Effect of Nano-Technology in Hydrogen Storage

A new era of Hydrogen fuel storage

R.Siva kumar1, T.Vijayprathap2.
B.E.Mechanical(III-Year), Sona College of Technology,Salem-5.
Contact no: 8526899442, Email id: kumarrsiva35@gmail.com1
Email id: nationvijayprathap@gmail.com2.

ABSTRACT

Hydrogen is the lightest of the

Hydrogen is the most abundant

elements with an atomic weight of 1.0.

element is the universe on the Earth its

Liquid hydrogen has a density of 0.07

mostly found as water. Hydrogen can

grams per cubic centimeter, whereas

easily separated from Oxygen in water

water has a density of 1.0 g/cc. and

via Electrolysis. This process is about

gasoline about 0.75 g/cc.

67% efficient. The alternative is to

When hydrogen is burned in air the

store hydrogen in a solid metal by

main product is water. Some nitrogen

forcing it into the gaps between the

compounds may also be produced and

atoms.

may have to be controlled.

By a strange property of

physics this actually holds more

Recent Development:

hydrogen in a smaller volume than

Japanese scientists are working on a

possible in liquid form. For this

method of splitting water using laser

purpose the lightest element Titanium

light beamed from a satellite in orbit.

is used in our study.

The alternative is to store hydrogen in

a solid metal by forcing it into the gaps
between the atoms.

Properties:
As a liquid its energy density per unit
volume is 1000 times higher.

By a strange

property of physics this actually holds

more hydrogen in a smaller volume
than possible in liquid form. For this

purpose the lightest element Titanium

compared with, for ex, Gasoline with equal

is used in our study.

energy content- about 30 times bigger volume

at 100 atm gas pressure. Condensed hydrogen
is about ten times denser but is much too
expensive to produce and maintain. There are
also obvious safety concerns with the use of
pressurized or liquefied hydrogen in vehicles.
Metal hydrides as Hydrogen storage devices:

Literature Review

Metals can absorb hydrogen in atomic

Use of Hydrogen as Fuel:

form and thereby act as hydrogen sponges.

It is believed that hydrogen will within

Around 50 metallic elements of the periodic

a few years become the fuel that powers most

table can absorb hydrogen in a great quantity

vehicles and portable devices. The reason is

and the possible choices of hydrogen storage

the depletion of oil and the relatively facile

materials are, therefore, enormous. Many

production

various

scientific and engineering studies have been

renewable source of energy- hydroelectric,

carried out of the absorption/desorption of

wind, solar, geothermal- with water being the

hydrogen in metals and development of such

only raw material needed. To release the

hydrogen storage devices. Daimler-Benz, for

energy, hydrogen can be burned in an efficient

example, produced in the early 1980s a car

and clean way in a fuel cell to form water

fuelled by hydrogen where the storage tank

again, or made to drive an electrochemical cell

was a chunk of Fe-Ti metal alloy. The volume

as in the commonly used nickel hydride

of this storage device is less than a factor of

battery. As concerns over air pollution and

two greater than the equivalent gasoline tank,

global warming increase, the incentive to

but the problem is that hydride is 20 times

switch to clean and efficient hydrogen

heavier. The only successful commercial large

economy becomes grater and the transition

scale

may occur well before oil reserves are

hydrogen storage so far is the metal hydride

depleted. While hydrogen has many inherent

battery, which has supplied battery power to

advantages, there remains a problem with

many small electrical appliances such as

storage

Pressurized

mobile phones and portable computers. Metal

hydrogen gas takes a great deal of volume

hydrides have so far not become useful as

of

and

hydrogen

from

transportation.

application

of metal

hydrides

as

storage devices for hydrogen gas even though

the first patent on this process. The process

they have some distinct advantages over

was initially referred to as milling/mixing.

pressurized hydrogen gas, both improved

The term mechanical alloying was actually

safety and reduced volume.

coined by Ewan C. McQueen.

Mechanical Alloying;

Experimental work

Mechanical Alloying (MA) is a high-

TiH2 in the powder form is taken as the

energy ball milling technique; in which

starting material and is milled in a ball mill

elemental blends are tend to achieve alloying

under dry conditions for various time intervals

at the atomic level. In addition to elemental

(2h, 5h, 7h and 10h) with Ball to Powder ratio

blends, pre-alloyed powders and ceramics,

of 20:1. Heat treatment is carried out in a

such as oxides, nitrides, etc., can also be used

muffle type furnace for 1h in each case.

to produce alloys and composites by these

Characterisation of the metal hydride is done

techniques. This technique was developed

using XRD and DSC.

around 1996 by Benjamin and his co-workers

X-ray diffraction results of as received

as a part of the program to produce oxide

and milled samples are shown in figure 1.

dispersion strengthened (ODS) NI-base super

XRD results confirmed the as received sample

alloys for gas turbine applications. The initial

as TiH2 as in Fig 1. Even up to 10h of milling

experiments by Benjamins group were aimed

at BPR ratio of 20:1 there is no formation of

at coating the oxide particles with Ni by ball

new phase except the decrease in the intensity

milling. Such a process was known 40 years

of TiH2 peaks with the addition of tungsten

earlier from the work of Hoyt, who reported

carbide peaks as impurity. Hence DSC is

coating of WC with Co by ball milling. In

carried out with the milled and the as received

1966, Benjamins group to the production of

samples. XRD plot of unmilled and milled

alloy turned attention by high-energy ball

heat-treated samples are shown in figure 2,

milling. The first experiments on this direction

which

were on the production of thoria dispersed

dehydrogenation

nickel (commonly known as TD nickel) and

process. TiHx forms at lower temperatures and

NI-Cr-Al-Ti alloy with Thoria dispersions.

the formation of Ti shows the end of the

The success of both these experiments led to

dehydrogenation

clearly

indicates
process

process.

is

that
a

The

the

two-step

peak

transformation

temperatures

are

well

Figures

separated in milled samples when compare to

unmilled samples and the separation increases
with milling time. The peak temperatures
decrease with increase in the milling time.
The observed effects of milling of the
are

due

to

the

decrease

in

dehydrogenation temperatures and separation

between the peak temperatures. The separation
in the peak transformation temperatures is

Intensity (A.U)

hydride

TiH2

0h
2h
5h

clearly observed from the DSC plots shown in

7h
10h

Figure 3. The peak transformation temperature

20

30

40

50

60

70

80

90

2 (degree)

for the -Ti transformation and the TiHx

transformation is given in Table 1. Table 1
indicates

that

the

peak

transformation

temperature for -Ti transformation in the

unmilled and 10h milled powder differs by
65C

whereas

the

peak

transformation

TiH
2
TiH
x
-Ti

a margin of 170C. The TiHx thus formed as a

result of the first stage dehydrogenation is

Intensity(A.U)

temperature for TiHx transformation differs by

550 C

more stable when compared to TiH2.

A possible explanation for the decrease

in the first transformation temperature in the

20

30

40

750 C

50

60

70

80

90

2 (degree)

ease of decomposition of the high hydrogen

containing TiH2 phase due to decrease in the
particle size, increase in the specific surface
area and increase in the defect concentration
due to cold work.

Fig 1. XRD plot of milled TiH2 without

Fig 2.a.XRD plot of unmilled TiH2
Heat treatment

heat

treated at diff. temp.

TiH
2
TiH
x
-Ti

Intensity(A.U)

Table 1 Peak transformation temperatures for

TiHx and -Ti formation

0h
10 h
o

400 C

20

30

40

50

Hours

Peak

Peak

of

Temperatures of

Temperatures of

Milling

TiHx

-Ti

Transformation

Transformation

(C)
528
440
366
360
355

(C)
625
602
591
582
560

600 C

60

70

80

90

2 (degree)

10h

Discussion

7h
5h
2h
Heat Flow Exothermic

0
2
5
7
10

Nano TiH2 used as fuel should be first

0h

ignited to 355C and the exothermic reactions

thus produced will ignite the remaining TiH2. It
functions as an auto catalytic mechanism. This

100

200

300

400

500

600

700

800

Temperature ( C)

Fig 2.b. XRD plot of milled TiH2

(10h)

Fig 3. DSC plot of TiH2

heat treated at diff. temp

ignition can be brought about very easily by

the passage of electricity because Hydrogen
can be easily dissociated from Titanium. This
dissociated hydrogen is immediately used for
propulsion of the engine and hence the safety
hazard is eliminated.
Why TiH2 and why not cheaper MgH2?

The automobile industry has set 5% by

hydrogen

(i.e.,

weight as a target for efficient hydrogen

formation

of

storage in metals. The hydride, MgH2 can store

depending

upto 7% by weight (approx.) and TiH 2 can

dissociation process)

store upto 5% by weight of hydrogen

after

the

TiH0.7-1.1

upon

the

Why TiH2 and why not cheaper AlH2?

(approx.). Hence it is apparent that both TiH2

In case of Aluminium the formation of

and MgH2 can store hydrogen for automobile

hydride is too difficult comparing with the

industries. But the problems encountered with

hydride formation in Titanium. Because the

MgH2 are that

rate of formation aluminium hydride

The rate of absorption and

from aluminium and hydrogen is lower than

desorption of hydrogen is too

that of TiH2. Again the dissociation of

low

hydrogen is difficult in the case of aluminium.

donot

Oxide formation is more facilitated in

readily dissociate at the surface

Aluminium, than the formation of hydride. As

of Mg

oxygen will be deposited at the surface of

Hydrogen

molecules

Hydrogen

atoms

strongly

with

too

aluminium, the reactivity of aluminium is

magnesium

minimum at the surface than at the core

bind

portion and hence hydride formation is more

atoms
The above problems can be overcome by

Hence by comparing TiH2with light

using TiH2.
The

enthalpy

of

formation of TiH2 from Ti and

hydrogen

is

lower

when

compared to Magnesium.
Hydrogen

materials, it is shown that TiH2 is well suited

for hydrogen storage. This serves as a big
break through in the usage of hydrogen as a
potential source of fuel.

molecules

readily dissociate at the surface

of Titanium, being an active
metal

difficult.

Bonding of hydrogen
with Titanium is strong only
after dissociation of 50% of

Conclusion
Present situation requires immediate
care to be taken for the problem of
environmental

pollution

caused

by

the

combustion of fuels. Using of Hydrogen gives

a major advantage of creating a greener

environment

since

the

end

product

of

combustion is water that can be used to

produce hydrogen again.
Major results of this research work reveal the
following datas.
1) TiH2 dissociation occurs at some 200C
earlier for nano particles when compared with
conventional particles which facilitates the use
of TiH2 in the storage of hydrogen.
2) The dissociation oh hydrogen is easier in
the nano level when it is produced by
mechanical milling because of the two
following reasons.
a) A part of the energy is supplied by
the process of mechanical activation.
b)

Enthalpy

formation

is

also

facilitated by the process of mechanical

activation.
Hence TiH2 can be used as a good source of
hydrogen storage device which facilitates the
usage of hydrogen as a fuel.

Reference

www.nano.org.uk

www.nanowerk.com

www.hydrogen.energy.gov

www.interscience.willy.com