In Situ Reaction Induced Core–Shell Structure to Ultralow κ_lat and High Thermoelectric Performance of SnTe

Lead-free chalcogenide SnTe has been demonstrated to be an efficient medium temperature thermoelectric (TE) material. However, high intrinsic Sn vacancies as well as high thermal conductivity devalue its performance. Here, β-Zn₄Sb₃ is incorporated into the SnTe matrix to regulate the thermoelectric performance of SnTe. Sequential in situ reactions take place between the β-Zn₄Sb₃ additive and SnTe matrix, and an interesting “core–shell” microstructure (Sb@ZnTe) is obtained; the composition of SnTe matrix is also tuned and thus Sn vacancies are compensated effectively. Benefitting from the synergistic effect of the in situ reactions, an ultralow κ_lat ≈0.48 W m⁻¹ K⁻¹ at 873 K is obtained and the carrier concentrations and electrical properties are also improved successfully. Finally, a maximum ZT ≈1.32, which increases by ≈220% over the pristine SnTe, is achieved in the SnTe-1.5% β-Zn₄Sb₃ sample at 873 K. This work provides a new strategy to regulate the TE performance of SnTe and also offers a new insight to other related thermoelectric materials.