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Solar Hydrogen Production and Storage Techniques

Article  in  Recent Patents on Mechanical Engineering · June 2010

DOI: 10.2174/1874477X11003020154

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154 Recent Patents on Mechanical Engineering 2010, 3, 154-159

Solar Hydrogen Production and Storage Techniques

Gregoris Panayiotou1,2, Soteris Kalogirou*,1 and Savvas Tassou2

1
Department of Mechanical Engineering and Materials Science and Engineering, Cyprus University of Technology,
Limassol, Cyprus, 2Department of Mechanical Engineering, Brunel University, Uxbridge, Middlesex, UK

Received: May 7, 2010; Accepted: May 24, 2010; Revised: May 25, 2010

Abstract: The main disadvantage of Renewable Energy Sources (RES) systems is their variability and dependence on
environmental conditions. This problem can be overcome by storing energy in the form of hydrogen either for long or
short term. One of the most promising types of such systems is the solar hydrogen energy system (SoHyS) where
essentially the electricity produced by the PVs is stored in the form of hydrogen by using a variety of storage methods and
means. The hydrogen can be then reconverted to electricity on demand by using a fuel cell. In this work a brief description
of SoHyS and their characteristics is presented along with recent patents on some of the main system components such as
the electrolyser and the storage techniques and devices. The future trends of research in this area would be on more
efficient electrolysers and more advanced and lightweight storage media in order to increase the overall effectiveness of
the system.
Keywords: Solar hydrogen, electrolyser, hydrogen storage, material-based, metal hydrides.

1. INTRODUCTION many different configurations and topologies exist and their

formation depends on a variety of specific parameters such
Essentially, a solar-hydrogen energy system (SoHyS) is a
as whether the system is grid connected or stand-alone, if
system where the electricity produced by the PVs is stored in
batteries are used, if the PVs are directly coupled to the
the form of hydrogen in a storage device and reconverted to
electrolyser and many more.
electricity by using a fuel cell whenever is needed and in
general consists of the following main parts: The first patent [1] on this type of systems concerns a
personal hydrogen fuelling station capable of producing
• Photovoltaic (PV) panels to produce the required
hydrogen from solar radiation at a good efficiency via
electricity for the electrolysis process
combined photovoltaic and thermal energy and then storing
• Electrolyzer, either proton exchange membrane (PEM) hydrogen safely at a home or business site. This system
or alkaline, for the electrolysis of water to hydrogen and consists of: 1) solar energy conversion subsystem to capture
oxygen solar radiation by using both PVs and a solar thermal system;
2) electrolyzer that uses the converted electricity and heat to
• Storage ‘device’ which can be a high pressure storage
split water into hydrogen and oxygen; 3) hydrogen storage
tank, a low pressure storage tank or a material-based
container comprising a metal hydride, chemical hydride, or
canister. Also combinations of the above can be used
other solid or liquid phase material as a storage medium to
• Fuel cell for the direct conversion of the chemical capture and store the generated hydrogen; and 4) control
energy of hydrogen to electricity. means to regulate uptake or release of hydrogen from the
Finally, a series of other components are used according storage container. The configuration of this SoHyS can be
to the configuration of each SoHyS such as hydrogen puri- seen in Fig. (1). This invention demonstrates the feasibility
fying units, power conditioning and control system, maxi- of using primarily renewable energy sources to produce and
mum power point tracker (MPPT), DC/AC inverter, safely store hydrogen to meet personal transportation needs.
electrical load, pressure regulating valves and batteries. The The key aspects for the further commercialisation of the
type of storage to be used in such a system is the parameter presently invented home hydrogen fuelling station are the
that defines whether a compressor is needed to increase the improvement of the efficiencies of PV modules and the
hydrogen pressure. decrease of the cost of fuel cell systems. In this way, this
system will become even more affordable and will have a
This kind of systems can be used for a variety of pur- major impact on the global efforts to curtail carbon dioxide
poses such as producing power for small and medium scale emissions and other pollutants associated with the production
stand-alone applications, interconnected to the electricity and use of fossil fuels.
grid or even for transportation purposes. Nowadays,
A patent concerning a teaching aid for demonstrating a
*Address correspondence to this author at the Department of Mechanical
SoHyS was developed in order to demonstrate the usefulness
Engineering and Materials Science and Engineering, Cyprus University of of such a system in a way easy to understand and compre-
Technology, P.O. Box 50329, 3603 Limassol, Cyprus; Tel.:+35725002621; hend [2]. More specifically, the system demonstrated in this
Fax: +35725002637; Cell: +35799698508; patent consisted of five basic parts namely photovoltaic
E-mail: [email protected]

1874-477X/10 $100.00+.00 © 2010 Bentham Science Publishers Ltd.

Solar Hydrogen Production and Storage Techniques Recent Patents on Mechanical Engineering 2010, Vol. 3, No. 2 155

mean the breaking off by using electricity. So consequently,

electrolysis of water (H2O) means the splitting of water to its
two basic components hydrogen (H2) and oxygen (O2).
The decomposition of water is occurring due to an
electric current passing through it. This is achieved when an
electrical power source is connected to two electrodes, or
two plates (typically platinum or stainless steel) which are
submersed in water. The reactions taking place during water
electrolysis are shown below and as it can be seen hydrogen
appears at the cathode (the negatively charged electrode) and
oxygen appears at the anode (the positively charged elec-
trode). As it can be also be observed the generated amount
(moles) of hydrogen is twice that of oxygen, and both are
proportional to the total electrical charge that is passing
through the solution.
Anode reaction: H2O  2H+ + 2e- + O2 (1)
+ -
Cathode reaction: 2H + 2e  H2 (2)
Overall reaction: H2O  H2 +  O2 (3)
The efficacy of electrolysis is increased through the
addition of an electrolyte such as a salt, an acid or a base (i.e.
H2SO4, KOH) and the use of electrocatalysts such as Nafion
membrane. The basic types of commercially available
electrolysers are alkaline and PEM. Their main difference
lies to the fact that they use different types of electrolyte;
more specifically the traditional electrolyte used in the con-
Fig. (1). Schematic diagram of a home hydrogen fuelling station ventional alkaline water electrolysers is aqueous potassium
[1]. hydroxide (KOH) while in PEM electrolysers a solid acidic
polymer membrane is used most commonly Nafion.
panels, PEM electrolyser, fuel cell, load and digital multi- It is well known in the field of water electrolysis that the
metres. The main purpose of this patent is to provide a clear theoretical values of energy efficiency vary within 50-80%
explanation of the processes that take place in such a system. [4]. Of course, these values are not very representative since
they refer only to the efficiency of converting electrical
The optimisation of this kind of systems especially when energy into hydrogen's chemical energy and the energy lost
used on vehicles where the available space is limited is of in generating the electricity is not included.
great importance. Having this in mind a patent was made
concerning a method for configuring and optimising such a In this area the first patent [5] concerns the development
system when used on a vehicle [3]. More specifically, the of a high performance cathode for water electrolysers
optimisation of the systems’ efficiency is achieved by consisting of a metallic substrate which has a coating layer
matching the most efficient voltage of the PVs with the most containing substantially pure ruthenium oxide. This novel
efficient voltage required for the electrolysis. This resulted to type of cathode not only provides higher performance but
an increase of the overall performance of the system from also has longer life time especially in cases where unstable
2-6 % to 7 % using the same components [3]. This of course or intermittent power source is used.
is a very important fact since by increasing the performance The next invention [6] relates to an electrochemical cell
of the system the cost is consequently decreased. Also, stack having means for maintaining constant mechanical
another positive fact is that with the new simplified design load over the components in an electrochemical cell stack.
there is no longer a need to use charge controller, batteries More specifically, this is achieved by inserting a spherical-
and DC converter. The reduction on the cost of hydrogen is shaped elastic pad into the space between cell stack and
expected to be from $11 per kg to about $3 per kg. housing wall. This electrochemical cell stack is of Proton
In this work, two of the main parts of a SoHyS system Exchange Membrane (PEM) type and it can be used both in
are going to be discussed and the recent patents of the last the area of PEM fuel cells and PEM water electrolyser cells
years on those areas are going to be presented. More where protons constitute the carrier of ionic charge.
specifically, these parts are the electrolyser unit where the The next patent [7] is about a system which incorporates
hydrogen is produced and the storage methods which can a hybrid electrolyser device, formed by the combination of at
either be a high pressure storage tank, a low pressure storage least two different electrolysis technologies and at least one
tank or a material-based canister. controller which distributes hydrogen production between
2. ELECTROLYSER the electrolysers based on different technologies, so that
there is at least, a first type of electrolyser with a rapid
Electrolysis is a word coming from the combination of dynamic and at least a second type of electrolyser technology
two Greek words  (electro) and 
 (lysis) which with a substantially slower dynamic.
156 Recent Patents on Mechanical Engineering 2010, Vol. 3, No. 2 Panayiotou et al.

3. HYDROGEN STORAGE TECHNIQUES

The present techniques used to store hydrogen can be
summarized as follow:
-Gaseous Hydrogen Storage
-Cryogenic-Liquid Hydrogen Storage
-Material-Based Hydrogen Storage:
• Carbon-based materials
• Chemical Hydrides (CH)
• Metal Hydrides (MH)
The main issues and problems that appear in all kind of
hydrogen storage methods are: system weight, volume and
cost, efficiency, durability/operability, charging/discharging
rates, codes and standards, materials of construction, dispen-
sing technology, thermal management and system life-cycle
assessments. Fig. (2). Qualitative comparison of hydrogen storage technologies
and targets [9].
López et al. [8] examined three possible ways to store
hydrogen in a SoHyS system namely high pressure storage,
On the other hand, there are also several disadvantages
low pressure storage and metal hydride systems. Their
with this type of hydrogen storage that have to do with the
analysis also included an exergy analysis using data from a
hydrogen boil-off or evaporation, the energy required for
SoHyS facility of the Spanish Instituto Nacional de Tecnica
hydrogen liquefaction, volume, weight, and tank cost. The
Aeroespacial (INTA). The results of this analysis showed
that the worst and most inefficient way to store hydrogen is most important one is that about 30% of the heating value of
hydrogen is required for liquefaction which is a rather high
by using high pressure tanks.
energy requirement.
Currently, intensive research is taking place for several
other hydrogen storage methods which are trying to Carbon-Based Materials
overcome and solve the issues mentioned above.
Hydrogen storage in carbons is one of the most
These methods are: promising technologies due to the abilities of several carbons
 Advanced hydrogen-absorbing alloys nanostructures such as nanofibers, nanotubes and fullerenes
to absorb large quantities of hydrogen. Research has been
 Carbon nanomaterial ongoing for years on this technology while the use of laser
 Organic Hydrides technology has made it possible to produce a high percentage
of nanotubes with the exact diameter and level of purity
A comparison of most hydrogen storage technologies and
needed. According to Yildirim and Ciraci [10] carbon
targets in terms of both tank weight and volume according to
nanotubes covered in titanium atoms, provide the most
Mori and Hirose [9] can be seen in Fig. (2). efficient method for storing hydrogen known to date due to
the fact that despite their small size, they can hold 8% their
Gaseous Hydrogen Storage weight in hydrogen gas.
In this kind of storage, hydrogen is commonly stored at
high pressures between 350-700 bar, while the energy Chemical Hydrides (CH)
density of gaseous hydrogen is improved by storing hydro-
In this method of hydrogen storage, hydrogen containing
gen at higher pressures. As a result of high pressure, material
chemicals such as methanol, ammonia and cycloalkanes are
and design improvements are required in order to ensure tank used. This is a rather advantageous method for storing
integrity. Also compression technologies need to be opti-
hydrogen in fuel cell vehicles (FCV’s) due to the fact that in
mized in order to improve efficiencies and reduce the hydro-
standard temperature and pressure conditions (STP) all of the
gen production cost. The cost of high-pressure compressed
aforementioned substances are in liquid phase and so the
gas tanks is directly related by the cost of the carbon fibre
existing infrastructure for gasoline can be used. Chemical
that must be used for light-weight structural reinforcement.
hydrides have hydrogen storage capacities of about 6-8 wt%
while several of them have the ability to be reversible by
Cryogenic-Liquid Hydrogen Storage using the proper types of catalysts. In Table 1, the hydrogen
There are several advantages when storing hydrogen in a storage capacities of various media that can be used for
liquid state (LH2) with the most important two being that storing hydrogen according to Biniwale et al. [11] are
energy density and volumetric capacity are improved. For shown.
example the volumetric capacity of liquid hydrogen is A very interesting invention [12] concerns a hydrogen
0.070kg/l, compared to 0.030kg/l for 700 bar gas tanks and storing system where a combination of chemical and metal
as a result liquid hydrogen (LH2) tanks can store more
hydrogen in a given volume than compressed gas tanks.
Solar Hydrogen Production and Storage Techniques Recent Patents on Mechanical Engineering 2010, Vol. 3, No. 2 157

Table 1. Hydrogen Storage Capacity of Various Media [11]. process when storing hydrogen in MH canisters is shown in
Fig. (4). There are several types of metals and metal alloys
Hydrogen Content
that have the ability to absorb hydrogen under moderate
Storage Media pressure and temperature creating hydrides. A metal hydride
wt% mol/l tank contains granular metal which absorbs hydrogen similar
to the way a sponge absorbs water. Some of the most studied
Cyclohexane 7.2 27.77 hydrides according to Principi et al. [13] can be seen in
Methylcyclohexane 6.2 23.29 Table 2.

Tetralin 3.0 14.72

Table 2. Characteristics of Some of the Most Studied Hydrides
[13].
cis-Decalin 7.3 32.44

LiBH4 + 4H2O 8.6 2.4 Metals Hydrides Hydrogen Capacity (wt T for 1 Bar (oC)
%)

hydrides is used. In general the principle of operation works LaNi5 LaNi5H6 1.37 12
as follows: the chemical hydride evolves hydrogen sponta- FeTi FeTiH2 1.89 -8
neously upon exposure to water vapour while the metal
hydride reversibly absorbs/desorbs hydrogen based on Mg2Ni Mg2NiH 4 3.59 255
temperature and pressure. The hydrogen producing substance ZrMn2 ZrMn2H 2 1.77 440
(chemical hydride) can be formed in the shape of a pellet and
contained within a hydrogen and water vapour permeable Mg MgH2 7.60 279
and liquid water impermeable membrane. In Fig. (3) a Where: La: Lanthanum, Ni: Nickel, Fe: Iron, Ti: Titanium, Mg: Magnesium, Zr:
configuration developed in this invention is shown which is Zirconium, Mn: Manganese, H: Hydrogen.
of high importance since it introduces the idea of including a
fuel cell stack in order to develop a complete power system.
The fuel cell stack can be incorporated into the container by A number of hydrides are currently being studied for use
being rolled or stacked in a way to form a flexible film that as possible hydrogen storage material for various appli-
can be bent around the fuel or valves for ease of manu- cations. Consequently, the objective of the next invention
facture. The following layers are described for use in a cylin- [14] is to produce a metal hydride directly from a reaction
drical battery shape. Other layouts of layers may be used to between metal and water or metal and hydroxide or metal
form different shapes. The example layouts provide for the and aqueous hydrogen chloride. Also, the products of these
formation to two fuel cells coupled in series. Beginning reactions are to be provided in such a way that they are
inside power generator, a hydrogen generating fuel portion in mostly recyclable and may be used either as hydrides in
one embodiment includes a porous metal hydride within a many applications, or hydrides for on-board use with rever-
porous thermal conductor layer. The hydride and conductor sibility or for producing hydrogen on-board by chemical
layer are disposed within a chemical hydride. These fuels are reactions e.g. the chemical slurry method. By using this
provided within a selectively permeable membrane. A fixed synthesis route the need for separately forming hydrogen by
valve is disposed around the fuel mixture, and includes an expensive process and then to synthesize a hydride by
multiple openings such as slots for allowing hydrogen and metal-hydrogen reaction is dispensed.
water vapour to pass. Around the fixed valve is a moveable During the charging and discharging phase of the metal
valve, having openings that selectively line up with or cover hydride (MH) canister heat must be removed and added
the openings in the fixed valve. An anode support surrounds respectively in order to enhance and improve the processes
the valve assembly and supports a fuel cell stack that and the energy efficiency. The energy efficiency of the
receives hydrogen from the fuel and oxygen from ambient system will be lower, and the system more complex, if extra
air, and converts them to water vapour and electricity. The heat must be generated to remove the hydrogen from the
fuel cell stack resides within a container, that is formed with tank. This problem is attempted to be solved by the follow-
an external cathode electrode that is electrically coupled to a ing invention [15] where the storage tank and the fuel cell
cathode within the fuel cell stack via a tab. Openings are are mutually arranged in such a way so as to achieve a heat
provided in container to supply oxygen from ambient air to exchange relationship between the anode of the fuel cell and
the cathode of fuel cell stack. A pressure responsive valve the gas absorbing material, metal hydride, and consequently
diaphragm is coupled to a valve pin, for moving the enhance the hydrogen releasing process.
moveable valve to regulate the flow of hydrogen and water
vapour responsive to electrical demand placed on power The main disadvantage when using MH for storing
generator. A vent to ambient may be formed in the cathode hydrogen is their weight and due to that researchers on a
or other convenient location to provide ambient pressure to worldwide basis are trying to use lighter alloys and find
valve diaphragm [12]. methods of packing the hydrogen in higher concentrations.
Nevertheless various types of metal hydrides are available
commercially; representing a good solution for hydrogen
Metal Hydrides (MH)
storage where weight is not a problem.
By definition a hydride is a compound which consists of
Management of thermal energy is a key issue for all
hydrogen and one or more other elements. The typical
hydrogen storage methods due to its crucial role in aspects
158 Recent Patents on Mechanical Engineering 2010, Vol. 3, No. 2 Panayiotou et al.

Fig. (3). Cross sectional representation of a top portion of an example of a hydrogen power generator [12].

like charging/discharging rates and energy efficiency. More

specifically, during the charging and discharging phases heat
must be removed and added respectively so as to enhance the
processes and improve the energy efficiency. For this
purpose in another invention [16] auxiliary heating systems
that can supply heat to a hydrogen storage material, such as a
metal hydride, which is located inside a hydrogen storage
tank, have been developed. These systems involve the
catalytic combustion of hydrogen and oxygen in a catalytic
heater to produce heat and combustion products (about 242
kJ/mole H2 and water vapour). Consequently, the heat
produced from the catalytic combustion is then transferred,
either directly or indirectly, to the hydrogen storage material
to stimulate the release of additional hydrogen that could
again be stored in the hydrogen storage material. By the term
‘direct heating’ it is meant that the heat is transferred directly
Fig. (4). Hydrogen gas moves in toward the interface where the without using a heat transfer fluid. On the other hand by
hydrogen molecule is split into hydrogen atoms which are absorbed using ‘indirect heating’ it is indicated that heat is transferred
by the metal, whereby hydrogen is stored in the metallic matrix. to the hydrogen storage material by using a heat transfer
 Solar Hydrogen Production and Storage Techniques Recent Patents on Mechanical Engineering 2010, Vol. 3, No. 2 159

fluid such as water, mineral and synthetic oils. The energy duction of new more efficient metal hydrides, the reduction
efficiency of these systems may approach 100% in con- of their weight especially for vehicle applications and also
verting hydrogen gas to heat. The use of such systems can the thermal management during the absorption/ desorption
result to an important improvement of the overall efficiency processes in order to increase the overall efficiency of the
of a hydrogen-consuming device by reducing the energy load system. Examples of patents on these areas are given in this
required to deliver hydrogen from a hydrogen storage tank. paper.
A typical configuration of such a system consists of a
hydrogen storage tank, a catalytic heater and a circulation ACKNOWLEDGEMENTS
pump or other similar mechanism for moving the heat
transfer fluid between the catalytic heater and the hydrogen None declared.
storage tank in the case on which the heat is transferred
indirectly. CONFLICT OF INTEREST
On their work Førde et al. [17] proposed to thermally None provided.
integrate a PEMFC with a metal hydride (MH) canister by REFERENCES
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