Nagar Et Al 2023

Solar Compass 5 (2023) 100033
Contents lists available at ScienceDirect
Solar Compass
journal homepage: www.elsevier.com/locate/solcom
Recent developments in state-of-the-art hydrogen energy technologies –

Review of hydrogen storage materials
Rupali Nagar a, Sumita Srivastava b, Sterlin Leo Hudson c, Sandra L. Amaya d, Ashish Tanna e,
Meenu Sharma f, Ramesh Achayalingam c, Sanjiv Sonkaria g, Varsha Khare g,
Sesha S. Srinivasan h,∗
a
Nanomaterials for Energy Applications Lab, Applied Science Department, Symbiosis Institute of Technology (SIT), Symbiosis International (Deemed University), Lavale,
Pune 412 115, Maharashtra, India
b
Government Degree College, Nainbagh 249186 Tehri Garhwal, India
c
Department of Physics, Banaras Hindu University, Varanasi 221005, UP, India
d
Institución Universitaria Pascual Bravo, Facultad de Ingeniería, Grupo de Investigación e Innovación en Energía GIIEN, Calle 73 No 73A 226, CP 050001, Medellín,
Colombia
e
Department of Physics, RK University, Bhavnagar Highway, Tramba, Gujarat 360020, India
f
Mechanical Engineering, Energy Systems Research Laboratory, Indian Institute of Technology Gandhinagar, Gujarat 382355, India
g
Soft Foundry Institute, Seoul National University, Kwanak-gu, Seoul, 39-131, South Korea
h
Department of Engineering Physics, Florida Polytechnic University, 4700 Research Way, Lakeland, FL, USA
a r t i c l e i n f o a b s t r a c t
Keywords: Hydrogen energy has been assessed as a clean and renewable energy source for future energy demand. For har-
Hydrogen energy technologies nessing hydrogen energy to its fullest potential, storage is a key parameter. It is well known that important
Hydrogen storage hydrogen storage characteristics are operating pressure-temperature of hydrogen, hydrogen storage capacity,
Metal hydrides
hydrogen absorption-desorption kinetics and heat transfer in the hydride bed. Each application needs specific
Carbonaceous
properties. Every class of hydrogen storage materials has a different set of hydrogenation characteristics. Hence,
Nanoparticles
Metal organic frameworks it is required to understand the properties of all hydrogen storage materials. The present review is focused on
Perovskites the state-of–the–art hydrogen storage materials including metal hydrides, magnesium-based materials, complex
Fuel cells hydride systems, carbonaceous materials, metal organic frameworks, perovskites and materials and processes
based on artificial intelligence. In each category of materials’ discovery, hydrogen storage mechanism and reac-
tion, crystal structure and recent progress have been discussed in detail. Together with the fundamental synthesis
process, latest techniques of material tailoring like nanostructuring, nanoconfinement, catalyzing, alloying and
functionalization have also been discussed. Hydrogen energy research has a promising potential to replace fossil
fuels from energy uses, especially from automobile sector. In this context, efforts initiated worldwide for clean
hydrogen production and its use via fuel cell in vehicles is much awaiting steps towards sustainable energy
demand.
Abbreviations: IPHE, International Partnership for Hydrogen and Fuel Cells in the Economy; IEA, International Energy Agency; CEM, Clean Energy Ministerial; MI,
Mission Innovation; MT, Million Tons; IRENA, International Renewable Energy Agency; AEO, Annual Energy Outlook; US-DOE, United States Department of Energy;
LCOE, Levelized Cost of Electricity; SMR, Steam Methane Reforming; KWh, Kilo Watt-hour; MOF, Metal Organic Frameworks; FCTO, Fuel Cell Technologies Office;
AI, Artificial Intelligence; ML, Machine Learning; SWCNT, Single Wall Carbon Nanotube; MWCNT, Multiwall Carbon Nanotube; ANI, Artificial Narrow Intelligence;
AGI, Artificial General Intelligence; HSA, Hydrogen Storage Alloys; IMC, Intermetallic Compounds; Pa, Pascal; MPa, Mega Pascals; Atm, Atmosphere; BCC, Body
Centered Cubic; SS, Solid Solution; Ni-MH, Nickel-Metal Hydride; P-C-T (or PCT), Pressure Composition Temperature; Wt% (or wt%), weight percentage; kJ, Kilo
Joules; PEM, Proton Exchange Membrane; H/M, Hydrogen to metal ratio; CRMM, Controlled Reactive Mechanical Milling; HRBM, High-Energy Ball Milling; NPs,
Nanoparticles; PMMA, Poly(methyl methacrylate; CA, Carbon Aerogels; 2D and 3D, Two and Three Dimension; DFT, Density Functional Theory; RHC, Reactive
Hydride Composite; K, Kelvin (Temperature scale); C (or °C), Degree Celsius (Temperature scale); CC, Creative Commons; LOHC, Liquid Organic Hydrogen Carriers;
MWNT, Multiwall Nanotubes; GDY, Graphdiyne; TM, Transition Metal; H–H, Hydrogen-Hydrogen; FCEV, Fuel Cell Electric Vehicle.
∗
Corresponding author.
E-mail address: ssrinivasan@floridapoly.edu (S.S. Srinivasan).
https://doi.org/10.1016/j.solcom.2023.100033
Received 7 December 2022; Received in revised form 23 January 2023; Accepted 25 January 2023
2772-9400/© 2023 The Author(s). Published by Elsevier Ltd on behalf of International Solar Alliance. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)
R. Nagar, S. Srivastava, S.L. Hudson et al. Solar Compass 5 (2023) 100033
1. Introduction - overview and background of hydrogen energy other methods like thermochemical, wind, biomass gasification and so-
technologies lar radiation are to be considered although those are under preliminary
research level hence needs more experimental proof for the quantitative
An unprecedented raise of global mean temperature over the sev- production of hydrogen [8]. One can consider hydrogen as a prospec-
eral decades and associate global warming lead both developed and de- tive fuel, but it requires a huge effort to make it commercially viable.
veloping countries to device strategies for containing the global CO2 Though, in recent era researchers have made significant contributions in
emissions [1]. As it is known to everyone that conventional energy re- the production of hydrogen gas, intermediate storage, and utilization in
sources like fossil fuels such as petroleum products and coal have been PEM fuel cells by state-of-art methodologies (Fig. 1) [8]. The hydrogen
used for a long time and created an impact on the environment espe- storage is the bottleneck in implementing the hydrogen technologies to
cially greenhouse effect due to large production of CO2 gasses during the its fullest potential [10–12]. Looking into this, researchers are required
combustion of these fuels [2]. Due to this fact, researchers have focused to focus on storage of the hydrogen gas as a fuel. One of the solutions to
on alternate source of energy which should be environmentally friendly this problem is the reversible storage of hydrogen in solid state materi-
and easily available [3]. One of the sources is solar energy though due to als. There are a number of solid materials available which have proper-
efficiency of solar cell and sturdiness inspire research fraternity to find ties like microporous with high surface area, moisture sensitive complex
another source which could be mobile and economical for the future hydrides and gas sorption can be utilized [13].
prospectus [4]. In this review article, focus area is hydrogen as a fuel.
The lightest and most available material on the earth is hydrogen which
2. Hydrogen energy technologies – an international perspectives
can be useful as energy source. The hydrogen is a fuel with less or almost
zero emission of toxics as well non-polluting gas when it burns or used
The US administration’s bold “Hydrogen Earthshot” initiatives, “One-
as renewable energy sources [5]. As hydrogen is an alternate source has
for-One-in-One”, otherwise simply, “111” is driving and reviving the
extremely useful as a green fuel for the current time. The hydrogen fuel
hydrogen-based research and development to realize for the generation
is more than double efficiency than the other fuels like gasoline [6,7]
of “clean hydrogen” at the cost of $1.00 for one kilogram in one decade
There are number of techniques available to produce hydrogen and
[14]. This initiative triggers not only to develop “US Hydrogen Hubs”
utilize those with suitable aspects. Main source of hydrogen is the indus-
but also catalyze the international hydrogen research. Another bold goal
trial steam reforming method [7], where 96% of hydrogen is produced.
of this process on the international stage, a net zero or 100% renewable
It is a well-established technology to extract hydrogen from fossil fuel
energy consumption (or 100% clean grid) must be achieved by 2050
stocks [8]. Almost 10 million tons of hydrogen requirements of U.S. is
with a short-term to realize the 50% of set-forth goals by 2030 [15].
fulfilled using steam reforming every year [8]. While remaining 4% of
Another bold initiative from the EU Commission to adopt renewable
hydrogen can be produced via electrolysis process [9]. Electrolysis pro-
hydrogen to decarbonize at the cost-effective manner that is strategi-
cess is the most important and emerging technology, in this method,
cally developed by the REPowerEU; this leads to the “hydrogen acceler-
water can be split into hydrogen/oxygen using the electrical energy.
ator” where a domestic hydrogen production of 10 MT (million tons)
Fig. 1. Hydrogen Energy Technologies.
2
by 2030 [16]. Africa-EU Green Energy initiatives are on the horizon in survey and interview with hydrogen council member experts, Mckinsey
developing 40 GW (Gigawatts) of electrolyzer capacity to generate re- & Company predictively proposes increasing efforts to apply the use hy-
newable hydrogen and critical raw materials to support the green and drogen energy to various sectors of society with the expectation that by
digital technologies [17]. In 2021, the IPHE (International Partnership 2050, hydrogen will be accepted as the main energy source for mass
for Hydrogen and Fuel Cells in the Economy), the IEA (International transportation and will become the next generation green energy tech-
Energy Agency), and the CEM (Clean Energy Ministerial)/MI (Mission nology (Fig. 2e) for power/electricity generation [26]. US Department
Innovation) have collectively addressed the four issues and developed of energy (DOE) in its Annual Energy Outlook (AEO) of 2020 projected
the strategies for scaleup, accelerate and deploy the hydrogen energy threefold increases in the electricity generation based on renewable en-
technologies that not only enhance the reduction of carbon footprints ergy storage systems [28].
but also enable sustainable infrastructure [18]. Energy economy heavily depends on energy storage systems which
On the Asia-Pacific initiatives towards implementing hydrogen en- is a key player between supplies and utilization. As efficient energy stor-
ergy technologies, very recently, China announced its first ever bold age system boosts the efficiency by reducing potential losses. As an ex-
plan to reach its fullest potential of generating 100,000 tons to 200,000 cellent and cost-effective intermittent energy storage systems requires
tons of clean hydrogen and hence that lead to the reduction of CO2 emis- extensive research in a short space of time to achieve rapid solutions for
sions of 1MT to 2MT per year by 2025. By 2035, China seeks the coun- climate change and exhausting resources. However, energy generation
try’s major energy consumptions that are catered by the green sources, from electricity or gas energy sectors does not require storage. However,
especially hydrogen [19]. According to the 2019 IEA/IRENA’s report, storing the excess supply would help in supplementing the shortfall. In
South Korea’s bold plan and road map in volume production of at least their analysis spanning a period of years, M. Wieliczko et al. highlighted
6.2 million fuel-cell electric vehicles, commissioning 1200 hydrogen- the development of potential impact of technologies with low to high
enabled refilling stations and at least 15 GW of fuel cell for power gener- storage capacities on a timescale of ranging from seconds to months
ation by 2040 [20]. The road map of Japan has been pushing the bound- for the energy and climate problems [29]. Although such technologies
aries to cut down the cost of hydrogen by 2030 and by encouraging the namely supercapacitors, superconducting magnets, flywheels, pumped
deployment of ammonia in thermal power generation as a low-carbon hydel storage, compressed air energy storage and batteries offer solu-
transition fuel. Japan also strategically attempting to establish an inte- tions for a variety of applications (depending upon the requirements),
grated and international supply chain by 2030 for up-streaming (produc- but the challenge here is that no single technology can be used for a
tion), mid-streaming (storage and transportation) and down-streaming given range of applications [30]. Interestingly, among these technolo-
(utilization or consumption) the clean hydrogen [20]. India’s bold hy- gies, hydrogen is the only one energy technology which can fulfill the
drogen initiatives that propose to at least infuse four percent of hydro- requirements of various sectors as shown in Fig. 3a.
gen in the national energy mix by 2030 and at least 10 developmental In addition, role of hydrogen becomes even more important because
projects on nation-wide deployment of hydrogen energy technologies it can be produced not only by conventional SMR methods but also by
[22]. Based on the statistics and overview, it is undoubtedly clear that harnessing other renewable sources such as solar, wind and geothermal
the hydrogen energy technologies are the future vectorial strategies that among others. However, in spite of its advantage as a high specific en-
can fully replace the much-depleted fossil fuels, especially gasoline for ergy material, safety, and elevated cost due to its low energy density
automotive transportation and stationary power generation. (Fig. 3b) are the biggest challenges for hydrogen technology [31]. Hy-
drogen storage systems are classified into two categories based on the
3. Hydrogen: a green and sustainable energy resource type of stored hydrogen (Fig. 3c). In physical storage system which are
mainly liquid, or gaseous, free, or elemental hydrogen is stored. Another
The steady decline and depletion of natural energy resources has challenge is liquefaction of hydrogen which requires a high energy input
placed considerable demands for the alternative energy sources. In ad- (8–12 kW/h) [32].
dition, while an emerging climate crisis driven by global warming from For gaseous hydrogen although the density is much lower than liquid
greenhouse gas emissions [23,21] poses an imminent threat to modern- hydrogen, the high cost of containment to store at high pressures pose
day society, the energy shortfall must be met by sustainability for a major safety are concerns [33–35]. On the other hand, in materials-
growing global population and secure the imbalance to the environ- based hydrogen storage system hydrogen atom bonded to materials are
ment with clean energy. The inherent fluctuations associated with wind stored. Fig. 3d and e shows a comparative study done by the Fuel Cell
or solar energy as renewable sources may have an impact on sustainabil- Technologies Office (FCTO) on the materials in terms of hydrogen gravi-
ity requiring a constant and steady supply from the source. Further, the metric capacity as a function of hydrogen release temperature [36,37].
lack of long-term energy storage capabilities with existing technologies It took many years of investigations to develop these materials which
underlines the growing importance for alternative strategies which can are still facing challenges of cost, reproducibility, and recyclability along
work alongside renewable forms. Hence, an alternative sustainable but with high temperature desorption. Despite all these years of explorations
continual energy source is necessary for power generation while renew- material with desired thermodynamic, kinetic, and physical properties
able technology evolves. In this quest, hydrogen is the most promising combination is missing. This suggest that in place of trial and error using
candidate for the cleaner energy as a plentiful resource for zero-carbon periodic table a well-trained investigation based on AI (Artificial Intel-
emission [22–24]. Interestingly, hydrogen emits pure water vapor upon ligence) and ML (Machine Learning) are required. AI/ML will help not
reaction with oxygen or upon combustion therefore, hydrogen-based only to identify the elemental, structural combinations but also will provide
technologies is likely to be one of the most significant determinants in us the pathway for efficient synthesis.
reducing the carbon emission and thus playing an unprecedented role
in driving fuel economy. 4. AI/ML concepts in hydrogen storage materials’ design
The Hype cycle methodology has been instrumental in understand-
ing current and future impact of the most pivotal and exciting techno- Increasing role of AI in changing our life is of paramount impor-
logical fields by estimating technological growth and maturation points. tance. AI is helping us to live in more comfortable and safer world.
In view of the insight from the Garner Hype and Amara Hype cycle Fig. 4a suggests that AI has three main stages: artificial narrow intel-
analysis for energy storage technology put forward by Khodayari et al. ligence (ANI), artificial general intelligence (AGI) and artificial super
and Fredrik Uddenfeldt [25,26] which suggests that chemical hydrogen intelligence (ASI). Out of these three stages first stage of AI is safe and
storage technology is still at the innovation stage (Figs. 2a and 2b), the useful for humankind. Recently research using ANI has become increas-
projected low cost of hydrogen as a fuel source in comparison could be ingly important in all sectors of research and development including hy-
an attractive and real alternative (Fig. 2c and d) [27]. Further, based on drogen storage research (Fig. 4b). Khare et al. have outlined the impor-
3
Fig. 2. (a) Chemical Hydrogen Storage at the Innovation Stage of the industrial revolution
Fig. 2. (b) The HYPE cycle.
tance of interconnectivity of disciplines and further utilizing this trans- understand and identify the performance limits of hydrogen storage sys-
disciplinary approach in AI to enhance the utility of AI for materials tem [39]. In this work, the prediction of two hypothetical MOFs were
discovery [38]. Web of science search with the keywords of hydrogen shown to be associated with superior capability compared to the best
storage technology and AI suggests that research on AI for hydrogen performing MOFS synthesized to date. Interestingly, hypothetical MOFS
storage technology triggered in all areas of importance. However, there predicted to enhance the net deliverable of energy by 30% when filled
are only 95 publications so far in past 10 years but frequency of publica- in a tank at cryo-compression condition (20k, 100 atm.) resulting in
tions in recent 3–4 years has increase manifold. There have been many 30% increase in volumetric capacity. Further Jager et al. have worked
algorithm techniques (Fig. 4c) to predict materials and properties of the on a different scale i.e. on nanosized clusters for optimizing the predic-
hydrogen storage system (Fig. 4d). tion methods for assessing conditions for best property optimization. In
Thornton et al. utilized the findings of a very inspiring project called their work using machine learning algorithms, Jager et al. scanned a
‘The Materials Genome’ where millions of materials were predicted single and multiple nanoclusters applying atomic structural descriptors
based on sequencing and modeling. In their work Thornton et al., tar- (SOAP, MBTR and ACSF) and this was predicted to be the best descriptor
geted hydrogen storage system using a materials genome database to for the prediction of hydrogen adsorption (free) energy. This study con-
4
Fig. 2. (c) Cost analysis of green hydrogen (US$ per kg) with natural gas and renewable electricity.
Fig. 2. (d) Timeline chart of green and gray hydrogen cost of production (US$ per kg).
cludes that the local symmetry is important for descriptor methods and 5. Hydrogen energy storage – a bird’s eye view
therefore near-symmetric systems are ideal for the descriptor methods
[40]. In an extensive work published in two volumes by Rahnama and The reversible hydrogen storage can be realized using metal hydrides
co-workers have combined statistical analysis with supervised machine and adsorbent materials. The hydrogen sorption capacity of materials is
learning algorithms to obtain the best machine learning algorithms for the most important factor to do hydrogen storage. Looking into the stor-
quick identification for a desired class of materials with optimized prop- age part, the thermodynamic properties affect including the enthalpy of
erties such as hydrogen absorption wt.% [41,42]. More research efforts molecular hydrogen adsorption and the enthalpy of hydride formation
have been implemented for the prediction of components of hydrogen or decomposition [13]. Hence, the kinetics of hydrogen adsorption, the
energy storage system which will be reviewed in detail in our future activation energy, the hydrogen diffusion coefficient and the apparent
work with a focus on AI for the components of hydrogen energy storage rate of hydrogen absorption and desorption would be the key factors.
systems. There are quite a few good techniques available to measure gas sorp-
5
Fig. 2. (e) Timeline chart of mass energy transportation and power generation.
Fig. 3. (a) Stored energy vs. storage time for various energy
technologies.
tion at laboratory scale which could be useful to determine the hydro- of hydrogen storage and related issues have been discussed especially
gen storage capacity of the materials. Not only the storage capacity of metal hydrides for sustainable energy applications [43].
the materials but also other physical and chemical properties are very
important to optimize the hydrogen storage solid specimens which in- 6. Metal hydrides and related systems
cludes the microstructural properties using X-ray diffraction and elec-
tron microscopy. The spectroscopic studies can be used to analyze vari- Compounds formed between metals and hydrogen are termed metal
ous chemical and molecular properties of the targeted storage materials. hydrides. Here the metal can be in form of an element, an alloy, or
Though, the analysis data of the targeted specimens are not enough to a metal complex. The nature of bonding between metal and hydrogen
give final sorption capacity of the potential storage materials for the depends on the electronegativity of the metal, which is responsible for
hydrogen [13]. A very recent comprehensive review on the prospects the type of electrons shared among metal and hydrogen. For low elec-
6
tronegative metals alkali (Group 1a) or alkaline earth metals (Group

2a), the electron is transferred from the metal to the hydrogen and thus
the ionic bond is formed. With the increase in the electronegativity of
the metal, the metal-hydrogen bond is metallic. With the even higher
value of electronegativity of metal, the bond becomes covalent in na-
ture. Metallic metal hydrides are formed from transition metals, lan-
thanides, and actinides. In this case, the electron energy levels of metal
and hydrogen overlap sharing delocalized electrons characterized by a
metallic bonding. The hydrogen atom is occupied in either a tetrahedral
or an octahedral void formed by metal atoms.
As mentioned above, in metal hydrides metal may be in form of
an element, alloy or intermetallic compound (IMC). Metal hydrides
formed by an element have limited properties. There is the large scope
and greater flexibility for tailoring the hydrogenation characteristics
through alloys and intermetallic compounds with a wider range of ap-
plications. Alloys and intermetallic compounds may be binary, ternary,
quaternary, and more complicated systems. The class of alloys capable
of storing hydrogen is also known as hydrogen storage alloys (HSA).
The major binary IMC systems used as HSA are AB5 (LaNi5 ), AB2
(TiMn2 ), A2 B (Mg2 Ni) and AB (TiFe) (Table 1). The few other classes
are A3 B (Nb3 Sn), AB3 (LaNi3 ), A2 B7 (Nd2 Ni7 ), A2 B17 (La2 Mg17 ), A6 B23
(Ho6 Fe23 ) etc. There may be more than one stable crystal structure
for each system. The characteristics of the binary IMC may not be al-
Fig. 3. (b) Specific energy density vs volumetric density of number of fuel ways available for a particular application. In such cases, partial sub-
sources. stitution at A, B or both sites with elements containing the same or the
similar number of outer shell electrons can be done. This substitution
Fig. 3. (c) Types of hydrogen storage technologies.

7
Fig. 3. (d) metal hydrides, chemical hydrogen, and adsorbents temperature of operation with respect to the hydrogen storage capacity
Fig. 3. (e) Sorption temperatures of various soft materials and complex hydrides with respect to hydrogen storage capacities.
may specifically tailor the IMC for required hydrogenation properties B is a transition element basically Ni. It is synthesized through vacuum
(Table 2). One more popular metal hydride corresponds to vanadium- induction melting. This type of intermetallic compound is very brittle
based solid solution. In the following, each class of IMC and their and easily reduced to the granular or powder form to fill hydride con-
progress (Fig. 5) will be discussed one by one. tainers. The hydrogen storage capacity of LaNi5 corresponds to 1.4 wt%
with plateau pressure ∼ 0.5 MPa. The heat of formation of LaNi5 H7 is
7.3 kcal per mol H2 [44].
6.1. AB5 system
It is the most easily operated intermetallic compound with the appli- 6.1.1. Crystal structure
cation at ambient conditions. In the AB5 system, A usually comes from AB5 -type IMCs have CaCu5 -type hexagonal structure with space
the rare earth (lanthanide) elements (at. no. 57–71) including Ca and group P6/mmm. Here the unit cell is hexagonal with one formula unit
8
Fig. 4. (a) Three main stages of AI, (b) AI in hydrogen storage technology, Different techniques of AI to predict (c) materials and (d) properties of the hydrogen
storage systems.
Table 1
Types of metal hydrides.
S.N. Class Crystal structure Representative compound
Composition Hydrogen Storage Plateau Operating Heat of hydride

capacity pressure temperature formation kcal
wt% (MPa) °C (mol H2 )−1
1 AB5 Hexagonal CaCu5 LaNi5 1.5 0.5 Room temperature 7.3

2 AB2 C14 Hexagonal TiMn2 2.0 1.4 Room temperature 7.2
3 A2 B C16 Hexagonal Mg2 Ni 3.8 0.1 300 15.3
4 AB BCC FeTi 1.9 0.5 40 6.7
5 Solid BCC (V0.9 Ti0.1 )0.95 Fe0.05 1.8 0.05 25 10.3
Solution (SS)
Table 2
Comparison of hydrogenation properties of metal hydrides.
Activation AB5 > AB2 > SS > A2 B > AB

Kinetics AB5 > AB2 > SS > A2 B > AB
Cyclic stability AB2 > SS > AB5 > AB > A2 B
Cost AB5 > AB2 > SS > A2 B > AB
Reversible hydrogen storage capacity AB2 > AB > SS > A2 B > AB5
Operating conditions AB5 > AB2 > SS > AB > A2 B
Sensitivity to impurity AB > A2 B > SS > AB5 > AB2
9
Fig. 5. Progress in metal hydride-based research.
per cell. The calcium atoms occupy the positions (0,0,0) and copper effective version, MmNi5 evolved. Mm represents an unrefined rare
atoms are found at positions (1/3, 2/3,0), (2/3, 1/3, 0), (1/2, 0, 1/2), (0, earth mixture commonly known as mischmetal. Mm usually contains
1/2, 1/2) and (1/2, 1/2, 1/2) [45]. The representative compound of this the four main rare earth elements Ce, La, Nd and Pr. The actual compo-
family corresponds to LaNi5 . The CaCu5 -type of structure is relatively sition of mischmetal depends on the mineral and ore body from which
common in AB5 compounds when the atomic diameter of the B atom it is derived. The typical composition (in weight%) corresponds to 48–
is smaller than that of the A atom. It happens within a range of radius 50% Ce, 32–34% La, 13–14% Nd, 4–5% Pr and 1.5% other rare earth.
ratio rA /rB from 1.3014 (NbBe5 ) to 1.7656 (RbAu5 ). In this hexagonal MmNi5 had been synthesized in early 1973 at Brookhaven National Lab
structure, the lanthanum atoms occupy the 1a crystallographic site in for H2 separation trials and a high-pressure H2 source tank [49]. The
the basal plane, while the nickel atoms occupy the 2c site in the basal choice of Mm for La results in very high plateau pressures and hystere-
(NI ) and the 3 g site in the Z = 1/2 plane (NII ). Each lanthanum atom sis. This may be adjusted by substitution at Mm and Ni.
is surrounded by six lanthanum atoms in the basal plane at distances
of 5.01 Å and by two lanthanum atoms in the c-direction located at 6.1.3. Development
about 3.98 Å. These La-La distances are to be compared with dLa-La : For lowering the high hysteresis and high plateau pressure, initially,
3.75 Å in the pure fcc lanthanum lattice. The NiII atoms are surrounded partial ternary substitutions were done to both the Mm and Ni sides of
by four NiII atoms at 2.46 Å, four NiII atoms (dNiII-NiII = 2.508 Å) and MmNi5 [50,51]. At the B site other transition elements were tried as
four lanthanum atoms (dNiI-La = 3.202 Å). It should be noted that these Al, Fe, Co, Si, Mn etc.[52–57] Almost up to 2010 AB5 -type compounds
Ni-Ni distances are comparable with dNi-Ni = 2.45 Å in the fcc nickel lat- were investigated for ternary substitutions at A, B and both sites for
tice in which the coordination number is 12, thus much larger than in the study of their basic hydrogenation characteristics. The earlier study
LaNi5 .There are in total 34 tetrahedral holes in one AB5 unit [46]. These was focused on material development for NiMH cells and storage pur-
are B4 tetrahedral holes (4 in subgroup 4 h), AB3 tetrahedral holes Type poses. Within the last decade many more applications have been com-
I (12 in subgroup 12o), AB3 tetrahedral holes Type II (12 in subgroup ing forward. To accommodate all these applications, the trends of multi-
12n), A2 B2 tetrahedral holes (12 in subgroup 12n). In the hexagonal element substitutions have increased. The nano version of the compound
AB5 structure, 9 sites are most probable for hydrogen occupancy. and the mixing of alloys were also tried by researchers. A computer sim-
ulation study has thrown new insights at the understanding level.
• 3 clusters of 4 type-II AB3 holes, centroids with subgroup 3f (HI site) The substitution at the B site is more common and has more op-
• 6 clusters of 1 A2 B2 hole and 2 type-I AB3 holes, centroids with tions. Each substituted elements plays a specific role in hydrogenation
subgroup 6 m (HII site) properties according to the specific application. The substitution of Al
at the Ni site lowers the plateau pressure of MmNi5 from 1.4 MPa to
6.1.2. Discovery around 0.2 MPa ?????[58,59]. Mn and Si are substituted for improve-
AB5 IMC was accidentally discovered at the Philips Eindhoven Labs ment in cyclic performance [60–62]. Co stops the corrosion of metal
about 1969 during work on AB5 permanent magnet materials SmCo5 hydride electrodes [63,64]. To improve the hydrogenation properties,
[47]. To study the positions of the H-atoms in SmCo5 hydride by NMR, melt-spun versions of IMC were also studied, which resulted in improved
AB5 compound LaNi5 was selected. The reaction of LaNi5 with H2 was kinetics [65–67]. Melt-spun versions reflected higher storage capacity,
remarkable compared to SmCo5 [48]. The reversible hydrogenation was fast kinetics, and fast activation in comparison to conventional induc-
confirmed with H/M > 1 at ambient temperature at a pressure of less tion melting. It has been noticed that more substitution at the Ni site
than 2.5 atm. Low hysteresis and fast kinetics were observed and LaNi5 reduces the hydrogen storage capacity of the parent alloy from 1.4 wt%
could also be easily activated at room temperature. Thus, a new and to 1.0 wt% [65–67]. Fe substitution has a reverse effect on hydrogen
exciting hydrogen storage alloy LaNi5 was discovered. Later on its cost- storage capacity. It increases the storage capacity due to the presence
10
of unfilled d-orbital [68]. The Ca substitution at A site is also known to has a cubic structure with eight AB2 formula units per unit cell (8 A-
enhance the storage capacity because of its lightweight [69]. However, atoms and 16 B-atoms). A representative C15 hydriding phase is ZrV2 .
the plateau pressure has been noticed to increase drastically. To lower In both cases, H-atoms tend to occupy [A2 B2 ] tetrahedral interstices
this high plateau pressure simultaneous substitution was done at the Ni [109]. The AB2 intermetallics may have some homogeneity range (i.e.,
site also by Al and Fe. A series of IMCs were studied on Ca substitu- A: B need not be exactly 1:2), unlike the AB5 line compounds. ZrMn2
tion [70,71]. High hydrogen storage capacity of 2.2 wt% was reported and ZrV2 have hydrogen storage capacities of 1.0 and 2.1 wt% respec-
following the composite pellet formation route for the synthesis of the tively [110]. The heat of the formation of hydrides of ZrMn2 and ZrV2
alloy. The multiphasic alloys have shown enhancements in all the hydro- have values close to 12.7 and 35.9 kcal per mole H2 [111,112].
genation characteristics of the LaNi5 alloy with a major phase of LaNi5
and minor phases of LaNi3 and La2 Ni7 [72–75]. 6.2.2. History
Nowadays multi-element substitutions are preferred to achieve the The first intentionally studied report on AB2 intermetallic com-
required properties for specific applications [76–78]. Especially in Ni- pounds is the formation of two AB2 hydrides: ZrCr2 H3.6 and ZrV2 H4.14
MH electrode material, various substitutions are done at Ni sites, with [113]. This early study was focused mostly on high temperature
the roles of each element. Such multi-element substitutions give stability (>538 °C) properties. Several years later the 1956 report of Trezeciak
to the electrode in alkaline electrolyte and lessen the pulverization, thus et al. [113], a major pioneering hydriding survey of many binary inter-
increasing cyclic stability with enhanced energy density[79–82]. metallic compounds was reported by Beck in 1962 [110]. However, AB2
In the recent decades, the nano-version of alloys has shown improve- hydride activity was virtually dormant for the next decade and became
ment in hydrogenation properties due to the larger surface area exposed quite active at several laboratories in the late 1970s.
to the hydrogen. This is achieved through mechanical alloying or ball-
milling of the bulk synthesized alloy [83–86]. Ball-milling has resulted 6.2.3. Development
in improved hydrogen storage capacity with fast activation process and In the AB2 system hydrogen storage capacities are not much if heavy
fast kinetics [87]. The use of a catalysts during ball milling has been A-atoms are incorporated (e.g., the rare earth elements or Zr). Using the
found to improve the hydrogenation properties further [88–92]. Widely lighter Ti as the A-element helps with a higher weight percent of hy-
used catalyst in AB5 compound corresponds to transition elements. Cat- drogen storage capacity [114]. The practically popular alloy of the AB2
alysts are known to favor hydrogen molecule dissociation and more en- class is TiMn2 having a C14 structure. Plateau pressure, hydrogen stor-
trance channel for hydrogen atom diffusion into the material at intersti- age capacity and other properties can be adjusted by substituting Zr for
tial sites. Ti and Cr for Mn. Zr substitution decreases the plateau pressure and
Several theoretical calculations and simulations works were also per- storage capacity [115]. For this alloy, plateau pressure is 1.4 MPa with
formed to expose the researchers to a better understanding of proper- a hydrogen storage capacity of 2.0 wt%. Several studies have been re-
ties[93–95]. Density functional theory has been proven to reveal infor- ported on the substitution of Ti with Zr and the substitution of Mn with
mation about energy levels and the positions occupied by hydrogen in Co, Cu, V, Fe, Ni and Cr. The hydrogen storage capacity for these alloys
the metal hydride [45,80,96,97]. Theoretical models have been devel- corresponds to 1.5 to 2.0 wt%, while plateau pressure is below 1.0 MPa
oped to predict the heat of formation, structural properties, and elec- at ambient temperature. Sometimes a multi plateau is also seen in this
tronic properties [44,98–104]. Recently AB5 -type IMCs have been ap- system. TiMn1.5 and Ti0.98 Zr0.02 V0.43 Fe0.09 Cr0.05 Mn1.5 are popular com-
plied in many new applications like actuators [102] and thermal man- positions in the AB2 system [116–119].
agement systems [103]. LaNi5 has been reported in other forms as well Melt-spun alloys have been prepared to improve the hydrogena-
for hydrogen storage purposes. Spray-dried composite microparticles of tion properties and electrochemical properties for application in Ni-MH
polyetherimide and LaNi5 have been studied as versatile materials for cells [120,121]. High catalytic activity disorder in multi-component al-
hydrogen storage applications [104]. LaNi5 has shown an excellent cat- loys has also been shown to improve the electrochemical capacity of
alytic effect on the hydrogen storage properties of aluminum hydride at 440 mAhg−1 [122]. It has been reported that the hydrogen absorption
mild temperatures [105]. Hydrogen absorption by ∼5 kg LaNi5 has been capacity of the TiMn2 -based alloys is mainly governed by the atomic
studied in a metal hydride reactor through simulation studies to show composition and atomic arrangement of the alloy within the TiMn2
that 290 and 375 s are required for 80% and 90% hydrogen storage phase [121]. The degradation of the cyclic property of the alloy ac-
saturation level in the reactor, respectively [106]. A monolayer model tively depends on the substituted elements in the hexagonal TiMn2 Laves
treated by statistical physics was applied employing the grand canoni- phase [123]. Centrifugal casting and gas atomization processes were
cal ensemble to describe P-C-T isotherms for absorption of hydrogen by applied to multiple-phase AB2 alloys by Young et al. [124]. They re-
LaNi3.6 Mn0.3 Al0.4 Co0.7 alloy to correlate with the experimental results ported that the centrifugal casting process provided the better cycle life.
[107]. The gas atomization process has lower production cost but suffers from
higher bulk oxygen content and thicker surface oxide, and thus infe-
6.2. AB2 system rior in all battery performance characteristics other than cycle life and
charge retention. Various changes in the structure incorporated through
The A elements in the AB2 system are from the IVA group (Ti, Zr, phase abundance, defect and off stoichiometric have direct effects on the
Hf) and/or rare earth series (at. no. 57–71) or Th. The B-elements can hydrogenation characteristics of the AB2 alloy [125–127]. Phase abun-
be a variety of transition or non-transition metals with a preference for dance has shown higher gas phase and electrochemical storage capac-
atomic numbers 23–26 (V, Cr, Mn, Fe). In this system also, a wide va- ities, lowering of the hydrogen equilibrium pressure, decrease in the
riety of substitutions are possible for both A- and B-elements. Substitu- half-cell high rate dischargeability, improvement of both charge reten-
tions may help in developing materials with hydrogenation properties tion and cycle life [102]. Defect in C15 Zr0.9 Ti0.1 V2 alloy improved the
for specific requirements. hydrogen absorption-desorption properties [103].
In a separate study carried out by Kazemipour
6.2.1. Crystal structure et al.Ti0.72 Zr0.28 Mn1.6 V0.4 alloy was synthesized using mechanical
The class of practical AB2 intermetallic compounds for hydrogena- alloying and innovative vacuum copper boat induction melting. They
tion purposes belongs to the Laves phase. Laves phase structures have showed that the samples consisted of two main phases, the C14 Lave
three varieties: C14, C15 and C36 [108]. The C14 and C15 are the most phase and the V-base solid solution phase. The hydrogen capacity of
important structures. The C14 phase has hexagonal structure, with 4 the induction melted samples was higher than that of the samples
AB2 formula units per equivalent trigonal unit cell (4 A-atoms and 8 B- produced by the mechanical alloying method [128]. Studies through
atoms). A representative hydriding C14 phase is ZrMn2 . The C15 phase density functional theory on the total energy, electronic structure and
11
bond of Zr(Cr0.5 Ni0.5 )2 alloy and its hydrides showed that A2 B2 sites small part of the maximum capacity. Generally During the synthesis
are preferentially occupied in the structure, followed by the AB3 while of Mg2 Nifinal product is typically a three-phase mixture of Mg2 Ni,
B4 remains empty. Among hydrogenations, the main contribution to MgNi2 and Mg. It may be noted that the MgNi2 phase does not hydride.
the density of states is due to the d electrons of all components of the Hence the alloy is usually melted to slightly higher Mg levels than the
structure [129]. TiMn2 has been reported to enhance the hydrogena- stoichiometric Mg2 Ni. Single-phase Mg2 Ni can be made by mechanical
tion properties of MgH2 nanocomposites synthesized through reactive alloying (high-energy ball milling) of elemental Mg and Ni powders
ball-milling [130]. Several recent studies have pointed out the effective [145] and by the reaction of Ni powder with Mg vapor [146].
application of AB2 alloys in electrochemical storage, compressor, and Zaluski et al. reported on the synthesis of Mg2 Ni through mechan-
easy activation for storage purposes [131,132]. High entropy alloy ical alloying using a high energy ball mill to enhance the kinetic and
has further enhanced the electrochemical capacity [133]. Qin et al. activation properties [147]. In a similar work reported by Singh et al.,
devoted their studies to demonstrating that ZrFe2 -based alloys with the nano version of Mg2 Ni alloy prepared through ball milling has been
a small Ga or Al substitution are suitable for high-pressure hydrogen found to show easy activation by annealing at 300 °C in a vacuum for
storage applications [134]. Few researchers reported the hydrogenation 30 min [148]. Mechanical alloying has also revealed the enhancement
characteristics of AB2 alloys based on machine learning [135,136]. in hydrogen diffusion and charge transfer reaction [149]. In a separate
Normally freshly crushed AB2 materials activate at room temper- work on ternary Mg2 Ni0.75 M0.25 ????(M = Ti, Cr, Mn, Fe, Co, Cu and
ature. Sometimes heating at a few 100 °C temperatures in a hydro- Zn) alloys synthesized by the ball milling; hydrogen desorption capac-
gen atmosphere is needed for activation. The kinetics of hydrogen ity reached the highest value after only two adsorption-desorption cy-
absorption-desorption is high. The intrinsic kinetics is faster than the cles after fluorination treatment [150]. In these alloys, 3.3 wt.% hy-
heat transfer [94]. Less than 5% of capacity loss was seen in com- drogen desorption was measured at 250 °C. Replacement of Ni by Cr,
mercial alloy Ti0.98 Zr0.02 V0.43 Fe0.09 Cr0.05 Mn1.5 during 2000 absorption- Mn and Co has lowered the decomposition plateau pressure; while Ti
desorption cycles with high purity H2 (0.1–5.0 MPa, 20–80 °C) [94]. The and Cu had the opposite effect and Fe and Zn had little effect. Mg2 Ni
AB2 s are considerably less expensive than the AB5 s. and Mg2 NiH4 have been reported showing the catalytic effects on the
hydrogen desorption characteristics of MgH2 [151]. The catalytic ef-
6.3. A2 B system ficiency of Mg2 NiH4 was found considerably higher than pure Ni and
Mg2 Ni phase. Cr doping to result in the alloy Mg2 Ni0.9 Cr0.1 showed
In the A2 B system, PCT data does not fall in the 0–100 °C tempera- stable absorption capacity, and improvement in absorption/desorption
ture range and 0.1–1.0 MPa pressure range for most of the IMC of this rates after cycling [152]. The use of MWCNTs coupled with TiF3 during
class. Hence it is less useful for ambient condition applications. Mg2 Ni is the ball milling process has improved the hydrogen desorption property
the representative hydride phase with an H/M value of 1.33, a hydrogen of Mg2 NiH4 reasonably [153]. It was noticed that in the presence of
storage capacity of 3.6wt%, 15.4 Kcal (mol H2 )−1 heat of hydride forma- above-mentioned catalysts, the dehydrogenation temperature, and the
tion 0.32 MPa plateau pressure at the temperature of 299 °C [137]. activation energy of Mg2 NiH4 were reduced to 230 °C from 244 °C and
53.24 kJ/mol from 90.13 kJ/mol respectively. Hence the addition of
6.3.1. Structure proper catalysts has been proven to be an effective strategy to decrease
Mg2 Ni has an Al2 Cu-type C16 hexagonal structure. It may be noted the desorption temperature and activation energy of Mg2 NiH4 hydrides.
that Mg2 NiH4 is not a metallic hydride in the sense of the other inter- Studies on the first-principle calculation have been performed to
metallic compounds [138]. It is a more complicated hydride. Mg2 NiH4 evaluate the hydrogen absorption energy on the Mg2 Ni surface and in
is not an interstitial hydride. Here Mg donates electrons to stabilize an the bulk alloy [154]. Reduction in hydrogen absorption enthalpy was
[NiH4 ]−4 complex. 4 hydrogen atoms are bonded with a single Ni atom observed through an ab initio study by substitution of Al, Ga, In, Si,
and the two electrons are donated by two Mg atoms each to stabilize the Ge and Sn at the Ni site in Mg2 Ni alloy [155]. Mg2 NiH4 powder was
[NiH4 ]−4 transition metal complex. The structure of Mg2 NiH4 is quite used for hydrogen generation via hydrolysis reaction in different types
different from the starting Mg2Ni structure. Mg2 FeH6 and Mg2 CoH5 of solutions. The extremely intense hydrogen kinetics was observed us-
A2 B stoichiometries are present only as hydride complexes. Mg2 Fe and ing an acidic solution [156]. Moreover, Mg2 NiH4 powder stored for
Mg2 Co phases do not exist without hydrogen in the binary metal sys- two months disclosed almost identical hydrogen generation volume as-
tems. received Mg2 NiH4 powder. The hydrolysis reaction between Mg2 NiH4
and the acidic solution was also applied for electricity production via
6.3.2. History the PEM fuel cell. Vanadium doping in Mg2 Ni during the ball milling
Historically Mg2 Ni was one of the earliest intermetallic compounds process has resulted in improved hydrogenation-dehydrogenation kinet-
that were reported to be usable as a rechargeable hydride [115]. Mg2 Ni ics with extended plateau region as compared to pure-Mg2 Ni [157]. A
can absorb up to 3.8 wt% hydrogens [139]. This capacity is very large in few other A2 B-type alloys have also been reported for hydrogen absorp-
comparison to AB5 and AB2 -type alloys [140]. Ni is known to improve tion properties. Partial substitution of Mo for Ti increased the hydrogen
the hydrogenation absorption-desorption capacity of Mg [141]. During storage capacity to 2.23 wt%. It was due to decreased dihydride stability
reaction with Mg, Ni forms Mg2 Ni and MgNi2 alloy. MgNi2 alloy does after Mo substitution [158]. Density functional theory calculations have
not absorb hydrogen, but Mg2 Ni absorbs a good quantity of hydrogen. been employed to study the improvement in the adsorption, dissociation
E:\Vendor–2\backup\FEB-2023\2-FB\SOLCOM100033The A2B and diffusion of hydrogen on the Zr2 Fe(101) surface through Mn doping
system has desorption pressure usually less than 0.1 MPa. To increase [159]. Zn substitution in Mg2 Ni alloy for Ni has shown a lowering in the
the desorption pressure various substitutions have been done at the A activation energy as 17.01 kJ/mol in comparison to 46.07 kJ/mol for
and B sites. Partial substitution of Al for Mg and Zn for Ni does lower the Zn-free Mg2 Ni. The equilibrium hydrogen pressure in the PCT curve
the desorption temperatures of Mg2 Ni a little, but it is difficult to reach of alloys was increased with increasing Zn content [160].
the pressure of 0.1 MPa at 100 °C [142]. The metallurgy and the basic
chemistry of the hydrides of A2 B systems are fundamentally different
compared to the AB5 , AB2 and AB families. Together with the principal 6.4. AB system
plateaux at very low pressures, Zr2 Pd, Hf2 Pd and Hf2 Cu have additional
plateaux at very high pressures (100 MPa) at room temperature [143]. Most of the practical AB compounds are based on TiFe and therefore
These interesting intermetallics have the "non-close-packed" tetragonal represent low raw materials costs. They are historically important to the
Cllb MoSi2 structure with various available interstitial sites [144]. early development of ambient temperature hydrides and their applica-
The additional plateaux cover about 0.3–0.6 H/M, i.e., a relatively tion to the first H2 -fueled vehicles.
12
6.4.1. Crystal structure phase. The samples showed the fastest hydrogenation kinetics, highest
The common AB structure corresponds to B1 CrB-type structure. hydrogen capacity and good cycling stability corresponding to x = 4.
Among AB compounds, practically applied alloys have simple B2 struc- Another report focused on the effect of air exposure on the first hy-
ture. It has a body-centered-cubic cell with one formula unit per unit drogenation kinetics of TiFe +4 wt% Zr +2 wt% Mn alloy [178]. In this
cell. One A-atom is shared by the cell corners and one B-atom resides study researchers observed that the air-exposed alloy could be success-
at the center of the cubic cell. Each cell contains 12 tetrahedral and 6 fully hydrogenated after ball milling and after cold rolling with some
octahedral interstices. H atoms occupy only the octahedral sites with loss in hydrogen storage capacity. To improve the hydrogen storage per-
the preference of [Ti4 Fe2 ] co-ordination. [Ti2 Fe4 ] octahedral sites may formances of TiFe-based alloys, TiFe0.8-m Ni0.2 Com (m = 0, 0.03, 0.05
also be filled at high H/M value [161]. and 0.1) alloys were synthesized. All the alloys were composed of the
majority phase of TiFe and the non-hydrogenated phase of Ti2 Fe. The
6.4.2. History secondary phase favored the lowering of activation temperature [179].
The first member of the AB hydride group was reported as ZrNi Zeaiter et al. have reported the effect of mechanical milling on the mor-
in 1958 as reversible hydride ZrNiH3 desorption plateau pressure of phological, structural and hydrogen sorption properties of powdered
0.1 MPa at 300 °C [162]. This material was not studied for one more TiFe0.9 Mn0.1 alloy [180]. Ball milling has lowered the activation tem-
decade due to the high temperature of 300 °C. The first practical room- perature and increased the hydride stability with a sloppy plateau in the
temperature AB hydride was TiFe, discovered at Brookhaven National PCT curve. Mn in TiFe alloy acted as a sacrificial element to prevent the
Lab in the U.S. around 1969 [163]. Two distinct hydrides (TiFeH and bulk oxidation of alloys [181]. A very interesting study was reported
TiFeH1. 95 ) resulted in two separate plateaus. In this class, most of the by Patel et al. on the easy activation of TiFe alloy at room tempera-
members have multi-plateau PCT curves. ture [182]. They showed that the chunks of the alloy under hydrogen
pressure can be activated without any additional grinding media. They
6.4.3. Development termed their process as self-shearing reactive milling and observed the
TiFe has a hydrogen storage capacity of 1.9 wt%, the heat of hydride full hydrogenation of FeTi alloys. In another study, TiFeMn has been
formation is 6.72 Kcal(mol H2 )−1 and plateau pressure of 0.5 MPa at reported as a useful metal hydride for forklifts using numerical simu-
40 °C. In the AB system useful IMC are ZrNi, TiFe and TiCo, among which lation [183]. The density functional theory studies made on hydrogen
TiFe is the most popular one [164,165]. In TiFe IMC Zr can be partially adsorption over TiFe surface and doped TiFe surface reflected that even
substituted for Ti and Mn, Ni, V, Nb and Si can be substituted for Fe a very small amount of dopant can influence the hydrogen adsorption
[166–168]. TiFe and TiFe0.85 Mn0.15 were the best-reported compounds properties of TiFe alloy [184].
during 1990 in the AB metal hydride system. Density functional theory calculations were applied to investigate
Chiang et al. studied the hydrogenation properties of TiFe, TiFe2 the effect of Al, Be, Co, Cr, Cu, Mn and Ni in the TiFe system. Enthalpy
and pure Ti during high-energy ball milling in a hydrogen atmosphere. of formation was approximated in terms of changes in lattice parameters
Through ball milling, TiFe could absorb hydrogen without activation without the need for Van’t Hoff plot [185]. TiFe0.85 Mn0.05 alloy has been
treatment [169]. To overcome the deterioration of the hydrogen ab- applied as a hydrogen carrier for an industrial hydrogen storage plant
sorption performances of TiFe-based hydrogen storage materials, sur- of about 50 kg of hydrogen [186]. In general, TiFe is very difficult to
face modifications have been reported by the deposition of metals (in- activate. It needs heating at a higher temperature of 300–400 °C for
cluding Palladium). This technique facilitated the hydrogenation of the activation to break the oxygen layer present at the surface. The intrinsic
material even after its exposure to air [170]. Benyelloul et al. found kinetics of TiFe and related alloys are slower than the AB5 compound,
that the insertion of hydrogen into the FeTi crystal structure causes an but heat transfer is rapid.
increase in the bulk modulus. Using density functional theory they ob-
served that the FeTi compound and its hydrides are ductile and that this 6.5. Solid solution alloy hydrides
ductility changes with changing the concentration of hydrogen [171]. In
separate research, plastic deformation created in intermetallics of TiFe The term "solid solution alloy" designates a primary element used
using groove rolling and high-pressure torsion has resulted in 1.7–2 wt% as a solvent into which one or more minor elements in form of solutes
of hydrogen absorption in the first few cycles thus improving the acti- are dissolved. In the case of a solid solution, the solute need not be
vation process significantly [172]. The samples were not deactivated by present at an integer or near-integer stoichiometric for the solvent. This
long-time exposure to the air. To further improve the activation process feature is entirely different from the intermetallic compounds discussed
and hydrogen storage capacity Cu and Y were incorporated in Ti-Fe- here. The solute is present in a random (non-ordered) substitutional or
Mn alloy as Ti0.95 Y0.05 Fe0.86 Mn0.05 Cu0.05 [173]. The melted alloy had a interstitial distribution within the basic crystal structure. Various solid
TiFe matrix with a Cu2 Y secondary phase. The addition of element Y en- solution alloys have been reported as reversible hydrides, in particular,
hanced the hydrogen storage capacity as 1.85 wt% at 20 °C. The activa- those based on the solvents Pd, Ti, Zr, Nb and V. Pd, Ti and Zr Solid
tion and kinetic properties of the hydrogenated alloy were improved due Solutions represent the largest family of solid solution hydrides consist-
to the presence of the secondary phase Cu2 Y. Due to its lightweight and ing of the face-cantered-cubic (A1)Pd-based alloys. Many of the Pd solid
low-cost TiFe was compared with LaNi5 for their application in metal solution alloys have PCT properties within the range of 0.1–1.0 MPa at
hydride beds [174]. Heat exchange was higher in the TiFe bed as com- 0–100 °C with a low hydrogen storage capacity of 1.0 wt.%, but they
pared to LaNi5 filled in a similar tank. Silva et al. reported their work on are costly.
Mg - 40 wt% TiFe nanocomposite prepared by high-energy ball milling. Hydrides of Ti- and Zr-base solid solution alloys are very stable.
This process has improved hydrogen absorption at room temperature Nb and V solid solutions have simple body-centered cubic (A2) crys-
[175]. To produce active nanocrystalline TiFe compound TiH2 and Fe tal structures and their dihydrides generally form a face-cantered cubic
powders were dry co-milled in a planetary ball mill for 5–40 h [176]. structure. In vanadium-based solid solution various elements Ni, Cr, Fe,
All samples absorbed hydrogen at 2 MPa without additional thermal Mo, Ge, Si, Sn, Ti, Mn and Zr were used [187]. A representative al-
activation cycles. Milling for Shorter time of 10 h resulted in easy hy- loy (V0.9 Ti0.1 )0.95 Fe0.05 was reported with PCT properties as 0.05 MPa
drogen absorption during the first cycle. However, the samples milled pressure at 25 °C, the heat of hydride formation as 10.3 kcal(mol H2 )−1
for longer times (25 and 40 h) have shown better results in terms of with a hydrogen storage capacity of 3.7 wt% and reversible capacity of
reversible and storage capacities (0.73 and 0.94 wt.%, respectively). In 1.8 wt% [188].
separate research carried out by Lv et al. hydrogen storage properties of Investigations were made on the interaction of hydrogen for the
air exposed TiFe + x wt.% (Zr+2 V) (x = 0, 4, 5 and 6) alloys were stud- mechanochemically synthesized composition of Ti45 Zr38 Ni17 solid so-
ied [177]. Doped samples had bcc TiFe main phase and hcp secondary lution alloy. The hydrogenation in this alloy started in the very first
13
cycle even at a hydrogen pressure of less than 0.1 MPa [189].Gao tions in the parent alloy. The present ongoing era (2011 onwards) is
et al. studied the pulverization mechanism of the multiphase Ti–V- the witness to advanced microstructural alteration in terms of composi-
based hydrogen storage alloy consisting of a V-based solid solution tion and structure. Nowadays multi-element compositions of multipha-
phase of the BCC structure and a C14 Laves phase of the compo- sic, composite, and disordered nature are preferred over simple parent
sition Ti0.8 Zr0.2 V2.7 Mn0.5 Cr0.6 Ni1.25 Fe0.2 alloy [190]. Fe substitution alloys. Various theoretical, simulation and first principle calculations
in hydrogen storage alloy Ti12 Cr23 V65 leading to the composition based on density functional theory have also come forward. The re-
Ti12 Cr23 V64 Fe1 resulted in the increase of the lattice strain and the de- search on metal hydrides had some recession within the time frame of
crease of the crystallite size by hydrogen absorption and desorption thus 2014–2020 due to their less hydrogen storage capacity in comparison
improving the cyclic durability [191]. Ti52 V12 Cr36 alloy was investi- to complex hydrides. But the ease of operation at normal temperature
gated by Kamble et al. for the first hydrogenation cycle [192]. They and pressure has proven metal hydrides as more feasible candidates for
observed that doping of 4% Zr and reduced particle size had a direct ef- application point of view. Therefore, the research on metal hydrides has
fect on lowering the incubation time. In separate research, studies were again gained a boom for the last few years.
performed on microstructural details of hydrogen diffusion and stor-
age in Ti25 V50 Cr25 and Ti10 V75 Cr15 alloys activated through the sur-
7. Magnesium-based and related systems
face and bulk severe plastic deformation [193]. Liu et al. have corre-
lated the order of entropy of alloy with hydrogen absorption and re-
Magnesium (the 7th most abundant element in the curst of the Earth
versible hydrogen desorption capacity on the alloys V35 Ti30 Cr25 Fe10 ,
with an abundance of 2.3%) and hydrogen (the universe’s most com-
V35 Ti30 Cr25 Mn10 , V30 Ti30 Cr25 Fe10 Nb5 and V35 Ti30 Cr25 Fe5 Mn5 [194].
mon element) reacts together and form the stable magnesium hydride
The partial substitution with niobium and iron in Ti25 Cr50 V25 hydro-
(MgH2 ).
gen storage alloy increased the cyclic durability of the alloy [195]. In
high entropy alloy TiVZrHfNb, it was observed that lower particle size
Mg+H2 ↔ MgH2+ ∆H
had affected improving the kinetics of hydrogen absorption-desorption,
while higher temperature decreased the incubation time for activa-
tion [196]. The hydrogen storage alloy specified by the composition Where, ∆H is the enthalpy of reaction, describing the thermody-
Ti10+x V80-x Fe6 Zr4 (x = 0, 5, 10, 15) resulted in the lowest incubation namic stability of hydride. The theoretical gravimetric and volumetric
time of 12 s and the highest storage capacity of 3.6 wt% [197]. High hydrogen content of MgH2 is 7.6 wt.% and 110 kgm−3 , respectively.
entropy equiatomic intermetallic alloy TiZrVCrNi has shown a stable This is at par with the required US-DOE target for onboard storage of
reversible hydrogen storage capacity of 1.52 wt% [198]. A hydrogen hydrogen for vehicular applications [200]. Due to this high gravimet-
storage capacity of 3.5 and 6 wt% H2 was noticed in nearly equimolar ric and volumetric hydrogen density, MgH2 is considered as a potential
alloys TiVCrMo and TiZrNbH with Mg addition [199]. candidate for solid state hydrogen storage. However, the high thermo-
The disordered and amorphous materials have certain more specific dynamic stability of MgH2 (enthalpy and entropy values are 74.7 kJ
advantages in context to hydrogenation characteristics. A disordered mol−1 and 130 JK−1 mol−1 ) hinders its hydrogen release/absorption (de-
material lacks long-range order in both composition and structure. Such /hydrogenation) kinetics at low temperatures [201]. This is due to the
disordered and multiphasic materials lie in between crystal and amor- fact that the bonding of hydrogen in MgH2 is partially ionic and par-
phous materials. Due to the increasing degree of disorder in the metal tially covalent in nature [202]. Moreover, the factors affecting the de-
hydride following trends in hydrogenation characteristics may be ob- /hydrogenation behavior of MgH2 are (i) surface oxide layer formation,
served: (ii) slow hydrogen diffusion rate in the bulk Mg, (iii) poor hydrogen
chemisorption on Mg, and (iv) low thermal conductivity [203]. Till date,
• The hydrogen storage capacity may increase. researchers have adopted several strategies to improve MgH2 ’s hydro-
• The plateau region in the pressure–concentration isotherm becomes gen storage properties and achieved significant improvement. Methods
short and slanted. such as (i) nanostructuring; reduction of grain size providing shorter dif-
• Lattice expansion upon hydrogenation becomes less and results in fusion path for hydrogen [204,205] (ii) mechanical alloying; destabilize
less pulverization during hydride/dehydride cycling. the hydride phase by alloy formation [206] (iii) nanoconfinement; pre-
• In disordered material more surface-active sites are available to fa- venting the grain growth by confining in porous scaffolds [207] (iv) ad-
cilitate chemical/electrochemical reactions. ditives; forming pathways that facilitate hydrogen diffusion through the
diffusion barriers [208] have been employed for improving the MgH2 ’s
hydrogen storage behavior. So far, several techniques have been devel-
6.6. Metal hydrides - summary
oped for the synthesis of MgH2 , such as mechanical milling, thin film de-
position, melt spinning, electrochemical deposition etc. [209]. Herein,
Thus, metal hydrides offer varieties of materials for hydrogen storage
we describe some of the recent progress made on MgH2 for improving
and their applications accordingly. All the classes of metal hydrides may
its hydrogen storage behavior.
be summarized as given in Table 1. Different classes of metal hydrides
have different hydrogenation characteristics. Some have high storage
capacity, while others may have easy activation at ambient conditions. 7.1. Nanostructuring
A comparison of important hydrogenation properties among metal hy-
drides is presented in Table 2. Hence, based on the requirement of spe- The properties of materials in the nano dimension may differ sig-
cific properties, metal hydrides may be chosen for applications. The nificantly when compared to their bulk form. Nanoparticles (NPs) ex-
metal hydride-based research development has been completed for al- hibits (i) increased in surface to volume ratio, resulting in increased
most 60 years (1962–1922). These 60 years may be divided into three exposure of surface atoms (ii) reduced diffusion path (iv) closer prox-
phases of progress (Fig. 2). The first or early phase within the time imity between different reacting solids, (iv) increased in the number of
range 1962–1995 includes the discovery and studies on fundamental grain boundary atoms [210]. Due to the larger volume contribution of
hydrogenation properties like pressure-composition isotherm, hydrogen phase boundaries, nanocrystalline solids exhibit a higher level of dis-
absorption-desorption kinetics, hydrogen storage capacity, the heat of order [211]. Hence, nanosizing of MgH2 leads to reduced grains with
formation, the structure of parent member and their ternary counter- high active interface/surface and short hydrogen diffusion path, which
parts. In the middle phase (1996–2010) investigations were focused on can accelerate the de-/hydrogenation kinetics of MgH2 /Mg. Nanosiz-
the adoption of different synthesis routes mainly ball-milling, reactive ing of MgH2 not only increases the hydrogen diffusion rate but also
ball-milling, melt-spinning etc. with emphasis on varieties of substitu- increases the surface exposure of MgH2 NPs [212]. Nanosizing affects
14
the stability of Mg-H bond resulting in an improvement in the thermo-

dynamic behavior of MgH2 . Theoretical studies predict that MgH2 NPs
may have reduced reaction enthalpy with improved kinetics when the
size of the particle is below 50 nm. However, significant improvement
in the thermodynamics of MgH2 NPs was observed for < 5 nm size par-
ticles [176,213,]. In general, the methods employed for nanoscaling of
MgH2 are mechanical milling, hydrogenolysis, melt infiltration, physi-
cal and chemical vapor deposition, chemical reduction, electrochemical
deposition and thermolysis of Grignard reagents [214,215]. Mechanical
milling [216] is one of the most widely used methods for the particle size
reduction and distribution of catalysts for MgH2 . Mechanical milling in-
troduces a number of changes in the pulverized material, such as particle
size reduction up to the order of few nanometers, an increase in specific
surface area, a decrease in the crystallite size in the order of nanome-
ters, increase in the crystal lattice defects and grain boundary volume
fraction, and the formation of oxide-free surfaces that aid in hydrogen
chemisorption [217].
Zaluska et al. [218,219] first reported the improved hydrogen stor- Fig. 6. Schematic of Mg NPs encapsulated by a polymer matrix, which is selec-
age behavior of ball milled MgH2 . It was observed that the hydrogen tively gas permeable [226].
sorption has dramatically improved due to the combined effect of sur-
face modification and nanocrystalline structure of MgH2 . Depending on
the ball milling condition, the onset temperature (TON ) for hydrogen (C4 H9 )2 Mg → MgH2 + 2C4 H8
desorption has been lowered by 100 °C. Varin et al. [220] have demon-
strated the synthesis of nanostructured MgH2 from elemental magne- With the effect of ball milling, the hydrogenolysis temperature was
sium powder in a hydrogen environment using controlled reactive me- significantly reduced to 100 °C. The nano-size effect significantly al-
chanical milling (CRMM). The nanocrystalline MgH2 with an average ters the thermodynamic properties of MgH2 with enthalpy value of
particle size of 338 nm shows a significant change in enthalpy from 69.78 kJmol−1 H2 and the TON for dehydrogenation was observed at
74 kJmol−1 H2 (for commercial polycrystalline MgH2 having an average 225 °C.
particle size of 35.9 μm) to 57 kJmol−1 . H2 (for nanocrystalline MgH2 ). Rambhujan et al. [215] have found that the MgH2 NPs obtained by
Hence, the TON for hydrogen desorption has decreased from 409.4 °C the thermolysis of di‑tert-butylmagnesium exhibits two-staged hydro-
(for commercial MgH2 ) to ∼325 °C (for nanocrystalline MgH2 ). TON for gen desorption attributed due to the presence of two MgH2 phases; the
hydrogen desorption was found to be decreased with decrease in the thermodynamically stable 𝛽-MgH2 and the metastable 𝛾-MgH2 phase,
particle size of MgH2 . It has been observed that the nanostructuring of leading to a lower hydrogen desorption temperature with improved hy-
MgH2 , leads to the formation of metastable 𝛾-MgH2 phase. The pres- drogen sorption kinetics.
ence of 𝛾-MgH2 improves the hydrogen kinetics and significantly modi- Even though several approaches have been proposed for the syn-
fies the thermodynamic parameters of MgH2 . Shen C. et al. [221] have thesis of Mg NPs, the high reactivity of Mg NPs in air leads the syn-
observed that the presence of 𝛾-MgH2 leads to a significant reduction thesis process to be a challenging task. Jeon et al.[226] synthesized
in hydrogen reaction enthalpy with Mg from 74. 8 to 57.7 kJmol−1 H2 an air-stable composite of Mg nanocrystals encapsulated in a polymer
with improved hydrogen sorption kinetics. Recently, Lototskyy et al. PMMA [poly(methyl methacrylate)] matrix, which permit only hydro-
[222] synthesized MgH2 NPs using high-energy reactive ball milling gen and not O2 or H2 O, thereby reactivity of Mg nanocrystals with
(HRBM) of Mg in the hydrogen atmosphere. The MgH2 NPs synthesized air is prevented (Fig. 6). The Mg nanocrystals were synthesized by
by HRBM shows improved hydrogen reaction kinetics and the TON for using organometallic Mg precursor bis(cyclopentadienyl) magnesium
dehydrogenation was lowered to 302 °C. However, with additives the (Cp2 Mg) and lithium naphthalide as a reducing agent. The PMMA en-
TON for dehydrogenation of MgH2 NPs synthesized using HRBM was capsulation not only protects the reactivity of Mg nanocrystals with air
reduced significantly to 200 °C. More recently, Baran et al.[223] em- but also effectively increases the hydrogen storage behavior without the
ployed high temperature, high pressure reactive ball milling (HTPRBM) use of any heavy metal catalysts.
for the synthesis of MgH2 NPs. A special milling jar with the capability of The MgH2 NPs undergo structural changes during hydrogen re-
temperature control and pressure sensor was used for HTPRBM. Huang lease and uptake cycles. The grain/particle size of MgH2 is reported
et al. [224]described the synthesis of MgH2 NPs on 40% graphene sheets to increase during hydrogen release and uptake cycles, resulting in an
by a one-step solvent-free hydrogenolysis method. The growth of MgH2 agglomeration of particles leading to macroscopic phase segregation
NPs on graphene sheets is achieved by the hydrogenolysis of (C4 H9 )2 Mg [227,228]. The macroscopic phase formation affects the hydrogen sorp-
through the following reaction tion kinetics. To prevent the macroscopic phase segregation, MgH2 NPs
can be scaffolded in porous materials.
(C4 H9 )2 Mg + 2H2 → MgH2 + 2C4 H10
7.2. Nanoconfinement
Here, the size of MgH2 NPs can be controlled by adjusting the
MgH2 to graphene sheets mass ratio. The TON for dehydrogenation of Nanoconfinement is the method of scaffolding nano dimensional par-
MgH2 NPs dispersed uniformly on graphene sheets is lowered to 270 °C. ticles inside the permanent nano dimensional pores of the host scaf-
Whereas, MgH2 NPs synthesized by the same method without graphene folds. Nanoconfinement includes two aspects: nanosizing and confine-
addition exhibits TON for dehydrogenation at 300 °C. ment [229]. Recently, nanoconfinement or nano-scaffolding of hydrides
Since the addition of 40% graphene acts as deadweight to the system, has emerged as an interesting field of research for altering reaction path-
the hydrogen storage capacity is reported to be ∼4.5 wt.%, which is sig- ways and tuning the thermodynamic and kinetic parameters of metal
nificantly less than that of pure MgH2 . Recently, Huang et al. [225] syn- hydrides at the nanoscale [230]. This method of scaffolding hydride
thesized MgH2 NPs with an average particle size of 8.9 nm by combin- NPs inside the porous networks can effectively enhance the gas-solid
ing ball milling and thermal hydrogenolysis of di-n-butylmagnesium, interface, shorten the hydrogen diffusion distance, and restricts particle
(C4 H9 )2 Mg through the following reaction. sintering and macroscopic phase segregations, thus overcoming both the
15
10 nm. The mesoporous CoS nono-boxes was first synthesized from ZIF-
67 MOF then the MgH2 NPs in CoS nano-boxes was derived by vacuum
assisted impregnation of dibutyl magnesium solution followed by hy-
drogenation at 180 °C under 48 atm. hydrogen pressure. The hydro-
genation and dehydrogenation enthalpies of Mg/MgH2 in CoS nano-
boxes derived through solvent impregnated method is estimated to be
−65.6 ± 1.1 kJmol−1 H2 and 68.1 ± 1.4 kJmol−1 H2 , respectively. The
enthalpy values are similar to that observed for the nanoconfined 5 to
20 nm MgH2 NPs in CA [198]. Apart from lowering the thermodynamic
parameters of MgH2 , the CoS nano-boxes scaffold plays an important
role on providing active catalyst for enhancing the hydrogen sorption
kinetics of Mg/MgH2 . Ren et al. [239] synthesized nanoconfined MgH2
in the slit pores of 2D graphene like TiO2 nanosheets. The MgH2 /TiO2
nanosheets heterostructure was synthesized by hydrogenation of Mg
NPs derived by impregnating dibutyl magnesium solution in the slit
pores of TiO2 nanosheets. The confined MgH2 in TiO2 nanosheets has
TON for dehydrogenation at 180 °C. Additionally, the confined MgH2
Fig. 7. Schematic representation of MgH2 NPs confined inside the pores of scaf-
exhibits superior hydrogen sorption kinetics and good cyclic stability
folding material. The scaffold restricts the movement of Mg/MgH2 during de-
/hydrogenation cycles and prevents the segregation of macroscopic phases.
with negligible degradation even after 100 cycles of de-/hydrogenation.
Zhu et al. [240] investigated MgH2 NPs confined in 3D architecture
of Ti3 C2 Tx MXene nanosheets. The synergistic nanosize effect and cat-
kinetic and thermodynamic barriers associated with MgH2 NPs during alytic effect by MXene leads to a significant reduction in the MgH2
de-/hydrogenation cycling. Here, the dimension of pores determines the TON for dehydrogenation to 140 °C with good cyclic stability without
dimension of particles confined in it. Experimental conditions such as loss in kinetics. Ren et al. [241] demonstrated the confinement effect
the application of external temperature and pressures may cause struc- of MgH2 /Ni NPs in MOF derived from N-doped hierarchically porous
tural deformation of scaffolding materials, affecting the pore structures. carbon nanofiber. The TON for desorption of MgH2 /Ni NPs in MOF is
For nanoconfinement of hydrogen storage materials, porous materials lowered to 200 °C and hydrogen absorption occurs at 100 °C. Thus the
which has high specific surface area, uniform distribution of pore sizes, ‘nanosize effect’ of the confined Mg/MgH2 plays a vital role for improv-
chemical inertness and possess structural stability during the multiple ing the reaction kinetics and modifying the thermodynamic parameters
de-/hydrogenation cycles are considered (Fig. 7). Moreover, the scaf- of MgH2 , which is favorable for hydrogen storage.
folds function as a deadweight to the hydrogen storage system and
hence lightweight materials are preferred. The most commonly used 7.3. Catalyzing
scaffolds are carbon aerogels [231], activated porous carbons [232],
metal-organic frameworks [233], porous polymer etc. [208] Catalyst doping is one of the most effective ways to enhance the hy-
Several methods have been adopted to infiltrate the MgH2 NPs inside drogen storage characteristics of MgH2 . Catalyst provides an alternative
the pores of the scaffolding materials such as (i) melt impregnation (ii) reaction path with lower reaction energy barrier. Research efforts on
solvent impregnation (iii) solution impregnation (iii) reactive gas evap- catalyst-assisted de-/hydrogenation behavior of MgH2 have made sig-
oration (iv) sol-gel auto combustion and solution mixture [234] etc. nificant progress on improving the thermodynamics, kinetics, and re-
In the melt impregnation method, the molten state of MgH2 is in- versibility of MgH2 . Till date several catalysts such as transition met-
filtrated into the pores of scaffolds by capillary condensation. With als [242,243], metal oxides [244–246], metal halides [247–250] metal
the benefit of physicochemical adaptability, carbon-based materials are carbide [251], metal sulfide [252,253] metal and oxide nanoparticles
often used as scaffolds. Generally, Carbon based porous scaffolds are [208,254–263] quantum dots [261], additives supported by carbon
considered for melt impregnation due to the wide range of porosity structures [230,264–272]s et al. have been investigated by researchers.
and chemical inertness during de-/hydrogenation cycles [235]. Gross Among the various catalyst additives, Nb2 O5 is one of the most effec-
et al.[236] employed melt infiltration method to confine MgH2 NPs in- tive and widely investigated catalyst precursors for MgH2 . With Nb2 O5
side the micro and mesopores of carbon aerogels. The infiltration of additive, the dehydrogenation temperature of MgH2 was significantly
molten Mg inside the pores of carbon aerogels (CA) followed by hy- reduced to a peak temperature at 230 °C and the hydrogen absorption
drogenation leads to the formation of confined MgH2 NPs in CA scaf- in Mg catalyzed by Nb2 O5 takes place even at 40 °C. This is attributed to
folds. The CA scaffolds have an average pore size of ∼13 nm and since the reduction of Nb2 O5 during hydrogenation of dehydrogenated MgH2
the confined MgH2 particles are in the range of 13 nm, no significant which leads to the formation of a catalytically active state. As Nb2 O5 re-
change in enthalpy of MgH2 is observed. However, significant improve- duces further its catalytic activity in MgH2 increases. Therefore, during
ment in the dehydrogenation kinetics of the confined MgH2 is observed. de-/hydrogenation cycles more reduction of Nb2 O5 occurs, resulting in
Furthermore, nanoconfinement of MgH2 in CA improves the efficacy of further reduction in hydrogen absorption temperature. It has been found
catalyst additive. Liu et al.[237] employed a solvent infiltration method that the chemical state of Nb and the initial structural stability of Nb2 O5
for the confinement of MgH2 NPs inside CA scaffold. The Mg NPs in is vital for realizing superior catalytic activity in MgH2 [270]. Shinzato
the size range of 5 to 20 nm confined in CA were derived by hydro- et al. [271] observed that the meta stable phase of Nb2 O5 exhibiting
genation of infiltrated dibutyl-magnesium. The ‘nanosize effect’ of Mg pillar crystallite morphology and pyrochlore structure show superior
leads to a significant reduction in the thermodynamic stability of MgH2 catalytic effect in improving the de-/hydrogenation kinetics of MgH2 .
with improved kinetic behavior. The hydrogen absorption/desorption Zhang et al. [272] found that the hydrogen desorption/absorption ki-
enthalpies of Mg/MgH2 in CA is estimated to be −65.1 ± 1.56 kJmol−1 netics of MgH2 /Mg are greatly improved by the superior catalytic effect
H2 and 68.8 ± 1.03 kJmol−1 H2 , respectively. of NbN NPs (∼20 nm size). The NbN catalyzed MgH2 released nearly
Recently, nanoconfinement of MgH2 with catalyst additives are be- 6.0 wt.% hydrogen in 12 min at 275 °C and the sample absorbs 6.0 wt.%
coming an interesting area of research for improving the kinetics and hydrogen within 24 min at 100 °C. The Nb3+ -N and Nb5+ -N valence
tuning the thermodynamics of MgH2 . Ma et al. [238] have described state of Nb4 N3 may be the key factor for increasing MgH2 ’s hydrogen
the nanoconfinement effect of MgH2 NPs in mesoporous CoS nano- storage capabilities. The catalytic effect of in-situ NbN and Nb2 O5 from
boxes scaffold. The confined MgH2 NPs were in the size range of 5 to N-doped Nb2 C supported Nb2 O5 (N–Nb2 O5 @Nb2 C) on MgH2 was in-
16
rier of H diffusion channels, promoting the hydrogen desorption and

absorption kinetics of MgH2 /Mg. Gao et al. [282] have employed self-
assembled TiO2 NPs (15 - 20 nm in size) intercalated between layers
of Ti3 C2 Tx MXene as a catalyst for improving MgH2 ’s hydrogen stor-
age characteristics. The interfaces not only serve as lower energy bar-
rier for hydrogen diffusion channels but also serve as a conduction path
for the electrons released from the multiple valence transition state of
Ti. In another study, Geo et al.[277] have described the facet depen-
dent catalytic effect of Ti3 C2 Tx MXene. The active edge facets have a
stronger affinity towards hydrogen than basal facets of Ti3 C2 Tx MX-
ene, resulting in the formation of more catalytically active metallic Ti
from edge facets of Ti3 C2 Tx . The TON for dehydrogenation of 5 wt.%
edge facet exposed Ti3 C2 Tx MXene catalyzed MgH2 was observed at
199 °C, which is 101 °C lower than that of ball milled MgH2 without
any additives. Haung et al. [283] described the catalytic effect of carbon-
wrapped Ni and Co NPs (8 - 16 nm) as catalysts in the MgH2 . Among
the two catalysts, carbon-wrapped Ni (Ni/C) exhibits superior effect in
improving the de-/hydrogenation kinetics of MgH2 . The 6 wt.% Ni/C
catalysed MgH2 sample has peak desorption temperature at 275.7 °C,
which is 142.7 and 54.2 °C lower than that of pristine MgH2 and ball
milled MgH2 . Furthermore, the Ni/C catalysed dehydrogenated MgH2
sample reabsorbs 5.0 wt.% H2 within 20 s at 100 °C. It has been observed
that higher concentration of Ni/C in MgH2 further improves MgH2 ’s de-
Fig. 8. Schematic representation of hydrogen spillover process during the hy-
drogen absorption process of Mg.
/hydrogenation behavior. Ma et al. [284] showed the superior catalytic
effect of carbon supported Ni NPs (Ni@C) towards improving the de-
/hydrogenation properties of MgH2 . The TON for hydrogen desorption
vestigated by Lan et al. [273] They observed that the catalyzed MgH2 of 5 wt.% Ni@C catalyzed MgH2 has been reduced to 187 °C, which is
sample exhibit TON for hydrogen desorption at 178 °C and the hydrogen 113 °C lower than that of ball milled MgH2 without any additives.
absorption temperature has been reduced to 90 °C. The catalyst additive Chen et al. [285] described the catalytic effect of carbon-
also helps to maintain a good de/redydrogenation cyclic stability. encapsulated ZrO2 (C/ZrO2 ) NPs (5 – 10 nm) in MgH2 . It has been
Recently, catalytically active hydrogen spillover receptors have observed that with carbon encapsulation ZrO2 exhibits superior cat-
gained significant research interest for enhancing the hydrogen sorp- alytic effect for improving the hydrogen release kinetics of MgH2. The
tion kinetics of MgH2 (Fig. 8). Here, during hydrogen spillover process, TON for hydrogen desorption of C/ZrO2 catalyzed MgH2 is observed at
the molecular hydrogen will get initially adsorbed on the surface of the 208 °C, which is 40 and 101 °C lower than that of ZrO2 and additive-
spillover receptor and get dissociated into atoms and the atomic hydro- free MgH2 . Wang et al. [286] reported the superior catalytic effect
gen can easily diffuse into Mg, which is generally poor for hydrogen of uniformly dispersed Ni NPs on porous hollow carbon nanospheres
chemisorption [274]. (Ni@PHCNSs) towards the de-/hydrogenation of MgH2 . The TON for
Hou et al. [275] have employed Ni/C as a catalyst for improving dehydrogenation of 5 wt.% Ni@PHCNSs catalyzed MgH2 was lowered
the hydrogen storage properties of MgH2 . They observed that the ad- to 190 °C. Moreover, the dehydrogenated sample absorbed hydrogen
dition of 9 wt.% Ni/C with MgH2 leads to a significant reduction in at 150 °C with improved kinetics. Wang et al. [256] demonstrated
the hydrogen release temperature to 195 °C and with improved hydro- the catalytic effect of vanadium oxide NPs on cubic carbon nanoboxes
gen sorption kinetics and good cyclic stability. The in-situ formation (nano-V2 O3 @C) towards the de-/hydrogenation of MgH2 . The 9 wt.%
of Mg2 Ni/Mg2 NiH4 serves as a ‘hydrogen pump’ in MgH2 for enhanc- nano-V2 O3 @C catalyzed MgH2 exhibits TON for hydrogen desorption
ing the hydrogen diffusion during de-/hydrogenation cycles. Shao et al. at 215 °C, which is 60 °C lower than that of MgH2 without any addi-
[276] explored the catalytic activity of TiO2 NPs (5 – 10 nm) supported tives. The dehydrogenated sample reabsorbed hydrogen even at room
on 3D ordered macropores (3DOM) as a catalyst for enhancing the hy- temperature under 50 atm hydrogen. Lan et al. [287] studied the cat-
drogen storage behavior of MgH2 . It has been observed that 5 wt.% alytic effect of nanoporous carbon encapsulated Ni and V2 O3 NPs ((Ni-
3DOM-TiO2 as an additive improves the de-/hydrogenation behavior of V2 O3 )@C) for enhancing the de-/hydrogenation kinetics of MgH2 . The
MgH2 . The in-situ formed multiple valence state Ti helps to destabilize 10 wt.% (Ni-V2 O3 )@C catalysed Mg/MgH2 sample absorbs hydrogen
MgH2 and the dehydrogenated sample shows hydrogen uptake at 100 °C even at room temperature. Zhao et al. [288] have employed core-shell
with reasonably good kinetics. Recently, catalyst nanoparticles derived CoNi@C as a catalyst for improving the hydrogen sorption properties
metal organic framework (MOF) and 2D Metal Carbides and Nitrides of MgH2 . The 8 wt.% core-shell CoNi@C catalyzed MgH2 exhibits TON
(MXenes) have gained enthusiastic research interest due to its unique for dehydrogenation at 173 °C and the dehydrogenated sample absorbs
structure, rich element composition and functional surface. [277] Gao 6 wt.% of hydrogen at 150 °C within 200 s. Ren et al. [289] stud-
et al. [278] reported the catalytic activity of Ni derived from MOF. ied the catalytic activity of core-shell structure of Ni/Fe3 O4 in porous
Yang et al. [279] used Ni@C derived from trimesic acid-Ni based metal carboxylate salts, MIL (Ni/Fe3 O4 @MIL) as a catalyst for im-
metal organic framework (TMA-Ni MOF) as a catalyst for enhancing proving the hydrogen storage properties of MgH2 . The TON for dehy-
the hydrogen storage characteristics of MgH2 . The formation of the drogenation of MgH2 with Ni/Fe3 O4 @MIL additive was observed at
Mg2 NiH4 phase serves as a ‘hydrogen pump’ for improving the ther- 244 °C. The formation of Mg2 Ni/Mg2 NiH4 in Ni catalyzed MgH2 serve
modynamic and kinetic parameters of MgH2 . Lakhnik et al. [280] syn- as a ‘hydrogen pump’ to improve MgH2 ’s hydrogen storage behavior
thesized MgH2 /Ti3 AlC2 MAX-phase composite by reactive ball milling [244,281,284,290,292,293].
followed by hydrogenation of Mg. The dehydrogenation tempera-
ture of MgH2 /7 wt.% Ti3 AlC2 MAX-phase composite is observed at 7.4. Alloying
236 °C. Zhang et al. [281] have investigated the MOF-derived bimetallic
Co@NiO as catalyst for enhancing MgH2 ’s hydrogen storage behavior. Another strategy to destabilize MgH2 and modify the reaction path-
The formation of Mg2 NiH4 /Mg2 CoH5 interfaces lowers the energy bar- way and thermodynamics is through the addition of reactive additives.
17
The reactive additive reversibly reacts with Mg and forms a new phase, example, magnesium-iron based complex hydrides and related systems
whose reaction enthalpy with hydrogen will be lower than that of the (for example, Mg catalyzed with neodymium oxides) showed of at least
formation reaction of MgH2 . Thus, the alloying additive destabilizes the 5–6 wt% reversible hydrogen storage capacities at temperatures close to
Mg-H bond and reduces the enthalpy of MgH2 through formation of new 200 °C and exhibited longer life cycles and are deployed in hydrogen en-
phase, thereby decreasing the dehydrogenation temperature of MgH2 . ergy applications, in heat pumps, and automotive [298]. Though the so
Zhong et al. [291] have described the use of Al as a reactive ad- called, the birth of complex hydrides evolved with the emergence of Mg-
ditive to destabilize MgH2 . Supersaturated Mg(Al) solid solution alloy based complex hydrides, that are known to the scientific community,
was prepared by ball milling and it was found that during hydrogenation the real breakthrough research in developing lightweight, high-capacity
and dehydrogenation, Mg(Al) solid solution and Mg17 Al12 intermetallic complex hydrides based on alkali, alkaline, metalloids and other non-
compound were formed reversibly. This transition of Mg(Al) solid solu- metals combinations [299]. In 1990s, Bogdanovic and coworkers discov-
tion and Mg17 Al12 leads to the thermodynamic destabilization of MgH2 . ered lightweight sodium aluminum tera- and hexa- hydrides with few
Thus, the dehydrogenation enthalpy of 5 and 10 at.% Al in Mg(Al) solid moles of catalytic transition metals/compounds doping [300,301,303]
solution was estimated to be 72.1 and 70.8 kJ mol−1 . The addition that triggers the hydrogen storage community for researching and ex-
of Al forms numerous hetero interfaces with high interfacial energy, ploring new sodium aluminum hydrides [301], lithium aluminum hy-
which could improve hydrogen diffusion and speed up the formation drides [302], and magnesium based complex hydrides [297] and related
of Mg/MgH2 , thereby lowering the hydrogenation/dehydrogenation en- systems that are not only push the boundaries of both thermodynamics
thalpy. Furthermore, the addition of Al increases the thermal conduc- and kinetics but also addressed the requirement of lightweight materials
tivity of Mg/MgH2 and improves the hydrogen sorption kinetics. Cer- for PEM fuel cells driven vehicles.
mak et al. [292] studied the hydrogen storage properties of Mg-In- In a very recent comprehensive review published from the interna-
amorphous carbon (Mg-In-CA) alloy synthesized by ball milling and ob- tional group of hydrogen experts of the Task 40, of the Hydrogen En-
served that the dehydrogenation enthalpy of MgH2 was decreased down ergy Technologies Program of the IEA, the advantages of the complex
to 51.5 kJmol−1 attributed to the formation of MgIn phase. The enthalpy hydrides and tunable systems are detailed with respect to their mate-
value was found to decrease with increase in concentration owing to rials’ design, synthesis, characterization and scale-up for hydrogen en-
the phase changes from Mg2 In to Mg3 In. Ershova et al. [293] observed abled applications [303]. In general, the complex hydrides, are catego-
that TON for desorption of hydrogenated Mg-Al-Fe alloy was observed rized according to their bonding characteristics. such as (i) alanes and
at 250 °C, which is 65 °C lower than that of Mg without any additives. alanates [304], (ii) borohydrides [305] and borates [306], (iii) amides
More recently, Lu et al. [294] have investigated the hydrogen storage and imides [307,308], (iv) ammines, and (v) reactive hydride complexes
behavior of carbon covered nanocrystalline Mg2 Ni. The hydrogenation (RHCs) and (vi) other novel complex hydride systems. The reactive hy-
of sample was achieved at room temperature and the TON for hydrogen dride complexes are in general composed of multinary complex hydride
desorption was lowered to 180 °C. The hydrogenation and dehydrogena- systems with the presence of core-shell catalytic nanoparticles, one such
tion activation energy of carbon covered nanocrystalline Mg2 Ni were system is reported based on the synthesis process, and DFT calculations
estimated to be significantly lower than that of pristine MgH2 . The hy- where the Ti (core) and Mg(shell) with hydrogen bonding are shown in
drogen desorption enthalpy of carbon covered nanocrystalline Mg2 NiH4 Fig. 9 [309]. The pristine and modified RHCs are currently under inves-
was determined to be 67.0 ± 0.5 kJ mol−1 . Thus, the combined effect tigation by the author of this review article. These RHCs are proposed
of nanocrystalline strategy, carbon encapsulation/support and alloying to enhance the hydrogen storage characteristics based on the nanocat-
help to improve the MgH2 ’s hydrogen storage properties. Thus, alloy- alytic effects of TiH2 /MgH2 core-shell effects in the candidate complex
ing of Mg with reactive additives helps to lower the hydrogen reaction multinary hydrides. The chemical reactions below demonstrate the pris-
enthalpy and enhances the hydrogen sorption kinetics of MgH2 . tine and modified RHCs and with enhancement of hydrogen uptake and
release from 6 to 9 mol of hydrogen (Table 3). Table 4 represents dif-
8. Complex hydrides and related systems ferent types of complex hydrides and their hydrogen storage capacities
at specific operating temperatures.
In Section 6 of the present paper discussion started with the metal
hydrides of AB5 , AB, A2 B, AB2 types for hydrogen storage. Ideally, the 9. Carbonaceous and related systems
metal hydrides shows either interstitial or substitutional hydrogen in-
tercalation where that enhances at least 25% volumetric expansion that This section discusses the uniqueness of carbon as an element and
leads to reversible hydrogen sorption behavior. Therefore, the volumet- then specific applications in the field of hydrogen storage.
ric hydrogen storage capacity in metal hydrides is much greater when
compared the gravimetric densities. The drawback with such metal hy- 9.1. Carbon: the extraordinary canvas
drides is in addition to the low gravimetric hydrogen storage capacities,
they are prepared by the combination of two, three or multi elements Carbon is one of the special and unique elements in the Periodic Ta-
from the periodic table, that are heavy, for examples, elements from lan- ble. It has atomic number 6 with electronic configuration of 1s2 2s2 2p2
thanide group (La, Ce, Mm, etc.) and from transition metals (Ni, Co, Fe, which gives it enormous options of formation of covalent bonds with
Ti, V etc.) [295]. For transportation and other automotive applications, itself or other elements of the Periodic Table. It forms bonds through hy-
the candidate materials supposed to have light weight with high gravi- bridization that can involve sp3 , sp2 and/or sp1 combinations. Its chem-
metric energy storage. Hence, in search of light weight metal hydrides, ically inert nature, good physical strength, mechanical flexibility, light
the Section 5 of this article demonstrated the magnesium hydrides and weightiness, and different allotropes gives researchers a canvas that can
related systems which are not only possess the highest hydrogen storage be engineered in various ways. For instance, it can be transformed into
capacity of 7.6 wt% but also, shows less weight penalty. However, these many forms namely, zero-dimensional fullerenes, one-dimensional car-
lightweight magnesium hydrides and systems offer the high reversibil- bon nanotubes, two-dimensional graphene, three-dimensional graphite,
ity at an expense of high temperatures, ∼325 °C and pressures close to hybrid structures thereof, activated carbon, etc., can be chemically mod-
sever tenths of atmosphere of hydrogen [296]. ified by attaching functional groups, decorated by nanoparticles of met-
The alloying, complex formation, catalytic doping, and nanoparticle als/metal oxides or non-metal nanoparticles, and doped by elements
formation of these magnesium greatly demonstrated the sorption behav- like N, B, etc. [338–341] Thus, a vast number of possibilities exist for
ior at affordable temperatures and pressures, but these modified ver- researchers to explore ‘carbon’ as a material. Further, the high surface
sions of hydrides still involved the usage of heavy metals such as transi- to volume ratio of the carbon nanomaterials gives them the edge of pos-
tion metals [297] and in some cases lanthanide group metals [298]. For sessing very high specific surface areas. The porosity along with high
18
Fig. 9. (a) Synthesis process and (b) DFT calculations of the structure of modified RHCs. Reprinted with permission from Tao, S. X., Notten, P. H. L., van Santen,
R. A., Jansen, A. P. J., First-principles predictions of potential hydrogen storage materials: Nanosized Ti(core)/Mg(shell) hydrides, Physical Review B 83 (2011)
195,403. 10.1103/PhysRevB.83.195403.by the American Physical Society. [309].
Table 3
Dehydrogenation and rehydrogenation reactions of RHCs.
Pristine reactive hydride complex - 2[n(LiBH4 ) + 3n(LiNH2 )] + 3n(MgH2 ) . . . . (1)

Modified reactive hydride complex - 2[n(LiBH4 ) + 3n(LiNH2 )] + 3n[(MgH2 ) + (nTiH2 )] .(2)
“n” signifies nano-form of host hydride.
Table 4
Types of complex hydrides, their hydrogen storage capacities, and operating temperatures.
Amides, imides and multinary complex hydrides Capacity Temperature [C] References
(wt.%)
LiNH2 + 2LiH = Li2 NH + LiH + H2 = Li3 N + 2H2 LiNH2 + 2LiH 10.5 300 T. Ichikawa et al. [310]
CaNH+CaH2 =Ca2 NH+H2 CaNH+CaH2 2.1 500 Roshan et al. [311]
Mg(NH2 )2 + 2LiH = Li2 Mg(NH)2 + 2H2 Mg(NH2 )2 + 2LiH 5.6 175 Chen et al.[312, 313]
3Mg(NH2 )2 + 8LiH = 4Li2 NH + Mg3 N2 + 8H2 3Mg(NH2 )2 + 8LiH 6.9 225 Aoki et al. [314]
Mg(NH2 )2 + 4LiH = Li3 N + LiMgN + 4H2 Mg(NH2 )2 + 4LiH 9.1 225 Leng et al. [315]
2LiNH2 + LiBH4 = “Li3 BN2 H8 ” = Li3 BN2 + 4H2 2LiNH2 + LiBH4 11.9 250 Pinkerton et al. [316]
Mg(NH2 )2 + 2MgH2 = Mg3 N2 + 4H2 Mg(NH2 )2 + 2MgH2 7.4 20 Hu et al. [317]
2LiNH2 + LiAlH4 = LiNH2 + 2LiH + AlN + 2H2 = Li3 Al +N2 + 4H2 2LiNH2 + LiAlH4 5 500 Xiong et al. [318]
3Mg(NH2 )2 + 3LiAlH4 = Mg3N2 + Li3 AlN2 + 2AlN+12H2 3Mg(NH2 )2 + 3LiAlH4 8.5 350 Xiong et al. [319]
Mg(NH2 )2 + CaH2 = MgCa(NH)2 + 2H2 Mg(NH2 )2 + CaH2 4.1 500 Yongfeng et al. [320]
NaNH2 + LiAlH4 = NaH + LiAl0.33 NH +0.67Al+ 2H2 NaNH2 + LiAlH4 5.2 200 Chua et al. [321]
2LiNH2 + CaH2 = Li2 Ca(NH)2 + 2H2 2LiNH2 + CaH2 4.5 215 Wu et al. [322]
4LiNH2 + 2Li3 AlH6 = Li3 AlN2 + Al +2Li2 NH + 3LiH + 15/2H2 4LiNH2 + 2Li3 AlH6 7.5 300 Kojima et al. [323]
2Li4BN3 H10 + 3MgH2 = 2Li3 BN2 + Mg3 N2 + 2 LiH + 12H2 2Li4 BN3 H10 + 3MgH2 9.2 250 Niemann et al. [324]
Borohydrides
2LiBH4 = 2LiH + 2B + 3H2 2LiBH4 + 2LiH 13.6 375 Zuttel et al. [325]
2LiBH4 + MgH2 =2LiH + MgB2 + 4H2 2LiBH4 + MgH2 11.5 355 Soulie et al. [326]
3Mg(BH4 )2– NH3 = Mg3 B2 N4 + 2BN +2B + 21H2 3Mg(BH4 )2 15.9 250 Nakamori et al. [327, 328],
Soloveichik et al. [329]
Ca(BH4 )2 = CaH2 + 2B + 3H2 Ca(BH4 )2 8.6 400 Kim et al. [330]
Zn(BH4 )2 = Zn + B2 H6 + H2 Zn(BH4 )2 2.1 115 Jeon el. al. [331], Srinivasan
et al. [332, 333]
Ammonia borane and Amido boranes
nNH3 BH3 = (NH2 BH2 )n + nH2 = (NHBH)n + 2nH2 NH3 BH3 12.9 135 Stephens et al. [334], Todd
et al. [335]
LiNH2 BH3 = LiNBH + 2H2 LiNH2 BH3 10.9 85 Xiong et al. [336]
NaNH2 BH3 = NaNBH + 2H2 NaNH2 BH3 7.5 85 Xiong et al.[336]
Ca(NH2 BH3 )2 = Ca(NBH)2 + 4H2 Ca(NH2 BH3 )2 8 167.5 Kim et al. [337]
19
Fig. 10. Different allotropes of carbon that differ in dimen-

sionality. Reprinted from D. Veeman, M.V. Shree, P. Sureshku-
mar, T. Jagadeesha, L. Natrayan, M. Ravichandran, P. Parama-
sivam, Sustainable Development of Carbon Nanocomposites:
Synthesis and Classification for Environmental Remediation,
Journal of Nanomaterials 2021 (2021) 5,840,645, Copyright
© 2021, content available under Creative Commons Attribu-
tion License [342].
specific surface areas lead to the presence of many adsorption sites. With
these desirable properties, carbon nanomaterials present themselves as
prospective materials in the field of solid-state hydrogen storage. Fig. 10
depicts the common allotropes of carbon that differ in their dimension-
ality [342].
9.2. The carbon connection
For solid state hydrogen storage, one requires a good volumetric or

gravimetric storage of hydrogen in near-ambient conditions, on-demand
desorption at ambient temperatures, quick and reversible storage, and
surety of a safe and economical means [300,343–346,347]. The storage
can be in the form of molecular or atomic hydrogen. The molecular or
atomic form of hydrogen storage depends upon the underlying mecha-
nism of storage. And it is here where the carbon nanomaterials make a
difference. Pure carbon nanomaterials are unsuitable for hydrogen stor-
age. However, functionalization of carbon support or decoration of car-
bon support with nanoparticles can significantly improve the hydrogen
storage properties. In case of carbon nanomaterials, the two mechanisms
have been reported in literature namely, (a) Kubas interaction and (b)
spillover mechanism. The spillover mechanism is a much-debated mech-
anism in literature where empirical evidence exists both in favor and
against it [277,348–352]. The two mechanisms are discussed in sections
Fig. 11. Some of the ways to functionalize carbon nanomaterials. This figure is
5.6 and 5.7 later. It has been discussed above that carbon can form bonds reproduced from M. Perovic, Q. Qin, M. Oschatz, From Molecular Precursors to
in multiple ways. Thus, when a hydrogen molecule approaches a pure or Nanoparticles—Tailoring the Adsorption Properties of Porous Carbon Materials
functionalized carbon network at close atomic distances, the hydrogen by Controlled Chemical Functionalization, 30 (2020) 1,908,371 available under
molecule’s bonding configuration gets affected resulting in physisorp- the Creative Commons CC-BY-NC license [350].
tion/chemisorption of molecular H2 or atomic H2 , respectively. In all
these approaches, the activation energy is reduced to facilitate either
formation of atomic hydrogen from molecular hydrogen or formation perature, the highest reported uptake capacities for activated carbon
of covalent bonds with the carbon support. Because this interaction is (5.5 wt.% H2 ), graphite (4.48 wt.% H2 ), carbon nanotubes (4.5 wt.% sin-
tunable by either using different carbon nanoforms, functionalization or gle tubes and 6.3 wt.% H2 multiwalled tubes), and nanofibers (6.5 wt.%
nanoparticle dispersion over the carbon support, supports the interac- H2 ) were reported. However, these are the best reported values and
tion energies, carbon-based hydrogen storage is a promising field. many research groups have reported lower hydrogen uptake capacities
than these values. Hence, a pure carbon network (combination of sp3 ,
9.3. Hydrogen uptake capacity of various carbon materials sp2 , sp1 ) cannot serve as a hydrogen storage material. The carbon ma-
terials can be functionalized using various schemes as shown in Fig. 11
A recent review of hydrogen storage by different carbon forms by [350]. Functionalized or doped carbon materials are promising materi-
Mohan et al. reports the highest values reported [349]. At room tem- als in this regard [346,347,351–358].
20
Nitrogen-doped activated carbon has been evaluated for H2 uptake cesses are well understood and can be carried out at large scale. How-
capacity. The activated carbon after treatment in the presence of am- ever, efficient, fast, and safe dehydrogenation needs to be achieved. In
monia gas was successfully doped with nitrogen and then subsequently this regard, some catalysts (Pt, Pd, Rh, etc.) have been used for im-
decorated by metal nanoparticles. The average size of the nanoparticles proving the kinetics of dehydrogenation. However, the goal is to use
used for decorating the nitrogen doped carbon network ranged from non-noble metal catalysts (Fig. 12).
35 nm for Ru to 64 nm Ni nanoparticles. The hydrogen uptake profiles Some theoretical studies too are pertinent for discussion. First prin-
were different at cryogenic temperatures as compared to room temper- ciples study on fullerenes have shown a theoretical capacity of 7.5 wt.%,
ature uptake profiles. While at cryogenic temperatures a sequential fill- which can be increased to 10.5 wt.% for Ti-doped fullerene in the
ing of pores (micro- followed by meso‑ and macro-pores) takes place, temperature range from 100 to 300 K. The study showed that 56 H2
and an overlap of Type I and Type IV Langmuir adsorption isotherm is molecules could be stored on the fullerene balls. The desorption of
seen suggesting a gradual transition from mono-to-multilayer adsorp- H2 molecules was shown to occur in the temperature range of 245–
tion. During the filling of micropores alone, the hydrogen molecules 256 K [361]. Multiwalled carbon nanotubes of varying diameters were
present at the surface cause an excess Gibbs energy which is seen to also investigated for hydrogen storage properties. A meager uptake of
increase the uptake capacity as pressure is increased. Whereas at room 0.01–0.6 wt.% of hydrogen could be successfully stored reaching 0.6–
temperature, the adsorption in all levels of pores was seen to occur. 0.87 wt.% [362]. Doping the carbon nanotubes improved the uptake
For nitrogen doped activated carbon, 57% increase was recorded for capacity marginally for Pd-MWNTs and the maximum reported value
nitrogen doped activated carbon at 100 MPa pressure and 298 K. For was 0.87 wt.% [363,364].
other systems, the maximum uptake capacity was observed to increase The next-generation graphene materials have been explored theo-
by 42% for Pt-decorated nitrogen-doped activated carbon. For Ni and retically [365,366]. Graphdiyne (GDY) is a two-dimensional carbon al-
Ru, the improvement in uptake capacity was relatively low at 10% and lotrope which has two stable di-acetylenic groups [367]. Theoretically,
8%, respectively [347]. Doping of nitrogen within the carbon network the GDY can store hydrogen storage via the van der Waals forces and
to form g-C3 N4 and then using Pd nanoparticles over g-C3 N4 support the interaction strength of about 60–70 meV per molecule. To enhance
resulted in a hydrogen uptake capacity of 1.8 wt.% and 2.5 wt.%, re- the interaction strength, GDY was doped with boron and later decorated
spectively at room temperature and 3 MPa hydrogen pressure. The up- with Ni to improve the hydrogen bonding. The theoretical study shows
take capacity could be improved to 2.6 wt.% and 3.8 wt.%, respectively that a significant enhancement of about 1.2 eV/H2 molecule is predicted
at lower temperatures of 0 °C [356]. In another study, Ni nanoparticles by exploring Ni-GDY in comparison to undoped or B-GDY. However, Ni-
dispersed over graphite network demonstrated 4.48 wt.% hydrogen up- GDY is unsuitable for room temperature adsorption/desorption of H2
take at 298 K and hydrogen pressure up to 10 MPa [357]. A dipole due to high binding energy. Boron doping proved beneficial as it fa-
induced hydrogen uptake mechanism was proposed for achieving this cilitates charge transfer from Ni to GDY resulting in better synergy be-
relatively higher gravimetric storage. However, high pressure conditions tween the Ni atoms and the supporting GDY network. An improvement
like 10 MPa make the material commercially less attractive. in the binding energy values was predicted when B-GDY was used, and
Ni atoms added suitably. The desorption temperature was also predicted
9.4. Ordered mesoporous carbons to be in the 300 K to 500 K range (Fig. 13). Thus, co-doping of GDY net-
work with B and Ni gives better options for hydrogen storage. Few other
Ordered mesoporous carbons have also been studied for hydrogen theoretical reports also discuss the utility of next-gen graphene derivates
storage properties after treating them in ammonia atmosphere. Hard in hydrogen storage. A lithium-doped graphene system was studied the-
template method was used by Giraudet et al. to synthesize nitrogen- oretically by Hussain et al. which was doped by replacing two hydrogen
doped mesoporous carbon. One of the important conclusions of the atoms by Li atoms [368]. The positive charges on Li atoms influenced the
study was that nitrogen doping was more influential for electrochemical polarization of approaching hydrogen molecules and resulted in van der
H2 storage indicating that nitrogen doping participated in redox reac- Waals bond formation between incoming hydrogen and the substrate. A
tions directly and that the effect on van der Waal’s types of forces was value of 9.37 wt.% and 12.12 wt.% were reported for zero and non-zero
not significant. However, the porosity of the mesoporous carbons played lattice strain, respectively. The binding energy was calculated as falling
a role at lower temperatures [358]. Other means to store hydrogen have in the range 0.15 to 0.20 eV [369,370].
also been reported. For instance, metal hydrides are known to suffer
from great thermodynamic stabilities thereby resulting in slow desorp-
tion kinetics and high temperatures of adsorption. However, improved 9.5. The mechanisms of hydrogen storage with carbonaceous materials
thermodynamic properties, better desorption kinetics and the better re-
versibility by LiBH4− MgH2 nanocomposites was demonstrated by mak- A carbon network (combination of sp3 , sp2 , sp1 ) purely cannot serve
ing use of a porous carbon aerogel scaffold by Nielsen and coworkers as a hydrogen storage material. Upon hydrogenation, a carbon network
[359]. The carbon aerogel scaffold with pores of maximum size of ∼ will get passivated soon and then not offer adequate and favorable ad-
21 nm served as a nano-sized confined system where the reversible sorption sites. Thus, there are no means to increase adsorption on these
reaction could take place. Composites of Ni, Co and Ni-Co were dis- materials. The interaction strength of adsorbed H2 molecule is feeble
persed over nitrogen doped graphene and tested for hydrogen storage. and may lead to undesirable desorption at ambient conditions. For room
The authors reported a 1 wt% release of hydrogen at 226 °C and with temperature storage, a range of 20–40 kJ/mol binding enthalpies has
Ni nanoparticles, 6.5 wt% H2 release was recorded at 325 °C. Thus, the been suggested. Cases where physisorption is the primary interaction
above studies show that hydrides alone may not be useful for hydro- between H2 molecules and the adsorbate, the binding enthalpies fall
gen storage while their composites with carbon support materials can below the suggested range. Examples include pure carbon-based nano-
be useful. materials, zeolites, or some metal organic frameworks. Cases where
Other systems containing carbon have also been proposed in the re- chemisorption is the primary interaction between hydrogen atoms and
cent past. Here, the subset of Liquid Organic Hydrogen Carriers (LOHCs) adsorbate, the binding enthalpies are quite high resulting in stronger
is promising as it is very easy to transport liquid fuel through the in- covalent bonds. Therefore, even if the adsorption events are favorable,
frastructure supporting the storage and distribution of petroleum-based their rates, high heat of adsorption and desorption processes pose a prob-
fuels. LOHCs store hydrogen in liquid state. These are organic in nature lem for room temperature storage. Therefore, routes that favor binding
and can attach to hydrogen atoms in liquid state and de-hydrogenate. energies from 20 to 40 kJ/mol need to be explored. Studies indicate that
Such systems that include cyclohexane, decalin, etc. are seen as easy either functionalized carbon supports, or nanoparticle dispersed carbon
substitutes for the present diesel/ petrol liquid fuels. Hydrogenation pro- supports are promising candidates. Depending upon the type of func-
21
Fig. 12. General principles for adjusting the kinetics of hydrogenation and dehydrogenation reactions with catalysis. (b) Illustration showing the catalytic hy-
drogenation/dehydrogenation mechanism for the capital CBH cycle. Reprinted with permission from M.S. Salman, N. Rambhujun, C. Pratthana, K. Srivastava, K.-F.
Aguey-Zinsou, Catalysis in Liquid Organic Hydrogen Storage: Recent Advances, Challenges, and Perspectives, Industrial & Engineering Chemistry Research 61 (2022)
6067–6105 [360]. Copyright 2022 American Chemical Society [360].
tionalization and nanoparticles, primarily two mechanisms are reported can bond with the metal nanoparticles and the spilled-over hydrogen
which are discussed now. atoms resulting in higher uptake capacities [356,359,373]. In both the
above mechanisms, nanoparticles act as catalysts. Smaller the size of
9.6. Kubas interaction the nanoparticles, better are their catalytic properties. However, smaller
nanoparticles have high cohesive energies. Thus, they tend to agglom-
Kubas interaction deals with the interaction of hydrogen molecules erate resulting in reduction of the loss of improved catalytic activity
in the presence of transition-metal (TM) nanoparticles. Studies show due to smaller-sized nanoparticles. Functionalized carbon support has
that the H–H bond loosens from the 0.74 Å bond length of free hydrogen shown tremendous improvement in this regard [348].
molecule to more than 0.84 Å for Kubas-type interaction. This loosening
of H–H bond occurs due to the interaction of hydrogen bonding electrons 9.8. The future of carbon nanomaterials in hydrogen storage
that are donated to empty 3d orbitals of TM nanoparticles and then back
donated to the anti-bonding of hydrogen. In the whole process, the H–H The benefits of carbon nanomaterials have been discussed in detail in
molecules get oriented towards the metal bonds as shown in Fig. 14. the earlier sections. Functionalized carbon nanomaterials also provide
This coordinated molecule can bind hydrogen to the metal and hence the right binding energy via the physico-chemical bonding options. As
improve the hydrogen storage. it is very easy to handle carbon nanomaterials and functionalize them,
their popularity as potential storage materials will always exist. Hence,
9.7. Spillover mechanism their use as hydrogen storage materials is promising. With predictions
of newer two-dimensional graphene derivatives, it is likely that the new
Spillover mechanism addresses the bonding of hydrogen over the generation of carbon nanomaterials picks up research efforts in the field
carbon support. In this type of mechanism, the support influences the of hydrogen storage and meets the DOE targets.
H–H bond strength, which loosens and two dissociated hydrogen atoms
form. The energy required for this dissociation is lowered by using 10. Metal organic frameworks (MOFs) and related systems
nanoparticles as catalysts over the carbon support. Dissociation of H2
molecules into H atoms is now discussed. In the presence of nanopar- Hydrogen storage is an emerging field of study for future transporta-
ticles, the polarizability of the H2 molecule is affected and hydrogen tion. After low-cost MOF-5 discovery, it was selected to be evaluated in
atoms get chemisorbed on the nanoparticles, which are usually metal- hydrogen storage. MOFs are organometallic materials or coordination
lic in nature. As the H-atoms chemisorb on metal nanoparticles, their polymers that contain a metallic center and organic ligands intercon-
H–H bond loses strength and ultimately breaks. If surface diffusion is nected with each other. They have been studied mainly in catalysis,
favorable on the support material (graphene, functionalized graphene, adsorption, and gas separation. Recent reviews are available in the lit-
nanoparticle-decorated graphene, etc. two-dimensional material), then erature [371–374]. Some important conclusions emerge: i) Gaining a
the H-atoms first saturate the nanoparticles, and then diffuse on the deeper understanding of the interaction between gas and MOFs mate-
underlying support. As H-atoms migrate from the catalyst nanoparti- rials will be possible through the computational and machine learning
cles and spill onto the support, the catalyst can dissociate subsequent techniques, it will promote the design and development of ideal MOFs
incoming H2 molecules and further dissociate them. Thus, a good syn- [374]. ii) Total hydrogen storage lies on 6–15 wt% at 77 K and high
ergy between the catalyst nanoparticles and carbon support can result pressure, which is good since the US DOE target is 5.5 wt%; but storing
in higher storage of hydrogen. Fig. 15 depicts the role of functionalized at room temperature, typically in 0.5–1wt%, is still a challenge. Impor-
graphene that favors spilling of the hydrogen atom over the graphene tant factors are shown in Fig. 16 [371]. iii) There are still challenges to
support [348]. Further, if the carbon support is functionalized, then it obtain MOFs modified with nanoparticles [372], and iv) MOF modifi-
22
Fig. 13. “Relaxed structures of pristine and B-doped GDY with Ni a) and b) inside the big pore; c) and d) on top of the small pore. Ni, C, and B atoms are blue, gray,
and green, respectively. All bond lengths and distances are in Å. Cyan and yellow isosurfaces (0.0025 e) show charge depletion and accumulation, respectively.”
Reprinted from Materials Today Energy, 16, E.V. Anikina, A. Banerjee, V. P. Beskachko, R. Ahuja, Influence of Kubas-type interaction of B–Ni codoped Graphdiyne
with hydrogen molecules on desorption temperature and storage efficiency, 100,421, Copyright (2020), with permission from Elsevier [367].
cations such as doping with metal ions, nanoparticles or formation of catalyst decreased dehydrogenation temperature since the beginning by
composites could favor hydrogen storage [375]. 160 °C, compared with un-doped MgH2 (Table 5, entry 2).
MOFs were discovered in 1999 [375]; they have been researched as In the other hand, through computational evaluation of near 7444
hydrogen storage material with a capacity of 5.2 wt% at 77 K and 50 MOF database H2 storage capacities were among 8.044 and 12.191 wt%
atm. [376]. Table 5 summarize the hydrogen storage capacity of recent at 77 K and 100 atm., this is the highest value of that was reported by
literature with a better potential than the former reference. Among ma- the authors (Table 4, entry 5). Jia et al. have recently reviewed the
terials, MgH2 occupies high hydrogen capacity of 7.6% w/w together use of MOF for hydrogen storage showing important facts prior to com-
with good reversibility and low cost, but high operating temperature mercial scale of MOF [374]; the most representative for hydrogen stor-
(>300 °C) and slow dehydrogenation kinetics seriously hinder its prac- age are illustrated in Table 5, entries 6 to 8. Also, by computational
tical application [281], however modification with Nobium oxide de- calculations Heterofullerene C48 B12 -impregnated MOF-5 and IRMOF-
creased the temperature (Table 5, entry 2). A MOF-derived bimetallic 10 have been evaluated in hydrogen storage showing adsorption up to
Co@NiO catalyst was synthesized and doped with MgH2 to enhance the 7.1 wt% (Table 5, entry 3). Several MOFs modified with copper were
capacity hydrogen desorption, and resorption kinetics. Doped Co@NiO evaluated by computational calculations with the best results in Table 5,
23
Table 5
Storage capacity of MOFs.
Entry MOF Storage capacity (wt%) Ref.
1 MgH2 + 9% (mass) Co@NiO composite 5.4 at 165 °C and 30 atm. Zhang et al. [281]
2 7 wt% Nb2 O5 @MOF doped MgH2 6.5 at 175 °C and 32 atm. Zhang et al. [378]
3 Heterofullerene C48 B12 -impregnated 7.1 at 77 K and 12 atm. (verified with computational Yu et al. [379]
IRMOF-10 calculation)
4 Cu-MOF-399 8.3 at 77 K and 50 atm. Srivastava et al. [380]
0.46 t 298 K and 140 atm.
(Computational calculations)
5 BOQQAD 12.191 at 77 K and 100 atm. Lu et al. [381]
(Computational calculation)
6 MOF-210 17.6 at 77 K and 80 atm. Furukawa et al. [382]
7 NPF-200 13.1 at 77 K and 100 atm. Zhang et al. [383]
8 NU-100 16.4 at 77 K and 70 atm. Sen Wang et al. [384]
9 BP-COF-5 8.57 at 77 K and 100 atm. Bian et al. [377]
10 she-MOF-1 12.6 at 77 K and 100 atm. Gomez-Gualdron et al. [385]
11 DUT-32 14.21 at 77 K and 80 atm. Grunker et al. [386]
12 NU 1501-Al 14.5 at 77 K and 100 atm. Chen et al. [387]
13 MOF-519 16 at 77 K and 100 atm. Rahali et al. [388]
14 Li- MOF-C30 6.6 at 300 K and 100 atm. Volkova et al. [389]
+
15 Zn BTC Rb 0.15 at 77 K and 1 atm Almasi et al. [390]
16 C4 H18 B2 Na2 O14 0.108 at 77 K and 1 atm. Ozer et al. [391]
entry 4. Bian et al. reported also by computational calculations boron-

phosphorus cube based covalent organic frameworks (BP-COFs), being
the best storage 8.57 wt% (Table 5, entry 9) [377]. Shet et al. have
reviewed MOF for hydrogen storage [373], the most representative ma-
terials are in Table 5, entries 10 and 11. NU-1501-Al exhibits a high BET
surface area equal to 7310 m2 g−1 that contributes to hydrogen storage
capacity (Table 5, entry 12). Through computational calculations MOF-
19 conformed by octahedral Al and modified with ligands (octametallic
inorganic secondary building units exhibited a high hydrogen storage
capacity (Table 5, entry 13). It is shown in Table 5, entries 15 and 16,
typical values of storage a low pressure, furthermore, increasing tem-
perature strongly reduce the adsorption capacity (Table 5, entry 14).
The literature review indicates that computational could accelerate
the finding of the best MOFs for hydrogen storage, but it is still an open
field in the production of selected structures based on MOFs. It is pre-
ferred materials with high surface areas, but factors such as composition,
adding ligands, or confinement effects are important to promote hydro-
Fig. 14. Kubas interaction depicting sigma donation and pi-back-donation.
Fig. 15. Schematic of hydrogen spillover on functionalized graphene [348].
24
Fig. 16. Factors affecting hydrogen storage.
Fig. 17. Important issues about perovskites.
gen storage capacity. The most reported methods of synthesis are based hydrides (being X atoms of Li, Na or K) perovskite type hydrides and re-
on precipitation (either hydrothermal treatment or not). ported that LiNiH3 had better results related to hydrogen storage capac-
ity and desorption temperature (4.40 wt%, 446.3 K) while KNiH3 had
11. Perovskites and related systems the lowest ones (3.30 wt%, 367.5 K). Among the conclusions mentioned
by the authors is the influence of X atom type from Li to K, due to the hy-
Another type of materials researched for hydrogen applications are drogen storage capacity decreases with the increasing of the mass of the
perovskites [392–395]. The first perovskite was discovered in 1839 by element in the perovskite; and they also found in this study, that these
the Prussian mineralogist Gustav Rose in mineral deposits in the Ural compounds are energetically, mechanically and dynamically stable and
Mountains with formula CaTiO3 [396]. Subsequently, synthetic per- synthesizable [392]. Another study, NaXH3 perovskite (being X atoms of
ovskites were obtained by different preparation routes. The crystal struc- Mn, Fe, Co) have also been investigated and the results of the structural
ture of this compound, initially thought to be cubic, was later shown optimizations showed that all these compounds have negative formation
to be orthorhombic. The general formula is derived from the compo- energy implying the thermodynamic stability and synthesizability. Re-
sition ABX3 . To some extent the multiplicity of phases that belong to garding the investigation on hydrogen storage characteristics of NaXH3
the perovskite family can be rationalized by assuming that perovskites compounds resulted in hydrogen storage capacities of 3.74, 3.70 and
are simple ionic compounds, where A and B are metal cations, and X 3.57 wt% for X equal to Mn, Fe and Co, respectively. The authors indi-
is non-metal anion [396]. Depending on the composition, perovskite cated that their study is the first investigation of NaXH3 perovskite type
can have quite different structures, such as oxides, oxyhydrides and hy- hydrides as known up to date and may provide remarkable contributions
drides; with several applications as shown in Fig. 17, where oxyhydrides to the future research in hydrogen storage applications [394]. Garara
and hydrides have also been investigated to measure hydrogen storage et al. [395] focused their research on hydrogen storage properties using
capacity. Gencer et al. approached their study on XNiH3 perovskite type the MgCoH3 perovskite were found a structure mechanically stable, for-
25
mation energy equal to −71.30 kJ.mol−1 .H2 , comparable value with the sities, quick fuel uptake and release, operation at standard room tem-
theoretical value −73.32 kJ.mol−1 .H2 , desorption temperature equal to perature, and atmospheric pressure [400]. These characteristics should
545.52 K, and storage capacity equal to 3.505 wt%. Hayat et al. pub- be optimized to produce a safe and balanced, cost-effective product.
lished in their work perovskites type hydrides with composition XCuH3 , There are numerous problems with the present hydrogen storage so-
(being X atoms of Co, Ni, or Zn); and their effect in the properties of each lutions, including complicated heat management systems, boil-off, low
material. efficiency, costly catalysts, stability problems, sluggish response times,
The results showed that NiCuH3 is more appropriate for hydrogen high working pressures, low energy densities, and dangers of violent and
storage. The gravimetric ratio of hydrogen storage capacities was deter- uncontrolled spontaneous reactions. Even though it is far from ideal, the
mined as 2.8 wt.%, 3.0 wt.%, and 2.7 wt.% for CoCuH3 , NiCuH3 and leading industry standard for compressed hydrogen now on the market
ZnCuH3 , respectively. Anti-ferromagnetism was reported for NiCuH3 offers a workable solution and shows that, in contrast to other technolo-
and ZnCuH3 while magnetism has been observed for CoCuH3 . Accord- gies, it can provide a storage alternative for mobility.
ing to the authors, the current study is the first computational attempt In this regard, we must assess the hydrogen storage possibilities for
of XCuH3 , which may contribute outstanding amelioration for future in- transportation-related applications. Refueling for transportation needs
vestigations in hydrogen storage applications [397]. Besides, they indi- to be quick, safety must come first, and the storage system’s size and
cate that regarding hydrogen storage capacity is consistent with the val- weight should be as small as feasible. It is essential to take the system
ues reported in the literature for different materials and concluded that into account to develop a viable solution that the industry can accept.
hydride perovskites XCuH3 are suitable materials for hydrogen storage Given present battery technology, it is critical to discuss whether hydro-
devices due to occurrence of sufficient value of hydrogen storage capac- gen storage is required for mobility applications.
ity, and large values of negative formation energy produce energetically Evaluation of hydrogen storage system-related parts, including the
stable and synthesizable materials [397]. tank, valves, piping, insulation, and reactants, while material-based
Regarding perovskite type oxyhydride, Gencer et al. [393] re- value solely considers reactants or materials that contain hydrogen
ported the gravimetric hydrogen storage capacity of CaTiO3 H6 equal to is needed [401]. In addition to gravimetric and volumetric require-
4.27 wt.% and the hydrogen desorption temperature is equal to 827.1 K. ments, the US Department of Energy has also addressed the difficulties
They compared with other materials as MgTiO3 Hx and CaTiO3 Hx per- in achieving other important system performance objectives, including
ovskite compounds and their hydrogen storage application that provides cost, charge and discharge kinetics, and durability. Each method has
some insights for the future theoretical and experimental studies. And benefits and drawbacks, and no technology is now available that can
they conclude that this type of research is crucial to promote usage of satisfy every need. Although there is still room for many advancements
hydrogen technology especially for on-board applications. In this sense, and fresh discoveries, hydrogen production, storage, and conversion
MgTiO3 and CaTiO3 perovskite compounds are investigated for hydro- have reached a technological level. The hydrogen storage is frequently
gen storage in terms of structural, mechanical, electronic and hydrogen viewed as the bottleneck of the hydrogen-based renewable energy indus-
storage properties systematically by using first-principle calculations. try. Numerous hydrogen storage techniques and materials have already
Another material, BaYO3 H3 was reported with a gravimetric hydrogen been discussed; further research is required.
storage capacity equal to 1.09 wt%. And they found that the composition
based in BaYO3 H9 , the structure is unstable, and it is not suitable for hy- 13. Conclusions
drogen storage purposes [398]. The authors conclude in this study that
the perovskites for solid state hydrogen storage method could be useful Research efforts are underway globally to address the energy and
in the future theoretical. environment challenges that the world faces. With growing awareness
and government initiatives all over the world, attempts and intentions
12. Hydrogen storage for mobility and energy applications are being converted into actions. While alternatives like nuclear, solar,
wind, geothermal, electrochemical, etc. energies are also being looked
The rising demand for energy production with lesser resource de- into, no one energy technology would be sufficient to meet the demands.
pletion and environmental damage leads to the development of high- In this regard, hydrogen energy presents a very good and competitive
performance, inexpensive, and environmentally friendly energy produc- alternative for vehicular energy demands. Hydrogen production, stor-
tion and storage technologies. The main factor in lowering greenhouse age and distribution are the three main concerns, of which safe and
gas emissions is the dependence on fossil fuels. In this regard, we are reversible storage of hydrogen is seen as the biggest bottleneck. This ar-
compelled to investigate new environmentally friendly energy sources ticle presents an overview of potential materials, the solid-state storage
for the expanding population and rising demand for electricity. In a fu- journey of hydrogen in different materials, existing challenges, their pro-
ture energy economy built on sources and carriers that are ecologically cessing, and design strategies. While alloying, nanostructuring, scaffold-
friendly, hydrogen is anticipated to play a significant role. Its advantages ing, hierarchical designs, 2-D materials, newer derivatives of existing
as a preferred fuel are lightweight, high-energy density, and the absence materials have shown a positive and upward trend in the storage capac-
of dangerous chemicals by-products from combustion. In addition, hy- ity of solid materials, the world still awaits its alternate commercial pro-
drogen is regarded as green energy because it can be produced using totype that meets the DOE targets. Combination of chemi-physisorption
renewable resources and is non-polluting. However, the lack of a secure mechanism may be the answer to the longstanding storage challenge
and convenient means of storage continues to be a significant obstacle that provides the pathway for tackling both the thermodynamic and ki-
to the widespread use of hydrogen as the preferred fuel in mobile trans- netic constraints.
portation [399]. To improve the performance of energy storage devices
like supercapacitors, Li-ion batteries, fuel cells and hydrogen storage Declaration of Competing Interest
systems, researchers focus on using hydrogen as an energy carrier for
the anticipated hydrogen economy. There is no conflict of interest found.
Fuel cell electric vehicles (FCEVs) would become more widely avail-
able and more quickly commercialized with a low-cost, lightweight, and Acknowledgements
small hydrogen storage system, which could help cut net carbon emis-
sions if hydrogen fuel is developed using low-carbon techniques. An in- The authors acknowledge their respective institutions for the support
depth understanding of the hydrogen storage technologies pertinent to to accomplish this review study. SSS and SLA would like to acknowl-
transportation applications is needed. The desirable characteristics of an edge the support of Fulbright Foundation (Project # FSP: P005908) of
ideal storage medium are high volumetric and gravimetric energy den- USA and Colombia for the exchange visit and collaborative discussions.
26
VK and SS7 acknowledges the support from the National Convergence [24] G.W. Crabtree, M.S. Dresselhaus, M.V. Buchanan, The hydrogen economy, Phys.
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Contents lists available at ScienceDirect

Recent developments in state-of-the-art hydrogen energy technologies –

Fig. 1. Hydrogen Energy Technologies.

Fig. 2. (b) The HYPE cycle.

tronegative metals alkali (Group 1a) or alkaline earth metals (Group

Fig. 3. (c) Types of hydrogen storage technologies.

S.N. Class Crystal structure Representative compound

Composition Hydrogen Storage Plateau Operating Heat of hydride

1 AB5 Hexagonal CaCu5 LaNi5 1.5 0.5 Room temperature 7.3

Activation AB5 > AB2 > SS > A2 B > AB

Fig. 5. Progress in metal hydride-based research.

the stability of Mg-H bond resulting in an improvement in the thermo-

rier of H diﬀusion channels, promoting the hydrogen desorption and

Pristine reactive hydride complex - 2[n(LiBH4 ) + 3n(LiNH2 )] + 3n(MgH2 ) . . . . (1)

“n” signiﬁes nano-form of host hydride.

Fig. 10. Diﬀerent allotropes of carbon that diﬀer in dimen-

9.2. The carbon connection

For solid state hydrogen storage, one requires a good volumetric or

Entry MOF Storage capacity (wt%) Ref.

entry 4. Bian et al. reported also by computational calculations boron-

Fig. 15. Schematic of hydrogen spillover on functionalized graphene [348].

Fig. 16. Factors aﬀecting hydrogen storage.

Fig. 17. Important issues about perovskites.

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