Chapters authored
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.
Part of the book: Thermoelectrics for Power Generation
Nanostructured Thermoelectric Chalcogenides
Thermoelectric materials are outstanding to transform temperature differences directly and reversibly into electrical voltage. Exploiting waste heat recovery as a source of power generation could help towards energy sustainability. Recently, the SnSe semiconductor was identified, in single-crystal form, as a mid-temperature thermoelectric material with record high figure of merit, high power factor and surprisingly low thermal conductivity. We describe the preparation of polycrystals of alloys of SnSe obtained by arc-melting; a rapid synthesis that results in strongly nanostructured samples with low thermal conductivity, advantageous for thermoelectricity, approaching the amorphous limit, around 0.3–0.5 W/mK. An initial screening of novel samples Sn1−xMxSe, by alloying with 3d and 4d transition metals such as M = Mn, Y, Ag, Mo, Cd or Au, provides for a means to optimize the power factor. M=Mo, Ag, with excellent values, are described in detail with characterization by x-ray powder diffraction (XRD), scanning electron microscopy (SEM), and electronic and thermal transport measurements. Rietveld analysis of XRD data demonstrates near-perfect stoichiometries of the above-mentioned alloys. SEM analysis shows stacking of nanosized sheets, with large surfaces parallel to layered slabs. An apparatus was developed for the simultaneous measurement of the Seebeck coefficient and electric conductivity at elevated temperatures.
Part of the book: Bringing Thermoelectricity into Reality
Structural Phase Transitions of Hybrid Perovskites CH3NH3PbX3 (X = Br, Cl) from Synchrotron and Neutron Diffraction Data
Methylammonium (MA) lead trihalide perovskites, that is, CH3NH3PbX3 (X = I, Br, Cl), have emerged as a new class of light-absorbing materials for photovoltaic applications. Indeed, since their implementation in solar-cell heterojunctions, they reached efficiencies above 23%. From a crystallographic point of view, there are many open questions that should be addressed, including the role of the internal motion of methylammonium groups within PbX6 lattice under extreme conditions, such as low/high temperature or high pressure. For instance, in MAPbBr3 perovskites, the octahedral tilting can be induced upon cooling, lowering the space group from the aristotype Pm3¯m to I4/mcm and Pnma. The band gap engineering brought about by the chemical management of MAPb(Br,Cl)3 perovskites has been controllably tuned: the gap progressively increases with the concentration of Cl ions from 2.1 to 2.9 eV. In this chapter, we review recent structural studies by state-of-the-art techniques, relevant to the crystallographic characterization of these materials, in close relationship with their light-absorption properties.
Part of the book: Perovskite and Piezoelectric Materials