Chapter02 Steadystate Part1asof2020!02!03 2

2.
Understanding the Steady-State

Behavior of Fuel Cells
Part I
Lecture Fuel Cell Technology, Chair for Process Systems Engineering (Prof. K. Sundmacher) Winter Term 2019/20 1
Recapitulation: Schematic of a Fuel Cell
Anode: A ↔ A + + e-
Cathode: B + A+ + e- ↔ AB
– +
Overall: A + B ↔ AB
e-
A (Fuel)
A e-
A+
B
AB
Anode MEA Cathode
Electrolyte B
Electrode (catalyst layer) (Oxidant)
Gas diffuision layer
Flow field
Steady-State Behavior
Current-cell potential characteristics
[V] / V
1 1
overpotential
Cell
Cellvoltage
potential Membrane poten-
Cathode over- tial difference
overpotential
0.8 0.8 Anode over-
potential
potential
[V]/ V
potential
0.6 0.6
CellVoltage
and and
0.4 0.4
potential
less
Voltage
0.2 cooling 0.2
Cell
0 0
0 4000 8000 12000 16000 0 4000 8000 12000 16000
Current density [A·m-2] Current density [A·m-2]
Bornhöft (2009) On Control of Fuel Cells. Diploma thesis, Otto-von-Guericke University Magdeburg.
Current-cell potential characteristics of a fuel cell
/ cell
V
U cell (i)  U cell,0   A (i)  C (i)   M (i)  Ri
Voltage U
Cellpotential
Reversible Losses caused Losses Further
cell by caused ohmic
Cell
potential electrochemi- by ion losses
cal reactions transport
(so-called in the
Current density i
electrode electrolyte
overpotentials)
Partial pressures pα
of the reactants in
Anode overpotential:  A (i )  f (i, pA (i ), TA (i,...)) the reaction zone
Cathode overpotential:  C (i )  f (i, pC (i ), TC (i,...)) Temperature T

in the reaction zone
Potential drop  M (i )  f (i,  (i, T ,...))
electrolyte: Electrolyte conductivity κ
U iU characteristics of fuel cells

(2c) U  f (I ) (1)
iU characteristics of load
• Constant load current (Galvanostat)
(2b) I  I load (2a)
• Constant load cell potential (Potentiostat)
(2d)
U  U load (2b)
• Constant load resistance
(2a) U(I)
I
U  Rload  I (2c)
0 • Constant load performance
Pload
U (2d)
I
Transient Behavior (not covered in this course)
1
1’ 1
1 0.6
2 Charge Concen- Water
dynamics tration and
0.8 0.58
[V] / V
dynamics tempe-
rature
[V]/ V
potential
1 dynamics
0.6 0.56
potential
2
1’
Voltage
CellVoltage
0.4 0.54
Cell
0.2 0.52
Isoline P=const
2
0 0.5
0 4000 8000 12000 10-6 10-4 10-2 100 102 104
Current density [A·m-2] Time [s]
Bornhöft (2009) On Control of Fuel Cells. Diploma thesis, Otto-von-Guericke University Magdeburg.
Contents
2. Steady-State Behavior of Fuel Cells

2.1 Potential Field of a Fuel Cell
2.2 Constitutive Relations
2.3 Integral Balance Equations
2.4 Putting Everything Together
Recommended Literature:
[1] C.H. Haman and W. Vielstich, Electrochemistry, Wiley-VCH, Weinheim, 1998.
[2] P. Heidebrecht, PhD thesis OvGU Magdeburg, VDI Verlag, Düsseldorf, 2005.
Electrode/Electrolyte Interface
Electrochemical reaction
at electrode/electrolyte interface
• Electrochemical reaction leads to a
separation of charges
• Charges arrange in a double layer structure
A
• Electric field occurs between separated
charges
Metal Electric
(Electron field
conductor)
Electrolyte
(Ion conductor)
Electric Potential at Charged Layers
Real double layer Poisson Equation: Ideal double layer (Helmholtz)

 2 
div grad   2  
z k  0 r
E  q
 E 
z  0 r  0 r
 
 E  E
z z
q    dz
 d q
Layer thickness
z Vol. rel. charge dens. z
Surf. rel. charge dens.
Electric
Field E E
(V/m)
Other idealized
Electric  
models:
Potential
- Gouy-Chapman
(V)
- Stern
Double Layer Models
Helmholtz Gouy-Chapman Stern
E E E
z z z
  
Potential Field of the Whole Cell Under Open Circuit Conditions
Anode Electrolyte Cathode
Charge q
dA +qA
density z
(C/m²)
-qA
Electric E qA
EA 
Field  0 r
z
(V/m)
EA
Electric  C,0 A   EA  d A
Potential dA
Ucell,0  qA 
 0 r
(V) A,0
 qA  CA
z
Potential Field of a Fuel Cell:
Things to Remember
Fuel cell under

open circuit conditions:
• Charges are separated in front of
the electrodes
• Charge separation leads to an
electric field and consequently to
a electric potential difference at
each electrode
(so-called equilibrium potential)
• The sum of both electrode
potentials gives the open circuit
potential of the cell
Fuel cell under load conditions

C,0
Ucell,0
A,0
Time
t=0
Electric current
2 Electrons
i
t
Reaction rates
ranode=0
rcathode=0
Ion flow rate

nelectrolyte=0

c,0
Ucell,0
a ,0
Time
t=t
Electric current
2 Electrons
i
t
Reaction rates
1 Molecule
ra 
t
1 Molecule
rc 
t
Ion flow rate
1 Charge
nelectrolyt e 
 t
Ucell,0
c
Ucell
a
Time
t=n·t
Electric current
2 Electrons
i
t
Reaction rates
2 Molecules
ra 
t
2 Molecules
rc 
t
Ion flux rate
2 Charges
nelectrolyte 
 t
Ucell,0
• All charge fluxes are

c equal  steady state
a Ucell • Decreased cell
potential under load
z
Potential Field of a Fuel Cell:
Things to Remember
Fuel cell under Fuel cell under

open circuit conditions: load conditions:
• Charges are separated in front of • Electric current disturbs the
the electrodes electrochemical equilibrium (leads
to changes of the charge densities
• Charge separation leads to an
of the electrodes)
electric field and consequently to
a electric potential difference at • Under load conditions, cell potential
each electrode is always lower than the equilibrium
(so-called equilibrium potential) cell potential (open circuit potential)
• The sum of both electrode
potentials gives the open circuit
potential of the cell
Equivalent Circuit Representation
 Conventions (1/3):
Ucell,0
Anodic Cathodic
double Elec- double • Cell Ucell=c-a
trolyte Potential
layer layer =c-a-m
c
c
Ucell
• Electrode c=c-mc
a
m
Potentials a=a-ma
ma
a,0 mc
• Potential Loss c=c-c,0
a
at Electrodes a=a-a,0
a (Overpotentials)
z
• Potential Loss m=ma-mc

Electrolyte
a m -c
Potential Field and Current-Cell Potential Characteristics
Ucell
 Ucell,0
Ucell(i=0)=Ucell,0
Anodic Cathodic
double Elec- double
layer trolyte layer
Ucell(i1)
no current Ucell(i1)
current i1
current i2>i1 Ucell(i2)

Ucell(i2)
z i
0 i1 i2
Contents
2. Steady-State Behavior of Fuel Cells

2.1 Potential Field of a Fuel Cell
2.2 Constitutive Relations
2.2.1 Open Circuit Potential
2.2.2 Electrochemical Reaction Kinetics
2.2.3 Mass Transport Kinetics
2.3 Integral Balance Equations
2.4 Putting Everything Together
Recommended Literature:
[3] P.W. Atkins and J. de Paula, Physical Chemistry, Oxford University Press,
Oxford, 2006.
Electrochemical Equilibrium – Nernst Equation
• The chemical potential μα follows from

(a) Fugacity and fugacity coefficient – typically used for gas mixtures
(Reference state: Mixture of ideal gases)
f
    RT lna a   f  p 
p
fugacity partial fugacity coefficient
pressure φ→1 if pα→0
(b) Activity and activity coefficient – typically used for solutions
    RT ln a a  x  
activity mole activity coefficient

fraction γ→1 if xα→1
Fugacity and activity coefficient can be calculated from the thermal state
equation or from empirical relations (e.g. NRTL, UNIQUAC, UNIFAC)
The electrochemical potential   is:
 e, metal   e, metal  ze Fmetal , w here ze  1

  ,s ln   ,s ln  zB Fsln , w here zB  (+/-n
m oror 0)
0
n+  ne   Z n+
Z Ym m 
 Y  nean
cath
 Zn+
m
,sln   Y, sln  n  e, an   Z,sln   Y n+
m
,sln  n  e, cath   0
 
n  e, cath   e, an   Zmn+   Y   Z   Y mn+
 
n  e, cath  Fc   e, an  Fa   Zn+
m
,sln
 mF sln   Y, sln   Z,sln   Y mn+ ,sln  mF sln
 nF c  a    r g
nFUcell ,0   r g Cell Potential under equilibrium conditions
 RT aZ n+  aY  r g 1
U cell,0  U cell,0    ( mn+  Y  Z  Ymn+ )
m
ln U cell,0
nF aZ  aY n+
m
nF nF Z
• In general it follows:
 R g  (T ) RT   
U cell,0   ln  a    activity of species α
(concentration measure)
nF nF   
• For an ideal mixture of ideal gases it follows


R g (T ) RT    p   partial pressure of species α
U cell,0   ln     
nF nF    p   standard pressure
 
temperature dependence of Ucell,0 composition and pressure dependence of Ucell,0
• with R ... ideal gas constant, F ... Faraday constant (= 96485 C/mol)
T ... temperature
n ... number of involved electrons According to reaction scheme.
να ... stoichiometric coefficient of α Obey the convention (next slide)!
• ΔRgθ [J/mol], the standard Gibbs enthalpie of the reaction, is given by

 R g  (T )   R h (T )  T   R s (T )
• with ΔRhθ [J/mol] the standard reaction enthalpie, from

 T

 R h (T )      h f , (T )   c p , ( ) d  
  
  heat capacity
  T  of species α
to be taken
formation enthalpy of species α
from thermo-
• and ΔRsθ [J/(mol·K)] the standard reaction entropy, from dynamic
tables, e.g.
 T
c p , ( )  NIST-webbook
 R s (T )     s f , (T )  
   
d 
  
  T 

formation entropy of species α
• Half-cell and overall reactions
Anode: OxA + ne- ↔RedA 2H+ + 2e- ↔H2

Cathode: OxC + ne- ↔RedC 0.5O2 + 2H+ + 2e-↔H2O
Overall: RedA + OxC ↔ RedC + OxA H2 + 0.5O2 ↔ H2O
• (Convention): overall reaction= cathode - anode

•Electrode potentials at open circuit conditions:
Anode: 2H+ + 2e- ↔H2 (for measurements left hand side, black pole of voltammeter )
Cathode: OxC + ne- ↔RedC (for measurements right hand side, red pole of voltammeter)
 R g  (T ) RT   
electrode  SHE   ln  a   
nF nF   
Calculations related to section 2.2.1
1. Calculate U cell,0 for the reaction:
H2 (g) + 0.5O2 (g) ↔ H2O (g)
at pα=pθ for 298, 600 and 1000 K. Assume that the heat capacities of the
reacting species are not temperature dependent in the required temperature
range.
For solution of the task 1 use the equation below and equations on slide 25.

 R g  (T ) RT   p  
U cell,0   ln    
nF nF    p  
 
2. Calculate thermodynamic efficiency (ηth ) for the same reaction at three
different temperatures given above. Show the dependence of ηth on
temperature graphically.
 R g
th 
 R h

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2.

Understanding the Steady-State

Anode MEA Cathode

Current-cell potential characteristics

Current-cell potential characteristics of a fuel cell

Cathode overpotential:  C (i )  f (i, pC (i ), TC (i,...)) Temperature T

U iU characteristics of fuel cells

2. Steady-State Behavior of Fuel Cells

Real double layer Poisson Equation: Ideal double layer (Helmholtz)

Helmholtz Gouy-Chapman Stern

Anode Electrolyte Cathode

Fuel cell under

Ion flow rate

• All charge fluxes are

Fuel cell under Fuel cell under

• Potential Loss m=ma-mc

a m -c

current i2>i1 Ucell(i2)

2. Steady-State Behavior of Fuel Cells

• The chemical potential μα follows from

activity mole activity coefficient

The electrochemical potential   is:

 e, metal   e, metal  ze Fmetal , w here ze  1

temperature dependence of Ucell,0 composition and pressure dependence of Ucell,0

• ΔRgθ [J/mol], the standard Gibbs enthalpie of the reaction, is given by

• with ΔRhθ [J/mol] the standard reaction enthalpie, from

• Half-cell and overall reactions

Anode: OxA + ne- ↔RedA 2H+ + 2e- ↔H2

Overall: RedA + OxC ↔ RedC + OxA H2 + 0.5O2 ↔ H2O

• (Convention): overall reaction= cathode - anode

1. Calculate U cell,0 for the reaction:

H2 (g) + 0.5O2 (g) ↔ H2O (g)

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