Reactive sintering process and thermoelectric properties of boron rich boron carbides

Dense boron rich boron carbides were reactive sintered by hot pressing at 2050 °C using elementary boroncarbon compositions with carbon contents of 9.1, 11.1, 13.3 and 18.8 at.%. The following material characteristics are presented: relative density, SEM images, EDX, X-ray diffraction and corresponding lattice parameters, Seebeck coefficient, electrical conductivity and thermoelectric power factor. Significant grain growth has been obtained with increasing boron content. A deeper understanding of the boron and carbon reaction and the overall sintering process is gained by thermal and chemical analysis in combination with X-ray diffraction. Additionally a thermal experiment with boron and carbon layers illustrates the solid state diffusion behaviour. The found results of boron carbide properties of this paper correspond with results by other authors. The aim is to correlate technological aspects of sintering procedure with material properties. This should help to improve the thermoelectric efficiency of boron carbide based materials.     

Thermoelectric and mechanical properties of melt spun and spark plasma sintered n-type Yb- and Ba-filled skutterudites

Here we present thermoelectric and mechanical properties of n-type filled-skutterudites produced by a combination of melt spinning of pre-melted charges with subsequent consolidation by spark plasma sintering, a process we refer to as MS-SPS. This combination of processing steps leads to phase-pure n-type filled-skutterudites and obviates more energy and time intensive annealing steps. We show that both the thermoelectric properties and the tensile fracture strength compare favorably to materials made by traditional methods. The process is scalable to at least 80 g billets, such that the transport properties measured on test bars harvested from these larger billets compare favorably to those measured on lab-scale billets (5 g total billet mass). ZT values approaching 1.1 at 750 K were observed in materials made by MS-SPS. In addition, the tensile fracture strength of test bars cut from an 80 g billet is ∼128 MPa at room temperature and decreases with increasing temperature. Fractography of the test bars reveals that the majority failed due to surface and edge flaws with few failures due to volume type flaws. This indicates that the powder metallurgical methods employed to produce these samples is mature.     

Thermoelectric Materials with Potential High Power Factors for Electricity Generation

The thermoelectric figure of merit ZT of materials limits the performance of a thermoelectric power generator. To date, the main gains from the worldwide effort in either engineered bulk materials or low-dimensional systems have been mostly based on the strategies of reducing the thermal conductivity. We explore several bulk thermoelectric materials that have respectable mecha- nical strength and chemical stability at elevated temperatures for potential power generation. Our strategy is to first explore the avenue of significantly increasing the power factor (PF), then the avenue of lowering thermal conductivity, perhaps by nanocompositing. We examine the layered cobaltates with sharp resonant peaks in the electronic density of states near the Fermi energy level due to strong electron correlation. We suggest that electron correlation may be used as a new tuning parameter to significantly increase the PF. We also report that a substantial increase (over 30%) in PF can be achieved in filled skutterudites (such as p-type CeFe₄Sb₁₂) through nonequilibrium synthesis by rapid conversion of the amorphous materials made by the melt spinning to single-phase crystalline materials under pressure. This process, in conjunction with the rattling to lower the lattice thermal conductivity, could further enhance the ZT values of the filled skutterudites.     

Intrinsic Seebeck Coefficient of Quantum Dots

The Seebeck coefficient S is an important performance characteristic of thermoelectric materials. In this paper we establish the fact that quantum dots and single-electron tunneling devices with narrow, well-spaced energy levels and sharp transmission resonances have a Seebeck coefficient independent of material parameters. By employing a delta function for the transmission resonances we arrive at an intrinsic expression for S in terms of the fundamental electronic charge e. We further confirm the validity of our result in the case of a transmission resonance with finite width.     

Approach to the Practical Use of Thermoelectric Power Generation

The results of research and development in the Japanese national project “Development for Advanced Thermoelectric Conversion Systems” are summarized, and the approaches to practical use of advanced thermoelectric modules and power generation systems are presented. The 5-year national project was successfully completed in March 2007. Three kinds of high- efficiency cascaded thermoelectric modules and two kinds of innovative Bi-Te thermoelectric modules were successfully developed. Heat cycle tests for three types of modules were also completed. Moreover, four types of advanced thermoelectric power generation systems were experimentally demonstrated for recovery of waste heat from the industrial and private sectors. In order to proceed further, thermoelectric power generation systems using practical heat sources were followed after installation of the developed modules. In parallel, various approaches for practical use by private companies, as well as plans for the next-phase project by the National Institute of Advanced Industrial Science and Technology (AIST) and the Engineering Advancement Association (ENAA), were also followed. The scenarios to proceed to the commercial phase of thermoelectric power generation are discussed on the basis of the results of the national project.     

Thermoelectric Properties of (Pb,Sn,Ge)Te-Based Alloys

The search for alternative energy sources is presently at the forefront of␣applied research. In this context, thermoelectricity for direct energy conversion from thermal to electrical energy plays an important role. This␣paper is␣concerned with the development of highly efficient p-type [(PbTe)(SnTe)(Bi₂Te₃)] _x (GeTe)_1−x alloys for thermoelectric applications using spark plasma sintering (SPS). Varying the carrier concentration of GeTe was achieved by alloying of PbTe, SnTe, and/or Bi₂Te₃. The rhombohedral to cubic phase transition temperature, T _c, was found to be sensitive to the degree of alloying. Highest power factor values (P ≤ 33 μW/cm K²) were obtained for (GeTe)_0.95(Bi₂Te₃)_0.05 composition.     

Nanostructured Bulk Silicon as an Effective Thermoelectric Material

Thermoelectric power sources have consistently demonstrated their extraordinary reliability and longevity for deep space missions and small unattended terrestrial systems. However, more efficient bulk materials and practical devices are required to improve existing technology and expand into large‐scale waste heat recovery applications. Research has long focused on complex compounds that best combine the electrical properties of degenerate semiconductors with the low thermal conductivity of glassy materials. Recently it has been found that nanostructuring is an effective method to decouple electrical and thermal transport parameters. Dramatic reductions in the lattice thermal conductivity are achieved by nanostructuring bulk silicon with limited degradation in its electron mobility, leading to an unprecedented increase by a factor of 3.5 in its performance over that of the parent single‐crystal material. This makes nanostructured bulk (nano‐bulk) Si an effective high temperature thermoelectric material that performs at about 70% the level of state‐of‐the‐art Si_0.8Ge_0.2 but without the need for expensive and rare Ge.     

Microwave-assisted synthesis of thermoelectric oxides and chalcogenides

The combination of microwaves with other classical synthetic methods may be considered as a powerful tool for the preparation of metal oxides and metal chalcogenides. This approach allows the modification of the reaction kinetic significantly by shortening the processing time to minutes and it minimizes the energy consumption during the synthesis. In this work, potential thermoelectric compounds, which enable the direct conversion of temperature gradients into useful electric energy, have been produced by means of microwave-chemistry routes. Pure phases of SnS_1-xSe_x (x = 0, 0.2, 1) have been synthesized in just 1 min by using microwave-hydrothermal synthesis. Moreover, Zn_0.98M_0.02O (M = Al, Ga) rods were formed by microwave-coprecipitation method in 5 min. Besides, 8 min of microwave-heating were enough for the combustion of Sr_1-xLa_xTiO_3-δ (x = 0, 0.05, 0.1). In all cases, the utilization of microwave radiation produces high-quality phases. A comprehensive study of the structural, microstructural and thermoelectric properties of the microwave-synthesized materials is here performed by means of X-ray diffraction, SEM, HRTEM and temperature dependence measurements of Seebeck coefficient, electrical conductivity and thermal conductivity.     

Grain boundary engineered,multilayer graphene incorporated LaCoO3 composites with enhanced thermoelectric properties

Enhancement of thermoelectric properties by virtue of decreased electrical resistance through grain boundary engineering is realised in this study. A robust strategy of optimisation of the transport properties by tuning the energy filtering effects at the interfaces by decreasing the interfacial electrical resistance is achieved in LaCoO₃ (LCO). This is accomplished by the incorporation of multilayer graphene within the parent LCO matrix containing multi-scale nano/micro grains. The present work has attained a substantial increment in electrical conductivity from a value of 96 Scm^-1 for bare LCO to ～5300 Scm^-1 at 750 K by incorporating 0.08 wt% multilayer graphene in LCO. No significant change in thermal conductivity is observed due to the presence of multilayer graphene in LCO. A zT of 0.33 at 550 K for 0.08 wt% multi-layer graphene incorporated LCO composite is achieved which is the highest thermoelectric figure of merit value for undoped LCO reported until now.     

Thermoelectric properties of non-stoichiometric CaMnO3-δ composites formed by redox-activated exsolution

A novel synthesis route for preparing well-defined composites based on CMO (CaMnO₃) has been established taking advantage of the unique phase relations in the system Ca-Mn-O at reducing- and oxidizing atmosphere, respectively. Samples corresponding to stoichiometric CMO and composites with 5 and 10 vol % of Ruddlesden-Popper (Ca₄Mn₃O₁₀)- and spinel (CaMn₂O₄)-phases, respectively, were prepared with final densities >91 %. The presence of secondary phases significantly enhanced the electrical conductivity compared to stoichiometric CMO. The highest electrical conductivity was observed for CMO with 10 vol % spinel varying between 55 and 75 S/cm at temperatures between 100 and 900 °C. This composition also exhibited the highest figure-of-merit (zT) in this study, reaching 0.083 at 800 °C.