Review on large-scale hydrogen storage systems for better sustainability

Abstract

Continuous population growth and enhanced living standards have caused a significant
rise in energy demand worldwide. Because of the intermittent nature of renewables (Solar,
Wind, Geothermal, etc.), their integration with large scale hydrogen generation and storage
units is required for sustainability. The present work reviews the worldwide develop-
mental status of large-scale hydrogen storage demonstrations using various storage
technologies such as compressed, cryogenic, liquid organic hydrogen carrier, and solid-
state hydrogen storage. It covers the classification of tank materials with distinguished
manufacturers based on pressure range (200e950 bar), cost (83e700 USD/kg), and windings
for compressed hydrogen storage. A brief summary of active and developing underground
storage sites in various parts of the world is also included. It also provides a comparative
review of different liquefaction cycle based installed systems and corresponding energy
input. The review summarizes industrial establishments working in the field of liquid
organic hydrogen carriers for H 2 storage and transportation. It also covers a brief review on
other adsorption and absorption based large-scale hydrogen storage systems. Furthermore,
the review lays down the roadmap of hydrogen infrastructure for developing countries like
India. A comparative overview of the economics of hydrogen production globally is also
presented

Full text

Review Article
Review on large-scale hydrogen storage systems
for better sustainability
P. Muthukumar
a,*
, Alok Kumar
b
, Mahvash Afzal
c
,
Satyasekhar Bhogilla
d
, Pratibha Sharma
e
, Abhishek Parida
f
,
Sayantan Jana
f
, E Anil Kumar
a
, Ranjith Krishna Pai
g
, I.P. Jain
h
a
Department of Mechanical Engineering, Indian Institute of Technology Tirupati, Tirupati, 517619, India
b
School of Energy Science and Engineering, Indian Institute of Technology Guwahati, Guwahati, 781039, India
c
Department of Mechanical Engineering, Islamic University of Science &Technology, Pulwama, 192122, India
d
Department of Mechanical Engineering, Indian Institute of Technology Jammu, Jammu, 181221, India
e
Department of Energy Science and Engineering, Indian Institute of Technology Bombay, Mumbai, 400076, India
f
Department of Mechanical Engineering, Indian Institute of Technology Guwahati, Guwahati, 781039, India
g
Technology Mission Division, Department of Science and Technology (DST), New Delhi, 110016, India
h
Centre for Non-Conventional Energy Resources, University of Rajasthan, Jaipur, 302004, India
article info
Article history:
Received 28 January 2023
Received in revised form
20 April 2023
Accepted 26 April 2023
Available online xxx
Keywords:
Hydrogen storage infrastructure
Hydrogen economy
Hydrogen storage materials
Liquefaction cycles
Tank material and windings
abstract
Continuous population growth and enhanced living standards have caused a significant
rise in energy demand worldwide. Because of the intermittent nature of renewables (Solar,
Wind, Geothermal, etc.), their integration with large scale hydrogen generation and storage
units is required for sustainability. The present work reviews the worldwide develop-
mental status of large-scale hydrogen storage demonstrations using various storage
technologies such as compressed, cryogenic, liquid organic hydrogen carrier, and solid-
state hydrogen storage. It covers the classification of tank materials with distinguished
manufacturers based on pressure range (200e950 bar), cost (83e700 USD/kg), and windings
for compressed hydrogen storage. A brief summary of active and developing underground
storage sites in various parts of the world is also included. It also provides a comparative
review of different liquefaction cycle based installed systems and corresponding energy
input. The review summarizes industrial establishments working in the field of liquid
organic hydrogen carriers for H
2
storage and transportation. It also covers a brief review on
other adsorption and absorption based large-scale hydrogen storage systems. Furthermore,
the review lays down the roadmap of hydrogen infrastructure for developing countries like
India. A comparative overview of the economics of hydrogen production globally is also
presented.
©2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
*Corresponding author. Department of Mechanical Engineering, Indian Institute of Technology Tirupati, Tirupati, 517619, Andhra
Pradesh, India.
E-mail addresses: pmkumar@iittp.ac.in (P. Muthukumar), alok176151007@iitg.ac.in (A. Kumar), abhishek.parida@iitg.ac.in (A. Parida),
j.sayantan@iitg.ac.in (S. Jana).
Available online at www.sciencedirect.com
ScienceDirect
journal homepage: www.elsevier.com/locate/he
international journal of hydrogen energy xxx (xxxx) xxx
https://doi.org/10.1016/j.ijhydene.2023.04.304
0360-3199/©2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article as: Muthukumar P et al., Review on large-scale hydrogen storage systems for better sustainability, International
Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.04.304

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Compressed gas storage of hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Materials and design of CGH2 tanks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Economics of CGH
2
tanks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Underground hydrogen storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Underground storage in aquifers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Underground storage in depleted oil and gas fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Underground storage in salt caverns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Challenges in underground hydrogen storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Liquefied hydrogen storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Hydrogen liquefaction cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Linde Hampson liquefaction cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Claude liquefaction cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Collins Helium Hydrogen liquefaction cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Large scale liquid hydrogen storage systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
NASA Kennedy space centre . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Australia-Japan liquid hydrogen alliance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Linde Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Air Liquide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
BMW hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Challenges of liquid hydrogen storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Boil-off loss and maximum allowable pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Energy intensive process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Hydrogen storage using chemical hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Present status of the LOHC technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Hydrogenious GmbH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Chiyoda cooperation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Hynertech Corporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Framatome . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
HySA infrastructure, South Africa . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Solid state hydrogen storage (SSHS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
System level development in MH based SSHS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Commercialized hydrogen storage solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Global hydrogen transportation infrastructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Global hydrogen energy structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Hydrogen storage infrastructure: an Indian perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Introduction
The world is witnessing an inevitable shift of energy de-
pendency from fossil fuels to cleaner energy sources/carriers
like wind, solar, hydrogen, etc. [1,2]. Governments worldwide
have realised that if there is any chance of limiting the global
rise in temperature to 1.5 C, hydrogen has to be given a
reasonable/sizable share in meeting the global energy de-
mand by mid of 20
th
century [3,4]. Hydrogen has the potential
to be a versatile energy carrier for EVs, Fuel cells, etc., and
environmentally friendly-green industrial feedstock [5e7].
Shifting towards a hydrogen based energy consumption
system will result in zero carbon transition energy systems,
which will finally mitigate/abate global CO
2
emissions [8e12].
Due to its excellent characteristics for multiple usages,
hydrogen has gained the centre of importance in global
governance. Presently the government of most countries are
promoting hydrogen energy research to avail low or zero-
carbon energy transition in the coming future. As per the
hydrogen council report published in Feb 2021, around 30þ
countries have published their hydrogen roadmap and have
funded over 200 hydrogen projects in the last year [10]. In
order to fulfil the global hydrogen demand, worldwide de-
velopments are taking place in strengthening each pillar of
international journal of hydrogen energy xxx (xxxx) xxx2
Please cite this article as: Muthukumar P et al., Review on large-scale hydrogen storage systems for better sustainability, International
Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.04.304

the hydrogen economy, i.e., hydrogen production, storage,
transportation and usage.
Hydrogen can be produced from various means such as
chemical, biological, electrical, solar, etc. However, hydrogen
produced from different means may significantly impact the
atmosphere. Though hydrogen is a colourless gas, based on
hydrogen production techniques and its related impact on the
atmosphere, the hydrogen colour code has been marked
(Fig. 1). When 1 kg of H
2
is produced through methane steam
reforming (ammonia production), it releases about 8e9kgof
CO
2
. When this CO
2
is released into the atmosphere, the
hydrogen produced is called ‘GREY hydrogen’ [13]. But when
carbon capture and storage (CCS) techniques are coupled with
such systems, the hydrogen produced is called ‘BLUE
hydrogen’ [14]. Hydrogen produced using gasification of coal,
such as lignite and bituminous, has been recognized as
BROWN and BLACK hydrogen, respectively. During the pro-
cess, around 45e50 kg of harmful gasses (mainly CO
2
and CO)
are produced for 1 kg of hydrogen production [13]. Hydrogen
produced through pyrolysis of methane at a very high tem-
perature is called ‘TURQUOISE hydrogen’ [15], with solid car-
bon produced as a by-product, which has huge commercial
value [16]. Hydrogen can be produced through several means
such as, water splitting through electrolysis, photolysis, photo
electrolysis, chemical and thermochemical means. However,
depending on the source of electricity used in the process of
electrolysis defines the colour of hydrogen. Generally, the
hydrogen produced from electricity obtained from the nuclear
plant is named ‘PINK’. The ones made from the fossil fuel
thermal power plant and nuclear thermal power plant (cata-
lytic splitting of water at high temperature) are known as
‘PURPLE’ and ‘RED’ correspondingly. Hydrogen produced
using renewable sources of electricity is known as ‘GREEN’
[13].
As per hydrogen production statistics of 2021, hydrogen
production of ~94 Mt was largely contributed by natural gas
(62%), followed by the use of coal (19%). Around 18% of the
global hydrogen production was met by refineries producing
naphtha. Rest of the hydrogen was produced by water elec-
trolysers (0.04%), oil (0.7%) and fossil fuel based generation
with CCUS (~0.7%) [17]. As projected by IEA, the hydrogen
produced from low-carbon sources (i.e., fossil fuel with CCUS
and water electrolysis) should attain a combined production
of 21 Mt hydrogen by 2030 in the Announced Pledges Scenario.
To fulfil the Net Zero ambitions by 2030, around 95 Mt
hydrogen should come from low carbon sources, which is
more than half of the projected cumulative global production
(Table 1). The projected production mix is 2:1 for electrolysis
and fossil fuel with CCUS [18].
As far as the demand side is concerned, in 2021, global
hydrogen demand was catered to primarily in refining in-
dustries (39.8 Mt), followed by ammonia (33.8 Mt) and methanol
production (14.6 Mt), respectively. Iron and Steel production
consumed approximately 5.2 Mt hydrogen. Apart from these
sectors, a comparatively small amount of hydrogen 40 kt was
consumed for transport, power generation, buildings, or
hydrogen derivative fuel production. Interestingly, the demand
in these new sectors grew by ~60% compared to 2020 levels. The
projected consumption of hydrogen in refineries as per
Announced Pledges Scenario by 2030 is approximately 40 Mt,
however, the same share is reduced to only 25 Mt subjected to
Net Zero ambitions by 2030. The hydrogen demand for derived
Fig. 1 eColour code of hydrogen according to their production process. (For interpretation of the references to colour in this
figure legend, the reader is referred to the Web version of this article.)
international journal of hydrogen energy xxx (xxxx) xxx 3
Please cite this article as: Muthukumar P et al., Review on large-scale hydrogen storage systems for better sustainability, International
Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.04.304

fuels is projected to increase up to 1 Mt and 7 Mt in Announced
Pledges Scenario and Net Zero scenario, respectively. Low-
carbon hydrogen consumption in industries would reach 7 Mt
hydrogen by 2030, whereas within the same timeline, around
6 Mt hydrogen consumption would be delivered by electrolytic
productions. For ammonia and methanol production, the
combined hydrogen consumption could go up to 58 Mt by 2030
in the Announced Pledges Scenario, whereas under the same
scenario, the hydrogen consumption for steel and iron pro-
duction could reach 2 Mt. Transport sector would use approx-
imately 8 Mt hydrogen (Announced Pledges Scenario) of which
2/3
rd
would contribute to shipping. In buildings, around 2 Mt
hydrogen would be used primarily blended with natural gas,
while around 5 Mt hydrogen would be consumed for power
generation in the Announced Pledges Scenario by 2030.
Though there are various means of hydrogen production;
however, most of the production techniques are not cost-
efficient, eco-friendly and environmentally clean and green.
Moreover, the hydrogen production process, in some cases, is
very complex. Stakeholders from all around the world are
building infrastructure and focusing on adopting electrolysis
using renewable sources (green hydrogen) as the primary
hydrogen production method. Countries worldwide have
taken as a principal goal to reduce the cost of green hydrogen
production in the near future. The estimated/targeted cost of
green hydrogen production targeted by some of the countries
is depicted in Fig. 2.
As hydrogen has a low-density, its storage is very crucial
for both mobile and stationary applications. However, sta-
tionary applications require less stringent conditions, but for
mobile applications, economic and conformal storage is still a
challenge [19]. Hydrogen storage technology is mainly divided
into two categories, i.e.
Physical-based storage: This comprises compressed, cold/
cryo-compressed and liquid hydrogen.
Material-based storage: This comprises adsorbent-based
(e.g., MOF-5, zeolites, carbon nanotubes, etc.), liquid
organic hydrogen carrier (e.g., BN-methyl cyclopentane),
chemical hydride (e.g., NH
3
BH
3
), interstitial hydride (e.g.,
LaNi
5
H
6
) and complex hydride (e.g., NaAlH
4
)
An in-depth literature study indicates that a substantial
number of review articles on hydrogen storage exist, which
broadly encompasses different production, storage and dis-
tribution methods and modern technological improvements.
A few articles also focus on the holistic overview of specific
material-based storage, e.g., Mg bases hydrides, Liquid mole-
cules, hollow spheres etc. The key contents of a few preceding
review articles linked to hydrogen storage are presented in
Table 2 for better comprehension. Nevertheless, this review
article first appraises the state-of-the-art hydrogen storage
techniques, their advantages and shortcomings in terms of
engineering perspective, and then reports the inclusive
developmental status of large-scale hydrogen storage. In
conclusion, it also provides insights into how the future
hydrogen energy network would look like and how the
hydrogen stakeholders could participate in transforming the
hydrogen energy space.
The past reviews adopted selective approach and covered
research and developments in a particular area related to
hydrogen, wherein discussions were focused on systematic
investigation and modification in the systems within a certain
period of time. Some of the reviews related to hydrogen
storage and its applications are depicted in Table 2. It can be
observed that, a significant number of review articles pub-
lished have discussed the technological advancements
related to hydrogen production, storage and its engineering
applications. However, a comprehensive review of worldwide
hydrogen storage infrastructure and available systems/plants
for large/industrial scale hydrogen storage is still lagging.
There is hardly any comprehensive review available, wherein
a complete picture of industrial-level developments and
working systems are acknowledged or reported. As hydrogen
infrastructure has grown significantly in the past one decade,
there is a necessity of such a comprehensive review, wherein
worldwide developmental status of hydrogen storage tech-
nologies is collected for the hydrogen community. The pre-
sent manuscript is an attempt to fill this literature gap by
reviewing the worldwide developmental status of hydrogen
storage infrastructure and technologies like compressed,
cryogenic, liquid organic hydrogen carriers and solid state
hydrogen storage. Furthermore, the review reports an over-
view of the economics of hydrogen production globally and
lays down the roadmap of hydrogen infrastructure for devel-
oping countries like India. The article also reviews the energy
efficiency of various liquefaction cycles and different winding
patterns for Type-IV hydrogen storage cylinders.
Compressed gas storage of hydrogen
Compressed gas hydrogen storage is a mature technology and
has seen the fastest growth of all the techniques for hydrogen
storage that have been under investigation. This is due to the
fact that it is the simplest method of hydrogen storage.
However, it is energy intensive as compressing hydrogen
which has an extremely low density of 0.083 kg/m
3
at NTP
requires a tremendous amount of energy. Usually, hydrogen is
stored in steel cylinders up to a pressure of 200 bar. These
constitute the most common hydrogen tanks used for general
industrial applications. With these cylinders, also known as
Table 1 eThe levelized cost (USD/kg) of hydrogen
production of different methods in 2021 and under Net
Zero ambitions in 2030 [17].
H
2
Production
technique
Levelized cost
(USD/kg) in 2021
Projected
levelized cost
(USD/kg) in 2030
Natural gas without
CCUS
1e2.5 0.5e2.5
Natural gas with
CCUS
1.5e3 0.9e2
Coal without CCUS 1.4e2.9 1.3e4
Coal with CCUS 1.7e3.2 1.2e2.4
Wind onshore 3.7e7.9 1.8e4.4
Wind offshore 4.9e8.7 1.9e5
Solar PV 3.9e8.7 1.25e4.5
Nuclear 3.4e6.9 2.7e5.9
international journal of hydrogen energy xxx (xxxx) xxx4
Please cite this article as: Muthukumar P et al., Review on large-scale hydrogen storage systems for better sustainability, International
Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.04.304

Type-I tanks, a gravimetric density of around 1% can be
attained, which is quite low [36]. Consequently, the storage
pressure must be increased so that the volumetric and gravi-
metric capacities are not compromised. These parameters
become even stricter when hydrogen storage for mobile ap-
plications is considered. There are mainly four types of tanks
used for compressed hydrogen storage.
Type-I tank: These are suitable for industrial use where
warehouses are readily available, and the cost of sophis-
ticated tank material and compressing hydrogen would
exceed the cost of warehousing.
Type-II tanks: In applications where the need for enhanced
volumetric capacity supersedes the cost considerations
and tanks lined with a thick aluminium or steel liner
wrapped with a fibre-resin composite mesh are used.
These metal composite liners enhance the load-bearing
capacity of the tanks allowing for higher pressures and
lower volumes. The cost is 1.5 times more than Type-I
tanks but offers a reduction in weight of up to 40% with
storage pressure of up to 300 bar [32].
Type-III tanks: In Type-II tanks, the liners cover only the
lateral surface area of the tank where the hoop stress is
experienced, whereas in Type-III tanks, the liner covers the
entire surface area of the tank [37]. As opposed to type-II
tanks, where the tank body is made of metal, in Type-III
tanks, the tank body is made of composite and has an
allowable pressure of 350e700 bar [38,39]. The liner acts
mainly as a sealing agent and shares only 5% of the me-
chanical load, the rest of which is borne by the composite
outer shell.
Type-IV tanks: These are made of synthetic material such
as carbon fibers resin with polymer-based liners. A poly-
mer like HDPE (high-density polyethylene) can be used as a
liner, whereas carbon fibre composites can be used to form
the overwrap. These can withstand pressures as high as
750 bar [40]. Being composed of composite materials, these
tanks are lightweight and hence ideal for mobile applica-
tions. The hydrogen tank employed in Toyota Mirai offers a
competitive gravimetric capacity of 5.7 wt.%, which is over
five times that of Type-I tanks. TypeeIV tanks have an
allowable pressure of 700 bar [37,41].
Fig. 3 provides a graphical summary of the differences
between different types of tanks. It also highlights the system
weight, volume and cost incurred in each type of tank to be
used to power a vehicle [37]. In addition to the tanks discussed
above, there is also a Type-V tank. It is a fully composite vessel
with a fiber-reinforced shell. Although it is much lighter than
Type-III or Type-IV tanks, the allowable pressure is limited to
less than 15 bar [36]. The design and performance aspects of
compressed hydrogen gas tanks are compared in Table 3.
Fig. 2 eEstimated/targeted cost of green hydrogen production world wide. (For interpretation of the references to colour in
this figure legend, the reader is referred to the Web version of this article.)
international journal of hydrogen energy xxx (xxxx) xxx 5
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Table 2 eSummary of the review articles.
Sl.No. Reference Keywords Content of review
1 Faye et al., 2022 [20] Hydrogen production, Hydrogen storage, Hydrogen
transportation
Hydrogen production, storage and transportation methods are appraised and
recommendations are given.
2 Yue et al., 2021 [21] Electrolyser, Fuel cell, Hydrogen, Power system,
Renewable energy
State-of-the-art hydrogen energy technologies for power systems, their operating
characteristics and techno-economic status are discussed.
3 Tashie-Lewis
et al., 2021 [22]
Paris Agreement, Fuel Cells, Turboelectric
Distributed Propulsion, Gas Turbines, Cryotank, CO
2
,
Pipeline, Electrolysis, Salt Domes
Overview of hydrogen production, storage, distribution and power conversion
technologies are reviewed with an emphasis on novel production techniques. Cost
analysis of hydrogen distribution is presented.
4 Hassan et al., 2021 [23] Hydrogen storage technologies, Composite pressure
vessels, Standard and codes, Physical hydrogen
storage, Material based hydrogen storage, Hydrogen
carrier
Different hydrogen storage technologies are overviewed according to their operating
principles, storage density, cost and suitable applications. Utilized vessels for
hydrogen storage are studied including optimal design, failure analysis, safety and
the corresponding codes, standards.
5 Ratnakar et al., 2021 [24] Hydrogen supply chain, Hydrogen production,
Liquefaction, Hydrogen storage, Insulation strategy,
Thermal modeling
Review of hydrogen production and storage technologies are given. Current status
and challenges associated large-scale LH
2
storage and transportation are discussed.
6 Zheng et al., 2021 [25] Energy storage, Liquid hydrogen rich molecules,
Hydrogen carriers, Nanocatalyst
State of the art liquid molecule-based hydrogen storage systems are discussed.
7 Fan et al., 2021 [26] Fuel cell, Hydrogen technology, Fuel cell vehicles,
Membrane electrode assembly, Hydrogen strategy
Key components of PEMFC and its application automotive applications are discussed.
Also, PEMFC related hydrogen generation, storage, and delivery infrastructure is
deliberated.
8 Ullah Rather S., 2020 [27] Hydrogen storage, Composites, Spillover, Sievert's
volumetric, Nanocrystalline, Sputtering
Synthesis, characterization, and hydrogen storage studies of carbon nanotubes and
their composites with metal, metal oxides, and hydrides are discussed.
9 Mehrizi et al., 2020 [28] Hollow sphere materials, Synthesis methods,
Hydrogen storage, Adsorption
Different types of hollow spheres (hollow carbons, hollow glasses, Boron nitrides and
metal hollow nano-spheres) and their storage capacity as well as kinetics are
reviewed for H
2
storage.
10 Sazali N., 2020 [29] Hydrogen sustainability, Environmental impact,
Renewable technologies, green energy, And
hydrogen applications
Embryonic technologies for Hydrogen production, separation and recovery are
discussed. Also state of the art hydrogen utilization technologies are reflected.
11 Thomas et al., 2020 [30] Decarbonisation, Hydrogen Energy, Hydrogen
Economy, Fuel cells, Environment, Sustainability
Global developments on hydrogen technologies and fuel cells are deliberated.
11 Abe et al., 2019 [31] Hydrogen economy, Hydrogen storage, Metal
hydrides, Catalysis, Nanostructuring,
Nanoconfinement
Contemporary progresses in the field of metal hydride-based hydrogen storage is
presented.
12 Moradi and Groth, 2019 [32] Hydrogen safety, Hydrogen storage, Hydrogen
delivery, Reliability, Safety, Risk assessment
State of the art hydrogen storage and delivery options are reviewed and associated
risk and reliability study is presented.
13 Andersson and
Gronkvist, 2019 [33]
Hydrogen storage, Large-scale, Chemical hydrides,
Liquefaction, Metal hydrides
Large-scale hydrogen storage technologies are reviewed. Thermodynamic,
engineering and economic aspects of different storage methods are deliberated.
14 Abdalla et al., 2018 [34] Hydrogen production, Renewable energy, Hydrogen
storage, Oxidation, Global warming
An overview of challenges associated with production, storage and transportation of
hydrogen is presented.
15 Preuster et al., 2017 [35] Hydrogen, Storage, Logistics, Compression,
Liquefaction, Hydrogenation, Dehydrogenation,
Liquid organic hydrogen carriers
Prospects and challenges of various hydrogen storage methods linked to renewable
energy conversion is discussed.
international journal of hydrogen energy xxx (xxxx) xxx6
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Materials and design of CGH2 tanks
The compressed hydrogen storage tanks are subjected to high
pressures with cyclic loading and temperature changes. The
design process needs to account for cyclic and temperature-
based stresses. Generally, the failure of pressure vessels is
based on burst pressure. It is the pressure at which the vessel
cracks and causes leakage of internal fluid [42]. However,
failure of the high-pressure tank is a complex phenomenon
and may occur due to mechanical (burst pressure) or thermal
(thermal fatigue) reasons. During charging and discharging,
coupling of these two phenomena may lead to additional
challenges. In addition, the liner strain should match the
composite strain for an improved tank life. Local strain in the
fibers can create gaps if there is insufficient resin binding,
leading to permeation [43]. This is exacerbated by the fact that
hydrogen is a small peculiar molecule with a tendency to leak.
The metallic parts in high-pressure tanks are mostly made
of Aluminium 6061 or 7061 and steel. The polymer parts are
reinforced with fibre such as carbon fibre reinforced polymer
(CFRP). This technology enhances the storage performance by
providing high strength at a much lower weight [44,45]. These
are produced by continuous filament winding, where fiber
filaments impregnated in resin are wound to a rotating
mandrel. The resin, such as vinyl ester, epoxy, etc., later so-
lidifies with the fiber. After the winding, the entire assembly is
cured by heating to a high temperature. After curing, the
mandrel is removed, leaving the hollow structure [42]. The
strength of the fibre-reinforced part is maximized when the
fiber direction coincides with the direction of the major prin-
cipal stress of the part. Thus, the type of fiber tape winding,
whether unidirectional, cross-ply or angle-ply, also has a
bearing on the strength of the resulting composite [46]. Fiber is
generally layered helically. However, as hoop stress is twice
the axial stress in a pressure vessel, more layers are added
circumferentially; these are known as hoop layers.
On the dome, it is not possible to layer the fibre circum-
ferentially without any support. For this reason, doilies that
are in-plane perpendicular layers are added to reinforce the
dome [47,48]. Fig. 4 (a) depicts the layering pattern on the type-
IV tank. Since carbon fiber constitutes 50e70% of the cost of
the tanks, optimisation studies have been carried out to
reduce the carbon fiber without compromising its strength.
Various studies have reported to study the effect of winding
thickness and winding pattern on the strength of the tank
[49e51]. Fig. 4 (b) shows the sectional view of the type-IV tank
manufactured by Doosan Mobility. The tank is equipped with
a high-density polymer liner encased in a carbon fibre-
reinforced composite body. A quick coupling mechanism is
provided, which allows for a plug-and-play connection in
discharge mode.
The selection of the right material for CGH
2
tanks is of vital
importance. In the case of type-III tanks, hydrogen comes into
direct contact with metallic parts, leading to a high possibility
of corrosion and embrittlement. Type-IV tanks do not involve
direct contact between hydrogen and metal liners, and they
are safe from corrosion. However, the issue in type-IV tanks is
that of permeation, especially at the high working pressures
involved. Temperature fluctuations in type-IV tanks also pose
a major design challenge, as most mechanical properties of
materials are thermally sensitive. Rapid charging and dis-
charging of tanks lead to tremendous temperature changes
Fig. 3 eGraphical summary of different types of tanks used for hydrogen storage.
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Table 3 eComparison of compressed hydrogen gas tanks.
Sl.No Type of CGH
2
tank
Construction Gravimetric
Capacity
Max Storage
Pressure (bar)
Volumetric Energy
Density (MJ/L)
Cost (USD/kg)
1. Type-I Metal body 1.1 200 1.4 83
2. Type-II Metal body with composite liner 2.1 300 2.9 86
3. Type-III Metal liner with composite overwrap 4.21 700 e700
4. Type-IV Composite body with composite liner 5.7 700 4.9 633
Fig. 4 e(a) Winding pattern on a type-IV tank and (b) Sectional view of the type-IV tank manufactured by Doosan Mobility
[49e51].
international journal of hydrogen energy xxx (xxxx) xxx8
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(Joule-Thomson effect) that are cyclic in nature. During
charging, pressurization causes the temperature within the
tank to rise up to 80 C at 700 bar, while in the reverse process,
the temperature can drop to 0 C leading to fatigue [52].
Economics of CGH
2
tanks
Currently, CGH
2
tanks are the only hydrogen storage pathway
that is at a commercial stage. Toyota has developed its in-
house CGH
2
tank for Mirai, which is equipped with three
layers: a plastic liner, a carbon fiber reinforced plastic layer
and a glass fiber reinforced plastic layer, which forms the
outermost layer [53]. The tank has a gravimetric density of
5.7 wt.%. Hexagon also offers CGH
2
storage options ranging
from type-I to type-IV under the brand name Purus [54]. They
also offer tube trailers for large-scale transportation and dis-
tribution of hydrogen. Marketed using the brand name Titan
XL, these trailers are capable of carrying around 880 kg of
hydrogen. Mahytec provides CGH
2
storage solutions, special-
izing in type-IV tanks ranging from 160 to 300 L capacity [55].
Doosan Mobility also manufactures ultralight type-IV tanks
with a maximum operating pressure of 350 bar. The carbon
fiber winding is optimized for maximum strength-to-weight
ratio [56].
Worthington industries manufacture type-III and type-IV
tanks with working pressures ranging from 200 to 880 bar
[57]. Most of the manufacturing companies are centred in
Europe, Japan and South Korea. While the market penetration
of hydrogen-based transport has increased significantly over
the years, it, however, shares a cyclic relationship with the
cost of production. As the demand increases, the production
costs are bound to come down, thereby increasing the popu-
larity and fuelling the demand. Table 4 summarizes the details
of CGH
2
type-IV tank manufacturers. Fig. 5 depicts the com-
parison of part-wise and cumulative system costs for different
tank configurations. The three configurations are roof-
mounted (S45RM), behind the cab (LX60BTC), and frame-
mounted (C116FM). The solid columns represent a produc-
tion rate of 10000 systems per year, whereas shaded columns
represent 200,000 systems per year. The cost of carbon fibre
accounts for a major portion of the total cost incurred, fol-
lowed by the balance of the plant. The costs are brought down
by around 20% as the production volume increases in the roof-
mounted and behind-the-cab configurations. Another point to
be noted is that the balance of plant cost decrease as the
production volume increases. According to Houcchins and
James'investigations into DFMA (Design for Manufacturing
Analysis) [58], it was found that for each of the three config-
urations of the 700 bar type-IV tank, the cost per kWh could be
reduced to USD 10e15/kWh for an annual production volume
of 200,000 units, with the frame-mounted configuration being
the least expensive and the roof-mounted configuration being
the most expensive.
A study performed by Marcinkoski et al. [59] and compiled
by Houcchins and James [60] indicated that the overall system
cost had dropped by 3.8% from 2015 to 2018 after adjusting for
inflation. The cost was reduced from USD 14.75/kWh to USD
14.19/kWh, with major reductions observed in carbon fiber,
resin used for winding, and equipment capital costs. A
reduction in carbon fiber cost could lead to a further reduction
in cost by more than 40%. Fig. 6 shows the potential cost
reduction in system cost for a production volume of 5,00,000
unit/year.
While the data projected above is for a production volume
of 5,00,000 unit/year, the costs can be brought down further if
the production volume increases further. Most car manufac-
turers, for instance, Maruti Suzuki and Hyundai, produce
around 5,00,000 units in India. However, their combined
requirement for type-IV tanks would be higher if they produce
FCEVs. This would in turn, bring down the carbon fiber and
other raw material costs significantly, leading to significant
growth in Compressed Gas Hydrogen storage and its
applications.
In China, the ENRIC group (Shijiazhuang Enric Gas Equip-
ment Co., Ltd) manufactures large hydrogen storage cylinders
for hydrogen refueling stations and hydrogen storage in-
ventory for factories and commercial buildings. The cylinders
are manufactured in different categories, which are depicted
in Table 5 [61]. Some of the commercial hydrogen installations
in china are depicted in Fig. 7 [62].
Underground hydrogen storage
The storage of gases in underground geological structures is
not a new technology. Carbon dioxide, for instance, has been
stored underground for quite a long. However, hydrogen, with
its high diffusivity and corrosive properties, poses unique
challenges in underground storage. Underground storage of
hydrogen involves allowing high-pressure hydrogen to be
stored in geological structures such as aquifers, caverns,
abandoned mines, exhausted natural gas and oil reserves, etc.
The primary advantage of underground hydrogen storage lies
in the cost-effectiveness and easy integration of the storage
Table 4 eList of CGH
2
manufacturers across the world.
Sl.no. Name of the manufacturer Location Salient features
1. Toyota Japan, USA, Europe 700 bar working pressure @ 5.7 wt.%
2. Hexagon Canada, USA, Europe, Singapore, China Pressure range 250e950 bar.
3. Mahytec France Maximum pressure 500 bar
4. Doosan Mobility South Korea Working pressure 350 bar
5. Worthington Industries Europe Working pressure range 200e880 bar
6. Nproxx Europe Working pressure range 350e700 bar
7. Ullit France Working pressure range 350e700 bar
8. Quantum Fuel Systems USA Working pressure 700 bar
international journal of hydrogen energy xxx (xxxx) xxx 9
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facility with the distribution pipelines. The major challenge is
to maintain the purity of hydrogen in these structures such
that it may be used in a fuel cell.
Fig. 8 highlights some of the challenges associated with
underground hydrogen storage. Besides the common losses of
gas, which may occur due to microbial activity or reaction
with the minerals present in the geological structures,
hydrogen may also be lost by getting trapped in pore-scale
capillaries. Fluctuating pressures during injection and
Fig. 5 eComparison of system cost breakdown for different tank configurations [59].
Fig. 6 eChanges in system cost (USD/kWh) in 700 bar Type-IV H
2
storage tank at production volume of 5,00,000 unit/year [59].
Table 5 eHydrogen Storage Tanks for Commercial
applications in China.
Design
Pressure (bar)
Cylinder volume
(liter of water)
Hydrogen
Storage (m
3
)
275 1200 257
552 2060 914
1030 692 395
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withdrawal of gas can also compromise the stability of the cap
rock. Therefore, a comprehensive assessment of the storage
site is imperative for the safe and efficient storage of
hydrogen.
Underground storage in aquifers
Aquifers are porous rock formations that hold groundwater.
Previously, aquifers have been used to safely store natural gas
and hence, offer an alternative for storing hydrogen gas.
However, due to the different chemical natures of hydrogen,
the investigation should be specific to a particular geological
formation. For instance, aquifers rich in iron or sulphur con-
tent may not be ideal for hydrogen as a significant amount of
hydrogen could be lost due to a reaction with these elements.
There is a possibility of biochemical transformation of
hydrogen triggered by the microbial ecosystem present in a
particular aquifer location which can lead to loss of gas. Also,
Fig. 7 eSome of the large stationary hydrogen storage installations in China.
Fig. 8 eGraphical representation of physical/geochemical/microbial reaction associated with storage of hydrogen in
depleted gas reservoirs [63].
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the porous rocks should have an impermeable rock ceiling to
prevent diffusion and hence leakage of gas into the atmo-
sphere. Hydrogen storage in aquifers has been successfully
accomplished. In France, Gaz de France stored 385 million m
3
of gas containing 50% of hydrogen at Beynes. It was in oper-
ation for eighteen years without any losses. However, there
was a change in the nature of the gas due to bacteriological
activity. Hydrogen storage in aquifers was also achieved in
France and the Czech Republic. At both locations, a mixture of
hydrogen and some other gas was stored [64].
Underground storage in depleted oil and gas fields
Depleted oil and gas fields are fortified with an impermeable
caprock and aquifers on the sides and the bottom. As they
have already been holding hydrocarbon reserves, the tight-
ness of the caprock is well-established. Hydrogen is generally
stored in depleted natural gas fields rather than oil fields.
Storage in oil fields can lead to hydrogen reacting with the
residual oil to form methane, leading to a loss of stored gas. On
the other hand, storage of hydrogen in natural gas fields can
be advantageous as the remnant gas present can act as a
cushion gas helping to maintain suitable pressure and
ensuring adequate deliverability. The remnant gas can, how-
ever, affect the purity of hydrogen stored. Since extensive
geological surveying is undertaken before the exploration of
and extraction from a gas field, therefore, adequate informa-
tion is already available about the area, which is a significant
economic advantage and can prove to be beneficial for
hydrogen storage.
Underground storage in salt caverns
Salt caverns are pits created in underground salt deposits by
solution mining. Solution mining refers to the production of
salt by injecting high-pressure water into underground salt
deposits. The brine thus formed is pumped to the surface, and
the dissolved salts are extracted [65].
The chemical resistivity of the salts to hydrogen and the
mechanical stability of the salt caverns to fluctuating pres-
sures make the salt cavern a feasible choice for hydrogen
storage. In addition, due to the presence of highly concen-
trated brine, microbial activity in salt caverns is negligible.
The walls of the cavern provide an impervious layer to the gas.
The physical volume of salt caverns can range from 100,000 to
1,000,000 m
3
[64]. Salt caverns exhibit a high storage efficiency
of around 98% while maintaining the purity of hydrogen
stored [66]. The salt deposits present across the globe are
mapped in Fig. 9. USA and Canada exhibit promising geolog-
ical features for underground hydrogen storage, with the USA
having an aggregate of over 2 million m
3
of hydrogen storage
facilities operated by Air-Liquid, Praxair and ConocoPhillips in
Texas. In Canada, Ontario Power Generation has evaluated
multiple sites for bulk storage of hydrogen and methane [67].
The Jintan salt mine in Jiangsu province in China is spread
over a vast area of 60.5 km
2
with a depth of 900e1100 m. It
offers a very promising alternative for large-scale hydrogen
storage [68].
Infrastructural developments in hydrogen storage are
taking place all over the world. In Utah, the USA, Mitsubishi
power and Magnum Developments are set to construct an
underground hydrogen storage facility, which will storage
hydrogen generated from an 840 MW gas turbine combined
cycle power plant. The construction is being carried out for a
300 GWh generation storage capacity. The pictorial view of the
construction plan is depicted in Fig. 10a[69].
A US-based start-up, ‘Green HydrogenInternational (GHI)’,is
building a 60 GW hydrogen city project with salt cavern-based
onsite hydrogen storage, which will be powered by wind and
solar. The plan is to produce and store clean rocket fuel for
SpaceX. The plant is located in South Texas. It is believed that,
on completion of the project, the production capacity can be up
to 2.5 million tonnes of green hydrogen a year. The supply will
be through thepipeline to Corpus Christiand Brownsville on the
Mexico border, wherein SpaceX's starbase is located. A pictorial
view of the ongoing project is depicted in Fig. 10b.
Challenges in underground hydrogen storage
Underground storage of hydrogen is a promising technique for
large-scale and long-term hydrogen storage. It is essential to
conduct extensive geological and economic studies before site
selection. The major challenges associated with underground
hydrogen storage are.
a) Hydrogen gas is a very small molecule with very low vis-
cosity and high diffusivity. The high diffusivity of hydrogen
leads to a viscously unstable flow as the permeability of the
aqueous phase is much lower. This leads to lateral
spreading, where the gas penetrates into water-saturated
zones (especially at high injection pressures) [70]. In the
lighter phase, i.e., the gas is trapped by the heavier phase,
i.e., water leading to a significant loss.
b) The primary challenge to underground hydrogen storage
from the microbial activity is biofilm. Biofilm is an aggre-
gate of dead bacteria, the cumulative metabolic waste of
the colony, and bacterial excretions. It is detached from the
solid surface due to the high injection velocity of the gas
and gets transported through the bulk of the gas. It not only
compromises the purity of the stored gas but can also
result in the clogging of pores. In the case of salt caverns
composed of sulphates and carbonates, bacterial activity
can lead to the formation of H
2
S and methane.
c) Hydrogen, due to its corrosive nature, can participate in
redox reactions with the constituent rocks, the most
notable being the pyrite (FeS
2
)epyrrhotite (FeS
1-x
) reac-
tion. This is further exacerbated by the presence of high
pressure and temperature. These reactions can alter the
overall chemistry of the water [71].
d) Hydrogen gas has a negative Joule-Thomson coefficient.
Continuous injection of hydrogen can result in increasing
the temperature of the geological structure, thereby
impacting the microbial life in the adjoining areas, which
in turn can affect the quality of hydrogen stored.
In spite of these challenges, underground hydrogen storage
(UHS) can be explored as an imminent hydrogen storage op-
tion. This is especially true in light of the growing market
share of renewable energy resources, which need to be
bolstered by a robust energy storage solution.
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Liquefied hydrogen storage
The gravimetric density of liquid hydrogen increases by
almost 1.5 times to 70.8 kg/m
3
, whereas there is a two-fold
improvement in the volumetric energy density to 8.5 MJ/L at
atmospheric pressure [73] when compared to gaseous
hydrogen stored at 700 bar. In order to exploit this superiority
of liquid hydrogen, hydrogen is liquefied at 253 C (20 K)
using various liquefaction cycles.
Fig. 9 eLocation and characterization of salt deposits across the world.
Fig. 10 e(a) Pictorial view of underground hydrogen storage project being developed at USA and (b) One of largest green
hydrogen project in Texas for producing and storing rocket fuel for SpaceX [69]. (For interpretation of the references to colour
in this figure legend, the reader is referred to the Web version of this article.)
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Hydrogen liquefaction cycle
Linde Hampson liquefaction cycle
Linde Hampson (L-H) is the simplest among the various
hydrogen liquefaction cycle. It was majorly developed to
liquefy air [72,73]. The Joule-Thomson expansion is used to
reduce the temperature of gases. However, Joule Thomson
cooling is only efficient for gases whose inversion tempera-
tures are closer to the ambient. Gases like hydrogen and he-
lium have inversion temperatures of about 200 K and 24 K,
respectively [74]; thus, they have a negative Joule-Thomson
coefficient at room temperature. As a result, hydrogen is
compressed to higher pressure and cooled below inversion
temperature before passing through the expansion valve. The
detailed process flow diagram and the corresponding T-S plot
is presented in Fig. 11a and b.
Hydrogen is isothermally compressed (minimum
compression work) to pressure P
2
at temperature T
1
. Subse-
quently, isobaric cooling is carried out in heat exchangers
with counter-flowing cooled gas. Hydrogen can only be
expanded by means of Joule-Thomson only after it has been
brought down below the inversion temperature, which
cannot only be achieved by heat exchangers. Therefore,
liquid nitrogen is used during pre-cooling to further lower
the temperature. Finally, hydrogen is expanded by passing it
through a throttling valve. A point to be noted in Fig. 11a and
b, at state point 8, hydrogen is in two phase regions. Only a
part of the gas is liquefied while the remaining gas is re-
circulated back to the compressor through heat exchangers.
Consequently, the Linde Hampson cycle for hydrogen lique-
faction is frequently viewed as an inefficient technique
[75,76]. Hence, researchers [75,77] have suggested imple-
menting a dual-stage hydrogen L-H cycle to raise efficiency
by reducing the compressor work. The detailed process flow
diagram is presented in Fig. 11c.
In this cycle, hydrogen is compressed in two stages from P
1
to P
2
, followed by P
3
at temperature T
1
. Subsequently,
hydrogen is passed through a number of heat exchangers at
constant pressure along with pre-coolers. Hydrogen at state
point 8 is expanded to state point 9 through a throttling valve.
Only the mass flow which contributes to the liquefaction is
transmitted forward for further cooling and Joule Thomson
expansion to form liquid hydrogen. The remaining portion of
the gas is sent back to the compressor through heat ex-
changers to complete the cycle. Reduced hydrogen mass flow
through the compressor means less compressor work as a
whole. The T-S plot of the dual-stage Linde Hampson cycle for
hydrogen liquefaction is shown in Fig. 11d. Peschka [75] re-
ported that the liquefaction work decreases by almost 28% in
the dual-stage L-H cycle when compared to the single stage.
Table 6 shows the comparison of the single and dual-stage
Linde Hampson cycle [75].
Despite the improved performance of the dual-stage Linde-
Hampson cycle over a single stage, it is still a less preferred
technique for hydrogen liquefaction due to its lower effi-
ciency, larger exergy loss and lower liquid fraction obtained
per cycle. Other methods, like Claude and Collins cycle are
promising alternatives compared to the Linde-Hampson
procedure.
Claude liquefaction cycle
In the Claude process, an additional expander is added to the
basic Linde Hampson circuit to obtain a substantial temper-
ature drop [24]. A significantly higher temperature drop is
obtained in isentropic expansion in comparison to the Joule-
Thompson expansion. Therefore, a major amount of the gas
(almost 80%) passes through the expander after compression
and isobaric cooling. Additionally, pre-cooling is not neces-
sary for Claude's technique. However, pre-cooling improves
the performance of the cycle [76]. The detailed process flow
diagram for the basic Claude cycle is shown in Fig. 11e. It is to
be noted that an isentropic expander can even cool hydrogen
up to condensation, thereby eliminating the need for further
isenthalpic expansion. However, the final step employs a
throttling valve to reduce issues brought on by the two-phase
flow within the expander [72,75,76].
The T-S plot for the Claude cycle is presented in Fig. 11f.
Further, improvement can also be achieved with the dual
pressure Claude process, similar to that of the dual-stage L-H
technique. Nandi and Sarangi [78] have examined this tech-
nique and have reported the optimized parameters to achieve
an efficient cycle.
Collins Helium Hydrogen liquefaction cycle
Numerous investigations on the development of hydrogen
liquefaction cycles have been conducted over the years. Due
to low efficiency and exergy losses, Linde Hampson liquefac-
tion is typically not used. Prior to cooling in the Claude
liquefaction method, the hydrogen pressure is increased to
200 bar [73,76]. Thus, due to safety concerns, the Collins cycle
was developed, which involves increasing the pressure
slightly higher enough to overcome the pressure drop
encountered while passing through heat exchangers. Helium
was used as the primary refrigerant to cool the hydrogen.
The detailed process flow diagram is presented in Fig. 11g.
Helium is initially compressed to pressure P
12
at temperature
T
1
(ambient temperature). In parallel, hydrogen is also com-
pressed to pressure P
2
. At room temperature, Helium is then
subjected to a series of isobaric cooling before passing it
through the isentropic expander. The temperature of helium
after the expansion is below 20 K (boiling point of hydrogen).
Hydrogen is thus cooled using helium in condensers before
passing through the throttle valve. It is also reported that
normal hydrogen is completely liquefied without being passed
through the throttling valve [76]. Hence, the return gas stream
is not encountered in this case. However, for para-hydrogen,
gaseous hydrogen is produced at the receiver chamber after
gaining heat of ortho-para conversion. The T-S plot is also
presented in Fig. 11h. It can be observed that the Collins He-H
2
cycle is a combination of the pre-cooled Linde Hampson cycle
and the Claude cycle.
Several studies have been conducted on the comparison of
the performances of the above-discussed cycles. Syed et al.
[79] discussed the exergy analysis on two modified Collins
cycles. It was concluded that economic and exergy analysis
aided in identifying the parameters and operating conditions
to reduce the liquefaction cost. Nandi and Sarangi [76] re-
ported an excellent comparative study of various liquefaction
cycles based on liquid hydrogen yield and energy input
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Fig. 11 eSchematic representations of (a) Process flow diagram of single stage L-H cycle (b) T-S plot for single stage L-H cycle
(c) Process flow diagram of dual stage L-H cycle (d) T-S plot for dual stage L-H cycle (e) Process flow diagram of Claude cycle (f)
T-S plot for Claude cycle (g) Process flow diagram of Collins He-H
2
cycle (h) T-S plot for Collins He-H
2
cycle.
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involved per kg of liquid H
2
. The study is summarized in Table
7. However, it is also reported that it is difficult to conclude the
superiority of a particular cycle above others. It is mostly
determined by the size of the liquefier, heat exchanger effec-
tiveness and expander efficiency.
Large scale liquid hydrogen storage systems
NASA Kennedy space centre
For decades NASA has been harnessing hydrogen fuel to
power the rocket and spaceships. Each rocket carries over 2.65
million liters of liquid hydrogen. To meet this demand, NASA's
Kennedy Space Center (KSC) has two large-scale liquid
hydrogen storage tanks [80]. In the mid-1960s, NASA con-
structed a pair of liquid hydrogen storage tanks at KSC. Each
can contain 3.22 million liters of fuel [81]. It spanned over 21 m
outer diameter with a maximum working pressure of 6.2 bar,
with insulation provided by evacuated perlite fill (~1200 mm
thick). Despite having such thick insulation, the boil-off loss
was found to be 0.0625% or 2000 L per day. Another liquid
hydrogen tank is currently being built, as of 2018 [22,82] which
can store an additional amount of 4.73 million liters of liquid
hydrogen. The spherical tank spreads to about 25.3 m in
diameter, supported by 15 legs. Unlike the former tank, insu-
lation is provided by glass bubbles thermal insulation system
(GBTIS) to prevent boil-off loss arising due to large tempera-
ture differences. This technique is claimed to reduce the boil-
off loss to 0.048% (about 2271 L per day). The newly con-
structed tank is shown in Fig. 12a.
Australia-Japan liquid hydrogen alliance
Australian-based Fortescue Metals Group and Japan's Kawa-
saki heavy industries, and Iwatani Corporation have collabo-
rated to establish large-scale liquid hydrogen production and
supply capabilities [83,84]. Under this agreement, liquefied
hydrogen carrier ship carrying liquid hydrogen will be trans-
ported from Australia to Japan. The Suiso frontier vessel has
four tanks, each holding 40 L, for a total combined capacity of
160 L [85]. The tanks are insulated by a vacuum Multi-Layer
Insulation system (MLIS) and Kawasaki Panel Insulation sys-
tem (KPIS) to prevent losses due to boil-off [86]. The tanks are
designed to sustain up to 4 bar internal pressure. The carrier
ship is shown in Fig. 12b.
Linde Engineering
Linde Engineering has been the pioneer in providing energy
solutions, including liquid hydrogen, over the decades. Collins
Helium Hydrogen liquefaction cycle is utilized for small ca-
pacity liquefaction plants (capacity up to 1000 L/h) [87].
Aluminium plate heat exchangers are generally used for
condensers. For a capacity over 1000 L/h, the Claude process is
implemented. Numerous liquefiers of varying capacities have
been established across the globe, like Beijing in China [88],
Leuna in Germany [89] etc. In 2007, Linde constructed one of
the largest liquefier plants in Germany at Leuna [89]. More
recently, in 2021, Linde collaborated with Korea Expressway to
build four liquid hydrogen refueling stations to promote and
establish a national hydrogen ecosystem [90]. Linde is also
determined to build the world's largest liquid hydrogen plant
at Hyosung, southeast Korea [90]. In July 2021, a liquid
hydrogen plant supplying 30000 kg of liquid hydrogen per day
was built in Texas [91]. Additionally, by 2023, Linde and
Daimler will build GenH
2
trucks, which operate on liquid
hydrogen. The partners will concentrate on a new method
called “subcooled”liquid hydrogen technology, in which
liquid hydrogen will be held under greater pressure with
additional unique temperature control to reduce boil-off loss
[92]. Fig. 12 (c) presents a Linde liquefier plant.
Air Liquide
Air Liquide has also been one of the pioneers in liquid
hydrogen production and storage. A large-scale liquid
hydrogen manufacturing facility with a daily output capacity
of about 255 tons per day for refueling stations was recently
erected by Air Liquide in the United States [93,94]. The com-
pany is also planning to install two production units in
Shanghai to bring down the CO
2
emissions generated from the
coal-based gasification unit installed at Shanghai Chemical
Industry Park Industrial Co. Ltd. The total production capacity
of both units is 4970 tons per day [95]. Air Liquide is also
responsible for having built a large-scale liquid hydrogen
generation plant for the first element fuel [96] in the western
US. The plant had a generation capacity of nearly 30 tons per
day.
BMW hydrogen
BMW developed the first liquid hydrogen-based luxury car,
BMW hydrogen [97], in 2007. The vehicle was equipped with a
liquid hydrogen storage system. The onboard hydrogen
Table 6 eComparison of Single and Dual stage Linde
Hampson Cycle [75].
Process Liquefaction work
considering the energy
expended for nitrogen
liquefaction (kWh/kg)
Liquefaction work
without considering
the energy expended
for nitrogen
liquefaction (kWh/kg)
Single stage
L-H
13.14 16.27
Dual stage
L-H
9.49 12.14
Percentage
of work
saved (%)
27.78 25.38
Table 7 eComparison among various cycles for liquefaction of hydrogen [76].
Cycle Inlet Pressure (MPa) Yield (%) Energy input per kg (MJ/kg)
Precooled L-H 6e10 12e17 260e285
Claude 1e316e20 100e140
Collins He-H
2
1.5e2.5 100 (normal H
2
) 54 (para H
2
) 120e200
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storage system consisted of a single 170 L capacity tank that
could carry up to 8 kg of hydrogen. The tank was designed to
sustain a maximum pressure of 5.1 bar [98]. An increase of
pressure by more than 5.1 bar due to boil-off will automati-
cally open up the valve to release the pressure. For insulation,
BMW developed its own 30 mm thick vacuum super-
insulation capable of a similar thermal insulation effect pre-
sented by 17 m of Styrofoam [100]. An average boil-off rate of
only 16 g/h was observed in the tank. Fig. 12 (d) presents an
image of BMW Hydrogen 7. A summary of the various liquid
hydrogen manufacturing and storage unit is presented in
Table 8.
Challenges of liquid hydrogen storage
Despite the growing global interest in liquid hydrogen storage,
there are certain issues that need to be taken into consider-
ation for effective system design.
Boil-off loss and maximum allowable pressure
Hydrogen has an ultra-low boiling point (20 K) when
compared to other gases (78 K for nitrogen and 90 K for oxy-
gen). The temperature difference between the ambient and
the liquid storage tank is huge. As a result, liquid hydrogen
absorbs heat from the wall and begins to evaporate. The
Fig. 12 eLarge-scale liquid hydrogen storage and production systems (a) liquid hydrogen storage plant at NASA [81], (b)
liquid hydrogen carrier ship from Australia to Japan [85], (c) liquid hydrogen production plant by LINDE [90] and (d) liquid
hydrogen-based car manufactured by BMW [97].
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evaporated hydrogen gas is often vented out of the system to
avoid building pressure. Hence, there is a constant loss in the
amount of hydrogen throughout the day. For instance, NASA's
KSC based liquid hydrogen tank has boil-off losses at the rate
of 2000 L per day. In order to prevent pressure build up, a
pressure relief valve must be employed to vent out the
hydrogen. Additionally, to withstand the pressure, a system-
atic tank design approach must be followed. Some examples
of insulation systems used are perlite, glass bubbles and
multi-layer insulation, etc. [100].
Energy intensive process
The liquefaction of hydrogen is an energy-intensive process.
Therefore, a proper choice of liquefaction technique must be
made based on the design capacity and operating conditions.
The hydrogen that blows off is already at a lower temperature.
In order to save a significant quantity of energy, this compo-
nent might be handled carefully. For instance, the evaporated
hydrogen gas can either be re-liquefied or can be stored again
using metal hydrides etc.
Hydrogen storage using chemical hydrides
This section addresses the available technologies for liquid
organic hydrogen carrier (LOHC) with the most recent dem-
onstrations, which took place on an industrial level and have
been commissioned around the globe. Several reviews based
on hydrogen storage technologies can be found in Refs.
[101e104]. Mori and Hirose [101] described about the infeasi-
bility of high pressure and cryogenic storage to power fuel cell
vehicle and hence, have proposed a hybrid system comprising
of metal hydride and high-pressure storage system. Further,
Satyapal et al. [102] reviewed various hydrogen storage tech-
nologies to meet 2010 US DOE targets and concluded that, it is
imperative to emphasize on gravimetric and volumetric
storage capacities of individual material rather than system
level targets. Additionally, Ren et al. [103] critically reviewed
adsorption and absorption-based hydrogen storage materials
and concluded that adsorption-based storage does not offer
any key advantage to scale up from lab-scale prototype to
large-scale application. Similar findings were reported by Lai
et al. [104]. Also, from recent research, it can be deduced that
the research dealing with hydrogen storage on a large scale is
very limited [35,105].
Hydrogen storage using conventional ways such as com-
pressed gas form and liquid hydrogen comes with disadvan-
tages of the safety risk, high cost, and transportation issues
[106,107]. The liquid organic hydrogen carrier solves these
major issues and provides low-cost hydrogen storage with
high safety and the capability to store a large amount of
hydrogen for long durations and transport hydrogen over very
long distances [108,109].
Multiple chemical hydrides such as ammonia, methanol,
formic acid and liquid hydrogen organic carriers exist in
literature showcasing the ability to store hydrogen [110]. The
chemical hydrides are known to stay in a liquid state for a
wide temperature range; therefore, they are suitable for
hydrogen handling and transportation. One significant
advantage of attracting these types of hydrides is that they do
not need additional infrastructure for their production. The
already established and existing industrial facilities of trans-
portation and storage are a big gain.
For methanol as a hydrogen storage medium, operating
conditions with pressure ranging between 10 and 80 bar and
temperature between 220 and 280 C are needed to store
hydrogen (hydrogenation). The process leads to a release of
excess heat which can be further recovered [111,112]. Again,
some thermal energy will be required to separate the
hydrogen to carry out the dehydrogenation process.
In the case of ammonia as a storage medium for hydrogen,
the main advantage is that it has a high storage capacity of
17.6 wt.% (10 bar). However, the major shortcoming is that
there is a high-temperature requirement for larger storage
plants during the release (dehydrogenation) process
[112e114]. Formic acid is an alternative to dehydrogenation
problems faced in methanol and ammonia-based hydrogen
storage. However, formic acid possesses a low storage ca-
pacity (4 wt.%).
On the other hand, LOHC-based hydrogen storage takes
place in two steps, i.e., first hydrogen is loaded (hydrogena-
tion) and second, it is unloaded (de-hydrogenation). The
storage of hydrogen in LOHC occurs as a result of a catalytic
reaction, and the same happens during dehydrogenation
[108,115,116]. Saksa et al. [115] and Preuster et al. [116]
mentioned the inefficiency of compressed and liquid
Table 8 eSummary of liquid hydrogen storage and manufacturing unit.
Sl. No. Operating Unit Year of Installation Storage/Production Capacity Country Reference
1 NASA 1969 455 Tons USA [81,82]
2 NASA 2018 336 Tons USA [81]
3 Fortescue Metals Group and
Kawasaki Heavy Industries
2021 0.011 Tons Australia-Japan [83e85]
4 Linde 2007 0.042 Tons/hr China [87]
5 Linde 2008 5 Tons/day Germany [88,89]
6 Linde 2020 43.3 Tons/day Korea [90]
7 Linde 2020 30 Tons/day Texas [91]
8 Linde 2021 30 Tons/day Germany [92]
9 Air Liquide 2021 255 Tons/day France [93]
10 Air Liquide 2019 NA China [95]
12 Air Liquide 2016 30 Tons/day USA [96]
13 BMW 2008 0.008 Tons Germany [99]
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hydrogen storage systems due to their lower energy density
and critically reviewed circular energy carriers such as
methanol, toluene, liquid hydrogen organic carriers. It was
also reported that these energy carriers had been seamlessly
integrated with the current technologies in countries like
Germany and Japan due to their safe, reliable and flexible al-
ternatives in storage size and duration for a sustainable
renewable energy supply chain. For the process of hydroge-
nation, mostly well-known LOHCs are toluene [117], dibenzyl
toluene [118], and N-ethyl carbazole [119,120]. This process's
operating pressure and temperature are around 10 bar and
200 C, respectively. It should be noted that the process of
dehydrogenation of LOHC is already having an existing
infrastructure in the industry. The LOHC, which is considered
to be very promising for hydrogen storage, is methyl-
cyclohexane and toluene, amongst many others [35,117,121].
These LOHCs usually have storage densities of around
5e6 wt.%. An experimental study by Jorschick et al. [122] re-
ported that it is possible to use only one catalyst for both hy-
drogenation and dehydrogenation processes by varying the
operating conditions accordingly. The LOHC after de-
hydrogenation, the carrier molecules need to be carried to
the place where they are re-hydrogenated.
Present status of the LOHC technology
The strong cooperation and synergies between R&D and
commercialization have led to the development and
commissioning of demonstration units at a global level. Some
of the major players in LOHC technology and their recent ac-
tivities in industrial developments are covered in the further
section. Table 9 shows the summarized form of leading
companies and their work so far in the field of LOHC
technology.
Hydrogenious GmbH
The company was founded in 2013 and provides innovative
use of LOHC and for H
2
storage &transport [123]. Hydrogen
produced from renewable energy sources is chemically
bonded to the LOHC in the hydrogenation system. The diesel-
like liquid has a high storage density and can be stored under
ambient pressure and temperature. It is hardly inflammable
and neither toxic nor explosive. Storage and transport are
thus particularly safe and efficient. The stored hydrogen is set
free on-demand by optimized releasing systems and can be
used for several applications [108,124].
The company demonstrated a hydrogenation and dehy-
drogenation unit for the handling of hydrogen. It was reported
that while charging takes place, a hydrogen storage limit of 12
tons can be reached, whereas, for the dehydrogenation part,
the limit of storage is between 12 and 500 kg on a daily basis.
The hydrogenation of LOHC is exothermic in nature, with a
heat release of 9 kWh at temperatures greater than 200 C,
which can be used further. Similarly, the hydrogen release
from the LOHC is done by providing heat at a temperature of
around 300 C. The bonding of hydrogen to LOHC takes place
through catalytic reactions. One cubic meter of LOHC can help
in storing 54 kg of hydrogen with oil remaining in liquid form
in wide temperature ranges [125,126]. Hydrogen storage in
LOHC can be used in many domains, such as at refueling
Table 9 eSummarized form of major companies/partners working in the field of LOHC technology.
Sl. No. Company Hydrogenation and
dehydrogenation compounds
Country Focus area Storage capacity Ref.
1. Hydrogenious
Technologies
Dibenzyltoluene
perhydrodibenzyltoulene
Germany Hydrogen logistics 54 kg H
2
storage in 1 m
3
tank of LOHC [127]
2. Chiyoda
Cooperation
Methyl cyclohexane and toluene Japan Large-scale hydrogen
logistics on an international level
e[128]
3. Hynertech eChina Hydrogen fuel cell transport/
Production of LOHC compounds
600 kg H
2
storage in 10 m
3
LOHC [129]
4. Framatome/
AREVA
H0-dibenzyltouluol and
H18-dibenzyltoulene
Germany Power-hydrogen-power 1 l of LOHC can store 2 kWh of energy [130]
5eMarlotherm SH South Africa Power to hydrogen 1 l of LOHC can store 2.2 kWh of energy [131]
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stations to fuel hydrogen vehicles, in industrial processes, and
as a storage medium by using the stored hydrogen to generate
electricity when there is a requirement. A picture of the demo
plant by Hydrogenious is shown in Fig. 13, wherein the plant is
of 100 kW capacity, and the hydrogen will be used to drive a
30-kW fuel cell [116,127].
Chiyoda cooperation
The company has developed a pilot facility working on the
LOHC technology in 2013 and termed the hydrogen storage
facility as SPRERA hydrogen [128,132]. Toluene reacts with
hydrogen using a catalytic process and liquefies at ambient
temperature and pressure, enabling large-scale, safe storage
and transportation. The Chiyoda cooperation started working
on a demonstration project dealing with the hydrogen supply
chain based on LOHC on an international level. The hydrogen
was transported from Brunie to Japan in ISO tankers to a
dehydrogenation plant in Kawasaki, Japan. The LOHC is cata-
lytically divided into hydrogen and toluene at the dehydroge-
nation plant. The toluene is returned to Brunei, and the
extracted hydrogen is further used for power production. The
company intends to spread hydrogen transportation on a larger
scale by using the already available existing tankers in the next
commercial phase. It is designated as the world'sfirstglobal
hydrogen supply chain, which started in 2020 from Brunei
Darussalam to Japan. The pilot plant went through various
performance tests during the starting phase of nearly 18
months. The plant consisted of a tank of methylcyclohexane
with 20 m
3
volume, a hydrogen carrier. This tank can take up
10000 Nm
3
of hydrogen, as shown in Fig. 14 [133,134]. Also, it
was seen that the pilot plant reached a hydrogen production of
50 Nm
3
/hr with methylcyclohexane converting at 95% [135].
In 2021, Chiyoda went on tohave an alliance with the Port of
Rotterdam Authority to extend the company's technology of
hydrogen transportation to a global level. The aim is to increase
the import of hydrogen to 20 million tons by the year 2050 [136].
Hynertech Corporation
The Hynertech company started in China in the year 2014 by
keeping in mind that LOHC technology is an attractive and
emerging area in China. The company aimed to work on a
pilot project to store hydrogen in the LOHC, also called
hydrogen oil [137]. In Sept. 2016, the company demonstrated
fuel cell vehicles working on the LOHC technology. In the
demo plant, a tank volume of 10 m
3
was used, wherein a total
of 600 kg of hydrogen could be stored. The pictorial view of the
demo facility is given in Fig. 15. The refueling station linked
with the storage plant could provide hydrogen fuel to at least
25 buses daily. The hydrogen was generated using hydro-
electric power and further provided to a 30-kW fuel cell. The
LOHC technology by Hynertech can store hydrogen at 55e60 g/
L, which is very good compared to conventional gaseous
storage (39 g/L at 70 MPa) [130].
The company also planned to start two new pilot plants
based in Hubei, China, to produce the LOHC [138]. In an alli-
ance by Hynertech Corporation in 2017, the company agreed
to set up a plant to manufacture the material to be used in
LOHC technology. In 2018, the project's initial phase got
completed, and it was projected to produce nearly 1 million
tons of LOHC [139]. The demonstration of the concept to
convert waste to hydrogen oil took place in Dec. 2021. The
hydrogen generated for this purpose was generated using
waste energy from the city. The company further demon-
strated a waste to hydrogen oil conversion system [140].
Framatome
Framatome is recognized for nuclear plants and is a manu-
facturer of the components dealing with nuclear. In the year
2014, Framatome began testing a LOHC plant based on the
theme of the generation of hydrogen from power and back to
electric power generation using that hydrogen. The LOHC
used in the plant was H0-dibenzyltoulene and H18-
dibenzyltoulene. The company presented a test setup for the
technology at Arzberg, Germany. A 75-kW electrolyser pow-
ered by a solar PV plant was incorporated into the system to
produce hydrogen at 10e15 Nm
3
/hr. Further, the stored
hydrogen was dehydrogenated and provided to a 5 kW fuel
cell [131,141]. The LOHC storage, electrolyser, fuel cell and PV
plant are shown in Fig. 16.
HySA infrastructure, South Africa
Framatome also supplied demonstration units of varied sizes
for the research facility in HySA infrastructure based in South
Africa. Regarded as the first African LOHC demonstration unit,
the HySA programme supplied three types of units within the
span of 3 years between years 2016e2018, as mentioned [132].
Fig. 13 eThe LOHC-based plant developed by Hydrogenious GmbH [116].
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Small size units- Capacity of hydrogen storage: 6 Nm
3
/day
Medium size units- Capacity of hydrogen storage: 24 Nm
3
/
day
Large size units- Capacity of hydrogen storage: 94 Nm
3
/day
Fig. 17 shows the photograph of the medium-sized plant
with hydrogenation and dehydrogenation units which was
commissioned in August 2016. The HySA infrastructure pilot
plant is connected to the PV plant capacity of 55 kW and an
Fig. 14 e(a) Schematic representation of Chiyoda Cooperation for large-scale storage using LOHC, (b) The demonstration
SPERA hydrogen plant based in Japan and (c) methyl cyclohexane tank [133,134].
Fig. 15 eHynertech's energy storage plant based on LOHC technology for the buses running on fuel cells [130].
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electrolyser. The maximum operating temperature is around
300 C. Several tests and experiments were carried out to
investigate to use of dibenzyletoulene as LOHC in the pilot
plant. At present, the teams at HySA have a tie-up with a
European Union supported project to bring down the cost of
large scale LOHC technology to around 3 V/kg.
Solid state hydrogen storage (SSHS)
Hydrogen can be conveniently stored in a solid state by the
principle of physisorption [144,145] or chemisorption
[146,147]. Solid state storage methods consume less energy
compared to the gaseous or liquefied form of storage and are
potentially safer storage options [148]. Solid state hydrogen
storage methods can be broadly classified into two categories,
i.e., physisorption-based and chemisorption based. These
physisorption-based storage materials are characterized by
enormous surface area and pore volume [149]. Although these
physisorbents exhibit excellent hydrogen uptake/release ki-
netics and substantial reversible storage capacity, the prac-
tical application of such materials is limited by the need for
ultra-low temperature requirement (77 K) at 1 atm pressure
[150]. Metal hydrides (MH) are an example of chemisorbents
which offer outstanding hydrogen storage characteristics at a
broad range of temperatures and pressure [151]. MH materials
can be categorically divided into three groups based on the
type of hydrogen bonding, i.e., intermetallic, complex and
Fig. 16 e(a), (b) Photographs of the integrated PV plant, LHOC, electrolyser and fuel cell demonstration unit and (c) schematic
representation of the evaluation of important parameters of the test facility [142,143].
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chemical hydrides [152]. The advantages and disadvantages of
various solid state hydrogen storage materials are summa-
rized in Table 10.
The US Department of Energy (DOE) has defined system-
level gravimetric and volumetric hydrogen storage targets
on-board light-duty automotive applications. Till 2025, the
storage targets are 55 g-H
2
/kg-system (gravimetric) and 40 g-
H
2
/liter system (volumetric). The total useable hydrogen ca-
pacity is considered as 5.6 kg, which must be refuelled within
3e5 min. The shortcoming of interstitial metal hydrides is that
they comprise heavy elements, which limits their gravimetric
storage capacities (wt.% <3%). Partial substitution of these
interstitial hydrides with suitable elements can augment
hydrogen storage capacity; however, it would still be less than
the required DOE targets. Among the other SSHS materials, a
few complex hydrides, chemical hydrides and elemental hy-
drides (e.g., MgH
2
) can theoretically achieve the storage den-
sity targets, although these materials either have reaction
kinetics too sluggish, are thermally stable or irreversible and
fall short to meet the on-board refueling criteria [161]. Ther-
mal de-stabilization, nano-confinement and catalyst addition
are some of the adopted techniques to mend the suitability of
complex hydrides for on-board applications. On the other
hand, chemical hydrides are completely irreversible. For Mg-
based hydrides, surface modification (e.g., ball milling) and
catalyst doping are proven techniques to positively influence
the kinetics and lower the reaction heat [162].
System level development in MH based SSHS
Brookhaven National Laboratory is recognized to be one of the
forerunners in building and testing large-scale MH-based
storage units [163]. In 1974, they built and tested a 72 m
3
(STP)
capacity hydrogen storage unit based on 400 kg Fe-Ti alloy,
which was used for electricity generation from the fuel cell.
The MH storage unit was equipped with an internal heat
exchanger and operated in the temperature range of 15e45 C.
In 1980, Guinet et al. [164] designed and tested two macro-
Fig. 17 eThe pilot plant in the HySA infrastructure based in South Africa. (a) PV installations linked with LOHC, (b) the
hydrogenation unit of pilot plant and (c) dehydrogenation unit of pilot plant [132].
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scale hydrogen storage reservoirs of 2e15 kg (at STP) capacity
with FeTi and Mg
2
Cu alloys, respectively. These industrial-
scale storage vessels packed with 80e900 kg hydride alloys
were operated in the temperature range of 100e400 C. Coiled
copper tubes and finned heat pipes were engaged in the hy-
dride vessels for necessary thermal management during
charging and discharging. Suzuki et al. [165] manufactured
and performed experiments on low pressure (working pres-
sure <10 atm) stationary hydrogen storage (capacity 16 m
3
)
unit filled with 106 kg MmNi
4.5
Mn
0.5
. The charging-
discharging tests were carried out at 15e75 C in the oper-
ating pressure range of 3e8 atm. They reported a maximum
hydrogen discharge flow rate of 50 LPM. Bernauer and Halene
[166] reported the operation of an industrial-scale ultrapure
hydrogen generation cum storage plant of 2000 Nm
3
capacity.
The MH-based hydrogen storage plant utilized 10000 kg
Ti
0.98
Zr
0.02
V
0.49
Fe
0.09
Cr
0.05
Mn
1.5
. The unit could deliver the
rated hydrogen quantity within an hour with the provision for
suitable heat transfer administration. The potential use of MH
in the vehicular application was first conceived by Hoffman
et al. [167]. The proposed propulsion concept was to drive
hydrogen flow from an Mg hydride tank to a Fe-Ti hydride
tank utilizing the exhaust heat from the IC engine. However,
the concept was not successful as the waste heat was not able
to dissociate hydrogen from the highly stable Mg hydride.
Billings Energy Research Corporation conducted test runs on
transformed hydrogen vehicles, including Monte Carlo, Pon-
tiac Grand Ville and Winnebago minibus, by introducing Fe-Ti
hydride tanks on board [168].
Although normal cruising operation in these vehicles was
sustained by hydrogen released from the hydride tank, the
weight of the tank and risks of hydride contamination from
oxygen and vapour was a concern. In the Daimler-Benz hy-
dride project [169], the use of a tube-bundled storage unit was
described, which was designed to store 5 kg hydrogen for a
~100 km operational range. The overall weight of the Ti-Fe
alloy-based storage unit was 365 kg, within which 280 kg of
active material was loaded in three similar modules. Another
promising vehicular storage technology was proposed where
a combination of low-temperature (TiFe) and high-
temperature (Mg
2
Ni) hydrides would be utilized to cater to
hydrogen consumption at varied operating conditions. Later,
the use of laves phase hydride material Ti
0.98
Zr
0.02
V
0.49
Fe
0.09-
Cr
0.05
Mn
1.5
was reported in a number of tests in Diamler Benz
vehicles [170].
Miller and Barnes [171] reported the operation of a PEM
fuel-cell powered locomotive for underground operation uti-
lizing 213 kg C-15 alloy (composition: manganese, titanium,
zirconium, iron, and other constituents). The MH storage unit
could be recharged with approximately 3 kg hydrogen at 7 bar
pressures within 1 h. Bossi et al. [172] demonstrated the
applicability of an MH-based hydrogen storage unit linked to
an automatic power generation and supply unit comprising a
3-kW fuel cell, battery bank and inverter unit. Around 50 kg
LaNi
4.65
Al
0.35
powder was loaded inside 37 tubes (4
30 470 mm) to supply approximately 6 Nm
3
hydrogen. At a
charging pressure of 5.7 bar(g), the MH tank could be charged
within 70 min. It was estimated that an average rate of 1.4 kW
thermal energy would be needed to attain the standby state.
Varkaraki et al. [173] designed, fabricated and experimented
Table 10 eVarious solid state hydrogen storage materials and their storage standpoint.
Hydrogen storage material/
Representative candidate
Hydrogen storage
capacity (wt.%)
Operating temperature
and pressure
Advantages Disadvantages Ref.
Carbon Nanotubes (CNT)/K-doped
MWNTs
Up to 14 77e298 K, 1e100 bar Extremely high surface area, light weight,
tailorable characteristics
Requirement of cryogenic temperature
and/or high pressure
[153,154]
Activated carbon/Polypyrrole- derived
activated carbon
Up to 7 77e298 K, 20e60 bar Fast adsorption/desorption kinetics, low
cost
Requirement of cryogenic temperature
and/or high pressure
[155]
Metal Organic Framework (MOF)/DUT-
32
Up to 14 77e298 K, 1e100 bar High surface area, porosity, thermal
stability
Requirement of cryogenic temperature
and/or high pressure, moisture
instability
[156]
Covalent Organic Framework/COF-102 Up to 7 77e298 K, 1e100 bar Crystalline, large surface area, low
density, high stability
Requirement of cryogenic temperature
and/or high pressure
[149,157]
Zeolites/Na-X Up to 2.5 77e298 K, 1e100 bar Crystalline, ease of synthesis Low gravimetric capacity even at low
temp/high pressure
[158]
Polymers of Intrinsic Microporosity
(PIM)/OFP-3
Up to 3.9 77 K, 1e10 bar Light-weight, high thermal/chemical
stability
Low gravimetric capacity [159]
Intermetallic MH ~2 298e333 K, 1e30 bar Tailorable characteristics, near ambient
operation
High cost, Low gravimetric capacity [160]
Complex MH Up to 18.5 373e673K, 50e150 bar Lightweight, low cost, high gravimetric
capacity
Slow kinetics, multi-step desorption [152]
Chemical MH Up to 19 363e473 K, 1 bar High gravimetric capacity Irreversibility, sluggish kinetics, multi-
step decomposition, difficulty in
handling by-products
[152]
international journal of hydrogen energy xxx (xxxx) xxx24
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on an uninterrupted power supply unit comprising a fuel cell,
electrolyser and hydrogen storage unit based on MH
(LaMm
1x
Ce
x
Ni
5
alloy). The MH storage unit (1.9 kg hydrogen)
could feed a 5-kW fuel cell for 5 h. More and Hirose [102]
demonstrated the charging and discharging of a high-
pressure (350 bar) MH tank with a 7.3 kg hydrogen storage
capacity. The tank was constructed by means of carbon fibre
reinforced polymer with aluminium lining. The tank filled
with Ti
1.1
CrMn alloy weighed around 420 kg. With the use of a
vehicle-sized heat exchanger, the high-pressure tank could be
charged by 80% capacity within 5 min. Bevan et al. [174] per-
formed test runs on fuel cell-powered canal boats using MH
based hydrogen storage system. The storage unit comprised
eight tube bundle modules containing 30 kg Ti
0.93
Zr
0.05
(-
Mn
0.73
V
0.22
Fe
0.04
)
2
alloy each, which could provide approxi-
mately 4 kg useable hydrogen. Test results showed that the
hydrogen could be fed at a rate of 40 LPM to a 1 kW FC unit for
10 h, even at 9 C. Johnson et al. [175] demonstrated for the
first time a complex hydride-based hydrogen storage unit
following the automotive drive cycle. The modular storage
unit contained approximately 86 kg of sodium alanate in four
identical shell and tube containment, which could provide
3 kg of useable hydrogen. The storage unit could be refuelled
up to 3.2 wt% within 10 min, while a hydrogen delivery rate as
high as 2 g/s was reported. A 100 kg hydrogen storage tank
based on MgH
2
, linked to a 60-kW electrolyser was demon-
strated by McPhy Energy [176]. Parra et al. [177] demonstrated
a low-carbon hydrogen storage system where an MgH
2
tank
was utilized to store and deliver around 4 kg of hydrogen to
feed PEMFC. Kubo et al. [178] built and tested a 1000 Nm
3
ca-
pacity hydrogen storage tank utilizing 7.2 tons MmNi
4.4-
Mn
0.1
Co
0.5
. The large-sized MH tank (1800 3150 2145 mm)
could be charged and discharged at maximum rates of 70
Nm
3
/h and 30 NL/min at the operating temperature range of
25e35 C. Recently, a few off-the-grid hydrogen storage pro-
jects have been demonstrated by GKN [179]. These stand-
alone solid-state hydrogen storage modules installed were in
the capacity in the range of 8e25 kg.
Commercialized hydrogen storage solutions
Commercialized hydrogen storage modules were first made
available in late 1970 by Billings Energy Corporation [163]. The
storage canister was an aluminium cylinder (4¼110 mm)
without any internal heat exchanger. It was filled with TiFe
hydride, which could deliver 2500 StL hydrogen. In a similar
time frame, Ergenics Inc. marketed intermetallic compound-
based hydrogen storage canisters of capacity 28e2550 StL. At
present, several establishments offer solid-state hydrogen
storage solutions. HYSTORSYS [180] provides scalable MH
modules in the hydrogen storage capacity range of 21e252 kg.
These MH tanks can be charged below 30 bar(g), and hydrogen
can be discharged at 1e10 bar(g) while operating at 5e40 C.
GRZ Technologies [181] offers hydrogen storage modules of
12.5 kg capacity operating between 1.5 and 30 bar pressure
(discharge-refueling) in the operating temperature range of
-20-50 C. These modules can be charged and discharged at a
maximum flow rate of 150 NL/min at 20 C. H Bank Technol-
ogy Inc [182]. offers AB
5
type MH-based storage modules of
capacity 10 StL to 16500 StL. Hydrogen can be charged and
discharged from these modules using natural air convection/
water baths. Whole Win (Beijing) Materials Sci. &Tech. Co.,
Ltd [183]. provides solid-state hydrogen storage canisters in
the capacity range of 30e80000 StL of different containment
construction. Recently, MH hydride canisters are also
commercially made available by Hydro2Power SRL [184],
MAHYTEC [185], Hydreixa [186], H2GO power [187] etc.
There are numerous solid-state hydrogen storage solutions
available today. However, none of the solid-state hydrogen
storage materials known to date can simultaneously match all
the DOE hydrogen storage goals. Physically bound hydrogen
storage offers a large hydrogen storage capacity with modifi-
able pore surface area per unit volume. However, it usually
requires cryogenic temperature conditions and high pressure
for hydrogen release. On the other hand, chemically bound
hydrogen can release hydrogen in near ambient temperature
and pressure conditions, although gravimetric storage ca-
pacity and slothful reaction kinetics impede their application
in the automotive industry. Metal hydride based hydrogen
systems, in general, are very well fit for large-scale stationary
applications. At present research, efforts are underway to
improve the hydrogen desorption conditions as well as kinetic
limitations of solid-state storage hydrogen storage materials.
Global hydrogen transportation infrastructure
Based on the availability of renewable energy sources and
their intensity, the technological readiness of supporting
infrastructure and government policies at place, the produc-
tion of green hydrogen is more favourable in certain parts of
the globe compared to others. Countries like Australia, USA,
Morocco and Norway hold the potential to lead the future
hydrogen trade market owing to the availability of renewable
sources and necessary infrastructure. On the other hand,
countries like Japan, India, China, France, Spain and part of
the EU would have to rely on the import of renewable
hydrogen owing to majorly lack of land/sources (Japan, South
Korea, EU) or infrastructure (India). The current global
hydrogen consumption is highly concentrated around North
America, Europe and East Asia. The combined demand of
these nations is approximately 65% of the total demand [188].
The levelized cost of green hydrogen of a few countries are
given in Table 11, mentioning their policy strategy to trade
hydrogen (green/blue/grey) [189].
Hydrogen can be transported by means of trucks, tube
trailers, pipeline or ships. The preferred mode of trans-
portation counts on transfer volume as well as distance. Car-
rying hydrogen in the form of compressed gas in trucks (steel
tube trailer: 380 kg H
2
at 250 bar, composite cylinders:
560e900 kg H
2
at 500e700 bar) can be cost effective up to 400 km
at a transport cost of 0.55e0.75 USD/kg [190e192]. For distances
exceeding 400 km and till 4000 km, hydrogen transport is
typically done in liquefied state at the cost of 0.75e2.6 USD/kg
[192]. The usual weight of hydrogen transported by liquid
trailers is approximately 4000e4300 kg H
2
. Hydrogen distribu-
tion pipelines can be used to transport a large volume of
hydrogen 10e100 tonnes per day (tpd) cost effectively till
1800 km or so (<2 USD/kg). Transmission pipelines can convey
hydrogen at even larger flow rates of 100e10000 tpd up to a
international journal of hydrogen energy xxx (xxxx) xxx 25
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distance of 5000e7000 km at 0.05e2 USD/kg. The capital in-
vestment required to build new hydrogen pipeline infrastruc-
ture is quite high. The possibility of using existing gas pipelines
depends on technical challenges associated with hydrogen
embrittlement of material and leak through joints/walls and
hydrogen compression costs [193]. Transportation of hydrogen
across long distances would again depend on cost of transport.
For a very large volume of transport, say 1000e10000 tpd across
international borders (say 7000e10000 km), the transport cost
exceeds 2 USD/kg, with the preferred method being liquid
hydrogen carried in ships [192].
The very first liquefied hydrogen transportation using ship
has been recently demonstrated in the HySTRA project in 2022.
The ship equipped with a 1250 m
3
liquefied storage capacity,
and weighing approximately 8000 tonnes, travelled 9000 km
from the port of Hastings, Australia to the port of Kobe, Japan
[194].
Both compression and liquefaction being energy intensive
processes, molecules like ammonia, LOHC and methanol are
also considered as a potential hydrogen carrier. Ammonia has
a hydrogen storage density of 17.6 wt.% and is widely used as
fertilizer and chemical feedstock. However, extraction of
hydrogen from Ammonia requires huge energy (30.6 kJ/mol).
LOHC molecules like Methylcyclohexance (MCH) can store
6.1 wt.% hydrogen at ambient conditions, although dehydro-
genation of MCH requires 68e70 [kJ/mol] energy at 350 C.
Similarly, methanol has a hydrogen capacity of 12.5 wt.% in
ambient temperature, but the recovery of hydrogen requires
moderate energy input (16.6 kJ/mol) at 290 C. The approxi-
mate levelized cost of hydrogen production, conversion,
storage, shipping and reconversion for four hydrogen carriers,
including liquid hydrogen, Ammonia, MCH, and Methanol is
provided in Table 12 [195].
Ammonia (NH
3
) is a very important chemical commodity
which finds its application in fertilizer synthesis (urea, DAP),
textile manufacturing, explosives, refrigerant, etc. Today
ammonia is being considered as a technically viable and
economically feasible option for hydrogen storage and trans-
port [196]. The key advantages of utilizing ammonia as
hydrogen energy carrier are high volumetric density (17.6 wt
%), higher boiling point (BP:33.34 C) compared to liquefied
hydrogen, low flammability, and seasoned production and
utilization technology. However, the toxicity of ammonia is a
serious concern. Also, incomplete combustion of ammonia or
ammonia-based fuel blends leads to difficult ignition, low
flame speed, NO
x
formation, etc., which must be taken care of
when utilizing it as a fuel [197].
Storage of ammonia is easier compared to liquid hydrogen
owing to its higher BP and hence for long duration storage, it is
converted to liquid form by cooling below 33 C or by pres-
surizing to 10 bar at ambient temperature. Additionally,
higher BP ensures less boil-off losses. Liquefied ammonia
(107.7 kg-H
2
/m
3
) also holds more hydrogen compared to liq-
uefied hydrogen (70.8 kg-H
2
/m
3
) per unit volume [195]. To
retrieve hydrogen back from ammonia, high temperature
thermal cracking (800 C, 20 bar) is performed in presence of
Nickel catalyst. Also, to obtain pure hydrogen and utilize it in
fuel cells or automobiles, additional purification and recom-
pression system must be in place after thermal cracking/
reconversion. Thermal cracking is a very energy intensive
Table 11 eProjected levelized cost of green hydrogen for a few countries and their hydrogen trading emphasis [189].
Country Projected
levelized cost in 2030 (USD/kg)
Projected levelized
cost in 2050 (USD/kg)
Hydrogen
(renewable/non-renewable)
trading emphasis
South Korea 2.6 1.64 Import
Japan 2.41 1.63 Import
USA 1.4 0.88 e
Russia 1.81 1.11 Export
UK 1.61 1.11 Export
France 1.62 1.08 Export
Germany 1.7 0.99 Import
Canada 1.3 0.96 Export
Spain 1.29 0.89 Export
Australia 1.31 0.74 Export
Chile 1.29 0.7 Export
India 1.6 0.59 Export
Table 12 eApproximate minimum levelized cost of different stages of hydrogen supply chain for Hydrogen, Ammonia,
MCH and Methanol [195].
Fuel Hydrogen Ammonia MCH Methanol
Production Cost (USD/kg) >1>2.2 >1.35 >1.22
Conversion cost (USD/kg) 1.7-3.6 (liquefaction) 0.75-1.5 (liquefaction) NA NA
Storage cost (USD/kg) >4.57 0.5 NA NA
Shipping cost (USD/kg) 1.7e2.6 0.56e0.82 1.37e2.07 0.68e0.87
Reconversion cost (USD/kg) NA 0.3e1.6 0.54e1.22 0.43-1.12
(dehydrogenation) þ>0.6 (CCS)
Total cost (USD/kg) >8.97 >4.31 >3.26 >2.93
international journal of hydrogen energy xxx (xxxx) xxx26
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Table 13 eGlobal hydrogen policies and roadmap.
Country &
Reference
Hydrogen
Demand
Fund
Allocation
(USD)
Production Target Demand Area Focus on Import/
Export &Focused
H
2
Production
Means
Key Strategies
European
Union [200]
18.55 MTPA 630 billion 12-14 MMTPA by
2030
Industry (Steel,
Chemical &Refining)
and Transportation
e
Low carbon Blue/
Green
Strengthening economic and financial mecha-
nisms using regulatory and legislative measures
Standardising strategy and giving priority to R&D
initiatives
Direct investment for infrastructural development
by strengthening economic and financial
mechanisms
Japan [201,202] 2 MMTPA 664 million 3 MMTPA by 2030
&20 MMTPA by 2050
Passenger vehicle,
Heating and Power
Generation
Import Blue Building strategy for restricting price
Focus on R &D activities.
Moulding govt. policies and investing in hydrogen
infrastructure.
South Korea
[203,204]
220 KTPA 653 million 3.9 MMTPA by 2030 &
27 MMTPA by 2050
Transportation and
Power Generation
Import Grey/Blue/
Green
Building international strategies for incorporating
hydrogen energy economy.
Funding for infrastructural development and
transport facilities.
Encouraging R&D through projects and funding.
United
States [205]
10 MMTPA 15 billion eRefining,
Transportation,
Heating and Power
Generation
e
Low Carbon Blue/
Green/Others
Focus on R&D to control the hydrogen production
cost.
Investment in building hydrogen infrastructure
and economic strategy
Improving international collaborations on
hydrogen
Australia
[206]
650 KTPA 487 million eChemical,
Transportation and
Heating
Export Clean Blue/
Green
Framing international policies for hydrogen
export.
Building hydrogen export infrastructure using sea
routes.
Building international strategies for incorporating
hydrogen energy economy.
China [207] 20-25 MMTPA 150-200
billion
35 MMTPA by 2030 &
60 MMTPA by 2050.
Chemical,
Transportation and
Power Generation
Export Grey/Blue/
Green
Direct investment in infrastructural development
by strengthening economic and financial
mechanisms.
Focus on hydrogen export infrastructure.
Russia [208] 6.1 MMTPA 127 million 2 MMTPA by 2035 &
15e50 MMTPA by
2050
Transportation and
Power Generation
Export Blue/Green Focus on investing in infrastructure for hydrogen
distribution.
Focus on building hydrogen storage infrastructure.
India [189,209] 25-30 MMTPA 100 billion 5 million tonnes by
2030
Refining, Steel,
Transportation,
Heating and Power
Generation
Export Blue/Green Focus on building infrastructure for blue and green
hydrogen production
Implementing transportation facilities for smooth
and safe hydrogen transfer
Building national and international strategies to
upgrade hydrogen economy infrastructure.
international journal of hydrogen energy xxx (xxxx) xxx 27
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process and thereby, it limits the power to fuel to power effi-
ciency of ammonia as hydrogen carrier compared to liquid
hydrogen itself [197]. A similar analysis has been put forward
by Cui and Aziz [198], where they have analyzed ammonia and
methanol as hydrogen carriers under diverse techno-
economical operation settings. It was concluded that energy
efficiency of hydrogen transport can be retained in cases
where ammonia or methanol is directly used as a feedstock
rather than reconversion to hydrogen. Moreover, in their
study, the optimum levelized cost of hydrogen transportation
in the form of liquid ammonia was estimated to be USD 1879/
t-H
2
by marine transport using ship. Ammonia is usually
transported as liquid in LPG like tankers, vessels, trucks, rail,
and ships [199]. Ammonia can also be stored in solid form by
bonding ammonia with metal complexes with decent storage
capacity (~10 wt.%) [196].
Fig. 18 eSteps adopted to switch to the hydrogen energy economy.
Fig. 19 ePictorial view of (a) largest liquid H
2
storage tank made in India [210] and (b) green hydrogen plant installed at OIL,
Jorhat, Assam. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of
this article.)
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Fig. 20 eA projected road map for building Indian hydrogen infrastructure.
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Out of the four hydrogen shipping options tabulated above,
it is quite evident that transporting methanol and MCH would
be the most economical choices, followed by ammonia and
liquid hydrogen. However, if the effective amount of hydrogen
transported across several thousand km is considered,
transporting hydrogen in the form of liquid ammonia would
be the best choice. Again the choice of hydrogen transport
vector would depend on many allied factors like availability of
infrastructure for hydrogen re-conversion, public awareness,
toxicity, hazards, regulatory mandates, etc.
Global hydrogen energy structure
Countries from all around the world have realised the fact that
there is no other way to restrict the global temperature rise to
1.5 C other than switching to renewable or carbon-free en-
ergy use. Hydrogen has been projected as an excellent alter-
native because of its multiple benefits and high energy
density. Strategic funding is being pumped into research and
infrastructure related to production, usage, export, import,
research, etc., for adopting the hydrogen energy economy as
the ultimate choice. In order to grow hydrogen and support
infrastructure to achieve import/export targets, the roadmap
of different countries is summarized in Table 13.
Hydrogen storage infrastructure: an Indian perspective
Like other countries, India is also accelerating the develop-
ment of hydrogen infrastructure to switch to a hydrogen
economy in the coming future. India plans to use hydrogen as
a future fuel and feedstock for automobiles and industries.
India has adopted a progressive step to do so, which is
depicted in Fig. 18 [209].
Recently an Indian multinational company INOXCVA
manufactured and released one of the largest liquid hydro-
gens storage tanks with a storage capacity of 238 m
3
. The tank
has been designed and made as per Korean gas safety stan-
dards and has been set as a demonstration project in South
Korea.
The first-of-its-kind hydrogen storage tank was manufac-
tured at the INOXCVA Kandla facility in Gujarat. The pictorial
view of the hydrogen storage tank is depicted in Fig. 19a.
Recently, Oil India Limited (OIL) commissioned India's first
green hydrogen plant with a production capacity of 10 kg per
day. The plant is located at Jorhat, Assam. The hydrogen is
produced using a 500 kW capacity solar power plant coupled
with AEM Electrolyser. The hydrogen produced is stored in the
compressed hydrogen cylinders at 150 bar. However, the
compression process is carried out using a mechanical
compressor. The pictorial view of the plant is depicted in
Fig. 19b.
NTPC with Bloom Energy India has also drawn a roadmap
to set Indian first green hydrogen microgrid at Vizag. The
hydrogen production will be carried out using 240 kW SOE,
which will take its power input from floating solar panels. The
hydrogen will be produced during day time (sunshine hours)
and will be stored in compressed form [211].
The key players working on building hydrogen storage
infrastructure in India are.
Air Liquide
INOX air product
Praxair
Larsen &Toubro Ltd. Tie-up with Eden (an Australian
company)
Linde (through BOC India)
Adani Group
Reliance Industries
In the NITI Aayog report [209], a key action plan is set on
green hydrogen production, storage and utilization in the
various sectors. On the basis of these key points, a roadmap is
projected for implementing a hydrogen economy in India. The
projected roadmap is depicted in Fig. 20.
Conclusions
Hydrogen as a clean fuel has wide applications due to its high
energy density, multiple production routes and ease of inte-
gration to renewable energy supply chain. This work exten-
sively reviewed the technologies available to store hydrogen
on a large scale. Particular emphasis is given to the recent
industrial-level developments in the field of hydrogen storage.
The major conclusions derived from the above sections can be
summarized as follows.
The selection of the right material for CGH
2
tanks is of vital
importance. In the case of type-III tanks, hydrogen comes
into direct contact with metallic parts, leading to a high
possibility of corrosion and embrittlement. Type-IV tanks
do not involve direct contact between hydrogen and metal
liners and are safe from corrosion. However, the issue in
type-IV tanks is that of permeation, especially at the high
working pressures involved. Temperature fluctuations in
type-IV tanks also pose a major design challenge, as most
mechanical properties of materials are thermally sensitive.
Rapid charging and discharging of tanks lead to tremen-
dous temperature changes (Joule-Thomson effect) that are
cyclic in nature. During charging, pressurization causes the
temperature within the tank to rise up to 80 C at 700 bar,
while in the reverse process, the temperature can drop to
0C leading to fatigue.
The system cost was reduced from USD 14.75/kWh to USD
14.19/kWh, with major reductions observed in carbon fiber,
a resin used for winding, and equipment capital costs. A
reduction in carbon fiber cost could lead to a further
reduction in cost by more than 40%. While the data pro-
jected above is for a production volume of 500 k/year, if the
production volume increases further, the costs can be
brought down. Most car manufacturers, for instance,
Maruti Suzuki and Hyundai, produce around 500 k units in
India. However, their combined requirement for type-IV
tanks would be higher if they produce FCEVs. This would,
in turn, bring down the carbon fiber and other raw material
costs significantly, leading to significant growth in com-
pressed gas hydrogen storage and application.
Underground storage of hydrogen is a promising technique
for large-scale hydrogen storage. Conducting an extensive
geological and economic study before site selection is
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essential. Despite many challenges, underground
hydrogen storage (UHS) can be explored as an imminent
hydrogen storage option. This is especially true in light of
the growing market share of renewable energy resources,
which need to be bolstered by a robust energy storage
solution.
Despite growing global interest in liquid hydrogen storage,
a few issues (i.e., Boil-off losses, Maximum allowable
working pressure, energy-intensivity) need to be consid-
ered for effective system design. Therefore, a proper choice
of liquefaction technique must be made based on the
design capacity and operating conditions. The hydrogen
that blows off is already at a lower temperature. In order to
save a significant quantity of energy, this component
might be handled carefully.
The LOHC technology is considered to be promising
compared to other chemical hydride-based storage
methods such as methanol, ammonia and formic acid.
LOHC technology is found to be a very competitive tech-
nology compared to the other conventional storage
methods to store hydrogen at a large scale and for a longer
duration. The ability of this technology to merge with the
existing industrial infrastructure is a significant advantage.
Many enterprises are promoting LOHC technology as a
promising way to establish a hydrogen-oriented economy
for a sustainable future.
Solid-state hydrogen storage materials available to date
cannot simultaneously match all the DOE hydrogen stor-
age goals. However, Metal hydride-based hydrogen sys-
tems generally are a very good fit for large-scale stationary
applications. At present research, efforts are underway to
improve the hydrogen desorption conditions and kinetic
limitations of solid-state storage hydrogen storage
materials.
The ideal hydrogen carrier for long distance transport
(inter-continental or maritime shipping) can be
ammonia, methanol, or LOHC (e.g., toluene, MCH) as
these chemical compounds can be liquefied at a lower
cost than that of hydrogen or naturally occurs in liquid
state like LOHC. Supply chain statistics show methanol
and MCH could be most inexpensive choices for hydrogen
carrier followed by ammonia and liquefied hydrogen. It
was also revealed that the energy efficiency of hydrogen
transport may be upheld when ammonia or methanol is
used directly as a feedstock rather than being converted
to hydrogen.
Declaration of Competing Interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
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