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Chlorine-free alkaline seawater electrolysis for

hydrogen production

Gidon Amikam, Paz Nativ, Youri Gendel*

Faculty of Civil and Environmental Engineering, Technion, Haifa, 32000, Israel

article info abstract

Article history: A new process for chlorine-free seawater electrolysis is proposed in this study. The first
Received 18 September 2017 step of the process is separation of Mg2þ and Ca2þ ions from seawater by nanofiltration.
Received in revised form Next, the NF permeate is dosed into the electrochemical system. There it is completely
26 January 2018 split into hydrogen and oxygen gases and NaCl precipitate. The electrochemical system
Accepted 12 February 2018 comprises an electrochemical cell operated at elevated temperatures (e.g.  50  C) and a
Available online xxx settling tank filled with aqueous NaOH solution (20e40 %wt) that operates at lower
temperatures (e.g. 20e30  C). High concentration of hydroxide ions in the electrolyzed
Keywords: solution prevents anodic chlorine evolution, while the accumulated NaCl precipitates in
Seawater electrolysis the settling tank. Batch electrolysis tests, performed in NaCl-saturated NaOH solutions,
Alkaline electrolysis showed absolutely no chlorine formation on Ni200 and Ti/IrO2eRuO2eTiO2 anodes at
Chlorine evolution [NaOH] > 100 g/kgH2O. Three long-term operations (9, 12 and 30 days) of the electro-
Hydrogen production chemical system showed no Cl2 or chlorate (ClO
3 ) production on both electrodes operated

at current densities of 93e467 mA/cm2. The Ni200 anode was corroded in the continuous
operation that resulted in formation of nickel oxide on the anode surface. On the other
hand, the system was successfully operated at 467 mA/cm2 with Ti/IrO2eRuO2eTiO2
electrodes in NaCl-saturated solution of NaOH (30 %wt) for 12 days. During this period no
formation of Cl2 and ClO
3 has been observed and precipitation of NaCl occurred only in

the settling tank. The performance of the system was stable during the operation as
indicated by the insignificant fluctuations in the applied cell potentials and measured
constant concentrations of NaOH(aq) and NaCl(aq) in the electrolyte solution. During 12
days of operation at z 470 mA/cm2 about 1.2 m3 of H2 and z150 g of solid NaCl were
produced in the system. Electrical energy demand of the electrolysis cell was 5.6e6.7 kWh/
m3H2 for the current density range of 187e467 mA/cm2.
© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

global energy demand are approximately 86, 6.8, 4.43 and

Introduction
Global energy consumption was z158 PWh in 2016 [1]. Con-
tributions of fossil fuels (oil, coal and gas), hydropower, nu-
clear power and renewable resources (e.g. solar and wind) to
2.77%, respectively [1]. Today more than 70% of electrical en-
ergy is generated from fossil fuels [2]. Concerns with global
CO2 emissions and increasing costs of fossil fuels motivate
intensive research for the development of technologies for
energy production from renewable resources such as wind

* Corresponding author.
E-mail address: ygendel@tx.technion.ac.il (Y. Gendel).
https://doi.org/10.1016/j.ijhydene.2018.02.082
0360-3199/© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Amikam G, et al., Chlorine-free alkaline seawater electrolysis for hydrogen production, International
Journal of Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.02.082
2 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 x x x ( 2 0 1 8 ) 1 e1 1
and solar energy [2]. Due to fluctuations in renewable energy
production and consumption rates “buffers” for energy stor-
age, such as electrochemical energy conversion and storage
systems (EECSs), are required. Most promising EECSs are:
redox flow cells [3], (regenerative) fuel cells [4], electro-
chemical conversion of CO2 (and water or H2) into fossil fuels
(e.g. formic acid) [5] and electrochemical capacitors [6].
Hydrogen gas is very attractive for energy conversion and
storage applications due to its high gravimetric energy density
(higher heating value (HHV) of about 142 MJ/kg and lower
heating value (LHV) of z120 MJ/kg at 25  C) and because H2 is a
“clean” fuel as the major product of its reaction with oxygen in
internal combustion engines and fuel cells is water. The
annual production of hydrogen is about 45 million metric tons
and its consumption increases by 6% per year [7]. Today
hydrogen is produced mainly from fossil fuels (mostly from
natural gas) using the steam reforming process [7] and only 4%
of hydrogen are produced by water electrolysis [8,9]. Large
amounts of highly pure hydrogen (99.999 vol%) can be pro-
duced using water electrolysis without consumption of fossil
fuels or nuclear resources and without emissions of gaseous
pollutants [8,9]. For these reasons water electrolysis is
considered today as the most important hydrogen production
technology [8,9]. Main research in hydrogen energy is focused
today on the development of energy efficient water electrol-
ysis systems (electrode materials, electrolytes, separators etc.)
and effective hydrogen storage methods required due to low
volumetric energy density of H2 (HHV z 11.7 MJ/m3, LHVz
9.9 MJ/m3 at 25  C).
Water electrolysis for hydrogen production
Water electrolysis (WE), described by Eq. (1), is an electro-
chemical process of O2 and H2 generation on anode (Eq. (2))
and cathode (Eq. (3)), respectively [8e11].
H2O / H2(g) þ 0.5O2(g)
2OH / 0.5O2 þ H2O þ 2e (E0r ¼ 0.401 V vs. SHE)
2H2O þ 2e / H2 þ 2OH (E0r ¼ 0.828 V vs. SHE)
During the WE process electrical and thermal energies
are converted into chemical energy of hydrogen gas. The
energy requirement of WE comprises electric energy DG
(that corresponds to the Gibbs' free energy change) and
thermal energy Q (that equals the product of process tem-
perature (T) and the entropy change (DS)), where
DG ¼ DHQ ¼ DH e TDS[8]. At standard temperature
(298.15 K) and pressure (1 atm) the values of DG, DS and DH
are 237.21 kJ/mol, 0.1631 kJ/(mol.K) and 285.84 kJ/mol,
respectively [8]. The cell potential required for the WE to
occur must be higher than the reversible potential (Vr) of
this process [8,9]. At standard conditions the Vr of WE is
1.229 V and it decreases with temperature increase. When
water electrolysis is conducted at adiabatic conditions all
reaction enthalpy is provided by the electricity. In this case
the thermo-neutral voltage (Vtn) is defined as a minimal
voltage required for WE [8,9]. At standard conditions the Vtn
of WE is 1.481 V and it changes only slightly with
Please cite this article in press as: Amikam G, et al., Chlorine-free alkaline seawater electrolysis for hydrogen production, International
Journal of Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.02.082
temperature (1.48 V at 25  C to 1.52 V at 1000  C) [8]. When
the electrolysis cell is operated between the Vr and Vtn the
process is endergonic. At cell potentials greater than Vtn the
process is exergonic, which means that heat should be
removed from the system if isothermal operation is
required [8,9]. At higher temperatures the demand of elec-
tric energy (DG) decreases while the demand for thermal
energy (TDS) increases [8]. Consequently, operation at
higher temperatures is advantageous because a bigger part
of overall energy can be supplied as heat, which (if avail-
able) in many cases is cheaper than electric energy [8,9].
Three major techniques of water electrolysis for hydrogen
production are the following: (1) alkaline electrolysis, (2)
polymer electrolyte membrane (PEM) electrolysis; and (3) solid
oxide electrolysis (or steam electrolysis) [8e11]. Alkaline water
electrolysis (AWE) is the mature electrochemical technique for
hydrogen production. The basic AWE cell comprises monop-
olar or bipolar electrodes (usually Ni-based) immersed into a
potassium or sodium hydroxide solutions (20e40 %wt.) [8e11].
Anodic and cathodic compartments of the AWE cell are
separated by a diaphragm (e.g. microfibrous chrysotile
asbestos, polysulphone-zirconium oxide composite, sulpho-
nated PEEK) or an anion-exchange membrane to prevent
parasitic crossover and mixing of H2 and O2 gases [11]. AWE is
normally operated at 60e100  C, at current densities of
200e400 mA/cm2, and its specific energy consumption is
4.2e5.9 kWh/m3. The major advantages of AWE over other
water electrolysis systems are: (i) the AWE a well-established
technology, (ii) the cost of electrode materials of AWE reactors
is relatively low; and (iii) the AWE systems have long opera-
tional life (>10 years) [10,11].
Anodic chlorine evolution in electrolysis of NaCl solutions
If chloride ions are present in the electrolyte solution, a
competing chlorine evolution reaction (CER) (Eq. (4)) may
(1) occur on the anode [12e14]:
(2) 2Cl / Cl2(g) þ 2e (4)
(3) The produced chlorine is subsequently absorbed in the
aqueous solution with pH > 3 via reactions (5) and (6) [15].
Cl2(g) þ H2O 4 HOCl þ Hþ þ Cl (5)
Cl2 þ OH 4 HOCl þ Cl (6)
According to the pH of the solution hypochlorous acid
(pH < 7.46) or/and hypochlorite ions (pH > 7.46) are formed
according to Eq. (7) [12e14].
HOCl 4 Hþ þ OCl Ka ¼ 107.46 (7)
Electrochemically produced active chlorine may be
oxidized to chlorate at the anode, reduced at the cathode to
the chloride form, or chemically transformed into chlorate
[14]. In the chlor-alkali processes (i.e. diaphragm, mercury and
membrane reactors) active chlorine is the major desired
product [16e19]. The global production rate of chlorine ex-
ceeds 65 million tons per annum and its used for production
 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 x x x ( 2 0 1 8 ) 1 e1 1 3

of polyvinylchloride (z33%), polyurethanes (z32%), chloro- current density and electrolyte composition. Higher current
methanes (z6%), epoxy resins (z4%) and other materials (e.g. efficiencies for chlorine evolution reaction are obtained at
titanium dioxide, bromine, hydrochloric acid, bleach and higher concentrations of chloride ions. This is due the lower
solvents) [17,18]. The chlorine is normally produced near the reversible electrode potential for CER (Eq. (4)) and enhanced
consumer to avoid economical and technological complica- mass transport (and adsorption) of chloride ions to the anode
tions regarding the transportation and storage of this toxic surface [19]. An increase in the current density increases the
compound [17,18]. Anodic oxygen evolution reaction (OER) current efficiency for chlorine production, however at very
and decomposition of active chlorine species in the electrolyte high anodic current densities the process becomes limited by
solution of the chlor-alkali process result in energy losses. For the mass-transport of chloride ions. This results in higher
this reason a very intensive research is being conducted for current efficiency for the OER [19]. Oxygen-containing anions

the last decades in order to understand the mechanisms of (e.g. PO3 2
4 , SO4 and NO3 ) have been reported to decrease the
OER and CER and to develop novel electrode materials with selectivity for anodic chlorine evolution [19]. Bune et al. [34]

higher selectivity towards the chlorine production [19e21]. studied the effect of PO3 2
4 , SO4 and ClO4 ions on Cl2 evolu-
Electrochemical chlorine production in seawater, brines and tion on Ti/TiO2eRuO2 anodes. They reported that adsorption
other chloride containing solutions is highly promising for the of phosphate and sulfate on the anode surface leads to
indirect oxidation of ammonia into the nitrogen gas and for decrease in Cl2 evolution rate and ClO 4 ions do not influence
water disinfection [22e25]. In these processes, similar to the the CER [34].
chlor-alkali, high current efficiencies for chlorine production Current efficiency for the chlorine evolution reaction in-
are required. creases at lower pH of the electrolyte solution [19,34]. The
The situation is different if water electrolysis is conducted Nernst equations corresponding to OER in alkaline media (Eq.
to produce hydrogen for the storage of renewable electrical (2)) and CER (Eq. (4)) are Eq. (8) and Eq. (9), respectively:
energy. Production of chlorine in seawater electrolysis aimed 0 1
1
at mass production of H2 must be prevented if chlorine is not RT @aH2 O fO2 2 A
Vr;OER ¼ 0
Vr;OER þ Ln (8)
utilized on-site as a raw material for industrial applications. nF a2HO
Moreover the Cl2 by-product of seawater electrolysis might
exceed the market demand for Cl2 [26,27]. Where: R e the universal gas constant (8.314 J/mol/K);
T e the absolute temperature (K); aH2 O activity of water
Chlorine-free seawater electrolysis, state-of-the-art (); aOH  - activity of hydroxide ions (); fO2 - fugacity of
oxygen gas (atm); F eFaraday constant (96485.3329 C/mol);
Seawater is potentially an endless source of water for elec- n ¼ 2, the stoichiometric number of electrons involved in
trochemical generation of hydrogen. Unfortunately, well- OER as described by Eq. (2).
established technologies of water electrolysis can not be !
applied directly for seawater electrolysis due to the anodic RT f 1=2
Vr;CER ¼ 0
Vr;CER þ Ln Cl2 (9)
chlorine evolution reaction and detrimental cathodic deposi- nF aCl
tion of Mg2þ and Ca2þ species [28]. Moreover, even seawater where: fCl2 e fugacity of chlorine gas (atm); aCl - activity of
treated by the reverse osmosis process for drinking water chloride ions ().
production can not be applied in PEM nor in steam electro- Fig. 1 represents the apparent reversible potentials for OER
lyzes, since ultrapure water (maximum total dissolved solids and CER at 25⁰ (calculated using Eq. (8) and Eq. (9), respectively)
(TDS) concentration z 0.5 ppm) is required for these processes as a function of NaOH and Cl concentrations in NaCl-
[29]. saturated aqueous solutions of sodium hydroxide, assuming
Until today, three major approaches for reducing chlo-
rine evolution during the electrolysis of NaCl solutions and
seawater have been reported: (a) operation at very low
1.6
current densities (<1 mA/cm2) [30], (b) implementation of Chlorine Evoluon Reacon
Revesrible Reducon Potenal

special catalysts to prevent Cl2 evolution [31,32]; and (c)

1.4
coating of an anode with a cation exchange membrane in 1.2
for CER and OER (V)

order to prevent Cl adsorption on the anode [33]. Approach 1

(a) is not practical as operations at very low current den-
0.8
sities are economically unfeasible; approach (b) is very
0.6
promising, however at the current stage this technology is Oxygen Evoluon Reacon
subjected to the deactivation of catalysts in long-term op- 0.4
erations [31,32]; method (c) might be economically prob- 0.2
lematic due to the high cost of CEMs.
0
0 100 200 300 400
Inhibition of Cl2 evolution by oxyanions. Main research
Concentraon of NaOH in NaCl-saturated soluon
hypothesis (gNaOH/kgH2O)

The selectivity between anodic evolution of chlorine and ox- Fig. 1 e Reversible reduction potentials for oxygen and
ygen during the electrolysis of NaCl solutions depends on chlorine evolution reactions as a function of NaOH
composition of the anode, applied potential, temperature, concentration in NaCl-saturated electrolyte solution.

Please cite this article in press as: Amikam G, et al., Chlorine-free alkaline seawater electrolysis for hydrogen production, International
Journal of Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.02.082
4 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 x x x ( 2 0 1 8 ) 1 e1 1
fugacity of Cl2 and O2 of 1 atm. Activities of water, Cl and OH
were calculated using the PHREEQC software implementing
the Pitzer specific-ion-interaction aqueous model [35]. Ac-
cording to Fig. 1, the difference in reversible potentials for OER
and CER is about 1 V in NaCl-saturated solutions with NaOH
concentrations of 20e40 %wt.
The detailed information regarding the thermodynamics
and kinetics aspects of anodic selectivity towards OER and
CER is available in several recent publications [19e21,36e39].
Interestingly, both PO3 2
4 and SO4 oxyanions that diminish
the evolution rate of Cl2 have pH buffering ability in 1 < pH < 8
range, while perchlorate does not have pH-buffering effect
due to the negative pKa ¼ 10.07 of the perchloric acid [40].
Consequently, it was hypothesized in this study that in
concentrated aqueous NaOH solutions anodic evolution of
chlorine can be completely inhibited due to: (i) the strong pH
buffering capacity of water at pH > 14; (ii) its possible
adsorption on the anode surface and (iii) mainly due to the
strong effect of the pH on the reversible potential of oxygen
evolution reaction (Fig. 1).
A proposed process for chlorine-free seawater electrolysis
Fig. 2 shows the principle of the proposed continuous process
for electrochemical chlorine-free H2(g) production from
seawater. The proposed process is based on four hypotheses
and phenomena: (i) anodic Cl2 production can be completely
inhibited by OH ions; (ii) solubility of NaCl in aqueous NaOH
solutions decreases due to the common ion effect that leads to
salting out of NaCl; (iii) solubility of NaCl in NaOH solutions is
higher at higher temperatures; and (iv) NaOH is not consumed
in water electrolysis.
At the first step of the proposed process nearly all divalent
ions (Mg2þ, SO2 4 and Ca2þ) are separated using a low-cost
nanofiltration (NF) process operated at z 10% water
Fig. 2 e Proposed process for chlorine-free seawater electrolysis for H2 (and O2) production.
Please cite this article in press as: Amikam G, et al., Chlorine-free alkaline seawater electrolysis for hydrogen production, International
Journal of Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.02.082
recovery [41]. The permeate produced in the NF step is intro-
duced further into the electrochemical system there it is
completely split into H2 and O2 gases. Consequently, NaCl
concentration gradually increases in the electrolyzed solution
until NaCl salt starts to precipitate. The electrochemical sys-
tem shown in Fig. 2 comprises a settling tank, which contains
aqueous solution of sodium hydroxide at concentrations
typical for alkaline water electrolysis (e.g. 20e40 %wt), satu-
rated with sodium chloride. Water in the settling tank is
continuously recirculated through the electrolysis cell.
Hydrogen and oxygen are produced on the cathode and the
anode of the electrolysis cell, respectively. The inlet flow rate
of the NF permeate into the settling tank is equal to the water
electrolysis rate. Due to the inhibitory effect of OH anions, no
Cl2 is produced within the electrolysis. High purity NaCl is
salted out from the electrolyte solution in the settling tank due
to the common-ion effect. To prevent precipitation of NaCl in
the electrolysis cell (and on other equipment of the system)
the cell is operated at higher temperatures (50  C). The
temperature of the solution in the settling tank is lower (e.g.
ambient temperature of 20e30  C) in order to promote the
NaCl precipitation.
Fig. 3 shows the estimated concentrations of dissolved
sodium chloride in NaCl-saturated aqueous solutions as a
function of NaOH concentration and temperature. Results
shown in Fig. 2 were obtained using the PHREEQC software
implementing the Pitzer specific-ion-interaction aqueous
model [37].
Fig. 3 demonstrates that NaCl solubility increases at higher
temperatures and decreases at higher NaOH concentrations.
In an ideal system, the NaOH reagent should be introduced
only once into the system since water electrolysis does not
change the bulk electrolyte solution pH.
The present study is dedicated to the proof-of-concept of
the chlorine-free alkaline seawater electrolysis.
 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 x x x ( 2 0 1 8 ) 1 e1 1
Fig. 3 e NaCl solubility in aqueous NaOH solutions
(PHREEQC software simulation [37]).
Materials and methods
Anodic chlorine evolution in NaCleNaOH solutions on
Ti/TiO2eIrO2eRuO2 and Ni200 anodes
The evolution of chlorine on commercial dimensionally stable
anode (DSA) and nickel plate (Ni200) electrodes was studied at
a constant current density of 62.5 mA/cm2 (provided by
Prova8000 programmable DC power supply) in a magnetically
stirred two-electrode cell. The catalyst layer of the applied
DSA comprises a mixture of TiO2, RuO2 and IrO2, as was
shown by the Energy Dispersive X-Ray Spectroscopy (EDS)
analysis (results not shown). A rectangular working anode
(overall surface area of 80 cm2, thicknesses of 2 and 3 mm for
DSA and Ni electrodes, respectively) was located between two
expended titanium meshes (37 cm2 each) coated with plat-
inum catalyst that were used as a cathode. The inter-electrode
gap was 3 mm. The Cl2 evolution studies were conducted in
NaCl-saturated solutions (180 ml) at varied NaOH concentra-
tions (1, 5, 10, 25, 50, 100, 200, 300 and 400 g/kgH2O) at 30  C and
50  C. Samples of electrolyte solutions were withdrawn peri-
odically from the electrolysis cell and analyzed immediately
for concentrations of active chlorine and chlorate ions.
Chronopotentiometry studies were conducted on Ni and DSA
electrodes in NaOH solutions (200, 300 and 400 gNaOH/kgH2O)
and in NaCl-saturated solutions with varied NaOH concen-
trations and temperatures (30  C and 50  C) to determine the
influence of NaCl(aq) on the energy consumption of the elec-
trolyzer for H2 production. In this set of experiments smaller
working electrodes (25 cm2) were applied. The current sweep
rate was 50 mA/s and the current density range was
0e200 mA/cm2. Within each experiment, 10 potentiometry
cycles were performed and results of three last cycles were
averaged and used for the analysis. A Vertex 10A (Ivium)
potentiostat/galvanostat was used in these experiments. For
the preparation of NaCl-saturated NaOH solutions sodium
Please cite this article in press as: Amikam G, et al., Chlorine-free alkaline seawater electrolysis for hydrogen production, International
Journal of Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.02.082
5
hydroxide reagent was dissolved first in deionized water.
Next, an excess amount of NaCl was added into the NaOH
solution and the mixture was magnetically stirred for at least
24 h in the stoppered glass bottle immersed into the heating
bath to achieve saturation of NaCl at the desired temperatures
(30  C and 50  C). After the dissolution step, the undissolved
NaCl particles were allowed to settle and a solid-free solution
was withdrawn from the bottle immediately before the
experiment. All NaOHeNaCl solutions were prepared from
analytical-grade chemicals (Merck Chemicals) and deionized
water (electrical conductivity < 2 mS/cm).
Experimental system for continuous electrolysis of NaCl
solutions
Fig. 4 shows the structure of the laboratory system applied for
the continuous electrolysis. The system comprised four major
units. During the system operation the electrolyte solution
was recirculated using the peristaltic pump (60 ml/min, Mas-
terflex 6e600 rpm, 16” L/S BPT tubing) from (1) the chilled
settling cylinder eelectrolyte holding vessel (the cold zone)
into (2) the heated stoppered round-bottom flask (the hot
zone), next to (3) the electrolysis cell followed by (4) a gas
separator (and back to the settling cylinder). Custom-made
undivided two-electrode flow-through electrochemical cell
was applied in the system shown in Fig. 4. The active area of
parallel rectangular electrodes and the interelectrode gap
(fixed by the thickness of the flexible PVC gasket) were
21.42 cm2 and 2 mm, respectively. A thermocouple was
installed into the glass socket located at the outlet of the
electrolysis cell. This thermocouple was used to control the
temperature of the electrolyte solution in the hot zone of the
system.
A double ewall settling cylinder was constructed from two
transparent PVC pipes. Internal pipe (length 45 cm, internal
diameter-65.24 mm, effective volume - 1.5 l) was used to hold
the electrolyte solution. Cooling solution (mixture of ethylene
glycol and water) was recirculated (10 l/min) between the
refrigerated circulator (FP50-MA, Julabo, operated at maximal
cooling capacity during every experiment) and the external
PVC pipe (length - 45 cm, internal diameter - 98.6 mm). Two
pipes were connected by the PVC flanges. The upper blind
flange had inlet and outlet connectors for the recirculation of
NaCleNaOH electrolyte solution, the sampling port and a
sealed connector for a mercury thermometer. The round-
bottom flask (250 ml) equipped with a custom-made glass
socket for the thermocouple (isolated from aqueous solution)
was inserted into the heating mantle located on top of the
magnetic stirrer. The heating mantle was controlled by the
thermocouple installed in the outlet of the electrolysis cell.
The gas separator was constructed from two transparent in-
ternal (int. diameter-12 mm, 99 cm long) and external (int.
diameter-32 mm, length-109 cm) PVC pipes. Nitrogen gas was
flowed into the gas separator to avoid contact between air and
the electrolyte solution to prevent CO2 adsorption and Na2CO3
precipitation in the system. Fig. 5 shows a laboratory system
applied in this study.
To determine the amount of water evaporated from the
system, two PVC columns (25 cm height, 32 mm int. diameter)
filled with silica gel (z200 g each) were installed on top of the
6 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 x x x ( 2 0 1 8 ) 1 e1 1

Fig. 4 e Laboratory setup applied for the continuous electrolysis experiments. A, and B e sampling ports,
TC e thermocouple.

gas separator. Portions of silica gel in upper and lower col-
umns were weighted and replaced daily. At the beginning of
every experiment the system was filled with a NaCleNaOH
solution (2000 ml) that was recirculated for about 12 h prior to
the initiation of the electrolysis process to stabilize tempera-
tures in cold and hot zones. During operation, NaCl solution
was injected into the system once a day. The volume of the
injected NaCl solution was equal to the volume of water
decomposed in the electrolysis cell (assuming 100% current
efficiency for water splitting). Samples of the electrolyte so-
lution were withdrawn daily from the system and analyzed
immediately for NaOH, Cl, Cl2 and ClO 3 . Deionized water was
Fig. 5 e Experimental system applied in experiments of
continuous chlorine-free electrolysis of NaCl solutions.
injected into the system daily to compensate the water
evaporation (calculated from the increase in silica gel weight).
To compensate for NaOH and NaCl withdrawn from the sys-
tem by sampling an equivalent volume of initial NaCleNaOH
solution was injected into the system immediately after
sampling. The electrolyzer was operated in a constant current
mode using the Vertex 10A (Ivium) potentiostat/galvanostat
(maximal current 10 A). Applied cell voltages were recorded
automatically every minute during each experiment. Tem-
peratures of the electrolyte solutions in the cold and hot zones
were recorded twice a day within each experiment and were
27e32  C and 55e60  C, respectively. The temperature at the
outlet of the electrolyzer was 44e48  C.
Three experiments were conducted using the system
shown in Fig. 5:
Exp#1. Anode and cathode materials e Ni200; Initial
composition of electrolyte solution in the system:
[NaOH] ¼ 300 g/kgH2O, [NaCl] ¼ 85 g/kgH2O; Fixed current
density e 467 mA/cm2; parameters of NaCl solution added in
to the system once a day: 80 ml of 31.32 gNaCl/l. Prior to the
initiation of the experiment 300 g of dry NaCl salt were added
into the settling column.
Exp#2. Anode and cathode materials e DSA; Initial
composition of the electrolyte solution in the system:
[NaOH] ¼ 300 g/kgH2O, [NaCl] ¼ 85 g/kgH2O; Fixed current
densities: 93.4, 187, 280, 373 and 467 mA/cm2, system was
operated for 5 days at current densities of 93.4e373 mA/cm2
and at 467 mA/cm2for another 10 days; Parameters of NaCl
solution that was added once a day into the system: 16, 32, 48,
64 and 80 ml/day of 31.32 gNaCl/l solution for operations at
fixed current densities of 93.4, 187, 280, 373 and 467 mA/cm2,
respectively. During the last three days of operation the

Please cite this article in press as: Amikam G, et al., Chlorine-free alkaline seawater electrolysis for hydrogen production, International
Journal of Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.02.082
 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 x x x ( 2 0 1 8 ) 1 e1 1
concentration of NaCl(aq) in the daily added solution was
increased to 350 gNaCl/l. Prior to the initiation of the experi-
ment 300 g of dry NaCl were added into the settling column.
Exp#3. Anode and cathode materials e DSA; Initial
composition of electrolyte solution in the system:
[NaOH] ¼ 300 g/kgH2O, [NaCl] ¼ 168 g/kgH2O (saturated with
NaCl at z 35  C); Fixed current density - 467 mA/cm2; Pa-
rameters of the NaCl solution that was added once a day into
the system: 80 ml/day of 125 gNaCl/kgH2O. Prior to the initi-
ation of the experiment 400 g of dry NaCl salt were added into
the settling column.
Analytical methods
Concentration of chloride ions was determined using the
mercury (II) thiocyanate method [42]. Concentrations of active
chlorine and chlorate ions were measured using the iodo-
metric titration method [43]. Sodium hydroxide concentration
was determined by titration of diluted samples with 1 M HCl
solution. The end-point of the titration was obtained using the
procedure described by Ref. [44].
Results and discussion
Anodic chlorine evolution in NaCleNaOH solutions on
Ti/TiO2eIrO2eRuO2 and Ni200 anodes
Fig. 6 shows the results of chlorine evolution experiments
conducted on DSA anode using NaCl-saturated aqueous so-
dium hydroxide solutions at NaOH concentrations of 1 and 5
gNaOH/kgH2O at 30  C and 50  C. Within each experiment
shown in Fig. 6 the concentration of active chlorine increased
linearly with time at the beginning of the experiment. After
some time the accumulation rate of active chlorine became
lower due to chlorate formation, cathodic chlorine reduction
and other processes that result in decomposition of active
chlorine [14,19]. The data from the linear part of each chlorine
evolution experiment were used to calculate the current effi-
ciency for the chlorine evolution reaction.
3000
2700 1 gNaOH/kgH2O, 30⁰C
Cl2 concentraon, (mg/L)
2400
2100 5 gNaOH/kgH2O, 30⁰C
1800
1500
1200 1 gNaOH/kgH2O, 50⁰C
900 5 gNaOH/kgH2O, 50⁰C
600
300
0
0 20 40 60
Time (min)
Fig. 6 e Chlorine production on DSA anode in NaCl-
saturated solutions at [NaOH] ¼ 1 and 5 g/kgH2O at 30 and
50  C. Fixed current density e 62.5 mA/cm2, electrolyte
volume e 180 ml, counter cathode e Ti/Pt mesh,
interelectrode gap e 3 mm.
Please cite this article in press as: Amikam G, et al., Chlorine-free alkaline seawater electrolysis for hydrogen production, International
Journal of Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.02.082
7
Table 1 concentrates the results of chlorine evolution ex-
periments conducted on DSA electrodes. As it appears from
Table 1 at NaOH concentrations higher than 100 g/kgH2O the
concentration of chlorine in the electrolyte solution was un-
detectable. Results of chlorine evolution experiments on DSA
show that Cl2 evolution reaction can be completely inhibited
by the OH ions, as it was hypothesized in the present study.
Ni electrodes applied in electrolysis experiments con-
ducted at [NaOH]  100 gNaOH/kgH2O have not been corroded
within 60 min of electrolysis and no active chlorine or chlorate
have been detected in the electrolyte solutions. It should be
noted, however, that active chlorine reacts rapidly with nickel
[19]. Consequently, the absence of active chlorine in the
electrolyte solution during the electrolysis with Ni electrodes
can be also due to the rapid decomposition of anodically
produced chlorine via its reaction with Ni anode [45]. In spite
the fact that Ni electrodes applied in short electrolysis ex-
periments did not show any visible corrosion, the chemical
stability of Ni anodes in the proposed process had to be tested
further in the long term electrolysis experiments.
Very intensive degradation of Ni200 electrodes has been
observed in electrolysis experiments conducted in NaCl-
saturated solutions with NaOH concentrations lower than
50 g/kgH2O. Fig. 7 shows the Ni electrode after electrolysis in
NaCl-saturated solution at [NaOH] ¼ 10 gNaOH/kgH2O.
Fig. 8 shows the results of chronopotentiometry studies
conducted on Ni200 anodes.
As become evident from Fig. 8, introduction of NaCl into
the NaOH electrolyte solutions resulted in higher applied po-
tentials. This means that H2 production from seawater using
the proposed process has higher energy demand than the
“conventional” alkaline electrolysis conducted at similar
NaOH concentrations. Similar trend was observed for the DSA
anode (results not shown). However, optimization of electro-
chemical cell design and electrolyte composition (e.g. NaOH
concentration) (which were out of the scope of the present
research) might improve the energy consumption of the pro-
posed process.
Continuous electrolysis of NaCl solutions
Fig. 9 shows the results of continuous exp#1 conducted with
Ni200 electrodes.
In this experiment initial concentration of NaCl(aq) in the
electrolyte solution was 85 g/kgH2O and sodium hydroxide
concentration was 300 g/kgH2O. This means that at the
beginning of the experiment electrolyte solution was not
saturated with NaCl and its concentration increased gradually
during the experiment due to (i) accumulation of NaCl which
was introduced into the system with daily injections of NaCl
solutions (mimicking the seawater in the proposed process),
and (ii) due to the slow dissolution of NaCl added into the
system in the dry form at the beginning of the experiment. No
80
formation of chlorate and active chlorine in the electrolyte
solution was detected during exp#1 conducted at current
density of 467 mA/cm2. Unfortunately, accumulation of black
particles in the solution was observed during the experiment.
Moreover, after nine days of operation the electrolysis process
was ceased, apparently due to the short-circuit in the elec-
trolysis cell, as indicated by a sharp decrease in the applied
8 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 x x x ( 2 0 1 8 ) 1 e1 1

Table 1 e Current efficiencies of chlorine evolution reaction on Ti/TiO2eRuO2eIrO2 anodes obtained in electrolysis
experiments conducted in NaCl-saturated solutions at varied NaOH concentrations. ND e not detectable.
Concentration of NaOH in NaCl-saturated Corresponding NaCl(aq) Current efficiency for Cl2
solutions (g/kgH2O) concentrations (calculated using PREEQC production (%)(DSA electrode)
software [30]) gNaCl/kgH2O
50  C 30  C 50  C 30  C
1 360.9 356.03 43.57 57.42
5 358.20 353.04 22.7 42.22
10 354.9 349.31 z0.051 0.31
25 345.08 338.16 ND z0.044
50 329.1 319.7 ND z0.012
100, 200, 300, 400 298.5; 243.6; 197.6; 161.73 283.3; 213,62; 150.4; 97.11 ND ND

decomposition or corrosion of the electrodes were observed

Fig. 7 e Ni200 electrode after ≈60 min of electrolysis in
NaCl-saturated solution with [NaOH] ¼ 10 gNaOH/kgH2O.
Fixed current density e 62.5 mA/cm2.
potential (Fig. 9). The EDS examination of black powder
formed on the anode surface (shown in Fig. 10) indicated that
the black layer was nickel oxide or hydroxide. Apparently, the
corrosion of Ni electrodes occurred due to the degradation of
the passive film induced by Cl ions that were present at high
concentration in the electrolyte solution. In our future studies
we plan a detailed investigation of chlorine evolution reaction
on Ni (and Raney Ni) electrodes in the proposed process.
Nickel oxide-hydroxide particles are capable to catalyze
degradation of active chlorine species (see Supplementary
Materials). In order to remove nickel oxide particles formed
during exp#1 the system was disassembled prior to the ex-
periments with DSA electrodes (exp#2 and exp#3), all com-
ponents were washed with deionized water and all opaque
fittings and tubes were replaced.
Fig. 11 shows the results of continuous exp#2 conducted
with commercial Ti/TiO2eIrO2eRuO2 electrodes. No
during 30 days of experiment #2. Concentration of NaOH
remained constant during the electrolysis and concentration
of NaCl increased gradually within 29 days until [NaCl] con-
centration became close to saturation. On day 30 it was
decided to increase the concentration of NaCl in the injected
solution from 31.32 to 350 gNaCl/kgH2O to test the system for
the susceptibility to clogging with precipitated NaCl salt.
Shortly after injection of 80 ml of NaCl solution with
[NaCl] ¼ 350 g/kgH2O the failure of the electrolyzer occurred
due to the clogging of the fitting located at the inlet of the
peristaltic pump. The fitting was replaced and the experiment
continued, unfortunately second failure occurred several
hours later due to the same reason. This time the failure
resulted in the delamination of both electrodes in the elec-
trolysis cell. Similarly to exp#1 no formation of active chlorine
and chlorate was observed in exp#2.
Fig. 12 shows the results of continuous exp#3. To prevent
clogging of the system the hot zone was relocated to point A of
the system (Fig. 4). Electrodes damaged in exp#2 were replaced
with new electrodes. The initial electrolyte solution in exp#3
comprised 300 g/kgH2O and was saturated with NaCl at z
35  C prior to the experiment (resulting measured NaCl con-
centration was 168 g/l). In this experiment electric current of
10A was applied (corresponding to current density of 467 mA/
cm2). 80 ml of sodium chloride solution (125 g/l) were injected
once a day into the system. As appears in Fig. 12 concentra-
tions of NaOH(aq) and NaCl(aq) remained unchanged during 12
days of experiment. No formation of active chlorine or

Fig. 8 e Chronopotentiometry results of Ni200 anode in NaOH solutions (200, 300 and 400 gNaOH/kgH2O) and NaCl-saturated
solution with NaOH concentrations of (A) 200 gNaOH/kgH2O, (B) 300 gNaOH/kgH2O and (C) 400 gNaOH/kgH2O. Black lines -
50  C, red lines - 30  C. Dashed lines e NaOH solutions, solid lines e NaOHeNaCl solutions. (For interpretation of the
references to color/colour in this figure legend, the reader is referred to the Web version of this article.)

Please cite this article in press as: Amikam G, et al., Chlorine-free alkaline seawater electrolysis for hydrogen production, International
Journal of Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.02.082
 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 x x x ( 2 0 1 8 ) 1 e1 1 9

4.0 125 2.85 300

120 280
3.5

NaOH and NaCl(aq) conc.

NaOH 260
115

[NaCl]aq (g/kgH2O)
2.80

Cell Voltage (V)

3.0 240
Cell Voltage (V)

110

(g/kgH2O)
220
2.5 105
2.75 200
2.0 Cell Failure 100 180
95 NaCl
1.5 160
2.70
90 140
1.0 85 120
0.5 80 2.65 100
0 2 4 6 8 10 0 2 4 6 8 10 12
Time (day)
Time (day)
Fig. 12 e Experimental results of continuous electrolysis of
Fig. 9 e Experimental results of continuous electrolysis of
NaCl solution conducted with Ti/TiO2eIrO2eRuO2
NaCl solution conducted with Ni electrodes (Exp#1).
electrodes (Exp#3).

Fig. 10 e Ni200 anode after nine days of electrolysis of

NaOHeNaCl solution in continuous system (exp#1).
Fig. 13 e Current density-voltage plot and rate of electrical
energy consumption by the electrolysis cell for H2
4.5 340 production within the proposed process.
NaOH
NaOH and NaCl(aq) conc.

4.0 290
Cell Voltage (V)

3.5 240
Cell Failure current densities for alkaline electrolysis are 200e400 mA/cm2
(g/kgH2O)

3.0 190 and power demand is 4.2e5.9 kWh/m3H2. It should be noted

10 A
8A that the energy demand obtained in this study does not
2.5 2A 4A 6A 140 include the energy required for heating and cooling of the
2.0 NaCl 90
electrolyte in the system, as well as pumping energy. More-
over, the cell applied in this study was undivided, while for
1.5 40 pure H2 production divided cells are obligatory.
0 5 10 15 20 25 30
Time (day)

Fig. 11 e Experimental results of continuous electrolysis of Conclusions

NaCl solution conducted with Ti/TiO2eIrO2eRuO2
electrodes (Exp#2). A new process for chlorine-free seawater electrolysis has been
proposed and investigated in this study. The major advantage
of the new process is that it uses seawater as a hydrogen
chlorate was observed in exp#3. The system did not show any source and not pure solutions of KOH or NaOH. It was shown
tendency for clogging. NaCl crystals that escaped from the that anodic chlorine evolution in NaCl-saturated solutions on
settling cylinder were dissolved very fast in the heated round- DSA electrodes could be completely inhibited by hydroxide
bottom flask. ions, if present in the electrolyzed solution at high concen-
Prior to the termination of exp#3 the system was operated trations (2.5 M). Due to the salting out effect of NaOH, valu-
at varied applied currents (1e10 A, 30 min each) to obtain the able NaCl(s) salt is formed in the process. The system was
polarization curve of the electrolyzer in the system. Fig. 13 successfully operated during 12 days for the electrolysis of
shows the obtained IeV curve and a corresponding electrical NaCl-saturated (z160 gNaCl(aq)/kgH2O at 50  C) aqueous so-
energy demand for H2 production. lution of 30%wt NaOH using Ti/TiO2eIrO2eRuO2 electrodes at
As it appears in Fig. 13, electrical energy consumption by fixed current density of z470 mA/cm2. Within 12 days of
the electrolysis cell of the proposed process was 5.6e6.7 kWh/ operation no chlorine evolution or chlorate production
m3H2 for current density range of 187e467 mA/cm2. Typical occurred, while concentrations of dissolved NaOH and NaCl

Please cite this article in press as: Amikam G, et al., Chlorine-free alkaline seawater electrolysis for hydrogen production, International
Journal of Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.02.082
10 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 x x x ( 2 0 1 8 ) 1 e1 1
salts remained constant. About 1.2 m3 of hydrogen gas and
150 g of NaCl were precipitated in the system, but no accu-
mulation of NaCl salt was observed outside the NaCl-settling
area.
Experiments conducted with nickel (Ni200) electrodes
showed no formation of active chlorine or chlorate in NaCl-
saturated electrolyte solutions at [NaOH]  2.5 M. However,
formation of nickel oxide on the Ni anode and electrochemical
cell failure occurred during the long-term experiments con-
ducted in NaCl-saturated solutions with [NaOH] of 30% wt.
Consequently, applicability of Ni anodes in the proposed
process is questionable and requires further detailed studies
of chlorine evolution reaction in NaCleNaOH electrolytes.
Further research is required for the development of divided
electrochemical cells, investigation of hydrogen evolution
reaction on different catalysts, optimizations of electrolyte
solution composition and applied operational parameters,
and overall engineering of the proposed technology. In addi-
tion, the fate of Kþ, HCO 
3 , Br , Si and other species originally
present in seawater should be investigated in long-term op-
erations of the proposed process.
The energy demand of electrochemical cell operated in this
study was higher than of conventional alkaline water elec-
trolysis processes. However, the system was not optimized to
minimize the energy consumption. Optimization studies lis-
ted above are expected to result in the development of the
proposed technology with energy demand comparable to
alkaline water electrolysis operated with pure KOH and NaOH
solutions.
Acknowledgements
Dr. Youri Gendel appreciates the financial support of the
Ravitz Foundation.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.ijhydene.2018.02.082.
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