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i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 9 5 6 e7 9 6 2

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Alkaline electrolysers: Model and real data analysis

Paola Artuso a,*, Rupert Gammon b, Fabio Orecchini c, Simon J. Watson d


a
Sapienza University of Rome, CIRPS, Interuniversity Research Centre for Sustainable Development, Piazza S. Pietro in Vincoli,
10, 00184 Rome, Italy
b
Bryte Energy Ltd., Loughborough Innovation Centre, Epinal way, Loughborough, Leicestershire LE11 3EH, United Kingdom
c
Universita` degli Studi Guglielmo Marconi, Via Plinio, 44, 00193 Roma, 00184 Rome, Italy
d
Loughborough University, Centre for Renewable Energy Systems Technology, Department of Electronic and Electrical Engineering,
Loughborough, Leicestershire LE11 3TU, United Kingdom

article info abstract

Article history: This paper presents an analysis of the data collected during a test of the 36 kW alkaline
Received 24 May 2010 electrolyser at West Bacon Farm (WBF), Loughborough, UK. This data is then used to verify
Received in revised form a software model of an electrolyser. The test consisted of collecting data under different
17 December 2010 operating conditions, in particular controlling the power supplied to the electrolyser.
Accepted 18 January 2011 The experiment was divided in four phases. In the first two phases, the electrolyser was
Available online 8 April 2011 operated at full power, in the third phase it was operated at 60% of maximum power and in
the forth it was operated at 20% of maximum power, which is the minimum permitted
Keywords: level. Each phase lasted approximately an hour.
Alkaline electrolyser During phase 1, the initial warm up period, the voltage remained almost constant, while
Simulation programme the current increased to a maximum of 428 A. After about an hour, the current suddenly
Experimental data dropped to 310 A, the voltage decreased from 92 V to 88 V and hydrogen production
Electrolyser model decreased from 7.3 Nm3/h to 6.6 Nm3/h, even though no change had been made to the
control parameters, which were still set to maximum power input. The temperature
continued upwards with only a slight reduction in its rate of increase and the pressure
stopped rising, remaining at 22 bar(g). This point marks the transition from phase 1 to
phase 2 and the reasons for the sudden discontinuity are investigated in this study.
Once the optimum operating temperature was reached, during phase 2, it was main-
tained within a limited range by the cooling system. The initial stack temperature, at the
beginning of phase 1, had been 17  C. The net power draw increased until the stack
temperature reached its maximum at 76  C after about 1 h 20 min.
Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction [4,5]. Electrodes are therefore located within an ion-conduct-


ing electrolyte (usually an aqueous alkaline solution of 30%
Renewable technologies, such as wind turbines and photo- potassium hydroxide KOH) and gaseous hydrogen is produced
voltaic arrays, can generate electricity, which might be used to at the negative electrode (cathode) while oxygen is produced
produce hydrogen via electrolysis with no resulting green- at the positive electrode (anode). The necessary exchange of
house gas emissions [1e3]. In an electrolyser, water is split charge occurs through the flow of OHe ions in the electrolyte
into hydrogen and oxygen by the input of electrical energy and current (electrons) in the electric circuit. In order to

* Corresponding author. Tel.: 39 06 44585400; fax: 39 06 44585779.


E-mail address: paola.artuso@uniroma1.it (P. Artuso).
0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.01.094
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prevent a mixing of the product gases, the two reaction areas The experiment was divided in three phases, in corre-
are separated by a gas-tight, ion-conducting membrane. This spondence of three different levels of the supplied power: in
type of system can produce high purity hydrogen that is the first phase the power was set to the maximum level, in the
suitable for use in fuel cells (FCs) in a range of stationary, second phase a 60% maximum power was considered, during
portable or vehicular applications. the last phase 20% maximum power was supplied, taking into
account it is the minimum switching on power of the
electrolyser.
2. Validation of the electrolyser model. HARI The first phase lasted 2 h, while the other two phases kept
project about 1 h each. The whole collected data is plotted in the Fig. 1,
where the several quantities featuring the electrolyser are
This work focused on the analysis of the data acquired from reported as a function of the time from 11.00 oclock in the
the electrolyser located in the West Bacon Farm (WBF), which morning to 3.00 pm.
is part of the demonstration project carried out in Lough- During the start up, while the voltage was almost constant,
borough, in United Kingdom. The project is called HARI. The the current increased until a maximum value of 428 A,
researchers working on this project developed the system reached after 1 h 20 min. After that, even if the control system
integration of several environmental friendly innovative was not modified and it was set to the maximum value, the
technologies to supply the energy required by the WBF [6,7]. In current suddenly dropped down to 310 A. In this instant, the
particular, the activity described in this paper dealt with the voltage decreased from 92 V to 88 V, hydrogen production
electrolyser and with the analysis of the possibility to apply decreased from 7.3 Nm3/h to 6.6 Nm3/h, the temperature
a model already available in literature [8,9]. During the test, curve had a modification of the slope, the pressure reached
real data was collected from the operating 36 kW alkaline the maximum equals to 22 bar(g). After 1 h 20 min a disconti-
electrolyser. The electrolyser worked in different operating nuity was noticed and in correspondence of that point, at the
conditions and the power was varied in three steps. same time, the electricity, the voltage and the hydrogen yield
The data acquired were: dropped down, the temperature slope curve varied, the pres-
sure draw reached a maximum and after that it was stabilized
 Current in Amperes at 22 bar(g). Because of this discontinuity, the analysis of the
 Voltage in Volts 100% power phase has been split into two parts.
 Pressure in bar(g) To process the data analysis, data from the electrolysers
 Temperature in degrees Celsius internal data acquisition (DAQ) system had to be synchro-
 Hydrogen produced in normal cubic metres. nized with that of the sites own DAQ system, which was

Fig. 1 e The data plots divided by four phases.


7958 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 9 5 6 e7 9 6 2

operating at a different sample rate. Once synchronised, the inside the electrolyser which switches on at a certain time.
acquired data allowed analysis of the operating conditions of The problem was to individualize what kind of control system
the electrolyser, both during the initial warm up period and switched on and why, because it was designed directly by the
during steady-state conditions at power inputs of 100%, 60% electrolyser manufacturers. Analyzing the plots in the Fig. 1,
and 20% of the maximum power. Analyzing the plots, the control system seemed to be activated by the pressure
summarized in the Fig. 1, four phases are finally individual- level. In fact, in the phase 1 the pressure increased to reach
ized, each of which had a duration of about 1 h: a certain point. After that, during the phase 2, the pressure
was constant, therefore the control system works in order to
- Phase 1: the warm up, providing 100% of the power usable by stabilize the pressure, once it joined the maximum plate
the electrolyser; value. The pressure control insured safe working conditions.
- Phase 2: the provided power was set to maximum, but the In addition, the constant pressure is suitable for conventional
electrolyser was working in steady-state conditions; electrolyser applications in industrial sector. In this kind of
- Phase 3: the input power was decreased to a value 60% of the applications an important target is to maintain a constant
maximum electrolyser working power; hydrogen flow, and it can be obtained by means of a uniform
- Phase 4: the power was supplied at 20% of the maximum pressure difference between the electrolyser and the ambient
electrolyser working power, which is the minimum oper- where the hydrogen is used.
ating level.
2.3. Phase 3
All this phases will be further discussed in detail in the
following paragraphs. For each phase, with the intent to During this phase, the current and power draws were very
eliminate some noise, the data had been averaged in the range smooth and the pressure reached the new working value,
of 1 min. equals to 18 bar(g), after about half an hour.
Excluding the warm up, in the phases 2, 3, 4 the working The hydrogen production decreased during the transition
conditions were quite stable and the averaged quantities of phase, reaching the value equals to 19.6 bar(g) when the
current, pressure, temperature, voltage, hydrogen production pressure was stabilized. Decreasing the energy provided to the
could be considered as characteristic of each phase, as electrolyser, a contemporary temperature reduction had been
reported in Table 1. recorded, because of the correspondent abatement of the heat
production inside the electrolyser. With regard to the
2.1. Phase 1 temperature, it had a wave shape between the values 67.7  C
and 73.7  C, excluding the transition phase from the 100%e
During the warm up, all the quantities increased constantly. 60% feeding power.
The hydrogen production was characterized by a disconti-
nuity after about 10 min, due to the fact the compressor 2.4. Phase 4
started to work when the pressure reached 19 bar(g). During
the warm up, the pump switched on after 7 min. Decreasing the feeding power, the attention focused on the
minimum working power required by the electrolyser. Looking
2.2. Phase 2 to the global graph reported in Fig. 1, there was a 10 min break
during which the electrolyser was switched off. It was not
After 1 h 20 min, without modifying any control system provoked by purpose, but it gave the opportunity to make some
quantity, the electrolyser changed suddenly the working considerations, with particular attention to the temperature
conditions. Albeit the data reported in Fig. 1 were averaged in which decreased from 75.6  C to 67.6  C, that means the heat
the range of 1 min, the current draw was still variable and it was quickly dispelled. By the analysis of this fact, the conclu-
had a shape pretty different from the other phases plots. sion was that if the electrolyser has to work in variable condi-
The reason of this unstable input current has been analyzed, tions, characterized by frequent switch on/off cycles, the stack
in accordance with the other quantities and considering the should be insulated to reduce the heat exchange between the
several components of the electrolyser. The attention focused stack and the ambient in order to maintain high temperature as
on the sudden variation in the electrolyser working conditions. long as possible. In variable working conditions, the system
The rising questions was why the electrolyser suddenly insulation could be a crucial aspect to be further analyzed in
changed the working conditions and all the plots had particular if Cool-Heat-Power (CHP) generating systems will be
a discontinuity in the same instant. designed in order to optimize the efficiency.
Considering that all the quantities varied in one instant, During the phase 3, the current was variable, but in
the conclusion was that there should be a control system a limited range between 102 A and 117 A. The wave shape of

Table 1 e The operating current, pressure, temperature, voltage and hydrogen production in each phase.
Phase Current (A) Pressure (bar) Temperature ( C) Voltage (V) H2 production (Nm3/h)

2 335.7 22.0 71 89 6.56


3 258.9 19.6 70 86 5.37
4 108.8 16.8 64 80 2.35
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the pressure plot was due to the compressor which switches


Table 2 e Comparison between the Julich Electrolyser and
on when the pressure in the buffer was higher than 19 bar(g). the WBF one.
When the compressor was working, the hydrogen pumped
Size Electrolyser Julich Electrolyser BEF
into the tank was more than the quantity produced by the
electrolyser, so that the pressure decreased until the Plate Power 26 kW 36 kW
compressor switched off when the pressure level was lower Plate Pressure 6 bar 25 bar
Cell Number 21 46
than 16 bar(g). With reference to the Fig. 2, how the variation
Cell Area 0.25 m2 0.1 m2
of the hydrogen production was reported. The inversion of the
Temperature 80  C 70  C
pressure draw trend is every 60 3000 , which is the distance
between the points A, B, C, D, E, F, G. Starting from the point A
to the point B, the compressor was working, thus the
the model formula. The best result was found modifying the t1
hydrogen flowed and the pressure decreased until the level
parameter from 1.002 A-1 m2  C to 0.0596 A-1 m2  C.
was so low that the compressor stopped working. From B to C
Once t1 was modified, the calculated voltage draws the
the hydrogen flow was low, because the compressor was not
black plot in the Fig. 3 b. The voltage computed and the real
operating, but the pressure was becoming higher and higher
voltage values are very similar with a maximum relative error
until it reached 18 bar, which is 1 bar less than the plate value.
equals to 2%, excluding the period when the electrolyser was
At the point C the compressor switched on again and the cycle
switched off. To deeper analyze the correspondence between
was repeated other two times.
the model data and the real one, the currentevoltage plot has
been drawn (ref. plot Fig. 4 a). The indicators are respectively:
rhombus for the phase 1, square for the phase 2, triangles for
3. Comparison between the real data and the the phase 3 and circles for the phase 4. The black continues
model line refers to the values of the paper [3], considering the
modified value of the t1 parameter, as it is reported above, and
Considering the available experimental data of the electro- considering a constant temperature of 70  C. The real data is
lyser in WBF, it was not possible to calculate all the parame- very close to the calculated one if the warm up phase is
ters following the procedure described in the paper [3] excluded. About this last, it is also interesting to observe that
reported as in the Eq. (1): the voltage is almost constant during this phase. The reason is
0 1 that the power control system which can control either the
t2 t3
r1 r2 $T t
B 1 T T2 C voltage or the current, in this case it is clearly controlling the
U Urev $I s$log@ $I 1A (1)
A A voltage at the maximum level, because the working condi-
tions were set to the 100% power. During this phase the
In fact, for each power, the electrolyser was characterized current constantly increased until the steady-stable
by a certain temperature, current, pressure and it was not
possible to vary only one of those quantities, but they all
changed contemporary because the control system could
operate only on the voltage. Taken this, it was considered the
possibility to apply the model as it is proposed in the paper.
The differences between the two alkaline electroysers are
summarized in the Table 2.
The input of the model was the current and the tempera-
ture, by means of which the voltage and the hydrogen
production were calculated. In the Fig. 3 the real voltage data
(in grey) and the calculated voltage data (in black) are reported
in order to visualize the difference. The plots shape were quite
similar, although they were translated each other (ref. plot a of
the Fig. 3). For this reason, it was investigated what would had
happen if only one parameter was changed. In other words,
the adopted procedure was to calculate the mean error
between the real voltage and calculated values. After that the
parameter value was computed in order to minimize this
error. All the procedure was processed for each parameter (r1,
r2, s, t1, t2, t3) and then the computed value was substituted in

Fig. 2 e The cycles of the phase 4. Fig. 3 e Comparison U real and U model.
7960 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 9 5 6 e7 9 6 2

conditions were reached. During the second phase, albeit the


current is quickly variable, the working electrolyser points lied
on the characteristic curve. In the course of the third phase,
the values of both the current and of the voltage were slightly
variable and all values were very close to the characteristic
curve, as it happened during the last phase.
To verify the model effectiveness, the second step was to
analyze the hydrogen production using Eq. (2) and Eq.(3):

I=A2
hF f2 (2)
f1 I=A2

nc I
n_ H2 hF (3)
zF

In the second plot of the Fig. 4 b, the real data plot is


reported together with other two, drawn considering two
different conditions:

1.H2 model: the f1 and f2 parameters were considered


constant and equals to the ones in the paper [3];
2.H2 model f2: f1 and f2 were considered dependent on the
current.

Analyzing the graph, the first solution seems not only more
simple, considering constant parameters, but also more
similar to the real data. The differences between the real data
and the first model solution were analyzed, phase by phase.
Starting from the left side of the Fig. 4 b, the real data is
characterized by a discontinuity when the compressor
switched on. In fact, only when the hydrogen production
reached 19 bar(g), the compressor started to work. The model
does not simulate the compressor and this caused noteworthy
errors during the start up and during low power supply level,
in the phase 4 (ref. Fig. 4 c), when the compressor switches on
and off during regular intervals.
During the phase 2, the computed hydrogen production is
more variable than the real quantities, because the model
does not consider the elasticity of the gas (compression-
decompression). In fact the model considers the gas produc-
tion as a function of the supplied electricity. Also other
quantities influenced the hydrogen yield, like the temperature
and the voltage, but they had lower effects. In conclusion, the
actual range of the hydrogen flow was actually smaller than
the range foreseen by the simulation, but this last included the
first one.
During the phase 3, at the beginning there was a transition
period when the real data was higher than the simulated one.
During this stage, which has persevered for about half an
hour, the real data was characterized by a descending trend, Fig. 4 e Comparison graphs between real and model data.
while the simulated data had a constant trend. The real
behaviour was influenced by the working conditions of the
previous phase. When the stationary conditions were
reached, the calculated data was correspondent to the real averaged values of the hydrogen flow (marked by circles in the
one. Fig. 4 c) are very similar to the real ones (marked with rhom-
During the last phase, the real hydrogen yield was depen- buses). Although the moment by moment hydrogen produc-
dent on the compressor working conditions. This provoked tion was not always well foreseen by the model, the integral
a step trend of the real hydrogen flow. The model did not quantity of the produced hydrogen has been calculated in
include what was downstream the electrolyser and for this order to verify if the model values matched the real ones. The
reason the hydrogen production was almost constant, but the integral of the hydrogen yield during the whole experimental
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period has been plotted in the Fig. 4 d. By means of this graph,


the good correspondence between the simulation and the real Nomenclature
data was evident, even though the real hydrogen quantity was
always a bit lower than the calculated one.
If the whole period is taken into account, the relative error A area of electrode, m2
equalled 0.89%, while the maximum absolute error was I power, A
0.51 Nm3. ncells number of electrolyzer cells
In conclusion, the model results matched moment by r parameter related to ohmic resistance of electrolyte,
moment real data when the electrolyser working conditions Wm2
were steady-stable. During the transition periods, the real s coefficient for overvoltage on electrodes, V
data was affected by factors which were not considered by the t coefficient for overvoltage on electrodes, A-1 m
model, as the compressor influence and the dynamic T temperature
hydrogen flow phenomena, but the model can be considered Ta ambient temperature,  C
efficient to evaluate the produced hydrogen quantity in Tr Array reference temperature, 28  C for commercial
a certain time, that is the integral of the hydrogen flow. policristalline PV modules.
Tmodule PV module temperature,  C
G radiance, W/m2
U voltage, V
Urev reversible voltage. For water, it equals to 1,228 V at
4. Conclusions
6 bar and 80  C
r1 8.05E-5 W m2
By the analysis of the real data of the electrolyser located in
r2 2.5E-7 W m2  C1
the WBF, in Loughborough, UK, some insights outcropped.
s 0.185 V
The electrolyser was realized to have an inside pressure
t1 1.002 A1 m2  C
control system designed by the manufacturer, which made
t2 8.424 A1 m2  C
the electrolyser to work at constant pressure after the
preliminary warm up. The electrolyser was designed to be fed t3 247.3 A1 m2  C2
by RES, which are insecure and variable, but still the start up hF Faraday efficiency, which is the ratio between the
required 1 h 20 min and the temperature drastically dropped ideal current necessary to obtain 1 mol of
down when the electrolyser was switched off. Therefore, the a substance (e.g. hydrogen) and the true required
current to produce the same quantity.
design of the electrolyser should be further improved in terms
f1 250 mA cm4
of thermal management and the stack should be properly
f2 0.96
insulated, in particular if the electrolyser is intended to be
n_ H2 molar flow rate
used in a waste heat recovery system which contemporary
F 96485 Cmol1 Faraday constant
produces hydrogen and heat.
z number of electrons transferred per reaction (2 in the
By a comparison between the model and the real data,
analysed case)
a good correspondence was pointed out, but slightly modi-
nc number of electrolyser cells
fying one of the original model parameters. In fact, using the t1
value in paper [3], the real voltage would have been always
lower than the real one, while using the t1 value computed in
this paper, the simulated voltage matches the real quantities.
Despite the moment by moment hydrogen flow was not references
suitably computed by the model, the simulation could care-
fully evaluate the total hydrogen produced during the test
with maximum absolute error of 0.51 Nm3 and the relative [1] Ghosh PC, Emonts B, Janen H, Mergel J, Stolten D. Ten
error equalled 0.89%. years of operational experience with a hydrogen-based
The experiments had to be terminated because the elec- renewable energy supply system. Solar Energy 2003;75:
469e78.
trolyser washers collapsed on the action of the inside stack
[2] Orecchini F, Naso V. La societa` NO OIL. Milan, Italy: Orme
pressure, thus the reliability needs to be further improved in
editori; 2003.
forthcoming products. [3] Orecchini F. The era of energy vectors. International Journal of
Hydrogen Energy November 2006;31(14):1951e4.
[4] Silvestroni P. editor. Fondamenti di Chimica. Milan, Italy:
MASSON; 1997.
[5] Cacciola G, Orecchini F, Vellone Idrogeno R. II sistema
Acknowledgements energetico, le celle a combustibile, gli usi finali. Ecoenergie;
2003. ISES Italia.
[6] Gammon Rupert, Roy Amitava, Barton John, Little Matthew.
The research has been supported by Regione Lazio Assessor-
Hydrogen and renewables integration (HARI). Report of the
ato allAmbiente e alla Cooperazione tra i popoli, in the
project, http://www.ieahia.org/pdfs/HARI.pdf; March 2006.
framework of the Programme Polo IdrogenoLazio [7] Rupert Gammon. The hydrogen and renewables integration
(2006e2009). In addition, the authors wish to tank Tony Mar- (HARI) project. http://www.fuelcellsuk.org/team/library/hari-
mont and his wife, Angela, for funding the HARI project. projectoverview.pdf.
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[8] ystein U. Modelling of advanced alkaline electrolyzers: [9] Zuccari F, Santiangeli A, Artuso P, DellEra A. PV-electrolyzer
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