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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
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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
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
(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)
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
(3)
F =
pO2
,
Pa
(4)
(8)
(5)
(6)
i iLoss
,
i
(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)
32
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
(10)
(11)
pH2
Pc
(15)
nI
.
2F F
FH2 Oeod = nd
i
MH2 O An,
F
(16)
(12)
(17)
(13)
(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)
Dw = D exp 2416
,
303 Tf c
(19)
< 2;
2 m 3;
0.8
Efficiency
where
D = 1010 ,
0.6
0.4
3 m 4.5;
(20)
0.2
0
0
500
m,dry
Mm,dry
a ,
Cwc =
m,dry
Mm,dry
c .
(21)
(22)
(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
1000
i (mA /cm2)
33
(27)
tm
,
m
(28)
.
m = (0.00514m 0.00326) exp 1268
303 Tel
(29)
(30)
34
x 10
10
200
400
600
800
1000
time (secs)
Fig. 5. Bottle pressure.
Current(A)
100
I (Amper)
80
60
40
20
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)
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
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
FH2Co
FH2Oco
36
(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
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
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
R
Ideal Gas Constant
300
Room Temp
H2 Flow
pb
-cCompresibility Factor
-c-
-c
Bottle Volume
MH2
H2 Molecular Mass
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.
References
[1] Onda K, Murakami T, Hikosaka T, Kobayashi M, Notu R,
Ito K. Performance analysis of polymerelectrolyte water
38