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March 27, 2012

Liquid-like Materials May Pave Way for New Thermoelectric Devices

CalTech researchers have identified a liquid-like compound whose properties give it the potential to be even more efficient than traditional thermoelectrics. The researchers studied a material made from copper and selenium. Although it is physically a solid, it exhibits liquid-like behaviors due to the way its copper atoms flow through the selenium's crystal lattice.

"It's like a wet sponge," explains Jeff Snyder, a faculty associate in applied physics and materials science in the Division of Engineering and Applied Science at the California Institute of Technology (Caltech) and a member of the research team. "If you have a sponge with very fine pores in it, it looks and acts like a solid. But inside, the water molecules are diffusing just as fast as they would if they were a regular liquid. That's how I imagine this material works. It has a solid framework of selenium atoms, but the copper atoms are diffusing around as fast as they would in a liquid."

The research, led by scientists from the Chinese Academy of Science's Shanghai Institute of Ceramics in collaboration with researchers from Brookhaven National Laboratory and the University of Michigan, as well as from Caltech.

The copper-selenium material has a thermoelectric figure of merit of 1.5 at 1000 degrees Kelvin, one of the highest values in any bulk material.

In this diagram, the blue spheres represent selenium atoms forming a crystal lattice. The orange regions in between the atoms represent the copper atoms that flow through the crystal structure like a liquid. This liquid-like behavior is what gives the selenium-copper material its unique thermoelectric properties.
[Credit: Caltech/Jeff Snyder/Lance Hayashida]


Nature Materials - Copper ion liquid-like thermoelectrics




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 Cu2−xSe, which reaches a zT of 1.5 at 1,000 K, among the highest values for any bulk materials. Whereas the Se atoms in Cu2−xSe 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 Cu2−xSe 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.

6 pages of supplemental material


Another thermoelectric material with a ZT of 1.8



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