Synthesis and Thermoelectric Properties of Tin-Filled Skutterudite, SnxCo4Sb12.

Takizawa, Hirotsugu; Itô, Masayuki; Uheda, Kyota; Endo, Tadashi

doi:10.2109/jcersj.108.1258_530

Cited by 17 publications

(5 citation statements)

References 2 publications

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“…These atoms form a cage-like structure with a large icosahedral void at the 2a site (0, 0, 0), which may accommodate various filler atoms F, including alkaline and alkaline earth metals, lanthanoids, actinoids, as well as halogens or in particular cases Y, Hf, 12,13 Pb and Sn. [14][15][16][17] A ternary skutterudite in the system Ni-Sn-Sb was first reported by Grytsiv et al 18 who defined a wide homogeneity range at 250 °C and 350 °C by establishing the isothermal sections in the Sn-Sb-NiSb-Ni 3 Sn 2 subsystem at these temperatures. Investigations by Mishra et al 19 in the Snrich part of the Ni-Sn-Sb phase diagram suggested that the phase equilibria determined by Grytsiv et al 18 lies within 10 °C above or below the declared temperatures.…”

Section: Introductionmentioning

confidence: 99%

Ba-filled Ni–Sb–Sn based skutterudites with anomalously high lattice thermal conductivity

et al. 2016

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Novel filled skutterudites BayNi4Sb12-xSnx (ymax = 0.93) have been prepared by arc melting followed by annealing at 250, 350 and 450 °C up to 30 days in vacuum-sealed quartz vials. Extension of the homogeneity region, solidus temperatures and structural investigations were performed for the skutterudite phase in the ternary Ni-Sn-Sb and in the quaternary Ba-Ni-Sb-Sn systems. Phase equilibria in the Ni-Sn-Sb system at 450 °C were established by means of Electron Probe Microanalysis (EPMA) and X-ray Powder Diffraction (XPD). With rather small cages Ni4(Sb,Sn)12, the Ba-Ni-Sn-Sb skutterudite system is perfectly suited to study the influence of filler atoms on the phonon thermal conductivity. Single-phase samples with the composition Ni4Sb8.2Sn3.8, Ba0.42Ni4Sb8.2Sn3.8 and Ba0.92Ni4Sb6.7Sn5.3 were used to measure their physical properties, i.e. temperature dependent electrical resistivity, Seebeck coefficient and thermal conductivity. The resistivity data demonstrate a crossover from metallic to semiconducting behaviour. The corresponding gap width was extracted from the maxima in the Seebeck coefficient data as a function of temperature. Single crystal X-ray structure analyses at 100, 200 and 300 K revealed the thermal expansion coefficients as well as Einstein and Debye temperatures for Ba0.73Ni4Sb8.1Sn3.9 and Ba0.95Ni4Sb6.1Sn5.9. These data were in accordance with the Debye temperatures obtained from the specific heat (4.4 K < T < 140 K) and Mössbauer spectroscopy (10 K < T < 290 K). Rather small atom displacement parameters for the Ba filler atoms indicate a severe reduction in the "rattling behaviour" consistent with the high levels of lattice thermal conductivity. The elastic moduli, collected from Resonant Ultrasonic Spectroscopy ranged from 100 GPa for Ni4Sb8.2Sn3.8 to 116 GPa for Ba0.92Ni4Sb6.7Sn5.3. The thermal expansion coefficients were 11.8 × 10(-6) K(-1) for Ni4Sb8.2Sn3.8 and 13.8 × 10(-6) K(-1) for Ba0.92Ni4Sb6.7Sn5.3. The room temperature Vickers hardness values vary within the range from 2.6 GPa to 4.7 GPa. Severe plastic deformation via high-pressure torsion was used to introduce nanostructuring; however, the physical properties before and after HPT showed no significant effect on the materials thermoelectric behaviour.

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Section: Introductionmentioning

confidence: 99%

Ba-filled Ni–Sb–Sn based skutterudites with anomalously high lattice thermal conductivity

et al. 2016

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“…The latter is a consequence of the rattling of the Ln atom situated in a large icosahedral void of the three-dimensional Sb atom network. The combination of these properties results in an unprecedented figure-of-merit of 1.4 (at 730 °C). − …”

Section: Introductionmentioning

confidence: 99%

MA_δSb_2-_δ (M = Zr, Hf; A = Si, Ge): A New Series of Ternary Antimonides and Not “β-ZrSb₂”

2003

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The ternary antimonides ZrSi δ Sb 2-δ , HfGe δ Sb 2-δ , and ZrGe δ Sb 2-δ were prepared by annealing of the elements in stoichiometric ratios below 800 °C. ZrSi δ Sb 2-δ was earlier erroneously described as the binary "β-ZrSb 2 ", which does not exist as such, because the incorporation of tetrel atoms is necessary for the formation of this structure. ZrSi δ Sb 2-δ has a small yet significant phase width with at least 0.066(7) e δ e 0.115(3), whereas the Ge analogues exist with larger tetrel concentration, i.e., ZrGe 0.211(5) Sb 1.789 and HfGe 0.205(6) Sb 1.795 . The whole series of title compounds crystallizes in the Co 2 Si type (space group Pnma), with lattice dimensions of, e.g., for ZrGe 0.211(5) Sb 1.789 , a ) 730.4(1) pm, b ) 395.13(6) pm, c ) 957.6(2) pm, V ) 0.27635(7) nm 3 , Z ) 4. The anionic substructure comprises infinite ribbons formed by the atom sites Q1 and Sb2, with Q1 being mixed occupied by Si or Ge and Sb atoms. These ribbons exhibit Q1−Q1 single bonds and Q1−Sb2 "half" bonds. Assuming the validity of the 8 − N rule, one can assign seven valence-electrons to Sb2 but only five to Q1, which might explain the preference of the tetrel atoms for the latter site.

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“…Skutterudites crystallize in the structure type of CoAs 3 (space group I m 3) of which the LaFe 4 P 12 structure is a filled variant. The chemical formula of these compounds can be described as E y T 4 X 12 , where T is a transition element of the VIII group in the 8c position (1/4, 1/4, 1/4); E occupies the icosahedral hole position 2a (0, 0, 0) which can be filled by a number of electropositive elements such as Ca, Sr, Ba, Tl, lanthanides and actinides, or under special conditions by Y, Hf [1,2] Pb and Sn [3][4][5][6] (high-pressure or multilayer precursor methods) and Na in nanowire state [7]; X is a pnictogen or one of the IVA-VIA elements at the 24g site (0, y, z). It is interesting to note that Sn atoms were found to be able to occupy the 24g site (Co 4 Sb 12−y Sn y [8], CoSn 6 Te 6 [9], La 1−x Co 4 Sb 12−y Sn y [10], Yb 1−x Co 4 Sb 12−y Sn y [11], Tl 1−x Co 4 Sb 12−y Sn y [12]) as well as the 2a site (Sn 1−x Fe 4 Sb 12 [13], Sn 1−x Co 4 Sb 12 [3][4][5][6]): Sn-filled skutterudites are generally characterized by an anomalously large isotropic atomic displacement parameter for tin in the 2a position.…”

Section: Introductionmentioning

confidence: 99%

A novel skutterudite phase in the Ni$ndash$Sb$ndash$Sn system: phase equilibria and physical properties

Grytsiv

Rogl

Berger

et al. 2002

J. Phys.: Condens. Matter

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A novel ternary phase, SnyNi4Sb12−xSnx, has been characterized and found to exhibit a wide range of homogeneity (at 250 °C, 2.4 ≤ x ≤ 5.6, 0 ≤ y ≤ 0.31; at 350 °C, 2.7 ≤ x ≤ 5.0, 0 ≤ y ≤ 0.27). SnyNi4Sb12−xSnx crystallizes in a skutterudite-based structure in which Sn atoms are found to occupy two crystallographically inequivalent sites: (a) Sn and Sb atoms randomly share the 24g site; and (b) a small fraction of Sn atoms occupy the 2a (0, 0, 0) position, with an anomalously large isotropic atomic displacement parameter. Eu0.8Ni4Sb5.8Sn6.2, Yb0.6Ni4Sb6.7Sn5.3 and Ni4As9.1Ge2.9 are isotypic skutterudites. Depending on the particular composition, metallic as well as semiconducting states appear. The crossover from semiconducting to metallic behaviour is discussed in terms of a temperature-dependent carrier concentration employing a simple model density of states with the Fermi energy slightly below a narrow energy gap. This model accounts for the peculiar temperature-dependent electrical resistivity. These skutterudites are characterized by a number of lattice vibrations, which were elucidated by Raman measurements and compared to the specific heat data. The Eu-containing compound exhibits long-range magnetic order at Tmag ≈ 6 K, arising from the Eu2+ ground state.

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Synthesis and Thermoelectric Properties of Tin-Filled Skutterudite, SnxCo4Sb12.

Cited by 17 publications

References 2 publications

Ba-filled Ni–Sb–Sn based skutterudites with anomalously high lattice thermal conductivity

Ba-filled Ni–Sb–Sn based skutterudites with anomalously high lattice thermal conductivity

MA_δSb_2-_δ (M = Zr, Hf; A = Si, Ge): A New Series of Ternary Antimonides and Not “β-ZrSb₂”

A novel skutterudite phase in the Ni$ndash$Sb$ndash$Sn system: phase equilibria and physical properties

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Synthesis and Thermoelectric Properties of Tin-Filled Skutterudite, SnxCo4Sb12.

Cited by 17 publications

References 2 publications

Ba-filled Ni–Sb–Sn based skutterudites with anomalously high lattice thermal conductivity

Ba-filled Ni–Sb–Sn based skutterudites with anomalously high lattice thermal conductivity

MAδSb2-δ (M = Zr, Hf; A = Si, Ge): A New Series of Ternary Antimonides and Not “β-ZrSb2”

A novel skutterudite phase in the Ni$ndash$Sb$ndash$Sn system: phase equilibria and physical properties

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MA_δSb_2-_δ (M = Zr, Hf; A = Si, Ge): A New Series of Ternary Antimonides and Not “β-ZrSb₂”