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1.
Nano Lett ; 15(2): 1349-55, 2015 Feb 11.
Artículo en Inglés | MEDLINE | ID: mdl-25574778

RESUMEN

To design superior thermoelectric materials the minority carrier blocking effect in which the unwanted bipolar transport is prevented by the interfacial energy barriers in the heterogeneous nanostructures has been theoretically proposed recently. The theory predicts an enhanced power factor and a reduced bipolar thermal conductivity for materials with a relatively low doping level, which could lead to an improvement in the thermoelectric figure of merit (ZT). Here we show the first experimental demonstration of the minority carrier blocking in lead telluride-silver telluride (PbTe-Ag2Te) nanowire heterostructure-based nanocomposites. The nanocomposites are made by sintering PbTe-Ag2Te nanowire heterostructures produced in a highly scalable solution-phase synthesis. Compared with Ag2Te nanowire-based nanocomposite produced in similar method, the PbTe-Ag2Te nanocomposite containing ∼5 atomic % PbTe exhibits enhanced Seebeck coefficient, reduced thermal conductivity, and ∼40% improved ZT, which can be well explained by the theoretical modeling based on the Boltzmann transport equations when energy barriers for both electrons and holes at the heterostructure interfaces are considered in the calculations. For this p-type PbTe-Ag2Te nanocomposite, the barriers for electrons, that is, minority carriers, are primarily responsible for the ZT enhancement. By extending this approach to other nanostructured systems, it represents a key step toward low-cost solution-processable nanomaterials without heavy doping level for high-performance thermoelectric energy harvesting.

2.
Nano Lett ; 14(9): 5398-404, 2014 Sep 10.
Artículo en Inglés | MEDLINE | ID: mdl-25157694

RESUMEN

In this article, we demonstrated that composition modulation of Ag2Te nanowires can be achieved during the self-templated transformation of Te nanowires into Ag2Te nanowires during solution phase synthesis, which provides a mean to tune the carrier density of the Ag2Te nanowires. Both nearly stoichiometric and Ag-rich nanowires have been synthesized, which give rise to p-type and n-type Ag2Te nanocomposites after hot press, respectively. The electrical and thermal properties of the two kinds of samples have been measured. Theoretical modeling based on the near-equilibrium Boltzmann transport equations has been used to understand the experimental results. We found that ZT of the heavily doped n-type sample reaches 0.55 at 400 K, which is the highest ZT value reported for Ag2Te at the same temperature mainly due to the reduced thermal conductivity by the nanostructures. Theoretical analysis on the carrier transport shows that the power factor is also very well optimized in the doped Ag2Te sample considering the reduced carrier mobility by the nanostructures.

3.
J Am Chem Soc ; 136(1): 442-8, 2014 Jan 08.
Artículo en Inglés | MEDLINE | ID: mdl-24279340

RESUMEN

Knowledge of structure-property relationships is a key feature of materials design. The control of thermal transport has proven to be crucial for the optimization of thermoelectric materials. We report the synthesis, chemical characterization, thermoelectric transport properties, and thermal transport calculations of the complete solid solution series Cu2ZnGeSe(4-x)S(x) (x = 0-4). Throughout the substitution series a continuous Vegard-like behavior of the lattice parameters, bond distances, optical band gap energies, and sound velocities are found, which enables the tuning of these properties adjusting the initial composition. Refinements of the special chalcogen positions revealed a change in bonding angles, resulting in crystallographic strain possibly affecting transport properties. Thermal transport measurements showed a reduction in the room-temperature thermal conductivity of 42% triggered by the introduced disorder. Thermal transport calculations of mass and strain contrast revealed that 34% of the reduction in thermal conductivity is due to the mass contrast only and 8% is due to crystallographic strain.

4.
J Am Chem Soc ; 136(34): 12035-40, 2014 Aug 27.
Artículo en Inglés | MEDLINE | ID: mdl-25058352

RESUMEN

Building on the good thermoelectric performances of binary superionic compounds like Cu2Se, Ag2Se and Cu2S, a better and more detailed understanding of phonon-liquid electron-crystal (PLEC) thermoelectric materials is desirable. In this work we present the thermoelectric transport properties of the compound Cu7PSe6 as the first representative of the class of argyrodite-type ion conducting thermoelectrics. With a huge variety of possible compositions and high ionic conductivity even at room temperature, the argyrodites represent a very good model system to study structure-property relationships for PLEC thermoelectric materials. We particularly highlight the extraordinary low thermal conductivity of Cu7PSe6 below the glass limit, which can be associated with the molten copper sublattice leading to a softening of phonon modes.

5.
J Am Chem Soc ; 135(2): 726-32, 2013 Jan 16.
Artículo en Inglés | MEDLINE | ID: mdl-23256607

RESUMEN

Inspired by the promising thermoelectric properties of chalcopyrite-like quaternary chalcogenides, here we describe the synthesis and characterization of the solid solution Cu(2)Zn(1-x)Fe(x)GeSe(4). Upon substitution of Zn with the isoelectronic Fe, no charge carriers are introduced in these intrinsic semiconductors. However, a change in lattice parameters, expressed in an elongation of the c/a lattice parameter ratio with minimal change in unit cell volume, reveals the existence of a three-stage cation restructuring process of Cu, Zn, and Fe. The resulting local anisotropic structural disorder leads to phonon scattering not normally observed, resulting in an effective approach to reduce the lattice thermal conductivity in this class of materials.

6.
Nat Mater ; 11(5): 422-5, 2012 Mar 11.
Artículo en Inglés | MEDLINE | ID: mdl-22406814

RESUMEN

Advanced thermoelectric technology offers a potential for converting waste industrial heat into useful electricity, and an emission-free method for solid state cooling. Worldwide efforts to find materials with thermoelectric figure of merit, zT values significantly above unity, are frequently focused on crystalline semiconductors with low thermal conductivity. Here we report on Cu(2-x)Se, which reaches a zT of 1.5 at 1,000 K, among the highest values for any bulk materials. Whereas the Se atoms in Cu(2-x)Se form a rigid face-centred cubic lattice, providing a crystalline pathway for semiconducting electrons (or more precisely holes), the copper ions are highly disordered around the Se sublattice and are superionic with liquid-like mobility. This extraordinary 'liquid-like' behaviour of copper ions around a crystalline sublattice of Se in Cu(2-x)Se results in an intrinsically very low lattice thermal conductivity which enables high zT in this otherwise simple semiconductor. This unusual combination of properties leads to an ideal thermoelectric material. The results indicate a new strategy and direction for high-efficiency thermoelectric materials by exploring systems where there exists a crystalline sublattice for electronic conduction surrounded by liquid-like ions.

7.
Adv Mater ; 24(27): 3622-6, 2012 Jul 17.
Artículo en Inglés | MEDLINE | ID: mdl-22689017

RESUMEN

CuGaTe(2) with a chalcopyrite structure demonstrates promising thermoelectric properties. The maximum figure of merit ZT is 1.4 at 950 K. CuGaTe(2) and related chalcopyrites are a new class of high-efficiency bulk thermoelectric material for high-temperature applications.


Asunto(s)
Cobre/química , Conductividad Térmica , Calor , Difracción de Rayos X
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