Enhanced Thermoelectric Properties of BaxEuyCo4Sb12 with Very High Filling Fraction

doi:10.3724/SP.J.1077.2012.12615

Abstract

Abstract:

Filled skutterudite is one of the most promising thermoelectric materials for power generation applications. We report the high-temperature thermoelectric properties including electrical conductivity, Seebeck coefficient, and thermal conductivity in single-phased polycrystalline dual-element-filled skutterudites Ba_xEu_yCo₄Sb₁₂(0<x<0.2, 0<y<0.3). The double-filled skutterudites are synthesized by the melting-quenching-annealing method and the bulk pellects are sintered by spark plasma sintering (SPS). High total filling fractions (x+y>40%) with very large power factor of Ba_xEu_yCo₄Sb₁₂over 60 μW/(cm•K²) at high temperature is obtained. The combination of Ba and Eu fillers inside the voids of the skutterudite structure provides a broad range of resonant phonon scattering and consequently a strong suppression in the lattice thermal conductivity is observed. The lattice thermal conductivity values for Ba_xEu_yCo₄Sb₁₂system are dramatically decreased and the lowest value is about 1.7 W/(m•K) at room temperature. Consequently, enhanced thermoelectric figure of merits (ZT) for Ba and Eu dual-element-filled CoSb₃ skutterudites are obtained at elevated temperatures, in particular ZT=1.3 at 850 K for Ba_0.19Eu_0.23Co₄Sb₁₂.

Key words: thermoelectric, filled-skutterudite, transport properties

CLC Number:

TQ174

WU Ting, BAI Sheng-Qiang, SHI Xun, CHEN Li-Dong. Enhanced Thermoelectric Properties of Ba_xEu_yCo₄Sb₁₂ with Very High Filling Fraction[J]. Journal of Inorganic Materials, 2013, 28(2): 224-228.

Figures/Tables 6

Fig. 1 Measured temperature dependence of the electrical conductivity (σ) in double-filled skutterudites

Fig. 2 Measured temperature dependence of the Seebeck coefficient (S) in double-filled skutterudites

Fig. 3 Measured temperature dependence of the Seebeck coefficient (S2σ) in double-filled skutterudites

Fig. 4 Measured temperature dependence of total thermal conductivity (κ) in double-filled skutterudites

Fig. 5 Measured temperature dependence of lattice thermal conductivity (κL) in double-filled skutterudites

Fig. 6 Measured temperature dependence of dimensionless figure of merit (ZT) in double-filled skutterudites

References 24

[1]	Slack G A. In: Rowe D M, editor. CRC Handbook of Thermoelectrics. Boca Raton, FL: CRC Press; 1995: 407.
[2]	Sales B C, Mandrus D, Williams R K. Filled skutterudite antimonides: a
	new class of thermoelectric materials.Science, 1996, 272(5266):1325-1328.
[3]	Sales B C, Mandrus D, Chakoumakos B C, et al. Filled skutterudite antimonides: electron crystals and phonon glasses. Phys. Rev. B, 1997, 56(23): 15081-15089.
[4]	Nolas G S, Cohn J L, Slack G A. Effect of partial void filling on the lattice thermal conductivity of skutterudites. Phys. Rev. B, 1998, 58(1):164-170.
[5]	Chen L D, Karahara T, Tang X F, et al. Anomalous barium filling fraction and n-type thermoelectric performance of BayCo4Sb12. J. Appl. Phy., 2001, 90(8):1864-1868.
[6]	Zhao X Y, Shi X, Chen L D, et al. Synthesis and thermoelectric properties of Sr-filled skutterudite SryCo4Sb12. J. Appl. Phy. , 2006, 99(5): 053711-1-4.
[7]	Puyet M, Lenoir B, Dauscher A, et al. High temperature transport properties of partially filled CaxCo4Sb12 skutterudites. J. Appl. Phy., 2004, 95(9): 4852-4855.
[8]	Morelli D T, Meisner G P, Chen B X, et al. Cerium filling and doping of cobalt triantimonide. Phys. Rev. B, 1997, 56(12): 7376-7383.
[9]	Nolas G S, Kaeser M, Littleton V R T, et al. High figure of merit in partially filled ytterbium skutterudite materials. Appl. Phys. Lett., 2000, 77(12):1855-1857.
[10]	Lamberton G A, Bhattacharya S, Littleton R T, et al. High figure of merit in Eu-filled CoSb3-based skutterudites. Appl. Phys. Lett., 2002, 80(4): 598-600.
[11]	Kuznetsov V L, Kuznetsov L A, Rowe D M. Effect of partial void filling on the transport properties of NdxCo4Sb12 skutterudites. J. Phys.: Condens. Matter, 2003, 15(29): 5035-5048.
[12]	Pei Y Z, Chen L D, Zhang W, et al. Synthesis and thermoelectric properties of KyCo4Sb12. Appl. Phys. Lett. , 2006, 89(22): 221107-1-3.
[13]	Pei Y Z, Yang J, Chen L D, et al. Improving thermoelectric performance of caged compounds through light-element filling. Appl. Phys. Lett. , 2009, 95(4): 042101-1-3.
[14]	Sales B C, Chakoumakos B C, Mandrus D. Thermoelectric properties of thallium-filled skutterudites. Phys. Rev. B, 2000, 61(4): 2475-2481.
[15]	Nolas G S, Takizawa H, Endo E, et al. Thermoelectric properties of Sn-filled skutterudites. Appl. Phys. Lett., 2000, 77(10): 52-54.
[16]	Nolas G S, Yang J, Takizawa H. Transport properties of germanium-filled CoSb3. Appl. Phys. Lett., 2004, 84(25): 5210-5212.
[17]	Uher C. In: Tritt T M, editor. Recent Trends in Thermoelectric Materials Research I, Semiconductors and Semimetals. CA: Academic Press, 2000:139.
[18]	Yang J, Zhang W, Bai S Q, et al. Dual-frequency resonant phonon scattering in BaxRyCo4Sb12. Appl. Phys. Lett. , 2007, 90(19): 192111-1-3.
[19]	Berardan D, Alleno E, Godart C, et al. Improved thermoelectric properties in double-filled Cey/2Yby/2Fe4-x(Co/Ni)xSb12 skutterudites. J. Appl. Phys. , 2005, 98(3):033710-1-6.
[20]	Lu Q M, Zhang J X, Zhang X, et al. Effects of double filling of La and Ce on thermoelectric properties of CemLanFe1.0Co3.0Sb12 compounds by spark plasma sintering. J. Appl. Phys. , 2005, 98:106107-1-3.
[21]	Tang X F, Li H, Zhang Q J, et al. Synthesis and thermoelectric properties of double-atom-filled skutterudite compounds CamCenFexCo4-xSb12. J. Appl. Phys. , 2006, 100(12): 123702-1-8.
[22]	Bai S Q, Pei Y Z, Chen L D, et al. Enhanced thermoelectric performance of dual-element-filled skutterudite BaxCeyCo4Sb12. Acta Mater. Appl., 2009, 57(11): 3135-3139.
[23]	Bai S Q, Shi X, Chen L D. Lattice thermal transport in BaxREyCo4Sb12(RE=Ce, Yb, and Eu) double-filled skutterudites. Appl. Phys. Lett. , 2010, 96(20): 202102-1-3.
[24]	Shi X, Kong H, Uher C, et al. Low thermal conductivity and high thermoelectric figure of merit in n-type BaxYbyCo4Sb12 double- filled skutterudites. Appl. Phys. Lett. , 2008, 92(18): 182101-1-3.

Enhanced Thermoelectric Properties of Ba_xEu_yCo₄Sb₁₂ with Very High Filling Fraction

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