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Introduction To Thermoelectricity
Introduction To Thermoelectricity
I T
Perfectly Basic Relations , M
Reflecting Wall
e n o
at T
Frequency ν
C h
Angular Frequency ω=2πν l t
Inside the Cavity
EM Wave In Wavelength λ
g rm a
Equilibrium at
a
Wavevector n e
magnitude k=2π/λ
Temperature T k G /T ) ion
Wavevector h
k=(k ,k ,k x y z
t ©c = νλlar ωrs= ck = c k + k + k 2 2 2
e
x y z
λ 9λ7 λ 97 e ∑∑∑
L = 9,2 ,..., n
x x
9 x
E n n x =1 n y =1 n z =1
k =n o
x
F ct
x
2 L ri 0 x 0 y 0 z
e
x ∞ ∞ ∞
l
E polarization
Two
= 2 ∫
dk
−∞
∫
dk x
∫
dk
(2π / L ) (2π / L ) (2π / L )
x −∞
hωf (ω , T )
y
y −∞
z
u (ω ) = hωf (ω ,e n
T )D(ω ) o
2V
∞
( ) h l t
8π ∫ hω C 1
= ω ω π
a
2
3
h f , T 4 k dk 3
=
πg ⎛ hωm
Planck’s law
n exp⎜⎜ r ⎟⎟ − 1
0
c 2 3
⎞
=
2V
∫
∞
⎛ω ⎞ ⎛ω ⎞
hωf (ω , T )4π ⎜ ⎟ d ⎜ ⎟
2
G a h e
⎝k T ⎠ n
8π 3
0 ⎝c⎠ ⎝c⎠
© • r / T
Intensity:
s i
energyo
B
r ig t S dAnv cu(ω ) hω
y o
0
o re c C I (ω ) p
=
4π
=
4π c
3
1
⎛ hω ⎞
0
C D rg i y
3 2
exp⎜⎜
⎝ k T
⎟⎟ −1
⎠
∞
ω7
= ∫ u (ω )d9 9 7 ne Solid Angle Per unit wavelength interval B
0
.9
2 r 2 ca . 9 l E dA I (ω )dω 4πch
I (λ ) =
1
dΩ = =
p
F o
D(ω)-density tr
of states i per
R 2
dλ λ 5
⎛ 2πhc ⎞
⎜⎜ ⎟⎟ −1
e c whole space
exp
⎝ k Tλ ⎠
El interval
unit volume per unit B
angular frequency 4π Planck’s law
–WARREN M. ROHSENOW HEAT AND MASS TRANSFER LABORATORY, MIT
Thermal Radiaton: Planck’s Law
I T
Q& ,
Wien’s displacement law M
e n o
λ T = 2898 Kμmh
C l t
g rm a
max
a n e
10
4
G /Th o n
© r i
EMISSIVE POWER (W/cm μm)
Emissive Power
t ola er 10s 3
2
i h
g t S nv
Q& (λ ) = AπI (λ )
yr c o
hω3
1o p ire C 10
2 5600 K
=A
⎛C g y
⎟⎟ − 1 D
4π c
2 2
exp⎜⎜
hω ⎞
7 ⎝ k T 9⎠ 7 ne r 10
1
2800 K
. 9 9 B
. 9 E
2 r 2 ca
Total l 0
1500 K
Q& = ∫F
∞ o
Q& (λ )dλ = c
4
Aσ
r
tT i 10
800 K
0
E le 10
-1
0 2 4 6 8 10
WAVELENGTH (μm)
–WARREN M. ROHSENOW HEAT AND MASS TRANSFER LABORATORY, MIT
I T
, M
Introduction to Thermoelectricity e n o
C h l t
g rm a
Gang Chen
a n e
G /T ion h
t © lar Department
Mechanical Engineering
r s
g h
Massachusetts
i o
Institute
S v e
of Technology
yr ct o n
o p ire C
D r g y
CURL: http://web.mit.edu/nanoengineering
9 7 97 ne
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2 r 2 ca . 9 l E
o
F ct ri
E le
–WARREN M. ROHS ENOW HEAT AND MASS TRANSFER LABORATORY, MIT
ROHSENOW MIT
Seebeck Effect I T
Hot, M
e n o
C h l t
g rm a
a n 1 he
G /T ion Conductor 2
Conductor
t © lar rs
ig h S o v e
yr ct o n
o p re C
C D i rg y Cold
9 7 97 ne
.9
2 r 2 ca . 9 l E Voltage
ig h S o 1
v e
yr ct o n
o p r e C
C D i rg y A
9 7 97 ne
2
Jean.9
Charles .
2 ca9
Athanase l E
Peltier
1785-1845 r
o
F ctr i Peltier Effect: Discovered in 1834
An electrical current creates a cooling or
t © lar rs
igh S o v e
yr ct Thomson o neffect predicted, 1855
o p ire C
C g y
William 7Thomson7 D e r
9
(Lord
. 9Kelvin)
. 99 E n
2 r 2 ca
1824 – 1907 l
o
F ct ri
E lehttp://www.sil.si.edu/silpublications/dibner-library-lectures/scientific-discoveries/text-lecture.htm
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h
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G /T ion Electrical
• • •
• •
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•
•
• •
• •
•
• •
• •
t © lar rs •
Field [V/m]
ig h S o v e
r
Current Density Jye = enc v t= en μ εo=nσε = ε / ρ Electrical
o p i e
r gy C Resistivity [Ωm]
C D r
9 7
Electron
Charge [C]
9 7
Electron
Density [1/m
n] e Drift
3
Velocity [m/s]
Mobility Electrical
9
2. r 2. cal 9 E [m /s.V] 2
Conductivity [1/Ωm]
i q
Fo ctr J q = qnv = e J e = ΠJ e
Heat Flux
le
E Heat Per Charge [J] Peltier Coefficient [J/A]
–WARREN M. ROHSENOW HEAT AND MASS TRANSFER LABORATORY, MIT
Peltier Effect T
M I
J,J n ,
he to e q1
1
C a l
Q g
n er m Q
a
G2 /Th ion
t © lar J , Jrs
ig h S o v e e q2
yr c t on
o p e
Qir(Peltier) C (Π 1−Π2)J
C D rg y =
9 7 97 ne
.9 . 9 l E
2 r 2 ca and cooling at junctions
• Heating
o
F ct ri
• Reversible with current direction
E le
–WARREN M. ROHSENOW HEAT AND MASS TRANSFER LABORATORY, MIT
Seebeck Effect
I T
Built-In Potential , M
e n o
h l t
•• • • • • • • • • C • a
V cold••••
• ••
• • •• •• • • • • n g •
r m V
hot
T cold••• • • a
•
G /T ion
• • h•e • T
hot
t © lar rs
ig h o
Temp. Gradient
S v e
y r c t o n
o p ire C
C
• Charge diffusion
D under
r g y a temperature gradient
9•7
9 7
Built-in potential
n e resisting diffusion
9 9
2. r 2.S = c-ΔV/ΔT E
l = -(V -V )/(T -T )
o i a
F ctr
hot cold hot cold
le
E S --- Seebeck Coefficient
–WARREN M. ROHSENOW HEAT AND MASS TRANSFER LABORATORY, MIT
Thomson Effect
I T
, M
heat release/absorption q(x)
e n o
C h l t
• • • • • • •ng• m a
T ••• •• • • • • a •e r • T
cold ••••
• • • • • • • • G• • /T
• • • h
• • ion
•
hot
t © current
lar r s
ig h S o v e
yr ct o n
o p ire C
C D r g y τ=
1 dq dT
9 7 97 ne
Thomson Coefficient
I dx dx
.9
2 r 2 ca . 9 l E
o tr
F cRelations:i
• Kelvin Π = ST; τ = T dS/ dT
E le
–WARREN M. ROHSENOW HEAT AND MASS TRANSFER LABORATORY, MIT
Properties are Temperature Dependent
IT
, M
e n o
C h l t
g rm a
a n e
G /T ionh
Images removed due to copyright restrictions.
© lar rs
Please see Fig. 2a,b in Poudel, Bed, et al. "High-Thermoelectric
Performance of Nanostructured Bismuth Antimony Telluride Bulk Alloys."
ht e
Science 320 (May 2, 2008): 634-638.
o
r i g S n v
p y ct C o
o re
C D i rg y
9 7 9 7 n e
9 9
2. r 2. cal E
o
F ct ri
E le
–WARREN M. ROHS ENOW HEAT AND MASS TRANSFER LABORATORY, MIT
ROHSENOW MIT
Thermoelectric Devices
I T
, M COLD SIDE
COLD SIDE
en o
C h l t- +
g rm a
a n Ne
h
G /T ioPn
I
HOT SIDE
t © lar rs
ig h So v e HOT SIDE
yr ct o n
o p re C
C D i rg y
9 7 97 ne
.9
2 r 2 ca . 9 l E
o
F ct ri
E le
–WARREN M. ROHSENOW HEAT AND MASS TRANSFER LABORATORY, MIT
I T
, M
e n o
C h l t
g rm a
a n e
G /Th on
Performance of Thermoelectric
© r
t ola er si Devices
i h
g t S nv
r
y ec Co
o p
C Dir rgy
9 7 97 ne
.9
2 r 2 ca . 9 l E
o
F ct ri
E le
–WARREN M. ROHSENOW HEAT AND MASS TRANSFER LABORATORY, MIT
Other Basic Relations: Heat Conduction
I T
Th , M
• Fourier Law for heat conduction
en o
h l t
q =g−Ck∇Tma
a n er
/T h
G ] Thermal on
Heat Flux [W/m
t © lar rs
2
i
Conductivity [W/m.K]
L g h o v e
i t S on heat conduction
Area A •yrOne-dimensional
o p re c C
C Di rgy Th − Tc
9 7 97 Qne= Ak = KΔT
.9
2 r 2 ca. 9 l E L
o
F ct ri kA
Thermal Conductance : K =
Tc le L
E
–WARREN M. ROHSENOW HEAT AND MASS TRANSFER LABORATORY, MIT
Device Analysis: Cooling
I T
• Ideal Devices
, M
Tc
Q c
e n o
No Joule Heating,
C h l t
No Heat Conduction
g rm a
Qc = (Πa np-Πn)•Ιe
p n G /Th ion
• ©
t la r
Real Devices:
r s
ig h S o v e
yr c tJoule
o n
Heating & Heat Conduction
o p ire C −
Th QCh D
Q
r gc=y (Π p-Π n)•Ι I 2R/2 - K (T -T )
h c
E le p n
Refrigerator Performance
Tc Qc I T
V = IR + ( S − S )(TM −T )
Voltage Drop: p
,
n
n o
h c
Coefficient of Performance: h e t
C a l
Q C ( p an
S − S g
n) C
IT − Kr m
( H C) I R
T − T −
1 2
φ= = e
G(Sp −/STnh) I ( THi−oTnC ) + I2R
2
W
T Qh h
t © lar rs
ig h S o v e T
yr c t T o
1n+ ZT M −
T
H
Optimize Current:p φ =
T − TC
C C
o ire
max
( y ) 1 + ZT + 1
C D rg H C M
9 7 9 7 n e T = 0.5(T +
T )
M h c
9 9
2. r 2. ca(Slp − Sn )2 E
( n)
2
S − S
Zi =
p
o
F ct r KR
=
⎛ L p ρp L ρ ⎞⎛ k p A p k A ⎞
El e ⎜
⎜ Ap
+ n n ⎟⎜
A n ⎟⎜ L p
+ n n ⎟
L
n
⎟
⎝ ⎠⎝ ⎠
Figure of Merit Z
I T
⎛ L p ρp L ρ ⎞⎛ k p A p k A n⎞ , M
KR = ⎜ + n n ⎟⎜ + n en ⎟ o
⎜ Ap
⎝ A ⎟⎜
n ⎠⎝ L
C h
L ⎟
n ⎠ l
t
p
g rm a
a n e L n A p ⎛ ρp k n ⎞
1/ 2
( KR )min = ( k pρp + k n ρn ) Gwhen/Th n
2
=⎜ ⎟
© r s o
L piA n ⎜⎝ ρn k p ⎟
h t o la er
r ig S nv
( Sp − Sn )
p y 2
ct o
Zmax = o ir C
e 2 yFor a single material: Z = =
S2
σS 2
( Ck pρp + Dk n ρn ) rg ρk k
9 7 97 ne
. 9 .
2 In a device,
2 9 pn a l E
pairs are used:
o r ric
F Areascoft each type of legs need to be optimized
(1)
(2) Two
E le types of legs should have comparable properties
(3) Current input to the device needs to be optimized
–WARREN M. ROHS ENOW HEAT AND MASS TRANSFER LABORATORY, MIT
ROHSENOW MIT
Typical Number I T
, M
e n o
• Bi2Te3-based materials ~300 C Kh l t
g m a
S=220 μV/K a
Powern e
Factor: r
S σ=48 μW/cm-K
2
k=1.5 W/mK ©
t ola er r s i
ZT=1
i h
g t S nv
• Device Leg: p 1y
r
mm x 1cmm xC2omm
o i re y
C D −3 r g
9
R 7=
L
=9 7
2 × 10
n e
= 0.02 Ω
. 9 1
2 r 2 ca .
σA 9 10 ×l10E
5 − 6
o r i
t electrically in series
F but thermally
Legs
le care
in parallel
E Image by michbich at Wikipedia.
–WARREN M. ROHSENOW HEAT AND MASS TRANSFER LABORATORY, MIT
Two Tc
thermocouples
soldered into
drilled holes
An Example I T
, M One Th
thermocouple
e n o soldered into
drilled holes
C h l t
g rm a
120 a n e Copper blocks (Th)
Ceramics
plate for
Theoretical prediction
100
ht o e
r ig S n v
80
p y ct o
o re C
60 C D i rg y • Match two leg size
9 7 97 ne • Minimize contact
40
9 9
2. r 2. cal E resistance
20 o
F ct ri T = 100 °C
• Optimize current
0
E le h
0 2 4 6 8 10
–WARREN
Current (A) M. ROHSENOW HEAT AND MASS TRANSFER LABORATORY, MIT
Temperature Dependence of Properties
I T
, M
e n o
C h l t
g rm a
a n e
G /T ionh
Images removed due to copyright restrictions.
Please see Fig. 2a,b,d,e in Poudel, Bed, et al.
© lar rs
"High-Thermoelectric Performance of Nanostructured
t
i g h So v e
Bismuth Antimony Telluride Bulk Alloys." Science 320 (May 2, 2008): 634-638.
yr ct o n
o p re C
C D i rg y
9 7 9 7 n e
9 9
2. r 2. cal E
o
F ct ri
E le
–WARREN M. ROHSENOW HEAT AND MASS TRANSFER LABORATORY, MIT
Differential Analysis
I T
, M
e n o
h l t
d ⎛ dT ⎞ g C
O
dS dT a 2
⎜ k ⎟ −anJT er + J ρ = 0
m
dx 2 ⎝ dx G ⎠ /TdT h dxon
i
©
t ola er r s
i h
g t S nv
r
y ecEffect, Usually o
o p
Thomson
ir C Neglected Joule Heating
C Boundary
D r g y
9 7 9 7 n e
Conditions (Cooling):
9 9
2L . r 2. cx=0: l E dT dT
o i a T given or q c = − k + ΠJ = −k + STc J
F ct r c
dx dx
x El
e
–WARREN M. ROHSENOW HEAT AND MASS TRANSFER LABORATORY, MIT
Thermoelectric Power Generation
I T
0.66
0.
0.6
, M
Efficiency
e n o ZT
EFFICIENCY
C h l t
CARNOTCYCLE
10
m
⎛ T ⎞ 1 + ZT −1
g m a 7
η =
⎜⎜1 −
⎟⎟
c ave
⎝
T ⎠ 1 + ZT
+
T a n e r
h
ave
T
c 0.4
G /T ion h 4T
4 THERMAL
T +T
h
t © lar r s
POWER
PLANT
T
T
=
c h
ig h 0.3 o
S v e 2
2
ave
2
yr ct o n ALKALI METAL
THERMAL TO
DIESE
IESELPPLA
LANT
o p ire C ELECTR
RC
IC
ICCELLS
STIR
IRLIN
ING
G
GENERATOR
C D rg
Constant Properties
0.2
y TPV
THERMIO
IONIC
IC
1
AUTOMOTIV
IVE
.9
2 r 2 ca . 9 l E THERMOELECTRIC
IC
o
F ctr i 0
1 2
POWERGGENERATORS
3 4 5 6 7 8 9 110
0
Thermoelectric Refrigeration
I T
, M 6
Coefficient of Performance
e n oCYCLE
5
C h CARNOT
l t
COEFFICIENT OF PERFORMANCE
STIRLING
COP =
T c
1 + ZT − T / T
ave h c
g m a
REFRIGERATORS
T −T 1 + ZT + 1 a n e r HOUSEHOLD
h c ave
G4 /Th REFRIGERATORS
i o n &
t © la r r s AIR-CONDITIONERS
ig h So3
v e THERMOELECTRIC
y r ct o n REFRIGERATORS
o p ire y2 C ZT STIRLING
CRYOCOOLERS m
C D rg 24
7 10
9 7 9 7 n e 0.5
1
.9
2 r 2 ca l . 9 E 1
o
F ct r i 0
© lar rs
http://www.marlow.com/thermoelectric-modules/
t
i g h So v e
y r ct o n
o p re C
C D i rg y
9 7 9 7 n e
9
2Power . 9
. Generators
2 ca E
froml Hi-Z
o r ri
F ct
E le Coolers from Marlow Industries
t © lar rs
Please see: http://www.roadtrucker.com/12-volt-coolers-accessories/
12-volt-coolers-products/igloo-40-quart-kool-mate-40-12-volt-thermo-electric-cooler-6402.jpg
i g h So v e
http://image.made-in-china.com/2f0j00kvZEKWVPgtlu/Refrigerator-BC-65A-.jpg
http://www.newdavincis.com/images/wc-1682%2016%20bottles.jpg
yr t o n
http://www.rmtltd.ru/datasheets/TO812.4MD04116xx.pdf
c
o p re C
http://www.medsystechnology.com/images/gem4000_w32a.jpg
C D i rg y
http://amerigon.com/ccs_works.php
9 7 9 7 n e
9 9
2. r 2. cal E
o
F ct ri
E le
.
–WARREN M. ROHS ENOW HEAT AND MASS TRANSFER LABORATORY, MIT
ROHSENOW MIT
yr ct o n
http://globalte.com/pdf/teg_5120_spec.pdf
o p re C
http://www.roachman.com/thermic/thermic1.jpg
C Di r
http://www.research.philips.com/newscenter/pictures/downloads/misc-sustainability_05-0_h.jpg
9 7 9 7 n e
9 9
2. r 2. cal E
o
F ct ri
E le
–WARREN M. ROHS ENOW HEAT AND MASS TRANSFER LABORATORY, MIT
ROHSENOW MIT
System Consideration
I T
M
Object being cooled
Tobject
Ceramic
substrate
Tcold Electrical
N P N P interconnect
Tambient
T
C
9 7 DC Power source
.9
2 r 2.
+
_
E l e
Sometimes, thermal systems more expansive
–WARREN M. ROHS ENOW HEAT AND MASS TRANSFER LABORATORY, MIT
ROHSENOW MIT
C D r g y
7 97 ne
Coolant
9
.9 . 9 l
2• Forrthermoelectric
2 ca E
devices, TH higher is better
• F o trimaximum heat intercepted from hot
However,
e c
gas lstream, mcp(Th,i-TH), decreases with TH
E
–WARREN M. ROHSENOW HEAT AND MASS TRANSFER LABORATORY, MIT
Vehicle Systems
I T
Main AC: TE Local cooling of seats: TE
, M
In US, transportation uses
~26%n
e to of total energy.
Radiator: TE
C h l
g rm a
a n e
G /T ion h
Catalytic converter: TE
t © lar rs
igh S o v e
y r c t o
Mechanical n
losses
o p ir9kJe C
C D rgy 10kJ Driving
Gasoline9
7 97 ne
9
100 .kJ
2 r 2 ca . 9 l E 6kJ
Auxiliary
o
F ct
10kJ ri
30kJ 35kJ
E l e
Parasitic
heat losses Coolant –WARREN Exhaust
M. ROHSENOW HEAT AND MASS TRANSFER LABORATORY, MIT
Prototypes
I T
, M
en o
C h l t
g rm a
a n e
Images removed due to copyright restrictions. Please see
G /T ionh
http://cdn-www.greencar.com/images/waste-exhaust-heat-generates-electricity-cars-efficient.php/bmw-teg-1.jpg
© lar rs
http://cache.gawkerassets.com/assets/images/12/2009/03/BMW_TEG.jpg
t
ig h So v e
yr ct o n
o p re C
C D i rg y
9 7 9 7 n e http://cache.gawker.com/
9 9
2. r 2. cal E
o
F ct ri
E le
–WARREN M. ROHSENOW HEAT AND MASS TRANSFER LABORATORY, MIT
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