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Synthesis and Characterization of Rare-Earth Tellurides and Their Composites For High-Temperature Thermoelectric Applications

  • Author(s): Cheikh, Dean
  • Advisor(s): Dunn, Bruce S
  • Bux, Sabah K
  • et al.
Abstract

Radioisotope thermoelectric generators (RTGs) are solid-state energy conversion devices and have been a vital power generation technology for deep space missions conducted by the National Aeronautics and Space Administration (NASA). At the heart of these generators are thermoelectric materials that convert heat given off by a radioisotope decay into electricity through the Seebeck effect. While these systems have demonstrated long-term reliability, the current state-of-practice materials have thermoelectric figures of merit, ZT, near 1, leading to low system level efficiencies of ~6.5%. The figure of merit is defined as ??=??2? where σ, S, κ, and T are electrical conductivity, Seebeck coefficient, thermal conductivity, and temperature, respectively. Development of higher ZT materials would enable future NASA missions to perform a greater number of scientific experiments and extend mission lifetimes.

Lanthanum telluride (La3-xTe4) is a state-of-the-art n-type high-temperature thermoelectric material, with a ZT of 1.1 at 1275 K. It has been demonstrated that the electrical resistivity and Seebeck coefficient of this material can be decoupled when nickel inclusions are added to form a composite. This new phenomenon, known as composite assisted funneling of electrons (CAFE), allows for the resistivity of the composite to decrease while leaving the Seebeck coefficient unaffected when 12-15 vol% nickel was incorporated.

The initial work presented in this dissertation focused on microstructural modifications to La3-xTe4-Ni composites to attain a better understanding of the CAFE mechanism. This investigation was conducted by varying the size of the nickel particles compared to what were used in the previous composite study. A 60% increase in ZT to a value of 1.9 at 1200 K for the composites with the smallest Ni particle size was obtained due to an increased Seebeck coefficient and decreased thermal conductivity.

The next study focused on the extension of the CAFE effect in La3-xTe4 to use inclusions other than nickel. Cobalt of a similar size to the nickel in the initial La3-xTe4-Ni composite work was used. A series of La3-xTe4-Co composites were synthesized and their thermoelectric properties characterized. A gradual decrease in resistivity was observed above 8 vol% cobalt, suggesting the CAFE mechanism was occurring. An 18% increase to the Seebeck coefficient was observed between 5-8 vol% cobalt, likely due to contamination on the cobalt powder, altering the carrier concentration of the matrix. The increase to the Seebeck coefficient allowed for a ZT of 1.5 at 1225 K to be achieved at 5 vol% cobalt.

The final investigation in this dissertation focused on the synthesis and thermoelectric characterization of praseodymium telluride (Pr3-xTe4). Density functional theory (DFT) calculations predicted a large peak in the density of states (DOS) of Pr3-xTe4 at its Fermi level compared to La3-xTe4, due to the 4f electrons of praseodymium. This change in the band structure was predicted to increase the Seebeck coefficient of Pr3-xTe4 over La3-xTe4. A series of Pr3-xTe4 with varying vacancy concentrations were mechanochemically synthesized and characterized. A 25% improvement in the Seebeck coefficient and 25% decrease in the thermal conductivity compared to La3-xTe4 was observed. The thermoelectric properties were found to optimize at a composition of Pr2.74Te4, reaching a ZT of 1.7 at 1200 K.

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