Graduation Year

2018

Document Type

Thesis

Degree

M.S.

Degree Name

Master of Science (M.S.)

Degree Granting Department

Physics

Major Professor

George S. Nolas, Ph.D.

Committee Member

Lillia M. Woods, Ph.D.

Committee Member

Sarath Witanachchi, Ph.D.

Keywords

enhanced ZT, figure of merit, lone-pair, phonon scattering

Abstract

Sustainable and renewable energy is an incredibly important area in today’s society and investigation into avenues to improve this wide ranging technology are underway in many different fields. Thermoelectric devices possess the ability for the direct solid-state interconversion of heat and electrical power, which not only allows for sustainable refrigeration but also waste heat recovery. One current restriction on the efficiency of thermoelectric devices is the disparity in thermoelectric performance of p-type and n-type materials. Furthermore, a key physical attribute shared by the majority of high performing thermoelectric materials is low thermal conductivity. Thus in this thesis three separate p-type material systems exhibiting low thermal conductivity will be discussed. The Cu-excessed quaternary chalcogenides, CuM2InTe4 (M = Zn, Cd), and ternary chalcogenide, CuSbS2, were investigated due to their intrinsically low thermal conductivity. Whereas, skutterudites typically have good electrical properties but do not exhibit an intrinsically low thermal conductivity. Nevertheless low thermal conductivity can be achieved by taking advantage of their unique crystal structure by filling large voids with loosely bound atoms that act as phonon scattering centers. Therefore double-filled Fe substituted skutterudites with nominal compositions Yb0.4In0.02Co3FeSb12 and Yb0.8In0.02Co2.5Fe1.5Sb12 were also investigated.

The CuM2InTe4 (M = Zn, Cd) and skutterudite specimens were synthesized by direct reactions, whereas the CuSbS2 specimens were synthesized by mechanical alloying. Structural and stoichiometric compositions were analyzed by a combination of X-ray diffraction, Rietveld refinement and energy dispersive spectroscopy. High-temperature transport properties were measured for all specimens and will be discussed in detail.

The Cu-excessed quaternary chalcogenides display intrinsically low thermal conductivity that appears to be unaffected by the change in electrical properties that is a result of differing stoichiometries. This may provide a possible route to furthering the enhancement of the thermoelectric properties of these materials. Similarly the CuSbS2 ternary chalcogenides display a very low thermal conductivity due to stereochemically active lone-pair electrons and would potentially allow an optimization of the power factor without a significant increase of the very low thermal conductivity, thus improving the figure of merit. For the case of p-type skutterudites, (Yb, In) double-filled skutterudites have a maximum ZT of 0.6, which is promising in the hunt for improved p-type materials. This fundamental investigation provides insight that can lead to a deeper understanding of all three material systems outlined in this thesis and provides a platform for new research in the quest for materials suitable for thermoelectric applications.

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