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A R T I C L E I N F O A B S T R A C T
Keywords: To meet ambitious targets for greenhouse gas emissions reduction in the 2035-2050 timeframe, hydrogen has
Paris Agreement been identified as a clean “green” fuel of interest. In comparison to fossil fuel use the burning of hydrogen results
Fuel Cells in zero CO2 emissions and it can be obtained from renewable energy sources. In addition to zero CO2 emissions,
Turboelectric Distributed Propulsion
hydrogen has several other attractive properties such as higher gravimetric energy content and wider flamma
Gas Turbines
Cryotank
bility limits than most fossil fuels. However, there are practical limitations to its widespread use at present which
CO2 include low volumetric energy density in the gaseous state and high well-to-wheel costs when compared to fossil
Pipeline fuel production and distribution. In this paper a review is undertaken to identify the current state of development
Electrolysis of key areas of the hydrogen network such as production, distribution, storage and power conversion technology.
Salt Domes At present high technology costs still are a barrier to widespread hydrogen adoption but it is envisioned that as
scale of production increases, then costs are likely to fall. Technical barriers to a hydrogen economy adoption are
not as significant as one might think as key technologies in the hydrogen network are already mature with
working prototypes already developed for technologies such as liquid hydrogen composite cryotanks and proton
exchange membrane fuel cells. It is envisioned that with continuous investment to achieve requisite scale that a
hydrogen economy could be realised sooner rather than later with novel concepts such as turboelectric
distributed propulsion enabled by a shift to hydrogen-powered network.
1. Introduction of its total power demand from renewables [6]. Iceland is another
country leading the way in renewable power generation where
At present, there is an increasing concern in the world today over geothermal energy provides approximately 68% of its total energy needs
issues such as energy security, energy availability, greenhouse gas [7].
emissions, and climate change. In addition to socio-political concerns, With the increasing use of renewable energy identified as a pathway
these issues are becoming of increasing economic concern to companies, to a low carbon future, the characteristics of this energy supply and its
institutions, and organisations around the world. The “Paris Agreement” effect on national grids have to be considered. Considering solar power
signed in 2016 by 196 Nations, set a goal of limiting global warming to conversion and wind energy, compared to fossil fuel use, power gener
well below 2, preferably 1.5◦ C compared to pre-industrial levels [1]. The ation from wind and solar is characterised by a high degree of inter
increasing adoption of low carbon technologies by institutions around mittency. This has major effects on existing grid power generation and
the world has been identified as the major method by which these tar transmission infrastructure which were not initially designed to handle
gets can be achieved. Some of the biggest corporations on the planet power supply from highly intermittent sources. To overcome this
such as Tesla, Apple, Siemens, Alphabet (Google), etc. have already problem, increasing development activity has been undertaken on the
started to lead the way in becoming carbon neutral [2, 3, 4] & [5], and integration of appropriate grid energy storage technologies to better
countries around the world are increasingly integrating renewable en manage power supply intermittency for a more efficient low-carbon grid
ergy into their national grids. Germany for instance has its “Ener power supply. Some of the technologies that have been considered for
giewende” program where it aims to achieve a 55% reduction in this include pumped hydro, compressed air energy storage (CAES),
emissions by 2030 compared to 1990 levels and currently produces 44% lithium-ion batteries, and hydrogen among others [8] & [9]. Hydrogen
* Corresponding author: Bernard Chukwudi Tashie-Lewis, School of Water, Energy, and Environment, Cranfield University, Cranfield, United Kingdom
E-mail address: ben_lewis1@outlook.com (B.C. Tashie-Lewis).
https://doi.org/10.1016/j.ceja.2021.100172
Received 21 March 2021; Received in revised form 25 July 2021; Accepted 21 August 2021
Available online 24 August 2021
2666-8211/© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
B.C. Tashie-Lewis and S.G. Nnabuife Chemical Engineering Journal Advances 8 (2021) 100172
Table 3
Flammability range of common comparable fuels [11]
Fuel Flammable range (%)
Hydrogen 4-75
Methane 5.3-15
Propane 2.2-9.6
Methanol 6-36.5
Gasoline 1-7.6
Diesel 0.6-5.5
Figure 1. The rate of oil discovery is falling while the rate of oil consumption is
increasing [10]
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B.C. Tashie-Lewis and S.G. Nnabuife Chemical Engineering Journal Advances 8 (2021) 100172
lower flammability level (LFL) and its higher flammability level (HFL) and tertiary measures. Primary measures include exclusion of causative
allows for the unique combustion engine and turbine performance. LFL risks such as leakage and formation of explosive mixtures by appropriate
and HFL are the minimum and maximum fuel concentration levels in the design (inertization, open-air installation, flame arrestors, etc.). Sec
air required to make the mixture flammable. If fuel content is outside ondary measures consist mainly of the avoidance of ignition sources of
fuel LFL and HFL, air-fuel mixtures will not be flammable either due to any kind (electrostatically or mechanically generated sparks). Tertiary
lack of fuel or oxygen. For many common fuels, a relatively small measures include ways of minimizing the dangerous results in the case
flammability range when compared to hydrogen means that industrial of a fire or explosion occurring. This is achieved by the installation of
producers have to make enhancements and include additional systems explosion-proof or explosion relief systems, hydrogen process
such as turbochargers so that their manufactured engines can perform shut-down systems, and suitable fire extinguishing systems [14].
better in low-pressure situations such as at high altitude. The wide Considering all of the advantages of using hydrogen in a future green
flammability range of hydrogen when compared to most fossil fuels, economy, this paper aims to set a foundation for any future research that
allows for it to be possible to design and build engines with more is to be undertaken in this space. With this paper, a review of the
structural simplicity to perform the same function (thrust or power progress that has been made in developing the technology needed to
generation) for multiple different operating points [11]. realise the hydrogen economy is undertaken. With a focus on power
At present, the major limitations behind widespread utilization of generation and transportation sectors; the state of present-day hydrogen
hydrogen today are concerns over overall lifecycle costs and perceptions production, distribution, storage and power conversion technology is
over fuel safety. The major drivers affecting lifecycle cost include pro discussed and analysed. Also of interest in this paper is the review of
duction cost, supply cost, market price, demand, storage costs, distri future technology options in aerospace that can be realised with a shift
bution costs, and investment costs. Considering cost concerns, the major to hydrogen system architectures.
driver affecting hydrogen cost is the characteristics of the source from
which hydrogen is extracted. In 2008 approximately 96% of Hydrogen 2. Hydrogen Production
produced in the world came from fossil fuels (see Table 4) and the share
hasn’t changed significantly since then. Ironically this doesn’t do much 2.1. Current Status
to solve the global warming problem and exacerbates the carbon cycle.
Not only is a considerable amount of energy lost from fossil fuel energy Hydrogen can be produced by several processes such as thermo
content, the infrastructure needed to extract hydrogen comes at a chemical processes, electrochemical processes, photochemical pro
considerable expense. If fuel is needed for use in a power conversion cesses, photocatalytic processes, or photo-electrochemical processes
device for end-use application such as a gas turbine, fuel cell, or piston [13]. With these processes hydrogen today is either produced from fossil
engine; it does not make sense to waste energy for a more expensive fuel fuels, water, or biomass. Unfortunately, fossil fuels are still the main
when a rational end-user could simply use a cheaper fuel which has resource for industrial mass-scale hydrogen production which only ex
greater energy content when considering well-to-wheel efficiencies. acerbates the carbon cycle. The most economical method of producing
However, hydrogen obtained via renewable energy powered electrolysis hydrogen from fossil fuels is via steam-methane reforming (SMR). In this
allows for better well-to-wheel efficiencies and potentially overall process, steam and methane are reacted to form carbon monoxide and
reduced fuel cost. Hindering progress in realising this at present is the hydrogen as by-products. The other main processes for producing
development challenge of carrying out electrolysis of water at practical hydrogen from fossil fuels include oil partial oxidation, oil cracking, coal
efficiencies and scale. It must be said though that if the cost of renewable gasification, and coal cracking. Hydrogen from coal accounts for 30% of
energy power generation continues to fall, then is expected the cost of production today and hydrogen from oil accounts for 18% of production
hydrogen produced from electrolysis to reduce as well. [11]. Although economical at present for producing hydrogen for ap
Considering the safety aspects of utilizing hydrogen as a fuel; plications in the space sector, ammonia production, and other miscel
hydrogen is not toxic yet extremely flammable. This flammability arises laneous applications; for widespread use as a fuel in a hydrogen
as a result of its laminar burning, buoyant, and propagation velocities economy, hydrogen produced from fossil fuels is not a sustainable so
being significantly higher than those of most other common fuels. lution because carbon dioxide, carbon monoxide, and other greenhouse
However, its vapour-from-liquid-generation speed is much higher than gases are still emitted into the atmosphere.
that of any liquid fossil fuel, and as such hydrogen fires only last about Hydrogen production from the water via the splitting of water
10-20% of the duration of a fossil fuel fire of the same volume. A safety molecules employing electrolysis has been the approach increasingly
hazard though is that hydrogen flames are nearly invisible in daylight so studied in recent history for sustainable production of hydrogen [11, 13]
visual detection of fire will take a slightly longer amount of time. Also, & [15]. Either water in the liquid phase or steam can be used for the
unlike fossil fuel fires, smoke inhalation of hydrogen fires is essentially electrolysis process. Challenges stated at present for water electrolysis
harmless since it is just water vapour. The challenge with handling include high production costs due to high capital investment, low con
hydrogen though is its sensitivity to detonation [11]. High laminar version efficiency, and electrical power cost. However, as renewable
burning velocity, as well as the high laminar flame speed of hydrogen, energy technology continues to mature, it is expected that the costs of
makes the transition to turbulent flame speeds exceeding 800 m s− 1 up electrical power should reduce with time. For instance, the cost of solar
to several km s− 1 easy. Hence, hydrogen is more sensitive to deflagration photovoltaic (PV) modules has reduced in cost by 99% since 1980 and
to detonation transition (DDT) than hydrocarbons. Safety precautions this cost reduction is expected to continue going forward [16]. Also,
when handling hydrogen include a combination of primary, secondary considering the significant amounts of energy wasted during off-peak
times at several renewable energy power plants without suitable en
ergy storage, the use of this energy to drive the water electrolysis process
Table 4 can reduce hydrogen production costs down further. For instance, it is
Global hydrogen production share by a source in 2008 [13] reported that in a particular wind farm in north-western Spain, a sizable
Source Bcma/yr Share (%) section of the farm has to be disconnected regularly from the power grid
Natural Gas 240 48
to maintain stability during the off-peak hours. According to the oper
Oil 150 30 ators, this off-operation wastes a total of 13 GWh of electrical energy per
Coal 90 18 year. This energy could conveniently be used to generate enough
Electrolysis 20 4 hydrogen to fuel a fleet of 728,000 cars for a year if each vehicle needs
Total 500 100
2.5 kg of hydrogen of refuelling per week. This calculation was based on
a
Bcm: billion cubic meters the assumption of a weekly journey of 400 km for each vehicle for a year
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B.C. Tashie-Lewis and S.G. Nnabuife Chemical Engineering Journal Advances 8 (2021) 100172
[11]. Considering efficiency; water electrolysis requires a minimum To achieve effective electrochemical power and hydrogen produc
energy of 39.4 kWh to produce 1 kg of hydrogen generation at full tion with robust, durable, and stable operation, electrodes are needed to
conversion efficiency. Typically though, most electrolyzers consume 50 ease oxygen reduction and water oxidation reactions, which are the
kWh to produce 1 kilogram of hydrogen and efforts are underway to major phases for both fuel cell and electrolysis operation, mainly at
increase the efficiency of the electrolysis process. The two main types of reduced temperatures. Hence, Ding et al. in [20] developed a triple
water electrolysis in use today are alkaline electrolysis and polymer conducting oxide of PrNi0.5Co0.5O3-δ perovskite as an oxygen electrode,
electrolyte membrane (PEM) electrolysis. Alkaline water electrolysis is a which at 400~600 ◦ C achieved superior electrochemical performance.
mature technology with efficiencies between 70% - 80% achievable. Moreso, reversible and self-sustainable operation was effectively estab
Alkaline electrolyzers typically operate at a process temperature of 343 lished by converting the produced hydrogen in electrolysis mode to
K-353 K. Pressurized alkaline electrolyzers; however, operate at a electricity without the addition of hydrogen.
somewhat elevated temperature of 363-403 K [13]. Ito et al. in [21] presented a Miscanthus Sinensis grass model due to its
Hydrogen is also produced from biomass and this represents a wide and easiness of cultivation in Japan. The hydrogen formation
cleaner approach to produce hydrogen than utilizing fossil fuels. The features and electrochemical performance of electrolysis cells employ
major challenge to large-scale hydrogen production from biomass is ing grass as a biohydrogen source were assessed at intermediary tem
whether the land being used for biomass production is competing with perature to obtain electrolysis. The constituents such as cellulose,
feedstock and dealing with the politics of this decision. For hydrogen holocellulose, extractives, and lignin were parted from Miscanthus
produced from biomass, the main processes for producing hydrogen Sinensis to comprehend the reactions of Miscanthus Sinensis in the elec
from biomass include pyrolysis, gasification, steam gasification, steam trolysis cell. The electrolysis properties of an electrolysis cell using lignin
reforming of bio-oils, and the enzymatic decomposition of sugars [13]. were degraded due to the comparatively low and high resistivity per
formance of current-voltage compared to those using pure cellulose or
2.2. Novel Production Techniques holocellulose as biohydrogen resources. The biohydrogen was made
with respect to Faraday’s law and continuously evolved at 0.1 A cm− 2
Appel et al in [17] proposed a photosynthetic hydrogen production for 3,000 seconds.
method using a photosystem I–hydrogenase (psaD-hoxYH ) fusion in Kurtoğlu et al. in [22] transformed red mud, one of the most pro
vivo. The NiFe-hydrogenase HoxYH of the cyanobacterium Synechocstis duced technologically advanced wastes into a catalyst with remarkably
sp. PCC 6803 was connected to its photosystem I subunit PsaD near the stable and high performance in the formation of hydrogen from
4Fe4S cluster FB, which ordinarily donates electrons to ferredoxin. The ammonia. The outcomes demonstrated that iron species generated after
proposed method was because hydrogen produced photosynthetically is reduction of the hydrogen chloride (HCl) absorbed red mud was
sustainable. Vitro semiartificial techniques have been implemented changed into ε-Fe2N throughout the ammonia decomposition initiation
successfully in which hydrogenases were connected to isolated photo period reaction at 700 ◦ C. The measurements catalytic reaction showed
systems for the production of hydrogen. The drawback with Vitro sys that the reformed red mud catalyst gives a record high hydrogen for
tems is they are short-lived in general, as metabolic processes that mation rate for a non-noble metal catalyst at this temperature. For
support self-maintenance and repair are missing. Moreso, photo example, constant hydrogen formation rates were measured as 196 and
system–hydrogenase fusions have been examined and tested only in 72 mmol H2 min− 1 gcat− 1 for the corresponding space velocities of 240
vitro. The resultant psaD-hoxYH mutant grows photo-autotrophically, 000 and 72 000 cm3 NH3 h− 1 gcat− 1, respectively, at 700 ◦ C. The
achieves a high concentration of photosynthetically produced outcome offer prospects to employ one of the main harmful industrial
hydrogen of 500 μM under anaerobic conditions in the light, and does wastes as an effective, stable, eco-friendly, and approximately zero-cost
not take up the generated hydrogen. Their findings demonstrated that catalyst for the production of COx-free hydrogen from ammonia
psaD-hoxYH photosynthetically produces hydrogen through both decomposition.
oxygenic photosynthesis and anoxygenic. Zhang et al in [23] presented a dehydrogenation route that applies to
Malerød-Fjeld et al. in [18] suggested a protonic membrane reformer different types of non-food-related daily waste and biomass, such as corn
(PMR) that converts steam methane reforming into high-purity straw, wheat straw, reed, bagasse, cardboard, newspaper bamboo
hydrogen in a single-stage process with near-zero energy loss. As a sawdust, and rice straw. Hydrogen (H2) up to 95% were obtained by a
reforming catalyst, a BaZrO3-based proton-conducting electrolyte was one-pot, two-step reaction with a 69 ppm molecularly distinct iridium
used and deposited as a thick film on a dual function porous Ni com catalyst containing an imidazoline moiety from formic acid, which was
posite electrode. Full methane conversion was achieved at 800 ◦ C by in turn acquired via a 1 v% dimethyl sulfoxide enhanced hydro
removing 99% of the formed hydrogen, which was concurrently com lysis–oxidation of biomass. Development of the undesirable side prod
pressed up to 50 bar electrochemically. By coupling distinct ucts CH4 and CO were not greater than 2 and 22 ppm, respectively,
thermo-chemical processes, a balanced thermal operation regime was while CO2 was acquired as carbonate. The subsequent hydrogen gas can
achieved. Modelled small-scale (10 kg H2 day− 1) hydrogen plant be used in proton exchange membrane (PEM) fuel cells.
showed a total energy efficiency of > 87%. The achieved results show Serra et al. in [24] proposed contactless hydrogen (H2) production
that the PMRs could be a competitive and promising alternative for through water electrolysis facilitated by the microwave-generated redox
industrial-scale hydrogen plants integrating CO2 capture due to future activation of solid-state ionic constituents at low temperatures
declining electricity prices. (<250 ◦ C). Water was decreased through reaction with non-stable
Li et al. [19] presented a nickel-molybdenum-nitride nanoplate fixed gadolinium-doped ceric dioxide (CeO2) which was formerly in situ
on carbon fibre cloth Ni-Mo-N/CFC for the simultaneous electrolytic electrochemically deoxygenated via microwave sole application. The
high-purity hydrogen production at the cathode and value-added microwave-motivated reduction was recognized by a prompt oxygen
formate at the anode in low-cost alkaline glycerol solutions. Mostly, (O2) discharge and electrical conductivity increase. The method was
when fitted with Ni-Mo-N/CFC at both cathode and anode, the elec cyclable, while energy efficiencies and hydrogen yields were power and
trolyzer needs cell voltage as low as 1.36 V to obtain 10 mA cm− 2 that is material-dependent. Deoxygenation of low-energy molecules (CO2 or
260 mV lower than that in alkaline aqueous solution. Also, 95.0% of H2O) led to energy carrier’s formation and aided the production of
formate production and 99.7% high Faraday efficiencies of H2 evolution Methane (CH4) when incorporated with a Sabatier reactor. This tech
were achieved. Considering the electrochemical efficient performances nique might be used for other reactions like oxidation or hydrocarbons
of Ni-Mo-N/CFC, the alkaline glycerol solutions formate productions synthesis.
and electrolytic H2 are considered future promising and efficient energy Studies in [25] explored the use of photoelectrochemical hydrogen
technology for clean and renewable energy supply. production with concentrated natural seawater produced by membrane
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B.C. Tashie-Lewis and S.G. Nnabuife Chemical Engineering Journal Advances 8 (2021) 100172
process. Key advantages of this process include the utilization of desired. At the national level, often the choice for a large-scale hydrogen
sea-water which is a near-limitless resource on earth and means that production and distribution network (see Figure 4) is the preferred op
relatively limited freshwater supply does not have to be used, and the tion for a hydrogen distribution network. Producing massive amounts of
presence of a large number of dissolved ion components in sea-water hydrogen in a single plant comes with highly reduced monetary capital
mean it can be utilized as an electrolyte in a photoelectrochemical sys investments per unit of fuel produced. As shown in Figure 5, assessments
tem for producing hydrogen with increased electrolysis efficiency. With show noticeable capital cost reductions as production capacity in
the process, natural seawater is first concentrated via polyamide (PA) creases. This means it is more economically effective to build MW-scale
nanofiltration (NF) membranes to concentrate the sea-water electrolyte hydrogen production facilities. This favours a large-scale nationwide
(see Figure 3) in a three-stream process. Then hydrogen is produced in a hydrogen production and distribution network as the larger the
light-sensitized enzymatic (LSE) system by coupling anodized TiO2 hydrogen production facility, the lower the unit cost per amount of
electrodes as the photoanode, cathode immobilized enzymes, and hydrogen produced.
modified seawater electrolytes in a photoelectrochemical (PEC) Additionally, another advantage of a large-scale distribution
configuration. For experiments undertaken in [25], PEC functionality network is plant concentration which makes it easier to manage, trou
was conducted in a membrane cell that had a two-compartment (anodic bleshoot and service hydrogen production and distribution facilities.
and cathodic elements separated by an NF membrane and a solar cell This also reduces the required human resources needed for the contin
panel) reactor. The cylindrical-shaped anodic compartment had a vol uous operation of the entire network [11]. A major disadvantage of this
ume of 80 ml (headspace volume of ca. 55 ml) and contained the approach however, is that the building of large-scale fuel production
seawater electrolyte solutions. The cathodic compartment was a plants results in more significant hydrogen storage penalties. In [13]
water-jacketed, cylindrical-shaped cell (80 ml, headspace volume of ca. studies show that the cost of hydrogen storage tanks rises significantly as
55 ml) with a silicone rubber gasket, which allowed the temperature to capacity increases. At the time of research, an industrial 50 kg hydrogen
be adjusted. The light source used for experiments was a 1000 W xenon tank costs slightly more than US$ 50,000 while a 150 kg tank will cost
lamp, which was filtered through a 10 cm IR water filter. Although ex around US$ 300,000. From modelling undertaken, hydrogen storage
periments were undertaken at a small scale, results showed that the rate tank price increases by US$ 100,000 for each 50 kg increase in hydrogen
of hydrogen production in the retentate of ca. 270 μmol cm− 2 h− 1 in the storage tank capacity. However, this study assumes hydrogen produced
photoelectrochemical system is greater than the hydrogen production in at a large-scale production facility will be stored in either gaseous or
seawater, showing that higher TDS leads to greater hydrogen liquid hydrogen storage tanks. Other storage options are being consid
production. ered and one promising technology option for large-scale hydrogen
Considering the identified novel hydrogen production techniques storage is the use of Salt Domes which are large geological structures
further, Table 5 shows a brief overview of some of the benefits and that have the potential to mitigate the high cost of storing hydrogen in
limitations of the identified techniques. Of the techniques identified, tanks [26].
studies in [21, 22] & [25] seem to be the most promising at present in The installation of large-scale hydrogen production facilities means
terms of producing large-scale low-cost hydrogen. that safe, reliable, and cost-effective fuel transmission and delivery
infrastructure is needed for a viable hydrogen economy. For the real
3. Hydrogen Distribution isation of the hydrogen economy, four major fuel transportation possi
bilities were analysed in [13] to assess capacity, efficiency, and
For a holistic assessment of the hydrogen economy, consideration estimated transmission costs. Table 6 shows a summary of the charac
has to be made to the macro-scale hydrogen production and distribution teristics of each of these methods. Considering hydrogen delivery
network that is to be employed. For certain nations a large-scale further, the most important factors affecting delivery cost (US$/kg) are
hydrogen production and distribution network may be desired; for scale and distance traversed. For a nation to effectively design its
others a small-scale facility or a combination of large, small, and hydrogen network infrastructure, an appropriate assessment of these
medium-scale facilities distributed throughout the country may be factors is highly important.
Figure 3. Schematic representation of membrane system for preparation of seawater electrolytes [25]
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B.C. Tashie-Lewis and S.G. Nnabuife Chemical Engineering Journal Advances 8 (2021) 100172
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B.C. Tashie-Lewis and S.G. Nnabuife Chemical Engineering Journal Advances 8 (2021) 100172
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B.C. Tashie-Lewis and S.G. Nnabuife Chemical Engineering Journal Advances 8 (2021) 100172
Table 6
Major hydrogen transmission methods [13]
Transmission Type Pipeline Tube trailer Liquid – road Liquid – ships
Suitability Short, medium, and large distance transfer of Short distance gas state Short and medium Very large quantities of gas for international
large and very large quantities in a gas state transfer distance transfer of large transportation
volumes of fuel
Investment Costs $200,000-$1,000,000 per km depending on the Around $300,000+ per $300,00-$400,000 per $465,000,000-$620,000,000 for each LH2
terrain truck truck barge
Operating and Around $0.03 per kg for pipeline compressors Driver labour at around 18 $ Driver labour at around Crew labour and fuel consumption costs
Maintenance h− 1 18 $ h− 1 unknown
costs
Efficiency Over 99.2% per 100 km 94% per 100 km 99% per 100 km 0.3% boil-off per day
(liquefaction efficiency
is around 75%)
Capacity Up to 100 tons h− 1 (3.9 GW) Up to 400 kg per truck Up to 4000 kg per truck Up to 10,000 tons per shipment
Energy required Electricity required for pipeline compressors Vehicle fuel consumption Vehicle fuel and Transport fuel
liquefaction energy
consumption
Advantages Large and very large quantities can be Small scale deployment Larger volumes than gas International transportation of massive
transported to any distance with high efficiency, possibilities transportation quantities for long distances
low running costs, and very low variable
expenses. This method also provides storage
and buffering possibilities
Disadvantages Relative expensive investment costs and Small scale delivery per Costs and inefficiency of There isn’t any industrial experience of
requirement of the very large amount of vehicle, energy inefficiency, liquefaction and boil-off shipping LH2. It’s not feasible until large
hydrogen delivery to be justified short-distance product losses supply and demand exist. Boil-off losses are
transportation more significant than road transport
Total transmission $0.10-$1.00 $0.50-$2.00 $0.30-$0.50 $1.80-$2.00
cost ($ kg− 1
100km− 1)
Figure 7. Hydrogen density at various pressures and temperatures [28] Figure 8. Schematic representation of the 4 typical pressure vessel types used
for gaseous hydrogen storage [27]
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B.C. Tashie-Lewis and S.G. Nnabuife Chemical Engineering Journal Advances 8 (2021) 100172
Pressure vessels are typically cylinders, but composite vessels may be Table 7
polymorphic or toroidal. The choice of which pressure vessel type Metal hydrides and hydrogen density capability [28]
hydrogen should be stored in is based on the final application which is a Metal Hydride Hydrogen Density (kg/m3)
compromise between technical performance and cost-competitiveness.
Magnesium (MgH2) 109.0
Hydrogen as an industrial gas for large-scale storage is usually stored Lithium (LiH) 98.5
in type I tanks, the pressure of which is from 150 bar to 300 bar (usually Titanium (TiH1.97) 150.5
200 bar). These are the most widespread pressure vessels today and are Aluminum (AlH3) 151.5
the cheapest. Type II tanks are preferred when only high pressures are Zirconium (ZrH2) 122.2
Lanthanum (LaNi5H6) 89.0
needed, which is typically for stationary applications. Type III and Type
IV vessels are preferable for portable and general transport applications
(e.g. use with fuel cells in the automotive industry), for which weight shows a list of potential metal hydride storage materials and the density
savings are essential. However, these vessels are much more expensive of the hydrogen achievable within the material.
[27]. From Table 7 it can be seen that the storage of hydrogen in metal
hydrides allows for high-density hydrogen storage greater than densities
4.2.2. Metal Hydrides achievable than both compressed gas hydrogen storage and liquid
Metal hydrides are metallic alloys that absorb hydrogen. Because of hydrogen (liquid hydrogen density at normal boiling point = 71.0 kg/
their ability to absorb and release hydrogen, these alloys can be used as a m3). However, this does not take into account how tank weight affects
storage mechanism. The release of hydrogen is directly related to the the system of interest for a given application. Studies in [32] for auto
temperature of the hydride. Metal hydrides will typically hold only motive applications showed that for a heavy metal hydride such as
about 1% to 2% of their weight in hydrogen. If active heating is supplied FeTiH1.9, tank weight of a metal hydride fuel-cell vehicle is much higher
to remove the hydrogen, this can increase to 5% to 7% of the hydride than the tank weight of a compressed hydrogen gas FCV. In the study,
weight. A metal hydride tank can be used to repeatedly store and release this resulted in a significant reduction in the driving range for each
hydrogen but a limiting factor on its ability to store hydrogen is the re-fuel of the metal hydride FCV when compared to the compressed
accumulation of impurities within the tanks. These impurities clog up hydrogen gas FCV. For a total fuel plus tank weight of 400 kg, a com
the spaces where hydrogen would usually be stored, reducing the tank’s pressed hydrogen gas FCV has approximately three times greater driving
capacity [28]. A simplified model of how hydrogen is stored and range than a metal hydride FCV. However, in the study, a heavy metal
absorbed in a metal hydride is shown in Figure 9. The amount of heat hydride was considered. For future development, the use of lighter metal
transferred, hydrogen absorbed and hydrogen desorbed in a typically hydrides could potentially result in this discrepancy being significantly
reversible metal hydride operating at room temperature and atmo reduced for future transport applications.
spheric pressure is typically a function of the metal alloy used to store
hydrogen [31]. 4.2.3. Boron- and Nitrogen-Based Hydrides
Key challenges to utilising metal hydride storage systems are (1) Boron- and nitrogen-based based hydrides such as sodium borohy
whether there is sufficient heat generated to extract hydrogen from the dride (NaBH4), hydrazine borane (N2H4BH3), hydrous hydrazine (N2H4.
hydride, and (2) the time lag between initial heating and release of the H2O), ammonia (NH3) and ammonia borane (NH3BH3) can also be used
hydrogen gas. Focusing on heat generation to extract hydrogen implies for the storage of hydrogen. With these hydrides, dehydrogenation re
that there is a need for an on-board heat generation and transfer system actions are the means by which hydrogen is released to provide the
whether this is from an internal combustion engine or fuel cell via hydrogen need for a given application. These hydrides are considered to
thermal components (e.g. heat exchangers). This imposes external be promising for chemical hydrogen because of their high hydrogen
design complexities and energy penalties on the general system which is content and the advantage of CO-free hydrogen produced [33]. The
utilizing hydrogen as a fuel with a metal hydride storage system which is challenge with employing these hydrides is the development of eco
not characteristic of other hydrogen storage options. Considering the nomic, highly efficient and stable catalysts that enable effective
metal hydride time lag, hydrides constructed of heavy metals such as hydrogen evolution from these hydrides. Increasing research has been
vanadium, niobium, and iron-titanium release hydrogen at ambient done in recent times [34, 35, 36] & [37] to develop more effective
temperatures which greatly diminishes the time lag effect. However, catalysts to allow for higher rates of hydrogen generation that would be
this, unfortunately, comes at an increased system weight penalty due to needed in a hydrogen economy.
the general physical compositions of these heavy metals. Lighter hy
drides do not impose the same system weight penalties as heavy-metal 4.2.4. Carbon Nanotubes
hydrides; however, they need to be heated from an auxiliary heat Carbon nanotubes are tubular carbon structures with a diameter of
source until the temperature is sufficient to release hydrogen. Table 7 about 2 nm. These structures are theoretically capable of storing
hydrogen within the tube structure. The storage mechanism is similar to
that of metal hydrides except for the amount of hydrogen capable of
being stored is much greater [28]. In carbonaceous materials such as
carbon nanotubes, the fundamental mechanism behind hydrogen
adsorption is the “Van der Waals” interactions that carbon atoms exert
on hydrogen molecules [8]. Hydrogen storage in carbon nanotubes is
still very far from being a practical reality as carbon nanotube fibre
development is still in its infancy.
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B.C. Tashie-Lewis and S.G. Nnabuife Chemical Engineering Journal Advances 8 (2021) 100172
demand via sphere heating when needed [28]. Engineered microspheres weight savings as a result of utilizing liquid hydrogen means signifi
provide great potential for the high-density storage of hydrogen. This is cantly less fuel is burnt which causes a snowball effect of increased
due to the high hoop stress values they are predicted to be able to aerodynamic efficiency, reduced vehicle weight, and reduced overall
withstand. It is estimated that a bed of 50 μm diameter engineered mi fuel cost per mission. Considering these benefits in mind, there have
crospheres can store hydrogen at 62 MPa with a safety factor of 1.5 and a already been recent successful efforts of technology demonstrator ve
hydrogen mass fraction of 10%. This allows for hydrogen stored with a hicles such as the Boeing Phantom Eye and the Aerovironment Global
density of 20 kg m− 3 [28]. Other advantages of capillary storage include Observer which have completed missions burning liquid hydrogen fuel
the following [30]: with installed cryotanks [40, 41] & [42].
mfuel
• They require less hydrogen infrastructure because the capillaries will ηtank = (1)
mfuel + mtank
be filled at the fuel plant before delivery to the filling station
• Capillaries are safer because each one acts as an individual high-
4.3.2. Tank and Insulation Design
pressure vessel containing only a small amount of hydrogen
Similar to compressed gas hydrogen storage, liquid hydrogen must
• The system is lightweight because minimal material is required for
be stored in specially designed cryogenic tanks (cryotanks). For a given
each capillary and many can be stored together in a larger tank
application and fuel amount, liquid hydrogen tanks are typically lighter
than compressed gas hydrogen tanks primarily due to the reduced
At present, capillary hydrogen storage greatly exceeds DOE targets in
amount of tank wall thickness needed for storage. For instance with
many areas. However, capillary storage does not meet the DOE targets
CFRP liquid hydrogen tanks, tank gravimetric efficiencies of greater
for volumetric capacity and a large amount of energy is needed to
than 93% are achievable [43] compared to only about 6.5% achievable
release hydrogen from the capillaries. The systems also have limited
with compressed gas hydrogen storage made with the same material
long-term durability. Therefore, they are not currently in use [30].
[27]. This is mainly because tanks for liquid hydrogen storage are usu
ally thin-walled pressure vessels surrounded by a thick layer of insu
4.3. Liquid Hydrogen Storage lation, with insulation mass not being very significant when compared
to the mass of the tank. In addition to weight concerns, tank materials
4.3.1. Overview must be resistant to hydrogen embrittlement, impermeable to hydrogen
As shown in Table 1, hydrogen has much higher energy content in gas, and capable of effective structural performance under the thermal
liquid form than in the compressed gas state. The main advantage of the loads imposed by liquid hydrogen storage. Considering these factors,
storage of liquefied hydrogen is its high density at low storage pressure. different from compressed gas hydrogen storage, liquid hydrogen tanks
These features enable compact lightweight storage and efficient delivery are typically made from one material to be able to more effectively deal
options [11]. However, since hydrogen liquefies at cryogenic tempera with tank expansion and contraction movements due to thermal effects
tures below minus 250◦ C, a consequence of this is that at least 35% of [28].
the fuel’s energy content is needed to liquefy it during the liquefaction Considering tank wall material further and accounting for physical
process [30]. Furthermore, utilizing gas liquefiers adds more sophisti phenomena previously discussed; the material used for tank wall con
cation to the hydrogen production system and imposes significant struction must possess high strength, high fracture toughness, high
operational constraints on the fuel system since liquid hydrogen needs to stiffness, as well as low density and low permeation to liquid hydrogen.
be stored cryogenically [28]. Some of these constraints are listed below Fracture toughness is particularly important, especially because at
as follows: cryogenic temperatures many materials exhibit brittle characteristics
[44]. Historically aluminium and aluminium-lithium alloys have been
• Cryogenic storage requires an airtight insulation system to reduce utilized as tank wall material for liquid hydrogen cryotanks due to their
the boil-off of the liquid hydrogen to maintain it at cryogenic minimal susceptibility to hydrogen embrittlement. In recent times
temperatures however, composite materials have been increasingly selected and used
• Handling liquid hydrogen necessitates the use of specialised equip as wall materials in liquid hydrogen cryotank design and construction
ment and processes. Also, the storage of the liquid hydrogen is time- [43, 44] & [45]. In recent times improved lay-up design and tank liner
limited (due to boil-off) so the fuel usually needs to be manufactured design combined with novel tank wall design has allowed for minimal
on-site or at a nearby location hydrogen permeability on par with aluminium alloys for composite
• The fuel tanks need to be maintained at constant pressure, usually materials, particularly with CFRP. In [43] Northrop Grumman (see
around 1.45 × 105 Pa to minimize boil-off. This necessitates an Figure 10) designed a honeycomb sandwich tank wall concept. The
appropriate venting system and procedure for the cryogenic storage design utilised a perforated honeycomb core in a dual role to reduce
system
• Liquid hydrogen tanks and lines must be sealed off from the atmo
sphere. If air enters the tanks it will freeze solid and can block the
flow lines.
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B.C. Tashie-Lewis and S.G. Nnabuife Chemical Engineering Journal Advances 8 (2021) 100172
weight, where the honeycomb core between the two structural face This structural robustness is what minimises the potential for cata
sheets served as a structural stiffening member for cryogenic insulation. strophic failure greatly aiding the choice of vacuum-jacketed blanket
With this novel design utilising CFRP, a clean tank gravimetric efficiency insulation systems for liquid hydrogen storage in the future hydrogen
of greater than 93% is achievable. Studies in [40] utilising this tank economy. Considering thermal performance, Table 8 shows the repre
design as a baseline, showed that vehicle endurances of greater than 5.5 sentative insulation performance of LRMLI compared to MLI. For a 1 atm
days is achievable for High-Altitude-Long-Endurance Unmanned Aerial case it can be shown that MLI is significantly thicker and heavier than
Vehicles (HALE UAVs) employing electrified propulsion systems. Key LRMLI for the same heat leak, with the LRMLI advantage increasing with
design features identified driving ultra long endurance performance on additional layers [46].
the simulated mission were high hydrogen energy content and the
increased amount of stored on-board hydrogen energy contnt due to 4.4. Cryocompressed Hydrogen Storage
lower tank weigh fraction.
In addition to tank wall design and material selection, tank insu A third form in which hydrogen can be stored is cryocompressed
lation is a very important factor that typically must be considered for hydrogen. This is a novel technology that combines compression and
effective liquid hydrogen storage. Tank insulation is necessary to reduce cryogenic storage of hydrogen to produce cryocompressed hydrogen.
the amount of boil-off from the storage tanks to within an acceptable Cryocompressed hydrogen includes pressurized liquid hydrogen, cooled
rate (ideally less than 0.4% for a typical long-range/long-endurance compressed hydrogen gas, and two-phase systems of liquid hydrogen
mission) [28] & [38]. Without the insulation, the boil-off rate would with vapour in the headspace [30, 47] & [48]. Although this technology
make the use of liquid hydrogen completely impractical. Also, insulation is more sophisticated than liquid hydrogen and gaseous hydrogen
greatly minimises frost build-up on tank and piping outer surfaces. The pressure tank technologies and allows for more novel system integration
primary requirements on insulation design must be that it is impervious options in several different applications. The inherent complexity of the
to air to eliminate the possibility of frozen air particles forming and it technology limits its use when bespoke high performance is needed, e.g.
must be capable of withstanding the extreme thermal cycling to which it the need for high tank gravimetric efficiency in Aerospace or the need
will be subjected. Also, for applications where weight savings are for high miles per gallon for automotive applications. This is because its
important for economical mission performance such as in trans inherent complexity results in significant increases in manufacturing
portation, any installed insulation system must be as light as possible. cost, maintenance cost, fuel energy content loss, and design complexity
Thus insulation systems must have low thermal conductivity, low for only modest improvements in tank efficiency and capacity. For
thermal diffusivity, and a low mass density [44]. aerospace applications where high tank gravimetric efficiency and high
At present, the two main types of insulation used for liquid hydrogen fuel density are a must, liquid hydrogen cryotanks are better optimized
cryotanks are vacuum-jacketed systems/multi-layer insulations (MLI) for this application where cryocompressed hydrogen tanks are bulkier,
and rigid closed-cell foams. MLI systems are characterised by lower heavier, and contain lower density fuel. All these penalties are present
density and thermal conductivities than rigid closed-cell foams, how for only a modest reduction in overall fuel energy content loss during the
ever, they are more susceptible to catastrophic failures that cause dra liquefaction process. For the highly competitive automotive sector, the
matic increases in hydrogen boil-off rate [28] & [44]. In recent times, likely use of fuel cells in synergy with hydrogen fuel means that any
however, new MLI configurations have been designed and tested that improvement in fuel density is not enough to offset the significant in
greatly minimise the potential for catastrophic failure while improving creases in tank costs and complexity with worse tank-to-well efficiency
thermal performance. These are Integrated Multi-Layer Insulation for the typical driving ranges automotive vehicles undertake. In sta
(IMLI) and Load-Responsive Multi-Layer Insulation (LRMLI) developed tionary applications such as power generation, cryocompressed
in [46] and shown in Figure 11. They are innovative new technologies,
where polymer substructures are integrated with radiation barriers to Table 8
provide improved ultra-high thermal insulation systems. IMLI is made Insulation Performance for 20 K cold side and 295 K hot side with one-
up of layers of metalized polymer film separated by a polymer sub atmosphere pressure comparing LRMLI with MLI [46]
structure that allows for precise layer spacing control, as well as polymer LRMLI LRMLI LRMLI MLI same LRMLI MLI same
spacers that are intended for ultra-low heat conduction, resulting in layers Heat Leak thickness heat leak mass heat leak
improved thermal insulation performance. The LRMLI dynamic system (W/m2) (cm) thickness (kg/m2) mass (kg/
compresses a dynamic beam under atmospheric pressure to support an (cm) m2)
integrated, thin vacuum shell and disconnects under vacuum to mitigate 1 76 0.25 9.83 1.75 3.00
heat leak through the spacer. For both IMLI and LRMLI, the use of 2 38 0.44 19.48 1.94 5.92
3 26 0.63 29.08 2.12 8.94
spacers bonded to each Mylar layer allows for precise spacing resulting
4 19 0.82 38.68 2.31 11.755
in a more structurally robust blanket than what is achievable with MLI.
Figure 11. Conceptual Drawings of Integrated MLI and Load Responsive MLI [46]
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B.C. Tashie-Lewis and S.G. Nnabuife Chemical Engineering Journal Advances 8 (2021) 100172
hydrogen may have limited use for certain niche applications such as needed to prevent excess pressurisation which can destroy holding
offshore gas turbines for pipelines but this can only be identified after a structures due to hydrogen vapour build-up during delivery, transfer,
detailed design analysis and design selection review. Cryocompressed and refuelling events. One such technology option for the off-board
hydrogen may also be used in general research facilities where both storage of liquid hydrogen is the use of ground storage Dewar vessels
liquid and gaseous hydrogen are needed for general research & tech employing a triple-jacketed construction [51]. These Dewar’s vessels
nology development needs in multi-use flexible test-beds. have inner shells which contain liquid hydrogen. The inner shell is then
surrounded by a vacuum space, a liquid-nitrogen-cooled radiation
shield, another vacuum space, and an outer shell. This structure, in
4.5. Large Scale Hydrogen Storage
addition to having several shells, must be able to resist a full vacuum at
least on the outer wall. Such a construction, although bulkier than
Before use in a power conversion device as fuel, hydrogen at times
typical lightweight composite cryotank designs used for on-board liquid
will need to be stored in off-board stationary reservoirs before fulfilling a
hydrogen storage [43], are characterised by significantly reduced
refuelling demand in an on-board system of interest (whether this is in a
boil-off rates and tank inactivity pressurisation that makes them suitable
car fuel tank or power generation facility fuel tanks). The refuelling
for long-term storage of liquid hydrogen.
facility can either be near the hydrogen production system of interest to
store excess hydrogen produced ahead of transport or at a fuelling sta
5. Power Conversion
tion on a nationwide hydrogen network before automotive vehicle de
mand. For storing hydrogen this way before use as on-board fuel, storage
5.1. Overview
requirements will be different as hydrogen may at times need to be
stored at single locations for extended periods of time before on-board
At the final point in the hydrogen cycle, consideration needs to be
demand. As such; fuel venting losses, fuel boil-off, energy expenditure,
made to the characteristics of the energy conversion technology used to
structural performance, and lifing concerns are of prime importance
provide power in a given system. Considering the most feasible options
when designing and building a large-scale hydrogen storage system.
at present, hydrogen can either be directly reacted with air (oxygen) in a
Considering these requirements of a large-scale hydrogen storage sys
fuel cell to provide electrical power to a system; or hydrogen can be
tem, storing hydrogen in the compressed gas form is often the preferred
directly burned in an internal combustion engine instead of a fossil fuel.
alternative for minimised cost, reduced fuel energy content loss, and
The choice of which energy conversion device to use is heavily depen
reduced volumetric footprint. However different from storage on-board
dent on the application for which power is needed. Fuel cells are electric
a vehicle or within a power generation unit, technologies other than
power generators that convert stored chemical energy in hydrogen
high-pressure tanks become attractive options when hydrogen is to be
directly to direct current (DC) electric energy. This “directly” means the
stored for a long period without fuel offtake. One such promising tech
energy conversion is not carried out via a heat engine and thus fuel cell
nology option is the storage of compressed hydrogen in large under
efficiency is not subject to the limit of Carnot efficiency [52]. With fuel
ground geological formations such as salt domes (see Figure 12). Salt
cells, theoretical maximum efficiencies can reach over 80% [53]. This
domes are extremely impervious to hydrogen, even under high pres
far exceeds the theoretical maximums achievable with heat engine
sures, and effectively prevent leakage [31]. The technical feasibility of
thermodynamic cycles, where considering material temperature con
utilising salt domes for large-scale hydrogen storage in Europe has been
straints, theoretical maximum efficiencies range from 40% to 50% not
investigated in recent times in [26, 49] & [50]. In Europe, the overall
considering combined cycle layouts [54] & [55]. As such, fuel cells have
technical storage potential is estimated at 84.8 PW, 27% of which
increasingly been considered for use as prime-movers in the automotive
constitutes only onshore locations.
sector [56, 57] & [58]. However, scalability concerns of present designs
In the aerospace sector, the increased need for liquid hydrogen
are limiting their consideration for use in the power generation sector
means that there is a greater need for large-scale off-board liquid
whereas lower power-to-weight ratios than what is achievable with gas
hydrogen storage infrastructure. As such, an appropriate liquid
turbines limit their applicability in the aerospace sector. Hydrogen can
hydrogen storage technology is needed different to on-board liquid
still be used directly as a fuel in these sectors, but directly in an internal
hydrogen tanks with very low fuel boil-off rates the main concern rather
combustion engine or hybrid internal combustion engine-fuel cell
thanconcerns over tank weight. Also, an appropriate venting system is
Figure 12. General hydrogen distribution network utilising large-scale storage in salt domes/caverns [26]
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configuration rather than via a standalone fuel cell stack. recirculation mode; in addition to the fuel cell stack, a practical PEM fuel
cell generator consists of a hydrogen supply subsystem, cooling sub
system, airflow subsystem, and a power conditioning module (see
5.2. Fuel Cells
Figure 14). For a PEM fuel cell generator, the airflow subsystem provides
filtered, conditioned air to the fuel cell stack. A cathode air filter, a
5.2.1. Overview
cathode air blower, and a humidifier are the main components of the
There are several different fuel cell types with the main difference
airflow subsystem. The air filter removes volatile gas and solid con
being the nature of the electrolyte. However, the basic operating prin
taminates from the process airstream by chemical absorption using
ciple of all types is the same (see Figure 13). At the anode, a fuel such as
activated carbon media and mechanical filtration. The cathode air
hydrogen is oxidised into protons and electrons, whilst at the cathode,
blower has a variable speed motor controlled by a separate motor
oxygen is reduced to oxide species, and then these react to form water.
controller. A hollow-tube membrane humidifier transfers heat and hu
Depending upon the electrolyte either protons or oxide ions are trans
midity from the fuel cell stack exhaust to the inlet airstream. Temper
ported through an “ion-conducting”, but electronically insulating elec
ature control is performed with a pump to circulate coolant to remove
trolyte, while electrons travel around an external circuit delivering
the heat generated in the fuel cell stack. The heat is removed from the
electric power [53]. A fuel cell stack is several individual cells combined
coolant through a fan-radiator assembly. The power conditioning
in series to provide the requisite voltage for a given application. The two
module provides the proper interface between the stack power and the
main types of fuel cells considered for application in the hydrogen
external load with components that include a bidirectional DC/DC
economy are solid oxide fuel cells (SOFC) and proton exchange mem
converter, a secondary battery, a programmable electronic load, and a
brane (PEM) fuel cells. SOFCs have a higher theoretical maximum effi
power controller.
ciency over 80% they can achieve [53] compared to a theoretical
For a PEM fuel cell generator, an adequate hydrogen supply sub
efficiency of up to 68% for PEM fuel cells [56]. However considering an
system is needed to provide the fuel cell stack with fuel at an appropriate
application for the automotive sector, SOFCs operated at significantly
pressure and quality to achieve the requisite performance and system
higher temperatures than PEM fuel cells, conventionally between 800◦ C
reliability. Figure 15 shows the schematic drawing of a recirculation
- 1000◦ C. In addition to being more expensive, the elevated tempera
mode hydrogen supply subsystem [59]. The major components of a
tures present significant thermal management challenges for vehicular
supply subsystem are solenoid valves, pressure regulators, check valve,
applications. For large-scale stationary electric power generation, this is
mass flow meters, gas/liquid separator, pressure sensors, current sensor,
not as much of an issue as SOFCs can be integrated as either standalone
voltage sensors, purge orifice, exhaust gas recirculation (EGR) pump,
devices for more efficient electricity generation or hybrid SOFC-internal
and a microcontroller. The anode for the PEM fuel cell system is supplied
combustion engine configurations for combined heat and power (CHP)
with hydrogen from a high-pressure source (e.g. 200+ bar compressed
generation with efficiencies exceeding 80% [53].
hydrogen gas pressure vessel) which is reduced to 4.0 bar - 7.0 bar by a
directly operated pressure regulator in the hydrogen inlet pipeline. Two
5.2.2. PEM Fuel Cells
normally closed hydrogen inlet isolation solenoid valves allow the
PEM fuel cells typically operate between 40◦ C - 80◦ C [8] & [59] and
hydrogen to flow into the system which is actuated by solenoid coils.
as such are more attractive for vehicular, residential, distributed power
The solenoid valves are part of a safety loop and shut off the flow of
generation and portable electric applications [57] & [59]. Key reasons
hydrogen in the event of a safety sensor trip. Additionally, these valves
for this include their high power density, low emissions, and
are plumbed in series to provide redundant protection. Furthermore, a
low-temperature operation. Practical energy conversion efficiencies of
pressure matching regulator valve is installed on the hydrogen inlet
conventional PEM fuel cells reach between 50%-60% [56] & [59] which
pipeline, which ensures that the pressure of the incoming hydrogen is
is markedly higher than the 30%-40% achievable with piston engines
comparable to the cathode inlet pressure. The motivation for this is
[60] and hence why PEM fuels cells have increasingly been considered
enhanced durability of the membrane-electrolyte assembly in the fuel
as a potential replacement for internal combustion engines in trans
cell by balancing the pressures across the electrolyte membrane.
portation [57]. Despite these advantages, key development challenges
Hydrogen that is not consumed in the anode is circulated back to the
facing PEM fuel cells include fluid flow management and thermal
anode via a hydrogen recirculation passage. An EGR pump is used to
management across the fuel stack and these factors result in the need for
recirculate the unused hydrogen from the anode exit to the anode inlet.
emergent systems and components integrated around the fuel cell stack
This recirculation circuit also has two additional functions. First, a
for effective power system operation. To improve PEM fuel cell dura
gas-liquid separator is installed in the recirculation passage to separate
bility and stability in commercial applications, advances in the design
the liquid water from the unused hydrogen that prevents the build-up of
and control of reactant flows across a PEM fuel cell stack are essential.
liquid water in the stack channels. Then, through an orifice and a purge
Studies in [59] considered architecture options for the advanced systems
valve, inert gases (such as nitrogen) and limit hydrogen are exhausted
integration of a PEM fuel cell generator. Considering three hydrogen
supply schemes of a flow-through mode, dead-end mode, and
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B.C. Tashie-Lewis and S.G. Nnabuife Chemical Engineering Journal Advances 8 (2021) 100172
Figure 15. Details of hydrogen recirculation mode of the fuel cell generator [59]
into the cathode inlet before reintroducing the unused hydrogen back 5.3. Internal Combustion Engines
into the main hydrogen passage. The use of high-quality hydrogen from
a non-fossil fuel source in the anode limits any harmful effects on the 5.3.1. Piston Engines
PEM fuel cell electrodes. A microcontroller controls decision-making in Considering automotive application, fuel cell technology although
the hydrogen supply subsystem to ensure proper operation of the PEM promising with the offer of higher efficiencies than what is achievable
fuel cell generator with data extracted from installed sensors and mass with piston engines, is still a long way from being competitive with
flow meters. piston engines on an economic basis. With hydrogen being able to be
PEM fuel cells are particularly attractive for power levels ranging directly used in piston engines as fuel, the use of piston engines as a
from low (less than 1 kW) to intermediate (up to 50 kW), and for ap prime mover in the hydrogen economy is a feasible option as a transition
plications requiring rapid start-up and quick response to load changes. technology up until the time fuel cell technology becomes cost-
The electrolyte in the PEM fuel cell is an ion-exchange polymer mem competitive against piston engines. An additional advantage of using
brane. The only liquid in the cell is water, which keeps corrosion piston engines in the hydrogen economy is that the level of technology
problems minor. The fuel cell must operate under conditions where maturity is much higher than what is currently the case with fuel cells,
water output does not evaporate faster than it is produced to avoid this means that operational system safety and reliability issues are most
membrane dehydration [57]. The emergent systems in the fuel cell likely to be lower with hydrogen piston engines than what is the case
generator such as the hydrogen supply subsystem, cooling subsystem, with hydrogen fuel cells at present. Considering spark-ignition engines,
airflow subsystem, and power conditioning module are specified to hydrogen can be added either through manifold induction or by the
ensure this is not the case for effective water management in the direct introduction of hydrogen into the cylinder. With hydrogen added
membrane to ensure high performance. to the cylinder for combustion purposes, the very wide flammability
limits of hydrogen (see Table 3) means that hydrogen engines can
5.2.3. Recent Industrial Development Efforts operate at extremely lean mixtures when compared to other conven
In recent times, several companies have advanced their fuel cell tional spark-ignition engine fuel options such as gasoline. As a result
development efforts for ever more increases in system performance and hydrogen piston engines achieve slightly higher efficiencies than gaso
reductions in manufacturing cost. A company called Ceres has devel line ones at a cost of slightly increased wall heat losses. The main
oped a SOFC called the “SteelCell®” which is a fuel cell that has multi- challenge though of operating hydrogen engines is architecting them to
fuel capability allowing it to operate on several different fuels from avoid abnormal combustion and backfiring problems associated with
natural gas to hydrogen allowing for a smooth transition to a hydrogen the very low ignition energy of hydrogen [60]. Table 9 shows a summary
economy from a fossil fuel one. Key advantages include the of the benefits and challenges of utilising hydrogen as a fuel for piston
manufacturing of steel to allow it to be cost-effective, robust, and scal engines along with identified ways of improving engine performance
able [61]. In CHP configurations, claimed efficiency of the fuel cell is up and reliability [60] & [63].
to 90% which is better than conventional SOFCs. Another organisation
called Bramble Energy has developed a novel PEM fuel cell called the 5.3.2. Gas Turbines
printed circuit board fuel cell (PCBFC). The key advantage of this For large-scale power generation, today gas turbines and diesel en
approach is the design of the fuel cell on a printed circuit board which gines are the main options for use as a powerplant. Although lower
allows for a reduced number of fuel cell stack components allowing for a specific fuel consumption (SFC) values are achievable with diesel en
more affordable fuel cell. The PCBFC has 3.8x fewer components than a gines compared to gas turbines; disadvantages to their use include lower
traditional fuel cell. Additionally, the cost of manufacturing a printed power-to-weight ratio, lower power-to-volume ratio, worse emissions,
circuit board is significantly reduced compared to the manufacture of higher maintenance costs, higher vibration levels, and lack of multi-fuel
components of a traditional fuel cell [62]. capability. Thus in recent times, the gas turbine has become a major
player in the power generation market. Additional contributing factors
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B.C. Tashie-Lewis and S.G. Nnabuife Chemical Engineering Journal Advances 8 (2021) 100172
experience of operating with hydrogen in both simple and combined Organisations such as NASA and the European Union have set highly
cycle layouts [71]. Thermal efficiencies of up to 43% in simple cycle and ambitious targets of up to 75% reduction in CO2 emissions, 90%
64% in combined cycle configurations are achievable with their engine reduction in NOx emissions, and a 70% reduction in fuel burn for
families for power ratings between 290-571 MW. Companies like Mit aviation technologies with entry-into-service (EIS) for the 2035-2050
subishi Power Systems, Siemens Energy, and Ansaldo Energia also have timeframe compared to typical to state-of-the-art aircraft in 2000 [74]
gas turbine product ranges that can run on liquid hydrogen [72]. & [75]. The use of liquid hydrogen as a fuel for jet engines brings into
For aircraft applications, the assessment of hydrogen cannot be play the potential for novel revolutionary engine system architectures
limited to only assessment at the powerplant level. The fact that liquid beyond its use as an engine fuel that can enable aviation technologies to
hydrogen is used as gas turbine fuel means that assessment needs to meet these targets. This is primarily due to the cryogenic nature of the
account for the storage of fuel onboard the aircraft. As previously stated, hydrogen storage on-board an aircraft and engine; liquid hydrogen can
liquid hydrogen has a volumetric energy density of about 3.6 times act as a highly effective heat sink which allows for the synergistic
lower than kerosene (see Table 1). Additionally, liquid hydrogen needs integration of several novel technologies that can significantly increase
to be stored in specially designed cryotanks while kerosene can be stored propulsion system performance. This is despite the system penalties that
in the easily-to-install lightweight bladder or integral tanks on a given arise from its use such as increased storage penalties, fuel cost, and fuel
airframe. As a consequence, for a conventional tube-and-wing aircraft energy content loss from the liquefaction process. A key technology that
design, the use of hydrogen is characterised by the installation of larger has been proposed to meet these targets is turboelectric distributed
and heavier tanks. Figure 16 shows a Boeing 737-sized airplane designed propulsion (TeDP), a novel electrified propulsion system concept that
to use liquid hydrogen [39]. The heavy cryogenic fuel tanks increase the synergistically takes advantage of liquid hydrogen for significant in
operating empty weight (OEW) of the aircraft by 13% above what is the creases in integrated aircraft-propulsion system performance.
case for the kerosene-fuelled aircraft. However, due to the higher TeDP is a radical novel propulsion system technology that electri
gravimetric energy density of the fuel compared to kerosene, the total cally decouples the gas turbines from the main propulsor units (either a
fuel mass is lighter and thus take-off weight is lighter. Engine down fan or a propeller) in the place of a mechanical transmission. The electric
sizing is possible with reduced take-off weight and fuel mass and this transmission is typically achieved through an electrical network that
engine size-reduction allows for slightly smaller wings. Significant wing consists of motors, generators, and power electronics (see Figure 17)
size reduction is limited by the need for the wing to generate enough lift [76]. Physically, this means that different from conventional jet engines
to carry the additional weight from installed cryotanks. Because of the is that propulsors can be situated anywhere on an airframe instead of
tanks, for a 500 n.mi mission, a relatively short mission range, about the fixed to the gas turbine because the mechanical coupling has been
distance from London to Milan, overall mission energy consumption is eliminated. With propulsors electrically decoupled from core gas tur
increased because the aircraft does not have a sufficient amount of time bines, multiple smaller and lighter propulsors can be utilized to provide
to fully utilize the energy content of the fuel on board to offset cryotank an equivalent amount of thrust as 2-4 large propulsors (due to an area
dead-weight penalties. From studies in [39], this represented a 28% sizing effect). Also, the expanded aircraft-engine design space allows for
increase in energy consumption over a 500 n.mi range mission. How designs that take advantage of novel aerodynamic phenomena such as
ever, as the mission range increases, the discrepancy in energy con boundary-layer-ingestion (BLI) and propeller-wing slipstream lift
sumption between a kerosene-fuelled aircraft and a hydrogen one augmentation for dramatic improvements in integrated
reduces. For the airplane in Figure 16, at 3000 n.mi range, about the aircraft-propulsion system performance such as an increase in aircraft
distance between London and New York, this difference reduces to only aerodynamic efficiency, increase in propulsion system propulsive effi
2%. In studies for larger aircraft flying longer ranges, total energy ciency, reduction in wing size, reduction in aircraft tail size, reductions
consumption reduction of up to 10.4% is possible for an Airbus in gas turbine size, reductions in gas turbine weight, elimination of
A340/Boeing 777 sized aircraft modelled with a hydrogen-powered aircraft control surfaces and an overall reduction in aircraft weight.
turbofan over a kerosene-powered turbofan with the same thermody Focusing on the propulsion system level and propulsion-airframe
namic cycle over a 4000 n.mi mission [73]. Modelling was carried out boundary, the below are stated benefits of employing TeDP technol
with NASA’s FLOPS simulation tool and Gasturb. ogy over conventional jet engines:
5.3.3. Enabling Turboelectric Distributed Propulsion • Significant increase in engine effective bypass ratios (eBPRs) for a
In civil aerospace, there have been additional targets and technology significant increase in propulsive efficiency due to the option to
goals set in addition to the Paris Agreement for new aircraft concepts install a larger number of propulsors on the aircraft with reduced
and propulsion system technologies for greener aircraft operation. weight and drag penalties.
• Reduced gas turbine noise due to increased electric power offtake
and increased eBPR
• Symmetric thrust in the event of a gas turbine or generator failure.
All propulsors can continue to operate at a reduced but symmetric
thrust with electric power output from the remaining turbogenerator
using a common bus network
Figure 16. Hydrogen-powered airplane design and performance compared to a Figure 17. A typical TeDP architecture showing electric power distribution
kerosene fuelled aircraft on a 500 n.mi mission [39] network [76]
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B.C. Tashie-Lewis and S.G. Nnabuife Chemical Engineering Journal Advances 8 (2021) 100172
• The potential for the use of differential thrust for aircraft yaw control Table 10
in novel flight modes Comparison of the power densities and efficiencies of conventional state-of-the-
• The incorporation of an energy storage device (e.g. battery, flywheel, art electric machinery to superconducting & cryogenic machinery for TeDP
etc.) allows for hybrid modes of operation in a hybrid electric application
distributed propulsion (HeDP) system architecture for increased Power Density
engine SFC Component State-of-the-art Conventional Superconducting & Cryogenic
(kW/kg) (kW/kg)
• Depending on the TeDP architecture configuration of choice, the
decoupling of gas turbines from propulsors allows for both devices to Generator 8.22a [79] 41.6c [77]
run at their optimal rotational speeds throughout a given flight en Motor 8.22a [79] 22.0d [77]
Power Converter 16.4 [78] 32.9e [78]
velope for maximum off-design system efficiency
Transmission 18.3b 227.1f [78]
Lines
Some major challenges associated with practical implementation of Transmission Efficiency
TeDP are (1) the effective management of increased system complexity; Component State-of-the-art Conventional Superconducting & Cryogenic
(kW/kg) (kW/kg)
(2) the weight increase to the overall propulsion system (in addition to
Generator 95.0%a [79] 99.98%c [77]
the gas turbine) from integrating motors, generators, and power elec Motor 95.0%a [79] 99.97%d [77]
tronics to the overall propulsion system for the power levels required for Power Converter 95.0% [78] 99.93%e [78]
propulsion; and (3) electric transmission loss minimisation. Studies for Transmission ≈ 100%b ≈ 100%f [78]
the N3-X aircraft, a Boeing 777-200LR class-sized aircraft that has a Lines
novel blended-wing-body (BWB) airframe employing TeDP, show that a) Halbach array architecture assumed – not accounting for power scaling effects
power ratings for electrical machines can reach up to 40 MW [77] & b) Assuming material used for transmission lines is copper
[78]. As such, the use of fully-superconducting machinery and cryogenic c) Use of MgB2 for stator and rotor material – 22 MW machine
power electronics have been identified as key enabling technologies for d) Use of MgB2 for stator and rotor material – 3 MW machine
TeDP. This is because they allow for significant increases in component e) Operation at cryogenic temperature
power densities and transmission efficiencies compared to current-day f) HTS transmission
state-of-the-art electric machines. Superconducting machines are built
with materials that lose all their electrical resistance below a critical cooling can then be subsequently used as an engine fuel for an
temperature which allows them to carry a significantly large amount of improvement in integrated aircraft-engine performance. The use of
current in small wires. This leads to light-weight, compact, very efficient liquid hydrogen use allows for powerplant operation with reduced SFC
motors and generators. Operating temperatures when using and ultimately a reduced fuel mass stored on the aircraft. Studies in [77]
high-temperature-superconducting (HTS) materials for superconducting for the N3-X aircraft, a Boeing 777-200LR class aircraft employing a
machines range between 20 K and 65 K [75]. Machines with power TeDP system with aggressive technology assumptions showed that
ratings up to 35 MW and 15,000 rpm have been designed and tested. The mission fuel burn could be reduced by 70%-72% compared to the more
higher-performance machines are aimed at military applications, but conventional Boeing 777-200LR-like aircraft without compromising
commercial prototypes are starting to emerge. A major development payload, range, or cruise speed.
challenge today is the production of machines with both fully super
conducting rotor windings and stator windings. Today most of the 6. Concluding Remarks
state-of-the-art machines considered superconducting are made with
only the rotor windings being superconducting. The stator windings, Public concerns over climate change has grown in recent times, and
that are the high-power windings that cause the majority of the losses, as such, more initiatives such as the Paris Agreement are being adopted
are made of copper and run at room temperature. From known studies, by more and more by Governments, organisations and institutions
only a few small experimental machines have been made with super around the world. This coupled with concerns over the sustainability of
conducting stator windings. fossil fuel use in the long-term have brought to the public view the need
For power converters, it has been shown that higher power density to invest-in and develop low carbon technologies for continued global
and higher efficiency can be achieved when the devices are operated at security. An attractive fuel option that has been proposed in recent times
cryogenic temperatures. This results from decreased forward resistance for the realisation of a green economy is hydrogen. Hydrogen is a fuel
in the transistors of more than an order of magnitude, higher switching that has a gravimetric energy content about 2.5 to 3 times greater than
speeds, lower resistance in interconnections, and some cases improved most fossil fuels and its combustion produces zero CO2 emissions. Other
heat transfer from the components to a cooling medium. The higher benefits of utilising hydrogen as a fuel include its attractive combustion
switching speed reduces the mass of the capacitors required for filtering characteristics such as its very low flashpoint (-231◦ C) and its wide
and reduces the switching losses. Table 10 shows a comparison of the flammability range (4%-75%). Considering the benefits further,
power density and efficiency goals set for superconducting machines hydrogen as a fuel can also be produced from surplus electricity gen
and cryogenic electric machinery versus typical values for current-day eration from renewable energy sources such as wind, solar, geothermal,
state-of-the-art [78]. To achieve the performance goals for electric ma etc. for significantly reduced carbon footprints when accounting for
chinery necessary in a TeDP architecture, an appropriate cooling system well-to-wheel transmission. As such a hydrogen economy centred on the
is needed. Cryocoolers are devices that typically reduce ambient con production, distribution, and storage of hydrogen as a fuel for power
ditions to cryogenic temperatures and they have been suggested as a generation purposes has been proposed as a significant step in the shift
method to cool TeDP systems. However present-day state-of-the-art to a low-carbon economy.
cryocoolers today only have power densities of about 55 W/kg and their Considering hydrogen technologies in more detail, the major systems
efficiencies reach up to 30% of Carnot efficiency. Thus their use imposes in the hydrogen economy that need to be developed and/or deployed in
additional weight penalties and power transmission losses on a TeDP the hydrogen economy are production infrastructure, the distribution
system leading to lower than expected aircraft fuel savings. As such network, storage technologies and power conversion device technolo
liquid hydrogen was proposed initially as a more lightweight solution gies. Each one of technology areas have already been developed to high
for system cooling due to installed liquid hydrogen cryotank systems levels of maturity with proof-of-concept commercial prototypes already
being lighter than present day state-of-the-art cryocoolers for the same developed as is the case with proton exchange membrane fuel cells that
thermal load. However, since liquid hydrogen is already being stored via electrolysis combine hydrogen and oxygen. The major challenge
on-board the aircraft for cooling, the same liquid hydrogen used for though with the uptake of key enabling systems and technologies in the
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B.C. Tashie-Lewis and S.G. Nnabuife Chemical Engineering Journal Advances 8 (2021) 100172
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