Thermoelectric materials, which can generate electricity from waste heat or be used as solid-state Peltier coolers, could play an important role in a global sustainable energy solution. Such a development is contingent on identifying materials with higher thermoelectric efficiency than available at present, which is a challenge owing to the conflicting combination of material traits that are required. Nevertheless, because of modern synthesis and characterization techniques, particularly for nanoscale materials, a new era of complex thermoelectric materials is approaching. We review recent advances in the field, highlighting the strategies used to improve the thermopower and reduce the thermal conductivity.

/pdf/complex-thermoelectric-materials-59e25n2qme.pdf

Complex thermoelectric materials.

The thermoelectric effect enables direct and reversible conversion between thermal and electrical energy, and provides a viable route for power generation from waste heat The efficiency of thermoelectric materials is dictated by the dimensionless figure of merit, ZT (where Z is the figure of merit and T is absolute temperature), which governs the Carnot efficiency for heat conversion Enhancements above the generally high threshold value of 25 have important implications for commercial deployment, especially for compounds free of Pb and Te Here we report an unprecedented ZT of 26 ± 03 at 923 K, realized in SnSe single crystals measured along the b axis of the room-temperature orthorhombic unit cell This material also shows a high ZT of 23 ± 03 along the c axis but a significantly reduced ZT of 08 ± 02 along the a axis We attribute the remarkably high ZT along the b axis to the intrinsically ultralow lattice thermal conductivity in SnSe The layered structure of SnSe derives from a distorted rock-salt structure, and features anomalously high Gruneisen parameters, which reflect the anharmonic and anisotropic bonding We attribute the exceptionally low lattice thermal conductivity (023 ± 003 W m(-1) K(-1) at 973 K) in SnSe to the anharmonicity These findings highlight alternative strategies to nanostructuring for achieving high thermoelectric performance

Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals

Herein we cover the key concepts in the field of thermoelectric materials research, present the current understanding, and show the latest developments. Current research is aimed at increasing the thermoelectric figure of merit (ZT) by maximizing the power factor and/or minimizing the thermal conductivity. Attempts at maximizing the power factor include the development of new materials, optimization of existing materials by doping, and the exploration of nanoscale materials. The minimization of the thermal conductivity can come through solid-solution alloying, use of materials with intrinsically low thermal conductivity, and nanostructuring. Herein we describe the most promising bulk materials with emphasis on results from the last decade. Single-phase bulk materials are discussed in terms of chemistry, crystal structure, physical properties, and optimization of thermoelectric performance. The new opportunities for enhanced performance bulk nanostructured composite materials are examined and a look into the not so distant future is attempted.

New and Old Concepts in Thermoelectric Materials

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

Thermoelectric power generation technology is now expected to help overcome global warming and climate change issues by recovering and converting waste heat into electricity, thus improving the total efficiency of energy utilization and suppressing the consumption of fossil fuels that are supposedly the major sources of CO2 emission. Thermoelectric oxides, composed of nontoxic, naturally abundant, light, and cheap elements, are expected to play a vital role in extensive applications for waste heat recovery in an air atmosphere. This review article summarizes our previous and ongoing studies on SrTiO3-based materials and further discusses nanostructuring approaches for both SrTiO3 and CaMnO3 materials. ZnMnGaO4 is taken as a model case for constructing a self-assembled nanostructure. The present status of thermoelectric oxide module development is also introduced and discussed.

Oxide Thermoelectric Materials: A Nanostructuring Approach

CuGaTe_2 with a chalcopyrite structure demonstrates promising thermoelectric properties. The maximum figure of merit ZT is 1.4 at 950 K. CuGaTe_2 and related chalcopyrites are a new class of high-efficiency bulk thermoelectric material for high-temperature applications.

Chalcopyrite CuGaTe(2): a high-efficiency bulk thermoelectric material.

We studied a high-performance thermoelectric material whose chemical formula is Ag9TlTe5. Ag9TlTe5 is simple and easy to prepare. Its highest dimensionless figure of merit (ZT) value is 1.23, obtained at 700K. The values of individual thermoelectric properties at 700K are 2.63×10−4Ωm for electrical resistivity, 319μVK−1 for Seebeck coefficient, and 0.22Wm−1K−1 for thermal conductivity. Ag9TlTe5 is a unique material combining extremely low thermal conductivity and relatively low electrical resistivity.

Ag9TlTe5: A high-performance thermoelectric bulk material with extremely low thermal conductivity

In the present study, we investigated the high-temperature thermoelectric (TE) properties of AgGaTe2 with chalcopyrite structure. We tried to enhance the TE properties of AgGaTe2 by reducing the Ag content. The reduction of Ag increased the carrier concentration, leading to enhancement of the dimensionless figure of merit (ZT). The maximum ZT value was 0.77 at 850 K obtained in Ag0.95GaTe2, which was approximately two times higher than that of stoichiometric AgGaTe2.

Thermoelectric properties of Ag1−xGaTe2 with chalcopyrite structure

We investigated the high-temperature thermoelectric properties of Cu1–xInTe2 (x = 0, 0.05, 0.1, 0.2) at 310–710 K. The electrical properties of this system were optimized by the presence of substoichiometric amounts of copper and additional phonon scattering by lattice defects and a secondary phase reduced the thermal conductivity of the system. The samples of Cu1–xInTe2 (x = 0, 0.05, 0.1, 0.2) all had dimensionless figures of merit in excess of 0.5 at 710 K with a maximum value of 0.54 for x = 0.1.

Atsuko Kosuga

Papers

Oxide Thermoelectric Materials: A Nanostructuring Approach

Chalcopyrite CuGaTe(2): a high-efficiency bulk thermoelectric material.

Ag9TlTe5: A high-performance thermoelectric bulk material with extremely low thermal conductivity

Thermoelectric properties of Ag1−xGaTe2 with chalcopyrite structure

High-temperature thermoelectric properties of Cu1–xInTe2 with a chalcopyrite structure