i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 4 ) 1 e1 3

Available online at www.sciencedirect.com

ScienceDirect

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

Review

Perspective on hydrogen energy carrier and its

automotive applications

Giovanni Cipriani a, Vincenzo Di Dio a, Fabio Genduso a,*, Diego La Cascia b,

Rosario Liga a, Rosario Miceli a, Giuseppe Ricco Galluzzo a
a
DEIM, Department of Energy Information Technology and Mathematical Modeling, University of Palermo,
Viale delle Scienze, 90128, Block 9, Palermo 90128, Italy
b
DICGIM, Department of Chemistry, Industrial Management, Informatics, and Mechanical Engineering,
University of Palermo, Italy

article info abstract

Article history: The paper outlines the concept of energy carrier with a particular reference to hydrogen, in
Received 8 January 2014 view of a more disseminated employment in the field of automotive applications. In
Received in revised form particular hydrogen production is analyzed considering the actual state of the art and
19 March 2014 recent technologies applied in production from the primary sources (fossil fuels, renewable
Accepted 23 March 2014 energies, and water electrolysis). Then the problem of hydrogen storage is considered both
Available online xxx from technical and economical point of views. In particular, differences between physical
and chemical storage are here considered with a particular glance to the most innovative
Keywords: technologies including carbon nanostructures. A review on the main problems in storage
Energy carrier and transportation is then shown with a particular attention given to infrastructures costs
Hydrogen that perhaps will address particular choices for the technologies of the next future.
Storage Automotive applications are called out, accounting the main current technologies and
Transportation notes on fueling station for hydrogen fed vehicle. The discussion of hydrogen safety in
automotive put in evidence the needs for sophisticated sensors, but a comparison with the
safety of gasoline and fire risks, evidences that some common incertitudes on hydrogen
usage should be overcome. Some other safety issues are introduced in the section of
hydrogen transportation. An overview of costs related hydrogen production, storage and
transportation is finally given. This aspect is of a capital importance for the future
dissemination of the hydrogen energy carrier.
Copyright ª 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

Introduction and quality of life are some of the main causes of the restless
growth in energy demand and in the concurrent increase in
The growth of the world population and the natural aspiration pollution (especially for CO2). Meeting this energy demand is
of new out-coming countries to achieve high economic levels most important technology challenge of the 21-st century

* Corresponding author.
E-mail addresses: fabio.genduso@unipa.it, genduso@dieet.unipa.it (F. Genduso).
http://dx.doi.org/10.1016/j.ijhydene.2014.03.174
0360-3199/Copyright ª 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Cipriani G, et al., Perspective on hydrogen energy carrier and its automotive applications,
International Journal of Hydrogen Energy (2014), http://dx.doi.org/10.1016/j.ijhydene.2014.03.174
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 4 ) 1 e1 3
[1e5], keeping however low levels of pollution and, thereby,
reducing the medium term risk of climate change. Such a
scenario should ideally be based on an energy carrier with
negligible environmental impact (either locally and globally)
[6,7]. Energy should be produced more by primary inter-
changeable and available energy sources and with preferably
distributed locations across a network.
Hydrogen is an energy carrier able to fully satisfy such
requisites because:

its air combustion produces energy and pure water only as
the unique reaction product;

it can be produced from fossil fuels and, hopefully, from
renewable sources;

its energy can be distributed quite easily, in accordance
with the end user requests and with the development of
new technologies for transportation and storage;

it may be used in different applications such as centralized
or distributed energy production, specific heat production
with an extremely reduced, impact.
In view of its special and environmental quality, hydrogen
as an energy carrier requires the development of optimum
technologies for production, transport, storage and usage
[8e15]. Once the technological issues are satisfied, the gradual
market introduction of hydrogen-powered vehicles will raise
along with the problem of organization and support of infra-
structure, guaranteeing the production and distribution
within the countries of this interesting fuel.
Technology, logistics and economic issues are, in this
case, strongly connected each other. The introduction of
hydrogen-powered vehicles is actually hampered by inade-
quate distribution networks, whose growth can not be
achieved without a critical mass market to justify the
necessary investment. The problem of planning logistics
and networks is further complicated by the large number of
existing technological alternatives. These strongly influence
costs, and the interdependence between the logistics
infrastructure and the technological choices made by vehi-
cles manufacturers [16e19].
The paper is clearly a summary of many possible issues,
some of which would have deserved a deeper analysis. It
want to introduce the reader into the consideration of
very promising technological field. Clearly, for the sake of
clarity and synthesis, every aspect can not be deeply
analyzed and discussed, but a large bibliography extent is
finally given.
Fig. 1 e Simplified scheme of catalytic reforming.
Please cite this article in press as: Cipriani G, et al., Perspective on hydrogen energy carrier and its automotive applications,
International Journal of Hydrogen Energy (2014), http://dx.doi.org/10.1016/j.ijhydene.2014.03.174
Hydrogen production
Since it is impossible to find hydrogen as available molecules
in nature, it has to be produced from other materials that
contain it. In particular, hydrogen can be produced from fossil
fuels and hydrocarbons, or even from renewable sources. In
the following, the most common processes for hydrogen
production are recalled [20e25].
Production from fossil fuels and hydrocarbons
Among the methods of hydrogen production from fossil fuels
and hydrocarbons, the most suitable are [26e34]:

catalytic steam reforming (steam reforming of natural gas
or oil);

steam reforming of methanol;

coal gasification;

partial oxidation of hydrocarbons;

alternative technologies (process or Kvaerner Termoc-
racking).
In the catalytic steam reforming, used only for light
hydrocarbons (methane and naphtha), it is possible to
identify three stages of hydrocarbon treatment: generation
of synthesis gas, shift reaction reforming, gas purific
ation [22].
As can be seen from the simplified block diagram of this
process (Fig. 1), after an initial desulfurization phase, the gas
passes through a reformer, constituted by a system of steel
pipes containing a nickel based catalyst, where the steam
enter obtaining a gas with a variable content of CO and CO2
between 10% and 15%. The shift reaction reforming allows to
decrease the CO and CO2 content up to 0.2e0.4% of volume.
The final stage allows the purification of the gas from the re-
sidual CO and CO2.
In the methanol steam reforming a molecule of methanol
(CH3OH) is separated into hydrogen and carbon monoxide:
the process consists in an initial decomposition of
methanol, followed by a shift reaction and subsequent
removal of CO2 [8].
Gasification is an high temperature endothermic reaction
of pulverized coal, pure oxygen and water steam, to produce a
gas mainly consisting of hydrogen and carbon monoxide. In
this process, finely chopped mixed coal and water forms a
mash pumped into the reactor, where oxidation reaction with
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 4 ) 1 e1 3 3

Fig. 2 e PDX process base reformer realized by Nuvera Fuel Cells.

pure oxygen finally happens. From the obtained gas, powders
photo-electrochemical conversion;
and traces of H2S are then eliminated.
water electrolysis.
Hydrogen can also be derived from residues of crude oil
and hydrocarbons processing, by a reaction with water steam The biomass is the biodegradable fraction of products,
and oxygen. The partial oxidation of liquid hydrocarbons waste and residues from agriculture (including vegetable and
(PDX) is a process used to produce hydrogen in all those cases animal organic fertilizers), forestry and related industries, as
in which natural gas is not economically available [35]. well as the biodegradable fraction of industrial and city
Structurally, the reactor conducting the partial oxidation is garbage [39]. Thermochemical processes currently used for
very similar to the reformer used in the steam reforming the production of hydrogen from biomass gasification and
process, but it does not contain any catalyst. Moreover, in this pyrolysis are fast [32,33,40,41].
case, the heat steam production is realized in a vertical reactor The gasification process starts from converting the
by combustion of a part of the incoming fuel with a controlled biomass into a synthesis gas by partial reaction with oxygen
air amount, without the need for additional contribution of and with the use of heat. The synthesis gas is composed pri-
external fuel (see Fig. 2). The main disadvantages, however, marily of hydrogen CO, methane CO2, water steam and other
are related to the need of pure oxygen and the significantly hydrocarbons, in dependence on the reactor type. This gas is
lower conversion efficiency, compared to that of the steam then chilled, purified from sulfur compounds, and submitted
reforming.
The previously described hydrogen production methods
determine a not negligible pollution of CO2. The Kvaerner and
Termocracking processes improve, instead hydrogen pro-
duction with lower pollution. These processes, however, have
higher costs and lower efficiencies. In particular, the Norwe-
gian Kvaerner Engineering has developed an innovative pro-
cess in which hydrocarbons are separated into atoms of
carbon and hydrogen (CH4 / C þ 2H2), using a plasma at of
1600  C. Hydrogen is then obtained without emission of car-
bon dioxide. In the Termocracking technology, however, the
reaction is the same of the previous process, but it is different
because the decomposition of the hydrocarbon molecule oc-
curs free of air and at high temperature water steam
atmosphere.

Production from renewable sources

The production of hydrogen from renewable sources is now

more and more interesting from the technological point of
view because of the development of some methodologies,
among which we mention the following [21,23,24,36e38]:

thermochemical processes from biomass;

thermochemical decomposition of water;
Fig. 3 e A plot of hydrogen uptake (WH2 at 77 K, 1 MPa)
versus BET surface areas SBET of nanoporous carbons and
composites, together with other high-performance
materials (AC and MOF).

Please cite this article in press as: Cipriani G, et al., Perspective on hydrogen energy carrier and its automotive applications,
International Journal of Hydrogen Energy (2014), http://dx.doi.org/10.1016/j.ijhydene.2014.03.174
4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 4 ) 1 e1 3

to reforming and shift reforming reactions, which two the way of hydrogen employments as for as all other tradi-
different processes to produce hydrogen and methanol. tional fuels.
Fast pyrolysis is a thermal degradation process of the The storage problem is the main one in automotive appli-
biomass that occurs in absence of oxidizing agents and cation, where weights and volumes should be kept as lower as
producing: possible. At the present stage the available hydrogen storage
technologies are classified as follows [8,10,12,51e86]:

a gaseous part, characterized by a medium-low calorific
value and containing CO, CO2, hydrocarbons, water steam
physical storage (compressed hydrogen also as liquid) in
and hydrogen; glass micro-balls;

a liquid fraction made up of low molecular weight organic
chemical storage in metal hydrides;
compounds such as aldehydes, alcohols and acids;
storage by means of carbon nanostructures.

a solid fraction, consisting of a higher molecular weight
residues.
Physical storage
The production of liquid fraction (bio-oil, with a calorific
value higher than the initial biomass) with fast pyrolysis is The easiest and cheapest way to accumulate and store
maximum, allowing to resolve the difficulties related to the hydrogen is to compress it in tanks, with technologies very
biomass transport. The actual conversion into hydrogen can similar to those used in the compression of natural gas. The
take place via a catalytic reforming of bio-oil product. storage tanks are normally made of aluminum, glass fiber or
The plants that exploit the decomposition process is based carbon fiber and polymeric materials. These tanks are very
on thermochemical water cycles in which hydrogen and ox- often used in automotive application (see also Section 5)
ygen are produced by the decomposition of water. This is done Hydrogen is stored at a pressure of about 25 MPa. However, for
by means of a series of chemical reactions in which chemical vehicle applications, new composite materials with a signifi-
intermediates (typically sulfuric acid) are formed and are cant reduction of weights and encumbrance are being
recycled inside the process. considered. A significant progress has been made with the
To operate at the necessary 1000e1300 K solar concentra- introduction of reinforced carbon and glass fibers tanks with a
tors, distributed into different areas, are used. Solar concen- weight 3e4 times lower than that of the common tanks and
trators provide heat at the temperature levels suitable for the pressures up to 35 MPa (potentially even 70 MPa).
different reactions. The conversion process consists in photo- The usual safety features are very high thanks to the
electrochemical split of the water molecule into oxygen and robustness of the tanks, to the introduction of nonexplosive
hydrogen using sunlight. The operation principle is similar to fuses in case of fire and to the presence of interrupting circuit
that of photovoltaic cells [42,43], where electronehole pairs in the case of impacts (see also Section 5.4) [58].
are created at the semiconductors underwater electrodes, The Daimler-Chrysler used compressed hydrogen on the
with a resulting current circulation and the resulting first two fuel cell car prototype (Fuel Cell car - FCV), NECAR
hydrogen generation. NECAR H and I, and the recent NECAR 4a. The P2000 FCV Ford
The main difficulties of this technology lie in the avail- and the Fiat 600 Electra are other examples of cars using
ability of semiconductors being good sunlight absorbers and hydrogen tanks. The applications of this storage technology is
stable in water at the same time. To this aim, cells with in- practically the same on the most part of fuel cells buses pro-
tegrated electrodes and protective films, achieving conversion totype. Hydrogen can be also stored in liquid form (at 253  C),
efficiencies up to 15% are under investigations.
Electrolysis is the combination of electrochemical phe-
Table 1 e Energy density of some energy carriers.
nomena determined by the circulation of an electric current
through an electrolyte. In particular, water electrolysis de- Energy Way of Energy density Energy
termines the decomposition of water into hydrogen and ox- carrier storage by weight density by
[kWh/kg] volume
ygen (the latter in a double volume compared to the first). Pure
[kWh/l]
water, although little dissociated, contains ions Hþ and OH
Hydrogen Gas (20 MPa) 33.3 0.53
which, because of the electric field action, migrate toward the
Gas (24.8 MPa) 33.3 0.64
cathode and the anode to form hydrogen and oxygen [44e48]. Gas (30 MPa) 33.3 0.75
However, given the low electrical conductivity of pure water, Liquid 33.3 2.36
electrolysis should be carried out in the presence of suitable (253  C)
dissolved electrolytes, in order to increase the conductivity of Metal hydrides 0.58 3.18
the solution. The compounds to be added in water can be Natural gas Gas (20 MPa) 13.9 2.58
Gas (24.8 MPa) 13.9 3.01
acids, bases or salts.
Gas (30 MPa) 13.9 3.38
Liquid 13.9 5.8
(162  C)
Hydrogen storage LPG Liquid 12.9 7.5
(Propane)
In automotive traction application hydrogen storage is a Methanol Liquid 5.6 4.42
capital issue [49,50]. Industry and researchers are using all Gasoline Liquid 12.7 8.76
Diesel Liquid 11.6 9.7
their resources to investigate within the safety limits, to find

Please cite this article in press as: Cipriani G, et al., Perspective on hydrogen energy carrier and its automotive applications,
International Journal of Hydrogen Energy (2014), http://dx.doi.org/10.1016/j.ijhydene.2014.03.174
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 4 ) 1 e1 3
raising its energy density, as can be seen from Table 1,
compared to that characteristic of other compressed gas.
However, the very low temperature implies considerable
problems, especially with regard to losses. In fact, being the
hydrogen at the boiling temperature, even a minimum heat
exchange produces evaporation and, therefore, a dangerous
emission which affects also the autonomy of the vehicle. The
phenomenon is particularly evident in small size cylindrical
tanks for vehicles, where the evaporation rate is 2e3% per day.
This phenomenon is less evident in spherical tanks of thou-
sands of m3 (because the spherical form allows to minimize
the heat exchange surface, with equal stored volume). In this
case losses are reduced to percentage fractions per day. These
storage systems are made of composite material with double
wall tanks and a vacuum inter-space (reservoirs of type
DEWAR) in order to minimize the exchanges by conduction
and convection.
This storage technique has a further disadvantage: it re-
quires a high amount of energy and is therefore a source of
considerable environmental impact. Among the FCV recently
produced with liquid hydrogen, the NECAR 4 of Daimler-
Chrysler and Opel HydroGen 1 are to be reminded. They also
use liquid hydrogen buses built by Ansaldo (3600 L tanks by
Messer Griesheim, located on the rooftop of the bus) and MAN
(3200 L Linde tanks, placed on the floor of the vehicle). Another
disadvantage of liquid hydrogen, finally, is the greater
complexity of the whole system, above all for distribution and
supplying, and the higher costs associated with.
Hydrogen storage in glass micro-spheres represents a
technology, studied along time, which exploits the hydrogen
permeability of the glass at high temperatures.
The micro-spheres (with diameters of 25 up to 500 mm),
heated up to 200e400  C, are filled with tens of MPa pressur-
ized hydrogen. The pressure limit is given by the micro-
spheres resistance, usually up to 340 MPa. To get hydrogen a
further heating of the glass causes the breakage of the micro-
spheres: in the latter case, obviously, the storage system can
be used only once, but glass can be however recycled. This
system is considered as a possible technology suitable for the
construction of a hydrogen tanks for motor vehicles, espe-
cially with regards to the intrinsic safety concerning any fuel
leak.
Chemical storage by metal hydrides
Some metal alloys can store hydrogen atoms within their
crystalline reticulum to form a hydride: the extremely positive
peculiarity of a metal hydrides accumulation is to maintain
the gas at environmental temperature and pressure, since
hydrogen penetrates into the crystal reticulum occupying the
interstitial sites [87e89]. The hydrogenation process is
exothermic (i.e. the device must be cooled while charging) and
takes place at pressures of 3e6 MPa. The dehydrogenation
requires, instead, heat (at a temperatures which depends on
the used alloy) and an initial at high pressure which is grad-
ually decreased. Hydrides are classified according to their
dehydrogenation temperature.
The actual research is addressing towards the identifica-
tion of hydrides characterized by low temperatures (below
100  C), so that they can be coupled with a polymeric
Please cite this article in press as: Cipriani G, et al., Perspective on hydrogen energy carrier and its automotive applications,
International Journal of Hydrogen Energy (2014), http://dx.doi.org/10.1016/j.ijhydene.2014.03.174
5
membrane fuel cells for vehicular applications. The main
advantages of such a storage technology are low pressures,
large energy densities greater than those of liquid hydrogen
(see Table 1).
A weakness of this technology is the weight of these stor-
age systems: in fact, for the same weight of different tech-
nologies, the vehicle exhibits an autonomy three times lower
than that obtainable with liquid hydrogen or compressed
hydrogen advanced tanks. In terms of safety, the risk of un-
wanted losses, even in case of a car impact, is really minimal
for this storage.
The technology of the hydrides is being studied in the
United States, Europe and Japan, where Toyota has developed
special titanium alloys, as part of its program of development
of Fuel Cell Vehicle [44e48].
Storage through carbon nanostructures
Since the early 90’s some particular forms of carbon graphite-
like aggregations have been investigated, because they are
able to accumulate hydrogen. Although hydrides generally
exhibit a high storage capacity of over 5 wt%, there are several
drawbacks such as the necessity of heating for hydrogen
release, slow re-hydrogenation rate, and poor cyclability.
Nanoporous materials, especially carbons, are free from most
of these problems [55,63,65,70,71,81,82,90], but the only
drawback is a lack of sufficient storage capacity, especially at
room temperature (ca 1 wt%). Thus, increasing physisorption-
based storage capability is the most important task for
nanoporous materials. Physisorption is based on the Van der
Waals forces between a solid surface and a hydrogen mole-
cule. The interaction is very weak and the heat of adsorption is
as low as 6/8 kJ/mol in nanoporous carbons [70,82]. On the
basis of physisorption, large surface area [61,91], large
micropore volume [55,65], and a suitable pore size [55,65,66]
are highly desirable for a large amount of adsorption. There
are two target temperature ranges for physisorption-based
hydrogen storage: liquid nitrogen temperature (77 K) and
room temperature. The values of hydrogen uptake
ðWH2 at 77 K; 1 MPaÞ are plotted against their BET surface
areas in Fig. 3, which reveals that WH2 is basically proportional
to SBET, and that the data of the nanocarbons having higher
WH2 =SBET values (ZTC, N-ZTC, and other) can be plotted along
a line of 10 mmol/m2, while those of OMC, OMC/M, AC, and
MOF are along a line of 7 mmol/m2.
Large surface area, a high fraction of micropores and a
stronger surface affinity are important for the hydrogen
storage based on physisorption at cryogenic temperature and
at room temperature [54,61,63,65,67,68]. Porous carbons have
the advantage of a stronger affinity compared to MOFs.
Particularly, ZTCs exhibit the best performances among all
other microporous materials. Although the highest amount of
storage 5.7 wt% at 77 K under 1 MPa, has been achieved by
CB850h having an SBET of 3150 m2/g, it is actually possible to
prepare ZTC with a higher SBET of up to 4100 m2/g. If such a
ZTC retains the specific adsorption amount (10 mmol/m2), the
hydrogen uptake is estimated to be 7.6 wt%. Of course, under
higher pressure, its storage amount is further increased; for
example, CB850h exhibits 6.9 wt% at 2 MPa [82], i.e., 1.2 times
larger than at 1 MPa.
6 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 4 ) 1 e1 3
In addition, the surface affinity of carbon materials to
hydrogen could be enhanced by lithium doping [59,79], and
thereby additional higher capacity might be achieved. The
experimental data on hydrogen storage by nanocarbons on
models at room temperature are shown in the diagram in Fig. 4.
While OMCs show very poor hydrogen capacity (<0.1 wt)
[53,54], much higher capacities have been reported for ZTCs by
Wang et al. [67,78] and Nishihara et al. By increasing hydrogen
pressure up to 34 MPa, the capacity reached 2.2 wt% [70], and
this is one of the highest storage values among nanoporous
carbons reported. Nevertheless, it is still far from the target for
practical use (>6 wt%). The highly microporous templated
nanocarbons, such as ZTCs, are superior to OMCs or other
templated nanocarbons with larger pores. Surprisingly, the
high-performance AC shows a storage capacity comparable to
those of ZTCs, indicating great potential for conventional ACs,
which enjoy both low production cost and ease of mass pro-
duction. In this case it is expected that the lithium doping in-
creases the physisorption amount up to 2O4 times [59,73].
Accordingly, the lithium doping into highly microporous car-
bons such as ZTC may be one of the interesting approaches to
achieve much higher storage capacity than 2.2 wt%.
Transport and distribution of hydrogen
technologies
In order to hold hydrogen as a common fuel, there is the need
of an efficient transportation and distribution network which
must meet the usual requirements to which users are accus-
tomed, such as security, quick and easy supply stations all
across the country. Hydrogen can be delivered via pipeline or
transported by means of land and/or naval vehicles [92,93].
At present the existing hydrogen distribution networks,
both in Europe and the United States, are pipelines within any
given industrial district [94]. The most obvious problem suf-
fered by pipeline [41,95] is the embrittlement of materials in
contact with the hydrogen that determines an increase of
losses along the pipe itself. The embrittlement can be reduced
by adopting metals pre-processing to minimize residual
stresses in the material [11,16,36,93,96,97].
The use of pipelines for the distribution of liquid hydrogen
would greatly increase the transport capacity, in front of
higher investment costs. In fact, pumping systems, cooling
and heat-insulated pipes become mandatory [98]. In this case,
safety problems are multiplied, because, in case of pipe leaks,
there would be a deep cooling of all the materials in contact
with hydrogen (with higher hazard for the personnel).
Furthermore, if the thermal insulation is not perfect, the all
around atmosphere with more than 50% oxygen content be-
comes extremely flammable. The problem of adapting the
existing natural gas pipeline for use with hydrogen is
currently under study, but there are no general conclusion on
the best way to face the problem [41,95].
If the hydrogen demand does not justify the massive
installation investment of dedicated pipeline, hydrogen can
be easily transported by road via trucks, using different stor-
age technologies analyzed above. In particular, this transport
is realized with tanks containing more cylinders of com-
pressed hydrogen or liquid hydrogen at a pressure of 20 MPa.
Please cite this article in press as: Cipriani G, et al., Perspective on hydrogen energy carrier and its automotive applications,
International Journal of Hydrogen Energy (2014), http://dx.doi.org/10.1016/j.ijhydene.2014.03.174
The second solution is obviously more advantageous from the
point of view of the energy transport, but involves higher costs
because of the required insulation and the refrigeration sys-
tems. As well as for transportation by pipeline, also in this
case, the costs are a function of the distance and the transport
of hydrogen in liquid form is not the most convenient solu-
tion, both for investments and for units of transported energy.
The transport by rail is intermediate between pipelines and
trucks transportation investments [9,17].
Hydrogen in automotive
The actual society development is strongly conditioned by
transportation and particularly by automotive. Conversely,
the adoption of new solutions can not introduce damages or
risks for the actual modern world. By analyzing the pollution
of NOx and COx chemical compounds due to road trans-
portation, it is evident that its reduction become mandatory
and some specific actions must be planned and managed [99].
To gain more effective actions in reducing pollution,
transportation requisites must be globally accounted in the
development of both new vehicular technologies and new
fuels exploitation [100]. Beyond the modern engine enhance-
ments, different solutions may be based on electric vehicles
with high efficiency motors for the most part of their torque -
speed range and with the further capability of energy recovery
during breaking.
Fuel cells vehicles
Nowadays, among the various proposed solutions, fuel cell
vehicles appear a viable solution within the medium - long
time range. Fuel cell cars started as an evolution of lead acid
battery fed cars whose main problems were the large weight
and extension of the battery pack and the long lasting time for
their recharge.
Hydrogen fuel cells drastically reduce both these problems
[99]. In general the architecture of such vehicles is essentially
hybrid, because both battery packs and fuel cell usage are
there proposed. This is in order to guarantee a better capa-
bility to cover all the requirements of normal operation,
transients (accelerations, braking, non regular mileages and
so on) and a longer life for the stack. A possible alternative to
battery packages is their substitution with storing energy ca-
pacitors. Thanks to capacitors capability of fast charges and
discharges, a better and prompt response to sudden load
variations can be guaranteed. Unfortunately the presence of
capacitors implies a greater complexity of the control system.
Nowadays three main vehicular architectures can be
considered really suitable. They are briefly described below.
1. Load leveler. In this architecture fuel cell delivered power is
slightly higher than that given by the battery packs. This
last ones are mainly used with high starting torques. Bat-
tery packages are then recharged in more favorable
running conditions. This configuration is well suited for a
typical urban cycle [101].
2. Range extender. In this architecture fuel cell delivered power
is lower (typically less than the 25%) than that given by the
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 4 ) 1 e1 3
battery packs. This configuration allows a greater auton-
omy and result well suited for high mileages with a
reduced space amount for the battery pack itself. It is also
the best configuration for large vehicles destined to the
transportation of both peoples and goods. A high power
stack would imply a more expensive system and should be
designed based on the peak power, even if this last is not
always requested. The larger space available allows the
presence of more than one battery pack. The stack can
work continuously with a good efficiency and a larger
lifetime.
3. Full power. In this architecture the whole power is delivered
by a fuel cell stack. An extra urban cycle with long mileages
and rare transients tend to discharge the battery pack
quickly. It is thus convenient that power is delivered from
the fuel cell stack. This configuration can however provide
a certain level of hybridization. The control system man-
ages the electric drive motoring extracting its energy from
the stack or from the small battery pack, according to the
vehicle or to the route characteristics.
Internal combustion engines vehicles
The modern technologies allow the direct usage of hydrogen
inside an internal combustion engine with some modifica-
tion made on the usual gasoline engines to adapt them to
hydrogen. In particular the principal modification regards
the electronics unit control to properly manage the pressure
in the injection and in hydrogen combustion. It is also
important to provide sensors to avoid self combustion in-
side the chamber, that is positive in traditional engine, but
completely undesired in hydrogen engines. The same en-
gine fed by hydrogen lose a certain amount of power with
respect to the gasoline usage because of the smaller energy
of the compound inside the cylinders. Furthermore, the
lower volumetric density of the air/hydrogen compound
does not facilitate an optimal fill in of the combustion
chamber.
The fuel cell vehicle efficiency is clearly higher than that
of the internal combustion engine vehicles. Yet the effi-
ciency of a low temperature thermal cycle is not satisfac-
tory and became suitable only at higher temperature
that are difficult to reach for structural issues and high
costs. Fuel cell vehicles have no pollution while hydrogen
internal combustion engines pollutes dangerous nitrogen
mixtures. The only advantage of hydrogen internal com-
bustion vehicles is their immediate availability thanks to
well known engine technologies eliminating CO and CO2
emissions.
Apart from some general aspects, the design of an internal
combustion engine must be clearly and carefully devoted to
the main characteristics and properties of hydrogen. The
paper [99] gives a large overview on hydrogen usage as fuel in
internal combustion engines and carefully accounts the
aspect of abnormal combustion avoidance, in order to gain
efficiency and to increase output power. For this reason in [99]
all the main engine components are analyzed to underline the
main criteria to follow in the proper design of an efficient
hydrogen fed engine.
Please cite this article in press as: Cipriani G, et al., Perspective on hydrogen energy carrier and its automotive applications,
International Journal of Hydrogen Energy (2014), http://dx.doi.org/10.1016/j.ijhydene.2014.03.174
7
Hydrogen fueling stations
By using consolidated technologies, different option are
available to realize hydrogen fueling stations:
1. Local production via electrolysis and different storage
forms (hydrides, gaseous, etc.);
2. local gaseous storage and transport with trucks as in the
case of fossil fuels;
3. liquid local storage and transportation with tracks;
4. local production from gaseous methane, purification and
storage in different forms (hydrides, gaseous hydrogen,
etc.);
5. pipe distribution and local compressing stations, as in the
case of natural gas.
Except for the last item, that needs a still non existing
hydrogen distribution network, all the other technologies are
well known and the only issues are in normative and com-
ponents standardization. There is in fact no commonly
accepted standard for hydrogen fueling stations. On the other
hand, hydrogen uncommon usage as a fuel implies that
applied conditions are often severe and restrictive. Yet, for
components standardization (e.g. for tanks valves and con-
nectors) there are no particular trends and any each manu-
facturer uses to refer to its own technical specifications
coherently with some other international standards referred
to particular environment with flammable gases.
Hydrogen safety in automotive
The main incertitude on hydrogen fuel diffusion are related to
safety issues, but, going beyond one’s personal perception, a
careful analysis reveals that hydrogen results less flammable
than gasoline. In fact, hydrogen self ignition temperature is
550  C whereas the gasoline one is 230e500  C, according to
different types. First of all, it must be emphasized that
hydrogen safety requirements in automotive are quite
different from those considered in transportation as for
pipelines as for transportation through trucks because of the
different concentrations and amounts of the managed
gaseous mass.
Hydrogen is very volatile and, possibly, it is very quickly
dispersed in the environment. It is also practically impossible
to make hydrogen explode except for very reduced spaces.
To find potentially dangerous hydrogen concentrations in
the air, different sensors are used to manage proper safety
control systems. Different, but common, commercial sensors
operate according to different hydrogen detection principles.
Among them catalytic beads, electrochemical and Metal-
Oxide-Semiconductor-sensors are the most exploited in the
current market.

The catalytic bead sensor typically contains two platinum
wires coated with beads, a sensing bead and a reference
bead. The reference bead compensates environmental ef-
fects, humidity and temperature. The two beads, a fixed
and a variable resistor, are mounted on a Wheatstone
bridge. When target gas comes, a catalytic combustion
takes place on sensing bead and generates combustion
8 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 4 ) 1 e1 3
heat causing an increase of sensing bead temperature.
Thus, platinum wire resistance changes causing the
Wheatstone bridge unbalance and provides an output
signal variable with the target gas concentration.

The electrochemical sensor consist of three electrodes
separated by an electrolytic solution. When target gas
penetrates the gas diffusion barrier it reaches the surface
of the first electrode. Thus, an electrochemical reaction
takes place releasing electrons which contribute to the
generation of an output signal. Thermal Conductivity
sensors are also mounted on a Wheatstone bridge with two
cells, a measurement and a reference cell.

Metal-Oxide-Semiconductor-Sensors (MOSS) consist of
three stacked layers, a substrate, usually Silicon, followed
by a thin oxide layer and finally a sensitive metal layer. The
operating principle is based on measuring the capacitance
variation caused by the changes in MOS device character-
istics due to the variation on the sensing layer in presence
of the target gas [102].
When burning, hydrogen is very quickly consumed, always
with direct upwards flames, and its thermal radiation wave-
length is very low, thus it is easily absorbed by the atmo-
sphere. It has been calculated, by experimental data, that the
fire of a gasoline vehicle lasts for 20e30 min, while for a
hydrogen vehicle it does not last more than 1e2 min. The low
thermal radiation, also implies that there is little contingency
(except for a direct exposure to the flames) for neighbors
materials to be burned, thus reducing the duration of the fire
and the danger of toxic pollution.
Hydrogen is not toxic, nor corrosive. Conversely, all fossil
fuels are asphyxiating and toxic to the human beings. Any
hydrogen leaks from tanks do not involve poisoning of soil
and groundwater.
Costs of hydrogen production, storage and
distribution
The development of hydrogen as an energy carrier requires
the preparation of a wide range of integrated infrastructure to
make the entire system reliable and cost-effective (produc-
tion, transportation, distribution, storage, end use) [103]. All
the infrastructure elements are strongly dependent each
other, so that the choice of methodology and technology for
the realization of the system may condition all the others,
both technically and economically [58,83,95,101,103e117] (see
Fig. 4).
The production can take place, according to the processes
described in Section 2 and the costs of which are briefly shown
in Fig. 5 [8,11] in:

large size centralized systems;

plants of smaller size throughout the country (on-site);

installations in vehicles.
In the first case the production would take place from
natural gas by catalytic steam reforming; this is the most
widely used more convenient and commercially mature
method, for the hydrogen large scale production [118,119].
Please cite this article in press as: Cipriani G, et al., Perspective on hydrogen energy carrier and its automotive applications,
International Journal of Hydrogen Energy (2014), http://dx.doi.org/10.1016/j.ijhydene.2014.03.174
The costs grow significantly in the case of production from
the coal gasification: this is due, mainly, to the greater
complexity of the technology and the need for a thorough
cleaning and gas purification. However, in countries such as
South Africa or China, the lower cost of coal with respect to
methane, can make this process very convenient. Using the
partial oxidation technology, the penalties under the technical
and energy are even stronger: there are, in fact, much greater
weight, volume and cost. The presence of oxygen in the re-
actors lead to problems similar to those of aboard compressed
hydrogen storage. For air picking up the resulting dilution of
the nitrogen stream (in addition to CO2) would reduce further
the power of the fuel cell. The cost increase compared to a
conventional vehicle is, in this case, approximately USD
3400e6300.
The centralized production requires significant storage and
distribution costs for end users [10,25,75,79,104,120,121]. Even
assuming a centralized production by catalytic steam
reforming plants, consider that a hydrogen transport for
55 km costs 8 times more than carrying an energy-equivalent
amount of gasoline for 3000 km.
Due to possible developments of compact reformer, the on-
site production will become, therefore, probably better than
that centralized distribution through pipeline, at least until a
sufficiently high demand increase.
Adopting smaller plants size but a better distribution
throughout the territory, the production would be advanta-
geous for catalytic steam reforming of natural gas, or by steam
reforming of methanol, or through electrolysis of water,
providing the necessary electricity through the existing dis-
tribution network or producing it locally from renewable
sources.
The electrolysis process, that achieves high flexibility and
no environmental impact if electricity generation, is based on
renewable sources such as wind and solar power, but these
sources are usually characterized by discontinuity of power
delivery. Indeed, during the periods of superabundant elec-
trical power production, the produced hydrogen can be stored.
The cost of production by electrolysis is the highest among all
Fig. 4 e A plot of hydrogen uptake WH2 at room
temperature, 10 MPa, versus BET surface areas SBET of
nanoporous carbons and composites, together with other
high-performance materials (AC and MOF).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 4 ) 1 e1 3
the technologies considered, but it is also the only process that
allows the production from water using electricity. The eco-
nomic investment is at least twice that required for the
reforming. In the case of on-site production smaller plants are
more expensive, but distribution costs results highly reduced.
As for the centralized system, even in the hydrogen
distributed production, investment and management costs of
the storage systems are very relevant. In particular, storage of
compressed hydrogen is characterized by high operating costs
due to the energy expenditure required to perform its
compression (7e18 kW/GJ) and to the low volumetric energy
density of the tanks (1.3e3.4 MJ/l with 32.4 MJ/l of gasoline)
[98].
Also for liquid hydrogen system operating costs are sig-
nificant, being essentially due to the consumption of elec-
tricity for compression and liquefaction (82e160 kW/GJ) and
can cover the 30% up to 80% of the entire storage cost.
Among the disadvantages of metal hydrides technology
[88] it is important to emphasize its high cost due to problems
of metal alloys availability, using rare earth [9].
In the third case, the hydrogen production through small-
scale reforming plants would be installed in vehicles, from
traditional fuels, such as gasoline, diesel or methanol and
natural gas, which would be distributed using existing infra-
structure [19,29]. In this way the transport costs would be
eliminated, but the car purchaser would be placed against the
costs of production and storage on board. Among the tradi-
tional fuels methanol plays an important role since, like the
others, it is easily transportable, but more easily convertible
into hydrogen.
In fuel fell vehicles fed by methanol, the presence on board
of the reformer and the gas purification from CO determines
an increase of cost of about USD 2300e3400, compared to a
conventional vehicle, and approximately of USD 1800e2200,
compared to a direct hydrogen-powered fuel cell vehicles
[72,122,123]. Since the methanol is also toxic, corrosive and
compatible only with certain elastomers, existing tanks
should be changed or replaced. With these adjustments, the
shipping cost per unit volume would be substantially equal to
Fig. 5 e Hydrogen production costs.
Please cite this article in press as: Cipriani G, et al., Perspective on hydrogen energy carrier and its automotive applications,
International Journal of Hydrogen Energy (2014), http://dx.doi.org/10.1016/j.ijhydene.2014.03.174
9
that of gasoline, while the cost of transport per unit of latent
energy is doubled [11,12].
In the case gasoline fed vehicles, all costs related to the
distribution infrastructure are erroneously deleted. In fact, to
avoid poisoning of the catalysts in the reformer, a tight control
of the sulfur content becomes necessary: therefore it is
essential a radical reorganization of the refineries.
Moreover, the producers are very often reluctant to invest
in significant plant modifications, standing the current
narrowness of the market. The cost of gasoline, however,
should not change too much, as the increased costs of the
desulfurization would be offset by the lower octane required.
The desulfurization may also be carried on board the vehicle:
however, the optimal solution from the economic point of
view [10] seems to be represented by the trade off between
reducing the sulfur content in the refineries and perfecting its
removal aboard by means of a cheap treatment systems (with
an estimated cost of USD 50 for a filter whose time-line
approach that of the vehicle).
Given the lack of a distribution network, the production of
hydrogen in vehicles will be the pursued solution in the short
term since it allows, in spite of the difficulties encountered by
the board reforming, a significant reduction of barriers in the
market entry.
One of the actual challenges is the reformer scale-down,
namely the creation of a small size reformer (a few units or
tens of Nm3/h) with cost per liter of hydrogen comparable to
that of plants large size. The research in the field of fuel cells is
leading to the development of compact, standardized and
high technology reformers, operating at pressures and tem-
peratures lower than those of the conventional reformer, with
advantageous investment costs compared to conventional
installations steam methane reforming. Furthermore, when
such plants are produced, the specific costs of hydrogen pro-
duction is unaffected by the size of the plant.
Limiting the attention to production costs with a particular
glance to the future, it can be observed that the further used
thermochemical processes include gasification and pyrolysis
of biomass. The price of hydrogen thus obtained is about three
10 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 4 ) 1 e1 3
times greater than the price of hydrogen obtained by the
Steam Reforming process. Therefore, these processes are
generally not considered as competitive with those of steam
reforming.
The price of hydrogen from gasification of biomass ranges
from 10 to 14 USD/GJ and that from pyrolysis 8.9e15.5 USD/GJ
[124]. It depends on the equipment, availability, and cost of
feedstock. Actually hydrogen productions methods can be
distinguished into commercial, near term and long term, ac-
counting their technological maturity and competitive prices.
In this way, steam reforming, partial oxidation, biomass
gasification end electrolysis can be considered as commercial.
Autothermal reforming from hydrocarbons is to be considered
as a near term, whereas Plasma reforming, photolysis, ther-
mochemical water splitting are to be considered as long
terms. Electrolysis is still an effective production method and
will be able to guarantee hydrogen availability for a long time
horizon [124].
Conclusions
The here analysis reported defines some elements that char-
acterizes the transitional scenario that will lead, in the me-
dium to long term, large scale introduction of hydrogen-
powered Fuel Cell vehicles. In this context, it is again appro-
priate to highlight the unique role and suggestive that meth-
anol could play in the transition to a hydrogen economy, in
fact, methanol:
1. is more easily transportable and storable than hydrogen or
natural gas;
2. is more easily converted into hydrogen on board the
vehicle compared to gasoline;
3. can be converted into hydrogen at temperatures signifi-
cantly lower (250e300  C against 800e900  C);
4. is characterized by a low volatility and a high lower
explosive limit;
5. has a good energy density, allowing the vehicle a range
similar to that of conventional vehicles;
6. is a chemically stable;
7. allows you to easily monetize natural gas made redundant
the wells;
8. enjoys relatively low market prices due to the current
excess capacity exists;
9. in the short to medium term infrastructure costs is
completely acceptable.
However, the transition from methanol (or oil) to hydrogen
to power a fuel cell determines, in addition to increased in-
vestment, even an increase of energy consumption. Fuel Cell
vehicles equipped with on board reformer, in fact, have a fuel
economy (distance per liter of fuel) reduced up to 60% of that
of vehicles fueled directly by hydrogen, due to leakage in the
fuel processor [11,12].
To fix the ideas, considering the conversion efficiency and
the fuel economy of various technological alternatives, with
the same energy input, you can feed 100 hydrogen vehicles
and 57 in methanol, compared with 82 conventional vehicles
with gasoline engine.
Please cite this article in press as: Cipriani G, et al., Perspective on hydrogen energy carrier and its automotive applications,
International Journal of Hydrogen Energy (2014), http://dx.doi.org/10.1016/j.ijhydene.2014.03.174
Considering, then, the entire cost in USD/km on the life
cycle as the sum of investment costs, the cost per unit of
distance relative to the hydrogen fuel cell vehicle (product
from natural gas) would become even smaller, since, for the
same cost per kilometer, purchase costs of vehicles with
gasoline and methanol fuel cells would be greater [125].
That assessment must not be misleading, since the use of
hydrogen imposes an additional cost to the consumer for the
construction of the production and distribution infrastructure
which is higher than that determined for methanol or gaso-
line. Nevertheless, in the long term, hydrogen wins due to
increased efficiency, lower total costs, to lower environmental
impact, the renewability and flexibility in the use of the
source.
Therefore, the methanol will probably be used during the
initial phase due to lower infrastructure costs and lower
vehicle costs compared to those using the Partial oxidation
technology for the reforming of gasoline.
The transition to hydrogen is expected to be only late and
gradual, with production initially on-site, via steam reforming
or electrolysis taking advantage of the existing infrastructure
for the distribution of natural gas and then more and more
centralized, when the economies of scale make for convenient
installation of dedicated pipelines.
Acknowledgments
This publication was partially supported by the PON
PON04a2_H “i-NEXT” Italian research program. This work was
realized with the contribution of SDES (Sustainable Develop-
ment and Energy Savings) Laboratory e UNINETLAB e Uni-
versity of Palermo.
references
[1] Ball M, Wietschel M. The future of hydrogen opportunities
and challenges. Int J Hydrogen Energy 2009;34(2):615e27.
[2] Ball M, Wietschel M, Rentz O. Integration of a hydrogen
economy into the German energy system: an optimising
modelling approach. Int J Hydrogen Energy
2007;32(10e11):1355e68.
[3] Midilli A, Dincer I, Ay M. Green energy strategies for
sustainable development. Energy Policy
2006;34(18):3623e33.
[4] Midilli A, Dincer I. Key strategies of hydrogen energy
systems for sustainability. Int J Hydrogen Energy
2007;32(5):511e24.
[5] Midilli A, Dincer I. Hydrogen as a renewable and sustainable
solution in reducing global fossil fuel consumption. Int J
Hydrogen Energy 2008;33(16):4209e22.
[6] Sherif S, Barbir F, Veziroglu T. Towards a hydrogen
economy. Electr J 2005;18(6):62e76.
[7] Sperling D, Cannon JS. The hydrogen energy transition,
moving toward the post petroleum age in transportation.
Elsevier Academic Press; 2009.
[8] Simader Genter R, Kordesch Karl V. Fuel cells and their
applications. Int J Hydrogen Energy 1996;34(10):1e375.
[9] Padro’ CG, Putsche V. Survey of the Economics of Hydrogen
Technologies. National Renewable Energy Laboratory,
Colorado (USA) Tech. Rep; September 1999.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 4 ) 1 e1 3
[10] Thomas CE, Reardon JP, Lomax Jr FD, Pinyan J, Kuhn Jr IF.
Distributed hydrogen fueling systems analysis, Proceedings
of the 2001 DOE Hydrogen Program Review NREL/CP-570-
30535, Arlington, Virginia; 2001. pp. 1e83.
[11] Caputo A. Utilizzo dell’idrogeno nell’autotrazione: Il
problema dell’infrastruttura distributiva. Termotec (Milano)
2002;56(4):80e93.
[12] Raissi AT, Block D. Hydrogen: automotive fuel of the future.
Power Energy Mag IEEE 2004;2(6):40e5.
[13] Momirlan M, Veziroglu T. Current status of hydrogen
energy. Renew Sustain Energy Rev 2002;6(1e2):141e79.
[14] Momirlan M, Veziroglu T. The properties of hydrogen as
fuel tomorrow in sustainable energy system for a cleaner
planet. Int J Hydrogen Energy 2005;30(7):795e802.
[15] Mulder G, Hetland J, Lenaers G. Towards a sustainable
hydrogen economy: hydrogen pathways and infrastructure.
Int J Hydrogen Energy 2007;32(10e11):1324e31.
[16] Agnolucci P. Hydrogen infrastructure for the transport
sector. Int J Hydrogen Energy 2007;32(15):3526e44.
[17] Wietschel M, Hasenauer U, de Groot A. Development of
European hydrogen infrastructure scenarios. CO2 reduction
potential and infrastructure investment. Energy Policy
2006;34(11):1284e98.
[18] Smit R, Weeda M, de Groot A. Hydrogen infrastructure
development in The Netherlands. Int J Hydrogen Energy
2007;32(10e11):1387e95.
[19] Ogden JM. Developing an infrastructure for hydrogen
vehicles: a Southern California case study. Int J Hydrogen
Energy 1999;24(8):709e30.
[20] Turner JA. Sustainable hydrogen production. Science
2004;305(5686):972e4.
[21] Barbir F. PEM electrolysis for production of hydrogen from
renewable energy sources. Sol Energy 2005;78(5):661e9.
[22] Ghenciu AF. Review of fuel processing catalysts for
hydrogen production in PEM fuel cell systems. Curr Opin
Solid State Mater Sci 2002;6(5):389e99.
[23] Grigoriev S, Porembsky V, Fateev V. Pure hydrogen
production by PEM electrolysis for hydrogen energy. Int J
Hydrogen Energy 2006;31(2):171e5.
[24] Marshall A, Borresen B, Hagen G, Tsypkin M, Tunold R.
Hydrogen production by advanced proton exchange
membrane (PEM) water electrolysers. Reduced energy
consumption by improved electrocatalysis. Energy
2007;32(4):431e6.
[25] Kalinci Y, Hepbasli A, Dincer I. Biomass-based hydrogen
production: a review and analysis. Int J Hydrogen Energy
2009;34(21):8799e817.
[26] Lindstrom B, Pettersson LJ. Hydrogen generation by steam
reforming of methanol over copper-based catalysts for fuel
cell applications. Int J Hydrogen Energy 2001;26(9):923e33.
[27] Lindstrom B, Agrell J, Pettersson L. Combined methanol
reforming for hydrogen generation over monolithic
catalysts. Chem Eng J 2003;93(1):91e101.
[28] Czernik S, French R, Feik C, Chornet E. Hydrogen by
catalytic steam reforming of liquid byproducts from
biomass thermoconversion processes. Ind Eng Chem Res
2002;41(17):4209e15.
[29] Breen J, Burch R, Coleman H. Metal-catalysed steam
reforming of ethanol in the production of hydrogen for fuel
cell applications. Appl Catal B Environ 2002;39(1):65e74.
[30] Liguras DK, Kondarides DI, Verykios XE. Production of
hydrogen for fuel cells by steam reforming of ethanol over
supported noble metal catalysts. Appl Catal B Environ
2003;43(4):345e54.
[31] Agrell J, Birgersson H, Boutonnet M, Melian-Cabrera I,
Navarro RN, Fierro JLG. Production of hydrogen from
methanol over Cu/ZnO catalysts promoted by ZrO2 and
Al2O3. J Catal 2003;219(2):389e403.
Please cite this article in press as: Cipriani G, et al., Perspective on hydrogen energy carrier and its automotive applications,
International Journal of Hydrogen Energy (2014), http://dx.doi.org/10.1016/j.ijhydene.2014.03.174
11
[32] Shoko E, McLellan B, Dicks A, da Costa JD. Hydrogen from
coal: production and utilisation technologies. Int J Coal Geol
2006;65(3 e 4):213e22.
[33] Stiegel GJ, Ramezan M. Hydrogen from coal gasification: an
economical pathway to a sustainable energy future. Int J
Coal Geol 2006;65(3e4):173e90 [hydrogen from Coal].
[34] Clemens T, Gong D, Pearce S. Study on the suitability of
New Zealand coals for hydrogen production. Int J Coal Geol
2006;65(3 e 4):235e42.
[35] Neef HJ. International overview of hydrogen and fuel cell
research. Energy 2009;34(3):327e33.
[36] Balat M. Potential importance of hydrogen as a future
solution to environmental and transportation problems. Int
J Hydrogen Energy 2008;33(15):4013e29.
[37] Fatsikostas AN, Kondarides D, Verykios XE. Production of
hydrogen for fuel cells by reformation of biomass-derived
ethanol. Catal Today 2002;75(1e4):145e55.
[38] Miceli R. Energy management and smart grids. Energies
2013;6(4):2262e90.
[39] Balat H, Kirtay E. Hydrogen from biomass present scenario
and future prospects. Int J Hydrogen Energy
2010;35(14):7416e26.
[40] Hetland J, Mulder G. In search of a sustainable hydrogen
economy: how a large-scale transition to hydrogen may
affect the primary energy demand and greenhouse gas
emissions. Int J Hydrogen Energy 2007;32(6):736e47.
[41] Haeseldonckx D, D’haeseleer W. The use of the natural-gas
pipeline infrastructure for hydrogen transport in a changing
market structure. Int J Hydrogen Energy 2007;32(10e11):1381e6.
[42] Cipriani G, Di Dio V, Ricco Galluzzo G. A photovoltaic
system suitable for the battery pack charging of an
electrically power assisted velocipede. In: SPEEDAM 2012-
21st International Symposium on Power Electronics,
Electrical Drives, Automation and Motion; 2012. pp. 1142e7.
[43] Di Dio V, La Cascia D, Liga R, Miceli R. Vehicles PEMFC power
system mathematical model for integrated design. J Energy
Power Eng 2013;7:746e51.
[44] Boscaino V, Miceli R, Capponi G, Casadei D. “Fuel cell
modelling and test: Experimental validation of model
accuracy,” in Power Engineering, Energy and Electrical
Drives (POWERENG), 2013 Fourth International Conference
on, May 2013, pp. 1795e1800.
[45] Boscaino V, Miceli R, Capponi G. “A circuit model of a 5kw
fuel cell,” in Clean Electrical Power (ICCEP), 2013
International Conference on, June 2013, pp. 447e452.
[46] Boscaino V, Miceli R, Capponi G, Ricco Galluzzo G. A review
of fuel cell based hybrid power supply architectures and
algorithms for household appliances. Int J Hydrogen Energy
16 January 2014;39(3):1195e209.
[47] Boscaino V, Miceli R, Capponi G. Matlab-based simulator of
a 5 kw fuel cell for power electronics design. Int J Hydrogen
Energy 2013;38(19):7924e34.
[48] Di Dio V, La Cascia D, Liga R, Miceli R. “Integrated
mathematical model of proton exchange membrane fuel
cell stack (PEMFC) with automotive synchronous electrical
power drive,” in Electrical Machines, 2008. ICEM 2008. 18th
International Conference on, 2008, pp. 1e6.
[49] Frenette G, Forthoffer D. Economic and commercial viability
of hydrogen fuel cell vehicles from an automotive
manufacturer perspective. Int J Hydrogen Energy
2009;34(9):3578e88.
[50] Romm J. The car and fuel of the future. Energy Policy
2006;34(17):2609e14.
[51] Vinay A, Duffy JJ. Efficiencies of hydrogen storage systems
onboard fuel cell vehicles. Sol Energy 2005;78(5):687e94.
[52] van den Berg AWC, Arean CO. Materials for hydrogen
storage: current research trends and perspectives. Chem
Commun; 2008:668e81.
12 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 4 ) 1 e1 3
[53] Campesi R, Cuevas F, Gadiou R, Leroy E, Hirscher M, Vix-
Guterl C, et al. Hydrogen storage properties of Pd
nanoparticle/carbon template composites. Carbon
2008;46(2):206e14.
[54] Campesi R, Cuevas F, Leroy E, Hirscher M, Gadiou R, Vix-
Guterl C, et al. In situ synthesis and hydrogen storage
properties of PdNi alloy nanoparticles in an ordered
mesoporous carbon template. Microporous Mesoporous
Mater 2009;117(1e2):511e4.
[55] de la Casa-Lillo MA, Darkrim FL, Amoros DC, Solano AL.
Hydrogen storage in activated carbons and activated carbon
fibers. J Phys Chem B 2002;106(42):10930e4.
[56] Conte M, Prosini P, Passerini S. Overview of energy/
hydrogen storage: state-of-the-art of the technologies and
prospects for nanomaterials. Mater Sci Eng B
2004;108(1e2):2e8.
[57] David E. An overview of advanced materials for
hydrogen storage. J Mater Process Technol
2005;162e163(1):169e77.
[58] DeLuchi M. Hydrogen vehicles: an evaluation of fuel
storage, performance, safety, environmental impacts, and
cost. Int J Hydrogen Energy 1989;14(2):81e130.
[59] Dimitrakakis GK, Tylianakis E, Froudakis GE. Pillared
graphene: a new 3-D network nanostructure for enhanced
hydrogen storage. Nano Lett 2008;8(10):3166e70.
[60] Berube’ V, Radtke G, Dresselhaus M, Chen G. Size effects on
the hydrogen storage properties of nanostructured metal
hydrides: a review. Int J Energy Res 2007;31(6e7):637e63.
[61] Haas M, Zielinski J, Dantsin G, Coe C, Pez G, Cooper A.
Tailoring singlewalled carbon nanotubes for hydrogen
storage. J Mater Res 2005;20(12):3214e23.
[62] Hall PJ. Energy storage: the route to liberation from the
fossil fuel economy? Energy Policy 2008;36(12):4363e7.
[63] Hirscher M, Panella B. Nanostructures with high surface
area for hydrogen storage. J Alloys Compd
2005;404e406(1):399e401.
[64] Jena P. Materials for hydrogen storage: past, present, and
future. J Phys Chem Lett 2011;2(3):206e11.
[65] Jorda’-Beneyto M, Suarez-Garcia F, Lozano-Castello’ D,
Cazorla-Amoros D, Linares-Solano A. Hydrogen storage on
chemically activated carbons and carbon nanomaterials at
high pressures. Carbon 2007;45(2):293e303.
[66] Kowalczyk P, Tanaka H, Holyst R, Kaneko K, Ohmori T,
Miyamoto J. Storage of hydrogen at 303 K in graphite slitlike
pores from Grand Canonical Monte Carlo simulation. J Phys
Chem B 2005;109(36):17174e83.
[67] Lachawiec AJ, Yang RT. Isotope tracer study of hydrogen
spillover on carbon-based adsorbents for hydrogen storage.
Langmuir 2008;24(12):6159e65.
[68] Li Y, Zhao D, Wang Y, Xue R, Shen Z, Li X. The mechanism
of hydrogen storage in carbon materials. Int J Hydrogen
Energy 2007;32(13):2513e7.
[69] Mori D, Hirose K. Recent challenges of hydrogen storage
technologies for fuel cell vehicles. Int J Hydrogen Energy
2009;34(10):4569e74.
[70] Nishihara H, Hou P-X, Li L-X, Ito M, Uchiyama M,
Kaburagi T, et al. High-pressure hydrogen storage in zeolite-
templated carbon. J Phys Chem C 2009;113(8):3189e96.
[71] Dillon A, Heben M. Hydrogen storage using carbon
adsorbents: past, present and future. Appl Phys A
2001;72(2):133e42.
[72] Ross D. Hydrogen storage: the major technological barrier to
the development of hydrogen fuel cell cars. Vacuum
2006;80(10):1084e9.
[73] Thomas R, Christophe B, Keith EG, Roland J-MP. Hydrogen
storage enhanced in Li-doped carbon replica of zeolites: a
possible route to achieve fuel cell demand. J Chem Phys
2009;130(17).
Please cite this article in press as: Cipriani G, et al., Perspective on hydrogen energy carrier and its automotive applications,
International Journal of Hydrogen Energy (2014), http://dx.doi.org/10.1016/j.ijhydene.2014.03.174
[74] Billur S, Farida L-D, Michael H. Metal hydride materials for
solid hydrogen storage: a review. Int J Hydrogen Energy
2007;32(9):1121e40.
[75] Arindam S, Rangan B. Net energy analysis of hydrogen
storage options. Int J Hydrogen Energy 2005;30(8):867e77.
[76] Louis S, Andreas Z. Hydrogen-storage materials for mobile
applications. Nature Nov 2001;414(6861):353e8.
[77] Strobel R, Garche J, Moseley P, Jorissen L, Wolf G. Hydrogen
storage by carbon materials. J Power Sources
2006;159(2):781e801.
[78] Wang L, Yang RT. Hydrogen storage properties of carbons
doped with ruthenium, platinum, and nickel nanoparticles.
J Phys Chem C 2008;112(32):12486e94.
[79] Wang Y, Li A, Wang K, Guan C, Deng W, Li C, et al.
Reversible hydrogen storage of multi-wall carbon
nanotubes doped with atomically dispersed lithium. J Mater
Chem 2010;20:6490e4.
[80] Xu W-C, Takahashi K, Matsuo Y, Hattori Y, Kumagai M,
Ishiyama S, et al. Investigation of hydrogen storage capacity
of various carbon materials. Int J Hydrogen Energy
2007;32(13):2504e12.
[81] Yang Z, Xia Y, Sun X, Mokaya R. Preparation and hydrogen
storage properties of zeolite-templated carbon materials
nanocast via chemical vapor deposition: effect of the zeolite
template and nitrogen doping. J Phys Chem B
2006;110(37):18424e31.
[82] Yang Z, Xia Y, Mokaya R. Enhanced hydrogen storage
capacity of high surface area zeolite-like carbon materials. J
Am Chem Soc 2007;129(6):1673e9.
[83] Yang J, Sudik A, Wolverton C, Siegel DJ. High capacity
hydrogen storage materials: attributes for automotive
applications and techniques for materials discovery. Chem
Soc Rev 2010;39:656e75.
[84] Yurum Y, Taralp A, Veziroglu TN. Storage of hydrogen in
nanostructured carbon materials. Int J Hydrogen Energy
2009;34(9):3784e98.
[85] Zhou L. Progress and problems in hydrogen storage
methods. Renew Sustain Energy Rev 2005;9(4):395e408.
[86] Zubizarreta L, Arenillas A, Pis JJ. Carbon materials for H2
storage. Int J Hydrogen Energy 2009;34(10):4575e81.
[87] Schuth F, Bogdanovic B, Felderhoff M. Light metal hydrides
and complex hydrides for hydrogen storage. Chem
Commun; 2004:2249e58.
[88] Alapati SV, Johnson J,K, Sholl DS. Identification of
destabilized metal hydrides for hydrogen storage using first
principles calculations. J Phys Chem B 2006;110(17):8769e76.
[89] ichi Orimo S, Nakamori Y, Eliseo JR, Zuttel A, Jensen CM.
Complex hydrides for hydrogen storage. Inst Mater Res
Univ Hawaii 2007;107(10):4111e32.
[90] Panella B, Hirscher M, Roth S. Hydrogen adsorption in
different carbon nanostructures. Carbon
2005;43(10):2209e14.
[91] Kojima Y, Kawai Y, Koiwai A, Suzuki N, Haga T, Hioki T,
et al. Hydrogen adsorption and desorption by carbon
materials. J Alloys Compd 2006;421(1e2):204e8.
[92] Farrell A, Keith DW, Jensen MW, Ross M. Hydrogen as a
transportation fuel. Environ Sci Policy Sustain Dev
2001;43(3):43e5.
[93] Farrell AE, Keith DW, Corbett JJ. A strategy for introducing
hydrogen into transportation. Energy Policy
2003;31(13):1357e67.
[94] “Promotion of the use of energy from renewable sources
and amending and subsequently repealing directives 2001/
77/EC and 2003/30/EC,” Tech. Rep; 2009.
[95] Yang C, Ogden J. Determining the lowest-cost hydrogen
delivery mode. Int J Hydrogen Energy 2007;32(2):268e86.
[96] Moore R, Raman V. Hydrogen infrastructure for fuel cell
transportation. Int J Hydrogen Energy 1998;23(7):617e20.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 4 ) 1 e1 3
[97] Zhao J, Melaina MW. Transition to hydrogen-based
transportation in China: lessons learned from alternative
fuel vehicle programs in the United States and China.
Energy Policy 2006;34(11):1299e309.
[98] Mazloomi K, Gomes C. Hydrogen as an energy carrier:
prospects and challenges. Renew Sustain Energy Rev
2012;16:3024e33. Elsevier.
[99] Fayaz H, Saidur R, Anuar FS, Islam MR. An overview of
hydrogen as a vehicle fuel. Renew Sustain Energy Rev
2012;16:5511e28. Elsevier.
[100] Sobrino F, Rodriguez Monroy C, Hernandez Perez JL. Critical
analysis on hydrogen as an alternative to fossil fuels and
biofuels. Renew Sustain Energy Rev 2010;14:772e80.
Elsevier.
[101] Dincer I. Environmental and sustainability aspects of
hydrogen and fuel cell systems. Int J Energy Res
2007;31(1):29e55.
[102] Kerroum I, El Matbouly H, Domingue F. Survey of
commercial sensors and emerging miniaturized
technologies for safety applications in hydrogen vehicles.
In: Sensors Applications Symposium (SAS), 2012 IEEE; Feb
2012. pp. 1e6.
[103] Tseng P, Lee J, Friley P. A hydrogen economy: opportunities
and challenges. Energy 2005;30(14):2703e20.
[104] Shayegan S, Hart D, Pearson P, Joffe D. Analysis of the cost
of hydrogen infrastructure for buses in London. J Power
Sources 2006;157(2):862e74.
[105] Shayegan S, Pearson P, Hart D. Hydrogen for buses in
London: a scenario analysis of changes over time in
refuelling infrastructure costs. Int J Hydrogen Energy
2009;34(19):8415e27.
[106] Tzimas E, Castello P, Peteves S. The evolution of size and
cost of a hydrogen delivery infrastructure in Europe in the
medium and long term. Int J Hydrogen Energy
2007;32(10e11):1369e80.
[107] Rajesh KA, Wang X, Rousseau A, Kumar R. Fuel economy of
hydrogen fuel cell vehicles. J Power Sources
2004;130(1e2):192e201.
[108] Andrews J, Shabani B. Re-envisioning the role of hydrogen
in a sustainable energy economy. Int J Hydrogen Energy
2012;37(2):1184e203.
[109] Dunn S. Hydrogen futures: toward a sustainable energy
system. Int J Hydrogen Energy 2002;27(3):235e64.
[110] Edwards P, Kuznetsov V, David W, Brandon N. Hydrogen
and fuel cells: towards a sustainable energy future. Energy
Policy 2008;36(12):4356e62.
[111] Elam CC, Padro’ CE, Sandrock G, Luzzi A, Lindblad P,
Hagen EF. Realizing the hydrogen future: the International
Please cite this article in press as: Cipriani G, et al., Perspective on hydrogen energy carrier and its automotive applications,
International Journal of Hydrogen Energy (2014), http://dx.doi.org/10.1016/j.ijhydene.2014.03.174
13
Energy Agency’s efforts to advance hydrogen energy
technologies. Int J Hydrogen Energy 2003;28(6):601e7.
[112] Ewan B, Allen R. A figure of merit assessment of the routes
to hydrogen. Int J Hydrogen Energy 2005;30(8):809e19.
[113] Kothari R, Buddhi D, Sawhney R. Comparison of
environmental and economic aspects of various hydrogen
production methods. Renew Sustain Energy Rev
2008;12(2):553e63.
[114] Lattin W, Utgikar V. Transition to hydrogen economy in the
United States: a 2006 status report. Int J Hydrogen Energy
2007;32(15):3230e7.
[115] Marban G, Valdes-Solis T. Towards the hydrogen economy?
Int J Hydrogen Energy 2007;32(12):1625e37.
[116] Mueller-Langer F, Tzimas E, Kaltschmitt M, Peteves S.
Techno-economic assessment of hydrogen production
processes for the hydrogen economy for the short and
medium term. Int J Hydrogen Energy
2007;32(16):3797e810.
[117] Mierlo JV, Maggetto G, Lataire P. Which energy source for
road transport in the future? A comparison of battery,
hybrid and fuel cell vehicles. Energy Convers Manag
2006;47(17):2748e60.
[118] Barreto L, Makihira A, Riahi K. The hydrogen economy in
the 21st century: a sustainable development scenario. Int J
Hydrogen Energy 2003;28(3):267e84.
[119] Bartels JR, Pate MB, Olson NK. An economic survey of
hydrogen production from conventional and alternative
energy sources. Int J Hydrogen Energy
2010;35(16):8371e84.
[120] Melaina MW. Initiating hydrogen infrastructures:
preliminary analysis of a sufficient number of initial
hydrogen stations in the US. Int J Hydrogen Energy
2003;28(7):743e55.
[121] Moore R, Hauer K, Ramaswamy S, Cunningham J. Energy
utilization and efficiency analysis for hydrogen fuel cell
vehicles. J Power Sources 2006;159(2):1214e30.
[122] Shinnar R. The hydrogen economy, fuel cells, and electric
cars. Technol Soc 2003;25(4):455e76.
[123] Scrivano G, Piacentino A, Cardona F. Experimental
characterization of PEM fuel cells by micro-models for the
prediction of on-site performance. Renew Energy
2009;34(3):634e9.
[124] Kalamaras CF, Efstathiou AM. Hydrogen production
technologies: Current state and future developments. In:
Hindawi conference paper in Energy; 2013. pp. 1e9.
[125] Winter C-J. Hydrogen energy. Abundant, efficient, clean: a
debate over the energy system of change. Int J Hydrogen
Energy 2009;34(14 Suppl. 1):1e52.