Ultra-fast synthesis and thermoelectric properties of Te doped skutterudites

The self-propagating-high-temperature-synthesis (SHS) technique is applied here for the first time to synthesize CoSb3 thermoelectric materials. Mixtures of Co and Sb powders were compacted into pellets which were ignited from one end. A single-phase skutterudite material was obtained in a very short period of time using the SHS process which is maintained by the heat released from the chemical reaction of Co with Sb. Thermodynamic parameters and kinetics of the SHS reaction are investigated. The ignition temperature, adiabatic temperature, and the propagation speed of the combustion wave in the synthesis of CoSb3 are 723 K, 861 K, and 1.25 mm s−1, respectively. Using the SHS technique followed by Plasma Activated Sintering (PAS), we synthesized high performance bulk skutterudites of composition CoSb2.85 Te0.15 with a ZT of 0.98 at 820 K, one of the highest ZT values for an unfilled form of skutterudites. Compared with the samples synthesized by the traditional methods, the synthesis time is shortened from the typical several days to less than 20 minutes. Our work opens a new avenue for ultra-fast, low cost, mass production fabrication of skutterudite-based materials, which may also be universally applicable for the synthesis of other thermoelectric materials.

[1]  V. A. Poluboyarov,et al.  Preparation of WC and W2C by self-propagating high-temperature synthesis using a mixture of tungsten, titanium, and carbon black powders , 2014, Inorganic Materials.

[2]  Z. Jagličić,et al.  Modified self-propagating high-temperature synthesis of nanosized La0.7Ca0.3MnO3 , 2013 .

[3]  B. Liu,et al.  Effect of Ti/Si ratio on the products of laser igniting self-propagating high-temperature synthesis in Cu–Ti–Si system , 2013 .

[4]  Li-Min Wang,et al.  High-pressure synthesis of phonon-glass electron-crystal featured thermoelectric LixCo4Sb12 , 2012 .

[5]  M. Subramanian,et al.  Rapid microwave synthesis of indium filled skutterudites: An energy efficient route to high performance thermoelectric materials , 2011 .

[6]  Qingjie Zhang,et al.  Structure and Transport Properties of Double-Doped CoSb2.75Ge0.25–xTex (x = 0.125–0.20) with in Situ Nanostructure , 2011 .

[7]  Miaofang Chi,et al.  Multiple-filled skutterudites: high thermoelectric figure of merit through separately optimizing electrical and thermal transports. , 2011, Journal of the American Chemical Society.

[8]  K. Salzgeber,et al.  Skutterudites: Thermoelectric Materials for Automotive Applications? , 2010 .

[9]  Jiong Yang,et al.  Systematic Study of the Multiple-Element Filling in Caged Skutterudite CoSb3 , 2010 .

[10]  Han Li,et al.  High performance InxCeyCo4Sb12 thermoelectric materials with in situ forming nanostructured InSb phase , 2009 .

[11]  Ji-Hui Yang,et al.  Automotive Applications of Thermoelectric Materials , 2009 .

[12]  Qiang Li,et al.  Thermoelectric Materials with Potential High Power Factors for Electricity Generation , 2009 .

[13]  Han Li,et al.  Rapid preparation method of bulk nanostructured Yb0.3Co4Sb12+y compounds and their improved thermoelectric performance , 2008 .

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

[15]  Jingfeng Li,et al.  Enhanced thermoelectric properties in CoSb3-xTex alloys prepared by mechanical alloying and spark plasma sintering , 2007 .

[16]  M. Ohtaki,et al.  Enhanced Thermoelectric Performance of Nanostructured ZnO: A possibility of selective phonon scattering and carrier energy filtering by nanovoid structure , 2006, 2006 25th International Conference on Thermoelectrics.

[17]  T. Hirai,et al.  Thermoelectric Properties of Te-doped CoSb3 by spark plasma sintering , 2005 .

[18]  M. Toprak,et al.  The Impact of Nanostructuring on the Thermal Conductivity of Thermoelectric CoSb3 , 2004 .

[19]  George S. Nolas,et al.  SKUTTERUDITES : A phonon-glass-electron crystal approach to advanced thermoelectric energy conversion applications , 1999 .

[20]  Thierry Caillat,et al.  Preparation and thermoelectric properties of the skutterudite‐related phase Ru0.5Pd0.5Sb3 , 1996 .

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

[22]  T. Hirano,et al.  SUPERLATTICE APPLICATIONS TO THERMOELECTRICITY , 1995 .

[23]  Donald T. Morelli,et al.  Low temperature properties of the filled skutterudite CeFe4Sb12 , 1995 .

[24]  R. Rice Microstructural aspects of fabricating bodies by self-propagating synthesis , 1991 .

[25]  Z. A. Munir,et al.  Self-propagating exothermic reactions: the synthesis of high-temperature materials by combustion , 1989 .

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

[27]  Han Li,et al.  Enhanced thermoelectric performance and novel nanopores in AgSbTe2 prepared by melt spinning , 2011 .

[28]  Junyou Yang,et al.  Effect of La filling on thermoelectric properties of LaxCo3.6Ni0.4Sb12-filled skutterudite prepared by MA–HP method , 2006 .

[29]  H. Feng,et al.  Combustion synthesis of advanced materials: Part II. Classification, applications and modelling , 1995 .

[30]  A. G. Merzhanov,et al.  History and recent developments in SHS , 1995 .

[31]  John J. Moore,et al.  Combustion synthesis of advanced materials: Part I. Reaction parameters , 1995 .