metals

Article
The Elusive Thomson Effect in Thermoelectric
Devices. Experimental Investigation from 363 K to 213
K on Various Peltier Modules
Valter Giaretto * and Elena Campagnoli
Energy Department Politecnico di Torino, 24 Corso Duca degli Abruzzi, 10129 Turin, Italy;
elena.campagnoli@polito.it
* Correspondence: valter.giaretto@polito.it; Tel.: +39-011-0904445




Received: 30 January 2020; Accepted: 20 February 2020; Published: 23 February 2020


Abstract: At steady state, in the governing equation of one-stage thermoelectric cooler, the heat
resulting from Fourier conduction is balanced by heat generation due to the Joule and Thomson effects
inside semiconductors. Since the heat flux observed at the junction of a semiconductor, r pair includes
the Peltier effect and the Fourier heat flux caused by both the aforementioned contributions, the
Thomson effect is easily masked by the Joule heat, which makes it elusive. With the aim of highlighting
the contribution of the Thomson effect, measurements were carried out in the temperature range
from 363 K to 213 K on different Peltier modules. The temperature dependence of the Seebeck and
Thomson coefficients was evaluated as well as the electrical resistivity, and thermal conductivity of
the Peltier modules examined. The results obtained show that the temperature dependence of the
thermoelectric properties can reduce the cooling capacity of the Peltier module compared to what is
declared in the technical datasheets of the commercial devices. The analyses allow us to conclude
that an increase in the Thomson effect could have a positive effect on the performance of the Peltier
only if it were possible to reduce the Joule contribution simultaneously.

Keywords: Thomson-effect; Seebeck coefficient; Peltier module; experimental investigation

1. Introduction
There are many technological areas in which wasted energy can be successfully harvested by
thermoelectric devices, such as residential building, automotive sector, and also railway rolling
stock [1–3]. Moreover, the thermoelectric coolers meet many opportunities in the refrigeration of
electronic systems [4–6], and in several laboratory applications, these devices can represent the optimal
solution to achieve low temperatures without using a refrigerant medium, since they are compact,
have no moving parts and vibrations, and are typically highly reliable. For example, to obtain low and
stable thermal levels for mimicking the effects induced on the biological tissue by a surgical cryoprobe,
single-stage Peltier devices have been assembled in a stack, by feeding each one with proper electrical
currents [7,8]. In the latter, the well-known complaint about the poor performance of these devices is
of little importance, but the relationship between the feeding current, the cooling capacity, and the
minimum temperature reached must be adequately known. With this aim, some different experimental
procedures can be found in the literature [6,9,10]. Although few of these suggest alternative methods
on determining the thermoelectric properties, the Thomson effect is commonly not considered in the
theoretical approach.
More in general, in order to use Peltier devices at thermal levels far from ambient conditions,
adequate characterization of the thermoelectric properties involved is required at different temperatures.
An advantage of this analysis is the knowledge of the temperature dependence of the Seebeck coefficient,

Metals 2020, 10, 291; doi:10.3390/met10020291 www.mdpi.com/journal/metals

Metals 2020, 10, 291 2 of 15

so the typically eluded Thomson effect can be considered properly. If on the one hand, the Thomson
effect makes less obvious the link between the cooling capacity and the temperature difference between
the junctions at a given feeding current, on the other hand, highlighting the role of this thermoelectric
effect is useful to understand its impact on the performance of thermoelectric devices.
In recent decades several Authors have paid attention to the Thomson effect considering its
influence on the performance of a thermoelectric generator [11] and cooler [12–15], also under transient
conditions [16]. For these Authors, a common conclusion regards the possible benefit on the device
performance that can be introduced by Thomson heat. They also indicate that the “bottleneck” is due
to the capability of the material, which can be resolved by optimizing the temperature dependence
of the Seebeck coefficient [17]. Along this path, an interesting theoretical work [18] suggests that a
thermoelectric cooler can be designed to achieve the full thermoelectric compatibility, thanks to which
the Thomson effect plays an important role in reaching very low temperature even if the figure of merit
is low. Moreover, many thermoelectric materials are being explored for power generation applications,
such as silicides [19], PbTe [20], half-Heusler alloys [21], and skutterudites [22], in which Thomson
effect can occur and improve the device performances. But, nowadays, the so-called “commercial
devices” are typically not designed to follow these criteria.
This paper presents the experimental investigations carried out on various commercial Peltier
modules over their whole operating temperature range. The thermal characterization of these devices
was performed by measuring the figure of merit and the electrical resistance of each module [23,24].
Moreover, the temperature on the hot and cold sides was measured on a few selected modules, and
equivalent values of some properties were calculated: the Seebeck coefficient, electrical resistivity, and
thermal conductivity of the thermoelectric materials with which modules are built. The analysis of the
results made it possible to put in evidence the Thomson effect intrinsic to the semiconductor materials
that constitute the investigated modules. The comparison between the thermoelectric effects that occur
inside these materials has shown that the Joule effect is dominant on the performance of such modules
and that the temperature dependence of both electrical resistivity and thermal conductivity seems
more important than the Thomson effect that takes place in the semiconductors employed.

2. Materials and Experimental Methods

The Peltier modules investigated are single-stage, marketed under different brands,
manufactured with a p-n series of Bismuth Telluride semiconductor material (Bi2 Te3 ), and assembled
between plates made of ceramic stuff that can be assumed as Al2 O3 . The number of pairs and some
geometric features of these modules, are shown in Table 1, assuming for all devices, the semiconductor
pillars as parallelepipeds with a square base.

Table 1. Number of pairs and some geometric features of the investigated Peltier modules.

Number Module Pillar Size Copper Ceramic Filling

Peltier
of Pairs Thickness Height L Side W Thickness Thickness Factor
Module
NP (mm) (mm) (mm) (mm) (mm) (%)

a.1 127 3.4 1.5 1.5 0.35 0.60 36

a.2 127 3.3 1.3 1.3 0.35 0.65 27
a.3 127 3.9 1.9 1.3 0.35 0.65 27
b 17 5.4 2.7 1.5 0.35 1.00 14
c* 50 1.3 0.3 0.6 0.05 0.45 56
* The external surface of the ceramic plates is metalized.

The geometric dimensions shown in Table 1 were obtained using a caliper, measuring the thickness
of the whole module, the thickness of the ceramic plate, and the size of the pillars (height and base
side). The agreement between the measured dimensions of the pillars and the dimensions of the
whole module (height L and width W) was verified by evaluating with a blade gauge the gap between
Metals 2020, 10, 291 3 of 15

the pillars and the thickness of the connecting copper elements to which the p-n semiconductors are
soldered to form the junctions. The filling factor, reported in the last column of Table 1, is the ratio
between the sum of the cross-sections of all the semiconductor elements and the entire surface area
of the ceramic plates. The filling factor can be useful to take into account the spreading-constriction
thermal resistance between pillars and ceramic plates.
The modules named a.1, a.2, and a.3 have the same number of pairs, with some differences in the
total thickness and size of the pillar, but quite a similar filling factor and assembly features. Therefore,
based on the performances declared by the manufacturer, similar values of the figure of merit were
expected for these three modules. Modules b and c are totally different from each other and from the
previous ones, in particular as regards the dimensions of the pillar, the filling factor, and assembly
characteristics; therefore, for the latter, rather different figures of merits are foreseen.
As known, the dimensionless figure of merit zT can be evaluated in a real device by measuring the
electrical quantities at the accessible external connections, since it can be obtained as the ratio between
the total developed Seebeck voltage and the total ohmic voltage drop. Separating the two contributions
is not trivial and is traditionally performed with a time-domain transient approach called the “Harman
method” [23]. The idea behind the method is that when a dc current, which flows through the device,
is switched off, the sudden voltage drop experienced at the device terminals is due to the ohmic voltage
that disappears with the current, while the thermoelectric voltage persists due to the thermal inertia of
the device, which prevents fast temperature variations. Based on this criterion, the figure of merit and
the ohmic series resistance of the tested thermoelectric modules were measured using a commercial
time-domain Harman type instrument [25] produced by RMT (Moscow, Russia), named z-meter model
DX 4090. The DX 4090 instrument also estimates the characteristic time and the maximum temperature
difference that can be reached between the junctions of the Peltier device under test.
Figure 1 shows the scheme of the experimental arrangement, whose main parts are the Thermostatic
Test Chamber (TTC), capable of operating from 203 K to 473 K with a stability of the set-point within
±0.1 K and the above-mentioned z-meter (DX 4090). Only the Peltier modules investigated were
inserted in TTC while the other measurement tools such as the reference resistor (Fluke 742A-1, R0 = 1)
shown in Figure 1, the voltmeters (Agilent 34420A 7 12 Digit) and the thermocouples measurement
bench (NI cDAQ-9178, TB-9212) not shown in the figure, were placed outside the TTC and kept
in thermal equilibrium with the laboratory. For achieving a Still Air Chamber (SAC) inside TTC,
a protective cylindrical screen has been arranged around the Device Under Test (DUT), avoiding on its
exposed surfaces the air turbulences induced by the internal fan. At each established TTC set points
chosen in the range 363 K, 213 K, the assigned test reference temperature was that picked on the inner
surface of the cylindrical screen of SAC.
During the tests, the actual output current I set by the DX 4090 was checked to measure the voltage
drop V 0 at the potential leads of the reference resistor R0 . This output current allows identifying the
resistance RC of the feeding cables (double red and black lines in Figure 1) by measuring the voltage
drop VDX and VDUT at the external connections of the DX 4090 and of the DUT, as shown in Figure 1.
In this way, the resistance R’ measured by the DX 4090 is influenced by the resistances R0 and RC ,
and the figure of merit z’ obtained is altered as if the p-n series of the DUT was more resistive.
The corrected values for the resistance R of the p-n series (including, in this case, the resistance of
connecting leads assembled at the factory) can be found subtracting R0 and RC , while the revised value
z is obtained considering for this case the equality zR = z0 R0 , so

∆VDX − ∆VDUT
R = R0 − (RC + R0 ) = R0 − R0 , (1)
∆V0

R0 ∆VDX
z = z0 = z0 . (2)
R ∆VDUT
With the correct R value of the DUT, by subtracting the ohmic component ∆VΩ = IR from the
measured voltage drop VDUT (or subtracting ∆VΩ0 = IR0 from V
DX ) it was possible to identify the total
due to the ohmic voltage that disappears with the current, while the thermoelectric voltage persists
due to the thermal inertia of the device, which prevents fast temperature variations. Based on this
criterion, the figure of merit and the ohmic series resistance of the tested thermoelectric modules were
measured using a commercial time-domain Harman type instrument [25] produced by RMT
Metals 2020, 10,
(Moscow, 291
Russia), named z-meter model DX 4090. The DX 4090 instrument also estimates4 of 15
the
characteristic time and the maximum temperature difference that can be reached between the
junctions of the Peltier device under test.
Seebeck voltage ∆VS produced at p-n junctions, associating to it the junction temperature difference
Figure 1 shows the scheme of the experimental arrangement, whose main parts are the
∆TS which produces this voltage, namely:
Thermostatic Test Chamber (TTC), capable of operating from 203 K to 473 K with a stability of the
set-point within ±0.1 K and the above-mentionedRz-meter (DX 4090).R0Only the Peltier modules
! !
investigated were ∆VS = ∆VDUTin−TTC
inserted ∆VDUT
IR =while ∆V0 measurement
the− other = ∆VDX −tools∆V0 such = 2NP ε∆TS , (3)
R0 R0 as the reference resistor
(Fluke 742A-1, R0 = 1) shown in Figure 1, the voltmeters (Agilent 34420A 7½ Digit) and the
where, NP is themeasurement
thermocouples number of thermoelectric pairs, and εTB-9212)
bench (NI cDAQ-9178, representsnotthe equivalent
shown in theSeebeck coefficient
figure, were placedof
the single
outside thejunction
TTC and of the assembled
kept in thermalpillar series.
equilibrium with the laboratory. For achieving a Still Air
Since the direct measurement of the actual
Chamber (SAC) inside TTC, a protective cylindrical screen junction temperature
has beenofarranged
an assembled thermoelectric
around the Device
is not an easy task, to obtain ε from the Seebeck voltage ∆V
Under Test (DUT), avoiding on its exposed surfaces the air turbulencesSinduced by the Equation
module expressed by (3),
internal fan.
theeach
At junction temperature
established set points∆T
TTC difference S was in
chosen estimated
the range on 363
the basis
K, 213 of K,
thethe
temperature
assigned difference ∆TP
test reference
measured on the outside surfaces of the ceramic plates, introducing
temperature was that picked on the inner surface of the cylindrical screen of SAC. suitable corrections.

Figure 1.
Figure Schemeof
1. Scheme ofthe
theexperimental
experimentalarrangement.
arrangement.DX DX4090
4090isisthe
thez-meter,
z-meter,TTC
TTCisis the
the Thermostatic
Thermostatic
Test Chamber,
Test Chamber, SAC is the Still Air Chamber, and DUT is the Device Under Test. Solid and
is the Still Air Chamber, and DUT is the Device Under Test. Solid and double doublered
red
andblack
and blacklines
linesare
are the
the feeding
feeding cables,
cables, while
while the
the dashed
dashed ones
ones represent
represent the signal wires.

Different solutions were considered to identify the temperature of the outside surfaces of the
ceramic plates. Around room temperature, with feeding currents less than 50 mA, a good temperature
uniformity on these plates was verified using an infrared camera (FLIR 6753sc, cooled array 640 × 512 px,
NETD < 18 mK). The operating range of the IR camera (253–623 K) has unfortunately inhibited its
use in carrying out experiments down to 213 K. So, the surface temperatures were measured using
type K thermocouples with exposed welded tip junctions (made using 0.076 mm diameter wires),
placed in contact with the ceramic plate using a thin, highly reflective aluminum adhesive tape.
The expected deviation between ∆TS and ∆TP (∆TS > ∆TP ) was estimated taking into account both the
thermal resistance of the ceramic layers (Al2 O3 ) and the pillars footprint area on the ceramic surface as
spreading effect determined by the filling factors shown in Table 1.
Considering the actual ceramic thickness of the investigated Peltier modules, assuming feeding
current in the range 25–40 mA, with some hypotheses on the maximum heat flux, exchanged at the
junction (less than 0.1 W with I = 40 mA), a maximum deviation between ∆TP and ∆TS was estimated of
the same order of accuracy expected in the temperature measurements. Despite this, in all experimental
tests, a temperature correction ∆T̂ in the range 0.05–0.1 K was nevertheless applied on the measured
∆TP .

3. Experimental Results
All Peltier modules were tested in the range from 363 K to 213 K, covering the gap with temperature
steps of about 30 K. Investigations were performed at a steady-state, checking the stability of the
set-point imposed on the basis of the temperature measured inside the SAC. As mentioned in the
previous section, the measured quantities were the voltage drops V 0 , VDX , and VDUT , as well as the
Metals 2020, 10, 291 5 of 15

resistance R0 of the module and the figure of merit z0 , the latter two measured using the DX 40490
(z-meter). The measurement protocol of the DX 4090 provides for polarity inversion; therefore, the
voltage drops VDX and VDUT , obtained at each reference temperature Tref , were obtained by averaging
the measured values with current I and −I, respectively. Following this approach for all modules, at
each Tref , the measurement was repeated twice, waiting between the two measurements for the time
necessary for the temperature to return to the set-point value.
The p-n series resistance R, the dimensionless figure of merit zT at Tref , and the Seebeck voltage
∆VS obtained by Equations (1)–(3) are summarized for the Peltier modules in Tables 2–6, specifying the
test current I imposed by the DX 4090.

Table 2. Peltier module a.1: p-n series resistance, the figure of merit, and Seebeck voltage (I = 41 mA).

Tref (K) R (Ω) zTref ∆Vs (mV) Tref (K) R (Ω) zTref ∆Vs (mV)
362.35 1.72 0.93 54.72 273.55 1.10 0.63 34.18
362.35 1.72 0.93 54.70 273.85 1.11 0.62 33.94
332.55 1.52 0.88 50.42 243.85 0.95 0.47 23.98
332.65 1.52 0.88 50.42 244.25 0.94 0.47 24.58
300.15 1.29 0.75 41.53 214.55 0.79 0.34 16.83
302.35 1.29 0.77 43.35 214.85 0.80 0.34 16.56

Table 3. Peltier module a.2: p-n series resistance, the figure of merit, and Seebeck voltage (I = 41 mA).

Tref (K) R (Ω) zTref ∆Vs (mV) Tref (K) R (Ω) zTref ∆Vs (mV)
362.25 1.98 0.95 64.64 273.45 1.29 0.62 38.86
362.35 1.98 0.96 64.73 273.75 1.29 0.62 39.42
332.55 1.77 0.88 57.28 244.05 1.12 0.48 28.32
332.65 1.76 0.88 57.51 244.35 1.11 0.48 28.80
300.55 1.49 0.75 47.13 214.55 0.91 0.35 20.69
302.15 1.51 0.75 48.48 214.85 0.93 0.35 20.00

Table 4. Peltier module a.3: p-n series resistance, the figure of merit, and Seebeck voltage (I = 41 mA).

Tref (K) R (Ω) zTref ∆Vs (mV) Tref (K) R (Ω) zTref ∆Vs (mV)
362.35 2.94 0.94 93.93 272.05 1.87 0.61 56.00
362.35 2.94 0.94 93.79 273.65 1.88 0.61 57.08
332.75 2.61 0.87 83.16 244.05 1.61 0.48 41.47
332.55 2.61 0.87 83.22 244.45 1.60 0.48 42.00
302.45 2.20 0.75 71.05 214.55 1.32 0.34 29.87
301.75 2.18 0.75 69.37 214.85 1.35 0.35 28.64

Table 5. Peltier module b: p-n series resistance, the figure of merit, and Seebeck voltage (I = 25 mA).

Tref (K) R (Ω) zTref ∆Vs (mV) Tref (K) R (Ω) zTref ∆Vs (mV)
362.95 1.15 0.38 10.82 273.15 0.52 0.40 6.06
363.05 1.15 0.37 10.74 273.15 0.52 0.40 6.02
332.45 0.78 0.47 8.32 243.85 0.42 0.32 4.48
332.55 0.76 0.47 8.34 243.85 0.42 0.32 4.48
302.45 0.61 0.47 7.41 213.55 0.35 0.23 3.87 *
302.45 0.62 0.47 7.42 213.55 0.35 0.23 3.87 *
* Measurement performed with feeding current I = 30 mA.
Metals 2020, 1, x FOR PEER REVIEW 6 of 15
Metals 2020, 10, 291 6 of 15
Table 6. Peltier module c: p-n series resistance, the figure of merit, and Seebeck voltage (I = 25 mA).

Table 6. Peltier module c: p-n series resistance, the figure of merit, and Seebeck voltage (I = 25 mA).
Tref (K) R (𝛀) zTref 𝚫VS (mV) Tref (K) R (𝛀) zTref 𝚫VS (mV)
363.05 Tref 1.25
(K) R (Ω) 0.87zTref ∆V s (mV)
23.05 T273.15
ref (K) R (Ω)0.83 zTref ∆Vs (mV)
0.57 13.64
363.05 1.25
363.05 1.25 0.870.87 23.18
23.05 273.15
273.15 0.83 0.82 0.57 0.57
13.64 13.40
332.35 363.05
1.11 1.25 0.800.87 23.18
20.45 273.15
243.85 0.82 0.70 0.57 13.40
0.44 9.78
332.35 332.35
1.10 1.11 0.800.80 20.45
20.66 243.85
243.85 0.70 0.70 0.44 0.439.78 9.78
332.35 1.10 0.80 20.66 243.85 0.70 0.43 9.78
302.35 0.95
302.35 0.95
0.700.70 17.31
17.31
213.85
213.85 0.58
0.58 0.31 0.31
8.07 *
8.07 *
302.35 0.96
302.35 0.96 0.700.70 17.06
17.06 213.85
213.85 0.58 0.58 0.31 0.31
8.07 * 8.07 *
* Measurement performed
* Measurement performedwith
withfeeding currentI I==3030mA.
feeding current mA.

The obtained p-n series resistance R, in addition to the resistance of the semiconductor pillars,
Theatobtained
includes p-n series
each junction bothresistance R, in addition
the resistance to the resistance
of the soldering material of andthethe
semiconductor
connecting copperpillars,
includesFor
element. at each junction
all the modules bothtested,
the resistance
the trend of the soldering material
of resistance and the connecting
R as a function copper
of the reference
element. Forofallthe
temperature thetest
modules
is showntested, the trend
in Figure 2a. of
The resistance
trends are R as a function
almost linearoffor
theall
reference
modules, temperature
with the
of the testofismodule
exception shownbin for Figure
which2a. The trends
a deviation arethe
from almost
linearlinear
trendfor all modules,
is observed with the exception
for temperatures higherof
module b for which a deviation from the linear trend is observed
than the ambient one. Assuming that the assembled thermoelectric materials have common andfor temperatures higher than the
ambient one.
comparable Assuming
properties, that the
Figure assembled
2b shows theirthermoelectric materials
equivalent electrical have common
resistivity obtained andbycomparable
means of
properties,
the geometryFigure
of the2bpillars
showsreported
their equivalent
in Tableelectrical resistivityisobtained
1. This resistivity by means
fairly similar of the geometry
for modules a.1, a.2,of
the pillars reported in Table 1. This resistivity is fairly similar for modules
and a.3, while it assumes quite different values for modules b and c. In particular, the dependence a.1, a.2, and a.3, whileofit
assumes quite
resistivity different values
on temperature for modules
for module b andfrom
b deviates c. Inlinearity
particular,
when the the
dependence of resistivity is
ambient temperature on
temperature
exceeded. The for module
dashed linebshown
deviates in from
Figurelinearity whena the
2b provides ambient temperature
comparison with the values is exceeded.
found in theThe
dashed line
literature [14],shown
whichinrepresent
Figure 2b a provides a comparison
possible trend with the
of the average values resistivity
electrical found in the forliterature
the p and[14],
n
which Bi
doped Te bulk
represent a possible
materials. trend
Theoflatter
the average electricalinresistivity
can be assumed agreement the pthe
forwith n doped Bi
andmeasured 2 Te3 bulk
trends for
materials.
the groupedThe latter can
modules “a” beand assumed
moduleinc,agreement
while the samewith the measured
cannot be saidtrends for theb.grouped modules
for module
“a” and module c, while the same cannot be said for module b.

(a) (b)
Figure
Figure2.2.(a)(a)Assembled
Assembled p-np-nseries
seriesresistance
resistanceR Rgiven
givenbybyEquation
Equation(1)(1)versus
versusthethetest
testreference
reference
temperature
temperature for eacheachPeltier
Peltier module;
module; (b) Equivalent
(b) Equivalent electricalelectrical
resistivityresistivity of thethermoelectric
of the assembled assembled
thermoelectric
materials versus materials versus test
test reference reference temperature
temperature for module.
for each Peltier each Peltier
Themodule.
dashedThelinedashed line a
represents
represents a possible
possible trend trend in temperature
in temperature of the average of the averageresistivity
electrical electrical for
resistivity
the p andfornthe p andBin2 Te
doped doped
3 bulk
2Te3 bulk materials,
Bimaterials, as found inasthe
found in the [26].
literature literature [26].

Thesimilar
The similarbehavior
behaviorforforthe
thePeltier
Peltiermodules
modules“a” “a”isisconfirmed
confirmedby bythe thedimensionless
dimensionlessfigure
figureofof
meritshown
merit shownininFigure
Figure3.3.For
Forthese
thesemodules,
modules,thethemeasured
measuredtrends
trendszTzTrefrefasasthe
thetemperature
temperaturechanges
changes
arepractically
are practicallycoincident
coincidentand
andnotnotsosodifferent
differentfrom
fromthat
thatobtained
obtainedfor modulec.c.On
formodule Onthe
theother
otherhand,
hand,
for module b the resulting figure of merit shows significantly different values
for module b the resulting figure of merit shows significantly different values and trends. and trends.
Since the values of zTref and found for the devices grouped as “a” are similar, it is possible to
assume that their Seebeck coefficients are also similar. Therefore, in the following to estimate the
Seebeck coefficient from the temperature difference ∆𝑇 measured on the ceramic plates, only
modules a.2, b, and c were considered.
 Metals 2020, 10, 291 7 of 15
Metals 2020, 1, x FOR PEER REVIEW 7 of 15

1.0
a.1
a.2
Metals 2020, 1, x FOR PEER REVIEW 0.8 a.3
7 of 15
b
1.0 c

zTref
0.6 a.1
a.2
0.8 a.3
0.4
b
c
zTref

0.6
0.2
200 250 300 350
0.4 Tref (K)

Figure3.3.Measured
Figure Measureddimensionless
dimensionlessfigure
figureof
ofmerit
meritfor
forthe
theinvestigated
investigatedPeltier
Peltiermodules
modulesversus
versusthe
thetest
test
0.2
reference temperature.
reference temperature.
200 250 300 350
Tref (K)
Since
Figure the valuesthe
4 shows of zT ref and
trend overfound
time of forthe
the devices grouped
temperature as “a”
difference ∆𝑇arefor similar,
tests atitmaximum
is possible(363 to
assume
K) and 3.that
Figure minimumtheir Seebeck
Measured dimensionless
temperature coefficients
figureK).
(213 are
of alsoforsimilar.
merit
Figure referTherefore,
the investigated
4a,b in
Peltier
to Peltier the following
modules
modules andto
versus
a.2 c, estimate
the test
respectively. the
Seebeck
referencecoefficient
temperature. from the temperature difference ∆T measured on the
Such a transient temperature difference is caused by the feeding current I, the characteristic time 𝑡
P ceramic plates, only modules
a.2, b, and cusing
estimated were the
considered.
DX 4090 is a useful parameter for the evaluation of the asymptotic value ∆𝑇 , .
Figure
In fact, 4
Figure shows the
4 showsthe
assuming trend
the trend
time over time
𝑡over
as ofparameter
time
the the temperature
of the temperature difference∆𝑇
difference
that characterizes ∆TPfor
the fortests
testsatat
response maximum
tomaximum
a step input (363
(363ofK)a
K) and
and minimum
minimum temperature
temperature (213
(213 K).
K). Figure
Figure 4a,b
4a,b refer
refer to to Peltier
Peltier modules
modules
first-order linear system (RC lumped model), it was possible to obtain the best fit of the values a.2a.2
and and
c, c, respectively.
respectively. Such ∆𝑇a
Such a transient
transient temperature
temperature difference
difference is is
caused caused
by theby the
feeding feeding
current
and evaluate the asymptotic temperature differences ∆𝑇 , shown in Figure 4a,b with dashed current
I, the I, the characteristic
characteristic time t time
0
𝑡
estimated
lines.
estimated
using using
the DX the DX
4090 is4090
a is
useful a useful
parameterparameter
for the for the evaluation
evaluation of the of
The agreement with the measured values is pointed out through the trends calculated with 𝑡 .fact, the asymptotic
asymptotic value value
∆T P,∞
∆𝑇
. In
, and
In fact,
∆𝑇 ,assuming
assuming the time
the time
, represented t0in 𝑡theas
as the the parameter
parameter
previous that characterizes
that characterizes
figures by the solidthelinesthe
response response
that to a step
reproduce to input
a the
stepof input
two of a
a first-order
sequential
first-order
linear linear
system
transients system
(RC (RC
lumped
established by lumped
model),
the model), itprotocol
it was possible
measurement was possible of theto
to obtain obtain
the
DX best the
4090.fit ofbest fit of the
the values ∆Tvalues ∆𝑇
P and evaluate
andtheevaluate the asymptotic temperature differences ∆𝑇 shown in Figure
asymptotic temperature differences ∆TP,∞ shown in, Figure 4a,b with dashed lines. The agreement 4a,b with dashed lines.
Thewith
agreement with the
the measured measured
values values
is pointed outisthrough
pointedthe outtrends
through the trends
calculated withcalculated
t0 and ∆TP,∞ with 𝑡 and
, represented
∆𝑇 in , represented in the previous figures by the solid lines that reproduce
, the previous figures by the solid lines that reproduce the two sequential transients established by the two sequential
transients establishedprotocol
the measurement by the measurement
of the DX 4090. protocol of the DX 4090.

(a) (b)
Figure 4. Examples of the transient temperature difference measured on the external surface of the
ceramic plates versus time for the two cases with maximum and minimum reference temperature.
Solid lines represent(a) the trend calculated with a lumped model that uses (b) the characteristic time 𝑡
provided by the DX 4090; dashed lines represent the asymptotic values ∆𝑇 , . (a) module a.2; (b)
Figure 4. Examples
Figure
module of the
4. c.Examples of transient temperature
the transient difference
temperature measured
difference measuredon the
on external
the external surface of the
surface of the
ceramic plates
ceramic versus
plates timetime
versus for the
for two cases
the two withwith
cases maximum
maximumand and
minimum
minimumreference temperature.
reference temperature.
Solid
Solid lineslines
Since the represent
represent
estimatedthe∆𝑇
the trend trend
,
calculated
calculated
are withwith
a a lumped
lumped
systematically model
model
lower that
than that
uses
the uses
the
actual the characteristic
characteristic
values of 𝑡 t0
time
timetemperature
the
difference ∆𝑇 of the junctions, as mentioned at the end of the previous
provided
provided by by
the the
DX DX 4090;
4090; dashed
dashed lines
lines represent
represent the the asymptotic
asymptotic values ∆𝑇
values ∆T
, . (a)
P,∞ . (a) module
module a.2; a.2;
(b) (b)
section, a temperature
module
module c. c.
correction ∆𝑇 has been imposed, such that ∆𝑇 = ∆𝑇 + ∆𝑇. In the performed tests, ∆𝑇 = 0.05 𝐾
,
was assigned to modules a.2 and c, and ∆𝑇 = 0.1 𝐾 to module b, due to the higher temperature noise
Since
Since the the estimated
estimated ∆T are are
∆𝑇Seebeck systematically
systematically lowerlower than
the the actual values of the temperature
noticed. Using the total , P,∞ voltage measured at than
the leads actual
of thesevalues
modules,of the temperature
Figure 5 shows the
difference ∆T of the junctions, as mentioned at the end of the previous section, a temperature correction
Seebeck∆𝑇voltage
difference of
S the junctions, as mentioned at the end of the previous section, a temperature
of a single pair as a function of the estimated Seebeck temperature difference ∆𝑇
∆T̂ has been imposed, such thatsuch∆TS = ∆T∆𝑇
P,∞ + ∆ T̂., In+the
∆𝑇performed tests, ∆T̂ tests,
= 0.05∆𝑇K was assigned
for the ∆𝑇
correction has
junctions. beenIn imposed,
Figure 5, it that
is possible to=observe
∆𝑇 the .linear
In thetrend
performed
of the Seebeck = 0.05
voltage 𝐾
with a
to modules
was greater
assigned a.2 and
to modules c, and
a.2 and∆ T̂ = 0.1
c, and ∆𝑇 K to module b,
= 0.1 𝐾 totomodule due to the
b, a.2
dueandhigher
to the temperature
higher noise
temperature noticed.
noise
slope in the case of module c compared modules b. The same slope found for the
UsingUsing
noticed. the total Seebeck
the total voltage
Seebeck measured
voltage at theatleads
measured of these
the leads modules, Figure 5 shows the Seebeck
latter two modules suggests similar Seebeck coefficients forofboth
these modules,
devices. Figure 5 shows the
Seebeck voltage of a single pair as a function of the estimated Seebeck temperature
In fact, the equivalent Seebeck coefficients of the single junction resulting from Equation (3) and difference ∆𝑇
for the junctions.
shown In Figure
in Figure 6a as a5,function
it is possible
of thetoreference
observe temperature
the linear trend of the
of the test,Seebeck
highlightvoltage withvalues
the same a
greater slope in the case of module c compared to modules a.2 and b. The same slope found for the
latter two modules suggests similar Seebeck coefficients for both devices.
In fact, the equivalent Seebeck coefficients of the single junction resulting from Equation (3) and
Metals 2020,
Metals 2020, 10,
1, x291
FOR PEER REVIEW 88 of 15
of 15

for modules a.2 and b, and higher values with a different trend for module c. In this figure, the solid
voltage of a single
lines indicate the pair as a function
second-order of the estimated
polynomial Seebeck
fit, whose temperature
equation, and∆Treference
difference
coefficients, S for the
junctions.
temperature 𝑇 are 5,
In Figure it is possible
shown to observe
inside the diagram thebox.
linear
Thetrend of the
dashed Seebeck
line in the voltage with a greater
figure represents the
/
slope in thetrend
theoretical case of
proportional to 𝑇
module c compared to
, asmodules
mentioneda.2 and b. The same
by Goldsmid [26]slope found
for the for the latter
thermoelectric two
power
of Bi Te suggests
modules . similar Seebeck coefficients for both devices.
Metals 2020, 1, x FOR PEER REVIEW 8 of 15

for modules a.2 and b, and higher values with a different trend for module c. In this figure, the solid
lines indicate the second-order polynomial fit, whose equation, coefficients, and reference
temperature 𝑇 are shown inside the diagram box. The dashed line in the figure represents the
/
theoretical trend proportional to 𝑇 , as mentioned by Goldsmid [26] for the thermoelectric power
of Bi Te .

5. Seebeck voltage of a single pair (total

Figure 5. (total Seebeck
Seebeck voltage divided by the number
number of pairs N
of pairs NPP)
versus the estimated
estimated temperature difference∆T
temperature difference ∆𝑇S of
ofthe
theSeebeck
Seebeckjunction.
junction.

In fact, the equivalent Seebeck coefficients of the single junction resulting from Equation (3) and
shown in Figure 6a as a function of the reference temperature of the test, highlight the same values
for modules a.2 and b, and higher values with a different trend for module c. In this figure, the solid
lines indicate the second-order polynomial fit, whose equation, coefficients, and reference temperature
T0 areFigure
shown 5. inside
Seebeckthe diagram
voltage box. The
of a single pair dashed line involtage
(total Seebeck the figure represents
divided the theoretical
by the number of pairs NPtrend
)
proportional to T 3/2 , as mentioned by Goldsmid [26] for the thermoelectric power of Bi Te .
versus the estimated
re f temperature difference ∆𝑇 of the Seebeck junction. 2 3

(a) (b)
Figure 6. (a) Equivalent single junction Seebeck coefficients versus test reference temperature for
modules a.2, b and c. The fitting equation and regression coefficients are shown in the diagram box.
The solid lines represent the fit trends, and the dashed line is the theoretical trend mentioned by
Goldsmid [26]; (b) Thomson coefficient trends for module c (i) and modules a.2 and b (ii). Parameters
m and n are those shown in (a), and 𝜏 values are the Thomson coefficients at 𝑇 .

(a) (b)
From the equations for 𝜀(𝑇), two temperature-dependent relationships were obtained for the
Thomson Figure
Figure coefficients
6.6. (a) 𝜏(𝑇) =
(a) Equivalent
Equivalent 𝑇𝑑𝜀(𝑇)/𝑑𝑇
single
single junctionfor
junction module
Seebeck
Seebeck c, and modules
coefficients
coefficients versus test
versus a.2reference
test and b marked,
reference hereafter
temperature
temperature for as
for
(i) and (ii) respectively.
modules
modules a.2,bband
a.2, Figure
andc.c. The
The 6bequation
fitting
fitting shows and
equation the trends
and regression
regressionforcoefficients
the Thomson
coefficients coefficient
are shown
are shown in the
in with respect
the diagram
diagram box. to
box.
temperature,
The solidand
Thesolid linesinside
lines representthethe
represent diagram
the fit
fit trends,boxand
trends, thethe
and reported
the dashedrelationship
dashed line
line isis the refers totrend
thetheoretical
theoretical bothmentioned
trend cases (i) and
mentioned by (ii);
by
parameters m and n are those shown in Figure 6a, while 𝜏 = 𝑚𝑇 is the Thomson coefficientmat the
Goldsmid
Goldsmid [26]; (b)
[26]; (b)Thomson
Thomson coefficient
coefficient trends
trends forformodule
module c (i)
c and
(i) andmodules
modules a.2 and
a.2 andb (ii).
b Parameters
(ii). Parameters
and ntemperature
m and
reference are those
n are shown
those 𝑇 in
shown = (a),
298.15𝐾.
andand
in (a), τ0 values
𝜏 values are the
are Thomson
the Thomson coefficients
coefficientsat T0at . 𝑇.
Finally, with the measured electric resistance R and the Seebeck coefficient estimated, from the
From
From the
well know theequations
relationequations forε𝜀(𝑇),
for
that expresses
(T ), two
the two temperature-dependent
temperature-dependent
figure
relationships were
of merit 𝑧 = (2𝑁 𝜀) relationships
/(𝑅 𝐾), the thermal were obtained
obtained
conductance
for
forthe
the
𝐾
Thomson
Thomson coefficients
coefficients τ𝜏(𝑇)
(T ) == Tdε(T )/dT for
𝑇𝑑𝜀(𝑇)/𝑑𝑇 for module
module c,c,and andmodules
modulesa.2 a.2and andb bmarked,
marked, hereafter
hereafter as
was obtained for modules a.2, b, and c, as shown in Figure 7a. Then, using the pillars geometry
as (i) and
(i) and (ii) (ii) respectively.
respectively. Figure 6b
Figure 6b thermal shows
shows the the trends for
trends forofthe the Thomson coefficient with respect to
reported in Table 1, the equivalent conductivity theThomson
assembled coefficient
thermoelectric with respect
materials to
temperature,
temperature, and
and inside
inside the
the diagram
diagram box
box the
the reported
reported relationship
relationship refers
refers to
to both
both cases
cases (i)
(i) and
and (ii);
(ii);
was estimated. Figure 7b displays the values found against the reference temperature of the test, and
parameters
parameters m and nnare
arethose shown in Figure 6a,
6a, while τ𝜏0 = = mT isisthe
theThomson
𝑚𝑇0conductivity coefficient at the
the dashed m lineandrepresents thosethe shown
trendinof Figure
the average whilethermal Thomson withcoefficient
respect toatthe the
reference temperature T = K.
for p and n𝑇 0 = 298.15𝐾.
reference temperature 298.15
temperature doped Bi2Te3 bulk materials found in the literature [27].
Finally,
Finally,withwiththe themeasured
measuredelectric resistanceRRand
electricresistance andthetheSeebeck
Seebeckcoefficient
coefficientestimated,
estimated,from fromthethe
2
that expresses the figure of merit z = (
well know relation that expresses the figure of merit 𝑧 = (2𝑁 𝜀) /(𝑅 𝐾), the thermal conductance 𝐾
well know relation 2N P ε ) / ( R K ) , the thermal conductance
was obtained for modules a.2, b, and c, as shown in Figure 7a. Then, using the pillars geometry
reported in Table 1, the equivalent thermal conductivity of the assembled thermoelectric materials
was estimated. Figure 7b displays the values found against the reference temperature of the test, and
the dashed line represents the trend of the average thermal conductivity with respect to the
temperature for p and n doped Bi2Te3 bulk materials found in the literature [27].
 Metals 2020, 10, 291 9 of 15

K was obtained for modules a.2, b, and c, as shown in Figure 7a. Then, using the pillars geometry
reported in Table 1, the equivalent thermal conductivity of the assembled thermoelectric materials was
estimated. Figure 7b displays the values found against the reference temperature of the test, and the
dashed line represents the trend of the average thermal conductivity with respect to the temperature
Metals 2020, 1, x FOR PEER REVIEW 9 of 15
for p and n doped Bi2 Te3 bulk materials found in the literature [27].

(a) (b)
Figure
Figure 7. (a)
7. (a) Thermal
Thermal conductance
conductance versus
versus thethe reference
reference temperature
temperature of of
thethe
testtest
forfor modules
modules a.2,a.2, b, and
b, and
c.; c.;
(b)(b) Equivalent
Equivalent thermal
thermal conductivity
conductivity of the
of the assembled
assembled thermoelectric
thermoelectric materials
materials versus
versus thethe reference
reference
temperature
temperature of of
thethe test
test forfor modules
modules a.2,a.2,
b, b,
andandc. c.
TheThe dashed
dashed lineline represents
represents a possible
a possible trend
trend in in
temperature of the average thermal conductivity for p and n doped
temperature of the average thermal conductivity for p and n doped Bi2Te2 3 bulk Bi Te3 bulkmaterials, as found in in
materials, as found
thethe literature
literature [27].
[27].

4. Discussion
4. Discussion
The results of the tests performed on various commercial Peltier modules, described in the previous
The results of the tests performed on various commercial Peltier modules, described in the
section, make it possible to highlight the temperature dependence of their thermoelectric properties,
previous section, make it possible to highlight the temperature dependence of their thermoelectric
in particular for the Seebeck coefficient ε, the electric resistivity ρ, and the thermal conductivity λ.
properties, in particular for the Seebeck coefficient 𝜀 , the electric resistivity 𝜌, and the thermal
These properties were mentioned as equivalent, because they were not obtained through investigations
conductivity 𝜆. These properties were mentioned as equivalent, because they were not obtained
carried out directly on semiconductor materials, but indirectly through the same materials assembled
through investigations carried out directly on semiconductor materials, but indirectly through the
in thermoelectric modules. Despite this, the values found and the comparison with the literature data
same materials assembled in thermoelectric modules. Despite this, the values found and the
gave them adequate reliability.
comparison with the literature data gave them adequate reliability.
The temperature dependence of the thermoelectric properties makes it difficult to predict the
The temperature dependence of the thermoelectric properties makes it difficult to predict the
actual performance of a device when used in the various temperature ranges. Furthermore, the impact
actual performance of a device when used in the various temperature ranges. Furthermore, the
of the Thomson effect on the performance of a device is not always so clear, especially when this effect
impact of the Thomson effect on the performance of a device is not always so clear, especially when
overlaps the Joule effect caused by electrical resistivity if the latter also depends on the temperature.
this effect overlaps the Joule effect caused by electrical resistivity if the latter also depends on the
The analysis was focused on the temperature dependence of the Seebeck coefficient ε that is
temperature.
responsible for the Thomson coefficients τ previously identified as (i) and (ii). The temperature
The analysis was focused on the temperature dependence of the Seebeck coefficient 𝜀 that is
dependence of the electrical resistivity ρ and of the thermal conductivity λ was also considered,
responsible for the Thomson coefficients 𝜏 previously identified as (i) and (ii). The temperature
adopting the values obtained for module c and a.2, in the cases (i) and (ii), respectively. Assuming
dependence of the electrical resistivity 𝜌 and of the thermal conductivity 𝜆 was also considered,
in the temperature range investigated there is a linear and a quadratic trend for the resistivity and
adopting the values obtained for module c and a.2, in the cases (i) and (ii), respectively. Assuming in
conductivity respectively, and taking into account what is specified for temperature dependence of the
the temperature range investigated there is a linear and a quadratic trend for the resistivity and
Seebeck coefficient (see Figure 6a), the general relationship of dependence on the temperature adopted
conductivity respectively, and taking into account what is specified for temperature dependence of
for these properties (y is the generic one) can be written as:
the Seebeck coefficient (see Figure 6a), the general relationship of dependence on the temperature
adopted for these properties (𝑦 is the generic one) can be written as: 2
y(T ) = y0 + m(T − T0 ) + n(T − T0 ) , (4)
𝑦(𝑇) = 𝑦 + 𝑚(𝑇 − 𝑇 ) + 𝑛(𝑇 − 𝑇 ) , (4)
where y0 is the value (ε0 , ρ0 , λ0 ) of the considered property at the reference temperature T0 . In Table 7,
where 𝑦 is the value (𝜀 , 𝜌 , 𝜆 ) of the considered property at the reference temperature 𝑇 . In
for a reference temperature T0 = 298.15 K, the coefficients y0 , m, and n are displayed for both cases (i)
Table 7, for a reference temperature 𝑇 = 298.15 𝐾, the coefficients 𝑦 , 𝑚, and 𝑛 are displayed for
and (ii). For cases (i) and (ii), the geometry of the pillars and the number of pairs are those reported
both cases (i) and (ii). For cases (i) and (ii), the geometry of the pillars and the number of pairs are
in Table 1 referring, respectively, to modules c and a.2. The effect produced by the temperature
those reported in Table 1 referring, respectively, to modules c and a.2. The effect produced by the
temperature dependence of the thermoelectric properties was obtained by assuming the steady-state
conditions and a one-dimensional thermal and electric field along pillars and solving the following
governing equation:
𝜆 − 𝑇 𝑗 + 𝜌𝑗 = 0, (5)
Metals 2020, 10, 291 10 of 15

dependence of the thermoelectric properties was obtained by assuming the steady-state conditions and
a one-dimensional thermal and electric field along pillars and solving the following governing equation:

d2 T
!
dε dT
λ 2 − T j + ρj2 = 0, (5)
dx dT dx

where j is the current density, and the term in round brackets is the Thomson coefficient. The first term
of Equation (5) represents the heat flux due to the Fourier conduction, while the second and the third
terms characterize the heat generation due respectively to the Thomson and Joule effects. Dirichlet
boundary conditions were imposed at the cold (x = 0, T = TC ) and hot (x = L, T = TH ) side, thus the
heat fluxes at these boundaries can be calculated as:

dT 
QC = 2NP I ( ε|x=0 TC ) − 2NP Aλ  , (6)
dx x=0

dT 
QH = 2NP I ( ε|x=L TH ) − 2NP Aλ  , (7)
dx x=L
where in both equations, the terms in round brackets are the Peltier coefficients on the cold and hot
sides, A is the cross-section of the pillar (A = W 2 ), while in both equations the first and second terms
represent Peltier and Fourier heat fluxes on the cold and hot sides respectively. The coefficient of
performance (COP) of the device can be expressed by:

COP = QC /(QH − QC ). (8)

Table 7. Coefficients for the temperature dependence relationship of ε, ρ, λ. (T0 = 298.15 K).

Case Property y0 m n
ε(T ), V/K 195.93 0.4675 −0.0013
(i) ρ(T ), m 11.390 0.0541 -
λ(T ), W/(m K) 1.4921 −0.0045 3.78·10−5
ε(T ), V/K 188.44 0.3033 −0.0021
(ii) ρ(T ), m 7.6813 0.0370 -
λ(T ), W/(m K) 1.9033 −0.0088 3.34·10−5

The solution for Equation (5) at any location x was obtained numerically by discretization of
the computational domain (0 < x < L). The domain was meshed with more than one hundred and
one-dimensional elements; the set of equations was solved with a recursive finite differences algorithm
(see, for example [28]), adopting a three-point approximation of the temperature gradient.
For both types of modules, (i) and (ii), using three different currents, I = IMAX , I = 0.375 IMAX ,
and I = 0.125 IMAX two cases were examined with constant hot side temperatures equal to TH = 298.15 K
and TH = 323.15 K respectively. IMAX = (A/L)TH εH /ρH is current with which QC,MAX is obtained
when the cold side is kept at the temperature TH , and εH , ρH , are the Seebeck coefficient and the
electrical resistivity at TH .
To explore these scenarios,  TC of the cold side was varied in steps of 1 K from TH
 √ the temperature
to TC,min assuming TC,min = 1 + 2zH TH − 1 /zH , with zH = ε2H /(λH ρH ), λH the figure of merit and
the thermal conductivity at TH , respectively. For each assigned TC , the temperature distribution along
the pillars was calculated by solving Equation (5), and therefore determining the heat fluxes on the
cold and hot sides with Equations (6) and (7), and the coefficient of performance with Equation (8).
Positive Thomson heat (second term of Equation (5)) plays the role of reducing heat generation by
Joule effect (third term of Equation (5)), and both cases (i) and (ii) show a positive Thomson heat at
the cold side. Figure 8, for the cases at TH = 298.15 K and TH = 323.15 K, shows the ratio between
Metals 2020, 10, 291 11 of 15

Thomson heat and Joule effect calculated on the cold side as a function of the relative cooling capacity
QC /Q
Metals 2020,
C,Max1, xfor
FORdifferent values of the relative feeding current I/IMAX .
PEER REVIEW 11 of 15

(a) (b)
Figure
Figure8. Coldside:
8.Cold side:ratio
ratiobetween
betweenThomson
Thomsonheat heatand
andJoule
Jouleeffect
effectversus
versusthe
therelative
relativecooling
coolingcapacity,
capacity,
solidline
solid linecase
case (i),
(i), dashed
dashed line
line case
case (ii).
(ii). (a) TH ==298.15
(a) 𝑇 298.15 𝐾;
K; (b) 𝑇H =
(b) T = 323.15 𝐾.
323.15 K.

Since
To the Joulethe
underline effect is always
Thomson positive,
effect the graphs
in relation to thein Figure 8 suggest
temperature an enhancement
dependence of the
of electrical
cooling capacity
resistivity inducedconductivity,
and thermal by the Thomson effect,
it can alsoin be
particular
useful for high values
to make of ∆T when
a comparison withtheanother
cooling
capacity decreases. By increasing the cooling capacity, ∆T goes
hypothetical scenario. In this scenario, the Seebeck coefficient is temperature dependent, to zero, and the Thomson heatas is
minimum, but
established its cases
in the value (i)increases
and (ii),with
whilethethe
current. To clarify
electrical the real
resistivity androle
the assumed by the Thomson
thermal conductivity are
effectindependent
both in improving ofthe
temperature (i.e., 𝜌 =it 𝜌is ,more
cooling capacity, 𝜆 = 𝜆interesting to compare
). Thes scenarios, for the
bothexperimental
cases (i) and results
(ii), is
obtained
shown with an9,ideal
in Figure 𝑇 = 298.15 𝐾,
withcircumstance. Inand
thisinideal case10,
Figure allwith 𝑇 = 323.15 𝐾.properties
the thermoelectric In the twoare assumed
figures, the
independent
trends of the temperature
of the relative cooling capacity(i.e., ε 𝑄= /𝑄
εH , ρ = asρaHfunction
, λ = λH ), ofand, therefore,
the relative the Thomson
temperature effect is
difference
Δ𝑇/Δ𝑇
zero, and ,the heat generation
compared by Joule
for different effect
values ofalong the pillars
the relative with current
feeding 𝐼/𝐼
a fixed current ,isare
constant.
quite similar.
With the adoption of the previous defined 𝑇 , , the maximum temperature difference depends
To underline the Thomson effect in relation to the temperature dependence of electrical resistivity
on
andtemperature
the thermal conductivity,
of the hotitside can chosen,
also be useful
named to Δ𝑇
make a=comparison
𝑇 − 𝑇 , with . another hypothetical scenario.
In this scenario, the Seebeck coefficient is temperature dependent, as established in the cases (i) and (ii),
while the electrical resistivity and the thermal conductivity are both independent of temperature (i.e.,
ρ = ρH , λ = λH ). Thes scenarios, for both cases (i) and (ii), is shown in Figure 9, with TH = 298.15 K,
and in Figure 10, with TH = 323.15 K. In the two figures, the trends of the relative cooling capacity
QC /QMax as a function of the relative temperature difference ∆T/∆TMax , compared for different values
of the relative feeding current I/IMAX , are quite similar. With the adoption of the previous defined
TC,min , the maximum temperature difference depends on the temperature of the hot side chosen, named
∆TMax = TH − TC,min .
In the previous diagrams, it can be seen that the results obtained with the temperature-independent
properties, represented by the dashed lines, show a linear trend with respect to the relative temperature
difference ∆T/∆TMax . The slope depends on the feeding current, i.e., −2NP [εH I − (A/L)λH ]/QC,Max ,
and reproduces the typical (a) trend proposed in datasheets of commercial (b) devices. On the contrary,
the experimental
Figure 9. 𝑇 =results 298.15 obtained,
𝐾 . Relativerepresented by the𝑄thick
cooling capacity /𝑄 solid lines,
against theshow the temperature
relative influence of the
difference Δ𝑇/Δ𝑇
temperature-dependent thermoelectric properties
for different relative feedingwithcurrents 𝐼/𝐼 reduced
an overall . The thickcooling capacity,
solid lines in particular
represent the
for both
performed experiment; the dashed lines refer to thermoelectric properties independent ofare no
high feeding currents, and temperature differences. With a low feeding current there
significant differences
temperature, the thinregardless
solid linesof the assumptions
indicate the scenarioabout
in whichthethethermoelectric properties,
Seebeck coefficient depends while
on theat high
currents, a reduced
temperature, cooling
while bothcapacity is observed
the electrical for alland
resistivity the the
temperature differences between
thermal conductivity the junctions.
are temperature
When ∆T approaches
independent: (a) case (i);the
zero, (b) reduced
case (ii). cooling capacity is caused by the different temperature gradients
resulting on the cold side. The temperature gradient is influenced by the temperature profile along the
pillars, which depends on the electrical resistivity and thermal conductivity. Furthermore, the thermal
gradient on the cold side in the case of temperature-dependent properties is higher than that found in
the ideal case of temperature-independent properties. In this way, with the same Peltier heat flux for
∆T = 0, the Fourier heat conduction increases. Therefore, with regard to case (ii), Figures 9b and 10b
show at the higher current a greater deviation from ideal conditions due to the higher thermal
resistivity and thermal conductivity, it can also be useful to make a comparison with another
hypothetical scenario. In this scenario, the Seebeck coefficient is temperature dependent, as
established in the cases (i) and (ii), while the electrical resistivity and the thermal conductivity are
both independent of temperature (i.e., 𝜌 = 𝜌 , 𝜆 = 𝜆 ). Thes scenarios, for both cases (i) and (ii), is
shown in Figure 9, with 𝑇 = 298.15 𝐾, and in Figure 10, with 𝑇 = 323.15 𝐾. In the two figures, the
Metals 2020, 10, 291 12 of 15
trends of the relative cooling capacity 𝑄 /𝑄 as a function of the relative temperature difference
Δ𝑇/Δ𝑇 , compared for different values of the relative feeding current 𝐼/𝐼 , are quite similar.
With the adoption
conductivity value of theTable
(see previous defined 𝑇with
7), compared , , Figures
the maximum
9a and temperature difference
10a, which refer to casedepends on
(i). At the
the temperature
lower of the hot side
currents investigated, thischosen,
fact wasnamed Δ𝑇
negligible. = 𝑇 − 𝑇, .

(a) (b)
Figure 9.9.TH𝑇 ==298.15
Figure 298.15K.𝐾Relative
. Relative cooling
cooling capacity
capacity QC /QMax𝑄 /𝑄
againstagainst the temperature
the relative relative temperature
difference
∆T/∆T
difference
Max Δ𝑇/Δ𝑇
for for
different different
relative relative
feeding feeding
currents I/Icurrents
MAX . The𝐼/𝐼
thick . The
solid thick
lines solid lines
represent represent
the the
performed
performed the
experiment; experiment;
dashed linestherefer
dashed lines refer properties
to thermoelectric to thermoelectric
independentproperties independent
of temperature, of
the thin
temperature,
solid the thin
lines indicate thesolid lines in
scenario indicate
whichthe thescenario
Seebeckin which thedepends
coefficient Seebeckon coefficient depends on
the temperature, the
while
temperature,
both while
the electrical both theand
resistivity electrical resistivity
the thermal and the
conductivity arethermal conductivity
temperature are temperature
independent: (a) case (i);
Metals 2020, 1, x FOR PEER REVIEW 12 of 15
(b) case (ii). (a) case (i); (b) case (ii).
independent:

(a) (b)
Figure
Figure 10.10. T𝑇H = = 323.15
323.15𝐾K.. Relative
Relativecooling capacity 𝑄
cooling capacity QC/𝑄
/QMax against
against the relative temperature
temperature
difference ∆T/∆T
difference Δ𝑇/Δ𝑇Max for different relative feeding currents 𝐼/𝐼
for different relative feeding currents I/I MAX . The thick solid lines represent the
. The thick solid lines represent the
performed
performedexperiment,
experiment, thethe
dashed lines refer
dashed lines torefer
thermoelectric properties properties
to thermoelectric independentindependent
of temperature,
of
the thin solid lines
temperature, indicate
the thin the scenario
solid lines indicateinthewhich the Seebeck
scenario in whichcoefficient
the Seebeckdepends on the
coefficient temperature,
depends on the
while both the while
temperature, electrical resistivity
both and theresistivity
the electrical thermal conductivity are temperature
and the thermal independent:
conductivity (a) case
are temperature
(i); (b) case (ii).
independent: (a) case (i); (b) case (ii).

The
In theassumption
previous that only the
diagrams, Seebeck
it can coefficient
be seen that the depends
results on the temperature
obtained allows us to
with the temperature-
better highlight
independent the contribution
properties, representedof the byThomson
the dashed effect. Onshow
lines, the cold side,trend
a linear as shown
with in Figureto8a,b,
respect the
the magnitude of the Thomson heat compared with the heat generation
relative temperature difference Δ𝑇/Δ𝑇 . The slope depends on the feeding current, i.e., by Joule effect is greater at
higher ∆T and with
−2𝑁 𝜀 𝐼 − (𝐴⁄𝐿)𝜆 /Q , lower cooling capacities. In addition, the Thomson heat, although
, and reproduces the typical trend proposed in datasheets of commercialreduced, does not
vanish
devices. at On
smaller ∆T and with
the contrary, greater coolingresults
the experimental capacity, and when
obtained, the temperature
represented difference
by the thick solidapproaches
lines, show
zero, it clearly increases with the feeding current. The thin solid lines
the influence of the temperature-dependent thermoelectric properties with an overall reduced in Figure 9a,b shows these
evidence. At the lowest current set, the effect induced by Thomson heat is practically
cooling capacity, in particular for both high feeding currents, and temperature differences. With undetectable anda
its
low influence
feedingiscurrent
observable
theredueareto no
thesignificant
increase in differences
the feeding current.
regardless At higher
of the temperature
assumptionsdifferences,
about the
the
thermoelectric properties, while at high currents, a reduced cooling capacity is observedproperties),
trend of the cooling capacity shifts toward the ideal condition (temperature-independent for all the
but remains even
temperature lower. Otherwise,
differences between with higher feeding
the junctions. When current and at the lower
Δ𝑇 approaches zero,temperature
the reduced difference,
cooling
the cooling capacity exceeds that obtained in the ideal condition because on
capacity is caused by the different temperature gradients resulting on the cold side. The temperature the cold side, the heat
generated by Joule effect is reduced due to the heat absorbed by the Thomson
gradient is influenced by the temperature profile along the pillars, which depends on the electricaleffect, and consequently
the local thermal
resistivity gradient
and thermal and the Fourier
conductivity. heat contribution
Furthermore, the thermal aregradient
reduced.on A the
further
coldconfirmation
side in the case of
of temperature-dependent properties is higher than that found in the ideal case of temperature-
independent properties. In this way, with the same Peltier heat flux for Δ𝑇 = 0, the Fourier heat
conduction increases. Therefore, with regard to case (ii), Figures 9b and 10b show at the higher
current a greater deviation from ideal conditions due to the higher thermal conductivity value (see
Table 7), compared with Figures 9a and 10a, which refer to case (i). At the lower currents investigated,
Metals 2020, 10, 291 13 of 15

this is given by the coefficients of performance reported in Figures 11 and 12, for which it is difficult
Metals 2020, 1, x FOR PEER REVIEW 13 of 15
to highlight
Metals 2020, 1, xan improvement
FOR PEER REVIEW in the performance of the device compared with the event that 13 only
of 15
the Seebeck coefficient is temperature-dependent (solid thin lines). Under these conditions, for the
(solid thin lines). Under these conditions, for the thermoelectric modules investigated, only with the
(solid thin lines).
thermoelectric Under investigated,
modules these conditions,
onlyfor thethe
with thermoelectric modulesa investigated,
maximum current, only with
small improvement the
in the
maximum current, a small improvement in the performance was observed.
maximum current,
performance a small improvement in the performance was observed.
was observed.

(a) (b)
(a) (b)
Figure 11. 𝑇 = 298.15 𝐾 . Coefficient of performance against the relative temperature difference
Figure 11. T𝑇H = 298.15
Figure 11. 298.15 𝐾K.. Coefficient
Coefficient of of performance
performance against
against the relative
relative temperature
temperature difference
difference
Δ𝑇/Δ𝑇 at different relative feeding current 𝐼/𝐼 , thick solid lines represent the performed
∆T/∆T
Δ𝑇/Δ𝑇 Max at different relative feeding current 𝐼/𝐼MAX
relative feeding current I/I , thick solid lines represent the performed
solid lines represent the performed
experiment, dashed lines refer to temperature-independent thermoelectric properties, thin solid lines
experiment,
experiment,dashed
dashedlines
linesrefer
referto
to temperature-independent
temperature-independentthermoelectric
thermoelectricproperties,
properties,thin
thinsolid
solidlines
lines
denote the scenario in which the Seebeck coefficient is temperature-dependent and both electrical
denote
denote the
the scenario
scenario in
in which
which the
the Seebeck
Seebeck coefficient
coefficient isistemperature-dependent
temperature-dependent and and both
both electrical
electrical
resistivity and thermal conductivity are temperature independent: (a) case (i); (b) case (ii).
resistivity
resistivityand
andthermal
thermalconductivity
conductivityare aretemperature
temperatureindependent:
independent:(a) (a)case
case(i);
(i);(b)
(b)case
case(ii).
(ii).

(a) (b)
(a) (b)
Figure 12. T𝑇H =
Figure 12. = 323.15
323.15 𝐾K.. Coefficient
Coefficient ofof performance
performance againstagainst the relative temperature
temperature difference
difference
Figure 12. 𝑇 = 323.15 𝐾 . Coefficient of performance against the relative temperature difference
∆T/∆T
Δ𝑇/Δ𝑇 Max at at different relative feeding current I/I 𝐼/𝐼MAX , thick solid lines represent
represent the
the performed
performed
Δ𝑇/Δ𝑇 at different relative feeding current 𝐼/𝐼 , thick solid lines represent the performed
experiment,
experiment, dashed
dashed lines
lines refer
refer to
to temperature-independent
temperature-independent thermoelectric
thermoelectric properties,
properties, thin
thin solid
solid lines
lines
experiment, dashed lines refer to temperature-independent thermoelectric properties, thin solid lines
denote
denote the
the scenario
scenario inin which
which the
the Seebeck
Seebeck coefficient
coefficient isis temperature-dependent
temperature-dependent and and both
both electrical
electrical
denote the scenario
resistivity in which the Seebeck coefficient is temperature-dependent and both electrical
resistivity and
and thermal
thermal conductivity
conductivityarearetemperature
temperatureindependent:
independent:(a) (a)case
case(i);
(i);(b)
(b)case
case(ii).
(ii).
resistivity and thermal conductivity are temperature independent: (a) case (i); (b) case (ii).
5. Conclusions
5. Conclusions
5. Conclusions
Based on what emerged from the experimental investigations and analyses, it is possible to affirm
Based on what emerged from the experimental investigations and analyses, it is possible to
Based
that the on what
intrinsic emerged
Thomson effectfrom the experimental
appears investigations
clearly when all and
the properties areanalyses, it is dependent.
temperature possible to
affirm that the intrinsic Thomson effect appears clearly when all the properties are temperature
affirm that the
Furthermore, intrinsic
it seems Thomson to
inappropriate effect appears
separate clearly when all the properties
the temperature-dependence are temperature
of the Seebeck coefficient
dependent. Furthermore, it seems inappropriate to separate the temperature-dependence of the
dependent.
from Furthermore,
the temperature it seemsofinappropriate
dependence to separateproperties
the other thermoelectric the temperature-dependence
as sometimes found in of the
the
Seebeck coefficient from the temperature dependence of the other thermoelectric properties as
Seebeck coefficient
literature. About thefrom the temperature
investigated commercial dependence of the and
Peltier modules other thermoelectric
their properties as
measured thermoelectric
sometimes found in the literature. About the investigated commercial Peltier modules and their
sometimessome
properties, foundfinal
in the literature.
remarks can beAbout the investigated
summarized as follows. commercial Peltier modules and their
measured thermoelectric properties, some final remarks can be summarized as follows.
measured
(1) Nothermoelectric
benefits on the properties, some final remarks
estimated performances can beoperating
in the whole summarizedrange ascan
follows.
be ascribed to the
(1) No benefits on the estimated performances in the whole operating range can be ascribed to
Thomson effect. In fact, the cooling capacity of the considered devices is always reducedbe
(1) No benefits on the estimated performances in the whole operating range can ascribed to
compared to
the Thomson effect. In fact, the cooling capacity of the considered devices is always reduced
the ideal
the Thomson
conditioneffect. In fact, the cooling capacity
of temperature-independent of the considered
properties. This behaviordevices is always
is because reduced
the Joule heat
compared to the ideal condition of temperature-independent properties. This behavior is because the
compared the
dominates to the ideal condition
thermal of temperature-independent
events inside the device. properties. This behavior is because the
Joule heat dominates the thermal events inside the device.
Joule heat dominates the thermal events inside the device.
(2) In datasheets commonly available, the Thomson effect is almost certainly not considered. In
(2) In datasheets commonly available, the Thomson effect is almost certainly not considered. In
fact, at a giving feeding current, the typical linear trend between cooling capacity and temperature
fact, at a giving feeding current, the typical linear trend between cooling capacity and temperature
difference among junctions identifies this eventuality (see Figures 9 and 10).
difference among junctions identifies this eventuality (see Figures 9 and 10).
Metals 2020, 10, 291 14 of 15

(2) In datasheets commonly available, the Thomson effect is almost certainly not considered.
In fact, at a giving feeding current, the typical linear trend between cooling capacity and temperature
difference among junctions identifies this eventuality (see Figures 9 and 10).
(3) In current bulk materials such as Bi2 Te3 , it seems difficult to improve the performances
by enhancing the Thomson effect while simultaneously reducing the Joule contribution. For this
purpose, the new class of thermoelectric materials mentioned in the literature [18–22] could introduce
stimulating chances.

Author Contributions: Conceptualization, investigation, writing—original draft preparation, V.G.; investigation,

writing—review and editing, E.C. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: We would like to thank M. Bressan for his support in the realization of the
experimental arrangement.
Conflicts of Interest: The authors declare no conflict of interest.

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