High temperature thermoelectric efficiency in Ba8Ga16Ge30

The high thermoelectric figure of merit (zT) of Ba8Ga16Ge30 makes it one of the best n-type materials for thermoelectric power generation. Here, we describe the synthesis and characterization of a Czochralski pulled single crystal of Ba8Ga16Ge30 and polycrystalline disks. Measurements of the electrical conductivity, Hall effect, specific heat, coefficient of thermal expansion, thermal conductivity, and Seebeck coefficient were performed up to 1173 K and compared with literature results. Dilatometry measurements give a coefficient of thermal expansion of 16×10^−6 K^−1 up to 1175 K. The trend in electronic properties with composition is typical of a heavily doped semiconductor. The maximum in the thermoelectric figure of merit is found at 1050 K with a value of 0.8. The correction of zT due to thermal expansion is not significant compared to the measurement uncertainties involved. Comparing the thermoelectric efficiency of segmented materials, the effect of compatibility makes Ba8Ga16Ge30 more efficient than the higher zT n-type materials SiGe or skutterudite CoSb3

Lattice thermal conductivity of self-assembled PbTe-Sb_2Te_3 composites with nanometer lamellae

In the system of PbTe and Sb_2Te_3, a metastable compound Pb_2Sb_6Te_(11) appears by solidification processing. It has been reported that this compound is decomposed into the two immiscible thermoelectric materials forming nanosized lamellar structure by heat treatments. The fraction transformed and the inter-lamellar spacing was systematically investigated. In this work, the thermal conductivities and the electrical resistivities have been measured as functions of annealing time through the transformation and the coarsening processes to clarify the effect of the fraction transformed and the inter-lamellar spacing. The thermal conductivity of Pb_2Sb_6Te_(11) is lower than that after the decomposition. The lattice part of the thermal conductivity of PbTe/Sb_2Te_3 lamellar samples decreases with decreasing inter-lamellar spacing. This is considered to be due to the coarsening of the microstructure

Engineering the Next Generation of Solid State Proton Conductors: Synthesis and Properties of Ba_(3−x)K_(x)H_(x)(PO_4)_2

A new series of compounds with general chemical formula Ba_(3−x)K_(x)H_(x)(PO_4)_2 has been successfully prepared. This particular stoichiometry was targeted as a candidate solid-state proton conductor because of its anticipated structural similarity to known M_(3)H(XO_4)_2 superprotonic conductors (M = Cs, Rb, NH4, K; X = Se, S) and to the known trigonal compound Ba_(3)(PO_4)_2. The materials were synthesized from aqueous solution using barium acetate, dipotassium hydrogen phosphate, and potassium hydroxide as starting materials. Through variations in the initial solution stoichiometry or the synthesis temperature, the final stoichiometry could be controlled from x ~ 0.5 to ~1. X-ray powder diffraction, energy dispersive spectroscopy chemical analysis, ^(1)H magic angle spinning (MAS) nuclear magnetic spectroscopy, and thermogravimetric analysis were all employed to establish potassium and proton incorporation. The diffraction data confirmed crystallization of a trigonal phase, and chemical analysis showed the (Ba+K):P ratio to be 3:2, consistent with the target stoichiometry. The conductivity of the Ba_(3−x)K_(x)H_(x)(PO_4)_2 materials, as measured by A.C. impedance spectroscopy, is about 3 orders of magnitude greater than the end-member Ba_(3)(PO_4)_2 material with only a slight dependence on x, however, it is substantially lower than that of typical superprotonic conductors and of the M_(3)H(XO_4)_2 materials in particular. The close proximity of Ba to the hydrogen bond site is proposed to explain this behavior. At 250 °C, the conductivity is 2.4 × 10^(−5) S/cm for the composition x = 0.80, which, when combined with the water insolubility and the relatively high thermal stability, may render Ba_(3−x)K_(x)H_(x)(PO_4)_2 an attractive alternative in selected electrochemical applications to known superprotonic conductors

High-Temperature Transport Properties of the Zintl Phases Yb_(11)GaSb_9 and Yb_(11)InSb_9

Two rare-earth Zintl phases, Yb_(11)GaSb_9 and Yb_(11)InSb_9, were synthesized in high-temperature self-fluxes of molten Ga and In, respectively. Structures were characterized by both single-crystal X-ray diffraction and powder X-ray diffraction and are consistent with the published orthorhombic structure, with the space group Iba2. High-temperature differential scanning calorimetry (DSC) and thermal gravimetry (TG) measurements reveal thermal stability to 1300 K. Seebeck coefficient and resistivity measurements to 1000 K are consistent with the hypothesis that Yb_(11)GaSb_9 and Yb_(11)InSb_9 are small band gap semiconductors or semimetals. Low doping levels lead to bipolar conduction at high temperature, preventing a detailed analysis of the transport properties. Thermal diffusivity measurements yield particularly low lattice thermal conductivity values, less than 0.6 W/m K for both compounds. The low lattice thermal conductivity suggests that Yb_(11)MSb_9 (M = Ga, In) has the potential for high thermoelectric efficiency at high temperature if charge-carrier doping can be controlled

Magnetodielectric coupling in Mn3O4

We have investigated the dielectric anomalies associated with spin ordering transitions in the tetragonal spinel Mn$_3$O$_4$, using thermodynamic, magnetic, and dielectric measurements. We find that two of the three magnetic ordering transitions in Mn$_3$O$_4$ lead to decreases in the temperature dependent dielectric constant at zero applied field. Applying a magnetic field to the polycrystalline sample leaves these two dielectric anomalies practically unchanged, but leads to an increase in the dielectric constant at the intermediate spin-ordering transition. We discuss possible origins for this magnetodielectric behavior in terms of spin-phonon coupling. Band structure calculations suggest that in its ferrimagnetic state, Mn$_3$O$_4$ corresponds to a semiconductor with no orbital degeneracy due to strong Jahn-Teller distortion.Comment: 6 pages, 7 figure

Synthesis, structure, magnetism, and high temperature thermoelectric properties of Ge doped Yb_(14)MnSb_(11)

The Zintl phase Yb_(14)MnSb_(11) was successfully doped with Ge utilizing a tin flux technique. The stoichiometry was determined by microprobe analysis to be Yb_(13.99(14))Mn_(1.05(5))Sb_(10.89(16))Ge_(0.06(3)). This was the maximum amount of Ge that could be incorporated into the structure via flux synthesis regardless of the amount included in the reaction. Single crystal X-ray diffraction could not unambiguously determine the site occupancy for Ge. Bond lengths varied by about 1% or less, compared with the undoped structure, suggesting that the small amount of Ge dopant does not significantly perturb the structure. Differential scanning calorimetry/thermogravimetry (DSC/TG) show that the doped compound's melting point is greater than 1200 K. The electrical resistivity and magnetism are virtually unchanged from the parent material, suggesting that Yb is present as Yb^(2+) and that the Ge dopant has little effect on the magnetic structure. At 900 K the resistivity and Seebeck coefficient decrease resulting in a zT of 0.45 at 1100 K, significantly lower than the undoped compound