Reducing Effective Mass for Advancing Thermoelectrics in Sb/Bi-Doped AgCrSe₂ Compounds

Liquid-like materials have attracted increasing attention, owing to their phonon–liquid electron–crystal feature. As a typical representative, the superionic conductor AgCrSe2 is regarded as a promising thermoelectric for its intrinsic ultralow lattice thermal conductivity. The primary challenge for achieving high thermoelectric performance is to enhance the inferior electronic performance in AgCrSe2 compounds. Thus, it is very significant to manipulate band effective mass to achieve a higher power factor. In this work, the Sb/Bi elements are doped at Cr sites in Ag0.97CrSe2, i.e., Ag0.97Cr1–x(Sb/Bi)xSe2, aiming at producing a better overlap of electron orbits between different atoms for sharpening the valence band and decreasing the effective mass. In comparison to pristine AgCrSe2, a considerable improvement (>50%) in the power factor (∼387 μW m–1 K–2 at 750 K) is realized upon 3% Sb doping. The single parabolic band model clarifies that the decreased effective mass and optimized carrier concentration contribute to the enhanced electronic property. Furthermore, an ultralow lattice thermal conductivity (∼0.2 W m–1 K–1) is well-maintained for the sample with 3% Sb doping as a result of the nearly unchanged superionic conduction. Eventually, a high peak figure of merit zT (∼0.7 at 750 K) is obtained in Ag0.97Cr0.97Sb0.03Se2. The current finding provides an excellent avenue for advancing thermoelectrics in AgCrSe2 materials.