MASS PRODUCTION OF Li-Al ALLOYS

BY THE STEP CONTROLLED

CASTING PROCESS

Guided by: Presented by:

VENKITESH K S KIRAN DEV
ASST.PROFESSOR IN ME APAMEME051
AIT AIT
 INTRODUCTION
The major challenge of the hydrogen
economy is efficient and safe storage of
hydrogen.
For hydrogen storage ,important things we
considered are safe ,compact ,reliable and
cost effective.
Current methods in hydrogen storage are
high pressure storage using gaseous
hydrogen, cryogenic tanks (liquefied
hydrogen), metal hydrides, graphene.
Metal hydrides possess unique ability to
absorb hydrogen and release it later.
 Lithium-Aluminum hydride, LiAlH4 was first
synthesized in 1947 as a powerful reducing agent.
Its hydrogen storage capacity is even higher than
that of NaAlH4.
LiAl-based complex hydrides can be produced by
chemical synthesis, direct synthesis , mechanical
alloying and mechano - chemical method.
Those methods have very complicated processes or
use many kinds of catalysts, therefore pure and
homogeneous Li-Al-based complex hydrides are
difficult to obtain in mass production.
 In order to improve upon the LiAl-base complex
hydrides production methods, this study proposed
a critical technology, step controlled casting
process (SCCP)
It is used for mass production of pure LiAl alloy
which is then hydrogenated to produce LiAl-based
complex hydrides.
 Experimental procedure
A weight of 2.0 kg mixture of Li and Al bulks
(20:80 wt.% respectively) was prepared from
commercial pure Li and Al.
Both of Li bulks (99.9% purity) and Al bulks
(99.9% purity) were cut to approximately 2 2 2
cm3 cubic.
Li bulks were cut under argon atmosphere.
There are mainly two process.
1. Conventional process
2. Step controlled casting process
1.Conventional process
In conventional melting process, the pure Al bulks
were melted at 750 C, then the pure Li bulks were
added.
However, expected precise composition was
difficult to obtain, since Li bulks floated on the Al
melt surface due to the large density difference
between Al and Li.
Li volatilizes easily in the air, resulting the
incorrect alloy composition , as shown in Fig. 2(a).
 2.Step controlled casting process
In order to avoid the volatilization of Li, step-
controlled casting process (SCCP) is developed to
produce Li-Al alloy by changing the steps opposite
to the conventional melting method.
Li bulks wrapped by Al foil were put into main
crucible (stainless steel) while Al bulks were
put into preheat Crucible (stainless steel). Al
bulks were preheated to 640C for 1.5 h by an
electric resistance furnace.
 Li bulks in main crucible were heated up to 640 C.
Al bulks were then pushed into main crucible by
feeding rod when the temperature of main
crucible reached 640 C.
Temperature of main crucible was then increased
to 750 C and melt mixture was stirred manually
using stirring rod for 0.5 h.
Li melt would react with Al melt rapidly so that
the volatilization of Li could be prevented.
The alloy mixture then cooled down to room
temperature. All processes were conducted under
argon atmosphere.
Structure and composition
characterization
X-ray diffraction (XRD) and inductively coupled
plasma-atomic emission spectroscopy (ICP-
AES)were performed to evaluate the structure and
composition of alloy.
The as-cast sample was mechanically ground to
600 grade SiC paper, and polished to 0.05m
aluminum oxide particles before the
microstructure observation, then, the as-cast LiAl
alloy were investigated by optical microscopy
(OM).
Bulk shape produced by conventional
method
Bulk shape produced by SCCP
Microstructure produced by SCCP.
Temperature-programmed
decomposition (TPD)
Samples were hydrogenated under 65 atm at
various temperatures for 12 h for estimating the
hydrogen storage properties.
The dehydrogenation property was also examined
by temperature-programmed decomposition
(TPD).
Hydrogenated LiAl sample (0.1 g) was loaded into
a vertical quartz tube reactor (3mm diameter) in
an electric tube furnace.
Argon gas (20 ml/min)was introduced into the
reactor at room temperature , and then the reactor
was heated to 600 C at a rate of 5 C/min.
Results and discussion
The appearance of the LiAl alloy produced by
conventional method could be seen in Fig.3(a)
The alloy produced by SCCP was brittle bulk with
silver-gray colour, as seen in Fig. 3(b).
Fig. 3(c) showed that the microstructure of the as-
cast LiAl alloy was a homogeneous microstructure
, while the white points were the bulk pores.
While solidification, this casting pores might
appear on the alloy surface due to no de gassing
step in SCCP.
 The XRD patterns of the raw Al and Li materials
were shown in Fig (a) and (b).
Fig.(c) indicated that the as-cast alloy produced by
conventional melting process only contained the
peak of Al. This was predicted due to the
volatilization of Li.
The XRD pattern of the as-cast LiAl alloy produced
by SCCP is shown in Fig. (d). All diffraction peaks
was corresponded to the JCPDS 71-0362 standard
of LiAl alloy, showing a single phase structure
without Li and Al residual.
 Result of XRD was verified using ICP-AES to
examine the chemical composition of the as-cast
alloy, and the result was tabulated in Table .
The as-cast alloy produced by conventional
melting process was mainly consisted of Al. This is
due to volatilazation of Li.
So only minor Li remained in the alloy.
On the other hand, the analytical compositions of
LiAl alloy produced by SCCP method were close to
the theoretical composition of 80 wt.% Al and
20wt.% Li, with slight impurities of Fe , Mn , Cr,
and O.
This result fitted the XRD result, consolidating a
single phase LiAl alloy was successfully produced
by SCCP.
The hydrogen storage properties of
LiAl alloy produced by SCCP
The effect of hydrogenation temperature on the
dehydrogenation properties of the as-cast LiAl alloy
was examined by TPD as shown in Fig. (a) to (c).
Two dehydrogenation peaks appeared in the TPD
curves of all the as-cast LiAl alloys. The first peak was
located at 247 to 284 C, while the higher one was
located at about 540 C.
These peaks should be observed due to hydrogen
releasing reactions which occur at different
temperature.
 In order to improve the hydrogenation properties,
as-cast LiAl alloy was ball milled under argon
atmosphere for 10 h.
The TPD results of ball milled LiAl alloys
hydrogenated at different temperatures was
displayed in Fig.(d) to (f).
The first and second peak was shifted to lower
dehydrogenation temperature.
The maximum amount of released hydrogen was
increased significantly after ball milling, from 0.77
to 2.40 wt.% for 400 C hydrogenation
temperature.
 These indicated that ball milling could decrease
the dehydrogenation temperature and improve the
amount of released hydrogen.
 X-ray diffraction was also employed to evaluate the
structure transformation before and after
hydrogenation/dehydrogenation.
LiAl alloy was hydrogenated only partially and
transformed to LiH and Al after hydrogenation.
After TPD test, LiH and Al returned to the initial
state of LiAl alloy.
LiAl alloy produced by SCCP was also reversed to
the initial state showing the reversibility of LiAl in
storing hydrogen.
 The evaluation of structure transformation before
and after hydrogenation/dehydrogenation was also
performed for the ball milled alloy.
The ball milled LiAl alloy hydrogenated at 350 C
was only partially hydrogenated, while ball milled
LiAl alloy hydrogenated at 400 C was fully
hydrogenated into LiH and Al.
As regards the enhancement of hydrogen storage
properties caused by ball milling, there is no
scientific explanation so far.
Detailed investigation concerning with the
improved hydrogen storage properties of ball
milled LiAl alloy shall be continuously carried on.
Conclusions
A new approach to mass production of LiAl alloy
was developed using SCCP method, and the high
purity of single phase LiAl was confirmed by XRD
and ICP-AES analysis.
Both as-cast and ball milled LiAl alloys had
reversibility in hydrogen absorption/desorption
which made it suitable for hydrogen storage.
The highest hydrogen capacity of 2.4 wt.% was
obtained from the ball milled LiAl alloy
hydrogenated under 65 atm at 400 C for 12 h.
References
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materials, methods and perspectives,Renew. Sust.
Energ. Rev. 50 (2015) 457469.
Y.H. Hu, E. Ruckenstein, H2 storage in Li3N.
Temperature-programmed hydrogenation and
dehydrogenation, Ind. Eng. Chem. Res. 42 (21) (2003)
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