Sabah Bux

Mechanochemical synthesis and thermoelectric properties of high quality magnesium silicide

Magnesium silicide and related alloys are attractive for thermoelectric applications due to their low toxicity, thermal stability, low density, relative abundance and low cost of production. Earlier work on the synthesis of Mg2Siviahigh energy ball milling resulted in incomplete product formation, oxide impurities, and contamination from milling media. Here we present an improved solid-state synthesis of n-type magnesium silicide using the mechanochemical technique of high energy ball milling of the elements followed by high pressure sintering using hot uniaxial compaction. This robust synthetic method permits a detailed investigation of thermoelectric properties as a function of Bi doping. The thermoelectric properties of Mg2Si1−xBix (0 ≤ x ≤ 0.021) samples are characterized from 300 K to 775 K. These results are analyzed within a single parabolic band (SPB) model to determine the effective conduction band parameters and identify regimes of non-SPB behavior.

Lithium intercalation and exfoliation of layered bismuth selenide and bismuth telluride

Alloys of bismuth telluride (Bi2Te3) are commonly used in thermoelectric devices. These materials possess a hexagonal layered structure comprised of five atom thick stacks of Te–Bi–Te–Bi–Te held together by weak van der Waals forces. Lithium cations can be intercalated between the layers using the reducing power of solvated electrons in liquid ammonia. After intercalation, lithium can be removed by exfoliation to create a stable colloidal suspension of thin sheets of Bi2Te3 or Bi2Se3 in water. Zeta potential measurements indicate that the colloids are charge stabilized. These colloidal suspensions can be deposited onto a variety of substrates to create two-dimensional thin films. Atomic force microscopy indicates that initially individual layers are deposited. The films are partially oriented as observed using X-ray powder diffraction. Annealing at temperatures as low as 85 °C can produce highly oriented films. Thus intercalation, exfoliation and deposition from a charge-stabilized colloid can provide a scalable process for synthesizing bulk quantities of nanostructured thermoelectric materials.

Synthesis and characterization of Mg2Si/Si nanocomposites prepared from MgH2 and silicon, and their thermoelectric properties

Silicon (Si) nanoparticles embedded in a Mg2Si matrix (Mg2Si/xSi) have been successfully synthesized at 623 K from MgH2 and Bi containing Si nanoparticle powders. The use of MgH2 in this synthetic route avoids the formation of oxides through the generation of hydrogen and provides a route to homogeneously mixed Si nanoparticles within a doped Mg2Si matrix. The samples were characterized by powder X-ray diffraction, thermogravimetry/differential scanning calorimetry (TG/DSC), electron microprobe analysis (EMPA), and scanning transmission electron microscopy (STEM). The final crystallite size of Mg2Si obtained from the XRD patterns is about 50 nm for all the samples and the crystallite size of Si inclusions is approximately 17 nm. Theoretical calculations indicate that ∼5 mol% concentrations of Si nanoparticles with diameters in the 5–50 nm range could decrease the lattice thermal conductivity of Mg2Si by about 1–10% below the matrix value. Reduction in thermal conductivity was observed with the smallest amount of Si, 2.5 mol%. Larger amounts, x = 10 mol%, did not provide any further reduction in thermal conductivity. Analysis of the microstructure of the Bi doped Mg2Si/xSi nanocomposites showed that the Bi dopant has a higher concentration at grain boundaries than within the grains and Bi preferentially substitutes the Mg site at the boundaries. The nanocomposite carrier concentration and mobility depend on the amount of Bi and Si inclusions in a complex fashion. Agglomerations of Si start to show up clearly in the Bi doped 5 mol% nanocomposite. While the inclusions result in a lower thermal conductivity, electrical resistivity and Seebeck are negatively affected as the presence of Si inclusions influences the amount of Bi dopant and therefore the carrier concentration. The x = 2.5 mol% nanocomposite shows a consistently higher zT throughout the measured temperature range until the highest temperatures where a dimensionless figure of merit zT ∼ 0.7 was obtained at 775 K for Mg2Si/xSi with x = 0 and 2.5 mol%. With optimization of the electronic states of the matrix and nanoparticle, further enhancement of the figure of merit may be achieved.

NANOCOMPOSITES TO ENHANCE ZT IN THERMOELECTRICS

The concept of using “self-assembled” and “force-engineered” nanostructures to enhance the thermoelectric figure of merit relative to bulk homogeneous and composite materials is presented in general terms. Specific application is made to the Si-Ge system for use in power generation at high temperature. The scientific advantages of the nanocomposite approach for the simultaneous increase in the power factor and decrease of the thermal conductivity are emphasized along with the practical advantages of having bulk samples for property measurements and a straightforward path to scale-up materials synthesis and integration of nanostructured materials into thermoelectric cooling and power generation devices.

The effect of light rare earth element substitution in Yb14MnSb11 on thermoelectric properties

After the discovery of Yb14MnSb11 as an outstanding p-type thermoelectric material for high temperatures (≥900 K), site substitution of other elements has been proven to be an effective method to further optimize the thermoelectric properties. Yb14−xRExMnSb11 (RE = Pr and Sm, 0 < x < 0.55) compounds were prepared by powder metallurgy to study their thermoelectric properties. According to powder X-ray diffraction, these samples are iso-structural with Yb14MnSb11 and when more than 5% RE is used in the synthesis the presence of (Yb,RE)4Sb3 is apparent after synthesis. After consolidation and measurement, (Yb,RE)Sb and (Yb,RE)11Sb10 appear in the powder X-ray diffraction patterns. Electron microprobe analysis results show that consolidated pellets have small (Yb,RE)Sb domains and that the maximum amount of RE in Yb14−xRExMnSb11 is x = 0.55, however, (Yb,RE)11Sb10 cannot be distinguished by electron microprobe analysis. By replacing Yb2+ with RE3+, one extra electron is introduced into Yb14MnSb11 and the carrier concentration is adjusted. Thermoelectric performance from room temperature to 1275 K was evaluated through transport and thermal conductivity measurements. The measurement shows that Seebeck coefficients initially increase and then remain stable and that electrical resistivity increases with substitutions. Thermal conductivity is slightly reduced. Substitution of Pr and Sm leads to enhanced zT. Yb13.82Pr0.18Mn1.01Sb10.99 has the best maximum zT value of ∼1.2 at 1275 K, while Yb13.80Sm0.19Mn1.00Sb11.02 has its maximum zT of ∼1.0 at 1275 K, respectively, ∼45% and ∼30% higher than Yb14MnSb11 prepared in the same manner.

High temperature thermoelectric properties of Zn-doped Eu5In2Sb6

The complex bonding environment of many ternary Zintl phases, which often results in low thermal conductivity, makes them strong contenders as thermoelectric materials. Here, we extend the investigation of A5In2Sb6 Zintl compounds with the Ca5Ga2As6 crystal structure to the only known rare-earth analogue: Eu5In2Sb6. Zn-doped samples with compositions of Eu5In2−xZnxSb6 (x = 0, 0.025, 0.05, 0.1, 0.2) were synthesized via ball milling followed by hot pressing. Eu5In2Sb6 showed significant improvements in air stability relative to its alkaline earth metal analogues. Eu5In2Sb6 exhibits semiconducting behavior with possible two band behavior suggested by increasing band mass as a function of Zn content, and two distinct transitions observed in optical absorption measurements (at 0.15 and 0.27 eV). The p-type Hall mobility of Eu5In2Sb6 was found to be much larger than that of the alkaline earth containing A5In2Sb6 phases (A = Sr, Ca) consistent with the reduced hole effective mass (1.1 me). Zn doping was successful in optimizing the carrier concentration, leading to a zT of up to 0.4 at ∼660 K, which is comparable to that of Zn-doped Sr5In2Sb6.

Thermoelectric properties of the Ca5Al2−xInxSb6 solid solution

Zintl phases are attractive for thermoelectric applications due to their complex structures and bonding environments. The Zintl compounds Ca(5)Al(2)In(x)Sb(6)and Ca(5)Al(2)In(x)Sb(6) have both been shown to have promising thermoelectric properties, with zT values of 0.6 and 0.7, respectively, when doped to control the carrier concentration. Alloying can often be used to further improve thermoelectric materials in cases when the decrease in lattice thermal conductivity outweighs reductions to the electronic mobility. Here we present the high temperature thermoelectric properties of the Ca(5)Al(2-x)In(x)Sb(6)solid solution. Undoped and optimally Zn-doped samples were investigated. X-ray diffraction confirms that a full solid solution exists between the Al and In end-members. We find that the Alu2009:u2009In ratio does not greatly influence the carrier concentration or Seebeck effect. The primary effect of alloying is thus increased scattering of both charge carriers and phonons, leading to significantly reduced electronic mobility and lattice thermal conductivity at room temperature. Ultimately, the figure of merit is unaffected by alloying in this system, due to the competing effects of reduced mobility and lattice thermal conductivity.

Thermoelectric properties and electronic structure of the Zintl phase Sr5In2Sb6 and the Ca5−xSrxIn2Sb6 solid solution

The Zintl phase Sr5In2Sb6 is isostructural with Ca5In2Sb6-a promising thermoelectric material with a peak zT of 0.7 when the carrier concentration is optimized by doping. Density functional calculations for Sr5In2Sb6 reveal a decreased energy gap and decreased valence band effective mass relative to the Ca analog. Chemical bonding analysis using the electron localizability indicator was found to support the Zintl bonding scheme for this structure type. High temperature transport measurements of the complete Ca(5-x)Sr(x)In2Sb6 solid solution were used to investigate the influence of the cation site on the electronic and thermal properties of A5In2Sb6 compounds. Sr was shown to be fully miscible on the Ca site. The higher density of the Sr analog leads to a slight reduction in lattice thermal conductivity relative to Ca5In2Sb6, and, as expected, the solid solution samples have significantly reduced lattice thermal conductivities relative to the end member compounds.

Enhanced thermoelectric properties of Sr5In2Sb6via Zn-doping

Zintl phases exhibit inherently low thermal conductivity and adjustable electronic properties, which are integral to designing high-efficiency thermoelectric materials. Inspired by the promising thermoelectric figure of merit of optimized A5M2Sb6 Zintl phases (A = Ca or Sr, M = Al, Ga, In), Zn-doped Sr5In2−xZnxSb6 (x = 0, 0.025, 0.05, 0.1) compounds were investigated. Optical absorption measurements combined with band structure calculations indicate two distinct energy transitions for Sr5In2Sb6, one direct (Eg ∼ 0.3 eV) and the other from a lower valence band manifold to the conduction band edge (Eg ∼ 0.55 eV). Sr5In2Sb6 exhibits nondegenerate p-type semiconducting behavior with low carrier concentration (∼4 × 1018 h+ cm−3 at 300 K). Charge carrier tuning was achieved by Zn2+ substitution on the In3+ site, increasing carrier concentrations to up to 1020 h+ cm−3. All samples displayed relatively low thermal conductivities (∼0.7 W m−1 K−1 at 700 K). The Zn-doped samples exhibited significantly higher zT values compared to the undoped sample, reaching a value of ∼0.4 at 750 K for Sr5In1.9Zn0.1Sb6.

Thermoelectric properties of the Zintl phases Yb5M2Sb6 (M = Al, Ga, In)

Zintl compounds with chemical formula Yb5M2Sb6 (M = Al, Ga, and In) form one of two known A5M2Pn6 structure types characterized by double chains of corner-linked MPn4 tetrahedra bridged by Pn2 dumbbells. High temperature electronic and thermal transport measurements were used to characterize the thermoelectric properties of Yb5M2Sb6 compounds. All samples were found to exhibit similar high p-type carrier concentrations, low resistivity and low Seebeck coefficients in agreement with the band structure calculations. These results, combined with previous studies, suggest that Yb5M2Sb6 compounds are semimetals (i.e., they lack an energy gap between the valence and conduction bands), in contrast to the semiconducting alkaline earth (Ca, Sr, Ba) and Eu based A5M2Sb6 compounds. Yb5M2Sb6 compounds have very low lattice thermal conductivity, comparable to other closely related A5M2Sb6 and A3MSb3 phases. However, due to the semimetallic behaviour, the figure of merit of investigated samples remains low (zT < 0.15).