F. Serrano-Sánchez

Record Seebeck coefficient and extremely low thermal conductivity in nanostructured SnSe

SnSe has been prepared by arc-melting, as mechanically robust pellets, consisting of highly oriented polycrystals. This material has been characterized by neutron powder diffraction (NPD), scanning electron microscopy, and transport measurements. A microscopic analysis from NPD data demonstrates a quite perfect stoichiometry SnSe0.98(2) and a fair amount of anharmonicity of the chemical bonds. The Seebeck coefficient reaches a record maximum value of 668 μV K−1 at 380 K; simultaneously, this highly oriented sample exhibits an extremely low thermal conductivity lower than 0.1 W m−1 K−1 around room temperature, which are two of the main ingredients of good thermoelectric materials. These excellent features exceed the reported values for this semiconducting compound in single crystalline form in the moderate-temperatures region and highlight its possibilities as a potential thermoelectric material.

Giant Seebeck effect in Ge-doped SnSe.

Thermoelectric materials may contribute in the near future as new alternative sources of sustainable energy. Unprecedented thermoelectric properties in p-type SnSe single crystals have been recently reported, accompanied by extremely low thermal conductivity in polycrystalline samples. In order to enhance thermoelectric efficiency through proper tuning of this material we report a full structural characterization and evaluation of the thermoelectric properties of novel Ge-doped SnSe prepared by a straightforward arc-melting method, which yields nanostructured polycrystalline samples. Ge does not dope the system in the sense of donating carriers, yet the electrical properties show a semiconductor behavior with resistivity values higher than that of the parent compound, as a consequence of nanostructuration, whereas the Seebeck coefficient is higher and thermal conductivity lower, favorable to a better ZT figure of merit.

Structural phase transition in polycrystalline SnSe: a neutron diffraction study in correlation with thermoelectric properties

SnSe has been recently reported as a promising and highly efficient thermoelectric intermetallic alloy. The present material has been prepared by arc melting, as mechanically robust pellets, consisting of highly oriented polycrystals. The evolution of its orthorhombic GeS-type structure (space group Pnma) and phase transition to TlI-type structure (space group Cmcm) at high temperature has been studied in situ by neutron powder diffraction (NPD) in the temperature range 295–873 K. This transition has been identified by differential scanning calorimetry measurements, yielding sharp peaks at 795 K. In addition, thermal transport properties were measured in a similar temperature range, and large Seebeck coefficients, as high as 1050 µV K−1 at 625 K, were found. The analysis from NPD data demonstrates an almost perfect stoichiometry, Sn0.998(8)Se, that does not evolve with temperature, and a progressive decrease of the anharmonicity of the chemical bonds upon entering the domain of the Cmcm structure.

Enhanced figure of merit in nanostructured (Bi,Sb) 2 Te 3 with optimized composition, prepared by a straightforward arc-melting procedure

Sb-doped Bi2Te3 is known since the 1950s as the best thermoelectric material for near-room temperature operation. Improvements in material performance are expected from nanostructuring procedures. We present a straightforward and fast method to synthesize already nanostructured pellets that show an enhanced ZT due to a remarkably low thermal conductivity and unusually high Seebeck coefficient for a nominal composition optimized for arc-melting: Bi0.35Sb1.65Te3. We provide a detailed structural analysis of the Bi2−xSbxTe3 series (0 ≤ x ≤ 2) based on neutron powder diffraction as a function of composition and temperature that reveals the important role played by atomic vibrations. Arc-melting produces layered platelets with less than 50 nm-thick sheets. The low thermal conductivity is attributed to the phonon scattering at the grain boundaries of the nanosheets. This is a fast and cost-effective production method of highly efficient thermoelectric materials.

Extra-low thermal conductivity in unfilled CoSb3-δ skutterudite synthesized under high-pressure conditions

Thermoelectric CoSb3-δ skutterudite was synthesized and sintered in one step under high-pressure conditions at 3.5 GPa in a piston-cylinder hydrostatic press. Structural analysis carried out from synchrotron x-ray powder diffraction data reveals a significant Sb deficiency in this material. The introduction of point defects in the form of Sb vacancies distributed at random in the structure leads to an impressive reduction (>50%) of the total thermal conductivity, κ, which is one of the main ingredients of good thermoelectric materials. This suggests phonon scattering effects originated in the Sb defects, which drives to a better improvement in κ than that achieved by the conventional strategy of filling the cages of the skutterudite structure with rare earths or other heavy cations. In parallel, changes in the electronic band structure caused by point variation of the stoichiometry produce an undesired increment in the electrical resistivity. Nevertheless, the low thermal conductivity combined with a high...

Nanostructured State-of-the-Art Thermoelectric Materials Prepared by Straight-Forward Arc-Melting Method

Thermoelectric materials constitute an alternative to harvest sustainable energy from waste heat. Among the most commonly utilized thermoelectric materials, we can mention Bi2Te3 (hole and electron conductivity type), PbTe and recently reported SnSe intermetallic alloys. We review recent results showing that all of them can be readily prepared in nanostructured form by arc-melting synthesis, yielding mechanically robust pellets of highly oriented polycrystals. These materials have been characterized by neutron powder diffraction (NPD), scanning electron microscopy (SEM) and electronic and thermal transport measurements. Analysis of NPD patterns demonstrates near-perfect stoichiometry of above-mentioned alloys and fair amount of anharmonicity of chemical bonds. SEM analysis shows stacking of nanosized sheets, each of them presumably single-crystalline, with large surfaces parallel to layered slabs. This nanostructuration affects notably thermoelectric properties, involving many surface boundaries (interfaces), which are responsible for large phonon scattering factors, yielding low thermal conductivity. Additionally, we describe homemade apparatus developed for the simultaneous measurement of Seebeck coefficient and electric conductivity at elevated temperatures.

Low thermal conductivity in La-filled cobalt antimonide skutterudites with an inhomogeneous filling factor prepared under high-pressure conditions

La-filled skutterudites LaxCo4Sb12 (x = 0.25 and 0.5) have been synthesized and sintered in one step under high-pressure conditions at 3.5 GPa in a piston-cylinder hydrostatic press. The structural properties of the reaction products were characterized by synchrotron X-ray powder diffraction, clearly showing an uneven filling factor of the skutterudite phases, confirmed by transmission electron microscopy. The non-homogeneous distribution of La filling atoms is adequate to produce a significant decrease in lattice thermal conductivity, mainly due to strain field scattering of high-energy phonons. Furthermore, the lanthanum filler primarily acts as an Einstein-like vibrational mode having a strong impact on the phonon scattering. Extra-low thermal conductivity values of 2.39 W m−1 K−1 and 1.30 W m−1 K−1 are measured for La0.25Co4Sb12 and La0.5Co4Sb12 nominal compositions at 780 K, respectively. Besides this, lanthanum atoms have contributed to increase the charge carrier concentration in the samples. In the case of La0.25Co4Sb12, there is an enhancement of the power factor and an improvement of the thermoelectric properties.

Low lattice thermal conductivity in arc-melted GeTe with Ge-deficient crystal structure

GeTe is a well-known thermoelectric material, with transport properties strongly dependent on the composition and crystal structure. Phase-pure polycrystalline GeTe has been prepared by a straightforward arc-melting technique, and its structural and physical properties are studied by neutron powder diffraction (NPD), electron microscopy, calorimetry, and transport measurements. The structural analysis from NPD data reveals a conspicuous Ge deficiency in the bulk structure (∼7% atomic vacancies), confirmed by the Hall-carrier concentration. The analysis of the atomic displacement parameters shows strong anisotropy of Ge ellipsoids, revealing a considerable anharmonicity of the chemical bonds. Concerning the thermoelectric properties, the samples display high electrical conductivity and reduced lattice contribution to the total thermal conductivity, exhibiting record-low 0.8 W m−1 K−1 at 770 K, as a consequence of the highly defective crystal structure. Both are essential ingredients of useful thermoelectric materials, indicating the applicability of defective GeTe in polycrystalline form.GeTe is a well-known thermoelectric material, with transport properties strongly dependent on the composition and crystal structure. Phase-pure polycrystalline GeTe has been prepared by a straightforward arc-melting technique, and its structural and physical properties are studied by neutron powder diffraction (NPD), electron microscopy, calorimetry, and transport measurements. The structural analysis from NPD data reveals a conspicuous Ge deficiency in the bulk structure (∼7% atomic vacancies), confirmed by the Hall-carrier concentration. The analysis of the atomic displacement parameters shows strong anisotropy of Ge ellipsoids, revealing a considerable anharmonicity of the chemical bonds. Concerning the thermoelectric properties, the samples display high electrical conductivity and reduced lattice contribution to the total thermal conductivity, exhibiting record-low 0.8 W m−1 K−1 at 770 K, as a consequence of the highly defective crystal structure. Both are essential ingredients of useful thermoelectri...