Introduction to Thermoelectric Effects

And Their Applications in

Energy and Environment

Shang-Fen Ren
Department of Physics, Illinois State University
Normal, IL 61790-4560

ren@phy.ilstu.edu

Research Supported by
National Science Foundation,
Research Corporation,
and Caterpillar, Inc
 Main Research Collaborators

Wei Cheng (Beijing Normal University)

Gang Chen (MIT)
Walter Harrison (Stanford)
Peter Yu and Sam Mao (UC-Berkeley)
Andrew McGilvray, Bo Shi, and Mahmoud Taher (Caterpillar)

Research Students (1994-present)

David Rosenberg, Latanya Molone, Garnet Erdakos, Heather Dowd, Jason

Stanford, Maria A. Alejandra, Chad Johnson, Kim Goodwin, Joel Heidman,
Paul Peng, Josh Matsko, Brian Mavity, Rory Davis, Nathan Tovo,
Victor Nkonga, Shelley Dexter, Scott Gay, Tim Hughes, Gabriel Altay, Louis Little,
Victor Nkonka, Benjamin Thompson, Jonathan Andreason, Zoe Paukstys,
Colin Connolly, Marcus Woo, Courtney Pinard, Danthu H.Vu,
Valerie Hackstadt, Derek Wissmiller, Scott Whitney, Chris S. Kopec,
Erika Roesler, Elizabeth Williams,Trina Karim, Mike Morrissey, Nick Jurasek,
Nathan Bogue, Mid-hat Abdulrhman, Maggie Hansen, Jade Exley
 Outline

Thermoelectric Effect

What is Thermoelectric Effect (TE)

Potential Applications of TE

TE and Nanotechnology

TE Applications in Energy and Environment

Research Collaboration on TE with Caterpillar

 Thermoelectric Effects

Discovered in 1821 by Thomas Johann Seebeck: observed a compass needle to move

when placed in the vicinity of a closed loop of two dissimilar metal conductors joined together at the
ends to make a circuit, when the junctions were maintained at different temperatures.
 Introduction to Thermoelectrics
Heat in Thermoelectric
Couple Thermoelectric
elements (legs)

Th

N P
Tc

- +
Current out

Two legs of a thermocouple.

Most materials with good thermoelectricity efficient
The magnitude of the thermoelectric
are semiconductors. Two legs are made by
voltage is proportional to the difference
N-type and P-type of semiconductors respectively.
of two temperatures.
 Thermoelectrics Nomenclature
Thermoelectric Device
(Module)

-
Thermoelectrics Nomenclature
Thermoelectric System/Application
Commercial Bulk TE Modules
 Thermoelectrics Power Generation
Thermal Power in

(Seebeck Effect)
Q
T
h
h
Electric Power out -

Po +
Tc

Carnot Efficiency

Th  Tc 1  ZTav  1 Po
 max  
Th Tc Qh
1  ZTav 
Th
Thermoelectrics Cooling (Peltier Effect)
Peltier Effects was discovered 13 years later.

Th
Electric Power in -

Pin
+

Tc

Thermal Power Out

Qc
Th
1  ZTav 
Tc Tc Qc
COPmax  
Th  Tc 1  ZTav 1 Pin
 Applications of Thermoelectrics (I)

TE Power Generation (Seebeck)

Power generation for special applications

Space
Military

Waste heat to energy (green energy)

 Applications of Thermoelectrics (II)
TE Cooling (Peltier)
High accuracy thermometer
Environmentally-friendly refrigerator
New air-conditioning
Cooling for electronics

Simple system, small volume,

high accuracy, high sensitivity, highly reliable,
long lifetime, environmentally friendly
 Thermoelectric Efficient
Figure of Merit ZT
 2
ZT= T

α is the Seebeck coefficient of the material (V/K)
 is the electrical resistivity of the material (Ωm)
 is the thermal conductivity of the material (W/mK)
Most materials have a ZT much less than 1.
Thermoelectric systems in automobiles requires a ZT of about 2.
To substitute conventional refrigerators requires a ZT of about 4

The heart of the research is to look for materials that

conduct electricity well but conduct heat poorly (phonon
glass and electron crystal (PGEC)).
Performance of Thermoelectric Generator as Function of ZT

For above temperatures, the Carnot efficiency is about 61 percent, making the TE generator
to be about 24 to 30 percent efficient with TE materials with ZT between 2 and 3.
Coefficient of Performance for Thermoelectric Cooling
as Function of ZT
Figure of Merit – Bulk
Portable Fridge
Bulk Module
Dehumidifier
Markets
Electronics Cooling Automobile

Offshore power generation

Chiller

Radioisotope thermoelectric
generator

Night vision
Climate Control Seat (CCS) System Vehicle Application

In high end cars (GM, Ford, Toyota, Nissan, Lexus, etc) .

Huge market!!! Over 4 million units sold so far.
Solid state refrigerators may replace traditional
compressor refrigerators in the future
 Progress in Thermoelectric Efficiency ZT
4
PbSeTe/PbTe
3.5 Quantum-dot
max
(ZT)max

Superlattices
3 (Lincoln Lab)
Merit (ZT)

Bi2Te3/Sb2Te3
OFofMERIT

2.5
Superlattices
(RTI) (Michigan
2 State)
Figure

1.5
FIGURE

Skutterudites
(Fleurial)
1 PbTe alloy
Bi2Te3 alloy

0.5 Si0.8Ge0.2 alloy

Dresselhaus
0
1940 1960 1980 2000 2020
Year YEAR
Thermoelectrics Materials: Bulk and
Bulk
Less than 5%
Nano-Scale Nano-Scale
Predicted with 30%
conversion efficiency conversion efficiency

• More than 40 years • Less than 10 years

• Niche applications • Potential for a wide
variety of applications
• Well established
product • Still being incubated at
small companies,
universities and national
labs
A World from Macro to Nanoscale
1 nm = 10-9 m
Introduction: Nanoscience and Nanotechnology
What is a Nanostructure?
The word “nano” means 10-9 . So a
nanometer is one billionth of a meter. In
general, nanostructures are objects in the
size range from tens to hundreds of
nanometers.
Nanoscience concerns the study of
objects in this size range, and
nanotechnology is to fabricate and
work on objects in this size range.
Why nano?
The nanoworld provides scientists with a
rich set of materials that can be useful of
probing the fundamental nature of matter.
These materials also have tunable
properties that makes them valuable for
many different real world applications.
 Examples of Nanostructures

48 Fe atoms on Cu (111) surface,

Quantum Corral, by D. Eigler,IBM Self-assembled Ge pyramid
Chemical Etching of Porous Silicon 10nm (www.nano.gov)
by Thomas Research Group

Carbon Nanotubes (Ren, et al.,

C60 discovered by Kroto in 1985 Stanford Science, 1998)
Properties of Nanostructures: Electron Density of States as a
Function of Dimensionality

Quantum well (QW) 2-D

Quantum wires(QWR) 1-D

Quantum Dots (QD) 0-D

Properties of Nanoscale Materials: CdSe Quantum Dots
 Properties of Nanoscale Materials: Size
and Band
Electrons: Blue shift of the electronic band gap
Gap

Uncertainty Principle
 US Energy Flow Trend (2002)
Massive Quantity of
“Waste” Energy

Imported Oil
97% Oil
Dependent

Unit: quads, (1quads =1 quadrillion BTU, 1 BTU=1055J)

Opportunities for Recovery of Waste Heat in
Transportation

30%

Combustion
Engine
100%

25
Gasoline
Gasoline

Mobility &
Accessories
5%
Friction &
Radiated

30%
Coolant

40%
Exhaust
Gas

Distribution of Fuel Energy in Passenger Vehicles

Goal for TE in Transportation, a Research Roadmap

By 2012, achieve at least 25% efficiency in

advanced thermoelectric devices for waste heat
recovery to potentially increase passenger and
commercial vehicle fuel economy by 10%.

DOE Initiative for a Science-Based

Approach to Development of Thermoelectric
Materials for Transportation Applications,
ORNL, Nov. 2007
 Technical Barriers

Unusual combination of properties

Matching n- and p- type materials

Performance often dependent on doping

Difficult metrology and lack of standards

Scale up of synthesis and processing of thin-film materials from lab

scale

Cost effective thermoelectric materials and devices

System issues critical to operation of thermoelectric devices

Science-based Approach for TE material Discovery

Computation
(Modeling &
Simulation)

New Synthesis &

Evaluation Materials Processing

Characterization
Materials Technology Flow for Solid State Waste
Heat Energy Recovery
Collaboration with Caterpillar

We have developed a physics-based model that simulates the

structure of multilayered nanostructures.
Our modeling tool is used to predict the TE property of various
multilayered structures with different structural configurations
and doping concentrations.
Our calculations have helped with the understating of the TE
property of nanostructure affected by various conditions, and
the results are used to guide the experimental research in
developing nanostructured thin-film based materials for high-
efficiency TE applications.
Potential Location for TE Generator
Caterpillar’s 550 HP Heavy Truck Equipped with TEG
TE Generator for Light Vehicles
TE Materials for Applications in Energy and Environment