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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.

+ Current out Two legs of a thermocouple. of two temperatures. 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. Introduction to Thermoelectrics Heat in Thermoelectric Couple Thermoelectric elements (legs) Th N P Tc . .

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) .

long lifetime. high accuracy. environmentally friendly . highly reliable. Applications of Thermoelectrics (II) TE Cooling (Peltier) High accuracy thermometer Environmentally-friendly refrigerator New air-conditioning Cooling for electronics Simple system. small volume. high sensitivity.

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)). . 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.

Performance of Thermoelectric Generator as Function of ZT For above temperatures. . making the TE generator to be about 24 to 30 percent efficient with TE materials with ZT between 2 and 3. the Carnot efficiency is about 61 percent.

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 .

Ford.Climate Control Seat (CCS) System Vehicle Application In high end cars (GM. Toyota. Lexus. Nissan. Huge market!!! Over 4 million units sold so far. etc) . .

Solid state refrigerators may replace traditional compressor refrigerators in the future .

5 Quantum-dot max (ZT)max Superlattices 3 (Lincoln Lab) Merit (ZT) Bi2Te3/Sb2Te3 OFofMERIT 2.8Ge0.5 Si0.5 FIGURE Skutterudites (Fleurial) 1 PbTe alloy Bi2Te3 alloy 0. Progress in Thermoelectric Efficiency ZT 4 PbSeTe/PbTe 3.2 alloy Dresselhaus 0 1940 1960 1980 2000 2020 Year YEAR .5 Superlattices (RTI) (Michigan 2 State) Figure 1.

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 .

So a nanometer is one billionth of a meter. In general. These materials also have tunable properties that makes them valuable for many different real world applications.Introduction: Nanoscience and Nanotechnology What is a Nanostructure? The word “nano” means 10-9 . Why nano? The nanoworld provides scientists with a rich set of materials that can be useful of probing the fundamental nature of matter. . nanostructures are objects in the size range from tens to hundreds of nanometers. and nanotechnology is to fabricate and work on objects in this size range. Nanoscience concerns the study of objects in this size range.

et al. C60 discovered by Kroto in 1985 Stanford Science. Examples of Nanostructures 48 Fe atoms on Cu (111) surface. by D. Eigler..nano. Quantum Corral.IBM Self-assembled Ge pyramid Chemical Etching of Porous Silicon 10nm (www. 1998) .gov) by Thomas Research Group Carbon Nanotubes (Ren.

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 .

(1quads =1 quadrillion BTU. US Energy Flow Trend (2002) Massive Quantity of “Waste” Energy Imported Oil 97% Oil Dependent Unit: quads. 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 .

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ORNL. 2007 . Nov. a Research Roadmap By 2012. DOE Initiative for a Science-Based Approach to Development of Thermoelectric Materials for Transportation Applications. achieve at least 25% efficiency in advanced thermoelectric devices for waste heat recovery to potentially increase passenger and commercial vehicle fuel economy by 10%.Goal for TE in Transportation.

and p. Technical Barriers Unusual combination of properties Matching n.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 .

. Our calculations have helped with the understating of the TE property of nanostructure affected by various conditions.Collaboration with Caterpillar We have developed a physics-based model that simulates the structure of multilayered nanostructures. and the results are used to guide the experimental research in developing nanostructured thin-film based materials for high- efficiency TE applications. Our modeling tool is used to predict the TE property of various multilayered structures with different structural configurations and doping concentrations.

Potential Location for TE Generator .

Caterpillar’s 550 HP Heavy Truck Equipped with TEG .

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TE Generator for Light Vehicles .

TE Materials for Applications in Energy and Environment .