Saneyuki Ohno

YCuTe2: a member of a new class of thermoelectric materials with CuTe4-based layered structure

Intrinsically doped samples of YCuTe2 were prepared by solid state reaction of the elements. Based on the differential scanning calorimetry and the high temperature X-ray diffraction analyses, YCuTe2 exhibits a first order phase transition at ∼440 K from a low-temperature-phase crystallizing in the space group Pm1 to a high-temperature-phase in P. Above the phase transition temperature, partially ordered Cu atoms become completely disordered in the crystal structure. Small increases to the Cu content are observed to favour the formation of the high temperature phase. We find no indication of superionic Cu ions as for binary copper chalcogenides (e.g., Cu2Se or Cu2Te). All investigated samples exhibit very low thermal conductivities (as low as ∼0.5 W m−1 K−1 at 800 K) due to highly disordered Cu atoms. Electronic structure calculations are employed to better understand the high thermoelectric efficiency for YCuTe2. The maximum thermoelectric figure of merit, zT, is measured to be ∼0.75 at 780 K for Y0.96Cu1.08Te2, which is promising for mid-temperature thermoelectric applications.

Band engineering in Mg3Sb2 by alloying with Mg3Bi2 for enhanced thermoelectric performance

Mg_3Sb_2–Mg_3Bi_2 alloys show excellent thermoelectric properties. The benefit of alloying has been attributed to the reduction in lattice thermal conductivity. However, Mg_3Bi_2-alloying may also be expected to significantly change the electronic structure. By comparatively modeling the transport properties of n- and p-type Mg_3Sb_2–Mg_3Bi_2 and also Mg_3Bi_2-alloyed and non-alloyed samples, we elucidate the origin of the highest zT composition where electronic properties account for about 50% of the improvement. We find that Mg_3Bi_2 alloying increases the weighted mobility while reducing the band gap. The reduced band gap is found not to compromise the thermoelectric performance for a small amount of Mg_3Bi_2 because the peak zT in unalloyed Mg_3Sb_2 is at a temperature higher than the stable range for the material. By quantifying the electronic influence of Mg_3Bi_2 alloying, we model the optimum Mg_3Bi_2 content for thermoelectrics to be in the range of 20–30%, consistent with the most commonly reported composition Mg_3Sb_(1.5)Bi_(0.5).

Thermoelectric properties of the Ca5Al2−xInxSb6 solid solution

Zintl phases are attractive for thermoelectric applications due to their complex structures and bonding environments. The Zintl compounds Ca(5)Al(2)In(x)Sb(6)and Ca(5)Al(2)In(x)Sb(6) have both been shown to have promising thermoelectric properties, with zT values of 0.6 and 0.7, respectively, when doped to control the carrier concentration. Alloying can often be used to further improve thermoelectric materials in cases when the decrease in lattice thermal conductivity outweighs reductions to the electronic mobility. Here we present the high temperature thermoelectric properties of the Ca(5)Al(2-x)In(x)Sb(6)solid solution. Undoped and optimally Zn-doped samples were investigated. X-ray diffraction confirms that a full solid solution exists between the Al and In end-members. We find that the Al : In ratio does not greatly influence the carrier concentration or Seebeck effect. The primary effect of alloying is thus increased scattering of both charge carriers and phonons, leading to significantly reduced electronic mobility and lattice thermal conductivity at room temperature. Ultimately, the figure of merit is unaffected by alloying in this system, due to the competing effects of reduced mobility and lattice thermal conductivity.

Thermoelectric properties of the Zintl phases Yb5M2Sb6 (M = Al, Ga, In)

Zintl compounds with chemical formula Yb5M2Sb6 (M = Al, Ga, and In) form one of two known A5M2Pn6 structure types characterized by double chains of corner-linked MPn4 tetrahedra bridged by Pn2 dumbbells. High temperature electronic and thermal transport measurements were used to characterize the thermoelectric properties of Yb5M2Sb6 compounds. All samples were found to exhibit similar high p-type carrier concentrations, low resistivity and low Seebeck coefficients in agreement with the band structure calculations. These results, combined with previous studies, suggest that Yb5M2Sb6 compounds are semimetals (i.e., they lack an energy gap between the valence and conduction bands), in contrast to the semiconducting alkaline earth (Ca, Sr, Ba) and Eu based A5M2Sb6 compounds. Yb5M2Sb6 compounds have very low lattice thermal conductivity, comparable to other closely related A5M2Sb6 and A3MSb3 phases. However, due to the semimetallic behaviour, the figure of merit of investigated samples remains low (zT < 0.15).

Enhancement of average thermoelectric figure of merit by increasing the grain-size of Mg3.2Sb1.5Bi0.49Te0.01

Zintl compound n-type Mg3(Sb,Bi)2 was recently found to exhibit excellent thermoelectric figure of merit zT (∼1.5 at around 700 K). To improve the thermoelectric performance in the whole temperature range of operation from room temperature to 720 K, we investigated how the grain size of sintered samples influences electronic and thermal transport. By increasing the average grain size from 1.0 μm to 7.8 μm, the Hall mobility below 500 K was significantly improved, possibly due to suppression of grain boundary scattering. We also confirmed that the thermal conductivity did not change by increasing the grain size. Consequently, the sample with larger grains exhibited enhanced average zT. The calculated efficiency of thermoelectric power generation reaches 14.5% (ΔT = 420 K), which is quite high for a polycrystalline pristine material.

Improving the thermoelectric performance in Mg3+xSb1.5Bi0.49Te0.01 by reducing excess Mg

The thermoelectric performance of Mg_(3+x)Sb_(1.5)Bi_(0.49)Te_(0.01) was improved by reducing the amount of excess Mg (x = 0.01-0.2). A 20% reduction in effective lattice thermal conductivity at 600 K was observed by decreasing the nominal xfrom 0.2 to 0.01 in Mg_(3+x)Sb_(1.5)Bi_(0.49)Te_(0.01), leading to a 20% improvement in the figure-of-merit zT. Since materials with different amounts of Mg have similar electronic properties, the enhancement is attributed primarily to the reduction in thermal conductivity. It is known that excess Mg is required to make n-type Mg_(3+x)Sb_(1.5)Bi_(0.49)Te_(0.01); however, too much excess Mg in the material increases the thermal conductivity and is therefore detrimental for the overall thermoelectric performance of the material.

Metal phosphides as potential thermoelectric materials

There still exists a crucial need for new thermoelectric materials to efficiently recover waste heat as electrical energy. Although metal phosphides are stable and can exhibit excellent electronic properties, they have traditionally been overlooked as thermoelectrics due to expectations of displaying high thermal conductivity. Based on high-throughput computational screening of the electronic properties of over 48 000 inorganic compounds, we find that several metal phosphides offer considerable promise as thermoelectric materials, with excellent potential electronic properties (e.g. due to multiple valley degeneracy). In addition to the electronic band structure, the phonon dispersion curves of various metal phosphides were computed indicating low-frequency acoustic modes that could lead to low thermal conductivity. Several metal phosphides exhibit promising thermoelectric properties. The computed electronic and thermal properties were compared to experiments to test the reliability of the calculations indicating that the predicted thermoelectric properties are semi-quantitative. As a complete experimental study of the thermoelectric properties in MPs, cubic-NiP2 was synthesized and the low predicted lattice thermal conductivity (∼1.2 W m−1 K−1 at 700 K) was confirmed. The computed Seebeck coefficient is in agreement with experiments over a range of temperatures and the phononic dispersion curve of c-NiP2 is consistent with the experimental heat capacity. The predicted high thermoelectric performance in several metal phosphides and the low thermal conductivity measured in NiP2 encourage further investigations of thermoelectric properties of metal phosphides.