Modifying Roles of CuSbSe2 in Realizing High Thermoelectric Performance of GeTe

Thermoelectric materials are widely researched for their energy conversion capabilities in the fields of power generation and refrigeration. And a superior thermoelectric conversion efficiency requires an excellent power factor and low thermal conductivity. Herein, a remarkable thermoelectric figure of merit（ZT） ∼ 2.6 at 673 K is realized in GeTe with 20% addition of CuSbSe2. Multiple synergistic effects of CuSbSe2 alloying collectively contribute to the excellent thermoelectric performance in GeTe. CuSbSe2 alloying effectively tunes ultrahigh carrier density of GeTe to the optimum. The introduction of Cu, Sb, and Se atoms create numerous point defects that scatter high‐frequency phonons. Additionally, surplus CuSbSe2 facilitates the formation of copper‐selenium phases, which embed at grain boundaries and generate interfaces after sintering. Combining the planar defects evolved from Ge vacancies, multi‐dimension defects effectively scatter multiple frequency phonons. An extraordinarily low lattice thermal conductivity of 0.3 Wm−1 K−1 at 673 K is obtained, approaching the theoretical estimation predicted by Cahill model. Eventually, the peak conversion efficiency of 7.4% is obtained in segmented device with ΔT of 419 K. The commingled effects of CuSbSe2 in GeTe further open up an elitist route to designing high‐performance materials. Modifying roles of CuSbSe2 alloying contribute to the optimized electrical properties and sharply reduced thermal conductivity in GeTe. Consequently, a superior conversion efficiency of 7.4% at a maximum ΔT of 419 K and a remarkable ZT of 2.6 are achieved in GeTe thermoelectric materials.