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Abstract: Nanostructured Ag0.8Pbm+xSbTem+2 (m ) 18, x ) 4.5) system thermoelectric materials have been
fabricated by combining mechanical alloying (MA) and spark plasma sintering (SPS) methods followed by
annealing for several days to investigate the effect on microstructure and thermoelectric performance. It
was found that appropriate annealing treatment could reduce both the electrical resistivity and the thermal
conductivity at the same time, consequently greatly enhancing the thermoelectric performance. A low
electrical resistivity of 2 10-3 Ohm-cm and low thermal conductivity of 0.89 W m-1 K-1 were obtained for
the sample annealed for 30 days at 700 K. The very low thermal conductivity is supposed to be due to the
nanoscopic Ag/Sb-rich regions embedded in the matrix. A high ZT value of 1.5 at 700 K has been achieved
for the sample annealed for 30 days.
1. Introduction
Tsinghua University.
Toyota Motor Corporation.
to minimize the thermal conductivity. For example, the phononglass electron-crystal approach as in Skutterudites5 and clathrates,6 where loosely bound atoms rattle in cage structures, and
the thin-film multilayer approach, where the introduction of
interfaces significantly reduces phonon propagation.1 Indeed,
artificial thin-film superlattice structures like Bi2Te3/Sb2Te32 and
PbSe0.98Te0.02/PbTe7-9 exhibit very low thermal conductivity,
and as a result, ZT values were significantly raised. The key
feature of these systems is the large number of interfaces
introduced by the inherent nanofabrication technique that in turn
reduce the lattice thermal conductivity. Interestingly, nanocomposites in bulks have been recently identified in the AgPbmSbTe2+m system where compositional fluctuations at the nanoscopic level seem to play a key role for the previously reported
high thermoelectric performance.10-13 Such nanoscopic inhomogeneities like intrinsically embedded nanodispersions
increase phonon scattering and hence reduce the thermal
conductivity, which enhances the ZT value provided that the
electrical conductivity is not degraded to a greater degree.
Therefore, the in-situ nanostructuring becomes a potential
(5) Sales, B. C.; Mandrus, D.; Williams, R. K. Science 1996, 272, 1325.
(6) Nolas, G. S.; Slack, G. A.; Schujman, S. B. Semicond. Semimet. 2001, 69,
255.
(7) Harman, T. C.; Taylor, P. J.; Walsh, M. P.; LaForge, B. E. Science 2002,
297, 2229.
(8) Harman, T. C.; Spears, D. L.; Manfra, M. J. J. Electron Mater. 1996, 25,
1121.
(9) Beyer, H.; Nurnus, J.; Bottner, H.; Lambrecht, A.; Roch, T.; Bauer, G.
Appl. Phys. Lett. 2002, 80, 1216.
(10) Hsu, K. F.; Loo, S.; Guo, F.; Chen, W.; Dyck, J. S.; Uher, C.; Hogan, T.;
Polychroniadis, E. K.; Kanatzidis, M. G. Science 2004, 303, 818.
(11) Quarez, E.; Hsu, K. F.; Pcionek, R.; Frangis, N.; Polychroniadis, E. K.;
Kanatzidis, M. G. J. Am. Chem. Soc. 2005, 127, 9177.
(12) Wang, H.; Li, J.-F.; Nan, C.-W.; Zhou, M.; Liu, W. S.; Zhang, B.-P.; Kita,
T. Appl. Phys. Lett. 2006, 88, 092104.
(13) Androulakis, J.; Hsu, K. F.; Pcionek, R.; Kong, H.; Uher, C.; DAngelo, J.
J.; Downey, A.; Hogan, T.; Kanatzidis, M. G. AdV. Mater. 2006, 18, 1170.
J. AM. CHEM. SOC. 2008, 130, 4527-4532
4527
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approach to enhance the thermoelectric performance of AgPbmSbTe2+m system bulk materials. Compared with thermoelectric
films, thermoelectric bulk materials are conducive to realization
of a large temperature difference and industrial applications.
AgPbmSbTe2+m bulk thermoelectric materials are promising for
electrical power generation at moderate temperatures ranging
from 600 to 900 K.
Our recent work12 revealed that a powder metallurgy process
combining mechanical alloying and spark plasma sintering is
suitable for fabricating the AgPbmSbTe2+m bulk materials, which
produces fine-grained materials with enhanced ZT values.
Compared with the material fabricated by melting and slow
cooling reported by Hsu et al.,10 the AgPbmSbTe2+m bulks
prepared by the combined MA and SPS methods may be very
hard to reach an equilibrium state. Therefore, the present work
was conducted to mainly study the effect of annealing treatment
on the thermoelectric performance and microstructure of Pbrich Ag0.8Pbm+xSbTem+2 (m ) 18, x ) 4.5) compound, which
was found to be the optimal composition showing the best
thermoelectric properties by our previous study.14 The thermoelectric performance is greatly enhanced and a large ZT value
of up to 1.5 is obtained by moderate annealing treatment. The
present work revealed the importance of the nanostructuring
approach to the development of high-performance thermoelectric
materials, which has been realized by a simple annealing method
in the AgPbmSbTe2+m system.
2. Experimental Section
2.1. Synthesis. The commercial elemental powders of Ag (99.9%,
powder, 150 m), Pb (99.9%, powder, 75 m), Sb (99.9999%, powder,
150 m), and Te (99.999%, powder, 150 m) were used as starting
materials. The mixtures of these powders were subjected to MA in a
planetary ball mill (QM-2L) using a hardened stainless steel vial and
balls. The weight ratio of balls to powder was kept at about 20:1, and
the mill vial was purged and filled with Ar + 5 atom % H2 atmosphere
to prevent the powders from oxidation during the milling process. The
milling was performed at 350 rpm for 4 h, and the MA-derived Ag0.8Pb22.5SbTe20 powders were consolidated by SPS at 673 K for 5 min
under an axial pressure of 50 MPa. The MA and SPS parameters were
confirmed to be suitable for synthesizing the compound from the
elemental powders by our previous studies.12,14 The sintered bulk
samples were sealed in vacuum (1 10-3 Pa) in glass tubes and
annealed for several days (3, 10, and 30 days) at 653 K.
2.2. High-Resolution Transmission Electron Microscopy and
X-ray Diffraction. The phase structures of the resultant samples were
examined by X-ray diffraction (XRD) using Cu KR radiation (Rigaku
RINT2000). The nanostructure of all the samples was examined using
transmission electron microscopy (field emission TEM, JEOL-2011).
Specimens used for the investigation were hand polished to about 5060 m with sand paper and subsequent diamond paste. Samples were
then thinned to electron transparency using a Gatan model 600 CDIF
precession ion-milling system at low angle (8-12). High-resolution
transmission electron microscopy images of several different locations
inside of the pieces were recorded at 200 kV.
2.3. X-ray Fluorescence Analysis. The chemical compositions of
all the samples were analyzed by X-ray fluorescence (XRF) using a
XRF-1800 spectrometer equipped with a Rh anode X-ray tube. A
reference sample was prepared by forming a powder compact via die
pressing using a powder mixture of Ag, Pb, Sb, and Te at a
stoichiometric proportion of Ag0.8Pb22.5SbTe20.
2.4. Electrical Transport Properties. The carrier concentration and
mobility were measured by the bar method using the Hall measurement
(14) Zhou, M.; Li, J.-F.; Wang, H. Chin. Sci. Bull. 2007, 52, 990-996.
4528 J. AM. CHEM. SOC.
3. Results
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sample
final composition
Ag0.8Pb22.5SbTe20
before annealing
annealed for 3 days
annealed for 10 days
annealed for 30 days
AgPb18SbTe20a
Ag0.8Pb22.1SbTe20.8
6.63
220
4.20
Ag0.7Pb19.7SbTe19.0
Ag0.7Pb19.6SbTe18.1
Ag0.7Pb19SbTe18.9
2.34
2.96
3.26
0.05
513
540
558
100
5.21
3.90
3.43
aThe
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Figure 3. Temperature dependence of (a) thermal diffusivity, (b) measured heat capacity, (c) thermal conductivity, and (d) ZT value for Ag0.8Pb22.5SbTe20
bulks before and after annealing for different times. (b) The data for AgPb18SbTe20 was from ref 10.
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Figure 4. Low-magnification TEM images of (a) unannealed sample and (b) the sample annealed for 30 days. HRTEM images of (c) unannealed sample
and (d) the sample annealed for 30 days.
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5. Conclusions