Thermoelectric technology, harvesting electric power directly from heat, is a promising environmentally friendly means of energy savings and power generation. The thermoelectric efficiency is determined by the device dimensionless figure of merit ZT(dev), and optimizing this efficiency requires maximizing ZT values over a broad temperature range. Here, we report a record high ZT(dev) ∼1.34, with ZT ranging from 0.7 to 2.0 at 300 to 773 kelvin, realized in hole-doped tin selenide (SnSe) crystals. The exceptional performance arises from the ultrahigh power factor, which comes from a high electrical conductivity and a strongly enhanced Seebeck coefficient enabled by the contribution of multiple electronic valence bands present in SnSe. SnSe is a robust thermoelectric candidate for energy conversion applications in the low and moderate temperature range.

https://science.sciencemag.org/content/sci/early/2015/11/24/science.aad3749.full.pdf

Ultrahigh power factor and thermoelectric performance in hole-doped single-crystal SnSe

There has been a renaissance of interest in exploring highly efficient thermoelectric materials as a possible route to address the worldwide energy generation, utilization, and management. This review describes the recent advances in designing high-performance bulk thermoelectric materials. We begin with the fundamental stratagem of achieving the greatest thermoelectric figure of merit ZT of a given material by carrier concentration engineering, including Fermi level regulation and optimum carrier density stabilization. We proceed to discuss ways of maximizing ZT at a constant doping level, such as increase of band degeneracy (crystal structure symmetry, band convergence), enhancement of band effective mass (resonant levels, band flattening), improvement of carrier mobility (modulation doping, texturing), and decrease of lattice thermal conductivity (synergistic alloying, second-phase nanostructuring, mesostructuring, and all-length-scale hierarchical architectures). We then highlight the decoupling of th...

Rationally Designing High-Performance Bulk Thermoelectric Materials

BACKGROUND Heat and electricity are two forms of energy that are at opposite ends of a spectrum Heat is ubiquitous, but with low quality, whereas electricity is versatile, but its production is demanding Thermoelectrics offers a simple and environmentally friendly solution for direct heat-to-electricity conversion A thermoelectric (TE) device can directly convert heat emanating from the Sun, radioisotopes, automobiles, industrial sectors, or even the human body to electricity Electricity also can drive a TE device to work as a solid-state heat pump for distributed spot-size refrigeration TE devices are free of moving parts and feasible for miniaturization, run quietly, and do not emit greenhouse gasses The full potential of TE devices may be unleashed by working in tandem with other energy-conversion technologies Thermoelectrics found niche applications in the 20th century, especially where efficiency was of a lower priority than energy availability and reliability Broader (beyond niche) application of thermoelectrics in the 21st century requires developing higher-performance materials The figure of merit, ZT, is the primary measure of material performance Enhancing the ZT requires optimizing the adversely interdependent electrical resistivity, Seebeck coefficient, and thermal conductivity, as a group On the microscopic level, high material performance stems from a delicate concert among trade-offs between phase stability and instability, structural order and disorder, bond covalency and ionicity, band convergence and splitting, itinerant and localized electronic states, and carrier mobility and effective mass ADVANCES Innovative transport mechanisms are the fountain of youth of TE materials research In the past two decades, many potentially paradigm-changing mechanisms were identified, eg, resonant levels, modulation doping, band convergence, classical and quantum size effects, anharmonicity, the Rashba effect, the spin Seebeck effect, and topological states These mechanisms embody the current states of understanding and manipulating the interplay among the charge, lattice, orbital, and spin degrees of freedom in TE materials Many strategies were successfully implemented in a wide range of materials, eg, V2VI3 compounds, VVI compounds, filled skutterudites and clathrates, half-Heusler alloys, diamond-like structured compounds, Zintl phases, oxides and mixed-anion oxides, silicides, transition metal chalcogenides, and organic materials In addition, advanced material synthesis and processing techniques, for example, melt spinning, self-sustaining heating synthesis, and field-assisted sintering, helped reach a much broader phase space where traditional metallurgy and melt-growth recipes fell short Given the ubiquity of heat and the modular aspects of TE devices, these advances ensure that thermoelectrics plays an important role as part of a solutions package to address our global energy needs OUTLOOK The emerging roles of spin and orbital states, new breakthroughs in multiscale defect engineering, and controlled anharmonicity may hold the key to developing next generation TE materials To accelerate exploring the broad phase space of higher multinary compounds, we need a synergy of theory, machine learning, three-dimensional printing, and fast experimental characterizations We expect this synergy to help refine current materials selection and make TE materials research more data driven We also expect increasing efforts to develop high-performance materials out of nontoxic and earth-abundant elements The desire to move away from Freon and other refrigerant-based cooling should shift TE materials research from power generation to solid-state refrigeration International round-robin measurements to cross-check the high ZT values of emerging materials will help identify those that hold the most promise We hope the renewable energy landscape will be reshaped if the recent trend of progress continues into the foreseeable future

http://science.sciencemag.org/content/sci/357/6358/eaak9997.full.pdf

Advances in thermoelectric materials research: Looking back and moving forward

The past two decades have witnessed the rapid growth of thermoelectric (TE) research. Novel concepts and paradigms are described here that have emerged, targeting superior TE materials and higher TE performance. These superior aspects include band convergence, "phonon-glass electron-crystal", multiscale phonon scattering, resonant states, anharmonicity, etc. Based on these concepts, some new TE materials with distinct features have been identified, including solids with high band degeneracy, with cages in which atoms rattle, with nanostructures at various length scales, etc. In addition, the performance of classical materials has been improved remarkably. However, the figure of merit zT of most TE materials is still lower than 2.0, generally around 1.0, due to interrelated TE properties. In order to realize an "overall zT > 2.0," it is imperative that the interrelated properties are decoupled more thoroughly, or new degrees of freedom are added to the overall optimization problem. The electrical and thermal transport must be synergistically optimized. Here, a detailed discussion about the commonly adopted strategies to optimize individual TE properties is presented. Then, four main compromises between the TE properties are elaborated from the point of view of the underlying mechanisms and decoupling strategies. Finally, some representative systems of synergistic optimization are also presented, which can serve as references for other TE materials. In conclusion, some of the newest ideas for the future are discussed.

https://www.onlinelibrary.wiley.com/doi/pdf/10.1002/adma.201702816

Compromise and Synergy in High-Efficiency Thermoelectric Materials.

The long-standing popularity of thermoelectric materials has contributed to the creation of various thermoelectric devices and stimulated the development of strategies to improve their thermoelectric performance. In this review, we aim to comprehensively summarize the state-of-the-art strategies for the realization of high-performance thermoelectric materials and devices by establishing the links between synthesis, structural characteristics, properties, underlying chemistry and physics, including structural design (point defects, dislocations, interfaces, inclusions, and pores), multidimensional design (quantum dots/wires, nanoparticles, nanowires, nano- or microbelts, few-layered nanosheets, nano- or microplates, thin films, single crystals, and polycrystalline bulks), and advanced device design (thermoelectric modules, miniature generators and coolers, and flexible thermoelectric generators). The outline of each strategy starts with a concise presentation of their fundamentals and carefully selected examples. In the end, we point out the controversies, challenges, and outlooks toward the future development of thermoelectric materials and devices. Overall, this review will serve to help materials scientists, chemists, and physicists, particularly students and young researchers, in selecting suitable strategies for the improvement of thermoelectrics and potentially other relevant energy conversion technologies.

Advanced Thermoelectric Design: From Materials and Structures to Devices

The widespread use of thermoelectric technology is constrained by a relatively low conversion efficiency of the bulk alloys, which is evaluated in terms of a dimensionless figure of merit ( zT ). The zT of bulk alloys can be improved by reducing lattice thermal conductivity through grain boundary and point-defect scattering, which target low- and high-frequency phonons. Dense dislocation arrays formed at low-energy grain boundaries by liquid-phase compaction in Bi 0.5 Sb 1.5 Te 3 (bismuth antimony telluride) effectively scatter midfrequency phonons, leading to a substantially lower lattice thermal conductivity. Full-spectrum phonon scattering with minimal charge-carrier scattering dramatically improved the zT to 1.86 ± 0.15 at 320 kelvin (K). Further, a thermoelectric cooler confirmed the performance with a maximum temperature difference of 81 K, which is much higher than current commercial Peltier cooling devices.

http://science.sciencemag.org/content/sci/348/6230/109.full.pdf

Dense dislocation arrays embedded in grain boundaries for high-performance bulk thermoelectrics

The thermoelectric properties of Zn-, In-, and I-doped Cu1.7Bi4.7Se8 pavonite homologues were investigated in the temperature range from 300 to 560 K. On the basis of the comprehensive structural analysis using Rietveld refinement of synchrotron radiation diffraction for Cux+yBi5–ySe8 compounds with the inherently disordered crystallographic sites, we demonstrate a doping strategy that provides a simultaneous control for enhanced electronic transport properties by the optimization of carrier concentration and exceptionally low lattice thermal conductivity by the formation of point defects. Substituted Zn or In ions on Cu site was found to be an effective phonon scattering center as well as an electron donor, while doping on Bi site showed a moderate effect for phonon scattering. In addition, we achieved largely enhanced power factor in small amount of In doping on Cu site by increased electrical conductivity and moderately decreased Seebeck coefficient. Coupled with a low lattice thermal conductivity orig...

Effects of doping on transport properties in Cu-Bi-Se-based thermoelectric materials

The present invention provides a nanocomposite thermoelectric material which includes: a primary phase including Bi, Te, and Se at a certain composition; and a secondary phase including Cu and Te at a certain composition. The nanocomposite thermoelectric material of the present invention shows an increased seebeck coefficient and decreased heat conductivity at the same time. So, the nanocomposite thermoelectric material shows an excellent performance index increase effect and can be usefully used for the implementation of a thermoelement with high efficiency.

Hyeon A. Mun

Papers

Dense dislocation arrays embedded in grain boundaries for high-performance bulk thermoelectrics

Effects of doping on transport properties in Cu-Bi-Se-based thermoelectric materials

Nanocomposite thermoelectric material and process for preparing the same