Ba6Ge2Se12 and Ba7Ge2Se17: Two Centrosymmetric Barium Seleno-Germanates with Polyatomic Anion Disorder.

Herein, the crystal structures and physical properties of two previously unreported barium seleno-germanates, Ba6Ge2Se12 and Ba7Ge2Se17, are presented. Ba6Ge2Se12 adopts the P21/c space group with a = 10.0903(2) Å, b = 9.3640(2) Å, c = 25.7643(5) Å, and ß = 90.303(1)°, whereas Ba7Ge2Se17 crystallizes in the Pnma space group with a = 12.652(1) Å, b = 20.069(2) Å, c = 12.3067(9) Å. Both structures feature polyatomic anion disorder: [Se2]2- in the case of Ba6Ge2Se12 and [GeSe5]4- in the case of Ba7Ge2Se17. The anion disorder is verified by comparing pair distribution functions of ordered and disordered models of the structures. These anions are split unevenly across two possible sets of atomic coordinates. The optical band gaps obtained from the powdered samples are found to be 1.75 and 1.51 eV for Ba6Ge2Se12 and Ba7Ge2Se17, respectively. Differential scanning calorimetry experiments indicate that the compounds are stable under the exclusion of air up to at least 673 K. The thermal diffusivity measurements revealed thermal conductivities reaching values as low as 0.33 W m-1 K-1 in both compounds at 573 K.

Developing Contacting Solutions for Mg2Si1-xSnx-Based Thermoelectric Generators: Cu and Ni45Cu55 as Potential Contacting Electrodes.

Magnesium silicides can be used for thermoelectric energy conversion as high values of figure of merit zT were obtained for n-type (1.4 at 500 °C) and p-type (0.55 at 350 °C) materials. This, however, needs to be complemented by low resistive and stable contacting to ensure long-term thermogenerator operation and minimize losses. In this study, we selected Cu and Ni45Cu55 as contacting electrodes for their high electrical conductivity, similar coefficient of thermal expansion (CTE), and good adhesion to Mg2(Si,Sn). Both electrodes were joined to Mg2Si0.3Sn0.7 pellets by hot pressing in a current-assisted press. Microstructural changes near the interface were analyzed using SEM/EDX analysis, and the specific electrical contact resistance rc was estimated using a traveling potential probe combined with local Seebeck scanning. Good contacting was observed with both electrode materials. Results show low rc with Cu, suitable for applications, for both n- and p-type silicides (<10 µΩ·cm2), with the occurrence of wide, highly conductive diffusion regions. Ni45Cu55 joining also showed relatively low rc values (∼30 µΩ·cm2) for n- and p-type but had a less inhomogeneous reaction layer. We also performed annealing experiments with Cu-joined samples at 450 °C for 1 week to investigate the evolution of the contact regions under working temperatures. rc values increased (up to ∼100 µΩ·cm2) for annealed n-type samples but remained low (<10 µΩ·cm2) for p-type. Therefore, Cu is a good contacting solution for p-type Mg2(Si,Sn) and a potential one for n-type if the diffusion causing contact property degradation can be prevented.

High efficiency Mg2(Si,Sn)-based thermoelectric materials: scale-up synthesis, functional homogeneity, and thermal stability.

Considering the need for large quantities of high efficiency thermoelectric materials for industrial applications, a scalable synthesis method for high performance magnesium silicide based materials is proposed. The synthesis procedure consists of a melting step followed by high energy ball milling. All the materials synthesized via this method demonstrated not only high functional homogeneity but also high electrical conductivity and Seebeck coefficients of around 1000 Ω-1 cm-1 and -200 µV K-1 at 773 K, respectively. The measured values were similar for all the samples extracted from the ∅50 mm and ∅70 mm compacted pellets and were stable upon thermal cycling. Thermal stability experiments from 168 hours to 720 hours at 723 K revealed no significant change in the material properties. The low thermal conductivity of ∼2.5 W m-1 K-1 at 773 K led to a maximum figure of merit, zT max, of 1.3 at the same temperature and an average value, zT avg, of 0.9 between 300 K and 773 K, which enables high efficiency in future silicide-based thermoelectric generators.

Nano- and Microstructure Engineering: An Effective Method for Creating High Efficiency Magnesium Silicide Based Thermoelectrics.

Considering the effect of CO2 emission together with the depletion of fossil fuel resources on future generations, industries in particular the transportation sector are in deep need of a viable solution to follow the environmental regulation to limit the CO2 emission. Thermoelectrics may be a practical choice for recovering the waste heat, provided their conversion energy can be improved. Here, the high temperature thermoelectric properties of high purity Bi doped Mg2(Si,Sn) are presented. The samples Mg2Si1-x-ySnxBiy with x(Sn) ≥ 0.6 and y(Bi) ≥ 0.03 exhibited electrical conductivities and Seebeck coefficients of approximately 1000 Ω-1 cm-1 and -200 µV K-1 at 773 K, respectively, attributable to a combination of band convergence and microstructure engineering through ball mill processing. In addition to the high electrical conductivity and Seebeck coefficient, the thermal conductivity of the solid solutions reached values below 2.5 W m-1 K-1 due to highly efficient phonon scattering from mass fluctuation and grain boundary effects. These properties combined for zT values of 1.4 at 773 K with an average zT of 0.9 between 400 and 773 K. The transport properties were both highly reproducible across several measurement systems and were stable with thermal cycling.

Sb- and Bi-doped Mg2Si: location of the dopants, micro- and nanostructures, electronic structures and thermoelectric properties.

Due to increasing global energy concerns, alternative sustainable methods to create energy such as thermoelectric energy conversion have become increasingly important. Originally, research into thermoelectric materials was focused on tellurides of bismuth and lead because of the exemplary thermoelectric properties of Bi2Te3 and PbTe. These materials, however, contain toxic lead and tellurium, which is also scarce and thus expensive. A viable alternative material may exist in Mg2Si, which needs to be doped and alloyed in order to achieve reasonable thermoelectric efficiency. Doping is a major problem, as p-type doping has thus far not produced competitive efficiencies, and n-type doping is problematic because of the low solubility of the typical dopants Sb and Bi. This investigation shows experimentally that these dopants can indeed replace Si in the crystal lattice, and excess Sb and Bi atoms are present in the grain boundaries in the form of Mg3Sb2 and Mg3Bi2. As a consequence, the carrier concentration is lower than the formal Sb/Bi concentration suggests, and the thermal conductivity is significantly reduced. DFT calculations are in good agreement with the experimental data, including the band gap and the Seebeck coefficient. Overall, this results in competitive efficiencies despite the low carrier concentration. While ball-milling was previously shown to enhance the solubility of the dopants and thus the carrier concentration, this did not lead to enhanced thermoelectric properties.