Important Definitions for Thermoelectricity

Seebeck Effect (1822)

" When two dissimilar conductors, A & B,
constitute a circuit, a current will flow as long
as the junctions of the two conductors are
at different temperatures."
A

T α= dE/dT T+∆T

A is positive to B if electrons flow from A to B

at the colder junction
Peltier Effect (1834)
" When an electric current flows across a junction of two
dissimilar conductors, heat is liberated or absorbed."

T -∆T P = dQ/dI T +∆T

1 2

B
If electrons flow from A to B at the hotter junction,
heat is liberated at the hot junction and absorbed at the
cold junction
Question- Can we tell which Junction will absorb or
release heat due to the Peltier effect?

A
G
T α= dE/dT Τ+∆Τ

B
The direction of the electron flow [which is opposite to
the current flow by convention] at the hot junction in a
Seebeck series is from the metal occuring later in the
series to the metal occuring earlier in the series.

Bi, Ni, Co, Pd, Pt, Cu, Mn, Hg, Pb, Sn, Au, Zn, Cd, Fe, Sb, Te.

For example, if A=Cu and B=Fe, then the electron flow is as

pictured.
------------------------------------------------------
For the Peltier effect(where Q is the heat
absorbed):
A

Τ −∆Τ PAB= dQ/dI Τ +∆Τ

1 2

The direction of the Seebeck electron flow is

opposite to the electrons flowing from the battery.
(Otherwise we would have an unstable situation).

P is positive if A is positive to B
AB
P = −P
AB BA
 Important Definitions for Thermoelectricity

Thompson Effect

" The change of heat content of a single conductor of unit

cross section when a quantity of electricity flows along it
through a temperature gradient of 1°K"

T1 T2 T1
T1 < T 2 Single
Conductor
P 0 P2
1

T1 -DT T2 T1 +DT

P 0 P2
1
Electrons

σ =(dQ/dI)• ( 1/dT)

Constant Temperature Bath

Electrons flowing against the thermal gradient

will absorb energy whereas electrons flowing
down the thermal gradient will lose energy
Thermoelectric Conversion

Seebeck found that the thermally induced emf, Eth, is

related to the thermoelectric power , ε , as follows;
__________________
 dE 
ε =  th 
 dT 
 
The Seebeck coefficient, αxy , for materials x, and y is;
dExy
αxy (T) = ( dT )

= εx(T)-εy(T)

Want to combine high Seebeck coeffient with low electrical

resistivity and low thermal conductivity.
=========================================
Note the relationship between Seebeck (α) , Peltier( P), and
Thompson (σ) effects.

dPab
α = dT + (σb -σa)

Operating principles of thermoelectric converter (3 Figures)

==========================================
The induced voltage is ( with no current);

V = αn,p ( TH-TL)

where αn,p =αn +αp

Adding a load, L

VL =αn,p (TH-TL) -(Rn +Rp)I

The p leg total internal resistance is ;

rplp
Rp = A
p
and similarly for the n leg.
==========================================
The total power output is ;

W L = RL I2

Using Kirchoff’s law to calculate the current;

α (T -T )
n,p H L
I = ----------------
(R + R +R )
L p n
We define the efficiency of the thermoelectric unit as

WL
ηTE = Q
in
The thermal power input, Qin, consists of three
components:

1.) Direct Heat Conduction Across the

Semiconductor Elements,
2.) Thermal energy required to compensate for
the Peltier cooling at the hot shoe,
3.) Minus the Joule heating in the load

Note that it is assumed that half the Joule heating occurs at

each junction.

Substituting ;
kpn Apn
κp,n = lpn

we find that

(Rp+Rn)I2
Qin =(κp+κn)(TH-TL) + αn,pITH− 2
Defining
RL
m = (R +R )
p n

Then
ηTE=ηth•ηmat
where;
(TH-TL)
ηth = T (Carnot)
H
and
  
 
 m 
ηmat =  
  (
ηth (m + 1) R p + Rn κ p + κ n
2
)( )  
 (m + 1) − + 
  2 α n2,p T H  
This term must be minimized, i.e.,
 
 
 
 
{(
d R + R κ + κ
)( )}

2
 p n p n =0
   ln   
   
  A
 n   
 d 
 lp  
   
   Ap   

When this is done,

m opt = 1 + Z T
Where

«««  TH + TL 
T =
 2 
and

(α )
2
n + αp
Z =
[ ]
2
κ nR n + κ pR p
at the optimum conditions

( ηTE )opt = ηth

(m opt − 1)
 TL 
 + m opt 
TH 

If the p and n type materials have the same thermal

conductivities and electrical resistivities, then the figure of
merit becomes;

Z= α 2
kρ
__________________________________________

Typical Figure of Merit Values @ 300°K

Material Seebeck Coeff. FOM(Z)

3x10 −6
Metals 5 µV/°K
°K
2x10 −3
Semicond. 200 µV/°K
°K
5x10 −17
Insulators 1000 µV/°K
°K