Fracture structure and thermoelectric enhancement of Cu2Se with substitution of nanostructured Ag2Se.

Recently, copper chalcogenides have attracted great attention due to their potential application for mid- to high-temperature thermoelectric power generation. In this work, we report the thermoelectric properties of Cu2Se compounds with different sample preparation processes and the inclusion of a nanoscale Ag2Se powder synthesized with a unique wet chemistry procedure. The Cu2Se compounds were prepared by solid state reaction (SSR), fast quenching (FQ) and mechanically alloyed with nanostructured Ag2Se (NM) followed by hot pressing. High temperature transport properties were assessed by the Seebeck coefficient, electrical conductivity and thermal conductivity measurements. Structural characterization demonstrates that the nano-Ag2Se included sample is multi-phase with several nanoscale features not seen in the Cu2Se samples prepared in the standard method. As a result, the Cu2Se-NM sample possesses a miniscule thermal conductivity, with values as low as 0.5 W m-1 K-1. Fortunately, the nano-inclusions present in the Cu2Se-NM sample do not significantly disrupt electronic transport, preserving the power factor at a consistently high value over a broad range of temperatures. Consequently, the nano-Ag2Se included sample exhibits large average ZT values and a maximum of 1.85 at 800 K that rivals some of the best thermoelectrics currently available. Here, we present microstructural and transport evidence that the wet chemistry technique implemented in our study enables the optimization of thermoelectric performance in superionic conductor Cu2Se.

Developing High-Performance and Low-Cost Paint Thermoelectric Materials for Low-Midtemperature Applications.

Most thermoelectric (TE) materials used to convert heat energy into electrical energy are expensive and, to a certain degree, toxic. Moreover, due to the chemical complexity in the synthesis process, some of the TE materials are not reproducible. Similarly, the scarcity of TE materials hampers their scalability. To address the above issues, this study presents an inexpensive, nontoxic, scalable, and highly reproducible paint-based TE module for the conversion of heat energy to electrical energy. Transport properties with structural analysis indicate that the electrical conductivity of the paint TE material is controlled by the concentration of graphite and sodium silicate, while the Seebeck coefficient is dominated by the ratio of n- and p-type Bi-Sb-Te. The results indicate that the as-developed TE module can withstand an operating temperature of up to 160 °C. At a temperature of 57 °C, the highest power factors of the as-synthesized n- and p-type TE paints are 1.34 and 1.42 µW/(cm K2), respectively. It is also found that the TE module can have a higher output voltage when the cold side of the TE module is allowed to float in the air in comparison to that when it is in contact with the human body. The performance of the paint-based TE module is measured on five parts of the body, namely, the chest, palm, leg, wrist, and neck; the wrist has the highest open-circuit voltage of 1.9 mV, indicating its suitability for wearable applications. Finally, at a temperature gradient of 30 °C, a maximum output power of 6.8 µW is attained.

Minute-Made, High-Efficiency Nanostructured Bi2Te3 via High-Throughput Green Solution Chemical Synthesis.

Scalable synthetic strategies for high-quality and reproducible thermoelectric (TE) materials is an essential step for advancing the TE technology. We present here very rapid and effective methods for the synthesis of nanostructured bismuth telluride materials with promising TE performance. The methodology is based on an effective volume heating using microwaves, leading to highly crystalline nanostructured powders, in a reaction duration of two minutes. As the solvents, we demonstrate that water with a high dielectric constant is as good a solvent as ethylene glycol (EG) for the synthetic process, providing a greener reaction media. Crystal structure, crystallinity, morphology, microstructure and surface chemistry of these materials were evaluated using XRD, SEM/TEM, XPS and zeta potential characterization techniques. Nanostructured particles with hexagonal platelet morphology were observed in both systems. Surfaces show various degrees of oxidation, and signatures of the precursors used. Thermoelectric transport properties were evaluated using electrical conductivity, Seebeck coefficient and thermal conductivity measurements to estimate the TE figure-of-merit, ZT. Low thermal conductivity values were obtained, mainly due to the increased density of boundaries via materials nanostructuring. The estimated ZT values of 0.8-0.9 was reached in the 300-375 K temperature range for the hydrothermally synthesized sample, while 0.9-1 was reached in the 425-525 K temperature range for the polyol (EG) sample. Considering the energy and time efficiency of the synthetic processes developed in this work, these are rather promising ZT values paving the way for a wider impact of these strategic materials with a minimum environmental impact.

Experimental and Theoretical Investigation of the Effect of Filler Material on the Performance of Flexible and Rigid Thermoelectric Generators.

Thermoelectric generators have found many applications where the heat source can be either flat or curved. For a curved heat source, flexible thermoelectric generators are generally used. A filler material with low thermal conductivity can provide additional mechanical support to the thermoelectric module and can reduce convection and radiation losses. Herein, the effect of three different filler materials on the output performance of rigid and flexible thermoelectric generators is investigated. At first, theoretical models are derived and the experimental study validated the models. The experimental study revealed that the flexible thermoelectric modules outperformed the rigid modules; this is due to the reduction of the number of thermal junctions in the flexible modules and due to the differences in the thermal conductivities of the flexible and rigid substrates. Likewise, among TE modules without filler/with air between the TE legs, with polyurethane foam filler material, and with polydimethylsiloxane filler material, air has the lowest thermal conductivity, and therefore, the thermoelectric generator without filler generates higher output power and higher power density than when the other two filler materials are used. For the fixed temperature gradient, the highest power densities for the flexible and rigid thermoelectric generators without filler are 155 and 137.7 µW/cm2 for temperature gradients of 10.8 and 10.3 °C, respectively.

Exploring resonance levels and nanostructuring in the PbTe-CdTe system and enhancement of the thermoelectric figure of merit.

We explored the effect of Cd substitution on the thermoelectric properties of PbTe in an effort to test a theoretical hypothesis that Cd atoms on Pb sites of the rock salt lattice can increase the Seebeck coefficient via the formation of a resonance level in the density of states near the Fermi energy. We find that the solubility of Cd is less than previously reported, and CdTe precipitation occurs to create nanostructuring, which strongly suppresses the lattice thermal conductivity. We present detailed characterization including structural and spectroscopic data, transmission electron microscopy, and thermoelectric transport properties of samples of PbTe-x% CdTe-0.055% PbI(2) (x = 1, 3, 5, 7, 10), PbTe-1% CdTe-y% PbI(2) (y = 0.03, 0.045, 0.055, 0.08, 0.1, 0.2), PbTe-5% CdTe-y% PbI(2) (y = 0.01, 0.03, 0.055, 0.08), and PbTe-1% CdTe-z% Sb (z = 0.3, 0.5, 1, 1.5, 2, 3, 4, 5, 6). All samples follow the Pisarenko relationship, and no enhancement of the Seebeck coefficient was observed that could be attributed to a resonance level or a distortion in the density of states. A maximum ZT of approximately 1.2 at approximately 720 K was achieved for the PbTe-1% CdTe-0.055% PbI(2) sample arising from a high power factor of approximately 17 microW/(cm K(2)) and a very low lattice thermal conductivity of approximately 0.5 W/(m K) at approximately 720 K.

Composition Tuning of Nanostructured Binary Copper Selenides through Rapid Chemical Synthesis and their Thermoelectric Property Evaluation.

Reduced energy consumption and environmentally friendly, abundant constituents are gaining more attention for the synthesis of energy materials. A rapid, highly scalable, and process-temperature-sensitive solution synthesis route is demonstrated for the fabrication of thermoelectric Cu2-xSe. The process relies on readily available precursors and microwave-assisted thermolysis, which is sensitive to reaction conditions; yielding Cu1.8Se at 200 °C and Cu2Se at 250 °C within 6-8 min reaction time. Transmission electron microscopy (TEM) revealed crystalline nature of as-made particles with irregular truncated morphology, which exhibit a high phase purity as identified by X-ray powder diffraction (XRPD) analysis. Temperature-dependent transport properties were characterized via electrical conductivity, Seebeck coefficient, and thermal diffusivity measurements. Subsequent to spark plasma sintering, pure Cu1.8Se exhibited highly compacted and oriented grains that were similar in size in comparison to Cu2Se, which led to its high electrical and low thermal conductivity, reaching a very high power-factor (24 µW/K-2cm-1). Density-of-states (DOS) calculations confirm the observed trends in electronic properties of the material, where Cu-deficient phase exhibits metallic character. The TE figure of merit (ZT) was estimated for the materials, demonstrating an unprecedentedly high ZT at 875 K of 2.1 for Cu1.8Se sample, followed by 1.9 for Cu2Se. Synthetic and processing methods presented in this work enable large-scale production of TE materials and components for niche applications.