Multifilled nanocrystalline p-type didymium – Skutterudites with ZT > 1.2

Abstract The influence of double, triple and multi-filling of didymium, Ca, Ba, Sr and Yb in Fe 3 CoSb 12 on the thermoelectric performance was investigated. Ball-milling followed by hot pressing was used for sample preparation to gain dense and nanostructured samples. Almost all of the samples studied in this work have a ZT higher than 1, some even reach ZT > 1.2 at 700 K or at 800 K and an average ZT up to 1.0 in the temperature range from 300 K to 800 K. Thermal expansion, hardness and the elastic moduli were investigated exemplarily for two alloys with ZT > 1.2. With these results we can claim to have very promising p-type skutterudites for thermoelectric devices.

[1]  Tiejun Zhu,et al.  Nanostructuring and thermoelectric properties of bulk skutterudite compound CoSb3 , 2007 .

[2]  M. B. Maple,et al.  Thermal expansion of skutterudites , 2010 .

[3]  George S. Nolas,et al.  High figure of merit in Eu-filled CoSb3-based skutterudites , 2002 .

[4]  G. J. Snyder,et al.  Complex thermoelectric materials. , 2008, Nature materials.

[5]  A. Borshchevsky,et al.  High figure of merit in Ce-filled skutterudites , 1996, Fifteenth International Conference on Thermoelectrics. Proceedings ICT '96.

[6]  Mukherjee,et al.  Thermal expansion study of ordered and disordered Fe3Al: An effective approach for the determination of vibrational entropy. , 1996, Physical review letters.

[7]  C. Uher,et al.  Low thermal conductivity and high thermoelectric figure of merit in n-type BaxYbyCo4Sb12 double-filled skutterudites , 2008 .

[8]  C. Uher,et al.  CERIUM FILLING AND DOPING OF COBALT TRIANTIMONIDE , 1997 .

[9]  Han Li,et al.  Synthesis and thermoelectric properties of double-atom-filled skutterudite compounds CamCenFexCo4−xSb12 , 2006 .

[10]  R. K. Williams,et al.  Filled Skutterudite Antimonides: A New Class of Thermoelectric Materials , 1996, Science.

[11]  B. Sales,et al.  FILLED SKUTTERUDITE ANTIMONIDES : ELECTRON CRYSTALS AND PHONON GLASSES , 1997 .

[12]  Filled skutterudite antimonides: Validation of the electron-crystal phonon-glass approach to new thermoelectric materials , 1997 .

[13]  Ctirad Uher,et al.  Skutterudite-Based Thermoelectrics , 2005 .

[14]  Zhifeng Ren,et al.  The great improvement effect of pores on ZT in Co1−xNixSb3 system , 2008 .

[15]  Hannu Mutka,et al.  Breakdown of phonon glass paradigm in La- and Ce-filled Fe4Sb12 skutterudites. , 2008, Nature materials.

[16]  George S. Nolas,et al.  Effect of partial void filling on the lattice thermal conductivity of skutterudites , 1998 .

[17]  Jihui Yang,et al.  Dual-frequency resonant phonon scattering in BaxRyCo4Sb12 （R=La, Ce and Sr） , 2007 .

[18]  Takashi Goto,et al.  Synthesis and thermoelectric properties of p-type- and n-type-filled skutterudite RyMxCo4−xSb12(R:Ce,Ba,Y;M:Fe,Ni) , 2005 .

[19]  Berger,et al.  Crystal field effects and thermoelectric properties of PrFe 4 Sb 12 skutterudite , 2002 .

[20]  A. Grytsiv,et al.  Thermoelectric properties of novel skutterudites with didymium: DDy(Fe1−xCox)4Sb12 and DDy(Fe1−xNix)4Sb12 , 2010 .

[21]  O. Anderson,et al.  A simplified method for calculating the debye temperature from elastic constants , 1963 .

[22]  Y. Pei,et al.  Synthesis and Thermoelectric Properties of (Sr,Yb)yCo4Sb12 Double Filled Skutterudites , 2006, 2006 25th International Conference on Thermoelectrics.

[23]  W. Jeitschko,et al.  LaFe4P12 with filled CoAs3‐type structure and isotypic lanthanoid–transition metal polyphosphides , 1977 .

[24]  Peter Rogl,et al.  A new generation of p-type didymium skutterudites with high ZT , 2011 .

[25]  C. Uher,et al.  Low-temperature transport properties of the filled skutterudites CeFe 4-x Co x Sb 12 s , 1997 .

[26]  L. D. Chen,et al.  Synthesis and thermoelectric properties of Sr-filled skutterudite SryCo4Sb12 , 2006 .

[27]  Lei Zhang,et al.  Synthesis of filled skutterudite compound La0.75Fe3CoSb12 by spark plasma sintering and effect of porosity on thermoelectric properties , 2004 .

[28]  M. Dresselhaus,et al.  New Directions for Low‐Dimensional Thermoelectric Materials , 2007 .

[29]  Jiong Yang,et al.  Enhanced thermoelectric performance of dual-element-filled skutterudites BaxCeyCo4Sb12 , 2009 .

[30]  C. Uher,et al.  Structure and Lattice Thermal Conductivity of Fractionally Filled Skutterudites: Solid Solutions of Fully Filled and Unfilled End Members , 1998 .

[31]  J. Gubicza,et al.  MWP-fit: a program for multiple whole-profile fitting of diffraction peak profiles by ab initio theoretical functions , 2001 .

[32]  George S. Nolas,et al.  High figure of merit in partially filled ytterbium skutterudite materials , 2000 .

[33]  E. Bauer,et al.  Thermoelectric performance of mischmetal skutterudites MmyFe4−xCoxSb12 at elevated temperatures , 2010 .

[34]  G. Meisner,et al.  Predication of an ultrahigh filling fraction for K in CoSb3 , 2006 .

[35]  E. Bauer,et al.  MmFe4Sb12- and CoSb3-based nano-skutterudites prepared by ball milling: Kinetics of formation and transport properties , 2009 .

[36]  E. Bauer,et al.  High thermoelectric performance of triple-filled n-type skutterudites (Sr,Ba,Yb)yCo4Sb12 , 2009 .

[37]  Jingfeng Li,et al.  Thermoelectric property of fine-grained CoSb3 skutterudite compound fabricated by mechanical alloying and spark plasma sintering , 2007 .

[38]  H. Hng,et al.  Synthesis and high temperature thermoelectric properties of calcium and cerium double-filled skutterudites Ca0.1CexCo4Sb12 , 2009 .

[39]  H. Kabelka,et al.  Mechanical properties of filled antimonide skutterudites , 2010 .

[40]  Jihui Yang,et al.  Thermoelectric Properties of n-Type Multiple-Filled Skutterudites , 2009 .

[41]  G. A. Slack,et al.  Some properties of semiconducting IrSb3 , 1994 .

[42]  Tamás Ungár,et al.  Correlation between strength and microstructure of ball-milled Al–Mg alloys determined by X-ray diffraction , 2004 .

[43]  D. Bérardan,et al.  Double filling in skutterudites: A promising path to improved thermoelectric properties , 2006 .

[44]  Yan Li,et al.  Nanostructures and enhanced thermoelectric properties in Ce-filled skutterudite bulk materials , 2006 .