Journal of Energy Storage 55 (2022) 105714

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Journal of Energy Storage

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

Review article

Optimal hydrogen carrier: Holistic evaluation of hydrogen storage and

transportation concepts for power generation, aviation, and transportation
Marcel Otto *, Katerina L. Chagoya, Richard G. Blair, Sandra M. Hick, Jayanta S. Kapat
University of Central Florida, Orlando, FL, USA

A R T I C L E I N F O A B S T R A C T

Keywords: The storage of excess electrical generation, enabled through the electrolytic production of hydrogen from water,
Hydrogen storage would allow “load-shifting” of power generation. This paves the way for hydrogen as an energy carrier to be
Hydrogen turbines further used as a zero‑carbon fuel for land, air, and sea transportation. However, challenges in hydrogen storage
Alternative fuels
and transportation ultimately pose restrictions on its wider adaption along horizontal and vertical vectors. This
Safety
paper investigates chemical energy carriers ranging from small molecules such as ammonia and methane to
Transportation
formic acid as well as other more complex hydrocarbons in response to this timely engineering problem. The
hydrogenation and dehydrogenation of such carrier molecules require energy lowering the effective net heating
value of hydrogen up to 32 %. Different carrier approaches are discussed in the light of availability, energetics,
water requirements, and suitability for applications in power generation, shipping, trucking, and aviation,
supplemented by a comprehensive safety review making this study unique in its field. It is found that hydrogen
delivered without a carrier is ideal for power generation applications due to the large quantities required.
Aviation would benefit from either ammonia or hydrogen and is generally a field challenging to decarbonize.
Ammonia appears also to be a good medium for shipping hydrogen between continents and to power container
ships due to its high energy density and lower liquid temperature compared with hydrogen. At the same time,
ammonia can also be used to power the ship's engine. Long-haul trucking would benefit the most from cryogenic
or compressed hydrogen due to the lower quantities required and purity requirements of the fuel cells.

unprecedented energy storage requirements [14,15] and a paradigm

1. Introduction shift within the power generation industry [16]. At the same time,
power generation accounts for “only” 25 % of the emitted greenhouse
1.1. Hydrogen economy as a mitigation strategy for global warming gases in the USA. Industry and Transportation account for an additional
23 % and 29 %, respectively [17,18]. Deep decarbonization can only be
Early justifiable concerns about global warming and climate change achieved by addressing these three interconnected sectors together
voiced by the Club of Rome [1] together with the oil crisis of 1973 [2] which has caused reignited global interest in the Hydrogen Economy
created an imperative to develop an alternative, ideally renewable, en­ [19].
ergy ecosystem powered by fuels other than hydrocarbons [3,4]. Multiple arguments support the consideration of hydrogen as one of
Partially due to its abundant availability on Earth and its very high the key elements in decarbonizing various industry sectors. Hydrogen
energy density, hydrogen emerged as a suitable replacement for hy­ (1) is a clean fuel that burns without the emission of COx and soot, (2) is
drocarbons and fuel for heat [5,6]. The oil glut of the 1980s [7] delayed abundantly available [20], (3) and can be easily produced by electrolysis
the transition to a Hydrogen Economy until the 2000s when environ­ using electrical energy and water [21] as shown in Fig. 1. This not only
mental concerns about climate change arose anew, amplified by peaking makes hydrogen an ideal fuel but also a medium for energy storage.
oil prices due to global shortages [8,9]. Record-breaking global surface With high-grade heat (adiabatic flame temperature in air of 2400 K at 1
temperatures can be directly linked to the emission of hydrocarbon atm) and a lower heating value (LHV) about 2.5 times larger than typical
combustion products [10,11]. Carbon-neutral energy sources such as hydrocarbons (120 kJ/g for H2 vs 43 kJ/g, 43.6 kJ/g, and 47.1 kJ/g for
solar, wind, and geothermal have penetrated the market deeper every Diesel, Jet-A, and natural gas, respectively [22,23]), hydrogen is an
year [12,13]. The intermittent nature of renewables, however, requires excellent zero-emission hydrocarbon replacement for combustion

* Corresponding author.
E-mail address: [email protected] (M. Otto).

https://doi.org/10.1016/j.est.2022.105714
Received 26 July 2022; Received in revised form 13 September 2022; Accepted 17 September 2022
Available online 5 October 2022
2352-152X/© 2022 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
M. Otto et al. Journal of Energy Storage 55 (2022) 105714

Nomenclature TES Thermal Energy Storage

TEU Twenty-foot Equivalent Unit
Abbreviation TSCF Thrust Specific Fuel Consumption
EIA Energy Information Administration TRL Technology Readiness Level
CAES Compressed Air Energy Storage
CFATS Chemical Facility Anti-Terrorism Standard Symbols
CAPEX Capital Expenditure H Enthalpy
EV Electric Vehicle S Entropy
FCHEV Fuel Cell Hybrid Electric Vehicle Greek symbols
GT Gas Turbine Δ Delta
HFO Heavy Fuel Oil η Efficiency
LCOE Levelized Cost of Electricity
LHV Lower Heating Value Subscript
LOHC Liquid Organic Hydrogen Carrier eff Effective
MOF Metal Organic Framework rxn Reaction
OEM Original Equipment Manufacturer
SFC Specific Fuel Consumption

significantly contributed to the wider field of hydrogen as an energy-

carrying vector. In terms of application, Ravi and Aziz provided a
detailed review on clean hydrogen for mobility [36]. Faye et al. per­
formed a critical technology assessment of hydrogen generation, stor­
age, and transportation [37]. The hydrogen supply chain and challenges
in the storage and transportation of large quantities of hydrogen are
discussed by Ratnakar et al. [38].
As previously discussed, the assessment of technologies for the
Hydrogen Economy requires a system-based approach and evaluation
within the entire energy ecosystem. Complementary to other existing
studies such as [36–39], the potential of hydrogen as a replacement fuel
will be discussed with respect to eight use cases ranging from power
generation to transportation of passengers and goods; each with its
inherent energy storage requirements. The first four case studies focus
on hydrogen as a replacement fuel for gas turbines of various sizes, used
as mechanical drives or for power generation. Cases 4 and 5 discuss
hydrogen-powered aircraft of European and American makers for con­
Fig. 1. Electrolysis of water requires 9 l of distilled water and approximately 50 tinental flights. Continental and intercontinental transportation of goods
kwh to generate 1 kg of hydrogen using an electrolyzer with 70 % elec­
are discussed in case studies 6 through 8, respectively. Whereas the
trical efficiency.
paper builds upon the important work by [36–39], the novelty and main
differentiator are the holistic evaluation based upon realistic use-cases
processes. with practical guidance on safety and material challenges.
Undeniably, a multitude of roadblocks and technical challenges exist
in the large-scale fuel transition from hydrocarbons to hydrogen. This
includes, but is not limited to, (1) pipeline and equipment embrittlement 1.2. Power generation, transportation, and energy storage
[24], (2) deviating combustion dynamics [25], (3) safety concerns
associated with the high reactivity [26], (4) the low efficiency and The contribution of renewable energy sources in the global power
expensive electrolysis process for hydrogen production from renewable portfolio has risen despite a worldwide growing energy demand. Ac­
energy sources [27], and most importantly (5) the challenge of long- cording to data from the Energy Information Administration (EIA), a 50
term hydrogen storage [28,29]. % increase in energy production is projected between 2018 and 2050
Despite the need to curb greenhouse gas emissions, the business [40]. It has been reported that the supply of energy from solar and wind
impact and cost associated with the previously listed roadblocks and can exceed 36 % of the daily electricity demand in certain markets [41].
challenges given in (1)–(5) are currently seen as the key prohibitors in However, electricity from such renewable sources cannot be generated
making the hydrogen economy competitive to an economy primarily at the same rate and volume as from conventional fossil fuels; creating a
revolving around fossil fuels in a global market place [30]. Locally, mismatch between demand and supply. This phenomenon partially
policies such as Germany's Erneuerbare-Energien-Gesetz (Renewable En­ contributed to the 2020 rolling blackouts in California [42], and the
ergy Sources Act) [31], a CO2 tax [32], or carbon credits [33] as a means sensitivity of power grids to load imbalances was dramatically show­
of global market intervention [34] and other global governance mech­ cased during the 2021 Texas power crisis [43,44]. It can be concluded
anisms [35], may shift and potentially accelerate the transition process. that a need already exists for energy storage and it will only become
However, the technical challenges associated with the Hydrogen Econ­ more critical with increasing renewable energy market penetration. This
omy remain yet to be addressed. is corroborated by the draft roadmap for the “Energy Storage Grand
The present paper aims to address the challenges of energy storage in Challenge” [45] where energy is seen as the key enabler of power gen­
general as well as energy storage in the form of hydrogen with a eration decarbonization. Furthermore, the U.S. Department of Energy's
comprehensive discussion on hydrogen carriers suitable for power Energy Earthshots Initiative from 2021 aims to reduce the cost of clean
generation, industry, and transportation. Other authors have already hydrogen from currently $5 per kg by 80 % to $1 per 1 kg in 1 decade
[46] with similar programs in Asia, Australia, and Europe.

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M. Otto et al. Journal of Energy Storage 55 (2022) 105714

The US' annual power generation capacity is in the order of 1100GW vanadium and its ions which increases with the oxidation state [67].
with roughly 43 % stemming from natural gas, 21 % from coal, 24 % One advantage of the energy carrier fossil fuel is the scalability of its
from renewables, and 9 % form nuclear. In contrast, the storage capacity use from low power 50 cc moped reciprocating engines to the kilowatt
is only in the order of 24 GW [17,45,47]. This does not exclusively apply range of cars, to the megawatt range of gas turbines for power genera­
to the USA but is a general trend found in many economies depending on tion; altogether spanning almost six orders of magnitude. Similar char­
fossil fuels. As of today, storage systems can cover only 10 % of the acteristics are expected of any potential chemical energy carrier and are
production of renewables. >90 % of the storage capacity is realized by eventually met by one: Hydrogen. Hydrogen can be produced at roughly
pumped hydro, the most mature technology amongst all, which lends 70 % efficiency [68] via electrolysis of water using excess energy
itself more to seasonal energy storage rather than short-term load providing an energy sink in a highly integrated power grid [29,69].
shifting and peak shaving [48] as shown in Fig. 2. The major drawback Batteries and hydrogen are the most flexible and scalable energy
of this mechanical energy storage technology is probably its nature carrier solutions amongst the previously introduced technologies and
invasiveness upstream and downstream of the basin [49] as well as the will play major roles in the transition to a renewable energy society
scarcity of water in many regions of the world [50,51]. without carbon emissions. Both have their respective strengths and
Thermal energy and battery storage account for approximately 2.6 % weaknesses that eventually will determine their specific deployment for
and 2.9 % of the current US energy storage capacity, respectively. Of various use cases. It is apparent from the diagram in Fig. 2 that batteries
both, batteries are more popular and widely adopted [52] as they are appear to be the better solution for lower system capacities and storage
available for small devices such as handheld electronics but also exist for duration from seconds to hours. Hydrogen, as a chemical energy storage
large-scale energy storage [53,54] as depicted in Fig. 2 which shows the system, is suited for larger-scale applications and storage durations
typical discharge time and storage capacity per system. The baseline for ranging from hours to several weeks. This is mainly due to the cost
battery energy storage is the Li-Ion battery. Smaller footprints due to structure of battery storage and the self-discharge over longer periods
higher energy volumetric energy densities are a characteristic and [57]. A comparative analysis of Li-Ion and Hydrogen electricity storage
advantage of Sodium-Sulfur and Sodium-Metal Halide batteries [53,55]; with regard to the expected LCOE in 2030 is shown in Fig. 3 with data
hence they are the preferred option where size matters – such as on-site
storage. Besides the critical and environmentally questionable sourcing
of a battery's main components (such as Lithium [56]), battery self-
discharge [57], hysteresis effects [58], temperature dependency [59],
and fire safety [58,60] are additional points to consider when deciding
on energy storage systems [61].
Larger capacities and storage durations are characteristic of flow
batteries and therefore are a middle ground between conventional bat­
tery technology and chemical storage [62,63]. Typically, two liquids are
pumped through the flow battery which is short for redox flow or
reduction-oxidation flow battery. One or both liquids are infused with
electroactive chemicals and are separated by a selective ion-permeable
membrane which enables ion transport and hence the flow of elec­
trical current. The specific electrolyte solutions are formed during
charge-up and can be stored in large tanks. Most typical is the use of
vanadium ions at different oxidation states [64]. The high initial capital
cost amortizes over the long lifetime of the system (between 20 and 30
years) and therefore positively impacts the LCOE [65,66]. The down­ Fig. 3. Comparison of hydrogen and Li-ion electricity storage. Li-ion batteries
sides are the high weight of the electrolytes which results in low volu­ are more cost-effective for shorter storage durations whereas hydrogen breaks
metric and gravimetric energy densities as well as the toxicity of even around 8 h of storage based on data presented in [70].

Fig. 2. The typical discharge duration of an energy storage system is plotted against the typical discharge capacity. Single systems can span various time and power
scales. A fine line cannot always be drawn between storage duration and discharge duration as both partially correlate via the discharge energy rate. Also, the energy
storage capacity is to be understood as a metric at which rate energy can be converted into electricity and not total storage capacity in terms of MWh. the figure
contains information compiled from data found in [53,72–74].

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M. Otto et al. Journal of Energy Storage 55 (2022) 105714

published in [70]. Fig. 4, two distinct regions can be identified. First, chemically-bound
According to the presented data, batteries are the more economical energy carriers such as fossil fuels and hydrogen have the highest
solution for storage for up to 8 h when their levelized cost of electricity gravimetric and volumetric densities listed where the volumetric density
(LCOE) breaks even with hydrogen. LCOE from Li-Ion is 67 % more depends on whether the chemical compound is a liquid or a compressed
expensive when stored for 24 h. Whereas the cost for hydrogen-based gas. Secondly, all types of battery storage are grouped together and
systems is nearly unaffected by storage duration, the negative econ­ generally have comparatively lower densities. Capacitors, super­
omy of scale for Li-Ion causes a cost increase. Longer storage durations capacitors, and pumped hydro do not cluster together as the two
require larger batteries which in turn require more cells, chemicals, and aforementioned categories and cover wider ranges of both energy
electrolytes; a volume-based dependency is given. This is in stark densities.
contrast to hydrogen storage systems permitting energy storage for In the light of the recent advancements and research efforts toward a
longer time scales. A detailed breakdown of hydrogen storage costs for hydrogen economy, its high specific and volumetric energy density as
different storage approaches such as high pressure, underground stor­ well as suitability for long-term storage, the current study will highlight
age, etc. with respect to CAPEX and operating cost can be found in [71]. the various forms of hydrogen storage concepts.
The previous discussion on energy storage systems allows for the
conclusion that the available technologies are highly segmented and
1.3. Hydrogen storage
often fundamentally different. There is no one-fits-all solution to the
question of ideal energy storage. On the one side, there is pumped hydro
The fundamentals of hydrogen storage are discussed and summa­
for large capacity and duration storage with very large footprints. On the
rized in a multitude of research articles and papers [75,76]. The number
other side are chemical energy carriers and batteries that excel over a
of practical hydrogen storage methodologies varies depending on the
wide range of capacity and storage durations. Additional complexity to
references consulted. However, the main storage approaches are, start­
the question of energy storage is added when moving systems such as
ing with the two most established technologies, (1) compressed and (2)
trucks, cars, and airplanes are considered. Here, the available choices
liquified cryogenic hydrogen. Hydrogen can also be (3) physisorbed
are even more limited and further restricted by the readiness of the
onto the surfaces of highly porous materials, (4) chemisorbed, or bound
targeted storage technology. Other metrics to consider are the specific
into (5) chemical compounds including metal hydrides.
density (also referred to as gravimetric density) and the volumetric
Compressed hydrogen, either at low or high pressures up to 700 bars,
density. Gravimetric density is the ratio between stored energy and the
requires suitable pressure vessels with partially large wall thicknesses
system or storage medium. Volumetric density is the ratio between
which can make them quite heavy. However, more recent advancements
stored energy and the volume the storage medium or system occupies.
in composite structures and novel manufacturing methods resulted in
Both metrics are quite important to consider when solutions for weight
more lightweight carbon fiber tanks [77]. As shown in Fig. 4, com­
or space-restricted applications are thought of; for example, zero-
pressed hydrogen and batteries have similar volumetric densities
emission aircraft (weight) and mobile phones (space). Upon studying
although the gravimetric densities (not considering the weight of the

Fig. 4. Volumetric and gravimetric energy densities for the most common storage applications in direct comparison. Chemical compounds typically score high for
both densities whereas battery-based storage technology requires more volume and mass to store energy. Pumped hydrogen and capacitors rank lowest in both
categories. The color-coding of the categories is identical to the one found in Fig. 2.

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M. Otto et al. Journal of Energy Storage 55 (2022) 105714

containment vessel) are much higher. carrier molecule. This study aims to present the optimal hydrogen car­
Higher energy per volume levels can be achieved by liquifying rier molecule for each case using a holistic and inter-disciplinary
hydrogen. Cryogenic hydrogen requires complex storage to avoid boil- approach including engineering sciences, chemistry, techno-
off and is not suitable for dynamic applications in which the liquid economics, and regulatory compliance.
could be sloshing. Constant cooling is required to maintain a tempera­
ture below the boiling point at 20 K and remove any parasitic heat 2. Use cases and metrics for assessment
leakage into the system as well as the thermal energy of the exothermic
ortho- to para‑hydrogen conversion [78,79]. The need for proper insu­ Three different types of heat engines with unique thermodynamic
lation makes the design complex as vacuum jackets and a suspension cycles are used to cover the majority of the energy conversion needs
system between the inner and outer tank are required to reduce the heat from fuel to mechanical or electrical energy. First, Rankin cycle-based
leakage into the stored liquid [80]. Additional roundtrip energy losses steam turbines, a closed-loop power system to which heat is added via
are due to the work required for liquefaction which accounts for a heat exchange process. Heat is typically added to the system from
approximately 28 % of the LHV of hydrogen [81]. nuclear fission or the combustion of coal. A working fluid, usually water,
Physisorption is the process of physically adsorbing a gas on the is evaporated and expanded over a turbine which causes the turbine to
surface of a solid using the relatively weak Van der Waals force between spin. The mechanical energy of such systems is primarily used for power
adsorbent and adsorbate. The adsorbate can reach a liquid-like density generation and is in the order of hundreds of Megawatts to Gigawatts
while staying in the gas phase removing the need for liquefaction work. and is unlikely to be replaced by the combustion of hydrogen. Secondly,
Adsorbates are typically materials with high porosity or large surface-to- Brayton (Joule) cycle-based gas turbines are also a type of rotating
volume ratios such as aerogels [82–84], activated carbon [85], carbon turbomachinery with the difference that heat is added directly within
nano tubes [86–88], or metal-organic frameworks (MOF) [89–91]. the machine through the combustion of natural gas or oil. The three
Challenges remain in the process of scaling up the physisorption storage main application fields of such engines are power generation, mechan­
approach from laboratory scale to the capacities required by industry ical work for industrial processes, and aircraft propulsion. It is expected
[47]. that gas turbines will be the backbone of a hydrogen-fuel-based
In contrast to physisorption, the electron density is shared between ecosystem as they can be adapted and retrofitted to pure hydrogen
adsorbate and adsorbent during the process of chemisorption. The group and hydrogen blends [104,105]. Third and last, reciprocating engines,
of Liquid Organic Hydrogen Carrier (LOHC) counts toward this category typically based on the Otto or Diesel cycle, are commonly found in
[92–94]. The liquid state of the complex organic molecule before and transportation systems such as automobiles, trucks, and ships. Fuel is
after the hydrogenation process aims to provide ease and convenience in combusted in a cylinder, expands, and moves a piston connected to a
handling the substances at ambient conditions. The downsides of LOHCs crankshaft which is connected to the drivetrain of a road vehicle or the
are typically photocatalytic behavior of the carrier molecule [95,96] and propeller of a ship. Efforts exist to replace conventional fossil-derived
relatively high molecular weight relative to the amount of adsorbed fuels such as gasoline, diesel, and heavy fuel oil with hydrogen
hydrogen. The lines between chemisorption and chemical bonds are [106,107], but it is expected in an hydrogen dominated marketplace
blurry so that additional chemical substances could be counted toward a that smaller reciprocating engines will be replaced by battery-powered
wider category of organic hydrogen carriers. For instance, the carrier or fuel-cell and battery-powered hybrid systems [108]. Whereas
molecules COx, benzene, and toluene result in the hydrogenated mole­ battery-powered systems shift the power generation requirement from
cules Formic Acid or Methane, Cyclohexane, and Methylcyclohexane, the vehicle to the grid and eventually a power plant, fuel-cell hybrid
respectively. It can be derived from the listing that CO2 works twofold: system still needs fuel on board for the local in-vehicular power
on the one hand, CO2 can be hydrogenated resulting in Formic Acid, on generation.
the other hand, CO2 can be converted into Methane through the Sabatier As previously mentioned, the three sectors of power generation, in­
reaction [97]. On the same token, the Fischer Tropsch process [98] dustry, and transportation account for roughly one-third of the global
converts CO to Methane, too. In terms of inorganic hydrogen, the most CO2 emissions. Thorough decarbonization can only be achieved by
noteworthy carriers are nitrogen to ammonia or hydrazine and boron addressing all three areas. Hence, the use cases are chosen to reflect
resulting in boron hydrides [99]. Boron hydride as a metalloid bridges applications across all three sectors and all three major heat engine
the gap between inorganic hydrogen carriers and metal hydrides such as types.
aluminum hydrides or magnesium hydrides which are discussed at
length in [100]. Metal hydrides encompass simple hydrides such as the 2.1. Industrial drives and power generation
aforementioned magnesium hydride, transition metals, and complex
metal hydrides of salts where the hydrogen is nonstoichiometrically Stationary gas turbines come with power ratings from the sub-
bound in between the ionic lattice structure [101–103]. Three examples Megawatt range to several hundred Megawatts in a single cycle
of complex metal hydrides are sodium aluminum hydride, lithium configuration. Industrial gas turbines are not bound to a grid frequency
aluminum hydride, and lithium borohydride. and can spin freely. Conversely, aero-derivative and heavy-duty gas
This paper focuses on identifying and evaluating different com­ turbines for power generation are bound to the local grid frequency. The
pounds that can be utilized as carriers of hydrogen and that can be stored function of the former is usually to provide process heat and mechanical
and transported more economically and safely. With the objective to energy for industrial applications such as pumping (upstream) or
identify the ideal hydrogen storage and transportation carrier suitable compression (midstream). These machines typically are operated indi­
for power generation, transportation, and aviation, a down selection has vidually and are not part of a larger grid. Power generation turbines,
to be made based on multiple criteria, as listed later; this selection is however, are part of a larger grid that must balance supply and demand.
beyond the review contained in this paper. One key aspect in this The integration of such turbines into a renewable energy-dominated
evaluation of carrier molecules that is highly relevant to the wide power grid is outlined in Fig. 5 where, in the transition period, natural
adaption nevertheless sparsely discussed and considered in scientific gas is blended with hydrogen to achieve operation from 100 % green
publications is safety and regulatory compliance. hydrogen. As described earlier, grid stability is essential for daily and
In summary, the technical challenges that come with the transition seasonal load shifting or even during catastrophic events such as
from the current state-of-the-art technology to hydrogen fuel and stor­ extreme weather or other blackout conditions. Due to their excellent
age alongside system-inherent requirements, demands, and limitations startup and turn-down behavior, gas turbines are an excellent comple­
are unique to each proposed use case. Therefore, a careful case-to-case- ment to fluctuating renewables and baseload such as nuclear power. The
based assessment is required to identify the ideal use case-specific aforementioned Texas incident of 2021 prompts to the provision of at

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M. Otto et al. Journal of Energy Storage 55 (2022) 105714

Fig. 5. The potential integration of hydrogen as a mid-to-longterm storage system into the power grids of the future.

least seven days' worth of nominal power which in this case translates to so that thrust-specific fuel consumption is more appropriate. Industry-
on-site fuel storage for 100 % generation capacity. This case study dis­ standard is to provide such information in imperial units: the thrust-
cusses three power classes of gas turbines, listed in Table 1. specific fuel consumption (TSFC) per engine of pound fuel per pound-
The discussion of hydrogen as a fuel replacement for natural gas will force thrust per hour (lbm/lbf.h) can only be derived from models or
evolve around three setups. It is assumed that the machines are capable publications such as [111] or estimated databases such as [112] since no
of hydrogen combustion and achieve the same nameplate power and data is provided by CFM specifically. It should be noted that the openly
efficiency when converted from natural gas. This is a valid assumption available values vary between different sources. The actual fuel con­
since many OEMs already claim hydrogen blends beyond 30 % and aim sumption for an exemplative flight can be calculated with the aircraft's
to be 100 % hydrogen ready by 2050. The LHV of hydrogen is 120 MJ/ cruising thrust and flight duration. A typical route on which a 737 or
kg compared to 47.1 MJ/kg of natural gas. Consequently, less hydrogen A320 is operated could be Orlando to New York. The non-stop flight
per unit power is required. time between MCO and JFK is 2.5 h. Therefore, the total Jet A-1 fuel
consumptions for the 737max and A320neo aircraft during the proposed
2.2. Hydrogen-powered aircrafts trip are 6587 kg and 5783 kg, respectively. With heating values of 43.6
MJ/kg for Jet A-1 [113] and 120 MJ/kg for Hydrogen, a hydrogen
Two representative aircraft (in the 150–200 passenger range) are equivalent fuel consumption of 2393 kg and 2101, respectively, can be
Boeing's 737 MAX 9 and Airbus' A320neo. Typical configurations of the calculated under the assumption that the turbine efficiency and thrust
Boeing jet allow between 178 and 193 passengers. The Airbus jet is do not vary with fuel. This assumption can be justified in the same way
slightly smaller with a passenger capacity of roughly 150–180. Both as for stationary turbines in the previous section. After all, it turns out
aircraft are narrow bodies and are powered by two CFM Leap 1 engines that both aircraft are quite similar in their requirements and consump­
[109,110]. Aircraft engines are quite similar to the gas turbines already tion so they can be combined into one use case. The key metrics are
described in the previous section. The main difference is that not only listed in Table 2.
mechanical energy is produced by the engines but also thrust. The me­
chanical energy of the shaft powers a large fan which itself generates 2.3. Zero-emission transportation of goods
thrust by moving a large amount of air. Aircraft gas turbines are typi­
cally more compact than stationary gas turbines as weight is more Today, goods and cargo are transported by four main modes of
important. They also rotate much faster as they are not limited to any transportation: road (trucks), rail, aircraft, and cargo ships. Aircraft are
grid frequencies. previously discussed in the context of passenger transportation, and it
Aircraft fuel consumption is typically given as specific fuel con­ can be assumed that most railways are electrified so on-board hydrogen
sumption (SFC) which is given in the units of mass per time. The engines transportation is not required, hence the focus will be on heavy-duty
operate at different thrust levels between ground, take-off, and landing trucks and cargo ships. >70 % of domestic freight in North America is

Table 1
Overview of power generation use cases and metrics.
Case Name Type Fuel Nameplate Power Nominal Nominal Heat Rate [J/ Storage Duration
[MW] Efficiency kWh] [d]

#1 SGT-A05 Industrial GT for mechanical work Natural 5 32.3 % 1.12E7 7

gas
#2 SGT-A65 Aeroderivative for power Natural 44 40.4 % 8.92E6 7
generation gas
#3 SGT6- Heavy-duty for power generation Natural 260 40 % 9E6 7
5000F gas

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M. Otto et al. Journal of Energy Storage 55 (2022) 105714

Table 2
Assumptions and values for Case #4 Boeing and Case #5 Airbus.
Case Name Engines Fuel TSFC cruise TSFC cruise Thrust Thrust Flight Fuel Consumption [kg Fuel Consumption
[lb/lbf.h] [kg/kN.s] cruise [lbf] cruise [kN] Duration [h] Jet A] [113] [kg H2]

#4 Boeing 2x CFM Jet 0.53 15 5480 24.38 2.5 6587 2393

737max Leap 1B A-1
#5 Airbus 2x CFM Jet 0.51 14 5000 22.24 2.5 5783 2101
A320neo Leap 1A A-1

transported via trucks; 75 % in Europe, which accounts for 30 % of study, the same approach is chosen as with the aircraft assuming that the
Europe's greenhouse gas emissions caused by road traffic [114,115]. efficiency of the propulsion system remains the same after switching to
Heavy-duty trucks in the USA are categorized as Class 8 with weight an hydrogen or battery-powered system (Table 3).
limits of 33,001 pounds (14,969 kg) and above. The United Kingdom
and European Union consider heavy-duty trucks in the weight range
2.4. Metrics for assessment
between 7500 and 40,000 kg. Although, heavy-duty trucks only account
for a small fraction of the truck fleet (~2.5 % in the USA) >20 % of the
The identified hydrogen delivery vectors (carrier molecules and
fuel consumption is attributed to them as a conventional, normal loaded
hydrogenated molecule pairs) will be discussed in the light of five major
Class 8 truck consumes around 55.6 l of Diesel per 100 highway kilo­
aspects: (1) Roundtrip energy requirements, (2) storage and trans­
meter [116,117]. Popular alternatives are fully electric, battery-
portation of carrier and hydrogenated molecules, (3) environmental and
powered trucks (EV) [118,119], fuel cell hybrid electric vehicles
safety concerns, and (4) commercialization. Each category is further
(FCHEV) [120,121], and overhead power lines as discussed in Europe
segmented as follows:
[122]. The fuel economy of EV and FCHEV are 190 kWh/100 km [116]
and 10 km/kg [123], respectively. US Department of Transportation (US
1. Roundtrip energy requirement
DOT) guidelines require breaks every 8 h so a distance of 560 miles (900
a. Forward reaction (hydrogenation) energy requirement
km) can be covered assuming an average velocity of 70 miles per hour.
b. Forward reaction energy barrier
Germany, for example, permits 9 h of uninterrupted driving, however,
c. Forward reaction: availability of catalysts
the speed for heavy-duty trucks is limited to 60 km/h so that no >540
d. Dehydrogenation (if applicable)
km can be driven without a break. Two potential trips that could be
e. Total Energy requirement
accomplished in the respective driving window are from the port of New
f. Energy barrier
Orleans, Louisiana to Nashville, Tennessee a distance of 530 miles (853
g. Availability of catalyst
km), or from Essen at the center of the highly industrial Ruhr region in
2. Storage and transportation for H2/molecule
Germany to Berlin (540 km).
a. Temperature and pressure
Cargo ships were once limited to 5000 TEU to pass through the old
b. Energy density (in terms of LHV)
Panama Canal: Panamax ships. TEU, a twenty-foot equivalent unit, is the
c. Specific energy (in terms of LHV)
number of standard-sized containers a ship can carry. The new Panama
3. Environmental and Safety Concerns
Canal permits ships to pass with up 14,000 containers. However, the
a. Toxicity
typical size of cargo ships between Europe and Asia in the order of
b. Volatility and fumes
18,000 TEU and more; these ships can hold >17 million liters of fuel.
c. Flammability
The fuel consumption of such vessels is challenging to estimate as it is
d. Regulatory restrictions
highly dependent on speed. According to [124], 14,500 TEU ships
4. Commercialization
consume typically 100 tons of Heavy Fuel Oil (HFO) per day at sea with
a. Scale-up of process
an LHV of 41.8 MJ/kg [125]. It should be noted that the fuel con­
b. Availability and cost of carrier molecule and catalyst
sumption is heavily dependent on the cruising speed and an increase
from 18 (extra-low steaming) to 20 knots per hour (slow steaming) can
A qualitative assessment of the carrier‑hydrogenated molecule pairs
almost double the consumption [126]. A vessel steaming the 12,000
will be given in the results and discussion section as condensed tabulated
nautical miles between Shanghai and Rotterdam usually spends 30 days
information as one point of reference database alongside a discussion of
at sea resulting in a consumption of around 3000 tons of fuel releasing
key points when considering the carrier molecules. This information is
up to 5700 tons of CO2 per journey. As of today, 90 % of the worldwide
then leveraged together with use cases to enable a holistic assessment of
container ship fleet is powered by heavy fuel oils which produce large
the ideal carrier per application. The findings are color-coded based on a
quantities of NOx, SOx, soot, as well as other toxic emissions. In this case
traffic light pattern, a technique used in similar studies such as Gray

Table 3
Assumptions and values for the transportation of goods, including Cases CLASS 8 Trucks in Germany (#6) and in the USA (#7), as well as #8 cargo ships for a
representative Asia-Europe transportation route.
Case Location Assumed daily travel distance [127] Fuel Road type Fuel Economy Fuel Consumption

#6 Germany 540 Diesel Highway 55.6 l/100 km 255 kg

H2 + electric Highway 10 km/kg 54 kg
electric Highway 190 kWh/100 km 1026 kWh
#7 USA 900 Diesel Highway 55.6 l/100 km 403 kg
H2 + electric Highway 10 km/kg 85 kg
electric Highway 190 kWh/100 km 1620 kWh

Case Type Travel Distance [km] Fuel Travel Duration [d] Fuel Economy [t/d] Fuel Consumption [t] Cargo Rating [TEU]

#8 Post-Panamax 22,224 Heavy Fuel Oil 30 100 3000 14,500

7
M. Otto et al. Journal of Energy Storage 55 (2022) 105714

et al. [39]. three hydrogen atoms are separated from the nitrogen carrier molecule
via catalytic cracking (Pathway 3).
3. Results and discussion As with any other chemical reaction, the hydrogenation and dehy­
drogenation processes of Pathways 2 and 3 require energy transfer. The
3.1. Hydrogen transportation pathways hydrogenation reaction is typically an exothermic reaction that releases
heat after the activation energy is overcome. Assuming that the activa­
Three potential pathways of hydrogen transport, storage, and con­ tion energy must be added to the system and the released heat from the
sumption are considered and depicted in Fig. 6. Option 1, direct trans­ reaction cannot be converted to useful work, the hydrogenation process
portation and storage of hydrogen serves as a baseline. Here, hydrogen is requires energy. When catalysts are used, the activation energy
directly stored and transported without the involvement of any chemical requirement can be reduced. Conversely, the dehydrogenation process is
reaction. This can be achieved by storage as a liquid, gas, or in a phys­ endothermic and requires an energy input as well. Hence, energy must
isorbed state; all modes were discussed in the introduction of this paper. be expended for the hydrogenation and dehydrogenation process as
Pathway options 2 and 3 require an additional molecule that serves as a described in the discussion around Pathway 3.
hydrogen carrier. This carrier molecule is hydrogenated by attaching The discussion on the ideal carrier molecule will consider the energy
one or more hydrogen atoms to its chemical structure. Consequently, requirements for either reaction as well as a consideration of activation
through reaction, the original hydrogen carrier molecule and the hy­ energy for typical reaction conditions.
drogenated molecule are two different chemical substances. Now, two
scenarios are possible: In the case of Pathway 2, the hydrogen is not 3.2. Carrier molecules
separated from the carrier molecule prior to its consumption, and this is
the main difference from the third option. In contrast, for Pathway 3, the For this review, seven hydrogen carrier molecules were identified
transported hydrogen is split from its carrier molecule which may or and are subject to further analysis. Five of the seven molecules are hy­
may not be recovered. Potentially, the same carrier molecule can be part drocarbons, one oxide of carbon, and one elemental gas. An overview of
of the Pathways 2 and 3 at the same time depending on the application all seven carriers including their corresponding hydrogenated pendants
and system design. One example is ammonia from the hydrogenation of is given in Table 4. For both the carrier and the hydrogenated carrier, the
nitrogen. Ammonia could be directly combusted (Pathway 2) or the table is also populated with a chemical's IUPAC and common name, its
chemical formula, and the CAS Number.

3.3. Hydrogenation and dehydrogenation

The hydrogenation and dehydrogenation energetics play a crucial

role when assessing the ideal hydrogen carrier molecule. The hydroge­
nation reaction, which is typically exothermic, requires activation en­
ergy and is subject to the process efficiency. A more in-depth discussion,
however, would exceed the scope of this paper. Hence, in the context of
this study, only the dehydrogenation energy, endothermic reaction, is
considered as a round-trip efficiency loss accompanied by a discussion of
Gibb's free energy for the (de)hydrogenation reactions to serve as a
qualitative pointer for the spontaneity of the reaction.
Therefore, the two relationships can be defined as an effective LHV
(Eq. (1)) and a roundtrip transportation loss (Eq. (2)), respectively. It
should be noted that the roundtrip transportation loss is only related to
the expended energy during dehydrogenation and does not take cry­
ocooling or boil-off etc. into account.
LHVeff = LHV − ΔHdehydrogenation (1)
/
LHV ΔH (2)
dehydrogenation

The consideration of energetic losses has a direct impact on the

gravimetric and volumetric densities of such chemical hydrogen car­
riers. Consequently, effective densities were added to Fig. 4 to account
for this fact.
A detailed overview regarding the forward and backward energy
budget, the entropy generation, as well as Gibb's free energy based on
the most common hydrogenation parameters are given in Table 5
alongside the quantified roundtrip losses.
Hydrogenation of carrier molecules requires bond activation on
active surfaces and mobility of active species across those surfaces. For
all carriers, the hydrogen molecule's bonding orbital is broken by either
sharing electron density with the surface or donation of electron density
into the σ* anti-bonding orbital of H2. For hydrocarbon carriers the
electron density is either shared between the pi (olefinic) bonding or­
bitals or electron density from the surface is donated into empty pi anti-
bonding orbitals. In either case, the C– – C bond is weakened allowing
subsequent reaction with atomic hydrogen; this process is called bond
Fig. 6. Carrier reaction pathways. activation. Carbon dioxide requires activation of the C– – O bond and

8
M. Otto et al. Journal of Energy Storage 55 (2022) 105714

Table 4
Overview of the hydrogen carrier and hydrogenated molecules discussed in this paper listed by chemical formula and CAS number.
Carrier Hydrogenated carrier

Name (common name) Formula CAS Name (common name) Formula CAS

Formic acid H2CO2 64-18-6

Carbon dioxide CO2 124-38-9
Methane CH4 74-82-8
Nitrogen N2 7727-37-9 Ammonia NH3 7664-41-7
Benzene C6H6 71-43-2 Cyclohexane C6H12 110-82-7
Toluene C6H5CH3 108-88-3 Methylcyclohexane C6H11CH3 108-87-2
1,3-Dimethylbenzene
C6H4(CH3)2 108-38-3 1,3-dimethylcyclohexane C6H10(CH3)2 638-04-0
(m-Xylene)
1,2,4-Trimethylbenzene
C6H3(CH3)3 95-63-6 1,2,4-trimethylcyclohexane C6H9(CH3)3 2234-75-5
(Pseudocumene)
1,2,3,4-Tetramethylbenzene C6H2(CH3)4 488-23-3 1,2,3,4-tetramethylcyclohexane C6H8(CH3)4 3726-45-2

nitrogen the N– – N bond. Bond activation for each molecule is observed

– 3.3.2. Nitrogen
over different metals, oxides, and nitrides depending on the overlap of Diatomic nitrogen (N2) can be hydrogenated to produce ammonia
surface states with the carrier molecules. over various catalysts via the reaction shown in Eq. (5).
Dehydrogenation follows a similar mechanism where the C–H,
N2 (g) + 3H2 (g) → 2NH 3 (g) (5)
O–H, or N–H bond is activated, but the rate of H2 desorption is greater catalyst

than the rate of H–H bond activation leading to a net production of

However, commercial production via the Haber-Bosch process with
hydrogen. For carbon-containing compounds, there is a risk of over-
iron/iron oxide catalysts is most commonly used. Ruthenium-based
dehydrogenation leading to catalytic deactivation through the forma­
systems have also been implemented commercially, but the catalyst
tion of carbon depositions (coking) on the surface. A good hydrogena­
cost is significantly higher. The energetic requirements of the Haber-
tion catalyst is not necessarily a good dehydrogenation catalyst.
Bosch process have led to a large amount of work looking to lower the
The next section provides a detailed discussion of the underlying
temperature and pressures required for ammonia synthesis [131]. The
chemistry of the targeted hydrogen carriers and suitable catalysts for the
goal is to reduce temperature and pressure from 400 to 450 ◦ C and 197
hydrogenation and dehydrogenation reactions.
bar to 300–400 ◦ C and 1–10 bar. The major energy requirement is
maintaining the high temperatures and recent work has shown ammonia
3.3.1. Carbon dioxide
production at room temperature and pressures from 1 to 100 bar
Carbon dioxide is a versatile hydrogen carrier and can react with
[132,133]. Dehydrogenation of ammonia or the reverse Haber-Bosch
hydrogen via two unique mechanisms. Each mechanism requires a
process is typically performed over iron- and cobalt-based catalysts,
different catalyst and produces distinct products. The hydrogenation
though ruthenium is the most active metal for this reaction [134].
reaction shown in Eq. (3) below will form formic acid.
CO2 (g) + H2 (g) → H2 CO2 (l) (3) 3.3.3. Hydrocarbons
There are a number of hydrocarbon carrier molecules. All of these
catalyst

CO2 (g) + 4H2 (g) → CH 4 (g) + 2H2 O (l) (4) molecules carry hydrogen through the hydrogenation of olefinic bonds
catalyst in the carrier based on their respective reactions as shown in Eqs. (6)
Currently, the conversion of carbon dioxide to formic acid has been through (10).
catalyzed both homogeneously and heterogeneously [128]. Homoge­ C6 H6 (l) + 3H2 (g) → C6 H12 (l) (6)
neous catalysts have focused on ruthenium and iridium complexes while catalyst

heterogeneous catalysts are mostly based on the noble metals. However,

C6 H5 CH 3 (l) + 3H2 (g) → C6 H11 CH 3 (l) (7)
metal-free systems based on frustrated Lewis acid/base pairs [113] and catalyst

boron nitride [129] have also been studied. Eq. (4) illustrates the for­
mation of methane gas via the Sabatier reaction. The catalysts for this C6 H4 (CH 3 )2 (l) + 3H2 (g) → C6 H10 (CH 3 )2 (l) (8)
catalyst
reaction are typically nickel-based due to cost. Ruthenium is also
attractive for this reaction but has a significantly higher cost [130]. The C6 H3 (CH 3 )3 (l) + 3H2 (g) → C6 H9 (CH 3 )3 (l) (9)
use of carbon dioxide as a carrier molecule is an appealing choice as it catalyst

could result in the capture and sequestration of atmospheric CO2 which

C6 H2 (CH 3 )4 (l) + 3H2 (g) → C6 H8 (CH 3 )4 (l) (10)
would be beneficial to reducing atmospheric levels. However, direct catalyst

combustion of these carbon-containing products presents another chal­

These reactions are typically carried out over nickel or noble metal
lenge: The burning of formic acid produces carbon dioxide gas, coun­
catalysts and are a robust well-understood technology which has been
teracting any prior atmospheric CO2 capture with the intention of
implemented in the food, petroleum, and pharmaceutical industries. The
negative emissions. The case is similar to methane. Implementing sub­
catalyst of choice here is high surface area nickel, or Raney Nickel. Its
sequent reactions to these, such as RWGS, may mitigate these drawbacks
high activity and propensity to hydrogenate aromatic structures are an
by ensuring CO2 is not released again. The utilization of the third
advantage in this application. Dehydrogenation of the reaction products
pathway (above), dehydrogenation of the carrier molecule, could be
requires careful catalyst selection, as over-dehydrogenation will result
another solution so long as the CO2 remains sequestered.
in loss of the carrier molecule as carbon and eventual deactivation of the
Here, the roundtrip energy considerations are twofold as two path­
catalyst (through coking). Less active noble metal catalysts are typically
ways are imaginable for CO2. First, formic acid undergoes the hydro­
chosen to prevent this from occurring [135]. Industrially, Clariant's
genation – dehydrogenation cycle whereas the Sabatier reaction yields a
CATOFIN® process is used to realize olefins from alkanes, however, it is
combustible product itself. In this, the LHV of methane will be compared
not a closed-loop, and losses to coking would be critical in this appli­
to the combined LHV of 4 H2 moles required to form 1 mol of methane.
cation. All of these molecules are based on an aromatic (benzene) ring
166 kJ/mol are lost for each mole of methane which accounts for a
backbone. This is advantageous as the aromatic structure stabilizes the
roundtrip loss of 20.7 %.
carrier from excessive dehydrogenation over very active catalysts.

9
M. Otto et al. Journal of Energy Storage 55 (2022) 105714

However, benzene is a carcinogen and has been banned from commer­

cial use. With one methyl group, toluene is considered safer but is also

LHV_eff Transportation
seeing restrictions on its use in favor of xylenes (Eq. (8)) which contain
two methyl groups. Molecules with large degrees of methylation (5 and

13 %
28 %
28 %
27 %

27 %

29 %

13 %
32 %
Roundtrip (kJ/mol loss 6 degrees) are not available commercially. The ideal molecules for this
application are compounds containing between two and four methyl
groups (as in Eqs. (8)–(10)). Compounds in the lower range are liquid at

210.4
173.1
174.6
177.4

176.6

171.1

211.4
274.6
Energy Cost H2)

handling temperatures and obtainable in multi-ton quantities. Addi­

tionally, the mass fraction of hydrogen stored increases with a lower
methyl group count.
(kJ/mol
Carrier)
Overview of the hydrogen carrier molecules and their key chemical properties. The roundtrip energy requirement is calculated and a corrected H2 LHV is given for each carrier molecule.

− 81.9 − 15.2 31.6

193.9 − 193.7 45.9

31.1 − 218.4 206.7
26.9 − 212.3 202.2
15.7 − 199.7 193.8

8.5 − 199.4 196.2

− 8.3 − 209.6 212.7

112.4 − 292.1 252.7

Total

3.3.4. Roundtrip efficiencies

Energy

In summary, ammonia and formic acid, derived from nitrogen and

S carrier ΔSrxn Gibbs

mol)
molecule (J/K) Free

(kJ/

CO2, respectively, are the most efficient carrier molecules from an en­
ergetics point of view with transportation losses ranging from 12.7 %
and 13 %. Larger hydrocarbons range from 26.7 % (1,3-dimethylcy­
clohexane) to 29.3 % (1,2,3,4-tetramethylcyclohexane) with losses two
(J/mol.K)

times greater than the aforementioned alternatives. The overview of the

@ STP

213.8
173.3
221.0
253.8

283.4

290.8

191.6
213.8

roundtrip energy cost, the effect on the net hydrogen LHV, and percent
transportation losses are comparatively given in Fig. 7. The combustion
hydrogen in Hf (kJ/ Hydrogenation

of methane yields the highest net energy after hydrogenation, however,

also results in the largest amount of energy lost in the hydrogenation
(kJ/mol)

− 393.5 − 31.6

0.0 − 91.9
49.0 − 206.7
12.0 − 202.2
− 24.4 − 193.8

− 58.6 − 196.2

− 90.2 − 212.7

− 393.5 − 252.7

process. For hydrocarbons, one molecule can bind several hydrogen

Volumetric Carrier ΔH

atoms. Further, the use of a nitrogen carrier would circumvent the

possibility of catalyst deactivation, since diatomic nitrogen is devoid of
mol)

carbon atoms, preventing coke formation.

1187.4
1244.0
1054.0

3393.5
3670.0
953.4

828.3

766.6

3.4. Carrier safety and risk assessment

(# atoms) available 1 l(l)

When choosing fuel generation sources, it is important to closely

Weight (g/ml) available fraction

17.8 %
25.2 %

examine the regulatory, environmental, health, and security re­

%
%
%
%

4.8 %

4.3 %
Mass

4.4
7.2
6.2
5.4

quirements of a storage choice. Using the information in Table 6, an

H2

analysis of available materials can be conducted to assess these con­

cerns. The table is structured as follows. The top half of entries pertain to
the unhydrogenated molecule and the bottom half of entries are the
Density H

2
6
6
6

3
4

corresponding hydrogenated carrier. The columns contain major safety

and regulatory information. Due to the varying granularity and abun­
1.22
0.78
0.77
0.80

0.78

0.80

0.86
0.66

dance of the information, differences in regulations, e.g. European and

(g/mol)

US-American, and end-user-specific risk tolerance, no one-fits-all kind of

C6H10(CH3)2 112.2

C6H9(CH3)3 126.2

C6H8(CH3)4 140.3
46.0
84.2
98.2

17.0
16.0
Mol.

assessment applies. Rather, the tabulated data and information provided

serve as a single-point reference with additional references to dig deeper
Hydrogenated Molecule Molecular

C6H11CH3

than an all-encompassing encyclopedia. Hence, the risk assessment and

Formula

H2CO2
C6H12

discussion will mainly identify specific risk tendencies such as

NH3
CH4
tetramethylcyclohexane
trimethylcyclohexane
dimethylcyclohexane
Methylcyclohexane
Cyclohexane
Formic Acid

Ammonia
Methane
1,2,3,4-
1,2,4-
1,3-
(g/mol)
Weight

106.2

C6H3(CH3)3 120.2

C6H2(CH3)4 134.2
Mol.

44.0
78.1
92.1

28.0
44.0
C6H4(CH3)2
Molecular

C6H5CH3
Formula

C6H6
CO2

CO2
N2
1,2,3,4-tetramethylbenzene
1,3-dimethylbenzene (m-

1,2,4-trimethylbenzene
Hydrogen Carrier
(Common name)

Carbon dioxide

Carbon dioxide
Xylene)

Nitrogen
Benzene
Toluene

Fig. 7. Bar chart comparing the roundtrip energy cost per mole of carrier
Table 5

molecule, the loss-corrected LHV per mole of transported hydrogen, and the
roundtrip efficiency.

10
 M. Otto et al.
Table 6
Risk evaluation of the hydrogen carrier and hydrogenated carrier molecules.
Chemical name Melting Boiling Flash Hazard NFPA Statutes DOT Haz Class IDLH [ppm] Water LEL to Incompatibilities Notes
(CAS#) point point point classification [136,145,146] & Packing [147] Solubility UEL
(Physical State @ STP) (◦ C) (◦ C) (◦ C) (UN ID) [143] Group [143] [%] [%]
(ERG#) [144]

Hydrogen (1333–74-0) − 259 − 253 − 253 Flamm. Gas Flamm. DHS STQr = 10,000 2.1 N.D. N/A 4, Titanium, Tank embrittlement -
(Gas) UN ID 1049 ERG gas lbs., EPCRA = 10,000 N/A 75 Oxidizers, Lithium, tank certification
#115 lbs., RMP - CAA 112r Halogens expenses [137], 100 m
TQ = 10,000 lbs (330 ft) initial
evacuation [144],
Special Provision N89 -
steel UN pressure
receptacle must bear the
“H” mark
Nitrogen (7727-37-9) (Gas) − 214 − 196 N/A Simple Asphyx. Non- EPCRA = 10,000 lbs 2.2 N/A N/A N/A N/A Cryogenic storage has
UN ID 1066 flamm. N/A additional hazards
ERG # 121
Carbon dioxide (124–38-9) − 79 N/Aa N/A Simple Asphyx. Non- EPCRA = 10,000 lbs 2.2 40,000 ~0.2 N/A N/A Refrigerated Liquid,
(Gas) UN ID 1013 ERG flamm. N/A Storage has additional
# 120 hazards
Benzene (71–43-2) (Liquid) 6 80 − 11 Flamm. Liq., Class IB CERCLA RQ = 10 lbs. 3 500 0.07 1.4, 8 Acids, Bases, Carcinogen with low
Carcinogen, Acute EPCRA 313 TRI, RQ II (Carcinogen) Halogens, Strong reportable quantity
Env Haz, Chronic 18 lbs. EPCRA = oxidizing agents, (outdoor release), Low
Env Haz, 10,000 lbs. RCRA Metallic salts IDLH, Vapors will travel
UN ID 1114 U019 along low-lying areas
ERG #130 and concentrate; no
dissipation.
11

Toluene (108–88-3) − 95 111 4 Flamm. Liq., Class IB CERCLA RQ = 1000 3 500 0.07 1.27, Oxidizers Reproductive Hazard,
(Liquid) Reproductive Haz, lbs. EPCRA 313 TRI II 7.1 Low IDLH, Vapors will
Chronic Env Haz, RCRA U220 travel along low-lying
UN ID 1294 ERG areas and concentrate;
# 130 no dissipation.
1,3-dimethylbenzene − 48 139 29 Flamm. Liq., Class IC CERCLA RQ = 1000 3 900 slight 1.1, 7 Oxidizers Recognized
(synonym: m-Xylene) Acute Tox, Acute lbs. EPCRA 313 TRI III Environmental hazard.
(108–38-3) (Liquid) Env Haz, Chronic RCRA U239 May be a reproductive
Env Haz, UN ID hazard. Low IDLH,
1307 ERG # 130 Vapors will travel along
low-lying areas and
concentrate; no
dissipation.
1,2,4-trimethylbenzene − 44 168 44 Flamm. Liq., Class II EPCRA 313 3 25 (NIOSH) 0.01 0.9, Oxidizers
(synonym: Acute Tox, Skin TRIEPCRA 10,000 lbs III 6.4
Pseudocumene) (95–63- Corr/Irritant,
6) (Liquid) Serious Eye

Journal of Energy Storage 55 (2022) 105714

Damage/Irritant,
STOTb –
Respiratory
UN ID 1993ERG #
128
1,2,3,4-tetramethylbenzene 26 203 68 Flamm. Liq., Class III EPCRA 10,000 lbs Combustible/ N.D. N/A N.D. Oxidizers * info from SDS review,
(488–23-3) (Liquid) Acute Tox, Skin Non-Reg Not fully characterized
Corr/Irritant, III
Serious Eye
Damage/Irritant,
STOT –
Respiratory
(continued on next page)
 M. Otto et al.
Table 6 (continued )
Chemical name Melting Boiling Flash Hazard NFPA Statutes DOT Haz Class IDLH [ppm] Water LEL to Incompatibilities Notes
(CAS#) point point point classification [136,145,146] & Packing [147] Solubility UEL
(Physical State @ STP) (◦ C) (◦ C) (◦ C) (UN ID) [143] Group [143] [%] [%]
(ERG#) [144]

UN ID N/AERG #
N/A
1,2,4,5-tetramethylbenzene 79 197 54 Flamm. Solid Flamm. EPCRA 10,000 lbs 4.1 N.D. 3.48 mg/L N/A Oxidizers
(synonym: Durene) UN ID 1325 ERG Solid II
(95–93-2) (Solid) # 133
Pentamethylbenzene 53 231 91 Flamm. Solid, Flamm. EPCRA 10,000 lbs 4.1 N.D. N/A N/A Oxidizers * info from SDS review,
(700–12-9) (Solid) Skin Irritant, Eye Solid TSCA listed III Not fully characterized
Irritant
UN ID 1325ERG #
133
Hexamethylbenzene 165 264 129 Not classified Non-haz EPCRA 10,000 lbs. Non-Reg N.D. insol N/A Oxidizers * info from SDS review,
(synonym: mellitene) (GHS), Non- TSCA listed** III Not fully characterized
(87–85-4) combustible solid **TSCA conflicting
(Solid) UN ID N/AERG # information
N/A
Formic Acid (90 % aq. 8 101 69 Corrosive, Flamm. Class II CERCLA RQ = 5000 8 (3) 30 misc 18, 57 Oxidizers, Bases,
solution) (64–18-6) Liq., Acute Toxic lbs. EPCRA 313 TRI II Conc. Sulfuric
(Liquid) UN ID 1779 ERG RCRA U123 Acid, Active
# 153 Metals, Cyanide
Cyclohexane (110–82-7) 7 81 − 20 Highly Flamm., Class IB CERCLA RQ = 1000 3 1300 (10 % insol 1.3, Oxidizers, Rubber, REACH use restricted,
(Liquid) Irritant, Chronic lbs. EPCRA 313 TRI II LEL) 8.4 Plastics 57, 75
Aquatic Haz RCRA U056 CWA RQ Marine pollutant
UN ID 1145ERG # = 1000 lbs (IMDG)
128
12

Methylcyclohexane − 126 101 − 4 Highly Flamm., Class IB EPCRA 10,000 lbs 3 1200 (LEL) insol 1.1, Plastics Marine pollutant,
(108–87-2) (Liquid) Irritant, Chronic II 6.7
Aquatic Haz Though not considered
UN ID 2296 a DOT marine pol
ERG # 128
1,2-dimethylcyclohexane N/A 127 9 Flamm., Irritant, Class IB EPCRA 10,000 lbs 3 N.D. insol N.D. Oxidizers * info from SDS review,
(cis- and trans-) (583–57- Aspiration Tox, II Not fully characterized
3) (Liquid) Chronic Aquatic
Tox
UN ID 2263 ERG
# 128
1,2,3-trimethylcyclohexane N/A 151 Highly Flamm., Class IB EPCRA 10,000 lbs 3 N.D. insol N.D. Oxidizers * info from SDS review,
(1678-97-3) (Liquid) (Health Haz N.D.) II Not fully characterized
UN ID 3295 ERG
# 128
1,2,3,4- N/A 84 40.5 Flamm. Class II EPCRA 10,000 lbs N.D. N.D. N.D. N.D. N.D. * info from CAS

Journal of Energy Storage 55 (2022) 105714

tetramethylcyclohexane UN ID N/AERG # N.D. Common Chemistry
(3726-45-2) (Liquid) N/A review,
Not fully characterized
1,2,3,4,5- N/A 176.7 52.5 Flamm. Class II EPCRA 10,000 lbs N.D. N.D. N.D. N.D. N.D. * Not fully characterized
pentamethylcyclohexane UN ID N/AERG # N.D.
(1839-64-1) (Liquid) N/A
1,2,3,4,5,6- N/A 192.5 63.9 Flamm. Class EPCRA 10,000 lbs N.D. N.D. N.D. N.D. N.D. * Not fully characterized
hexamethylcyclohexane UN ID N/A ERG # IIIA N.D.
(1795–13–7) (Liquid) N/A
Ammonia (anhydrous) − 78 − 33 N/A Corrosive Gas, treated DHS STQr = 10,000 2.2* 300 34 15, Oxidizers, Corrosive to copper &
(7664-41-7) (Liquid) (gas) Poison Gas as flamm lbs. (≤1 %) EPCRA N/A 25 Acids, galvanized surfaces,
gas* 302 (EHS) TPQ 500 Halogens * classified as a 2.3
(continued on next page)
M. Otto et al. Journal of Energy Storage 55 (2022) 105714

carcinogenic, explosive, and so on complemented by the introduction of

Liquid to Gas expansion

outliers and high/low-risk substances.

(toxic gas) for air and

A review of benzene and substituted benzenes reveals not only

maritime shipments
flammability but that the liquids pose a risk to health and the environ­

ratio: 1 to 627
ment. The substituted cyclohexanes produced through full hydrogena­
tion of aromatic carriers are more benign. While they are flammable, the
Notes

more well-characterized species appear to avoid some of the deleterious

effects seen with aromatic molecules.
Formic acid appears to be an attractive industrial byproduct.
Though, adoption may be limited by the classification as a flammable,
Incompatibilities

corrosive liquid with exposure concerns; the molecule has a permissible

exposure limit of 5 ppm and is immediately dangerous to life and health
Halogens,

Halogens,
Oxidizers

Oxidizers
(IDLH) at 30 ppm. In contrast, ammonia is reported to be IDLH at 300
ppm.
The three gaseous species (ammonia, methane, and refrigerated
LEL to

methane) present a challenge beyond health and environmental con­

UEL
[%]

15

15

cerns. All are listed in the Chemical Facility Anti-Terrorism Standards

5,

5,

(CFATS) by the Department of Homeland Security [136] as a release

Solubility

hazard at concentrations ≤1 %. This may be a small concern, however,

Water

as hydrogen is also similarly regulated by the Department of Homeland

[%]

3.5

3.5

Security.
A dedicated comprehensive discussion on hydrogen and liquid
IDLH [ppm]

hydrogen safety can be found in [137] and the U.S. Department of En­
ergy provides an extensive database for Hydrogen Safety, Codes, and
20,000

20,000
[147]

Standards [138]. From a general survey of the available literature, codes

and standards, and regulations, it appears that the regulatory environ­
ment is very segmented and varying standards exist across the globe.
DOT Haz Class

Choosing a fuel source becomes a challenge in a globalized world and

Group [143]
& Packing

across continents applications such as air travel and shipping. It is

imperative to harmonize international standards and develop unified
N/A

N/A
2.1

2.1

building and equipment standards.

= 100 lbs. RMP - CAA

lbs. (≤1 %)RMP - CAA

112r TQ = 10,000 lbs

112r TQ = 10,000 lbs

lbs. EPCRA 304 RQ =
100 lbs. CERCLA RQ

DHS STQr = 10,000

DHS STQr = 10,000

lbs. (≤1 %) RMP -

3.5. A few words on hydrogen material compatibility

CAA 112r TQ =
[136,145,146]

10,000 lbs

Material compatibility with hydrogen is key for all applications.

Statutes

Hydrogen embrittlement is typically discussed in the context of trans­

portation through pipelines [139] but a discussion of other typical
metals and their alloys are required. The book by Gangloff and Somer­
day [140] provides an excellent overview of hydrogen embrittlement in
flamm

flamm
NFPA

a variety of materials including aluminum, titanium, and nickel-based

gas

gas

super alloys.
Aluminum and its alloys are typical aircraft materials due to their
UN ID 1005 ERG

UN ID 1971 ERG

UN ID 1972 ERG
Cryogen, Strong
Strong reducing

low weight. It is reported that aluminum and its alloys are not prone to
reducing agent
(UN ID) [143]
(ERG#) [144]
classification

Flamm. Gas,

Flamm. Gas,

hydrogen embrittlement [141]. The same cannot be said for titanium

and its alloys which are also lightweight but high-temperature
Hazard

# 125

# 115

# 115
agent

compatible: higher hydrogen concentrations promote a rapid ductile

to brittle transition through the formation of titanium hydrides
[140,142].
− 188

− 188
Flash
point
(◦ C)

Nickel-based superalloys are another key component for hot gas path
components in modern gas turbines which do not follow a specific trend.
Some superalloys are relatively unaffected by hydrogen embrittlement
Boiling

− 162

− 162
point

whereas others such as Inconel 718 experience severe embrittlement.

(◦ C)

Additional details can be found in the aforementioned book by Gangloff

and Somerday [140].
Melting

Another key component in aviation and power generation gas tur­

− 165

− 165
point
(◦ C)

Single Target Organ Toxicity.

bines is thermal barrier coating (TBC). From a materials standpoint, it is

also noteworthy that the higher water content in the exhaust gas of a
Methane, refrigerated liquid
(cryo.) (74–82-8) (Liquid)

hydrogen-powered gas turbine can cause moisture-induced TBC spall­

Methane (74–82-8) (Gas)

ation [148,149] and premature component failure due to an increased

(Physical State @ STP)
Table 6 (continued )

heat load on the metal substrate as TBC is partially transparent to the

altered radiative spectrum of heated water vapor.
Chemical name

Sublimes.

In addition to embrittlement, the fact that many metals act as a

catalyst for hydrogen cannot be neglected either: Hydrogen's flash point,
(CAS#)

as tabulated in Table 6, is above its boiling point which can cause im­
mediate combustion; this reaction is catalyzed by many common metals.
b
a

13
M. Otto et al. Journal of Energy Storage 55 (2022) 105714

Table 7
Listing of use cases and associated key parameters related to hydrogen.
Case# Type Fuel Consumption Fuel Consumption Water requirement Anticipated Storage Volume [m3]
conventional [t] Hydrogen Equivalent [t] [1000 l]
H2 @ 350 H2 @ 690 LH2b Li-Ion LNH43
bara bar3 Battery

1 5 MW PP 199 78 704 3339 2082 1103 3562 814.6

(SC)
2 44 MW 1400 550 4956 23,506 14,656 7767 25,077 5734
(SC)
3 260 MW 8347 3276 29,543 140,112 87,360 46,298 149,475 34,184
(SC)
4 737 MAX 6.587 2.393 21.6 102.4 63.8 33.8 109.2 25
5 A320neo 5.783 2.101 18.9 89.9 56 29.7 95.9 22
6 Truck 0.255 0.054 0.49 2.31 1.44 0.76 1.4 0.56
Germany
7 Truck USA 0.403 0.085 0.77 3.66 2.28 1.21 2.22 0.89
8 Cargo Ship 3000 1.045 9423 44,694 27,867 14,769 51,605 10,904
a
Does not consider pressurized tank.
b
Does not consider insulation or cryocooler system.

3.6. Use case specific optimized hydrogen strategy required which reduces the overall efficiency of the turbine plant.
Synthetic fuels appear not to be ideal for power plant applications and
The final segment ties the findings together and discusses safety, are more suitable for applications that are harder to decarbonize such as
energetic requirements, and technology challenges in the context of the aviation. The cost of Fischer Tropsch synthetic fuels is on the order of
introduced use cases. Table 7 summarizes the calculation results. It is $3.60–9.20 per gallon according to Li [152]. This is about three times
found that the required quantities of hydrogen vary wildly between the cost of current gasoline prices. The main cost driver is the cost of
several kilograms for truck uses, to a couple of tons for airplanes, to electricity to make the e-fuel in the first place. Power generation as a
thousands of tons for power generation backup fuel. Considering that stationary system does not require the flexible transportation advan­
the mass of hydrogen in water is just above 11 %, the corresponding tages of e-fuels. Hence, the extra premium to be paid for such fuels is not
water requirements become staggering and a major consideration for justified for this use case.
large-scale applications. Not unsubstantial is the amount of water needed as shown in Table 7.
The first batteries had energy densities in the order of 11 Wh/kg. One week at full load requires between 704,000 to almost 30,000,000 l
Today, roughly 150 years later, best-in-class batteries can achieve 300 of water to produce the required hydrogen. Since access to water is still a
Wh/kg and the growth over time is more linear than exponential [150]. major concern for many people around the globe, and the fact that many
Diesel supplies two orders of magnitude more power at 13,750 Wh/kg. gas turbine plants are located in arid sections of the world, the water
For the same amount of energy, a multiple of mass (and volume) is consumption issue is critical when considering the hydrogen economy.
required. According to the data in Fig. 8 through Fig. 11, the volume Novel cycle designs that aim to recycle the water from the exhaust gas
requirements also change drastically with the choice of energy carrier. could be a mitigation strategy [153] but are based on different archi­
Once hydrogen, with or without a carrier, is delivered to its intended tectures and hardware than gas turbines. Therefore, they do not permit
use, a multitude of options exist for how the hydrogen or its carrier, the reuse of existing infrastructure.
respectively, can be used. It will be shown that the dehydrogenation If hydrogen cannot be produced on-site, the fuel has to be trans­
process, the difference between Pathways 2 and 3, is not necessary and ported to the plant either in the form of pure hydrogen through pipelines
technology exists to also make the hydrogenated molecule useable. The (with the previously mentioned challenge of hydrogen embrittlement)
implications thereof and the mitigation strategies are additionally dis­ or hydrogen carried by another molecule or means. All alternative
cussed in the following segment. pathways require hydrogenation and/or dehydrogenation roundtrip
efficiency losses that can account for significantly decreased overall
3.6.1. Power generation efficiency resulting in elevated operational cost for fuel; already the
For a seven days reserve fuel backup range, the storage footprints are major cost associated with gas turbine power plants. The immediate
displayed comparatively in Fig. 8 for the Li-Ion battery systems in black, toxicity of a carrier gas might be a secondary concern as most power
to pressurized hydrogen at 350 and 690 bars, respectively, in blue and plants are located in densely populated remote areas, however, some
red, to liquefied hydrogen in green, and eventually ammonia in black. vapors are heavier than air and collect on the ground without much
The required space for an assumed cube range between 15 × 15 meters diffusion. Additionally, the marine pollution potential has to be
for a 5 MW nameplate gas turbine to 55 × 55 meters for a 260 MW gas considered since many plants require access to rivers or oceans to pro­
turbine. Compressed hydrogen requires a similarly large storage volume vide cooling water for turbomachinery equipment.
compared to battery systems. The liquid hydrogen and ammonia-based If power cannot be generated by other renewable means, or energy
storage approaches significantly reduce the volume requirements, storage is required over longer durations, hydrogen without a carrier is
respectively. Both seem to be interesting solutions as hydrogen and the ideal vector for power generation applications.
ammonia can be burned directly, mixed, or blended with natural gas
with minor to moderate changes to the gas turbine assets [151]. Here, 3.6.2. Aircraft
the storage approach utilizing e-methanol, meaning hydrogen produced Rather than swapping Jet A-1 in favor of hydrogen in the aircraft
from renewable energy sources undergoing the Sabatier reaction, can be turbine engine, an airplane could also be propelled by a fuel cell that
promising as it is very similar to today's natural gas. powers an electric motor that in turn moves a propeller for thrust. The
At this scale, however, the negative energetics of this reaction could fuel conversion efficiency of a fuel cell is comparable to an aircraft en­
make the fuel too expensive for commercial operation. The same reason gine with both approximately 50 % [154,155], respectively. This means
prohibits the use of other carriers introduced in this paper. Although the that the same amount of hydrogen fuel is required for a hybrid electric
hydrogenation reaction is exothermic, formic acid and the other carbon- propelled and combustion engine propelled aircraft under the assump­
based carrier molecules cannot be burned directly. Dehydrogenation is tions given. It is understood that the fuel-cell hydrogen system could be

14
M. Otto et al. Journal of Energy Storage 55 (2022) 105714

Fig. 8. Volume requirements for various storage methods and gas turbines sizes
(black = NH3, green = LH2, red = H2@690 bars, blue = H2@350 bars, yellow
= Li-ion Battery). (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)

substituted in favor a of battery system utilizing the same turboprop

propulsion technology. It should be noted that turboprop engines ach­
ieve similar propulsive efficiencies as modern high-bypass engines,
however, peak efficiencies occur at much lower cruise velocities. In fact,
80 % propulsive efficiency is achieved around 350 and 500 mph
airspeed for turboprop and high-bypass turbo jet engines, respectively
[156]. Hence, it can be concluded that (hybrid)electric aircraft are
suitable for smaller and short distances whereas hydrogen-powered
turbojet aircraft are preferred for longer distances and faster cruise
speeds.
One liter of kerosene contains as much energy as 3000 l of hydrogen
at ambient pressure and temperature, 6 l at 600 bar, or 4 l of hydrogen
liquefied at − 253 ◦ C. Volume aspects cannot be neglected when
considering commercial airliners as the number of passengers in the
aircraft cannot be reduced in favor of additional fuel storage as it would
increase the fuel consumption per passenger mile and the cost per ticket.
The data presented in Fig. 9 visualizes the storage size for the various
hydrogen carrier approaches benchmarked against a Li-Ion battery. The
battery in yellow is the least space-effective solution not to mention the
large weight associated with it. Further, compressed gaseous hydrogen
at different pressure levels has slightly decreasing volume requirements.
The weight-associated challenges of the fuel storage systems related
to pressurized hydrogen or insulation and refrigeration system for liq­
uefied hydrogen are discussed in [109] and a novel approach leveraging
ammonia's high boiling point is introduced and followed by a compre­
hensive analysis of ammonia production emissions in contrast to sus­
tainable aviation fuels (SAF). This is due to the fact that liquid ammonia
presents very volume-effective hydrogen storage with the potential of
conformal tanks as no complicated cryocooling system is required nor
are heavy and round vessels. Furthermore, according to their study,
ammonia can be used as an aircraft fuel with several benefits, for
example, it stays as a liquid at cruising altitude without the need for
cooling. Further, cracking ammonia to hydrogen is an endothermic
process. The provided heat can be utilized to cool the compressor exit
flow or for cooling the internal passages of the turbine airfoils. It is re­
ported that efficiency increases following this strategy are expected.
Nitrogen is a major component of the air's composition; therefore,
releasing the byproduct of the cracking process is feasible. This is not the
case for toluene and benzene; their cracking would not reduce the
overall mass since the byproducts have to be returned to the ground for
re‑hydrogenation. Also, the aromatic hydrocarbons exhibit a much
lower mass fraction of hydrogen per unit carrier so it is disqualified for
further aerospace application considerations.
Whilst Airbus is heavily pursuing a pure hydrogen strategy, Sus­
tainable Aviation Fuel (SAF) is a viable solution in the transition period
or for long-haul flights. The explosivity of hydrogen is certainly a
concern for the aviation industry on the ground- and in particular flight
operations. Instead of explosivity, the toxicity of ammonia is a challenge
despite its benefits.
It is challenging to identify a clear ideal carrier for aircraft. E-fuels,
hydrogen itself, and ammonia are all suitable candidates with their
respective advantages and drawbacks.

3.6.3. Ground and ship transportation

Using the stored energy to move the vehicle is the main purpose for
the transportation use cases. The question of which propulsion strategy
is eventually chosen is not a straightforward decision. In the case of
trucks, four major avenues can be considered for hydrogen and its car­
riers: (1) burn the carrier directly if possible e.g. LNH3 [157,158], (2)
supply the carrier directly to a fuel cell as again possible for ammonia-

(caption on next column)

15
M. Otto et al. Journal of Energy Storage 55 (2022) 105714

Fig. 9. Volume requirements for various storage methods and aircraft types Fig. 10. Volume requirements for various storage methods and Transportation
(black = NH3, green = LH2, red = H2@690 bars, blue = H2@350 bars, yellow scenarios in Europe and USA (green = LH2, red = H2@690 bars, Blue =
= Li-ion Battery). (For interpretation of the references to color in this figure H2@350 bars, yellow = Li-ion Battery). (For interpretation of the references to
legend, the reader is referred to the web version of this article.) color in this figure legend, the reader is referred to the web version of
this article.)

based systems [159], or crack ammonia to hydrogen and nitrogen and

(3) power a fuel cell of hydrogen, or (4) burn hydrogen directly in a combusted. These options are mainly open for methane, formic acid, and
combustion engine. Avenues (3) and (4) are probably the most common ammonia where the former two still emit CO2 and soot. The U.S.
concepts and are well researched. The challenges of higher thermal NOx Department of Energy places the technology readiness level (TRL) of
concentrations, however, have already been brought up in this paper ammonia in gas turbines at 1–2 whereas other sources indicate TRL 4–5
[151,160]. Options (1) and (2) are interesting as no negative energy [161]. The internal combustion engine for ammonia that is currently
penalty through endothermic dehydrogenation has to be added to the under development is considered more mature with TRL 9 [161–163]
system energetics. Admittedly, not all of the proposed carriers can be and is also considered for marine two-stroke engines [164] by e.g. MAN

16
M. Otto et al. Journal of Energy Storage 55 (2022) 105714

transportation of the fuel consumed by the carrier is of interest, but also

fuel as cargo. High volumetric storage densities enable the transport of
larger quantities of fuel per vehicle. This can significantly reduce the
cost of transportation and provide a different perspective on the data
presented in Fig. 10 and Fig. 11. For example, the cost of shipping liquid
ammonia from the coast of Australia 20,000 km to the port of Rotterdam
is in the order of 6–8 Euro Cents per kilogram, making it an economi­
cally competitive hydrogen carrier. Besides the volumetric density,
cooling requirements are also of concern as they increase the energy
requirement of fuel consumption of the transportation vessel unless
passive cooling is possible which most likely causes weight penalties. It
could be concluded that ammonia is a strong candidate for marine
shipping, a result that is corroborated by other studies [164,173]. In
contrast to marine shipping, the fuel requirements for transportation of
goods on the road are much smaller amounts of fuel as shown in Table 7
and in Fig. 10. Thus, it can be assumed that weight penalties for pres­
surized or cryogenic hydrogen storage or the larger storage volume are
not as critical as for the other use cases. Consequently, hydrogen appears
to be the ideal fuel for road transportation. However, safety aspects and
boil-off amongst others indicate that hydrogen might not be ideal to be
transported. Tube trailers for hydrogen transportation are common but
come at a high cost [174] as shown in Table 8. The key takeaway here is
that the transmission and storage costs of ammonia are each about one
order of magnitude lower than for hydrogen.
Table 8, adapted from the ARPA-E's REFUEL program (DE-FOA-
0001562), provides a comparative cost analysis of gasoline, hydrogen,
Fig. 11. Volume requirements for various storage methods for cargo ships ammonia, and electricity. The primary references and pertaining as­
traveling between Shanghai and Rotterdam (black = NH3, Green = LH2, red = sumptions can be found in the corresponding solicitation [175] and
H2@690 bars, blue = H2@350 bars, yellow = Li-ion Battery). (For interpreta­ accompanying material [176].
tion of the references to color in this figure legend, the reader is referred to the
web version of this article.) 4. Conclusions

The need for energy storage and transportation is clear as fossil fuels
Table 8 are phased out. The advantages and disadvantages of mechanical energy
Comparative cost analysis of gasoline, hydrogen, ammonia, and electricity
storage and battery energy storage were discussed and compared against
adapted from ARPA-E REFUEL [175].
chemical energy storage centered around hydrogen, which is touted to
Gasoline Hydrogen Ammonia Electricity be an integral part of a carbon-emission-free future. Hydrogen storage
Fuel cost [$/kg] 0.54 1.95 0.325 and transportation challenges were identified. Carrier molecules were
Fuel cost, [$/kWh] 0.047 0.058 0.063 0.065 introduced to mitigate the main challenges, including high flamma­
Transmission Cost [$/kWh] 0.001 0.06 0.004 0.038
bility, volatility, low volumetric energy density, and system re­
Storage Cost [$/kWh] 0.001 0.03 0.007 0.160
Conversion Efficiency [%] 30 55 55 92
quirements arising from cryogenic storage conditions. It was found that
Source-to-use energy cost hydrogen carriers can be used along three pathways that are combina­
0.159 0.292 0.135 0.285
[$/kWh] tions of hydrogenation and dehydrogenation reactions. Disparities be­
tween the round-trip energetics of the carriers were found; however,
catalysts play a major role to bridge that gap. Scenarios surrounding
Energy Solutions [165]. Their technical approach also includes selective power generation, aviation, shipping, and trucking were defined and
catalytic reduction (SCR) as proposed for ammonia aircraft engines discussed in terms of hydrogen challenges, energetics, and safety as well
[109] and is already industry standard in the field of power generation as the existing technological challenges. Furthermore, this review paper
for NOx control. The topic of ammonia combustion is extensively dis­ put a particular focus on the safety aspect of the carrier and hydroge­
cussed in [166]. nated molecules and changes required to the use case systems to be
In this context, it is also imperative to discuss the implications of suitable for hydrogen and its potential carriers. It was found that no
hydrogen purity. Whereas combustion processes are relatively robust to ideal hydrogen carrier exists, and each application is a trade-off of
small mole fractions of gaseous carrier molecules such as ammonia, multiple advantages and disadvantages that can be regionally different:
methanol, etc. [151,167], fuel cells require high purity hydrogen to
prevent the degradation of the fuel cell catalyst [168]. This limits the • Power generations can draw the largest benefits from the use of
carrier choice for high-purity applications as cracking and reconversion hydrogen directly.
of the carrier to hydrogen is never 100 % efficient [109]. • Aviation is challenging to decarbonize with many roadblocks. E-
Alternatively, as proposed in approach (2), methane, formic acid fuels, hydrogen, and ammonia as a carrying vector come with their
[169], and ammonia can be theoretically used for fuel cells. Methane advantages and disadvantages. At this point, no ideal hydrogen
fuel cells require operational temperatures above 650 ◦ C [170]. The carrier can be named.
choice of materials in this range becomes an issue alongside carbon • Trucking requires only relatively small amounts of hydrogen
depositions [171]. Formic acid fuel cells have a very high power density compared to all other use cases. Here, the direct storage of hydrogen,
and show potential for micro-power generation according to [172]. either cryogenic or compressed, appears to be the most suitable and
Details on the state and outlook of ammonia fuel cells can be found in economical solution in conjunction with the high purity re­
[159] which suffer from low power densities and long-term stability. quirements of fuel cells.
In the light of ground transportation and shipping, not only the

17
M. Otto et al. Journal of Energy Storage 55 (2022) 105714

• In the case of marine shipping, ammonia's volumetric and combus­ [25] E. Ninnemann, et al., New insights into the shock tube ignition of H2/O2 at low to
moderate temperatures using high-speed end-wall imaging, Combust. Flame 187
tion properties besides economic considerations make it the ideal
(2018) 11–21.
energy carrier. This is not only true for the consumed fuel itself but [26] M. Marinelli, M. Santarelli, Hydrogen storage alloys for stationary applications,
also as a carrier to transport green energy and hydrogen. J. Energy Storage 32 (2020), 101864.
[27] Y. Zhang, Q. Hua, L. Sun, Q. Liu, Life cycle optimization of renewable energy
systems configuration with hybrid battery/hydrogen storage: a comparative
Declaration of competing interest study, J. Energy Storage 30 (2020), 101470.
[28] M. Kaur, K. Pal, Review on hydrogen storage materials and methods from an
electrochemical viewpoint, J. Energy Storage 23 (2019) 234–249.
The authors declare that they have no known competing financial [29] F. Klumpp, Comparison of pumped hydro, hydrogen storage and compressed air
interests or personal relationships that could have appeared to influence energy storage for integrating high shares of renewable energies—potential, cost-
comparison and ranking, J. Energy Storage 8 (2016) 119–128.
the work reported in this paper. [30] S. Shafiee, E. Topal, When will fossil fuel reserves be diminished? Energy Policy
37 (1) (2009) 181–189.
Data availability [31] R. Wüstenhagen, M. Bilharz, Green energy market development in Germany:
effective public policy and emerging customer demand, Energy Policy 34 (13)
(2006) 1681–1696.
Data will be made available on request. [32] B. Lin, X. Li, The effect of carbon tax on per capita CO2 emissions, Energy Policy
39 (9) (2011) 5137–5146.
[33] M. Wara, Is the global carbon market working? Nature 445 (7128) (2007)
Acknowledgment 595–596.
[34] P.C. Stern, K.B. Janda, M.A. Brown, L. Steg, E.L. Vine, L. Lutzenhiser,
M. Otto like to further acknowledge the support from UCF's Preem­ Opportunities and insights for reducing fossil fuel consumption by households
and organizations, Nat. Energy 1 (5) (2016) 1–6.
inent Postdoctoral Program (P3).
[35] H. Heubaum, F. Biermann, Integrating global energy and climate governance: the
changing role of the international energy agency, Energy Policy 87 (2015)
References 229–239, https://doi.org/10.1016/j.enpol.2015.09.009.
[36] S.S. Ravi, M. Aziz, Clean hydrogen for mobility – quo vadis? Int. J. Hydrog.
Energy 47 (47) (2022) 20632–20661, https://doi.org/10.1016/j.
[1] D.H. Meadows, J. Randers, D.L. Meadows, The Limits to Growth (1972), Yale
ijhydene.2022.04.158.
University Press, 2013.
[37] O. Faye, J. Szpunar, U. Eduok, A critical review on the current technologies for
[2] R.B. Barsky, L. Kilian, Oil and the macroeconomy since the 1970s, J. Econ.
the generation, storage, and transportation of hydrogen, Int. J. Hydrog. Energy 47
Perspect. 18 (4) (2004) 115–134.
(29) (2022) 13771–13802, https://doi.org/10.1016/j.ijhydene.2022.02.112.
[3] B.C. Farhar, Trends in US public perceptions and preferences on energy and
[38] R.R. Ratnakar, et al., Hydrogen supply chain and challenges in large-scale LH2
environmental policy, Annu. Rev. Energy Environ. 19 (1) (1994) 211–239.
storage and transportation, Int. J. Hydrog. Energy 46 (47) (2021) 24149–24168,
[4] F.N. Laird, C. Stefes, The diverging paths of german and United States policies for
https://doi.org/10.1016/j.ijhydene.2021.05.025.
renewable energy: sources of difference, Energy Policy 37 (7) (2009) 2619–2629.
[39] N. Gray, S. McDonagh, R. O'Shea, B. Smyth, J.D. Murphy, Decarbonising ships,
[5] J. Benemann, Hydrogen biotechnology: progress and prospects, Nat. Biotechnol.
planes and trucks: an analysis of suitable low-carbon fuels for the maritime,
14 (9) (1996) 1101–1103.
aviation and haulage sectors, Adv. Appl. Energy 1 (2021), 100008, https://doi.
[6] A. Züttel, A. Remhof, A. Borgschulte, O. Friedrichs, Hydrogen: the future energy
org/10.1016/j.adapen.2021.100008.
carrier, Philos. Trans. R. Soc. A Math. Phys. Eng. Sci. 368 (1923) (2010)
[40] A. Kahan, EIA Projects Nearly 50% Increase in World Energy Usage by 2050, Led
3329–3342.
by Growth in Asia, Available:, EIA, 2019 https://www.eia.gov/todayinener
[7] D. Gately, M. Adelman, J.M. Griffin, Lessons from the 1986 oil price collapse,
gy/detail.php/id=41433.
Brook. Pap. Econ. Act. 1986 (2) (1986) 237–284.
[41] Enerdata. "Share of wind and solar in electricity production." https://yearbook.
[8] D.J. Murphy, C.A. Hall, Energy return on investment, peak oil, and the end of
enerdata.net/renewables/wind-solar-share-electricity-production.html (accessed
economic growth, Ann. N. Y. Acad. Sci. 1219 (1) (2011) 52.
11/30/2020, 2020).
[9] P. Newman, T. Beatley, H. Boyer, Resilient Cities: Responding to Peak Oil and
[42] P. Colbertaldo, S.B. Agustin, S. Campanari, J. Brouwer, Impact of hydrogen
Climate Change, Island Press, 2009.
energy storage on California electric power system: towards 100% renewable
[10] C. Parmesan, G. Yohe, A globally coherent fingerprint of climate change impacts
electricity, Int. J. Hydrog. Energy 44 (19) (2019) 9558–9576.
across natural systems, Nature 421 (6918) (2003) 37–42.
[43] V. Penney, How Texas' power generation failed during the storm, in: Charts, The
[11] S. Solomon, M. Manning, M. Marquis, D. Qin, Climate Change 2007-The Physical
New York Times, New York, NY, 2021.
Science Basis: Working Group I Contribution to the Fourth Assessment Report of
[44] P.R. White, J.D. Rhodes, E.J.H. Wilson, M.E. Webber, Quantifying the impact of
the IPCC, Cambridge University Press, 2007.
residential space heating electrification on the Texas electric grid, Appl. Energy
[12] N. Panwar, S. Kaushik, S. Kothari, Role of renewable energy sources in
298 (2021), 117113, https://doi.org/10.1016/j.apenergy.2021.117113.
environmental protection: a review, Renew. Sustain. Energy Rev. 15 (3) (2011)
[45] U.S. Department of Energy, Energy Storage Grand Challenge, Draft Roadmap,
1513–1524.
Available: https://www.energy.gov/sites/prod/files/2020/07/f76/ESGC%20Dr
[13] C.R. Matos, J.F. Carneiro, P.P. Silva, Overview of large-scale underground energy
aft%20Roadmap_2.pdf, 2020.
storage technologies for integration of renewable energies and criteria for
[46] A. Majumdar, J.M. Deutch, R.S. Prasher, T.P. Griffin, A framework for a hydrogen
reservoir identification, J. Energy Storage 21 (2019) 241–258.
economy, Joule 5 (8) (2021) 1905–1908, https://doi.org/10.1016/j.
[14] Z. Dostál, L. Ladányi, Demands on energy storage for renewable power sources,
joule.2021.07.007.
J. Energy Storage 18 (2018) 250–255.
[47] M. Otto, M. Sargunaraj, A. Riahi, J. Kapat, A novel long-duration hydrogen
[15] O. Palizban, K. Kauhaniemi, Energy storage systems in modern grids—matrix of
storage concept without liquefaction and high pressure suitable for onsite
technologies and applications, J. Energy Storage 6 (2016) 248–259.
blending, in: Presented at the ASME Turbo Expo 2021: Turbomachinery Technical
[16] M. Sterner, et al., "Storage demand in power supply," in handbook of energy
Conference and Exposition, Virtual, Online, June 7–11, 2021, 2021. GT2021-
storage, Springer (2019) 51–136.
59393.
[17] U.S. Energy Information Administration (EIA), Annual Energy Outlook 2020,
[48] S. Rehman, L.M. Al-Hadhrami, M.M. Alam, Pumped hydro energy storage system:
Available: https://www.eia.gov/outlooks/aeo/, 2020.
a technological review, J. Renew. Sustain. Energy 44 (2015) 586–598.
[18] U.S. Environmental Protection Agency, Inventory of U.S. Greenhouse Gas
[49] C.-J. Yang, R.B. Jackson, Opportunities and barriers to pumped-hydro energy
Emissions and Sinks: 1990-2019, Available:, United States Environmental
storage in the United States, Renew. Sustain. Energy Rev. 15 (1) (2011) 839–844.
Protection Agency, 2021 https://www.epa.gov/sites/production/files/2021-04/
[50] L. Scherer, S. Pfister, Global water footprint assessment of hydropower, Renew.
documents/us-ghg-inventory-2021-main-text.pdf.
Energy 99 (2016) 711–720, https://doi.org/10.1016/j.renene.2016.07.021.
[19] S.O. Amrouche, D. Rekioua, T. Rekioua, S. Bacha, Overview of energy storage in
[51] S. Pfister, L. Scherer, K. Buxmann, Water scarcity footprint of hydropower based
renewable energy systems, Int. J. Hydrog. Energy 41 (45) (2016) 20914–20927.
on a seasonal approach-global assessment with sensitivities of model assumptions
[20] K.T. Møller, T.R. Jensen, E. Akiba, H.-W. Li, Hydrogen-a sustainable energy
tested on specific cases, Sci. Total Environ. 724 (2020), 138188, https://doi.org/
carrier, Prog. Nat. Sci. Mater. Int. 27 (1) (2017) 34–40.
10.1016/j.scitotenv.2020.138188.
[21] M. Carmo, D.L. Fritz, J. Mergel, D. Stolten, A comprehensive review on PEM
[52] M. Mahmoud, M. Ramadan, A.-G. Olabi, K. Pullen, S. Naher, A review of
water electrolysis, Int. J. Hydrog. Energy 38 (12) (2013) 4901–4934.
mechanical energy storage systems combined with wind and solar applications,
[22] National Research Council and National Academy of Engineering, The Hydrogen
Energy Convers. Manag. 210 (2020), 112670.
Economy: Opportunities, Costs, Barriers, and R&D Needs, The National
[53] B. Dunn, H. Kamath, J.-M. Tarascon, Electrical energy storage for the grid: a
Academies Press, Washington, DC, 2004.
battery of choices, Science 334 (6058) (2011) 928–935, https://doi.org/10.1126/
[23] H. Afeefy, J. Liebman, S. Stein, in: P.J. Linstrom, W.G. Mallard (Eds.), Neutral
science.1212741.
thermochemical data in NIST Standard Reference Database Number 69, NIST
[54] H. Pan, Y.-S. Hu, L. Chen, Room-temperature stationary sodium-ion batteries for
Standard Reference Database Number 69, National Institute of Standards and
large-scale electric energy storage, Energy Environ. Sci. 6 (8) (2013) 2338–2360.
Technology, Gaithersburg MD, 2005.
[24] M. Louthan Jr., G. Caskey Jr., J. Donovan, D. Rawl Jr., Hydrogen embrittlement
of metals, Mater. Sci. Eng. 10 (1972) 357–368.

18
M. Otto et al. Journal of Energy Storage 55 (2022) 105714

[55] A. Bito, Overview of the sodium-sulfur battery for the IEEE Stationary Battery [89] M. Schlichtenmayer, B. Streppel, M. Hirscher, Hydrogen physisorption in high
Committee, in: IEEE Power Engineering Society General Meeting, 2005, IEEE, SSA microporous materials–a comparison between AX-21_33 and MOF-177 at
2005, pp. 1232–1235. cryogenic conditions, Int. J. Hydrog. Energy 36 (1) (2011) 586–591.
[56] T.C. Wanger, The lithium future—resources, recycling, and the environment, [90] B. Panella and M. Hirscher, Hydrogen physisorption in metal–organic porous
Conserv. Lett. 4 (3) (2011) 202–206. crystals, Adv. Mater. 17 (5) (2005) 538–541.
[57] L.S. Schell, J.G. Reed, L. Zhao, J. Brouwer, S. Samuelsen, Comparing the levelized [91] S.P. Shet, S.S. Priya, K. Sudhakar, M. Tahir, A review on current trends in
cost of returned energy (LCORE) values for hydrogen-based conversion pathways potential use of metal-organic framework for hydrogen storage, Int. J. Hydrog.
and batteries, ECS Trans. 96 (1) (2020) 43. Energy 46 (21) (2021) 11782–11803.
[58] H. Chen, T.N. Cong, W. Yang, C. Tan, Y. Li, Y. Ding, Progress in electrical energy [92] D. Teichmann, K. Stark, K. Müller, G. Zöttl, P. Wasserscheid, W. Arlt, Energy
storage system: a critical review, Prog. Nat. Sci. 19 (3) (2009) 291–312. storage in residential and commercial buildings via liquid organic hydrogen
[59] M. Aneke, M. Wang, Energy storage technologies and real life applications–a state carriers (LOHC), Energy Environ. Sci. 5 (10) (2012) 9044–9054.
of the art review, Appl. Energy 179 (2016) 350–377. [93] D. Teichmann, W. Arlt, P. Wasserscheid, R. Freymann, A future energy supply
[60] M. Beaudin, H. Zareipour, A. Schellenberglabe, W. Rosehart, Energy storage for based on liquid organic hydrogen carriers (LOHC), Energy Environ. Sci. 4 (8)
mitigating the variability of renewable electricity sources: an updated review, (2011) 2767–2773.
Energy Sustain. Dev. 14 (4) (2010) 302–314. [94] P.M. Modisha, C.N. Ouma, R. Garidzirai, P. Wasserscheid, D. Bessarabov, The
[61] W.B. Kirby, Linden's Handbook of Batteries, 5th edition, McGraw-Hill Education, prospect of hydrogen storage using liquid organic hydrogen carriers, Energy Fuel
York, 2019 (in en). 33 (4) (2019) 2778–2796, https://doi.org/10.1021/acs.energyfuels.9b00296.
[62] M. Skyllas-Kazacos, M. Chakrabarti, S. Hajimolana, F. Mjalli, M. Saleem, Progress [95] H. Tong, S. Ouyang, Y. Bi, N. Umezawa, M. Oshikiri, J. Ye, Nano-photocatalytic
in flow battery research and development, J. Electrochem. Soc. 158 (8) (2011) materials: possibilities and challenges, Adv. Mater. 24 (2) (2012) 229–251,
R55. https://doi.org/10.1002/adma.201102752.
[63] W. Wang, Q. Luo, B. Li, X. Wei, L. Li, Z. Yang, Recent progress in redox flow [96] P. Preuster, C. Papp, P. Wasserscheid, Liquid organic hydrogen carriers (LOHCs):
battery research and development, Adv. Funct. Mater. 23 (8) (2013) 970–986. toward a hydrogen-free hydrogen economy, Acc. Chem. Res. 50 (1) (2017)
[64] P. Alotto, M. Guarnieri, F. Moro, Redox flow batteries for the storage of 74–85.
renewable energy: a review, Renew. Sust. Energ. Rev. 29 (2014) 325–335. [97] C. Vogt, M. Monai, G.J. Kramer, B.M. Weckhuysen, The renaissance of the
[65] K.E. Rodby, T.J. Carney, Y.A. Gandomi, J.L. Barton, R.M. Darling, F.R. Brushett, Sabatier reaction and its applications on earth and in space, Nat. Catal. 2 (3)
Assessing the levelized cost of vanadium redox flow batteries with capacity fade (2019) 188–197.
and rebalancing, J. Power Sources 460 (2020), 227958. [98] H. Schulz, Short history and present trends of fischer-tropsch synthesis, Appl.
[66] C. Minke, M.A.D. Ledesma, Impact of cell design and maintenance strategy on life Catal. A Gen. 186 (1) (1999) 3–12, https://doi.org/10.1016/S0926-860X(99)
cycle costs of vanadium redox flow batteries, J. Energy Storage 21 (2019) 00160-X.
571–580. [99] M. Rueda, Ó. Benito-Román, A. Girella, P. Cofrancesco, C. Milanese, Hydrogen
[67] B. Venkataraman, S. Sudha, Vanadium toxicity, Asian J. Exp. Sci. 19 (2) (2005) storage properties of magnesium borohydride infiltrated in silica aerogel using
127–134. solvated and pressure methods, J. Energy Storage 31 (2020), 101674.
[68] D. Stolten, B. Emonts, Hydrogen Science and Engineering, 2 Volume Set: [100] K.T. Møller, et al., Complex metal hydrides for hydrogen, thermal and
Materials, Processes, Systems, and Technology, John Wiley & Sons, 2016. electrochemical energy storage, Energies 10 (10) (2017) 1645.
[69] C. Chen, Y. Lu, L. Xing, Levelling renewable power output using hydrogen-based [101] F. Schüth, B. Bogdanović, M. Felderhoff, Light metal hydrides and complex
storage systems: a techno-economic analysis, J. Energy Storage 37 (2021), hydrides for hydrogen storage, Chem. Commun. 20 (2004) 2249–2258.
102413. [102] N. Rusman, M. Dahari, A review on the current progress of metal hydrides
[70] M. Ducker, UTSR Panel Discussion, Large Scale Energy Storage, Available:, in: material for solid-state hydrogen storage applications, Int. J. Hydrog. Energy 41
University Turbine Systems Research Project Review MEETING, U.S. Department (28) (2016) 12108–12126.
of Energy, National Energy Technology Laboratory, Orlando, 2019 https://www. [103] B. Sakintuna, F. Lamari-Darkrim, M. Hirscher, Metal hydride materials for solid
netl.doe.gov/sites/default/files/2019-11/2019%20UTSR%20Project%20Review hydrogen storage: a review, Int. J. Hydrog. Energy 32 (9) (2007) 1121–1140.
%20Mtg/Panel%20Session/Michael%20Ducker.pptx. [104] C. TerMaath, E. Skolnik, R. Schefer, J. Keller, Emissions reduction benefits from
[71] R. Ahluwalia, T. Hua, J. Peng, R. Kumar, System level analysis of hydrogen hydrogen addition to midsize gas turbine feedstocks, Int. J. Hydrog. Energy 31 (9)
storage options, in: Proceedings of the 2008 US DOE Hydrogen Program Annual (2006) 1147–1158.
Merit Review, 2019. [105] I.A. Gondal, Hydrogen integration in power-to-gas networks, Int. J. Hydrog.
[72] J. Coleman, S. Bragg-Sitton, E. Dufek, An Evaluation of Energy Storage Options Energy 44 (3) (2019) 1803–1815.
for Nuclear Power, Idaho National Lab.(INL), Idaho Falls, ID (United States), [106] C. White, R. Steeper, A. Lutz, The hydrogen-fueled internal combustion engine: a
2017. technical review, Int. J. Hydrog. Energy 31 (10) (2006) 1292–1305.
[73] M.C. Lott, S.-I. Kim, C. Tam, D. Houssin, J. Gagné, Technology Roadmap: Energy [107] H. Eichlseder, T. Wallner, R. Freymann, J. Ringler, The potential of hydrogen
Storage, International Energy Agency (IEA), France, 2014. internal combustion engines in a future mobility scenario, in: SAE Technical
[74] D.D. Papadias, J.-K. Peng, R.K. Ahluwalia, Hydrogen carriers: production, Paper, 0148-7191, 2003.
transmission, decomposition, and storage, Int. J. Hydrog. Energy (2021), https:// [108] T. Wilberforce, et al., Developments of electric cars and fuel cell hydrogen electric
doi.org/10.1016/j.ijhydene.2021.05.002. cars, Int. J. Hydrog. Energy 42 (40) (2017) 25695–25734.
[75] S. Koohi-Fayegh, M.A. Rosen, A review of energy storage types, applications and [109] M. Otto, L. Vesely, J. Kapat, M. Stoia, N. Applegate, G. Natsui, Ammonia as an
recent developments, J. Energy Storage 27 (2020), 101047. aircraft fuel: thermal assessment from airport to wake, in: Turbo Expo: Power for
[76] A. Züttel, Materials for hydrogen storage, Mater. Today 6 (9) (2003) 24–33. Land, Sea, and Air, American Society of Mechanical Engineers, 2022.
[77] T. Hua, et al., Technical assessment of compressed hydrogen storage tank systems [110] L. Vesely, J. Kapat, C. Bringhenti, J.T. Tomita, M. Stoia, JK, sCO2 waste heat
for automotive applications, Int. J. Hydrog. Energy 36 (4) (2011) 3037–3049. recovery system for aircraft engines, in: Presented at the AIAA Scitech 2022
[78] C. Winnefeld, T. Kadyk, B. Bensmann, U. Krewer, R. Hanke-Rauschenbach, Forum, San Diego, CA & Virtual, January 3-7, 2022, 2022. AIAA 2022-1407.
Modelling and designing cryogenic hydrogen tanks for future aircraft [111] D. Kellari, E.F. Crawley, B.G. Cameron, Influence of technology trends on future
applications, Energies 11 (1) (2018) 105, https://doi.org/10.3390/en11010105. aircraft architecture, J. Aircr. 54 (6) (2017) 2213–2227, https://doi.org/
[79] R. Schmitt, P. Jonville, The Storage of Hydrogen and the Problems It Involves, 10.2514/1.C034266.
Battelle Memorial Inst., 1975. [112] All I Know About Aviation. "Fuel Consumption of Popular Aircraft." https://
[80] F. Zhang, P. Zhao, M. Niu, J. Maddy, The survey of key technologies in hydrogen alliknowaviation.com/2019/12/14/fuel-consumption-aircraft/ (accessed 10/1/
energy storage, Int. J. Hydrog. Energy 41 (33) (2016) 14535–14552. 2021, 2021).
[81] S.S. Bhogilla, Design of a AB2-metal hydride cylindrical tank for renewable [113] K. Mentoor, L. Twigge, J.W.H. Niemantsverdriet, J.C. Swarts, E. Erasmus, Silica
energy storage, J. Energy Storage 14 (2017) 203–210. nanopowder supported frustrated Lewis pairs for CO2 capture and conversion to
[82] O. Czakkel, B. Nagy, G. Dobos, P. Fouquet, E. Bahn, K. László, Static and dynamic formic acid, Inorg. Chem. 60 (1) (2021) 55–69, https://doi.org/10.1021/acs.
studies of hydrogen adsorption on nanoporous carbon gels, Int. J. Hydrog. Energy inorgchem.0c02012.
44 (33) (2019) 18169–18178. [114] B. Sharpe, R. Muncrief, Literature review: real-world fuel consumption of heavy-
[83] A. Swanger, J. Fesmire, Cryogenic flux capacitor for advanced molecular and duty vehicles in the United States, China, and the European Union, International
energy storage applications, in: IOP Conference Series: Materials Science and Council on Clean Transportation, Washington DC, 2015.
Engineering 755, IOP Publishing, 2020, p. 012051, no. 1. [115] S.M. Lajevardi, J. Axsen, C. Crawford, Examining the role of natural gas and
[84] A.M. Swanger, J.E. Fesmire, Cryogenic Flux Capacitor for Solid-state Storage and advanced vehicle technologies in mitigating CO2 emissions of heavy-duty trucks:
On-demand Supply of Fluid Commodities, Available:, 2019. modeling prototypical British Columbia routes with road grades, Transp. Res. Part
[85] N. Bader, A. Ouederni, Optimization of biomass-based carbon materials for D: Transp. Environ. 62 (2018) 186–211.
hydrogen storage, J. Energy Storage 5 (2016) 77–84. [116] N.R. Baral, et al., Biomass feedstock transport using fuel cell and battery electric
[86] A. Züttel, P. Sudan, P. Mauron, T. Kiyobayashi, C. Emmenegger, L. Schlapbach, trucks improves lifecycle metrics of biofuel sustainability and economy, J. Clean.
Hydrogen storage in carbon nanostructures, Int. J. Hydrog. Energy 27 (2) (2002) Prod. 279 (2021), 123593.
203–212. [117] S. Davis, S. Diegel, R. Boundy, Transportation energy data book (Oak Ridge
[87] M. Rzepka, P. Lamp, M. De la Casa-Lillo, Physisorption of hydrogen on National Laboratory, Oak Ridge, TN), in: Technical Report ORNL-6992, 2016.
microporous carbon and carbon nanotubes, J. Phys. Chem. B 102 (52) (1998) [118] H. Liimatainen, O. van Vliet, D. Aplyn, The potential of electric trucks–an
10894–10898. international commodity-level analysis, Appl. Energy 236 (2019) 804–814.
[88] S.H. Barghi, T.T. Tsotsis, M. Sahimi, Chemisorption, physisorption and hysteresis [119] S. Sripad, V. Viswanathan, Performance metrics required of next-generation
during hydrogen storage in carbon nanotubes, Int. J. Hydrog. Energy 39 (3) batteries to make a practical electric semi truck, ACS Energy Lett. 2 (7) (2017)
(2014) 1390–1397. 1669–1673.

19
M. Otto et al. Journal of Energy Storage 55 (2022) 105714

[120] M. Ehsani, Y. Gao, S. Longo, K.M. Ebrahimi, Modern Electric, Hybrid Electric, and Clean Air Act, Available: https://www.epa.gov/sites/default/files/2015-03/
Fuel Cell Vehicles, CRC Press, 2018. documents/list_of_lists.pdf, 2021.
[121] E. Çabukoglu, G. Georges, L. Küng, G. Pareschi, K. Boulouchos, Fuel cell electric [147] M.E. Barsan, NIOSH Pocket Guide to Chemical Hazards (DHHS Publication,
vehicles: an option to decarbonize heavy-duty transport? Results from a Swiss NIOSH, Cincinnati, OH, 2007 (in eng).
case-study, Transp. Res. Part D: Transp. Environ. 70 (2019) 35–48. [148] V. Déneux, Y. Cadoret, S. Hervier, D. Monceau, Effect of water vapor on the
[122] P. Plötz, T. Gnann, P. Jochem, H.Ü. Yilmaz, T. Kaschub, Impact of electric trucks spallation of thermal barrier coating systems during laboratory cyclic oxidation
powered by overhead lines on the European electricity system and CO2 emissions, testing, Oxid. Met. 73 (1) (2010) 83–93.
Energy Policy 130 (2019) 32–40. [149] M. van Roode, A.K. Bhattacharya, M.K. Ferber, F. Abdi, Creep Resistance and
[123] J. Kast, R. Vijayagopal, J.J. Gangloff Jr., J. Marcinkoski, Clean commercial water vapor degradation of SiC/SiC ceramic matrix composite gas turbine hot
transportation: medium and heavy duty fuel cell electric trucks, Int. J. Hydrog. section components, in: Turbo Expo: Power for Land, Sea, and Air 43963, 2010,
Energy 42 (7) (2017) 4508–4517. pp. 455–469.
[124] IMO, Third IMO Greenhouse Gas Study 2014, Executive Summary and Final [150] C.A. Lundgren, K. Xu, T.R. Jow, J. Allen, S.S. Zhang, Lithium-ion batteries and
Report, Available:, 2014. materials, in: Springer Handbook of Electrochemical Energy, Springer, 2017,
[125] N. Ash, I. Sikora, B. Richelle, Electrofuels for Shipping: How Synthetic Fuels From pp. 449–494.
Renewable Electricity Could Unlock Sustainable Investment in Countries Like [151] B. Stiehl, et al., Impact of three gaseous fuels on the reactor length and pollutant
Chile, Environmental Defense Fund, London, UK, 2019. formation under lean gas turbine conditions, in: Turbo Expo: Power for Land, Sea,
[126] T. Notteboom, P. Cariou, Fuel surcharge practices of container shipping lines: Is it and Air, American Society of Mechanical Engineers, 2022.
about cost recovery or revenue making, in: Proceedings of the 2009 International [152] X. Li, P. Anderson, H.-R.M. Jhong, M. Paster, J.F. Stubbins, P.J.A. Kenis,
Association of Maritime Economists (IAME) Conference, IAME Copenhagen, Greenhouse gas emissions, energy efficiency, and cost of synthetic fuel production
Denmark, 2009, pp. 24–26. using electrochemical CO2 conversion and the Fischer-Tropsch process, Energy
[127] D. Blackmon, Texas must fix its chronic power grid resiliency issues or risk Fuel 30 (7) (2016) 5980–5989, https://doi.org/10.1021/acs.
becoming another California, in: Forbes, 2021. Jersey City, NJ. energyfuels.6b00665.
[128] A. Álvarez, et al., Challenges in the greener production of formates/formic acid, [153] L. Vesely, M. Otto, J. Kapat, H2/O2 direct fired sCO2 power system coupled with
methanol, and DME by heterogeneously catalyzed CO2 hydrogenation processes, electrolysis and storage, Appl. Energy (2022) (under review).
Chem. Rev. 117 (14) (2017) 9804–9838, https://doi.org/10.1021/acs. [154] B.C. Steele, A. Heinzel, Materials for fuel-cell technologies, in: Materials for
chemrev.6b00816. Sustainable Energy: A Collection of Peer-reviewed Research and Review Articles
[129] K.L. Chagoya, et al., Mechanically enhanced catalytic reduction of carbon dioxide From Nature Publishing Group: World Scientific, 2011, pp. 224–231.
over defect hexagonal boron nitride, ACS Sustain. Chem. Eng. 9 (6) (2021) [155] E. National Academies of Sciences and Medicine, Commercial Aircraft Propulsion
2447–2455, https://doi.org/10.1021/acssuschemeng.0c06172. and Energy Systems Research: Reducing Global Carbon Emissions, The National
[130] S. Renda, A. Ricca, V. Palma, Study of the effect of noble metal promotion in Ni- Academies Press, Washington, DC, 2016.
based catalyst for the Sabatier reaction, Int. J. Hydrog. Energy 46 (22) (2021) [156] Rolls Royce, The Jet Engine, John Wiley & Sons, 2015.
12117–12127, https://doi.org/10.1016/j.ijhydene.2020.05.093. [157] H. Kobayashi, A. Hayakawa, K.D.Kunkuma A. Somarathne, Ekenechukwu
[131] V.S. Marakatti, E.M. Gaigneaux, Recent Advances in Heterogeneous Catalysis for C. Okafor, Science and technology of ammonia combustion, Available: Proc.
Ammonia Synthesis, ChemCatChem 12 (23) (2020) 5838–5857, https://doi.org/ Combust. Inst. 37 (1) (2019) 109–133, https://doi.org/10.1016/j.
10.1002/cctc.202001141. proci.2018.09.029.
[132] G.-F. Han, et al., Mechanochemistry for ammonia synthesis under mild [158] D. Erdemir, I. Dincer, A perspective on the use of ammonia as a clean fuel:
conditions, Nat. Nanotechnol. 16 (3) (2021) 325–330, https://doi.org/10.1038/ Challenges and solutions, International Journal of Energy Research 45 (4) (2021)
s41565-020-00809-9. 4827–4834, https://doi.org/10.1002/er.6232.
[133] S. Reichle, M. Felderhoff, F. Schüth, Mechanocatalytic room-temperature [159] G. Jeerh, M. Zhang, S. Tao, Recent progress in ammonia fuel cells and their
synthesis of ammonia from its elements down to atmospheric pressure, potential applications, J. Mater. Chem. A 9 (2) (2021) 727–752.
Angewandte Chemie International Edition (2021), https://doi.org/10.1002/ [160] J. Li, H. Huang, N. Kobayashi, Z. He, Y. Nagai, Study on using hydrogen and
anie.202112095 vol. n/a, no. n/a, 2021/10/15. ammonia as fuels: Combustion characteristics and NOx formation, International
[134] F. Schüth, R. Palkovits, R. Schlögl, D.S. Su, Ammonia as a possible element in an Journal of Energy Research 38 (9) (2014) 1214–1223, https://doi.org/10.1002/
energy infrastructure: catalysts for ammonia decomposition, Energy & er.3141.
Environmental Science 5 (4) (2012) 6278–6289, https://doi.org/10.1039/ [161] J.S. Cardoso, V. Silva, R.C. Rocha, M.J. Hall, M. Costa, D. Eusébio, Ammonia as an
C2EE02865D. energy vector: Current and future prospects for low-carbon fuel applications in
[135] E. Gianotti, M. Taillades-Jacquin, J. Rozière, D.J. Jones, High-purity hydrogen internal combustion engines, J. Clean. Prod. 296 (2021), 126562, https://doi.
generation via dehydrogenation of organic carriers: a review on the catalytic org/10.1016/j.jclepro.2021.126562.
process, ACS Catal. 8 (5) (2018) 4660–4680, https://doi.org/10.1021/ [162] C. Zamfirescu, I. Dincer, Using ammonia as a sustainable fuel, J. Power Sources
acscatal.7b04278. 185 (1) (2008) 459–465, https://doi.org/10.1016/j.jpowsour.2008.02.097.
[136] Chemical Facility Anti-Terrorism Standards, U.S. Department of Homeland [163] A. Valera-Medina, H. Xiao, M. Owen-Jones, W.I.F. David, P.J. Bowen, Ammonia
Security, Available: https://www.cisa.gov/chemical-facility-anti-terrorism- for power, Prog. Energy Combust. Sci. vol. 69 (2018) 63–102, https://doi.org/
standards, 2007. 10.1016/j.pecs.2018.07.001.
[137] M. Aziz, Liquid hydrogen: a review on liquefaction, storage, transportation, and [164] J. Hansson, S. Brynolf, E. Fridell, M. Lehtveer, The potential role of ammonia as
safety, Energies 14 (18) (2021) 5917. marine fuel—based on energy systems modeling and multi-criteria decision
[138] Hydrogen and Fuel Cell Technologies Office (HFTO). "Safety, Codes and analysis, Available: Sustainability 12 (8) (2020) 3265 https://www.mdpi.com/
Standards." https://www.energy.gov/eere/fuelcells/safety-codes-and-standards 2071-1050/12/8/3265.
(accessed. [165] MAN, MAN B&W two-stroke engine operating on ammonia, Available: htt
[139] D. Hardie, E. Charles, A. Lopez, Hydrogen embrittlement of high strength pipeline ps://www.man-es.com/docs/default-source/document-sync/man-b-w-two-str
steels, Corros. Sci. 48 (12) (2006) 4378–4385. oke-engine-operating-on-ammonia-eng.pdf, 2020.
[140] R.P. Gangloff, B.P. Somerday, Gaseous Hydrogen Embrittlement of Materials in [166] O. Herbinet, P. Bartocci, A.G. Dana, On the use of ammonia as a fuel–a
Energy Technologies: The Problem, Its Characterisation and Effects on Particular perspective, Fuel Commun. 11 (2022), 100064.
Alloy Classes, Elsevier, 2012. [167] J. Shao, R. Choudhary, D.F. Davidson, R.K. Hanson, S. Barak, S. Vasu, Ignition
[141] B. Somerday, C.San Marchi, Aluminum Alloys: Heat-treatable Alloys, 7XXX-series delay times of methane and hydrogen highly diluted in carbon dioxide at high
(Code 3230), 2008. pressures up to 300 atm, Proc. Combust. Inst. 37 (4) (2019) 4555–4562, https://
[142] D. Shih, I. Robertson, H. Birnbaum, Hydrogen embrittlement of α titanium: in situ doi.org/10.1016/j.proci.2018.08.002.
TEM studies, Acta Metall. 36 (1) (1988) 111–124. [168] A. Murugan, A.S. Brown, Review of purity analysis methods for performing
[143] United States Department of Transportation, Hazardous Materials Table, quality assurance of fuel cell hydrogen, Int. J. Hydrog. Energy 40 (11) (2015)
Available: https://www.govinfo.gov/content/pkg/CFR-2012-title49-vol2/pdf/CF 4219–4233, https://doi.org/10.1016/j.ijhydene.2015.01.041.
R-2012-title49-vol2.pdf, 2012. [169] N.M. Aslam, M.S. Masdar, S.K. Kamarudin, W.R.W. Daud, Overview on direct
[144] United States Department of Transportation, Emergency Response Guidebook formic acid fuel cells (DFAFCs) as an energy sources, APCBEE Procedia 3 (2012)
(ERG), Available: https://www.phmsa.dot.gov/hazmat/erg/emergency-response 33–39, https://doi.org/10.1016/j.apcbee.2012.06.042.
-guidebook-erg, 2020. [170] E.P. Murray, T. Tsai, S.A. Barnett, A direct-methane fuel cell with a ceria-based
[145] Comprehensive Environmental Response, Compensation, and Liability Act anode, Nature 400 (6745) (1999) 649–651, https://doi.org/10.1038/23220.
(CERCLA), 42 U.S.C. § 9601, Chapter 103, 9601-9675, Available: https://www.go [171] E. Putna, J. Stubenrauch, J. Vohs, R. Gorte, Ceria-based anodes for the direct
vinfo.gov/app/details/USCODE-2019-title42/USCODE-2019-title42-chap103&co oxidation of methane in solid oxide fuel cells, Langmuir 11 (12) (1995)
llectionCode=USCODE, 1980. 4832–4837.
[146] United States Environmental Protection Agency, EPA 550-B-21-001, List of Lists: [172] S. Ha, R. Larsen, R.I. Masel, Performance characterization of Pd/C nanocatalyst
Consolidated List of Chemicals Subject to the Emergency Planning and for direct formic acid fuel cells, Journal of Power Sources 144 (1) (2005) 28–34,
Community Right-To-Know Act (EPCRA), Comprehensive Environmental https://doi.org/10.1016/j.jpowsour.2004.12.031.
Response, Compensation and Liability Act (CERCLA) and Section 112(r) of the [173] N.De Vries, Safe and Effective Application of Ammonia as a Marine Fuel, 2019.

20
M. Otto et al. Journal of Energy Storage 55 (2022) 105714

[174] K. Reddi, A. Elgowainy, N. Rustagi, E. Gupta, Techno-economic analysis of (ARPA-E), Available: https://arpa-e-foa.energy.gov/FileContent.aspx?
conventional and advanced high-pressure tube trailer configurations for FileID=e070d735-6ab4-446a-adc9-da275c569ef4, 2016.
compressed hydrogen gas transportation and refueling, Int. J. Hydrog. Energy 43 [176] G. Soloveichik, M. Acharya, H. Cheeseman, D. Wicks, D. Tew, Renewable energy
(9) (2018) 4428–4438. to fuels through utilization of energy dense liquids (REFUEL), Available: htt
[175] U.S. Department of Energy, Renewable energy to fuels through utilization of ps://arpa-e.energy.gov/sites/default/files/02%20Kickoff%20REFUEL%20vision.
energy-dense liquids (refuel)," Advanced Research Projects Agency – Energy pdf, 2016.

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