energies

Article
Dynamic Emulation of a PEM Electrolyzer by
Time Constant Based Exponential Model
Damien Guilbert 1, * and Gianpaolo Vitale 2
1 Group of Research in Electrical Engineering of Nancy (GREEN), Université de Lorraine/IUT de Longwy,
54401 Longwy, France
2 ICAR, Institute for High Performance Computing and Networking, Italian National Research Council of
Italy, 90146 Palermo, Italy; gianpaolo.vitale@icar.cnr.it
* Correspondence: damien.guilbert@univ-lorraine.fr; Tel.: +33-372-749-984




Received: 24 December 2018; Accepted: 20 February 2019; Published: 24 February 2019


Abstract: The main objective of this paper is to develop a dynamic emulator of a proton
exchange membrane (PEM) electrolyzer (EL) through an equivalent electrical model. Experimental
investigations have highlighted the capacitive effect of EL when subjecting to dynamic current
profiles, which so far has not been reported in the literature. Thanks to a thorough experimental
study, the electrical domain of a PEM EL composed of 3 cells has been modeled under dynamic
operating conditions. The dynamic emulator is based on an equivalent electrical scheme that takes
into consideration the dynamic behavior of the EL in cases of sudden variation in the supply current.
The model parameters were identified for a suitable current interval to consider them as constant and
then tested with experimental data. The obtained results through the developed dynamic emulator
have demonstrated its ability to accurately replicate the dynamic behavior of a PEM EL.

Keywords: proton exchange membrane electrolyzer; modeling; dynamic behavior; PEM emulator

1. Introduction
Over the last years, fossil fuel reserves have significantly decreased due to growing demand.
Indeed, fossil fuels are widely used in transportation, industrial and electric power sectors [1].
As a result, intensive use of fossil fuels has had negative impacts and is the main source of air
pollution and the primary emitter of carbon dioxide and others greenhouse gas [2,3]. Given that
the transportation sector is one the most significant emitters of greenhouse gases, new energy
fuel must be developed with the aim to minimize the environmental impact from global warming
and meteorological phenomena. Recently, some automotive manufacturers (e.g., Toyota, Honda,
and Hyundai) have been interested in hydrogen, with an aim to develop fuel cell electric vehicle
prototypes [4,5]. Compared to conventional vehicles that burn fossil fuels, hydrogen combustion only
releases water.
At the present time, hydrogen can be manufactured from diverse resources such as fossil fuels,
nuclear energy and renewable energy sources (wind, photovoltaic). One of the most attractive and
promising solutions for producing hydrogen is water electrolysis based on renewable energy sources.
Indeed, water electrolysis a process that uses electricity to split pure water into hydrogen and oxygen.
This chemical reaction is carried out by means of an electrolyzer (EL) [6].
Different kind of ELs can be differentiated by their electrolyte and charge carrier: alkaline EL,
proton exchange membrane (PEM) EL and solid oxide (SO) EL [7,8]. Currently, Alkaline and PEM
technologies are commercially available, whereas solid oxide technology is still in research and
development. Alkaline technology is the most mature and widespread compared to PEM technology
(still under development). On one hand, this technology has a longer lifetime and lower global cost

Energies 2019, 12, 750; doi:10.3390/en12040750 www.mdpi.com/journal/energies

Energies 2019, 12, 750 2 of 17

than PEM ELs. On the other hand, it suffers from having low current density and operating pressure,
consequently affecting system volume and hydrogen production costs [7]. In comparison, PEM ELs
have several benefits over alkaline ELs, such as high power density and cell efficiency, fast system
dynamics, wide partial load range, and high adaptability in terms of operation [7]. However, PEM
ELs present several disadvantages in regards to platinum catalysts costs and lifetime. Due to their
benefits over alkaline ELs, PEM ELs are an attractive option for integration into power grids, including
renewable power generating systems [9,10]. For this reason, a PEM EL has been considered for carrying
on this work.
The availability of a model to reproduce the behavior of a real system is crucial to study, as well
as to verify how it can be incorporated with its power electronic circuit. As a matter of fact, an EL must
be connected to a power converter to be properly supplied, and an equivalent model allows the whole
system to be simulated and tested, avoiding the expensive damaging of the PEM EL. The same need
occurs with fuel cell systems. The detailed dynamic behavior in which a transient of several seconds is
noticeable in the current density is described in [11], where the dynamic response of current density is
given by a three-dimensional transient model assessed in [12]. In [13], an electrical circuit to represent
the dynamic behavior (employed both for battery and fuel cell) is proposed; this circuit is similar to
the one proposed in our paper, but it considers only one time constant. These papers have confirmed
their hypotheses, while the present paper aims at obtaining an equivalent circuit of the PEM EL to
emulate during hydrogen production. This approach is similar to the one described in [14] that has
been carried out for a proton exchange membrane fuel cell (PEMFC); here the model is derived in a
suitable current interval to consider its parameters as constants.
Only recently, several PEM EL models have been reported in the literature [15–29]. However,
the major part of the proposed models is static and does not take into consideration the dynamic
behavior of the EL, which is particularly interesting to investigate for power electronics applications.
In [22], Yigit and Selamet have proposed a dynamic mathematical model developed in a Matlab
Simulink environment.
In [24], Atlam and Kolhe have developed an equivalent electrical model for a PEM EL under
steady-state conditions. The static behavior of the EL is modeled by a reversible voltage in series
with a resistance related to the different overvoltages (activation, ohmic) during the operation.
In [25], Andonov and Antonov have proposed a Simulink implementation of a static model of an EL.
By comparison, a dynamic model obtained by using neural networks is reported in [26]; however, this
model cannot be exploited by a circuital simulator.
Based on the current state-of-the-art research [15–29], this paper analyzes the dynamic behavior
of a PEM EL subjected to fast current steps. The main objective here is to develop an equivalent
dynamic electrical model. Besides, the novelty of the current paper consists both of a method for the
identification of a dynamic circuit equivalent model that considers the contribution of double layer
capacitances, and on the design of an emulator intended as a system able to duplicate the operation of
equipment using different hardware, unlike computer simulations that require an abstract model of the
system to be simulated. On the basis of experimental tests performed on the investigated EL, two-time
constants corresponding to different exponentials were identified by a least squares regression (LSR)
algorithm. In the developed emulator, the input voltage and current have behaved as in the real
PEM EL. In addition, the equivalent circuit has reproduced losses and has allowed the upper limit of
hydrogen production to be assessed. Finally, the developed emulator is useful to test the performance
of power electronics converters in supplying the EL.
This paper is divided into five sections. After this introduction providing the current
state-of-the-art research and motivations for carrying out this work, Section 2 describes the proposed
and developed equivalent dynamic electrical model for a PEM EL. Then, in Section 3, the developed
experimental test bench is presented and the dynamic behavior of the PEM EL is emphasized.
Subsequently, in Section 4, the parameters of the electrical model are determined using a LSR algorithm.
Finally, in Section 5, the obtained results from the electrical model and experiments are compared
Energies 2019, 12, 750 3 of 17

in order to validate the proposed model. Losses, energy efficiency, and hydrogen production are
also investigated.

2. Dynamic Circuit Identification

The study
Energies isx focused
2018, 11, on a PEM EL. Currently, hydrogen can be obtained by three3 of
FOR PEER REVIEW different
18
solutions: alkaline, SO and PEM electrolysis cells. Among these, the last is based on a solid polymer
2. Dynamic
electrolyte Circuit
concept. several advantages such as high current density, which exceeds 2 A/cm2 ,
Identification
It offers
and the reduction
The studyofisoperational
focused on cost
a PEMandEL.
ohmic losseshydrogen
Currently, since it requires an electrolyte
can be obtained thinner
by three than the
different
alkaline EL. Moreover,
solutions: alkaline, SO the PEM
and PEMEL is able tocells.
electrolysis operate
Amongwith a wide
these, range
the last of power
is based input,
on a solid thanks to
polymer
electrolyte
the fast response concept.
of theItproton
offers several advantages
transport acrosssuch as high current
the membrane. density,
This which exceeds
last aspect 2 A/cm
is crucial when 2,
the
power andis the reduction
supplied by of operational
renewable cost and
energy ohmic losses
sources. since
Finally, theitPEM
requires
EL an electrolyte
performs an thinner than
electrochemical
the alkaline
compression, EL. Moreover,
delivering the PEM
hydrogen EL is able
at high to operate
pressure, with
which a wideits
makes range of power
storage input,
easier [7]. thanks to
the fast response of the proton transport across the membrane. This last aspect is crucial when the
The total chemical reaction to obtain hydrogen, including the Gibbs energy (237 kJ.mol−1 ) and
power is supplied by renewable energy sources. Finally, the PEM EL performs an electrochemical
the lost energy (48.6 kJ.mol−1 ), is taken by [7]:
compression, delivering hydrogen at high pressure, which makes its storage easier [7].
The total chemical reaction to obtain hydrogen, including the Gibbs energy1 (237 kJ.mol ) and
−1

H2 O
the lost energy (48.6 + 237.2
kJ.mol−1 ), iskJ/mol
taken by [7]:) + 48.6 kJ/mol(heat) → H2 + O2
( Gibbs (1)
2
1
2 O +PEM
The operation ofHthe 237.2EL
kJ / is ( Gibbs ) + 48
molshown in.6Figure
kJ / mol1. It) →
( heat 2 + noticed
canH be O2 (1)connected
that in the anode,
2
to a positive electric potential, the water is divided into protons and oxygen, providing electrons for
The operation of the PEM EL is shown in Figure 1. It can be noticed that in the anode, connected
the conduction according to the sub-reaction:
to a positive electric potential, the water is divided into protons and oxygen, providing electrons for
the conduction according to the sub-reaction: 1
H2 O → 2H + + O2 + 2e− (2)
1
H 2 O → 2 H + + O2 + 22e − (2)
2
The available electrons go outside the anode and contribute to the current (flowing into the anode),
The available electrons go outside the anode and contribute to the current (flowing into the
whereas the protons go through the membrane. Once the protons reach the cathode, they combine
anode), whereas the protons go through the membrane. Once the protons reach the cathode, they
with electrons coming from the terminal at negative potential, obtaining hydrogen:
combine with electrons coming from the terminal at negative potential, obtaining hydrogen:
2 H + 2H
+ 2e+− + H 2− → H2
→ 2e (3) (3)

FigureFigure 1. Proton
1. Proton exchangemembrane
exchange membrane (PEM)
(PEM) water
waterelectrolysis
electrolysisreactions. In theInanode,
reactions. the water
the anode, theiswater
divided into protons and oxygen providing electrons; in the cathode, the protons
is divided into protons and oxygen providing electrons; in the cathode, the protons combine combine with with
electrons coming from the terminal at negative potential, obtaining hydrogen.
electrons coming from the terminal at negative potential, obtaining hydrogen.
The power supplied to the PEM EL cannot be completely converted into high-pressure
hydrogen (the PEM EL is able to produce 1 l/h of hydrogen with a pressure of 10 bar) due to the
losses. Both the hydrogen production and the losses can be represented by a physical model
reproducing the related phenomenon. A resistor is used to emulate losses in the membrane and
losses in the two sub-reactions, as well as a voltage generator to produce the hydrogen. In addition,
Energies 2019, 12, 750 4 of 17

The power supplied to the PEM EL cannot be completely converted into high-pressure hydrogen
(the PEM EL is able to produce 1 l/h of hydrogen with a pressure of 10 bar) due to the losses. Both the
hydrogen production and the losses can be represented by a physical model reproducing the related
Energies 2018, 11, x FOR PEER REVIEW 4 of 18
phenomenon. A resistor is used to emulate losses in the membrane and losses in the two sub-reactions,
as well as a voltage generator to produce the hydrogen. In addition, the double layer of charge
the double layer of charge separation in the anode and in the cathode is obtained by two
separation in the anode and in the cathode is obtained by two capacitances. In this way, the dynamic
capacitances. In this way, the dynamic behavior caused by the finite time required by charge layers
behavior caused by the finite time required by charge layers to vary when a current variation is
to vary when a current variation is imposed is reproduced. The two double-layer capacitances can be
imposed
considered is reproduced.
equal following The two thedouble-layer
approach of capacitances
[14] applied can be
to considered
a PEMFC equal and following
validated the by
approach of [14] applied to a PEMFC and validated by measurements.
measurements. The different speed with which the two sub-reactions (1) and (2) occur The different speed with which
with be
the two sub-reactions (1) and
modelled by different time constants. (2) occur with be modelled by different time constants.
The
The equivalent
equivalentcircuit
circuitmodel
modeltotobebeidentified
identifiedis is
shown
shown in in
Figure
Figure2. The
2. ThetwotwoRCRC cellscells
represent the
represent
behavior in the cathode
the behavior in the cathode (R C
1 (R ) and in the anode
1 1C1) and in the anode (R C
2 (R ) respectively. The
2 2C2) respectively. The V voltage reproduces
int Vint voltage reproduces the
power converted into hydrogen, whereas the resistance
the power converted into hydrogen, whereas the resistance Rint reproduces R int reproduces the losses thein the membrane.
losses in the
Contrary
membrane. to the two capacitances
Contrary to the twothat can be assumed
capacitances that can equal,be the resistors
assumed differthe
equal, depending
resistors on the
differ
losses; one resistor models Gibbs energy and the heat loss in the anode,
depending on the losses; one resistor models Gibbs energy and the heat loss in the anode, and theand the other only the heat
loss
otherinonly
the cathode.
the heat loss in the cathode.
When
When aa current
currentisissupplied
suppliedtoto thethe
EL,EL, losses
losses during
during steadysteady
statestate
can be can be calculated
calculated as Jouleasterms,
Joule
terms, whereas the power converted into hydrogen is the product of
whereas the power converted into hydrogen is the product of the current by the Vint voltage. the current by the V voltage.
int When a
When a current transient occurs during a time interval after the variation, the
current transient occurs during a time interval after the variation, the voltage both in the anode voltage both in the anode
and
and cathode will not vary, and a slight variation will be observed in the voltage
cathode will not vary, and a slight variation will be observed in the voltage at the EL terminals. The at the EL terminals.
The voltage
voltage will will
thenthen
riserise
up up to the
to the final
final value
value after
after that
that aa newvalue
new valueofofthe
thestored
storedcharge
charge is is restored,
restored,
depending on the value of the double-layer
depending on the value of the double-layer capacitances. capacitances.

Figure 2. Equivalent electric scheme of the PEM electrolyzer (EL).

3. Experimental Test
3. Experimental Test Bench
Bench and
and Investigation
Investigation of
of the
the Dynamic
Dynamic Behavior
Behavior

3.1. Description of the Experimental Set-Up

3.1. Description of the Experimental Set-Up
Once the physical model has been assessed, there is need to acquire experimental data to
Once the physical model has been assessed, there is need to acquire experimental data to
identify the parameters R1 , R2 , Rint , C1 , C2 and V int . This was done using a suitable test bench.
identify the parameters R1, R2, Rint, C1, C2 and Vint. This was done using a suitable test bench. The
The developed experimental set-up to analyze the dynamic behavior of the PEM EL and to validate the
developed experimental set-up to analyze the dynamic behavior of the PEM EL and to validate the
equivalent dynamic electrical model is shown in Figure 3. It is composed of a DC power supply, a PEM
equivalent dynamic electrical model is shown in Figure 3. It is composed of a DC power supply, a
EL, low-pressure metal hydride storage hydrogen tanks and a PC to control the DC power supply.
PEM EL, low-pressure metal hydride storage hydrogen tanks and a PC to control the DC power
Pure water was supplied to the PEM EL by a pure water tank from (SGWATER, Berlin, Germany).
supply. Pure water was supplied to the PEM EL by a pure water tank from (SGWATER, Berlin,
Germany). The water flow rate was controlled by a liquid mass flow controller from
(HELIOCENTRIS, Berlin, Germany). The range included was between 0 and 7.5 liters per minute.
The water flow rate was controlled automatically according to the operation of the EL.
Energies 2019, 12, 750 5 of 17

The water flow rate was controlled by a liquid mass flow controller from (HELIOCENTRIS, Berlin,
Germany). The range included was between 0 and 7.5 L per minute. The water flow rate was controlled
automatically according to the operation of the EL.
Energies 2018, 11, x FOR PEER REVIEW 5 of 18

Figure 3.3.Developed
Developed experimental
experimental set with
set up up with theEL:
the PEM PEM EL:power
(1) DC (1) DC power
supply, (2) supply, (2) digital
digital oscilloscope,
oscilloscope,
(3) (3) current
current clamp, (4) PEMclamp, (4) PEM
EL stack, EL stack,
(5) digital (5) digital
multimeter, multimeter,
(6) dSPACE (6) (7)
board, dSPACE board,
pressurized (7)
pure
pressurized
water tank. pure water tank.

The PEM EL under investigation is the NMH2 1000 from HELIOCENTRIS HELIOCENTRIS (HELIOCENTRIS,
Berlin, Germany). Although
Although the
the HELIOCENTRIS
HELIOCENTRIS NMH2 NMH2 10001000 system
system includes several ancillary
devices (e.g.,
(e.g., power
powerconverters),
converters),only
onlythe
thestack (and
stack (andthethe
data acquisition
data system)
acquisition has has
system) beenbeen
usedused
in this
in
research. The main characteristics of the PEM EL are provided in Table 1, while the components
this research. The main characteristics of the PEM EL are provided in Table 1, while the components of the
experimental set up set
of the experimental areup
described in Table
are described in2.Table 2.
During the test, the DC power supply gave a step current to the PEM EL. It was sampled,
together with the voltage at Table Mainterminals,
the 1.stack features of by
the the
investigated PEM EL.
digital oscilloscope; data were memorized
and elaborated on by the (dSPACE, Bièvres,
Parameters
France) platform
Value
to obtain
Unit
the value of the circuit
parameters by the algorithms described in the following section.
Rated electrical power 400 W
Stack operating voltage range 7.5–8 V
Table 1. Main
Stack features
current range of the investigated
0–50 PEM EL.
A
Delivery output pressure 0.1–10.5 bar
Parameters Value Unit
Cells number 3 -
Rated electrical power
Active area Section 400 50 W2
cm
Stack operating voltage
7.5–8 V
range
Table 2. Components of the measurement system.
Stack current range 0–50 A
Component
Delivery output Producer Model
0.1–10.5 bar
DC Powerpressure
Supply TDK GEN60-55
PureCells
waternumber
tank SGWATER 3 SG- 2000
Digital Oscilloscope Tektronix MDO3054
Active area Section 50 cm2
Current clamp Chauvin Arnoux PAC10
PEM EL HELIOCENTRIS NMH2 1000
Table 2. Components of the
Digital multimeter measurement system.179
Fluke
dSPACE board dSPACE DS1104
Component
Hydrogen tank Producer
HELIOCENTRIS Model
760 NI
DC Power Supply TDK GEN60-55
Pure water tank SGWATER SG 2000
During the test, the DC power supply gave a step current to the PEM EL. It was sampled, together
Digital Oscilloscope Tektronix MDO3054
with the voltage at the stack terminals, by the digital oscilloscope; data were memorized and elaborated
Chauvin
Current clamp PAC10
Arnoux
PEM EL HELIOCENTRIS NMH2 1000
Digital multimeter Fluke 179
dSPACE board dSPACE DS1104
Hydrogen tank HELIOCENTRIS 760 NI
Energies 2019, 12, 750 6 of 17

on by the (dSPACE, Bièvres, France) platform to obtain the value of the circuit parameters by the
algorithms described in the following section.
Energies 2018, 11, x FOR PEER REVIEW 6 of 18

3.2. Analysis of the Dynamic Behavior of the PEM EL

4.2. Analysis of the Dynamic Behavior of the PEM EL
Experimental tests
Experimental were
tests werecarried
carriedoutoutininorder
order to to emphasize
emphasize the thecapacitive
capacitive effect
effect of PEM
of the the PEM
EL EL
whenwhen
subjecting to current steps. The first results obtained are shown in Figures
subjecting to current steps. The first results obtained are shown in Figures 4 and 5. As can be 4 and 5. As can be
seen in Figures
seen 4 and4 5,and
in Figures the5,capacitive effecteffect
the capacitive was was
all the
all more visible
the more andand
visible important
importantforfor
current
currentvalues
values
greater thangreater than 2 during
2 A. Indeed, A. Indeed,theduring
first lowthecurrent
first lowstep
current
(2 A),step
the(2ELA),voltage
the EL reached
voltage reached its
its permanent
valuepermanent valuefor
quickly, while quickly, whilevariation
the second for the second
at 4 Avariation at 4 A the
the EL voltage EL voltage
varied varieduntil
very slowly very reaching
slowly its
until reaching its value in steady state (≈30 s). For this reason, it can be
value in steady state (≈30 s). For this reason, it can be deduced that precise modeling would requirededuced that precise
modeling would require variable circuit parameters, but it is out of the scope of this work which is
variable circuit parameters, but it is out of the scope of this work which is focused on a method to
focused on a method to identify the components of the equivalent circuit. For this reason,
identify the components of the equivalent circuit. For this reason, identification has been optimized for
identification has been optimized for a suitable current interval adopting constant parameters of the
a suitable current
equivalent interval adopting constant parameters of the equivalent circuit.
circuit.

−1),− 1 ), channel
Figure 4. Demonstration
Figure 4. Demonstration of the capacitive
of the effect
capacitive effectofofthe
theEL.
EL. Channel
Channel 1:1:EL
ELvoltage
voltage(2 (2 V.div
V.div channel 2: 2:
Energies
EL EL2018,
current 11,A.div
current
(2 x (2
FOR −PEER
1 ), time:
A.div −1 ),REVIEW s.div−1..
time:1010s.div −1 7 of 18

The required time for the stabilization of the PEM EL voltage due to the displacement of the
charges inside the anode and the cathode elongated all the more as the current increased. This
phenomenon is particularly noticeable in Figure 5. Moreover, this figure clearly shows an operating
limit of the PEM EL when the current reaches its maximum threshold (sudden voltage drop). This
was an abnormal operation of the PEM EL due to its degradation and was not considered in our
model. To conclude, the dynamics of the PEM EL were characterized by two transient phenomena:
(1) slowness of the evolution reaction of the oxygen in the anode, and (2) rapidity of the evolution
reaction of the hydrogen in the cathode. These two phenomena resulted in the equivalent electrical
diagram (Figure 2) by the two RC branches that will be characterized by two different time
constants.

Figure 5. Operating
Figure 5. Operatinglimits
limits of of
thethePEM
PEMEL.
EL. Channel
Channel 1:1:EL
ELvoltage
voltage (2 V.div
(2 V.div −1 ), channel
−1), channel 2: EL current
2: EL current (2
−
A.div1 −
−1), time: 10 s.div−1
(2 A.div ), time: s.div . . 1

4. PEM Electrolyzer Modelling

The equivalent circuit model has been obtained on the basis of experimental testing performed
on the PEM EL. Firstly, the static characteristics has been obtained, then the time constants of the
dynamic model were identified and calculated by linear regression. Finally, an implementation in a
Simulink environment has been performed and the equivalent circuit model has been assessed.
Energies 2018, 11, x FOR PEER REVIEW 8 of 18

Energies 2019, 12, 750 7 of 17

were obtained: Vint = 4.38 V, Rtot = 0.441 Ω. From the waveform of Figure 6, the following
considerations can be made: The characteristic resistances Rint can be calculated considering the
response
Theafter and before
required time the
for step current and atofthe
the stabilization theend PEMof the
ELtransients.
voltage dueUnder the displacement
to the hypothesis thatof
the
theequivalent capacitance
charges inside is quite
the anode and high so that immediately
the cathode elongated allafter
the the
morecurrent
as theis current
varied the drop
increased.
voltage occurs only is
This phenomenon at particularly
the Rint terminals,
noticeable the voltage
in Figure measured beforethis
5. Moreover, the figure
step current
clearly(at t = 0−)
shows an
represents the reversible
operating limit of the PEMvoltage
EL when Vint. The internal
the current reachesresistance can threshold
its maximum be calculated considering
(sudden the
voltage drop).
voltage
This wasafter
an the currentoperation
abnormal step at t =of0+,
theit PEM
gives:EL due to its degradation and was not considered in our
Rint = (Vt =0+ − Vint ) it =0+
model. To conclude, the dynamics of the PEM EL were characterized by two transient phenomena:
(4)
(1) slowness of the evolution reaction of the oxygen in the anode, and (2) rapidity of the evolution
Whenofall
reaction thetransients
hydrogenare finished,
in the cathode. theThese
voltage two is phenomena
proportionalresulted
to the supply current, and
in the equivalent their
electrical
ratio gives(Figure
diagram the total
2) equivalent
by the two resistance
RC branches Rtot:that will be characterized by two different time constants.

4. PEM Electrolyzer Modelling Rtot = (Vt→∞ − Vint ) it→∞ (5)

At the
The end of the
equivalent transients,
circuit thebeen
model has voltage at the
obtained on PEM EL of
the basis terminals is given
experimental by performed
testing the producton
between
the PEMand
EL. the totalthe
Firstly, resistance, giving a constraint
static characteristics has beentoobtained,
the resistances
then theR1time
andconstants
R2: of the dynamic
model were identified and calculated by linear regression. Finally, an implementation in a Simulink
environment has been performed and
R1 + Rthe
2 =equivalent
Rtot − Rint circuit model has been assessed. (6)

The values of R1 and R2 are calculated on the basis of the time constants identified by the
4.1. Experimental Test
dynamic model supposing that the two equivalent capacitances C1 and C2 are equal. From data
shownUsing the experimental
in Figure 6, the followingset-up described
values in obtained:
have been the previous section, some tests were performed
to obtain a database from which information on the dynamic behavior of the EL could be collected.
R = 0.088Ω; Rtot = 0.441Ω; Vint = 4.38V (7)
Specifically, the PEM ELintwas supplied with step current transients.
InAn example
Figure of equation
7, the the voltage andinterpolating
of the current measured on the
straight lineEL terminals is
considering Rtotshown
and Vin Figure
int by 6. In
(7) has this
been
test, after
included asthe power
well. waswith
This fits turned
dataon, the current
obtained was
by LSR, butincreased
the error from 2.34 Adata
with static to 4increases
A at t =with
20 s;the
the
duration of the
current as expected.test was equal to 100 s waiting for the end of the transient. Different steps of current
were considered for supplying the PEM EL.

Figure
Figure6.6.Example
Exampleofofvoltage
voltagetransient.
transient.

4.2. Static Model Identification

The values of voltage and current measured at the end of each transient were used to identify the
static characteristic sketched in Figure 7. These values were calculated at the end of each transient by
linear regression when the EL tended to a steady-state operation. It can be noted that the data were
sampled in a range from 0.04 A/cm2 to about 0.16 A/cm2 , which is of interest for the identification
of the model. On the one hand, in this interval, the parameters could be considered as constant.
Energies 2019, 12, 750 8 of 17

It is an approximation compared with the whole operating range of the EL. Indeed, it can be noted
that the more the current is high, the more the error between data acquired by static measurements
and those obtained by LSR increases, which was due to the fact that the time required to reach
steady-state conditions increased with the current. This confirms that identification with constant
parameters is valid in a limited operating range. On the other hand, it is sufficient to assess the
methodology that can be applied whatever the selected interval of currents. In the case under study,
it represents the operating conditions in which the dynamic model was identified. A least-square
regression (LSR) algorithm was used (see Appendix A). From the linear regression on experimental
data, the internal resistance was calculated by the slope and the reversible voltage by extrapolating the
straight line achieving the electromotive force at zero current. The following values were obtained:
V int = 4.38 V, Rtot = 0.441 Ω. From the waveform of Figure 6, the following considerations can be made:
The characteristic resistances Rint can be calculated considering the response after and before the
step current and at the end of the transients. Under the hypothesis that the equivalent capacitance
is quite high so that immediately after the current is varied the drop voltage occurs only at the Rint
terminals, the voltage measured before the step current (at t = 0−) represents the reversible voltage
Vint. The internal resistance can be calculated considering the voltage after the current step at t = 0+,
it gives:
Energies 2018, 11, x FOR PEER REVIEW Rint = (Vt=0+ − Vint )/it=0+ 9 of(4)
18

Figure 7.
Figure 7. Static
Static characteristic
characteristic obtained
obtained by
by linear
linear regression
regressionand
andexperimental
experimentalmeasurements.
measurements.

When
From all
thetransients are finished,
static sampled the voltage
operating point, is
theproportional
input power to the supplyby
required current, and EL
the PEM theircan
ratio
be
gives the total
calculated equivalent
as well. This isresistance Rtot : 8. It can be noted that this relationship is not linear, which
shown in Figure
can be explained by considering that the losses give a quadratic contribution according to the
Rtot = by
current. Indeed, this is well approximated ∞ − Vint ) /it→polynomial
(Vta→second-order ∞ curve. (5)

At the end of the transients, the voltage at the PEM EL terminals is given by the product between
and the total resistance, giving a constraint to the resistances R1 and R2:

R1 + R2 = Rtot − Rint (6)

The values of R1 and R2 are calculated on the basis of the time constants identified by the dynamic
model supposing that the two equivalent capacitances C1 and C2 are equal. From data shown in
Figure 6, the following values have been obtained:
Energies 2019, 12, 750 9 of 17

Rint = 0.088 Ω; Rtot = 0.441 Ω; Vint = 4.38 V (7)

In Figure 7, the equation of the interpolating straight line considering Rtot and V int by (7) has been
included asFigure
well. 7.This fitscharacteristic
Static with data obtained
obtained byby linear
LSR, but the error
regression andwith static data
experimental increases with the
measurements.
current as expected.
From
Fromthe thestatic
staticsampled
sampledoperating
operatingpoint,
point,the theinput
inputpower
powerrequired
requiredbybythethePEMPEMELELcan canbebe
calculated
calculatedasas
well.
well.This
Thisis is
shown
shown inin
Figure 8. 8.It Itcan
Figure canbebenoted
notedthat
thatthis
thisrelationship
relationshipis is
not linear,
not which
linear, which
can be explained by considering that the losses give a quadratic contribution
can be explained by considering that the losses give a quadratic contribution according to the according to the current.
Indeed, this
current. is wellthis
Indeed, approximated by a second-order
is well approximated polynomialpolynomial
by a second-order curve. curve.

Figure
Figure 8. 8. Input
Input power
power vs.vs.
thethe current
current density
density supplied
supplied to to
thethe PEM
PEM EL.
EL.

4.3. Dynamic
4.3. Model
Dynamic Identification
Model Identification
InIn
order
orderto obtain the dynamic
to obtain model,
the dynamic the transient
model, has been
the transient considered
has considered.
been considered It is possible
considered. It is
that there were two exponential transients corresponding to two different time constants.
possible that there were two exponential transients corresponding to two different time constants. This is
consistent with the considerations
This is consistent explainedexplained
with the considerations in Sectionin2.Section
The time constants
2. The of the dynamic
time constants model
of the dynamic
have
model have been obtained using an LSR algorithm as well (see Appendix A). In this case, sinceare
been obtained using an LSR algorithm as well (see Appendix A). In this case, since the curves the
exponential,
curves are some manipulations
exponential, have been performed
some manipulations have been in applying
performed theinLSR algorithm,
applying as explained
the LSR algorithm, inas
the following.
explained in the following.
InInthe
thecase
caseunder
understudy,
study,with
witha asuitable
suitablechoice
choiceofoftime
timeorigin,
origin,the
thevoltage
voltageprofile
profilecan
canbebe
approximated
approximated as:as:
t
v(t) = (Vo − V∞ )e− τ + V∞ (8)

where V 0 is the value of the voltage at the instant t = 0+, V ∞ is the value of the voltage at the end
of the transient (t → ∞) and τ is the time constant of the exponential function. Equation (8) can be
rewritten as
Y = αX + β (9)

With the position

(
Y (t) = log(V∞ − v(t)); X=t
(10)
α = −1/τ; β = log(V∞ − Vo )
The coefficients to be identified were α and β. The identification was performed both on the
exponential curve measured at the beginning of the transient, and on the remaining curve describing
exponential curve measured at the beginning of the transient, and on the remaining curve describing
the slower transient. The first identification has given the time constants of the anode reaction, and
the latter corresponds to the cathode reaction.
In order to minimize noise, filtering was performed by a rolling mean algorithm on 20 samples.
A zoom of the two transients together with the filtered data is shown in Figure 9.
Energies 2019, 12, 750 10 of 17
The vector of the sampled data contained 2000 samples; to identify the two time constants, the
intervals 677–695 and 800–1960 were considered as a trade-off between a suitable number of data to
be processed
the and the
slower transient. Theexponential curve has
first identification to be approximated.
given The values
the time constants of thereaction,
of the anode time constants
and the
obtained
latter were:
corresponds to the cathode reaction.
In order to minimize noise, filtering was performed by a rolling mean algorithm on 20 samples.
τ 1 = 1.304s; τ 2 = 11.848s (11)
A zoom of the two transients together with the filtered data is shown in Figure 9.

Figure 9. Zoom of the transient with exponential curves.

The vector ofthe

Considering theconstraints
sampled data contained
(6) and 2000
(11), and samples;that
assuming to identify
the two the two time constants,
capacitances are equal, the
intervals
following677–695 and 800–1960
values could werefor
be calculated considered as a trade-off
their equivalent between
resistances a suitable number of data
and capacitances:
to be processed and the exponential curve to be approximated. The values of the time constants
 R1 = 0.035 Ω; C1 = 37 .26 F
obtained were:  (12)
 R 2 = 0.318 Ω; C 2 = 37 .26 F
τ1 = 1.304 s; τ2 = 11.848 s (11)

Considering the constraints (6) and (11), and assuming that the two capacitances are equal, the
5. Results
following values could be calculated for their equivalent resistances and capacitances:
The equivalent circuit shown in Figure 2 has been implemented in a Simulink environment, and
(
the data obtained by the simulation Rhave been compared with the experimental results to validate
1 = 0.035 Ω; C1 = 37.26 F
(12)
the model. In the subsequent static test (including efficiency, hydrogen production and temperature
R2 = 0.318 Ω; C2 = 37.26 F
assessment of the PEM EL) and dynamic test, the behavior of the PEM EL when soliciting by step
5. Results
The equivalent circuit shown in Figure 2 has been implemented in a Simulink environment, and
the data obtained by the simulation have been compared with the experimental results to validate
the model. In the subsequent static test (including efficiency, hydrogen production and temperature
assessment of the PEM EL) and dynamic test, the behavior of the PEM EL when soliciting by step
currents, has been reproduced are performed. All tests have been performed by acquiring experimental
data through the test rig described in Section 3.

5.1. Static Test

Firstly, the efficiency has been assessed by comparing the estimated data given by the emulator
calculated by:
P I · Vint
η= H = (13)
Pin I · Vint + I 2 · ( R1 + R2 + Rint )
where PH is the power converted into hydrogen and Pin is the electrical power supplied to the PEM
EL. The power converted into hydrogen is given by the product between the V int voltage and the
current, whereas the losses have been calculated as the square of the current multiplied for the
equivalent resistance into the anode, cathode, and membrane, respectively. It can be noted that
 Pin I ⋅Vint + I 2 ⋅ (R1 + R2 + Rint )
where PH is the power converted into hydrogen and Pin is the electrical power supplied to the PEM
EL. The power converted into hydrogen is given by the product between the Vint voltage and the
current, whereas the losses have been calculated as the square of the current multiplied for the
Energies 2019, 12, 750 11 of 17
equivalent resistance into the anode, cathode, and membrane, respectively. It can be noted that the
losses are quadratic according to the current, whereas the power converted into hydrogen is linear
according
the to the
losses are current.according
quadratic As a result, the current,
to the overall efficiency
whereas the decreases
poweraccording
convertedtointothe hydrogen
current. The is
efficiency
linear calculated
according to theby (13) has
current. Asbeen compared
a result, with efficiency
the overall experimental pointsaccording
decreases obtained tobythe
thecurrent.
ratio of
the efficiency
The produced calculated
hydrogen by and(13)
thehas
power
beensupplied
compared towith
the PEM EL, where
experimental the produced
points obtained byhydrogen
the ratiois
ofgiven by substituting
the produced hydrogen the supplied currentsupplied
and the power into the to first
theFaraday’s
PEM EL, lawwhere of the
electrolysis
produced to hydrogen
obtain the
ishydrogen
given by flow rate NH2
substituting the [mol/s],
suppliedthen multiplying
current this Faraday’s
into the first value by law
the higher heatingtovalue
of electrolysis obtain ofthe
the
hydrogen (ΔH = 286 kJ/mol). The comparison is shown in Figure 10.
hydrogen flow rate NH2 [mol/s], then multiplying this value by the higher heating value of the
hydrogenThe (∆H
curves shown
= 286 in Figures
kJ/mol). 10 and 11is are
The comparison showninfluenced
in Figureby10.the hypothesis of considering a
limited operating range for the identification of
The curves shown in Figures 10 and 11 are influenced by the a constant parameters
hypothesis model. In particular,
of considering each
a limited
temperature
operating range hasfor
been obtained at the
the identification of chosen
a constant operating
parameterspoint. For this
model. reason, a polarization
In particular, each temperaturecurve
obtained
has with constant
been obtained temperature
at the chosen operating is point.
not shown.
For thisInreason,
addition, the calculated
a polarization production
curve obtained with of
hydrogen exploits a Faraday’s efficiency value close to one (this is an approximation
constant temperature is not shown. In addition, the calculated production of hydrogen exploits a in the chosen
current interval).
Faraday’s efficiencyFor thisclose
value reason, both
to one the
(this is efficiency and theinhydrogen
an approximation the chosen production rate have
current interval). Forto be
this
considered
reason, both astheupper limits.
efficiency and the hydrogen production rate have to be considered as upper limits.

Energies 2018, 11, x FOR PEER REVIEW 12 of 18

produced hydrogen is linear with the current density, and the corresponding curve is shown in
Figure 11. Figure10.
10.Upper
Upperlimit
limitof
ofthe
theefficiency
efficiencyfor
forthe
thePEM
PEMEL.
EL.
Figure

As far as the hydrogen production is concerned, it has been calculated by the emulator on the
basis of the product between the internal voltage and the current and compared with experimental
points. The produced hydrogen is often given in literature with standard liter per minute (slpm)
units defined in standard conditions of T = 288.15 K (i.e., 15 °C) and P = 101.3 kPa. As expected, the

Figure
Figure 11.11. Upper
Upper limit
limit ofof
thethe
ofof hydrogen
hydrogen production
production vs.vs. current
current density.
density.

Finally, the measured temperature has been used to calculate the thermal resistance Rth of the
PEM EL. It is useful to predict the temperature on the basis of the environmental temperature and on
the power supplied to the PEM EL.
The thermal resistance has been obtained by applying the LSR to the quantity:
Energies 2019, 12, 750 12 of 17

As far as the hydrogen production is concerned, it has been calculated by the emulator on the
basis of the product between the internal voltage and the current and compared with experimental
points. The produced hydrogen is often given in literature with standard liter per minute (slpm)
units defined in standard conditions of T = 288.15 K (i.e., 15 ◦ C) and P = 101.3 kPa. As expected,
the produced hydrogen is linear with the current density, and the corresponding curve is shown in
Figure 11.
Finally, the measured temperature has been used to calculate the thermal resistance Rth of the
PEM EL. It is useful to predict the temperature on the basis of the environmental temperature and on
the power supplied to the PEM EL.
The thermal resistance has been obtained by applying the LSR to the quantity:

TEL − Tenv
Rth = [◦ C/W] (15)
Pw
where Tenv is the environment temperature equal to 23 ◦ C during the test, TEL is the operating
temperature of the PEM EL measured after the end of the thermal transient and Pw is the power
supplied to the PEM EL. The temperature has been measured by a sensor located on top of the surface
and by a thermographic camera as well. However, since the thermographic camera gives a mean
temperature of the EL, the curve of Figure 12 is drawn by data coming from the sensor. The temperature
has been then estimated by the equation:

TEL = Tenv + Rth · Pw (16)

Results are shown in Figure 12.

Energies 2018,
In all the11,three
x FORtests,
PEER REVIEW
a good agreement between measured and estimated data is shown. 13 of 18

Figure12.
Figure 12.Experimental
Experimentaland
andestimated
estimatedtemperature
temperatureof
ofthe
thePEM
PEMEL.
EL.

5.2. Dynamic Test

In all the three tests, a good agreement between measured and estimated data is shown.
In order to validate the dynamic behavior of the emulator, a transient has been considered in
5.1. Dynamic
which Test current went firstly from 5.45 A to 6.25 A at t = 14 s and then to 7.4 A at t = 110 s.
the supply
The transient
In orderhas a duration
to validate theequal to 200
dynamic s. In Figure
behavior 13,emulator,
of the the simulation results
a transient have
has been
been compared
considered in
with the experimental data and with the traditional static model without considering the capacitive
which the supply current went firstly from 5.45 A to 6.25 A at t = 14 s and then to 7.4 A at t = 110 s.
effects. It can has
The transient be noted that equal
a duration the curve
to 200representing
s. In Figure the voltage
13, the duringresults
simulation transients
havefits
beenbetter with
compared
experimental data compared
with the experimental to the
data and withstatic
themodel.
traditional static model without considering the capacitive
effects. It can be noted that the curve representing the voltage during transients fits better with
experimental data compared to the static model.
 which the supply current went firstly from 5.45 A to 6.25 A at t = 14 s and then to 7.4 A at t = 110 s.
The transient has a duration equal to 200 s. In Figure 13, the simulation results have been compared
with the experimental data and with the traditional static model without considering the capacitive
effects. It can be noted that the curve representing the voltage during transients fits better with
Energies 2019, 12, 750
experimental data compared to the static model. 13 of 17

Figure13.
Figure 13.Comparison
Comparison among
among thethe PEM
PEM ELEL voltage:
voltage: experimental,
experimental, obtained
obtained by dynamic
by dynamic model
model and and
by
by static
static model.
model.

The
Theerror
errorbetween
betweenexperimental
experimentaldata dataandandthe
thedynamic
dynamicmodel
model(expressed
(expressedinin%)
%)isisshown
showninin
Figure
Figure 14, where
14, where it can
it canbe
benoted
Energies 2018, 11, x FOR PEER REVIEWnotedthat
thatthe
thedynamic
dynamic model
model shows
shows aamaximum
maximum error
errorequal
equal to
toabout
14 of4%,
about 4%,
18
whereas
whereasthe thepercent
percenterror
errorgiven
givenbybythe
thestatic
staticmodel
modelincreases
increasestoto15%.
15%.Once
Oncevalidated,
validated,the
thedynamic
dynamic
model, losses
model, losses and power balance have been calculated during transients. In In Figure
Figure 15,
15, the voltage
drops into the cathode, into the anode and into the membrane membrane areare sketched
sketched together
together with
with the
the supply
supply
Figure 16
current. Figure 16 reproduces the power balance considering the power losses into the cathode, into
the anode and into the membrane, as well as the power converted into hydrogen.

Figure
Figure 14.
14. Error
Error percentage
percentage obtained
obtained comparing
comparing the
the experimental
experimental data
data with
with the
the dynamic
dynamic model
model (top)
(top)
and the static model (bottom).
and the static model (bottom).
 Figure 14. Error percentage obtained comparing the experimental data with the dynamic model (top)
and the static model (bottom).
Energies 2019, 12, 750 14 of 17

Energies 2018,15.
Figure
Figure 11,Voltage
15. xVoltage
FOR PEER
dropREVIEW
drop intothe
into thecathode,
cathode,into
intothe
theanode
anodeand
andinto
intothe
themembrane
membranetogether
togetherwith 15 of 18
withthe
the
supplycurrent.
supply current.

Figure 16.Power
Figure16. Powerbalance
balanceofofthe
thePEM
PEMEL.
EL.

ItItcan bebe
can noted thatthat
noted by increasing the supply
by increasing power,power,
the supply all power
all terms
power onterms
the PEMon EL
thehave
PEMincreased
EL have
asincreased
expected.asInexpected.
particular, near to the rated current (about 7.4 A in the test), about 50 W
In particular, near to the rated current (about 7.4 A in the test), about have been
50 W
supplied
have been to the PEM EL
supplied andPEM
to the aboutEL30andW about
have been
30 Wconverted
have beeninto hydrogen.
converted intoThis is consistent
hydrogen. This is
according
consistenttoaccording
the rise oftotemperature shown in Figure
the rise of temperature shown12.in Figure 12.

6.6.Conclusions
Conclusions
Based
Basedon onthe
thecurrent
currentstate-of-the-art
state-of-the-artresearch,
research,the
thepaper
paperaimed
aimedatatdeveloping
developingananequivalent
equivalent
dynamic
dynamic electrical model for a PEM electrolyzer. The originality of this workresided
electrical model for a PEM electrolyzer. The originality of this work residedinintaking
takinginto
into
consideration the dynamic behavior of the PEM electrolyzer during sudden variations of the input
current. In this specific operating case, the electrolyzer behaves like a capacitor.
The novelty of the paper was to assess the methodology for identifying the exponential time
constant equivalent circuit based on a least squares regression algorithm. For this reason, a limited
current operating range was chosen to identify a constant parameters model. Even if this interval
considered lower current densities compared to the literature, it had the merit of assessing a
Energies 2019, 12, 750 15 of 17

consideration the dynamic behavior of the PEM electrolyzer during sudden variations of the input
current. In this specific operating case, the electrolyzer behaves like a capacitor.
The novelty of the paper was to assess the methodology for identifying the exponential time
constant equivalent circuit based on a least squares regression algorithm. For this reason, a limited
current operating range was chosen to identify a constant parameters model. Even if this interval
considered lower current densities compared to the literature, it had the merit of assessing a
methodology that can be applied in different current ranges by suitable values of the parameters.
Furthermore, this model can be employed to test the behavior of power converters supplying the
electrolyzer without risk of damage.
Through experimental results and the use of a least squares regression algorithm, the parameters
of the equivalent dynamic electrical model were determined. The comparison between experiments
and the obtained results from the developed model demonstrated the accuracy of the model to replicate
the real dynamic behavior of an electrolyzer. In addition, the emulator was able to correctly reproduce
the temperature, efficiency, and production of hydrogen.
In summary, this electrical model could be useful in exploiting an emulator for experiment
purposes, while avoiding the use of an electrolyzer.

Author Contributions: Conceptualization, D.G. and G.V.; methodology, D.G. and G.V.; validation, D.G. and G.V.;
investigation, D.G. and G.V.; writing—original draft preparation, D.G. and G.V.; writing—review and editing,
D.G. and G.V.
Funding: This research received no external funding.
Acknowledgments: The authors would like to thank the technical staff at the IUT of Longwy, Serge Merafina, for
his valuable advices regarding the development and realization of the experimental test bench.
Conflicts of Interest: The authors declare no conflict of interest.

Appendix A
The LSR algorithm minimizes the Euclidean distance between the points yi and f (xi ) given by:
n
S= ∑ (yi − f (xi ))2 (A1)
k =1

If the function to be identified is linear in respect to m parameters pk (where the number of the
parameters m is supposed much lower than the measurements n), it can be written as:
m
f (x) = ∑ pk f k ( x ) (A2)
k =1

The following linear system can be defined:

y∼
= Ap (A3)

where:  
f 1 ( x1 ) f 2 ( x1 ) . . . f m ( x1 )
 f (x ) f (x ) f m ( x2 ) 
A= 1 2 2 2
(A4)
 
. . ... .

 
f 1 ( xn ) f 2 ( xn ) . f m ( xn )
   
p1 y1
 p   y2 
p= 2  y= (A5)
   
 .  .

 
pm yn
Energies 2019, 12, 750 16 of 17

The minimization of the quantity S is obtained by minimizing the norm of the residual:

kr k = ky − Apk (A6)

It corresponds to impose that the derivative of the square of the norm with respect to the
coefficients pk is equal to zero:
!
∂ kr k2 n m
= ∑2 ∑ yi − aij p j aij = 0 (A7)
∂pk i =1 j =1

Rewriting (A6) in matrix form:

(y − Ap)T A = 0 (A8)

If the rank of A is complete, ATA can be inverted and the vector p is given by:
  −1
p = AT A AT y (A9)

In this work, the LSR algorithm has been applied to identify the static characteristic, which is
linear as shown in Figure 5, and the time constants of the transients of a dynamic model. In this case,
the exponential curve has been multiplied by an algorithm to obtain a linear function in which the
slope is the time constant.

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