A technique for suppressing sublimation of key elements from skutterudite compounds in advanced thermoelectric devices has been demonstrated. The essence of the technique is to cover what would otherwise be the exposed skutterudite surface of such a device with a thin, continuous film of a chemically and physically compatible metal. Although similar to other sublimation- suppression techniques, this technique has been specifically tailored for application to skutterudite antimonides.

The primary cause of deterioration of most thermoelectric materials is thermal decomposition or sublimation—one or more elements sublime from the hot side of a thermoelectric couple, changing the stoichiometry of the device. Examples of elements that sublime from their respective thermoelectric materials are Ge from SiGe, Te from Pb/Te, and now Sb from skutterudite antimonides. The skutterudite antimonides of primary interest are CoSb3 [electron-donor (n) type] and CeFe3xCoxSb12 [electron-acceptor (p) type]. When these compounds are subjected to typical operating conditions [temperature of 700 °C and pressure <10–5 torr (0.0013 Pa)], Sb sublimes from their surfaces, with the result that Sb depletion layers form and advance toward their interiors. As the depletion layer advances in a given device, the change in stoichiometry diminishes the thermal-to-electric conversion efficiency of the device.

In a Powder-Metallurgy Process used to fabricate a segment of a thermoelectric device, the particles of thermoelectric material are sintered by heat and pressure, which is also exploited to bond the sintered mass to the outer layer of titanium foil.
The problem, then, is to prevent sublimation, or at least reduce it to an acceptably low level. In preparation for an experiment on suppression of sublimation, a specimen of CoSb3 was tightly wrapped in a foil of niobium, which was selected for its chemical stability. In the experiment, the wrapped specimen was heated to a temperature of 700 °C in a vacuum of residual pressure <10–5 torr (0.0013 Pa), then cooled and sectioned. Examination of the sectioned specimen revealed that no depletion layer had formed, indicating the niobium foil prevented sublimation of antimony at 700 °C. This was a considerable improvement, considering that uncoated CoSb3 had been found to decompose to form the lowest antimonide at the surface at only 600 °C. Evidently, because the mean free path of Sb at the given temperature and pressure was of the order of tens of centimeters, any barrier closer than tens of centimeters (as was the niobium foil) would have suppressed transport of Sb vapor, thereby suppressing sublimation of Sb.

Guided by the aforementioned experiments, a powder-metallurgy process for fabricating skutterudite was modified to provide for covering the outer surfaces of the segments with titanium foils. In the unmodified process, the thermoelectric material, in powder form, is hot-pressed in a graphite die, then removed, then further processed. The combination of high temperature and pressure in the die acts to promote bonding between particles, and as such, is ideal as a means of adding an adherent sublimation- suppressing outer layer. Hence, the process is modified by simply lining the inner wall of the die with a foil of the barrier material before filling the die with the thermoelectric powder (see figure).

In preparation for further experiments, the modified process was used to fabricate specimens of n- and p-type skutterudites covered with adherent 25- μm-thick foils of titanium. In the experiments, these specimens were heated in a vacuum under the same conditions as in the experiments described above, then sectioned and examined. Like the niobium foils in those experiments, the titanium foil outer layers in these experiments were found to have suppressed sublimation of Sb.

This work was done by Jeffrey Sakamoto, Thierry Caillat, Jean-Pierre Fleurial, and G. Jeffrey Snyder of Caltech for NASA's Jet Propulsion Laboratory.

This invention is owned by NASA, and a patent application has been filed. Inquiries concerning nonexclusive or exclusive license for its commercial development should be addressed to the Patent Counsel, NASA Management Office–JPL. Refer to NPO-40040.


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Coating Thermoelectric Devices to Suppress Sublimation

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This article first appeared in the September, 2007 issue of NASA Tech Briefs Magazine.

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