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

Abstract

Here, in this study, novel filled skutterudites Ba yNi 4Sb 12-xSn x (y max = 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 Ni 4(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 Ni 4Sb 8.2Sn 3.8, Ba 0.42Ni 4Sb 8.2Sn 3.8 and Ba 0.92Ni 4Sb 6.7Sn 5.3 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 andmore » Debye temperatures for Ba 0.73Ni 4Sb 8.1Sn 3.9 and Ba 0.95Ni 4Sb 6.1Sn 5.9. 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 Ni 4Sb 8.2Sn 3.8 to 116 GPa for Ba 0.92Ni 4Sb 6.7Sn 5.3. The thermal expansion coefficients were 11.8 × 10 -6 K -1 for Ni 4Sb 8.2Sn 3.8 and 13.8 × 10 -6 K -1 for Ba 0.92Ni 4Sb 6.7Sn 5.3. The room temperature Vickers hardness values vary within the range from 2.6 GPa to 4.7 GPa. Lastly, 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.« less

Authors:
 [1];  [2];  [3];  [4];  [4];  [4];  [1];  [5];  [6];  [1];  [4];  [7];  [8];  [1];  [1];  [9]
  1. Univ. of Vienna (Austria)
  2. Univ. of Vienna (Austria); Christian Doppler Laboratory for Thermoelectricity, Vienna (Austria); Technische Universitat Wien (Vienna University of Technology), Austria
  3. Univ. of Vienna (Austria); Christian Doppler Laboratory for Thermoelectricity, Vienna (Austria);Technische Universitat Wien (Vienna University of Technology), Austria
  4. Technische Universitat Wien (Vienna University of Technology), Austria
  5. Julich Research Centre (Germany). Julich Centre for Neutron Science (JCNS)
  6. Julich Research Centre (Germany). Julich Centre for Neutron Science (JCNS); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  7. Masaryk University, Brno (Czech Republic)
  8. Christian Doppler Laboratory for Thermoelectricity, Vienna (Austria); Technische Universitat Wien (Vienna University of Technology), Austria
  9. Univ. of Vienna (Austria); Christian Doppler Laboratory for Thermoelectricity, Vienna (Austria)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1302928
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 45; Journal Issue: 27; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Paschinger, W., Rogl, Gerda, Grytsiv, A., Michor, H., Heinrich, P. R., Mueller, H., Puchegger, S., Klobes, B., Hermann, Raphael P., Reinecker, M., Eisenmenger-Sitter, Ch., Broz, P., Bauer, Ernst, Giester, G., Zehetbauer, M., and Rogl, Peter F. Ba-filled Ni–Sb–Sn based skutterudites with anomalously high lattice thermal conductivity. United States: N. p., 2016. Web. doi:10.1039/C6DT01298A.
Paschinger, W., Rogl, Gerda, Grytsiv, A., Michor, H., Heinrich, P. R., Mueller, H., Puchegger, S., Klobes, B., Hermann, Raphael P., Reinecker, M., Eisenmenger-Sitter, Ch., Broz, P., Bauer, Ernst, Giester, G., Zehetbauer, M., & Rogl, Peter F. Ba-filled Ni–Sb–Sn based skutterudites with anomalously high lattice thermal conductivity. United States. doi:10.1039/C6DT01298A.
Paschinger, W., Rogl, Gerda, Grytsiv, A., Michor, H., Heinrich, P. R., Mueller, H., Puchegger, S., Klobes, B., Hermann, Raphael P., Reinecker, M., Eisenmenger-Sitter, Ch., Broz, P., Bauer, Ernst, Giester, G., Zehetbauer, M., and Rogl, Peter F. 2016. "Ba-filled Ni–Sb–Sn based skutterudites with anomalously high lattice thermal conductivity". United States. doi:10.1039/C6DT01298A. https://www.osti.gov/servlets/purl/1302928.
@article{osti_1302928,
title = {Ba-filled Ni–Sb–Sn based skutterudites with anomalously high lattice thermal conductivity},
author = {Paschinger, W. and Rogl, Gerda and Grytsiv, A. and Michor, H. and Heinrich, P. R. and Mueller, H. and Puchegger, S. and Klobes, B. and Hermann, Raphael P. and Reinecker, M. and Eisenmenger-Sitter, Ch. and Broz, P. and Bauer, Ernst and Giester, G. and Zehetbauer, M. and Rogl, Peter F.},
abstractNote = {Here, in this study, 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. Lastly, 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.},
doi = {10.1039/C6DT01298A},
journal = {Dalton Transactions},
number = 27,
volume = 45,
place = {United States},
year = 2016,
month = 6
}

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  • The great reduction in thermal conductivity of skutterudites upon filling the ''void'' sites with rare-earth (RE) ions is key to their favorable thermoelectric properties but remains to be understood. Using lattice dynamic models based on first-principles calculations, we address the most popular microscopic mechanism, reduction via rattling ions. The model withstands inelastic neutron scattering and specific-heat measurements, and refutes hypotheses of an anharmonic RE potential and of two distinct localized RE vibrations of disparate frequencies. It does indicate a strong hybridization between bare La vibrations and certain Sb-like phonon branches, suggesting anharmonic scattering by harmonic RE motions as an importantmore » mechanism for suppression of heat conductivity. (c) 2000 The American Physical Society.« less
  • We report a phenomenological model to calculate the high-temperature lattice thermal conductivity of filled skutterudite antimonides. The model needs no phonon resonant scattering terms. Instead, we assume that umklapp processes dominate the high-temperature phonon scattering. In order to represent the anharmonicity introduced by the filling atom, we introduce a Gaussian term into the relaxation time of the umklapp process. The developed model agrees remarkably well with the experimental results of RE{sub f}Co{sub 4}Sb{sub 12} and RE{sub f}Fe{sub 4}Sb{sub 12} (RE = Yb, Ba, and Ca) alloys. To further test the validity of our model, we calculate the lattice thermal conductivity of nanostructuredmore » or multi-filled skutterudites. The calculation results are also in good agreement with experiment, increasing our confidence in the developed anharmonicity model.« less
  • The relations between the thermal conductivity of cagelike structures and their crystal parameters are investigated using a two-dimensional toy model. The model consists of host atoms on a rectangular lattice with fillers at the center of each rectangle. The effect of mass and size of the filler on thermal conductivity is investigated using equilibrium molecular-dynamics simulations. We show that the thermal conductivity decreases with increasing atomic displacement parameter while it has local minima versus the filler to host mass ratio. Similar trends were observed in experiments on filled skutterudites. The trends are explained by analyzing the effect of the fillermore » on the phonon dispersion and relaxation times of the host material.« less