Thermo-electric Module for Exhaust Heat Recovery

A Dissertation Submitted in partial fulfilment of the

FOR THE DEGREE OF MASTER OF SCIENCE (Integrated) IN PHYSICS

Under Academic Autonomy

COLLEGE OF ENGINEERING AND TECHNOLOGY,
BHUBANESWAR

Submitted By
RITIK MOHANTY
Regd. No: 1512106038

Under the Guidance of

DR. AVINNA MISHRA

DEPARTMENT OF PHYSICS
College of Engineering and Technology
(A Constituent College of BPUT, Odisha, Rourkela)
TECHNO CAMPUS, GHATIKIA, BHUBANESWAR, ODISHA-751029
2019-2020
 COLLEGE OF ENGINEERING AND TECHNOLOGY
(An Autonomous and Constituent College of BPUT, Odisha)
Techno campus, Po: Mahalaxmi Vihar
BHUBANESWAR-751029 ODISHA, INDIA
NAAC ‘A’

CERTIFICATE
This is to certify that the project report entitled, “Thermo-electric Module for Exhaust
Heat Recovery” Submitted by Ritik Mohanty in partial fulfilment of the requirements of the
award of Integrated Master of Science in Applied Physics, at the College of Engineering and
Technology, Bhubaneswar is an authentic work carried out by him under our supervision.

To the best of our knowledge, the matter embodied in the project has not been submitted to
any other university / institute for the award of any Integrated M.Sc. degree.

Signature of the HOD Signature of Guide

Date: ……………………….. Date: …………………
 DECLARATION

I Ritik Mohanty, ( Regd. No: 1512106038) hereby submit my report entitled “Thermoelectric
Module for Exhaust Heat Recovery” for the consideration for the award of the degree of
Integrated M.Sc. in Applied Physics, is a research work carried out by me at College of
Engineering and Technology, Bhubaneswar under the guidance of Dr. Avinna Mishra. All the
work contained in the report is my original work except where otherwise acknowledged and
has not been submitted in part or in full by me for any degree to this or any other university
or to an examining body in India or abroad. The complete thesis is prepared and written by
me.

Ritik Mohanty
Integrated M.Sc. in Applied Physics
Regd. No: 1512106038

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 PREFACE
It is a great opportunity for me to have the Integrated Master of Science in CET
Bhubaneswar. In the accomplishment of this degree I am submitting a project report on
“Thermo-electric module for exhaust heat recovery” subject to the limitation of time efforts
and resources every possible attempt has been made to study the problem deeply. The whole
project is measured the question, the data further analysed and interpreted and the result
obtained.

The whole project has been divided into 4 chapters. In the 1st chapter I have discussed about
the background of the problem and thermo-electric effect and my project objective. In the 2nd
chapter I have thoroughly discussed about the construction and working of the thermo-
electric module (TEM) and various thermoelectric materials that are used for the making of
the TEMs. Also I have discussed the advantages, application of TEMs and lastly I have
mentioned some the recently used industrial modules for exhaust heat recovery. In the 3rd
chapter I have discussed about the fabrication of the 4legged Oxide thermo-electric module
and some mathematical expressions for calculation of the module efficiency. 4th chapter is
my result and discussion section, here I have showed some graphical results found by the
experimental analysis.

I have tried my best to present all the aspects related with the topic Thermo-electric module.
However I accept the sole responsibility of any possible error of omission and will be grateful
to the reader of project who bring mistake to my notice.

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 ACKNOWLEDGEMENT
I take this opportunity to express my deepest gratitude and sincere thanks to Dr. Avinna
Mishra for his guidance and support throughout my project work. Despite of his busy
schedule, he gave a lot of time to this project and shared his knowledge and experience,
which helped me in giving a successful shape to this project.

I would also like to express my regards to Dr. Babita Ojha (Head of the Department of
Physics) for giving me this opportunity. Further I am thankful to all my teachers and staff
members of the Department of Physics for the cooperation during this work.

Last but not the least, I express my gratitude to my parents and all my all friends for their
constant support who were directly or indirectly helped me for successfully completing this
project.

Page | iii
 ABSTRACT
As far we know limitation of energy source has become the most important problems that we
are facing now a days. Approximately 70% of world’s useful energy is going into the earth’s
atmosphere as a form of waste heat. So to create a clean and sustainable energy source we
have to reclaim the waste heat from the automobiles, nuclear and thermal power plants,
factories and similar sources. So by using an energy converter we can directly manage our
losses and solve the waste heat problem. The thermo-electric module (TEM) is an energy
converting device which uses the thermo-electric materials having energy conversion
characteristics. The TEM use heat (temperature gradient) energy as input and give electrical
energy as output using the thermoelectric principles like seebeck effect, peltier effect. So here
I have focused on the study on the performance of the TEM and what are the major factors
that are affecting the output power. Also I have briefly discussed about the thermoelectric
materials and recent reported commercial TEM and detailed study on the power output and
current output and factors affecting the power and efficiency of a 4 legged Oxide TEM
having p type leg as Ca3Co4O9 with Mo doped and n type leg as CaMnO3 with Bi doped.

Page | iv
 CONTENTS
List of figures vi

List of tables vii

Abbreviations viii

Chapter 1 Introduction 1

1.1 Background 1

1.2 Thermo-electric effect 2

1.3 Project Objective 4

Chapter 2 Thermo-electric module 5

2.1 Construction 5

2.2 Working 6

2.3 State of art 7

2.3.1 Thermo-electric materials 7

2.3.2 Materials of Interest 8

2.4 Advantages of Thermo-electric module 19

2.5 Application of Thermo-electric module 20

2.6 Recently used Thermo-electric modules 21

Chapter 3 Fabrication & Efficiency of Thermo-electric module 22

3.1 Fabrication of TEM 22

3.2 Calculation of Efficiency 24

Chapter 4 Result and Discussion 29

Conclusion 34

Future work 35

Reference 36

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 LIST OF FIGURES
Figure Title of the Figure Page No.
No.
1 Schematic of waste heat. 1
2 Seebeck effect. 2
3 Peltier effect. 3
4 Cross-sectional view of TEM. 5
5 Working of a TEM. 6
6 TE Materials according to its temperature range. 18
7 General characteristic graph between the efficiency vs 19
temperature.
8 Variation of the Output power and Max Temperature of the 21
recently used TEMs.
9 Schematic steps for fabrication of TEM. 22
10 Schematic of a 4 legged TEM. 23
11 Real Photograph of a 4 legged Oxide module during fabrication 24
in laboratory.
12 Equivalent electrical resistance circuit of Oxide TEM. 26
13 Variation of Seebeck coefficient and temperature of hot end. 29
14 Variation of output voltage and temperature of hot end. 30
15 Variation of output voltage and temperature of hot end. 30
16 Variation of resistance of the module and temperature of hot end. 31
17 Variation of output power and temperature of hot end. 31
18 Variation of output current and temperature of hot end. 32
19 Variation of maximum power and temperature of hot end. 33
20 Variation of maximum current and temperature of hot end. 33

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 LIST OF TABLES
Table No Title of the table Page No.
1 Materials used in recent TEMs representing its temp. and output 21
power

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 ABBREVIATIONS
TE Thermo-Electric
TEM Thermo-electric Module
EMF Electromotive force
DC Direct current
RTG Radioisotope thermoelectric generator
DFT Density functional theory
PGEC Phonon glass electron crystal
CCD Charge coupled device
CID Charge induced device
PCR Polymerase chain reaction

Page | viii
 CHAPTER 1

INTRODUCTION

1.1 Background:-

As far we know limitation of energy source has become the most important problems that we
are facing now a days. Approximately 70% of world’s useful energy is going into the earth’s
atmosphere as a form of waste heat. As we supply a certain amount of heat for completing a
process but due to some factors like radiation and conduction etc. a large amount of heat is
going in form of waste. So study says that only the 34% of the primary heat energy is used
and rest 66% heat energy is going in the form of waste which is simultaneously affecting the
earth’s atmosphere and in habitant too. So to create a clean and sustainable energy source we
have to reclaim the waste heat from the automobiles, nuclear and thermal power plants,
factories and similar sources. So by using an energy converter we can directly manage our
losses and solve the waste heat problem.

Figure 1: Schematic view of waste heat, figure is adopted from sciencedirect.com

Thermo-electric module and Thermo-electric technology can be considered as a promising

and feasible alternative solution for the above cited problems. The thermo-electric module
(TEM) is an energy converting device which uses the thermo-electric materials having energy
conversion characteristics. The TEM use heat (temperature gradient) energy as input and give

Page | 1
electrical energy as output using the thermoelectric principles like seebeck effect, peltier
effect. The TEM enables us to convert the heat energy into electrical energy irrespective of
the source size and without the using of the moving parts or production of environmentally
hazardous waste.

1.2 Thermoelectric effect:-

It is the direct conversion of heat into electricity or electricity into heat through two related
mechanisms, the seebeck effect and the peltier effect when two metals are placed in electrical
contact.

 Seebeck effect:- The seebeck effect was discovered by the German physicist Thomas
Johann Seebeck in the 1800s. This phenomenon states that applying some
temperature gradient to the thermocouple will create some potential difference across
the wires which will result some electrical current.

Figure 2: Seebeck effect, figure is adopted from peltierinfo.com

In this process as the n type is doped with negative charge carriers (electrons) and p
type is doped with positive charge carriers (holes), when we apply some temperature

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 gradient to the one junction then electrons and holes will move from the hotter side to
the colder side. Then EMF is induced inside the circuit which will create some
potential difference across the wires resulting some current as output.

 Peltier effect:- The peltier effect was discovered by the Jean Charles Athanase
Peltier in the 1834. This phenomenon states that when electric current is passed
through the circuit of a thermocouple heat is evolved at one junction i:e, one junction
will be cooled and other will become hot.

Figure 3: Peltier effect, figure is adopted from peltierinfo.com

In this process as the n type is doped with negative charge carriers (electrons) and p type is
doped with positive charge carriers (holes), so while supplying the DC current the charge
carriers negative electrons and positive holes will transport the heat from one junction to
another. If we change the polarity of the DC power source it will reverse the heat flow.

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1.3 Project objective:-

Waste heat from automobiles, factories, and similar sources offer a high quality energy
source equal to about 66% of total primary energy, but it is difficult to reclaim due to its
source amount being small and widely dispersed. Thermo-electric module system offers the
only feasible method of overcoming these problems by converting heat energy directly into
electrical energy irrespective of source size and without the use of moving part or production
of environmentally deleterious/harmful waste. So my project objective is to;

 To study on the performance of the thermo-electric module and what are the major
factors affecting the output power.
 Challenges on the fabrication and efficiency of the TEMs.
 Detailed discussion on a 4 legged TEM having p type leg as Ca3Co4O9 with Mo
doped and n type leg as CaMnO3 with Bi doped.
 Also to give an idea to make an effective TEM in future for power generation from
the waste heat source.

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 CHAPTER 2

THERMO-ELECTRIC MODULE

A thermoelectric module is a semiconductor based equipment that function as a generator of

electricity by using a temperature gradient between two-sides of the module. Also it can be
used as small heat pump by using DC current for moving heat from one side to another.

Figure 4: Cross-sectional view of a TEM, figure adopted from [L.G Chen et al]

2.1 Construction:-

A practical thermoelectric module (Figure 4) generally consists of two or more element of n

type and p type doped semiconductor material called as legs that are connected electrically in
series and thermally in parallel with each other by means of metal strips. The metal strips are
thin strips for interconnection. These metal strips can be made up of Ag/Cu/Stainless steel.
These thermoelectric elements and their electrical interconnects typically are mounted
between two ceramic substrates. Normally the Alumina substrate is used for this due to its
thermally conducting and electrically insulating nature. Also alumina have the tendency to
resist high temperature and it can maintain high strength and hardness. The substrates hold
the overall structure together mechanically and electrically insulate the individual elements
from one another and external mounting surfaces.

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Most thermoelectric range in size from approximately 2.5-50 mm(0.1 to 2.0 inches) square
and 2.5-5mm(0.1 to 0.2 inches) in height. A variety of different shapes, substrate materials,
metallization pattern and mounting options are available.

2.2 Working:-

A thermoelectric module can be used for power generation. In this mode, a temperature
differential applied across the module will generate current. When the module face attached
to the heat sources, then temperature gradient is created in the TEM which results the current
as output.

Figure 5: Working of a TEM. Figure adopted from [56]

So in the above picture a commercial TEM is attached simultaneously with the multi-meter
and a bulb. When heat is supplied from the source which will result the bulb glow along with
some current counting showing in the multi-meter.

Also by applying a low DC power to a Thermo-electric module, heat will be moved through
the module from one side to another. One module face, therefore will be cooled while the
opposite face simultaneously heated. It is important to note that this phenomenon maybe
reversed where by a change in the polarity (positive or negative) of the applied DC voltage
will cause heat to be moved in the opposite direction. Consequently, a thermoelectric module
may be used for both heating and cooling thereby making it highly suitable for precise
temperature control applications.

Cooling capacity of TEM is known as the heat actively pumped through the thermoelectric
module. It is proportional to the magnitude of the applied DC electric current and the thermal

Page | 6
conditions on each side of the module. By varying the input current from zero to maximum, it
is possible to regulate the heat flow and control the surface temperature.

2.3 State of Art:-

2.3.1 Thermo-electric Materials:-

The materials which shows the thermoelectric effect in strong or convenient form is known as
the thermoelectric materials. The usefulness of a thermo-electric material in thermoelectric
systems is determined by the device efficiency. These are determined by the materials
electrical conductivity, thermal conductivity, seebeck coefficient which change with
temperature. The maximum efficiency of a thermoelectric material is determined by its figure
of merit. The maximum efficiency of the energy conservation process (for both power
generation and cooling) at a given point in the material is determined by the thermoelectric
materials figure of merit ZT, which is given by

𝜎𝑆2 𝑇
𝒁𝑻 =
𝑘

Which contains the seebeck coefficient S, electrical conductivity σ, thermal conductivity k

and temperature T.

The efficiency of a thermoelectric device for electricity generation is given by 𝜂

𝑒𝑛𝑒𝑟𝑔𝑦 𝑝𝑟𝑜𝑣𝑖𝑑𝑒𝑑 𝑡𝑜 𝑡ℎ𝑒 𝑙𝑜𝑎𝑑

𝜂=
ℎ𝑒𝑎𝑡 𝑒𝑛𝑒𝑟𝑔𝑦 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝑎𝑡 ℎ𝑜𝑡 𝑗𝑢𝑛𝑐𝑡𝑖𝑜𝑛

In recent years thermoelectric materials are finding application in increasing energy

conversion of solar cells. The thermo-electric module’s performance measured in terms of
conversion efficiency which depends on the thermoelectric materials “Figure of Merit”
denoted by ZT. High figure of merit materials (around ZT= 3 to 4) convert more than 40% of
waste heat to useful electrical energy. The thermoelectric properties vary with materials and
their structures, dopants and fabrication methods. The overall effect of variation of material’s
properties should result in enhancement of figure of merit. Optimizing the thermoelectric
properties of materials for enhancing figure of merit (ZT) depends on material’s electronic
structure, the charge carrier concentration and phonon’s behaviour.

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Enhancing ZT by optimizing thermoelectric properties is critical in bulk (micro level grains)
thermoelectric materials because of the mutual independence of electrical and thermal
properties. However researchers produced and developed some good and bulk thermoelectric
materials by alloying, controlling microstructure and doping with certain materials. Nano
technology plays a key role in development of the figure of merit due to unique properties of
nanoparticles and nanograins. Thermoelectric properties of materials at nano scale can be
altered independently or separately, affecting the figure of merit. Researchers adopted
approaches such as control of crystallographic texture, modulation by doping, reduction in
grain size to nano level, preparing nano composites by incorporating nano inclusions into the
thermoelectric materials. Nano structuring of the material may cause increase in the figure of
merit values relative to bulk materials with decrease in thermal conductivity due to phonon
scattering and/or increasing in the power factor due to quantum confinement. Presently
bismuth telluride and skutterudites are being used in the manufacture of the thermoelectric
modules due to their high figure of merit values. But these materials are toxic, of high cost,
high weight. Further these are not suitable for middle range temperature application i.e; from
250-6500 C. Materials which have ZT value more than 1.5, low weight and low cost are
sufficient for middle range temperature applications like automotive exhaust, gas turbine
exhaust, dying and baking ovens etc., where weight is an important factor. The materials
which are of light weight, low cost of constituent element and ZT values 1 or more can be
used in the thermoelectric applications instead of Tellurium Antimony Germanium and Silver
(TAGs) and Te (telluride) based thermoelectric materials.

2.3.2 Materials of Interest:-

Strategies to improve thermo-electrics include both advanced bulk materials and the use of
low-dimensional system. Such approaches to reduce lattice thermal conductivity fall under
three general material type.

(1) Alloys: Create point defects, vacancies, or rattling structures (heavy ion species with large
vibrational amplitudes contained with partially filed structural sites) to scatter phonons within
the unit cell crystal.

(2)Complex crystal: Separate the phonon glass from the electron crystal using approaches
similar to those for superconductors (the region responsible for electron transport should be
an electron crystal of a high mobility semiconductor, while the phonon glass should ideally

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house disordered structures and dopants without disrupting the electron crystal, analogous to
the charge reservoir in high Tc super-conductors). [5]

(3)Multiphase nanocomposites: scatter phonons at the interfaces of nanostructured materials,

be they mixed composites or thin film super lattices. [6]

1) Bismuth chalcogenides and their nano structures:-

Materials such as Bi2Te3 and Bi2Se3 comprise some of the best performing room temperature
thermo-electrics with a temperature-independent figure of merit, ZT between 0.8 to 1.0. As
Bi and Sb which have narrow band gaps and low thermal conductivity and may be suitable as
thermoelectric materials. We believe that materials with more complex composition and
structures should have complex electronic structures which may give rise to high
thermoelectric powers according to Mott formula. If there is something special about bismuth
in giving rise to simultaneously high electrical conductivity and thermoelectric power, it
should be manifested in other compounds of Bi as well.

Therefore if we explore more complex chalcogenides if Bi hoping that some (or all) of the
key properties would be superior to those Bi2Te3. Because a structure with a large unit cell is
expected for complex materials, which in turn would decrease the acoustic mode phonon
velocities that are responsible for the transfer of heat in materials, we expect that structurally
and compositionally more complex bismuth chalcogenides would, most likely, have a low
lattice thermal conductivity. The relatively weak Bi-Te bonding and the large atomic masses
contribute as well to the low phonon velocities. Therefore, exploratory synthesis in this
region of the periodic table becomes a reasonable activity and, as the preliminary results
show, quite promising. So we can get more complex chalcogenides compound using a low
temperature synthesis method. Also we can get new phases of bismuth by reacting the metal
with alkali metal chalcogenides salts in poly-chalcogenides melts. [7]

Nano structuring these materials to produce a layered super lattice structure of alternating
Bi2Te3 and Sb2Te3 layers produce a device within which there is good electrical conductivity
but perpendicular to which thermal conductivity is poor. The result is an enhanced ZT
(approximately 2.4 at room temperature for p-type) [8]. This high value of ZT has not been
independently confirmed due to the complicated demands on the growth of such super
lattices and device fabrication; however the material ZT values are consistent with the
performance of hot-spot coolers made out of these materials and validated at Intel Labs.

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Bismuth telluride and its solid solutions are good thermoelectric materials at room
temperature and therefore suitable for refrigeration applications around 300K. The
Czochralski method has been used to grow single crystalline bismuth telluride compounds.
These compounds are usually obtained with directional solidification from melt or powder
metallurgy processes. Materials produced with these methods have lower efficiency then
single crystalline ones due to the random orientation of crystal grains, but their mechanical
properties are superior and the sensitivity to structural defects and impurities is lower due to
high optimal carrier concentration.

The required carrier concentration is obtained by choosing a non-stoichiometric composition,

which is achieved by introducing excess bismuth or tellurium atoms to primary melt or by
dopant impurities. Some possible dopants are halogens and group IV and V atoms. Due to the
small bandgap (0.16 eV) Bi2Te3 is partially degenerate and the corresponding Fermi-level
should be close to the conduction band minimum at room temperature. The size of the band-
gap means that Bi2Te3 has high intrinsic carrier concentration. Therefore, minority carrier
conduction cannot be neglected for small stoichiometric deviations. Use of telluride
compound is limited by the toxicity and rarity of tellurium. [1]

2) Lead telluride:-

As the efficiency of thermoelectric energy converters is limited by the material thermoelectric

figure of merit (ZT). The recent advances in ZT based on nano structures limiting the phonon
heat conduction is nearing a fundamental limit. The thermal conductivity cannot be reduced
below the amorphous limit. Hermans and his team explored enhancing the Seebeck
coefficient through a distortion of the electronic density of states and report a successful
implementation through the use of the thallium impurity levels in lead telluride (PbTe). Such
band structure engineering results in doubling of ZT in p-type PbTe to above 1.5 at 773
kelvin. [9]

Later G J Snyder and his team reported about the thermo electric transport properties of p-
type PbTe:Na, with high hole concentrations of approximately 1020 cm-3, are reinvested from
room temperature to 750 K. Here Sodium is doped in Lead telluride. The greatly enhanced
Seebeck coefficient at these doping levels can be understood by the presence of a sharp
increase in density of states around the Fermi level. As a result, the thermoelectric figure of
merit, ZT , reaches ~1.4 at 750K. The influence of these heavy hole carriers may contribute
to a similarly high ZT observed in related p-type PbTe-based system such as TI (Titanium)-

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doped PbTe and nano structured composite materials [10]. And also use of nano structuring
to reduce phonon thermal conductivity, which has led to the investigation of a variety of
complex material systems. In this vein, it is well known that a high valley degeneracy
(typically greater than or equal to 6 for known thermo-electrics) in the electronic bands is
conducive to high ZT, and this in turn has stimulated attempts to engineer such degeneracy
by adopting low dimensional nano structures. Here Snyder and his team demonstrate that it is
possible to direct the convergence of many valleys in a bulk material by tuning the doping
and composition. By this route, we achieve a convergence of at least 12 valleys in doped
PbTe1-x Sex alloys, leading to an extraordinary ZT values of 1.8 at about 850 kelvin. Band
engineering to converge the valence (or conduction) bands to achieve high valley degeneracy
should be a general strategy in the search for and improvement of bulk thermoelectric
materials, because it simultaneously leads to a high Seebeck coefficient and high electrical
conductivity. Snyder’s group determined that both thallium and sodium after the electronic
structure of the crystal increasing electrical conductivity. They also claim that selenium
increases electric conductivity and reduces thermal conductivity. [11, 12]

In 2012 another team used lead telluride to convert 15 to 20 percent of waste heat to
electricity, reaching a ZT of 2.2, which they claimed was the highest yet reported.

The recent successful strategy of nano structuring to reduce thermal conductivity has
achieved record-high ZT values in the range 1.5-1.8 at 750-900 kelvin, but still falls short of
the generally desired threshold value of 2. Nano structures in bulk thermos-electrics allow
effective phonon scattering of a significant portion of the phonon spectrum, but phonons with
long men free paths remain largely unaffected. Here Biswas and his team show that heat
carrying phonons with long mean free paths can be scattered by controlling and fine tuning
the mesoscale architecture of nano structured thermo-electric materials. Thus, by considering
sources of scattering on all relevant length scales in a hierarchical fashion from atomic-scale
lattice disorder and nanoscale endotaxial precipitates to mesoscale boundaries we achieve the
maximum reduction in lattice thermal conductivity and a large enhancement in the
thermoelectric performance of PbTe. By taking such a panoscopic approach to the scattering
of heat carrying phonons across integrated length scales, we go beyond nano structuring and
demonstrate a ZT value of ~2.2 at 915 kelvin in p-type PbTe endotaxially nano structured
with SrTe at a concentration of 4 mole percent and meso structured with powder processing
and spark plasma sintering. This increase in ZT beyond the threshold of 2 highlights the role
of, and need for, multiscale hierarchical architecture in controlling phonon scattering in bulk

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thermos-electrics, and offers a realistic prospect of the recovery of a significant portion of
waste heat. [13]

3) Inorganic Clathrates:-

Inorganic clathrates have general formula AxByC46-y (type-1) and AxByC136-y (type-2), where
B and C are group III and IV elements, respectively, which form the framework where
“guest” A atoms (alkali or alkaline earth metal) are encapsulated in two different polyhedral
facing each other. The differences between type I and II come from the number and size of
voids present in their unit cells. Transport properties depend on the framework’s properties,
but tuning is possible by changing the “guest” atoms. [1]

The most direct approach to synthesize and optimize the thermos-electric properties of
semiconducting type I clathrates is substitutional doping, where some framework atoms are
replaced with dopant atoms. In addition, powder metallurgical and crystal growth techniques
have been used in clathrate synthesis. The structural and chemical properties of clathrates
enables the optimization of their transport properties as a function of stoichiometry. The
structure of type II materials allows a partial filling of the polyhedral, enabling better tuning
of electrical properties and therefore better control of the doping level. Partially filled variants
can be synthesized as semiconducting or even insulating.

Blake et al have predicted ZT~0.5 at room temperature and ZT~1.7 at 800 kelvin for
optimized compositions. Kuznetsov et al measured electrical resistance and Seebeck
coefficient for three different I clathrates above room temperature and by estimating high
temperature thermal conductivity from published low temperature data they obtained ZT~0.7
at 700 kelvin for Ba8Ga16Ge30 and ZT~0.87 at 870 kelvin for Ba8Ga16Si30. [14]

4) Electrically conducting organic materials:-

Organic materials are attractive thermos-electric materials due to their light weight, bio-
degradability. But their figure of merit is still low for commercial application (~0.42) due to
the poor electrical conductivity. [15]

5) Skutterudite thermo-electrics:-

Skutterudites have chemical composition of LM4X12, where L is rare earth metal which is the
optional component, M is the transition metal, and X is a metalloid, a group V element or a
Pnictogen such as phosphorus, antimony or arsenic. These materials exhibit ZT>1.0 and can

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potentially be used in multistage thermoelectric devices. Unfilled, these materials contain
voids, which can be filled with low-coordination ions (usually rare earth elements) to reduce
thermal conductivity by producing sources for lattice phonon scattering, without reducing
electrical conductivity. It is also possible to reduce the thermal conductivity in skutterudite
without filling these voids using a special architecture called nano and micro pores. [16, 17]

6) Oxide thermo-electrics:-

Normally thermo-electric modules are composed of intermetallic compounds, such as Bi2Te3,

Pb-Te and Si-Ge. Practical applications of materials like these have, however, been delayed
by problems due to their low melting or decomposition temperatures, their content of harmful
or scare elements, and also their cost. Recently, oxide compounds have attracted attention as
promising thermo-electric materials due to their potential to overcome these problems. [18]

Homologous oxide compounds (such as those of the form (SrTiO3)n(SrO)m – the Ruddlesden
Popper phase) have layered super lattice structures that make them promising candidates for
use in high-temperature thermoelectric devices. [1] These materials exhibit low thermal
conductivity perpendicular to the layers while maintaining good electronic conductivity
within the layers. Their ZT values can reach 2.4 for epitaxial SrTiO
3 films, and the enhanced thermal stability of such oxides, as compared to conventional high-
ZT bismuth compounds, makes them superior high-temperature thermos-electrics. [19]

Interest in oxides as thermoelectric materials was reawakened in 1997 when a relatively high
thermoelectric power was reported for NaCo2O4 [20]. In addition to their thermal stability,
other advantages of oxides are their low toxicity and high oxidation resistance.
Simultaneously controlling both the electric and phonon systems may require nanostructured
materials. Layered Ca3Co4O9 exhibited ZT values of 1.4–2.7 at 900 K. If the layers in a given
material have the same stoichiometry, they will be stacked so that the same atoms will not be
positioned on top of each other, impeding phonon conductivity perpendicular to the
layers. Recently, oxide thermos-electrics have gained a lot of attention so that the range of
promising phases increased drastically. Novel members of this family include ZnO,
MnO2, and NbO2. [21, 22, 23]

7) Compound of Mg and Gr IV elements:-

Mg2BIV (BIV=Si, Ge, Sn) compounds and their solid solutions are good thermoelectric
materials and their ZT values are comparable with those of established materials. The

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appropriate production methods are based on direct co-melting, but mechanical alloying has
also been used. During synthesis, magnesium losses due to evaporation and segregation of
components (especially for Mg2Sn) need to be taken into account. Directed crystallization
methods can produce single crystals of Mg2Si, but they intrinsically have n-type conductivity,
and doping, e.g. with Sn, Ga, Ag or Li, is required to produce p-type material which is
required for an efficient thermoelectric device. Solid solutions and doped compounds have to
be annealed in order to produce homogeneous samples – with the same properties throughout.
At 800 K, Mg2Si0.55−xSn0.4Ge0.05Bix has been reported to have a figure of merit about 1.4, the
highest ever reported for these compounds. [24, 25].

8) Half-Heusler alloys:-

Half-Heusler (HH) alloys have a great potential for high-temperature power generation
applications. Examples of these alloys include NbFeSb, NbCoSn and VFeSb. They have a
cubic MgAgAs-type structure formed by three interpenetrating face-centred-cubic (FCC)
lattices. The ability to substitute any of these three sub-lattices opens the door for wide
variety of compounds to be synthesized. Various atomic substitutions are employed to reduce
the thermal conductivity and enhance the electrical conductivity. [26]

Previously, ZT could not peak more than 0.5 for p-type and 0.8 for n-type HH compound.
However, in the past few years, researchers were able to achieve ZT≈1 for both n-type and p-
type. Nano-sized grains is one of the approaches used to lower the thermal conductivity via
grain boundaries- assisted phonon scattering. [27] Other approach was to utilize the
principles of nanocomposites, by which certain combination of metals were favoured on
others due to the atomic size difference. For instance, Hf and Ti is more effective than Hf and
Zr, when reduction of thermal conductivity is of concern, since the atomic size difference
between the former is larger than that of the latter. [28]

9) Silicon and Germanium:-

Bulk Si exhibits a low ZT of ~0.01 because of its high thermal conductivity. However, ZT
can be as high as 0.6 in silicon nanowires, which retain the high electrical conductivity of
doped Si, but reduce the thermal conductivity due to elevated scattering of phonons on their
extensive surfaces and low cross-section. [29]

Combining Si and Ge also allows to retain a high electrical conductivity of both components
and reduce the thermal conductivity. The reduction originates from additional scattering due

Page | 14
to very different lattice (phonon) properties of Si and Ge [30]. As a result, Silicon-
germanium alloys are currently the best thermoelectric materials around 1000 ℃ and are
therefore used in some radioisotope thermoelectric generators (RTG) (notably the MHW-
RTG and GPHS-RTG) and some other high temperature applications, such as waste heat
recovery. Usability of silicon-germanium alloys is limited by their high price and moderate
ZT values (~0.7); however, ZT can be increased to 1–2 in Si-Ge nanostructures owing to the
reduction in thermal conductivity. [31]

10) Sodium Cobaltate:-

By using X-ray and neutron scattering techniques on crystal of Sodium cobaltate which is
done at the European Synchrotron Radiation Facility (ESRF) and the Institut Laue-Langevin
(ILL) in Grenoble were able to suppress thermal conductivity by a factor of six compared to
vacancy free sodium cobaltate. The experiment is agreed with corresponding density
functional calculations. In this technique we observed large an-harmonic displacements of
Na0.8CoO2 . [32, 33]

11) Amorphous materials:-

In 2002, Nolas and Goldsmid suggested that systems with the phonon mean free path larger
than the charge carrier mean free path can exhibit an enhanced thermoelectric efficiency. [34]
So after this a ground breaking idea was accomplished in Cu-Ge-Te[35], NbO2 [36], In-Ga-
Zn-O [37], Zr-Ni-Sn [38], Si-Au [39], and Ti-Pb-V-O [40] amorphous system. Generally,
amorphous thermos-electrics give rise to extensive phonon scattering, which is still a
challenge in crystalline thermo-electrics.

12) Functionally graded materials:-

Functionally graded materials make it possible to improve the conversion efficiency of

existing thermos-electrics. These materials have a non-uniform carrier concentration
distribution and in some cases also solid solution composition. In power generation
applications the temperature difference can be several hundred degrees and therefore devices
made from homogeneous materials have some part that operates at the temperature where ZT
is substantially lower than its maximum value. This problem can be solved by using materials
whose transport properties vary along their length thus enabling substantial improvements to
the operating efficiency over large temperature differences. This is possible with functionally

Page | 15
graded materials as they have a variable carrier concentration along the length of the material,
which is optimized for operations over specific temperature range. [1]

13) Nano materials and Super lattices:-

In addition to nano structured Bi2Te3/Sb2Te3 super lattice thin films, the silicon nano wires,
nano tubes and quantum dots show potential in improving thermo-electric properties [41].
Superlattices which is the nano structured thermo-couples are also good for thermo-electric
device manufacturing process, but their production is expensive for general application due to
fabrication process based on thin film growth methods. Also due to reduced phonon
scattering interface structures often also exhibit a decrease in electrical conductivity. [42]

14) Graphene:-

Graphene is known for its high electrical conductivity and Seebeck coefficient at room
temperature. [43, 44] However, from thermoelectric perspective, its thermal conductivity is
notably high, which in turn limits its ZT. Several approaches were suggested to reduce the
thermal conductivity of graphene without altering much its electrical conductivity. These
include, but not limited to, the following:

Doping with carbon isotopes to form isotopic heterojunction such as that of 12C and 13C.
Those isotopes possess different phonon frequency mismatch, which leads to the scattering of
the heat carriers (phonons). This approach has been shown to affect neither the power factor
nor the electrical conductivity. [45]

Wrinkles and cracks in the graphene structure were shown to contribute to the reduction in
the thermal conductivity. Reported values of thermal conductivity of suspended graphene of
size 3.8 µm show a wide spread from 1500 to 5000 W/(m·K). A recent study attributed that
to the microstructural defects present in graphene, such as wrinkles and cracks, which can
drop the thermal conductivity by 27%.These defects help scatter phonons. [46]

Introduction of defects with techniques such as oxygen plasma treatment. A more systemic
way of introducing defects in graphene structure is done through O2 plasma treatment.
Ultimately, the graphene sample will contain prescribed-holes spaced and numbered
according to the plasma intensity. People were able to improve ZT of graphene from 1 to a
value of 2.6 when the defect density is raised from 0.04 to 2.5 (this number is an index of
defect density and usually understood when compared to the corresponding value of the un-

Page | 16
treated graphene, 0.04 in our case). Nevertheless, this technique would lower the electrical
conductivity as well, which can be kept unchanged if the plasma processing parameters are
optimized. [43]

Functionalization of graphene by oxygen. The thermal behaviour of graphene oxide has not
been investigated extensively as compared to its counterpart; graphene. However, it was
shown theoretically by Density Functional Theory (DFT) model that adding oxygen into the
lattice of graphene reduces a lot its thermal conductivity due to phonon scattering effect.
Scattering of phonons result from both acoustic mismatch and reduced symmetry in graphene
structure after doping with oxygen. The reduction of thermal conductivity can easily exceed
50% with this approach. [44]
15) Tin selenide:-

In 2014, researchers at Northwestern University discovered that tin selenide (SnSe) has a ZT
of 2.6 along the b axis of the unit cell. [47, 48] This is the highest value reported to date. This
high ZT figure of merit has been attributed to an extremely low thermal conductivity found in
the SnSe lattice. Specifically, SnSe demonstrated a lattice thermal conductivity of
0.23 W·m−1·K−1, which is much lower than previously reported values of 0.5 W·m−1·K−1 and
greater. [49] This SnSe material also exhibited a ZT of 2.3±0.3 along the c-axis
and 0.8±0.2 along the a-axis. These excellent figures of merit were obtained by researchers
working at elevated temperatures, specifically 923 K (650 °C). As shown by the figures
below, SnSe performance metrics were found to significantly improve at higher temperatures;
this is due to a structural change that is discussed below. Power factor, conductivity, and
thermal conductivity all reach their optimal values at or above 750 K, and appear to plateau at
higher temperatures. However, these reports have become controversial as reported in Nature
because other groups have not been able to reproduce the reported bulk thermal conductivity
data. [50]

Although it exists at room temperature in an orthorhombic structure with space group Pnma,
SnSe has been shown to undergo a transition to a structure with higher symmetry, space
group Cmcm, at higher temperatures. [49] This structure consists of Sn-Se planes that are
stacked upwards in the a-direction, which accounts for the poor performance out-of-plane
(along a-axis). Upon transitioning to the Cmcm structure, SnSe maintains its low thermal
conductivity but exhibits higher carrier mobilities, leading to its excellent ZT value. [51] One
particular impediment to further development of SnSe is that it has a relatively low carrier

Page | 17
concentration: approximately 1017 cm−3. Further compounding this issue is the fact that SnSe
has been reported to have low doping efficiency. [52]

However, such single crystalline materials suffer from inability to make useful devices due to
their brittleness as well as narrow range of temperatures, where ZT is reported to be high.
Further, polycrystalline materials made out of these compounds by several investigators have
not confirmed the high ZT of these materials.

These above stated materials are the most recent reported thermo-electric materials are used
for fabricating the thermo-electric module.

Also the thermo-electric materials are divided into three groups based on the temperature
range applications. Low temperature range (<1770C) thermos-electric materials such as
bismuth based alloys etc, intermediate or middle range (1770C-5770C) thermo-electric
materials such as lead based alloys etc and high temperature range (>10270C) thermo-electric
materials such as SiGe based alloys etc [1,2] as shown in figure

Figure 6: TE Materials according to its temperature range, figure adopted from [1]

The thermo-electric module’s performance depends on the material’s electron and thermal
transport characteristics. Researchers are trying to develop materials which have high figure
of merit values optimizing their thermo-electric properties using different approaches.

Ideal thermo-electric materials- In mid 1990s, Glen A.Slack presented the concept ‘Phonon
Glass Electron Crystal’ (PGEC) related to thermo-electric materials. According to the

Page | 18
concept, the ideal thermo-electric materials are materials which conduct electricity like
crystal and conduct heat like glass at same time. [3]

Commercial thermo-electric materials- The materials having ZT values above 2 or approach

to 3 are considered as commercial thermo-electric materials and also the materials should be
available at low price, high stability with respect to temperature and give sufficient output
with good performance. Only the materials having ZT values above 2 or approach to 3 have
capability to convert into some useful electrical energy from waste heat with sufficient
conversion efficiency [4] as shown in figure

Figure 7: General characteristic graph between the efficiency vs temperature, figure adopted
from [57]

2.4 Advantages of Thermo-electric module:-

 No moving parts.
 Small and lightweight.
 Maintenance free.
 Acoustically silent and electrically quiet.
 Heating and cooling with the same module (including temperature cycling).
 Wide operating temperature range.
 Highly precise temperature control (to within 0.1 0C).
 Operation in any orientation, zero gravity and high G-levels.
 Environmentally friendly.
 Sub-ambient cooling.

Page | 19
  Cooling to very low temperatures.

2.4 Application of TEM:-

As TEM are since from 90’s so it has a lot of application. [69, 70]

 It is used in avionics and space application. RTG known as the Radio isotope
Thermoelectric Generator convert the heat generated by the decay of plutonium-
238(plutonium dioxide 238PuO2) fuel into electricity.
 Mostly used for the small power generators and coolers.
 Used for automotive waste heat recovery from vehicles. FIAT, FORD, BMW,
Renoter and Amerigon are using this technology in their manufactured vehicles.
 Used for making the Cold chambers and cold plates.
 Used in Black-box cooling. It the cooling cabinet that is used to protect the essential
electronics equipment from the atmospheric humidity, temperature and moisture.
 Used in the charge coupled device (CCD) and charge induced devices (CID).
 For constant heat bath apparatus TEM is used.
 For Electronic package cooling, Micro-processer cooling and Immersion cooling it is
used.
 Also it have the medical applications like Thermal cycling devices. This device
analyses DNA and Blood cell by the reaction called PCR (Polymerise chain reaction).
 Also used in Thermal viewers and weapon sights and in night vision equipment.
 Now a days some laser manufacturing companies using TEM for the making of laser
diode cooler.

Page | 20
2.4 Recently used TEMs:-

These are some commercial Thermo-electric module which are used widely in industrial
sectors. Here is the table representing the materials that are used for making the TEM, the
temperature ranges and output power achieved. [58]

Materials 𝜟𝑻(in Kelvin) TMAX(in 0C) Power(in Watt)

Bi2Te3 300 300 20
Half Heusler 500 600 15
Skuterrudites 510 600 25
Zn4Sb3/Mg2SiSn 105 125 0.009
Calcium/Manganese 750 800 12.3
Oxide

Silicon based alloy 500 600 3.6

Calcium/Manganese 435 600 11
Oxide with Bi2Te3

Table 1: Materials used in recent TEMs representing its temperature and output power

Also we can plot a graph representing the maximum temperature along with the output power

Figure 8: Variation of the Output power and Max Temperature of the recently used TEMs

Page | 21
 CHAPTER 3

FABRICATION AND EFFICIENCY OF THERMOELECTRIC

MODULE

3.1 Fabrication of TEM:-

For fabrication of thermo-electric module there are various steps, i:e,

Figure 9: Schematic steps for fabrication of TEM

In the 1st step we have to fix the no of legs that should be present in the TEM. Then what are
the leg type we have to focus on. The leg type includes the size, dimension and the type of
the thermo-electric materials used in the legs. Currently people are choosing the thermo-
electric materials having high figure of merit for better output power.

After that we have make the legs by using an effective leg making method. Besides the
traditional and sintering process we can also make the legs by hot pressing technique. In hot
pressing technique it is the simultaneous application of heat and pressure. It is used for
making hard and brittle materials. It can allow resistance heating up-to temperature of 24000C
and pressure up-to 50MPa can be applied.

Then we have to join the legs with each other by means of metal contact (metal strips). For
this also we have to make the metal strips which is usually made by metals like Silver,
Copper and Stainless steel.

Then we have to make the glue/wax that is needed to fix the legs with the metal strips and
also with the ceramic substrate. Normally Ag paste is used as wax because of its high
electrical conductivity nature. Then we have to select the substrate for the outer layers.
Alumina is used normally as the substrate due to its electrical resistivity and thermal
conductivity nature and also it can maintain high strength and hardness. Lastly we have to

Page | 22
mount the legs and interconnection inside the substrate and connect wires for at the two
output ends for voltage output.

So here we are fabricating 4 legged thermo-electric module composed of oxide

thermoelectric material. The schematic diagram can be depicted as follows

Figure 10: Schematic of a 4 legged TEM

The above schematic diagram shows a typical thermoelectric module assembly. Both p type
and n type thermoelectric material are used in thermoelectric module. In p type we have used
Ca3CO4O9 doped with Mo and n type we have used CaMnO3 with Bi doped. Here the
prepared legs have the dimensions of 12mm height and 8mm diameter and the legs are
cylindrical in nature. The legs are joined with each other by means of stainless steel thin
strips. Lastly the load resistance RL is connected at the output ends for the VOut measurement.

This arrangement causes heat to move through the module which creates voltage drop across
the wires and results some electrical current. Most thermoelectric cooling modules are
fabricated with an equal no of N type and P type elements where one N and P element pair
form a thermoelectric “couple”. For example, the module illustrated above has two pairs of N

Page | 23
and P elements and is termed a “two-couple module”. The photograph of the prepared
module is showed below.

Figure 11: Real Photograph of a 4 legged Oxide module during fabrication in laboratory.

3.2 Calculation of Efficiency:-

Output Power:-

The open circuit voltage (V0) can be defined as the potential difference between the two
output ends when it is disconnected from any circuit. It is also the voltage when no load is
connected to the circuit [59]. So V0 of a thermo-electric module can be expressed as

𝑶𝒑𝒆𝒏 𝒄𝒊𝒓𝒄𝒖𝒊𝒕 𝒗𝒐𝒍𝒕𝒂𝒈𝒆(𝑽𝟎 ) = 𝑵𝒋𝒖𝒏𝒄𝒕𝒊𝒐𝒏𝒔 × (𝜶𝑷 − 𝜶𝒏 ) × (𝑻𝒉𝒐𝒕 − 𝑻𝒄𝒐𝒍𝒅 )

Where 𝑁𝑗𝑢𝑛𝑐𝑡𝑖𝑜𝑛𝑠 = No of junctions

𝛼𝑃 = seebeck coefficient for p type leg

𝛼𝑛 = seebeck coefficient for n type leg

𝑇ℎ𝑜𝑡 = Temperature of the hot side

𝑇𝑐𝑜𝑙𝑑 = Temperature of the cold side

With the addition of a resistive load (RLoad which is the cumulative resistance of the circuit)
to the TEM, the electrical circuit of the module is closed. A current is induced, and the

Page | 24
voltage at the terminals of the thermo-electric module drops which is called as load voltage
(VL), because part of the generated voltage (V0) is dropped within the module itself due to the
internal resistance of TEM.

The expression for load voltage is

(𝑹𝒍𝒐𝒂𝒅 × 𝑽𝟎 )
𝑳𝒐𝒂𝒅 𝒗𝒐𝒍𝒕𝒂𝒈𝒆(𝑽𝒍 ) =
(𝑹𝒍𝒐𝒂𝒅 + 𝑹𝒊𝑻𝒐𝒕𝒂𝒍 )

The resulting power and current load are calculated as follows

𝑽𝒍 𝟐 𝑹𝒍𝒐𝒂𝒅 × 𝑽𝟎 𝟐
𝑷= =
𝑹𝒍𝒐𝒂𝒅 (𝑹𝒍𝒐𝒂𝒅 + 𝑹𝒊𝑻𝒐𝒕𝒂𝒍 )𝟐

𝑽𝟎
𝑰=
(𝑹𝒍𝒐𝒂𝒅 + 𝑹𝒊𝑻𝒐𝒕𝒂𝒍 )

The maximum electrical power can be calculated according to the theorem of maximum
power transfer (Jacobi law), in which the power output is maximized when the load
resistance equal to the internal resistance of the thermo-electric module (RiTotal =RLoad).

𝑽𝟎 𝟐
𝑷𝒎𝒂𝒙 =
𝟒 × 𝑹𝒊𝑻𝒐𝒕𝒂𝒍

𝑽𝟎
𝑰𝑷𝒎𝒂𝒙 =
𝟐 × 𝑹𝒊𝑻𝒐𝒕𝒂𝒍

Where, 𝑅𝑖𝑇𝑜𝑡𝑎𝑙 = Total internal resistance, which is dependent upon the type of the nature of
the material. Total internal resistance is the resistance offered due to which power supply
drops the voltage (potential difference) at the output ends.

Factors affecting Output power:-

Resistance:-

So there are a lot of factors which affect the output power. But among them resistance affects
the most to the performance of the thermo-electric module. As we know,
𝑽𝟐
𝑷=
𝑹

So for maximum power resistance should be minimum.

Page | 25
Let us consider our Oxide TEM having 4 legs. So their various resistance offered by the
module can be depicted as

Figure 12: Equivalent electrical resistance circuit of Oxide TEM

So the total resistance can be represented as RTotal ,i:e

RTotal = 2RP+2RN+5RM+8RC

Rp is the resistance offered by the p type leg, Rn is the resistance offered by the n type leg, RM
is the resistance offered by the metal strips and RC is the contact resistance offered by the
wax joints.

𝐿×𝜌
As RMaterial = 𝐴

And

1×𝜌
RContact Factor = (due to negligible thickness L is taken as 1)
𝐴

𝑳𝒑 𝝆𝒑 𝑳𝒏 𝝆𝒏 𝑳𝒎 𝝆𝒎 𝝆
RTotal =𝟐 +𝟐 +𝟓 + 𝟖 𝑨𝒄
𝑨𝒑 𝑨𝒏 𝑨𝒎 𝒄

Efficiency:-

The efficiency of TEM is given by, which is the ratio between the energy provided to the load
and the heat energy absorbed at hot junction. [60]

Page | 26
 𝑒𝑛𝑒𝑟𝑔𝑦 𝑝𝑟𝑜𝑣𝑖𝑑𝑒𝑑 𝑡𝑜 𝑡ℎ𝑒 𝑙𝑜𝑎𝑑(𝑃)
𝜂=
ℎ𝑒𝑎𝑡 𝑒𝑛𝑒𝑟𝑔𝑦 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝑎𝑡 ℎ𝑜𝑡 𝑗𝑢𝑛𝑐𝑡𝑖𝑜𝑛(𝑄)

Mathematically η can be expressed as

𝑻𝑪 √𝟏 + ̅̅
𝒛𝑻̅̅ − 𝟏
𝜼 = (𝟏 − )
𝑻𝒉 √𝟏 + 𝒛𝑻
̅̅̅̅ + 𝟏

Where, 𝑇𝐶 =Temperature of cold end

𝑇ℎ =Temperature of hot end

2
𝑇̅ (𝑆𝑝 −𝑆𝑛 )
̅̅̅=
𝑧𝑇 [ √𝜌𝑛 𝜅𝑛 +√𝜌𝑝 𝜅𝑝 ]2

𝑇̅= average temperature between hold and cold surfaces

S= seebeck co-efficient

𝜅= electrical conductivity

𝜌 = resistivity

Also η can be expressed as

𝟏
𝜶𝒄 𝑻𝒄 + 𝒖
𝒄
𝜼=𝟏−
𝟏
𝜶𝒉 𝑻𝒉 + 𝒖
𝒉

𝐽
Where, relative current density 𝑢 = 𝜅△𝑇

α =seebeck coefficient

κ = electrical conductivity

o The relative current density (u) is the ratio of the electric current density (𝐽) to the
heat flux (△ 𝑇) by thermal conduction (𝜅).

o The maximum efficiency of a Thermo-electric module is computed by finding the 𝑢

for the hot and cold junctions which maximizes the above efficiency equation.

Page | 27
Compatibility:-

Compatibility factor means how the component are compatible with each other inside the
TEM. The value of relative current density (u) which maximizes the reduced efficiency is
defined as‘s’, which is the thermo-electric (power generation) compatibility factor. [60]

Mathematically,

√𝟏 + 𝒛𝑻 − 𝟏
𝒔=
𝜶𝑻

Where, α is the seebeck coefficient

zT is the figure of merit

The compatibility factor(s) is a temperature dependent materials property derived from the
𝛼, 𝜅 𝑎𝑛𝑑 𝜌.So ‘s’ cannot be changed with device geometry or the alteration of electrical or
thermal currents.

Shape factor:-

Shape factors “S” which in reality correspond to equivalent section area to thickness ratio for
a given geometry. As shape factors are available for a limited set of geometries but they can
be easily computed for the custom geometries using numerical tool technique such as
ANSYS CFX. [59]

Mathematically shape factor can be expressed as

𝑸̇
𝑺=
𝜟𝑻 × 𝒌

Since the shape factor is mainly a geometric factor, it is valid for a given geometry. And in
practice it does not vary with the temperature field, only a marginal variation maybe observed
due to the temperature dependence of conductivity. Which when integrated across the
geometry, may yield very slight difference in S for different temperature differences between
the hot and cold sources.

Page | 28
 CHAPTER 4

RESULT AND DISSCUSION

After the study on the proposed 4 legged Oxide thermo-electric module, the results are
discussed below.

Result 1

The under mentioned graph shows the variation of seebeck coefficient for both p type and n
type leg vs temperature of the hot end of the module.

Figure 13: Variation of Seebeck coefficient and temperature of hot end.

Fig. 13 shows the Seebeck coefficient for p type leg range from 120 to 180 µV/K and in n
type it ranges from -265 to -340 µV/K at the temperature from 400 K to 900 K. So we can say
that the Seebeck coefficient is increasing with the increase in temperature. i:e, they are
directly varying with each other .

Result 2:-

The output voltage can be measured by connecting multi-meter to the output terminals of the
module. When the temperature of the module changes we can see some voltages resulting in
the multi-meter. Here there are 2 graphs representing the output voltage one with the
temperature of the hot end another with the temperature gradient of the module.

Page | 29
The graph 14 describes the variation of output voltage with the temperature of hot end.

Figure 14: Variation of output voltage and temperature of hot end

From fig. 14 it can be concluded that within the temperature range from 360 K to 755 K we
can have the corresponding voltage output from 2.56 to 39.52 mV. Here the voltage is
increasing along with the increase in the temperature. The under mentioned graph 15 is the
graph between the output voltage with the temperature gradient of the module.

Figure 15: Variation of the output voltage (Vout) Vs temperature difference (ΔT).

From the graph 15 we can say that temperature gradient ranging from 50 K to 370 K we can
get the corresponding voltage output from 2.56 to 39.52 mV. Here the voltage is increasing
along with the increase in the temperature gradient.

Page | 30
Result 3:-

So in the graph 16 we have varied the resistance of the module along with the temperature of
the hot end.

Figure 16: Variation of the resistance and temperature of hot end of the module.

The nature of the graph says that resistance of the module decreasing along with increasing in
the temperature. So the varied inversely with each other. So here the resistance fall from 0.45
ohm to 0.15 ohm in the temperature range from 360 K to 951 K.

Result 4:-The under mentioned graph describes about the output power with the temperature
responses.

Figure 17: Variation of output power and temperature of the hot end

Page | 31
Here the Output power varies directly with the increase in temp. So desired output power can
be generated when then temperature is more. The power is calculated by mathematical
expression by using the voltage and resistance of module. The output power vary from
125mW to 478mW at the corresponding temperature range from 312K to 482K.

Result 5:-If we plot the graph between the output current along with the temperature of the
hot end, the nature of the graph will be like the undermentioned graph.

Figure 18: Variation of the output current and temperature of the hot end

Here the Output current varies directly with the increase in temperature. So desired output
current can be generated when then temperature is more. The current is calculated by
mathematical expression by using the voltage and resistance of module. The output current
vary from 7.23mA to 14.07mA at the corresponding temperature range from 312K to 482K.

Result 6:-

The maximum electrical power and the maximum electrical current can be calculated
according to the theorem of maximum power transfer (Jacobi law), in which the power output
is maximized when the load resistance equal to the internal resistance of the thermo-electric
module.

Page | 32
So here Graph 19 shows the response of maximum power can be achieved by the module
with certain temperature ranges. And Graph 20 shows the response of maximum current can
be achieved by the module with certain temperature ranges.

Figure 19: Variation of maximum power and temperature of hot end

Here the maximum power of the module ranges from the 256mW to 976mW from the
temperature range 312K to 482K. So maximum power curve shows that the maximum power
achieved by the module can be more when temperature is more.

Figure 20: Variation of maximum current and temperature of hot end

Here the maximum current of the module ranges from the 25.32mA to 49.4mA from the
temperature range 312K to 482K. So maximum current curve shows that the maximum
current achieved by the module can be more when temperature is more.

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 CONCLUSION

A 4 legged thermo-electric module of 50X50 mm2 dimension with 14mm height was
fabricated manually using Ca3CO4O9 (p type) and CaMnO3 (n type) in the laboratory.
Preliminary structural characterizations like XRD and SEM confirms the complete formation
of single phase of desired leg compounds. A systematic and self-assembled set up was
developed using source meter, multi-meter along with heating and cooling arrangement for
testing the performance of developed module. A precise temperature measurements were
made using k type thermocouples at hot junctions and cold junctions. Suitable precautions
were taken during the measurement in order to avoid heat loss. The module was observed to
generate a maximum power of 976mW and maximum current of49.4mA at an applied
difference of 400Kelvin. The output power and current is found to be 478mW and 14.07mA
respectively. As the efficiency play a vital role in determining the modules effectiveness and
productivity. So the efficiency is calculated to be 8%.

The efficiency can be maximized by choosing the best TEM having figure of merit and
adopting the best fabrication process and reducing the contact resistances.

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 FUTURE WORK

After the detailed study on various thermoelectric materials and a 4 legged oxide module, I
am currently planning to fabricate a 4 legged thermoelectric module using Bi2Te3 and Bi2Se3
as they have ZT value 0.8 to 1.0 and they are room temperature independent. The dimension
of the module should be of square 25mm×25mm and thickness of 10mm. The legs of the
module having length of 10mm and diameter of 2mm.

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