Transport and Mechanical Properties of High-ZT Mg2.08Si0.4−x Sn0.6Sb x Thermoelectric Materials

Mg₂(Si,Sn) compounds are promising candidate low-cost, lightweight, nontoxic thermoelectric materials made from abundant elements and are suited for power generation applications in the intermediate temperature range of 600 K to 800 K. Knowledge on the transport and mechanical properties of Mg₂(Si,Sn) compounds is essential to the design of Mg₂(Si,Sn)-based thermoelectric devices. In this work, such materials were synthesized using the molten-salt sealing method and were powder processed, followed by pulsed electric sintering densification. A set of Mg_2.08Si_0.4?x Sn_0.6Sb _x (0 ≤ x ≤ 0.072) compounds were investigated, and a peak ZT of 1.50 was obtained at 716 K in Mg_2.08Si_0.364Sn_0.6Sb_0.036. The high ZT is attributed to a high electrical conductivity in these samples, possibly caused by a magnesium deficiency in the final product. The mechanical response of the material to stresses is a function of the elastic moduli. The temperature-dependent Young’s modulus, shear modulus, bulk modulus, Poisson’s ratio, acoustic wave speeds, and acoustic Debye temperature of the undoped Mg₂(Si,Sn) compounds were measured using resonant ultrasound spectroscopy from 295 K to 603 K. In addition, the hardness and fracture toughness were measured at room temperature.     

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.     

Effect of geometric dimensions on thermoelectric and mechanical performance for Mg2Si-based thermoelectric unicouple

The generating efficiency of thermoelectric generation (TEG) depends not only on the thermoelectric (TE) performance of TE device, but also on its mechanical performance. And choosing suitable TE materials and geometric dimension can improve the working performance of TE device. Mg₂Si is one of the most promising TE materials in the medium temperature range, and Mg₂Si-based TE devices have broad application prospects. In this paper, a three-dimensional finite model of the Mg₂Si-based TE unicouple used for recovering vehicle exhaust waste heat is constructed for the performance analysis. The TE performance and mechanical performance of the Mg₂Si-based TE unicouple under the influence of different geometric dimensions are investigated, respectively. The curves of the output power, the power conversion efficiency and the thermal stress distribution varying with different geometric dimensions are discussed in detail. The calculated result would be helpful for further understanding of the TE and mechanical properties of the Mg₂Si-based TE unicouple, and it can also provide guidance for further strength check and optimum geometric design of TE unicouples in general.     

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.     

Improvement of Electrical Contact Between TE Material and Ni Electrode Interfaces by Application of a Buffer Layer

A single ??-structure thermoelectric (TE) module based on p-type NaCo₂O₄, n-type Mg₂Si, and Ni electrode was fabricated by the spark plasma sintering (SPS) method. The NaCo₂O₄ powder was synthesized by using a metal?Ccitric acid complex decomposition method. Bulk Mg₂Si prepared by melt quenching was ground into a powder and sieved to particle size of 75???m or less. To obtain a sintered body of NaCo₂O₄ or Mg₂Si, the powder was sintered using SPS. Pressed Ni powder or mixed powder consisting of Ni and SrRuO₃ powder was inserted between these materials and the Ni electrode in order to connect them, and electrical power was passed through the electrodes from the SPS equipment. The open-circuit voltage (V _OC) values of a single module in which TE materials were connected to the Ni electrodes by using pressed Ni powder was 82.7?mV, and the maximum output current (I _max) and maximum output power (P _max) were 212.4?mA and 6.65?mW at ??T?=?470?K, respectively. On the other hand, V _OC of a single module in which TE materials and an Ni electrode were connected with a mixed powder (Ni:SrRuO₃?=?6:4 volume fraction) was 109?mV, and I _max and P _max were 4034?mA and 109?mW at ??T?=?500?K, respectively. These results indicate that the resistance at the interface between the TE materials and the Ni electrode can be decreased and the output power can be increased by application of a buffer layer consisting of Ni and SrRuO₃.     

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.     

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.     

Development of an Mg2Si Unileg Thermoelectric Module Using Durable Sb-Doped Mg2Si Legs

Mg₂Si unileg structure thermoelectric (TE) modules, which are composed only of n-type Mg₂Si legs, were fabricated using Sb-doped Mg₂Si. The Mg₂Si TE legs used in our module were fabricated by a plasma-activated sintering method using material produced from molten commercial doped polycrystalline Mg₂Si, and, at the same time, nickel electrodes were formed on the Mg₂Si using a monobloc plasma-activated sintering technique. The source material used for our legs has a ZT value of 0.77 at 862 K. The TE modules, which have dimensions of 21 mm × 30 mm × 16 mm, were composed of ten legs that were connected in series electrically using nickel terminals, and the dimensions of a single leg were 4.0 mm  × 4.0 mm × 10 mm. From evaluations of the measured output characteristics of the modules, it appeared that the electrical resistance of the wiring that is used to connect each leg considerably affects the power output of the unileg module. Thus, we attempted to reduce the wiring resistance of the module and fabricated a module using copper terminals. The observed values of the open-circuit voltage and output power of the Sb-doped Mg₂Si unileg module were 496 mV and 1211 mW at ΔT = 531 K (hot side: 873 K; cool side: 342 K).     

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.     

Molecular Dynamics Simulation on Mechanics of Mg2Si Nanofilm

Molecular dynamics simulation has been carried out to study the mechanical properties of Mg₂Si nanofilm. For the binary thermoelectric material Mg₂Si with antifluorite crystal structure, a modified Morse potential energy function in which the bond-angle deformation has been taken into account is developed and employed to describe the atomic interactions to shed light on its mechanical properties. In the simulation, the radial distribution function of Mg₂Si nanofilm is computed to validate its crystal structure, and the stress–strain responses of the nanofilm are examined at room temperature. It is found that the mechanical properties of Mg₂Si nanofilm are quite different from those of bulk Mg₂Si due to the impact of surface atoms of the nanostructures. The size effect and the temperature effect on the mechanical properties of Mg₂Si nanofilm are discussed in detail.     

High Performance Mg2(Si,Sn) Solid Solutions: a Point Defect Chemistry Approach to Enhancing Thermoelectric Properties

A point defect chemistry approach to improving thermoelectric (TE) properties is introduced, and its effectiveness in the emerging mid‐temperature TE material Mg₂(Si,Sn) is demonstrated. The TE properties of Mg₂(Si,Sn) are enhanced via the synergistical implementation of three types of point defects, that is, Sb dopants, Mg vacancies, and Mg interstitials in Mg₂Si_0.4Sn_0.6‐xSb_x with high Sb content (x > 0.1), and it is found that i) Sb doping at low ratios tunes the carrier concentration while it facilitates the formation of Mg vacancies at high doping ratios (x > 0.1). Mg vacancies act as acceptors and phonon scatters; ii) the concentration of Mg vacancies is effectively controlled by the Sb doping ratio; iii) excess Mg facilitates the formation of Mg interstitials that also tunes the carrier concentration; vi) at the optimal Sb‐doping ratio near x ≈ 0.10 the lattice thermal conductivity is significantly reduced, and a state‐of‐the‐art figure of merit ZT > 1.1 is attained at 750 K in 2 at% Zn doped Mg₂Si_0.4Sn_0.5Sb_0.1 specimen. These results demonstrate the significance of point defects in thermoelectrics, and the promise of point defect chemistry as a new approach in optimizing TE properties.     

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.     

Development of a Thermal Buffering Device to Cope with Temperature Fluctuations for a Thermoelectric Power Generator

To stabilize the heat input to a thermoelectric generator (TEG) and protect it from large temperature fluctuations, a thermal buffering device (TBD) was fabricated and examined using a typical Bi-Te TEG module and a brand-new Mg₂Si TEG module. The TBD comprises two adjoining heat storage containers, each containing different alloys, which can be optimized for the temperature range of the TEG. The combination of two alloys in series diminishes the thermal fluctuations, stabilizing the heat input to the TEG module. This is achieved by having two metallic materials with large enthalpies of fusion that can be placed between the heat source and the TEG. The combination of the two alloys can be optimized for the temperature ranges of Bi-Te, Pb-Te, or Co-Sb. For the Bi-Te TEG, 15Al-85Zn and 30Sn-70Zn alloys were used for the heat source side and the TEG side, respectively. The corresponding alloys for the Mg₂Si TEG were 20Ni-80Al and 7Si-93Al. With the use of a TBD, the Bi-Te TEG exhibited no notable damage even in the rather high temperature range beyond ??573?K. For the Mg₂Si TEG, no operational damage of the Mg₂Si TEG module was observed even with a temperature of 1020?K.     

Thermal Cycling Effects on the Thermoelectric Properties of n-Type In,Ce-Based Skutterudite Compounds

n-Type In-filled CoSb₃ is a known skutterudite compound that has shown promising thermoelectric (TE) properties resulting in high dimensionless figure of merit values at elevated temperatures. Use in various waste heat recovery applications will require survival and operation after exposure to harsh thermal cycling environments. This research focused on uncovering the thermal cycling effects on TE properties of n-type In_0.2Co₄Sb₁₂ and In_0.2Ce_0.15Co₄Sb₁₂ skutterudite compositions as well as quantifying their temperature-dependent structural properties (elastic modulus, shear modulus, and Poisson??s ratio). It was observed that the Seebeck coefficient and resistivity increased only slightly in the double-filled In,Ce skutterudite materials upon thermal cycling. In the In-filled skutterudites the Seebeck coefficient remained approximately the same on thermal cycling, while the electrical resistivity increased significantly after thermal cycling. Results also show that the thermal conductivity marginally decreases in the case of In-filled skutterudites, whereas the reduction is more pronounced in In,Ce-based skutterudite compounds. The possible reason for this kind of reduction can be attributed to grain pinning effects due to formation of nanoinclusions. High-temperature structural property measurements (i.e., Young??s modulus and shear modulus) are also reported. The results show that these structural properties decrease slowly as temperature increases and that the compounds are structurally stable after numerous (up to 200) thermal cycles.     

Vacancy and Temperature Effects on Mechanical Properties of Single-Crystal Bulk Mg2Si: A Molecular Dynamics Study

The mechanical properties of single-crystal bulk Mg₂Si have been investigated using the molecular dynamics simulation method, in which a many-body potential energy function including bond and angle interactions is adopted to predict the mechanical properties. Virtual tension tests of specimens under different conditions, including Mg vacancy and temperature effects, were carried out by controlling the strain along the principal crystallographic direction. The simulation results show that single-crystal bulk Mg₂Si exhibits a nonlinear elastic stress–strain response and the mechanical properties degrade significantly with increasing vacancy content. Moreover, the effect of temperature on the mechanical properties of single-crystal bulk Mg₂Si is also discussed in detail.     

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.     

Solid-State Synthesis of Te-Doped Mg<Subscript>2</Subscript>Si

Te-doped Mg₂Si (Mg₂Si:Te _m , m = 0, 0.01, 0.02, 0.03, 0.05) alloys were synthesized by a solid-state reaction and mechanical alloying. The electronic transport properties (Hall coefficient, carrier concentration, and mobility) and thermoelectric properties (Seebeck coefficient, electrical conductivity, thermal conductivity, and figure of merit) were examined. Mg₂Si was synthesized successfully by a solid-state reaction at 673 K for 6 h, and Te-doped Mg₂Si powders were obtained by mechanical alloying for 24 h. The alloys were fully consolidated by hot-pressing at 1073 K for 1 h. All the Mg₂Si:Te _m samples showed n-type conduction, indicating that the electrical conduction is due mainly to electrons. The electrical conductivity increased and the absolute value of the Seebeck coefficient decreased with increasing Te content, because Te doping increased the electron concentration considerably from 10¹⁶ cm⁻³ to 10¹⁸ cm⁻³. The thermal conductivity did not change significantly on Te doping, due to the much larger contribution of lattice thermal conductivity over the electronic thermal conductivity. Thermal conduction in Te-doped Mg₂Si was due primarily to lattice vibrations (phonons). The thermoelectric figure of merit of intrinsic Mg₂Si was improved by Te doping.     

单晶SiC微纳米压痕的力学行为及仿真分析

为了研究单晶SiC的微观力学性能和加工方式,开展了单晶6H SiC（0001）的微纳米压痕试验,并采用ABAQUS软件对纳米压痕过程进行了数值仿真及完成了试验验证。结果表明,单晶SiC在加载阶段的变形机理与压入载荷无关;硬度和弹性模量表现出了明显的尺寸效应;球形压头作用下的应力值最小,玻氏压头和维氏压头作用下的应力值相同,大于圆锥压头的应力值;压痕裂纹类型有主裂纹、侧向裂纹、主次型裂纹、平直型裂纹、间断型裂纹,裂纹的平均长度随着加载力的增加而逐渐增加。