MATERIAL & TECHNOLOGY_Thermoelectrics
Cito conveniens pro beo metuo Emergo circumvenio,
tot depopulatio et sed Penna invitus.
Electricity from Hot Air
Even the most efficient motor generates more heat than propulsion. Thermoelectric
generators, however, could convert some of this unused energy into electricity –
something that Juri Grin and his colleagues at the Max Planck Institute for Chemical
Physics of Solids in Dresden are hoping to achieve. They are currently searching for
particularly suitable materials for this endeavor.
TEXT CHRISTIAN MEIER
T
he terms Juri Grin uses sound chemical compounds that can be used degrees Celsius. The temperature in
strange. He talks about recy- for this. Juri Grin’s team of researchers space is below minus 270 degrees. The
cling or harvesting waste at the Max Planck Institute in Dresden resulting temperature difference of
heat. Waste recycling, yes – is investigating two special classes of more than 1,000 degrees provides ide-
that is commonplace. But these substances. al conditions for generating electricity
waste heat recycling? And harvesting with a thermoelectric material incor-
apples, okay, but how does one harvest A TEMPERATURE DIFFERENCE porated into the hull of the probe, sur-
waste heat? CREATES THE VOLTAGE rounding the radioactive core, because
Juri Grin thinks this is absolutely it is precisely this kind of temperature
imperative. “We humans allow our- Materials that convert heat into elec- gradient that promotes thermoelectric
selves a great luxury,” says the Director tricity have been known since the be- energy conversion.
at the Max Planck Institute for Chemi- ginning of the 19th century. Physicist The temperature difference means
cal Physics of Solids in Dresden. “We Thomas Johann Seebeck discovered that the charge carriers have a higher
convert only around one third of the them quite by accident. Thermoe- energy in hot parts of the material than
primary energy contained in coal, gas lectrics, which consist of electrical con- in cold ones. This produces a voltage
or oil into usable energy such as elec- ductors or semiconductors, have also that increases as the difference in tem-
tricity or heat to heat our homes, for ex- been in use in technical applications perature increases.
ample.” The rest escapes unused into for some time: each thermocouple The plan is for this principle of pow-
the atmosphere as waste heat. “We can makes use of the thermoelectric effect er generation to no longer be limited to
no longer afford to do this, if for no to measure temperature. These materi- such extreme applications as space trav-
other reason than that of climate als also produce electricity, especially el, because cars and power stations also
change,” says Juri Grin. where other power sources are not produce ample heat that currently es-
To change this situation, the chem- available, or where the power source capes unused. For this reason, in 2008,
ist and his colleagues are working on a used must suffer no wear and tear, thus a German automotive manufacturer in-
particular way to recycle waste heat. not requiring maintenance – in space stalled a thermoelectric generator in a
The fundamental idea is that thermo- probes that orbit distant planets and test vehicle. It converts part of the heat
Photo: Bastian Ehl
electric materials, or thermoelectrics moons, for instance. of the exhaust gas into electricity for
for short, will convert at least some of Inside the probes, a radioactive the onboard electronics, thus saving
the energy that currently goes unused substance decays in a reactor, generat- fuel – a not inconsiderable 5 to 8 per-
into electricity. There are various ing a temperature of several hundred cent, according to the company. >
80 MaxPlanckResearch 1 | 11
Candidate for an efficient thermoelectric material: The crystal structure of intermetallic clathrates
can be recognized in the model. One atom sits at each corner of the polyhedrons, and the cavities
in their interiors provide room for further atoms. A voltage can be generated in such materials if they
are exposed to a temperature gradient.
The great potential of such thermoelec-
tric generators becomes evident with a
simple calculation: if only 10 percent
of the cars in Germany, or around five
million cars, were equipped with a ther-
moelectric generator that produced one
kilowatt of electric power, and if each
of these generators were active 200
hours per year, 100 million liters of fuel
could be saved.
The only problem with this prom-
ising scenario is that there are as yet
no thermoelectric generators with
sufficient power, as thermoelectrics
currently don’t convert heat into elec-
tricity very efficiently. Researchers all
over the world, including Juri Grin
and his colleagues, want to change
this. They are developing thermoelec-
tric materials that have as high a qual-
ity factor as possible.
THERMAL AND ELECTRICAL
CONDUCTIVITY ARE COUPLED
The quality factor, or ZT for short, is a
numerical measure of how effectively
a material converts thermal energy
into electrical energy, and depends on
three physical quantities – it increases
as the Seebeck coefficient increases.
Named after the discoverer of thermo-
electricity, this material characteristic
indicates the voltage that is produced
between the ends of a thermoelectric
material for one degree difference in
temperature. The quality factor also
increases when the electrical conduc-
tivity is as high as possible. The elec-
trical conductivity determines how
top: This instrument can be used to measure
the electrical resistance of a sample. The
Photos: Bastian Ehl (2)
material is examined in a noble gas atmos-
phere to protect it from oxygen.
bottom: Technician Ralf Koban prepares a
sample holder in order to determine the
thermoelectric properties. This involves
working in a glove box filled with noble gas.
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MATERIAL & TECHNOLOGY_Thermoelectrics
well the charge carriers flow through eral opinion was that this seemingly
the material. Finally, the thermal con- unsolvable dilemma prevented effi-
ductivity determines how fast the tem- cient thermoelectric materials from be-
perature difference, which generates ing developed; the topic no longer gen-
the voltage, is equalized. Thus, to erated any interest.
achieve a high quality factor, the ther- “But then materials were discovered
mal conductivity of a material should whose electrical and thermal conduc-
be as low as possible. tivity are partially decoupled,” says Juri
The aim is therefore to find or de- Grin. This offered a way out of the con-
velop materials that have a high elec- ductivity dilemma. And since it coin-
trical conductivity but a low thermal cided with the optimization of further
conductivity. And that is precisely the material characteristics, efficient ther- View into a skutterudite with filling: The red
problem: in conventional metals and moelectric generators suddenly seemed spheres represent cobalt, rhodium or iridium
atoms, and the blue ones phosphorous, arsenic
semiconductors, thermal and electrical possible. The scientist thinks this stim- or antimony. Calcium or barium atoms (yellow)
conductivity are coupled. Both proper- ulated research. The German Research are located in the voids of the lattice. Octahe-
ties are determined by the number of Foundation is now also supporting this dral structural elements are outlined in gray.
charge carriers, which transport current research in the “Nanostructured Ther-
and also make a significant contribu- moelectrics” priority program. pend on whether the bonds are of an
tion to heat conduction. ionic nature – that is, based on electro-
The electrical conductivity can be DIFFERENT CHEMICAL BONDING static forces between ions – or whether
changed, for instance, by introducing SOLVES THE DILEMMA neighboring atoms are bound together
foreign atoms into the crystal lattice of by shared electron pairs and form co-
a thermoelectric material. These foreign Juri Grin and his colleagues begin the valent bonds. They discovered that the
atoms contribute higher or lower num- search for efficient thermoelectric ma- two properties can be decoupled to a
bers of electrons to the conducting elec- terials with a fundamental question: certain extent in clever combinations
trons than the main components do. “We want to find out how the type of of ionic and covalent bonding. Under-
But what the quality factor gains from chemical bonding in a material affects standing these relationships helps the
the increasing electrical conductivity is its physical properties,” explains Grin. scientists systematically synthesize
canceled out by the increase in thermal So the researchers are investigating how thermoelectric materials with as high a
conductivity. Until the 1990s, the gen- electrical and thermal conductivity de- quality factor as possible. >
Graphic: MPI for Chemical Physics of Solids, Scientific Report 2009
HOW A THERMOELECTRIC GENERATOR WORKS
The fundamental building block of a thermoelectric generator and holes at the hot end of each leg have a higher kinetic en-
– a thermoelectric module – resembles the Greek letter “pi,” ergy than those at the cold end, more charge carriers travel
consisting of two legs that are electrically connected. One of from the hot end to the cold end than move in the opposite di-
the legs is a so-called n-conductor (the n stands for negative), rection in a given time. Negative charge thus collects at the
the other a p-conductor (the p stands for positive). While (neg- cold end of the n-leg, and positive charge at the cold end of the
atively charged) electrons provide the current flow in n-con- p-leg. A thermoelectric device built in this way generates a
ductors, this is done in p-conductors by positively charged voltage that can be used for technical applications. However,
charge carriers, so-called holes. such a module produces too little current for most such appli-
The module is hot at the top, so on the side of the bar, and cations, so many of them are connected in series, like batter-
cold at the bottom, at the ends of the legs. Since the electrons ies in a flashlight.
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MATERIAL & TECHNOLOGY_Thermoelectrics
➜
1 2 3
Building chemical cages: The molecular building blocks (1) of the clathrates consist of silicon (blue) and a metal (red)
such as sodium, potassium or barium. They form silicon polyhedrons (2), which surround the metal atoms like cages.
The polyhedrons stack up to form a voluminous structure (3).
The researchers in Dresden consider riod of time at these temperatures,” Absorbing phonons makes it possible
two classes of materials to be particu- says the researcher. And it should not to decrease the thermal conductivity
larly promising: filled skutterudites expand too much when it becomes hot, without affecting the electrical conduc-
and intermetallic clathrates. The two or it can hardly be permanently incor- tivity. “We found that this is possible in
classes of substances are composed of porated in a generator. materials that contain both covalent
different chemical elements and have A material that fulfills these require- and ionic bonds,” explains Grin, as is
different crystal structures. Skutteru- ments can be identified only with an the case with intermetallic clathrates.
dites consist of phosphorous, arsenic in-depth knowledge of chemistry and In the clathrates, for example, cov-
or antimony, as well as selected ele- physics. “In addition to the effect of the alent bonds link most atoms of one or
ments of the iron and cobalt group or chemical bonding, we must also under- more types of elements to form a lat-
the group of platinum metals. Clath- stand how the physical properties de- tice: cavities that resemble soccer balls
rates, in contrast, contain elements of pend on the type of structure,” says in shape and that are formed by penta-
the fourteenth group of the periodic Grin. The microstructure describes the gons or hexagons then stack up to form
system, namely germanium and sili- form, size and chemical composition of a delicate structure. The voids in the
con, and of the thirteenth group, such the microscopically small grains that lattice accommodate ions of a different
as aluminum, or of the transition met- make up a solid. element. The charged particles sit there
als, such as nickel. Both the skutteru- as if in a cage, trapped by the electric
dites and the clathrates are particular- ATOMS OSCILLATING field of the clathrate lattice, meaning
ly interesting as thermoelectrics if they IN THEIR CAGES they form an ionic bonding.
contain additional metal atoms or The lattice of the covalently bond-
ions. These are located in cavities that To begin with, however, the most im- ed atoms and the ions in the cages each
are present in the crystal structures of portant question is: how can electrical play different roles. While the walls
the materials. and thermal conductivity be influ- conduct the electric current, the ion in
“We are aiming for a comprehensive enced as separately as possible? Nature the cage scatters phonons that pass
Graphics: MPI for Chemical Physics of Solids (3)
understanding of these compounds,” provides at least a starting point for though the crystal lattice. If a phonon
explains Juri Grin, because a high qual- the answer. After all, in a material, heat impacts on the cage, the ion is deflect-
ity factor is not sufficient to recom- is transported not only by the free ed from its most stable position in the
mend a material for generators in cars, electrons, which also flow in an elec- center of the cage. This impulse causes
for example. “It is also important that tric current. This component of the it to oscillate in its cage like a bead in a
the material be at its most efficient be- thermal conductivity necessarily in- child’s rattle. This can be visualized by
tween 300 and 600 degrees Celsius,” creases with electrical conductivity. imagining that the oscillating ion ab-
adds his colleague Michael Baitinger, But heat is also conducted by sound sorbs the energy of the phonon just like
because the temperature of car exhaust waves, or, in the language of the scien- a heavy metal sphere under a skyscrap-
gases is in this range. “The material tists, by phonons, which travel er absorbs the oscillations of the build-
must also remain stable over a long pe- through the material. ing during an earthquake.
84 MaxPlanckResearch 1 | 11
left: Chemistry uses a voltage: Ph.D. student Xianjuan Feng prepares a reaction in an arc furnace. A voltage between two
electrodes produces an arc with a temperature of several thousand degrees in which the starting materials react with each other.
right: Chemistry uses a current: In the induction furnace, a conducting coil generates eddy currents in the carbon crucible and
the metallic starting materials, and heats them up in such a way that the chemical conversion takes place.
In more accurate physical terms, the pound. “In our calculations, we vary Physics department, they are also deter-
heat excites the lattice of the covalent- the chemical composition, the arrange- mining the physical properties on which
ly bonded atoms and the trapped ions ment of the atoms and the crystal struc- the quality factor depends.
to execute oscillations at different fre- ture,” explains Juri Grin. Over the years, the researchers
quencies. The two oscillations damp have thus identified and produced cla-
each other so that the heat is not con- A STARTING POINT FOR EFFICIENT thrates whose quality factors are com-
ducted well on this path. This mecha- THERMOELECTRIC MATERIALS parable with the bismuth telluride that
nism can be enhanced without affect- is already used in practice. “We also see
ing the electrical conductivity. The calculations show where in the crys- a possibility to develop even more ef-
This is precisely what Juri Grin and tal structure which type of bond – cova- ficient thermoelectrics with this ap-
his colleagues achieved. They synthe- lent or ionic – predominates. Com- proach in the future,” says Juri Grin.
sized both clathrates and skutterudites pounds that are shown to crystallize in Meanwhile, the researchers in Dres-
with different compositions and tested a covalently bonded lattice and whose den are tackling another problem that
their suitability as thermoelectrics. But voids surround ions are deemed to be could prevent the technical application
Photos: Bastian Ehl (2)
rather than choosing randomly from promising candidates. The chemists are of the clathrates and skutterudites:
the seemingly endless number of pos- now trying to synthesize these and then their manufacture. For laboratory pur-
sible chemical compositions, the re- analyze their precise composition and poses, the chemists usually synthesize
searchers first use quantum-chemical crystal structure. Together with their col- these substances by direct reaction of
models of the chemical bonds in a com- leagues from Frank Steglich’s Solid State the starting materials through melting
1 | 11 MaxPlanckResearch 85
Bodo Böhme often produces new compounds in the arc furnace (left), but he and his colleagues also test other synthesis
methods (right): Here, Böhme presents a sample container containing the powders of starting materials. A gas flows over
them and they react to form the target compound.
or solid-state reactions. But it takes a lot they tested the spark-plasma sintering churning out the finished material like
of effort before this method provides method, abbreviated SPS, for example. gravel on a conveyer belt.
the desired material, and then it yields This method is already used in indus- Even during their experiments
only relatively small quantities. The try for the densification of metallic or with plasma sintering, the chemists
product usually does not have a uni- ceramic powders and the formation of also tested means other than pressure
form composition because all sorts of parts with a defined shape. A strongly and current pulses to force the solid
atomic arrangements are created in compacted powder is processed with starting materials to react. Eventually,
the melt. A material must thus under- DC pulses that are only a few millisec- the method of choice – at least for the
go subsequent treatment with heat onds long but very powerful, so that production of the clathrates – proved
for days, weeks, or sometimes even the powder grains slightly deform and to be to use an oxidizing agent – hy-
months, making this method com- fuse together. drogen chloride gas, to be precise. The
pletely useless to industry. researchers feed the gas, which pro-
“We wanted to further develop the A CHEMICAL AGENT duces hydrochloric acid when dis-
preparation methods by having the IMPROVES CONTROL solved in water, into a reactor contain-
starting materials react with each oth- ing a powder of the starting substance.
er in solid form,” explains Bodo Böhme, “We discovered that it is also possible As the oxidizing agent now wafts over
whose work focuses on the synthesis. to do chemistry with this technique,” the starting compound containing
These methods allow chemists to pro- says Grin. Under the conditions creat- all elements involved, it triggers the
duce new compositions of thermoelec- ed with the SPS method, the atoms can chemical partner selection.
tric materials. They need only to get the wander to and fro between the grains “This technique opens up a new
starting materials to strike up a chemi- and undergo reactions. But this meth- chapter in the preparation of metallic
cal relationship when the substances od is not suitable for the large-scale in- materials, such as the clathrates,” says
are lying grain to grain and not getting dustrial production of thermoelectrics Juri Grin. It allows chemists to influ-
Photos: Bastian Ehl (2)
involved with each other. because, like the melting, it provides ence the composition of thermoelectric
In different approaches, the Dres- only individual samples whose prop- materials more accurately than before.
den-based researchers initially gath- erties may also differ slightly from one Exactly which atoms are incorpo-
ered indications that even solid mate- another. Industry would like to have a rated is decisive for the number of
rials can be moved to react – when method that operates continuously, electrons that contribute to the con-
86 MaxPlanckResearch 1 | 11
MATERIAL & TECHNOLOGY_Thermoelectrics
ductivity. The method can also be re- generators for this. Juri Grin and his thermoelectric generators – and maybe
alized on an industrial scale. colleagues are thus slowly approaching in a few years, this expression will no
Their comprehensive approach their goal of recycling waste heat with longer sound so strange.
thus enabled Juri Grin’s team of re-
searchers to increase the efficiency of
the thermoelectric materials, while at
the same time making them easier to GLOSSARY
handle during their industrial produc-
Thermoelectric quality factor Intermetallic clathrates
tion and actual application. To this A measure of how well a material converts Usually consist of elements of the third
end, they are collaborating with the thermal energy into electrical energy. and fourth main group of the PSE. They
Fraunhofer Institutes for Manufactur- Seebeck coefficient
form (often together with transition
ing Technology and Advanced Materi- metals) a voluminous framework for
Indicates the voltage created between the
the crystal structure whose voids
als (IFAM) and for Ceramic Technolo- two ends of, for example, a rod of thermo-
provide space for atoms or ions of
gies and Systems (IKTS). electric material if their temperature dif-
further elements, such as alkali, alka-
fers by one degree.
In this cooperation, which is sup- line earth or rare earth metals.
ported by the Free State of Saxony, the Group of the periodic system
(Filled) skutterudites
Comprises the chemical elements in a
Max Planck researchers are searching Consist of elements of the fifth group
given column in the periodic system of the
for the suitable thermoelectric materi- of the PSE and a transition metal of
elements (PSE), such as the halogens or
the iron, cobalt or nickel group. Their
als and methods to produce them. The the noble gases. The elements in a group
crystal structure has cavities that pro-
IFAM researchers form the powdery have similar properties, but become more
vide space for further atoms or ions.
substances obtained in this process into metallic the further toward the bottom
of the PSE an element is.
work pieces that can be incorporated in
generators. Staff at the IKTS design the
1 | 11 MaxPlanckResearch 87