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International Journal of Hydrogen Energy 31 (2006) 29 38

www.elsevier.com/locate/ijhydene

Dynamic modelling of a proton exchange membrane


(PEM) electrolyzer
Haluk Grgn
Yildiz Technical University, Electrical-Electronics Faculty, Istanbul 80750, Turkey
Available online 26 May 2005

Abstract
This paper describes a dynamic model for PEM electrolyzer based on conservation of mole balance at the anode and
the cathode. A further feature of the model is it includes water phenomena, electro-osmotic drag and diffusion, through the
membrane. The model considers PEM electrolyzer to be composed of four ancillaries: anode, cathode, membrane and voltage
ancillary. Additionally, hydrogen storage dynamics is presented. The developed model is suitable for determining control
strategy that will ensure efcient and reliable operation of the electrolyzer. Moreover, the dynamic model can be integrated
with renewable energy systems models to design, analyze and optimize sustainable energy systems. The study illustrates the
dynamic interactions within a PEM electrolyzer and shows the necessity of the proposed approach of separate ancillaries.
2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

1. Introduction
Electrolyzers are unique devices to produce pure hydrogen and oxygen. They could be widely distributed and rated
to meet the hydrogen and oxygen requirements of different
users such as units for individuals, renewable energy systems, fuelling stations and industrial applications. Among
the other types of electrolyzers PEM electrolyzers are very
simple and compact. Besides they ensure high purity and
efciency at high current density levels. In PEM electrolyzers, the bonds between the hydrogen and oxygen in the H2 O
are broken by electromotive force and the catalytic action
of the platinum when dc voltage is supplied. The membrane
separates the H2 from the O2 . The hydrogen protons, H + ,
migrates through the membrane and recombines at the cathode with the returning electrons, e , and form hydrogen,
H2 . PEM electrolyzers offer the potential for low cost in
mass production, if inexpensive membranes are developed.
Last but not least, the other notable advantage of PEM electrolyzers is that the PEM electrolyzer can be used as a fuel
Tel.: +90 212 259 70 70 (2781); fax: +90 212 259 4967.

E-mail address: halukgorgun@alum.rpi.edu.

cell to produce electricity from hydrogen and oxygen with


small modications.
In addition to the cell stack an electrolyzer must have a
dc power supply, a water pump, watergas separators as illustrated in Fig. 1. Although electrolyzers produce both H2
and O2 by splitting water electrochemically only few applications uses both products. Most of the time electrolyzer is
considered as a hydrogen generator. Electrolyzers are categorized as anode feed system or cathode feed system depending on where the water enters the unit. When the electrolyzer is used for just hydrogen generator, cathode feed
system could be a good option because the separator which
separates oxygen and water is eliminated at the anode and
oxygen is ventilated with water. The penalty in this case is
that mass transfer limitations occurs and only low current
densities can be achieved. In this study, anode feed electrolyzer modelling is studied since most of the commercial
electrolyzers and military units are anode feed electrolyzers.
However, it should be mentioned that modelling of cathode feed electrolyzer can be accomplished with couple of
changes in water transport phenomena.
Applications of electrolyzers include: O2 for life support, fuel cells, sustainable energy systems, providing H2 for

0360-3199/$30.00 2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2005.04.001

30

H. Grgn / International Journal of Hydrogen Energy 31 (2006) 29 38

DC Power
Supply
-

Seperator H2

H 2O in
Water Pump

O2

Seperator

H2 Bottle

PEM Electrolyzer
Fig. 1. PEM electrolyzer.

corrosion control, gas chromatograph sensors, metal forming and welding. Electrolyzers are currently being studied
by several researchers from industry, academia and military and research results are being published at an increasing rate. There are several studies to model electrolyzers
and renewable energy systems. Among them, Onda [1] has
developed a two dimensional mathematical model to analyze PEM electrolyzer. Ulleberg [2] has shown a model for
alkaline electrolyzers based on thermodynamics and heat
transfer theory. More recently on renewable energy systems,
Klouwani et al. [3] have demonstrated stand alone renewable energy system with hydrogen storage. Khan et al. [4]
have presented modelling of a small windfuel cell hybrid
energy system. In an earlier study, Busquet et al. [5] have
established an empirical approach to model a electrolyzer or
a regenerative fuel cell. In general, electrolyzer, renewable
energy or regenerative fuel cell studies have been formulated
electrolyzers with just Faradays Law. There is a need for an
electrolyzer model which explains its dynamics in detail and
is suitable for dynamic simulation together with renewable
energy systems. This paper gives a detailed control oriented
model for a PEM electrolyzer based on mole balance in the
anode and the cathode subsystems. The model is capable of
characterizing PEM electrolyzer and essential for determining control strategy that will ensure efcient and reliable
operation of the electrolyzer. Besides, the PEM electrolyzer
dynamic model can be employed in the optimization of sustainable energy systems. This paper is organized as follows:
model details are presented in Section 2. Simulation studies
demonstrated in Section 3. Finally, conclusions are given in
Section 4.

2. Modelling
To clearly quantify the dynamic interactions, the PEM
electrolyzer is considered to have four ancillaries: anode,
cathode, membrane and voltage ancillary. Each ancillaries
dynamics and interaction between them are contemplated.
Voltage ancillary calculates electrolyzer applied voltage

level by using Nernst Equation, ohmic polarization and


activation polarization. Membrane ancillary computes
water content, electro-osmotic drag, water diffusion and
conductivity of the membrane. The anode ancillary dynamically calculates oxygen and water ows and partial
pressures. Similarly, hydrogen and water partial pressures
and their ows are obtained in the cathode subsystem.
Storage ancillary shows storage dynamics of the generated
hydrogen in a bottle by taking account the initial hydrogen level in it and compressibility of the hydrogen. The
Simulink Model of the electrolyzer is shown in Fig. 2 and
in the following subsections, the model is explained in
detail.
2.1. Anode ancillary
Electrochemically, all electron transfer reactions are considered oxidation and reduction. The substance gaining electrons is oxidizing the substance that is losing electrons. The
anode electrode is the electrode where the oxidation occurs
in electrolyzers by denition. In this side of the electrolyzer
the states are oxygen, and water molar hold-ups. The dynamics in the model are:
N O2 = FO2 ai FO2 ao + O2g ,
N H2 Oa = FH2 Oai FH2 Oao FH2 Oeod FH2 Od ,

(1)

where, FO2 ai , FO2 ao , FH2 Oai , FH2 Oao (mol/s) are cathode
inlet and outlet molar ows of oxygen and water, respectively. One should note that FO2 ai is zero because only input is the water, this term is written to show the general
complete mole balance dynamics. FH2 Oeod and FH2 Od are
electro-osmatic drag and diffusion ows. O2g is the rate of
oxygen generated at the anode.
The partial pressures of the oxygen and water at the anode
are
pO2 =

NO2 RT el
Va

and

pH2 Oa =

NH2 Oa RT el
,
Va

(2)

H. Grgn / International Journal of Hydrogen Energy 31 (2006) 29 38

31

Current
P02

pelec

101325

px

Electrolyzer pressure
TSTACK

Tel

Fef

Faref
H2

Faraday Efficiency
Fia

FH20n

Fia

Water in
Tic

Cathode Ancillary

Vel

Vel

Clock

FH20m
Ourrent
t

FH20m

Fia
Ph2

Current

pelec

Fic

Curd

1/A
5

landern
lamn

Current Density
Fic

Tel

Fic

Tst

lamn
Voltage Ancillary

Cu
Faef

Membrane Ancillary
FH2

FH20n

H2 Flow pb

Pb
Bottle Pressure

Cathode Ancillary

Storage Ancillary

Fig. 2. PEM electrolyzer simulink diagram.

where Va (m3 ) is the anode volume, and the total anode


pressure, Pa , is
Pa = pO2 + pH2 Oa .

(3)
F =

Oxygen mole fraction at the anode outlet is as follows:


yO2 =

pO2
,
Pa

(4)

and the ows are computed as


Fao = FO2 ao + FH2 Oao ,
FO2 ao = yO2 Fao ,
FH2 Oao = (1 yO2 )Fao ,

(8)

where iLoss is internal current and hydrogen loss that could


be result of oxygen travel from anode to cathode or hydrogen
travel from cathode to anode in general iLoss is less than
1% of the operating current density.

(5)

Cathode is the electrode where the reduction takes place


in electrolyzers by denition. The states of the cathode side
of the electrolyzer are hydrogen and water molar hold-ups,
NH2 and NH2 Oc , respectively,

(6)

N H2 = FH2 ci FH2 co + H2g ,


N H2 Oc = FH2 Oci FH2 Oco + FH2 Oeod + FH2 Od ,

where kco is the cathode outlet ow coefcient. Finally, the


rate of oxygen generated is
nI
 ,
O2g =
4F F

i iLoss
,
i

2.2. Cathode ancillary

where the anode total out-ow, Fco , is obtained by


Fao = kao (Pa Pa0 ),

where n is the number of the electrolyzer cells, I is the


electrolyzer current, F is the Faraday constant and F is
Faraday efciency which is given as [6,7],

(7)

(9)

where FH2 ci and FH2 Oci (mol/s) are cathode electrode hydrogen and water inlet molar ows and they are equal to
zero since there is no in ows. FH2 co are FH2 Oco (mol/s)

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H. Grgn / International Journal of Hydrogen Energy 31 (2006) 29 38

are cathode outlet molar ows of hydrogen and water, respectively, FH2 Oeod (mol/s) and FH2 Od (mol/s) are
electro-osmotic drag and diffusion from anode electrode
through the membrane, and H2g is the rate of hydrogen
generated.
The partial pressures of hydrogen and water in the cathode
are obtained from the ideal gas law as in the anode,
pH2 Oc =

NH2 Oc RT el
Vc

and

pH2 =

NH2 RT el
,
Vc

where kco is ow coefcient and P0 is the cathode out


pressure. The rate of hydrogen reacted is calculated as
H2g =

Membrane ancillary is of importance to understand the


water transport phenomena in electrolyzers. There are two
main water ows occurring through the membrane: Electroosmatic drag and diffusion. Both of them are function of the
water content of the membrane.
When the H + protons moves through the membrane, water molecules accompany them. This phenomenon is wellknown as electro-osmotic drag and this water transportation
is expressed by

(10)

(11)

Similar to the anode, hydrogen and water molar ows at the


cathode are computed from cathode out total ow and mole
fractions.
yH2 =

pH2
Pc

(15)

2.3. Membrane ancillary

where Vc (m3 ) is the cathode volume, and the total cathode


pressure is
Pc = pH2 + pH2 Oc .

nI
 .
2F F

FH2 Oeod = nd

i
MH2 O An,
F

(16)

where MH2 O is molecular weight of water, A is the area of


the cell and nd is the electro-osmotic drag coefcient which
is given as

(12)

and the ows are

nd = 0.00292m + 0.05m 3.4 1019 ,

Fco = FH2 co + FH2 Oco ,


FH2 co = yH2 Fco ,
FH2 Oco = (1 yH2 )Fco ,

(17)

where m is the arithmetic mean of both s for the anode


and the cathode which are calculated by their own water
activities by (18). Membrane water content,  is given as
in [8]

(13)

where the cathode subsystem out-ow, Fco , is


Fco = kco (Pc P0 ),

 = 0.43 + 17.81aa 39.85aa2 + 36aa3 ,


 = 14 + 1.4(aa 1), 1 < aa  3.

(14)

10
9
8

Volt (Volts)

7
6
5
4
3
2
1
0
0

200

400

600

800

i (mA/cm2)
Fig. 3. Electrolyzer polarization.

1000

1200

1400

0 < aa  1,
(18)

H. Grgn / International Journal of Hydrogen Energy 31 (2006) 29 38

The water diffusion coefcient is computed as





1
1

Dw = D exp 2416
,
303 Tf c

(19)

 < 2;

D = 1010 (1 + 2(m 2)),

2  m  3;

D = 1010 (3 1.67(m 3)),


D = 1.25 1010 , m  4.5.

0.8

Efficiency

where
D = 1010 ,

0.6

0.4

3  m  4.5;
(20)

Water diffusion through the membrane is given from Ficks


rst law of diffusion as follows:
(Cwc Cwa )
FH2 Od = Dw
MH2 O An,
tm

0.2

0
0

500

m,dry
Mm,dry

a ,

Cwc =

m,dry
Mm,dry

c .

(21)

(22)

2.4. Voltage ancillary

(23)

where E is open circuit voltage, Vact is activation polarization, Vohm is ohmic polarization. Open circuit voltage, E, is
dened as Nernst Equation [9]

1/2
RT el pH2 pO2
ln
E = E0 +
,
(24)
2F
aH2 O
where E0 is the standard potential, R is the universal gas
constant, Tel is the cell temperature and aH2 O is water activity between anode and electrolyte for simplicity it is assumed here to be 1. Standard voltage E0 is
Gf
E0 =
,
2F

(25)

where Gf is Gibbs free energy of formation. The activation polarization is obtained by
 
i
RT el
ln
Vact =
,
(26)
2F
i0

1500

Fig. 4. Electrolyzer efciency.

where  is charge transfer coefcient, i is the current density


and i0 is the exchange current density.
The ohmic polarization is calculated by
Vohm = iRohm ,

Electrolyzers operates in either current mode or voltage


mode. When they are run in voltage mode, voltage is applied
to the electrolyzer and depending on the operating conditions
the electrolyzer draws the current from the source and after
a couple of transient cycles it has its steady state value. This
mode is suitable for when photovoltaic source is used for an
electrolyzer. However, most of the commercially available
electrolyzers run in current mode and operating voltage of
an electrolyzer is given as
Vel = E + Vact + Vohm ,

1000
i (mA /cm2)

where tm is the thickness of the membrane and Cwc and Cwa


are water concentration for the cathode and anode surface
of the membrane, respectively, and they are expressed as
Cwa =

33

(27)

where the membrane resistance, Rohm , is


Rohm =

tm
,
m

(28)

where m is the conductivity of the membrane which is


calculated from water content of the membrane, m , and the
electrolyzer temperature, Tel , as follows [10]:



1
1

.
m = (0.00514m 0.00326) exp 1268
303 Tel
(29)

2.5. Storage ancillary


Produced H2 by electrolyzer is stored in H2 bottle. Constant H2 ow lls up the bottle until its pressure reaches
up the electrolyzer cathode pressure. The dynamics of the
storage is obtained as follows:
P = z NH2 RT b ,

Pb
bi
MH2 Vb

(30)

where Pbi is the initial H2 pressure in the bottle, z is the


compressibility factor of the hydrogen. The compressibility
factor is a function of temperature and pressure, it is equal
to 1 when the pressure is below 2000 psi at room temperature but it is higher than 1 when the pressure is above

34

H. Grgn / International Journal of Hydrogen Energy 31 (2006) 29 38

x 10

10

Bottle Pressure (Pascal)

200

400

600

800

1000

time (secs)
Fig. 5. Bottle pressure.

Current(A)
100

I (Amper)

80
60
40
20

Hydrogen Flow (mole/secs)

1.5

x 10

100

200

300

400

500
time (secs)

600

700

800

900

1000

600

700

800

900

1000

Hydrogen Flow

0.5

100

200

300

400

500
time(secs)

Fig. 6. Electrolyzer current transients.

H. Grgn / International Journal of Hydrogen Energy 31 (2006) 29 38

35

R
O2g
1
Current

pO2

n*u[1]/(4*F)

1
s

4
faref

NO2

1
pO2
Pa
+
+

yo2

6
Water in

1
s

pH2Oa

5
FH2Om
3
Tel

Fia

Psata
Fao
2
Peleo

0.95

FO2a0

FH2Oa0

Fig. 7. PEM electrolyzer anode ancillary simulink diagram.

1/Vc
u[2]*u[1]

H2g

pH2

n*u[1]/(2*F)

1
Current

1
s

NH2

1
ph2

4
faref

Pc

+
+

1
s

(u[1]/u[2])

FH2Om

NH2Oc

yh2

pH2Oc

f(u)

2
Fic

P satc

Tel

Fco
2
P elec

0.45
3
FH2
x

Fig. 8. PEM electrolyzer cathode ancillary simulink diagram.

FH2Co

FH2Oco

36

H. Grgn / International Journal of Hydrogen Energy 31 (2006) 29 38


1
FH20eod

(u[1]*u[2])F

u[1]*MH2O*A*n

1
FH20m

0029*u[1] 2+0.05*u[1]-3.4e-19

lamm

lamm

am

Diamm

nd

+
+

FH2Om

Dlam

2
lamm

u[1]*expt(2416*((1/303)-(1/u[2])))

DW

4
Tst

am

2
Fia

u[1]*(u[2]-u[3])tm

FH2Od

Gain

3
Fic
CVC
aca lamc

larnc
CVa
u[1]*romd/Mmd

aen lama

lama
u[1]*romd/Mmd

Fig. 9. PEM electrolyzer membrane ancillary simulink diagram.

2000 psi [11]: At higher pressure values it affects the bottle


pressure dynamics remarkably. Tb and Vb are the bottle
temperature and volume, respectively. It is assumed that the
bottle temperature is constant through the storing process
since the process is slow.

down from 50 to 10 A, and again it is increased to 70 A


at t = 300 s. These gures exhibit that the model can capture the transient dynamic behavior of the PEM electrolyzer
(Figs. 711).

4. Conclusion
3. Simulation results
This section presents simulation results for a PEM electrolyzer. For the simulations we implement the model derived in Section 2 in Matlab-Simulink. Simulation studies
are pursued assuming PEM electrolyzer stack consists of
n=3 cells, with Am =50 cm2 active area each, and with tm =
0.0051 cm thickness. Electrolyzer operating temperature and
pressure are chosen as T =300 K and P =101325 Pa. Figs. 3
and 4 shows polarization and efciency of the stack, respectively. Fig. 5 illustrates hydrogen bottle pressure changes.
The bottle pressure can be set one value so that when it
is reached, current ow is stopped. In Fig. 6, current transients are introduced and responding hydrogen partial pressure are presented. At t = 300 s operating current is stepped
up from 20 to 50 A, and at t = 500 s the current is stepped

A dynamic PEM electrolyzer model has been developed


by exploiting conservation of mole balance. Special attention has been given to the modelling of subsystems to clearly
quantify the dynamic interactions of a PEM electrolyzer. The
integrated model is implemented by using Matlab-Simulink.
Simulation studies demonstrated that the model can capture
the transient dynamic behavior of the PEM electrolyzer. This
model is essential for determining control strategy that will
ensure efcient and reliable operation of the electrolyzer.
Furthermore, the PEM electrolyzer dynamic model can be
integrated with renewable energy systems models to design, analyze and optimize sustainable energy systems. The
extension of this study will be to fully validate the model
with PEM electrolyzers in Connecticut Global Fuel Cell
Center.

H. Grgn / International Journal of Hydrogen Energy 31 (2006) 29 38

pH2

0.00001

37

pH2
pO2

0.00001

1
pO2

Stack Tem p

Tfc
OCV

+
+

1
Vel

number of stack2
+

Vohm
Tfc
lam dam

5
lamdam

Rmohm

Rmohm

Vohm

1.482

io

10
Limiting Current1

Elf

Va2

Tfc
+

v32

0.3

Fig. 10. PEM electrolyzer voltage ancillary simulink diagram.

R
Ideal Gas Constant

300
Room Temp

H2 Flow

pb

-cCompresibility Factor
-c-

-c

Bottle intial pressure

Bottle Volume
MH2

H2 Molecular Mass

Fig. 11. PEM electrolyzer storage ancillary simulink diagram.

Acknowledgements
The author would like to acknowledge Dr. Frano Barbir
and Mr. Trent Molter of Connecticut Global Fuel Cell Center
for very useful discussions and suggestions that contributed
this paper.
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