Energy 190 (2020) 116420

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Evaluation of hydrogen production via electrolysis with ion exchange

membranes
B. Yuzer a, b, *, H. Selcuk a, G. Chehade b, M.E. Demir b, I. Dincer b, c
a
Department of Environmental Engineering, Engineering Faculty, Istanbul University-Cerrahpasa, Istanbul, Turkey
b
Clean Energy Research Laboratory, Faculty of Engineering and Applied Science, University of Ontario Institute of Technology, 2000 Simcoe Street North,
Oshawa, Ontario, L1H 7K4, Canada
c
Department of Mechanical Engineering, Yildiz Technical University, Istanbul, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: In this study, the ion exchange membranes are proposed and tested in an electrolysis process for
Received 19 July 2019 hydrogen production from acidic and alkaline solutions. The results of the experiments are then
Received in revised form compared to evaluate the effect of ion exchange membranes on the performance of the electrolysis
19 October 2019
process. This study shows that the ion exchange membranes can improve the performance of the
Accepted 22 October 2019
Available online 23 October 2019
electrolysis reactor and supply high pH differences between compartments due to the membrane’s
feature of low electrical resistance and high resistance to pH changes. All anion exchange membrane,
cation exchange membrane, and bipolar membrane are used individually as a separator between anode
Keywords:
Electrolysis
and cathode chamber of electrolysis reactor to evaluate the effect of these ion exchange membranes on
Hydrogen production system efficiency. Also, the comparison of using ion-exchange membranes to generate hydrogen in the
Ion exchange membranes acidic-alkaline electrolysis reactor is studied for the first time in this study. The electrolysis reactor is
Efficiency tested using various electrochemical techniques and analyzed thermodynamically. The maximum
Energy hydrogen production rate is determined with the bipolar membrane as 11.4 mmol/h, while the highest
energy and exergy efficiencies are found for the reactor configuration with anion exchange membrane as
82% and 68%, respectively.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction biochemical, reverse electro-electrodialysis, electro-thermal,

The combustion of carbon-based fuels such as coal and petro-
leum releases carbon dioxide (CO2) to the atmosphere causing
extreme weather patterns while the waste products are severely
polluting the environment. In order to move towards a sustainable
and environmentally benign world, it is essential to replace carbon-
based fuels with sustainable green energy. Hydrogen, the simplest
element in the periodic table, consists of a large proton and a single
electron charge on its valence shell, is considered an energy-
efficient low polluting fuel [1]. However, hydrogen does not pre-
sent inherently in nature. It is found in water and many fuels such
as gasoline, natural gas, methanol, and propane. Thus, hydrogen
requires some processes to be produced. Methods, such as
renewable and nuclear energy, photo-assisted electrolysis,
* Corresponding author. Department of Environmental Engineering, Engineering
Faculty, Istanbul University-Cerrahpasa, Istanbul, Turkey.
E-mail address: byuzer@istanbul.edu.tr (B. Yuzer).
photo-thermal, and thermochemical water splitting are primarily
carbon-free, thus are considered promising candidates for a
diversified energy supply [2e6]. The electrolysis contributes to 4%
of the global hydrogen production, while it is an efficient way to
store and transport energy. Researches continue to improve the
overall system efficiency by using different electrode materials and
membrane separators between anode and cathode compartments.
Coupling alternatives, storage mediums and electrolyzer mem-
brane assemblies are progressing to ensure better efficiencies.
Kotowicz et al. [7] proposed a methodology to determine the effi-
ciency of hydrogen production systems that takes into account the
power needs of its subsidiary systems. They presented a set of
laboratory test results on a PEM water electrolyzer-based hydrogen
generator for a wide range of system loadings. The output charac-
teristics of the electrolyzers, including that of the entire hydrogen
generator, were calculated using the power supply monitored for
its auxiliary devices. Based on the results of the experimental tests,
the authors have proposed generalized characteristics of hydrogen
generator efficiency. Mohammadi and Mehrpooya [8] have

https://doi.org/10.1016/j.energy.2019.116420
0360-5442/© 2019 Elsevier Ltd. All rights reserved.
2 B. Yuzer et al. / Energy 190 (2020) 116420
Nomenclature
a Number of electrons transformed to produce
hydrogen
F Faraday constant (96485 A s/mol)
HHV Higher heating value (kJ/mol)
I Electric current (A)
t Time (sec)
n_ Mol flow rate (mol/sec)
V Volume (L)
W _ Work rate (kW)
Greek Letters
h Efficiency
Acronyms
IEMs Ion-exchange membranes
reviewed different methods of coupling electrolyzers with various
renewable energy sources to determine the most efficient system
and it is indicated that the most promising renewable energy
source to produce hydrogen is hydroelectric. In addition, types of
membrane and electrolytes can affect the reactor performance
considerably. Ion-exchange membranes (IEMs) have gained much
interest in electromembrane processes such as electrodialysis,
diffusion dialysis, energy conversion, energy storage, and also in
electrolysis. Ogungbemi et al. [9] have discussed the use of mem-
branes in fuel cell applications to produce energy and concluded
that composite membranes can increase the cell voltage and overall
performance of the cell by up to 11% and 17%, respectively. Sakr
et al. [10] have used acrylic separator and polymeric membrane to
separate the anode and cathode compartments in an alkaline water
electrolysis cell. They have reported that the hydrogen production
efficiency was higher when using the membrane as a separator
instead of the acrylic separator. IEMs are divided into 3 subsets of
membranes: anion exchange membrane (AEM), cation exchange
membrane (CEM), and bipolar membrane (BPM). Generally, AEMs
and CEMs are used in the electrolysis process to produce chlorine
and caustic soda or hydrogen and oxygen. Also, they are the key
elements in energy storage processes like batteries. There are two
types of batteries reported by Strathman [11], such as “concentra-
tion flow battery” and neutralization flow battery.” AEM and CEM
are usually used in concentration flow batteries, and the open cell
voltage depends on the ion concentration gradients of the two
adjacent compartments composed by IEMs. Weng et al. [12] have
used both AEM and CEM as separators in a three-electrolyte elec-
trochemical energy storage system and indicated that the proposed
method had reduced the internal resistance of the battery system,
which resulted in higher Coulumbic and voltage efficiencies.
On the other hand, BPMs are used in neutralization flow bat-
teries [13]. The electrical potential is generated by the difference
between Hþ and OH ion concentrations between the anion- and
cation-exchange layers of the BPM, called “open voltage” of the
battery. The open cell voltage of this battery depends on the Hþ and
OH ion concentrations, and open-cell voltage is the main differ-
ence between these two batteries. Li et al. [14] investigate the
performance of a modified BPM as diaphragms for hydrogen pro-
duction from water electrolysis. The related BPM is synthesized by
plasma-induced polymerization, and the performance analysis is
conducted by measuring the cell voltage and H2 production rate for
cells operated with or without the presence of the BPMs, as a
AEM Anion exchange membrane
BPM Bipolar membrane
CEM Cation exchange membrane
CV Cyclic voltammetry
IL Interfacial layer
OCP Open circuit potential
PEM Proton exchange membrane
PEG Polyethylene glycol
PVA Polyvinyl alcohol
Subscripts and Superscripts
En Energy
Ex Exergy
H2 Hydrogen
m Molar
function of current densities. The results show that the hydrogen
production efficiency of the cell is improved by about 10e20% by
using the modified BPMs as diaphragms.
AEMs can be used in electrochemical applications, mostly in fuel
cells due to their ability to work in low-temperature mediums and
non-precious metals as a catalyst [15,16]. The most dominant
transport mechanisms in AEMs are diffusion, migration, convec-
tion, and Grotthuss mechanism, which transport OH through the
membrane surface. Recently, Hibbs et al. [17] developed AEMs by
varying the amount of ammonium, resulting in high ion exchange
capacity. The study was compared to that of proton exchange
membrane (PEM). The results show that the self-diffusion coeffi-
cient was higher in AEM, but the binding-water in the membrane
was lower when compared to PEM. Ito et al. [18] have increased the
hydrogen pressure in an AEM electrolyzer in order to test elec-
trolysis performance, and they indicate that the hydrogen barrier
ability of the AEM is superior to a PEM. The lower mobility of the
OH is associated with slow water diffusion. Grew and Chiu [19],
conducted research to identify the factoring limit for OH transport
in the AEM. Their study concluded that the Grotthuss mechanism
contributes to the proton transport in aqueous solution and the
main mechanism for OH transport. However, other researchers
showed that the OH transport is limited to the solvation shell and
discompose the hydrogen bond network [20,21]. Thus, it can be
said that AEMs contributes to the OH transport and hydrogen
network in an alkali solution. Taking the mechanism of an AEM in a
fuel cell and reversing the reaction into an electrolysis cell, the
transport phenomena of the OH across the membrane from the
anode and formation of Hþ on the cathode can be attained. In an
AEM electrolysis reactor, the cathode and anode form the external
circuit, which provides DC power. The internal circuit is separated
by the AEM in an alkaline electrolyte. Water at the anode side
combines with the transported OH across the membrane, and
electron transfer occurs in the external circuit; thus water and
oxygen are the products of the half-reaction. While at the cathode
side, the hydrogen network bond breaks to form hydrogen ions
with electron transfer hydrogen ions become hydrogen gas, which
forms on the electrode surface [22]. The half-reactions take place
when the theoretical, applied potential is greater than Gibbs free
energy. However, in practice, the minimum applied potential is
higher than the theoretical potential due to the ohmic resistance
and to overcome the kinetics of the electrolyte, which is typically
higher than 1.85 V at normal operating conditions [23].
 B. Yuzer et al. / Energy 190 (2020) 116420 3

Fig. 1. Schematic presentation of the experimental setup and parts of the electrolysis reactor.

CEMs are made mainly from cationic groups which are directly two layers, can generate hydroxide ions (OH) and protons (Hþ)
deposited on the polymer backbones, and they preclude the pas- simultaneously making it the best candidate for producing acid and
sage of anions and allows cations from passing through the mem- base. Water dissociation occurs throughout the interface of the
brane. CEMs are mostly functional in the diffusion dialysis for base BPMs showing promising technology that is still under investiga-
recovery. Recent studies suggested that the sulfonic acid group is tion. BPMs are similar to p-n type junction semiconductors, though
the best cation-exchange functional groups due to its strong acidity the junction formed at the BPM interfacial layer (IL) creates a
and high conductivity [24,25]. Although developed technologies on depletion region causing the bias over potential. BPMs are generally
chain-type characterization for CEMs, low cation conductivity is prepared by layer by layer casting of cation exchange layer and
apparent and restricting the potential practical applications in anion exchange layer, in the presence of heat, pressure and/or ad-
electrodialysis. In order to improve the functionality and conduc- hesive. This results in a thin layer commonly known as the inter-
tivity of CEMs Bae et al. [26] proposed an interconnected cation- facial layer between the anion and cation layer. When an electrical
conducting channel on the backbone material using sulfonation potential is applied to the membrane, ions are removed from the
co-polymers, the CEMs showed high proton conductivity due to the interfacial layer between the two membrane layers. When only
inter-connected ionic channels. However, BPM, which is composed water remains at the interfacial layer, the water dissociates to
of an anion layer, a cation layer, and an interfacial layer between the protons and hydroxide ions continuously due to the driving force of
an electrical potential gradient in the BPM. The transportation of
the electrical charges is driven by these protons and hydroxide ions
Table 1 generated in the BPM. The IL is developed according to chemical
Properties of ion-exchange membranes.
composition and structure based on the mechanism of proton
Membrane Type Anion exchange Cation exchange transfer. Chabi et al. [27] have prepared BPMs and assessed their
Functional group Strong basic Strong acidic suitability for solar-driven water-splitting process. It is revealed
Ammonium Sulfonic acid
that the interface between CEM and AEM produces a large electric
Perm selectivity >0.95 >0.95
KCl (0.1/0.5 N) Acid (0.7/3 N)
field, which enables fast water dissociation. In this study, the effects
Resistivity/W cm2 z1.8 z2.5 of ion-exchange membranes on the electrolysis process are evalu-
Active membrane area, cm2 64 64 ated comparatively by using acid (H2SO4) and base (NaOH) solu-
Water content (wt %) z14 z9 tions as electrolytes in the cathode and anode compartments,
Max operational temperature,  C 60 50
respectively. In the literature, studies generally focus on the use of
Thickness, mm 180e220 160e200
Membrane size, mm 110  110 110  110 one type of ion-exchange membrane to produce hydrogen in the
Ionic form Cl Naþ electrolysis process [28e30]. However, in this particular research,
4 B. Yuzer et al. / Energy 190 (2020) 116420

three different types of ion-exchange membranes (anion exchange

membrane, cation exchange membrane, and bipolar membrane)
are tested and compared with each other for the first time by using
acidic and alkaline electrolytes at the cathode and anode com-
partments, respectively. Strong acidic, sulfonic acid based cation
exchange membrane, and strong basic ammonium based anion
exchange membrane are selected in this study. The bipolar mem-
brane consists of the laminate of the cation and the anion exchange
membrane layer. The performance evaluation of the membranes is
performed due to their impact on the hydrogen production process.
The membranes are characterized by electrochemical methods.
The pH gradient between anode and cathode compartments
reduces the required energy and thermodynamic voltage for
hydrogen production [31] because the system consumes the acid
and base, which reduces the initial applied electrochemical po-
tential difference. Ion exchange membranes provide pH gradients
between anolyte and catholyte solutions. However, the consumed Fig. 3. Cyclic voltammetry graph for ion exchange membranes in the electrolysis
acid and base have to be replaced or regenerated. At this point, BPM process (distance between anode and cathode electrodes is 2.2 cm, anolyte: 1 M NaOH,
can be used to increase the acidity and alkalinity of the electrolytes catholyte: 1 M H2SO4).
by producing OH and Hþ ions continuously. Another important
parameter is the distance between the anode and cathode elec-
trodes. Two different distances (0.8 cm and 2.2 cm) are tested to by using thick and thin rubber frames. Also, the solution volume of
observe the effect on hydrogen production via electrolysis process. the electrolysis reactor is increased from 50 mL to 140 mL by
increasing the distance between the electrodes.
Ion exchange membranes are placed between anode and cath-
2. Experimental apparatus and procedure ode sides and separated by rubber frames in order to adjust the
distance between anode and cathode electrodes. The generated
In this section, the design and construction processes of the hydrogen gas is collected from the channels placed on the elec-
reactor, preparation processes of the electrolyte solutions, data trolysis reactor.
collecting instruments, and performance assessment methods are The electric power supplied by a potentiostat to the electrolysis
described under sub-sections. reactor and all the data obtained stored in a computer connected to
the potentiostat. Also, the open circuit potential (OCP), cyclic vol-
2.1. Electrolysis reactor tammetry (CV) graphs, and current densities are monitored for all
ion exchange membranes at two different electrode distances by
Electrodialysis cell (PCCell GmbH, Heusweiler, Germany) is using potentiostat. The hydrogen gas production is measured by
modified by installing a graphite bipolar plate as the anode gas flow meter connected to the exit of the reactor and then
(64 cm2) and perforated 304 stainless steel (29 cm2) to produce collected in a column to measure the total collected gas volume by
hydrogen gas as in Fig. 1. The electrolysis process performance is water displacement method (Fig. 1).
evaluated based on the conditions affecting hydrogen production,
such as the following: 2.2. Ion exchange membranes

 Using monopolar and bipolar ion exchange membranes for the
separation of anode and cathode chamber.
 The distance between anode and cathode electrodes are
adjusted to 2.2 cm and 0.8 cm
The adjustment of the distance between two electrodes is made
Commercial ion exchange membranes such as anion exchange
membrane, cation exchange membrane, and bipolar membrane are
purchased from PCCell GmbH, Germany. The ion-exchange mem-
branes are produced for standard desalination applications in the
electrodialysis process; however, in this study, they are tested for
hydrogen production in the electrolysis reactor. The AEM is highly

Fig. 2. Open circuit potential graph for ion exchange membranes in electrolysis process (a) distance between anode and cathode electrodes is 2.2 cm, (b) distance between anode
and cathode electrodes is 0.8 cm (anolyte: 1 M NaOH, catholyte: 1 M H2SO4).
 B. Yuzer et al. / Energy 190 (2020) 116420 5

Fig. 4. Cyclic voltammetry graph for (a) monopolar membranes and (b) bipolar membrane in electrolysis process (distance between the anode and cathode electrodes is 0.8 cm,
anolyte: 1 M NaOH, catholyte: 1 M H2SO4).

alkaline and composed of ammonium group, while the CEM is
highly acidic and composed of sulfonic acid. These membranes are
the standard ion exchange membranes for the water desalination
processes. Using these membranes in the electrolysis process will
provide integration of different processes such as water treatment
and hydrogen production at the same time. The properties of ion
exchange membranes are given in Table 1 derived from the
supplier.
2.3. Electrolyte solutions
Since the resistivity of electrolyte solutions affect the energy
losses in the electrolysis process, the overall energy losses in an
electrolysis reactor can be minimized when acidic and basic elec-
trolytes are used on the cathode and anode sides of the reactor
respectively [32]. Anode compartment is filled with 1 M NaOH, and
the cathode compartment is filled with 1 M H2SO4 as electrolyte
solutions.
2.4. Experimental procedure
One ion exchange membrane is installed to the electrolysis
reactor between the anode and cathode compartments and
replaced with another after one set of the experiment ended. After
the assembling of the reactor, cathode and anode compartments
are filled with H2SO4 (1 M) and NaOH (1 M) electrolytes, respec-
tively. First, the OCP and CV graphs obtained for the electrolysis
reactor with each membrane by using the potentiostat. Then,
electrolyte solutions are replaced with the new ones, and the
hydrogen production capability of the electrolysis reactor with each
membrane is monitored by applying the constant voltage to the
reactor for 30 min under the same conditions. The applied poten-
tials are decided according to the CV graphs that give the required
current density to initiate the hydrogen production, and the ob-
tained hydrogen production rates are extrapolated to 1 h. All the
experiments are conducted at the standard ambient temperature
(25  C) and pressure (1 atm). At these conditions, Faraday, energy,
and exergy efficiencies are calculated.
2.5. Efficiency and performance assessment
The energy, exergy, and Faraday efficiencies of the electrolysis
system are calculated in order to evaluate the system performance
from various perspectives. The Faraday efficiency is an important
parameter to compare system efficiencies in the electrolysis pro-
cess. It refers to the value of the transformed current in hydrogen
evaluation reaction, and it is the ratio of hydrogen volume obtained
during the experiment to the theoretical hydrogen volume that is
produced at the applied current.
The Faraday efficiency is calculated by:

Fig. 5. Graph of current densities for ion exchange membranes in electrolysis process during hydrogen production (a) the distance between anode and cathode electrodes is 2.2 cm,
applied potential for BPM: 3.7 V, monopolar membranes 1.9 V and (b) the distance between anode and cathode electrodes is 0.8 cm, applied potential for BPM: 2.7 V, monopolar
membranes 1.9 V (anolyte: 1 M NaOH, catholyte: 1 M H2SO4).
6 B. Yuzer et al. / Energy 190 (2020) 116420

Fig. 6. Graphs of (a) hydrogen production rates, (b) Faraday efficiencies, (c) energy efficiencies, (d) exergy efficiencies for ion exchange membranes in electrolysis process during
hydrogen production (applied potential for BPM: 3.7 V, monopolar membranes 1.9 V distance between anode and cathode electrodes is 2.2 cm, anolyte: 1 M NaOH, catholyte:
1 M H2SO4).

Here hex is the exergy efficiency hH_ 2 is the hydrogen mol flow (mol/
VH2 sec) exH2 is the exergy value of the hydrogen (kJ/mol) and W _ e is the
hFaraday ¼ experimental
I:t:Vm
(1) amount of energy that is given to the system (kW).
a:F

Here VH2 is the hydrogen volume produced during the experiment
(L), I is the electric current (A), t is the experiment time (sec), Vm is
the molar volume of the hydrogen (L), a is the number of electrons
transformed to produce hydrogen gas at the cathode, and F is the
Faraday constant (96485 A s/mol).
The energy efficiency is the ratio of the energy values of useful
products obtained in an electrolysis process to the total amount of
consumed energy in the electrolysis process. The following formula
is used to calculate the energy efficiency of the system:
nH_ 2 $HHVH2
hen ¼ _e
(2)
W
Here hen is the energy efficiency hH_ 2 is the hydrogen mol flow (mol/
sec) HHVH2 is the higher heating value of the hydrogen (kJ/mol) and
_ e is the amount of energy that is given to the system, work rate
W
(kW).
Similarly, the exergy efficiency is the ratio of the exergy values of
useful products obtained in an electrolysis process to the total
amount of exergy inlet to the electrolysis process. The following
formula is used to calculate the exergy efficiency of the system:
nH_ 2 $exH2
hex ¼ _e
(3)
W
3. Results and discussion
The testing of OCP is commonly performed before any electro-
chemical characterization to obtain information about the nature of
the reactor. Since the OCP is dependent on the dissolved oxidant
and metal passivity, it is used as an indicator of such conditions.
Strathmann [11] reported that the open cell voltage of the con-
centration flow battery is proportional to the concentration dif-
ference of the two adjacent ionic solutions separated by the AEM or
CEM. Also, the OCP is calculated as 0.23 V assuming monovalent salt
concentration is 1 mol in brine solution at the concentrate
compartment and 0.01 mol at the dilute concentration. Similar OCP
results are obtained for the configurations with IEM and 2.2 cm of
electrode distance, as shown in Fig. 2. The lowest OCP is observed as
average 150 mV for the AEM membrane.
Also, it can be said that BPM exhibits the p-n type junction
semiconductors’ [33] or neutralization flow battery properties [11];
thus, the highest open-circuit voltage is observed around 850 mV
for BPM which is the similar value reported in the literature [33].
This means the higher electrical potential is generated by BPM, and
electrolysis system is charged by BPM due to the acid and base
concentration gradient at the BPM surfaces.
When the distance between anode and cathode electrodes de-
creases to 0.8 cm, the OCP potentials of the monopolar membranes
decrease to a negative value, and OCP of the BPM is reduced to
around 700 mV (Fig. 2 (b)). This indicates that the lower distance
 B. Yuzer et al. / Energy 190 (2020) 116420
Fig. 7. Graphs of (a) hydrogen production rates, (b) Faraday efficiencies, (c) energy efficiencies, (d) exergy efficiencies for ion exchange membranes in electrolysis process during
hydrogen production (applied potential for BPM: 2.7 V, monopolar membranes 1.9 V, distance between anode and cathode electrodes is 0.8 cm, anolyte: 1 M NaOH, catholyte:
1 M H2SO4).
between electrodes results in the discharge of the electrical po-
tential in the electrolysis cell, and the required overpotential
decreased by this way. Also, when the distance between electrodes
decreases to 0.8 cm, almost the same results of the OCP are ob-
tained for the AEM and CEM.
The experimental protocol to conduct CV experiment is per-
formed by sweeping the potential of the stainless steel electrode/
working electrode back and forth within a pre-set regime, and
recording the current flow. The recorded peaks present in both the
forward and reverse scan refer to the corresponding oxidation-
reduction reactions. The cyclic voltammetry graph obtained at the
2.2 cm electrode distance, given in Fig. 3. The required voltage in
order to get the same current density values for the ion exchange
membranes is the highest for BPM and lowest for the AEM.
The increase in the system performance is observed from the CV
graphs given in Fig. 4 when the distance between electrodes
decreased to 0.8 cm. The higher current densities obtained with
lower voltages when the electrode distance is reduced. This
improvement is caused by the decrease of electrolyte resistivity by
decreasing the distance.
After electrochemical characterization, the reactor is subjected
to an overpotential, and the stainless steel electrode in polarized
cathodically. Under such conditions, electrons flow through the
outer circuit. The magnitude of the current passing through the
working electrode and the counter electrode is recorded. The
constant voltage values applied to the electrolysis reactor to pro-
duce hydrogen, and the change in current densities are monitored
7
continuously. Based on the OCP and CV results where the distance
of electrodes is 0.8 cm, the applied voltages are set as 2.7 V and 1.9 V
for BPM and monopolar membranes, which correspond to the same
level of current densities. The current density values for ion ex-
change membranes while the distance between electrodes is
2.2 cm are given in Fig. 5 (a). In the literature, the applied current
density values for alkaline and polymer membrane electrolyzers
vary between 200 and 400 mA/cm2 and 600e2000 mA/cm2 [23].
The obtained current densities are low with respect to the results
given in literature; however, the hydrogen production is still high
with ion-exchange membranes.
When the distance between the electrodes is decreased to
0.8 cm, higher current density values are obtained with ion-
exchange membranes, as shown in Fig. 5 (b). The applied poten-
tial for the BPM is 2.7 V and 1.9 V for the monopolar membranes. It
is interesting that similar to the OCP measurements, the same trend
is seen with the AEM and the CEM for current density values.
Almost the same current density values obtained with monopolar
membranes. Since the current density values decrease by the time
with monopolar membranes, the stable current density values
obtained with the BPM.
Hydrogen production rates of ion exchange membranes are
given in Fig. 6 (a) for the distance between electrodes is 2.2 cm. The
highest production rate is obtained with the BPM; however, the
applied potential is twice of the monopolar membranes. The
Faraday efficiencies of the BPM and the AEM are calculated as 100%
for both while it is calculated as 98% for the CEM, as shown in Fig. 6
8 B. Yuzer et al. / Energy 190 (2020) 116420
(b). The energy efficiencies of the electrolysis process with ion-
exchange membranes are given in Fig. 6 (c), and the same values
are obtained (77%) for the AEM and the CEM. On the other hand,
41% of energy efficiency is achieved with the BPM. The same trend
is seen for the exergy efficiency values since 63% of exergy effi-
ciencies obtained with the AEM and the CEM. 34% of exergy effi-
ciency is calculated for the BPM (Fig. 6 (d)).
As it is expected, the hydrogen production rates are increased
with the decreasing electrode distance. The hydrogen production
rate is given in Fig. 7 (a) and calculated as 11.4 mmol/h with the
BPM and 8.2 mmol/h for the AEM. The Faraday efficiencies of the
BPM and the AEM are calculated as 100% for both, as shown in Fig. 7
(b). Energy efficiency for the BPM is increased by the decreasing
electrode distance; however, it is still low with respect to monop-
olar membranes (Fig. 7 (c)). The exergy efficiency values are given
in Fig. 7 (d). The highest energy and exergy efficiencies are found
81% and 67%, respectively. It is evident that BPM has the lowest
exergy efficiency value while it has the highest hydrogen produc-
tion rate.
The results of this study are compared with literature. Nazemi
et al. [31] investigate the monopolar alkaline electrolyser operates
with acidic and basic electrolyte types at room temperature where
the electric current density is 20 mA/cm2. The electric potential of
the electrolyser is reported as between 1.2 V and 2.2 V and the
hydrogen conversion rate of 98.8%. In this study, current density is
obtained in the range of 0.10e0.20 A/cm2 at the cell potential of
1.9 V for monopolar membranes. Similarly the conversion rate is
obtained in the same range as presented in Fig. 7 (b). Li et al. [29]
investigated an electrochemically neutralized energy-assisted
alkaline electrolyze with bipolar membrane assembly. The elec-
trolyser used acidic and basic electrolytes similar to this study and
operated under 3.0 V to obtain 10 mA/cm2 of current density with a
Faraday efficiency of 100%. In this study, 15 mA/cm2 of current
density is obtained under 3.7 V of cell potential and a Faraday ef-
ficiency of 100% which show similar trend with data published in
the literature.
4. Conclusions
In this study, the performances of the AEM, CEM, and BPM in the
electrolysis process for hydrogen production are evaluated
comparatively. Also, the effect of distance between anode and
cathode electrodes on the electrolysis process is examined. The
open-circuit potential is measured as 850 mV, and this is resulted in
a higher overpotential for the BPM due to the water dissociation at
the junction of the ion exchange membranes. The BPM membrane
shows a stable current density value as 20 mA/cm2 during
hydrogen production. On the other hand, the current density value
decreases from 20 mA/cm2 to 7 mA/cm2 as a result of the replace-
ment of the membrane to monopolar ion-exchange membranes.
The higher hydrogen production obtained as 11.4 mmol/h with the
BPM; however, the lowest energy and exergy efficiencies were
calculated as 55% and 45% for the BPM, respectively.
The distance between anode and cathode electrodes affects
system performance. When the distance decreased from 2.2 cm to
0.8 cm, the energy and exergy efficiencies, the hydrogen production
rates, and the current density values increased around 34%, 32%,
47%, and 42% in the electrolysis process, respectively.
Using ion-exchange membranes in the acid/base electrolysis
process for hydrogen production gives promising results. For
further studies, using spent acid and alkali liquors from the metal
industry in this process will decrease the environmental impact of
those waste solutions while producing hydrogen energy.
Acknowledgment
The authors would like to thank the EU, and the Natural Sciences
and Engineering Research Council of Canada for funding, in the
frame of the collaborative international Consortium ECOSAFE-
FARMING financed under the ERA-NET WaterWorks2015 Cofunded
Call. This ERA-NET is an integral part of the 2016 Joint Activities
developed by the Water Challenges for a Changing World Joint
Programme Initiative (Water JPI).
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