Point Defect Engineering: Co‐Doping Synergy Realizing Superior Performance in n‐Type Bi₂Te₃ Thermoelectric Materials

Bi₂ Te₃ has attracted great attention because of its excellent thermoelectric (TE) performance around room temperature. However, the TE property of the n-type Bi₂ Te₃ is still relatively low compared to the p-type counterpart, which seriously hinders its commercial application with a combination of the n-type and p-type materials. Herein, an effective process of Cl and W co-doping is employed into the n-type Bi₂ Te₃ materials to enhance its TE properties. The Bi1.996 W0.004 Te2.476 Cl0.024 Se0.5 sample achieves a peak and average ZT over 1.3 and 1.2, respectively, at temperature range of 300-575 K. A 24-leg TE module of this n-type material and a home-made p-type Bi₂ Te₃ sample can produce a high efficiency over 6% at a temperature gradient of 235 K, which possesses a 71% improvement compared with a commercial Bi₂ Te₃ module. This high performance is ascribed to the effect of the Cl and W doping. This co-doping not only significantly increases the Grüneisen parameter but also successfully induces interstitial atoms in the van der Waals gap, which lead to a low lattice thermal conductivity (κl ) of 0.31W m⁻¹ K⁻¹ and a boosted charge transport. This finding represents an important step to promote the development of the n-type Bi₂ Te₃ materials.