Abstract
Cu3SbSe4, featuring its earth-abundant, cheap, nontoxic and environmentally-friendly constituent elements, can be considered as a promising intermediate temperature thermoelectric (TE) material. Herein, a series of p-type Bi-doped Cu3Sb1 − xBixSe4 (x = 0-0.04) samples were fabricated through melting and hot pressing (HP) process, and the effects of isovalent Bi-doping on their TE properties were comparatively investigated by experimental and computational methods. TEM analysis indicates that Bi-doped samples consist of Cu3SbSe4 and Cu2 − xSe impurity phases, which is in good agreement with the results of XRD, SEM and XPS. For Bi-doped samples, the reduced electrical resistivity (ρ) caused by the optimized carrier concentrations and enhanced Seebeck coefficient derived from the densities of states near the Fermi level give rise to a high power factor of ~ 1000 µWcm− 1K− 2 at 673 K for the Cu3Sb0.985Bi0.015Se4 sample. Additionally, the multiscale defects of Cu3SbSe4-based materials involving point defects, nanoprecipitates, amorphous phases and grain boundaries can strongly scatter phonons to depress lattice thermal conductivity (κlat), resulting in a low κlat of ~ 0.53 Wm− 1K− 1 and thermal conductivity (κtot) of ~ 0.62 Wm− 1K− 1 at 673 K for the Cu3Sb0.98Bi0.02Se4 sample. As a consequence, a maximum ZT value ~ 0.95 at 673 K is obtained for the Cu3Sb0.985Bi0.015Se4 sample, which is ~ 1.9 times more than that of pristine Cu3SbSe4. This work shows that isovalent heavy-element doping is an effective strategy to optimize thermoelectric properties of copper-based chalcogenides.
Outstanding thermoelectric properties of solvothermal-synthesized Sn1−3xInxAg2xTe micro-crystals through defect engineering and band tuning