Direct Electrolysis of Seawater
Direct Electrolysis of Seawater
A R T I C L E I N F O A B S T R A C T
Handling Editor: Dr C O Colpan                        Seawater is the largest resource on earth which makes the hydrogen production directly from seawater an
                                                      economically attractive solution if the corrosion problems are solved. Traditionally in the electrolysis analysis,
                                                      both electrodes are made of metals. The produced oxygen and chlorine in the electrolysis process cause high rates
                                                      of corrosion resulting in using expensive alloys to slow down the corrosion process. A novel solution to the
                                                      corrosion problem is introduced, tested, and experimentally proved. The novelty of the solution relies on
                                                      replacing the classic high-cost positive electrodes with a non-metallic, low cost, one [1,2]. The non-metallic
                                                      electrode is made of surface rock portions with high pore volume and high pores connectivity and saturated
                                                      with saline water. The experimental results are compared to the freshwater Proton Exchange Membrane PEM
                                                      electrolyzers. The comparison proved that the novel solution solved the corrosion challenges of the metallic
                                                      electrodes with excellent efficiency and hydrogen purity.
1. Introduction                                                                        Pierozzi et al. (2022) [8] and Kumar et al. (2019 [9]) discussed the
                                                                                       advantages of the PEM in its ability to adjust the input power which
    The PEM technology: According to the Department of Energy report                   made it suitable for irregular renewable power sources. They also
[3], water molecules are separated into hydrogen and oxygen using the                  pointed out the simplicity of PEM manufacturing, operation and its high
Proton Exchange Membrane, PEM electrolyzers, with an external elec                    hydrogen purity. PEM also features high working current densities,
tric source. PEM separates hydrogen and oxygen by having a selective                   excellent efficiency, and a rapid response time. Its compact design and
barrier that only permits protons to flow through. When protons arrive                 small footprint make it appealing for industrial applications.
at the cathode, they mix with electrons to generate hydrogen gas. Ox                      The PEM Challenges: Lebedev (2019) [10] highlighted an impor
ygen gas is produced at the anode. PEM electrolyzer is used in a variety               tant challenge to the PEM electrolyzer which lies in the degradation of
of applications due to their scalability and relative compactness.                     the proton exchange membrane itself particularly at elevated tempera
    The PEM advantages: Carmo et al. (2013) [4] and Grigoriev et al.                   tures or under exposure to contaminants.
(2022) [5] showed that PEM electrolysis offers multiple benefits                           The PEM characterization: Benghanem et al. (2024) [11] have
compared to other hydrogen production methods. It cuts the need for                    carried out a comprehensive analysis of solar-powered hydrogen pro
added purification procedures by producing high-purity hydrogen up to                  duction systems with two types of water electrolysis: alkaline (AWE) and
99.995%. Also, Buttler et al. (2018) [6] showed that high                              proton exchange membrane (PEM) by examining the impact of several
electrical-to-hydrogen conversion efficiencies, which in certain situa                factors such as input voltage, electrolyte concentration, and electrode
tions surpass 80%, are reached by PEM systems. Siracusano et al. (2018)                composition on the hydrogen production rate. They concluded that PEM
[7] compared the PEM electrolysis benefits over alkaline electrolysis.                 electrolyzers require a lower voltage and hence lower energy con
They showed that PEM systems run at lower temperatures, typically                      sumption from solar panels compared to AWEs in producing the same
20–80 ◦ C, compared to alkaline electrolysis which requires elevated                   volume of hydrogen. This conclusion showed that the PV-PEM system
temperature reaching 50–150 ◦ C. They also showed that PEM technol                    has higher efficiency than the PV-Alkaline system. They also found out
ogy has an excellent dynamic reaction which enables PEM to control                     that aluminum electrodes can produce a higher hydrogen production
hydrogen production by changing the input energy requirements.                         rate compared to copper and stainless-steel electrodes due to the
 * Corresponding author.
   E-mail address: moustafa.oraby@aucegypt.edu (M. Oraby).
https://doi.org/10.1016/j.ijhydene.2024.10.219
Received 25 July 2024; Received in revised form 12 October 2024; Accepted 15 October 2024
0360-3199/© 2024 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and
similar technologies.
M. Oraby et al.                                                                                             International Journal of Hydrogen Energy 92 (2024) 1256–1265
aluminum’s higher conductivity and high resistance to corrosion caused               the cost of water electrolysis systems and how the performance of these
by the electrolyte solution. Furthermore, they highlighted that in AWEs              technologies might evolve over time to address the uncertainties of
the hydrogen flow rate increased with the increase of the concentration              future developments in water electrolysis.
of saline water and the input voltage resulting in a flow rate of 45.2                   Wang, Y. et al. (2023) [16] addressed the future economic feasibility
ml/min pure hydrogen with an input voltage of 45 V. Finally, their study             of PEM water electrolysis for green hydrogen production by applying a
concluded that for the same experimental time of 10h with the                        multi-scenario analysis of its cost reduction in China from 2020 to 2060.
maximum incident solar irradiation of 1050 W/m2, the accumulated                     Wang, Y. and his coauthors predicted a potential drop in the cost of
hydrogen production rate from the PEM electrolyzer was 10300 ml/day                  hydrogen production through PEM water electrolysis, from $7.26/kg in
with specifications of 1.67V cell voltage and 2 A/cm2 current density,               2020 to almost $2.60/kg by 2060 based on various factors. Those factors
while it was 3600 ml/day, and 450 ml/day when using an alkaline                      are technological advancements in PEM electrolysis such as improve
electrolyzer with the 30% KOH solution and seawater, respectively, and               ment in PEM electrolyzer, favorable economic changes such as the
specifications of 1.72V cell voltage and 0.7 A/cm2 current density.                  economy, fluctuating electricity prices, and supportive policies and in
    Kumar, S. et al. (2023) [12] have conducted a detailed review in                 centives such as carbon taxes on fossil fuel-based hydrogen production
their study, discussing the potential of the Proton Exchange Membrane                and subsidies for PEM technology. Overall, those assumptions were
(PEM) water electrolysis as the most promising technology for green                  estimated and forecasted by using bottom-up cost analysis, scenario
hydrogen production. They highlighted the advantages of the PEM                      analysis, learning curve method, and H2A model which provide valu
water electrolysis such as its compact system design with high hydrogen              able insights into the potential for PEM water electrolysis to become
purity, high energy efficiency, high operating current densities, and                cost-effect.
rapid dynamic response when coupled with renewable energy sources.                       Another technology used in producing green hydrogen from fresh
They also concluded that although PEM water electrolysis is already                  water, or slightly alkaline water, which also has the potential of
commercially available in the market, significant advancements are                   lowering the cost of hydrogen production is the Anion Exchange Mem
needed to minimize its high cost compared to blue hydrogen. They                     brane, AEM, water electrolysis. The AEM electrolysis is a water elec
recommended a reduction in cost since if the cost dropped from the                   trolysis utilizing a semi-permeable membrane that conducts the
current CAPEX of 587$/kW to 200$/kW will significantly enhance the                   hydroxide ions OH− like the PEM in conducting the protons. AEM uses
contribution of water electrolysis to the global production of green                 fresh water or low alkaline solutions since adding alkaline solutions
hydrogen.                                                                            increases the membrane conductivity which increases the catalyst uti
    Bin, S. et al. (2024) [13] have gone a step further and conducted an             lization. Normally the AEM operates at 1.0 A/cm2 and 1.8 V in pure
in-depth analysis of high-pressure PEM water electrolysis for large-scale            water and 1.57 V in alkaline water. Varcoe et al. (2014) [19] and Dekel
commercial hydrogen production. They showed that high-pressure PEM                   et al. (2018) [20] discussed the advantages of the AEM in using a low
electrolysis further reduces the overall cost of PEM electrolysis                    cost transition metal catalyst instead of the high cost metal catalyst
compared to traditional low-pressure electrolysis cells by cutting the               required in PEM. The AEM uses the Aemion membrane which has a
need for a costly hydrogen compressor and significantly decreasing                   limitation in the operating hours due to its stability as a function of time.
energy consumption. Besides, they highlighted other associated chal                 The current is carried by hydroxide ions through a dense polymeric
lenges for further research such as membrane degradation, hydrogen                   anion exchange membrane.
cross-osmosis, membrane shedding, and hydrogen embrittlement.                            Considerable efforts are undergoing to enhance the stability of the
    Shiva Kumar et al. (2022) [14] took a different approach in their                Aemion. Khataeeet et al. (2022) [21] tested the chemical and electro
study and chose to review various water electrolysis technologies from               chemical durability above a hindered hours of Aemio anion exchange
techno-commercial prospects. They elaborated that the choice of the                  membranes in a flow cell where the anode and the cathode are made of
right water electrolysis technology for green hydrogen production is                 nickel felt as the electrodes material. The membranes were analyzed by
based on the following factors: scalability, maintenance requirements                NMR spectroscopy after the AEM tests, and the results showed no sign of
and cost of materials used in electrodes such as membranes and other                 severe chemical degradation.
components. They discussed advantages and limitations of the common
three water electrolysis, namely.                                                    2. The experimental setup
1. Mature technology but low efficiency for alkaline water electrolysis                  The experimental setup is designed to characterize the SeaWater
2. High efficiency but more expensive for PEM electrolysis                           ELectrolyzer, SWEL-V, and to compare it to the Proton Exchange
3. Higher efficiency but under development for solid oxide water                     Membrane, PEM, electrolyzer. All experiments are performed under
   electrolysis.                                                                     normal atmospheric pressure and temperature. The PEM electrolyzer
                                                                                     used in this paper is manufactured by the Hydro-Genius Professional
    In terms of Hydrogen production rate, they showed that the highest               Electrolyzer, Fig. 1a and Fig. 1b with an active area of an active area of
four PEM electrolysis systems are M5000 model by Nel company, Nor                   80 mm Width, 85 mm Length, and 34 mm Thickness and with membrane
way, with 5000 Nm3/hr and energy consumption of 4.5 kWh/Nm3,                         surface area 25 cm2. The maximum operating voltage for this PEM
followed by HyLYZER4000 model by Cummins company, Canada, with                       electrolyzer ranges between 0 and 3.0 V. The SeaWater ELectrolyzer,
4000 Nm3/hr, Silyzer300 model by Siemens company, Germany, with                      SWEL-V, Fig. 2, has the advantage of producing green hydrogen directly
100–2000 Nm3/hr, and M400 model by Proton onsite company, USA,                       from seawater without any prior treatments. The seawater(s) used in this
with 417 Nm3/hr.                                                                     experimental work are samples taken from the Egypt’s Mediterranean
    Schmidt et al. (2017) [15] took a unique approach and forecasted the             Sea and Red Sea. The published chemical compositions of both the red
capital costs of water electrolysis by eliciting predictions from fuel cell          sea water (17) and the mediterranean sea water (18) are shown in
experts and applying P-10, P-50 and P-90 estimates to minimize any                   Table 1.
anchoring bias. According to their study, it is predicted by 2030 that the               Another very important advantage of the SWEL-V electrolyzer are its
PEM electrolysis price will range from 850 to 1650 €/kW due to                       simple design, no corrosion, no membranes, no catalysts and above all
increased research and development funding and production scale-up.                  its ability to operate at any volt and current. Full details of the SWEL-V
On the other hand, they found that the capital costs of alkaline water               physics, the no corrosion process, the rock composition and analysis and
electrolysis and solid oxide water electrolysis are estimated to range               a full comparison between the rock and the metallic electrodes prop
from 750 €/kW and 1050–4250 €/kW respectively. Such predictions                      erties and characteristics are fully discussed in previous publications of
were based on expert-driven insights to know what factors can influence              the author (references 1 and 2).
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                                                                                        The hollow rock plug and the rubber connector are filled with
                                                                                    seawater. The positive voltage terminal is connected to the graphite
                                                                                    brush which in turn connects to the bottom of the hollow rock plug
                                                                                    cathode to complete the electric circuit. The negative voltage terminal is
        Fig. 1a. Hydro-Genius Professional PEM electrolyzer schematic.
                                                                                    connected to the metallic anode. When the current flows, the hydrogen
                                                                                    is generated and travels upward to the anode where it passes through the
                                                                                    T-connector to a graded tube. The hydrogen volume is then measured
                                                                                    using the graded tube, Fig. 4. There is no limit of power voltage or
                                                                                    current for the SWEL-V which is one of the drawbacks of the PEM.
                                                                                    Table 1
                                                                                    Water composition of red sea and mediterranean sea [17,18].
                                                                                     Constituent               Red Sea. ppm                   Mediterranean Sea, pp,
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4.1. Experiment-1
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Table 2                                                                                              Table 5
PEM electrolyzer – experiment (1).                                                                   SWEL-V efficiency – Experiment (1).
                                                Cumulative Time,   Cumulative Hydrogen                Efficiency - Salt                         4.70                          cc/w.min
                                                min                Volume cc                                                                   282.05                        cc/w.hr
                                                                                                                                               282047.67                     cc/kw.hr
      Fresh water                             0.00               0.00
                                                                                                                                               0.2820                        CM/kw.hr
      Input volt         1.7         V          11.57              2.00
                                                                                                                                               39.71                         Kw.hr/1 Kg of H
      Input              0.02        Amp        23.24              4.00
                                                                                                                                               83.93%                        Efficiency
      current
      Input              0.034       Watt       35.46              6.00
      power
                                             47.59              8.00
                                                                                                     the PEM electrolyzer, Table-2, the current is set to 0.05 amp while the
                                             60.02              10.00                             voltage was 2.0 V providing a power of 0.1 Watt. For the SWEL-V, the
                                             73.32              12.00                             1.8 V dragged a current to a 0.05 amp resulting in a comparable input
                                                                                                     power of 0.09 W. The hydrogen production was measured as a function
                                                                                                     of time every 2 cubic cm. Table 6 and Table 7 show the results for the
Table 3                                                                                              PEM and the SWEL-V respectively.
SWEL-V electrolyzer – experiment (1).                                                                    The accumulated hydrogen production versus the accumulated
                                                Cumulative Time    Cumulative Hydrogen
                                                                                                     production time is plotted for both the PEM and the SWEL-V, Fig. 6. The
                                                min                Volume cc                         production time for the SWEL-V salt water is slightly slower in this set of
                                                                                                     experiments because the input power of the SWEL-V is lower than the
          Salt water                          0.00               0.00
          Input volt         1.2         V      11.00              2.00                              PEM (0.09 W versus 0.1).
          Input              0.03        Amp    21.88              4.00                                  The efficiency of hydrogen production is calculated for both the PEM
          current                                                                                    and the SWEL-V using equation (1). The details of the calculations are
          Input              0.036       Watt   33.15              6.00
                                                                                                     shown in Tables 8 and 9.
          power
                                             47.20              8.00
                                                                                                         The efficiency of the SWEL-V reached the same efficiency of the PEM.
                                             59.08              10.00
                                             70.91              12.00
                                                                                                     4.3. Experiment-3
                                                                                                     Table 6
4.2. Experiment-2
                                                                                                     PEM electrolyzer – experiment (2).
              In this experiment, the input current is raised to a higher value. For                                                        Cumulative Time        Cumulative Hydrogen
                                                                                                                                            min                    Volume cc
                                                                                              1260
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Table 7                                                                                 Table 12
SWEL-V electrolyzer – experiment (2).                                                   The SWEL-V electrolyzer – experiment (3).
                                  Cumulative Time    Cumulative Hydrogen                                                     Cumulative Time        Cumulative Hydrogen
                                  min                Volume cc                                                               min                    Volume cc
Table 9
SWEL-V efficiency – Experiment (2).
                                                                                        Table 14
  Salt Efficiency                     4.28                     cc/w.min                 The SWEL-V efficiency.
                                     256.96                   cc/w.hr
                                     256959.31                cc/kw.hr                  Salt Efficiency                        3.49                           cc/w.min
                                     0.2570                   CM/kw.hr                                                        209.42                         cc/w.hr
                                     43.59                    Kw.hr/1 Kg of H                                                 209424.08                      cc/kw.hr
                                     76.17%                   Efficiency                                                      0.2094                         CM/kw.hr
                                                                                                                               53.48                          Kw.hr/1 Kg of H
                                                                                                                               62.32%                         Efficiency
Table 11
The PEM electrolyzer – experiment (3).                                                  comparisons showed that the SWEL-V and the PEM provided the same
                                  Cumulative Time    Cumulative Hydrogen                production rates and the same efficiencies for all variable power. The
                                  min                Volume cc                          advantage of the SWEL-V electrolyzer is its ability to use the seawater
      Fresh water               0                  0                                  directly without any requirements of desalination as is the case in the
      Input volt    2.5    V      1.33               2                                  PEM electrolyzer. Also, the use of the rock electrode in the SWEL-V
      Input         0.18   Amp    2.25               4                                  resulted in the elimination of the corrosion process compared to that
      current                                                                           in the PEM electrolyzer.
      Input         0.45   Watt   3.62               6
      power
                               5.12               8                                  6. Efficiency or rate is a choice
                               6.32               10
                               7.52               12                                    The choice between high production rates versus production effi
                                                 
                                                                                        ciency is a particularly important factor in hydrogen production. From
                                                                                        the above three different experiments, it was clear that the efficiency is
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decreased as a function of the input power. This is because the higher the
input power the higher the losses during hydrogen production. It is
noticed that some of the input power is dissipated as heat in the system
resulting in lowering efficiency. Table 15 and Fig. 8 show efficiency and
the production rate as a function of the input power.
8. Methodology
                                                                                                Fig. 8. Production rate and efficiency vs. Input power.
    Fig. 11cshows the gas analysis of the Step-1 where a high volume of
air passes through the collecting bag from the long tube. As expected,
the analysis showed the existence of Oxygen and Nitrogen. Fig. 12 shows
the analysis of Step-2 where the oxygen and the nitrogen peaks are
significantly reduced since the volume of the connecting tube containing
air is less than that in STEP-1. This observation showed that the pro
duced hydrogen from the SWEL-V has a very high purity percentage and
the impurities that are picked by the chromatography are due to the air                             Fig. 10a. The hydrogen collection plastic bag.
intentionally passing through the collecting bag due to the connecting
plastic tubes and not from the SWEL-V electrolyzer.                                   10. Conclusions
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M. Oraby et al.                                                                                                 International Journal of Hydrogen Energy 92 (2024) 1256–1265
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