▪ Abstract Recently there has been a resurgence of research efforts related to the investigation of new and novel materials for small-scale thermoelectric refrigeration and power generation applications. These materials need to couple and optimize a variety of properties in order to exhibit the necessary figure of merit, i.e. the numerical expression that is commonly used to compare one potential thermoelectric material with another. The figure of merit is related to the coefficient of performance or efficiency of a particular device made from a material. The best thermoelectric material should possess thermal properties similar to that of a glass and electrical properties similar to that of a perfect single-crystal material, i.e. a poor thermal conductor and a good electrical conductor. Skutterudites are materials that appear to have the potential to fulfill such criteria. These materials exhibit many types of interesting properties. For example, skutterudites are members of a family of compounds we call...

SKUTTERUDITES : A phonon-glass-electron crystal approach to advanced thermoelectric energy conversion applications

This review highlights the use and great potential of liquid metals as exotic and powerful solvents (i.e. fluxes) for the synthesis of intermetallic phases. The results presented demonstrate that considerable advances in the discovery of novel and complex phases are achievable utilizing molten metals as solvents. A wide cross-section of examples of flux-grown intermetallic phases and related solids are discussed and a brief history of the origins of flux chemistry is given. The most commonly used metal fluxes are surveyed and where possible, the underlying principal reasons that make the flux reaction work are discussed.

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The metal flux: a preparative tool for the exploration of intermetallic compounds.

Publisher Summary This chapter describes the relevant physical, chemical, and materials issues pertaining to skutterudites and includes the latest exciting developments. As the search for novel, promising thermoelectrics intensifies; skutterudites have emerged as prospective candidates for achieving figures of merit well in excess of unity. The name “skutterudite” is derived from a small mining town in Norway called “Skutterud,” where a CoAs3-based mineral had been mined extensively. The compounds identical in structure to CoAs3—the structures first identified by Oftedal in 1928—have since been known as skutterudites. Skutterudite structure offers interesting possibilities to alter both the electronic and lattice properties. The chapter discusses the structural aspects and bonding of binary skutterudites and filled skutterudites. The inability to prepare pure binary skutterudites with transition metals other than those of the Co group does not mean that cobalt cannot be partially replaced by its immediate neighbors in the periodic table—iron and nickel. The lattice thermal conductivity is one of the key parameters determining the thermoelectric figure of merit. It is, thus, essential to understand the lattice dynamics in skutterudites and to have a good grasp of the phonon density of states. Skutterudites are compounds with the highest pnicogen concentration forming stable compounds with Co, Rh, and Ir at ambient conditions. The fundamental point about the binary skutterudites is that they are diamagnetic solids.

Chapter 5 Skutterudites: Prospective novel thermoelectrics

Fully filled skutterudites RFe_(4)Sb_(12) (R = Ca, Sr, Ba, La, Ce, Pr, Nd, Eu, and Yb) have been prepared and the high-temperature electrical and thermal transport properties are investigated systematically. Lattice constants of RFe_(4)Sb_(12) increase almost linearly with increasing the ionic radii of the fillers, while the lattice expansion in filled structure is weakly influenced by the filler valence charge states. Using simple charge counting, the hole concentration in RFe_(4)Sb_(12) with divalent fillers (R = Ca, Sr, Ba, Eu, and Yb) is much higher than that in RFe4Sb12 with trivalent fillers (R = La, Ce, Pr, and Nd), resulting in relatively high electrical conductivity and low Seebeck coefficient. It is also found that RFe_(4)Sb_(12) filled skutterudites having similar filler valence charge states exhibit comparable electrical conductivity and Seebeck coefficient, and the behavior of the temperature dependence, thereby leading to comparable power factor values in the temperature range from 300 to 800 K. All RFe_(4)Sb_(12) samples possess low lattice thermal conductivity. The correlation between the lattice thermal resistivity WL and ionic radii of the fillers is discussed and a good relationship of W_L ~ (r_(cage)−r_(ion))^3 is observed in lanthanide metal filled skutterudites. CeFe_(4)Sb_(12), PrFe_(4)Sb_(12), and NdFe_(4)Sb_(12) show the highest thermoelectric figure of merit around 0.87 at 750 K among all the filled skutterudites studied in this work.

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High-temperature electrical and thermal transport properties of fully filled skutterudites RFe4Sb12 (R = Ca, Sr, Ba, La, Ce, Pr, Nd, Eu, and Yb)

Thermal conductivity, resistivity, Seebeck coefficient, and structure measurements of CoSb3 with tin interstitially placed in the voids are reported. These tin-filled skutterudites were synthesized under high pressure and temperature conditions; they cannot be synthesized under “normal” synthesis approaches. The tin atoms exhibit very large atomic displacement parameters indicating a large “rattling” motion inside their atomic “cages.” The disorder induced by the Sn atoms is a very good phonon scattering mechanism. The thermal conductivity of these compounds is very low with a temperature dependence that is atypical of simple solids. The tin-filled compounds exhibit n-type semiconducting behavior with relatively high Seebeck coefficients for compounds whose electronic properties have not been optimized. The potential for thermoelectric applications is discussed.

Thermoelectric properties of Sn-filled skutterudites

We have synthesized a series of stable and metastable rare earth element−iron antimonides, controlling both composition and structure using multilayer reactants. The stable rare earth iron element antimonides have the filled skutterudite structure (LaFe4P12) with a stoichiometry of 1 for the rare earth element. The metastable rare earth element−iron antimonides could be prepared with the entire sequence of rare earth elements. The lattice parameters of these metastable compounds were always larger than those of the corresponding more stable analog, and the occupancy of the rare earth element cation was found to be less than 1. Reitveld analysis of Lu1-xFe4Sb12 suggests that the late rare earth element compounds have a new distorted filled skutterudite structure. Structural trends are discussed in terms of their potential use as thermoelectric materials.

Julie H. Edvalson

Papers

Systematic Study of New Rare Earth Element−Iron−Antimony Skutterudites Synthesized Using Multilayer Precursors

Systematic Study of New Rare Earth Element‐Iron‐Antimony Skutterudites Synthesized Using Multilayer Precursors.