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1. Introduction
Magnetic, Electrical and Optical Applications of Intermetallic Compounds. Edited by J. H. Westbrook and R. L. Fleischer 1995,
2000 John Wiley & Sons Ltd
SABAT
e A B=n AB /
v>
Figure 2. Thermoelement (thermocouple) (a) connected as a thermoelectric generator and (b) connected as a thermoelectric heat
pump (cooler)
Working
junction
Cooled
junction
Here
Figure 3. Thermoelectric modules: (a) single-stage module; and (b) multistage (cascade) cooling module
SC, SM
Figure 5. Apollo lunar surface experimental package powered by a SNAP-27 thermoelectric generator (reproduced by permission
of NASA and the Jet Propulsion Laboratory)
To and from
radiator
panels
Power converter
assembly
Accumulator and
gas separator
TEM pump
Assembly
joint
Thaw
heat pipe
To and from
reactor
Thermal strap
Figure 6. The power converter assembly for the SP-100 project to power a space platform (reproduced by permission of
G. Stapfer of the Jet Propulsion Laboratory)
Figure 7. A commercial unit 'Cryotherm', a thermoelectric cryoextractor with cooling element, power supply and remote-control
pedal (reproduced by permission of Informelectro, 1985, Moscow)
ZT=
[*-<^5/2ri'
(7)
T(K)
Te (at%)
Figure 8. Partial phase diagram of the Bi-Te system (data from
Glatz, 1965)
n-type
p-type
T(K)
T(K)
T(K)
T(K)
T(K)
T(K)
Figure 10. Tempeature dependence of the thermoelectric properties along the trigonal c axis of solid solution Bi085Sb015
(a low-temperature, n-type thermoelectric material): (a) thermopower S and electrical conductivity a; and (b) thermal conductivity
X and figure of merit Z (data from A. F. Ioffe Physical-Technical Institute)
T(K)
Te (at%)
Figure 11. Phase diagram of the Pb-Te system (data from Lin et al.t 1989)
n-type
p-type
T(K)
T(K)
7"(K)
T(K)
Figure 12. Temperature dependence of the thermoelectric properties of medium-temperature thermoelectrics based on AIVBV1
compounds: (a) thermopower S and electrical conductivity a for n-type material (doped PbTe); (b) S and a for p-type material
(doped PbTe); (c) thermal conductivity x for the same materials of n-type and p-type; and, (d) figure of merit Z for the same
materials of n-type and p-type (data from A. F. Ioffe Physical-Technical Institute)
n-type
p-type
T(K)
T(K)
T(K)
T(K)
Figure 13. Temperature dependence of the thermoelectric properties of solid-solution Si 07 Ge 03 (a high-temperature thermoelectric
material): (a) thermopower S and electrical conductivity a for n-type material; (b) 5 and a for p-type material; (c) thermal conductivity
X for the same materials of n-type and p-type; and (d) figure of merit Z for the same materials of n-type and p-type (data from
Dismukes et al.t 1964)
thermoelectrics remains fairly low. The best of the lowtemperature, medium-temperature and high-temperature
materials reach only a level of ZT** 1.0, which restricts
TE applications to the domain of low-power devices,
and rather expensive ones at that.
6.2 Prospects of a Broadening
of TE Applications: Significance of
Intermetallic Compound Studies
Viewed from a purely technical standpoint, the not-yetexploited potential of TE conversion appears very
promising, if one recalls what was said in Section 4.
To cite an example, consider the idea of Ioffe of
incorporating TE panels into the walls of houses and
T(K)
Si (wt%)
*On the latter topics, the reader may wish to refer to the
chapters in Vol. 1 by Singh (6), Pintschovius (7), Braunovic (41)
and White (44).
T(K)
T(K)
Figure 15. Temperature dependence of the thermoelectric properties of a single crystal of MnSi, 72, a highly anisotropic p-type
thermoelectric material (for two principal crystallographic directions relative to the tetragonal axis): (a) thermopower S and electrical
conductivity or; and, (b) thermal conductivity x (data from A. F. Ioffe Physical-Technical Institute)
thermoelectric figures of merit. But a practical thermoelectric material has also to be a sufficiently good
conductor, and it is more probable that among all
kinds of compounds intermetallics will be such good
conductors. Some work has been carried on in the
investigation of potential thermoelectrics in recent
years, although it cannot be considered as sufficient.
The most interesting materials with high figures of merit
turned out to be Cu2Se-type selenides which surpass
AIVBVI-based materials in the medium-temperature
range. Unfortunately one is forced to renounce the
possibility of their practical application till their
diffusive and mechanical properties are improved.
Transition metal silicides are another interesting and
promising group of materials.* They are formed from
cheap components and can be used in air at high
temperatures. Some of them are very interesting for
their physics and for potential applications arising from
one peculiarity: anisotropy of properties. For example,
the higher silicide of managanese, MnSi172 (tP120)
(see Figure 14 for a partial phase diagram), shows
anomalously high anisotropy of the thermopower over
an unusually wide temperature range (Figure 15). The
figure of merit of this silicide is high enough that it can
be considered as a potential competitor to the Si-Ge
alloys. Other potential high-temperature materials,
such as rare-earth chalcogenides, boron and some
borides, have been under investigation too. This topic
is considered in detail in the review by Wood (1988).
In the early book by Ioffe (1957) metals were
considered as having absolutely no potential as TE
See also Chapter 15 by Masumoto, Katsui, and Matsuoka.
7. Electrical Applications
102ARZf?
T-(0C)
Figure 16. Temperature dependence of the relative change of
electrical resistivity (R7-R20oc)/^2oc f t n e a l l o v NG45F,
based on the intermetallic compound NiMn (Molotilov, 1974)
Addendum
This addendum includes new references of the same
character as earlier and some general remarks on new
ideas in the field of thermoelectric materials.
There is as yet no special journal on thermoelectrics
or thermoelectric energy conversion. This is why
anyone who is interested in exploring the whole
spectrum of thermoelectric studies should resort to
the annual proceedings of the International Conference
on Thermoelectrics, references to which are listed (Rao,
1992; Matsuura, 1994; Mathiprakasam and Heenan,
References
DiSalvo, F. J. (1999) Science, 285, 703.
IEEE (1996) Pr oc. 15 th International Conference on
Thermoelectrics. (Passadena, CA, USA). Institute of
Electrical and Electronics Engineers Catalog Number
96TH8169, USA.
IEEE (1997) Pr oc. 16th International Conference on
Thermoelectrics. (Dresden, Germany). IEEE Catalog
Number 97TH8291, USA.
IEEE (1998) Pr oc. 17th International Conference on
Thermoelectrics. (Nagoya, Japan). IEEE Catalog
Number 98TH8365, USA.
Mahan, G., Sales, B., and Sharp, J. (1997) Physics Today,
50(3), 42.
Mahan, G. D. (1998) Solid State Physics, Vol. 51, ed.
Ehrenreich, H. and Spaepen, F. Academic Press, p. 81.
Mathiprakasam, B., and Heenan, P. (eds.) (1994) Proc. 13th
International Conference on Thermoelectrics. American
Institute of Physics Conf. Proc. N316, N.Y., USA.
Matsuura, K. (ed.) (1994) Proc. 12th International Conference
on Thermoelectrics. The Institute of Electrical Engineers
of Japan, Tokyo, Japan.
Rao, K. R. (ed.) (1992) Proc. 11th International Conference on
Thermoelectrics. The University of Texas at Arlington,
Texas, USA.
Rowe, D. M. (ed.) (1995) CRC Handbook of Thermoelectrics.
CRC Press. Boca Raton.
Tritt, T. M., Mahan, G., Lyon, H. B. Jr., and Kanatzidis, M. G.
(eds.) (1997) Thermoelectric MaterialsNew Directions
and Approaches'. Mater. Res. Soc. Proc. Vol. 478.
Tritt, T. M., Lyon, H. B. Jr., Mahan, G., and Kanatzidis, M. G.
(eds.) (1998) 'Thermoelectric Materials 1998The Next
Generation Materials for Small-Scale Refrigeration and
Power Generation Applications', Mater. Res. Soc. Proc.
Vol. 545.
Tritt, T. M. (1999) Science, 283, 804.
Vedernikov, M. V. (ed.) (1995) Proc. 14th International
Conference on Thermoelectrics. A. F. Ioffe PhysicalTechnical Institute, St. Petersburg, Russia.