Enhancing Thermoelectric Performance of AgSbTe₂-Based Compounds via Microstructure Modulation Combining with Entropy Engineering

Modulation of the microstructure and configurational entropy tuning are the core stratagem for improving thermoelectric performance. However, the correlation of evolution among the preparation methods, chemical composition, structural defects, configurational entropy, and thermoelectric properties is still unclear. Herein, two series of AgSbTe2-based compounds were synthesized by an equilibrium melting–slow-cooling method and a nonequilibrium melting–quenching–spark plasma sintering (SPS) method, respectively. The equilibrium method results in coarse grains with a size of >300 μm in the samples and a lower defect concentration, leading to higher carrier mobility of 10.66 cm2 V–1 s–1 for (Ag2Te)0.41(Sb2Te3)0.59 compared to the sample synthesized by nonequilibrium preparation of 1.83 cm2 V–1 s–1. Moreover, tuning the chemical composition of nonstoichiometric AgSbTe2 effectively improves the configurational entropy and creates a large number of cation vacancies, which evolve into dense dislocations in the samples. Owing to all of these in conjunction with the strong inharmonic vibration of lattice, an ultralow thermal conductivity of 0.51 W m–1 K–1 at room temperature is achieved for the (Ag2Te)0.42(Sb2Te3)0.58 sample synthesized by the equilibrium preparation method. Due to the enhanced carrier mobility, optimized carrier concentration, and low thermal conductivity, the (Ag2Te)0.42(Sb2Te3)0.58 sample synthesized by the equilibrium preparation method possesses the highest ZT of 1.04 at 500 K, more than 60% higher than 0.64 at 500 K of the same composition synthesized by nonequilibrium preparation.