Synopsis

Table of Contents

Introduction 2
Literature Review 4
Justification and Likely Benefits 6
Objectives 6
Plan of Work and Methodology 6
Place of Work and Facilities Available 8
Reference and Bibliography 8

1
ABSTRACT
Hydrogen is considered as potential energy carrier for mobile and stationary storage use.
However the main issue is practical hydrogen storage material for use as fuel. Solid state
hydrides offer high hydrogen storage capacity and show improvements both in
volumetric and gravimetric capacity. But there is limited knowledge on hydrogen
absorption mechanism and composition of material after release of hydrogen. Obtaining a
detailed understanding of the relations between crystallographic structure of solid state
materials and hydrogen storage is a requirement for a possible guided search. Then
design of similar transportation in the future. And detailed experimental transportation
information of the electronic structure of solid state hydride has not been studied so far.
Here in our thesis we will focus on metal hydrides, such as MgH2, NaAlH4, LiAlH4, LiH,
LaNi5H6, TiFeH2 and other Metal hydride and will study its properties as a parental
material and also by doping it with different dopants. The dopants we use depends upon
the facts how it will affect the band gap of material under study. So, in order to
characterize hydride states responsible for transportation properties of Hydrogen storage
materials relevant for technology; we use computational approach. This goal will be
achieved by WIEN2K as well as BoltzTraP code which will allow us to simultaneously
access the valence-band electronic structure as well as core level states.

INTRODUCTION
Globally the climate change and pollution are the recent main environmental issues, so
the need of clean energy source is increasing. Hydrogen has gained attraction because of
its vast availability as one of the components of water. The byproduct of reaction between
hydrogen and oxygen is water and heat, not any greenhouse gas like CO 2. Hydrogen as
an energy carrier is a model candidate both for stationary and mobile applications along
with preventing the bad effects on environment in contrast to oil. Appreciating the vast
proficiencies of Hydrogen, it’s considered as best candidates for future work in
automobile industry. This will reduce the dependence of countries, without natural
resources, on the import of oil. The difficultly is of storage for the technological needs
like transportation and mobile applications [1]. In transportation sector, hydrogen is
considered as a promising energy carrier for replacing hydrocarbon fuel. Which can be
achieved by solid state media
storage [2]. Hydrogen has almost three times more gravimetric energy density in
comparison to petrol [3]. Hydrogen storage is categorized as; Solid-state hydride
storages, molecular hydrogen with porous solid adsorption, Liquid hydrogen, and high-
pressure hydrogen. However, in last few years a detailed study is going on solid state
hydride material. These have a good volumetric density and considered safe and most
effective for storing hydrogen [4]. Ideal hydrogen storing materials have capability of
large storage, and low molar weight and also they should be inexpensive [5]. The
material required should maintain the performance even after repeated absorption and
desorption. Comprehensive studies have been conducted to determine structure of crystal,
phase transitions and bonding properties at different temperatures and pressures [6, 7].
Hydrogen storage materials are obtained by number of methods like high pressure gas
cylinders, physisorption, chemical reactions, complex hydrides and metal hydrides etc [8,
9]. A summary of few of the system materials is given in the following paragraph.
Different hydrides are studied for both mobile and stationary requirements of hydrogen
storage. But there is no known material that has given any promising results so far.
Mg-based metal hydrides: Magnesium and its alloys are heat resistant, recyclable,
abundantly available, have high storage capacity and low cost. Recently, attention is
given to magnesium hydride due to its high energy density (9 MJ/kg of MgH 2) for
hydrogen storage. MgH2 has hydrogen capacity of 7.7 wt%. The main disadvantage is
that hydrogen discharge creates high temperature and it has high reactivity with oxygen
and the air [10]. Complex hydrides are also considered as light weight storage materials.
H2 evolves when the complex hydrides have contact with water. On reaction with
hydrogen, the lithium, beryllium and sodium make solid state compounds. For LiBH 4
hydrogen content is of 18 wt%. Because of thermo dynamical and kinetic limitations, the
usage of complex hydrides as a hydrogen storage material has been a challenge. Complex
hydrides such as amides [NH2]-, alanates [AlH4]- and borohydrides[BH4]- shows
stabilized results by doping of metal cations. Borates are stable, light weight and do not
decompose on high temperature. They have high hydrogen storage capacity. While
alanates are also light weight and have high hydrogen storage capacity but they
decompose at high temperatures. Sodium alanates are also considered as potential
candidate for hydrogen storage material because of its low cost and 5.6 wt% storage
capacity of hydrogen [11]. Lithium and potassium alanates are complex hydrides of
aluminum and hydrogen and they have high hydrogen
content capacity. The hydrogen content is 10.5 wt% for LiAlH 4. However, LiAlH4 is
unstable and easily decomposes. The equilibrium pressure of hydrogen is extremely
elevated [12]. Intermetallic compounds are formed by combining a stable hydride
element and an unstable hydride element. They were also considered as the candidates for
hydrogen storage materials but this idea stayed only to prototype stage because of low
hydrogen storage [13].
Non-carbonaceous nanotubes are categorized as the promising hydrogen storage
materials, like titanium sulfide (TiS2), molybdenum sulfide (MoS2) and boron nitride
(BN). BN nanotubes contained 1.8 to 2.6 wt% of hydrogen content. The less absorption
of hydrogen is due to close ends of the tube [14]. While titanium sulfide could hold
foreign atom between S-Ti-S due to van der Waals forces. But its capacity of hydrogen
absorption is noted to be decreasing with increase in temperature [15]. Microporous
metal-organic frameworks (MOF) are crystalline metals and showed interesting
hydrogen absorption capacity as pressure is increased. Mesoporous transition metal
oxides have high surface area and framework structure. It is observed that absorption
level are increased by doping with other fullerides [16].

LITERATURE REVIEW
In 1943, discovery of sodium borohydride NaBH 4 by Schlesinger and their coworkers
was done [17]. It is commonly used as reducing agent in organic synthesis due to high
gravimetric and volumetric hydrogen density [18]. Density functional theory is a valued
tool for the prediction of new metal hydrides for H-storage. DFT benefits in explaining
hydride properties like, hydrogen bonding, electronic structure, vibrational energies and
elastic behavior.
Ghellab et al studied the optical, electronic and structural properties of LiBH 4 and NaBH4
by first principle calculations [19]. Results showed that on low temperature the materials
crystalize as tetragonal phase. The materials had band gap between 5 to 7.7 eV which
referred to its insulating behavior. It was observed that at low energies the reflectivity of
the materials is smaller but a drastic increase appears at intermediate and high energies.

P. Jena gave a review of hydrogen storage materials from past, in present and for future.
As the impact of hydrogen storage for energy requirements is undeniable. It was indicated
that there is still need to explore more appropriate materials for storage. The present
research momentum should be maintained with Identification of the perfect crystal
structure, their stable phases, and the kinetics [20].

Niemann discussed different nanomaterials as hydrogen storage material. It was

suggested that nano materials like nano-magnesium hydrides, carbon nanocompsites,
metal organic frameworks, boron nitride nanotubes, alanates, and carbon nanocomposites
are considered as possible candidates for storing hydrogen at larger scale. As nano-
materials shows high volume ratio and surface area. Nano-materials show the good
electrical, optical, magnetic and mechanical properties for their potential application in
hydrogen storage [21].

Seayad and Antonelli gave an overview of composite materials and non-carbonaceous

nanostructures. Mainly they focused on complex hydrides and other composite materials.
The study on alanates showed that 5% reversible adsorption is achieved which is closer to
the U.S. Department of Energy (DOE) target of 6%. By doping the metal hydrides they
have gained an increase research interest as their reversibility is increased. Different
theoretical and observed hydrogen sorption captivity materials are discussed in details in
the study [22].

Cheng et al studied electronic/crystal structure and the vacancies of hydrogen in lithium

amides doped with Ti and Nb using first principle study. Their calculations indicated that
the doping of Ti and Nb atom was favorable for Li as Hydrogen vacancies were created
adjacent to the substitution. Density of states showed that the N-H bond was covalent
while N-Li was ionic bond. They recommended that doping Ti and Nb could improve the
hydrogenation of lithium amide and dehydrogenation as well [23].
Kim Suggested that hydrogen storage materials bialkai borohydride LiK(BH4) has
10.64% hydrogen content. First principle study was used to examine the structure of
KBH4 and NaBH4 which revealed that both have crystal structure and the entropy related
to the sites of hydrogen atoms contributes in finding the stable states. It was revealed that
LiK(BH4)2 is unstable when decomposed in LiBH4 and KBH4 [24].
Yang et al studied the overview of hydrogen storage material research which indicated
that hydrogen has a widespread use as a fuel replacement option in automobiles. As it has
high gravimetric H2 density and low volumetric density and water is a byproduct, as a
result of thermodynamic reactions. The review gave detailed study of materials which
have properties required for becoming a candidate for hydrogen storage materials. Their
review
also discussed the computational and experimental techniques used to determine the
properties required for good storage materials. They categorized the materials in four
systems as chemical hydrides, metal hydrides, complex hydrides and sorbent systems
[25].

JUSTIFICATION AMD LIKELY BENEFITS

Numerical computation is now an essential tool in condensed matter physics and material
science as it can explain the material properties. Properties of materials are often not
accessible directly from experiments for many reasons. For example, the sample size of
certain materials may not be sufficiently large enough for few experiments. One big
advantage of computational calculations is to study hypothetical systems that are not yet
produced. However, as the reliability of computational results is always verified by the
experimental results, both the computational methods and the experimental methods
should be considered being complementary to each other.

Here, we will focus on clarifying the stability of the phase and then the
geometrical and electronic structures and the optical properties of the material. A
compact and lightweight energy carrier is the most expected application of a hydrogen
storage material. Moreover, other uses of hydrogen storage materials will be reported to
be emulsion explosives, high-energy solid rocket propellants and optical sensors, thermal
energy storage, batteries, , thin films for solar collectors, smart windows, cooling/heating
devices, and sensors.

Apart from finishing the tasks outlined above, we will publish papers in the
international journals.

OBJECTIVES
The main objective of the thesis is to do a detailed study of optical and electronic
structure of solid state hydride doped by class of dopants (as for example Ti, Nb, and
transition metals). Even though, various theoretical studies of these materials exist in the
literature, a detailed study of correlation effects in these materials is missing. Here we
propose to perform DFT (LSDA+DMFT) calculations by means of the Wien2k (RSPt)
code based on the full-potential linear muffin-tin orbital (FP-LMTO) method.
PLAN OF WORK AND METHODOLOGY
Many body wave functions could be used to determine physical properties of a crystal.
As solving Schrödinger’s wave equations for all the particles in a crystal is really
problematic, even with the use of fast speed processing computers;like supercomputers.
Hohenberg and Kohn proposed density functional theory (DFT) and made the problem
simpler. So Kohn in 1998 shared a noble prize in chemistry. The theory was use of
density functional instead of electron wave function to solve the problem (Hohenberg and
Kohn, 1964). They reduced 3N variables for N particles to three variables of the
electronic density, i.e, x, y and z. The theory gives an exact solution to the problem. It is
extreme reliable theory for calculation and understanding of the structural, magnetic,
optical and electronic properties of the metals, semiconductors, semi-metals and
insulators.
Kohan-Sham equations can be used for calculating optoelectronic properties of the
Hydrogen storage materials. Kohan-Sham equations in atomic units are:
1 𝜌(𝑟⃗ )𝜌(𝑟⃗ ⃗ )
𝐸 = 𝑇 [𝜌] + ∫ 𝜌(𝑟⃗) 𝑑𝑟⃗ + ∫ 𝑑𝑟⃗𝑑 𝑟⃗⃗, + 𝐸 [𝜌]
𝑉 , (1)
0 𝑒𝑥𝑡 2 |⃗𝑟,⃗ −𝑟⃗| 𝑒𝑥𝑡

The first term in above equation represents kinetic energy operator, the second term is
external potential from the nucleus, and the third is Coulomb potential while the fourth
term is exchange correlation potential. Kohan-Sham equations are solved iteratively till
self-consistency is attained. These iteration cycles are required because of
interdependency between orbital’s and potentials. In the Kohan-Sham scheme the
electron density is attained by summing over all the occupied states (Kohn and Sham,
1965).
In the full potential linearize augmented plane wave method (Blaha, 2001; Madsen,
2001; K. Schwarz 2002) scheme both, the potential and charge density are expended into
two different bases. Expended potential is:

 Vlm (r)Ylm (r). .....................................(a)

 lm
V (r)  

 ................................... (b)

 V K eikr
k
(2)
Where, Eq. 2(a) shows for inside and 2(b) for the outside of the atomic sphere. Inside the
sphere the wave function is expanded in spherical harmonics, lmax, and in the interstitial
region it is expanded in the plane wave basis. Inside sphere the potential is spherically
symmetric while outside the sphere it is constant. The core electrons are treated fully
relativistically and the valence electrons are treated semi-relativistically (Schwarz, 2003).
Suitable RMT, Kmax and K points are selected for these systems.
The Optical properties; like dielectric function, energy loss function, reflectivity and
absorption coefficient etc can be calculated using FP-LAPW method. These discussions
provide a good theoretical approach for experimentalists to think about the inner picture
of the ternary oxide.
The exchange correlation potential will be handled with local density approximation
(LDA), generalized gradient approximation (GGA), Englo & Vassco GGA and modified
Becke–Johnson (mBJ).

PLACE OF WORK AND FACILITIES AVAILABLE

REFERENCE AND BIBLIOGRAPHY

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15. Chen, Jun, et al. "Titanium disulfide nanotubes as hydrogen-storage materials." Journal of the American
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21. Niemann, Michael U., et al. "Nanomaterials for hydrogen storage applications: a
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