Chapter02 Steadystate PartII Asof2020!02!03 2

2.
Understanding the Steady-State

Behavior of Fuel Cells
Part II
Lecture Fuel Cell Technology, Chair for Process Systems Engineering (Prof. K. Sundmacher) Winter Term 2019/20 1
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:
[4] A.J. Bard and L.R. Faulkner, Electrochemical Methods, Wiley, Hoboken, 2001
[5] A.J. Bard, M. Stratmann and E.J. Calvo, Encyclopedia of Electrochemistry, Vol. 2
Interfacial Kinetics and Mass Transport, Wiley-VCH, Weinheim, 2003
r
Electrochemical Reaction Kinetics
Butler-Volmer Equation
• Driving forces for electrochemical reactions:
(a) deviation from equilibrium composition
(b) deviation from the equilibrium electrode potential (i.e. overpotential )
• So-called Butler-Volmer equation turned out to be appropriate to quantify
the reaction kinetics for an electrochemical equation
Red ↔Ox + ne-
i0  cred + nF  cox  1 

-   nF   
r  exp    exp    (*)
nF  cred , 0  RT  cox,0  RT 
exchange current density Concentration charge transfer

• under coefficient Nernst
equilibrium equation!
• Convention : conditions
- Reduction accelerated by negative 
- Oxidation accelerated by positive      0 cox,0 , cred,0 
Electrochemical Reaction Kinetics
Butler-Volmer Equation
• Sometimes used:
Activation overpotential act and concentration overpotential con
 = act + con
• Relation between reaction rates and current density are given by
the charge balances for each electrode
0  i  F  rjA n j
j
0  i  F  rkC nk
k
Influence of exchange current density
c  c , 0
i0  104 A cm2
n 1
r
T  298K Red ↔Ox + ne-
  0.5 i0  106 A cm2
i0  108 A cm2
Here: absence of
i0ref increases mass transport
resistances!
i0ref    nF   1    nF  
r  1 exp A   1 exp A  
nF   RT   RT 
Butler-Volmer kinetics
Approximation near equilibrium
Close to equilibrium:
BV kinetics nF
  0V    0V
RT
It holds that:
x0  exp x   1  x
Butler-Volmer equation near equilibrium:

c  c , 0 i0ref  nF   1   nF  
i0ref nF r  exp    exp  
r  n 1 nF   RT   RT 
nF RT
T 298K i0ref  nF  1   nF 
  1    1   
i0  106 A cm2 nF  RT  RT 
  0.5 i0ref nF
  Linear in !
nF RT
r
Red ↔Ox + ne-
(Very Useful!) Approximation of Butler-Volmer Equation:
Tafel Kinetics
Butler-Volmer equation:
r  r  r
i0ref   nF 
r  exp   1   nF 
 RT  i0ref nF  i0
ref
nF   exp    exp 
nF  RT  nF  RT 
BV kinetics If   0
nF   1   nF 
 exp    exp 
 RT   RT 
c  c , 0  r  r
n 1 i0ref  (1   )nF  Tafel
 r  r   exp 
T 298K nF  RT  kinetics
i0ref  1   nF  i0  106 A cm2

r  exp    0.5 If   0
nF  RT  nF   1   nF 
 exp    exp 
 RT   RT 
 r  r
i0ref nF  Tafel
 r  r  exp 
nF  RT  kinetics
r
Red ↔Ox + ne-
Butler-Volmer Kinetics: Determination of Parameters – Tafel Plot
Tafel equation:
nF 
log i  log i0 
1   nF  i  i0  exp   ;   0
 RT 
2.303RT
nF
 ln i  ln i0  
Extrapolated RT
Tafel plot
 1   nF 
i  i0  exp   ;   0
Measurement  RT 
points
 ln i  ln i0 
1   nF 
RT
logi0 nF
log i  log i0  
RT
BV kinetics • Plot log i vs.  Tafel plot
• Slope of curve yields α
• Extrapolation from linear Tafel
Region to =0 yields i0
i0  106 A cm2
c  c ,0
r
n  1, T  298K ,   0.25 Red ↔Ox + ne-
Contents

2.2.1 Open Circuit Potential
2.2.2 Electrochemical Reaction Kinetics
2.2.3 Mass Transport Kinetics
Recommended Literature:
[6] Krishna, R.; Wesselingh, J.A.: The Maxwell-Stefan approach to mass transfer,
Chem.Eng.Sci. 52 No.6 (1997) 861-911
[7] Perry, R.H.; Green,D.: Perry’s Chemical Engineers’ Handbook 7th ed., McGraw-
Hill Int. Eds., New York (1998), section 5: Heat and Mass Transfer
Influence of Mass Transport Resistances on
Current-Cell Potential Characteristics
without with
mass transport resistances mass transport resistances
U cell,0 U cell,0
Cell potential Ucell

U cell  U cell,0  A  C U cell  U cell,0  A  C

0  i  nFrA ( A , pA  p ) 0  i  nFrA ( A , pA (i))
0  i  nFrC (C , pC  p ) 0  i  nFrC (C , pC (i))
Current density i Current density i

i  ilim
Influence of Mass Transport Resistances on
Current-Voltage Characteristics
U cell,0
Hydrogen partial pressure
pH
2 ,in

Gas
channel
Reaction
zone
Current density i i  ilim Current density i i  ilim

A
p A
  2 F 

Tafel kinetics for anodic hydrogen
oxidation H2 ↔ 2H+ + 2e-
i  i0 
H2
exp  A 

 pH2 , 0  RT 

Physical Picture and Things to Remember
• Partial pressures of the educts

in the reaction zones decrease
with increasing current density;
Gas
channel Electrolyte
Reasons:
(a) Reactant depletion
(b) Mass transport resistances
• Decreasing educt partial
p pressures leads to an additional
Reaction zone
i=0 increase of the overpotentials
pH2,in
• Remark: Not only educt
H2 partial depletion causes potential
i↑
pressure in the
losses,
reaction zone
pAH2 at certain i e.g. PEMFC:
i=ilim - water transport through
z polymer membrane
- two-phase flow in GDL
Transport Processes in Porous Structures
in Fuel Cells
Porous structures in PEMFC:

(1) Diffusion layers:
Carbon fibre material,
pore diameters 1..100 µm,
porosity 0.50 .. 0.80
(2) Catalyst layers:
Metal/carbon black particles
agglomerated with polymers,
pore diameters 1..100 µm,
porosity 0.30 .. 0.80
(3) Polymer electrolyte membrane:
Swollen ion-exchange resin,
pore diameters 1..4 nm,
porosity 0.10 .. 0.50
Modes of mass transport in fuel cells
In fuel cells uncharged and charged mobile species are subjected to several driving forces:
DRIVING FORCES: uncharged species charged species
concentration gradients DIFFUSION
pressure gradients CONVECTION (VISCOUS FLOW)
electrical potential gradients ELECTRO-OSMOSIS MIGRATION
ELECTRO-OSMOSIS:
A charged molecule drags other uncharged molecules along with it.
e.g. solvatised ions: Solvent molecules form a “solvation shell” around the ion
H
H proton MIGRATES
O H in electric field…
+ H
O H+
…solvation water
-
O H
shell is
H dragged along with it
Mass transport in porous structures
“Reality” Pseudo-homogeneous approach

Mobile species move through pores Mobile species move through
(pore walls = solid material) stagnant “dust” of solid particles
Free pore
volume fraction
=
porosity
V pores
 pores 
Vtotal
DRIVING FORCES are reason for movement of mobile species.

FRICTION occurs between all mobile species and solid matrix (stagnant “dust” particles).
Maxwell-Stefan Approach
DIFFUSION CONVECTION MIGRATION FRICTION of α with

other comp. β matrix M
x j  x j

c c B0 F j
 T , p   V p  c vis p  c z   
RT RT  DM RT   D eff
 D eff
M
Mechanical equilibrium for species α c molar concentration [mol m-3]

between DRIVING FORCES (left) and R univers. gas constant [J mol-1 K-1]
FRICTION (right) ! T temperature [K]
 chemical potential [J mol-1]
V molar volume [m3 mol-1]
p pressure [Pa]
B0 permeability coefficient [m2]
 vis viscosity [Pa s]
z charge number [-]
 electrical potential [V]
x mole fraction (mobile species) [-]
j molar flux densities [mol m-2 s-1]
Ref.: Krishna, R.; Wesselingh, J.A. Chem.Eng.Sci. 52 D binary diffusion coefficient [m2 s-1]
No.6 (1997) 861-911 n absolute mole numbers [mol]
General solution of Maxwell-Stefan equations
Maxwell-Stefan equations are implicit with respect to fluxes !
x j  x j

c c B0 F j
 T , p   V p  c vis p  c z    eff
RT RT  DM RT  
eff
D DM
(DF) [B]( j)
vector of driving forces transport matrix vector of flux densities
Explicit solution: ( j )  [ B ]1 ( DF )
1 xk
Diagonal elements of [B]: Bii  eff   eff
DiM k i Dik
xi
All other elements of [B]: Bij (i  j )   eff
Dij
Important remarks to Maxwell-Stefan equations
In general for k species only (k-1) MS equations are independent

To solve the equation system another independent (k-th) equation is necessary
(often called “bootstrap condition”):
In porous systems:
(k-1) mobile species
(k-1) MS equations
“bootstrap” condition:
“dust” (k-th species=solid matrix, index “M”) is stagnant: jM  0
In free mixtures (no porous matrix):

k mobile species
(k-1) MS equations
“bootstrap” condition: k
e.g. Gibbs-Duhem# restriction: 

c 
1
T   p
#Describes the relationship between changes in chemical potential for components in a thermodynamical system.
Application of Maxwell-Stefan equations –
Ideal Gas Mixture in Porous Matrix
Ideal liquid, no charged species: e.g. in anode diffusion layer of DMFC
1 x p x j  x j

B0 j
a  x z  0  c  c vis  
x z  DM z   eff
D DeffM
c p x j  x j

B0 j

c
c  const x    c vis  
 

c z  DM z   eff
D DeffM
Ideal gas, no charged species: e.g. gas diffusion in porous catalysts !

p p
a  f  and ideal gas law: pV  n RT  p  c RT  c 
p RT
 c
1 a

p p  p / p   
1 p
standard pressure (105 Pa) a z RT p z RT z
DUSTY-GAS Model:
1 p p p x j  x j

B0 j
    eff
RT z RT  vis DM z   eff
D DM
Application of Maxwell-Stefan equations –
The most simple case
Ideal liquid, no charged species, no convection, no porous matrix:
p
a  x z  0 0
z
c x j  x j

j
  
z   eff
D DeffM
Only two species: (1)=solute, (2)=solvent x2  1

Infinitely diluted solution: x1  0
c1 x2 j1  x1 j2


z D12
c
  D12 1  x2 j1  x1 j2
z
c1
  D12  j1 FICK’s Law
z
The diffusion coefficients (I)
Difference between “normal” and “effective” binary MS diffusion coefficients:

“normal”: In free mixtures (no porous matrix)
“effective”: In porous matrix => porosity  pores and tortuosity  have to be accounted for.
 pores  pores
D 
eff
D Porosity-to-tortuosity factor best determined experimentally !
 
 pores
Simple estimates for microporous structures: (a)  4 (b)   1pores
.5

“Matrix friction” binary MS diffusion coefficients:
 pores  pores d pore 8RT

based on Knudsen diffusion DeffM  DKnudsen 
   M
M
3
- For gases often negligible influence of matrix friction molar mass [kg mol-1]
(as long as pores are “wide”: > 0.1 µm
- If adsorption to matrix might occur: Watch out! Additional surface diffusion!
The diffusion coefficients (II)
Mobile species’ binary MS diffusion coefficients:

(a) Gases: kinetic gas theory1, estimation methods2a,3
usually yield very accurate results
(b) Liquids: estimation methods2b,3
often only coarse estimation possible
better: fitting to experiments using ARRHENIUS-type approach
 E
A
1 1 

D 
eff
D exp     
 R  T T 
(c) Solvents in polymers: fitting to experiments using modified ARRHENIUS-type approach
 E
A
1 1 

D 
eff
D  f (solventcontent)  exp     
 R  T T 
[1] Wesselingh, J.A.; Krishna, R.: Mass transfer in Multicomponent Mixtures 1st ed., Delft University Press (2000), p. 95
[2] Reid, R.C.; Prausnitz, J.M.; Poling, B.E.: The properties of gases & liquids 4th ed., McGraw-Hill, New York (1987),
a) p. 577 b) p. 597
[3] Perry, R.H.; Green,D.: Perry’s Chemical Engineers’ Handbook 7th ed., McGraw-Hill Int. Eds., New York (1998), p. 2-370
Other mass-transport models
c F 
NERNST-PLANCK equation: j   D  z D c  c v
z RT z
DIFFUSION MIGRATION CONVECTION
In principle only valid if species α is highly diluted (based on FICK diffusion)!
(can also be derived from MS, similar to procedure shown for FICK’s law)
Convective transport in polymer electrolytes (PEM): conc. of mobile charged species
(PEM fuel cell membranes: c H  )
SCHLÖGL equation for mass average velocity: k  k p p

v c /  F  vis
(from MS equations with some simplifications !)  vis z  z
k , k p : electrokinetic/hydraulic permeability [m²] ELECTRO-OSMOTIC FLOW
Very “popular” for PEM fuel cells: current density [A m-2]
cH 2O i
DRAG-COEFFICIENT model for PEM: jH 2O   DH 2O  nd
z F
number of uncharged molecules j dragged along with each charged molecule (exp. result)
Contents

Integral Balance Equations
Integral balances for Assumptions:

(a) Anode (material balance) - steady-state
(b) Cathode (material balance) - inert components do not take
(c) Energy balance part in reaction and are not
transported through membrane
- PEMFC as example system
(a) Material balances anode
• Hydrogen balance
iA
0G x A A
in H 2,in G x A
out
A
H 2 ,out 
2F
G … Molar flow rate [mol/s]
• Total material balance xα … Mole fraction
i … current density [A/m2]
iA
0  G G A
in
A
out  A … Cell size [m2]
2F F … Faraday constant [As/mol]
(b) Material balances cathode

• Oxygen balance
iA
0G x C C
in O 2 ,in G x C
out
C
O 2 ,out 
4F
• Water balance
iA
0  G x C
out
C
H 2 O ,out 
2F
• Total material balance
iA
0  GinC  Gout
C

4F
(c) Energy balance

• Electric Power
Pel  Ui  A
• Thermal power (to be removed from cell)

Pth   R h  GinA xHA 2,in  Gout
A
xHA 2,out  Pel 
 
 c pA,inGinA  c Cp ,inGinC  Tin  T 
Energy released in the cell Energy required to heat

cold inlet gases from Tin to T
Efficiency
Ui  A
el  A

GH 2,in    R h 
 R g  U  nF i A
el  
 

 R h   R g nF  GinA xHA 2,in
      
th  ec  fu el
Fuel utilization
Electrochemical efficiency
Thermodynamic efficiency
Very useful special case:

Operation at constant fuel utilization and constant cathode stoichiometry
GinA xHA 2,in  Gout

A
xHA 2,out GinC xOC2,in
 fuel  C 
GinA xHA 2,in GinC xOC2,in  Gout
C
xCC2,out
! !
 const  const
→ Required hydrogen and oxygen inlet flow follows from:
iA 1 iA C
G x A A
  GinC xOC 2,in  
2 F  fuel
in H 2,in
4F
→ Average composition of gases in anode and cathode channel is given by:
1   fuel
x A
H2 
1
A
  fuel xAH2,in = 0.8
xH 2,in
0.6
0.4
0.2
→ Average composition of gases in anode and cathode channel is given by:
xCO2,in = 0.21
1
1 C xCH2O,in = 0
xOC 2  
1 1
 C
xO 2,in 
C
2 xCO2
xHC 2O  C
1 1

xOC 2,in C xCH2O
Contents


2.4.1 Inventory Model
2.4.2 Dimensioning of Fuel Cell Stacks
Putting Everything Together: Inventory Model
• Combination of integral balances • Allows the expression of variables

(Ch. 2.3) and constitutive relations of interest as functions of
(Ch. 2.2.1, 2.2.2) gives a generic
- Current density, i
model
- Fuel utilization, ηfuel
• Further assumptions/conditions - Cathode stoichiometry, ΛC
- Cell temperature, pressure
- Simple models for mass transport
- Composition, temperature
within porous structures (Fick’s law)
of anode and cathode feed
- Simple model for mass transport
- Design parameters
within membrane (Ohm’s law)
- Operation at constant fuel • Different cases
utilization and constant cathode
(a) Base case
stoichometry
(b) Improved cathode mass transport
- Air cathode
(c) Oxygen cathode
(d) Poor membrane
(e) Poor anode
(a) Base Case
Inlet
Ucell Channel
Reaction zone
Cathode
Inlet
Membrane
Anode Channel
Reaction zone
ηfuel = 0.9 ΛC = 1.5 xAH2,in = 0.8 xCO2,in = 0.21
(a) Base Case
ηfuel ƞth
ηec
ηel
pfuel
pth
pel
(b) Improved Cathode Mass Transport
Inlet
Ucell
Channel
Reaction zone
Cathode
Inlet
Membrane
Anode Channel
Reaction zone
(c) Oxygen Cathode
Inlet
Ucell
Channel
Reaction zone
Cathode
Inlet
Membrane
Anode Channel
Reaction zone
(d) Poor Membrane
Inlet
Channel
Cathode
Ucell Reaction zone
Inlet
Membrane
Anode Channel
Reaction zone
(d) Poor Anode
Inlet
Ucell
Channel
Reaction zone
Cathode
Inlet
Membrane
Anode
Channel
Reaction zone
Contents


2.4.1 Inventory Model
2.4.2 Dimensioning of Fuel Cell Stacks
Putting Everything Together: Dimensioning of Fuel Cell Stacks
• In a simple design task, the following • The following variables are

variables are known unknown
- Desired Power, P - Cell size, A
- Gas composition and temperature - Current density in the
of anode and cathode feed design point, i
- Operating temperature and - Cell potential in the design point, U
pressure - Fuel utilization, ηfuel
- Cathode stoichiometry, ΛC
- Efficiency, ηel
• Three of the unknowns have to be fixed,

the rest follows from the following equations
- iU characteristics: U = f(i, ηfuel, ΛC, Tcell, pcell, xA/Cα,in, TA/Cin, p)
- Electrical Power: Pel = Ui ∙ A
- Efficiency: ηel = ηth ∙ ηec(U) ∙ ηfuel
Putting Everything Together: Dimensioning of Fuel Cell Stacks
Example: PEM fuel cell
1250 W/m2
750 W/m2
250 W/m2
Calculations related to section 2.4.2
1. Design a PEMFC fed with reformer gas and air. The following variables
are known:
- Anode feed: xAH2,in=0.5, TAin=T θ
- Cathode feed: xCO2,in=0.21, TCin=T θ
- Operating conditions: pcell =105 Pa, Tcell =T θ
- Desired power: Pel =100 kW
The cell should be operated with the following parameters: ΛC=1.5, ηfuel=95%
and ηel = 40%.
A) Calculate the Ucell,0 for given conditions.
B) Determine the required cell size (A). Tip:
Calculate first the required cell potential (U). After that determine the value of
the current density from U-i characteristics at the page 42.
C) Calculate GHA 2,in , GOC2,in and Pth
D) Determine the cell size, U and ηel for the fuel cell operating at 1.1 A /cm2.

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2.

Understanding the Steady-State

2. Steady-State Behavior of Fuel Cells

i0  cred + nF  cox  1 

exchange current density Concentration charge transfer

Butler-Volmer equation near equilibrium:

i0ref  1   nF  i0  106 A cm2

2. Steady-State Behavior of Fuel Cells

Cell potential Ucell

U cell  U cell,0  A  C U cell  U cell,0  A  C

Current density i Current density i

Cell potential Ucell

Current density i i  ilim Current density i i  ilim

• Partial pressures of the educts

Porous structures in PEMFC:

DRIVING FORCES: uncharged species charged species

concentration gradients DIFFUSION

pressure gradients CONVECTION (VISCOUS FLOW)

electrical potential gradients ELECTRO-OSMOSIS MIGRATION

“Reality” Pseudo-homogeneous approach

DRIVING FORCES are reason for movement of mobile species.

DIFFUSION CONVECTION MIGRATION FRICTION of α with

Mechanical equilibrium for species α c molar concentration [mol m-3]

Maxwell-Stefan equations are implicit with respect to fluxes !

Explicit solution: ( j )  [ B ]1 ( DF )

In general for k species only (k-1) MS equations are independent

In free mixtures (no porous matrix):

Ideal liquid, no charged species: e.g. in anode diffusion layer of DMFC

Ideal gas, no charged species: e.g. gas diffusion in porous catalysts !

Ideal liquid, no charged species, no convection, no porous matrix:

Only two species: (1)=solute, (2)=solvent x2  1

Difference between “normal” and “effective” binary MS diffusion coefficients:

 pores  pores d pore 8RT

Mobile species’ binary MS diffusion coefficients:

SCHLÖGL equation for mass average velocity: k  k p p

k , k p : electrokinetic/hydraulic permeability [m²] ELECTRO-OSMOTIC FLOW

Very “popular” for PEM fuel cells: current density [A m-2]

2. Steady-State Behavior of Fuel Cells

Integral balances for Assumptions:

(b) Material balances cathode

(c) Energy balance

• Thermal power (to be removed from cell)

Energy released in the cell Energy required to heat

Very useful special case:

GinA xHA 2,in  Gout

→ Required hydrogen and oxygen inlet flow follows from:

→ Average composition of gases in anode and cathode channel is given by:

→ Average composition of gases in anode and cathode channel is given by:

2. Steady-State Behavior of Fuel Cells

2.4 Putting Everything Together

• Combination of integral balances • Allows the expression of variables

ηfuel = 0.9 ΛC = 1.5 xAH2,in = 0.8 xCO2,in = 0.21

2. Steady-State Behavior of Fuel Cells

2.4 Putting Everything Together

• In a simple design task, the following • The following variables are

• Three of the unknowns have to be fixed,

Example: PEM fuel cell

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