An investigation into Hydrogen Storage

methods
Introduction
Since 1977 the public have been told that the world is running out of oil [1] and other fossil
fuels such as natural gas and coal. The timescales for these to run out varies in different
sources, for example some say that natural gas will be gone in 35 years and oil in 70 years
[2], it has also been stated that oil could run out in 50 years or in 120 years depending on
consumption trends [3] and yet further sources have claimed that the world is not running out
of oil, that there are trillions of barrels worth of oil to be found in South America, Africa and
the Artic [1].
Regardless of how long our planets oil reserves will last it is still a finite resource, on top of
which we know that the emissions from fossil fuels are harmful to the environment. The BBC
reported that if temperatures remain as predicted then 2015 will be the first year that global
temperatures have risen by 1oc above the preindustrial average [4].
This is clearly a large issue and so many countries have set targets to increase the amount of
sustainable fuels that are used. The EU for example have issued a legally binding target of
20% final energy consumption by 2020 (that is to say 20% of Europes energy usage must
come from sustainable sources) to achieve this the national targets range from 10% in Malta
to 49% in Sweden [5].
Hydrogen is seen as the answer to the worlds desire for a less polluting fuel source as it is
lightweight, highly abundant and its products are environmentally benign [6] not only that
but its product (H2O) is a useful and desired product in its own right. The main disadvantages
to this technology are finding a solution that can not only store Hydrogen but store it in a
form that is easy to use and to make it as convenient and competitive as current fuel sources.
This report will detail current and future directions of research for Hydrogen storage and how
materials engineering can help improve its size, performance and future prospects as a
leading fuel source.

Materials for Hydrogen Storage

As mentioned in the introduction, one of the largest barriers to Hydrogen becoming a rival
fuel source to fossil fuels is storing it in a suitable way. As is the case with any gaseous fuel
because Hydrogen has a low volumetric density it requires a storage method that compacts,
compresses or otherwise densifies the fuel [7] in order for it to be used effectively in
transportation and other mobile industries.
There are 6 basic Hydrogen storage methods, as can be seen in Table 1 below, although these
six can be more easily split into 3 distinct groups: Highly compressed gas, Cryogenic Liquid
and using a Solid State Matrix as a storage system. Each of these will be briefly explored in
this report, with particular attention being paid to the 3rd group and the new directions that
research in this area is heading.

Table 1: Basic methods of Hydrogen Storage [8]

Highly compressed gas

Hydrogen can be compressed, normally to pressures between 200 and 800 bar (as can be seen
in Table 1 above). At ambient temperature and atmospheric pressure 1kg of gas has a volume
of 11m3 [8], instead when compressed to 200 bar it can be stored in a tank of 225 litres [6]
which is 2% of its initial volume.
As this shows, and as can be derived from the ideal gas equation an increase in pressure on a
gas leads to a decrease in volume and increase in density. This is exactly what is needed for
the storage of Hydrogen and other gas fuels. The technology needed to store Hydrogen
through compression is simple and containers can be easily made using materials such as
aluminium or steel.
Despite its ease, convenience, and as can be seen in Table 1, generally good performance
compared to other storage methods, compressing Hydrogen for storage does have its
disadvantages. Firstly due to the high pressures involved, additional pressure controls are
needed to ensure the Hydrogen is released safely. The compression of the gas is also
dangerous [6,8], Japan for example has banned the use of compression vessels on the roads in
ordinary cars [6].
Cryogenic Liquid

A safer option for Hydrogen storage is to lower it to Cryogenic temperatures, these are
defined as from 123K to absolute zero (0K) [9], liquid Hydrogen is generally stored at 21.2K
as this is Hydrogens condensation point at 1 bar [6] (which is atmospheric pressure). It must
be stored in an open system to prevent overpressure as the critical temperature of Hydrogen is
33K [8]. The critical temperature is the temperature above which a substance cannot exist as
a liquid [10] so if the pressure were to rise above 1 bar, or if the temperature were to rise due
to another factor the Hydrogen would become gaseous which would result in huge
overpressure in a closed system.

Table 1 shows that storing Hydrogen as a liquid results in a comparatively good volumetric
density and it is at a safe pressure however there are other issues with storing Hydrogen as a
liquid. Firstly the need to store it in an open system means that any heat transfer through the
containers leads to a direct loss due to evaporation. This can be mitigated (through
catalytically burning it with the air in the container or collecting it again as a metal hydride)
such that BMW claim to have got the losses down to below 1.5mass% per day [8]. Despite
this, losing fuel is still a concern if Hydrogen is going to be used in the transportation
industry where vehicles could potentially be left inactive for long periods of time.
A further issue with storing Hydrogen as a liquid is the process that is used to compress, chill
and condense the fuel in the first place. Although possible it is a very costly process and uses
a large amount of energy which means the system as a whole has a low energy efficiency.
These three issues then, Hydrogen boil-off (loss of fuel), cost and energy inefficiency limit
the possible use of this storage system to applications where cost of Hydrogen is not an issue
and the gas is consumed in a short time, e.g. air and space applications [8].
Store in Solid State Matrix

The final, and perhaps most promising, storage method is to store Hydrogen in a Solid State
Matrix. This method utilises other materials to store Hydrogen through adsorption, there are
two main types of adsorption Chemical adsorption, known as Chemisorption and Physical
Adsorption, which is known as Physisorption. One major advantage to using these methods
of Solid State Storage is the increase in safety compared to the other methods that have been
investigated as some form of conversion of energy input is required to release the Hydrogen
for subsequent use [11].
In general it can be said that Physisorption has higher energy efficiency and faster
adsorption/desorption cycles whereas Chemisorption results in the adsorption of larger
amounts of gas, but is not always reversible and requires higher temperatures to release the
gas [11].
Chemisorption

As the name suggests Chemisorption performs adsorption of materials via a chemical

reaction between Hydrogen and the storage material. Some materials that react with
Hydrogen can reversibly store it, that is to say the Hydrogen can be retrieved by raising the
temperature at a suitable pressure. Others form very strong chemical bonds such that the
Hydrogen is not readily retrievable, when it is in this state it is known as being irreversibly
stored.
This form of storage does not mean that the Hydrogen is stored there forever, merely that a
further chemical reaction must take place to release it. The heat released by this chemical
reaction can be captured and used, this method though is not particularly appropriate for use
in the transportation industry where ease of access as well volume of Hydrogen stored is vital
[11].

Researchers believe that metal hydrides may represent ideal storage systems for Hydrogen,
especially for the transport industry [12]. Table 1 above shows that using metals for storage
results in good volumetric density and that it is useable at room temperature and atmospheric
pressure, as well as being fully reversible.
Metal Hydrides are a category of promising materials that exhibit the potential to fulfil the
defined targets for energy storage [11]. These hydrides can be split into three groups, simple
metal hydrides are composed of transitional metals such as Magnesium, intermetallic
compound hydrides include TiFe, ZrMn2, LaNi5, and Mg2Ni [12] and complex metal hydrides
which involve a range of elements, like intermetallic compound hydrides, yet do not produce
metallic hydrides such Mg2Ni or NiH4 [13]. As such these can be referred to as either
intermetallic compound hydrides or complex metal hydrides since they abide by both
definitions.
Metal Hydrides have a good energy density by volume [11] which as has been stressed
several times throughout this report is very important in the transportation industry. These
Hydrides can also be formed in either liquid or solid states, typically the liquid hydrides can
be used at room temperature whereas solids can require temperatures of circa 120oC [11].
Generally metal hydrides store more Hydrogen than the other methods described since they
have a higher Hydrogen storage density (MgH2 has 6.5 H atoms/cm3) as opposed to
compressed gas (0.99 H atoms/cm3) or liquid Hydrogen (4.2 H atoms/cm3) [11]. While not all
of this Hydrogen can be released it has been shown that the reversible storage capacity of
these materials is typically between 50-90% of their maximum capacity [12]. This means that
they can definitely store more per volume than compressed gas and in many instances more
than liquid Hydrogen too.
It has been discovered that other forms of Magnesium hydrides (which include a variety of
other elements) have different adsorption and desorption rates, optimising these rates are
crucial in meeting governmental targets that have been set for refuelling time for Hydrogen
cars and for the range restrictions that have been placed on them.
Metal Nitrides, Amides and Imides have shown high Hydrogen capacity at lower operating
temperatures compared to many other chemisorption methods [11]. For example Lithium
Nitride has been found to be able to hold 11.4% of its weight in Hydrogen (50% more than
Magnesium Hydride) and more than many other hydrides which normally store between 24% [11]. Metal Imides have been found to have a maximum storage capacity of 7.0wt%
however both of these materials require, at useable pressures, temperatures that are too high
for practical use [11].

However experiments have been carried out that suggest the addition of alkali earth metals
could decrease the Hydrogen storage temperatures and decrease the desorption pressures
[11], which would make the Hydrogen easier to extract. On top of which further work is also
being carried out into looking at using lightweight complex hydrides in a further effort to
reduce weight. Both of these advances show how the properties of metal hydrides are being
continuously improved, moving the world closer to real and competitive Hydrogen storage
solutions.
Physisorption

Chemisorption materials discussed in the previous section are often referred to as atomic
storage materials (dissociative materials) whereas Physisorption materials are known as
molecular storage materials or (nondissociative materials) [12]. Chemisorption bonds on an
atomic level whereas in Physisorption adsorption happens on a molecular level, where the
Van der Waals forces hold the molecules together.
The materials used for Physisorption of Hydrogen are materials that are porous on a
nanoscale such as zeolites, Metal-Organic Frameworks (MOFs) and other porous carbon
materials such as carbon nanotubes and graphene.
It has been reported, for example, that carbon nanotubes and graphite nanofibers exhibit high
Hydrogen storage capacities and that carbon materials with higher microporosity have
extremely enhanced adsorbing properties toward gaseous molecules [11]. It has been found
that the storage capacity of these materials is directly proportional to the BET surface area
and that the temperature is also of importance (with higher temperatures exhibiting higher
adsorption rates).
As has been alluded to earlier an advantage of Physisorption as an adsorption technique is
that the Hydrogen uptake is fully reversible. However it is also known that Physisorption
cannot store as much Hydrogen as the Chemisorption process, with Graphene showing 3.3wt
% and active carbon showing 1.5wt% [6], even with the reduced reversibility of
Chemisorption more Hydrogen can still currently be stored through these processes.
However materials other than carbon based materials can also store Hydrogen through
Physisorption, NaY (a zeolite material) was found to have a storage capacity of 1.8wt% and
Zn4O (a metal-organic framework) was found to have a capacity of 3.7wt% [8]. All of these
results are promising, in so far as showing that these processes work for Hydrogen storage, in
many cases they are also still better than compressed gas and liquid Hydrogen storage
methods.
The main advantages to Physisorption for Hydrogen storage are the low operating pressures,
relatively low cost of materials and the simple design of the storage systems [8]. All three of
these are important for the technology to be used on a common basis, especially within the
transport industry. However the low Hydrogen densities achieved, and the low temperatures
required are significant drawbacks [8].

Challenges to developing Hydrogen Storage systems

One of the biggest concerns in using Hydrogen as a fuel source are the safety aspects that
have plagued its use since the Hindenburg disaster. It has since been suggested in more recent
analysis that the Hindenburg disaster was actually caused by the highly flammable material
that was used in for the skin, rather than the Hydrogen that it contained [6]. Nevertheless the
safety concerns of using Hydrogen as an energy source, and particularly the concerns with its
storage, are still valid. This is one of the biggest advantages of using Solid State Storage
systems as some form of energy input is required to release the Hydrogen [11].
There are still barriers and challenges to the use of the Solid State Storage systems, not least
of all the fact that many of the Carbon materials that have been proposed have not been
sufficiently characterised [6]. Much more research then is still required, not just into the
specific area of Hydrogen storage, but also into understanding the materials that could make
this possible.
Chemisorption materials are very expensive and still suffer from issues of irreversibility, they
can also suffer from needing very high, and therefore impractical, temperatures to release the
Hydrogen. Physisorption on the other hand does not have these problems yet has much
poorer capacity at mild temperatures [11].

Conclusion
Hydrogen is seen by many as the answer to the worlds fuel problems, yet as described in this
report there are still issues surrounding its storage. On the basis of this investigation Solid
State Storage is by far the best solution to the issue of storing Hydrogen. With the advances
made in materials science and the continual research into identifying and characterising
potential storage materials a workable, practical and sustainable to the worlds fuel problems
will be found with Hydrogen storage.

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