High Thermoelectric Performance in PbSe–NaSbSe2 Alloys from Valence Band Convergence and Low Thermal Conductivity

PbSe is an attractive thermoelectric material due to its favorable electronic structure, high melting point, and lower cost compared to PbTe. Herein, the hitherto unexplored alloys of PbSe with NaSbSe2 (NaPbmSbSem+2) are described and the most promising p‐type PbSe‐based thermoelectrics are found among them. Surprisingly, it is observed that below 500 K, NaPbmSbSem+2 exhibits unorthodox semiconducting‐like electrical conductivity, despite possessing degenerate carrier densities of ≈1020 cm−3. It is shown that the peculiar behavior derives from carrier scattering by the grain boundaries. It is further demonstrated that the high solubility of NaSbSe2 in PbSe augments both the thermoelectric properties while maintaining a rock salt structure. Namely, density functional theory calculations and photoemission spectroscopy demonstrate that introduction of NaSbSe2 lowers the energy separation between the L‐ and Σ‐valence bands and enhances the power factors under 700 K. The crystallographic disorder of Na+, Pb2+, and Sb3+ moreover provides exceptionally strong point defect phonon scattering yielding low lattice thermal conductivities of 1–0.55 W m‐1 K‐1 between 400 and 873 K without nanostructures. As a consequence, NaPb10SbSe12 achieves maximum ZT ≈1.4 near 900 K when optimally doped. More importantly, NaPb10SbSe12 maintains high ZT across a broad temperature range, giving an estimated record ZTavg of ≈0.64 between 400 and 873 K, a significant improvement over existing p‐type PbSe thermoelectrics.The high solubility of NaSbSe2 in PbSe is exploited to facilitate convergence of L‐ and Σ‐valence bands and to produce strong point defect phonon scattering. These processes yield enhanced power factors and low lattice thermal conductivity over ≈300–700 K, which together give NaPb10SbSe12 outstanding thermoelectric performance with a maximum ZT ≈ 1.4 at 873 K and ZTavg ≈0.64 over 400–873 K.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/151353/1/aenm201901377.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/151353/2/aenm201901377-sup-0001-S1.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/151353/3/aenm201901377_am.pd

3D Printing & Open Access Databases for Crystallographic College Education

Presentation gives an overview of available open access databases of crystals and crystal structures, as well as discussions of how newly developed 3D printing technologies can be used to teach crystallography at the college level. Offers advice regarding conversion of crystallographic information files to 3D printing files, and shares news from the 3D printing of crystallographic models community

Crystallographic Education in the 21st Century

There are many methods that can be used to incorporate concepts of crystallography into the learning experiences of students, whether they are in elementary school, at university or part of the public at large. It is not always critical that those who teach crystallography have immediate access to diffraction equipment to be able to introduce the concepts of symmetry, packing or molecular structure in an age- and audience-appropriate manner. Crystallography can be used as a tool for teaching general chemistry concepts as well as general research techniques without ever having a student determine a crystal structure. Thus, methods for younger students to perform crystal growth experiments of simple inorganic salts, organic compounds and even metals are presented. For settings where crystallographic instrumentation is accessible (proximally or remotely), students can be involved in all steps of the process, from crystal growth, to data collection, through structure solution and refinement, to final publication. Several approaches based on the presentations in the MS92 Microsymposium at the IUCr 23rd Congress and General Assembly are reported. The topics cover methods for introducing crystallography to undergraduate students as part of a core chemistry curriculum; a successful short-course workshop intended to bootstrap researchers who rely on crystallography for their work; and efforts to bring crystallography to secondary school children and non-science majors. In addition to these workshops, demonstrations and long-format courses, open-format crystallographic databases and three-dimensional printed models as tools that can be used to excite target audiences and inspire them to pursue a deeper understanding of crystallography are described