Direct Electrolysis of Seawater
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
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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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References
[1] Oraby M, Alsakaf A. Green hydrogen production directly from seawater with No
corrosion using a nonmetallic electrode: a novel solution and a proof of concept. Int
J Energy Res 2023;2024:5576626. 11 pages, Jan-2024.
[2] Oraby M. Methods and systems for producing hydrogen gas using electrolysis of
saltwater using electrodes of sedimentary rock portion. United States Patent 2024/
001112463 A1 2024.
[3] Department of Energy. Hydrogen production: electrolysis. June 6, 2024.
[4] Carmo M, Fritz DL, Stolten D. A comprehensive review of PEM water electrolysis.
J Power Sources 2013;280:89–114.
[5] Grigoriev SA, Flores-Díaz M, Peña MA, Concepcion JJ, Koper MT. “PEM water
electrolysis for hydrogen production: fundamentals, advances, and prospects”.
Carbon Neutrality 2022;2(1):1–23.
[6] Buttler A, Steele D. Hydrogen production: current technology and future
challenges. Royal Society of Chemistry; 2018.
[7] Siracusano O, Cascone MV, Rozea CN. “Recent advances in PEM electrolysis for
large-scale hydrogen production. J Appl Electrochem 2018;48(3):209–36.
Fig. 12. Oxygen and Nitrogen impurities – Short connector. [8] Pierozzi N, De Bacco P, Tascino C, Arcangeletti G, Tucceri F, De Simone G, Piazzi L,
Agogliati P. Emerging solutions in offshore green hydrogen production and storage.
2022.
Ethical statement [9] Kumari S, White R, Spurgeon JM. Solar hydrogen production from seawater vapor
electrolysis. Electrochemical Society; 2016.
[10] Lebedev NN. A review of proton exchange membrane water electrolysis on
The author hereby confirms abiding with all ethics including copy degradation mechanisms and mitigation strategies. Int J Hydrogen Energy 2019;44
rights, trademarks, commercial statements, …etc. (18):9830–43.
[11] Benghanem M, Almohamadi H, Haddad S, Mellit A, Chettibi N. The effect of
voltage and electrode types on hydrogen production powered by photovoltaic
Funding system using alkaline and PEM electrolyzers. Int J Hydrogen Energy 2024;57:
625–36.
This is to acknowledge that the authors received no specific funding [12] Kumar SS, Lim H. Recent advances in hydrogen production through proton
exchange membrane water electrolysis – a review. Sustain Energy Fuels 2023;7
for this work. (15):3560–83.
[13] Bin S, Chen Z, Zhu Y, Zhang Y, Xia Y, Gong S, Zhang F, Shi L, Duan X, Sun Z. High-
Declaration of competing interest pressure proton exchange membrane water electrolysis: current status and
challenges in hydrogen production. Int J Hydrogen Energy 2024;67:390–405.
[14] Shiva Kumar S, Lim H. An overview of water electrolysis technologies for Green
This is to declare that the authors are interested to submit their work Hydrogen production. Energy Rep 2022;8:13793–813.
to be reviewed and published at the Journal of International Journal of [15] Schmidt O, Gambhir A, Staffell I, Hawkes A, Nelson J, Few S. Future cost and
Hydrogen Research. performance of water electrolysis: an expert elicitation study. Int J Hydrogen
Energy 2017;42(52):30470–92.
[16] Wang Y, Wen C, Tu J, Zhan Z, Zhang B, Liu Q, Zhang Z, Hu H, Liu T. The multi-
scenario projection of cost reduction in hydrogen production by Proton Exchange
1264
M. Oraby et al. International Journal of Hydrogen Energy 92 (2024) 1256–1265
Membrane (PEM) water electrolysis in the near future (2020–2060) of China. Fuel Nijmeijer Kitty, Scott Keith, Xu Tongwen, Zhuang Lin. Anion exchange membrane
2023;354:129409. in electrochemical energy systems. Energy Environm So 2014;7(10):3135–9.
[17] Abdel-Aal EA, Farid ME, Hassan FSM, Mohamed AE. Desalination of Red Sea water [20] Dekel Dario R. Review of cell performance in anion exchange membrane fuel cells.
using both electrodialysis and reverse osmosis as complementary methods. Egypt J J Power Sources January 2018;375:158–69.
Petroleum 2015. https://doi.org/10.1016/j.ejpe.2015.02.007. [21] Khataee Amirreza, Shirole a Anuja, Jannasch Patric. Andries Kruger Anion
[18] Nessim RB, Tadros HRZ, Abou Taleb AEA, Moawad MN. Egyptian J Aquatic Res exchange membrane water electrolysis using Aemion membranes and nickel
2015. https://doi.org/10.1016/j.ejar.2015.01.004. electrodes. J Mater Chem 2022;10:16061.
[19] Varcoe John R, Atanassov Plamen, Dekel Dario R, Herring Andrew M,
Hickner Michael A, Kohl Paul A, Kucernak Anthony R, Mustain William E,
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