Synthesis and thermoelectric properties of double-atom-filled skutterudite compounds CamCenFexCo4−xSb12

Single-phase CamCenFexCo4−xSb12 compounds filled by Ca and Ce were synthesized by using melting-quench-diffusion annealing reaction method. The structure and thermoelectric properties of double atoms filled skutterudite compounds were investigated. The results of Rietveld refinement indicate high reliabilities of filling fractions consistent with the inductively coupled plasma atomic emission spectrometry (ICP-AES) analysis, CamCenFexCo4−xSb12 compounds possess skutterudite structure, and Sb-icosahedron voids were filled with Ca or Ce. The thermal parameter BCa∕Ce (6.0) of Ca∕Ce is much larger than that of BSb (0.3) and BFe∕Co (0.3) of Sb and Fe∕Co. The specific chemical states of atoms were obtained from x-ray photoelectron spectroscopy quantitative analysis, which shows that Sb has five chemical states and the relative content is correlative with the total filling fraction; the filling atoms have three filling positions and tend to fill the center position of the Sb-icosahedron voids, preferentially. Wi...

[1]  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 .

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

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

[4]  G. Nolas,et al.  Thermoelectric properties of Yb-filled Ge-compensated CoSb3 skutterudite materials , 2005 .

[5]  G. Kotzyba,et al.  Crystal Structure and Properties of Some Filled and Unfilled Skutterudites: GdFe4P12, SmFe4P12, NdFe4As12, Eu0.54Co4Sb12, Fe0.5Ni0.5P3, CoP3, and NiP3 , 2000 .

[6]  D. Rowe.  CRC Handbook of Thermoelectrics , 1995 .

[7]  T. Hirai,et al.  Synthesis and thermoelectric properties of p-type barium-filled skutterudite Ba_yFe_xCo_4−xSb_12 , 2002 .

[8]  E. Bauer,et al.  Evidence for rattling behavior of the filler atom(L)in the filled skutteruditesLT4X12(L=Ce,Eu,Yb;T=Fe,Ru;X=P,Sb)from EXAFS studies , 2004 .

[9]  S. Alvarez,et al.  Importance of the X4 ring orbitals for the semiconducting, metallic, or superconducting properties of skutterudites MX3 and RM4X12 , 1990 .

[10]  H. Sugawara,et al.  Transport and thermal properties of Ce- and Pr-filled skutterudites , 2003 .

[11]  High-temperature thermoelectric properties of n-type BayNixCo4-xSb12 , 2001, ICT 2001.

[12]  T. Hirai,et al.  Effects of Ce filling fraction and Fe content on the thermoelectric properties of Co-rich Ce_yFe_xCo_4−xSb_12 , 2001 .

[13]  Singh,et al.  Electronic structure of Ce-filled skutterudites. , 1996, Physical review. B, Condensed matter.

[14]  B. Sales,et al.  Lattice dynamics of filled skutterudites:La(Fe,Co)4Sb12 , 2003 .

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

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

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

[18]  C. Uher,et al.  Anomalous barium filling fraction and n-type thermoelectric performance of BayCo4Sb12 , 2001 .

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

[20]  Keppens,et al.  Disparate atomic displacements in skutterudite-type LaFe3CoSb12, a model for thermoelectric behavior. , 1999, Acta crystallographica. Section B, Structural science.

[21]  Jean-Pierre Fleurial,et al.  Properties of single crystalline semiconducting CoSb3 , 1996 .

[22]  M. Dehmas,et al.  High temperature transport properties of partially filled CaxCo4Sb12 skutterudites , 2004 .

[23]  D. Bérardan,et al.  Improved thermoelectric properties in double-filled Cey∕2Yby∕2Fe4−x(Co∕Ni)xSb12 skutterudites , 2005 .

[24]  H. Lutz,et al.  Structure refinement of skutterudite-type cobalt triantimonide, CoSb3 , 1987 .