Chapter 4

Basic &
Thermodynamics of Fuel
Cells

Energy Technology Lab, ME, NCU 1

What’s Coming Up
 Basics of fuel cells
 Review of basic thermodynamic terms
 Er: the reversible cell potential and the effects of
temperature, pressure, and concentration.
 : the energy conversion efficiency
 r: the reversible (maximum) energy conversion
efficiency.
 The issue of r>100%. It is real or just a hype
 Fuel cell system efficiency

Energy Technology Lab, ME, NCU 2

Basic of Fuel Cells

Energy Technology Lab, ME, NCU 3

What is A Fuel Cell ?

 A fuel cell is an electrochemical device that converts the
chemical energy of the reactants (both fuel and oxidant)
directly into electrical energy.

 A fuel cell is an energy conversion device, just like

batteries and heat engines.

Energy Technology Lab, ME, NCU 4

Working Principle

Anode reaction:
2H2 4H+ + 4e-
Cathode reaction:
O2 + 4H+ + 4e- 2H2O
Overall reaction:
2H2 + O2 2H2O + Heat

More like a power generating device than a battery.

Energy Technology Lab, ME, NCU 5

PEFC Schematic and Single Cell

Structure

1. Electrodes
2. Porous backing
(Carbon paper or clothes)
3. Catalysts
4. Membrane

Energy Technology Lab, ME, NCU 6

Basic structure
 Electrodes - Anode / Cathode
 Provide a surface site where gases (fuel and oxygen)
ionization or de-ionization reaction can take place
 Conduct ions away from or into the 3-phase (gas-
electrode-electrolyte) interface
 Provide a physical barrier that separates the bulk gas
phase and the electrolyte
 Electrolyte
 Conducts ionic charge (but not electron) between two
electrodes
 Provides a physical barrier to prevent the fuel and oxidant
gas from directly mixing

Energy Technology Lab, ME, NCU 7

Basic structure
 Requirements for Electrodes:
 Highly active for electrochemical reactions
 Good electron collector and conductor
 Chemically stable in the reducing and oxidizing
environment
 Mechanically strong to resist deformation
 Requirements for Electrolyte:
 High ion diffusivity
 Good electron insulator
 Low gas permeability

Energy Technology Lab, ME, NCU 8

Cell Potential
 Ideally, the electric potential (difference) between the
cathode (+) and anode (-) of an electrochemical cell is
determined by
 the reactions occur on both electrodes

 the operating temperature.

 In practice,
 Cell potential is also limited by the polarization

(potential loss) due to internal non-ideal

performances.
 Cell potential typically decreases as more current is

drawn from the cell (i.e., more power is output from

the cell).
Energy Technology Lab, ME, NCU 9

History of Fuel Cells

 A device discovered in 1839

 A device served in space mission since 1960s
 A device closely examined during energy crises
 A device running buses in Vancouver, Canada
 A device under heavy R/D
 A device currently too expensive
 A device …

Energy Technology Lab, ME, NCU 10

Types of Fuel Cells
 Difference in electrodes, electrolytes and
electrochemical reactions.
 Difference in operating temperature* (High,
Intermediate, low).
 Difference in fuels (PEFC and DMFC).

Energy Technology Lab, ME, NCU 11

Glossary

 SOFC – solid oxide fuel cell

 MCFC – molten carbonate fuel cell
 PAFC – phosphoric acid fuel cell
 AFC – alkali fuel cell
 PEFC – polymer electrolyte fuel cell
 PEMFC – proton-exchange-membrane fuel cell
 SPEFC – solid polymer electrolyte fuel cell
 DMFC – direct methanol fuel cell
* PEFC=PEMFC=SPEFC

Energy Technology Lab, ME, NCU 12

Comparison of Low-T and High-T FC

Low Temperature High Temperature

Start up Fast Slow

Working pattern Allow frequent on-off Continuous operation

Materials High-T tolerance &

thermal expansion
compatibility
Fuel impurity Low High
tolerance
Internal reforming Impossible Possible

Waste heat Low quality High quality

Energy Technology Lab, ME, NCU 13

Types of H2/O2 Fuel Cells

PEFC AFC PAFC MCFC SOFC

Operation 60-80oC 60-90oC 200oC 650oC 800oC

temperature
Electrolyte IEM KOH H3PO4 carbonate YSZ

Conducting ion H+ OH H+ CO32 O2

Catalyst Pt Pt Pt Ni Perovskite

Main material Graphite Metal Graphite Steel Ceramic

Efficiency 50-60% 50-60% 55% 60-65% 55-65%

Energy Technology Lab, ME, NCU 14

A PEFC System

Energy Technology Lab, ME, NCU 15

Review of Basic Terms

Energy Technology Lab, ME, NCU 16

Standard reference state
 Recall the standard reference state is defined as

Tref  25C (298.15K ) 

 STP
Pref  1 atm (101,325Pa ) 

Energy Technology Lab, ME, NCU 17

Enthalpy of Reaction
 Enthalpy of Reaction
 The amount of heat released (or absorbed) during an
isobaric chemical reaction in a closed system when the final
temperature returns to the initial value.

work

Q
T1, P1 T1, P1
Reaction
ni,1 ni,2

Initial Final
Energy Technology Lab, ME, NCU 18
Enthalpy of Reaction
 For a constant pressure process (isobaric):

Q H final  H initial   H R
enthalpy of reaction

 If HR<0, heat released, the reaction is called exothermic.

 If HR>0, heat absorbed, the reaction is called endothermic.

Energy Technology Lab, ME, NCU 19

Enthalpy of combustion
 Enthalpy of combustion
 The amount of heat released when a fuel (usually H/C)
reacts completely with oxidant (usually oxygen) to form
stable products (usually H2O & CO2)
 a special case of the enthalpy of reaction.

Energy Technology Lab, ME, NCU 20

Heating value
 Heating value: absolute value of the enthalpy of
combustion. It depends on:
 initial state of the fuel and oxidant
 final state of the products (liquid or gas H2O)
 condition of combustion processes (e.g., constant pressure
or constant volume)

Energy Technology Lab, ME, NCU 21

Heating value
 Higher Heating value ≡ HHV
 Lower Heating value ≡ LHV
 HHV－LHV ≡ Enthalpy of vaporization (or condensation)
for the product H2O
 e.g., for methane
 HHV=55,528 kJ/kg
 LHV =50,016 kJ/kg HHV  1.1 LHV

Energy Technology Lab, ME, NCU 22

Enthalpy of Formation
 When a compound is formed from its elements ( e.g.
Methane, CH4, from C and H2), heat transfer occurs.

Energy Technology Lab, ME, NCU 23

Enthalpy of Formation
 Consider the following

C Reaction Chamber Methane

CH4
2H2
Reactants Products
Qnet
TR = 298 K TP = 298 K
PR = 1 atm PP = 1 atm

C  2 H2  CH4
Energy Technology Lab, ME, NCU 24
Enthalpy of Formation
 The conservation of energy for a steady-flow process is

Ein  Eout C  2 H 2  CH 4
Qnet  H Reactants  H Products
Qnet  H Products  H Reactants

Qnet  
Products
N e he  
Reactants
N i hi

Qnet  1hCH 4  (1hC  2hH 2 )

Energy Technology Lab, ME, NCU 25

Enthalpy of Formation
 We need to establish a common reference state for the
enthalpies of reacting components.
 The enthalpy of the elements or their stable compounds is
defined to be ZERO at 25oC (298 K) and 1 atm.

Qnet  1hCH 4  1(0)  2(0) 

 hCH 4

C  2 H 2  CH 4

Energy Technology Lab, ME, NCU 26

Enthalpy of Formation
 This heat transfer is called the enthalpy of formation
for methane, hf . The superscript (o) implies the 1 atm
o

pressure value.
 During the formation of methane from the elements at
298 K, 0.1 MPa, heat is given off (an exothermic reaction)
such that
kJ
Qnet  h fo CH  74,850
4 kmolCH4

Energy Technology Lab, ME, NCU 27

Enthalpy of Formation
 The enthalpy of formation of the elements in their stable
form is taken as zero.
 The enthalpy of formation of the elements found naturally
as diatomic elements, such as nitrogen, oxygen, and
hydrogen, is defined to be zero.

Energy Technology Lab, ME, NCU 28

Enthalpy of Formation


Energy Technology Lab, ME, NCU 29

Enthalpy of Formation


Energy Technology Lab, ME, NCU 30

Enthalpy at other T and P
 Absolute enthalpy of a substance hi(T, P):
= standard Enthalpy of formation + enthalpy change

 For ideal gases :

 hi (T , P )  h 0f ,i (Tref )   hs ,i (T , P )   h L ,i ( T , P )
T
 hs ,i (T , P )   hs ,i (T )   CP dT ; hi (T , P )  hi (T )
Tref

Energy Technology Lab, ME, NCU 31

Reversible cell potential

Energy Technology Lab, ME, NCU 32

Open-circuit voltage
(or Reversible cell potential) Er :
_
+
Er

W Control volume

Exhaust
Q
(Reaction Products)

Anode Electrolyte Cathod

Fuel Oxidant
(Say H2 ) (usually O2 or Air)
Thermal bath @ T

Energy Technology Lab, ME, NCU 33

Open-circuit voltage
 Assume steady-state, steady-flow process and neglect
kinetic and potential changes, the first law states

 system   enthalpy   enthalpy   heat   work 
 energy       out    in    out 
   in       

  Nh    Nh
      Nh
    Q  W
dEc.v .  
dt  Fuel OX  in  EX  out

(1)
where N the mole flow rate (moles/sec)
h - enthalpy per mole

Energy Technology Lab, ME, NCU 34

Open-circuit voltage
 Eq. (1) can be put into the form,

N Fuel  hin  hout   Q  W  0 (2)

where
N OX N EX
hin  hFuel  hOX ; hout  hEX

N Fuel 
N Fuel (3)

Energy Technology Lab, ME, NCU 35

Open-circuit voltage
 The 2nd Law
0
 system 
 entropy    entropy    entropy    entropy associted    entropy 
         
 change   in   out   with heat transfer   generation 
 

S gen   Ns     Ns    Ns   
    Q
 EX  out
(4)
 Fuel OX  in T

Energy Technology Lab, ME, NCU 36

Open-circuit voltage
 The 2nd Law dictates that
Sgen  0 (5)

(4)  Q   TS gen  N Fuel ( sin  sout )T (6)

N OX N EX
where sin  [ s fuel  sOX ]i n ; sout  sEX

N Fuel 
N Fuel
 Or, on a unit mole basis,
( sgen  S gen N Fuel )
Q
 q  T ( sout  sin )  Ts gen (7)
N Fuel
Energy Technology Lab, ME, NCU 37

Open-circuit voltage
 Substituting (6) into (2) gives
W  N Fuel ( hin  hout )  N Fuel T ( sin  sout )  TS gen

 On a unit mole basis: ( w  W N )
Fuel

w  hin  hout  T ( sin  sout )  Tsgen

 h  T s  Tsgen
 [h  Ts ]out  [h  Ts ]in  Tsgen

Energy Technology Lab, ME, NCU 38

Open-circuit voltage
 Note : h-Ts = g － Gibbs free energy/mole of fuel

w  g  Tsgen (8a)

 Since T >0 & sgen >0 (2nd Law)

 w  g
 For reversible process
w  g  wmax
(8b)

Energy Technology Lab, ME, NCU 39

Open-circuit voltage
 It is conventional in fuel cell analysis that (8b) be
expressed in terms of per mole of fuel consumed, i.e.,

w  g
Gibbs free energy change /mole of fuel

Work done /mole of fuel

Energy Technology Lab, ME, NCU 40

Open-circuit voltage
 For the cell system shown earlier:

w  E n N0 e
where
 e - Electronic charge =1.602×10
-19 coulomb/electron

 N0 - Avagadro's no =6.023x10
23 electrons/mole of

electron
 n - No of moles of electrons transferred /mole of fuel

 E - Electromotive force or cell potential

(voltage=J/coulomb)

Energy Technology Lab, ME, NCU 41

Open-circuit voltage
 Note:

 electrons  19 coulomb 

No e   6.023 1023  1.602  10 
 mole of electrons   electrons 
coulomb
 96,487
mole of electrons
F  Faraday constant 

Energy Technology Lab, ME, NCU 42

Open-circuit voltage
g
 Er   (9)
nF
which is the reversible cell potential.

 Note : g  h  T s is a function of the system T and P,

as well as the amount of reactant supplied (NOX/NFuel).

Energy Technology Lab, ME, NCU 43

Open-circuit voltage
 If the electrochemical reaction occurs at the standard
pressure and temperature (1 atm and 25 ºC), the
resulting cell potential is usually called standard reversible
cell potential, denoted Ero

g 0
E 
0
r (10)
nF

Energy Technology Lab, ME, NCU 44

Example
 For example H2 and O2 are used as reactants to form H2O
and electric output. i.e., the cell reaction is
1
H 2  O2  H 2O (l )
2

 Here, H2 — Fuel, O2 — oxidant

1
N OX / N Fuel  , N EX / N Fuel  1
2

Energy Technology Lab, ME, NCU 45

Example
N OX N EX
hin  hFuel  hOX ; hout  hEX
 Then 
N Fuel 
N Fuel
 g   h  T  s  ( hou t  hin )  T ( sout  sin )
1
(3)  hin  hH 2  hO2 , hout  hH 2O ( l )
2
1
(7 )  sin  s H 2  sO2 , sout  s H 2O ( l )
2
 Going to Tables for the enthalpy and entropy values, e.g.,
Table A-26 of Cengel and Boles (2002) gives at 25℃and 1
atm

Energy Technology Lab, ME, NCU 46

Example

hHo 2  0 J/mole, sHo 2  130.68 J/mole K



hOo2  0 J/mole, sOo 2  205.04 J/mole K

hHo 2O  285,830, sHo 2O  69.92 J/mole K
1 0
h  hout  hin  h
0
 (h  hO2 )
0
H 2O ( l )
0
H2
2
 285,830 J/mole of fuel

Energy Technology Lab, ME, NCU 47

Example
1

so  sout  sin  sHo 2O ( l )  ( sHo 2  sOo 2 )
2
1
 69.92  (130.68   205.04)
2
 163.28 J/mole of fuel  K
g o  ho  T so  285,830  (273  25)(163.28)
 237,173 J/mole of fuel

Energy Technology Lab, ME, NCU 48

Example
Hence, from (10) ＆ n=2 moles of electron
transferred/mole of H2
g o
 Er  
o

nF
237,173 J/mole fuel

2 mole electrons/mole fuel  96, 487 coulombs/mole electron
 1.229 (volt)(=J/coulomb)

 Note: in the above calculations, we have assumed the

reaction product H2O is in liquid form. For

H 2  O2  H 2O ( g ), Ero  1.185 Volt

Energy Technology Lab, ME, NCU 49

Standard reversible cell potential

 Similarly, the standard reversible cell potential Ero can be

calculated for any other electrochemical reactions.
 Some of the fuel cell reactions and Ero are given in Tables.

Energy Technology Lab, ME, NCU 50

Standard reversible cell potential
 Standard heats of reaction and corresponding theoretical standard
reversible potentials and theoretical free-energy efficiencies (Go/Ho)

Fuel Reaction n -Ho -Go Eorev %

(kJ/mol) (kJ/mol) (V)

Hydrogen 2 286.0 237.3 1.229 82.97

H 2  0.5O2  H 2O(l )
H 2  Cl2  2 HCl( aq ) 2 335.5 262.5 1.359 78.33

H 2  Br2  2 HBr( aq ) 2 242.0 205.7 1.066 85.01

Methane CH 4  2O2  CO2  2 H 2O(l ) 8 890.8 818.4 1.060 91.87

Propane C3 H 8  5O2  3CO2  4 H 2O(l ) 20 2221.1 2109.3 1.093 94.96

Energy Technology Lab, ME, NCU 51

Standard reversible cell potential

Fuel Reaction n -Ho -Go Eorev %
 (kJ/mol) (kJ/mol) (V)

Carbon CO  0.5O2  CO2 2 283.1 257.2 1.066 90.86

monoxide
Carbon 2 110.6 137.3 0.712 124.2
C  0.5O2  CO
4 393.7 394.6 1.020 100.2
C  O2  CO2
Methanol 6 726.6 702.5 1.214 96.68
CH 3OH  1.5O2  CO2  2 H 2O(l )
Ammonia NH 3  0.75O2  1.5H 2O(l )  0.5 N 2 3 382.8 338.2 1.170 88.36

Hydrazine 4 622.4 602.4 1.560 96.77

N 2 H 4  O2  N 2  2 H 2O(l )

Energy Technology Lab, ME, NCU 52

General reaction
 Note: for a general electrochemical reaction
N N

  M i i    M i i



i 1



i 1
Reactants Products

e.q. : H 2  12 O2  H 2O
M1  H 2 , M 2  O2 , M 3  H 2O
 H   Fuel
2
 1
 O  12 ,  H O  0
2 2

 H  0,  O  0,  H O  1

2 2 2

Energy Technology Lab, ME, NCU 53

General reaction
1 N

 (3)  hin  hR 
 Fuel

  h
i 1
i Mi

1 N
hout  hp 
 Fuel

  h
i 1
i Mi

1 N
 (7)  sin  s R 
 Fuel

  s
i 1
i Mi

1 N
sout  sp 
 Fuel

  s
i 1
i Mi

Energy Technology Lab, ME, NCU 54

General reaction
g
 (9)  Er   ; where  g   h  T  s
nF
 1 N


  h  h P - h R 
 F
 (     ) h
i 1
i i Mi


s  s  s  1
N

 P R
 F
 (     ) s
i 1
i Mi

1 N
 g  gP  gR 
 F
 (     ) g
i 1
i Mi

Energy Technology Lab, ME, NCU 55

Effects of temperature on
reversible cell potential

Energy Technology Lab, ME, NCU 56

Effects of temperature on
reversible cell potential
g
  Er   (note: both Er & g depend on T & P)
nF
 E  1  g 
  r   
 T  P nF  T  p
 Recall in thermodynamics:
 By definition, g = h–Ts and h = u + Pv

dg  dh  Tds  sdT


dh  du  Pdv  vdP

Energy Technology Lab, ME, NCU 57

Effects of temperature on
reversible cell potential

  dg  du  Pdv  vdP  Tds  sdT

Tds  du  Pdv g  g ( P, T )
 g   g 
 dg  vdP  sdT dg    dP    dT
 P T  T  P

g g 
( )T  v  ( )T  v 
P P 

g g
 ( )P  s  ( ) P  s 
T T 
Energy Technology Lab, ME, NCU 58
Effects of temperature on
reversible cell potential
 E  1  g  s

  r     (11)
 T  P nF  T  P nF

1
 So if s < 0, (like H 2  O 2  H 2O shown in the
2
previous example), Er will decrease with increasing cell
operation temperature;
 If s > 0, then Er will increase with T, e.g.,
1
C(s) O 2CO

2
Energy Technology Lab, ME, NCU 59

Effects of temperature on
reversible cell potential

 If s = 0, then Er will be independent of T. e.g.,

CH 4  2O2  CO2  2 H 2O
 Assume s = constant (a good approximation for many
electrochemical reactions, provided T-To is not too large),
then integrate (11) w.r.t. temperature while keeping
pressure constant to give,
T  s T 
To r To  nF
dE  dT

Energy Technology Lab, ME, NCU 60
Effects of temperature on
reversible cell potential
 s 
 Er T , P   Er To , P      dT 
T

To nF 


 To , P 

 s 
 Er T , P   Er  To , P    T  To 


 nF To ,P 
(12)

Energy Technology Lab, ME, NCU 61

Effects of temperature on
reversible cell potential

 For the reaction

J
H 2  12 O2  H 2O( l ) , s  163.25
moleK
 Hence at T=80 °C, the reversible cell potential Er is (p =1
atm),
163.25  
Er  1.229(volt)  (80 C  25 C)  1.182( V )
296,487
 A reduction of 3.7 %.

Energy Technology Lab, ME, NCU 62

Effects of temperature on
reversible cell potential

 The slope is (@ 25°C & 1 atm)

 s  163.25 mV
      0.846
 nF To ,P  296,487 C

 Note: Eq. (12) is an approximation only.

 Strictly, the reversible cell potential should be calculated
from Eq. (9), i.e., Er  g / nF . Such calculation has
been done, and the result can be found in Fig. 1.

Energy Technology Lab, ME, NCU 63

Effects of temperature on
reversible cell potential

Energy Technology Lab, ME, NCU 64

Effects of temperature on
reversible cell potential
Combustion Reaction 298K 600K 1000K

  
Erev % Erev % Erev %
(V ) (V ) (V )
1.03 100 1.03 100 1.03 100
C  O2  CO2
0.74 124 0.86 148 1.02 178
2C  O2  2CO

2CO  O2  2CO2 1.34 91 1.18 81 1.01 69

CH 4  2O2  CO2  2 H 2O( g ) 1.04 100 1.04 100 1.04 100

2 H 2  O2  2 H 2O( g ) 1.18 94 1.11 88 1.00 78

Energy Technology Lab, ME, NCU 65

Effects of temperature on
reversible cell potential

 For most fuel cell systems, s is negative, hence the

reversible cell potential Er will drops with a temperature
increase. However, for fuel cell reaction
C( s )  12 O2( g )  CO( g )
The entropy change at STP is s°=89 [J/mole-K] > 0. So,
Er for this fuel cell reaction will increase with temperature.
 Figure. 2 gives Er as a function of T for many fuel cell
reaction.

Energy Technology Lab, ME, NCU 66

Effects of temperature on
reversible cell potential

Energy Technology Lab, ME, NCU 67

Effects of temperature on
reversible cell potential

 If NP and NR represent the number of moles of products

and reactants which are in gaseous state, and N =NP -NR
represents the change in the number of moles of gas
species during the reaction, then as a rough rule of thumb,
 1. S > 0 for N >0 (due to increasing disorder), and Er
increases with T;
 2. S < 0 for N <0, due to increasing order, Er decreases
with T.
 3. S  0 for N =0, and Er is almost independent of T.

Energy Technology Lab, ME, NCU 68

Effects of pressure on
reversible cell potential

Energy Technology Lab, ME, NCU 69

Effects of pressure on reversible

cell potential
g
  Er  
nF
 E  1  g   g 
  r       v
 P T nF  P T  P T

 Here v-volume change of the gaseous species in the

reaction / mole of fuel

Energy Technology Lab, ME, NCU 70

Effects of pressure on reversible
cell potential

 Assume all the reactant and product gases can be treated

as ideal gases

N P RT N R RT NRT
v  v P  v R   
P P P
 Er  1  g  v NRT 1
       
 P T nF  P T nF nF P


Energy Technology Lab, ME, NCU 71

Effects of pressure on Er

 Now integrate from Po to P while keeping T fixed,

NRT  P 
Er T , P   E 
0
r ln   
nF  P0 
where N is the number of mole change of gaseous
species in the reaction per mole of fuel

Energy Technology Lab, ME, NCU 72

Effects of pressure on Er

 For example, H2(g) +½O2(g) → H2O()

 N = 0 – (1+½) = -1.5 mole/mole fuel

mole J
( 1.5)  8.314  298 K
 NRT mole fuel mole  K
 
nF mole electron coloumb
2  96, 487
mole fuel mole electron
 19.3 mV

 The variation of Er vs. P is shown in Fig. 3

Energy Technology Lab, ME, NCU 73

Effects of pressure on Er

Energy Technology Lab, ME, NCU 74

Effect of concentration on
reversible cell potential

Energy Technology Lab, ME, NCU 75

Effects of concentration on Er

 All the results obtained so far are strictly valid for pure
fuel and pure oxidant as reactants for the fuel cell
reaction.
 In reality, both fuel and oxidant streams are diluted by
many other species for a variety of reasons.
 H2 as fuel is often humidified with water vapor.
 If H2 is obtained from hydrocarbon fuel by reforming
process, then the fuel stream is a mixture of H2 , CO2, H2O(g),
CO, … .

Energy Technology Lab, ME, NCU 76

Effects of concentration on Er

 Oxygen (air) is also required to contain sufficient amount

of water vapor before entering the solid polymer fuel cell.
 Clearly the fuel cell performance will be affected by the
concentration of fuel and oxidant in the anode and
cathode streams, such as the reversible cell potential Er.

Energy Technology Lab, ME, NCU 77

Effects of concentration on Er

 Assume the fuel, oxidant and exhaust stream are

respectively a mixture of ideal gases.
 Refer back to the schematic fuel cell system shown
previously, the 1st and 2nd law analysis leading to Eqs.
(9) &(10) are still valid since all other species do NOT
participate in the fuel cell reaction (energy conversion).

Energy Technology Lab, ME, NCU 78

Open-circuit voltage
(or Reversible cell potential) Er :
_
+
Er

W Control volume

Exhaust
Q
(Reaction Products)

Electrolyte
Anode Cathod

Fuel Oxidant
(Say H2 ) (usually O2 or Air)
Thermal bath @ T

Energy Technology Lab, ME, NCU 79

Effects of concentration on Er
g

 Er   (9)
nF
g 0
Er0   (10)
nF

Energy Technology Lab, ME, NCU 80

Effects of concentration on Er

 However, the fuel energy change, g in Eq.(9), should be

evaluated at the mixture temperature and the partial
pressure of the fuel, oxidant and exhaust (reaction
products) for the fuel, oxidant and exhaust stream,
respectively.
 Let Pi be the partial pressure of a component in an ideal
gas mixture, then the Gibbs free energy of the component
is gi (T, Pi) where T is the mixture temperature.

Energy Technology Lab, ME, NCU 81

Effects of concentration on Er

 gi T , Pi   hi T   Tsi T , Pi  (15)

for ideal gas, h is a function of T only

 The Gibbs equation:
dh v
ds   dP
T T
 But for ideal gases
v R

T P

Energy Technology Lab, ME, NCU 82

Effects of concentration on Er

 So, for component i :

dhi R
dsi   dPi
T Pi
 Integration at constant T and from Pi to P for the pressure
gives

si (T , P)  si (T , Pi )   R(ln P  ln Pi )
Pi
 si (T , Pi )  si (T , P)  R ln (16)
P

Energy Technology Lab, ME, NCU 83

Effects of concentration on Er


 gi T , Pi   hi T   Tsi T , Pi 
Pi
 gi (T , Pi )  hi (T )  Tsi (T , P )  RT ln
P
Pi
gi (T , Pi )  gi (T , P )  RT ln (17)
P
mixture total pressure

partial pressure of component i

Energy Technology Lab, ME, NCU 84

Effects of concentration on Er

 For a general electrochemical reaction:

N N

  M
i 1
i i   i M i
i 1

1 N
g (T , Pi ) 
 F
 (     ) g (T , P )
i 1
i i i i

1 N 1 N  Pi 
   ( 
 F i 1 i i i
   ) g (T , P )    (
 i
 F 
i 1 
   
i ) RT ln
P 
 

Energy Technology Lab, ME, NCU 85

Effects of concentration on Er
1 N 1 N  Pi 
    ( 
 F i 1 i i i
   ) g (T , P )    (
 i
 F 
i 1 
   
i ) RT ln
P 
 

 g (T , P )  N Pi  i  i 
 RT ln  ( ) 
 i 1 P 
 
 KP
RT
 g (T , Pi )  g (T , P )  ln K P (18)
 F
Pi
 X i (19)
P
Energy Technology Lab, ME, NCU 86
Effects of concentration on Er
g
 Now substituting (18) into (9) yields Er  
nF
RT
Er (T , Pi )  Er (T , P )  ln K P (20)
 F nF
 This is the general form of the Nernst Equation.

Energy Technology Lab, ME, NCU 87

Effects of concentration on Er

 Example: for the reaction H2(g) +½O2(g) → H2O()

 If the molar fraction of H2 in the fuel stream is 0.5, the molar
fraction of O2 in the oxidant stream is 0.21 (air), and the fuel
cell operates at 25 °C and 1 atm, calculate the reversible cell
potential.

Energy Technology Lab, ME, NCU 88

Effects of concentration on Er

 Solution: ∵ fuel cell operates at the STP ( To =25°C

& Po = 1 atm)
RTo
(20)  Er (To , Pi )  Er (To , P )  ln K P
 F nF
 From the example given before
 Er (T0 , P0 )  Er0  1.229 V
 For an ideal gas, Pi /P = Xi , the molar fraction

Energy Technology Lab, ME, NCU 89

Effects of concentration on Er
 K P  X H12 X O21/ 2
 (Note: the product H2O is in the liquid state, hence is NOT
included in the calculation.)

J
8.314  298 K  ln 0.5 1  0.210.5 
Er (T0 , Pi )  1.229 V  moleK
mole electron coloumb
1 mole fuel  2  96,487
mole fuel mole electron
 1.229 V  0.0189 V
 1.210 V
Clearly the reversible cell potential decreases as the reactant
concentration is lowered.
Energy Technology Lab, ME, NCU 90
Energy Conversion
Efficiency

Energy Technology Lab, ME, NCU 91

Energy Conversion Efficiency

 Usually,
useful energy output
 
energy available for conversion

Energy Technology Lab, ME, NCU 92

Energy Conversion Efficiency

 It is well known that 100 % efficiency is possible by the

first law, but is not possible by the second law for many
energy conversion systems that produce power output by
means of thermal energy, such as steam and gas turbines,
internal combustion engines, etc.
 These thermal energy conversion systems are often
referred to as heat engines.

Energy Technology Lab, ME, NCU 93

Energy Conversion Efficiency

 Here we will focus on the energy conversion efficiency of

power generation systems, especially fuel cells.
 For the fuel cell system shown in Fig. 1, on a per unit
mole of fuel basis, the first law requires

hin  hout  q  w  0 

N OX N EX
where hin  hFuel  hOX ; hout  hEX 

N Fuel 
N Fuel

Energy Technology Lab, ME, NCU 94

Open-circuit voltage
(or Reversible cell potential) Er :
_
+
Er
 Control volume
W

Exhaust
Q
(Reaction Products)

Anode Electrolyte Cathod

Fuel Oxidant
(Say H2 ) (usually O2 or Air)
Thermal bath @ T

Energy Technology Lab, ME, NCU 95

Energy Conversion Efficiency

 It indicates that the enthalpy change (–h) provides the

energy available for conversion (h= hout - hin ).
 On the other hand, the second law (6) requires

q  T s  Ts gen 
and the energy output as work (8a) is

w  g  Ts gen 

Energy Technology Lab, ME, NCU 96

Energy Conversion Efficiency

 So the energy conversion efficiency is

w g  Tsgen
  (25)
h h
 Note that both h and g are negative for power
generation systems including fuel cells as is clear from the
tables shown previously in the chapter.
 sgen is the entropy production per unit mole of fuel and by
the second law

Energy Technology Lab, ME, NCU 97

Energy Conversion Efficiency

s gen  0
where the equality holds for all reversible processes and
“>” holds for any irreversible process.
 Therefore, the maximum possible efficiency allowed by
the second law is,

g
 r T , P   (26)
h

Energy Technology Lab, ME, NCU 98

Energy Conversion Efficiency

 In the above derivation of Eq. (26), no assumption

specifically related to fuel cells had been made.
 The only assumption made was that the energy
conversion system for power production is reversible for
all the processes involved.
 Thus Eq. (26) is valid for any power production systems,
be it electrochemical converter like fuel cells or thermal
energy converter like heat engines, as long as the process
is reversible.

Energy Technology Lab, ME, NCU 99

Energy Conversion Efficiency

 We will demonstrate below that the maximum possible

efficiency for heat engines – the well-known Carnot
efficiency – is really the second law efficiency, and thus
equivalent to Eq. (26).
 Consider a heat engine operating between two
temperature thermal energy reservoirs (TER), one at high
temperature TH and the other at low temperature TL.

Energy Technology Lab, ME, NCU 100

2T heat engine model

 TH TER

qH
c.v.

2T W
Heat Engine

qL

TL TER
Energy Technology Lab, ME, NCU 101

Energy Conversion Efficiency

 First law: w  qH  q L
qL qH TL

s
Second law: gen    qL  qH  TL sgen
TL TH TH
w qH  qL T T
   1  L  L sgen (27)
qH qH TH qH
 The maximum efficiency is achieved if the process is
reversible (sgen = 0), i.e.,
TL
  1 (28)
TH
Energy Technology Lab, ME, NCU 102
Energy Conversion Efficiency

 This is the familiar Carnot efficiency of all 2T heat engines.

Since TL < TH, the maximum efficiency is always less than
100 % for heat engines.
 Now suppose the high temperature TER is maintained at
TH by the combustion of fuel with oxidant originally at the
temperature TL,

Energy Technology Lab, ME, NCU 103

Combustion model


Fuel + Oxidant Products
at P and TL at P and TL
with hR and sR TH TER with hP and sP

qH

Assumption: combustion is carried out in a

controlled manner such that the
products leave at P and TL.

Energy Technology Lab, ME, NCU 104

Energy Conversion Efficiency

 First law: qH  hR  hP  h TL , P 

 Second law:
qH
sR  sP   sgen , TER  0
TH
 TH  qH  sR  sP  sgen , TER  (29)

Or,
h TL , P  h TL , P 


TH  
s TL , P   s gen , TER s TL , P   s gen , TER

Energy Technology Lab, ME, NCU 105

Energy Conversion Efficiency

 Substitution of (29) into (27) gives

TL TL
  1  sgen (27)
TH qH
TL  s  sgen , TER  TL
 1  s gen
h  h
T s  TL , P  TL
 1 L 
h  TL , P  h
 s gen  s gen , TER 

Energy Technology Lab, ME, NCU 106

Energy Conversion Efficiency
h TL , P   TL s TL , P  TL

h TL , P 

h
 sgen  sgen, TER 
g TL , P  TL
 
h TL , P  h
 sgen  sgen , TER  (30)

 If all the processes are reversible, then

g TL , P 
r  (31)
h TL , P 
Energy Technology Lab, ME, NCU 107

Energy Conversion Efficiency

 Any reversible heat engine operating under the maximum

temperature limit allowed by the complete combustion of
fuel-oxidant mixture has the same efficiency as that of a
reversible isothermal fuel cell using the same fuel and
oxidant and operating at the same temperature as that of
low temperature TER (TL).

Energy Technology Lab, ME, NCU 108

Energy Conversion Efficiency

 The often-heard statement that fuel cell is not subject to

the Carnot efficiency limitation imposed on heat engines is
partly correct and partly incorrect, depending on the angle
that you look at.
 It is correct because fuel cell do not require two
temperature TERs to operate, and certainly there are no
TH and TL involved. Clearly the Carnot efficiency does not
apply to fuel cell operations.

Energy Technology Lab, ME, NCU 109

Energy Conversion Efficiency

 It is incorrect because the Carnot efficiency is in essence

the second law efficiency which imposes upper limit on
any energy conversion systems, including both
electrochemical converters and heat engines.
 From the preceding analysis, it is shown that both heat
engines and fuel cells are subject to the same second law
limitation.
 Then why do we often hear the statement that fuel cells
have higher efficiency than the corresponding heat
engines? There are several reasons:

Energy Technology Lab, ME, NCU 110

Energy Conversion Efficiency

 (1) The theoretical TH is not achieved in practice. Since flame

temperature is usually above 2000 K, many incomplete
combustion products such as CO, NO, C (particulates), OH, O,
N, …, are formed, leading to a lower temperature TH' than the
theoretical value TH (TH' < TH).
 (2) Due to material considerations (metallurgical), even TH' has
to be lowered in heat engine so that metal components can have
sufficient mechanical strength.

Energy Technology Lab, ME, NCU 111

Energy Conversion Efficiency

 For example, the maximum allowable temperature for gas
turbine is about 1000 K (with good cooling of turbine
blades). If the ambient environment is considered as the
low temperature TER, taking TL = 300 K,
TL 300
 r  1   1  0.7
TH 1000
as opposed to the theoretical TH, which may be taken as
2000 K,
TL 300
r  1   1  0.85
TH 2000

Energy Technology Lab, ME, NCU 112

Energy Conversion Efficiency

 (3) The heat rejected to the lower temperature TER is not

achieved in practice as the temperature TL; instead, usually at a
temperature TL' > TL . e.g., TL'  500 K for gas turbines, hence

TL 500
 r  1   1  0.5

TH 1000

Energy Technology Lab, ME, NCU 113

Energy Conversion Efficiency

 Considering other losses involved, heat engines usually

have lower than 40 % energy conversion efficiency. For
automobile engines, a rough estimate is that:
 1/3 of chemical energy of fuels lost to the cooling water
(metallurgical)
 1/3 of chemical energy of fuels converted to useful work
 1/3 of chemical energy of fuels lost by exhaust stream to
the environment

Energy Technology Lab, ME, NCU 114

Energy Conversion Efficiency

 That is,  r  0.33 which is much smaller then the

theoretical  max .
 On the other hand, fuel cells can be operated isothermally
at a temperature sufficiently low (so that no limitation is
imposed by materials), and sufficiently close to the
ambient temperature so that the degree of the
irreversibility is much less than the corresponding heat
engines.

Energy Technology Lab, ME, NCU 115

Energy Conversion Efficiency

 For example, PEMFC can be operated at T  80 C, at

which qL is rejected to the environment (TL  300 K), as
compared to gas turbines (TL'  500 K). Even though
there are other losses for fuel cells, overall, fuel cells still
have higher efficiency than conventional heat engines.

Energy Technology Lab, ME, NCU 116

Energy Conversion Efficiency

 Therefore, the important point about the fuel cells is not

that it is not Carnot efficiency limited, but it is free from
the high temperature limit imposed by materials on any
reversible heat engine giving the same second law
efficiency.

Energy Technology Lab, ME, NCU 117

Energy Conversion Efficiency

 Like any energy conversion system, fuel cells can never

achieve the 2nd law efficiency given by Eqs. (26) or (31).
 For fuel cells, useful amount of work (electrical energy)
are obtained only when a reasonably large current I is
drawn, but the cell potential decreases from its reversible
cell potential because of irreversible losses when I is
increased.

Energy Technology Lab, ME, NCU 118

Fuel Cell Losses

Energy Technology Lab, ME, NCU 119

Fuel Cell Losses

 Fuel cell losses are contributed to by both reversible and
irreversible losses. The reversible loss is equal to the heat
transferred (lost) to the environment. From Eq. (23),

q  T s  Tsgen  h  g  Tsgen 

where T is the temperature of the fuel cell.

Energy Technology Lab, ME, NCU 120

Fuel Cell Losses
 For most fuel cell systems, s is negative, indicating heat
is transferred from the fuel cell to the environment. As a
result,
g g
r   1
h g  T s
 However, for the reaction
C( s )  12 O2( g )  CO( g )
s is positive.

Energy Technology Lab, ME, NCU 121

Fuel Cell Losses

 Physically it indicates that the fuel cell absorbs heat from

the ambience and converts it into electrical energy along
with the chemical energy from carbon.
 Therefore, the efficiency for this fuel cell is larger than
100 %. In fact, r = 124 % at STP, r = 137 % at 150 C
and 1 atm, r = 163 % at 500 C and 1 atm, r = 197 %
at 1000C and 1 atm.
 Why does r change with T ?

Energy Technology Lab, ME, NCU 122

Fuel Cell Losses
g g  Er Er
    
h g  T s  E  T s  Er 
E  T  
 T  p
r r
nF

 For C( s )  12 O2( g )  CO( g ) , s >0, r > 100 %, and r ↑

as T ↑.
 But for most reactions, s <0,  r < 100 %, and r ↓ as
T ↑.
  Er / T  p
 − (0.1 ~ 1.0) mV/K at 25C and 1 atm,
 r  90 %.

Energy Technology Lab, ME, NCU 123

Theoretical reversible cell potentials and

maximum intrinsic efficiencies of selected
reactions at various temperatures.


298 K 600 K 1000 K

Reaction o
(V) % o
(V) % o
(V) %
Erev Erev Erev
C + O2  CO2 1.03 100 1.03 100 1.03 100

2 C + O2  2 CO 0.74 124 0.86 148 1.02 178

2 CO + O2  2 CO2 1.34 91 1.18 81 1.01 69

CH4 + 2 O2  CO2 + 2 H2O(g) 1.04 100 1.04 100 1.04 100

2 H2 + O2  2 H2O(g) 1.18 94 1.11 88 1.00 78

Energy Technology Lab, ME, NCU 124

Fuel Cell Losses
 The analysis above indicates that for most fuel cell
reactions, r decreases as T increases.
 This effect is important in considering high- temperature
fuel cells, such as SOFC.
 However, the irreversible losses will decrease drastically
as temperature is increased, so the power output
increases.

Energy Technology Lab, ME, NCU 125

Irreversible Losses

Energy Technology Lab, ME, NCU 126

Irreversible Losses
 As current is drawn from a fuel cell to produce electrical
energy output, the cell potential decreases from its
reversible value due to irreversible losses. These losses
are often called polarization, overpotential, or overvoltage
in literature.
 They originated primarily from three sources: activation
polarization, ohmic polarization, and concentration
polarization.

Energy Technology Lab, ME, NCU 127

Typical plot of cell potential vs. current for fuel

cells illustrating regions of control by various
types of overpotentials.

Energy Technology Lab, ME, NCU 128

Activation Polarization, act
 Activation polarization occurs when the charge transfer
reaction is slow across the electrode–electrolyte interface,
and a portion of the electrode potential is lost in driving
the electron transfer rate up to the rate required by the
current-demand.
 So act is directly related to the rate of electrochemical
reactions.

Energy Technology Lab, ME, NCU 129

Activation Polarization, act

 act depends on many factors such as the nature of
electrode material, ion-ion interactions, ion-solvent
interactions, the characteristics of the electric double layer
at the electrode-electrolyte interface, etc.

Energy Technology Lab, ME, NCU 130

Activation Polarization, act
 act may be reduced by
 increasing the operating temperature T (Tafel or Butler－
Volmer equation);
 increasing active surface area of the electrode (i.e., lowering
the local current density.
 increasing the activity of the electrode through the use of a
suitable electrocatalyst.

Energy Technology Lab, ME, NCU 131

Activation Polarization, act

 act may be also interpreted as the potential difference
required to push the reaction species overcome an
activation barrier in order for the electrochemical reaction
to proceed forward.

Energy Technology Lab, ME, NCU 132

Activation Polarization, act
 Activation (barrier) energy
(or activation mountain)

reactants
hR
h
hP Products

Reaction Progress Variable

Energy Technology Lab, ME, NCU 133

Ohmic Polarization, ohm

 Ohmic Polarization ohm (Resistance Polarization)
 It arises due to electrical resistance in the cell, i.e.,
 resistance to the flow of ions in the electrolyte (ionic);
 resistance to the flow of electrons and ions through the
electrode (electronic and ionic);
 resistance to the flow of electrons through, the terminal
connections (electronic)

Energy Technology Lab, ME, NCU 134

Ohmic Polarization, ohm
 Both electrolyte and fuel cell electrodes obey Ohm's law.

  ohm  IR 

 total cell resistance = electronic + ionic + contact

resistance
 The Ohmic losses are mainly due to ionic losses through
the electrolyte.

Energy Technology Lab, ME, NCU 135

Ohmic Polarization, ohm

 ohm can be reduced by decreasing the electrode
separation and enhancing the ionic conductivity of the
electrolyte, and electronic conductivity of electrodes.

Energy Technology Lab, ME, NCU 136

Contribution to polarization in PAFCs.

Energy Technology Lab, ME, NCU 137

Concentration Polarization, conc

 conc is caused by mass transfer limitations on the

availability of the reactants in the vicinity of the electrode-
electrolyte interface.
 As a reactant is rapidly consumed at the electrode by
electrochemical reaction to yield current output, mass
diffusion/convection limitations reduce the availability of
reactants, leading to a corresponding loss in output
voltage.

Energy Technology Lab, ME, NCU 138

Concentration Polarization, conc

 conc can also be caused by the over accumulation of

reaction products which block the reactants from reaching
the reaction sites.

Energy Technology Lab, ME, NCU 139

Concentration Polarization, conc

 conc is contributed to by several processes:

 slow diffusion in the gas phase in the electrode pores;
 solution/dissolution of reactants/products into/out of the
electrolyte;
 diffusion of reactants/products through the electrolyte
to/from the electrochemical reaction site －major
contribution to conc .

Energy Technology Lab, ME, NCU 140

Concentration Polarization, conc

 conc usually becomes significant (or even prohibitive) at

high current density which demands high rate of mass
transfer to meet current output requirement.

 Actual Fuel Cell Potential E:

E  Er  act .  conc .  ohm  Er (35)

Energy Technology Lab, ME, NCU 141

Total Heat Loss From Fuel Cell

q T
 s  nF( act.  conc.  IR)
Reversible heat loss
  (36)
Irreversible heat loss

 Note: q<0 means heat loss from a fuel cell.

 The rate of heat loss per mole fuel consumed in the fuel
cell can be expressed as an equivalent power loss given
by
 T s 
Pheat loss I  act .  conc .  IR   (37)
 nF 

Energy Technology Lab, ME, NCU 142

Other Losses
 Thermal efficiency,
g
 r T , P   (26)
h
 Voltage Efficiency E :

E
E  1 (38)
Er

Energy Technology Lab, ME, NCU 143

Other Losses
 Current Efficiency, I (Faradaic Efficiency):
I
I  (39)
 dN 
nF  F 
 dt 
where dNF/dt is the rate of fuel consumption in the fuel
cell (in mole/s)

Energy Technology Lab, ME, NCU 144

Other Losses
 When part of the reactants participates in a non-
productive side reaction, such as reactants cross-over,
incomplete conversion of reactants to desired products, I
would be less than one.
 For most practical fuel cell systems, I  100 %.

Energy Technology Lab, ME, NCU 145

Other Losses
 Overall Free Energy Conversion Efficiency overall :
 overall   r   E   I (40)

 Fuel Cell System Efficiency s :

 s   overall   auxi (41)

For auxiliary subsystems such as fuel pretreatment

Energy Technology Lab, ME, NCU 146

Other Losses
 The actual fuel cell efficiency (overall efficiency)

 overall   r   E   I (40)
where r : thermal efficiency (max. allowable)= g/h
E : voltage efficiency = E/Er
I : current efficiency  100 % for fuel cell
operating under practical conditions

Energy Technology Lab, ME, NCU 147

Other Losses
g E g E E
  overall   1   
h E r h  g / nF  h / nF
 where –h/nF = Etn — thermoneutral voltage, a voltage, a
fuel cell would have if all the chemical energy is converted
to electric energy.

E
 overall  (42)
Etn

Energy Technology Lab, ME, NCU 148

Other Losses
 For
1
H 2( g )  O2( g ) 
STP
H 2O( l ) , Etn  1.48V, overall  0.83
2
1
H 2( g )  O2( g ) 
STP
H 2O( g ) , Etn  1.24 V, overall  0.95
2
 In fuel cell analysis at 25 C and 1 atm, typically HHV is
taken for -h. So, Etn  1.48 V.

Energy Technology Lab, ME, NCU 149

Lower-heating-value efficiency

Energy Technology Lab, ME, NCU 150

Stoichiometry
 In a real fuel cell, gas composition changes between the
inlet and outlet of a fuel cell because reactants are
consumed to yield current output and reaction products
are formed along the way. The change in gas composition
results in a loss in cell potential.

RT
Er (T , Pi )  Er (T , P )  ln K P (20)
 F nF

Energy Technology Lab, ME, NCU 151

Stoichiometry
 Therefore, for practical fuel cell operations, reactants are
usually supplied more than the stoichiometric amount
required for the desired current output.
 Thus, the amount of reactants supplied is often expressed
in terms of st.

moles of reactants supplied, N 

F,in
stoichiometry=
moles of reactants consumed by reaction, N 
F,consumed

(43)

Energy Technology Lab, ME, NCU 152

Utilization
 e.q., in solid polymer fuel cells, st.  1.2 for H2 and 2 for
O2.
 Alternatively, reactant supply may be given in terms of
utilization,

moles of reactants consumed by reaction, N 

Ut  F,consumed

moles of reactants supplied, N  (44)

F,in

 U t  1 / st

Energy Technology Lab, ME, NCU 153

Utilization
 Assume no gas cross-over or leakage out of the cell,

N F ,in N F ,in 1
stFuel    (45)
  
N F ,in  N F ,out N F ,consumed U t ,Fuel
 Similarly, one can write an equation for the oxidant.

Energy Technology Lab, ME, NCU 154

Utilization
 Effect of reactant utilization on cell potential. Clearly as Ut
increases, cell potential decreases rapidly, such that 100%
Ut is practically an unwise design.

Energy Technology Lab, ME, NCU 155

Utilization
 For a H2-air fuel cell, a change in the gas composition that
leads to a 60mV cell potential loss at near room
temperature corresponds to a 300mV change at 1200 °C.
So gas composition changes are more serious for high
temperature fuel cells.
 Since in-cell fuel utilization will never be 100% in practice,
the in-cell efficiency (or cell potential E) calculation must
take utilization factor into account.

Energy Technology Lab, ME, NCU 156