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.

The present study was focused on the analysis of the electric and thermal properties of spark plasma sintered thermoelectric material. The crystal structure, microstructure, electric and thermal properties of the sintered body were evaluated by measuring XRD, SEM, electric resistivity, Hall effect and thermal conductivity. The sintered body showed anisotropic crystal structure. The c-axis of the crystal aligned in a parallel direction with applied pressure during spark plasma sintering. The degree of the crystal alignment increased with increasing sintering temperature and sintering time. The electric resistivity and thermal conductivity of the sintered body showed anisotropic characteristics result from crystal alignment.

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.

Thermoelectric-thick films were fabricated by using a screen printing process of n and p-type bismuth-telluride-based pastes. The screen-printed thick films have approximately 30 in thickness and show rough surfaces yielding an empty gap between an electrode and the thick film. The gap might result in an increase of an electrical resistivity of the fabricated thick-film-type thermoelectric module. In this study, we suggest a conductive metal coating onto the surfaces of the screen-printed paste in order to reduce the contact resistance in the module. As a result, the electrical resistivity of the thermoelectric module having a gold coating layer was significantly reduced up to 30% compared to that of a module without any metal coating. This result indicates that an introduction of conductive metal layers is effective to decrease the contact resistivity of a thick-film-typed thermoelectric module processed by screen printing.

Bismuth-telluride based thermoelectric powders were fabricated by two-step planetary milling process which produces bimodal size distribution ranging . The powders were reduced in hydrogen atmosphere to minimize oxygen contents which cause degradation of thermoelectric performance by decreasing electrical conductivity. Oxygen contents were decreased from 0.48% to 0.25% by the reduction process. In this study, both the as-synthesized and the reduced powders were consolidated by the spark plasma sintering process at for 10 min at the heating rate of and then their thermoelectric properties were investigated. The sintered samples using the reduced p-type thermoelectric powders show 15% lower specific electrical resistivity () than those of the as-synthesized powders while Seebeck coefficient and thermal conductivity do not change a lot. The results confirmed that ZT value of thermoelectric performance at room temperature was improved by 15% due to high electric conductivity caused by the controlled oxygen contents present at bismuth telluride materials.

Carbon-nanotube-embedded bismuth telluride (CNT/) matrix composites were fabricated by a powder metallurgy process. Composite powders, whereby 5 vol.% of functionalized CNTs were homogeneously mixed with alloying powders, were successfully synthesized by using high-energy ball milling process. The powders were consolidated into bulk CNT/ composites by spark plasma sintering process at for 10 min. The fabricated composites showed the uniform mixing and homogeneous dispersion of CNTs in the matrix. Seebeck coefficient of CNT/ composites reveals that the composite has n-type semiconducting characteristics with values ranging to with increasing temperature. Furthermore, the significant reduction in thermal conductivity has been clearly observed in the composites. The results showed that CNT addition to thermoelectric materials could be useful method to obtain high thermoelectric performance.