Topic:
Thermoelectric Aerogels
❖ Submitted By:
Muhammad Naeem 2021102
Habibullah 2021108
Muhammad Suleman 2021118
Umar Azan Shabir 2021121
❖ Session:
2020-2024
❖ Department:
BS Physics
Government S.E. Graduate College
Bahawalpur
❖ Aims & Objectives
Thermoelectric materials offer an alternative opportunity to tackle the energy crisis and environmental problems
by enabling the direct solid-state energy conversion between heat and electricity and offering eco-friendly
solutions for power generation and refrigeration. Graphene aerogels (GAs) have been promising materials due
to ultralow thermal conductivity and high electrical conductivity has enhanced power factors. Various
optimization strategies were recorded to improve the performance of the graphene aerogels (Gas) as a mid-
temperature TE material. The analyses and reviews of the methodologies showed a noticeable improvement in
the electrical conductivity and Seebeck coefficient, with a noticeable decrement in the thermal conductivity,
thereby enhancing the graphene aerogels figure of merit value for its use in the TE fields such as
microgenerators, and flexible and wearable devices. In this review, the effect of doping and the structures of
graphene aerogels will be reviewed. which is versatile materials with applications in various fields. This review
will help the researcher to understand the properties and possible applications of aerogel- based materials.
❖ CONTENTS
➢ Introduction to Thermoelectricy
➢ Aspects of Material Choice
➢ Thermoelectric Materials
➢ Introduction To Graphene
➢ Introduction To Aerogels
➢ Graphene Aerogels
➢ Properties of Graphene Aerogels
➢ Applications of Graphene Aerogels
➢ Synthesis Techniques of Graphene Aerogels
➢ Future Work
➢ References
❖ THERMOELECTRICITY
Introduction
“The interconversion of heat into electricity and vice versa is known as thermoelectricity”.
Thermoelctricty is based on three effects known as thermoelectric effects which are given below:
1) Seebeck Effect
2) Peltier Effect
3) Thomson Effect
1. Seebeck Effect
➢ In 1821 Thomas Seebeck, a German physicist discovered that when two
dissimilar metal ( Seebeck used copper and iron) wires are joined at two
ends to form a loop, a voltage is developed in the circuit if the two junctions
are kept at different temperatures. The pair of metals forming the electrical
circuit is called a thermocouple .
➢ The potential difference (Seebeck voltage) developed across the juctions,
maintained at temperature TH and TC (Tc<Th) is given by:
∆V = SAB (TH-TC)
where the coefficient of proportionality is known as the thermoelectric
power or the Seebeck coefficient.
➢ By convention, Seebeck coefficient's sign is the sign of the potential of the
cold end with respect to the hot end. Thus if SAB is positive, conventional
current flows from A to B at the hot junction. Seebeck coefficient is not a Figure 1: Seebeck Effect [1].
constant but dependant on temperature..
❖ Graphical Explanation
Tn( Neutral Temperature)
➢ Neutral Temperature: The temperature at which thermo emf max
emf is at its peak value.
+ Thermo emf
➢ Inversion Temperature: The temperature at which the
thermo emf becomes zero and at which the polarity of
thermocouple changes.
➢ The relation between V and T is Parabola.
- Thermo emf
Figure 2: Relation between Thermo emf
and Temperature [2].
❖ Applications
➢ In thermoelectric generators that function as heat engines;
➢ In power plants to convert waste heat into (extra) power;
➢ In automobiles as automotive thermoelectric generators, to increase fuel efficiency;
➢ In high-frequency electrical power sensors;
.
2. Peltier Effect
➢ In 1834 Jean Peltier, a French watch maker, discovered a second
thermoelectric effect. If a current flows through a circuit containing
junction of two dis-similar metals, it leads to an absorption or liberation of
heat at the junctions.
➢ The amount of heath liberated to (or absorbed from) the surroundings in
order that the junction may be kept at the same temperature is proportional
to the current I passing through the junction:
➢ Q = 𝜋AB I
➢ where the constant 𝜋AB is called the Peltier coefficient .
➢ The Peltier coefficient depends on the pair of materials A and B of the
junction and also on the junction temperature.
Figure 3: Peltier Effect [3].
❖ Applications
It is used in:
➢ Refrigerators: The Peltier effect can be used to create a refrigerator that is compact and has no circulating fluid or
moving parts
➢ Dehumidifiers: The cooling effect of Peltier heat pumps can be used to extract water from the air in dehumidifiers.
Climate-controlled jackets are beginning to use Peltier elements.
➢ Satellites: The effect is used in satellite and spacecraft to counter the effect of direct sunlight on one side of a craft by
dissipating the heat over the cold shaded side, where upon the heat is dissipated by thermal radiation into space.
➢ Fibre Optics Applications: In fiber optic applications, where the wavelength of a laser or a component is highly
dependent on temperature, Peltier coolers are used along with a thermistor in a feedback loop to maintain a constant
temperature and thereby stabilize the wavelength of the device.
3. Thomson Effect
➢ “When an electric current is passed through a conductor having a
temperature gradient over its length, heat will be either absorbed
by or expelled from the conductor. Whether heat is absorbed or
expelled depends upon the direction of both the electric current
and temperature gradient. This is known as the Thomson Effect”.
➢ William Thomson (later well known as Lord Kelvin) discovered a
third thermoelectric effect which provides a link between Seebeck
effect and Peltier effect.
➢ If a current density J is passed through a homogeneous conductor, the
Thomson effect predicts a heat production rate per unit volume:
➢ q= − KJ. ∇T
➢ where ∇T is the temperature gradient, and K is the Thomson Figure 4: Thomson Effect [4].
coefficient.
Types of Thomson Effect
➢ Positive Thomson Effect:
• Current flows from lower T to high T, heat is absorbed through the system.
For Example: Sn, Au, Ag, Zn, Cd, Sb.
➢ Negative Thomson Effect:
• Current flows from lower T to high T, heat is liberated through the system.
For Example: Bi, Ni, Pt, Co, Hg.
➢ Nill Thomson Effect:
• Current flows from low T to high T or High T to low T, heat is neither liberated nor absorbed through the system.
For Example: Pb
Thermoelectric Figure of Merit
➢ The usefulness of a material in thermoelectric systems is determined by the device efficiency. This is
determined by the material’s electrical conductivity (σ), thermal conductivity(κ), and Seebeck
Coefficient(S), which change with temperature. The maximum efficiency of the energy conversion process
(for both power generation and cooling) at a given temperature of a material is determined by the
thermoelectric materials figure of merit is given by:
𝝈𝑺𝟐𝑻
ZT = 𝑲
which contains the Seebeck Coefficient S, thermal Conductivity K, electrical conductivity σ, and
temperature T.
Aspects of Materials Choice
The good thermoelectric material should posses:
❑ Large Seebeck Coefficient
❑ High Electrical Conductivity
❑ Low Thermal Conductivity
Table 1: Aspects of Materials Choice
TE Parameters
Electrical Conductivity (G) Seebeck Coefficient (S) Thermal Conductivity (K)
Materials
Low
Very High High
Metals (~10μV/K)
(~107S/m) (~102W/mK)
Extremely Low Low
Insulators High
(~10-10S/m) (~102-104W/mK)
Moderate High Low
Semiconductors
(103S/m) (~120μV/K) (~10W/mK)
Thermoelctric Materials
For inorganic semiconductors, proper doping can improve the carrier
concentration in thermoelectric material by changing their electronic band
structure. Therefore, as the appropriate dopant atoms continue to grow, the
number of states in each level will also increase. The energy states close to the
Fermi level can promote electron transport. Thus, by introducing defects, doping
can introduce an additional energy level between the two bands, thereby
increasing conductivity.
Figure 5 shows the Seebeck coefficient and conductivity varying with the
change of the carrier concentration. Obviously, the charge-carrier concentration
has a great effect on them, and with the increase in carrier concentration, the
conductivity increases but the Seebeck coefficient decreases. Thus, to improve σ,
doping is an effective way to improve the thermoelectric performance.
Figure 5: The electrical properties of the
thermoelectric materials vary with the carrier
concentration[5]
Examples
1) Bismuth Telluride (Bi2Te3): Its operate at room
temperature.
2) Lead Telluride (PbTe): Best working temperature is
about 500-700K.
3) Silicon-Germanium: Best working temperature is
about 1300℃.
Figure 6: Thermoelectric Materials [6].
Introduction to Graphene
➢ Graphene is a two-dimensional material made up of a carbon atom arranged
in a hexagonal lattice [Link]'s a single layer of atoms, with each carbon Table 2: Properties of Graphene[8]
atom bonded to three neighbors in a strong and flexible framework Properties of Graphene
Apperance Black Solid
Molecular Weight 12.01amu
Melting Point 2650-3697 °C
Boiling Point 4200 °C
Electrical Conductivity 100-1000 s/m
Density 2.267 g/m³
Thermal conductivity 5000 W/mk
Band gap Zero
Figure 7: Hexagonal structure of graphene[7].
Introduction to Aerogels
➢ Aerogels are ultra-lightweight, porous, and translucent materials with unique properties. Aerogel material has ultralow density
ranges from 0.03-0.3 g/cm³, high porosity (99.98% air), low thermal conductivity of the order of 0.01-0.1 w/mk, high electrical
conductivity, large surface area 100-1000m²/g, high chemical stability, and mechanical strength some of the aerogel materials are
Silica aerogels, carbon aerogels , polymer aerogels , metal oxide aerogels , graphene aerogels and hybrid [Link] we will
discuss graphene-based aerogels along with their properties and applications
Figure 8 (a) Evolution of the aerogels. (b) The number of papers published every year during the last decades[9].
Graphene Aerogels
Table 3: Properties of Graphene Aerogels
Graphene based aerogels (GAs) are 3D materials
that can be lighter than air. Due to their fascinating Properties of graphene aerogels
properties, such as, high mechanical strength and Density[10] 0.1-10 mg/cm³
electrical conductivity, thermal resistance and
Porosity[11] More than 90%
adsorption capacity they have attracted a lot of
interest currently. Specific surface 100-3000 m²/g
area[12]
Electrical 10-100 S/m
conductivity[13]
Mechanical 10-100 MPa
strength[14]
Elasticity More than 80%
Thermal stability[15] Upto 1000°C
Thermal conductivity 0.01 /MK
Applications of Graphene Aerogels
➢ Graphene aerogels have diverse applications, including sensors, air
filtration, catalysis, energy storage, water purification, biomedical,
adore removal and thermal [Link] offers sustainable
solutions for various industries, transforming the way to purify
water and store [Link] there unique properties, graphene
aerogels are set to revolutionize multiple fields.
Figure 9: Properties of graphene aerogels.
Typical Synthesis Techniques for
Graphene Aerogels
1. Hydrothermal Reduction Process
The hydrothermal process for synthesizing graphene aerogels
involves:
➢ Mixing graphene oxide with water and reducing agent.
➢ Sealing the mixture in an autoclaves.
➢ Heating the mixture at high temperature.
➢ Formation of reduced graphene oxide hydrogels.
➢ Supercritical drying or freeze-drying to obtain graphene
aerogels.
This process allows for the creation of lightweight, porous and Figure 10: Schematic diagram of the fabrication of
conductive graphene aerogel. graphene aerogels by a hydrothermal process with
different reducing agents[16].
2. Chemical Reduction Method
The chemical reduction process for synthesizing graphene
aerogels involves:
➢ Dispersion of graphene oxide (GO) in a solvent.
➢ Addition of a reducing agent (e.g., hydrazine, L-ascorbic
acid).
➢ Reduction of GO to form reduced graphene oxide (rGO)
hydrogel.
➢ Gelation and formation of 3D network.
➢ Drying (supercritical or freeze-drying) to obtain aerogel.
Figure 11: Typical graphene aerogel synthesis
Chemical reduction offers a versatile method for synthesizing schematics showing the experimental steps and
graphene aerogels with tailored properties. synthesis conditions using graphite as the precursor[17].
3. Sol-Gel Method
The sol-gel process for synthesizing graphene aerogels involves:
➢ Dispersion of graphene oxide (GO) in a solvent.
➢ Formation of a gel-like network through chemical reactions.
➢ Gelation and aging.
➢ Drying (supercritical or freeze-drying) to obtain aerogel.
The sol-gel process offers a flexible method for synthesizing Figure 12: Schematic showing the sol–gel
graphene aerogels with tailored properties. synthesis of graphene-based aerogels[18].
Future work Plan
➢ In this review, the effect of doping and the structures of graphene aerogels will be reviewed. Based on the
knowledge of previous research papers we will make comparison how the doping of the graphene with
different element will enhance the thermoelectric properties of graphene aerogels such as electrical
conductivity, thermal conductivity and seeback coefficient.
References
1. McKelvey, J.P., Solid state physics for engineering and materials science. 1993: Krieger
2. Rowe, D.M., CRC handbook of thermoelectrics: macro to nano. CRC/Taylor and Francis, Boca Raton, FL, 2006
3. Chen, A. and P.K. Wright, Medical applications of thermoelectrics. Modules, Systems, and Applications in Thermoelectrics, 2012. 26.
4. Pollock, D.D., The theory and properties of thermocouple elements. 1971: ASTM International.
5. Rosi, F., Thermoelectricity and thermoelectric power generation. Solid-State Electronics, 1968. 11(9): p. 833-868.
6. Snyder, G.J. and E.S. Toberer, Complex thermoelectric materials, in Materials for sustainable energy: a collection of peer-reviewed research and review articles from Nature Publishing Group. 2011, World Scientific. p. 101-110
7. Snyder, G.J., & Toberer, E.S. (2011). Complex Thermoelectric Materials. In Materials for Sustainable Energy: A Collection of Peer-Reviewed Research and Review Articles from Nature Publishing Group (pp. 101–110). World Scientific.
8. Graphene: an emerging material for biological tissue engineering – Scientific Figure on ResearchGate. Available from: [Link] -graphene-as-materials_tbl1_264023420 [accessed 22 Sept 2024]
9. L. Zuo, Y. Zhang, L. Zhang, Y. E. Miao, W. Fan, and T. Liu, "Polymer/Carbon-Based Hybrid Aerogels: Preparation, Properties and Applications," Materials (Basel), vol. 8, pp. 6806-6848, Oct 09 2015., Wikipedia, the free encyclopedia,
[Link]
10. Yu et al. (2018). Ultralight graphene aerogel for efficient water purification. Nano Research, 11(5), 5778–5785. DOI: 10.1007/s12274-018-2034-6.
11. Wu et al. (2020). Pore structure and mechanical properties of graphene aerogels. Journal of Physical Chemistry C, 124(15), 8339–8346. DOI: 10.1021/[Link].0c02511.
12. Zhang et al.. (2019). Graphene aerogel with high surface area and electrical conductivity. Journal of Materials Chemistry A, 7(22), 14311–14318. DOI: 10.1039/C9TA04341C
13. Zhang, Y., et al.. (2019). Graphene aerogel with high surface area and electrical conductivity. Journal of Materials Chemistry A, 7(22), 14311-14318. doi: 10.1039/C9TA04341C
14. Lee et al. (2008). Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science, 321(5887), 385–388. DOI: 10.1126/science.1157996
15. Li, J., et al. (2020). Ultralight graphene aerogel for thermal insulation. ACS Applied Materials & Interfaces, 12(11), 13451-13458. doi: 10.1021/acsami.0c0243
16. Super-compressible and mechanically stable reduced graphene oxide aerogel for wearable functional devices - Scientific Figure on ResearchGate. Available from: [Link]
hydrothermal-process-with_fig1_370831896 [accessed 4 May 2025].
17. <ahref="[Link] src="[Link]
2/publication/320827542/figure/fig3/AS:941867596275738@1601570142289
18. Carbon Aerogels - Scientific Figure on ResearchGate. Available from: [Link] [accessed 4 May 2025].
꧁𓊈𒆜Thank you𒆜𓊉꧂