RESUMO
Thermal properties strongly affect the applications of functional materials, such as thermal management, thermal barrier coatings, and thermoelectrics. Thermoelectric (TE) materials must have a low lattice thermal conductivity to maintain a temperature gradient to generate the voltage. Traditional strategies for minimizing the lattice thermal conductivity mainly rely on introduced multiscale defects to suppress the propagation of phonons. Here, the origin of the anomalously low lattice thermal conductivity is uncovered in Cd-alloyed Mg3 Sb2 Zintl compounds through complementary bonding analysis. First, the weakened chemical bonds and the lattice instability induced by the antibonding states of 5p-4d levels between Sb and Cd triggered giant anharmonicity and consequently increased the phonon scattering. Moreover, the bond heterogeneity also augmented Umklapp phonon scatterings. Second, the weakened bonds and heavy element alloying softened the phonon mode and significantly decreased the group velocity. Thus, an ultralow lattice thermal conductivity of ≈0.33 W m-1 K-1 at 773 K is obtained, which is even lower than the predicated minimum value. Eventually, Na0.01 Mg1.7 Cd1.25 Sb2 displays a high ZT of ≈0.76 at 773 K, competitive with most of the reported values. Based on the complementary bonding analysis, the work provides new means to control thermal transport properties through balancing the lattice stability and instability.
RESUMO
Recently, YbCd2Sb2-based Zintl compounds have been widely investigated owing to their extraordinary thermoelectric (TE) performance. However, its p orbitals of anions that determined the valence band structure are split due to crystal field splitting that provides a good platform for band manipulation by doping/alloying and, more importantly, the YbCd2Sb2-based device has yet to be reported. In this work, single-phase YbCd1.5Zn0.5Sb2 is successfully obtained through precise chemical composition control. Then, YbMg2Sb2-alloying increases the cationic vacancy defect formation energy and further optimizes carrier concentration. Moreover, the band structure of YbCd1.5Zn0.5Sb2 is subtly manipulated, and the underlying mechanism is experimentally explored. Combined with the reduced lattice thermal conductivity, a high peak ZT value of â¼1.43 at 700 K is obtained for YbCd1.425Zn0.475Mg0.1Sb2. Subsequently, choosing Fe90Sb10 as the diffusion barrier layer and adopting the transient liquid phase bonding technique, for the first time, it is demonstrated that YbCd2Sb2/Mg3(Sb, Bi)2 TE module with an ultrahigh conversion efficiency of ≈9.0% at a heat difference of 430 K. More importantly, this module displays good thermal stability. This work paves the way for YbCd2Sb2 materials and devices in mid-temperature heat recovery.
RESUMO
Environmentally friendly Mg3Sb2-based materials have drawn intensive attention owing to their promising thermoelectric performance. In this work, the electrical properties of p-type Mg3Sb2 are dramatically optimized by the regulation of Mg deficiency. Then, we, for the first time, found that Zn substitution at the Mg2 site leads to the alignment of p x,y and p z orbital, resulting in a high band degeneracy and the dramatically enhanced Seebeck coefficient, demonstrated by the DFT calculations and electronic properties measurement. Moreover, Zn alloying decreases Mg1 (Zn) vacancies formation energy and in turn increases Mg (Zn) vacancies and optimizes the carrier concentration. Simultaneously, the Mg/Zn substitutions, Mg vacancies, and porosity structure suppress the phonon transport in a broader frequency range, leading to a low lattice thermal conductivity of ~0.47 W m-1 K-1 at 773 K. Finally, a high ZT of ~0.87 at 773 K was obtained for Mg1.95Na0.01Zn1Sb2, exceeding most of the previously reported p-type Mg3Sb2 compounds. Our results further demonstrate the promising prospects of p-type Mg3Sb2-based material in the field of mid-temperature heat recovery.