Layered Cobaltates

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Introduction

Thermoelectric (TE) elements can generate heat from a voltage gradient (Peltier refrigerators) or a voltage from a temperature gradient (thermogenerators). The search for new thermoelectric materials has become an important issue since there exists numerous sources of waste-heat which could be converted to electrical energy by using non polluting thermoelectric devices. The efficiency of such a device is characterized by the figure of merit defined as Z=S2/ρκ, where S is thermoelectric power, ρ the resistivity and κ the thermo-conductivity. Materials used in TE devices usually have ZT in the order of 1, where T is the absolute temperature. The highest thermoelectric performance materials are intermetallic compounds such as Bi2Te3/Sb2Te3 alloys. The drawbacks of the conventional TE materials are that they have low melting, decomposition, and oxidation-temperatures, and they have content of harmful or rare elements, and notably deficient in the temperature range of waste heat (600-1000K).

In 1997, it was discovered that large thermoelectric power and low resistivity could coexist in the Na0.5CoO2 [I. Terasaki et al., Phys. Rev. B 56, R12685 (1997)], which made this compound an attractive candidate for TE applications. Soon after, the related cobaltates which posses the similar properties have been synthesized and investigated. Those cobaltates all have layered crystal structures, and all share the hexagonal CoO2 blocks as a common unit. NaxCoO2 has relatively simple structure because of the smaller size of the Na atoms. The other cobaltates have misfit-layered structure with rock salt type structures in between the CoO2 layers. The charge-carrier transport in those cobaltates is thought to be restricted mainly to these CoO2 planes, and they seem to be crucial in the high thermoelectric power properties.

Schematic structure of NaxCoO2 with the CoO2 layer and the Na ion separating layers. (Figure reproduced from K. Takada, et. al., Nature 422, 53 (2003). Schematic misfit structure of [Ca2CoO3][CoO2]1.62 with the CoO2 layer (red) and the Ca2CoO3 three-layer rock salt structure. (Figure reproduced from C. Simon's webpage: http://www-crismat.ismra.fr/physique/pagessp-activities-thermoelectricity.htm)  

Our Research

The origin of the coexistence of metallicity with a large thermoelectric power is still unclear. Two models have been proposed. The first one takes into account the spin degeneracy associated to the different cobalt valency and spin states [W. Koshibae et al., Phys. Rev. B 62, 6869 (2000)]. In the second one [D. J Singh, Phys. Rev. B 61, 13397 (2000)], a two-band model has been proposed: a band of light carriers responsible for metallicity coexists with a narrow band of heavy carriers in which the Fermi energy level lies. A peak in the Density of States near EF would be responsible for the large thermoelectric power.

In our group, we are trying to make different polycrystalline and single crystal cobaltates, and cobaltate thin films as well. Magnetic, electrical and thermal transport properties are studied using our Quantum Design PPMS, MPMS SQUID Magnetometer and other home made systems. Our goal is to investigate the mechanism of the high thermoelectric power, to improve the thermoelectric performance and to make TE devices using these layered cobaltates for practical application.

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Last Modified: January 31, 2008
Please forward all questions about this site to: Kim Mohanty


DOE, Office of Science One of ten national laboratories overseen and primarily funded by the Office of Science of the U.S. Department of Energy (DOE), Brookhaven National Laboratory conducts research in the physical, biomedical, and environmental sciences, as well as in energy technologies and national security. Brookhaven Lab also builds and operates major scientific facilities available to university, industry and government researchers. Brookhaven is operated and managed for DOE's Office of Science by Brookhaven Science Associates, a limited-liability company founded by the Research Foundation for the State University of New York on behalf of Stony Brook University, the largest academic user of Laboratory facilities, and Battelle, a nonprofit, applied science and technology organization.

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