Progress in Nuclear Energy 123 (2020) 103317

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Progress in Nuclear Energy

journal homepage: www.elsevier.com/locate/pnucene

Review

Comparative review of hydrogen production technologies for nuclear hybrid

energy systems✩
Roxanne Pinsky a,b ,∗, Piyush Sabharwall b , Jeremy Hartvigsen b , James O’Brien b
a
University of Michigan, 2355 Bonisteel Blvd, Ann Arbor, MI, USA
b
Idaho National Laboratory (INL), Idaho Falls, ID, USA

ARTICLE INFO ABSTRACT

Keywords: Nuclear hybrid energy systems (NHES) have potential to capitalize on (1) producing multiple commodities,
Nuclear hybrid energy systems (NHES) i.e. electricity and hydrogen as well as (2) allowing for electricity grid load following, with hydrogen
Hydrogen production production during low electricity prices. Using nuclear thermal energy and electricity (from the reactor itself)
Electrolysis
makes hydrogen production an economically attractive option. The reactor can continuously operate at full
Thermochemical water splitting
capacity, sending excess heat and electricity towards hydrogen production, which could either be sold or
Hybrid water splitting
Steam methane reforming
converted back to electricity using fuel cells at high price times. Several hydrogen production technologies
exist, but in this study the focus is on processes that require heat and electricity. These candidates include
alkaline water electrolysis, proton exchange membrane (PEM) electrolysis, solid oxide electrolysis cells (SOEC),
thermochemical sulfur–iodine (S–I), calcium-bromide (Ca-Br) cycles, hybrid sulfur (HyS) and copper–chlorine
(Cu–Cl) cycles. Each have different minimum temperature requirements which can be coupled to Generation
III and IV reactor outlet temperatures: low (<300 ◦ C), medium (<750 ◦ C), and high (<950 ◦ C). Energy input
and material process flow diagrams were created for all technologies at compatible reactor temperatures
and compared to the most common commercially operating hydrogen production method: steam methane
reforming (SMR). Technology readiness levels (TRLs) and costs were also compared. The TRL of most systems
is still below commercial development, and hydrogen productions costs are still too high to be economic
without additional policy and/or other developments.

1. Introduction
Hybrid nuclear energy systems utilize multiple energy resources to
couple multiple subsystems and produce energy commodities as out-
puts (Antkowiak et al., 2012). This allows a nuclear energy system to
operate at full capacity and either produce electricity for grid base-load
power or use excess heat and electricity to produce a new commodity.
As climate change advances due to increases in greenhouse gases, the
need for renewable, cleaner alternatives to fossil fuels becomes more
urgent. Pollutants from fossil fuels are already estimated to be high
enough to affect public health and the environment specifically at high
density populations within the US (Holladay et al., 2009). Hydrogen
(H2 ) fuel is a potential commodity that is clean, renewable and can be
produced using thermal energy from a nuclear plant.
Hydrogen is a promising alternative fuel (Holladay et al., 2009).
It has the highest energy content compared to any other known fuel,
as shown in Table 1 (Nikolaidis and Poullikkas, 2017). However,
hydrogen is not readily available in nature, despite the fact that it is by
far the most abundant element in the universe, and must be produced
from a variety of different methods (Nikolaidis and Poullikkas, 2017).
These methods can include fossil fuel based hydrogen production,
biomass based hydrogen, and hydrogen from water, requiring heat and
electricity (Holladay et al., 2009).
Hydrogen may be safely stored and transported through conven-
tional means. It may be stored as a compressed gas, cryogenic liquid
or solid hydride (Nikolaidis and Poullikkas, 2017). It can then produce
energy from fuel cells or used as a fuel for transportation, heating,
metal production (such as the reduction of iron oxide to iron), or pro-
duction of gasoline, methanol, ethanol, ammonia, and other high value
chemicals (Holladay et al., 2009; Nikolaidis and Poullikkas, 2017). As
of 2017 the annual production of H2 reached 0.1 GT, used mainly for
petroleum refining and treating metals, with a small fraction for fueling
cars (Nikolaidis and Poullikkas, 2017). The demand for hydrogen fuel

✩ This work was supported in part by the U.S. Department of Energy, Office of Science, United States, Office of Workforce Development for Teachers and
Scientists (WDTS), United States under the Science Undergraduate Laboratory Internships Program (SULI).
∗ Corresponding author at: University of Michigan, 2355 Bonisteel Blvd, Ann Arbor, MI, USA.
E-mail address: rzpinsky@umich.edu (R. Pinsky).

https://doi.org/10.1016/j.pnucene.2020.103317
Received 16 November 2019; Received in revised form 11 February 2020; Accepted 24 February 2020
Available online 4 March 2020
0149-1970/Published by Elsevier Ltd.
R. Pinsky et al.
Table 1
Higher and lower (LHV) heating value of various fuels
(Nikolaidis and Poullikkas, 2017).
Fuel HHV (MJ/kg) LHV (MJ/kg)
Hydrogen 141.9 119.9
Methane 55.5 50
Ethane 51.9 47.8
Gasoline 47.5 44.5
Diesel 44.8 42.5
Methanol 20 18.1
Fig. 1. Influence of renewable energy shown in California electricity prices over a
day (Forsberg, 2019).
is expected to increase over the next few decades (Nikolaidis and
Poullikkas, 2017; El-Shafie et al., 2019).
Coupling hydrogen production to a nuclear energy system offers
a multitude of advantages. Politically, the inconsistency of importing
fossil fuels can lead to increases in prices and uncertainty in energy sup-
ply. Environmentally, hydrogen does not emit greenhouse gases when
combusted or produced from greenhouse gas free sources (i.e. produced
using heat and electricity from solar or nuclear and producing hydrogen
from water or biomass). Hydrogen has the potential to provide clean,
domestic energy for increased economic and energy security (Holladay
et al., 2009).
Current nuclear reactors operate for base load electricity produc-
tion, which accounts for 60% of electricity demand (Antkowiak et al.,
2012). However, the other 40% requires systems that can operate
for load-following conditions. This is because renewable energies such
as solar and wind peak at certain times (i.e. solar increases substan-
tially during the middle of the day), which can lead to volatile daily
prices (Forsberg, 2019). The prices can fluctuate to negative values
during high renewable capacities (Forsberg, 2019). Fig. 1 shows the
negative electricity prices arising from increased renewable (solar)
energy in California over the course of a day (Forsberg, 2019). In these
cases, capacity payments may be required to keep generator systems
online when there is low wind or solar input (Forsberg, 2019). As re-
newable energy increases, the fraction of base-load energy will shrink,
and more effort will be placed load-following technologies. Nuclear
systems alone are not economically effective when participating in this
load following structure, because they would not consistently able to
operate at full capacity. Thus, producing other commodities, such as
hydrogen, will provide another lucrative option and make the whole
system more economically attractive.
The nuclear reactor coupled to hydrogen production has the poten-
tial for higher overall energy use efficiency and better utilization of
capital equipment (Antkowiak et al., 2012). This is because the nuclear
reactor can operate at full capacity, but also follow the electricity grid
as it varies throughout the day. When electricity prices are low, or
negative, the reactor can use a subsystem to convert heat or electricity
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Progress in Nuclear Energy 123 (2020) 103317
into hydrogen. This hydrogen may then be converted back to energy
during times of high electricity demand using fuel cells or be sold as
its own commodity. Fig. 2 shows the routes a nuclear reactor may
take for hydrogen production, depending on available reactor outlet
temperature.
As stated previously, there are a multitude of ways hydrogen may be
produced. The focus of this paper is on renewable hydrogen production
from water that requires only excess heat and electricity that can
be produced from the thermal energy of a nuclear reactor. These
water-based hydrogen production technologies are also compared to
the most common method of hydrogen production today — steam
methane reforming, which is used in approximately 48% of current
production (Department of Energy (DOE) Office of Energy Efficiency
& Renewable Energy, 2019). This method requires fossil fuels for
production and therefore releases greenhouse gases including carbon
dioxide (CO2 ).
The temperature of the water is also an important consideration.
Nuclear reactors have outlet temperatures that vary from approxi-
mately 300 to 950 ◦ C, depending on the design (Forsberg, 2019;
Goldberg and Rosner, 2011). Generation III reactors primarily consist
of Light Water Reactors (LWRs), which are the predominant reactor in
the United States. These are considered low temperature reactors and
have outlet temperatures estimated at 300 ◦ C. Generation IV reactors
are pushing on the average outlet temperature. For the purpose of
analysis, the LWR and Generation IV reactors have been split into
three categories: low (<300 ◦ C), medium (<750 ◦ C), and high (<950
◦ C, though realistically likely <900 ◦ C) outlet temperatures. The outlet
temperature can determine what hydrogen production methods are fea-
sible. Table 2 includes a summary of the three temperature categories,
including reactor type, outlet temperature, and average plant size. Note
that the conversion from thermal to electric power is estimated at 40%
for this and all further analysis. This efficiency could be achieved by
advanced reactors, whereas for the LWRs the efficiency varies between
30 to 33%. Also note that this is not an exhaustive list of all the
potential concepts, but shows that reactors are being designed in all
three different temperature ranges.
This paper offers an overview of hydrogen production technologies,
with a focus on water-based hydrogen production methods. It also
includes an overview of storage and potential uses of hydrogen, such
as for fuel or conversion back to electricity. Finally, a comparison
is made on several hydrogen production methods, including steam
methane reforming, thermochemical water splitting, water electrolysis,
and hybrid technologies. This comparison includes the technological
readiness levels, hydrogen costs, and heat and electricity requirements
for all methods. It also includes a comparison of methods for high
(<950 ◦ C), medium (<750 ◦ C), and low (<300 ◦ C) water temperature
inputs to indicate possible hydrogen production methods for several
reactor classifications.
2. Hydrogen production technologies overview
A brief review of current and future hydrogen production methods
is discussed. The majority of current hydrogen production technology
comes from fossil fuel production. 96% of commercial hydrogen comes
from a combination of natural gas (48%), heavy oils and naptha (30%),
and coal (18%), which are mainly reformed using steam methane
reforming (SMR) (Nikolaidis and Poullikkas, 2017; Department of En-
ergy (DOE) Office of Energy Efficiency & Renewable Energy, 2019).
The other 4% of hydrogen production comes from water electrolysis
using alkaline electrolyzers, a renewable technology (Zeng and Zhang,
2010). Hydrogen production can be divided into production from fossil
fuels and production from renewable resources. Renewable resources
include both biomass hydrogen production and water splitting. Table 3
includes a summary of current and developed hydrogen production
technologies, feedstock, operating temperature range, efficiency, and
developmental stage.
R. Pinsky et al. Progress in Nuclear Energy 123 (2020) 103317

Fig. 2. Possibilities for nuclear hybrid hydrogen generation, including electricity for grid power and hydrogen production.

Table 2
Categorization of low, medium, and high temperature reactors for analysis (Goldberg and Rosner, 2011; Boardman, 2017; El-Emam and Özcan, 2019;
Yildiz and Kazimi, 2006).
Outlet temp (◦ C) Power𝐴𝑣𝑔 Power𝐴𝑣𝑔 Reactor Temp (◦ C) Power
(MWt) (MWe) (MWt)
Low (<300 ◦ C) 2500 1000 Light Water Reactor (LWR) 300 2500
Advanced Gas Reactor (AGR) 650–750 1550
Sodium Cooled Fast Reactor (SFR) 450–550 1250a
Medium (<750 ◦ C) 1800 720 Lead Cooled Fast Reactor (LFR) 480–570 1350a
Super Critical Water Reactor (SCWR) 500–625 2500
Molten Salt Fast Reactor (MSFR) 650–750 2500
Very High Temperature Reactor (VHTR) 900–950 600
High (<950 ◦ C) 1400 560 Gas Cooled Fast Reactor (GFR) 750–850 1450a
Molten Salt Reactor (MSR)b 750–950 2000
a Averaged from multiple reactor designs.
b
Advanced High Temperature Reactor (AHTR) design.

Table 3
Summary of current and future hydrogen production technologies. Note that ‘‘near term’’ estimates less than 5 years, ‘‘medium term’’ 5–10 years, and ‘‘long term’’ greater
than 10 years to commercial maturity (Holladay et al., 2009; Nikolaidis and Poullikkas, 2017; El-Shafie et al., 2019; Rashid et al., 2015; Dagle et al., 2017; Schmidt
et al., 2017).
Technology Production sub-method Feedstock Temperature range (◦ C) Efficiency (%) Maturity
SMR Hydrocarbons 700–1000 74–85 Commercial
POX Hydrocarbons 800–1000 60–75 Commercial
ATR Hydrocarbons 700–1000 60–75 Near term
Fossil fuel based Pyrolysis Hydrocarbons 1000–1400 51 Near term
Plasma reforming Hydrocarbons 900–1300 9–85 Long term
Aqueous phase reforming Carbohydrates 220–270 35–55 Medium term
Ammonia reforming Ammonia 800–900 28.3 Near term
Biomass gasification Biomass 800–1000 35–50 Commercial
Photolysis Water + Sunlight Ambient 0.5 Long term
Dark fermentation Biomass Ambient 60–80 Long term
Photo fermentation Biomass + Sunlight Ambient 1.9 Long term
MEC Biomass + Electricity Ambient 78 Long term
Renewable based Alkaline electrolysis Water + Electricity 40–90 62–82a Commercial
PEM electrolysis Water + Electricity 20–100 67–82a Commercial
SOEC Water + Electricity + Heat 700–1000 <110a Medium term
Thermochemical
Water + Heat 500–1000+ 20–45 Long term
Water splitting
PEC/Photoelectrolysis Water + Sunlight Ambient 12.4 Long term
a
Voltage efficiency (%) based on HHV of hydrogen (may be greater than 100%).

2.1. Production from fossil fuel reforming
Fossil fuel hydrogen production technologies are commercially
available or developed and cheap due to low fossil fuel costs (Nikolaidis
and Poullikkas, 2017). The main fossil fuel technology is hydrocarbon
reforming, in which a hydrocarbon fuel, such as natural gas and coal,
is converted through various reforming technologies into hydrogen,
carbon monoxide (CO), CO2 , and other byproducts. Methane fuel pro-
cessing (from natural gas) is the most common commercial hydrogen
production method (Holladay et al., 2009). The biggest challenge to
hydrocarbon reforming processes comes from the catalyst poisoning
due to sulfur, which is contained in most hydrocarbon fuels (Holladay
et al., 2009).

3
R. Pinsky et al.
The main hydrocarbon reforming processes consist of SMR, partial
oxidation (POX), and autothermal reforming (ATR). In the reform-
ing process, hydrocarbons react with either steam in an endothermic
process (in SMR process), oxygen in an exothermic reactor (in POX pro-
cess), and both reactions combined for ATR (Nikolaidis and Poullikkas,
2017). The reactions all produce CO, so they all undergo a water-gas-
shift reaction to convert the CO into CO2 and H2 (see SMR section
for details). SMR has the advantages of extensive commercialization,
no pure oxygen required (only steam), lower process temperatures,
and high H2 to CO ratios relative to the other hydrocarbon reforming
methods (Holladay et al., 2009). However, SMR has the highest air
emissions. A further description of the SMR process is provided in the
following section. POX, also a commercially available technology, has
been proposed to produce hydrogen for automobile fuel cells and com-
mercial applications (Nikolaidis and Poullikkas, 2017). This process has
a slightly lower efficiency than SMR based on methane’s higher heating
value (see Table 3). Since POX consists of a reforming reaction that is
exothermic, coke and hot spot formation are prevalent which makes
thermal management difficult (Holladay et al., 2009; El-Shafie et al.,
2019). Additionally, POX is capital intensive since the process requires
pure oxygen (Nikolaidis and Poullikkas, 2017). However, POX is the
best hydrocarbon reforming process to produce hydrogen from heavy
feedstocks such as coal and heavy oil residues (Nikolaidis and Poul-
likkas, 2017). Autothermal reforming combines the benefits of both
SMR and POX: it uses heat from the exothermic POX reaction to assist in
the endothermic SMR reaction to increase the H2 /CO ratio (Nikolaidis
and Poullikkas, 2017). ATR is not at the commercial stage yet but
will have lower investments costs than SMR or POX, a lower operating
temperature than POX, and the potential for rapid stop and start times
when it is (Holladay et al., 2009; Nikolaidis and Poullikkas, 2017).
Other fossil fuel-based hydrogen technologies include pyrolysis,
plasma reforming, aqueous phase reforming, and ammonia reforming.
None of these technologies have reached commercial maturity. Pyroly-
sis is the process in which a hydrocarbon is decomposed into hydrogen
and carbon in the absence of water or oxygen. It can be done with
biomass/organic material and is used for producing carbon nanotubes
and spheres (Holladay et al., 2009). Pyrolysis has the advantage of
simplicity, as it does not require processing steps such as water gas shift
and CO2 removal, making it cheaper to produce hydrogen (Nikolaidis
and Poullikkas, 2017). However, any water or oxygen in the process
may be detrimental causing excess CO and CO2 emissions, and the
H2 separation process may be expensive due to the low proportion
of hydrogen in the mixture (Holladay et al., 2009; Nikolaidis and
Poullikkas, 2017).
Plasma reforming includes the same reactions as hydrocarbon re-
forming, but energy and radicals are provided by a plasma (Holladay
et al., 2009). Developed plasma reforming technology has the potential
to decrease costs, decrease deterioration of catalysts, decrease reactor
size and weight, increase response time, and increase the ability to
effectively reform heavy hydrocarbons (Holladay et al., 2009). Since
only free radicals are increased in temperature, overall reaction tem-
peratures may be lower. However, high electricity requirements and
electrode erosion prove challenging for this technology (Holladay et al.,
2009). Plasma reforming is subdivided into two categories: thermal
and non-thermal plasma. Thermal plasma involves raising temperature
of both free radicals and neutral species to elevated temperatures,
and therefore has high power requirements (El-Shafie et al., 2019).
Non-thermal plasma reforming involves increasing only the temper-
ature of electrons, keeping neutral gas temperature low. There are
a few non-thermal plasma techniques: gliding arc plasma, dielectric
barrier discharge, microwave plasma, and corona discharge, and these
techniques may see efficiencies anywhere between 9 and 85%.
In developed aqueous phase reforming, hydrogen is produced from
oxygenated hydrocarbons or carbohydrate at low temperatures (220–
270 ◦ C), and pressures of 25–30 MPa (Holladay et al., 2009). Because
this technique operates at low temperatures, a water gas shift reactor
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Progress in Nuclear Energy 123 (2020) 103317
can be combined with the reforming reactor for simplicity (Holladay
et al., 2009). Future research efforts are focused on improving catalyst
technology to prevent methanation and decreasing reactor size (due to
moderate space time yields) (Holladay et al., 2009).
Ammonia reforming utilizes ammonia instead of hydrocarbons (Hol-
laday et al., 2009). Ammonia is made from nitrogen and hydrogen
(NH3), and the reforming allows for the recovery of previously stored
hydrogen. It has been proposed as a method for portable fuel cell
applications due to the extensive pipelines of ammonia that already
exist (as ammonia is a common fertilizer) (Holladay et al., 2009).
Ammonia reforming has low cost and a low environmental impact (El-
Shafie et al., 2019). It may be directly coupled with a high temperature
fuel cell, or decomposed in a plasma reactor (El-Shafie et al., 2019).
2.1.1. Steam Methane Reforming (SMR)
SMR is the largest, most commercially developed hydrogen produc-
tion technology. For this reason, an in-depth process is described and
this method will be compared to potential nuclear hybrid technologies.
An overview of this process is shown in Fig. 3.
Natural gas or other methane containing hydrocarbons, such as
ethane, propane, butane, pentane, or light and heavy naptha are first
sent to either a steam system to combust, heating steam, or a sulfur
removing device (Nikolaidis and Poullikkas, 2017). The sulfur remov-
ing process is important because sulfur can poison catalysts in the
reformer and be detrimental to the reactions. Sulfur removal is typically
done either with chemical reactions or adsorptive technology. The main
commercial approach is the use of hydrodesulfurization (HDS) chemical
reactions (Holladay et al., 2009). In HDS, catalysts hydrogenate the
sulfur bearing molecules to release H2 S (Holladay et al., 2009). A
common adsorptive technique is using activated carbon to absorb the
sulfur (Holladay et al., 2009).
Steam from the steam system and clean methane (CH4 ) then go
to a reformer, where a catalyst activates the following endothermic
reaction:
CH4 + H2 O → CO + 3H2 (1)
Catalysts may be non-precious metals (such as nickel) or Group
VIII precious metals such as platinum or rhodium (Holladay et al.,
2009). Nickel catalysts are typically used in industry because they
do not limit the reaction and are cheaper (Holladay et al., 2009).
Other alkaline components may be added to the catalyst to suppress
coke formation (Holladay et al., 2009). Additionally, to suppress coke
formation the reaction takes place at high temperatures (700–1000 ◦ C),
pressures up to 3.5 MPa and steam to carbon ratios of 3.5 (Nikolaidis
and Poullikkas, 2017). Once reformed, the syngas made of CO and H2
are conditioned in a water-gas-shift reactor. Here, water and CO are
reacted with a catalyst to create more hydrogen and CO2 (Department
of Energy (DOE) Office of Energy Efficiency & Renewable Energy,
2019). This is shown in the following reaction:
CO + H2 O → CO2 + H2 (2)
The CO2 and other impurities are removed in a process called
pressure-swing adsorption to leave nearly pure hydrogen (Department
of Energy (DOE) Office of Energy Efficiency & Renewable Energy,
2019). Excess water is treated and cooled, and may be recycled back
into the steam system. Additionally, CO2 may be captured via a carbon
capture and storage system, where the CO2 may be stored in a geologic
reservoir or under water to reduce greenhouse gas emission to the at-
mosphere. Based on the HHV of methane, SMR has efficiencies between
74% and 85% (Nikolaidis and Poullikkas, 2017).
R. Pinsky et al.
Fig. 3. Steam Methane Reforming (SMR) process (McKellar, 2010).
2.2. Production from renewable resources
Although hydrogen production from renewable resources is cur-
rently low, it is expected to dominate over conventional technologies
in the long term (Nikolaidis and Poullikkas, 2017). The two main
methods of producing hydrogen come from biomass and water splitting.
Biomass is the second largest renewable resource, under hydropower,
in the United States and will likely become the main substitute to
petroleum (Holladay et al., 2009). Biomass consists of a wide array
of sources such as animal residue, plant residue, sawdust, aquatic
plants, waste paper, grasses, wood, and much more (Holladay et al.,
2009; Nikolaidis and Poullikkas, 2017). CO2 is released during biomass
hydrogen production, but only in the amount absorbed by organisms
while they were still living, which is considerably smaller in magnitude
than fossil fuels (Nikolaidis and Poullikkas, 2017).
Biomass hydrogen production processes can be further subdivided
into biological and thermochemical processes. Thermochemical pro-
cesses include biomass gasification and others, such as pyrolysis, com-
bustion, and liquefaction. Biological processes include photolysis, dark
and photo fermentation, and microbial electrolysis cells. Thermochem-
ical biomass production is predominantly gasification, a mature and
commercially available technology (Holladay et al., 2009). In gasifi-
cation, biomass is converted into a hydrogen-rich gas in the presence
of oxygen or air with the use of catalysts (Nikolaidis and Poullikkas,
2017). Gasification produces methane and CO, which can be further
converted into hydrogen with SMR and water gas shift reactors (Niko-
laidis and Poullikkas, 2017). Biomass gasification has relatively low
thermal efficiencies due to moisture that must be vaporized in the
biomass (Holladay et al., 2009). It also can suffer from increased
costs due to the necessity of cleaning large amounts of tar produced
in gasification as well as large amounts of resources spent gathering
biomass for commercial-scale production (Holladay et al., 2009).
Biological processes, on the other hand, are still early in the de-
velopmental stage. They use organic material (micro-organisms) that
consume water and produce hydrogen. Biological processes have the
main disadvantage of low production and yield rates (Nikolaidis and
Poullikkas, 2017). Researchers continue to discover and develop micro-
organisms to advance biological processes (Holladay et al., 2009).
Within biological hydrogen production, there is photolysis, dark fer-
mentation, photo fermentation, and microbial electrolysis cells. Photol-
ysis utilizes the fact that some micro-organisms, such as green algae and
cyanobacteria, produce hydrogen with excess solar energy (Holladay
et al., 2009). It only requires water and sunlight, which is inexpensive
and globally available (Holladay et al., 2009). However, a large sur-
face area is required to collect enough sunlight, and organisms cease
producing hydrogen in the presence of oxygen (a by-product of water
splitting) (Holladay et al., 2009). Efficiencies are also theoretically
limited to less than 1% (Holladay et al., 2009).
Dark fermentation uses anaerobic bacteria, in the dark, under oxy-
gen free conditions, to ferment carbohydrate rich substrates (Nikolaidis
and Poullikkas, 2017). Pure, simple sugars such as glucose is a pre-
ferred substrate, but is relatively expensive and unavailable in large
quantities (Nikolaidis and Poullikkas, 2017). An advantage of dark
fermentation is that space is not an issue, as no light is required
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Progress in Nuclear Energy 123 (2020) 103317
for a continuous stream of hydrogen to be produced (Nikolaidis and
Poullikkas, 2017). Alternatively, photo fermentation (also known as
photosynthetic bacterial hydrogen production), utilizes purple non-
sulfur bacteria on the nitrogenase functionality (Holladay et al., 2009).
Similar to photolysis, the bacteria produce hydrogen with sunlight,
though in this case through fermentation. The advantage of photo fer-
mentation over photolysis is that oxygen does not inhibit the reaction,
however, the fermentation process is slow and requires a relatively high
amount of energy (Holladay et al., 2009).
Microbial electrolysis cells (MEC) decompose biological material
directly through electrohydrogenesis. MEC is a modified microbial fuel
cell, where an external voltage is applied to the cell, in an anaerobic
state, for acetate substrate decomposition (Holladay et al., 2009). The
minimum theoretical applied voltage for this process is 0.11 V, but
practically is likely greater than 0.3 V due to ohmic resistance and
electrode overpotentials (Holladay et al., 2009). Complexity is high in
these cells due to excess methane produced that must be intermittently
removed (Holladay et al., 2009).
Finally, water splitting processes can be divided into three group:
water electrolysis, thermochemical water splitting, and photoelectro-
chemical water splitting (PEC), also known as photoelectrolysis. Water
splitting is the cleanest hydrogen production method as there are no
greenhouse gases emitted. These processes all utilize some method to
split water in the following reaction:
2H2 O → 2H2 + O2 (3)
Water electrolysis is the process where a potential difference is
placed between two electrodes, in an electrolyte, to break apart water
into its components. Electrolysis is the reverse process of the fuel cell,
in which hydrogen and oxygen are combined to produce electricity and
water. Electrolysis requires a source of water, which is inexpensive,
and electricity. Commercial products exist, which are made of alkaline
electrolyzers (Holladay et al., 2009). Alkaline electrolysis breaks liquid
water apart. Developed electrolysis methods include proton exchange
membrane (PEM) electrolysis, which also operates in the liquid water
region, and solid oxide electrolysis cells (SOEC), or high temperature
electrolysis, which operates with steam (700–1000 ◦ C) (Nikolaidis
and Poullikkas, 2017). High temperature electrolysis is less expensive
than other electrolysis methods. In SOEC, part of the electrical energy
requirement is replaced with thermal to achieve the required steam
temperature. High electrolysis costs, due to the electricity requirement,
currently prevent electrolysis from dominating hydrogen production
on a large scale (Nikolaidis and Poullikkas, 2017). High pressure elec-
trolyzers are currently being developed to reduce costs of compressing
hydrogen post-electrolysis (Holladay et al., 2009). Due to the poten-
tial of electrolysis methods in production of H2 , an in-depth process
diagram of each electrolysis method is studied in this effort.
Thermochemical water splitting involves using only heat to split
water. Based on the Gibbs free energy to split water in a single step
Eq. (3), the minimum temperature required to create hydrogen is over
1700 ◦ C for partial dissociation, and over 4000 ◦ C for total dissoci-
ation (Grimes et al., 2007). This temperature is extremely high for
most heat sources, so there has been heavy development in creating
multiple step cycles to reduce reaction temperatures. These cycles
R. Pinsky et al.
produce hydrogen and oxygen and recycle the chemicals through the
steps. Thus far, over 100 cycles in over 800 literature papers have been
identified, operating at a multitude of temperature ranges at various
stages of development (Rosen, 2010). The lower temperature cycles
may achieve minimum temperatures around 500 ◦ C while others have
a maximum temperature over 1000 ◦ C. Cycles of interest to nuclear
hybrid technology will be further discussed in the Nuclear Hybrid
Candidates section. These cycles are more developed and have been
hypothesized to work with reactors already, including the sulfur–iodine
and calcium–bromine cycles (Yildiz and Kazimi, 2006; McKellar, 2010).
Additionally, beyond a simple thermochemical cycle involving only
water and heat, hybrid processes where one step involves electrolysis
have also been developed. The main hybrid processes in focus are the
hybrid sulfur cycle and copper–chlorine cycle.
PEC or photoelectrolysis is another developed process which only
requires water and sunlight. In PEC, sunlight is absorbed in semicon-
ductor materials, and if the photon has an energy greater than the
bandgap, and electron–hole pair is created which splits water into its
components (Nikolaidis and Poullikkas, 2017). The minimum voltage
required is 1.23 V, based on the Gibbs free energy of liquid water. A
high bandgap energy is necessary to split the water which can decrease
overall efficiency (Nikolaidis and Poullikkas, 2017). Efficiency is also
decreased due to imperfections in semiconductor crystalline struc-
ture (Holladay et al., 2009). Additionally, high costs are involved given
limitations in semiconductor materials and efficiencies (Nikolaidis and
Poullikkas, 2017).
All hydrogen production technologies previously discussed are
shown in Table 3. Although any of these processes that require either
heat or electricity could be coupled to a nuclear reactor, the main
interest is generating clean, efficient energy when coupled to the
reactor. Therefore, the main interest is in water splitting, specifically
electrolysis and thermochemical water production.
3. Hydrogen for energy storage
Once hydrogen is produced, it may either be used for energy storage
and eventually converted back to heat or electricity, or as an energy
carrier, as shown in Fig. 2. For energy storage, fuel cells are the
solution. Fuel cells are clean sources of flexible power, either heat or
electricity, are silent, and have relatively high energy efficiencies (Rand
and Dell, 2007; Gielen and Simbolotti, 2005). Fuel cells include an
electrolyte to conduct ions, a positive and negative electrode, a plate
to connect cells, and current collectors. Stacks of fuel cells are used
to generate a desired amount of power, ranging from a few watts to
multi-MW, which allows them to be extremely versatile.
Fuel cells are essentially the opposite of electrolysis, as it takes
in oxygen and hydrogen and produces water and power. In fact, de-
velopment of fuel cells is beneficial to both technologies. As shown
in the Nuclear Hybrid Candidates section on water electrolysis, fuel
cells may simply run in reverse of electrolyzers. Alkaline electrolyte
(AFC), proton-exchange membrane (PEMFC) fuel cells, and solid oxide
fuel cells (SOFC), all share similar names, properties, and temperature
ranges as their electrolysis counterparts. Alternative fuel cells exist that
can take in non-hydrogen fuel, such as the direct methanol fuel cell
(DMFC) which takes methanol as input (Rand and Dell, 2007).
For energy storage, the AFC, PEMFC, and SOEC are ideal for
nuclear-hydrogen systems. This is because they use the same materials
as their electrolysis cells. Therefore, electrolysis can take place in the
same cell during times of low electricity, hydrogen and oxygen (or air)
stored for future use, and then be used as fuel cells to create electricity
to supply to the grid. AFC and PEMFC, both of which have been
commercially developed (though less developed for PEMFCs) report
low start-up times (less than 10 min), enabling a quick switch to energy
production (Rand and Dell, 2007). However, the SOFC still reports
long start up times (1-5 h), which is a potential problem for quick
switches (Rand and Dell, 2007). SOFCs are still in the developmental
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Progress in Nuclear Energy 123 (2020) 103317
stage, like the SOECs. An additional problem is poisoning via CO2 (due
to impure inputs), which can include a cost penalty. AFC and PEMFC
are susceptible to this CO2 poisoning (Gielen and Simbolotti, 2005).
SOFC has fewer problems with impurities, but faces a wide array of
materials challenges due to their high operating temperatures (700–
1000 ◦ C) (Rand and Dell, 2007). The overall efficiency of converting
energy from a nuclear plant to hydrogen and back to electricity through
a fuel cell could be as low as 12% due to energy conversion losses, elec-
trolyzer and fuel cell efficiencies, and losses in hydrogen compression
and electricity transmission/distribution (Rand and Dell, 2007).
Fuel cells may be supplied by pipelined hydrogen or directly from
hydrogen on site (Rand and Dell, 2007). The hydrogen generated in a
nuclear plant may have a fuel cell directly attached to produce elec-
tricity to the grid during times of high electricity costs. Alternatively,
the hydrogen produced at a nuclear plant may be pipelined and sent to
fuel cells in other areas to produce heat and/or electricity at a specific
location.
Storage of hydrogen is generally simpler for energy storage ap-
plications when compared to energy carrying (propulsion) applica-
tions (Rand and Dell, 2007). It also is cheaper to store bulk hydrogen
from large centralized plants (up to four times cheaper than distributed
plants, approximately 100 times smaller) (Rand and Dell, 2007).
To store hydrogen, it must be compressed, typically anywhere from
20 to 80 MPa. This may be done adiabatically, isothermally, or in a
multi-stage process (Rand and Dell, 2007). A multi-stage process will
likely require an energy input of around 10% of the HHV to compress
to 50 MPa, corresponding to potentially large ( 20%) electrical en-
ergy losses in the system (Rand and Dell, 2007; Bossel and Eliasson,
2003). Adiabatic compression requires more energy than multistage,
and isothermal requires less for all pressures (Bossel and Eliasson,
2003).
There may be diffusion problems with compression, as H2 is the
smallest molecule and therefore has relatively high diffusivity. Al-
ternative storage methods include liquefaction, which can have high
energy penalties (21% of HHV for large capacity plants (greater than
1000 kg H2 /hr), and up to 110%, greater than the HHV of hydrogen,
for advanced 1 kg/hr plants), storing hydrogen in a metal hydride
(which has several pending heat transfer engineering problems), or
chemical storage (which may be expensive or require high tempera-
tures) (Rand and Dell, 2007; Gielen and Simbolotti, 2005; Bossel and
Eliasson, 2003). However, economies of scale exist that can reduce
liquefaction capital costs by a factor of 4 by increasing production by a
factor of around 20 (Gielen and Simbolotti, 2005). Fig. 4 compares the
energy requirements for compression to 20 and 80 MPa adiabatically,
isothermally, and in a multi-stage process with liquefaction energy
penalties (Bossel and Eliasson, 2003).
4. Hydrogen as energy carrier
Hydrogen has been used as an energy carrier to propel spacecraft
since the 1960s. Work is being developed to use hydrogen for other
propulsion needs, such as transportation. Hydrogen cars offer a clean
alternative to vehicles powered by petrol or diesel but is not cur-
rently competitive due to lower performances (reduced efficiencies)
and higher prices (Rand and Dell, 2007).
Hydrogen as a fuel is low density (0.09 kg/m3 ) at standard temper-
ature and pressure. It also has a low boiling point of 20.3 K (and liquid
density of 70.8 kg/m3 ), requiring sophisticated technology to contain
in this state. Hydrogen also has the highest standard heat of formation
compared to other conventional fuels (higher heating value HHV) of
141.9 MJ/kg. However, due to the low density of hydrogen, higher
volumes are required to reach HHV densities compared to compressed
or liquified methane or petrol (Rand and Dell, 2007). For comparison,
methane has a density of 0.72 kg/m3 and a HHV of 55.5 MJ/kg (Bossel
and Eliasson, 2003).
R. Pinsky et al.
Fig. 4. Energy comparison (as a % of H2 HHV) for several hydrogen storage
methods (Bossel and Eliasson, 2003).
Hydrogen has several drawbacks as a fuel source. It can be excep-
tionally dangerous if leaked into an enclosed space, as it takes only
1/14th the energy needed to ignite compared to natural gas, and the
flame is nearly invisible (Rand and Dell, 2007). Special, expensive
cryostat units are needed for liquid fuel storage with vacuum and multi-
level insulation (Rand and Dell, 2007). The cost of this specialized
equipment is one reason hydrogen has not advanced as a widely
popular fuel beyond use in space exploration (Rand and Dell, 2007).
However, given the use of hydrogen in space exploration, it is clearly
possible to technologically manage handling and storage problems.
Fuel cells are not exclusively used for energy storage. They have
been used to convert energy on spacecraft since the 1960s (Rand
and Dell, 2007). There have been significant efforts to develop fuel
cells for propulsion, specifically focusing on automobiles (Gielen and
Simbolotti, 2005). Fuel cells have also been proposed for energy appli-
cations ranging from submarines and aircraft to consumer electronics
such as laptops. However, further development is necessary in the
renewables sector of hydrogen production, otherwise hydrogen used
as an energy carrier will be produced from fossil fuels mitigating the
purpose of using hydrogen as a clean energy source (Rand and Dell,
2007).
PEMFCs are the proposed fuel cell of choice for transportation
initiatives (Gielen and Simbolotti, 2005). Currently, PEMFC stack costs
exceed US $2000/kW, which must be lowered to around $50/kW (auto-
motive costs, not stationary generation costs) to be competitive (Gielen
and Simbolotti, 2005). It has been estimated that a current reduction to
$100/kW is feasible (Gielen and Simbolotti, 2005). Fuel cells also need
to improve durability and reliability before they are ready for commer-
cial transportation (Gielen and Simbolotti, 2005). The goal is mobile
operation of 3000–5000 h for cars and 20,000 h for buses (Gielen and
Simbolotti, 2005).
Storage of hydrogen for energy carrying applications are important,
because the storage units must be small and light enough to be on
the vehicle. Currently, only the compressed gas storage method is
practical for hydrogen fueled automobiles. Developments in composite
containers, as opposed to steel, have been made but still have problems
with high costs, energy penalties from compression, and safety issues
(rapid loss of hydrogen) (Rand and Dell, 2007). The U.S., as of 2015,
targeted 10.8 MJ/kg as a benchmark for vehicle storage as of 2015, a
difficult target to meet (Rand and Dell, 2007).
Pipelining hydrogen also has challenges. While the hydrogen can
go through natural gas pipelines, there may be significant material
degradation due to the use of high-carbon steel that hydrogen reacts
with. Instead, new pipeline would likely need to be laid, consisting of
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Progress in Nuclear Energy 123 (2020) 103317
low-carbon steel. This is an expensive task (Rand and Dell, 2007). Hy-
drogen pipelines do currently exist, with several thousand km currently
installed (Gielen and Simbolotti, 2005). Hydrogen fueling stations also
currently exist, with 115 in the US as of 2005 (Rand and Dell, 2007).
However, if hydrogen became widely used as a fuel for cars, new
infrastructure would need to be in place, which could be 40%–50%
more expensive than natural gas infrastructure (Rand and Dell, 2007).
Additionally, hydrogen pipelines require significantly more energy
per unit volume than natural gas pipelines, mainly for continual com-
pression of the fuel. Around 1.4% of hydrogen flow in a pipe is lost
per 150 km to energize compressors, compared to 0.3% of methane
(natural gas) for the same energy flow (Bossel and Eliasson, 2003).
This is an energy increase from natural gas pipelines by a factor of
4.7. The volumetric energy density of hydrogen is low, so for the same
energy flow, 3.1 times the volumetric flow, and therefore more energy,
is required compared to natural gas (Bossel and Eliasson, 2003). This
is calculated from the volumetric HHV of hydrogen and methane, 12.7
MJ/m3 and 40.0 MJ/m3 , respectively.
5. NHES hydrogen candidates
Reactor temperatures range from 300–950 ◦ C for Generation III and
IV reactors. These reactors may utilize excess heat and electricity dur-
ing off peak times for the production of hydrogen. The main interests
in producing hydrogen fall under water electrolysis, thermochemical
water splitting, and a hybrid of the two systems. The next sections
will include background, processes, and assumptions used for modeling
these candidates at various temperatures and power levels.
5.1. Water electrolysis
Water electrolysis, as mentioned previously, involves the decom-
position of water into H2 and O2 Eq. (3). The reaction has specific
energy requirements based on the temperature and pressure of the
water. The Gibbs free energy change of water formation, 𝛥𝐺, enthalpy
change of water formation 𝛥𝐻, and entropy change 𝛥𝑆 (multiplied by
temperature T) determine the minimum theoretical required voltage
to decompose water as a function of temperature and pressure (Santos
et al., 2013):
𝛥𝐺 = 𝛥𝐻 − 𝑇 𝛥𝑆 (4)
Note that the reactions taking place at the anode and cathode are
dependent on the electrolysis type (materials based), but the overall
reaction leads to the same overall voltage requirement. Also note
that, for simplicity of the electrolysis model, pressures are assumed
to be 1 atm. It is known that efficiencies decrease slightly (due to
increased voltage requirements) for higher pressure systems but can
lead to power savings because the hydrogen is produced at a higher
pressure (Marangio et al., 2009). However, this analysis does not take
into account energy required to compress and store hydrogen, only to
produce it through various methods.
The Gibbs free energy determines the equilibrium cell voltage
𝐸𝐸𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 , or the absolute minimum voltage required for electrolysis
to occur, as shown in Eq. (5) (Zeng and Zhang, 2010):
𝛥𝐺 = 𝑛𝐹 𝐸𝐸𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 (5)
For water, n, the number of moles of electrons transferred in the
reaction is 2 and F is the Faraday constant, at 96485 C/mol. At 25 ◦ C,
1 atm (standard temperature and pressure), 𝛥𝐺 = 237.1 kJ/mol and
𝐸𝐸𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 = 1.23 V. The equilibrium voltage describes the minimum
electrical energy demand for electrolysis. Fig. 5 shows how temperature
effects Gibbs free energy, enthalpy, and entropy (O’Brien et al., 2010).
Note that there is a drop in energy demand once water becomes
a vapor. Also note that, at the equilibrium voltage, the reaction is
endothermic and will not proceed without an additional heat source.
R. Pinsky et al.
Fig. 5. Energy demand for water electrolysis at various temperatures and 1
atm (O’Brien et al., 2010).
Another important voltage to note is the thermoneutral voltage,
𝐸𝑇 ℎ𝑒𝑟𝑚𝑜𝑛𝑒𝑢𝑡𝑟𝑎𝑙 . The thermoneutral voltage is the voltage required for no
heat to be added (it is the transition point between endothermic and
exothermic reactions). It remains relatively constant with temperature,
as it depends mostly on the heat of formation of water (285.8 kJ/mol
for liquid and 241.8 kJ/mol for gas at atmospheric pressure). It is
related to the enthalpy change in Eq. (6) (Zeng and Zhang, 2010):
𝛥𝐻 = 𝑛𝐹 𝐸𝑇 ℎ𝑒𝑟𝑚𝑜𝑛𝑒𝑢𝑡𝑟𝑎𝑙 (6)
The thermoneutral and equilibrium voltages are good for describing
theoretical minimum energy requirements, but they are lower than
the expected required voltage, 𝐸𝑐𝑒𝑙𝑙 . Real electrolysis cells have prob-
lems such as activation overvoltage or overpotentials on the cells and
resistances throughout that must be accounted for. These loss terms
may increase energy consumption by around 1.5–2.2 times more than
theoretical (Rashid et al., 2015). The cell voltage required is described
in Eq. (7) (Zeng and Zhang, 2010).
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐸𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 + 𝜂𝐴 + 𝜂𝐾 + 𝑖𝑅𝑐𝑒𝑙𝑙 (7)
where 𝜂𝐴 is the anode overvoltage, 𝜂𝐾 is the cathode overvoltage, and
𝑖 is the current density. 𝑅𝑐𝑒𝑙𝑙 is the sum of all area specific resistances
in the cell: electric, anode, cathode, bubbles (resistance due to partial
coverage of electrodes by bubbles), and membranes (Santos et al.,
2013). It is estimated to be somewhere between 0.01–2 Ω cm2 for
simplicity, but the resistance is dependent on materials (electrolysis
type) and temperature (Phillips et al., 2017; Siracusano et al., 2018;
Hauch, 2008). The term 𝑖𝑅𝑐𝑒𝑙𝑙 (V) consists of the ohmic losses in the
cell. Resistance can be minimized by minimizing the interelectrode
gap and optimizing the current density based on electrode surface
morphology and electrolyte concentrations (Phillips et al., 2017). There
may also be a diffusion overvoltage that exists in the case of mass
transport limitations (Marangio et al., 2009). This typically occurs at
high current densities. However, in this model, it is assumed that there
is a continuous supply of water, and the current density stays low
enough that mass transport limitations are not reached.
To find anode and cathode activation overpotentials, which are
functions of the current density i, the Butler–Volmer equation applies,
and is shown in Eq. (8) (Marangio et al., 2009):
𝛼1 𝐹 𝛼 𝐹
𝑖 = 𝑖0 [𝑒𝑥𝑝( 𝜂 ) − 𝑒𝑥𝑝(− 2 𝜂𝑎𝑐𝑡 )] (8)
𝑅𝑇 𝑎𝑐𝑡 𝑅𝑇
where 𝑖0 is the exchange current density (which depends on electrode
material), 𝛼1,2 are transfer coefficients, and 𝜂𝑎𝑐𝑡 is the activation over-
voltage (of either the cathode or anode). If the transfer coefficients
are assumed to be equal, then the following expressions are used to
find the anode (A) and cathode (K) overpotentials, where 𝛼𝐴 = 2 and
𝛼𝐾 = 0.5 (Marangio et al., 2009):
𝑅𝑇 𝑖 𝐻𝐻𝑉 ∗ H2,𝑃 𝑟𝑜𝑑𝑅𝑎𝑡𝑒
𝜂𝐴 = 𝑎𝑟𝑐𝑠𝑖𝑛ℎ( ) (9)
𝛼𝐴 𝐹 2𝑖0,𝐴
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Progress in Nuclear Energy 123 (2020) 103317
𝑅𝑇 𝑖
𝜂𝐾 = 𝑎𝑟𝑐𝑠𝑖𝑛ℎ( ) (10)
𝛼𝐾 𝐹 2𝑖0,𝐾
Note that different authors cite exchange current densities orders of
magnitude different for the same electrode material and temperature,
as seen in Carmo et al. (2013). Therefore, the chosen 𝑖0 for the different
water electrolysis models is only one estimate and is assumed to be
constant with temperature.
Hydrogen and oxygen production rates can also be calculated based
on the total cell current I. The total current may be calculated based on
the total cell area and current density. The production rates are given
in Eqs. (11) and (12) (Marangio et al., 2009). The oxygen production
rate in mol/s is half as much as hydrogen (see Eq. (3)) but is 8 times
larger when converted to kg/s, given that the oxygen molecule is 16
times larger than hydrogen (approximately 32 g/mol compared to 2
g/mol).
mol 𝐼
H2,𝑃 𝑟𝑜𝑑𝑅𝑎𝑡𝑒 [ ]= (11)
s 2𝐹
mol 𝐼 H2,𝑃 𝑟𝑜𝑑𝑅𝑎𝑡𝑒
O2,𝑃 𝑟𝑜𝑑𝑅𝑎𝑡𝑒 [ ]= = (12)
s 4𝐹 2
The total energy consumed per normal volume (at standard temper-
ature and pressure) of hydrogen can also be calculated in the following
equation (Guenot et al., 2015):
kWh 𝑛𝐹
𝑊𝑒 [ ]= 𝐸 = 2.393 ∗ 𝐸𝑐𝑒𝑙𝑙 (13)
Nm3 𝑡𝑉𝑚 𝑐𝑒𝑙𝑙
where 𝑉𝑚 is the molar volume of an ideal gas at 1 atm and 25 ◦ C, equal
to 0.0224 Nm3 (N stands for normal volume of ideal gas), and 𝑡 is the
number of seconds in an hour for conversion (equal to 3600), 𝐹 is the
Faraday constant, and 𝑛 is 2 for the electrolysis process.
One important property of electrolysis, like with fuel cells, is the
ability to stack and scale beyond one cell. A total number of cells can
be estimated to give a total power and heat requirement and total
hydrogen and oxygen production rates. Additionally, it should be noted
that there is a heat requirement, estimated with 𝑇 𝛥𝑆, as well as an
electricity requirement from the cell voltage. For alkaline and PEM
electrolysis, the heat requirement already exists in the water, since
these processes occur with liquid water, so only electrical energy must
be provided. For SOEC, however, water must be converted to steam
and elevated to 700–1000 ◦ C, so the heat requirement may not be
neglected. Since nuclear reactors provide heat and electricity, this is
not an issue for coupling SOEC.
The last important set of equations to model electrolysis are process
efficiencies (Zeng and Zhang, 2010). There are a few efficiencies com-
monly used. The faradic efficiency is the same as the voltage efficiency,
and describes the ratio of voltage needed to split water based on Gibbs
free energy to voltage needed for electrolysis:
𝐸𝐸𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
𝐹 𝑎𝑟𝑎𝑑𝑖𝑐 𝐸𝑓 𝑓 𝑖𝑐𝑖𝑒𝑛𝑐𝑦 % = ∗ 100 (14)
𝐸𝐶𝑒𝑙𝑙
Thermal efficiency is another measure of how well the electrolysis
system works, and it measures the ratio of thermoneutral voltage,
which is based on the enthalpy change of water decomposition, to the
cell voltage.
𝐸𝑇 ℎ𝑒𝑟𝑚𝑜𝑛𝑒𝑢𝑡𝑟𝑎𝑙
𝑇 ℎ𝑒𝑟𝑚𝑎𝑙 𝐸𝑓 𝑓 𝑖𝑐𝑖𝑒𝑛𝑐𝑦 % = ∗ 100 (15)
𝐸𝐶𝑒𝑙𝑙
Finally, the efficiency can also be measured in terms of the higher
heating value (HHV) of hydrogen. It is the ratio of power output (taken
as the amount of power gotten from the amount of hydrogen produced
and the HHV value) to power input for electrolysis (Kabza, 2010). This
is typically the quotable efficiency as it measures how efficient the
system is at producing hydrogen. In these models the assumed conver-
sion efficiency from heat to electricity is 40%. (McKellar, 2010). The
hydrogen production efficiency, as shown in Eq. (16), is typically lower
than the thermal or faradic efficiency due to electricity conversion
efficiencies.
H2,𝑃 𝑟𝑜𝑑. 𝐸𝑓 𝑓 𝑖𝑐𝑖𝑒𝑛𝑐𝑦 % = ∗ 100
𝐼𝑉
R. Pinsky et al.
285.83 ∗ 1000 [J∕mol] ∗ H2,𝑃 𝑟𝑜𝑑𝑅𝑎𝑡𝑒 [mol∕s]
= ∗ 100
𝐸𝑙𝑒𝑐𝑡𝑟𝑖𝑐𝑖𝑡𝑦 [W]∕0.4 + 𝐻𝑒𝑎𝑡 [W]
(16)
The equations as described above provide the foundation for model-
ing alkaline, PEM, and SOEC electrolysis. Each electrolysis process has
specific processes, temperatures, and materials that change the inputs
of ion exchange current density, running current density, and resistance
into the model. It is assumed that the electrode area for all cells is
225 cm2 based on the model from Bragg-Sitton et al. (2014). The total
power input is based on reactor size, and the total number of cells
necessary to utilize this output is not necessary for comparison to other
water splitting processes.
5.1.1. Alkaline electrolysis
Alkaline electrolysis, as stated previously, is the most commercially
developed electrolysis method. It operates in the temperature range
of around 40–90 ◦ C but has been quoted to operate as low as 20
◦ C (Rashid et al., 2015; Sapountzi et al., 2017). In alkaline electrolysis,
water is split at the cathode and OH−travels to the anode (Holladay
et al., 2009), as shown in Eqs. (17) and (18).
Anode:
4OH− → O2 + 2H2 O + 4𝑒− (17)
Cathode:
2H2 O + 2𝑒− → H2 + 2OH− (18)
Hydrogen is produced at the cathode and oxygen at the anode. The
product gases are separated by a diaphragm, which is permeable to
the OH−carrier as well as water (Carmo et al., 2013). The electrodes
are both submerged in a liquid electrolyte. The electrolyte is a liquid
and can either be potassium hydroxide KOH or sodium hydroxide
NaOH, where KOH is the most common (Zeng and Zhang, 2010). While
there are many electrode materials that work (such as cobalt or iron),
nickel is the most popular due to its high activity and availability
combined with low cost (Zeng and Zhang, 2010). The exchange current
density 𝑖0 of nickel has been reported to be around 1.1*10−4 A/cm2
at the cathode (in a 50% KOH electrolyte at 80 ◦ C) and 4.2*10−6
A/cm2 at the anode (Miles et al., 1976). These were the values used
to calculate anode and cathode overpotentials. Pressure operation can
range from atmospheric to 12 MPa for advanced electrolyzers (Gielen
and Simbolotti, 2005).
The operational current density has been reported anywhere from
0.1 to 0.4 A/cm2 (Holladay et al., 2009; Phillips et al., 2017; Carmo
et al., 2013). For modeling purposes, the current density was chosen
to be 0.3 A/cm2 , as this was within the range quoted in the majority
of the literature. The resistance 𝑅𝑐𝑒𝑙𝑙 is difficult to calculate because it
depends on the particular cell itself, but for the purpose of the model is
estimated to be 0.2 Ω-cm (Santos et al., 2013). Not much more water
than that used to produce hydrogen is needed as cooling is limited,
given the low operational temperatures. The total water consumption
has been estimated to be around 11.5 times the amount of hydrogen
produced (Genovese et al., 2009).
A schematic of the alkaline electrolysis is shown in Fig. 6, including
common materials.
Some advantages of alkaline electrolysis include stable, pure hydro-
gen production (though slightly less pure than PEM) with non-noble
catalysts, and mature technology (Carmo et al., 2013; Sapountzi et al.,
2017). Suppliers of this electrolysis technology include De Nora SAP,
Nel, Hydrogenics, Teledyne Energy Systems and General Electric (Sa-
pountzi et al., 2017). It is also highly scalable, because the cells
are stackable. However, some disadvantages are corrosion from the
electrolyte, gas permeation through the diaphragm, and slow dynam-
ics (Sapountzi et al., 2017). It can also suffer from limited current
densities and low pressure operation (in large scale units), forcing large
volume designs (Rashid et al., 2015; Carmo et al., 2013).
9
Progress in Nuclear Energy 123 (2020) 103317
Fig. 6. Schematic of Alkaline electrolysis.
5.1.2. Proton Exchange Membrane (PEM) electrolysis
Proton exchange membrane (PEM) electrolysis, also known as
polymer-electrolyte membrane electrolysis, uses a polymer electrolyte
as opposed to a liquid as seen in alkaline electrolysis. It operates at
similar temperatures, 20–100 ◦ C, and converts liquid water (Rashid
et al., 2015). Recent developments have been investigated to oper-
ate at temperatures around 200 ◦ C for fuel cell applications, which
translate to electrolysis applications (Sapountzi et al., 2017). PEM uses
perfluorosulfonic acidic polymer solid electrolytes which also act as the
membrane (Rashid et al., 2015). PEM electrolysis may be operated at
high pressures, up to 40 MPa, which will lower the energy requirements
for compressing hydrogen for storage (Gielen and Simbolotti, 2005).
These membranes allow for the proton, the charge carrier, to pass
through while preventing other gases from moving. The reactions that
occur in PEM are shown in Eqs. (19) and (20) (Holladay et al., 2009):
Anode:
2H2 O → O2 + 4H+ + 4𝑒− (19)
Cathode:
2H + 2𝑒− → H2
+
(20)
Electrodes are typical noble catalysts, typically platinum Pt for
the cathode and iridium Ir for the anode, which both have rela-
tively high activity (Rashid et al., 2015). Other electrode materials
include rhodium, rubidium, palladium, gold, and oxides of these cata-
lysts (Rashid et al., 2015). The exchange current density at the cathode
is estimated to be 1*10−3 A/cm2 and 1*10−7 A/cm2 at the anode (Choi
et al., 2004). A schematic of the overall PEM process is shown in Fig. 7.
PEM electrolyzers have low ionic resistances which allow them
to operate at high current densities, anywhere between 0.6 and 3
A/cm2 (Holladay et al., 2009; Siracusano et al., 2018; Carmo et al.,
2013). For modeling purposes, the current density was set at 2 A/cm2 .
High current density operation with relatively low ohmic resistances
lead to high efficiencies and compact production rates. Literature val-
ues of ohmic resistance were found as a function of temperature and
estimated to be 0.2 Ω-cm at 30 ◦ C, 0.1 Ω-cm at 60 ◦ C, and 0.08 Ω-
cm at 90 ◦ C (Siracusano et al., 2018). Like alkaline water electrolysis,
the total water consumption was estimated around 11.5 times the
amount of hydrogen produced, as little cooling is necessary during the
process (Genovese et al., 2009).
There are several advantages of PEM electrolysis. The solid elec-
trolyte allows for compact design and, combined with the high reactiv-
ity of the electrodes, leads to fast response times (<10 min) (Boardman,
2017; Sapountzi et al., 2017). Highly pure hydrogen is also produced in
R. Pinsky et al.
Fig. 7. Proton Exchange Membrane (PEM) electrolysis process.
the process (Sapountzi et al., 2017). PEM cells are also highly scalable.
On the downside, acidic electrodes cause degradation, limiting opera-
tion lifetime, and the polymer membranes have high costs (Sapountzi
et al., 2017). These are the main limitations to current widespread com-
mercialization. However, up to MW-scale PEMs exist, by the company
Proton OnSite (OnSite, 2019). Although PEM’s have been commercial-
ized to the MW-scale, GW-scale PEMs are still in the research and
development stage with a technology readiness level (TRL) of 4.
5.1.3. Solid Oxide Electrolysis Cells (SOEC)
SOEC operates close to the output temperatures of nuclear reactors,
which gives this technology a unique advantage over its ambient
temperature counterparts. It operates using steam and is sometimes
called high temperature electrolysis (HTE), as opposed to liquid water,
at temperatures between 700 and 1000 ◦ C (Rashid et al., 2015). A solid
electrolyte is also used, making SOEC compact and have quick response
times like PEM electrolysis, though in this case the electrolyte is a
ceramic. It is unique in that the high temperature requirements force a
heat input as well as an electricity input. SOEC is the least developed
electrolysis method, still in the bench scale. SOEC can be operated at
pressures up to around 3 MPa (Gielen and Simbolotti, 2005).
An oxygen ion is the energy carrier for the steam electrolysis
reaction. The reactions that take place on the anode and cathode are
shown in Eqs. (21) and (22) (El-Shafie et al., 2019):
Anode:
2O− → O2 + 4𝑒−
2
Cathode:
H2 O + 2𝑒− → H2 + O−
2 electrolysis processes, they can face problems such as slow response
The most common electrode materials are nickel-zirconia (Ni-YSZ)
cermet at the cathode and strontium-doped lanthanum manganite
(LSM), potentially with YSZ at the anode (O’Brien et al., 2010; Hauch,
2008). The exchange current densities for SOEC are much higher than
previously seen electrodes at 2*10− 1 A/cm2 for the Ni-YSZ cathode and
5.3*10− 1 A/cm2 at the LSM/YSZ anode (Chan and Xia, 2002). Resis-
tance ranges in literature from 0.25 to 0.4 Ω-cm (O’Brien et al., 2010;
Bragg-Sitton et al., 2014), but a value of 0.4 Ω-cm was taken to mimic
a study done by Idaho National Laboratory (INL), in reference (Bragg-
Sitton et al., 2014). The current density is typically somewhere between
alkaline and PEM (0.3–1 A/cm2 (Gielen and Simbolotti, 2005)), and
around 0.7 A/cm2 for the INL reference study (Bragg-Sitton et al.,
2014). A large amount of water is required for SOECs, estimated at 83.3
times the hydrogen production, because of cooling (McKellar, 2010).
The process diagram for SOEC is shown in Fig. 8.
Progress in Nuclear Energy 123 (2020) 103317
Fig. 8. Solid Oxide Electrolysis Cell (SOEC) or High Temperature Electrolysis (HTE)
process.
SOEC is a promising technology with high application flexibility,
high scalability, pure hydrogen (though less pure than other electrolysis
methods due to residual steam) production, and enhanced reaction
kinetics and thermodynamics at higher temperatures (reducing the
equilibrium cell voltage) with low capital costs (Boardman, 2017;
Sapountzi et al., 2017). Some disadvantages come in the form of
degradation of electrodes and ceramic electrolyte at high temperature
operation. This means low durability and lack of stability which must
be improved before SOEC can become commercially available (Rashid
et al., 2015; Sapountzi et al., 2017). Hydrogen is also the least pure
in this method (relative to electrolysis methods, due to residual steam
in the system given the oxygen charge carrier). There is a developing
technology which uses a solid ceramic membrane with steam (500–
1000 ◦ C), with an H+ charge carrier like PEM, that can produce high
purity hydrogen (Sapountzi et al., 2017). This technology is still in
early development and will not be considered for further analysis,
but is a potential solution to produce pure hydrogen at lower steam
temperatures.
5.2. Thermochemical water splitting
Thermochemical water splitting, as previously described, is one or
more endothermic chemical reactions that require heat to split water.
The two contenders considered for this study are the sulfur–iodine
(S–I) and calcium-bromide (Ca–Br) cycles. Thermochemical cycles are
(21) less developed than electrolysis processes. In these cycles, chemicals
are recycled throughout the system, so inputs and outputs consist
of water and water products, respectively. Though thermochemical
cycles primarily utilize heat, rendering them more cost effective than
(22)
rates, large size, and involve hazardous chemicals that may produce
less pure hydrogen (Boardman, 2017).
5.2.1. Sulfur–iodine cycle (S–I)
The sulfur–iodine (S–I) cycle is the most developed thermochemical
cycle, with a high interest pertaining to hybrid nuclear facilities. It was
proposed by General Atomics in the mid-1970’s (Yildiz and Kazimi,
2006). Two proof of concept facilities and laboratory-scale experiments
have been performed for this cycle (Ping et al., 2018). The S–I cycle
has been down-selected in the United States as well as other countries,
such as Japan, as the most promising thermochemical cycle (El-Emam
and Özcan, 2019; Varrin et al., 2011). The chemical reactions that take
place in each step are shown in the following Ping et al. (2018) and
Varrin et al. (2011):
H2 SO4 𝐷𝑒𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 ∶ 2H2 SO4 → 2SO2 + O2 + 2H2 O (> 800 ◦ C) (23)
10
R. Pinsky et al.
Fig. 9. Sulfur–Iodine (S–I) thermochemical process (Varrin et al., 2011).
Fig. 10. Calcium–Bromine (Ca–Br) also known as the UT-3 thermochemical water
splitting diagram.
Source: Adapted from Sakurai et al. (1996).
𝐵𝑢𝑛𝑠𝑒𝑛 ∶ I2 + SO2 + 2H2 O → H2 SO4 + 2HI (120 ◦ C)
HI 𝐷𝑒𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 ∶ 2HI → H2 + I2 (> 300 C) ◦
In the S–I cycle, the H2 SO4 acts as the oxygen carrier while the HI
carries hydrogen (Varrin et al., 2011). Mass balances and optimization
studies have been conducted for all reactions to maximize reaction
rates and minimize undesired products from alternative reactions oc-
curring (Ping et al., 2018). The S–I process can be seen in Fig. 9. Note
that the decomposition reactions are both endothermic, but the Bunsen
reaction is exothermic. The limiting reaction is the H2 SO4 reaction, due
to the high temperature requirements. This decomposition reaction is
why the S–I process may only be coupled to high temperature nuclear
reactors if no external heat is desired.
5.2.2. Calcium–bromine cycle (Ca–Br) or UT-3 cycle
The calcium–bromine (Ca–Br) cycle was discovered at the Univer-
sity of Tokyo in Japan, which is why it is also referred to as the
UT-3 cycle (Yildiz and Kazimi, 2006). While considered a promising
candidate for nuclear hybrid processes, it is less technologically mature
than its competitor, the S–I cycle, and therefore has not been further se-
lected in down-selection processes (Varrin et al., 2011). The minimum
temperature required for this process is around 760 ◦ C (Sakurai et al.,
1996), which potentially could be met with a high temperature reactor,
and also a potential for medium temperature reactors with external
heating. The UT-3 process can be divided into four chemical reactors
as shown in Fig. 10. A unique advantage of the UT-3 cycle is that it
only involves solids and gases, which are easier to separate than the all
liquid reagents of the S–I cycle (Yildiz and Kazimi, 2006).
The chemical reactions and temperatures required that take place
in each reactor are shown in the following Sakurai et al. (1996) and
Teo et al. (2005):
Ca 𝑅𝑒𝑎𝑐𝑡𝑜𝑟 1 ∶ CaBr 2 + H2 O → CaO + 2HBr (760 ◦ C)
◦
Fe 𝑅𝑒𝑎𝑐𝑡𝑜𝑟 1 ∶ 3FeBr 2 + 4H2 O → Fe3 O4 + H2 + 6HBr (560 C)
◦ HCl 𝑃 𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛 ∶ 2CuCl2 + H2 O → CuO ∗ CuCl2 + 2HCl (400 ◦ C)
Fe 𝑅𝑒𝑎𝑐𝑡𝑜𝑟 2 ∶ Fe3 O4 + 8HBr → 3FeBr 2 + Br 2 + 4H2 O (220 C)
Ca 𝑅𝑒𝑎𝑐𝑡𝑜𝑟 2 ∶ 2CaO + 2Br 2 → 2CaBr 2 + O2 (572 ◦ C)
Progress in Nuclear Energy 123 (2020) 103317
Fig. 11. Hybrid Sulfur (HyS) hydrogen production schematic (Varrin et al., 2011).
5.3. Hybrid water splitting
Hybrid water splitting involves a thermochemical cycle in conjunc-
tion with electrolysis. The main contenders in the hybrid splitting
process are the hybrid sulfur cycle developed by Westinghouse and
the copper–chlorine cycle. Hybrid cycles have similar disadvantages
and advantages as thermochemical cycles alone, mainly: slow response
rates, large reactor sizes, utilize hazardous chemicals, and are less
developed than purely electrolysis, but are more cost effective than
electrolysis alone (Boardman, 2017).
5.3.1. Hybrid sulfur cycle (HyS) or westinghouse cycle
The hybrid sulfur cycle (HyS) has been the most promising hybrid
cycle, having been down-selected as a candidate for future NHES use in
the United States (Varrin et al., 2011). It was proposed by Westinghouse
in 1975 as a hybrid version of the S–I cycle, and shares the H2 SO4
(24) decomposition step (El-Emam and Özcan, 2019; Yildiz and Kazimi,
(25) 2006). In addition, there is an electrolysis step which uses a polymer
based membrane to produce hydrogen (Varrin et al., 2011). The process
is shown in Fig. 11.
The chemical reactions that take place for H2 SO4 decomposition and
SO2 electrolysis are shown in the following Varrin et al. (2011) and
Le Duigou et al. (2007):
H2 SO4 𝐷𝑒𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 ∶ 2H2 SO4 → 2SO2 + O2 + 2H2 O (> 800 ◦ C) (30)
𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑠𝑖𝑠 ∶ SO2 + 2H2 O → H2 SO4 + H2 (< 100 ◦ C) (31)
One potential advantage of the HyS cycle exists with the location of
hydrogen production. The processes that require heat must be placed
relatively close to the nuclear plant to minimize losses, which includes
the decomposition step of this process. However, the electrolysis step,
which actually produces the hydrogen, may be placed a safer distance
away from the plant as it only requires electricity (Yildiz and Kazimi,
2006).
5.3.2. Copper–chlorine (Cu–Cl) cycle
The copper–chlorine cycle, like the Ca–Br cycle, has shown promise
but is not as technologically mature as other processes (Varrin et al.,
2011). However, it has a lower minimum temperature requirement,
around 500 ◦ C (Naterer et al., 2009), than the other thermochemi-
cal processes which would allow it to couple with medium or high
temperature as opposed to only high temperature reactors.
There are three Cu–Cl cycles proposed: a 3-step, 4-step, and 5-step
cycle. The 4-step cycle was chosen for this study because it combines
two steps of the 5-step cycle to reduce heat requirements and complex-
ity, and has lower heat requirements than the 3-step process (Ozbilen
et al., 2011). The chemical reactions that take place in the 4-step cycle
(26) are shown in the following reactions (Naterer et al., 2009), and a
diagram of this process is shown in Fig. 12.
(27)
(32)
(28)
𝐷𝑒𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛∕O2 𝑃 𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛 ∶ 2(CuO ∗ CuCl2 ) → 4CuCl + O2 (500 ◦ C)
(29)
(33)
11
R. Pinsky et al. Progress in Nuclear Energy 123 (2020) 103317

Fig. 12. Copper–Chlorine (Cu–Cl) hybrid cycle diagram.

Source: Adapted from Naterer et al. (2009).

Fig. 13. Process flow diagram for (a) Alkaline water electrolysis (Holladay et al., 2009;
Rashid et al., 2015; Santos et al., 2013; Phillips et al., 2017; Carmo et al., 2013;
𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑠𝑖𝑠 ∶ 2CuCl + 2HCl → H2 + 2CuCl2 (> 430 ◦ C) (34) Miles et al., 1976; Genovese et al., 2009), and (b) PEM water electrolysis (Holladay
◦ et al., 2009; Rashid et al., 2015; Marangio et al., 2009; Siracusano et al., 2018; Carmo
𝐷𝑟𝑦𝑒𝑟 ∶ CuCl2 (𝑎𝑞) → CuCl2 (𝑠) (< 100 C) (35) et al., 2013; Genovese et al., 2009; Choi et al., 2004) given a nominal low temperature
reactor.
The oxygen production step requires the highest temperatures. The
electrolysis process shown only requires low (ambient) temperatures,
but is combined with another (chemical) step that increases the mini-
mum temperature to around 430 ◦ C.
The Cu–Cl electrolysis step has been experimentally demonstrated
for long durations by Canadian Nuclear Laboratories, Pennsylvania
State University, and the University of Ontario Institute of Technol-
ogy (Naterer et al., 2017). The electrolyzer can be PEM but more
research is needed to develop a membrane that limits Cu crossover
to the cathode (hydrogen producing side) (Naterer et al., 2017). One
challenge with the Cu–Cl process is related to materials due to lim-
ited knowledge of corrosion resistance in materials by molten Cu–Cl
(Naterer et al., 2017).

6. Results and discussion

NHES hydrogen candidates were compared based on their energy

input and hydrogen production rates for low, medium, and high tem-
perature reactors. They were also compared relative to their technology
readiness level (TRL) and cost per kg of H2 production.

6.1. Process flow diagrams

Process flow energy and material input and output diagrams were
created for the three reactor categories. These models assume the entire
reactor thermal output (as shown in Table 2) is converted to a either
electricity, heat, or both. The power cycle conversion rate is assumed to
be 40%. As the reactor temperature category increases, there are more
possible hydrogen production methods.

6.1.1. Low temperature reactors
Low temperature reactors cover the category of LWRs, which may
output water at temperatures around 300 ◦ C. The only nuclear hybrid
candidates that operate below this temperature are alkaline and PEM
electrolysis. The average LWR power output is assumed to be 2500
MWt, and all power is assumed to be used for hydrogen production.
Therefore, the following energy and material process flow diagrams,
Fig. 13, shows electricity and heat (which total to 2500 MWt), and
water consumption to produce hydrogen and oxygen. Given the as-
sumptions made for modeling alkaline and PEM electrolysis, both
produce reasonably similar amounts of hydrogen for a given thermal
power input.
Fig. 14. Process flow diagram for (a) Alkaline water electrolysis (Holladay et al., 2009;
Rashid et al., 2015; Santos et al., 2013; Phillips et al., 2017; Carmo et al., 2013;
Miles et al., 1976; Genovese et al., 2009), (b) PEM water electrolysis (Holladay et al.,
2009; Rashid et al., 2015; Marangio et al., 2009; Siracusano et al., 2018; Carmo et al.,
2013; Genovese et al., 2009; Choi et al., 2004), (c) SOEC electrolysis (McKellar, 2010;
Rashid et al., 2015; Hauch, 2008; Bragg-Sitton et al., 2014; Chan and Xia, 2002), (d)
SMR (McKellar, 2010), and (e) Cu–Cl cycle (Nikolaidis and Poullikkas, 2017; Ozbilen
et al., 2011) given a nominal medium temperature reactor.
6.1.2. Medium temperature reactors
Medium temperature reactors encompass AGRs, SFRs, SCWRs, LFRs,
and MSFRs, to name a few, with an output temperature less than 700–
750 ◦ C. The nominal size was calculated to be 1800 MWt (Goldberg

12
R. Pinsky et al. Progress in Nuclear Energy 123 (2020) 103317

and Rosner, 2011). All processes that can couple with low temper-
ature reactors (alkaline and PEM electrolysis) can also couple with
medium temperature reactors but are less ideal due to wasted heat.
Additionally, SOEC electrolysis and Cu–Cl cycle can operate at these
reactor temperatures. An energy and material process flow diagram
was also created for nuclear-assisted SMR, which requires 700–1000 ◦ C
steam and the additional input of natural gas (which is combusted to
give the heat requirement). Fig. 14 shows these process flow diagrams.
Note that since SMR only requires a small amount of electricity, an
extremely large amount of hydrogen could be produced with the 720
MWe provided by a nuclear reactor. In reality, the amount of natural
gas used for this much electricity would probably be a limiting factor.
Excluding SMR, SOEC and the Cu–Cl cycles can produce much more
hydrogen than either low temperature electrolysis method.

6.1.3. High temperature reactors

High temperature Generation IV reactors, such as the VHTR, MSR,
or GFR, will likely be able to provide outlet temperatures higher
than 900 ◦ C, and possibly up to 950 ◦ C. The average power output
of the three previously listed reactors hovers around 1400 MWt. All
candidates could work with these reactors, but again the ones that
require higher operating temperatures will be more efficient since less
heat needs to be wasted in the process. However, as shown in Fig. 15,
the Cu–Cl process would produce the most hydrogen, but would waste
heat to lower the temperature. The SMR would still be limited by
natural gas, not electricity.

6.2. Technology readiness level

The technology readiness level (TRL) is a means to describe the ex-

tent of development necessary to reach the state of commercialization.
It can range from theoretical principle, at TRL 1, to operational plant, at
TRL 9. Fig. 16 shows the correspondence of TRL number to technology
status (Boardman, 2017).
The TRL was estimated for all hydrogen production candidates
(Boardman, 2017; El-Emam and Özcan, 2019; Ping et al., 2018; Varrin
et al., 2011; Naterer et al., 2017). The minimum TRL of any component
of the technology was taken, as the limiting factor in development
is the component with the lowest TRL. Fig. 17 shows the TRL levels
for all previously described candidates. SMR and alkaline electrolysis
are the only current commercially available technologies. Electrolysis
processes are also more developed than any thermochemical or hybrid
process.

6.3. Cost comparison

Table 4 includes a range of cost per unit kg of hydrogen for

each method. Thermal-based water splitting methods are expected to
be more cost effective because the cost of electricity is significantly
higher than the cost of heat (due to conversion) (El-Emam and Özcan,
2019). Similarly, production costs for electrolysis, requiring significant
electricity, is highly dependent on electricity prices.
As seen in the process flow diagrams, SMR technology incurs ex-
tremely high costs due to orders of magnitude more hydrogen pro-
duced. In reality, SMR is the cheapest technology currently in a $/kg
scenario (Table 2). Otherwise SOEC and S–I would likely be the cheap-
est when coupled with a high temperature reactor, as these technolo-
gies have previously been chosen for further development (Varrin et al.,
2011). There are situations where hybrid systems may be profitable —
when hydrogen, electricity, and natural gas prices are high, or severe
CO2 costs are included (Ruth et al., 2017). However, with the volatility
of prices, flexible hybrid configurations are not currently valuable
enough to overcome capital costs (Ruth et al., 2017). Further policy will
likely need to be implemented (aiming at cleaner energy production)
to make hybrid systems profitable (Ruth et al., 2017). The Department
of Energy (DOE), as of late 2019, has issued contracts with three
Fig. 15. Process flow diagram for (a) Alkaline water electrolysis (Holladay et al., 2009;
Rashid et al., 2015; Santos et al., 2013; Phillips et al., 2017; Carmo et al., 2013;
Miles et al., 1976; Genovese et al., 2009), (b) PEM water electrolysis (Holladay et al.,
2009; Rashid et al., 2015; Marangio et al., 2009; Siracusano et al., 2018; Carmo et al.,
2013; Genovese et al., 2009; Choi et al., 2004), (c) SOEC electrolysis (McKellar, 2010;
Rashid et al., 2015; Hauch, 2008; Bragg-Sitton et al., 2014; Chan and Xia, 2002), (d)
SMR (McKellar, 2010), (e) S–I cycle (Varrin et al., 2011), (f) Cu–Cl cycle (Nikolaidis
and Poullikkas, 2017; Ozbilen et al., 2011), (g) Ca–Br cycle (Sakurai et al., 1996; Teo
et al., 2005), and (h) HyS cycle (Varrin et al., 2011) given a nominal high temperature
reactor.
nuclear power plants to add electrolysis-based hydrogen production
to existing LWR plants, to demonstrate the capabilities and long-term
competitiveness of nuclear hydrogen production and improve plant
economics (Patel, 2019).

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R. Pinsky et al. Progress in Nuclear Energy 123 (2020) 103317

Table 4
Inputs and outputs per kg of hydrogen produced, TRL, and unit cost for candidate NHES technologies (Holladay et al., 2009; Nikolaidis and Poullikkas, 2017; Boardman, 2017;
El-Emam and Özcan, 2019; McKellar, 2010; Rashid et al., 2015; Santos et al., 2013; Phillips et al., 2017; Siracusano et al., 2018; Bragg-Sitton et al., 2014; Miles et al., 1976;
Genovese et al., 2009; Choi et al., 2004; Chan and Xia, 2002; Ping et al., 2018; Varrin et al., 2011; Sakurai et al., 1996; Teo et al., 2005; Ozbilen et al., 2011; Naterer et al.,
2017; Ruth et al., 2017; James et al., 2016; Spath and Mann, 2000).
Electrolysis Thermochemical Hybrid
Alkaline PEM SOEC SMR S–I Ca–Br HyS Cu–Cl
T𝑀𝑎𝑥 (C) 60 80 30 60 90 700 800 900 870 710 910 760 710 910 500
Pressure (MPa) 0.1 0.1 0.157 4.1 3.85 2 4 0.1–2
TRL 9 6–8 5 9 4 <3 3–4 <3
H2 Yield efficiency (HHV) (%)a 29.8 29.4 25.2 27.0 27.0 36.0 35.8 35.6 79.4 35.6b 25.2b 39.0 31b 35.6b 43.2
Inputs (/kg H2 )
Electricity (MJ) 180.0 181.9 214.9 199.5 199.1 146.7 146.4 146.2 1.4 51.5 75.0 25.3 59.0 82.8 67.2
Heat (MJ) 26.2 27.4 24.4 26.2 28.1 26.7 29.7 32.7 – 269.3 375.0 301.4 309.8 178.0 161.1
Water (kg) 11.5 11.5 11.5 11.5 11.5 83.3 83.3 83.3 10.3 9.4 9.0 9.0 9.0 9.0 9.0
Nat gas (kg) – – – – – – – – 2.9 – – – – – –
Outputs (/kg H2 )
H2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
O2 8 8 8 8 8 8 8 8 0 8 8 8 8 8 8
CO2 0 0 0 0 0 0 0 0 4.7f 0 0 0 0 0 0
Production cost (est. $US2019 ) $5.92c $3.56–5.46c $2.24–3.73c $1.54–2.30d $2.18–5.65c $7.06e $2.29–6.27c $2.36–3.86c
a Assuming a power cycle conversion efficiency of 40%.
b Note efficiency highly dependent on process assumptions, which change between these studies, and if temperature is lower than minimum required, external heat must be supplied
(710 ◦ C) studies (Varrin et al., 2011).
c Cost based on US$2019 (El-Emam and Özcan, 2019).

d
Cost based on US$2017 and incorporating inflation to 2019 (Ruth et al., 2017).
e
Cost based on US$1995 and incorporating inflation to 2019 (Sakurai et al., 1996).
f
CO2 estimate may be low; alternative literature quotes as much as 10.6 kg/kg H2 (Spath and Mann, 2000).

Fig. 16. TRL number descriptions (Boardman, 2017).

7. Conclusion

With increasing renewable energy sources along with increasing

Fig. 17. TRL of various NHES hydrogen production candidates (Boardman, 2017;
El-Emam and Özcan, 2019; Ping et al., 2018; Varrin et al., 2011; Naterer et al., 2017).
pressure to promote clean, sustainable energy, nuclear hybrid energy
systems are a potential way to keep nuclear competitive. With renew-
able energy, grid power becomes increasingly volatile, leading to less
base-load power systems, like nuclear, to flexible energy producers.
These flexible energy producers are typically greenhouse gas emitting
coal or natural gas plants. With nuclear hydrogen hybrid technology,
an alternative commodity, hydrogen, could be produced to allow for
grid load-following. This hydrogen can be used for energy storage
and convert back to energy during high electricity prices, or has the
potential to be an energy carrier, to be used as fuel for transportation.
Hydrogen does not produce CO2 , rendering it a much cleaner fuel than
currently used petroleum or natural gas.
Several hydrogen producing nuclear hybrid technologies were in-
vestigated in this study. The NHES candidate technologies (along with
the comparison SMR), including temperature, pressure, TRL, efficiency,
hydrogen cost, and inputs and outputs are summarized in Table 4.
These technologies only require water, heat and/or electricity, all of

14
R. Pinsky et al.
which are abundant around a nuclear plant, to produce hydrogen. Al-
kaline water electrolysis is currently the only widespread, commercially
available, large scale clean hydrogen production technology, but other
technologies have shown rapid development and promise, along with
potentially lower production costs.
Additionally, these hydrogen production technologies operate at
various temperatures, which allows them to match closely with the
current (Generation III) and future (Generation IV) reactor fleet. These
nuclear reactors may be loosely subdivided into three categories: low
output temperatures (<300 ◦ C), medium (<750 ◦ C), and high tem-
peratures (<950 ◦ C). Within these categories, only low temperature
electrolysis is currently available for low temperature reactors, but
thermochemical and electrolysis methods could potentially be coupled
with high temperature systems. Energy and material process flow di-
agrams were created for hybrid technologies at all reactor category
levels. When coupled with around 2000 MWt power from a nuclear
reactor, these technologies can generate between 200–500 tons/day of
hydrogen, with no CO2 emissions. Current hybrid technologies are not
cost effective, and will require either increased electricity prices, CO2
subsidies, or increased hydrogen prices to overcome capital costs. How-
ever, new contracts from DOE will provide funding to nuclear power
plants to demonstrate hydrogen production capabilities to improve the
competitiveness of hybrid technology and improve plant economics.
Declaration of competing interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
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