Reaction Engineering of PEM

Fuel Cells
How should we operate a fuel cell, from the
single cell level to the stack level?
What operating and control variables, what
are system parameters?
0.25

120
100

ignited state

0.2

Current Density (A/cm2)

Power (mW/cm2)

RL=4

80
60
40
20

water removal

0.15

extinguished state

RL=6

0.1

RL=8
RL=10
RL=15

0.05
RL=20

0
0

10

15

Resistance (ohm)

20

25

0
0

0.2

0.4

0.6

Water Activity (Pw/Po)

0.8

Reactor Performance
e-

hydrogen in

water out

H+
Polymer Electrolyte

What are the key

variables that
characterize the fuel
cell performance?
What are the figures of
merit?
What are the system
parameters and how
should they be
controlled?

load

anode
H2
2H+

oxygen in

cathode
=
O 2 2O
=
O + 2H+
H2 O

System Variables and System

Parameters Cell Level
System Parameters
Heat input/removal
Pressure
Feed gas flow rates and
composition
Load resistance
Preconditioning
Initial state of
membrane
Cell construction

System Variables
Cell current and
voltage
Temperature
Local gas composition
Membrane water
content

What happens if?

The load on the fuel cell changes?

The hydrogen flow rate changes?
The oxygen flow rate changes?
The water content of the membrane
changes?
The temperature of the cell changes?
The pressure in the cell changes?

What do I need to know to design

and control a fuel cell?
How to start up the cell.
How the responds to changes in system
parameters and disturbances.
How to control the cell for desired power
output and fuel utilization.

Model Fuel Cell for Kinetic

Measurements
R e la tiv e H u m id ity S e n s o r
R e lie f V a lv e

H y d ro g e n in

G r a p h ite P la te

RL
N a fio n M e m b ra n e

I
E le c tr o d e a s s e m b ly

O x y g e n In

T h e rm o c o u p le

Key elements of PEM STR Fuel Cell

Gas cavities and flow rates are matched to
assure uniform composition of the gas in
both the anode and cathode
Measurement of relative humidity
Precise control over gas flow rates
Precise control over pressure

PEM STR Fuel Cell

One-dimensional, uniform compositions in
the gas phases and in the membrane
Differential reactor direct correlation of
state variables for the system
Information can be employed to predict
performance of an integral reactor

STR PEM Fuel Cell

Flow controllers

Fuel cell

Load

Fuel Cell Details

Membrane Electrode
Assembly

RH Sensor

Mass Balances for the Fuel Cell

Anode (hydrogen)

Cathode (oxygen)

FAin PHin FAout PH

0.5 i
H
RT

FCin POin FCout PO

0.25 i
H
RT

Water balance
F out PwA F in PwA,in FCout PwC FCin PwC,in
A
A
RT

0 .5 i H

Coupling of Reaction and

Transport
Water Production in Fuel Cell
depends on mass transfer to the electrodes, charge transfer
reactions at the electrodes, proton transport in membrane,
membrane resistance and the load resistance

0.5 i H 0.5

V'

Rmembrane Rload

Simple lumped parameter, Rmembrane is the effective MEA

resistance that accounts for numerous non-idealities.
Rmembrane is a function of water activity in the membrane.

How to characterize the fuel cell

Polarization Curve

Power Performance

1.2

120
100

Decreasing resistance
Power (mW/cm2)

voltage (volts)

1
0.8
0.6
0.4

80
60
40

0.2

20

0
0

100

200
current (mA)

300

400

10

15

Resistance (ohm)

Same data presented in two different ways

20

25

Significance of Power Performance Curve

Power IV

F u e l C e ll
Rm

'
Voc

RL

Rm RL

Voc

Max Power occurs when RL=Rm

120

RL

100

Power (mW/cm2)

80
60
40

Rm

20
0
0

10

15

Resistance (ohm)

20

25

Test Study Autohumidification

PEM Fuel Cell
What is the concept of autohumidification?
Water to hydrate the membrane is supplied by
the water formed by reaction.

What are the implications?

Mass transfer from the cathode to the
membrane must be greater than mass transfer
through the electrode to the gas phase.

O x y g e n F lo w
c a th o d e
H + d iffu s io n
H 20
d iffu s io n

m e m b ra n e
anode

H y d r o g e n flo w

Water formed at the cathode diffuses into the membrane

hydrating the membrane providing the necessary
hydration for proton transport. The water circulates
through the membrane!

Start-up of a PEM Fuel Cell

Dry membrane in-situ by flowing ~ 100 cm3/min
of dry N2 through the fuel cell @ 60C for 24 hrs.
Flow 10 cm3/min of N2 with ~100%RH at 25C
through the fuel cell for 104-105 s.
Set fuel cell temperature and start H2 and O2 flow
at 10 cm3/min
Close circuit with a known load resistance (5 )

Critical Phenomena- Ignition of

the PEM fuel cell
1000

1000

100

5 ohm load

Current (mA)

Current (mA)

100

10

10

30 ohm load

0.1
1

10

100

1000

Time (s)

0.1
1

10

100

1000

10000

Time (s)

Start-up from different initial water

loading

Quenching from high

load resistor

10000

Why do we see ignition in a PEM

fuel cell?
Water Production in Fuel Cell
Depends on proton transport in membrane
V'
0.5 i H 0.5
Rmembrane Rload
14
12
10
8
6
4
2
0
0

W
aterM
oleculesperSO
3

Membrane Resistivity (ohm-cm)

1.E+07
1.E+06
1.E+05
1.E+04
1.E+03
1.E+02

p ro to n c u rre n t

0.2 0.4 0.6 0.8

W
aterVaporActivity

m e m b r a n e r e s is ta n c e

1.E+01
1.E+00
0

0.2

0.4

0.6

Water Activity (Pw/Po)

0.8

w a t e r p r o d u c t io n

m e m b r a n e h y d r a tio n

Balancing Transport and Reaction

O x y g e n F lo w
c a th o d e
H + d iffu s io n
H 20
d iff u s io n

m e m b ra n e
anode

H y d r o g e n flo w

tdiffusion > tconvection

water evaporates and dehydrated membrane
tdiffusion < tconvection
water produced by reaction can hydrate membrane

Predicting Steady State

Multiplicity
0.25

ignited state

0.2

Current Density (A/cm2)

RL=4

water removal

0.15

extinguished state

RL=6

0.1

RL=8
RL=10
RL=15

0.05
RL=20

0
0

0.2

0.4

0.6

Water Activity (Pw/Po)

0.8

Temperature Dependence of Water

Generation and Water Removal
Water generation 0.5

V'

Rmembrane Rload

Water removal

F out PwA FCout PwC

Specific Conductivity (S/cm)

1.E+00

RT

1.E-01
1.E-02
1.E-03

80 C

PwA ~ Pwo (T ) Pw (To

100 C

1.E-04

120 C
140 C

1.E-05

H vap 1 1
To
T
)e

Empirical Fit
1.E-06
1.E-07
1.E-08
0.0

0.2

0.4

0.6

0.8

Water Activity

Water generation is
insensitive to temperature

1.0

Water removal increases with

increasing temperature

Effect of changing temperature and

load resistance
0.25

Current Density (A/cm2)

0.2

increasing T

0.15

0.1

0.05

Increasing RL
0
0

0.1

0.2

0.3

0.4

0.5

0.6

Water Activity (Pw/Po)

0.7

0.8

0.9

Steady State Data of Autohumidification Fuel

Cell
Cell Temperature
(C)

Load
Resistance ()

Steady State Current

(mA/cm2)*

Water Removed at
Anode (nmol/cm2-s)

Water Removed at
Cathode (nmol/cm2-s)

35

0.5
5
15
0.5
5
15
0.5
5
15
0.5
5
15
0.5
5
15
0.5
5
15

164 (849)
78 (404)
31 (161)
180 (932)
80 (166)
32 (166)
176 (912)
78 (404)
31 (161)
145 (751)
76 (394)
30 (156)
130 (674)
72 (373)
30 (156)
54 (280)
31 (161)
13 (67)

400
205
70
430
180
90
420
175
65
350
175
80
325
160
85
125
70
40

460
200
85
520
215
85
500
220
90
400
200
80
370
200
75
160
90
40

50
65
80
95
105

Water Partitioning
FAin

FAout

H2

H2

H 2O

A
xH

2O

A
xH
2O

C
xH

2O

xC
H 2O
FCin

O2

FCout

O2

i2
FAin i i
2
2
(1 ) i
2

FCin (1 ) i i
2
4

H 2O

FAout FAin i i
2
2
FCout FCin (1 ) i i
2
4

Data demonstrate partion

coefficient of 0.5 0.05

Effect of Flow Rates

120
140

80
Current (mA)

Cell Current

100

60
O2 10 mL/min

40

O2 5 mL/min

120

H2 flow 10 mL/min

100

H2 flow 5 mL/min

80

H2 flow 2 mL/min

60
40

O2 2 mL/min

20

20

H2 flow (mL/min)

10

12

10

12

O2 Flow mL/min

Only at high utilization of the reactants is there any significant effect of

the flow. At low to moderate reactant utilization the reaction rate is
principally governed by proton transport through the polymer electrolyte.

Membrane Resistance and

Maximum Power
120

20
15

O2 flow 2 mL/min
O2 flow 5 mL/min
O2 flow 10 mL/min

10
5

Max Cell Power (mW/cm2)

MEA Resistance (ohm)

25

100
80
O2 flow 2 mL/min
60

O2 flow 5 mL/min
O2 flow 10 mL/min

40
20
0

0
0

10

H2 Flow rate (mL/min)

Effective membrane resistance

increases at low hydrogen flows

10

H2 flow (mL/min)

Power goes through a

maximum near stoichiometric
feed

Effects of Concentration on Cell

Current
140

120
Max Cell Power (mW/cm2)

120

Cell Current (mA)

100
80

PO~0.8

60

PO~0.9
PO~0.95

40

Thermodynamic
limit

20

100
80
H2 flow 2 mL/min
60

H2 flow 5 mL/min
H2 flow 10 mL/min

40
20
0
0

0
0.8

0.85

0.9

0.95

1.05

10

O2 flow (mL/min)

Hydrogen pressure at anode (bar)

Current appears to decrease

faster than predicted by
thermodynamic (Nernst) limit

Power increases with hydrogen

flow, and is insensitive to
oxygen flow

Effects of Reactant Flow

As hydrogen availability decreases with water
formation it creates an effective resistance.
Rate is insensitive to hydrogen utilization up to 40%, at
higher hydrogen utilization the current and power fall
off, above 80% utilization rates become negligible

Oxygen flow affects the hydration level of the

membrane.
As long as the oxygen flow is greater than
stoichiometric it has little effect on the power

Effect of changing temperature and

load resistance
0.25

Current Density (A/cm2)

0.2

increasing T

0.15

0.1

0.05

Increasing RL
0
0

0.1

0.2

0.3

0.4

0.5

0.6

Water Activity (Pw/Po)

0.7

0.8

0.9

Surprise More Steady States

Heating the cell to 95 C in an effort to extinguish the
current led to the discovery of an intermediate stable
steady state!
120

800

fixed RL
100

700

Cell Power (mW)

low water
content
stable

600
Voltage (mV)

high water content

stable

500
400
300
increasing
load resistance

200

80

60

40

20

100

0
0

0
0

50

100

150

Current (mA)

200

250

10

15

20

Load Resistance (ohm)

25

30

Long transients to jump between steady states

120
Load resistance
changed at 175 s

Cell Current (mA)

80

cell current

110
100

anode RH
60

90
80

cathode RH
40

70
60
50

20

40
0
0

500

1000

1500
Time (s)

2000

2500

30
3000

Relative Humidity Sensors

100

The relative humidity

of the anode is
delayed by ~100 s
compared to the
current and the
cathode RH

Jump from high to intermediate steady

state
40
39
38
37

36
34

anode RH

cell current

32

33
30
31

28
cathode RH
26

29

24
27

22

25
0

5000

10000

15000
Time (s)

20000

25000

20
30000

Relative Humidity

Cell Current (mA)

35

In going from a high

water content steady state
to low water content
steady state the anode RH
leads the current and
cathode RH

W a te r A c tiv ity
1

50

lo w w a te r c o n te n t s ta b le

3 s ta b le s ta te s

f i r s t i g n i t i o n l im i t

150

200

h ig h w a te r c o n te n t s ta te s ta b le

s e c o n d i g n it io n l i m i t

100

C u rre n t (m A )

By measurement of
the stable steady
states, and
hysteresis loop
points the points of
ignition can be
bracketed. This is
used to determine
the water
generation curves.

250

increasing T
RL=1

200

RL=2

water removal
150

Cell Current (mA)

Water generation and

removal curves from
experimental data. Notice
that the hysteresis loop is
bounded by a small region
of resistances. The load
resistances displaying
multiple steady states
changes with the
temperature.

RL=4

RL=6

100

RL=8
RL=10
RL=12.5
RL=15

50

RL=20

0
0

0.2

0.4

0.6

0.8

Water Activity in Membrane (Pw/Po)

1.2

Phase Plane
Temperature/Reactant Flow

Phase Plane Temperature/Load

Resistance

Three stable steady states only seen

above 70 C
140
10

120

Power (mW)

95 C

80

80 C
65 C

60

50 C

40

MEA Resistance (ohm)

100

7
low water content

6
5
4
3
2

high water content

20

0
20

0
0

10

15

Load Resistance (ohm)

20

25

30

40

50

60

70

Temperature (deg C)

80

90

100

Why??
A p p lie d P r e s s u r e b y
C u r r e n t C o lle c to r P la t e s

Membrane Resistivity (ohm-cm)

Membrane swelling pinned

S w e llin g P r e s s u r e o f
P o ly m e r M e m b r a n e

1.E+07

1.E+06

1.E+05

1.E+04

1.E+03

constrained membrane
1.E+02

1.E+01

unconstrained membrane

1.E+00
0

0.2

0.4

0.6

0.8

Water Activity (Pw/Po)

Nafion is clamped between electrodes and cant swell or

contract with water uptake/loss. It needs to do work to push
against the electrodes. It also must be above Tg to flow.

Steady State and Pseudo Steady

State
800
700

800

high water content

stable

low water
content
stable

600

700

high water content

600

500

Voltage (mV)

Voltage (mV)

900

fixed RL

400
300

500
400
300

increasing
load resistance

200

decreasing
load resistance

low water content

200
100

100

0
0

50

100

150

200

250

Current (mA)

True steady state polarization

curves, each point was permitted
>5000 s to stabilize

50

100

150

200

Current (mA)

Pseudo steady state, entire

polarization curve was
obtained in 100 s

250

Characteristic Times for Steady State

Increasing the water content due to decrease load resistance
sulfonic acid density
40
characteristic response time

s
2
current density/2
j ( A / cm )

Decreasing the water content due to increased load resistance

sulfonic acid density
10 4
characteristic response time

s
o
water evaporation rate Pw (bar )

Challenges of Humidity Control

Reaction Rate and mass transfer of water into the membrane
are weak functions of temperature, evaporation is
exponentially dependent on temperature. Humidification
control is complicated at higher temperatures.
Temperature distributions in multi-cell stacks create variability
in local humidity control. Humidity variations create
variations in reaction rate.
Multicell stacks must be adequately heated everywhere to
avoid water condensation, while avoiding dehydration.
Cell construction and sealing of the MEA assembly between
the bipolar plates is a critical design feature
Swelling pressure of a ionomer membrane is critical property
for controlling water content in the membrane.

What else are we learning?

Dynamic response to changes in external
load
Dynamic response to changes in
temperature
Effect of history of operation
Steady state operation???

Response to Temperature
Changes
120

Temperature rise 65C-95C

4 ohms
15 ohms
22 ohms

100

Multiple steps suggest

changes at the two
electrode/membrane
interfaces

Current (mA)

80

60

40

20

0
0

1000

2000

3000
Time (s)

4000

5000

6000

Recording Polarization Curves after conditioning at different loads

Equilibrium Comparisons at 70C

0.8

0.8

0.7

0.7

0.6

0.6

0.5

0.5
Voltage (mV)

Voltage (mV)

Equilbrium comparisons at 60C

0 ohms
20 ohms

0.4

0 ohms
20 ohms

0.4

0.3

0.3

0.2

0.2

0.1

0.1

0
0

50

100

150

200

250

50

100

Equilibrium Comparison at 80C

200

250

200

250

Equilibrium Comparisons at 90C

0.8

0.8

0.7

0.7

0.6

0.6

0.5

0.5
0 ohms
20 ohms

0.4

Voltage (mV)

Voltage (mV)

150
Current (mA)

Current (mA)

0 ohms
20 ohms
0.4

0.3

0.3

0.2

0.2

0.1

0.1

0
0

50

100

150
Current (mA)

200

250

50

100

150
Current (mA)

How Steady is Steady State?

Current Variations at 80C
in STR PEM Fuel Cell Feed RH 12%

250

R = 4.4 ohms
Period: 3217 sec
Jump: 5.2 mA
Jump time: 1567 sec

R = 1.9 ohms
Period: 6717 sec
Jump: 36 mA
Jump time: 1983 sec

200

Current Variations at 80C

in Autohumidification PEM fuel cell
250

Current (mA)

Humidify
feed

150

R = 4.4
R = 1.9
100

200
50

0
0

10000

20000

30000

40000

50000

60000

70000

80000

90000

Time (sec)

100

R=2
R = 2.6
R = 3.2
R = 4.8

50

Current Variations at 65C

in STR PEM Fuel Cell Feed RH 20%

250

R = 7 ohms
Period: 11267 sec
Jump: 2.9 mA
Jump time: 1633 sec

R = 3.9 ohms
Period: 12300 sec
Jump: 7.7 mA
Jump time: 1750 sec

R = 1.4 ohms
Period: 11567 sec
Jump: 36 mA
Jump time: 1550 sec

200

0
10000

20000

30000

40000

50000

60000

70000

80000

90000

R=7
R = 3.9
R = 1.4

100000

Time (sec)

PEM Operation at
constant feed, constant T,
and constant load

Current (mA)

Current (mA)

150

Decrease
Temp

150

100

50

0
20000

30000

40000

50000

60000
Time (s)

70000

80000

90000

100000

100000

Improving membrane/electrode contact

vs. squeezing water out of membrane
A p p l ie d P r e s s u r e b y
C u r r e n t C o lle c to r P la te s

8
7
S w e llin g P r e s s u r e o f
P o ly m e r M e m b r a n e

5
4
3
2

60

35
34.5

current oscillations observed

34

0
0

0.5

1.5

2.5

33
55

32.5
32
31.5

Turns past finger tight

31
30.5
50
20000

22000

24000

26000

Time (s)

28000

30
30000

Power (mW)

33.5
Current (mA)

MEA Resistance (ohm)

Where do we stand?
We dont really understand all the physics
and chemistry of PEM fuel cell operation
Coupling of chemical/mechanical/electrical
properties in PEM fuel cells gives rise to
complex dynamics

Acknowledgements
Sonia Tulyani for humoring me to demonstrate ignition
in PEM fuel cells
Joel Moxley for patience to take the initial data that
showed five steady states
Caterina Teuscher for discovering chaos and
autonomous oscillations
Joanne Chia for modeling the autohumidification PEM
fuel cell and demonstrating the effects of cell sealing
Princeton University for support of the senior theses to
build the STR PEM fuel cell reactor