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Decoupled Water Splitting for Green

Hydrogen Production: Reshaping
Water Electrolysis
By Avner ROTHSCHILD
Department of Materials Science and Engineering, Technion – Israel Institute of Technology, Haifa,
Israel
Hen DOTAN
H2Pro, 2 Ha-Tokhen street, Caesarea Business and Industrial Park, Israel
And Gideon GRADER
Department of Chemical Engineering, Technion – Israel Institute of Technology, Haifa, Israel

Green hydrogen production at scale is essential to fight global warming and climate change. The present
water electrolysis technologies present significant barriers to meet this challenge, due to high system
and operational costs that emerge from the need to divide each cell into gas-tight cathodic and anodic
compartments to avoid mixing hydrogen with oxygen, and from intrinsic energy losses in the complex
oxygen evolution reaction. Recent efforts to overcome these barriers include transformative approaches
to decouple the hydrogen and oxygen evolution reactions using soluble redox couples or solid redox
electrodes that mediate the ion exchange between the primary electrodes such that hydrogen and oxygen
are generated at different times and/or different cells. This leads the way to membraneless electrolyzer
architectures that can enhance safety, reduce system costs, and provide operational advantages such
as high-pressure hydrogen production. In particular, E-TAC water slitting offers these advantages as
well as ultrahigh efficiency and compact design of rolled electrode assemblies, opening new frontiers for
advanced water electrolysis.

Introduction reactions occur concurrently in the same electrolytic

cell(3). Therefore, a Nafion membrane (in PEMWE)(4)
Green hydrogen produced from water using electri- or Zirfon diaphragm (in AWE)(5) divides the cell into
city from renewable energy sources such as solar and two gas-tight compartments to avoid hazardous
wind is essential to reduce CO2 emissions, especially in H2/O2 mixing, as illustrated schematically in Figure 1
hard-to-abate industrial sectors such as steel, cement from the page 145. This membrane electrolysis archi-
and ammonia production. Such hydrogen is a critical tecture complicates the electrolyzer’s construction by
component in the energy transition to fight climate adding gaskets and compression sealing over large
change. Energy economy analysts estimate it will contri- areas to prevent H2/O2 crossover. This adds substan-
bute between 12 and 22% of the global energy demand tial costs and limits operation at high pressures and
in 2050(1). The present technologies for green hydrogen low-purity water.
production are alkaline water electrolysis (AWE) and
polymer electrolyte membrane water electrolysis Energy conversion efficiency is another grand challenge
(PEMWE). In addition, high-temperature solid oxide for this energy-intensive technology, where alkaline
water electrolysis (SOWE) emerges as a new techno- electrolyzers consume between 50 and 78 kWh per kg
logy that promises ultrahigh efficiency but struggles to
achieve long-term stability, especially under thermal
(3)
CHATENET M., POLLET B. G., DEKEL D. R., DIONIGI
F., DESEURE J., MILLET P., BRAATZ R. D., BAZANT M. Z.,
cycling, as well as low cost(2). EIKERLING M., STAFFELL I., BALCOMBE P., SHAO-HORN Y.
One thing in common to all three technologies is the & SCHÄFER H. (2022), ‟Water electrolysis: from textbook
knowledge to the latest scientific strategies and industrial deve-
coupling between the hydrogen and oxygen evolution
lopments”, Chem. Soc. Rev. 51, pp. 4583-4762.
reactions (HER and OER, respectively), where both
  AYERS K., DANILOVIC N., HARRISON K. & XU H. (2021),
(4)

‟PEM electrolysis, a forerunner for clean hydrogen”, Electrochem.

Soc. Interface 30, p. 67.
(1)
SÖNNICHSEN N. (2022), ‟Global hydrogen demand estimates BRAUNS J., SCHÖNEBECK J., KRAGLUND M. R., AILI D.,
(5)

as share of total energy 2050”, by outlook scenario, Statista. HNÁT J., ŽITKA J., MUES W., JENSEN J. O., BOUZEK K. &
(2)
International Renewable Energy Agency ‒ IRENA (2020), TUREK T. (2021), ‟Evaluation of diaphragms and membranes as
‟Green Hydrogen Cost Reduction: Scaling up Electrolysers to separators for alkaline water electrolysis”, J. Electrochem. Soc.
Meet the 1.5⁰C Climate Goal”, report. 168, 014510.

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144
of hydrogen produced(2), which translates to a system schemes, as in the case of E-TAC water electroly-
efficiency of 50 to 79% based on the higher heating value sis(12), and provides new opportunities to reshape water
(HHV) of hydrogen (39.4 kWh/kgH ). PEM electrolyzers electrolysis and potentially overcome the fundamental
2
consume a bit more energy (50-83 kWh/kgH ) than their barriers of this two centuries-old technology(13).
2
alkaline counterparts, whereas high-temperature solid
oxide electrolyzers present higher efficiency (45-55
kWh/kgH ) but also higher capital costs and shorter
2
Decoupled water electrolysis (DWE)
lifetime compared to their low-temperature alkaline and
DWE was first reported by Symes and Cronin in 2013,
PEM counterparts(2). Thus, 25 to 50% of the electrical
based on adding to the electrolyte a soluble redox couple
energy is lost in vain in traditional water electrolysis. The
(SRC) that functions as an electron-coupled-proton
lion’s share of this loss, in state-of-the-art electrolyzers,
buffer and mediates the proton exchange between the
arises from the OER due to a thermodynamic barrier
anodic and cathodic reactions (OER and HER, respec-
that emerges from the four proton-coupled electron
tively), as illustrated schematically in Figure 1b from the
transfer steps necessary to produce an O2 molecule,
page 145 (14). Despite generating oxygen and hydrogen
which leads to a high overpotential of 0.3-0.4 V at the
in different stages, a membrane was still required to
onset of oxygen evolution(6).
prevent redox shuttling between the anode and cathode,
These drawbacks burden the cost of green hydrogen and the efficiency was lower (52%HHV) than in conven-
production, and the dependence on critical raw materials tional water electrolysis. Low efficiency is an inherent
of alkaline, PEM and solid oxide electrolyzers limits disadvantage of this method since the oxidation and
their scale-up potential(7). Overcoming these barriers reduction overpotentials of the SRC add up to those of
is necessary to reach green hydrogen production(2) at the OER and HER, thus necessitating a larger voltage
terawatt scale in order to support the Net Zero transi- than in conventional water electrolysis (13). Subsequent
tion. Incremental improvements of present technologies studies pursuing this approach introduced different SRCs
support reaching short-term goals, but frontier research and operation schemes, but the efficiency remained
and innovation that aim at developing breakthrough low and a membrane was still necessary (10,11 and 13)
materials and processes for next generation technolo- Another disadvantage common to all the systems
gies are necessary to achieve long-term goals. Thus, reported employing this approach is the use of platinum
advanced materials and novel cell designs for next group metal (PGM) catalysts due to operation in acidic
generation water electrolysis technologies is a topmost electrolytes where non-noble metals and their oxides
research priority towards Net Zero(8). In particular, are unstable.
membraneless cell architectures present a promising
A different DWE approach was reported by Chen
potential for cost reduction, compact and more efficient
et al.(15) and by Landman et al.(16), using solid redox
systems as well as operational advantages such as
electrodes (SRE) instead of SRC, and operating in
high-pressure hydrogen production(9). Specifically,
alkaline instead of acidic electrolytes. Using nickel (oxy)
decoupled water electrolysis (DWE) where the HER
hydroxide electrodes from rechargeable alkaline batte-
and OER are decoupled in time and/or place presents
ries (e.g., the cathodes in NiCd batteries) as auxiliary
an emerging concept that attracts growing interest in
electrodes that mediate the OH– exchange between
the past decade(10) and (11). This decoupling leads the way
the cathode and anode of alkaline water electrolysis,
to safe operation without membranes in some DWE
the electrolytic cell is divided into two separated cells
that generate hydrogen and oxygen remotely from each
other, as illustrated schematically in Figure 1c from the
page 145. This enables operation without membranes/
diaphragms, paving the way for membraneless
(6)
MAN I. C., SU H.‐Y., CALLE‐VALLEJO F., HANSEN H. A.,
MARTÍNEZ J. I., INOGLU N. G., KITCHIN J., JARAMILLO T. F.,
NØRSKOV J. K. & ROSSMEISL J. (2011), ‟Universality in oxy- (12)
DOTAN H., LANDMAN A., SHEEHAN S. W., MALVIYA K.
gen evolution electrocatalysis on oxide surfaces”, ChemCatChem D., SHTER G. E., GRAVE D. A., ARZI Z., YEHUDAI N., HA-
3, pp. 1159-1165. LABI M., GAL N., HADARI N., COHEN C., ROTHSCHILD A. &
KIEME S. l. S, MOLINKA T., LEHNER F., FULL J., SAUER A.
(7)
GRADER G. S. (2019), ‟Decoupled hydrogen and oxygen evolu-
& MIEHE R. (2021), ‟Critical materials for water electrolysers at tion by a two-step electrochemical – Chemical cycle for efficient
the example of the energy transition in Germany”, Int. J. Energy overall water splitting”, Nature Energy 4, pp. 786-795.
Res. 45, pp. 9914-9935. (13)
LANDMAN A., ROTHSCHILD A. & GRADER G. (2021), ‟New
(8)
Hydrogen Europe Research (2022), position paper titled “For electrolyzer principles: Decoupled water splitting”, in Hydrogen
a long perspective impact of European Research and Industrial Production by Water Electrolysis, edited by SMOLINKA T. &
Sectors”. GÄRCHE J., Elsevier.
ESPOSITO D. V. (2017), ‟Membraneless electrolyzers for low-
(9) (14)
SYMES M. D. & CRONIN L. (2013), ‟Decoupling hydrogen
cost hydrogen production in a renewable energy future”, Joule 1, and oxygen evolution during electrolytic water splitting using an
pp. 651-658. electron-coupled-proton buffer”, Nature Chemistry 5, pp. 403-409.
MCHUGH P. J., STERGIOU A. D. & SYMES M. D. (2020),
(10)
CHEN L., DONG X., WANG W. & XIA Y. (2016), ‟Separating
(15)

‟Decoupled electrochemical water splitting: From fundamentals to hydrogen and oxygen evolution in alkaline water electrolysis using
applications”, Adv. Energy Mater 10, 2002453. nickel hydroxide”, Nature Communication 7, 11741.
IFKOVITS Z. P., EVANS J. M., MEIER M. C., PAPADANTO-
(11)
LANDMAN A., DOTAN H., SHTER G. E., WULLENKORD M.,
(16)

NAKIS K. M. & LEWIS N. S. (2021), ‟Decoupled electrochemical HOUAIJIA A., MALJUSCH A., GRADER G. S. & ROTHSCHILD
water-splitting systems: a review and perspective”, Energy Envi- A. (2017), ‟Photoelectrochemical water splitting in separate oxy-
ron. Sci. 14, pp. 4740-4759. gen and hydrogen cells”, Nature Materials 16, pp. 646-651.

Hydrogène et décarbonation © Annales des Mines

 145
decoupled water electrolysis (MLDWE). The disadvan- reduced electrochemically at the cathode while oxygen
tage of replacing the mobile SRC that flows with the evolved at the anode of an electrolytic cell, and then
electrolyte from one cell to another by stationary SRE transferred into another cell where it was oxidized
is that this requires batch operation to regenerate the chemically and released hydrogen upon contact
auxiliary electrodes when they reach their maximal with a platinum catalyst (without applying electricity).
capacity, whereas SRCs support continuous operation The electrolytic efficiency was 62%HHV, lower than
as in traditional electrolyzers (10, 11 and 13) Although the in conventional water electrolysis, and a membrane
reported systems are less efficient than AWE (15 and 16) was used to prevent redox shuttling in the electrolytic
for the same reason as described above for the case cell. Other ECCs with different SRCs were reported,
of SRC, they might serve unique purposes such as in acidic electrolytes, using PGM catalysts and achie-
photoelectrochemical water splitting with centralized ving lower efficiency than in conventional water
hydrogen production (16 and 17). electrolysis (10,11 and 13).
Another DWE approach was reported by Rausch
et al.(18), introducing an electrochemical – Chemical E-TAC water splitting
cycle (ECC) whereby an SRC (silicotungstic acid) was
An exciting breakthrough in DWE was reported by
Dotan et al. in 2019, introducing an electrochemical –
(17)
LANDMAN A., HALABI R., DIAS P., DOTAN H., MEHLMAN Thermally-activated chemical (E-TAC) cycle that divides
A., SHTER G. E., HALABI M., NASERLADEEN O., MENDES the OER into two sub-reactions and enables opera-
A., GRADER G. S. & ROTHSCHILD A. (2020), ‟Decoupled pho-
tion at near thermoneutral conditions (12). In the first
toelectrochemical water splitting system for centralized hydrogen
production”, Joule 4, pp. 448-471. stage (E), a cobalt-doped nickel hydroxide anode was
charged to nickel oxyhydroxide while hydrogen evolved
(18)
RAUSCH B., SYMES M. D., CHISHOLM G. and CRONIN
L. (2014), ‟Decoupled catalytic hydrogen evolution from a mole- at the cathode. This stage was done in a cold (~25°C)
cular metal oxide redox mediator in water splitting”, Science 345, alkaline electrolyte (lye), and it was stopped before
pp. 1326-1330.

Figure 1: Schematic illustrations of the basic operation at cell level in: a) alkaline water electrolysis; b) decoupled water elec-
trolysis with a soluble redox couple; c) decoupled water electrolysis with solid redox electrodes; and d) electrochemical – thermally-
activated chemical (E-TAC) decoupled water electrolysis.

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146
oxygen started to evolve at the charged anode, such over traditional membrane electrolysis which is limited
that only hydrogen was produced in this stage. Then, in to a parallel plate architecture where compression
the second stage (TAC), the cold lye was replaced by a sealing prevents H2/O2 crossover between the catho-
hot (95°C) lye that induced a fast spontaneous reaction dic and anodic compartments. Operating in alkaline
between the charged anode and water, regenera- electrolyte where nickel-based materials can replace
ting the anode back to its initial state while producing the PGM catalysts used in acidic electrolytes (as in
oxygen, 4NiOOH + 2H2O → 4Ni(OH)2 + O2, as illus- PEMWE) means that all the cell components can be
trated in Figure 1d from the previous page. The heat made of Earth-abundant elements. The E-TAC process
generated in this exothermic reaction heats the system also presents technological challenges that emerge
in the TAC stage, whereas the heat absorbed in the from batch operation with thermal swings between
endothermic electrochemical reaction cools the system the E and TAC stages, as well as from capacity and
in the E stage. Therefore, in an ideal system, no exter- rate limitations for charge storage at the nickel (oxy)
nal energy source is needed to supply the required heat hydroxide anodes. These challenges are addressed by
for the thermal swings of the E-TAC cycle. H2Pro, an Israeli startup company that develops ultra-
efficient high-pressure (50 bar) water electrolysis
The E-TAC process presents important advantages
systems for green hydrogen production at scale,
such as ultrahigh efficiency (98.7%HHV, at cell level) and
based on the innovative E-TAC process(21). H2Pro
membraneless operation (12), identifying it as a promising
started operating in 2019, and has since raised more
competitive alternative to conventional water electroly-
than USD 100 million. Amongst the high profile inves-
sis(19)and(20). Its membraneless architecture leads the
tors are Breakthrough Energy Ventures, Horizons
way to simple cell designs, such as rolled electrodes
Ventures and Temasek Holdings as well as Yara and
that can be piled up to form a compact stack, as shown
Arcelor Mittal. The company has grown to nearly
in Figure 2. This demonstrates a unique advantage
100 employees, mostly in R&D. The company concen-
trates on the development of its special rolled electrodes
SYMES M. D. (2019), ‟Decoupled electrolysis – Just add hot
(19)

water”, Nature Energy 4, pp. 730-731. (21)

ROTHSCHILD A., LANDMAN A., DOTAN H., SHTER G. &
(20)
CENTI G. (2022), ‟Across the board: Gabriele Centi on decou- GRADER G. (2020), Methods and system for hydrogen produc-
pling electrocatalytic reactions to electrify chemical production”, tion by water electrolysis, United States Patent No. 2020/0040467
ChemSusChem 15, e202200007. A1.

Figure 2b: Rolled electrodes ‒ Photo©H2Pro.

Figure 2a: E-TAC electrodes ‒ Photo©H2Pro.

Figure 2d: two E-TAC reactors containing such stacks ‒

Figure 2c: A stack of rolled electrodes ‒ Photo©H2Pro.
Photo©H2Pro.

Hydrogène et décarbonation © Annales des Mines

 147
and systems as shown below. It plans to complete its levels and fronts including green hydrogen production,
first factory in 2023/24 and start sales in 2024/25. H2Pro storage, transportation, compression, purification and
is stating that the unique advantages of the E-TAC more. Clearly the production step is a key enabling step
technology will allow it to sell multi megawatts systems in the long and complex chain required to win this battle.
for as low as 200 $/kW, before the end of the decade. Decoupled water electrolysis wherein the hydrogen and
H2Pro economic analysis predicts that the low Capex of
oxygen evolution reactions are decoupled in time and/
the system and their high efficiency will allow to achieve
or place present new opportunities to enhance safety,
the Energy Earth-shot initiative goal of 1$ for 1 kg of
green hydrogen before the end of the decade(22). reduce system costs, and provide operational advan-
tages such as high-pressure hydrogen production, with
respect to traditional electrolyzes. In particular, E-TAC
Summary and conclusions water splitting presents all these advantages and more,
offering ultrahigh efficiency and compact design of
In conclusion, it is clear that there is a global consensus
rolled electrodes. These unique advantages readily
that large scale production of green hydrogen is essen-
tial for mankind to win the battle against global warming lend themselves to automation and robotic production
and climate change. This battle will be fought on many of large area rolled electrodes, much like the fabrica-
tion of batteries. This endows the E-TAC technology
with a significant advantage in large scale production of
(22)
https://www.energy.gov/eere/fuelcells/hydrogen-shot#:~:text=
The%20first%20Energy%20Earthshot%2C%20 electrodes and systems for green hydrogen production
launched,%221%201%201%22 at terawatt scale.

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