Thermoelectric Properties of Solution Synthesized Nanostructured Materials.

Thermoelectric nanocomposites made by solution synthesis and compression of nanostructured chalcogenides could potentially be low-cost, scalable alternatives to traditional solid-state synthesized materials. We review the progress in this field by comparing the power factor and/or the thermoelectric figure of merit, ZT, of four classes of materials: (Bi,Sb)2(Te,Se)3, PbTe, ternary and quaternary copper chalcogenides, and silver chalcogenides. We also discuss the thermal conductivity reduction associated with multiphased nanocomposites. The ZT of the best solution synthesized materials are, in several cases, shown to be equal to or greater than the corresponding bulk materials despite the generally reduced mobility associated with solution synthesized nanocomposites. For the solution synthesized materials with the highest performance, the synthesis and processing conditions are summarized to provide guidance for future work.

Flexible prototype thermoelectric devices based on Ag2Te and PEDOT:PSS coated nylon fibre.

p- and n-type Ag2Te nanocrystals are coated separately onto nylon fibres to create flexible composites. A prototype thermoelectric device made using such fibres produces ∼0.8 nW in a 20 K temperature difference. This is improved to over 5 nW by using a conducting polymer as the p-type material.

Environmentally benign synthesis of ultrathin metal telluride nanowires.

Metal telluride nanowires are attractive materials for many applications, yet most synthesis recipes require hazardous reducing agents such as hydrazine or sodium borohydride. We describe a two-step synthesis of various metal tellurides with nanowire morphology using a nonhazardous reducing agent, ascorbic acid. In the first step, Te grows one-dimensionally to form ultrathin nanowires; in the second step, these nanowires are converted to metal telluride nanowires by adding metal precursors. Analysis of the reaction products versus time provides insights into the growth and conversion mechanisms as well as the reaction rates.

Large-scale solution-phase production of Bi2Te3 and PbTe nanowires using Te nanowire templates.

We report the first demonstration of large scale (>10 g) and high yield (>80%) production of ultrathin (<15 nm) PbTe and Bi2Te3 nanowires in a low-cost solution-based process using Te nanowire templates. The PbTe or Bi2Te3 nanowires can be compressed into high relative density disks with nanoscale grains.

Structure and thermoelectric properties of spark plasma sintered ultrathin PbTe nanowires.

Solution-synthesized thermoelectric nanostructured materials have the potential to have lower cost and higher performance than materials synthesized by solid-state methods. Herein we present the synthesis of ultrathin PbTe nanowires, which are compressed by spark plasma sintering at various temperatures in the range of 405-500 °C. The resulting discs possess grains with sizes of 5-30 µm as well as grains with sizes on the order of the original 12 nm diameter PbTe nanowires. This micro- and nanostructure leads to a significantly reduced thermal conductivity compared to bulk PbTe. Careful electron transport analysis shows suppressed electrical conductivity due to increased short-range and ionized defect scatterings, while the Seebeck coefficient remains comparable to the bulk value. The PbTe nanowire samples are found unintentionally p-type doped to hole concentrations of 2.16-2.59 × 10(18) cm(-3). The maximum figure of merit achieved in the unintentionally doped spark plasma sintered PbTe nanowires is 0.33 at 350 K, which is among the highest reported for unintentionally doped PbTe at low temperatures.

Measurement of thermal conductivity of PbTe nanocrystal coated glass fibers by the 3ω method.

Fiber-based thermoelectric materials can conform to curved surfaces to form energy harvesting devices for waste heat recovery. Here we investigate the thermal conductivity in the axial direction of glass fibers coated with lead telluride (PbTe) nanocrystals using the self-heated 3ω method particularly at low frequency. While prior 3ω measurements on wire-like structures have only been demonstrated for high thermal conductivity materials, the present work demonstrates the suitability of the 3ω method for PbTe nanocrystal coated glass fibers where the low thermal conductivity and high aspect ratio result in a significant thermal radiation effect. We simulate the experiment using a finite-difference method that corrects the thermal radiation effect and extract the thermal conductivity of glass fibers coated by PbTe nanocrystals. The simulation method for radiation correction is shown to be generally much more accurate than analytical methods. We explore the effect of nanocrystal volume fraction on thermal conductivity and obtain results in the range of 0.50-0.93 W/mK near room temperature.

Flexible nanocrystal-coated glass fibers for high-performance thermoelectric energy harvesting.

Recent efforts on the development of nanostructured thermoelectric materials from nanowires (Boukai, A. I.; et al. Nature 2008, 451, (7175), 168-171; Hochbaum, A. I.; et al. Nature 2008, 451, (7175), 163-167) and nanocrystals (Kim, W.; et al. Phys. Rev. Lett. 2006, 96, (4), 045901; Poudel, B.; et al. Science 2008, 320, (5876), 634-638; Scheele, M.; et al. Adv. Funct. Mater. 2009, 19, (21), 3476-3483; Wang, R. Y.; et al. Nano Lett. 2008, 8, (8), 2283-2288) show the comparable or superior performance to the bulk crystals possessing the same chemical compositions because of the dramatically reduced thermal conductivity due to phonon scattering at nanoscale surface and interface. Up to date, the majority of the thermoelectric devices made from these inorganic nanostructures are fabricated into rigid configuration. The explorations of truly flexible composite-based flexible thermoelectric devices (See, K. C.; et al. Nano Lett. 2010, 10, (11), 4664-4667) have thus far achieved much less progress, which in principle could significantly benefit the conversion of waste heat into electricity or the solid-state cooling by applying the devices to any kind of objects with any kind of shapes. Here we report an example using a scalable solution-phase deposition method to coat thermoelectric nanocrystals onto the surface of flexible glass fibers. Our investigation of the thermoelectric properties yields high performance comparable to the state of the art from the bulk crystals and proof-of-concept demonstration also suggests the potential of wrapping the thermoelectric fibers on the industrial pipes to improve the energy efficiency.