Tetrahedrite Thermoelectrics: From Fundamental Science to Facile Synthesis

Abstract

Thermoelectric materials have a long and storied history in the research and development of semiconductor materials, being the first such class of materials to be investigated. Thermoelectrics may be used to convert heat to electricity or, alternatively, to liberate or absorb heat upon electrical excitation. They thus find application in thermoelectric generators for converting heat from a primary source or a waste stream to useful electrical power, and as solid state heating and cooling devices. In spite of their great potential in such important applications, thermoelectrics have suffered from a number of drawbacks that have hindered their utilization on a large scale. Chief among these is the fact that most high performance thermoelectric materials are comprised of elements that are in relatively low abundance. Additionally, their synthesis typically involves complex and multi-step processes, hindering manufacturability. Thermoelectric materials derived from Earth-abundant sources are thus of strong current interest, from both scientific and economic points of view. One of these, the family of semiconductors based on tetrahedrite compounds, has generated enormous interest over the last decade due to not only its potential low cost, but also for its fascinating science. In this review, we summarize the state of the art of tetrahedrite as a thermoelectric, with special emphasis on the relationship between crystal structure and bonding in the crystal and its unusually low lattice thermal conductivity; on its fascinating electronic structure; and on the wide array of compositions that have been synthesized and whose thermoelectric properties have been studied. We further highlight some rapid and facile synthesis techniques that have been developed for these compounds which, in combination with their potential low material cost, may open the door to widespread application of these fascinating materials.

Multinary Tetrahedrite (Cu12–x–yMxNySb4S13) Nanoparticles: Tailoring Thermal and Optical Properties with Copper-Site Dopants

“…Elemental compositions for all tetrahedrite nanoparticles were within the compositional range of Cu 12−14.5 Sb 4−4.5 S 13 that is commonly observed in natural and synthetic tetrahedrite materials. 24,[39][40][41]61,62 The elemental compositions determined by EDS mapping for all ternary undoped, quaternary singledoped, and quintenary codoped tetrahedrite nanoparticles are available in Table 1. An SEM image alongside EDS maps (Figure 4d−i) taken for the Cu 11 Fe 0.5 Mn 0.5 Sb 4 S 13 codoped tetrahedrite nanomaterials indicates that constituent elements and dopants were distributed homogeneously throughout the sample, confirming that no amorphous impurities were found in the tetrahedrite nanomaterials.…”

Thermoelectric properties of Gd and Se double substituted tetrahedrite

“…On the other hand, tetrahedrite, a naturally occurring mineral with inexpensive, less harmful, and earth-abundant constituents, offers a possible substitute for contemporary state-of-the-art thermoelectric materials. 11,12 The compound Cu 12 Sb 4 S 13 , known as tetrahedrite, is a mineral sulfide that develops with the space group I 4̄3 m above 88 K. 13 The BCC unit cell has two formula units; each formula unit contains two types of copper atoms, Cu(1) at 12 d and Cu(2) at 12 e , and two kinds of sulfur atoms, S(1) at 24 g and S(2) at 2 a Wyckoff sites respectively. The antimony atom sits at 8 c Wyckoff site.…”

“…S1: Rietveld refined patterns of the samples (a) x = 0, (b) x = 0.2, (c) x = 0.6, and (d) x = 0.8; Table S1: Rietveld refinement results for Gd and Se double substituted samples; Tables S2-S6: The Wyckoff sites and atomic coordinates (x, y, z) for all the samples; Table S7: Lattice parameters of the Cu 3 SbS 4 phase in the double substituted samples; hand, tetrahedrite, a naturally occurring mineral with inexpensive, less harmful, and earth-abundant constituents, offers a possible substitute for contemporary state-of-the-art thermoelectric materials. 11,12 The compound Cu 12 Sb 4 S 13 , known as tetrahedrite, is a mineral sulfide that develops with the space group I4 ˉ3m above 88 K. 13 The BCC unit cell has two formula units; each formula unit contains two types of copper atoms, Cu(1) at 12d and Cu(2) at 12e, and two kinds of sulfur atoms, S(1) at 24g and S(2) at 2a Wyckoff sites respectively. The antimony atom sits at 8c Wyckoff site.…”

Thermoelectric Performance of Tetrahedrite (Cu12Sb4S13) Thin Films: The Influence of the Substrate and Interlayer

“…Since Suekuni et al reported the thermoelectric properties of Cu 12 Sb 4 S 13 for the first time in 2012, 5,8 improve their thermoelectric performance. Wang 14 Thin-film thermoelectric materials offer numerous advantages, including low costs, low weights, and niche deployment opportunities.…”