Applied Thermal Engineering: S. Srinivasa Murthy, E. Anil Kumar

Advanced materials for solid state hydrogen storage: Thermal
engineering issues
S. Srinivasa Murthy
a,
*
, E. Anil Kumar
b
a
Department of Mechanical Engineering, Indian Institute of Technology Madras, Chennai 600036, Tamil Nadu, India
b
Discipline of Mechanical Engineering, Indian Institute of Technology Indore, Indore 453446, India
h i g h l i g h t s
Advanced materials suitable for solid state hydrogen storage are discussed.
Issues related to thermodynamic and thermo-physical properties of hydriding materials are brought out.
Hydriding and dehydriding behavior including sorption kinetics of complex hydrides with emphasis on alanates are explained.
a r t i c l e i n f o
Article history:
Received 20 December 2013
Received in revised form
26 March 2014
Accepted 10 April 2014
Available online xxx
Keywords:
Solid state hydrogen storage
Physisorption
Chemisorption
Alanates
Complex hydrides
Thermo-physical properties
a b s t r a c t
Hydrogen has been widely recognized as the Energy Carrier of the future. Efcient, reliable, economical
and safe storage and delivery of hydrogen form important aspects in achieving success of the Hydrogen
Economy. Gravimetric and volumetric storage capacities become important when one considers
portable and mobile applications of hydrogen. In the case of solid state hydrogen storage, the gas is
reversibly embedded (by physisorption and/or chemisorption) in a solid matrix. A wide variety of ma-
terials such as intermetallics, physisorbents, complex hydrides/alanates, metal organic frameworks, etc.
have been investigated as possible storage media. This paper discusses the feasibility of lithiume and
sodiumealuminum hydrides with emphasis on their thermodynamic and thermo-physical properties.
Drawbacks such as poor heat transfer characteristics and poor kinetics demand special attention to the
thermal design of solid state storage devices.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
Depletion of fossil fuels and the increased awareness of their
negative ecological impacts have necessitated the need for envi-
ronmentally benign alternatives. Characterized by its high gravi-
metric energy content and clean conversion, hydrogen is
considered as a very promising alternative. Cost effective, efcient
and safe means of storage and delivery of hydrogen is essential to
make this a reality.
Hydrogen in compressed, liqueed or solid state is the possible
means of storage. Compressing hydrogen to very high pressures
(about 700 bar) or liquefaction at cryogenic temperatures (20 K)
present several safety and design challenges [1,2]. Hence, solid state
hydrogen storage emerged as a safe and viable alternative, espe-
cially for mobile and portable applications.
Hydrogen can be physisorbed by sorbents such as porous carbon
and zeolite, whereas metal hydrides and complex hydrides can
store hydrogen through chemisorption and chemical reaction
respectively. Important requirements for potential applications
include high storage capacity, low cost, favorable operating tem-
peratures and pressures, low hysteresis, easy activation, high
cyclability, low density and low specic heat. Intermetallics and
complex hydrides can be used to store hydrogen reversibly at their
respective operating conditions, with suitable techniques for heat
transfer enhancement. The DoE (USA) targets for on-board
hydrogen storage in automobiles is given in Table 1 [3].
Intermetallics like LaNi
5
are easily reversible at moderate tem-
peratures and pressures and exhibit fast sorption kinetics. How-
ever, they are characterized by poor gravimetric storage capacity
(1.5e2.5 wt.%). Table 2 shows the comparison of the gravimetric
storage capacity of some intermetallic hydrides [4]. High capacity
hydrides like MgH
2
, are reversible only at temperatures above
* Corresponding author. Fax: 91 44 2257 0545/4652.
E-mail addresses: ssmurthy@iitm.ac.in, ssmurthy.iitm@gmail.com (S. Srinivasa
Murthy).
Contents lists available at ScienceDirect
Applied Thermal Engineering
j ournal homepage: www. el sevi er. com/ l ocat e/ apt hermeng
http://dx.doi.org/10.1016/j.applthermaleng.2014.04.020
1359-4311/ 2014 Elsevier Ltd. All rights reserved.
Applied Thermal Engineering xxx (2014) 1e14
Please cite this article in press as: S. Srinivasa Murthy, E. Anil Kumar, Advanced materials for solid state hydrogen storage: Thermal engineering
issues, Applied Thermal Engineering (2014), http://dx.doi.org/10.1016/j.applthermaleng.2014.04.020
250
C [5] i.e., beyond the optimumtemperature range of operation

for PEM fuel cells (w80

C) [6]. High density and cost of the
reversible low temperature hydrides also limit their practical us-
ability. The volume change associated with these hydrides during
absorption and desorption cycles are also higher than complex
hydrides [7]. With inherent low thermal conductivity of hydrogen
storage materials, heat transfer is often the major rate limiting
parameter [8e10]. Temperature of the storage bed has a signicant
impact on the reaction rate. Minimizing of refueling time is an
important objective in the development of mobile hydrogen stor-
age devices. Appropriate temperature levels need to be maintained
in the storage bed so as to get maximum sorption performance.
Excess cooling and overheating of the bed lead to poor sorption
performance [11,12]. The initial reaction rate is a characteristic of
the material used while the later reaction is controlled by heat
transfer [13]. It has been observed that absorption reaction com-
mences from cooler regions of the storage bed, normally near to
heat exchanger surfaces [9]. A metal hydride reactor embedded
with multi tubular heat exchanger previously reported by the
author, improved sorption kinetics by enhancing heat transfer
within the bed [11]. Major developments in metal hydride based
hydrogen storage were recently reviewed by this author [14].
2. Complex hydrides
Complex hydrides, mostly alanates or borates of lithium, sodium
and potassium have hydrogen retaining capacity up to 18 wt.%.
These hydrides based on sodium and lithium store 7.4 wt.% and
10.5 wt.% respectively [15] while borates like sodium borohydride
and lithium borohydride have higher theoretical storage capacities
of 10.4 wt.% [16] and 18 wt.% [17] respectively. Their high hydrogen
content, lower weight and lesser costs make them attractive for
portable and mobile applications. However, their low thermal
conductivity and high heat of reaction limits their application in
practical systems. They also decompose in a multi-step reaction at
high temperatures and pressures, exhibiting slowkinetics and poor
reversibility. LiAlH
4
can be easily dehydrogenated in a three step
reaction similar to NaAlH
4
, but its hydrogenation occurs at very
high pressures [15]. The third dissociation step of sodium and
lithium alanates occurs at temperatures 425

C and 680

C
respectively [15,18,19], which is beyond the desired temperature
range for practical hydrogen storage applications. LiBH
4
can
reversibly store over 8 wt.% hydrogen at temperatures above 325
C
with magnesium additives and Titanium based catalysts [20].
Desorption of the compound at low temperature is negligible
(0.3 wt.%). Another complex hydride, Lithiumnitride (Li
3
N) releases
most part of its capacity only above 230

C [19]. Mixtures of such
hydrides have been tried by different investigators to improve the
overall sorption characteristics [21e24]. Among different mixtures
of LiAlH
4
and LiBH
4
, 2:1 ratio specimen exhibited a maximum
desorption of 6.6 wt.% H
2
in the presence of TiCl
3
catalyst precursor
at temperatures below 220

C [25].
In this paper thermodynamic properties, modeling of kinetics,
measurement of thermophysical properties of Alanates are
reviewed. Heat and mass transfer characteristics, Numerical
Simulation, Design optimization of hydrogen storage devices (with
NaAlH
4
) are discussed.
2.1. Sodium aluminum hydride
Ashby et al. [26,27], were one of the earliest to synthesize so-
dium aluminum hydride and study its sorption characteristics.
Sodium aluminum hydride, NaAlH
4
decomposes into sodium hex-
ahydride (Na
3
AlH
6
) and aluminum, accompanied with evolution of
hydrogen in the rst step. In the second step Na
3
AlH
6
decomposes
into sodium hydride (NaH), aluminum metal and hydrogen at
elevated temperatures and pressures [28]. Dehydrogenation
returns the crystalline alanate [29]. These are shown in the
following reactions:
3NaAlH
4
4Na
3
AlH
6
2Al 3H
2
(Reaction 1)
Na
3
AlH
6
2Al 3H
2
43NaH 3Al 4.5H
2
(Reaction 2)
The rst and second reactions release 3.70 wt.% and 1.85 wt.% of
H
2
respectively. Sodium alanate, in its pure form takes nearly 22 h
to attain saturation at 200

C and much slower at lower tempera-
tures. The rate of reaction is almost negligible at 160

C. The studies
also revealed the effect of Titanium doping in sodium alanates. Ti
doping was found to increase the sorption kinetics drastically,
simultaneously improving cyclability and storage capacity. Addi-
tion of catalysts in small amounts remarkably improved its sorption
performance [30]. These results generated greater interest in the
development of complex hydrides for portable applications. Jensen
et al. [31] reported that signicant decomposition of neat alanate
occurs only above the melting point of the material at 183

C, while
melting of the material doesnt affect the reaction kinetics [7].
Several studies were conducted subsequently to understand
modied kinetics and dopant action in the lattice. Considering the
favorable operating conditions and available thermodynamic data,
sodium alanate can be used for practical hydrogen storage appli-
cations. Moreover, alanates can be produced in laboratory scale
from NaH and aluminum powder with aluminum reduced TiCl
3
[32].
2.1.1. Role of catalyst
It is well established that catalysts improve the sorption kinetics
drastically. The above mentioned reactions of the sodiumalanate at
200

C were completed within an hour when doped with 2 mol% of
Ti(OBu)
4
precursors [30]. Characteristic fast and slow kinetic re-
gimes were observed in the desorption curve indicates the two step
reaction [33]. It has been conrmed by different studies that the
addition of Titanium as catalyst enhances the sorption capacity and
improves reversibility under moderate conditions while main-
taining important thermodynamic properties [6,15,30,31,33e37].
Zidan et al. [35]conrmed superior decomposition of Ti/Zr doped
Sodium alanate below 100

C. Addition of catalysts into pure ala-
nate in any manner decreases dehydrogenation temperature and
enhances kinetics [38].
Table 1
DOE targets for on-board hydrogen storage for automobiles [3].
Storage parameter Units 2017 goals Ultimate
System gravimetric capacity % 5.5 7.5
System volumetric capacity kg H
2
/L system 0.04 0.07
Operating temperature

C 40/60 40/60
Operational cycle life Cycles 1500 1500
System ll time (5 kg) Min 3.3 2.5
Table 2
Hydrogen storage capacity of some metal hydrides [4].
Material Capacity in wt. % of H
2
Material Capacity in wt. % of H
2
LaNi
5
1.49 ZrCr
2
1.82
MmNi
5
1.46 Ca 4.8
Ti 4.0 CaNi
5
1.87
TiFe 1.86 CeNi
5
1.5
TiCr
1.8
2.43 Mg 7.66
Zr 2.2 MgNi 3.6
ZrMn
2
1.77 Mg 2 wt.% Ni 7.48
S. Srinivasa Murthy, E. Anil Kumar / Applied Thermal Engineering xxx (2014) 1e14 2
While Ti doping was found superior for NaAlH
4
, Zirconium was
reported as better catalyst for Na
3
AlH
6
[35] even though both were
found to improve cyclability and promote faster dehydriding. The
effects of several catalyst precursors like TiCl
3
, TiCl
4
, Zr(OPr)
4
,
Ti(OBu)
4
have been studied. Though the latter two had consider-
able effect on bed performance, they were found to lower the cyclic
capacity due to damage caused by the oxygen on the hydride sur-
face. This may be accounted to the loss of material due to oxide
formation [7,39]. The liquid organo-metallic alkoxide precursors
also affect the purity of hydrogen liberated. Sandrock et al. [7] re-
ported that 2 mol % of alkoxide leads to 22% additional weight on
the system.
The loading of Titanium also found to have varied the effect on
catalysis. During absorption, 0.9 mol % of Ti doped sample failed to
shownoticeable response while 2e9 mol % doped samples reached
saturation within 2 h. Though higher loading of dopant improves
rate of dehydriding, it has a negative impact on hydrogen storage
capacity. The addition of Ti catalyst results in the decrease of the
activation enthalpy and thereby reaction temperature. Signicant
differences were reported in activation enthalpies of NaAlH
4
and
Na
3
AlH
6
as shown in Table 3 [34].
The dopant action is irrespective of the halide used with Tita-
nium [37,40]. Further, titanium powder alone as dopant did not
produce any effect on the reaction kinetics [40]. However, the
radius of cation is a critical parameter for effectiveness of catalyst.
Studies have revealed different mechanisms by which the
catalysis can occur. First principle method [41], X-ray diffraction
pattern [42e45], neutron inelastic scattering technique [41],
scanning electron microscopy [38,39]electron dispersive spectros-
copy [39] and Mossbauer spectroscopy [15] were commonly used
to understand the role of catalysts. While some studies [30,39,42],
reported that the dopants are segregated and remain in the surface
of the material, the others suggested that they substitute for so-
dium in the bulk of the lattice.
2.2. Lithium alanates
LiAlH
4
, was rst synthesized by Finholt et al. [46] as early as in
1947 and was used as a reducing agent of organic compounds.
Desorption of hydrogen proceeds in three-step reaction with the
decomposition of lithium tetrahydroaluminate into trilithiumhex-
ahydroaluminate, aluminum and hydrogen [47e50].
3 LiAlH
4
/Li
3
AlH
6
2Al 3H
2
(Reaction 3)
Li
3
AlH
6
/3LiH Al 3/2H
2
(Reaction 4)
3 LiH 3Al /3 LiAl 3/2H
2
(Reaction 5)
The reaction is initiated by the melting of LiAlH
4
which trans-
forms into solid Li
3
AlH
6
and Al during release of hydrogen. The
maximum hydrogen storage capacity of LiAlH
4
is 10.6 wt.% [50]
which decomposes according to above reactions with the release
of 5.3 wt.% by Reaction (3), which occurs at around 423e448 K [47e
49]. Reactions (4) and (5) occur at 453e493 K and 623e673 K with
a hydrogen release of 2.6 wt. %, and 3.6 wt. %, respectively
[48,49,51,52]. The reaction temperature depends upon heating rate
[53]. Since the decomposition of LiH occurs at very high tempera-
ture, only 7.9 wt. % hydrogen is considered available for practical
applications [49,50]. Reactions (3) and (4) are endothermic pro-
cesses with DH of 22e58 kJ/(mol H
2
) [49e51,54] respectively and
Reaction (5) is an exothermic process with DH of 116.3 kJ/(mol H
2
)
[54].
Doping LiAlH
4
with Ti-based and V-based catalysts result in
lowering of decomposition temperatures of Reactions (3) and (4).
The addition of VCl
3
and TiCl
3
x 1/3AlCl
3
in LiAlH
4
signicantly
decreases the decomposition temperature [48,49]. Among the two,
VCl
3
is more effective [48]. It has been shown that doping with
TiCl
3
1/3AlCl
3
facilitate isothermal dehydrogenation at 373e
548 K at a time scale of 50 min to a few hours. Ball milling of pure
LiAlH
4
decreases the decomposition temperature by 60

C of
Reactions (3) and (4) [49,52]. Pure LiAlH
4
does not decompose
during ball milling at ambient temperatures [55], whereas LiAlH
4
doped with catalytic additives e.g. TiCl
3
, TiCl
4
, VCl
3
and FeCl
3
rapidly decomposes during milling [48,55]. Doping with TiCl
3
and
TiCl
4
results in decrease in desorbed amount of hydrogen because it
eliminates the rst step of hydrogen decomposition. The doping
was done by ball milling the mixture of LiAlH
4
and TiCl
3
/TiCl
4
. XRD
studies for LiAlH
4
doped with TiCl
3
and TiCl
4
showed the presence
of Li
3
AlH
6
, which indicated that the solid state reaction,
LiAlH
4
/Li
3
AlH
6
Al H
2
(rst step of desorption), had occurred
during ball milling. Also addition of the titanium lead to loss of
storage capacity as titaniumwas reduced by alanate ion during ball
milling process. While, doping with TiH
2
and other elemental iron
does not affect the desorption capacity [52].
The comparison between maximum hydrogen desorption ca-
pacity of LiAlH
4
with different catalyst in the temperature range
430e450

C is presented in Fig. 1. Unmilled LiAlH
4
shows higher
desorption capacity than other catalyst doped LiAlH
4
. Signicant
decrease in desorption capacity after 1 h ball milling can be seen.
This decrease is because of high energy involved during ball
milling process. The decrease in desorption capacity of TiH
2
doped
LiAlH
4
is very less and close to ball milled LiAlH
4
. It can be
considered that the decrease in desorption is due to ball milling
alone [52]. The desorption capacity of TiCl
3
doped and TiCl
4
doped
LiAlH
4
is very less because it eliminates the release of hydrogen in
Reaction (3), rather other catalyst doped LiAlH
4
shows approxi-
mately same desorption capacity. Doping with catalyst results in
decrease in decomposition temperature and desorption capacity in
each step of reaction.
Table 3
Wt. % of H
2
absorbed and activation enthalpy at different doping levels [34].
Doping level (mol% Ti) Wt. % of hydrogen Activation enthalpy
NaAlH
4
Na
3
AlH
6
0 5.12 118.1 120.7
0.9 4.94 72.8 97.1
2 4.25 79.5 97.1
4 3.85 80 97.5
6 2.91 78.5 98.2
Fig. 1. Comparison of desorption capacity of unmilled LiAlH
4
, ball milled LiAlH
4
, LiAlH
4
doped with TiH
2
, AlCl
3
, Ti, Fe, C-black, V, Ni, FeCl
3
, TiCl
4
and TiCl
3
at temperature 430e
450

C.
Fig. 2 shows the hydrogen desorption capacity of TiCl
3
1/
3AlCl
3
-doped LiAlH
4
at different temperatures. The release of
hydrogen is more with the increase in reaction temperature
whereas the reaction time decreases.
2.2.1. Dehydriding behavior of carbon admixed LiAlH
4
Authors group has extensively [56,57] investigated dehydroge-
nation kinetics of LiAlH
4
eCarbon composites. The effect of carbon
content and catalytic effect of carbon nanobres on dehydrogena-
tion kinetics were studied. Four different types of carbons, Vulcan
XC72R (250 m
2
g
1
), Black Pearls 2000 (1500 m
2
g
1
), CDX 975
(240 m
2
g
1
) and Mesoporous carbon (1400 m
2
g
1
) were used.
Carbon nanofibers were synthesized using NieCu catalyst.
2.2.2. Effect of type of carbon
The effect of carbon on the dehydrogenation kinetics is visual-
ized by isothermal dehydrogenation curves for all LiAlH
4
eC
(Vulcan XC72R, Black Pearls 2000, CDX 975 and Mesoporous car-
bon) composite samples as shown in Fig. 3.
Same isothermal dehydrogenation temperature was applied to
all composites. For comparison the dehydrogenation kinetics of
pure LiAlH
4
milled for 45 min, decomposed at the same tempera-
ture (403 K) was included as a reference. It was observed that
dehydrogenation kinetics improved considerably by addition of
various carbon materials. The enhancement is nearly 4e5 times for
the Black Pearls 2000, CDX 975, mesoporous carbon and w2 times
for the Vulcan XC-72R in comparison to pure LiAlH
4
(at 45 min). The
dehydrogenation prole of the Vulcan XC-72R admixed LiAlH
4
re-
sembles the as-received LiAlH
4
curve. On the other hand, the Black
Pearls 2000, CDX 900, mesoporous carbon containing composites
give higher rates signicantly altering the curve prole. It suggests
that the reaction does not follow the same mechanism in all the
cases. It follows different paths in the case of Black Pearls 2000, CDX
975 and mesoporous carbon admixed LiAlH
4
.
Among the four carbons, Black Pearls and CDX 975 show high
desorption kinetics. The rate is higher for the mesoporous carbon in
the initial stages and drops down slowly. The rate is not directly
proportional to surface area of the carbon. The order of dehydriding
reaction rate is, Black Pearls wCDX >mesoporous carbon >Vulcan
XC72R. Hence the change in the rate cannot be solely attributed to
the surface area of the carbon.
2.2.3. Dehydrogenation kinetics of CNFs admixed LiAlH
4
Composite
The isothermal dehydrogenation kinetic traces of composite
materials based on lithium aluminum hydride admixed with car-
bon nanobers and Vulcan XC72R are shown in Fig. 4.
These curves were plotted by calculating the total hydrogen
released (at 408 K under atmospheric pressure) in terms of weight
percentage with respect to the dehydrogenation time under dy-
namic conditions.
For comparison, the dehydrogenation kinetics of pure LiAlH
4
milled for 45 min, decomposed at the same temperature, 408 K is
included. The dehydrogenation kinetics improved considerably by
the addition of Vulcan XC72R carbon and remarkably with carbon
nanobers.
3. Modeling of sorption kinetics
Several numerical models have been formulated to dene the
hydrogenation/dehydrogenation processes. An isotropic and uni-
form hydride bed with thermo-physical properties independent of
hydrogen loading, temperature and cycling has been reported by
Hardy [58].
Fig. 2. Variation of Hydrogen desorption capacity and reaction time with temperature
for TiCl
3
1/3AlCl
3
-doped LiAlH
4
.
Fig. 3. Dehydrogenation proles for the (-) pure LiAlH
4
(C) 5 wt.% Vulcan XC72R
admixed LiAlH
4
(A) 5 wt.% mesoporous carbon admixed LiAlH
4
(:) 5 wt. % CDX 975
admixed LiAlH
4
(;) 5 wt.% Black pearls 2000 admixed LiAlH
4
.
Fig. 4. Dehydrogenation kinetics of LiAlH
4
admixed with CNFs, LiAlH
4
admixed with
Vulcan carbon and LiAlH
4
.
As suggested by El Osairy et al. [59,60] for analysis of LaNi
5
H
6
system, the rate of reaction can be dened as a function of tem-
perature, pressure and composition.
_
dc
j
dt
_
f T f P f C (1)
The function of temperature in the rate equation is represented
by the Arrhenius term. The pressure function is the driving force for
sorption represented by the differential between supply pressure
and equilibrium pressure. The last term represents the concentra-
tion of reactant as a function of hydrogen to metal atom ratio. Even
though they used a rst order reaction to arrive at the composition
term, the order of reaction may be different for alanate. The power
term is used to represent the order of the reaction in United
Technologies Research Center (UTRC) model [58].
_
dc
j
dt
_
Aie
E
i
=RT
1
i
_
P P
e;i
P
e;i
_
C
k
c
i
(2)
where,
ln
_
P
e;i
1 bar
_

DH
R
RT

DS
R
R
(3)
Similar to intermetallics, hydriding undergoes nucleation and
growth in alanates. Rudman [61] has explained the use of nucle-
ation theory in the development of hydriding and dehydriding ki-
netic models. Accordingly, Lozano et al. [12] used the Johnsone
MehleAvrami (JMA) equation to arrive at the composition term.
This term is dened as a function of transformed fraction (f),
which is the mass ratio of hydrogen m
H2
absorbed to the
maximum absorption capacity m
H2;max
. This function can be ob-
tained by numerical tting with experimental values. Both ab-
sorption steps in the hydride formation can be represented with
JMA model with n 1.3. Model suggested by Kirchner and Fichtner
[62] reported different values of n equal to 1.1 and 1.4 for rst and
second reaction steps respectively.
a
m
H2
m
H2max
(4)
The model put forward by Lozano et al. [12] considers
continuous formation of reaction products. The effect of reactant
materials as well as the inert components present in the bed was
included in the model. But, the models suggested by Luo and
Gross [63] represented independent formation of the products.
They considered the rst hydrogenation step as a rst order re-
action and second step as a second order reaction. Due to the
presence of excess aluminum during the rst reaction, only the
concentration of NaH affects its progress. Hence it is represented
as a rst order reaction. Lozano et al. [12] used low bed thickness
cells to achieve isothermal condition during experiments. Same
reaction rate can be achieved at two sets of pressure and tem-
perature values. Higher pressures yield better kinetics at con-
stant temperature. Due to higher plateau pressure of second
absorption reaction, it progresses considerably slower than the
former.
The rate of dehydrogenation increases with increase in tem-
perature [33] and decrease in pressure with impact of temperature
being more signicant. Hydrogen back pressure is a major param-
eter controlling the desorption process. The rate of dehydrogena-
tion approaches zero when the hydrogen back pressure equals the
equilibrium pressure for the product formation. The desorption
reaction can be considered to occur sequentially. The desorption
PCI curves show a delay or a break when the desorbed weight
fraction approaches 2.5% [63,12]. Lozano et al. [12] approximated
the rst desorption reaction to a zero order reaction i.e., the rate of
desorption remains constant throughout the desorption step and
second step as a rst order reaction (similar to [33]) with index n
in JMA equation evaluated as unity. First order conditions are valid
only when (P P
e,i
/Pe,i) > 0.7. First and the second desorption
reaction steps commences only above 114

C and 147

C irre-
spective of hydrogen pressure.
The kinetic model proposed by Luo and Gross [63] is given
below:
Formation of NaAlH
4
dH wt:%
dt
K
oa1
e
E
aa1
RT
ln
_
P
appl
P
eq 1
_
3:9 H wt:%;
1:67 < H wt:% < 3:9
(5)
Formation of Na
3
AlH
6
dH wt:%
dt
K
oa2
e
E
aa2
RT
ln
_
P
appl
P
eq 2
_
1:67 H wt:%;
H wt:% < 1:67
(6)
Decomposition of NaAlH
4
dH wt:%
dt
K
od1
e
E
ad1
RT
ln
_
P
ed1
P
appl
_
H wt:% 1:67;
1:67 < H wt:% < 3:9
(7)
Decomposition of Na
3
AlH
6
dH wt:%
dt
K
od2
e
E
ad2
RT
ln
_
P
eq2
P
appl
_
H wt:%; H wt:% < 1:67
(8)
The rate of reaction is calculated using UTRC kinetics model
[58,64] as given below:
Formation of Na
3
AlH
6
r
1F
C
eqv
A
1F
exp
_
E
1F
RT
_
_
PC; T P
eq1
T
P
eq1
T
_
(9)
Decomposition of Na
3
AlH
6
r
1B
C
eqv
A
1B
exp
_
E
1B
RT
_
_
P
eq1
T PC; T
P
eq1
T
_
(10)
Formation of NaAlH
4
r
2F
C
eqv
A
2F
exp
_
E
2F
RT
_
_
PC; T P
eq2
T
P
eq2
T
_
(11)
Decomposition of NaAlH
4
r
2B
C
eqv
A
2B
exp
_
E
2B
RT
_
_
P
e2
T PC; T
P
eq2
T
_
(12)
m
1

dC
1
dt

_
_
r
1F
_
3C2t
Ceqv
eC
2sat
T
_
X1F
if P P
eq1
T
r
1B
_
C1t
Ceqv
_
X1B
if P < P
eqv1
T and C
1
_
t
_
0
(13)
m
3
dC
3
dt

_
_
r
2F
_
C3t
Ceqv
eC
3sat
T
_
X2F
if PP
eq2
T
r
2B
_
3C2t
Ceqv
_
X2B
if P<P
eqv2
TandC
2
_
t
_
0
(14)
m
2

_
m
1
m
3
3
_
(15)
C
eqv
C
10
C
20
C
30
(16)
According to the kinetic model by Lozano et al. [12], Rate of
reaction is dened as,
da
dt
k
^
T; p Ae
Ea
RT
*f
_
p; p
eq
_
(17)
For rst absorption step,
a
SI/II

m
SII
m
SII
m
SI
(18)
da
SI/II
dt
1:33k
SI/II
_
1 a
SI/II
_
_
ln
_
1
1 a
SI/II
__
:25
(19)
f
SI/II
_
p; p
eq
_

_
p p
eq
_
p
eq
(20)
For second absorption step,
a
SII/III

m
SIII
m
SIII
m
SII
(21)
da
SII/III
dt
1:33k
SII/III
_
1 a
SII/III
_
_
ln
_
1
1 a
SII/III
__
:25
(22)
f
SII/III
_
p; p
eq
_

_
p p
eq
_
p
eq
(23)
For rst desorption step,
a
SIII/II

m
SII
m
SIII
m
SII
(24)
da
SIII/II
dt
k
SIII/II
(25)
f
SIII/II
_
p; p
eq
_

_
_
_
p p
eq
_
p
eq
_
_
2
1:04
_
_
_
p p
eq
_
p
eq
_
_
(26)
For second desorption step,
a
SII/I

m
SI
m
SII
m
SI
(27)
da
SII/I
dt
k
SII/I
_
1 a
SII/I
_
(28)
f
SII/I
_
p; p
eq
_

_
_
_
p p
eq
_
p
eq
_
_
2
0:46
_
_
_
p p
eq
_
p
eq
_
_
(29)
The subscripts I, II and III represent NaH, Na
3
AlH
6
and NaAlH
4
respectively.
4. Determination of thermo-physical properties
Dedrick et al. [65] determined thermal wall resistance and
effective thermal conductivity of the alanate bed with respect to
composition, cycle number and hydrogen pressure using numerical
and analytical methods. The effect of bed temperature is found to
be negligible. Thermal conductivity in the range of 0.6 W/m-K was
obtained at moderate operating pressures. Improvement of ther-
mal conductivity will result in better heat transfer and thereby
better kinetics [9]. Gross et al. [66] reported 0.2 W/m-K as thermal
conductivity of alanate bed which is less than that of intermetallic
hydrides. Poor conductivity could be attributed to high inter-
particle thermal resistance as in metal hydrides. Hardy and Anton
[67] reported 0.325 W/m-K as the thermal conductivity for bed in
their kinetic scoping model. Lozano et al. [68] estimated alanate
bed conductivity at 120

C in the range of 0.55 W/m-K. Van Hassel
et al. [69] experimentally found the thermal conductivity of alanate
based bed using TPS method while homogenization method can be
utilized when considering the microscopic bed behavior [70]. The
effective thermal conductivity of the bed can also be measured by
using transient techniques as demonstrated for intermetallics [71e
75]. The effective thermal conductivity values of Sodium alanate
beds reported in the literature are summarized in Table 4.
The specic heat capacity of a hydride is determined by the
amount of hydrogen content given by NeumanneKopp rule [76].
The value of heat of reaction for both absorption and desorption
reaction steps were calculated by Bogdanovic et al. from PCI mea-
surements [15]. The enthalpy of formation and entropy of forma-
tion are given in Table 5. Sandrock et al. [34] have reported the
activation enthalpy and rate constant at different doping levels.
Kiyobayashi et al. [77] determined the activation enthalpy and re-
action rate of dehydrogenation of Ti/Zr doped sodium alanate.
Castrillo et al. [78] dened thermal conductivity as a function of
contact factor and porosity. Bennett et al. [79] studied the effect of
varying thermal conductivity using a model similar to Sun and
Deng model [80] to take into account the effect of bed temperature
and pressure and reported signicant increase in accuracy.
An experimental setup for measuring effective thermal con-
ductivity of hydride was constructed at authors lab according to
ASTM E-1225 Standard [81]. PTFE disk was used as reference ma-
terial. The PTFE disk thermal conductivity was measured using a
Square Guarded Hot Plate (SGHP) apparatus. The hydride bed and
PTFE are in disk shape with 85 mm diameter and 20 mm thickness.
They are sandwiched between hot and cold plates. Hot plate is
heated with a disk heater and cold plate is cooled by circulating
Table 4
Thermal conductivity of Sodium alanate as reported by various authors.
Reference Thermal
conductivity
(W/m-K)
Condition
Dedrick et al. [65] 0.5 1 bar 1.84 mol % TiCl
3
0.62 g/cm
3
0.68 100 bar
Gross et al. [66] 0.2 4 mol% TiCl
3
0.62 g/cm
3
Hardy [58] 0.325 4 mol% TiCl
3
0.72 g/cm
3
Sulic et al. [74] 9.09 Undoped 345 MPa
1.37 Ti doped pellets
w8.5 Doped with 5 mol%
expanded graphite
Pohlmann
et al. [75]
w6 3 mol% ENG 300 MPa
w12 6 mol% ENG
w30 16 mol% ENG
coolant. Required boundary conditions are imposed and one
dimensional heat transfer conditions are achieved. The tempera-
ture gradients in metal hydride bed and reference material are
measured at steady state. The heat transfer in series through the
metal hydride bed and reference material at steady state was
calculated from Fouriers lawand from this; the k
e
of metal hydride
bed is calculated. The complete details of experimental setup,
procedure and data reduction are given in authors recent paper
[82]. Effective thermal conductivity is measured at different oper-
ating conditions and the effects of hydrogen gas pressure and
concentration, bed temperature are studied.
At a particular average temperature, as hydrogen pressure
changes concentration of the hydride bed also changes. Hence,
practically it is not possible to study the effect of gas pressure alone
while using hydrogen as lling medium. So inert gases namely
argon, helium and nitrogen are also used as lling gases to study
the effect of gas pressure. Fig. 5 shows the variation of effective
thermal conductivity (k
e
) of MmNi
4.5
Al
0.5
for different lling gases.
As expected for packed beds, k
e
increases with increasing pressure
in the form of the tilted S shaped curve. This is obviously due to
the increase in gas thermal conductivity with pressure. This vari-
ation may be divided into three regions. In the low pressure region
up to about one bar, k
e
of MmNi
4.5
Al
0.5
bed is independent of
pressure. In this region the density of the gas is low in the voids of
the bed. Therefore the mean free path of the gas molecules is large
compared to the void size, which is assumed to be equivalent to the
average particle size of the bed. However, with increase in gas
pressure, density of the gas in the pores increases due to which the
mean free path of the gas decreases. When the mean free path of
the gas molecules approaches the size of the voids, collision of gas
molecules is high resulting in higher gas conductivity. In this region
of about 1e15 bar gas conductivity increases with pressure and
thereby k
e
also increases. With further increase of gas pressure, the
mean free path of the gas molecules is much lower than the
effective size of the voids. In this region, the process of heat transfer
by the gas is similar to that in innite space and do not inuence the
conductivity of the gas. Thus for gas pressures above 15 bar, k
e
remains nearly constant with increase in pressure. For most of the
metal hydrides the middle region (where the inuence of pressure
on k
e
is felt) lies in plateau region of hydriding or dehydriding
process. Hence, in addition to the effect of hydrogen pressure, the
effect of concentration should also be considered. However, with
inert gases as lling mediumthe effect of gas pressure alone is seen.
Effective thermal conductivity of the bed is found to be propor-
tional to the thermal conductivity of the lling gas. Thermal con-
ductivity of hydrogen is the highest of all the gases. The thermal
conductivity of heliumis nearer to that of hydrogen (k
He
k
H2
*0.8).
At pressures near to 0.1 bar, k
e
is independent of the lling gas,
because heat conduction at these low pressures is due to conduc-
tion in particle grid. The effect of gas conductivity on k
e
increases
with pressure. The difference between values of k
e
obtained under
hydrogen and helium atmospheres increases with pressure as the
concentration increases and stabilizes at the maximum concen-
tration. In the pressure independent region, the difference between
k
e
values obtained from hydrogen and helium atmospheres
approximately represents the increase in k
e
due to hydrogen con-
centration [82].
To estimate k
e
at wide range of operating conditions, it is
required to develop a mathematical or empirical relation. Several
mathematical models have been proposed in literature for the
prediction of k
e
of packed beds of porous materials. Due to the
differences in basic characteristics between metal hydride beds and
conventional packed beds, these models are unsuitable for metal
hydride packed beds. Authors group has extended models devel-
oped by Zehner and Schlunder [83], Yagi and Kunii [84], Dietz [85]
and Masamune and Smith [86] to incorporate the consequences of
hydrogen absorption and desorption. The extended models are
then used for simulation of experimental data on ETC of
MmNi
4.5
Al
0.5
hydride packed bed [87].
The results obtained from the extended models are compared
with the experimental results as shown in Fig. 6. The extended
models of YagieKunii and ZehnereSchlunder predicted the values
of ETC which are very closely matching with the experimental re-
sults. Extended MasamuneeSmith model was also very close in the
high pressure region while it shows some deviation in the lower
pressure region. The reason behind this could be consideration of
pendular voids by MasamuneeSmith. In case of MH beds, the ge-
ometry of voids cannot be assumed to remain same for all ranges of
pressure. The swelling of hydride particles results into variation in
the void geometry also. Dietz model, although shown the trend
similar to that obtained in experimental results, but the values were
under-predicted throughout the range of pressure. Dietz has sug-
gested the contact between particles to be point contact and also
Table 5
Value of dissociation enthalpy and entropy [58].
Sorption reaction DH
R
/R DS
R
/R
3NaH Al 1.5H
2
/Na
3
AlH
6
4475 14.83
Na
3
AlH
6
2Al 3H
2
/3NaAlH
4
6150 16.22
Fig. 5. Variation of effective thermal conductivity with pressure for different lling
gases.
Fig. 6. Comparison of ETC values obtained from extended model with experimental
results.
has xed the geometry of bed and arrangement of particles in the
bed. Moreover variation in porosity due to hydrogen absorption
could not be incorporated into this model as the model did not
suggest the k
e
to be directly dependent on porosity of bed.
5. Effect of heat and mass transfer
Early studies in hydrogen storage revealed that proper heat
transfer mechanismcan improve reaction rate [8e10]. An overview
of heat and mass transport in metal hydride systems were pre-
sented by the author [14]. Though the mechanism of hydriding is
different in complex hydrides and intermetallic hydrides, the effect
of heat and mass transfer in the bed largely remains the same.
Complex metal hydrides, similar to intermetallic hydrides are
characterized by low thermal conductivity. Due to large heat of
formation, insufcient heat transfer rate lead to sensible heating of
the bed leading to higher temperature rise in sorption bed during
absorption and the reverse for desorption, resulting in poor system
performance. The effect of heat transfer controlled reaction rate is
predominantly higher for hydride beds than mass transfer inu-
enced rates [88]. Further, high temperature operation of bed lead to
pulverization.
The principal bed parameters contributing to heat and mass
transfer are thermal conductivity of powder bed, hydrogen and the
bed porosity [89], while the operating parameters have a signicant
effect on the existing values. The thermal conductivity of bed in-
creases on hydrogen absorption, while its augmented also with
temperature increase coupled with increase of pressure in mod-
erate range [14,65,70,82,90]. Cycling of bed increased the conduc-
tivity by a factor of 1.3, while decreased permeability by half [91].
Decreased particle size as a result of pulverization due to cycling
and high temperature operation, increases the packing density at
lower part of the reactor [92,93]. Expansion and contraction of
metal powders during operation result in poor thermal contact
with the reactor wall which consequently increases thermal wall
resistance [94]. It must be noted that even the wall thickness of the
storage device has signicant inuence on sorption performance
[66]. Hence, a heat transfer oriented design of hydrogen storage
device is essential [95,96]. Apparently, the break in the absorption
curve signifying the transformation of Na
3
AlH
6
was found to reduce
as an effect of cycling [91]. Several heat transfer augmentation
techniques have been hence suggested as discussed in the
following sections.
5.1. Material modication and processing
Any change in the composition of neat alanates amounts to
material modication. It was mentioned in the section on catalysis
that the presence of impurities in the form of doping, additives etc.
enhances reaction kinetics. Metal hydride powder combined with
additives, such as carbon, expanded natural graphite, graphite
pellets and diamond powder can improve the thermal conductivity
of bed thus improving heat transfer [5,38,69,76,89,97e100]. Porous
metallic matrix formed by compacting LaNi
5
with powders of
aluminum, copper and nickel sustained several cycles while
improving sorption [101]. Chemical modication through such
additives enhances sorption performance while preserving ther-
modynamic properties, though the presence of additives results in
a loss of hydrogen capacity [89,102]. 10% loss is reported for
graphite additions [100]. This decrease can be compensated to
some level by adding more quantity of alanate compacts and a
buffer volume [69]. The presence of an expansion volume increases
the thermal resistance at the heat exchanger, reducing heat transfer
and kinetic performance while convective heat transfer gains
importance [103]. Metal hydrides encapsulated in copper have
higher thermal conductivity at higher packing fractions and are
cyclically stable. But, their kinetic characteristics deteriorate with
number of cycles [102]. While compaction of hydrides increases
conductivity and density, porosity and permeability decreases. This
leads to signicant mass transfer limitations [104]. It has been
observed that the mass transfer controlled reaction rate dropped
below heat transfer controlled rate in an annular disc type reactor
lled with hydride compacts [88].
Sodium alanate, ball milled in the presence of carbon could
absorb and desorb hydrogen faster at lower temperature and even
faster than neat form in the absence of titanium catalyst [5].
Pelletized alanates with graphite additives can be used for revers-
ible hydrogen storage. Pelletized alanate, over a range of 69e
345 MPa resulted in improved density and increased effective bed
thermal conductivity to 9.09 W/m-K. Thermal conductivity of the
material kept increasing with pellet die pressure while porosity
declined, of which no major detrimental effects are reported
[74,75]. At lower pressures, graphite added alanate pellets have
higher conductivity than Ti doped ones, while the trend reverses at
high pressures. Decomposition of the material may occur during
pelletization decreasing the effective thermal conductivity. This
could probably be the reason for lower conductivity value of Ti
doped alanate pellets compared with neat alanate pellets. Cycling
leads to expansion of pellets back into powder form resulting in
degradation of conductivity, though no negative impact on kinetics
and storage capacity were observed over 50 cycles [74]. Mechanical
connement of pellets can solve this problem. The graphite addi-
tives also slowed down the degradation of thermal conductivity of
mechanically conned pellets. Enhanced thermal conductivity of
bed is found to decrease the volume expansion [105]. Pelletized
hydride powder composites encapsulated with copper reported a
thermal conductivity of 5 W/m-K and porosity of 0.35 [106].
However, longer activation times are reported for pelletized bed
[74].
Ball milling of the catalyzed sample was also found to improve
the kinetics considerably [37]in addition to increase in density
[107]. Anton [37] studied the effect of milling time on reactor
performance. To achieve maximum catalytic activity and homog-
enization longer milling time is necessary. However, it leads to
dehydrogenation during the milling process and tend to decrease
the reaction rate [37]. This can be prevented by proper cooling of
the vial during ball milling [45]. Ball milling alone was found to be
good enough to improve the sorption kinetics and lowtemperature
operation [5]. The renement of microstructure during ball milling
does not change the thermodynamic properties of complex hy-
drides while it results in the better dispersion of additives in the
specimen [108].
5.2. Improved heat transfer mechanisms
The heat transfer in the hydride bed needs to be augmented to
achieve effective thermal management in hydride reactors. Even
though external cooling of reactors is preferable from heat transfer
and sorption kinetics points of view [109], the importance of heat
removal through internal heat transfer enhancement methods
cannot be ignored [73]. Various such methods have been proposed
to enhance hydride bed heat transfer. High heat removal rates can
be achieved by introducing annular metal inserts [110], copper wire
matrix [90] and metallic foam [8,111,112]. The presence of
aluminum foam enhances the effective thermal conductivity of
hydride beds [8]. LaNi
5
based storage device inserted with
aluminum foam [111] increased the effective thermal conductivity
of hydride bed to 10 W/m-K. The shape, size and porosity of the
hydride bed are signicant in dening its effective conductance.
Larger fraction of aluminum in the reactor improves sorption while
decreases the storage capacity [113]. Using numerical techniques,
Wang et al. [99] evaluated the effective thermal conductivity of the
bed against fraction of aluminum presence in the bed. Improved
surface area for heat transfer was obtained using multiple heat
exchangers and hydrogen lters embedded in the reactor. Various
congurations with different numbers of such tubes were studied
by the author [11]. A multiple tubular reactor with annular jacketed
external cooling improved heat transfer over the one without such
arrangement [104]. It must be noted that the rate of reaction is
higher near the heat exchanger surface and attains saturation faster
[114] while the reaction front propagates from heat exchanger
surface [11]. Effect of thermal mass of heat exchanger tubes affects
sorption characteristics to a lesser extent [115] and the inuence of
the coolant side heat transfer coefcient increases initially and
saturates at larger values [114].
For larger bed sizes with higher heat transfer requirement, greater
fraction of aluminum presence is required [113]. The best way to
enhance heat transfer towards outside is to choose a more favorable
geometry to increase the thermal ow in the direction of largest ex-
changesurface[116] or useradial ns originatingfromheat exchanger
surface [117]. Variation with charging time and effect of operational
parameters in a spiral coil heat exchanger with and without ns was
studied by Dhaou et al. [118].Souahlia et al. [119,120] conducted
parametric studies on a metal hydride based hydrogenstorage device
with a nned heat exchanger tube. Effect of longitudinal ns on
improvement inkinetics is more thanthe transverse ns, though by a
very narrow margin [121]. Improved thermal conductivity using
graphite additions enabled to increase the n pitch distance by three
folds, well above the DOE prescribed minimum [100]. Bhouri et al.
[122] proposed a metal hydride reactor inserted with aluminum
honeycomb structure, with and without external cooling to provide
effective conduction path. In a similar device, introducing heat
exchanger tubes between metallic inserts or using a number of hon-
eycomb unit cells for internal cooling further enhanced sorption
performance [94]. Further, the same authors proposed shell and tube
type bedinwhichsodiumalanatewas lledintubes withinternal ns
[123] and studied effect of nned reactors in absorption and desorp-
tion. Raju and Kumar [105] proposed a multi-tubular reactor with
aluminumns. Hardyand Anton [64,67] evaluatedthe heat andmass
transfer performance of sodium alanate based two dimensional
(without ns) andthreedimensional (withns) models withmultiple
heat exchanger tubes and hydrogen lters. The presence of ns
improved sorption kinetics implying the importance of heat transfer
as the rate controlling parameter [64,67,118e120,123,124]. Fins with
perfect contact between solidesolid interfaces are desirable, other-
wise leading to performance degradation [123]. The thickness of n
need not be considered as an important parameter while absorption
as even small thickness can signicantly improve sorption. Perfor-
mances of such systems are limited only by intrinsic kinetics. But,
during desorptionthe kinetics is signicantlyenhancedby increase in
n thickness. However, larger n thickness lowers gravimetric and
volumetric capacities. Number of cooling tubes improve performance
in both sorptionprocesses while desorptionprocess is more sensitive
to cooling tube requirement. During desorption, the presence of more
ns and cooling tubes is important to impart heat into the hydride
bed. Too small a value (less than 0.025 cm) of honeycomb cell wall
thickness decreases sorption performance while increases slightly in
the range of 1 mm. The region near ns and heat exchanger surfaces
desorb at much faster rate. The effect of heat transfer surface area is
more signicant in this case than effective thermal conductivity
[97,123,124]. Gambini et al. [125] determined the effect of operational
parameters using lumped parameter numerical model. The temper-
ature and pressure of hydride system decreases with increase in po-
wer output while heat ux follows the reverse trend. The aspect ratio
of the reactor is an important parameter whenthe conductivity of the
bed is low [99]. Low value of radius to height ratio is preferred for
maximum sorption performance [114]. Not the least, it was also re-
ported that geometric conguration of the reactor does not affect the
mechanism of hydriding [11].
The temperature prole of the reactor bed is signicantly
inuenced by the coolant ow rate. While improving kinetics,
increased ow rate has no effect on the amount of hydrogen
absorbed was observed [94,126]. Under active cooling, inuence of
aluminum foam inserts were more pronounced [99]. The sorption
performance is also signicantly affected by hydrogen inlet design.
Sintered steel lter on a cylindrical orice supported by a cap with 4
holes reported remarkable improvement in sorption. This resulted
in higher temperature peak indicating more formation of hydride
[120]. The sorption parameters are strongly inuenced by bed
pressure and coolant temperature. Higher temperatures favored
desorption while lower coolant temperatures were preferred for
absorption [76].
Giving an another outlook, Chung et al. [127] developed a
heat pipe based metal hydride model for thermal management
which had obvious advantages over conventional cooling sys-
tems. Though the reactor performance improved over the one
without heat pipe, its applicability on practical systems can be
ascertained in comparison with nned models with heat
exchangers.
6. Numerical studies on sorption performance in storage
devices
Numerical simulation of sorption performance of hydrogen
storage devices can be achieved by solving a set of coupled equa-
tions governing heat and mass transfer. Mayer et al. [128] obtained
solutions by simultaneously solved for heat transfer by conduction
and mass transport at constant pressure while the effects of
convective and radiation heat transfer were neglected. Convective
heat transfer favors the reaction kinetics initially, while it inhibits in
the latter part of reaction due to transport of heated hydrogen into
the bulk [129]. The effect of exchange of heat with hydrogen gas
may not be signicant but the pressure drop for hydrogen ow will
be signicant in larger beds. This effect can be modeled using
Darcys law considering the storage bed as homogenous [9]. The
equilibrium pressure at which the reaction takes place can be
determined using the equation given by Nishizaki et al. [130],
considering the effect of plateau slopes and hysteresis. The effect of
plateau slope and hysteresis were neglected in many studies
[11,64,67,126,127]. Jemni and Nasrallah [131] expressed equilibrium
pressure as a function of hydrogen to metal atomic ratio (H/M).
Same authors [132] also proposed that the effect of hydrogen
concentration can be neglected for absorption while it is critical for
desorption. The effect of driving forces can be modeled by using
logarithmic functions [61]. Though the effect was demonstrated by
Miyamoto et al. [133], linearly dependent functions [134] similar to
shrinking core models prevail [135]. A normalized pressure
dependent function as suggested by Ron [136] can be used for
studying overall reaction rates. In a three dimensional model, en-
ergy interactions and ow of the coolant uid may also be
considered [64,66]. Several of the numerical studies conducted in
the early days used nite difference method [9,116,128,137,138] to
arrive at the solution. Commercial packages such as FEM based
COMSOL Multiphysics
[11,64,67,94,121e124,139,140], CFD based

ANSYS FLUENT
[92,117], PHEONICS
[126] and gPROMS
[110,141,142] were used to simulate the sorption performance of

storage bed and plot results effectively. Recent developments such
as Lattice Boltzmann and molecular modeling for simulating
hydrogen sorption are not yet reported in literature, but may give
better insight to the thermal design of the storage device.
6.1. Numerical studies on sorption performance in storage devices
with heat transfer augmentation structures
Mohan et al. [143]have studied heat and mass transfer simula-
tion of cylindrical, liquid cooled, hydrogen storage device with and
without aluminum honeycomb structure. This aluminum structure
with multiple cells imparts good heat transfer properties, light
weight and structural stability. In this study, TiCl
3
catalyzed NaAlH
4
is used as the storage material. As hydrogen is inducted to the bed,
reaction commences. The hydrogen absorption in sodium alanate
consists of two consecutive reactions:
NaH Al 1:5H
2
41=3Na
3
AlH
6
2=3Na
3
AlH
6
H
2
(Reaction 6)
1=3Na
3
AlH
6
2=3Na
3
AlH
6
H
2
4NaAlH
4
(Reaction 7)
These reactions can proceed one after the other under suitable
thermodynamic conditions. As soon as NaHand Al hydrogenated to
Na
3
AlH
6
by Reaction (6), Na
3
AlH
6
and Al can react further with H
2
to form NaAlH
4
by Reaction (7). These two reactions are associated
with corresponding heat release upon absorption of H
2
.
This heat can be transported to the coolant by means of hon-
eycomb structure. The numerical simulations of the above
computational model are carried out in COMSOL Multiphysics
[144] commercial software. The 2D geometrical model in suitable

le format is generated in AutoCAD
drawing package. It is sub-

sequently exported to COMSOL Multiphysics
for further pre and

post processing.
Fig. 7 shows the effect of aluminum honeycomb with ns on
average bed temperature of the bed. The presence of aluminum
structure enhances the heat transfer rate and thereby bed tem-
perature and its respective peak decreases. This causes corre-
sponding rise in hydrogen sorption rate, as shown in Fig. 8.
7. Design and optimization of storage devices
The reactor performance has been reported to be sensitive to
activation energy of the material, effective thermal conductivity,
heat of formation and equilibriumpressure [74,145]. The design of a
reactor must consider the above factors. Multiple heat exchanger
type and metal insert type reactors, though improve performance,
result in the increase of system weight thereby reducing the
gravimetric capacity of the system. Portable systems demand low
system weight and high gravimetric and volumetric hydrogen
storage capacity. The design procedure for any reactor must take
into consideration the inuence of heat and mass transfer and the
mechanical design elements [146]. The author identied bed size of
the reactor as a signicant parameter in the design [11] and pro-
posed a methodology to obtain the minimum system weight at
specic charging levels [139]. The selection of bed material and bed
size was the critical parameters as reported by Castrillo et al. [78]
for reactor optimization.
Optimization of hydride reactor, by identifying critical param-
eters improves cycle time. Proper positioning of annular metal in-
serts and suitable coolant ow rate improved absorption time by
60% [110]. The sorption performance increases with increase in
surface to volume ratio of hydride tube. Optimum coolant velocity
along with number and position of heat exchangers are critical for
better performance [141]. Optimization of nned tubes can be done
by increasing n radius and decreasing n thickness keeping the n
volume constant. Longer ns at smaller n spacing provide better
sorption [147,148]. Garrison et al. [121] reported that small coolant
size tube and closer ns are necessary for high gravimetric
hydrogen storage. Lozano et al. [140] optimized a model equipped
with an internal heat exchanger tube. Owing to larger bulk density
of powder compacts, more amounts of material than neat alanate
powder can be stored in similar systems. Hence compacts can be
easily optimized for weight considerations. Also, it encourages to
dene the mass of hydrogen absorbed rather than using weight
percentage. Hence addition of compacts decreases the parasitic
weight of the system. The storage device is optimized for maximum
hydrogen absorption at minimumtime with respect to coolant ow
rate by an online controlled optimization strategy using an explicit
parametric controller [142] and open-loop optimal controller [149].
The coolant ow rate and temperature at the exit of annular heat
exchanger were identied as the major parameters [142].
8. Important aspects of the operation of practical systems
At high packing fraction and long cycle life, the stress on the
reactor walls due to volume expansion of hydrides might be sig-
nicant. Pulverization of hydride powder results in the shifting of
material towards the lower end of the reactor. This may lead to
considerable engineering problems [93,146]. Okumura et al. [93]
have reported the dominance of tangential stress developed in
the system due to non-uniform expansion in the system diameter.
Impurities present in the hydrogen gas lead to accumulation of
foreign materials into the metal hydride voids, resulting in the
decrease of hydrogen partial pressure and an early temperature
peak. This leads to decrease in sorption performance. The blowing
off the impurities repeatedly results in higher loss of hydrogen
[150].
Hydrogen has a specic energy of 142 MJ/kg [2] and normal fuel
cell demand is 1.2 MJ/km i.e., a distance of 100 km can be traveled Fig. 7. Effect of Al-honeycomb and ns on average temperature of bed.
Fig. 8. Effect of Al-honeycomb and ns on hydriding.
using 1 kg of hydrogen in automobiles. Wenger et al. [151] reported
the major constraints of a fuel cell as high volumetric storage,
efcient heat transfer, low temperature operation and cold start.
Raju and Kumar [105] developed a sodium alanate based model to
numerically evaluate the performance of the system during driving
conditions making a way forward in the realization of hydrogen
energy for mobile application. Though characteristics of sodium
alanate are well suited for fuel cell operation, poor gravimetric
storage limits its applicability in portable systems for trans-
portation [152] unless a highly efcient design in developed. Maeda
et al. [153] have discussed the applicability of hydrogen storage cell
in a cogeneration system. The system also focuses on utilizing the
heat of reaction for other applications such as air-conditioning to
improve overall system efciency.
9. Concluding remarks
Simple intermetallic hydrides, which have been widely inves-
tigated, are in advanced stages of practical applications. However,
for mobile applications, efforts to improve their gravimetric storage
densities have not been very successful. Due to this, attention is
being given to complex metal hydrides which show signicant
promise. There are severe challenges to employ these materials in
practice, the major ones being, lack of thermophysical and revers-
ibility data. Optimal thermal design of such devices is one of the
keys to the success of hydrogen as the fuel of the future.
Acknowledgements
Thanks are due to the Department of Science and Technology,
Ministry of New and Renewable Energy, Government of India, for
their funding support towards hydrogen storage research.
Prof. S. Srinivasa Murthy is grateful to his colleagues Prof. B.
Viswanathan and Prof. M. P. Maiya and to his former doctoral stu-
dents Dr. L. Hima Kumar and Dr. G. Mohan for their contributions to
the research results presented here.
Nomenclature
A pre-exponential factor of Arrhenius formula [s
1
]
A
1B
pre-exponential factor of Arrhenius formula of Na
3
AlH
6
decomposition [s
1
]
A
1F
pre-exponential factor of Arrhenius formula of Na
3
AlH
6
formation [s
1
]
A
2B
pre-exponential factor of Arrhenius formula of NaAlH
4
decomposition [s
1
]
A
2F
pre-exponential factor of Arrhenius formula of NaAlH
4
formation [s
1
]
C concentration of H
2
[mole H
2
/m
3
of interparticle void]
C
1
concentration of NaAlH
4
[mole/m
3
]
C
2
concentration of Na
3
AlH
6
[mole/m
3
]
C
3
concentration of NaH [mole/m
3
]
C
10
initial concentration of NaAlH
4
[mole/m
3
]
C
20
initial concentration of Na
3
AlH
6
[mole/m
3
]
C
30
initial concentration of NaH [mole/m
3
]
E
a
energy of activation of Arrhenius formula [J/mol]
E
aa1
activation energy of NaAlH
4
formation [J/mol]
E
ad1
activation energy of NaAlH
4
decomposition [J/mol]
E
aa2
activation energy of Na
3
AlH
6
formation [J/mol]
E
ad2
activation energy of Na
3
AlH
6
E
1B
energy of activation of Arrhenius formula of Na
3
AlH
6
E
1F
energy of activation of Arrhenius formula of Na
3
AlH
6
formation [J/mol]
E
2B
energy of activation of Arrhenius formula of NaAlH
4
E
2F
energy of activation of Arrhenius formula of NaAlH
4
formation [J/mol]
function of p and p
eq
that acts as diving force for the
absorption reaction, -
H wt. % weight percent of H in sample
d(H wt.%)/dt rate of change of H in alanates formed () or
decomposed (), as H wt. %
k bed thermal conductivity [W/m
C]
k
^
rate constant [s
1
]
k
e
effective thermal conductivity of the bed [W/m
C]
K
0al
pre-exponential factor of rate constant of NaAlH
4
formation[s
1
]
K
0a2
pre-exponential factor of rate constant of Na
3
AlH
6
formation [s
1
]
K
0dl
pre-exponential factor of rate constant of NaAlH
4
decomposition [s
1
]
K
0d2
pre-exponential factor of rate constant of Na
3
AlH
6
decomposition [s
1
]
m
H2
mass of hydrogen that could be desorbed [kg]
m
H2max
maximum mass of hydrogen that could be desorbed [kg]
m
1
rate of concentration of NaAlH
4
m
2
average rate of concentration of NaAlH
4
and NaH
m
3
rate of concentration of NaH
p hydrogen back pressure [bar]
P
appl
applied pressure [bar]
P
e,i
plateau pressure at temperature T [bar]
p
eq
equilibrium pressure [bar]
P
eq1
plateau pressure of NaAlH
4
at a given temperature [bar]
P
eq2
plateau pressure of Na
3
AlH
6
at a given temperature [bar]
R gas constant [J/molK]
r
1B
rate of dissociation of NaAlH
4
from Na
3
AlH
6
[mol/m
3
-s]
r
1F
rate of formation of NaAlH
4
from Na
3
AlH
6
[mol/m
3
-s]
r
2B
rate of dissociation of Na
3
AlH
6
from NaH [mol/m
3
-s]
r
2F
rate of formation of Na
3
AlH
6
from NaH [mol/m
3
-s]
S
I
mixture of 3 mol NaH, 3 mol Al and 9/2 mol H
2
S
II
mixture of 1 mol Na
3
AlH
6
, 3 mol Al and 3 mol H
2
S
III
3 mol NaAlH
4
T temperature [K]
Greek symbols
DH
R
enthalpy of reaction on a molar basis of species [J/(mol)]
DS
R
entropy of reaction on a molar basis of species [J/(mol K)]
a transformed fraction
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Advanced materials for solid state hydrogen storage: Thermal

C [5] i.e., beyond the optimumtemperature range of operation

[11,64,67,94,121e124,139,140], CFD based

[126] and gPROMS

[110,141,142] were used to simulate the sorption performance of

[144] commercial software. The 2D geometrical model in suitable

drawing package. It is sub-

for further pre and

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