School of Energy Science and Engineering

Indian Institute of Technology, Guwahati, Assam

RENEWABLE ENERGY SYSTEMS (EN661)

(July-November Semester 2021)

EN 672 ASSIGNMENT- 9 Date: 18/11/ 2021

Topic: Storage of Hydrogen as Metal Hydride

Submitted By,

Monikesh Kakoty (214351006)

Introduction

Hydrogen (H2) has a variety of physicochemical qualities which have already caused it for
becomes extensively utilized mostly in the chemical processing of products in both research labs
and industry manufacturers. Such applications include in coupled with growing usage of
hydrogen in power generating technologies as well as in mobility. Apart from the petrochemical
sector, where hydrogen is used almost instantly after it has been produced out of a hydrocarbon
source, most uses demand hydrogen to somehow be stored in some way once it has been
produced before it can be used [1].Therefor hydrogen storage is an important concern inside the
hydrogen economics, affecting production, delivery, and uses. A review of Storing hydrogen
using metal halides is presented in this study.

Basic Principles of Hydrogen Storage in Materials [2]

Certain materials with in periodic table are able to store hydrogen mostly in state of hydrides by
the direct dissociative chemisorption and other one is electrochemical split of water. As
hydrogen is also a good reactive substance it can react with various metals as well some the
alloys to developed chemical complexes.
Figure 1: Pressure composition temperature curve and transition of phases [2]

The PCI curves, as illustrated in Fig.1 , can explain process of hydride production for gaseous
hydrogen. At first host lattice present in the system starts to dissolve some amount of hydrogen
as a solid solution, known as the α phase of the solution. It is less in concentration as only some
portion of the hydrogen is dissolved. As the pressure of the hydrogen increases, the concentration
of hydrogen increases, which leads to the formation of the β phase and here the hydride is
completely formed. Hydrogen is distributed in atoms on the interstitial sites of the host metal
lattice that exist.

Relatively lighter metals such as Lithium(Li), Beryllium(Be), Sodium(Na), Magnesium(Mg)and

Aluminium (Al), create a broad range of metal hydrides compounds. They are absolutely
fascinating owing to not heavy in terms of mass as compare to other metals and the quantity of
hydrogen atoms each metal atom,
Figure 2: Density variation of different hydrides [3]

Mg-centered hydrides [4]

Mg-based materials are widely explored mostly towards the potentially unlimited quantity of
Mg, the 8th most widespread element in the earth crust (2.3%)

Miserably, magnesium based hydride seems to have a challenging thermodynamics condition

with comparatively large heat release enthalpy, which makes it unsuitable for transportable
utilization. Different ways to improving the thermodynamics and kinetics of hydrogen discharge
and absorption in magnesium hydride have been investigated. The following
methods are common examples to enhance efficiency : utilization of catalytic additives,
nanoconfinement, nanostruc-turing by ball milling

Improving surface and kinetic properties by ball milling

The surface of the metal plays an essential role during dissociation as it can provide smooth
transit to the High amount of hydrogen, After the formation of a certain amount of halides, a
layer grows over it, which lead to the reduction in hydride formation and it is known as halide
layer. Due to the continuous revelation to the environment, chances of formation of an oxide
layer is increased, which can slow down the synthesis of halides further. Ball-milling, which
creates new surfaces throughout operation, is a cost-effective method for achieving desirable
surface qualities in metal hydrides. The primary consequences of ball-milling include large
surface, the generation of micro/ nanostructures, and the formation of flaws mostly on surface
and within the material. The generated lattice imperfections may promote hydrogen diffusion by
offering a large number of locations with lower energy of diffusion.

Using catalyst

Catalysis is among the important variables in improving hydrogen absorption kinetics in metal
hydride systems allowing for the rapid and efficient dissociation of hydrogen. By including a
suitable catalyst towards solution, the kinetics have been enhanced. Catalysis enhances the
hydrogen adsorption kinetics in metal hydrides, allowing for quick and efficient hydrogen
separation. Appropriate catalysts, although when used in low quantities, improve the creation of
a hydride to a considerable level. Titanium and vanadium inhibit oxidation of the surface of
materials, increasing removal rate over several cycles.

Complex hydrides

Complex hydrides are one more sort of lower mass material for hydrogen storage. Complex
hydrides produced by light elements such as boron, nitrogen, or aluminum always seem to have
high hydrogen densities but poor thermo dynamical and kinetic characteristics, as well as
restricted reversibility. The finding of reversibility in NaAlH4 first triggered a change in
thinking in hydrogen storage development into complex anions Like a result, study was
expanded to encompass metal borohydrides, such as LiBH4, as well as nitrogen-
centered hydrides. Metal borohydrides M(BH4)n exhibit large gravimetric hydrogen densities
and hence have piqued the interest of hydrogen storage researchers. The complex hydride anions
comprised mostly of covalent bonds.[5]

Sodium alanates [6]

Sodium aluminium hydride (NaAlH4) appears to be a viable option for deployment as a feasible
hydrogen storage substance, because of its potentially storage capability of around 5.5 wt
percent, cheap cost, and bulk accessibility. Complex aluminium hydrides, despite their high
storage capability, are still not recognized recharging hydrogen transporters owing to
irreversibility and weak kinetics. These complex hydrides, on the other hand, could be become
reversible through adding suitable transition metals as catalysts. The inclusion of
titanium improves the kinetics of both the dehydrogenation and rehydrogenation reactions of
NaAlH4.

Metal borohydrides [5]

Borohydrides sometimes known called tetra hydroborate exist as class of complex hydrides
wherein hydrogen are in covalent bond with the BH4 complex anion's core atoms.Metal
borohydrides M(BH4)n exhibit large gravimetric hydrogen densities and hence have piqued the
interest of hydrogen storage researchers. The fundamental distinction within complex and regular
halide is the creation of bonds in the compound, which is an Ionic or covalent in nature while
absorbing the hydrogen. Because boron hydrides are relatively stable from the thermodynamics
point of view, current studies have mostly centered on lowering the breakdown enthalpy through
destabilising the LBH4. Furthermore, attempts are being undertaken to optimise the reaction
mechanism of borohydrides by generating nanoscale substances and integrating the hydride into
nanoporous frameworks that hinder aggregation and sintering throughout cycles.

Nanoporous hydride γ -Mg(BH4)2 [7]

Remarkably, innovative materials with particularly unusual characteristics, such as nanoporous -

Mg(BH4)2, store hydrogen adsorb to internal surfaces while still being chemically attached to
boron. Multiple structural diverse nature of boron hydrides found in the form of γ-, α-, δ-, β-
Mg(BH4)2. Mg(BH4)2 is a promising solid hydrogen storage material around a relatively high
gravimetric hydrogen concentration of around 14 wt% H2.A conventional fuel cell oriented
automobile may require 5 kilogram hydrogen to obtain a mileage of 500 km, which is around 60
m3 of gas, then only a volume of 34 L as well as a mass of 34 kg if it has been contained with in
new magnesium borohydride, δ-Mg(BH4)2.

Intermetallic compounds [8]

Intermetallic metal hydrides have been commonly generated by pairing an element which
can creating a stable hydride with compound that forming an unstable hydride. The intermetallic
hydride's empirical formula is ABxHn.

AB5-Type

LaNi5 has to be the highly investigated compound inside this category, and many studies already
have been conducted on its crystal structure, thermo dynamical property , and electrochemical
characteristics . It has hexagonal crystal structure which is remain same throughout the
hydrogenation process. LaNi5 has highly beneficial qualities, however it is somewhat costly
owing to the existence of costly elemental Lanthanum(La). Because of their economic
opportunities, researchers have explored the impacts of milling, mechanical alloying and melting
with other metals, as well as surface treatment procedures which including carbon monoxide
processing.

AB-Type

FeTi is a notable hydrogen absorbing compound that has a place with the intermetallic
compound family and has an all out hydrogen potental of generally 1.85 wt% with minimal
expense parts. The activating operation of FeTi is problematic because of the arrangement of Ti
oxide layer The introduction of catalyst components, such as Pd(Palladium), during alloying
across various ambient conditions greatly improves the initialization kinetics of FeTi. To get the
high quantity of hydrogen in the combination, both intense pressure as well as temperature are
necessary.

AB2 -Type

Compound AB2 is obtained from the leave phase kind of crystal structure and has gained a lot of
interest as a possible hydrogen storing compound. The possible AB2 varieties are achieved using
Ti and Zr mostly on A position, while the elements B are mostly characterized by diverse
intregation of 3d atoms, such as V, Cr, Mn, and Fe. It has a reasonably high storage capacity,
quick kinetics, a prolonged life, and relatively inexpensive. These hydrides, on the other hand,
are very much stable at ambient temperature.AB2 category compounds appear being more
susceptible to gas contaminants than AB5 containing compounds on overall. As a result, a tiny
quantity of oxygen can harm the AB2 s, while it functions as a reactan again for AB5, limiting
storage capacity marginally. These kinds of compounds are poisoned by CO, however capacity
can be recovered by recycling into clean hydrogen. Because of its high storage capability, the
Laves phase family of substances must have risen in popularity in the recent period.

BCC Solid Solution [6[

It has been found that newly developed BCC(Body Centered Cubic) solid solution alloys
absorbed higher hydrogen then typical intermetallic compounds. Due to their outstanding
hydrogen capabilities ,Ti(Titanium) oriented BCC phase alloys have been researched in
numerous institutions in recent times. Ti–Cr–Mn–V–Fe-centered alloys have storage capabilities
of around 3 wt %, with enhancing the vanadium concentration in the alloy accelerates hydrogen
absorption and improves capacity, simultaneously reducing the plateau pressure of hydrogen
desorption. In the discussed alloy, raising the Cr concentration and adding Mn is required to
enhance the actual hydrogen capacity with raising the plateau pressure, and to reduce
expenditure by lowering the V concentration.
Figure 3: Uses of different types of Metal Hydrides [1]

Conclusion

Because existing hydrogen fuel storage systems of pressurised H2 gas as well as cryogenic liquid
(H2)have safety and permeability issues, as well as high costs, these may not fulfill the country's
hydrogen economic potential utilization and ambitions. Over the last several years, a large
variety of unique metal hydrides have been found, and scientific understanding of this group of
substances has grown enormously. The availability of hydrides, as well as their structural and
property variety, provides fresh promise for solid hydrogen storage, including portable appliance.
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