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 4 2 ( 2 0 1 7 ) 1 3 6 6 e1 3 7 4

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Analytical modelling and experimental validation

of proton exchange membrane electrolyser for
hydrogen production

F.Z. Aouali a,*, M. Becherif b, H.S. Ramadan b,c, M. Emziane d, A. Khellaf e,

K. Mohammedi a
a
LEMI Laboratory, Boumerdes University, 35000, Algeria
b
FEMTO-ST UMR CNRS 6174, FCLab FR CNRS 3539, UTBM, 90010 Belfort cedex, France
c
Zagazig University, Faculty of Engineering, Electrical Power and Machines Dept., 44519, Zagazig, Egypt
d
Solar Energy Materials & Devices Lab., Masdar Institute of Science & Technology, Abu Dhabi, United Arab
Emirates
e
CDER, route de l'Observatoire, Bouzareah, 16340, Algiers, Algeria

article info abstract

Article history: Proton Exchange Membrane (PEM) Electrolysers (ELSs) are considered as pollution-free with
Received 27 February 2016 enhanced efficiency technology. Hydrogen can be easily produced from different resources
Accepted 17 March 2016 like biomass, water electrolysis, natural gas, propane, and methanol. Hydrogen generation
Available online 8 July 2016 from water electrolysis, which is the splitting of water molecules into hydrogen and oxy-
gen using electricity, can be beneficial when used in combination with variable Renewable
Keywords: Energy (RE) technologies such as solar and wind. When the electricity used for water
Hydrogen production electrolysis is produced by a variable RE source, the hydrogen stores the unused energy for
Proton exchange membrane a later use and can be considered as a renewable fuel and energy resource for the transport
Water electrolysis and energy sectors.
This paper aims to propose a novel graphical model design for the PEM-ELS for
hydrogen production based on the electrochemical, thermodynamical and thermal equa-
tions. The model under study is experimentally validated using a small-scale laboratory
electrolyser. Simulation results, using Matlab-Simulink™, show an adequate parameter
agreement with those found experimentally. Therefore, the impact of the different pa-
rameters on the electrolyser dynamic performance is introduced and the relevant
analytical-experimental comparison is shown. The temperature effect on the PEM-ELS
dynamic behaviour is also discussed.
© 2016 Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC.

Renewable Energy (RE) and Energy Efficiency (EE) are effective

Introduction solutions for reducing Green House Gas (GHG) emissions and
providing the energy needed. Adopting clean and emission-
Global warming and the energy crisis are the most important free energy cycle is considered to be a major break-through
challenges facing mankind and need to be addressed. in this regard and policymakers have highlighted the use of

* Corresponding author.
E-mail address: [email protected] (F.Z. Aouali).
http://dx.doi.org/10.1016/j.ijhydene.2016.03.101
0360-3199/© 2016 Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC.
 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 4 2 ( 2 0 1 7 ) 1 3 6 6 e1 3 7 4 1367

Nomenclature T temperature, K
t time, s
A MEA area, cm2
V cell Voltage, V
A coefficient for specific heat
Vrev the standard reversible voltage
C concentration, mol/m3
VEL voltage of the electrolyser, V
c coefficient for specific heat
Vtn thermoneutral voltage
Cp water thermal capacity, J/Kg K
m_ H2 O the water mass flow exiting from the membrane
CO2 ;me the O2 concentration at the membraneeelectrode
electrode assembly (MEA) environment
interface
n_ the molar flow rates of consumed water
CH2 ;me the H2 concentration at the membraneeelectrode
Q_ H2 O out the heat flow
interface
aa charge transfer coefficients at the anode and
CH2 O;me the H2 O concentration at the
anode
membraneeelectrode interface
ac charge transfer coefficients at the anode and
CH2 O;me;cat refers to the water concentrations at the
cathode
cathode
DH enthalpy variation during the reaction
CH2 O;me;an refers to the water concentrations at both
DS entropy variation during the reaction
membrane sides
DSq_cond the heat loss by conduction
Cth,stack stack thermal capacity
DSq H2 O out the entropy flow
Ctank
H2 O water tank heat capacity
DG Gibbs free energy
d coefficient for specific heat
dw the membrane thickness, mm
Dw water diffusion coefficient
hdiff,an the diffusion overvoltages at the anode
EE energy efficiency
hdiff,cat the diffusion overvoltages at the cathode
e thickness, m
hf Faraday's efficiency
e
electron charge
l conductivity, W/m
etank tank thickness, m
f heat flow, J
Eact
anod the activation over potential at the anode
fwater_atm the water tank thermal energy accumulation
Eact
cath the activation over potential at the cathode
sm membrane conductivity, s/cm
Erev standard reversible voltage
Enernst Nernst potential Subscripts
Eohm ohmic overpotential act activation
F Faraday constant, C/mol anod anode
Gref irradiance, W/m2 Cond conduction
H molar enthalpy, J/mol Conv convection
Hþ hydrogen ions cath cathode
H2 hydrogen diff diffusion
H2O water
Abbreviation
H3Oþ hydroxonium ion
CCS carbon capture and storage
H height, m
CO2 carbon dioxide
I cell current, A
DC direct current
J cell current density, A/cm2
ELS Electrolyser
j0.A exchange current density at the anode
EMR Energetic Macroscopic Representation
j0.C exchange current density at the cathode
FC Fuel Cell
n number of electrons transferred during the
GHG green house gas
reaction
KOH potassium hydroxide
nd electro-osmotic drag coefficient
MEA membrane electrode assembly
Ncell Number of electrolytic cells
NaOH sodium hydroxide
P pressure
O2 oxygen
PH2 partial pressures of H2
O2
oxygen ions
PO2 partial pressures of O2
PEM Proton Exchange Membrane
Rt thermal resistance, W/K
PEMWE Proton Exchange Membrane Water Electrolyser
R universal gas constant, J/mol K
RE Renewable energy
Re Ohmic resistance
SOEC Solid Oxide Electrolysis Cells
r cylinder tank internal radius, m
S molar entropy, J/mol K
1368 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 4 2 ( 2 0 1 7 ) 1 3 6 6 e1 3 7 4

renewable energy and its optimization in order to overcome model of a PEM electrolyser that consists of a steady-state
this serious issue [1,2]. Recent studies have suggested that electrical model and a linear dynamic thermal model, and is
hydrogen will play an important role as an energy carrier for deduced from physical laws and electrochemical equations.
sustainable development in the future [3,4] as it is fed to Fuel The estimation of the major parameters of the model, i.e.,
Cells (FCs) to produce carbon-free emissions [5]. temperature, voltage and current are calculated using identi-
Hydrogen is considered to be the cleanest fuel of the future fication and data fitting techniques based on experimental
because of its high energy mass and volume densities and measurements. The authors highlighted the model potentials
provides options for the storage and transport of energy for in detecting and isolating faults on actuators, sensors or
both transportation and stationary applications. The produc- electrolyser system [11]. Agbli et al. presented a PEM electro-
tion of hydrogen from RE also helps solve the intermittency lyser graphical model via an appropriate Energetic Macro-
issues associated with RE generation. The hydrogen energy scopic Representation (EMR). The modelling of multi-physics
storage capacity is very high as one kilogram of hydrogen components through EMR highlights the electrochemical,
contains approximately 33 kWh of energy. The drivers for a thermodynamical, thermal and fluidic phenomena interact-
global hydrogen economy are energy security, sustainability ing simultaneously within the electrolyser. The authors
GHG and pollution reduction and economic profitability. Fig. 1 studied the dynamic performance of the stack temperature
shows the different methods of hydrogen production where and the water supply tank. The interaction between the
the energy needed for this process can be conventional, nu- temperature and the main electrical parameters identified
clear or renewable. From a life-cycle point of view, hydrogen through Matlab™/Simulink curve fitting tools was considered,
produced from renewable sources can be considered as and an acceptable agreement between simulation and
renewable and clean hydrogen compared to hydrogen experimental results was highlighted [12]. To improve the
reforming [6,7]. Water splitting, a technique that attracted efficiency of hydrogen production by water electrolysis, Rau
researchers recently, is the most environmental friendly et al. [13] combined IIIeV multijunction solar cells with PEM
process for hydrogen production. electrolysis. They experimentally measured the efficiency of
In the literature, many studies that deal with the Proton hydrogen production from six modules and found its
Exchange Membrane (PEM) electrolyser modelling and maximum value in the order of 16.8% for one module. The
experimentation were reported [6e15]. For high pressure effect of temperature on the performance of the PEM elec-
hydrogen production, Onda et al. [8] have considered the trolysis, particularly the currentevoltage characteristics was
polymer electrolyte membranes to estimate both temperature analyzed. Higher current at lower voltage is the main advan-
and pressure variations for ideal hydrogen production power tage of the proposed concept which leads to significant system
of water electrolysis. For higher pressures, the voltage is efficiency enhancement.
significantly influenced by temperature variations, and higher Yunfeng et al. [14] reviewed the proprieties of alternative
temperature results in lower voltages. In addition, the voltage materials for the deployment of PEMFC including their con-
is proportional to pressure. At higher pressures, larger volt- ductivity, mechanical stability, and fuel permeability.
ages are reached. Dedigama et al. [9] proposed a simple elec- Comparative studies between diverse designs of membrane
trochemical model for studying the overvoltage of a polymer structures were presented, and some strategies for improving
electrolyte membrane water PEM electrolyser under ambient the performance of these materials were developed. Meng
conditions, and the simulation results significantly matched et al. [3] examined the JeV characteristics of a PEM water
the experimental data. Marr and Li developed an electro- electrolyser for hydrogen production and an electrochemistry
chemical model of the PEM FCs [10]. model was developed taking into account the activation and
In order to describe the polarization curves of the electro- ohmic overpotentials. The simulation results were compared
lyser, Lebbal and Lecoeuche [11] introduced a novel combined to experiments with a good agreement. The sensitivity

Fossil Fuels Nuclear Energy Renewable Energy Primary

Energy
Natural Gas Coal Thermochemical High Solar Source
Water Splitting Temperature Photovoltaic Wind Biomass
Electrolysis

Steam Electrolysis Gasification Method

Reforming Gasification

Carbon Capture and Storage

(CCS)

End Use Hydrogen Energy

Fig. 1 e Hydrogen production methods.

 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 4 2 ( 2 0 1 7 ) 1 3 6 6 e1 3 7 4 1369

analysis also indicated that the higher the operating temper- The splitting of water molecules, or electrolysis, is the
ature the lower is the cell potential, and the anode activation oldest known electrochemical process and has been used in
overpotential is the major source of voltage loss. the commercial production of hydrogen since the early 1900s
Dedigama et al. [9] proposed a simple electrochemical [20]. The electrolyser stack physically consists of several
model to analysis the effect of overpotential on the perfor- series-connected cells. The water electrolysis operation en-
mance of Polymer Electrolyte Membrane Water Electrolyser ables hydrogen H2 and oxygen O2 generation through an
(PEMWE). The validation of the model was carried out with electrolytic process in which the water molecule is decom-
experimental data obtained from a lab-scale PEMWE. The posed into H2 and O2 gases by applying a DC voltage as
performance analysis showed that the activation and ohmic depicted in Fig. 2.
overpotentials are dominant under low current density oper- Through the PEM membrane, the protons flow from the
ation and the anode activation overpotential governs the anode to the cathode and the electrons flow towards the
operating potential of the cell under the operating conditions cathode through an outer electrical circuit as illustrated in
considered. Based on electrochemical equations, Marangio Fig. 2. At the cathode, the recombination of electrons and
et al. [15] developed a model of electrolyser stack to investi- protons leads to H2 production [21,22]. It is worth noting that
gate the performance of a high pressure PEMWE. The model 3.9% of the world's hydrogen demand is met using water
has the potential to calculate the theoretical open-circuit electrolysers [23].
voltage via a thermodynamic analysis of the process and For the water electrolysis process, the overall chemical
real voltage during operation by calculating the different reaction is presented by Equation (1):
overvoltages as a function of the current. The results were
compared to the experiments with adequate agreement. 2H2 O þ electricity/O2 þ 2H2 þ heat (1)
Despite their importance, the modelling and analysis of In water electrolysis, the oxidation equation at the anode
PEM electrolyser for hydrogen production have not been electrode is given by:
widely discussed. Therefore, the main contribution of this
paper is the development of a PEM electrolyser model for 2H2 O/O2 þ 4Hþ þ 4e
(2)
hydrogen production through water electrolysis. An identifi- In addition, the reduction equation at the cathode elec-
cation approach is applied to the experimental validation of trode for H2 generation is:
the PEM electrolyser model. Moreover, a sensitivity analysis is
implemented to investigate the behaviour of the PEM elec- 4Hþ þ 4e
/2 H2 (3)
trolyser electrical parameters with respect to different oper-
The energy-enthalpy equality can be applied, then:
ating conditions, particularly the temperature.
The rest of the paper is organized as follows. Section PEM DH þ DG/TDS (4)
electrolyser technology extensively describes the PEM elec- 
where DH ¼ 285.83 kJ/mol at 1 bar and 25 C for water splitting,
trolyser prototype and Section PEM electrolyser modelling
no heat absorption/emission by the system is considered.
provides the modelling. In Section experimental results, the
Therefore, the thermoneutral voltage Vtn estimated at this
simulation results and the experimental analysis are dis-
condition is:
cussed. Moreover, the proposed model validation is pre-
sented, and the conclusion is drawn in Section conclusion. DH
Vtn ¼ ¼ 1:482 V (5)
nF
The DG necessary for the water-splitting reaction is
237.178 kJ/mol at 25  C and 1 bar [24].
PEM electrolyser technology Therefore, the standard reversible voltage denoted as Vrev
can be calculated as:
Electrolysis cells are characterized by their electrolyte type
[16]. The PEM is very promising electrolysis technology [17].
The PEM electrolyser has a polymer membrane and porous
electrodes and it is based on the use of a polymeric proton
exchange membrane as the solid electrolyte (polymer elec-
trolyte membrane). It was first proposed by General Electric
for fuel cell, and later, electrolyser applications [18]. The
polymer electrolyte membrane is an acid electrolyte polymer
of Nafion and is responsible for providing high proton con-
ductivity, low gas crossover, compact system design and high
operation pressure. The low membrane thickness (20e300 mm)
is in part the reason for many of the advantages of the solid
polymer electrolyte [19]. Water reacts at the anode to form
oxygen and hydroxonium ion (H3Oþ). The electrons flow
through an external circuit and the hydroxonium ion (H3Oþ)
selectively moves across the PEM to the cathode where the
hydrogen ions combine with electrons from the external cir-
cuit to form hydrogen gas (H2). Fig. 2 e The PEM electrolyser internal structure [9].
1370 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 4 2 ( 2 0 1 7 ) 1 3 6 6 e1 3 7 4

DG
Vrev ¼ ¼ 1:229 V (6)
nF
For the reaction process defined in Equation (7) considering
standard conditions, the Gibbs free energy change is:

1
DG ¼ GH2 þ GO
GH2 O (7)
2 2
The Gibbs energy depends on the temperature T and the
pressure P and are connected via Equation (8):

DGH2 O; H2 ;O2 ðT; PÞ ¼ DHðT; PÞ þ TDSðT; PÞ (8)

For the electrolyser operating at low pressure below 7 bar

for the CETH GENHY 100 electrolyser, the stack's voltage cur-
rent curve is not significantly modified by the pressure [25].
The enthalpy H and entropy S have been evaluated using Fig. 3 e Electrolyser staXX7 of H-TEC (Stack 7 cells) [9].
Equations (9) and (10) which are valid for a temperature range
from 300 to 4000 K.
PEM electrolyser modelling
4 5 2 3 4 7
HðTÞ ¼ aj T þ bj T 4 þ cj T 2 þ dj T 4 (9)
5 3 7 The entire PEM electrolyser model comprises four physical
models: an electrical model, an electrochemical model, a
1 1 4 3
SðT; PÞ ¼ aj lnðTÞ þ 4bj T4 þ 2cj T2 þ dj T4
RlnP (10) thermodynamic model and a thermal model.
3
Therefore, the modelling in the thermodynamic field has Electrical model
been conducted neglecting the influence of the pressure, then:

DGH2 O;H2 ;O2 ðTÞ ¼ DHðTÞ þ TDSðTÞ (11) Considering a current imposed to the PEM cell, the relation-
ship between the electrolytic cell voltage and cell current can
Other specific thermodynamic functions have been be represented as the sum of the Nernst potential, activation
reached according to the National Institute of Standards and over potential and ohmic over potential. The theoretical
Technology [26]. model is expressed as [27]:

t2 t3 E VEL ¼ E þ hðIEL Þ þ Eohm (14)

DSH2 O;H2 ;O2 ¼ A$lnðtÞ þ B$t þ C vþD
2 þG (12)
2 2 2t
DG
t2 t3 t4 E E ¼ Erev ¼ (15)
DHH2 O;H2 ;O2 ¼ AT þ B þC þD
þF
H (13) nF
2 3 4 t
where, h(IEL) is the over potential due to losses, VEL is the PEM
with t ¼ TðKÞ
103 electrolysis voltage, n is the number of transferred electrons
The parameters A, B, C, D, E, F, G and H in Equations (12) of the reactions presented in Equations (2) and (3) which
and (13) are listed in Table 1. equals 2, Erev is the standard reversible voltage and Eohm is the
In this study, an electrolyser staXX7 from H-TEC composed ohmic over potential.
of 7 cells with an electrical power of 50 W, an active area of The molar flow rates of consumed water and generated
16 cm2 and a membrane thickness of 130 mm was used. At the gases can be written according to Faraday's law:
bottom and upper levels, four feeding water channels and four
evacuation channels are connected as shown in Fig. 3. The IEL
n_ ¼ n_H2 O ¼ n_H2 ¼ 2 n_O2 ¼ Ncell hf (16)
water and hydrogen outlets are the four pipes connected to the 2F
cathode. Two thermocouples are located into the cathode where Ncell is the number of electrolytic cells associated in
outlet channels within the two middle ones as close as possible series, IEL is the current across the cell electrodes, hf Faraday's
to the proton exchange membrane (MEA) for measuring the efficiency, defined as the relation between the real hydrogen
stack temperature. In addition, a third thermocouple is placed flow-rate and the theoretical one, is caused by parasitic cur-
within the water tank. Therefore, the voltage is estimated rent losses. For PEM electrolysers, it is generally assumed to be
considering a specified imposed current [12]. more than 99% [28,29].

Table 1 e The parameters of the thermodynamic functions.

A B C D E F G H
H2O
203.6060 1523.290
3196.413 2474.455 3.855326
256.5478
488.7163
285.8304
H2 33.066178
11.363417 11.432816
2.772874
0.158558
9.980797 172.707974 0
O2 31.32234
20.23531 57.86644
36.50624
0.007374
8.903471 246.7945 0
 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 4 2 ( 2 0 1 7 ) 1 3 6 6 e1 3 7 4 1371

Both H and G are temperature-dependent and the specific electrochemical reaction of the PEM electrolysis system, the
heat of hydrogen, oxygen and water are used for their calcu- water supply to the electrode-membrane interface is neces-
lation. The enthalpy H and entropy S of a chemical species (i) sary from which H2 and O2 would be produced. According to
are represented by Refs. [12,18]: the diffusion phenomena described by Fick's law, the mass
  flows are transported through the porous electrode. Both H2
b
 1 1
Hi¼H2 O; H2 ;O2 ¼ H0i þ aðT
T0 Þ þ 10
3 T2 eT20
c 105
and O2 gases produced in the electrolysis system should be
2 T T0
! removed as fast as possible to overcome any increase due to
e 1 1 mass transport limitations. The diffusion overvoltages at the

108 3
3
2 T T0 anode and the cathode, respectively, are given by Ref. [31]:
(17)
 
RTan CO2 ;me
hdiff;an ¼ ln (21)
c 1 4F CO2 ;me;o
Si¼H2 O; H2 ; O2 ¼ S0i þ aðlnT
lnT0 Þ þ b10
3 ðT þ T0 Þ
105 2
2 T  
! ! RTcat CH2 ;me
1 e 1 1 hdiff;cat ¼ ln (22)

2
108 3
3 4F CH2 ;me;o
T0 3 T T0
where CO2 ;me , CH2 ;me are the H2 and O2 concentrations at the
(18)
membraneeelectrode interface, respectively. The ohmic
The specific heat coefficients of Equations (17) and (18) (a, b, overvoltage across the PEM results from the membrane
c, d and e) are listed in Table 2. resistance to the hydrogen ions flow and is expressed as
The Nernst potential is the theoretical voltage where the [15,32e34]:
partial pressure of H2 and O2 gases is accounted for, then
∅
[12,29]: Eohm ¼ Re j ¼ j (23)
sm
DG RT
PH2 P 0:5
O2  where sm is the membrane conductivity (s/cm), ∅ is the heat
E ¼ Enernst ¼ ¼ Erev þ ln (19)
nF 2F aH2 O flow (W), and j and Re refer to the cell current density and
where P denotes the partial pressure, R ¼ 8.3144 J/mol K and ohmic resistance, respectively.
F ¼ 96 487 C/mol are respectively the universal gas constant As there is no mathematical model to determine the elec-
and Faraday's constant, the water activity aH2 O ¼ 1 (for liquid trochemical parameters related to the operating temperature,
water), PH2 and PO2 are the partial pressures of H2 and O2, the parameters aA, aC, j0,A, j0,c, sm of Equations (20) and (23)
respectively. can be estimated using Matlab™ parameter identification
tools (Fig. 4).
The heat flow is transferred from the environment to the
Electrochemical and thermodynamic model
tank and the entropy flow denoted by Q H2 O out and DSq_H2 O out
are expressed by:
The activation overpotential is defined as the overpotential
that the electrochemical reaction has to overcome for the


conversion of reactants into products. Therefore, the Butler- Q_ H2 O out ¼ m_ H2 O Cp T
TH2 O (24)
eVolmer equation is given by Ref. [30]:
Q_ H2 O out
DSq ¼ (25)
hEL ¼ Eact
anod þ Eact
cath H2 O out
T
! !
RT I RT I _ H2 O is the
where Cp: represents the water thermal capacity, m
¼ sinh
1 þ sinh
1 (20)
2aA F 2j0;A A 2aC F 2j0;C A water mass flow exiting from the membrane electrode as-
sembly (MEA) environment. The stack thermal model will be
where I is the current density (A/cm2), R is the universal gas
[11]:
constant, j0,A, j0,c are the exchange current density at the
anode and cathode, respectively, and aA, aC are the charge hX

dT  X
 i
transfer coefficients at the anode and cathode, respectively. Cth
stack ¼T DSq in
DSq out (26)
dt

Thermal model
P
ðDSq Þin is the sum of entropic flows of all heat sources.
The diffusion overvoltage, named concentration over- P
ðDSq Þout is the sum of entropic flows of all heat sinks.
potential, results from the reactants' concentrations change at
the electrode surfaces of the electrolysis considered. Due to
Three different phenomena, the electro-osmotic drag, the
back diffusion and the convection generated by pressure
gradient, result in the water flow through the membrane. The
Table 2 e Coefficients for specific heat.
pressure drop between anode and cathode, the convection of
a b c e water, and the diffusion of water are neglected. Therefore, the
H 2O 72.39 9.38 e e water drained through the membrane by electro-osmotic drag
H2 26.57 3.77 1.17 e and the total flux of water flow across the membrane is given
O2 34.35 1.92 -18.45 4.06 by:
1372 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 4 2 ( 2 0 1 7 ) 1 3 6 6 e1 3 7 4

Fig. 4 e The lookup table interpolation extrapolation of electrochemical parameters [9].

I fwater atm
n_H2 O mem ¼ nd (27) DSq conv ¼ (32)
F TH2 O
where nd is an electro-osmotic drag coefficient. The heat loss by conduction is given by:
The water flow arising from the anode to the cathode is:
l2prhtank

ADw
 fwater tank ¼ TH2 O
Tamb (33)
n_H2 O;diff ¼ nd CH2 O;me;cat
CH2 O;me;an (28) etank
dw
where A is the membrane electrode assembly area, Dw is the fwater tank
DSq cond ¼ (34)
water diffusion coefficient through the membrane, dw is the TH2 O
membrane thickness, and ðCH2 O;me;cat
CH2 O;me;an Þ refers to the where r is the cylinder tank internal radius (m) and htank is the
water concentrations at both membrane sides. The heat ex- water tank height (m).
change between the device and the surrounding atmosphere
is [35e38]: DSq cond conv ¼ DSq cond þ DSq conv (35)

1
Q_ losses ¼ ðT
Tamb Þ (29) mðtÞCtank
dTH2 O
¼ DSq þ DSq (36)
Rt H2 O
dT
H2 O out condconv

where Rt is the electrolyser overall thermal resistance (W/K), The thermal model parameters and the electrochemical
thus: parameters are respectively listed in Table 3 and Table 4.

Q_ losses
DSlosses ¼ (30)
T
For the water tank thermal energy accumulation: Experimental results


fwater atm ¼ pr2 h TH2 O
Tamb (31)
To clarify the PEM electrolyser dynamic performance, the
where r and h are cylinder tank internal radius and coefficient polarization curve of the electrolyser was analytically and
of heat transfer by convection, respectively. experimentally illustrated. The agreement between the
The entropy flow is given by: analytical and experimental-based dynamic behaviour was
verified. In Fig. 5, the VeI characteristic of the PEM electrolyser
was plotted considering a current variation from 0 A to 4 A
without operating temperature control. Therefore, the current
has been injected at a specified temperature to obtain the
Table 3 e Parameters of the thermal model [12].
polarization curve that corresponds to the PEM electrolyser
Cth_stack Stack thermal capacity (J/K) 21.06 103 modelling. From Fig. 5, an adequate agreement between the
Ctank H2 O Water tank heat capacity (J/Kg K) 95 103
analytical and experimental VeI polarization curves is
etank Tank thickness (m) 3 10
3
confirmed. In order to attain the PEM electrolyser's electrical
h Coefficient of heat transfer by 10
convection coefficient W m
2 K
1 static response through Equation (14), the electrochemical
r Cylinder tank internal radius (m) 34 10
3 parameters hEL and Eohm of Equations (20) and (23), respec-
l Heat conduction coefficient, 0.19 tively, should be initially identified via Matlab™-Simulink
W m
1 K
1 curve fitting tools.
htank Water tank height (m) 170 10
3 In Fig. 6, the VeI characteristics of the PEM electrolyser is
nd Electro-osmotic drag coefficient
1.834 þ 0.0126 T
shown for a current variation from 0 A to 1 A at different water

Table 4 e The electrochemical parameters.

T (K) 298 303 308 313 318 323 328 333
J0a 2.472 0.6551 0.9399 1.183 0.7921 1.071 0.8237 1.43
J0c 2754 1.408e4 1.048e4 5826 1.577e4 6373 1.885e4 6024
aA 0.8433 0.9656 0.8967 0.9431 0.9992 0.9498 0.9987 0.9484
ac 0.8911 0.7305 0.6393 0.6495 0.8919 0.8377 0.8769 0.5491
sm 0.4324 0.436 0.4755 0.506 0.5205 0.5411 0.5516 0.5762
 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 4 2 ( 2 0 1 7 ) 1 3 6 6 e1 3 7 4 1373

temperature increased from 297 to 309 K. Additionally, the

water tank temperature increases from 297 to 303 K. As the
electrochemical parameters obtained from the VeI experi-
mental data are temperature dependent, the acceptable
mismatch between the modelling and experimental results of
the stack and water tank were expected. The research chal-
lenges in both Hydrogen production [38] and use [39] are still
taking particular attention.

Conclusion
Fig. 5 e IeV characteristics of the PEM electrolyser.
In the present paper, a PEM electrolyser model for hydrogen
production by water electrolysis was developed. Based on the
temperatures according to Equation (14). H2 and O2 are prop- electrochemical modelling, the VeI characteristics of the PEM
erly produced despite current density transients. The current electrolyser were analyzed taking into consideration the
flow was measured and estimated up to a water temperature activation overpotential and ohmic overpotential. The PEM
of 60  C. From Fig. 6, nonlinear VeI characteristics are shown electrolyser model was validated through an identification
for the current rise up to 0.05 A. Therefore, the applied voltage approach and compared to the experimental results. This
V has been considered linearly proportional to the current I for model was applied to describe the polarization curves of the
the various proposed temperatures until a maximum injected PEM electrolyser from 25 to 60  C. The results showed an
current of 1 A. adequate agreement between both the modeling results and
The agreement between the modelling results and the lab-scale experimental data. In addition, acceptable mismatch
experimental data for both the PEM electrolyser stack and the between the analytical and experimental temperature dy-
water tank temperature profiles are shown in Fig. 7 on the namic performance for the PEM Electrolyser stack and water
basis of Equations (26) and (36), respectively. Considering an tank were found despite the temperature-dependant electro-
injected current of 4 A during approximately 55 min, the stack chemical parameters.

Fig. 6 e PEM electrolyser polarization curve at different water temperatures.

Fig. 7 e Analytical/experimental dynamic performance of the PEM electrolyser stack and water tank temperature. (a): Stack
temperature profile, (b): Water tank temperature profile.
1374 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 4 2 ( 2 0 1 7 ) 1 3 6 6 e1 3 7 4

references [20] Zoulias E, Varkaraki E, Lymberopoulos N, Christodoulou CN,

Karagiorgis GN. A review on water electrolysis. TCJST
2004;4(2):41e71.
[21] Carmo M, Fritz DL, Mergel J, Stolten D. A comprehensive
[1] Balat H, Kiraty E. Hydrogen from biomass-present scenario
review on PEM water electrolysis. Int J Hydrogen Energy
and future prospects. Int J Hydrogen Energy
2013;38:4901e34.
2010;35:7416e26.
[22] Herzog A. A hydrogen future? an economic and
[2] Balat M. Bioethanol as a vehicular fuel: a critical review.
environmental assessment of hydrogen production
Energy Sources Part A 2009;31:1242e55.
pathways. Natural Resources Defense Council; 2005.
[3] Meng N, Leung MKH, Leung DYC. Electrochemistry modeling
[23] Carpetis C. A study of water electrolysis with photovoltaic
of proton exchange membrane (PEM) water electrolysis for
solar energy conversion. Int J Hydrogen Energy
hydrogen production. In: World Hydrogen Energy
1982;7:287e310.
Conference (WHEC); 2006. Lyon, France.
[24] Grimes CA, Varghese OK, Ranjan S. Light, water, hydrogen;
[4] Meng N, Leung MKH, Leung DYC, Sumathy K. Potential of
the solar generation of hydrogen by water photoelectrolysis.
renewable hydrogen production for energy supply in Hong
US: Springer; 2008. ISBN 978-0-387-33198-0.
Kong. Int J Hydrogen Energy 2006;31:1401e12.
[25] Dahlberg R. Replacement of fossil fuels by hydrogen. Int J
[5] Turner JA. Sustainable hydrogen production. Science
Hydrogen Energy 1982;7:121e42.
2004;305:972e4.
[26] Bernardi DM, Verbrugge MW. Mathematical model of a gas
[6] Lutz AE, Bradshaw RW, Bromberg L, Rabinovich A.
diffusion electrode bonded to a polymer electrolyte. AIChE J
Thermodynamic analysis of hydrogen production by
1991;37:1151e63.
partial oxidation reforming. Int J Hydrogen Energy
[27] Tao Z. Control and energy management of a hybrid active
2004;29:809e16.
wind generator including energy storage system with
[7] Colella WG, Jacobson MZ, Golden DM. Switching to a U.S
supercapacitors and hydrogen technologies for microgrid
hydrogen fuel cell vehicle fleet: the resultant change in
application. PhD from the Ecole Centrale of Lille, France. 30
emissions, energy use, and greenhouse gases. J Power
June 2009.
Sources 2005;4:150e81.
[28] http://webbook.nist.gov.
[8] Onda K, Kyakuno T, Hattori K, Ito K. Prediction of production
[29] Perez H, Perez V, Page M, Beneito R. Monitoring and control
power for high-pressure hydrogen by high-pressure water
of hydrogen production and storage system consisting of
electrolysis. J Power Sources 2004;132:64e70.
water electrolysis and metal hybrids. Int J Hydrogen Energy
[9] Dedigama I, Ayers K, Shearing RP, Brett DJL. An
2010;35:912e9.
experimentally validated steady state polymer electrolyte € rgün H. Dynamic modelling of a proton exchange
[30] Go
membrane water electrolyser model. Int J Electrochem Sci
membrane (PEM) electrolyzer. Int J Hydrogen Energy
2014;9:2662e81.
2006;31:29e38.
[10] Marr C, Li X. An engineering model of proton exchange
[31] Ni M, Leung MKH, Leung DYC. Parametric study of solidoxide
membrane fuel cell performance. Int J Phys Eng Sci
steam electrolyzer for hydrogen production. Int J Hydrogen
1998;50:190e200.
Energy 2007;32:2305e13.
[11] Lebbal ME, Lecœuche S. Identification and monitoring of a
[32] Ganguly A, Ghosh S, Misra D. Modeling and analysis of solar
PEM electrolyser based on dynamical modelling. Int J
PV power system for greenhouse application with
Hydrogen Energy 2009;34:5992e9.
electrolyzer fuel cell back up. In: 3rd International
[12] Agbli KS, Pera MC, Hissel D, Rallieres O, Turpin C, Doumbia I.
Conference of Energy Sustainability, vol. 1; 2009. p. 19e23.
Multiphysics simulation of PEM electrolyzer:energetic
[33] Harrison KW, Hernandez-Pacheco E, Mann M, Salehfar H.
macrospic representation approach. Int J Hydrogen Energy
Semiempirical model to determining PEM electrolyser
2011;36:1382e98.
stack characteristics. J Fuel Cell Sci Technol 2006;3:220e3.
[13] Rau S, Vierrath S, Ohlmann J, Fallisch A, Lackner D,
[34] Dale NV, Mann MD, Salehfar H. Semiempirical model based
Dimroth F, et al. Highly efficient solar hydrogen generation-
on thermodynamic principles for determining 6 KW proton
an integrated concept joining III-V solar cells with PEM
exchange membrane electrolyser stack characteristics. J
electrolysis cells. Energy Technol 2014;2:43e53.
Power Sources 2008;185:1348e53.
[14] Yunfeng Z, Jing L, Liang M, Weiwei C, Hansong C. Recent
[35] Biaku CY, Dale NV, Mann MD, Salehfar H, Peters AJ, Han T. A
developments on alternative proton exchange membranes:
semiempirical study of the temperature dependence of the
strategies for systematic performance improvement. Energy
anode charge coefficient of a 6 kW PEM electrolyser. Int J
Technol 2015;3:675e91.
Hydrogen Energy 2008;33(16):4247e54.
[15] Marangio F, Santarelli M, Calı M. Theoretical model and jar R, Urbina A.
[36] Garcı́a-Valverde R, Miguel C, Martı́nez-Be
experimental analysis of a high pressure PEM water
Optimized photovoltaic generator-water electrolyser
electrolyser for hydrogen production. Int J Hydrogen Energy
coupling through a controlled DC-DC converter. Int J
2009;34:1143e58.
Hydrogen Energy 2008;33:5352e62.
[16] Kai Z, Dongke Z. Recent progress in alkaline water
[37] Ulleberg Ø. Modeling of advanced alkaline electrolyzers: a
electrolysis for hydrogen production and applications. Prog
system simulation approach. Int J Hydrogen Energy
Energy Combust Sci 2010;36:307e26.
2003;28:21e33.
[17] T. Denis, Alkaline vs PEM electrolysers: lessons learnt from
[38] Tabanjat A, Becherif M, Emziane M, Hissel D, Ramadan HS,
Falkenhagen and WindGas Hamburg, Hydrogen Days,
Mahmah B. Fuzzy logic-based water heating control
Prague, Czech Republic, 06.04.2016.
methodology for the efficiency enhancement of hybrid PV-
[18] Carmoa M, Fritza DL, Mergela J, Stoltena D. A comprehensive
PEM electrolyser systems. Int J Hydrogen Energy February
review on PEM water electrolysis. Int J Hydrogen Energy
2015;40(5):2149e61.
2013;38:4901e34.
[39] Becherif M, Ramadan HS, Cabaret K, Picard F, Simoncini N,
[19] Mazloomi SK, Nasri S. Influencing factors of water
Bethoux O. Hydrogen energy storage: new techno-economic
electrolysis electrical efficiency. Renew Sustain Energy Rev
emergence solution analysis. Energy Proced August
2012;16:4257e63.
2015;74:371e80.