Post on 19-Aug-2020
Department of Chemical and Environmental Engineering
Illinois Institute of Technology
Fuel Cell Systems: an Introduction
for the Engineer (and others)
Professor Donald J. Chmielewski Center for Electrochemical Science and Engineering
Illinois Institute of Technology
Presented to the
E3 Class
March 16th, 2010
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 2
What is a Fuel Cell?
???
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 3
Stationary (200 kW) Mobile (50 kW)
Applications
Toyota International Fuel Cells
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 4
What is a Fuel Cell?
Fuel Cell
H2
Electric Power
Air
H2O
Answer:
An electrochemical
device that converts
a fuel directly to
electrical power
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Illinois Institute of Technology 5
Where Does the Energy Come From?
Fuel Cell
H2
Electric Power
Air
H2O
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 6
Where Does the Energy Come From?
Fuel Cell
H2
Electric Power
Air
H2O
Answer:
The enthalpy released
by the reaction:
H2 + ½ O2 H2O
(H ~ 58 kcal/mole H2)
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Illinois Institute of Technology 7
The Fuel Cell Reactor?
Fuel Cell
H2
???
Air
H2O
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Illinois Institute of Technology 8
The Fuel Cell Reactor?
Fuel Cell
H2
Heat
Air
H2O
Problem:
Heat is
released but
not electric
power
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Illinois Institute of Technology 9
The Fuel Cell Reactor
Fuel Cell
H2 Air
H2O
Solution:
Two reactors
separated by
an electrolyte
membrane.
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Illinois Institute of Technology 10
The Fuel Cell Reactor
Fuel Cell
H2 Air
H2O
Ecell
Voltage * Current
= Electric Power
Current
Solution:
Two reactors
separated by
an electrolyte
membrane.
This allows for
manipulation
of electrons
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 11
Electrolyte Types
N2
N2
N2
H2
H2
H2
H2
H2
H2
O2
O2
O2
H+
e- e-
Anode
Electrolyte
Cathode
O2 N2
N2
O2
O2
N2
N2
N2
H2
H2
H2
H2
H2
H2
O2
O2
O2
O2-
e- e-
Anode
Electrolyte
Cathode
O2 N2
N2
O2
O2
H+
H+
H+
O2-
O2-
O2-
Polymer Membrane: Solid Oxide Membrane:
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 12
Polymer Electrolyte Membrane
Fuel Cell (PEMFC)
N2
N2
N2
H2
H2
H2
H2
H2
H2
O2
O2
O2
H+
e- e-
Anode
Electrolyte
Cathode
O2 N2
N2
O2
O2
H+
H+
H+
Electrolyte conducts
ions (H+), but not
electrons (e-).
Electrodes (Anode
and Cathode) conduct
electrons (e-), but not
ions (H+).
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 13
Solid Oxide Fuel Cell (SOFC)
N2
N2
N2
H2
H2
H2
H2
H2
H2
O2
O2
O2
e- e-
Anode
Electrolyte
Cathode
O2 N2
N2
O2
O2
Electrolyte conducts
ions (O=), but not
electrons (e-).
Electrodes (Anode
and Cathode) conduct
electrons (e-), but not
ions (O=).
O2-
O2-
O2-
O2-
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 14
Where Does the Water Go?
N2
N2
N2
H2
H2
H2
H2
H2
H2
O2
O2
O2
H+
e- e-
Anode
Electrolyte
Cathode
O2 N2
N2
O2
O2
N2
N2
N2
H2
H2
H2
H2
H2
H2
O2
O2
O2
O2-
e- e-
Anode
Electrolyte
Cathode
O2 N2
N2
O2
O2
H+
H+
H+
O2-
O2-
O2-
Polymer Membrane: Solid Oxide Membrane:
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N2
N2
N2
H2
H2
H2
H2
H2
H2
O2
O2
O2
H+
e- e-
Anode
Electrolyte
Cathode
O2 N2
N2
O2
O2
N2
N2
N2
H2
H2
H2
H2
H2
H2
O2
O2
O2
O2-
e- e-
Anode
Electrolyte
Cathode
O2 N2
N2
O2
O2
H+
H+
H+
O2-
O2-
O2- H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O H2O
H2O
H2O
Where Does the Water Go?
Polymer Membrane: Solid Oxide Membrane:
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Illinois Institute of Technology 16
Where Do the Electrons Go?
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Illinois Institute of Technology 17
Interconnect/Bipolar plate:
(La,Sr)CrO3 or High Temp Alloy
Anode: Ni - (Zr,Y)O2- cermet
Electrolyte: (Zr,Y)O2-
Cathode: (La,Sr)MnO3
Fuel H2
Air
SOFC Configuration:
Where Do the Electrons Go?
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Illinois Institute of Technology 18
Fuel Cell Stack
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Illinois Institute of Technology 19
Current Collectors
ElectrolyteAnode
CathodeO=
O2
H2OH
2
e-
e-
e-
e-
SOFC:
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 20
The Electrode Electrolyte Assembly
Anode
Grains
ElectrolyteAnode
CathodeO=
O2
H2OH
2
e-
e-
e-
e- e-
H2H2O
O=Electrolyte
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 21
The Three Phase Region
Anode
Grains
Ni
H2O
e-
H2H2O
O=Electrolyte
Ni
NiNiNi
YSZNiYSZ
YSZ
YSZ
YSZ
Ni
Ni
H2O H
2
YSZ
O= e-
Ni YSZ
NiNi
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 22
Design Issues
ElectrolyteAnode
CathodeO=
O2
H2OH
2
e-
e-
e-
e-
SOFC:
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Illinois Institute of Technology 23
How Much Fuel Does a Fuel Cell Use?
Fuel Cell
H2 Air
H2O
Ecell
Voltage * Current
= Electric Power
Current
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Illinois Institute of Technology 24
How Much Fuel Does a Fuel Cell Use?
Fuel Cell
H2 Air
H2O
Ecell
Voltage * Current
= Electric Power
Current
Reaction rate is
proportional to
current density
F
2 n
jrH
AreajCurrent *
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Illinois Institute of Technology 25
How Do We Calculate Current Density?
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Illinois Institute of Technology 26
How Do We Calculate Current Density?
A fuel cell looks
like a battery to
the electrical
world.
Current output
depends on the
load.
Ecell
Eo
Rint
Load
DC
Fuel Cell I=j*Acell
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Illinois Institute of Technology 27
Review of Circuits 101
Eload
Eo
Rint
DC
Battery I
Rload
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Illinois Institute of Technology 28
Review of Circuits 101
Eload
Eo
Rint
DC
Battery I
Rload
Equation #1:
Eload = Eo - I*Rint
Equation #2:
Eload = I*Rload
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 29
Review of Circuits 101
Eload
Eo
-Rint
I
Eload
= Eo - R
int*I
Equation #1:
Eload = Eo - I*Rint
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 30
Review of Circuits 101
Eload
Eo
-Rint
I
Rload
Eload
= Eo - R
int*I
Eload
= Rload
*I
Equation #1:
Eload = Eo - I*Rint
Equation #2:
Eload = I*Rload
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 31
Review of Circuits 101
Eload
Eo
-Rint
I
Rload
Eload
= Eo - R
int*I
Eload
= Rload
*I
Equation #1:
Eload = Eo - I*Rint
Equation #2:
Eload = I*Rload
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 32
How Much Fuel Does a Fuel Cell Use?
F
/2 n
AIrH
Eload
Eo
-Rint
I
Rload
Eload
= Eo - R
int*I
Eload
= Rload
*I
2
2
sec m
Hofmoles
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 33
Fuel Used is Proportional to Current
F
/2 n
AIr cell
H
2
2
sec m
Hofmoles
Fuel Cell
H2 Air
H2O
Ecell
Voltage * Current
= Electric Power
Current
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 34
Changing the Reaction Rate
Eload
Eo
-Rint
I
Eload
= Eo - R
int*I
Eload
= Rload
*I
Eload
Eo
Rint
DC
Battery I
Rload
F
/2 n
AIrH
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 35
Circuit Perspective of the SOFC
Ecell
Eo
Rint
Load
DC
Solid Oxide Fuel Cell I=j*Acell
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Illinois Institute of Technology 36
Circuit Perspective of the SOFC
Ecell
Eo(P
H2,P
O2, P
H2O)
Rint
(Tcell
)
Load
DC
Solid Oxide Fuel Cell I=j*Acell
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 37
Resistance in the SOFC
Zirconia Electrolyte Cathode (~30 μm)
Electrolyte (10-200 μm)
Anode ( up to 1 mm)
Bipolar Plate (3-10 mm)
Air
Fuel
Rint= r (T ) * ( thickness / Area )
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Illinois Institute of Technology 38
Eload
Eo
I
Rload
Eload
= Eo - R
int*I
Lower T
Circuit Perspective of the SOFC
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 39
Circuit Perspective of the SOFC
Ecell
Eo(P
H2,P
O2, P
H2O)
Rint
(Tcell
)
Load
DC
Solid Oxide Fuel Cell I=j*Acell
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 40
Equilibrium Voltage
OH
OHmo
P
PPRTgE
2
22
2/1
log22 FF
Fuel Cell
H2 Air
H2O
Eo
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Illinois Institute of Technology 41
Eload
Eo
I
Rload
Eload
= Eo - R
int*I
Lower P
Circuit Perspective of the SOFC
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Illinois Institute of Technology 42
Circuit Perspective of the PEMFC
Ecell
Eo(P
H2,P
O2, P
H2O, j )
Rint
(Tcell
, j )
Load
DC
PEM Fuel Cell I=j*Acell
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Illinois Institute of Technology 43
0 2000
PEMFC Polarization Curve
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Illinois Institute of Technology 44
PEMFC Polarization Curve
0 2000
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Illinois Institute of Technology 45
How Much Heat Does a FC Generate?
eOHOHfgen PrHQ 22
)( ,
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Illinois Institute of Technology 46
How Much Heat Does a FC Generate?
0 200 400 600 800 10000
0.2
0.4
0.6
0.8
1
1.2
1.4
Current Density (mA/cm2)
Cel
l V
olt
age
(V)
0 200 400 600 800 10000
0.05
0.1
0.15
0.2
0.25
0.3
0.35
Po
wer
Den
sity
(w
atts
/cm
2)
E
eP
cell
eOHOHfgen PrHQ 22
)( ,
celle VjP *
F
2 n
jrH
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 47
How Much Heat Does a FC Generate?
0 200 400 600 800 10000
0.2
0.4
0.6
0.8
1
1.2
1.4
Current Density (mA/cm2)
Cel
l V
olt
age
(V)
0 200 400 600 800 10000
0.05
0.1
0.15
0.2
0.25
0.3
0.35
Po
wer
Den
sity
(w
atts
/cm
2)
E
eP
cell
2/25.0 cmwPe
F
/4.0
2
2 n
cmArH
2
, /49.022
cmwrH OHOHf
2
,
/24.0
22
cmw
PrHQ eOHOHfgen
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Illinois Institute of Technology 48
Stationary (200 kW) Mobile (50 kW)
Applications
Toyota International Fuel Cells
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 49
The Fuel Cell System
Fuel
Processor Fuel Cell
Stack
Spent-Fuel
Burner
Thermal & Water Management
Air
Air
Fuel
H2
Exhaust
H2O
CO2
Electric Power
Conditioner
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Illinois Institute of Technology 50
Stationary Applications
International Fuel Cells
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 51
Flat-Plate Hydrogen Fed SOFC
Fuel Cell Stack
Anode
Flow
Cathode
Flow
Cathode
2 O=
V
-
+
Solid
Electrolyte
Anode
2H2
2H2O
O2+ 4 e- 2 O=
2H2+ 2 O= 2 H
2O +4 e-
O2
4 e-
4 e-
HEATRELEASED
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Illinois Institute of Technology 52
Plug Flow Reactor Analogy
Feed Exhaust
Reaction
Rate
Conventional Design
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Illinois Institute of Technology 53
Figure taken from Selimovic Dissertation, Lund University, (2002).
Thermal Stresses in the Literature
Peters et al., state that
“ Large temperature gradients in either direction can cause damage to one or more of the components or interfaces due to thermal stresses”
Yakabe et al., state that
“ … the internal stress would cause cracks or destruction of the electrolytes”
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 54
Fuel Cell Stack
Air Channel
Fuel Channel
InterconnectCathode
Anode
Electrolyte
Internal Reforming SOFC
CH4
Air Flow
H2OCO
2H2 H
2O
O=
Fuel Flow
O2
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Illinois Institute of Technology 55
Internal Reforming
44224 3 CHrefCH
kCkrHCOOHCH ref ++
+ +
eq
COH
COOHfshiftCO
k
K
CCCCkrHCOOHCO fshift 22
22
,
,222
is very large Endothermic
is also large Exothermic fshiftk ,
refk
2
1222
2 OHOH Hr+ Exothermic
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 56
Plug Flow Reactor Analogy (Internal Reforming)
ReformingReaction Rate
Reforming HeatGeneration
ElectrochemicalReaction Rate
ElectrochemicalHeat Generation
Combined HeatGeneration
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Illinois Institute of Technology 57
Figure taken from Selimovic Dissertation, Lund University, (2002).
Impact of Internal Reforming
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Illinois Institute of Technology 58
Effective Structure of IR SOFC
• Heat and steam produced not used by reforming.
• Pre-heating steam is expensive.
• Steam in the feed lowers hydrogen utilization (reaction rate is a function of hydrogen to steam ratio).
ElectrochemicalSection
ReformingSection
Pre-Heater
222
224 3
COHOHCO
COHOHCH
++
++
OHOH 22 +
Methane
Steam
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Illinois Institute of Technology 59
Exhaust
Feed
Feed
Distributed Feed Plug Flow Reactors
Distributed Feed Design
• Makes PFR act like a CSTR.
• Improves Yield and Selectivity.
• Improves Thermal Management.
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Illinois Institute of Technology 60
Hydrogen Fed Simulations
Solid Temperature Profile
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Illinois Institute of Technology 61
Simulation of the
Internal Reforming Case
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Illinois Institute of Technology 62
2-D Distributed Feed Design
Side FeedChannels
z1 z
2z
3z
4z
5
Active Area WallInactive Area
zx
Section of a stack layer
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Illinois Institute of Technology 63
Fuel Cell Stack
Air Channel
Fuel Channel
InterconnectCathode
Anode
Electrolyte
Internal Reforming SOFC
CH4
Air Flow
H2OCO
2H2 H
2O
O=
Fuel Flow
O2
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Illinois Institute of Technology 64
Mobile Applications
Toyota
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 65
The Fuel Cell System
Fuel
Processor Fuel Cell
Stack
Spent-Fuel
Burner
Thermal & Water Management
Air
Air
Fuel
H2
Exhaust
H2O
CO2
Electric Power
Conditioner
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 66
Hydration Model for MEA
MEA
Anode
In
(H2, H
2O) H
2
Cathode
Air in
Cathode
Exhaust
O2
H2O
N2
Solid Material Current Collector
H+
H+
H+
H+
H+
H+
H+
H+
Anode
Exhaust
H2O
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Illinois Institute of Technology 67
Hydration Model for MEA
MEA
Anode
In
(H2, H
2O) H
2
Cathode
Air in
Cathode
Exhaust
O2
H2O
N2
Solid Material Current Collector
H+
H+
H+
H+
H+
H+
H+
H+
Anode
Exhaust
H2O
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Illinois Institute of Technology 68
Water Transport in the Membrane
ELECTRO-OSMOTIC DRAG
DIFFUSION
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 69
Concentration Profiles
GDL Membrane GDLAnode Gas Cathode Gas
δm δ cδ a
2
( )an
H OC
( )ˆ mem
oC
( )( )
20mem
H OC
2
( ) ( )mem
H OC z
( )ˆm
memC2
( )ca
H OC
2
( ) ( )mem
H O mC
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Illinois Institute of Technology 70
The Fuel Cell System
Fuel
Processor Fuel Cell
Stack
Spent-Fuel
Burner
Thermal & Water Management
Air
Air
Fuel
H2
Exhaust
H2O
CO2
Electric Power
Conditioner
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 71
Why On Board Fuel Processing?
Transportation
Applications
PEMFCFuel
Processors
Liquid Fuel
Storage Tank
CmHn
H2
CO
H2O
CO2
PEMFCHydrogen
Storage Tank
H2
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Illinois Institute of Technology 72
CO Poisoning
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 73
High Temperature Membranes
Humidity with Increases ,
ty,Conductivi Electrical
)(TP
PxRH
satw
xw = 0.35
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Illinois Institute of Technology 74
Fuel Processing Reactors
PEMFCPreferential
Oxidation
(PrOx)
Water-
Gas
Shift
(WGS)
Reformer
Hydrocarbon Feed
Large Hydrocarbons Cracked:
H2 / CO ratio ~2 Most CO converted to CO2: ~ 1% CO remaining
CO levels down to ~ 10 ppm
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Illinois Institute of Technology 75
Reforming Reactors
Steam Reforming
Partial Oxidation
Autothermal Reforming
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Illinois Institute of Technology 76
Steam Reforming
22 )2/( HnmmCOOmHHC nm +++
222 HCOOHCO ++
Fuel
Steam
Heat
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 77
Catalytic Partial Oxidation (CPOX)
22 )2/( HnmmCOOmHHC nm +++
222 HCOOHCO ++Fuel
Air OHnmCOOnmHC nm 222 2/)2/( +++
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 78
Autothermal Reforming (ATR)
22 )2/( HnmmCOOmHHC nm +++
222 HCOOHCO ++Fuel
Air OHnmCOOnmHC nm 222 2/)2/( +++
Steam
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Illinois Institute of Technology 79
Start-up and Regulation of an ATR
ATR
TT
TC
Air Flow In
Fuel Flow In
Water Flow In
Reformat Flow Out
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Illinois Institute of Technology 80
The Effect of Water Injection
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 81
Closed-loop Water Injection
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Illinois Institute of Technology 82
Slower Water Injection Rate
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 83
Fuel Processing Reactors
PEMFCPreferential
Oxidation
(PrOx)
Water-
Gas
Shift
(WGS)
Reformer
Hydrocarbon Feed
Large Hydrocarbons Cracked:
H2 / CO ratio ~2 Most CO converted to CO2: ~ 1% CO remaining
CO levels down to ~ 10 ppm
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 84
Water Gas Shift Reactors
( )eq
s
CO
s
H
s
OH
s
CO Kyyyykr )(
2
)(
2
)(
2
)(
33
222 HCOOHCO ++
High
Temp
WGS
Medium
Temp
WGS
Low
Temp
WGS
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Illinois Institute of Technology 85
Preferential Oxidation Reactors
222
1COOCO +
PrOx
OHOH 2222
1+
Reformat
Air
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 86
Preferential Oxidation Reactors
222
1COOCO + OHOH 222
2
1+
Reformate
Air
100oC 100oC
Intercooler Intercooler
Prox
Stage 1
Prox
Stage 2
Prox
Stage 3
Air Air
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 87
Preferential Oxidation Reactors
0
0.5
1
1.5
2
2.5
0 0.5 1 1.5 2 2.5 3 3.5
Inlet CO Concentration (%)
Hyd
rog
en
Co
nve
rete
d (
%)
1-Stage3-Stage
2-Stage
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Illinois Institute of Technology 88
The Fuel Cell System
Fuel
Processor Fuel Cell
Stack
Spent-Fuel
Burner
Thermal & Water Management
Air
Air
Fuel
H2
Exhaust
H2O
CO2
Electric Power
Conditioner
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 89
Hybrid Fuel Cell Vehicle
FC Kfc
iafcifc
Vfc
iab
ib
Vb
Rb
Eb
ia
Ra
La
VaKb
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 90
Separation of Time-Scales
FC Kfc
iafcifc
Vfc
iab
ib
Vb
Rb
Eb
ia
Ra
La
VaKb
5 10 15 20 25 30 35
-200
0
200
400
600
800
1000
Power Profles [W]
time, sec
Pload
(sp)
Battery
Fuel Cell
Armature
Vehicle
kbatPmot
+-
kfc
x
Pfc
+-
x
Pbat
Pmot(sp)
Pbat(sp)
VfcFUEL CELL
VOLTAGE
CONTROLLER
Vfc(sp)
PI
PI
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Illinois Institute of Technology 91
Hybrid Fuel Cell Vehicle (Double Storage Configuration)
iascapiscap
Rscap
Escap
iarm
Rarm
Larm
DC-DC
Converter
iabatibat
Rbat
Ebat
DC-DC
Converter
iafcifc
EfcDC-DC
Converter
Fuel
Cell
Power Bus
warm
Earm
kfc kbat kscap
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Illinois Institute of Technology 92
Supervisory Control
Vehicle
Power
System
+ -Pscap
(sp) Pscap
kscap
Supervisory
Controller
Pmotor
+ -Pbat
(sp) Pbat
kbat
+ -Pfc
(sp) Pfc
kfc
PI
PI
PI
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 93
The Fuel Cell System
Fuel
Processor Fuel Cell
Stack
Spent-Fuel
Burner
Thermal & Water Management
Air
Air
Fuel
H2
Exhaust
H2O
CO2
Electric Power
Conditioner
Department of Chemical and Environmental Engineering
Illinois Institute of Technology 94
Acknowledgements
• IIT Collaborators: Said Al-Hallaj J. Robert Selman
Ali Emadi Satish Parulekar Herek Clack Jai Prakash
• Argonne National Laboratory: Shabbir Ahmed Dennis Papadias Rajesh Ahluwalia Qizhi Zhang • Students: Kevin Lauzze Ayman Al-Qattan • Funding: Kuwait Institute for Scientific Research Graduate College and Armour College, IIT Argonne National Laboratory