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Hydrogen the future transportation fuel: From


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Article in Renewable and Sustainable Energy Reviews March 2015


DOI: 10.1016/j.rser.2014.11.093

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Renewable and Sustainable Energy Reviews 43 (2015) 11511158

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews


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

Hydrogen the future transportation fuel: From production


to applications
Sunita Sharma a,n, Sib Krishna Ghoshal b
a
Department of Applied Sciences, ITM University, Gurgaon, India
b
Department of Physics, AOMRG, Universiti Tecknologi Malaysia, Skudai 81310, Johor, Malaysia

art ic l e i nf o a b s t r a c t

Article history: Transportation of people and commodities being a socio-economic criterion needs clean energy and the
Received 12 December 2013 demand is kept on increasing with modernization. Consequently, generation of a fuel with safer,
Received in revised form efcient, economic and reasonably environmental friendly features is the key issue towards fullling
14 November 2014
such demands. Hydrogen seems to be an ideal synthetic energy carrier due to its lightweight, exclusive
Accepted 25 November 2014
abundance and environmentally benign oxidation product (water). However, storage remains a big
challenge. In this communication, recent developments in the production of hydrogen fuel, applications
Keywords: and storage together with the environmental impacts of hydrogen as energy carrier are emphasized.
Alternate fuel & 2014 Elsevier Ltd. All rights reserved.
Electrolysis
Hydrogen storage

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1151
2. Applications of hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1152
3. Hydrogen production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1152
3.1. Steam methane reforming. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1152
3.2. Gasication of coal and other hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1152
3.3. Electrolysis of water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1153
3.4. Hydrogen from biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1154
3.5. Hydrogen from nuclear energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1154
4. Hydrogen economy for transportation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1154
5. Benets and deciencies of hydrogen in transportation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1155
6. Hazard and safety issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1155
7. Hydrogen storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1156
8. Future aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1157
9. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1157
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1157
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1157

1. Introduction terawatt (TW) of carbon-free power need to be produced by the


mid-century [2]. The dramatic increase in the petroleum price, the
Undoubtedly, the global demand of enhanced energy produc- limited reserve of fossil fuels, the increased environmental worries
tion and environmental concerns are the mostly cited signicant related to greenhouse gas (GHG) emissions and global warming,
issues in the 21st century [1]. In order to satisfy the worlds the decay in overall human health and safety considerations
growing appetite for energy by keeping our planet safe, at least 10 enforced to search for alternative energy sources to power the
motor vehicles worldwide [3].
A signicant part of the world total energy being consumed by
n
Corresponding author. the transportation machineries [4] lead to the emission of harmful
E-mail address: sunphotonics@gmail.com (S. Sharma). gases in the atmosphere [5]. Presently, a large portion ( 65%) of

http://dx.doi.org/10.1016/j.rser.2014.11.093
1364-0321/& 2014 Elsevier Ltd. All rights reserved.
1152 S. Sharma, S.K. Ghoshal / Renewable and Sustainable Energy Reviews 43 (2015) 11511158

the global energy demand is met by the uid fossil fuels due their to liquid (GTL) synthesis technology, rocket fuel, IC engine fuel,
easy availability and convenient use. However, the fossil fuel high temperature industrial furnaces fuel etc. to cite a few [23].
production will gradually decrease over time [6]. Road vehicles Primarily, hydrogen is consumed for production of ammonia, other
consumes about half the globally produced oil [7]. By 2050, the chemicals and in petro-chemistry. Out of the total 500 billion cubic
projected global energy demand will be double or triple and the meter (Bm3) of hydrogen, ammonia production alone consumes
oil and gas supply is unlikely to be able to meet this requirement. 250 Bm3 followed by the production of other chemical products
Hydrogen and fuel cells are considered in many countries as an which consume about 65 Bm3, and petro-chemistry consume
important alternative energy vector for future sustainable energy 185 Bm3 of hydrogen, accounting for 50, 13 and 37%, respectively
systems in the stationary power, transportation, industrial and [7,23]. A recent report exploring various application of hydrogen
residential sectors [8]. afrms its signicant implications towards electricity generation,
Considering the altitude of local air pollution, climate change, cooking food, fuel for automobiles, hydrogen powered industries,
congestion, land use, accidents, and noise level, the current jet planes, hydrogen village and on the top for all our domestic
transportation systems will no longer remain sustainable. In the energy requirements [12].
mounting metro cities worldwide, local air pollution from road
transport is becoming an alarming issue for urban air quality. GHG
emissions from vehicles and fuel production are the other major
3. Hydrogen production
concern. In the near future, a continual increase in the GHG
emissions from the transport sector is predicted. The main reason
Hydrogen can be produced from varieties of feedstock includ-
for it is increasing global demand for fuel [5]. It is established that
ing fossil and renewable resources. As illustrated in Fig. 1, several
the burning of fossil fuels is responsible for the increased carbon
process technologies such as chemical, biological, electrolytic,
dioxide levels in the atmosphere (  3  1012 kg C/year) [9]. An
photolytic and thermo-chemical can be used for hydrogen produc-
increase in the average temperature on earth is caused by the
tion [24]. A detailed overview of diverse hydrogen production
dissolution of carbon dioxide in the oceans. Furthermore, the
technologies are reported by Holladay et al. [13]. Common hydro-
ocean water solubility of carbon dioxide gets decreased (  3%/K)
gen production methods include.
with the increase of water temperature. Once the average tem-
perature of the oceans is increased up to an optimum limit, then
the carbon dioxide solubility equilibrium between atmosphere 3.1. Steam methane reforming
and ocean will be shifted towards the atmosphere. Consequently,
this will lead an additional increase of the greenhouse gas in the Steam methane reforming (SMR) is a process in which the
atmosphere [10]. natural gas or other methane stream, such as biogas or landll gas
The exploitation of hydrogen as the energy carrier in different reacts with steam in the presence of a catalyst to produce
sectors in avoiding the emission of harmful gases remains highly hydrogen and carbon dioxide. According to DOE of USA (2010),
debatable. However, it is not cost-effective at present. Many SMR is approximately 72% efcient in hydrogen generation when
solutions for hydrogen supply are likely to emerge depending on starting with natural gas. Conversely, on a lower heating value
level of demand, resource availability, geographic factors and basis [25] SMR produces a hydrogen rich gas that is typically on
progress on hydrogen technologies. Initially, utilization of hydro- the order of 7075% hydrogen on a dry mass basis, along with
gen should develop in large cities having air pollution problems or smaller amounts of methane (26%), carbon monoxide (710%),
island nations with high imported fuel costs. and carbon dioxide (614%) [26].
This review examines the possible applications of hydrogen, its It is worth mentioning that, natural gas reforming produces
various production methods, and usage in different sectors parti- about half of the global supply of hydrogen and remains the most
cularly in transport, possible paths forward and the issues asso- commonly used method for hydrogen production [11,2729].
ciated with a transition toward large-scale exploitation. The However, it is not an attractive production route for mature
economics of hydrogen application in transport sector, actions hydrogen economy. This is due to the fact that order-of magnitude
and policies that might be needed for successful development of increase in demand would deplete our nite reserves. Moreover,
hydrogen energy systems are also emphasized. the concentration of gas reserves in relatively few regions of the
world could lead to geopolitical tension and unstable supplies.
Environmental impact is also a major concern because reforming
2. Applications of hydrogen natural gas to hydrogen produces as much pollution and CO2 as
burning the natural gas directly. Generation of hydrogen from
Majority of the recent literature [7,1115] focuses on the natural gas is a well established process. If sufcient quantities are
applications of hydrogen in every part of our social life including produced to power the worlds cars and light trucks it would strain
industrial, domestic or space. Generally, hydrogen is primarily the worlds supply of conventional methane, making natural gas as
used in petroleum rening [16,17], ammonia production [18,19] geopolitically sensitive as oil [30].
and, to a lesser extent, metal rening such as nickel, tungsten,
molybdenum, copper, zinc, uranium and lead [20,21]. It amounts
to more than 50 million metric tonnes worldwide in 2006 [22,14]. 3.2. Gasication of coal and other hydrocarbons
In the future, hydrogen is likely to be used as fuel in almost all
applications where fossil fuels are used today. For transportation The partial oxidation (POX) process termed as gasication,
in particular, hydrogen would offer immediate benets in terms of generates hydrogen from a wide range of hydrocarbon fuels,
reduced pollution and cleaner environment [11]. including coal, heavy residual oils, and low-value renery pro-
Hydrogen is being majorly used for synthesis of ammonia and ducts. In this process, the hydrocarbon fuel is made to react with
other nitrogenated fertilizers, rening and desulphurization oxygen in a less than stoichiometric ratio, yielding a mixture of
(hydrogenation reactions, hydrodesulphurization), hydrogenation carbon monoxide and hydrogen at 1200 to 1350 1C [25]. The
of hazardous wastes (dioxins, PCBs), chemical plants, food pre- production of hydrogen is dominated mainly by reforming of
paration, synthesis of methanol, ethanol, dimethyl ether (DME), natural gas and heavy oil, gasication of coal, heavy oil and
alternative fuels synthesis by FischerTropsch (FT) synthesis, gas petroleum coke [14].
S. Sharma, S.K. Ghoshal / Renewable and Sustainable Energy Reviews 43 (2015) 11511158 1153

Fig. 1. Hydrogen as an energy carrier linking multiple production methods and sources to various fuel cell applications (Adapted from Karl Harrison, University of Oxford) [8].

3.3. Electrolysis of water an electrolyser device. The two most common types of electro-
lysers are alkaline that uses a potassium hydroxide electrolyte and
Electrolysis is the process where water molecules are split PEM which employs a solid polymer membrane electrolyte. Hydro-
directly into hydrogen and oxygen molecules using electricity and gen can be produced via electrolysis of water. Electrolysis is
1154 S. Sharma, S.K. Ghoshal / Renewable and Sustainable Energy Reviews 43 (2015) 11511158

currently performed from a few kW up to 2000 kW per electrolyser. during the acidogenic phase of anaerobic digestion of organic
The electrolysis reaction creates pure oxygen as a by-product along material, photo-fermentative processes, two stages dark/fermentative,
with pure hydrogen [25]. In contrast, a photo-electro-chemical and hydrogen production by water-gas shift [13]. Hydrogen can also
water-splitting process is a zero emission process and uses free be produced from high temperature fuel cells [25].
solar energy [28]. Balat et al. acknowledged that natural gas to be the major
Based on the estimated cost ranges by the National Academy of source of hydrogen production accounting 48% of the total share,
Sciences/Engineering and the US Department of Energy (with oil being the second with 30% followed by coal with 18% and
close agreement), grid power electrolysis in the US would produce electrolysis contributing 4% of the total share [7]. Petros et al.
hydrogen at delivered costs of $67/kilogram (kg) at present, with compared seven hydrogen production methods namely steam
future potential of about $4/kg. Alternately, the wind electrolysis- methane reforming (SMR), partial oxidation of hydrocarbons
derived hydrogen would cost about $711/kg at present, with (POX), coal gasication (CG), biomass gasication (BG), the photo-
future potential delivered costs of $34/kg, including the full costs voltaicelectrolysis system (PVEL), the wind turbineelectrolysis
of production from the wind power system. Meanwhile, the solar system (WEL), the hydropowerelectrolysis system (HEL) with
hydrogen splitting would be more expensive, on the order of $10 respect to ve criteria-CO2 emissions. These criteria are based on
30/kg at present, with future delivered costs of $34/kg [25]. the cost of operation and maintenance (O&M), capital, feedstock
Although, the advantages in producing extremely pure hydro- and hydrogen production. Using Analytical Hierarchy Process
gen/oxygen via water electrolysis is known for around two (AHP) it is shown that in the majority of cases the processes that
centuries [29,30], however its applications are still limited to combine renewable energy sources with electrolysis (PVEL, WEL
small scale and for unique situations where access to large scale and HEL) are found to be better than the conventional processes
hydrogen production plants is not possible or economical, such as (SMR, POX, CG and BG) and are higher in ranking. On the contrary,
marine, rockets, spacecrafts, electronic industry and food industry the conventional hydrogen production processes (SMR, POX, CG
as well in medical elds. Presently, water electrolysis represents and BG) rank last in most of the cases. More specically, in most of
only 4% of the world hydrogen production [14,31,32]. the cases (9 out of 15), the rst ranking in hydrogen production
process is the hydropowerelectrolysis system (HEL) and the
3.4. Hydrogen from biomass worst (9 out of 15) is coal gasication (CG) [47].
Today, natural gas reforms, coal gasication and water electro-
Biomass conversion technologies are divided into two cate- lysis being proven technologies for hydrogen production are applied
gories: thermo-chemical and biochemical processes. Thermo- on an industrial scale worldwide. Steam reforming of natural gas is
chemical processes tend to be less expensive because they can the most used process in the chemical and petro-chemical indus-
be operated at higher temperatures and therefore achieve higher tries. It is currently the cheapest production method and has the
reaction rates. They involve either gasication or pyrolysis (heat- lowest CO2 emissions of all fossil fuel generation routes. However,
ing biomass in the absence of oxygen) to produce a hydrogen-rich electrolysis is more expensive and only practical if high-purity
stream of gas known as syngas (a blend of hydrogen and carbon hydrogen is required. With an assumed escalation in natural gas
monoxide) [25]. prices, coal gasication is expected to become the utmost econom-
Hydrogen can also be produced from bio-renewable feedstock ical option from around 2030 onwards. Alternately, biomass gasi-
via thermo-chemical conversion processes such as pyrolysis, gasi- cation for hydrogen production is still at infancy now. It is expected
cation, steam gasication, steam reforming of bio-oils, and super- to become the cheapest renewable hydrogen supply option in the
critical water gasication of biomass. Gasication of biomass has coming decades although biomass has restricted potential and
been identied as a possible system for generating renewable competes with other biofuels as well as heat and power generation.
hydrogen. This is benecial to exploit biomass resources, to develop Biomass gasication is applied in small decentralised plants during
a highly efcient clean way for large-scale hydrogen production. the early phase of infrastructure rollout and in centralised plants in
Thus, is has less dependence on insecure fossil energy sources [3]. later periods. Steam reformers and electrolysers can also be scaled
Several of the processes available to make hydrogen from biomass down and implemented on-site at fuelling stations (although still
can yield other useful outputs such as adhesives, carbon black, more expensive), while coal gasication or nuclear energy are for
activated carbon, polymers, fertilizers, ethanol, various acids, large-scale, central production only and therefore restricted to later
FischerTropsch diesel fuel, waxes, and methanol [33]. phases with high hydrogen demand [5]. The energy security and
environmental aspects of various hydrogen production methods
3.5. Hydrogen from nuclear energy have been discussed by Herzog [33].

Hydrogen production is possible via various nuclear energy


based schemes. These include nuclear thermal conversion of water 4. Hydrogen economy for transportation
using various chemical processes such as the sodiumiodine cycle,
electrolysis of water using nuclear power. Furthermore, high- Renewable energy sources (e.g. wind, tidal and biomass) might
temperature electrolysis that also uses nuclear system waste heat provide hydrogen locally, but certainly will not match the volumes
to lower the electricity required for electrolysis [34]. While the use of global hydrogen requirement [8]. In the rst place, renewable
of nuclear energy for hydrogen production is attractive from pathways for producing hydrogen avoid global warming pollution.
carbon-limiting perspective, it raises other serious environmental Finally, depending on the viability of carbon capture and storage, it
and health concerns related to the mining and processing of may therefore prove more prospective. However, these options are
uranium, the potential for accidents, the management and dis- generally more expensive at present [33]. Yet, even with the
posal of radioactive waste [33]. included costs of CO2 recovery and sequestration, hydrogen
In the past, research in the area of bio-hydrogen has substantially production from fossil fuels is estimated to be much less expensive
been enhanced due to increased attention towards sustainable than electrolytic hydrogen in large-scale markets [48]. A recent
development and waste management [13,3546]. The main biopro- report from US Department of Energy indicated that solar is most
cess technologies used for bio-hydrogen production include: photo- likely the only source of renewable energy which is capable of
lytic hydrogen production from water by green algae or cyanobacteria producing enough hydrogen required to supply a hydrogen econ-
(also called direct photolysis), dark-fermentative hydrogen production omy [8].
S. Sharma, S.K. Ghoshal / Renewable and Sustainable Energy Reviews 43 (2015) 11511158 1155

Full benets of hydrogen as a clean, versatile, and efcient fuel Hydrogen is a non-toxic, clean energy carrier that has a high
may be realized only if hydrogen is produced from renewable specic energy on a mass basis. In other words, the energy content
energy sources. Likewise, hydrogen may be generated from renew- of 9.5 kg of hydrogen is equivalent to that of 25 kg of gasoline [54].
able energy sources through a variety of pathways and methods, According to Balat et al. [7], physical and chemical properties of
but only a few of them are commercially viable today [11]. hydrogen in comparison to gasoline and methane exhibit wide
Favourable economics can also be achieved by integrating the range of ammability. Therefore, hydrogen engines can be oper-
production of hydrogen with the creation of electricity and other ated more effectively on excessively lean mixtures than gasoline
valuable co-products. For instance, coupling electrolysers with engines. As little as 4% hydrogen by volume mixed with air can
renewable electricity generators could provide a means of storing produce a combustible mixture. Hydrogen possesses much lower
intermittent wind or solar power that becomes available during ignition energy (0.02 MJ), greater diffusivity and higher ignition
off-peak hours when it would otherwise have little value [33]. temperature compared to the other fuels. Unlike many other fuels,
Currently, the cost of hydrogen is more than twice as much as that hydrogen is detonable over a very wide range of concentrations
of diesel and petrol. Substantial progress is needed to make when conned and is very difcult to detonate if unconned. The
environmentally sustainable hydrogen production pathways speed of hydrogen ame is nearly an order of magnitude higher
which are cost-competitive with petroleum fuels. Even by assum- than that of gasoline. Compared to gasoline, the reasonably greater
ing that hydrogen powered vehicles will be signicantly more ability of hydrogen to disperse in air makes it advantageous. This
efcient than their conventional gasoline-powered counterparts enhanced dispersion is majorly attributed to: (1) the ease forma-
[23,33]. tion of a uniform mixture of fuel and air, and (2) the rapid
Right now, the utilization of hydrogen is governed by economic dispersion of hydrogen when leak develops. Thus, unsafe condi-
arguments instead of energetic considerations. Electrical energy is tions have to be either avoided or minimized. The possession of
transferred to hydrogen in electrolysis of water. The production, very low density of hydrogen results two problems when used in
storage and transfer of hydrogen necessitate high-grade electrical an internal combustion engine. They are: (1) a very large volume is
energy. Hydrogen competes with grid electricity for stationary necessary to store enough hydrogen to give a vehicle an adequate
applications. Truly, hydrogen economy can be established only if it driving range, and (2) the energy density of a hydrogenair
is energetically cost-effective. Subsequently, it will affect the entire mixture, and hence the power output, is reduced [7].
energy supply and distribution system. An estimation of the Diverse processes that convert various fuels to other forms of
energy for production, packaging, transport, storage and transfer energy at the user end are reported by Nejat et al. [6]. It is clearly
of pure hydrogen is required to operate a hydrogen economy. The demonstrated that all other fuels except hydrogen can be con-
relative energy consumption associated with the delivery of verted to energy through combustion only. However, hydrogen
pressurized hydrogen is unacceptable in comparison to other can be converted to other forms of energy in ve different ways:
liquid fuels such as methanol, gasoline etc. For the delivery of (1) directly to steam, (2) to heat through catalytic combustion,
same amount of gaseous hydrogen about thirty two times more (3) acting as a heat source and/or heat sink through various
diesel fuel is required than in case of liquid gasoline. However, chemical reactions, (4) to ame combustion and (4) through
fairly less amount of diesel is needed for liquid hydrogen. Never- electrochemical processes directly to electricity. In nutshell, hydro-
theless, the liquefaction of hydrogen requires enormous amount of gen is the most versatile fuel [6].
energy [49,50]. The higher heat of combustion feature of hydrogen compared
to other fuels such as petroleum, parafn, graphite (coal), castor
oil, wood, makes it a promising fuel [12]. It is expected that
5. Benets and deciencies of hydrogen in transportation emissions of CO2 will reach 8.210.0 Gt around 2020 and the
global climate change due to this emissions is possibly the most
Lately, with ever increasing energy costs owing to the dwind- important environmental problem that human beings have ever
ling availability of oil reserves, production and supply, concerns faced [55]. Hydrogen powered vehicles are zero emission devices
with global warming and climate change blamed on man-made at the point of use, with consequential local air quality benets.
CO2 emissions associated with the use of fossil fuel (particularly Hydrogen powered fuel cells could contribute to reducing or
coal), hydrogen has become very popular. Hydrogen is highly eliminating emissions of CO2 and other greenhouse gases from
benecial for countless reasons: (1) it is perceived as a clean fuel, road transportation vehicles [3,5]. Hereafter, hydrogen powered
emits almost nothing other than water at the point of use; (2) it energy systems appear to be an attractive future alternative to
can be produced using any energy sources, with renewable energy current fossil fuel-based energy systems [3].
being most attractive; (3) it works with fuel cells and together may
serve as one of the solutions to the sustainable energy supply and
(4) use puzzle in the long run, so-called hydrogen economy [14].
Hydrogen has the highest specic energy content of all con- 6. Hazard and safety issues
ventional fuels and is the most abundant element in the universe
[3,7]. It possesses a high energy yield of 122 kJ/g, which is 2.75 Nejat et al. [6] demonstrated that hydrogen being low density
times larger than hydrocarbon fuels [51]. Liquid hydrogen pos- and high diffusion coefcient are far safer than other fuels. More-
sesses very density of 0.07 g/cm3 which is one tenth of gasoline. over, higher specic heat of hydrogen efciently slows down the
These properties qualify both advantages and disadvantages to temperature increase for a given heat input. Generally, wider
hydrogen. The advantage is that hydrogen stores approximately ignition limits, lower energies and temperatures for ignition make
2.6 times more energy per unit mass than gasoline, implying that a fuel less safe, as they increase the extent of re commencement.
hydrogen is more energy efcient than gasoline. Conversely, the A fuel is considered to be less safe if it possesses higher ame
disadvantage is that it needs an estimated 4 times more volume temperature, explosion energy and ame emissivity, because its
than gasoline to store that energy. It is demonstrated that a 15 re would be more damaging. A comparison on the safety aspects
gallon tank of gasoline that stores 90 pounds of gasoline has an of gasoline and methane with hydrogen revealed that hydrogen
equivalent energy output of a 60 gallon tank of hydrogen that was the safest fuel with a safety factor of 1. The safety factor of
stores only 34 pounds of hydrogen [23,52,53]. This clearly indi- methane and gasoline are determined to be 0.8 and 0.53, respec-
cates that hydrogen storing remains a severe challenge. tively [6].
1156 S. Sharma, S.K. Ghoshal / Renewable and Sustainable Energy Reviews 43 (2015) 11511158

Hydrogen gas being very light (density  6.9% of air) is more The volumetric and gravimetric density of hydrogen in a storage
diffusive than air (by 4 times) and gasoline (by 12 times). There- material is crucial for mobile and stationary applications. It can be
fore, a hydrogen leak rapidly dissipates as it rises from its source, stored by using following different methods and phenomena: (1)
reducing the risk of re or explosion. Due to its non-toxicity, a high-pressure gas cylinders (up to 800 bar), (2) liquid hydrogen in
hydrogen leak would not cause environmental damage. In a cryogenic tanks (at 21 K), (3) adsorbed hydrogen on materials with
conned space, hydrogen could lead to re or explosion if mixed a large specic surface area (at To100 K), (4) absorbed on inter-
with air. Any re started would burn out quickly as the hydrogen stitial sites in a host metal (at ambient pressure and temperature),
gets dissipated. It is difcult to make a hydrogenair mix explo- (5) chemically bonded in covalent and ionic compounds (at ambient
sion. A transient spark can set it off but in open air it will burn pressure), or (6) through oxidation of reactive metals, e.g. Li, Na, Mg,
rather than explode. Hydrogen driven vehicles are found to have Al, Zn with water [10]. The method for storing hydrogen and their
lower risks than petrol vehicles in conned spaces because petrol general use is described by Balat et al. [7]. Pipelines are also used for
leaks often create a larger cloud of ammable gas. Hydrogen onsite storage of hydrogen. Piping systems are usually several miles
blazes having little radiation of heat do not burn anything unless long, and in some cases may be hundreds of miles long. Because of
it is placed immediately next to the ame. Another safety the great length and therefore excessive volume of these piping
advantage of hydrogen is associated with its clear ame that systems, a slight change in the operating pressure of a pipeline
cannot sear skin at a distance. This is because of the little thermal system can result in a large change in the amount of gas contained
radiation emitted by the ame due its lack of soot content. within the piping network. Minor alterations in operating pressure
Furthermore, hydrogen storage containers being much tougher within the pipeline can be made to handle uctuations in supply
than petrol tanks are less likely to cause a big leak [19]. Not only and demand, avoiding the cost of onsite storage [59].
this, hydrogen can be safely transported in pipelines. Nonetheless, Various hydrogen storage options for mobile applications is
when mixed with air, hydrogen can burn in lower concentrations reviewed by Schlapbach and Andreas. Conventional Hydrogen
and this can cause safety concerns [55]. storage, Hydrogen adsorption on solids of large surface area,
Hydrogen storage by metal hydrides, alanates and other light
hydrides are emphasized [53]. Jain reports on various hydrogen
storage devices include metal hydrides, complex hydrides, carbon
7. Hydrogen storage nanotubes, glass spheres, zeolites and chemical storage [12].
Hydrogen storage is one of the major issues affecting the future
Hydrogen storage being the most critical issue must be solved hydrogen economy. The traditional hydrogen storage facilities,
before establishing a technically and economically viable hydrogen both for stationary and for mobile applications are complicated
fuel system [5]. There are essentially two ways to run a road because of its very low boiling point (20.2 K) and extremely low
vehicle on hydrogen. First, hydrogen in an internal combustion density of 0.09 kg/NA m3 in gaseous state and exceptionally high
engine is burnt rapidly with oxygen from air. Second, hydrogen is density of 70.9 kg/NA m3 in liquid phase [7]. Hydrogen is currently
burnt electrochemically with oxygen from air in a fuel cell, which stored in vehicles as a gas in high-pressure cylinders (at up to
produces electricity (and heat) and drives an electric engine [53]. 700 bar) or as a liquid at 20 K in cryogenic reservoirs [7,56].
The main drawback of using hydrogen as a transportation fuel is However, the current methods are limited by several factors. One
associated with its huge on-board storage tank because of extre- disadvantage of these methods is signicant energy loss, which
mely low density of hydrogen [7]. Vehicles need compact, light, mounts up to 40% to liquefy and up to 20% of the energy content of
safe and affordable containment for on-board energy storage. hydrogen is required to compress the gas. Another critical issue
A modern, commercially available car is optimized for mobility that restricts the use of high pressure and cryogenic storage
and not for prestige. For a range of 400 km, a normal vehicle burns mainly focuses on public perception and acceptability associated
about 24 kg of petrol in a combustion engine. To cover the same with the use of pressurised gas and containment of liquid hydro-
range only 8 kg hydrogen is needed for the combustion engine gen [8].
version or 4 kg hydrogen for an electric car with a fuel cell [53]. Hydrogen storage requires a major technological breakthrough
The immediate challenge is to nd a storage material that and this is likely to occur in the most viable alternative to
satises three competing requirements including (i) high hydro- compressed and liquid hydrogen implying its storage in solids or
gen density, (ii) reversibility of the release/charge cycle at moder- liquids from. Its storage in liquid form is difcult because very low
ate temperatures in the range of 70100 1C to be compatible with temperatures are required to liquefy hydrogen [55]. Several classes
the present generation of fuel cells and, (iii) fast release/charge of solid-state hydrogen storage materials demonstrate higher
kinetics with minimum energy barriers to hydrogen release and energy density than that of liquid hydrogen (for example, LiBH4).
charge. The rst one needs materials with strong chemical bonds However, intensive research is needed to improve storage materi-
and close atomic packing. The second necessitates materials als hydrogen absorption/desorption characteristics. The most pro-
structures with weak bonds that are breakable at moderate mising hydrogen storage routes are in solid materials that
temperature. The third requires loose atomic packing to facilitate chemically bind or physically adsorb hydrogen at volume densities
fast diffusion of hydrogen between the bulk and the surface, as greater than that of liquid hydrogen.
well as adequate thermal conductivity to prevent decomposition Fig. 2 illustrates a owchart displaying various hydrogen
by the heat released upon hydrating. Although several materials storage methods. Hydrogen storage for transportation presents a
have been found that satisfy one or more of the requirements, major materials research challenge. Achieving a storage medium
none has proven to full all three. In addition to these basic by combining a hydrogen density greater than liquid and with fast
technical criteria, viable storage media must satisfy cost, weight, kinetics that allows rapid charging and discharging is an out-
lifetime, and safety requirements as well [56,57]. Hydrogen being standing quest. Many conventional bulk materials have been
the lightest, simplest and most abundant element in nature can be explored and rejected as storage media because they do not meet
stored physically by changing its state conditions (temperature, these criteria. However, nanoscience opens new opportunities for
pressure, phase), and chemically or physio-chemically in various addressing this challenge, with the potential for high surface areas
solid and liquid compounds (metal hydrides, carbon nanostruc- and hybrid structures that enable multifunctional performance,
tures, alanates, borohydrides, methane, methanol, light hydrocar- such as low-energy dissociation of hydrogen molecules on the
bons) [58]. surface and rapid diffusion of atomic hydrogen to the interior [56].
S. Sharma, S.K. Ghoshal / Renewable and Sustainable Energy Reviews 43 (2015) 11511158 1157

Compressed hydrogen gas


tanks
Gaseous and liquid storage
Liquid hydrogen tanks

Absorption
Materials-based hydrogen
Hydrogen storage
storage Adsorption

Metal Hydrides Chemical reaction

Hydrolysis reaction

Chemical hydrogen storage


Hydrogenation/
dehydrogenation reactions

Carbon-based materials, High


surface area sorbents and new New chemical approaches
materials and concepts

Fig. 2. Flow chart depicting various hydrogen storage methods.

8. Future aspects only water. Above all, it is also believed to be a very safe fuel. The
major challenge in using hydrogen as a fuel is its storage. Various
Presently, there are three major technological barriers to be storage routes have been suggested (compressed gas, cryogenic,
resolved for a transition from a carbon-based energy system to a metal hydrides, carbon nanotubes) and many research and devel-
hydrogen-based economy. Most importantly, cost of efcient and opment activities are underway for realising the most economical
sustainable hydrogen production and delivery must considerably and highly efcient storage routes.
be reduced. New generations of hydrogen storage systems for both
vehicular and stationary applications must be developed. Finally,
the cost of fuel-cell and other hydrogen-based systems must also Acknowledgements
be reduced [8]. The major future markets for hydrogen depend
primarily upon four aspects [60]: (1) the future cost of hydrogen, The authors thank Dr. A.K. Tiwari and Ms. Shikha Jain from
(2) the rate of advances of various technologies that use hydrogen, University of Petroleum and Energy Studies, Dehradun for the
(3) potential long-term restrictions on greenhouse gases, and useful discussions to frame this article. Financial support from
(4) the cost of competing energy systems. Hydrogen holds the Ministry of Education Malaysia (Vot. 05H36 GUP and 4F424 FRGS)
promise as a dream fuel of the future with many social, economic is respected.
and environmental benets to its credit. It has the long-term
potential to reduce the dependence on foreign oil and lower the
carbon and criteria emissions from the transportation sector [7]. References
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