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

Controlling the structure of thermoelectric materials on all length scales (atomic, nanoscale and mesoscale) relevant for phonon scattering makes it possible to increase the dimensionless figure of merit to more than two, which could allow for the recovery of a significant fraction of waste heat with which to produce electricity.

High-performance bulk thermoelectrics with all-scale hierarchical architectures

Thermoelectric generators, which directly convert heat into electricity, have long been relegated to use in space-based or other niche applications, but are now being actively considered for a variety of practical waste heat recovery systems—such as the conversion of car exhaust heat into electricity. Although these devices can be very reliable and compact, the thermoelectric materials themselves are relatively inefficient: to facilitate widespread application, it will be desirable to identify or develop materials that have an intensive thermoelectric materials figure of merit, zT, above 1.5 (ref. 1). Many different concepts have been used in the search for new materials with high thermoelectric efficiency, such as the use of nanostructuring to reduce phonon thermal conductivity, which has led to the investigation of a variety of complex material systems. In this vein, it is well known, that a high valley degeneracy (typically ≤6 for known thermoelectrics) in the electronic bands is conducive to high zT, and this in turn has stimulated attempts to engineer such degeneracy by adopting low-dimensional nanostructures. Here we demonstrate that it is possible to direct the convergence of many valleys in a bulk material by tuning the doping and composition. By this route, we achieve a convergence of at least 12 valleys in doped PbTe_(1) − _(x)Se_(x) alloys, leading to an extraordinary zT value of 1.8 at about 850 kelvin. Band engineering to converge the valence (or conduction) bands to achieve high valley degeneracy should be a general strategy in the search for and improvement of bulk thermoelectric materials, because it simultaneously leads to a high Seebeck coefficient and high electrical conductivity.

Convergence of electronic bands for high performance bulk thermoelectrics

Advanced thermoelectric technology offers a potential for converting waste industrial heat into useful electricity, and an emission-free method for solid state cooling. Worldwide efforts to find materials with thermoelectric figure of merit, zT values significantly above unity, are frequently focused on crystalline semiconductors with low thermal conductivity. Here we report on Cu_(2−x)Se, which reaches a zT of 1.5 at 1,000 K, among the highest values for any bulk materials. Whereas the Se atoms in Cu_(2−x)Se form a rigid face-centred cubic lattice, providing a crystalline pathway for semiconducting electrons (or more precisely holes), the copper ions are highly disordered around the Se sublattice and are superionic with liquid-like mobility. This extraordinary ‘liquid-like’ behaviour of copper ions around a crystalline sublattice of Se in Cu_(2−x)Se results in an intrinsically very low lattice thermal conductivity which enables high zT in this otherwise simple semiconductor. This unusual combination of properties leads to an ideal thermoelectric material. The results indicate a new strategy and direction for high-efficiency thermoelectric materials by exploring systems where there exists a crystalline sublattice for electronic conduction surrounded by liquid-like ions.

Copper ion liquid-like thermoelectrics

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

Thermoelectric transport properties of p-type PbTe:Na, with high hole concentrations of approximately 1020 cm−3, are reinvestigated from room temperature to 750 K. The greatly enhanced Seebeck coefficient at these doping levels can be understood by the presence of a sharp increase in the density of states around the Fermi level. As a result, the thermoelectric figure of merit, zT, reaches ∼1.4 at 750 K. The influence of these heavy hole carriers may contribute to a similarly high zT observed in related p-type PbTe-based systems such as Tl-doped PbTe and nanostructured composite materials.

/pdf/high-thermoelectric-figure-of-merit-in-heavy-hole-dominated-1ndsops8nh.pdf

High thermoelectric figure of merit in heavy hole dominated PbTe

High Seebeck coefficient by creating large density-of-states effective mass through either electronic structure modification or manipulating nanostructures is commonly considered as a route to advanced thermoelectrics However, large density-of-state due to flat bands leads to large transport effective mass, which results in a simultaneous decrease of mobility In fact, the net effect of such a high effective mass is a lower thermoelectric figure of merit, zT, when the carriers are predominantly scattered by phonons according to the deformation potential theory of Bardeen–Shockley We demonstrate that the beneficial effect of light effective mass contributes to high zT in n-type thermoelectric PbTe, where doping and temperature can be used to tune the effective mass This clear demonstration of the deformation potential theory to thermoelectrics shows that the guiding principle for band structure engineering should be low effective mass along the transport direction

/pdf/low-effective-mass-leading-to-high-thermoelectric-30d7kv73w3.pdf

Low effective mass leading to high thermoelectric performance

PbSe was expected to have a smaller bandgap and higher thermalconductivity than PbTe. Instead, these values are about the same at high temperature leading to comparable thermoelectric figure of merit, with zT> 1 achieved in heavily doped p-type PbSe.

Aaron D. LaLonde

Papers

Convergence of electronic bands for high performance bulk thermoelectrics

High thermoelectric figure of merit in heavy hole dominated PbTe

Low effective mass leading to high thermoelectric performance

Heavily Doped p-Type PbSe with High Thermoelectric Performance: An Alternative for PbTe

Lead telluride alloy thermoelectrics