Design of Apparatus for Ni/Mg2Si and Ni/MnSi1.75 Contact Resistance Determination for Thermoelectric Legs

In recent decades, thermoelectricity has been widely studied as a potential new source of renewable energy. One of the major challenges to improve the efficiency of thermoelectric (TE) devices is to minimize the contact resistance between the active material and the electrodes, since this represents the major loss of charge in a TE module. This article describes the fabrication of an apparatus for TE leg characterization built with commercial and custom-made parts based on the analog one-dimensional transmission-line method. This device permits contact resistance measurements of bulk TE legs. p- and n-type TE materials, Mg₂Si_0.98Bi_0.02 and MnSi_1.75Ge_0.02, respectively, were metallized with nickel foils and used as test materials for contact resistance characterization. Contact resistance values of 0.5 mΩ mm² for Ni/Mg₂Si_0.98Bi_0.02 junctions and 4 mΩ mm² for Ni/MnSi_1.75Ge_0.02 junctions have been measured. Contact resistance measurements are discussed depending on materials processing and the experimental measurement conditions.     

Thin-Film Thermoelectric Modules for Power Generation Using Focused Solar Light

We demonstrated the fabrication of thin-film thermoelectric generators and evaluated their generation properties using solar light as a thermal source. Thin-film elements of Bi_0.5Sb_1.5Te₃ (p-type) and Bi₂Te_2.7Se_0.3 (n-type), which were patterned using the lift-off technique, were deposited on glass substrates using radiofrequency magnetron sputtering. After annealing at 300°C, the average Seebeck coefficients of p- and n-type films were 150???V/K and ?104???V/K, respectively, at 50°C to 75°C. A cylindrical lens was used to focus solar light to a line shape onto the hot side of the thin-film thermoelectric module with 15 p?Cn junctions. The minimum width of line-shaped solar light was 0.8?mm with solar concentration of 12.5 suns. We studied the properties of thermoelectric modules with different-sized p?Cn junctions on the hot side, and obtained maximum open voltage and power values of 140?mV and 0.7???W, respectively, for a module with 0.5-mm p?Cn junctions. The conversion efficiency was 8.75?×?10^?4%, which was approximately equal to the value estimated by the finite-element method.     

Development of Skutterudite Thermoelectric Materials and Modules

Multifilling with La, Ba, Ga, and Ti in p-type skutterudite and Yb, Ca, Al, Ga, and In in n-type skutterudite remarkably reduces their thermal conductivity, resulting in enhancement of their dimensionless figure of merit ZT to ZT?=?0.75 for p-type (La,Ba,Ga,Ti)₁(Fe,Co)₄Sb₁₂ and ZT?=?1.0 for n-type (Yb,Ca,Al,Ga,In)_0.7(Co,Fe)₄Sb₁₂. A thermoelectric module technology suitable for these skutterudites including diffusion barrier and electrode materials has been established. The diffusion barrier materials allow the electrode to coexist stably with the p/n skutterudites in the module??s working temperature range of room temperature to 600°C. Under conditions of hot/cold-side temperatures of 600°C/50°C, a skutterudite module with size of 50?mm?×?50?mm?×?7.6?mm exhibited generation performance of 32?W power output and 8% thermoelectric conversion efficiency.     

Power-Generation Performance and Durability of a Skutterudite Thermoelectric Generator

By using a p-type (La, Ba, Ga, Ti)₁(Fe, Co)₄Sb₁₂ skutterudite with a dimensionless figure of merit, ZT, = 0.75 at 500°C and an n-type (Yb, Ca, Al, Ga, In)_0.7(Co, Fe)₄Sb₁₂ skutterudite with ZT = 1.0 at 500°C, we fabricated a thermoelectric power-generation module capable of working at high temperatures (up to 600°C). When its hot and cold sides were at 600°C and 30°C, respectively, the power output of a 50 mm × 50 mm × 7.6 mm skutterudite module was 34 W and its thermoelectric conversion efficiency was 8%. In a durability test with the module’s hot and cold sides continuously maintained at 600°C and 80°C, respectively, for 8000 h, power generation first decreased by approximately 6% in the initial 300 h then remained constant.     

On the thermoelectric properties and band gap of silicon–germanium alloys in the high-temperature region

For n- and p-type Si_0.85Ge_0.15 alloys, the thermoelectric properties (thermopower, resistivity, thermal conductivity, and thermoelectric efficiency) are determined in the range from room temperature to 1200°C. The measurements are carried out with an upgraded device [1] by absolute and steady-state methods with thermal screens. The device is upgraded to extend the working-temperature range to ~1500 K. On the basis of these data, the energy-related capabilities of the alloy are estimated; the thermal band-gap width is calculated in the temperature range of ~1300–1400 K.     

Interface Microstructure and Performance of Sb Contacts in Bismuth Telluride-Based Thermoelectric Elements

A thermoelectric joint composed of p-type Bi_0.5Sb_1.5Te₃ (BiSbTe) material and an antimony (Sb) interlayer was fabricated by spark plasma sintering. The reliability of the thermoelectric joints was investigated using electron probe microanalysis for samples with different accelerated isothermal aging time. After aging for 30 days at 300°C in vacuum, the thickness of the diffusion layer at the BiSbTe/Sb interface was about 30 μm, and Sb₂Te₃ was identified to be the major interfacial compound by element analysis. The contact resistivity was 3 × 10^?6 ohm cm² before aging and increased to 8.5 × 10^?6 ohm cm² after aging for 30 days at 300°C, an increase associated with the thickness of the interfacial compound. This contact resistivity is very small compared with that of samples with solder alloys as the interlayer. In addition, we have also investigated the interface behavior of Sb layers integrated with n-type Bi₂Se_0.3Te_2.7 (BiSeTe) material, and obtained similar results as for the p-type semiconductor. The present study suggests that Sb may be useful as a new interlayer material for bismuth telluride-based power generation devices.     

Scavenging Elemental Sb Through Addition of NbSb2 to Mm0.9Fe3.5Co0.5Sb12 Skutterudites

Our previous work identified thermal instability of p-type skutterudite as a primary cause of degradation during thermoelectric generator operation at 650°C. Residual Sb in the microstructure was believed to be the cause of diminished thermal stability, especially above the melting point of Sb (631°C). This work investigated addition of Nb to p-type skutterudite to from NbSb₂, thus scavenging elemental Sb. The results of this work are reported, along with comprehensive thermoelectric property characterization of the p-type skutterudite?+?NbSb₂ composites.     

Fabrication of a Flexible Bismuth Telluride Power Generation Module Using Microporous Polyimide Films as Substrates

In this study, we investigated the effect of the structure of microporous p-type (Bi_0.4Te₃Sb_1.6) and n-type (Bi_2.0Te_2.7Se_0.3) BiTe-based thin films on their thermoelectric performance. High-aspect-ratio porous thin films with pore depth greater than 1 μm and pore diameter ranging from 300 nm to 500 nm were prepared by oxygen plasma etching of polyimide (PI) layers capped with a heat-resistant block copolymer, which acted as the template. The cross-plane thermal conductivities of the porous p- and n-type thin films were 0.4 W m^?1 K^?1 and 0.42 W m^?1 K^?1, respectively, and the dimensionless figures of merit, ZT, of the p- and n-type BiTe films were estimated as 1.0 and 1.0, respectively, at room temperature. A prototype thermoelectric module consisting of 20 pairs of p- and n-type strips over an area of 3 cm × 5 cm was fabricated on the porous PI substrate. This module produced an output power of 0.1 mW and an output voltage of 0.6 V for a temperature difference of 130°C. The output power of the submicrostructured module was 1.5 times greater than that of a module based on smooth BiTe-based thin films. Thus, the thermoelectric performance of the thin films was improved owing to their submicroscale structure.     

Performance of a Thermoelectric Module Based on n-Type (La0.12Sr0.88)0.95TiO3−δ and p-Type Ca3Co4−xO9+δ

Here, we present the performance of a thermoelectric (TE) module consisting of n-type (La_0.12Sr_0.88)_0.95TiO₃ and p-type Ca₃Co_4?xO_9+δ materials. The main challenge in this investigation was operating the TE module in different atmospheric conditions, since n-type has optimum TE performance at reducing conditions, while p-type has optimum at oxidizing conditions. The TE module was exposed to two different atmospheres and demonstrated higher stability in N₂ atmosphere than in air. The maximum electrical power output decreased after 40 h when the hot side was exposed to N₂ at 600°C, while only 1 h at 400°C in ambient air was enough to oxidize (La_0.12Sr_0.88)_0.95TiO₃ followed by a reduced electrical power output. The module generated maximum electrical power of 0.9 mW (～?4.7 mW/cm²) at 600°C hot side and δT?～?570 K in N₂, and 0.15 mW (～?0.8 mW/cm²) at 400°C hot side and δT?～?370 K in air. A stability limit of Ca₃Co_3.93O_9+δ at ～?700°C in N₂ was determined by in situ high-temperature x-ray diffraction.

     

Highly Textured Mn15Si26 Film Obtained by High-Temperature Treatment

The growth of higher manganese silicide (HMS) films on monocrystalline silicon (100) has been investigated. This growth was performed by solid-state reaction. Using electron beam evaporation a single layer of manganese was deposited on a silicon substrate. The samples so prepared were heat treated in a classical furnace under vacuum. A highly textured film was obtained after treatment at 890°C for 18 h. The obtained HMS was identified as Mn₁₅Si₂₆. The texture relationship is (105) [100] Mn₁₅Si₂₆ ∥ (100) [100] Si. Mn₁₅Si₂₆ has a tetragonal cell; hence, the angle between the c-axis and the normal of the sample surface is 60°. Since this value is far from 0° and 90°, a large transverse thermoelectric effect is expected in these samples. As a consequence the HMS films could be used in anisotropic electromotive force-thermogenerators.     

Fabrication and Evaluation of a Thermoelectric Microdevice on a Free-Standing Substrate

Using shadow masks prepared by standard microfabrication processes, we fabricated in-plane thermoelectric microdevices (4 mm × 4 mm) made of bismuth telluride thin films, and evaluated their performance. We used Bi_0.4Te_3.0Sb_1.6 as the p-type semiconductor and Bi_2.0Te_2.7Se_0.3 as the n-type semiconductor. We deposited p- and n-type thermoelectric thin films on a free-standing thin film of Si₃N₄ (4 mm × 4 mm × 4 μm) on a Si wafer, and measured the output voltages of the microdevices while heating at the bottom of the Si substrate. The maximum output voltage of the thermoelectric device was 48 mV at 373 K.     

Solution Growth and Thermoelectric Properties of Single-Phase MnSi<Subscript>1.75−<Emphasis Type="Italic">x</Emphasis></Subscript>

We have investigated the crystal growth of single-phase MnSi_1.75−x by a temperature gradient solution growth (TGSG) method using Ga and Sn as solvents and MnSi_1.7 alloy as the solute, and measured the thermoelectric properties of the resulting crystals. Single-phase Mn₁₁Si₁₉ and Mn₄Si₇ crystals were grown successfully using Ga and Sn as solvents, respectively. The typical size of a grown ingot of Mn₁₁Si₁₉ was 2 mm to 4 mm in thickness and 12 mm in diameter, whereas Mn₄Si₇ had polyhedral shape with dimensions in the range of several millimeters. The single-phase Mn₁₁Si₁₉ has good electrical conduction (ρ = 0.89 × 10⁻³ Ω cm to 1.09 × 10⁻³ Ω cm) compared with melt-grown multiphase higher-manganese silicide (HMS) crystals. The Seebeck coefficient, power factor, and thermal conductivity were 77 μV K⁻¹ to 85 μV K⁻¹, 6.7 μW cm⁻¹ K⁻² to 7.2 μW cm⁻¹ K⁻², and 0.032 W cm⁻¹ K⁻¹, respectively, at 300 K.     

Stress Analysis and Output Power Measurement of an n-Mg2Si Thermoelectric Power Generator with an Unconventional Structure

We examine the mechanical stability of an unconventional Mg₂Si thermoelectric generator (TEG) structure. In this structure, the angle θ between the thermoelectric (TE) chips and the heat sink is less than 90°. We examined the tolerance to an external force of various Mg₂Si TEG structures using a finite-element method (FEM) with the ANSYS code. The output power of the TEGs was also measured. First, for the FEM analysis, the mechanical properties of sintered Mg₂Si TE chips, such as the bending strength and Young’s modulus, were measured. Then, two-dimensional (2D) TEG models with various values of θ (90°, 75°, 60°, 45°, 30°, 15°, and 0°) were constructed in ANSYS. The x and y axes were defined as being in the horizontal and vertical directions of the substrate, respectively. In the analysis, the maximum tensile stress in the chip when a constant load was applied to the TEG model in the x direction was determined. Based on the analytical results, an appropriate structure was selected and a module fabricated. For the TEG fabrication, eight TE chips, each with dimensions of 3 mm × 3 mm × 10 mm and consisting of Sb-doped n-Mg₂Si prepared by a plasma-activated sintering process, were assembled such that two chips were connected in parallel, and four pairs of these were connected in series on a footprint of 46 mm × 12 mm. The measured power generation characteristics and temperature distribution with temperature differences between 873 K and 373 K are discussed.     

Phase Content Influence on Thermoelectric Properties of Manganese Silicide-Based Materials for Middle-High Temperatures

The higher manganese silicides (HMS), represented by MnSi _x (x = 1.71 to 1.75), are promising p-type leg candidates for thermoelectric energy harvesting systems in the middle-high temperature range. They are very attractive as they could replace lead-based compounds due to their nontoxicity, low-cost starting materials, and high thermal and chemical stability. Dense pellets were obtained through direct reaction between Mn and Si powders during the spark plasma sintering process. The tetragonal HMS and cubic MnSi phase amounts and the functional properties of the material such as the Seebeck coefficient and electrical and thermal conductivity were evaluated as a function of the SPS processing conditions. The morphology, composition, and crystal structure of the samples were characterized by scanning electron microscopy, energy-dispersive x-ray spectroscopy, and x-ray diffraction analyses, respectively. Differential scanning calorimetry and thermogravimetric analysis were performed to evaluate the thermal stability of the final sintered material. A ZT value of 0.34 was obtained at 600°C for the sample sintered at 900°C and 90 MPa with 5 min holding time.     

Model of Heat Exchangers for Waste Heat Recovery from Diesel Engine Exhaust for Thermoelectric Power Generation

The performance and operating characteristics of a hypothetical thermoelectric generator system designed to extract waste heat from the exhaust of a medium-duty turbocharged diesel engine were modeled. The finite-difference model consisted of two integrated submodels: a heat exchanger model and a thermoelectric device model. The heat exchanger model specified a rectangular cross-sectional geometry with liquid coolant on the cold side, and accounted for the difference between the heat transfer rate from the exhaust and that to the coolant. With the spatial variation of the thermoelectric properties accounted for, the thermoelectric device model calculated the hot-side and cold-side heat flux for the temperature boundary conditions given for the thermoelectric elements, iterating until temperature and heat flux boundary conditions satisfied the convection conditions for both exhaust and coolant, and heat transfer in the thermoelectric device. A downhill simplex method was used to optimize the parameters that affected the electrical power output, including the thermoelectric leg height, thermoelectric n-type to p-type leg area ratio, thermoelectric leg area to void area ratio, load electrical resistance, exhaust duct height, coolant duct height, fin spacing in the exhaust duct, location in the engine exhaust system, and number of flow paths within the constrained package volume. The calculation results showed that the configuration with 32 straight fins was optimal across the 30-cm-wide duct for the case of a single duct with total height of 5.5?cm. In addition, three counterflow parallel ducts or flow paths were found to be an optimum number for the given size constraint of 5.5?cm total height, and parallel ducts with counterflow were a better configuration than serpentine flow. Based on the reported thermoelectric properties of MnSi_1.75 and Mg₂Si_0.5Sn_0.5, the maximum net electrical power achieved for the three parallel flow paths in a counterflow arrangement was 1.06?kW for package volume of 16.5?L and exhaust flow enthalpy flux of 122?kW.     

Physical,Mechanical, and Structural Properties of Highly Efficient Nanostructured n- and p-Silicides for Practical Thermoelectric Applications

Cost-effective highly efficient nanostructured n-type Mg₂Si_1?x Sn _x and p-type higher manganese silicide (HMS) compositions were prepared for the development of practical waste heat generators for automotive and marine thermoelectric applications, in the frame of the European Commission (EC)-funded PowerDriver project. The physical, mechanical, and structural properties were fully characterized as part of a database-generation exercise required for the thermoelectric converter design. A combination of high maximal ZT values of ～0.6 and ～1.1 for the HMS and Mg₂Si_1?x Sn _x compositions, respectively, and adequate mechanical properties was obtained.     

Improvement in the Durability and Heat Conduction of uni-leg Thermoelectric Modules Using n-type Mg2Si Legs

We have fabricated several kinds of uni-leg thermoelectric (TE) modules using Sb-doped n-type Mg₂Si. In order to evaluate the influence of the structure of the modules on their durability with respect to heat-cycling, modules of two different types were evaluated. One was a conventional-structured module, in which the upper and lower surfaces of the legs were each fixed to a ceramic substrate. The other was a ‘half skeleton’ module, in which the ‘cold-side’ substrate was removed and a thermal-conductive sheet was used instead of a ceramic plate for the cold-side insulator. From the result of this evaluation, it was confirmed that, although some variation in the output power was observed for the ‘half-skeleton’ module, the power variation was markedly less than for the conventional-structured module. Additionally, to improve the output power of the module, we replaced the Al₂O₃ substrate with Si₃N₄, which has a higher thermal conductivity than the Al₂O₃ substrate. The observed output power of a module (25 mm × 24 mm × 8.3 mm) fabricated using the Si₃N₄ substrate was 1,293 mW at ΔT = 500 K. The output value of the module using the Si₃N₄ plate was improved by 29 % compared with the output value of the module using the Al₂O₃ substrate. Moreover, based on the structures of these modules, a 36 mm × 41 mm × 8.3 mm module was fabricated. The expected value of the output power of the module was 1.9 W at ΔT = 500 K.     

Segmented thermoelectric unicouple for an operating temperature range of 30–320°C

The possibility of increasing the efficiency of a thermocouple in the temperature range of 30–320°C is studied using an approach associated with the development of segmented thermoelectric unicouples. n- and p-type thermoelectric unicouples are constructed from low-temperature thermoelectric materials based on bismuth telluride and the addition of an intermediate-temperature material based on PbTe and GeTe, respectively. The thermoelectric unicouples are fabricated by spark plasma sintering (SPS). This method provides a contact resistance of ≤10 μΩ cm. The properties of segmented and conventional unicouples are compared. The efficiency of segmented unicouples in comparison with conventional ones increases by almost 70% and attains 5.3% in the operating range of 30–320°C.     

Thermoelectric Properties of Multifilled Skutterudites with La as the Main Filler

Bulk multifilled n- and p-type skutterudites with La as the main filler were fabricated using the spark plasma sintering (SPS) method. The thermoelectric properties and thermal stability of these skutterudites were investigated. It was found that the interactions among the filling atoms also play a vital role in reducing the lattice thermal conductivity of the multifilled skutterudites. ZT = 0.76 for p-type La_0.8Ba_0.01Ga_0.1Ti_0.1Fe₃CoSb₁₂ and ZT = 1.0 for n-type La_0.3Ca_0.1Al_0.1Ga_0.1In_0.2Co_3.75Fe_0.25Sb₁₂ skutterudites have been achieved. Furthermore, the differential scanning calorimetry (DSC) results show that there is no skutterudite phase decomposition till 750°C for the La_0.8Ba_0.01Ga_0.1Ti_0.1Fe₃CoSb₁₂ sample. The thermal stability of the La_0.8Ba_0.01Ga_0.1Ti_0.1Fe₃CoSb₁₂ skutterudite is greatly improved. Using the developed multifilled skutterudites, the fabricated module with size of 50 mm × 50 mm × 7.6 mm possesses maximum output power of 32 W under the condition of hot/cold sides = 600°C/50°C.     

Low-Temperature Synthesis and Thermoelectric Properties of n-Type PbTe

n-Type PbTe compounds were synthesized at temperatures as low as 430°C. After synthesis, the materials were ground, cold pressed, and sintered at 600°C. The effect of this low-temperature synthesis on the structural features and thermoelectric properties of as-prepared and PbI₂-doped materials was investigated for the first time. The Seebeck coefficient, and electrical and thermal conductivity were measured in the temperature range 2 K ≤ T ≤  610 K. The results show that all materials exhibit n-type conduction and the thermoelectric properties are improved by doping. ZT values reach 0.5 at 610 K, and the discrepancies with the literature are discussed.