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commentary

An inconvenient truth about


thermoelectrics
Cronin B. Vining
Despite recent advances, thermoelectric energy conversion will never be as efficient as steam engines.
That means thermoelectrics will remain limited to applications served poorly or not at all by existing
technology. Bad news for thermoelectricians, but the climate crisis requires that we face bad news head on.

I
n the past, competition, peer review and
free-market forces could be relied on to
cull competing ideas to the general benefit
of society. Even if someone shamelessly
advocated a particular technology, the
invisible hand of the marketplace would
eventually sort out which solutions where
best for society as a whole. But the climate
crisis utterly disrupts this traditional
business-as-usual calculus for R&D
investment; unbridled advocacy need not
lead to solutions that are optimal, or even
acceptable. Indeed, by definition it is these
business-as-usual methods that led to

BMW Group
this crisis.
A better framework is needed such
that scientists, engineers and technology
advocates generally, first and foremost ask
themselves: can this technology contribute Figure 1 | Integrating thermoelectrics into vehicles for improved fuel efficiency. Shown is a BMW 530i
to solving the climate crisis? Although concept car with a thermoelectric generator (yellow; and inset) and radiator (red/blue).
the response will sometimes be ‘no’ or
‘not greatly’, an answer of ‘no’ can be as
important as ‘yes’ because it allows resources Basics of thermoelectric technology p‑type thermoelectric materials. The
to be more effectively redirected. By way The basic thermoelectric energy conversion key property in this regard is known as
of example, this commentary focuses on unit consists of two different (one n‑type the ‘thermoelectric figure of merit’ often
thermoelectric technology, a type of solid- and one p‑type) semiconducting materials written as ZT — a unitless combination
state ‘heat engine’ capable of converting heat connected together as a thermocouple. of three properties of a material: thermal
to electricity, or alternatively, converting Thermoelectric devices are typically in conductivity (κ), electrical resistivity (ρ)
electricity into cooling. the form of a module constructed from and Seebeck coefficient (S), as well as the
Thermoelectric technology has made a number of these thermocouples. Heat absolute temperature (T): ZT = S2T/κρ.
significant scientific progress in recent applied to one side of the module will ‘push’ The problem associtated with improving
years1 and its potential to reduce the electrons (in the n‑type material) and holes efficiency comes down to the materials
environmental impact of electrical power (in the p‑type) from the hot side to the science, physics and chemistry associated
generation and air conditioning has been cold side. In effect, heat drives an electrical with producing high-ZT semiconductors.
discussed2–5. Overall, the science, technology current, which can be used to perform work. ZT values for ‘best practice’ thermoelectric
and business of thermoelectrics have never In some sense, the electrons and holes are materials (most of which have been in
been stronger. Nevertheless, the opportunity analogous to the process whereby a steam use for decades) have maximum ZT
for a substantial impact on the climate crisis turbine is driven when heat causes steam values near 1. Like all heat engines, a
seems limited. Only a very few applications to expand. A thermoelectric module can thermoelectric device operates between
(notably recovery of vehicle waste heat and also be operated in reverse as a heat pump two temperatures: Thot (the heat source
automobile air conditioning), seem plausible to produce cooling (refrigeration). Key temperature) and Tcold (the heat rejection
in this respect, and even those applications advantages include high reliability, small temperature). Higher efficiency is
face stiff barriers. The scale of the climate size and no noise. By these measures of achieved mainly by operating over a wider
problem is such that even relatively minor performance, thermoelectric technology temperature range and using materials with
contributions are welcome, but we must is highly competitive. However, relatively the highest possible ZT — though efficiency
keep things in perspective and focus on the low efficiency means that much R&D improves only slowly with increasing ZT.
most promising solutions. is devoted to seeking better n‑type and Using materials available today, efficiency

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© 2009 Macmillan Publishers Limited. All rights reserved.


commentary

80 Even for vehicle waste heat, competition


Carnot efficiency from mechanical engines can be expected
Thermodynamic limit
70
ZT=infinity
to be fierce. Honda, for example, have tested
a system using a Rankine steam engine to
60
ZT=20, unlikely generate electricity from waste heat in a
Coal/Rankine
hybrid vehicle, increasing overall engine
Solar/Brayton
50 efficiency by 3.8% (ref. 11). BMW have
Efficiency (%)

Nuclear/Brayton+Rankine
for some years had a similar effort called
40 Solar/Stirling ZT=4, ambitious Turbosteamer, but their added device is
Nuclear/Rankine used to supplement the power train (rather
Solar/Rankine ZT=2, plausible eventually
30 than to generate electricity), improving fuel
efficiency by 15%. Either of these projects
20 seems to surpass the FreedomCar goal of
ZT=0.7, available today
Cement/Org. Rankine 10% fuel savings.
10 Geothermal/Kalina
Geothermal/Org. Rankine In 2006, the US Department of
Energy’s Office of Basic Energy Sciences
0
300 400 500 600 700 800 900 1,000 1,100 1,200 1,300 initiated support to develop improved
Heat source temperature (K) thermoelectric materials as part of their
solar energy project. The idea is simple
Figure 2 | Assessing thermoelectrics. Efficiency of ‘best practice’ mechanical heat engines compared with enough2,3: concentrate solar energy to
an optimistic thermoelectric estimate (see main text for description). create heat that a TEG turns into electricity.
Engineering work has not yet started,
though, because much higher ZT values are
is limited to perhaps 1/6 of the maximum A recent review 5 stated that ZT = 3 is needed first.
possible Carnot efficiency. the ultimate goal of thermoelectrics and Industrial waste heat (incinerators,
Thermoelectric technology is used for suggested that this “appears to be within cement, steel mills and so on) has also been
a variety of applications. For example, reach in the next several years”. Although discussed. NEDO (Japan) has invested
radioisotope thermoelectric generators scientifically plausible, no clear path for in thermoelectric R&D for waste heat
provide electrical power for deep-space such a development has been identified, and since at least 1997. Their most recent
missions. On Earth, the commercial engineering progress is therefore limited five-year, US$25 million programme was
market for thermoelectric power to existing, lower-ZT materials for the completed satisfactorily in 2007, with
generation is limited mainly to remote time being. reasonable progress made towards its goal
power applications, amounting to perhaps of 15% system efficiency. Other potential
US$25–50 million per annum for full Possible thermoelectric power applications have been occasionally
thermoelectric generator (TEG) systems. generation applications mentioned: geothermal, home co-generation
The world market for cooling modules The most promising thermoelectric power (fuel oil-fired furnaces or gas water-heaters
(thermoelectric modules only, not final generation application with ‘greentech’ plus TEGs) and woodstoves (efficient
products or systems) is thought to be implications is vehicle waste heat recovery cooking for the developing world).
about US$200–250 million per annum. to improve fuel economy. In this concept,
In the early 1990s, new ideas and new vehicle waste heat, usually from the exhaust, Possible thermoelectric cooling
funding spurred significant progress in is redirected to a TEG to produce electricity applications
thermoelectrics, some of which have been (Fig. 1). More drive-train power is available The most common refrigerant used in home
discussed in this journal. Yet only three to move the vehicle, and electricity is still and automobile air conditioners is R‑134a,
efforts have produced ZT values in excess available. Under the US Department of which does not have the ozone-depleting
of 2: Harman’s quantum-dot superlattice6 Energy’s ‘FreedomCar’ programme, teams properties of Freon that it replaced, but
with a reported ZT ~3.5 at 575 K (ref. 7), have been assembled to pursue this concept. is nevertheless a terrible greenhouse gas
Venkatasubramanian’s superlattice with The FreedomCar target is for both cars and and will be banned in new European cars
reported ZT ~2.4 at 300 K and ZT ~2.9 at trucks to improve overall fuel economy by 2011. Soon enough it will have to be
400 K (ref. 8), and Hsu’s lead antimony by 10%, and aims to reach production in banned entirely, and that means we need
silver telluride (LAST) bulk/‘nanodot’ the 2011–2014 timeframe. As none of the alternative air-conditioning technologies.
material with a reported ZT ~2.2 at 800 K nano/high-ZT materials are yet available, Thermoelectric cooling has been suggested
(ref. 9). Translation of these laboratory development is proceeding with the best as one such alternative, building on the
results to commercial quantities of materials available materials. Most likely, some successful use of thermoelectric cooler/
and/or efficient devices, however, does not improvement of ZT will be required for heaters in car seats4. The US Department of
seem imminent. commercialization, but even without this, Energy recently announced a US$13 million
Quite recently, ZT ~1.4 was reported the programme should provide better cost-shared programme to develop
for a ‘fine grain’ bulk bismuth–telluride cost/benefit estimates. Significant barriers this technology.
material, made by grinding nanometre- remain before deployment including costs,
sized powder and pressing the powder back heat transfer to thermoelectric modules, Efficiency of power plants and the
into a bulk solid10. A start-up company, dedicated radiators, system weight, effect of size
GMZ Energy, has announced intentions acceptance of change and competition Particularly for large-scale applications,
to produce commercial quantities of this with alternate conversion technologies as efficiency will be paramount and
substance, which would then become the well as with all other means of increasing future thermoelectric potential needs
highest-ZT material commercially available. fuel efficiency. to be compared to currently available

84 nature materials | VOL 8 | FEBRUARY 2009 | www.nature.com/naturematerials

© 2009 Macmillan Publishers Limited. All rights reserved.


commentary

technologies. Figure 2 illustrates the


efficiency (electrical power out/heat in) Table 1 | Climate crisis impact of thermoelectric technology.
for several heat sources (geothermal, Power scale (kWe) Examples Required device ZT Impact on climate crisis
industrial waste, solar, nuclear and coal) in
>1,000s Solar thermal ‘engine’ replacement >8–20 Highly unlikely
combination with several thermal-to-electric
conversion technologies (organic Rankine, >10s Industrial waste heat, geothermal >4 Unlikely
Kalina cycle, Stirling, Brayton and steam bottoming cycles
Rankine). The filled data points represent 0.5–several Vehicle waste heat, car cooling/ >1.5–2 To be determined
actual in-service power plants and the open heating, home co-generation
data points correspond to design studies, but <0.5 Remote power, ‘personal’ >0.5–1 (almost) None
based on actual demonstrated technologies. micropower, all existing applications
Also plotted is the estimated efficiency of
a thermoelectric converter. Note that the prohibits the use of mechanical engines, even if future R&D achieves a fully fledged,
efficiency has been estimated from ZT using it seems unlikely that thermoelectric device-level average of ZT = 4, it is still
a simplified but optimistic method. The technology has anything to contribute for probably insufficient to displace mechanical
assumptions tend to overestimate efficiency large-scale systems. engines for large-scale applications. Of
(to give thermoelectrics a fighting chance), Size, however, can favour thermoelectric course, ZT = 4 should greatly enhance the
but not grossly so. systems. Typical conversion systems become range and performance of niche applications
The systems shown in Fig. 2 represent less efficient as they are scaled down in that thermoelectric technology serves so
an estimate of ‘best practice’, meaning these size. Figure 3 illustrates this principle in a well today. But the impact on the climate
values are based on the actual performance purely schematic way (the numbers and crisis, even with ZT = 4, seems limited to
of up-to-date systems. These are not ‘best shape of the curves are illustrative only). the smaller scale, decentralized applications,
possible’ values as each of these technologies Thermoelectric converters have been built the most promising of which appears to
can be expected to improve in the future. that deliver reasonable efficiency at the be vehicle exhaust heat recovery. Even
The smallest mechanical engine represented milliwatt and even microwatt power level. there, the benefit is potentially around 10%
in Fig. 2 is the Solar/Stirling machine at The efficiency of mechanical engines drops improved fuel economy assuming all the
25 kWe. The others are at least nine-times off at much higher power levels. This means hurdles to market penetration are overcome.
larger and range up to 1,600 MWe for the there is a crossover point: below some The opportunity for thermoelectric
Nuclear/Brayton+Rankine study. Figure 2 power-level, thermoelectric technology technology to help in the climate crisis
illustrates an important point: existing, will tend to be more efficient. Increasing seems limited. ❐
practical mechanical systems are far more ZT will move the crossover point to higher
efficient than thermoelectrics, and are more power levels, increasing the range of Cronin B. Vining is at ZT Services, 2203 Johns Circle,
efficient than thermoelectrics are likely applications where thermoelectrics compete. Auburn, Alabama 36830-7113, USA.
to become in the foreseeable future. After Meanwhile, mechanical engine R&D focuses e-mail: nature@zts.com
fifteen years of R&D, the best reported (among other goals) on pushing the size
thermoelectric material has a maximum down — such is the nature of technology References
(not average) value of ZT = 3.5, is n‑type competition. No general value is possible as 1. Vining, C. B. in: European Conference on Thermoelectrics,
only (we need both) and is prohibitively the precise crossover point will be different ECT2007 (ed. Semenyuk, V.) (Odessa, Ukraine, 2007); <http://
ect2007.its.org/system/files/u1/pdf/02.pdf> .
expensive. But set that aside and assume for each application: one value for waste heat
2. Crabtree, G. W. & Lewis, N. S. Phys. Today 60, 37–42 (2007).
one can achieve ZT = 4 averaged over in cars, another for geothermal systems. If 3. Lewis, N. S. & Crabtree, G. W. Basic Research Needs for Solar
the entire temperature range, for both n‑ thermoelectrics are to have some impact Energy Utilization (US Department of Energy, 2005); <http://
and p‑type materials and with no losses. on the climate crisis, we should look at www.sc.doe.gov/bes/reports/abstracts.html#SEU>
Assume all of that and you have the solid applications that involve relatively low 4. Bell, L. E. Science 321, 1457–1461 (2008).
line labelled ZT = 4 in Fig. 2, which is still power levels (where thermoelectric can 5. Tritt, T. M., Böttner, H. & Chen, L. Mater. Res. Soc. Bull.
33, 366–368 (2008).
less efficient than existing, commercially compete), but occur in large numbers (in
6. Harman, T. C., Taylor, P. J., Spears, D. L. & Walsh, M. P.
available technology regardless of what order that it has an overall impact). Of the J. Electron. Mater. 29, L1–L4 (2000).
temperature range is of interest. Unless some applications considered until now, only a 7. Harman, T. C., Walsh, M. P., Laforge, B. E. & Turner, G. W.
extraordinary system consideration firmly few meet these criteria, as summarized in J. Electron. Mater. 34, L19–L22 (2005).
Table 1. Of these, vehicle waste heat appears 8. Venkatasubramanian, R., Silvola, E., Colpitts, T. & O’Quinn, B.
35 the most promising. Nature 413, 597–602 (2001).
9. Hsu, K. F. et al. Science 303, 818–821 (2004).
30
‘Engines’ 10. Poudel, B. et al. Science 320, 634–638 (2008).
25 Concluding remarks
Efficiency (%)

11. Kadota, M. & Yamamoto, K. in Advanced Hybrid Vehicle


20 Thermoelectric technology has made Powertrain 2008‑01‑310 (SAE International, 2008).
15 Improved TE admirable progress in recent years.
Laboratory ZT values have increased Acknowledgments
10
TE today several-fold, business has grown I wish to thank A. Gore, L. Bell, J. Snyder, J. Stockholm,
5 Crossover
C. Uher, B. LeSage, B. Nickerson, R. Venkatasubramanian,
significantly, start-ups have emerged and D. Rowe, T. Kajikawa, J.–P. Fleurial, T. Caillat, J. Heath,
0
1E-2 1E+0 1E+2 1E+4 1E+6 next-generation thermoelectric technology L. Whitlow, H. Böttner, E. P. Vining and many others
Power level (We) and devices are now appearing in cars in throughout the thermoelectric community for discussions
significant numbers. Yet the last fifteen and input. The opinions, errors and omissions, however, are
solely my own.
Figure 3 | Size can favour thermoelectrics. An years of basic (ZT) R&D has hardly
illustrative plot of efficiency versus size for affected products and the nanoscale ZT > 2 Additional information
thermoelectrics (TE) and ‘engines’ (see main text materials reported in the literature are The author declares competing financial interests: details
for description). not yet commercially available. Moreover, accompany the paper at www.nature.com/naturematerials

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