Inhibiting Mg Diffusion and Evaporation by Forming Mg-Rich Reservoir at Grain Boundaries Improves the Thermal Stability of N-Type Mg3 Sb2 Thermoelectrics.

N-type Mg3 Sb2 -based thermoelectric materials show great promise in power generation due to their mechanical robustness, low cost of Mg, and high figure of merit (ZT) over a wide range of temperatures. However, their poor thermal stability hinders their practical applications. Here, MgB2 is introduced to improve the thermal stability of n-type Mg3 Sb2 . Enabled by MgB2 decomposition, extra Mg can be released into the matrix for Mg compensation thermodynamically, and secondary phases of Mg─B compounds can kinetically prevent Mg diffusion along grain boundaries. These synergetic effects inhibit the formation of Mg vacancies at elevated temperatures, thereby enhancing the thermal stability of n-type Mg3 Sb2 . Consequently, the Mg3.05 (Sb0.75 Bi0.25 )1.99 Te0.01 (MgB2 )0.03 sample exhibits negligible variation in thermoelectric performance during the 120-hour continuous measurement at 673 K. Moreover, the ZT of n-type Mg3 Sb2 can be maintained by adding MgB2 , reaching a high average ZT of ≈1.1 within 300-723 K. An eight-pair Mg3 Sb2 -GeTe-based thermoelectric device is also fabricated, achieving an energy conversion efficiency of ≈5.7% at a temperature difference of 438 K with good thermal stability. This work paves a new way to enhance the long-term thermal stability of n-type Mg3 Sb2 -based alloys and other thermoelectrics for practical applications.

Gibbs Adsorption and Zener Pinning Enable Mechanically Robust High-Performance Bi2 Te3 -Based Thermoelectric Devices.

Bi2 Te3 -based alloys have great market demand in miniaturized thermoelectric (TE) devices for solid-state refrigeration and power generation. However, their poor mechanical properties increase the fabrication cost and decrease the service durability. Here, this work reports on strengthened mechanical robustness in Bi2 Te3 -based alloys due to thermodynamic Gibbs adsorption and kinetic Zener pinning at grain boundaries enabled by MgB2 decomposition. These effects result in much-refined grain size and twofold enhancement of the compressive strength and Vickers hardness in (Bi0.5 Sb1.5 Te3 )0.97 (MgB2 )0.03 compared with that of traditional powder-metallurgy-derived Bi0.5 Sb1.5 Te3 . High mechanical properties enable excellent cutting machinability in the MgB2 -added samples, showing no missing corners or cracks. Moreover, adding MgB2 facilitates the simultaneous optimization of electron and phonon transport for enhancing the TE figure of merit (ZT). By further optimizing the Bi/Sb ratio, the sample (Bi0.4 Sb1.6 Te3 )0.97 (MgB2 )0.03 shows a maximum ZT of ≈1.3 at 350 K and an average ZT of 1.1 within 300-473 K. As a consequence, robust TE devices with an energy conversion efficiency of 4.2% at a temperature difference of 215 K are fabricated. This work paves a new way for enhancing the machinability and durability of TE materials, which is especially promising for miniature devices.