The thermoelectric effect, which converts waste heat into electricity, holds promise as a renewable energy technology. Recently, bismuth telluride (Bi2Te3)-based alloys are being recognized as important materials for practical applications in the temperature range from room temperature to 500 K. However, conventional sintering processes impose limitations on shape-changeable and tailorable Bi2Te3 materials. To overcome these issues, three-dimensional (3D) printing (additive manufacturing) is being adopted. Although some research results have been reported, relatively few studies on 3D printed thermoelectric materials are being carried out. In this study, we utilize extrusion 3D printing to manufacture n-type Bi1.7Sb0.3Te3 (N-BST). The ink is produced without using organic binders, which could negatively influence its thermoelectric properties. Furthermore, we introduce graphene oxide (GO) at the crystal interface to enhance the electrical properties. The formed N-BST composites exhibit significantly improved electrical conductivity and a higher Seebeck coefficient as the GO content increases. Therefore, we propose that the combination of the extrusion 3D printing process (Direct Ink Writing, DIW) and the incorporation of GO into N-BST offers a convenient and effective approach for achieving higher thermoelectric efficiency.

Graphene oxide (GO) powder processed by Hummer's method is mixed with p-type Bi2Te3 based thermoelectric materials by a high-energy ball milling process. The synthesized GO-dispersed p-type Bi2Te3 composite powder has a composition of Bi0.5Sb1.5Te3 (BSbT), and the powder is consolidated into composites with different contents of GO powder by using the spark plasma sintering (SPS) process. It is found that the addition of GO powder significantly decreases the thermal conductivity of the pure BSbT material through active phonon scattering at the newly formed interfaces. In addition, the electrical properties of the GO/BSbT composites are degraded by the addition of GO powder except in the case of the 0.1 wt% GO/BSbT composite. It is found that defects on the surface of GO powder hinder the electrical transport properties. As a result, the maximum thermoelectric performance (ZT value of 0.91) is achieved from the 0.1% GO/BSbT composite at 398 K. These results indicate that introducing GO powder into thermoelectric materials is a promising method to achieve enhanced thermoelectric performance due to the reduction in thermal conductivity.

Bi2Te3 related compounds show the best thermoelectric properties at room temperature. However, n-type Bi2Te2.7Se0.3 showed no improvement on ZT values. To improve the thermolectric propterties of n-type Bi2Te2.7Se0.3, this research has Cu-doped n-type powder. This study focused on effects of Cu-doping method on the thermoelectric properties of n-type materials, and evaluated the comparison between the Cu chemical and mechanical doping. The synthesized powder was manufactured by the spark plasma sintering(SPS). The thermoelectric properties of the sintered body were evaluated by measuring their Seebeck coefficient, electrical resistivity, thermal conductivity, and hall coefficient. An introduction of a small amount of Cu reduced the thermal conductivity and improved the electrical properties with Seebeck coefficient. The authors provided the optimal concentration of Cu0.1Bi1.99Se0.3Te2.7. A figure of merit (ZT) value of 1.22 was obtained for Cu0.1Bi1.9Se0.3Te2.7 at 373K by Cu chemical doping, which was obviously higher than those of Cu0.1Bi1.9Se0.3Te2.7 at 373K by Cu mechanical doping (ZT=0.56) and Cu-free Bi2Se0.3Te2.7 (ZT=0.51).

Bismuth antimony telluride (BiSbTe) thermoelectric materials were successfully prepared by a spark plasma sintering process. Crystalline BiSbTe ingots were crushed into small pieces and then attrition milled into fine powders of about 300 nm ~ 2μm size under argon gas. Spark plasma sintering was applied on the BiSbTe powders at 240, 320, and 380˚C, respectively, under a pressure of 40 MPa in vacuum. The heating rate was 50˚C/min and the holding time at the sintering temperature was 10 min. At all sintering temperatures, high density bulk BiSbTe was successfully obtained. The XRD patterns verify that all samples were well matched with the Bi0.5Sb1.5Te3. Seebeck coefficient (S), electric conductivity (σ) and thermal conductivity (k) were evaluated in a temperature range of 25~300˚C. The thermoelectric properties of BiSbTe were evaluated by the thermoelectric figure of merit, ZT (ZT = S2σT/k). The grain size and electric conductivity of sintered BiSbTe increased as the sintering temperature increased but the thermal conductivity was similar at all sintering temperatures. Grain growth reduced the carrier concentration, because grain growth reduced the grain boundaries, which serve as acceptors. Meanwhile, the carrier mobility was greatly increased and the electric conductivity was also improved. Consequentially, the grains grew with increasing sintering temperature and the figure of merit was improved.