Heat conversion gets a power boost
Thermoelectric materials convert waste heat into electricity, but often achieve high conversion efficiencies only at high temperatures. Zhao
et al.
tackle this problem by introducing small amounts of sodium to the thermoelectric SnSe (see the Perspective by Behnia). This boosts the power factor, allowing the material to generate more energy while maintaining good conversion efficiency. The effect holds across a wide temperature range, which is attractive for developing new applications.
Science
, this issue p.
141
; see also p.
124
Thermoelectric technology enables the harvest of waste heat and its direct conversion into electricity. The conversion efficiency is determined by the materials figure of merit Here we show a maximum of ~2.8 ± 0.5 at 773 kelvin in n-type tin selenide (SnSe) crystals out of plane. The thermal conductivity in layered SnSe crystals is the lowest in the out-of-plane direction [two-dimensional (2D) phonon transport]. We doped SnSe with bromine to make n-type SnSe crystals with the overlapping interlayer charge density (3D charge transport). A continuous phase transition increases the symmetry and diverges two converged conduction bands. These two factors improve carrier mobility, while preserving a large Seebeck coefficient. Our findings can be applied in 2D layered materials and provide a new strategy to enhance out-of-plane electrical transport properties without degrading thermal properties.
Thermoelectrics interconvert heat to electricity and are of great interest in waste heat recovery, solid-state cooling and so on. The efficiency of thermoelectric materials depends directly on the average ZT (dimensionless figure of merit) over a certain temperature range, which historically has been challenging to increase. Here we report that 2.5% K-doped PbTe 0.7 S 0.3 achieves a ZT of 42 for a very wide temperature range from 673 to 923 K and has a record high average ZT of 1.56 (corresponding to a theoretical energy conversion efficiency of B20.7% at the temperature gradient from 300 to 900 K). The PbTe 0.7 S 0.3 composition shows spinodal decomposition with large PbTe-rich and PbS-rich regions where each region exhibits dissimilar types of nanostructures. Such high average ZT is obtained by synergistically optimized electrical-and thermal-transport properties via carrier concentration tuning, band structure engineering and hierarchical architecturing, and highlights a realistic prospect of wide applications of thermoelectrics.
p -type BiCuSeO, a layered oxyselenide composed of conductive (Cu2Se2)2− layers alternately stacked with insulating (Bi2O2)2+ layers, shows an enhancement of the electrical conductivity after substituting Bi3+ by Sr2+, from 470 S m−1 (BiCuSeO) to 4.8×104 S m−1 (Bi0.85Sr0.15CuSeO) at 293 K. Coupled to high Seebeck coefficients, this leads to promising values of the thermoelectric power factor that exceeds 500 μW m−1 K−2 at 873 K. Moreover, the thermal conductivity of these layered compounds is lower than 1 W m−1 K−1 at 873 K. Maximum ZT values reach 0.76 at 873 K, making this family promising for thermoelectric applications in the medium temperature range.
BiCuSeO system is achieved via heavily doping with Ba and refining grain sizes (200-400 nm), which is higher than any thermoelectric oxide. Excellent thermal and chemical stabilities up to 923 K and high thermoelectric performance confirm that the BiCuSeO system is promising for thermoelectric power generation applications.The thermoelectric (TE) energy conversion technology, which can be used to convert wasted heat into electricity, has received much attention in the past decade. The efficiency of TE devices is characterized by the dimensionless figure of merit, ZT ¼ (S 2 s/k)T, where S, s, k, and T are the Seebeck coefficient, the electrical conductivity, the thermal conductivity, and the absolute temperature, respectively. Until now, several classes of bulk materials with high ZT values have been discovered, 1,2 including nanostructured BiSbTe alloys, 3 filled skutterudites, 4 zinc antimonide, 5 AgPb 18+x SbTe 20 , 6 Tl doped PbTe 7 or (AgSbTe 2 ) 1Àx (GeTe) x alloys, 8 but they lack thermal and chemical stabilities in air. Therefore, TE oxides are expected to play an important role in extensive applications for waste heat recovery, on the basis of their potential advantage over heavy metallic alloys of chemical and thermal robustness. To date, several families of oxides have been developed as promising TE materials. Typical TE oxides include Ca 2.8 Ag 0.15 Lu 0.05 Co 4 O 9+d
We report on the high thermoelectric performance of p-type polycrystalline BiCuSeO, a layered oxyselenide composed of alternating conductive (Cu 2 Se 2 ) 2 À and insulating (Bi 2 O 2 ) 2 þ layers. The electrical transport properties of BiCuSeO materials can be significantly improved by substituting Bi 3 þ with Ca 2 þ . The resulting materials exhibit a large positive Seebeck coefficient of B þ 330 lV K À1 at 300 K, which may be due to the 'natural superlattice' layered structure and the moderate effective mass suggested by both electronic density of states and carrier concentration calculations. After doping with Ca, enhanced electrical conductivity coupled with a moderate Seebeck coefficient leads to a power factor of B4.74 lW cm À1 K À2 at 923 K. Moreover, BiCuSeO shows very low thermal conductivity in the temperature range of 300 (B0.9 W m À1 K À1 ) to 923 K (B0.45 W m À1 K À1 ). Such low thermal conductivity values are most likely a result of the weak chemical bonds (Young's modulus, EB76.5 GPa) and the strong anharmonicity of the bonding arrangement (Gruneisen parameter, cB1.5). In addition to increasing the power factor, Ca doping reduces the thermal conductivity of the lattice, as confirmed by both experimental results and Callaway model calculations. The combination of optimized power factor and intrinsically low thermal conductivity results in a high ZT of B0.9 at 923 K for Bi 0.925 Ca 0.075 CuSeO.
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