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.     

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.     

Power Generation Characteristics of Mg2Si Uni-Leg Thermoelectric Generator

Mg₂Si thermoelectric (TE) elements were fabricated by a plasma-activated sintering method using a commercial polycrystalline n-type Mg₂Si source produced by the Union Material Co., Ltd. This material typically has a ZT value of ??0.6. A monobloc plasma-activated sintering technique was used to form Ni electrodes on the TE elements. The dimensions of a single element were 4.0?mm?×?4.0?mm?×?10?mm, and these were used to construct a TE module comprising nine elements connected in series. To reduce the electrical and thermal contact resistance of the module, each part of the module, i.e., the elements, terminals, and insulating plates, was joined using a Ag-based brazing alloy. In addition, to maintain the temperature difference between the top and bottom of the module, a thermal insulation board was installed in it. The observed values of open-circuit voltage (V _OC) and output power (P) of a uni-leg structure module were 594?mV and 543?mW, respectively, at a maximum ??T?=?500?K.     

The Influence of Grain Boundary Scattering on Thermoelectric Properties of Mg2Si and Mg2Si0.8Sn0.2

The temperature dependences of the Seebeck coefficient, and electrical and thermal conductivities of bulk hot-pressed Sb-doped n-type Mg₂Si and Mg₂Si_0.8Sn_0.2 samples were measured in the temperature range from 300 K to 850 K together with the Hall coefficients at room temperature. The features of the complex band structure and scattering mechanisms were analyzed based on experimental data within the relaxation-time approximation. Based on the obtained model parameters, the possibility of improvement of the thermoelectric figure of merit due to nanostructuring and grain boundary scattering was theoretically analyzed for both Mg₂Si and the solid solution.     

Examination of a Thermally Viable Structure for an Unconventional Uni-Leg Mg2Si Thermoelectric Power Generator

We have fabricated an unconventional uni-leg structure thermoelectric generator (TEG) element using quad thermoelectric (TE) chips of Sb-doped n-Mg₂Si, which were prepared by a plasma-activated sintering process. The power curve characteristics, the effect of aging up to 500?h, and the thermal gradients at several points on the module were investigated. The observed maximum output power with the heat source at 975?K and the heat sink at 345?K was 341?mW, from which the ??T for the TE chip was calculated to be about 333?K. In aging testing in air ambient, a remarkable feature of the results was that there was no notable change from the initial resistance of the TEG module for as long as 500?h. The thermal distribution for the fabricated uni-leg TEG element was analyzed by finite-element modeling using ANSYS software. To tune the calculation parameters of ANSYS, such as the thermal conductance properties of the corresponding coupled materials in the module, precise measurements of the temperature at various probe points on the module were made. Then, meticulous verification between the measured temperature values and the results calculated by ANSYS was carried out to optimize the parameters.     

Convenient Melt-Growth Method for Thermoelectric Mg2Si

We have succeeded in growing single-crystalline-like n-type Mg₂Si bulk crystals by a convenient melt-growth method that requires no vacuum or inert gas. The Sb-doped, n-type Mg₂Si crystals had a density equivalent to the theoretical ideal of 1.99 g cm³ to 2.00 g cm^?3 and well-developed crystalline grains. Powder x-ray diffraction measurements and scanning electron microscopy observations confirmed the single-phase Mg₂Si nature of the grown crystals, with no MgO or unreacted Si and Mg observed. The crystals had high Hall mobility and power factor compared with Sb-doped sintered Mg₂Si crystals. The achieved ZT values were 0.10 at 300 K and 0.36 at 600 K for 0.317 at.%Sb-doped Mg₂Si.     

Solid-State Synthesis and Thermoelectric Properties of Sb-Doped Mg2Si Materials

Sb-doped magnesium silicide compounds have been prepared through ball milling and solid-state reaction. Materials produced were near-stoichiometric. The structural modifications have been studied with powder x-ray diffraction. Highly dense pellets of Mg₂Si_1?x Sb _x (0 ≤ x ≤ 0.04) were fabricated via hot pressing and studied in terms of Seebeck coefficient, electrical and thermal conductivity, and free carrier concentration as a function of Sb concentration. Their thermoelectric performance in the high temperature range is presented, and the maximum value of the dimensionless figure of merit was found to be 0.46 at 810 K, for the Mg₂Si_0.915Sb_0.015 member.     

Synthesis and Characterization of Al-Doped Mg2Si Thermoelectric Materials

Magnesium silicide (Mg₂Si)-based alloys are promising candidates for thermoelectric (TE) energy conversion for the middle to high range of temperature. These materials are very attractive for TE research because of the abundance of their constituent elements in the Earth’s crust. Mg₂Si could replace lead-based TE materials, due to its low cost, nontoxicity, and low density. In this work, the role of aluminum doping (Mg₂Si:Al = 1:x for x = 0.005, 0.01, 0.02, and 0.04 molar ratio) in dense Mg₂Si materials was investigated. The synthesis process was performed by planetary milling under inert atmosphere starting from commercial Mg₂Si pieces and Al powder. After ball milling, the samples were sintered by means of spark plasma sintering to density >95%. The morphology, composition, and crystal structure of the samples were characterized by field-emission scanning electron microscopy, energy-dispersive spectroscopy, and x-ray diffraction analyses. Moreover, Seebeck coefficient analyses, as well as electrical and thermal conductivity measurements were performed for all samples up to 600°C. The resultant estimated ZT values are comparable to those reported in the literature for these materials. In particular, the maximum ZT achieved was 0.50 for the x = 0.01 Al-doped sample at 600°C.     

Thermoelectric Behavior of Sb- and Al-Doped <Emphasis Type="Italic">n</Emphasis>-Type Mg<Subscript>2</Subscript>Si Device Under Large Temperature Differences

The thermoelectric (TE) characteristics of Sb- and Al-doped n-type Mg₂Si elemental devices fabricated using material produced from molten commercial doped polycrystalline Mg₂Si were examined. The TE devices were prepared using a plasma-activated sintering (PAS) technique. To complete the devices, Ni electrodes were fabricated on each end of them during the sintering process. To realize durable devices for large temperature differences, thermodynamically stable Sb-doped Mg₂Si (Sb-Mg₂Si) was exposed to the higher temperature and Al-doped Mg₂Si (Al-Mg₂Si) was exposed to the cooler temperature. The devices consisted of segments of Sb-Mg₂Si and Al-Mg₂Si with sizes in the following ratios: Sb-Mg₂Si:Al-Mg₂Si = 4:1, 1:1, and 1:4. A device specimen composed solely of Sb-Mg₂Si showed no notable deterioration even after aging for 1000 h, while some segmented specimens, such as those with Sb-Mg₂Si:Al-Mg₂Si = 1:1 and 1:4, suffered from a considerable drop in output current over the large ΔT range. The observed power generated by specimens with Sb-Mg₂Si:Al-Mg₂Si = 1:1 and 1:4 and sizes of 2 mm × 2 mm × 10 mm were 50.7 mW and 49.5 mW, respectively, with higher and lower temperatures of 873 K and 373 K, respectively. For the sample composed solely of Sb-Mg₂Si, a power of 55 mW was demonstrated. An aging test for up to 1000 h for the same ΔT range indicated drops in output power of between ∼3% and 20%.     

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.     

The Use of Transition-Metal Silicides to Reduce the Contact Resistance Between the Electrode and Sintered n-Type Mg2Si

The electrical and thermoelectric characteristics of n-type Mg₂Si equipped with electrodes of Ni and the transition-metal silicides CoSi₂, CrSi₂, TiSi₂, and NiSi were examined. To form the electrodes on the Mg₂Si matrix, a monobloc sintering method, i.e., simultaneous sintering of the electrode material during Mg₂Si sintering, was used. To obtain dense electrodes and to keep an appropriately low sintering temperature for the Mg₂Si matrix, a Ni binder was used for the CoSi₂, CrSi₂, and TiSi₂ monobloc sintering. The mixture ratio between the transition-metal silicide and the Ni was 50:50 in wt.%. The room-temperature I?CV characteristics of the fabricated CoSi₂, CrSi₂, and TiSi₂ electrodes with the Ni binder and NiSi electrodes were considered to be adequate for practical applications in as much as ohmic contacts were obtained. The contact resistance at the Mg₂Si/electrode interface decreased by 35% and 28%, respectively, for the CoSi₂ and CrSi₂ electrodes compared with our standard Ni electrode. The thermoelectric power output was measured at the practical operating temperature of 600?K, with ??T?=?500?K. The observed output powers for 3.0?mm?×?3.0?mm?×?7.5?mm samples equipped with CoSi₂, CrSi₂, and NiSi electrodes were 153?mW, 149?mW, and 125?mW, respectively, representing increases of 27%, 24%, and 4%, respectively, compared with the 120?mW measured for the sample with Ni electrodes.     

Thermoelectric Properties of p-Type Mg2Si0.25Sn0.75 Doped with Sodium Acetate and Metallic Sodium

We have investigated the thermoelectric properties of p-type Na-doped Mg₂ Si_0.25Sn_0.75 solid solutions prepared by liquid–solid reaction and hot-pressing methods. Na was introduced into Mg₂Si_0.25Sn_0.75 by using either sodium acetate (CH₃COONa) or metallic sodium (2 N). The samples doped with sodium acetate consisted of phases with antifluorite structure and a small amount of MgO as revealed by x-ray diffraction, whereas the sample doped with metallic sodium contained the Sn, MgO, and Mg₂SiSn phases. The hole concentrations of Mg_1.975Na_0.025Si_0.25Sn_0.75 doped by sodium acetate and metallic sodium were 1.84 × 10²⁵ m^?3 and 1.22 × 10²⁵ m^?3, respectively, resulting in resistivities of 4.96 × 10^?5 Ω m (sodium acetate) and 1.09 × 10^?5 Ω m (metallic sodium). The Seebeck coefficients were 198 μV K^?1 (sodium acetate) and 241 μV K^?1 (metallic sodium). The figures of merit for Mg_1.975Na_0.025Si_0.25Sn_0.75 were 0.40 × 10^?3 K^?1 (sodium acetate) and 0.25 × 10^?3 K^?1 (metallic sodium) at 400 K. Thus, sodium acetate is a suitable Na dopant for Mg₂Si_1?x Sn _x .     

Effect of Synthesis and Sintering Conditions on the Thermoelectric Properties of n-Doped Mg2Si

Magnesium silicide (Mg₂Si)-based alloys are promising candidates for thermoelectric (TE) energy conversion in the middle–high temperature range. The detrimental effect of the presence of MgO on the TE properties of Mg₂Si based materials is widely known. For this reason, the conditions used for synthesis and sintering were optimized to limit oxygen contamination. The effect of Bi doping on the TE performance of dense Mg₂Si materials was also investigated. Synthesis was performed by ball milling in an inert atmosphere starting from commercial Mg₂Si powder and Bi powder. The samples were consolidated, by spark plasma sintering, to a density >95%. The morphology, and the composition and crystal structure of samples were characterized by field-emission scanning electronic microscopy and x-ray diffraction, respectively. Moreover, determination of Seebeck coefficients and measurement of electrical and thermal conductivity were performed for all the samples. Mg₂Si with 0.1 mol% Bi doping had a ZT value of 0.81, indicative of the potential of this method for fabrication of n-type bulk material with good TE performance.     

Synchrotron Study of Ag-Doped Mg2Si: Correlation Between Properties and Structure

The crystal structure of Ag-doped Mg₂Si was investigated using synchrotron and neutron powder diffraction analysis, including in situ synchrotron x-ray powder diffraction patterns, recorded during a thermal cycle from room temperature up to 600°C. Rietveld refinement of diffraction patterns indicated that Ag doping results in partial substitution at Si sites. During heating, the Mg₂Si lattice parameters exhibited a shift in the temperature dependence at 300°C to 350°C, which was attributed to Ag precipitation out of Mg₂Si_1?x Ag _x solid solution. In turn, an increase of the Ag present in the Mg₂Si lattice after 350°C could be linked to thermally activated diffusion of Ag from β-AgMg phase. The Ag-dopant migration may explain previously outlined instabilities in the thermopower of Ag-doped Mg₂Si, e.g., the drop of the Seebeck coefficient value after heating to 150°C to 200°C and its subsequent increase after 350°C to 450°C.     

Modeling of Thermoelectric Properties of Magnesium Silicide (Mg2Si)

Thermoelectric (TE) materials based on alloys of magnesium (Mg) and silicon (Si) possess favorable properties such as high electrical conductivity and low thermal conductivity. Additionally, their abundance in nature and lack of toxicity make them even more attractive. To better understand the electronic transport and thermal characteristics of bulk magnesium silicide (Mg₂Si), we solve the multiband Boltzmann transport equation within the relaxation-time approximation to calculate the TE properties of n-type and p-type Mg₂Si. The dominant scattering mechanisms due to acoustic phonons and ionized impurities were accounted for in the calculations. The Debye model was used to calculate the lattice thermal conductivity. A unique set of semiempirical material parameters was obtained for both n-type and p-type materials through simulation testing. The model was optimized to fit different sets of experimental data from recently reported literature. The model shows consistent agreement with experimental characteristics for both n-type and p-type Mg₂Si versus temperature and doping concentration. A systematic study of the effect of dopant concentration on the electrical and thermal conductivity of Mg₂Si was also performed. The model predicts a maximum dimensionless figure of merit of about 0.8 when the doping concentration is increased to approximately 10²⁰?cm^?C3 for both n-type and p-type devices.     

Double-Doping Approach to Enhancing the Thermoelectric Figure-of-Merit of n-Type Mg2Si Synthesized by Use of Spark Plasma Sintering

We report significant enhancement of the thermoelectric figure-of-merit of Mg₂Si by double-doping with a combination of Bi, Pb, and Sb as doping elements. Addition of any two of these three elements to Mg₂Si increases the electrical conductivity by more than three orders of magnitude at 323 K, irrespective of the doping elements used. However, a corresponding decrease in the Seebeck coefficient is observed in comparison with undoped Mg₂Si. Irrespective of the combination of the three elements used for double doping, a figure-of-merit of approximately 0.7 at 873 K is obtained for Mg₂Si; this is primarily because of enhancement of the electrical conductivity.     

Solid-State Synthesis and Thermoelectric Properties of Al-Doped Mg2Si

The electronic transport and thermoelectric properties of Al-doped Mg₂Si (Mg₂Si:Al _m , m?=?0, 0.005, 0.01, 0.02, 0.03) compounds prepared by solid-state synthesis were examined. Mg₂Si was synthesized by solid-state reaction (SSR) at 773?K for 6?h, and Al-doped Mg₂Si powders were obtained by mechanical alloying (MA) for 24?h. Mg₂Si:Al _m were fully consolidated by hot pressing (HP) at 1073?K for 1?h, and all samples showed n-type conduction, indicating that the electrical conduction is due mainly to electrons. The electrical conductivity increased significantly with increasing Al doping content, and the absolute value of the Seebeck coefficient decreased due to the significant increase in electron concentration from 10¹⁶ cm^?3 to 10¹⁹ cm^?3 by Al doping. The thermal conductivity was increased slightly by Al doping, but was not changed significantly by the Al doping content due to the much larger contribution of lattice thermal conductivity over electronic thermal conductivity. Mg₂Si:Al_0.02 showed a maximum thermoelectric figure of merit of 0.47 at 823?K.     

Manufacturing Processes for TiO x -Based Thermoelectric Modules: from Suboxide Synthesis to Module Testing

An overview of different TiO _x synthesis methods with regard to enhancement of thermoelectric properties and transfer of the synthesis process to cost-efficient methods as well as joining techniques for module manufacture is presented. Different synthesis routes were applied and investigated, namely synthesis of TiO _x via reduction with less gas formation by mixing TiO₂ and TiC [powder-derived (PD)-TiO _x ], a bottom-up approach via a precursor route for synthesizing TiO _x directly [precursor-derived (PDC)-TiO _x ], and the combination by mixing TiO₂ with precursor (PDC-TiO _x /TiO₂). All the approaches resulted in adjustable phase composition with different oxygen contents and, therefore, adjustable electrical properties as well as different microstructures to enhance the physical and thermoelectric properties. The electrical resistivity could be adjusted from 1 mΩ cm to 1000 mΩ cm through the oxygen content of TiO _x . The research included investigations of cost-efficient production processes for thermoelectric material such as spray-drying, spark plasma sintering, hot pressing or pressureless sintering in terms of shaping, sintering, and machining, as well as joining techniques to build a complete thermoelectric module. To realize thermal and electrical connections, technologies for joining and packaging were developed. For a first demonstration of the feasibility of TiO _x -based thermoelectric modules for use at high temperatures, a unileg n-type module with footprint of 30 mm × 30 mm was designed. Low-volume fabrication yielded more than 20 single modules. Finally, the modules were successfully tested under conditions close to those of the desired applications with hot-side temperature up to 600°C.     

Comparing Doping Methodologies in Mg2Si/AgMg System

Morphological and optical characterizations for the Mg₂Si samples doped with Ag are presented. Two different doping methodologies with silver, namely in situ and ex situ doping, were studied for the case of Mg₂Si of self-propagating high-temperature synthesis. Electron microscopy measurements in both scanning and transmission configurations verified the presence of AgMg precipitates embedded in the Mg₂Si matrix and similar results were also yielded by FTIR spectroscopy. Finally, the dependence of silver content in both forms of dopant and inter-metallic constituent is studied upon doping technology.     

Effects of Al/Sb Double Doping on the Thermoelectric Properties of Mg2Si0.75Sn0.25

Al/Sb double-doped Mg₂Si_0.75Sn_0.25 materials were prepared by liquid–solid reaction synthesis and the hot-pressing technique. The effects of Al/Sb double doping on the thermoelectric properties were investigated at temperatures between room temperature and 900 K, and the resistivity and Hall coefficient were investigated at 80 K to 900 K. Al/Sb double-doped samples were found to be n-type semiconductors in the investigated temperature range. The absolute Seebeck coefficient (α), resistivity (ρ), and thermal conductivity (κ) for Al/Sb double-doped samples at room temperature were in the ranges of 152.5 μV K^?1 to 109.2 μV K^?1, 2.92 × 10^?5 Ω m to 1.29 × 10^?5 Ω m, and 2.50 W K^?1 m^?1 to 2.86 W K^?1 m^?1, respectively. The absolute values of α increased with increasing temperature up to a maximum, and decreased thereafter. This could be attributed to mixed carrier conduction in the intrinsic region. κ decreased linearly with increasing temperature to a minimum near the intrinsic region, then increased rapidly because of bipolar components. The highest ZT value measured was 0.94 at 850 K for Mg_1.9975Al_0.0025Si_0.75Sn_0.2425Sb_0.0075. Sb doping was effective for enhancement of ZT, because of a remarkable increase in the carrier concentration. However, Al doping was almost ineffective for enhancing ZT.