Renewable and Sustainable Energy Reviews 167 (2022) 112743

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Renewable and Sustainable Energy Reviews

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Hydrogen storage methods: Review and current status

Muhammad R. Usman a, b, *
a
Department of Petroleum and Chemical Engineering, Sultan Qaboos University, Muscat, 123, Oman
b
Institute of Chemical Engineering and Technology, University of the Punjab, Lahore, 54590, Pakistan

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

Keywords: Fossil fuels comprising coal, crude oil, and natural gas are non-renewable and greatly harmful to the environ­
Hydrogen economy ment. Hydrogen, on the other hand, is both sustainable and environmentally friendly. However, due to its light
Hydrogen storage weight and gaseous nature, it presents challenging problems of its storage, and the practical hydrogen storage is
Compressed hydrogen
perhaps the biggest hurdle in the success of the hydrogen economy on a large scale. Hydrogen can be stored in a
Complex hydrides
Liquid organic hydrogen carriers
variety of physical and chemical methods. Each storage technique has its own advantages and disadvantages. It is
the subject of this study to review the hydrogen storage strategies and to survey the recent developments in the
field.

1. Introduction requirement. Additionally, moderate operating conditions, low enthalpy

change, and fast kinetics of the hydrogen storage and release are the
Hydrogen has the highest energy content per unit mass (120 MJ/kg requirements. Safety, low cost, and public acceptance are the other
H2), but its volumetric energy density is quite low owing to its extremely important factors. There are numerous physical and chemical hydrogen
low density at ordinary temperature and pressure conditions. At stan­ storage techniques with their own features and storage capacity that
dard atmospheric pressure and 25 ◦ C, under ideal gas conditions, the may be proved favorable in the development of a future hydrogen
density of hydrogen is only 0.0824 kg/m3 where the air density under economy. It is the purpose of this study to review the currently available
the same conditions is 1.184 kg/m3. This low density of hydrogen results hydrogen storage methods and to give recommendations based on the
in an extremely low volumetric energy content of hydrogen that is 0.01 present developments in these methods.
MJ/L H2 at ambient conditions and 8.5 MJ/L H2 for the liquefied H2
(LH2) [1,2]. In comparison, the volumetric energy contents of methane 2. Hydrogen storage methods
and gasoline are 0.04 MJ/L and 32 MJ/L, respectively. The low volu­
metric energy density of hydrogen is certainly a great hurdle in the The followings are the principal methods of hydrogen storage:
economic and efficient storage of hydrogen and ultimately in the success
of the hydrogen economy. In a developed hydrogen economy, hydrogen Compressed hydrogen
is expected to be used both for the stationary as well as for the on-board Liquefied hydrogen
purposes. Hydrogen storage for a stationary application is far less Cryocompressed hydrogen
challenging than for an onboard application. For the stationary appli­ Physically adsorbed hydrogen
cations, the weight of the storage system that is gravimetric hydrogen Metal hydrides
density is less of a concern than the volume of the storage system or Complex hydrides
volumetric hydrogen density. For the on-board applications, on the Liquid organic hydrogen carriers (LOHC) or Liquid organic hydrides
other hand, both the gravimetric as well as volumetric densities are
crucial though volumetric energy density is relatively less important for Fig. 1pictorially represents the concept of these hydrogen storage
a large-sized vehicle. For the on-board storage adequate amount of methods whereas Table 1 gives a comparison among them.
hydrogen is required to travel a reasonable distance without refueling In the following sub sections, the above mentioned hydrogen storage
the vehicle. A storage method that gives both a high gravimetric energy methods will be discussed and their characteristic features will be
density and a high volumetric energy density is, therefore, a highlighted.

* Department of Petroleum and Chemical Engineering, Sultan Qaboos University, Muscat, 123, Oman.
E-mail address: mrusman.icet@pu.edu.pk.

https://doi.org/10.1016/j.rser.2022.112743
Received 21 July 2020; Received in revised form 14 June 2022; Accepted 26 June 2022
Available online 6 July 2022
1364-0321/© 2022 Elsevier Ltd. All rights reserved.
M.R. Usman Renewable and Sustainable Energy Reviews 167 (2022) 112743

2.1. Compressed hydrogen Table 1

Comparison of various hydrogen storage methods [1,7,11,84,89,92,99,125,
The most widely used method of hydrogen storage is the compressed 126].
hydrogen at high pressure [2,3]. The compression of hydrogen is not Storage method Hydrogen Volumetric Volumetric
only a well-developed technology [2, 4–7], but it also offers high rates of content (wt% density (g/L) energy density
hydrogen filling and release [3]. Additionally, no energy is used for the H2) (MJ/L)

release of hydrogen [8,9]. However, compression of hydrogen to a high Compression

pressure consumes about 13–18% of lower heating value of hydrogen [8, 1 bar, RT 100 0.0814a 0.01
350 bar, RT 100 24.5b 2.94
10] which affects the overall economics of the process. The good news is
700 bar, RT 100 41.4b 4.97
that the increase in pressure only slightly increases the power required 700 bar, RT, (inlc. Type 5.7 40.8 4.9
for the compression [9]. Hydrogen is stored in cylindrical vessels as IV tank)
spherical vessels are difficult to fit onboard. A light weight and low cost Liquid hydrogen
vessel material that can withstand high pressure is required. The 1 bar, − 253 ◦ C 100 70.8 8.5
1 bar, − 253 ◦ C (inlc. 14 51 6.12
selected material must be able to resist hydrogen diffusion and the likely tank)
embrittlement caused by the stored hydrogen. Cryo-compression
Based on the above criteria, four different types of vessels are used 350 bar, − 253 ◦ C 100 80 9.6
for the storage of compressed hydrogen gas [7, 11–13]. Metal hydrides
MgH2 7.6 110 13.2
Type I: These are the cheapest option [13]. The vessels are made of
FeTiH2 1.89 114 13.7
metallic materials and capable of withstanding pressure up to 30 bar Complex hydrides
[11,12]. For high hydrogen pressures or densities, the metal wall needs NaAlH4 7.5 80 9.6
to be relatively thick. This increases the weight of the storage vessel and Physical adsorbents
substantially decreases the net hydrogen gravimetric energy density. Activated carbon @77 K 5.0 38.5 2.4
and 30–60 bar
The vessels offer extremely low gravimetric energy density as about 1 wt
Zeolite (NaX) @77 K and 2.55 20 2.4
% H2 is only successfully stored [11,12,14] in a practical manner. The 40 barc
most common material of construction is steel or aluminum alloy [6,11]. MoF (MOF-210) @77 K 7.9 25.8 3.1
Type II: In these vessels, the metallic wall is wrapped with fiber resin and 80 bar
Liquid hydrogen organic carriers
composite on the cylindrical part [11,12]. Compared to Type I, they
Methylcyclohexane/ 6.2 47.3 5.68
have 30–40% less weight at the expense of 50% more cost [13]. toluene
Type III: These are made of carbon fiber composite materials (carbon perhydro- 6.2 56.0 6.72
fiber reinforced plastic, CFRP) lined with metal such as aluminum [2]. benzyltoluene/
They are strong and light weight, but have low thermal conductivity benzyltoluene

which may pose problem for low rate of heat release during the a
Calculated from ideal gas law.
compression of hydrogen [2]. They are suitable for applications b
Calculated from the standard form of the Peng-Robinson equation.
c
requiring 450 bar pressure [13]. However, they can be used up to 700 Assuming same density as activated carbon.
bar hydrogen pressure.
Type IV: Similar to Type III, these are made entirely of composite A kind of Type V vessel is a modification of Type IV with reinforcing
materials. However, they are different from Type III in that the liner in space filling skeletons [17] and designed to have even higher hydrogen
Type III is mostly metal liner which contributes ≥5% of mechanical volumetric and gravimetric densities. These vessels are, however, yet
strength [11,13]. For Type IV, the liner is mostly polymeric as that of not available commercially. More detailed construction features of the
high density polyethylene (HDPE) and hardly a metal [11,12]. They are hydrogen storage vessels are given by Barthelemy et al. [11].
also used to store hydrogen at 700 bar pressure. Type IV cylinders of Hydrogen stored at 700 bar in Type III or Type IV vessel may provide
Hexagon Composites [15] or NPROXX [16] are polymer lined, filament a practical solution with refueling time less than 3 min and driving 500
wound carbon fiber reinforced polymer (CFRP) structures. km [10]. At 700 bar with Type IV vessel, hydrogen has energy density of

Fig. 1. Concept of hydrogen storage methods.

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M.R. Usman Renewable and Sustainable Energy Reviews 167 (2022) 112743

5.7 MJ/L [7]. However, onboard pressurized vessels have less public [11,30] is used in the liquefaction process. Another issue is the boil-off
acceptance [4] and have increased risks of explosions due to sudden phenomenon, which is the loss of hydrogen due to energy input from the
possible shocks. Sophisticated valve technology is required to decrease surroundings. It is estimated that about 1.5–3% of hydrogen vaporizes
the pressure of 700 bar to engine inlet pressure. Ideally, energy can be per day [3,31]. The boil-off phenomenon also requires more open spaces
recovered during the expansion process [8], but it requires complicated for public parking and garages [32,33]. A double walled vacuum vessel
design and extra weight of turbine on the vehicle. Practical problems of with excessive and expensive insulation can be used to decrease the
refueling at 700 bar [18] and associated safety issues at the filling sta­ boil-off. Moreover, larger the container having smaller surface to vol­
tions are also there. Moreover, hydrogen fuel infrastructure including its ume ratio, the smaller will be the evaporation loss [9,31]. The special
transportation and dispensation (filling stations) is required [4,19]. design and insulation may increase the weight of the vessel thus reduce
Fuel cells vehicles working on compressed hydrogen are commer­ the gravimetric energy density. Liquid hydrogen infrastructure [1,14]
cialized and more and more vehicles are sold and running on the roads. and possible public acceptance are additional challenges [30].
Examples are Toyota Mirai (2021) and Hyundai Nexo (2018, an Although, BMW and GM/Opel have developed test vehicles such as
improvement over the previous generation, Hyundai Tucson) both of BMW Hydrogen 7 (hydrogen consumption in an internal combustion
which use compressed H2 at 700 bar, three Type IV cylinders, and travel engine) and GM Hydrogen 3 (hydrogen to be used in a series of fuel
more than 600 km in single charge [20,21]. Commercial Hyundai truck cells), respectively based on liquefied hydrogen [2,31], but owing to the
uses hydrogen at 350 bar and can travel ~400 km in one fill [22]. extreme low temperature conditions and boil-off phenomenon there is
Hydrogen fuel infrastructure is also developing in different parts of the no potential for the liquefied hydrogen to be used on-board [11] espe­
world though at rather slow pace. One such example of hydrogen stor­ cially in small to medium vehicles. Where the dormancy period is small,
age and distribution is developed by Hexagon Composites Company liquefied hydrogen has the potential. Commercially it is used in space­
[23]. crafts where cost has no issue and dormancy period is not available.
Compressed hydrogen gas can also be stored in glass microspheres of Recently, Sinot has developed a 112 m long fuel cell yacht, Aqua, that
the size, say, 5–500 μm [9]. The microspheres offer reasonable (5.4 wt runs on liquid hydrogen [34].
%) gravimetric H2 density [24]. The microspheres can be loaded with
high pressure hydrogen gas (350–700 bar) [24] on off-site and delivered 2.3. Cryo-compression
to the filling station [2,4], thus eliminating the need for the hydrogen
infrastructure [2]. They appear to be safer than compressed hydrogen in In the cryo-compression the aspects of both the compressed gaseous
cylinders as the bulk hydrogen storage is at low pressure. Moreover, the hydrogen and the cryogenic hydrogen are combined. The hydrogen is
glass spheres do not necessarily require a cylindrical or spherical shape stored at cryogenic temperatures and under minimum hydrogen pres­
of tanks. However, the glass microspheres or similar structures offer low sure of 250–350 bar [3,27,35,36], much higher than the critical pressure
volumetric energy density and require energy [9] and high temperature of hydrogen (13 bar). In comparison to the liquefied hydrogen, the
for the release of hydrogen, i.e., temperatures of 200–300 ◦ C [24]. They cryo-compressed hydrogen offers higher densities, ~80 g/L [4,11,13],
slowly release hydrogen at ordinary temperatures thus hydrogen is lost nearly 10 g/L higher than the density of liquefied hydrogen, and greatly
during the handling and transportation and they are susceptible to reduced boil-off losses [11,12]. Ahluwalia et al. [37] observed
breakage during charging, discharging, and transportation [9]. dormancy period that lasts more than 7 days without the loss of
Underground geological caverns can also store hydrogen [1,6,25, hydrogen while filling the cryo-compressed hydrogen vessel 85% to its
26]. This solution is suitable for long period of storage [1,6], however, full capacity. However, a more expensive double walled, Type III vessel
there may be issues of hydrogen purity due to impurities present in the is to be used [11] and increased energy input is required [12]. The rates
caverns [1]. HyUnder project in Europe [25] is an example of under­ of hydrogen release and refueling the tanks remain rapid [13,36] and
ground hydrogen storage in salt caverns. the availability of hydrogen infrastructure as demanded by compressed
hydrogen and liquefied hydrogen is still a challenge [1].
2.2. Liquefied hydrogen storage
2.4. Metal hydrides
In the liquid or cryogenic form hydrogen (LH2) has much higher
density and therefore volumetric energy density increases to a large Hydrogen chemically interacts with metals and metal alloys to form
extent. The density of liquid hydrogen reaches to around 71 g/L at metal hydrides. The hydride is formed when a hydrogen molecule is
− 253 ◦ C [6] where its energy density becomes equal to 8 MJ/L H2 [2]. It dissociated into atomic hydrogen at the surface and then diffuses into
can, therefore, be said that 4 cylinders of LH2 are equivalent to 1 gas­ the bulk and chemisorbed in the metal or alloy structure [11,18]. This
oline tank. Considering the weight of insulation and the tank weight, chemisorption may cause the lattice to expand to about 20–30% of its
though, a lower value is achieved. The critical temperature of hydrogen original volume [10]. The hydride formation occurs either by direct
is − 240 ◦ C (above which hydrogen cannot be liquefied), therefore reaction of hydrogen with the metal or by the electrochemical dissoci­
hydrogen has to be cooled below its critical temperature for the lique­ ation of water molecule [16,31]. The two reaction mechanisms are
faction. Hydrogen is liquefied to − 253 ◦ C (normal boiling temperature shown below [9,38]:
of hydrogen) [27] for storage as liquid. Similar to compression of
hydrogen, liquid hydrogen storage is a well-established technology [7]. Mechanism 1: Direct hydrogen reaction: M + x/2H2 ↔ MHx
Liquefied hydrogen offers high rates of hydrogen release similar to
Mechanism 2: Electrochemical dissociation of water: M + x/2H2O + x/2 e‒ ↔
compressed hydrogen [7] and low adiabatic expansion energy at cryo­ MHx + x/2 OH−
genic condition [13,27,28]. The low adiabatic expansion energy is
useful in avoiding damage when H2 will be suddenly leaked through an where, M is a metal or alloy.
opening. As the liquid hydrogen density is nearly 1.5–2 times as that When the hydride is formed the heat energy (of chemisorption) is
obtained with hydrogen compressed at high pressure, the tank size re­ evolved, whereas in the reverse reaction (desorption) to release the
duces to an acceptable value. Storage is at low pressures so rather thin hydrogen to be utilized in a commercial facility, an equal amount of
and cheap storage tanks can be used. In the liquid form hydrogen is energy has to be provided from an outside source. The reversible reac­
non-corrosive [29] and stainless steel and aluminum alloy vessels with tion is caused either by decreasing the pressure or by increasing the
sufficient insulation are used for the cryogenic storage. However, the temperature [39]. An understanding of the thermodynamics of the
cost of liquefaction is high so is the energy used for the liquefaction [1,9, process is thus important. An account of thermodynamic
18]. It is realized that about 30–40% of net heating value of hydrogen pressure-composition-temperature (PCT) measurement of a metal

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M.R. Usman Renewable and Sustainable Energy Reviews 167 (2022) 112743

hydride can be read in Møller et al. [10] and Graetz [39]. nanostructuring, and nanoconfinement. For example, it is known that
The metal hydrides can offer higher hydrogen storage capacity than ball milling decreases the particle size and the crystal grain size, de­
the compression and the liquefaction [2,3,6,11,18] and store hydrogen creases the diffusional resistance, and creates defects in crystals [31].
at moderate temperature and pressure [2,3,18]. As the operating con­ Reducing the particle size increases the surface area of the material and
ditions are less severe than the gas compression and the liquefaction, the thereby the rate of adsorption is enhanced (as adsorption is a surface
use of metal hydride is a safer option than the two [27]. Moreover, the phenomenon). Shorter diffusional paths decrease the time for hydrogen
loading and the release of hydrogen can be carried out as many times as to reach at the active sites of the metal or alloy. Crystal defects create
required unless impurities hinder the operation [40]. Moreover, gener­ more amorphous phase which improves the thermodynamics [2,46].
ally many metal hydrides require moderate energy (20–55 kJ/mol H2) More elaborated discussion about the above mentioned methods for
[39]. On the other hand, metal hydrides have drawback of having low improving the properties of the metal hydrides can be found in Ren et al.
sorption and desorption kinetics, high hydrogen release temperature, [41], Reardon et al. [47], Wu [48], Pukazhselvan et al. [49], Wang and
and formation of undesirable gases during discharging the hydrogen Wang [50], Zhu et al. [51] and Abe et al. [6].
[39,41]. For the on-board applications, there should be enough energy Among the metal hydrides, MgH2 has gained much attention in the
in the exhaust gases that can be used for the hydrogen release service. literature and widely studied by the researchers. It has been found to
Otherwise, a part of hydrogen must be burned to provide the remaining store a large amount of hydrogen, i.e., it offers high gravimetric energy
energy requirements which decreases the hydrogen energy density of density and the volumetric energy density of MgH2 is nearly two times
the hydride [39]. It is important to mention here that Proton Exchange the volumetric energy density of liquid hydrogen [43]. Also, as Mg metal
Membrane (PEM) fuel cells may not be able to provide the heat energy at is inexpensive and abundantly available [3,10], MgH2 can be easily and
more than 80–100 ◦ C [31,39]. The optimum range where PEM cells cheaply produced in bulk quantities. However, magnesium hydride is
operate are 1–10 bar and 0–100 ◦ C, and enthalpy change of 30–48 formed at high temperature and pressure conditions. It is formed at
kJ/mol H2 [31]. Moreover, on the refueling station, the exothermic heat temperature ~300 ◦ C and a pressure of >30 bar [43] where 75 kJ/mol is
has to be managed and thus thermal management may be a problem for released during the hydrogenation [44]. Moreover, the kinetics of the
this type of hydride [42]. MgH2 formation is quite slow [31,43] and, as discussed above, the
Metal hydrides are binary or intermetallic hydrides. Binary light hydrogen release temperature is not suitable for PEM cells.
metal hydrides offer high volumetric and gravimetric energy densities Being promising, much attention is given in improving the properties
[10]. However, the dehydrogenation/hydrogenation conditions (tem­ of MgH2. This includes decreasing the temperature and enhancing the
peratures and/or pressures) are high, e.g., LiH has 7.7 wt% energy, but it rates of the hydrogenation/dehydrogenation. Good kinetics of the hy­
requires minimum of 900 ◦ C [33] for the dehydrogenation. In other drogenation/dehydrogenation has been obtained at 150 ◦ C by micro-
cases these hydrides do not undergo reversible reaction under low to and nano-structuring, or particle size reduction by ball milling [31].
moderate operating conditions. Among the metal hydrides, MgH2 is an Zaluska et al. [44] found that ball milling effectively reduces the crystal
interesting material as it contains 7.6 wt% hydrogen content equivalent grain size and greatly reduces the time of loading the hydrogen in MgH2.
to 9 MJ/kg Mg [43], and the hydrogen release temperature is relatively Ruele et al. [52] reported that ball milling MgH2 increases the desorp­
low, 350–400 ◦ C [44], though still high for PEM fuel cell applications. tion rates and decreases the desorption temperature. They reasoned that
Intermetallic hydrides are formed by combining two metals with the effect increases with an increase in milling time which causes a
hydrogen. They are formed from heavy transition metals and are decrease in the crystal size.
reversible at low temperature and pressure conditions [11,45]. It is Alloying to form Mg2NiH4 has better kinetics and shows lower
possible to achieve high volumetric energy densities, however, low enthalpy change of hydriding, 65 kJ/mol [43], with temperature of
gravimetric densities, < 3 wt% hydrogen [27,41,45], are not favorable hydriding as 280 ◦ C at 1 bar [31]. Mg2FeH6, Mg17La, and Mg17Al12 are
to use these materials in commercial applications. LaNi5, FeTi, and the other examples of alloying that have shown fast kinetics. Alloying,
Mg2Ni are examples of intermetallic hydrides and their gravimetric however, reduces the gravimetric density, e.g., Mg2NiH4 contains 3.6 wt
energy density is 1.4 wt%, 1.89 wt% [6], and 3.59 wt%, respectively. % hydrogen [50] and Mg2FeH6 shows 5.5 wt% H2 [50]. Both these
LaNi5 and FeTi are of special interest as they offer low desorption values are less than the parent MgH2 capacity (7.6 wt%). Sometimes the
temperature and pressure [1]. A list of selected metal hydrides along hydriding energy actually increases as in the case of Mg2FeH6 reaction,
with their hydrogen capacities is shown in Table 2. the enthalpy change is higher and equals to 77.4 kJ/mol [53]. Apart
So far, we have learnt that generally the metal hydrides can have from alloying with a metal, two different hydrides or a hydride and, say,
good energy densities, but the kinetics of the hydrogenation and dehy­ carbon can be mixed to utilize the better part of each component in the
drogenation is slow. Moreover, the hydrogen release temperature is final hydride composite [31,50]. Johnson et al. [54] used a mixture of
relatively high. The improvement in these properties can possibly be LiBH4 (complex hydride) and MgH2 and found improvement in the ki­
made by decreasing the particle size, reducing the crystal grain size, netics. The weight percent H2 capacity of MgH2 increased to 11.4 wt%
alloying, adding additives to produce composites, using catalysts, and the corresponding enthalpy change for the reaction lowered to 45
kJ/mol H2. Li et al. [55] used graphite with MgH2 and observed that the
hydrogen loading temperature decreases to 200 ◦ C. Other examples of
Table 2 hydride composites are MgH2–NaAlH4, MgH2–Mg(AlH4)2, and
Hydrogen storage characteristics of metal hydrides [6, 31, 43, 44, 50, 53, 54, 74, MgH2–AlH3. No improvement in the kinetics of desorption is observed
83, 127–130]. when Si is used as additive [52]. A catalyst presence is also observed to
Metal hydride H2 capacity Desorption Desorption enthalpy enhance the kinetics of the process. Zaluska et al. [44] observed the
(wt%) temperature (◦ C) (kJ/mol H2) effect of Pd and Fe catalysts and found that both are very effective. They
MgH2 7.6 >300 75 observed that with Pd catalyst, the hydrogen absorption time was
Mg2NiH4 3.59 >280 65 reduced to more than half the value when there was no Pd present. They
Mg2FeH6 5.5 >300 77.6 also employed other catalysts but found less favorable results. Cui et al.
FeTiH2 1.89 >30 28 [56] employed Ti with MgH2 and observed that at 250 ◦ C, 5 wt%
LaNi5H6 1.4 >100 31
MgH2–LiAlH4 9.4 >250 45
hydrogen is desorbed in first 15 min. Borkhordarian et al. [57] studied
(1:1 M) the effect of a series of metal oxides on the kinetics of hydrogen
MgH2–NaAlH4 7.6 >175 – desorption/sorption. Nb2O5 was found the best performing catalyst. At
(1:1 M) temperature of 300 ◦ C and under vacuum conditions, in the presence of
MgH2–LiBH4 11.4 45
>350
0.5 mol% Nb2O5, nearly entire 7 wt% H2 was desorbed within 90 s

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M.R. Usman Renewable and Sustainable Energy Reviews 167 (2022) 112743

whereas at 300 ◦ C and 8.5 bar, nearly 7 wt% was absorbed within 60 s. A 200–400 ◦ C and high pressure in the range of 10–40 MPa for the rehy­
rather detailed review of the catalysts used with MgH2 is provided by drogenation [62]. These drawbacks can be addressed and the
Jain et al. [58]. improvement in the thermodynamics and kinetics can be achieved by
The MgH2 metal hydride is successfully used for the stationary catalysis, ball milling, alloying, and nano-engineering.
hydrogen storage applications [10], however the limitation discussed Bogdanović and Schwickardi [69] did a breakthrough work when
above restricts its use for the on-board applications. Additional research they found that doping NaAlH4 with Ti-containing species greatly de­
is demanded to further improve the properties of MgH2 to be used for the creases the kinetics and thermodynamics of the dehydrogenation and
on-vehicle applications. the rehydrogenation of NaAlH4. They observed an 80–85 ◦ C decrease in
AlH3 is also a promising binary metal hydride [2,9,46]. It has high the desorption temperature of hydrogen [68]. Also, they reasoned that
hydrogen content 10.1 wt% [2,46,59] and high volumetric energy increasing the amount of the dopant increases the kinetics, but decreases
density as the density is 1.48 g/mL [2,46]. It dehydrogenates at rela­ the gravimetric energy density of the hydride [62]. Only a small amount
tively low temperature of ~100 ◦ C [49]. However, AlH3 is difficult to of 2–4 mol% is used as the optimum value [62]. Although Bogdanović
undergo reversible reaction and needs immensely high hydrogen pres­ and Schwickardi [69] used wet chemistry for doping Ti, but in a more
sure for the hydrogen charging [59]. The regeneration of hydride cannot preferred way, doping can be carried out by ball milling the catalyst and
be carried out on-board. Additional work is required to modify the hy­ the hydride, under applicable hydrogen atmosphere. Many catalytic
dride properties to follow more practical conditions of hydrogen loading materials have been tried afterward with NaAlH4, but Ti halides such as
and release. TiCl3 and TiF3 have proved their superior catalytic properties when used
with NaAlH4. Both of them improve the associated thermodynamics and
kinetics and accelerate the reversibility. However, TiCl3 is considered a
2.5. Complex metal hydrides
standard catalyst for NaAlH4 even though TiF3 gives similar results and
better energy density. This is due to the excessive cost of TiF3 over TiCl3.
Complex metal hydrides are formed when hydrogen atoms cova­
ScCl3 and CeCl3 also show better promise than Ti catalysts, but again the
lently bond to a central atom in a coordination complex such as
costs are extremely high [62]. Pitt et al. [70] used a series of metal
[AlH6]− 3, [AlH4]− 1, [BH4]− 1, and [NH2]− 1 and a cation (e.g., Li, Mg,
chlorides and concluded that ZrCl4 is another qualified catalyst for
and Zn) stabilizes the anion [27,39,60,61]. The hydrides are mostly
improving the kinetics of the hydrogen sorption. Further detail about the
formed out of lighter elements of Groups I, II, and III of the periodic table
catalytic effects on the properties of the complex hydrides is provided by
[45] and therefore offer higher storage densities. The storage properties
Liu et al. [68].
of some selected complex metal hydrides are shown in Table 3.
Ismail et al. [71], Ismail et al. [72], Rafi-ud-Din et al. [73], and
Bendyna et al. [74] studied the thermodynamic properties and kinetic
2.5.1. Alanates
properties of the composite NaAlH4 with MgH2, i.e., NaAlH4–MgH2 with
Alanates are aluminum containing complex hydrides. They are either
7.6 wt% H2. The composite showed improved desorption properties
octahedrally coordinated or tetrahedrally coordinated by hydrogen
compared to the MgH2 and NaAlH4 hydrides when used independently.
atom [10,39]. In the former case they are hexahydroaluminates and in
LiAlH4 is another high energy density complex hydride that has
the latter case they are tetrahydroaluminates. Examples of alanates are
gravimetric energy density equals to 10.6 wt%. However, the reversible
sodium alanates, lithium alanates, magnesium alanates, potassium ala­
hydrogen contents are only 7.9 wt% due to the formation of aluminum
nates, calcium alanates, and mixed metal alanates.
hydride which requires excessively harsh operating conditions for the
Sodium aluminum hydride (NaAlH4) is widely studied complex hy­
hydrogen release. Also both the kinetics of hydriding/dehydriding and
dride. It contains 7.4 wt% total amount of H2 [62], however, practically
the reversibility are poor [12]. In fact, it is characterized as irreversible
only 5.6 wt% H2 [1,12] can be released. The hydrogen is released ac­
hydride [38,39,62] owing to the extreme rehydrogenation conditions.
cording to the following two-step reaction [62–64]:
LiAlH4 is also not stable [38,62] and decomposed at low temperature
3NaAlH4 → Na3AlH6 + 2Al + 3H2 [62]. Moreover, it is sensitive to oxygen and moisture [9] and the cost of
LiAlH4 is also higher than NaAlH4 [62]. It is therefore suggested not
Na3AlH6 → 3NaH + Al + 3/2H2 suitable, in the form of LiAlH4, for the hydrogen storage applications.
In the first step 3.7 wt% H2 is released, while 1.9 wt% H2 is released Catalytic effects and hydride addition as in LiAlH4–MgH2 (9.4 wt%)
in the second step [38,65]. The average enthalpy change for the two have shown to improve the properties of LiALH4. KAlH4 is though
reactions is 41 kJ/mol H2 [66]. NaH produced in the second reaction reversible, but the hydrogen capacity is lower than NaAlH4. The
requires excessive temperature (425 ◦ C) for the hydrogen release [3], reversible hydrogen capacity is only 3.5 wt% [75].
therefore, hydrogen available in NaH is considered irreversible. NaAlH4
is easy to produce in mass productions [12,38] and it is relatively 2.5.2. Borohydrides
inexpensive [38,67]. On the other side, it requires high temperatures, Boronhydrides contain high hydrogen content up to 10 to 18 wt%
185–260 ◦ C, for H2 release [62–64] and undergoes low H2 release ki­ [58]. Examples of borohydrides are sodium borohydrides, lithium bo­
netics [2,62,68]. It also poses difficulty of reversibility as it requires rohydrides, magnesium borohydrides, and calcium borohydrides. The
hydrogen is released from a borohydride either by hydrolysis or by the
decomposition reaction [3,8,62].
Table 3
Hydrogen storage properties of complex metal hydrides [12, 38, 39, 58, 62–64,
Hydrolysis:
66, 77, 79, 83].
NaBH4 + 2H2O → 4H2 + NaBO2
Complex metal H2 capacity Desorption Desorption enthalpy
hydride (wt%) temperature (◦ C) (kJ/mol H2) Decomposition:
a
LiAlH4 10.6/7.9 >160 5.8 Mg(BH4)2 → MgH2 + 2B + 3H2
NaAlH4 7.4/5.6a >185 41a
LiBH4 18.5/13.5a >380 67a MgH2 → Mg + H2
LiNH2–LiH 10.4/5.5a >180 44a
Mg(NH2)2–LiH 5.6 >150 54 Intermediate products can also be present in some borohydrides such
Complex metal hydrides can be classified into the following three major cate­ as in the decomposition of LiBH4 [58].
gories: alanates, borohydrides, and amides-imides. Boron hydrides are more stable than alanates [2,18,76,77], but they
a
Reversibly released.

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M.R. Usman Renewable and Sustainable Energy Reviews 167 (2022) 112743

also show slow kinetics [77,78]. Alkali borohydrides have very high release, greater than 400 ◦ C temperature is required [39].
dehydrogenation enthalpy and high H2 release temperature [39]. Substituting Mg(NH2)2 in place of LiNH2 or MgH2 in place of LiH can
Moreover, toxic boron hydrides are produced as byproducts though in improve the original hydride properties. Mg(NH2)2–LiH reversibly re­
small amounts during the dehydrogenation reaction [76,77]. These leases 5.6 wt% H2 (enthalpy of reaction equals to 54 kJ/mol H2) and
byproduct boranes can contaminate the hydrogen supply and can desorption takes place at 150–250 ◦ C [79]. Moreover, the ammonia
damage the fuel cell system [76] and decrease the storage capacity of the formed readily reacts with LiH and extinguished [64]. On the other
hydrides with time [62,76]. Boranes are hygroscpopic and require spe­ hand, LiNH2–MgH2 contains 4.5 wt% H2, but the enthalpy of desorption
cial needs to handle and store [18,79], however, they do not have is only 40 kJ/mol [67]. KH and RbH doping effectively catalyzes the
explosive reaction with water [77]. kinetics and the reversibility of the Mg(NH2)2–LiH. Furthermore, the
LiBH4 is perhaps the most important complex hydride of this class addition of LiBH4 in LiNH2–MgH2 to produce ternary hydride compos­
[80]. It has hydrogen capacity of 18.5 wt% and enthalpy change of ite, LiNH2–MgH2–LiBH4, enhances the kinetics and the enthalpy of
hydriding is 67 kJ/mol H2 [39,77], but it is very hard to decompose [38] desorption decreases to 24 kJ/mol.
to release hydrogen. It releases 13.5 wt% H2 [38,39] at >380 ◦ C [39]
and 4.5 wt% hydrogen remained fixed in LiH. The decomposition of LiH 2.6. Physical adsorption
requires extremely high temperature as discussed above. Moreover,
LiBH4 formation is even more demanding requiring greater than 650 ◦ C In the physically adsorbed form hydrogen is adsorbed at the surface
and 150 bar H2 pressure [38]. Adding SiO2 to LiBH4 is shown to improve of the solids and the adsorption follows van der Waals interactions or
the quantity of H2 release at lower temperature. Züttel et al. [33] pro­ dispersive forces. Unlike hydrogen stored in many metal hydrides and
posed that SiO2 ensures 13.5 wt% release of H2 at 200 ◦ C. TiCl3, an complex metal hydrides, the hydrogen is stored reversibly in physically
extremely good catalyst for alanates, is not found suitable to be used adsorbed form [18,45]. Physically adsorbed hydrogen offers high rates
with LiBH4 as it causes the formation of stable and irreversible Ti(BH4)3 of adsorption (loading) and desorption (unloading) [10,18,82] and the
[77,81]. Addition of MgH2 to LiBH4 (1:2 M ratio) releases the hydrogen refueling time is not an issue [7]. The enthalpy of adsorption/desorption
at much lower temperature. The rehydrogenation occurs at 230–250 ◦ C is only 1–10 kJ/mol [9] and due to these low values involved in the
and 100 bar, thus makes LiBH4 reversible [62]. Total H2 capacity of adsorption/desorption of hydrogen, the heat transfer problems are far
LiBH4–MgH2 is 11.4 wt%, however, 8 wt% can be released reversibly easier to be managed [13]. Moreover, there are no losses of hydrogen
[62,77]. due to byproduct formation [18]. The materials which are candidates for
Another important borohydride is NaBH4. It contains 10.8 wt% of the hydrogen storage by physical adsorption include microporous car­
H2, but it requires high temperature of 400 ◦ C for the decomposition to bon structures, metal organic frameworks, and zeolites. These adsorbent
NaH and B [77]. Alkali metal amidoboranes, LiNH2BH3 and NaNH2BH3, materials are mostly well developed and have high surface area. As
are also worth mentioning. They offer 10.9 wt% and 7.5 wt% H2 ca­ adsorption is a surface phenomenon, high surface area is undoubtedly a
pacity, respectively, with H2 release temperature as low as ~90 ◦ C [82], requirement.
and they also do not give any harmful products. However, they are not Carbon based materials can be prepared in a manner that provides
reversible [82]. A borohydride that is liquid at room temperature and high surface area. Zhou et al. [84] determined that activated carbons
pressure conditions is Al(BH4)3 [45]. It has high hydrogen content of 17 contain 5 wt% H2 at 77 K and 30–60 bar. Recently, Zhao et al. [82,85]
wt% [45], however, it is not widely studied and additional research is has reported the hydrogen capacity in single walled carbon nano tubes
needed in this direction. (SWCNTs) as 1.73 wt% at 77 K and 10 MPa. Liu et al. [86] used various
types of CNTs (inclusive SWCNTs and MWCNTs) with and without post
2.5.3. Amides-imides modifications and found the H2 storage capacity at room temperature
Amides and imides are complex hydrides containing nitrogen atom. and 12 MPa is less than 1.7 wt%. Reader is referred to Yürüm et al. [87]
The general formula for amides and imides can be written, respectively, for a detailed review of hydrogen uptake on carbonaceous materials.
as M(NH2)x and M(NH)x. Examples of amides and imides are lithium, Zeolites are microporous ordered aluminosilicates with appreciable
magnesium, and calcium amides and imides. Both amides and imides surface area. CaX zeolite has shown the H2 capacity of 2.19 wt% at 15
offer high hydrogen storage content and low hydrogen release temper­ bar and 77 K [88]. Du and Wu [89] have measured hydrogen capacity of
ature [3]. However, they have substantially low rates of hydrogen 2.55 wt% at 77 K and 40 bar over NaX (565 m2/g) and observed that at
hydriding/dehydriding and therefore in the absence of a catalyst or 20 ◦ C and 40 MPa the value dropped to 0.4 wt% only. Chung [90]
additive they are not suitable for the practical purpose. Moreover, studied various kinds of zeolites for hydrogen storage at 30 ◦ C and found
ammonia is formed during the dehydrogenation reaction of amides and that USY has shown the maximum hydrogen capacity of 0.4 wt% at a
imides [2,9,38,39]. The produced ammonia can damage the fuel cell pressure of 50 bar.
assembly and especially the catalyst and the membrane [2]. The Metal organic frameworks are versatile and can be modified in a
ammonia also consumes a bit of H2 [38,39] and decreases the cycling number of different ways. They offer the highest surface area of all H2
ability [39] of the hydride due to the loss of nitrogen. Additionally, they storage materials, e.g., MOF-210 has shown 6240 m2/g surface area
are sensitive to the atmospheric exposure and affected by the presence of [91], the highest experimentally measured surface area. MOF-210 has
water [9]. shown hydrogen capacity of 7.9 wt% at 77 K and 80 bar [92]. Li et al.
The most common and widely recognized amide is lithium amide, [93] used MOF-5 and found that MOF-5 has the capacity of 4.5 wt% H2
LiNH2. LiNH2–LiH contains total of 10.4 wt% H2 [38]. The hydrogen is storage at 77 K near ambient pressure and only 1.0 wt% at 20 bar and
released according to the following stoichiometry: room temperature. Farha et al. [94] reported hydrogen capacities over
NU-100 (6143 m2/g) as 9.0 wt% at 56 bar and 77 K. Langmi et al. [92]
LiNH2 + 2LiH → Li2NH + LiH + H2
comprehensively reviewed the hydrogen storage capacities of MOFs and
Li2NH + LiH → Li3N + H2 concluded that at room temperature hydrogen capacities of MOFs are
generally less than 1 wt%. Additionally, MOFs have low thermal con­
LiNH2 is decomposed to produce lithium imide, Li2NH, and ductivity of the order of 0.3 W/(m⋅K) [95] which can create thermal
hydrogen is released. In the second reaction Li2NH is dehydrogenated management issues [7].
and additional hydrogen is evolved. The first reaction is only reversible Physical adsorbents of hydrogen show quite low room temperature
[18] and 5.5 wt% H2 is released [64] with 44 kJ/mol H2 enthalpy capacity. It is reasonable only at cryogenic temperatures and or higher
change [58]. The desorption commences at 180 ◦ C [83], but the kinetics pressures. It is important to mention here that there will be desorption
of the reaction is unacceptably slow [58]. For total absorbed H2 to losses similar to the boil-off losses, discussed in the case of liquid

6
M.R. Usman Renewable and Sustainable Energy Reviews 167 (2022) 112743

hydrogen storage, if hydrogen will be physically adsorbed at cryogenic [100]. Keeping all this in consideration, methylcyclohexane can be
temperatures. We limit our discussion about physical adsorbents as the regarded as a better selection than the other two hydrides discussed
physical adsorbents exhibit no potential to be used for the hydrogen above. Additionally, methylcyclohexane has density and viscosity close
storage applications. to that of gasoline and has normal boiling point of 100.9 ◦ C in the vi­
cinity of the normal boiling point of water. At 38 ◦ C (100 ◦ F), the vapor
pressures of methylcyclohexane and toluene are 11.2 kPa and 7.2 kPa,
2.7. Liquid organic hydrogen carriers respectively (the vapor pressure of water at this temperature is 6.6 kPa).
Table 4 shows the comparison among the three hydrides mentioned
In a liquid organic hydrogen carrier (LOHC) or liquid organic hy­ above.
dride, hydrogen is stored chemically by reacting with a hydrogen defi­ Methylcyclohexane/toluene system, the so called MTH (Methyl­
cient organic molecule. The organic hydride is dehydrogenated in the cyclohexane-Toluene-Hydrogen) system is a widely studied hydrogen
reactor and the necessary hydrogen is released for the power production storage system. The hydrogen capacity is 6.2 wt% corresponding to 5.5
either in a stationary power plant or in an on-vehicle application. The MJ/L hydrogen [99]. The catalyst, Pt/Al2O3, is well developed reform­
dehydrogenated product is removed at the filling station and the organic ing catalyst and the kinetics of the dehydrogenation required for the
hydride is recharged. The dehydrogenated organic hydride is trans­ design of the dehydrogenation reactor is also available [101]. Moreover,
ported to an off-site hydrogenation facility and hydrogenated and the the heat transfer problems associated with high endothermicity and
organic hydride is finally conveyed to the filling station. During the diffusion in the catalyst bed are also addressed [102,103]. Usman and
whole cycle, the carbon atom remains in the cycle and does not leave Cresswell [103] inspired by the Hrein Energy’s [104] hybrid
into the atmosphere. Fig. 2 shows the concept of organic hydride cycle methylcyclohexane-gasoline concept has simulated a prototype
for on-board and stationary applications. MTH-gasoline system and found encouraging results applicable in the
The organic hydrides possess reasonably high reversible hydrogen future on-vehicle applications. In a later study, Usman and Cresswell
capacity ranging between 1.7 and 7.3 wt% and are liquids at room [99] proposed a storage tank design that can accommodate the liquid
temperature. The biggest advantage of using an organic hydride is that hydride and its product of dehydrogenation in a minimum volume.
the current infrastructure of bulk storage and transportation of gasoline The problem with cycloalkanes is that their dehydrogenation tem­
can be effectively utilized [96–98]. peratures and the enthalpy of reaction (dehydrogenation/hydrogena­
In earlier studies only cycloalkanes such as cyclohexane, methyl­ tion) are quite high. As an example, methylcyclohexane
cyclohexane (MCH), and decalin remained the main focus of attention. dehydrogenation is associated with 205 kJ/mol MCH or 68.3 kJ/mol H2
These cycloalkanes contain 6.2–7.3 wt% [99] reversible hydrogen [99] and the equilibrium conversion of ~100% is achieved at 325 ◦ C and
storage capacity. The dehydrogenation product of cyclohexane is ben­ 1 bar. These problems to some extent can be addressed by introducing a
zene and that of decalin is naphthalene. Benzene is carcinogenic while heteroatom in the cycloalkane ring [105–107]. Pez et al. [105] proposed
naphthalene is solid at room temperature. Toluene, the dehydrogena­ that if a nitrogen atom or to a lesser extent oxygen is introduced within
tion product of methylcyclohexane dehydrogenation, on the other hand, the cycloalkane ring, the dehydrogenation enthalpy can be substantially
is non-carcinogenic and liquid at ambient conditions. Moreover, toluene reduced. Clot et al. [106] computationally developed additional nitro­
is widely handled at industrial scale. It is easier to start the hydrogen gen containing organic hydrides and proposed that the use of N atom
economy based on methylcyclohexane and toluene due to the bulk substantially decreases the dehydrogenation temperature. They
availability of toluene and that the bulk production of toluene is a observed that for the five-membered cycloalkanes the effect is stronger
well-established technology. than six-membered ring for reducing the enthalpy of reaction and the
Under typical operating conditions, the equilibrium conversion is the hydrogen release temperature. Moreover, they found that the position of
highest for decalin, but the lowest for the cyclohexane [100]. The N in the ring also affects the thermodynamic and kinetic properties.
methyl group in methylcyclohexane renders relatively easy dehydro­ Experimentally Cui et al. [107] and He et al. [108] have confirmed the
genation of methylcyclohexane to toluene than cyclohexane to benzene

Fig. 2. Concept of an LOHC cycle.

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M.R. Usman Renewable and Sustainable Energy Reviews 167 (2022) 112743

Table 4
Hydrogen storage properties of liquid organic hydrogen carriers (LOHCs) [1, 97–99, 115, 116, 131].
Organic Hydride Dehydrogenated H2 capacity (wt Energy (MJ/L Dehydrogenation temperature Dehydrogenation enthalpy (kJ/mol
product %) Hydride) (◦ C) H2)

Cyclohexane Benzene 7.2 6.67 325 68.8

Methylcyclohexane Toluene 6.2 5.68 325 68.4
Decalin Naphthalenea 7.3 7.57 325 66.5
Dodecahydrocarbazole Carbazolea 6.7 10.4 170 51.1
Dodecahydro-N- N-ethylcarbazolea 5.8 6.48 170 50.6
ethylcarbazole
perhydro-benzyltoluene Benzyltoluene 6.2 6.72 >270 71
perhydro-dibenzyltoluene Dibenzyltoluene 6.2 6.96 >270 71
Indoline Indole 1.7 2.17 110 51.9
1,2-BN-cyclohexanea – 4.7 5.76 150 38.9
3-methyl-1,2-BN- – 4.7 5.04 <80 –
cyclopentane
a
Solid at room temperature.

above mentioned improvement in thermodynamics and kinetics of this dehydrogenation temperatures not less than 270 ◦ C [116] perhaps not
type of hydride. However, it is found that N-based heterocyclic com­ suitable for their use for the on-board applications. Moreover, cyclic
pounds are liable to decomposition and result in unwanted degradation ability is reduced above 330 ◦ C where byproducts formation is crucial
products [109,110]. [1]. The high viscosity of these hydrides is also needed to be analyzed
Recently, Verevkin [111] by both experimentally and computation­ when considering these heating oils for the practical hydrogen storage
ally identified that oxygen containing cycloalkanes (diphenyl ether de­ applications.
rivatives), due to their low vapor pressure and high hydrogen storage Other liquid organic hydrogen carriers of interest are indoline and
capacity, can also be considered as favorable candidates for the BN (boron and nitrogen) based cycloalkanes. Indoline has low dehy­
hydrogen storage applications. drogenation enthalpy as well as low dehydrogenation temperature,
Dodecahydro-N-ethylcarbzole is widely discussed liquid organic 110 ◦ C [122], but the gravimetric hydrogen capacity is only 1.7 wt%
hydride [112]. The gravimetric hydrogen capacity is 5.8 wt% [110], [98]. Introducing BN in a cycloalkane is a newer way of producing
somewhat lower than cyclohexanes, but it involves lower enthalpy of hydrogen storage material. 1,2-BN cyclohexane [123] and methyl BN
dehydrogenation equals to 51 kJ/mol [98] and decreased dehydroge­ cyclopentane [123] are the examples. These BN containing organic
nation temperature (170 ◦ C) [113,114]. Moreover, as an ethyl group is hydrides have reasonably high gravimetric densities and show fast ki­
attached to the N atom, the system is inherently less liable to catalyst netics [124]. For example, 1,2-BN cyclohexane has 4.7 wt% hydrogen
deactivation [98] than the dodecahydrocarbazole/carbazole system capacity and dehydrogenates at 80 ◦ C. However, the problems with
shown in Table 2. However, although dodecahydro-N-ethylcarbazole is regeneration of the BN based hydrides and the high costs [97] are the
liquid, but its product of dehydrogenation N-ethylcarbazole, is solid at key issues for the practical applications [99]. Their low temperature
room temperature (68 ◦ C melting point). Handling of solids especially dehydrogenation within the range of PEM cells operating conditions
for on-board systems is highly inconvenient. However, by restricting the demands further research for improving the hydrogenation properties.
conversion to a lower value (~20%) [115] or by using a solvent suitable
for this purpose, this issue can be resolved though yielding lower energy 3. Conclusion and recommendations
densities. Moreover, the dehydrogenation temperature is not in the
range of PEM cells exhaust temperature and that hydride has the ten­ Various hydrogen storage options are reviewed and their dis­
dency to deethylation above 270 ◦ C [116]. Based on N-ethylcarbazole, it tinguishing characteristics are discussed. It is revealed that both lique­
is difficult to start hydrogen economy as it is not abundantly available fied hydrogen and cryocompressed hydrogen may not be able to find
[116] and the associated cost is therefore high. their way in the future hydrogen economy due to the extremely low
Commercially available heat transfer oils such as benzyltoluene and temperature requirements for the liquefaction of hydrogen. Owing to
dibenzyltoluene can be hydrogenated to store hydrogen [116–118]. the low room temperature hydrogen capacities, physical adsorbents are
Both ethylbenzene and diethylbenzene being commercially used are not practically suitable materials for hydrogen storage. Compressed
well studied chemicals and their properties and safety data are well hydrogen in cylinders is a well-established technology and it is the most
documented. They are liquid at room temperature, thermally stable to a practical storage method for the stationary purposes such as in hydrogen
much higher temperature, and have low vapor pressure. The hydroge­ based power plants. With the development of sophisticated gas cylin­
nated product of benzyltoluene is perhydro-benzyltoluene and that of ders, compressed hydrogen in cylinders has also shown promise for the
dibenzyltoluene is perhydro-dibenzyltoluene, each of them is also a on-board hydrogen storage. A hybrid compressed hydrogen system is
liquid at room temperature. Both of these hydrides contain 6.2 wt% H2 expected to find its clear role in the future hydrogen economy. Metal
[116], somewhat higher than dodecahydro-N-ethylcarbazole. hydride such as MgH2 and complex metal hydride such as LiBH4 have
Comparing the two, diethyldenzene is cheaper [118] and has lower shown the potential and additional research for improving their ther­
vapor pressure due to which its liquid phase dehydrogenation is possible modynamics and kinetics is required. Among the liquid organic hydride
[119]. However, much higher viscosities of diethylbenzene and its hy­ carriers (LOHCs), during the interim period, owing to the gasoline like
drogenated product pose transportation problems and slow rates in the properties of methylcyclohexane and toluene where the current infra­
dehydrogenation and hydrogenation reactions [118]. A better solution structure of gasoline transportation, with the necessary modifications,
is proposed by some researchers [115,118,120] while mixing the two can be used, the well-studied methylcyclohexane/toluene system (MTH
hydrides to reduce the viscosity and to increase the reaction rates. The system) is recommended for the on-board applications. Along with, a
concept of reactive distillation introduced by Geiβelbrecht et al. [121] mixed hydride system of perhydro-benzyltoluene and perhydro-
can open the door for lower vapor pressure hydride systems, so the dibenzyltoluene is suggested suitable to the stationary applications.
perhydro-benzyltoluene/benzyletoluene could become more important Some recently proposed LOHCs that have shown potential need further
in the future. High enthalpy of the dehydrogenation reaction (71 kJ/mol research before being considered for the practical applications.
H2) of these hydrides close to methylcyclohexane and high

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M.R. Usman Renewable and Sustainable Energy Reviews 167 (2022) 112743

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