Marlow Industries, Inc.

DEVELOPMENTS IN THERMOELECTRIC POWER

GENERATION TECHNOLOGY

Jim Bierschenk

Advanced Concepts in Semiconductor Materials and

Devices for Energy Conversion
December 7th and 8th Sheraton Washington North Beltsville, Maryland

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Marlow Industries, Inc.
a subsidiary of II-VI Incorporated
About Marlow Industries, Inc.
Headquarters: Dallas, TX (USA) Thermoelectric quality and performance
Industry: Thermoelectric Solutions at industry competitive prices.

Structure: Operating Subsidiary

Founded: 1973
Employees 500+
Manufacturing: Dallas, Vietnam

About II-VI Incorporated

Headquarters: Saxonburg, PA (USA)
Industry: Materials
Structure: Public/(NASDAQ) IIVI Marlow Industries- Dallas, TX
Founded: 1971 Center of Technical Excellence
Employees >6000 II-VI named for their material origin
FY10 Revenue $345M in the compounds listed under II
and VI columns on the periodic
table: Zn, Cd, S, Se, and Te.
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 Marlow Vertical Integration

TEC Sub-
Assembly System
Assembly

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TE Cooling Markets and Applications
Defense, Space & Photonics
▪ Thermal Night Sights
▪ Range Finders and Target Designators
▪ FLIR Calibration Systems
Telecommunications
▪ Long Haul Laser Transmitters and Pump Lasers
▪ Short and Mid Range Laser
Transmitters/Receivers
Medical
▪ Thermal Cyclers for Polymerase Chain
Reactions
▪ Liquid and air refrigerated
compartments for blood analyzers
Industrial
▪ Heated & Cooled automotive car seats
▪ Point-of-sale boxes/small refrigerators
▪ Semiconductor processing equipment
Consumer
▪ Water chillers, wine chillers, refrigerators
▪ Personal cooling – bedding, chairs, etc.
▪ Gaming Applications

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TE Cooling vs. Power Generation

Medical Energy
Harvesting
Telecom Industrial
Direct
Power Gen

Space Automotive Waste

Heat
Recovery

Defense
Marlow TE Consumer Marlow TE Co-
Cooling Power Gen Generation

Material research driven by waste heat

Many diverse markets/applications
Extensive product customization
Flexible manufacturing capability
Thermal & mechanical design capability
Highest performing suite of TE materials
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recovery applications
Many diverse markets/applications
Extensive product customization
Flexible manufacturing capability
Thermal & mechanical design capability
High performance generator materials
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 TE Power Generation
Application Areas
Energy Harvesting Waste Heat Recovery
Microwatt to low milliwatt power to perpetually power Convert heated waste exhaust streams to electric power
wireless sensors for improve efficiency

• Battlefield sensors Heat Source/ColdSource

• Automotive WHR
• Engine health monitoring • Improve fuel economy
(temperature, vibration, etc) & reduce CO2 emissions
• Structural health monitoring Q Ambient Air • Minimize Fuel Consumption
(aircraft, building, bridges, etc) on stationary generators
• HVAC controls • Convert Industrial Waste Heat to Electricity

Direct Power Generation Co-Generation

Burn a hydrocarbon fuel to produce heat – convert heat Heat produced from burning high energy density fuel.
to electrical using TE Generator
• Self-powered military equipment
• Battery Replace Technology • Tent heaters
• Unattended Ground Sensors • Cooking equipment (ration
• Soldier power tray heaters, griddles)
• Robot/UAV power sources • Cleaner burning 3rd world
• Battery Chargers cook stoves
• Auxiliary Power Units • Self powered fans for wood stoves and mosquito
catchers
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Marlow Power Generation

▪ Marlow’s power generation focus is to develop:

– Volume production processes for new high
temperature materials
– Volume production device assembly processes
– Single and multistage (cascade capability)
– Device and system level thermal and mechanical
modeling
– Material, device and subsystem test capability
– Understand long term reliability
▪ Focus on both low temperature (Bi2Te3) and high
temperature applications

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Energy Harvesting – Why Now?

Heat Source/ColdSource

▪ Evolution of low power sensors,

transmitters and power Q Ambient Air
management electronics have
made TE energy harvesting
practical

Energy harvesting (also known

as power harvesting or energy
scavenging)
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Thermoelectric Energy Harvesting

Thermal Components N P N P N P N P

Heat RLoad
Electrical Components
Source

Thermoelectric Power
Management TSource
Generator Step-up, Charging, Storage,
Voltage Regulation
HSR ΔTHS
Heat TH
Sensor
Sink
Transmitter RTEG ΔTTEG
TC
11 CSR ΔTCS
TAmb

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Optimal TEG Design

The optimal TEG design for an energy

harvesting application:
▪ Thermally matches the combined hot and cold
side thermal resistances
▪ Electrically matches the electrical load
RTEG ,t RLoad
m= =1 n= =1
HSR + CSR RTEG ,e

▪ Has sufficient couples to provide the minimum

threshold voltage for the step-up electronics at
the desired source-to-ambient ΔT
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Interdependence of Thermal and Electrical

The electrical load resistance −1

impacts the thermal   TH2
N 
RTEG ,t = + 
characteristics of the TEG  ( n + 1) R RTEG ,t ,o
 TEG ,e 

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Energy Harvester TEG Transition

Traditional small TE Cooler

Can Be used As Energy
Harvesting TEG

Examples Marlow Energy Harvesting Devices, many of which

were co-developed with Sandia National Lab

Prior to low threshold voltage electronics, low ΔT energy harvesting required:

• TEGs with hundreds of couples (V is proportional to # couples and ΔT)
• High thermal resistance (i.e. large TE element aspect ratios)
Today, with threshold voltages as low as 20 mV, low cost, traditional small TE
devices can be used
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Marlow High Temperature
TEG Strategy

▪ Enable a diverse array of thermoelectric

power generation applications and markets by
developing:
– Volume production capability of TE generator
devices that can operate to 500 C
– Volume production capability for a suite of mid
range TE materials
– Accurate thermal and mechanical modeling of
TEG modules and systems
– Test capabilities for materials, devices and
subsystems
– Quantified reliability
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Power Generation Materials

P Type Materials N Type Materials

Bi2Te3

▪ What power generation materials does Marlow use?

– “High Temp” Bi2Te3 (both crystalline and MAM formats)
– “PbTe” P and N, TAGS
– P and N Skutterudites
▪ Internal and University funded research on other new materials

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Managing the ZT Envelope
Material B
Material A Material C

• Functionally Graded ~ 1.0

Materials

ZT
– Elements made of single alloy
with graded composition
and/or doping Temperature

• Segmentation capability
– Elements made of 2+ alloys
joined with metal layers that
prevent interaction

• Cascading preferred
– Multistage module with
single P and N materials in
each stage

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“Traditional” high volume TE module assembly
processes used for TE Generator assembly

▪ Single & cascade TE devices

▪ Brazes used instead of solder
▪ Screen print braze paste w/ flux
▪ Wet paste 1-time reflow in CAB
Furnace Prototype 50 mm square PbTe Module
▪ “Segmented” top ceramic to reduce
thermal stresses (i.e. diced into
smaller ceramic pieces after
assembly)
▪ Simple tools, minimal capital
equipment Marlow CAB Furnace for Braze Assembly
▪ Common device assembly process for both PbTe and
Skutterudite materials (different barrier)
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Prototype TE Generators

2 stage Skutterudite/Bi2Te3 modules

50 mm square Skutterudite modules

2 stage PbTe/Bi2Te3 25 mm square PbTe

modules modules
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TE Device Test Development

▪ In-house TEG efficiency tester

– Vacuum or inert atmosphere
– 500 C capability
– Up to 40 mm cross sections
– Unique device calibration to quantify heat losses
– Material Seebeck and resistivity tests to 500 C
▪ Production test capabilities using Harman
technique module tester at elevated
temperatures
▪ Cycling and constant temperature aging test
stand in development
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Device Level Modeling
▪ Equations governing thermoelectric
device behavior (Ioffe, Goldsmid, No Heat Load

etc) were derived assuming 20

constant TE material properties 10

Experimental
ANSYS
Model Program
– For improved accuracy, these equations 0
HS=85°C
Numerical Refinement

are typically used with temperature -10

dependent properties

CS (C)
HS=50°C
-20
– For cooling, the equations lose accuracy -30
at large ΔT
-40

▪ These fundamental equations were -50

HS=25°C

re-derived without the underlying -60

1 1.2 1.4 1.6 1.8 2 2.2 2.4
assumption of constant material Current (A)

properties
– Provides more accurate modeling of TE
coolers and power generators with large d  dT  d dT I 2 
ΔTs  kA   IT + =0
– Validated with experiment and with full
dx  dx  dT dx A
3D thermoelectric simulations in ANSYS

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Thermoelectric System Modeling

Total Power (W)

9
1400-1600
7 1200-1400
1000-1200
# Seg
5 800-1000

▪ Model Validation
600-800
3 400-600
200-400
1
0-200 – System test on engine
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30

60

100

140

200

# Devices Per Segment

dyno for automotive
W/kg waste heat recovery
system
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16-18
14-16
– Output matches Marlow
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# Seg
12-14 system model
10-12
5
8-10 prediction
3 6-8
4-6

1 2-4
30

60
16

100

140

200

0-2
# Devices Per Segment
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DOE CRADA
Oak Ridge National Lab/Marlow

▪ Objective: “To evaluate materials and

devices for waste-heat recovery Task 1 Task 2
applications in automotive and heavy Evaluate Evaluate
Candidate Supporting
vehicle applications up to 500°C.“ TEMs Materials
▪ Project Goals:
– Thermoelectric and mechanical material
Task 3
properties for TE material TED FEA
– Thermal and mechanical material Modeling and
properties for any supporting material Verification
– Develop ANSYS models to evaluate TE
devices in automotive applications
– Develop life prediction models Task 4
– Experimental verification of models Final Reporting

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Power Generation
Benefits from Improved in Bi2Te3
▪ High ZT Inorganic Colloidal Nanocrystal
thermoelectric material Colloidally synthesized nanocrystals
in a host inorganic semiconductor
– Bulk material format addresses matrix
a wide range of heat flux
applications Electron
– Phonon blocking to reduce hopping
Low electrical resistance diffusion
lattice thermal conductivity barriers
– Quantum confinement
enhancement of the Seebeck Phonon
coefficient blocking
– Scalable, low cost material
fabrication process
• Device format and design that minimizes all
thermal and electrical losses
– High voltage, low current Compacted high ZT
operation enabled by Build- bulk TE material
in-Place TEC assembly
process
– Low electrical contact BIP TEC fabrication method
resistance on a bulk TE
material
High ZT material ➔ High ZT devices
Program: Active Cooling Module (ACM)
Program Mgr: Avi Bar-Cohen

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 THANK YOU!

Marlow Industries, Inc.

10451 Vista Park Road
Dallas, TX 75283

Jim Bierschenk
214-342-4281
jbierschenk@marlow.com

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