Thermoelectric performance enhancement of Mg2Sn based solid solutions by band convergence and phonon scattering via Pb and Si/Ge substitution for Sn.

In this study, the thermoelectric properties of Mg2Sn0.98-xPbxSb0.02 were first studied, and then Mg2Sn0.93-xSixPb0.05Sb0.02 and Mg2Sn0.93-xGexPb0.05Sb0.02 were accordingly investigated. The results showed that the formation of Mg2Sn0.98-xPbxSb0.02 solid solutions effectively reduced the lattice thermal conductivity of Mg2Sn. The room temperature lattice thermal conductivity of Mg2Sn0.98Sb0.02 is ∼5.2 W m(-1) K(-1) but only ∼2.5 W m(-1) K(-1) for Mg2Sn0.73Pb0.25Sb0.02, a reduction of ∼52%. Further alloying Mg2Sn0.98-xPbxSb0.02 with Mg2Si or Mg2Ge to form Mg2Sn0.93-xSixPb0.05Sb0.02 or Mg2Sn0.93-xGexPb0.05Sb0.02 reduced the lattice thermal conductivity significantly due to enhanced phonon scattering by point defects as well as nanoparticles. Moreover, bipolar thermal conductivities were suppressed due to the larger bandgap of Mg2Si and Mg2Ge than Mg2Sn. Furthermore, similar to the pseudo-binary Mg2Sn-Mg2Si and Mg2Sn-Mg2Ge systems, band convergence was also observed in pseudo-ternary Mg2Sn0.93-xSixPb0.05Sb0.02 and Mg2Sn0.93-xGexPb0.05Sb0.02 materials. The convergence of conduction bands led to higher PFs at lower temperatures for Mg2Sn0.93-xSixPb0.05Sb0.02 and Mg2Sn0.93-xGexPb0.05Sb0.02 materials. As a result, higher peak ZTs of ∼1.3 for Mg2Sn0.63Si0.3Pb0.05Sb0.02 and ∼1.2 for Mg2Sn0.68Ge0.25Pb0.05Sb0.02 were achieved.

Understanding Oxidation Resistance of Half-Heusler Alloys for in-Air High Temperature Sustainable Thermoelectric Generators.

High temperature waste heat recovery has gained tremendous interest to generate useful electricity while reducing the harmful impact on the environment. Thermoelectric (TE) solid-state materials enable direct conversion of heat into electricity with high efficiency, thereby offering a practical solution for waste heat recovery. Half-Heusler (hH) alloys are the leading TE materials for medium to high temperature applications, as they exhibit a high figure of merit and mechanical strength at temperatures as high as 973 K. Here we investigate the most promising hH alloys represented as MNiSn, MCoSb, and NbFeSb systems (M = Hf, Zr, and Ti) and provide fundamental understanding of their in-air thermal stability at high temperatures under realistic operating conditions required for energy generation. The understanding of oxidation resistance of TE materials is crucial for their practical deployment in extreme environments without vacuum sealing. The n-type MNiSn and p-type NbFeSb compounds are found to exhibit excellent oxidation resistance at a high temperature of 873 K. The oxidation resistance is enhanced through the presence of an intermetallic Ni-Sn layer for MNiSn and Nb-TiO2 double layer for (Nb,Ti)FeSb. A unicouple thermoelectric generator (TEG) fabricated from thermally stable materials demonstrated consistent performance for more than 150 h at 873 K in air. These results demonstrate the significance of TE materials in waste heat recovery systems.

Filiform Metal Silver Nanoinclusions To Enhance Thermoelectric Performance of P-type Ca3Co4O9+δ Oxide.

Cd doping and metallic Ag additives in Ca3Co4O9+δ polycrystalline materials are shown to result in improved thermoelectric (TE) transport properties. Carrier concentration and mobility were optimized through the combination of doping and compositional modulation approaches. The formation of filiform Ag nanoinclusions between the interlayers and grain boundaries enhances the anisotropic carrier transport, leading to higher carrier mobility. A spin entropy enhancement due to the change of the net valence of Co induced by Cd substitution on the Ca site was confirmed by X-ray photoelectron spectroscopy. High carrier mobility and enhanced spin entropy results in higher electrical conductivity and Seebeck coefficient, leading to the increase of the power factor. In conjunction, mass fluctuation between Cd and Ca on the same crystal site along with the increase of metallic Ag nanoinclusions effectively lowers thermal conductivity. Consequently, the figure-of-merit, zT, has been improved to 0.31 at 950 K for 10 wt % Ag-modified Ca2.9Cd0.1Co4O9+δ specimen, which is a significant improvement compared to the pristine material. This dual-mode control of electron and phonon transport by including Ag additives and Cd doping offers an approach for tuning the correlated TE parameters.

High Power Density Body Heat Energy Harvesting.

Thermoelectric generators (TEGs) can convert body heat into electricity, thereby providing a continuous power source for wearable and implantable devices. For wearables, the low fill factor (area occupied by legs over the TEG base area) TEG modules are relevant as they provide large thermal gradient across the legs and require less material, which reduces the cost and weight. However, TEGs with a fill factor below 15% suffer from reduced mechanical robustness; consequently, commercial modules are usually fabricated with a fill factor in the range of 25-50%. In this study, TEG modules with a low and high fill factor are demonstrated and their performance is compared in harvesting body heat. Fabricated modules demonstrate ∼80% output power enhancement as compared to commercially available designs, resulting in high power density of up to 35 µW/cm2 in a steady state. This enhanced power is achieved by using two-third less thermoelectric materials in comparison to commercial modules. These results will advance the ongoing development of wearable devices by providing a consistent high specific power density source.

Improved Thermoelectric Performance of Tellurium by Alloying with a Small Concentration of Selenium to Decrease Lattice Thermal Conductivity.

Phonon scattering through alloying is a highly effective way to reduce lattice thermal conductivity due to the mass difference between the host and alloyed atoms and strains caused by the different atoms. In this work we investigate the thermoelectric properties of Te between 323 and 623 K. By varying the alloying concentration of Se, a minimum lattice thermal conductivity was achieved with ∼10% (by stoichiometry) alloying of Te by Se. Additionally, Sb has been used as a dopant to increase the carrier concentration of the system. With reduced lattice thermal conductivity by Se alloying and increased carrier concentration by Sb doping, the room-temperature figure of merit ( ZT) increased by 60%, leading to an average ZT of ∼0.8 in Te0.88Se0.10Sb0.02, which corresponds to an engineering figure of merit ( ZT)eng ∼ 0.5 between 323 and 623 K and an efficiency of ∼8% in the same temperature range. The results indicate that the combination of Se alloying and Sb doping is successful in improving the thermoelectric properties of Te.

Ultrahigh Power Factor in Thermoelectric System Nb0.95M0.05FeSb (M = Hf, Zr, and Ti).

Conversion efficiency and output power are crucial parameters for thermoelectric power generation that highly rely on figure of merit ZT and power factor (PF), respectively. Therefore, the synergistic optimization of electrical and thermal properties is imperative instead of optimizing just ZT by thermal conductivity reduction or just PF by electron transport enhancement. Here, it is demonstrated that Nb0.95Hf0.05FeSb has not only ultrahigh PF over ≈100 µW cm-1 K-2 at room temperature but also the highest ZT in a material system Nb0.95M0.05FeSb (M = Hf, Zr, Ti). It is found that Hf dopant is capable to simultaneously supply carriers for mobility optimization and introduce atomic disorder for reducing lattice thermal conductivity. As a result, Nb0.95Hf0.05FeSb distinguishes itself from other outstanding NbFeSb-based materials in both the PF and ZT. Additionally, a large output power density of ≈21.6 W cm-2 is achieved based on a single-leg device under a temperature difference of ≈560 K, showing the realistic prospect of the ultrahigh PF for power generation.