存在着尺寸效应。本文为了研究薄膜的另一个热学性质比热是否也具有尺寸效应 ,提出了一种用于薄膜热容测量的新方法 ,其相应的实验器件为一悬膜结构。从理论上阐述了其测量原理 ,结合ANSYS热学模拟设计并利用微机械加工技术制作出SiO2 悬膜结构 ,悬膜由两个悬臂支撑 ,在悬膜上制作了Pt薄膜电阻同时用于加热和测温。这种结构加快了样品、悬膜和加热 /测温电阻之间的热传递 ,减小了悬膜的热损失 ,提高了测量精度。     

Development of a Thermal Conductivity Measurement System Using the 3ω Method and Application to Thermoelectric Particles

For this study, we developed a thermal conductivity, κ, measurement system using 3ω method. We checked the system accuracy by measuring κ for a glass substrate (1737; Corning). Conventional evaporated aluminum wire and ink-jet printed silver wire were used as sensor wires. The system realized a κ measurement of glass within 10 % error. We estimated κ of aggregated p-type (Bi_1?x Sb _x )₂Te₃ particles using a two heat flow model. The estimated thermal conductivity of the sample κ _sample are 0.06–0.27 WK^?1 m^?1, which is smaller than the bulk value.     

Thermal Properties of Tissue Equivalent Phantom Materials

Thermal conductivity, specific heat, density, and thermal diffusivity were determined for standard RF and microwave phantom materials. Thermal conductivity data for seven phantom materials of varying aluminum content were analyzed using mixture theories. With the thermal diffusivity values obtained, worst case errors in SAR determination due to thermal conduction for adipose-muscle planar phantoms were estimated.     

Thermoelectric Figure of Merit Enhancement in Bi2Te3-Coated Bi Composites

This study examines the thermoelectric behavior of composites containing hydrothermally processed tellurium-coated bismuth particles of various sizes. Since only a very thin layer of Bi₂Te₃ forms on the particle surface, the high-pressure compacted composite is still dominated by bismuth as the main ingredient (??96% Bi). Thermoelectric figure of merit ZT values are derived from measurements of thermal conductivity, electrical resistivity, and Seebeck coefficient. As expected, a ZT value almost three times higher than that of bismuth is found. This enhancement appears to be caused mainly by lowered thermal conductivity due to the significant number of grain boundaries, short phonon mean free path in the coating layers, and lattice mismatch.     

Enhanced Thermoelectric Properties of BiCuSeO/Polyaniline Composites

BiCuSeO/polyaniline (BCSO/PANI) bulk composites have been successfully fabricated by a ball-milling and hot-pressing method. Microstructure analysis shows that BCSO particles are well mixed and dispersed in the PANI matrix. Our results indicate that the Seebeck coefficient can be increased substantially by adding BCSO filler to the PANI matrix, especially for 40 wt.% BCSO (5–87 μV K^?1). Electrical conductivity and thermal conductivity both change slightly with the increasing filler content. The highest figure of merit, ZT, among these bulk composites is 0.004 at 341 K, which is almost 500 times greater than that of pure PANI.