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First-principles study of the paths of the

decomposition reaction of LiBH4
a a
Riccarda Caputo & Andreas Züttel
a
EMPA, Swiss Federal Laboratories for Materials Testing and Research, Department of
Mobility, Energy and Environment, Division Hydrogen & Energy Abt138, Überlandstrasse 129,
CH-8600 Dübendorf, Switzerland
Available online: 20 Apr 2010

To cite this article: Riccarda Caputo & Andreas Züttel (2010): First-principles study of the paths of the decomposition
reaction of LiBH4 , Molecular Physics, 108:10, 1263-1276

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 Molecular Physics
Vol. 108, No. 10, 20 May 2010, 1263–1276

RESEARCH ARTICLE
First-principles study of the paths of the decomposition reaction of LiBH4
Riccarda Caputo* and Andreas Züttel
EMPA, Swiss Federal Laboratories for Materials Testing and Research, Department
of Mobility, Energy and Environment, Division Hydrogen & Energy Abt138,
Überlandstrasse 129, CH-8600 Dübendorf, Switzerland
(Received 29 October 2009; final version received 21 December 2009)

A clear description of the paths of thermal decomposition of complex borohydrides represents a crucial
step forward to their utilisation as a reservoir of hydrogen and hence as materials for solid state hydrogen
storage. We present in this work a theoretical study of the possible paths of decomposition of LiBH4 by means
of density functional theory approach. Our first-principles calculations showed the possibility to form linear
chains of tetraborate of lithium in the residue of decomposition, among other thermodynamically competitive
reactions. Their analytical formula LiBHx agreed with the quantitative analysis already reported by Schlesinger
Downloaded by [ETH Zurich] at 07:18 17 November 2011

and co-workers in the 1940s. The structure showed the formula unit Li4B4H10, and the analytical formula
LiBH2.5, of which the Gibbs free energy of formation was 111.76 kJ mol1. The lattice stability was confirmed
by the phonon calculations, which revealed all positive normal modes. Comparatively, the formation of lithium
dodecaborate(12) is presented and discussed. The calculated standard Gibbs free energy of the decomposition
reactions considered in the present work were in the range (158,286) kJ mol1 of LiBH4 decomposed.
Keywords: hydrogen storage; DFT calculations; lithium borohydride; lithium borides; lithium tetraborate

1. Introduction process pyrolysis, because it requires high tempera-

The use of hydrogen as a possible energy carrier has to
overcome one major problem: the optimisation of the
materials for its storage. Among all the materials
studied up to date, none fully meets all the require-
ments for a practical lightweight, large capacity, fast
sorption kinetics of a hydrogen storage system.
In addition, the ideal material should be durable,
inexpensive and safe. Clearly, nowadays the definitive
answer has not yet been addressed: a compromise
between all the requirements has to be found in order
to search for a solution for technological applications.
Complex borohydrides have been extensively studied
for having large gravimetric and volumetric hydrogen
densities.1 Among them, lithium borohydride has
caught enormous attention because of its light weight
and therefore high gravimetric hydrogen content
(18.51% wt. H2). The big limiting step to using
LiBH4, as a hydrogen storage material, strictly depends
on the poor reversibility of cycling the desorption–
absorption processes [1]. Experimentally, the process
of the hydrogen release proceeds via thermal decom-
position. The thermolysis in that case is an endother-
mic process which requires heat to break the boron–
hydrogen bonds and hence release hydrogen. Generally
speaking, we should more appropriately call the
tures, and of course it produces evaporation of smaller
molecules during the process and can induce polymer-
isation of the residual solid phase of decomposition.
The metallo borohydrides, and in particular lithium
borohydride, are generally stable in dry air and melt at
a relatively high temperature with decomposition and
gas release, as has been reported since the first study by
Schlesinger and co-worker [2] and then revised
by other authors [1,3–9]. The pyrolysis reported by
Schlesinger represents, to our knowledge, one of the
first quantitative chemical analyses of the decomposi-
tion reaction the compound can undergo by heating.
A careful revision of the chemical analysis reported by
Schlesinger somehow supports and confirms our
first-principles calculations and helped to reveal the
origin of the irreversibility, still nowadays discussed
and not yet clearly described for LiBH4. Based on our
calculations, we suggested that the poor reversible
hydrogen storage capacity of LiBH4 has to be searched
for in the ternary phase formation between lithium,
boron and hydrogen, Li–B–H, which can be formed
under specific experimental ( p, T ) conditions. Our
results, which we discuss in the present work, strongly
suggested and indicated that the metal boride forma-
tion is an important step in the whole process of

*Corresponding author. Email: riccarda.caputo@empa.ch

ISSN 0026–8976 print/ISSN 1362–3028 online

ß 2010 Taylor & Francis
DOI: 10.1080/00268970903580141
http://www.informaworld.com
 1264 R. Caputo and A. Züttel
hydrogen release from LiBH4. On the other hand, the
lack of very accurate quantitative and qualitative
chemical analysis of the possible products of decom-
position, both in the solid phase (residue of decompo-
sition) and in the gas phase, makes the theoretical
approach even more important in order to shed light
on which species could be energetically favoured
and formed in the products. In the present work,
we present a first-principles study of some of the
possible decomposition paths of reaction of LiBH4
with particular regards to the residue mentioned
already in Schlesinger’s work and the binary (Li–B)
and ternary (Li–B–H) phases. We considered some of
the stoichiometrically allowed reactions of decomposi-
tion, based on the mass conservation law, and we
calculated the corresponding enthalpies and Gibbs
free energies of reaction. All the compounds were
fully optimised in order to properly get the corre-
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sponding ground-state structures. The temperature
dependence of the enthalpy of formation, DrH(T )
was accounted for by performing phonon calculations
of all the species involved in the reactions reported in
the present work.
2. Computational methods
We used plane-wave and pseudo-potential based
methods in the framework of Density Functional
Theory (DFT). We used CASTEP [10], as implemented
in Materials Studio 4.4 to optimise ionic positions and
lattice parameters of all the structures of the com-
pounds reported in the present work: LiBH4(s), LiB(s),
Li2B6(s), B2H6(g), Li(s), LiH(s), H2(g), LiBHx(s), -B
[11]. Norm-conserving pseudo potentials, represented
in the reciprocal space, were used for all the atoms
together with a fine mesh of k-points, with an energy
conversion threshold of 0.01 meV atom1, a maximum
displacement of 0.001 Å and a maximum force of
0.001 eV Å1, yielding high accuracy for the energy and
atomic displacements. For lithium the standard
Troullier–Martins type pseudopotential with 1s orbital
in the core region with two electrons and one electron
in the valence shell was used. Similarly, the pseudo-
potential used for boron was a norm-conserving type
with two electrons (1s orbital) in the core region and
the three electrons in the valence shell, with the local
potential of p-type. The potential used for hydrogen
was a soft pseudo Coulomb potential, as it is the
default potential in the Materials Studio 4.4.
The k-point mesh (quality fine in the CASTEP
settings) was used to generate the k-point separation
of 0.04 Å1. The Perdew–Burke–Ernzerhof 96 and the
Generalised Gradient form (GGA-PBE) of the
exchange-correlation functional were used.
Full geometry optimisation was run for all the
structures investigated and both internal atomic
coordinates and lattice parameters were relaxed. The
thermodynamic properties, in particular the specific
heat was derived via phonon calculations using
CASTEP Linear Response (DFPT), as implemented
in the CASTEP code [12]. In particular, the temper-
ature dependence of the enthalpy, entropy, free energy
and lattice heat capacity of all the species were
evaluated in the quasi-harmonic approximation, as
implemented in CASTEP, using Density Functional
Perturbation Theory [13]. A double check of the lattice
stability was performed using Quantum-Espresso code
[14] (PWSCF), which is a computer code for
electronic-structure calculations within Density
Functional Theory and Density Functional
Perturbation Theory, using pseudo-potentials and a
plane-wave basis set. The Car–Parrinello molecular
dynamics code (CPMD) [15] was used for our prelim-
inary investigation of the molecular dynamics
as reported in Section 3. Nevertheless, all the energies
reported in Tables 1 and 2 together with the corre-
sponding optimised structures were calculated consis-
tently using CASTEP calculations by means of the
same convergence criteria as regards the cutoff energy,
the k-point sampling mesh and the functionals.
3. Results and discussion
Generally, the thermal decomposition of gas-phase
releasing compounds can be considered as follows:
X X
ð p, T Þ
LiBH4 ! solidi þ gasj : ð1Þ
i j
In principle, without putting forward any hypothesis
on the chemical composition of the solid and
gas phases, the former can be composed by any
possible binary and ternary phase, namely Li–H, B–H,
Li–B, Li–B–H, whilst the gas phase can be formed
by H2,B2H6 and any other thermodynamically allowed
volatile compounds that can be formed under the
specific ( p, T ) conditions at which the decomposition
is carried out. In terms of first-principles calculations,
we postulated different reaction paths and for
each of them calculated the enthalpy of reaction.
Of course, for each species on both sides of reactant
and products, the ground-state structure was deter-
mined and the relative thermodynamic stability
at the finite temperature via phonon analysis was
ascertained.
 Molecular Physics 1265

Table 1. Calculated thermodynamic data and lattice parameters of the species reported in the present work. The energies
were expressed in kJ mol1 and the lattice parameters a, b, c in Å. For B2H6, the parameters reported in the table were the
boron–boron and boron–hydrogen bond lengths. The values reported were the enthalpy of formation of the corresponding
ground-state structure at T ¼ 0 K, (Df H(0)), including the zero point energy, calculated as a sum over the harmonic frequencies,
(Df HZPE), the Gibbs free energy of formation at T ¼ 298.15 K, Df G298, the lattice parameters and the symmetry group. The Gibbs
free energy, Df G298 ¼ Df H298  T Df S298, was computed via linear response calculations of the phonon spectra per
each compound, from R which the specific heat cp was calculated. The Gibbs free energy was calculated as harmonic free
energy: F ¼ E þ 1 g(!) log(2sinh(h !/2)), d!. Accordingly, the enthalpy and the entropy at any T for each species were
RT RT
obtained via numerical integration: HðT Þ ¼ 0 cp dT, and SðTÞ ¼ 0 ðcp =TÞ dT.

Species Df H(0) Df H(0)ZPE Df G298 a, b, c, , ,  Symmetry group

a
LiBH4(orth) 239.988 290.470 269.306 8.484, 4.348, 5.750 Pnma (IT 62) [24]
LiBH4(hexag) 211.373 177.344 152.475 4.276, 4.276, 6.948 P63mc (IT 186)
LiH 91.686 84.989 73.759 3.912  (IT 225)
Fm3m
LiB 23.951 21.371 22.228 3.974, 3.974, 3.083 P63/mmc (IT 194)
Li2B6 42.760 8.298b 4.727 4.163, 4.163, 4.472 P4/mmm (IT 123)
LiBH2.5 153.792 127.312 111.176 6.924, 4.839, 4.229 Triclinicc
90.22, 106.69, 83.89
LiBH2 72.612 – – 6.906, 4.904, 3.966 Triclinic
83.79, 101.85, 83.83 No symmetry group
Li2B12H12d 945.95 – – 9.579 Pa3 (IT 205)
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B2H6 66.876 8.229 þ33.247 1.735 (B–B), 1.312 1.191 (H–B) bond
(B–H) bridge

Notes: aFor comparison see [1,8,28,38] and note 3.

b
That optimised structure, comparable to the experimental structure [20], showed lattice instabilities.
c
We searched for the symmetry group and the best fit of the optimised structure resulted with a symmetry group CM, IT
number ¼ 8. Accordingly, the lattice parameters were 13.27 Å, 4.23 Å, 4.84 Å,  ¼ 90, 83.69, 90. The maximum component
of the stress tensor was 0.005 GPa, and the maximum component of the forces (Cartesian component) was 0.007 eV Å1.
Nevertheless, by the phonon calculations, no lattice instability was found. In fact, all the normal modes of vibration had positive
frequencies.
d
The structure was optimised starting from [34], but showed imaginary modes, therefore we could not calculate the temperature
dependence of the enthalpy of formation.

Table 2. Enthalpy of P
reactions of some of P the possible decomposition paths of LiBH4, according to the following general
1
reaction: LiBH4(s) ! i Solidi (Li, B, H) þ j Gasj (B, H) þ H2. The enthalpy of reaction is expressed in kJ mol of LiBH4
decomposed. The hydrogen yield () was the molar ratio between the mole of hydrogen released per mole of LiBH4 decomposed.
The phases considered for each species were: orthorhombic-LiBH4, bcc-Li, -rhombohedral boron [11], LiH, LiB, Li2B6 [42].
With regards to B2H6 and H2, the structures were respectively optimised as an isolated molecule in a large cubic lattice.

Reactant Solid phase products Gas phase products

LiBH4 Li B LiH LiB Li2B6 B2H6 H2  Dr H(0) DrG(298 K)

1 1 1 – – – – 2 2.00 239.988 269.306

2 – 2 2 – – – 3 1.50 148.302 195.551
1 – – – 1 – – 2 2.00 216.037 247.082
3 2 – – 1 – 1 3 1.00 209.712 272.983
2 2 – – – – 1 1 0.50 206.550 285.934
2 – – 2 – – 1 – 0.00 114.865 212.175
4 – 2 2 2 – – 7 1.75 182.170 221.317
8 – – 4 2 1 – 14 1.75 182.812 226.279
6 4 – – – 1 – 12 2.00 232.861 268.518

4LiBH4 ! LiBH2.5 þ 3H2 0.75 86.196 158.130

a
4LiBH4 ! 4LiBH2 þ 4H2 1.00 167.376
a
14LiBH4 ! Li2B12H12 þ 12Li þ B2H6 þ 19H2 1.36 167.643
a
15LiBH4 ! Li2B12H12 þ 12Li þ LiB þ B2H6 þ 21H2 1.40 170.869

Note: aDue to lattice instabilities of LiBH2 and Li2B12H12, it was not possible to calculate the specific heat and hence derive
the thermodynamic values at finite temperature.
 1266 R. Caputo and A. Züttel

3.1. Decomposition into binary products
The general observation, reported in the literature [1]
(and references therein), is that LiBH4 decomposes at
T ¼ 553.15 K according to the reaction:
LiBH4 ! LiH þ B þ 32H2 : ð2Þ
The reported path of decomposition, very often
proposed as the most likely mechanism for thermal
decomposition, showed the intrinsic difficulty in
making reversible the reaction of re-hydrogenation
of the bi-phasic solid products, LiH and B: they hardly
combine to form back exactly to the orthorhombic
structure of LiBH4. Therefore, a loss of hydrogen
capacity should be expected on cycling the desorption–
absorption processes. This implied that somehow
hydrogen had to be retained in the solid phase.
Furthermore, the hydrogenation of the amorphous
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via first-principles modelling [24], a method already
successfully applied for the ground-state structure
determination of Mg(BH4)2 [25]. If we consider only
the enthalpy of reaction at T ¼ 0 K, all of the reaction
paths reported in Table 2 fall in the interval 114.87 kJ
mol1 of LiBH4, for reaction No. 6, which did not
involve any release of hydrogen in the gas phase, up to
the complete decomposition back into the elements,
which required 239.98 kJ mol1 of LiBH4. Accounting
for the zero-point energies and the thermal contribu-
tions, for the reversed thermodynamics of the reactions
No. 2 and No. 6, the latter possessed a higher free
energy than the former, due to an entropic contribu-
tion that accompanied the formation of diborane.
Nevertheless, the reaction path involving the formation
of a ternary phase Li–B–H, with the analytical
formula LiBH2.5 and H2, showed the lowest enthalpy
of reaction at T ¼ 0 K and the lowest free energy of

(or polycrystalline) boron can form under high hydro-

reaction per mole of LiBH4. The reaction paths,
gen pressure and high temperature (which are the
which involved a phase separation between a metallic
experimental ( p, T ) conditions) different boranes,
phase, formed by elemental lithium and any
and some of these can be retained in the solid state.
binary phases, formed by lithium borides, LimBn
It is clear that in order to make the entire process of
(where the ratio m : n depends on the particular
absorption and desorption univocally, or at least in a
( p, T ) conditions), did involve the possibility to form
manageable way, reversible, it should be possible to
boranes either in the gas phase or in the solid phase.
hydrogenate the residue and to form a suitable
Actually, the possibility to form a metallic phase was
hydrogenated phase, in which the hydrogen atoms
very similar to one of the theoretically found paths of
will be loosely bound to either lithium or boron atoms.
thermal decomposition for NaBH4, in which the
On the basis of our calculations, we inferred that the
formation of a metallic phase (sodium) and a
hydrogenation of boron was energetically unfavour-
non-metallic metal boride phase were found [26,27].
able, at least for -boron [11], but also that it can form
Nevertheless, because the thermal decomposition tem-
so many different binary phases (B, H) and ternary
perature is higher than the melting point of lithium
phase (Li, B, H), for which the reversed reaction back
(Tm ¼ 453.69 K, whereas the thermal decomposition of
to LiBH4 is hardly fully achieved. In fact, we should
LiBH4 is experimentally carried out at 548 K), it was
expect either the formation of a ternary phase Li, B, H
energetically possible that the lithium melt reacted with
or a phase separation between LiH and any possible
boron to form any possible borides. Reaction No. 2 in
boranes, formed after hydrogenation of the residue of
Table 2 showed a favoured free energy of reaction, and
the thermal decomposition of LiBH4 [16,17].
clearly the residue was formed by two distinct phases:
Restricting, our analysis to only binary phase forma-
boron, and lithium hydride, which could not further
tion in the residue, we considered the possibility to
react with boron, because of its high melting
form, upon decomposition, two of the possible lithium
point (Tm ¼ 965.15 K), unless H2O is present in the
boride phases, namely LiB and Li2B6, together with
reaction chamber and the reaction could continue with
LiH and the pure separated phases of Li and B. In the
the formation of lithium borates. Generally, in the
gas phase we considered the possibility to form B2H6
literature the enthalpies of decomposition reactions
and H2. The binary phase diagram Li–B [18] shows the
refer to the mole of hydrogen released [28] and
possibility of a compound formation at x ¼ 0.5 (molar
reference therein. We preferred in the present work
fraction), which corresponds to LiB [19–23].2 Some of
to refer to the mole of LiBH4 reacted for the sake
the thermodynamic data of the compounds considered
of generality.
as possible products of the thermal decomposition of
LiBH4 are reported in Table 1. Among the known
phases of LiBH4, we considered the orthorhombic
phase of which the thermodynamic properties are 3.2. Decomposition in ternary products
calculated and reported in Table 1. The orthorhombic Besides the possible reaction paths reported in Table 2,
structure reported here was obtained completely we also considered the formation of intermediates with
 Molecular Physics 1267

an analytical formula LiBH2.5 and LiBH2, as we

deduced from Schlesinger’s experiment [2]. We mod-
elled the corresponding structures according to the
piece of information our preliminary molecular
dynamics calculations pointed out: hydrogen atoms,
each on a different (BH4) group, followed a two-fold
and a three-fold dynamics hopping from one group to
the other, and then bonding together to form H2 and
hence leaving a (BH3) unit in the residue. The
continuation of that hypothetical mechanism model,
led to the structural formula, Li4B4H10 and Li4B4H8,
equivalent to the analytical formula we deduced from
the quantitative analysis reported by Schlesinger [2],
namely, LiBH2.5 and LiBH2. Accordingly, we calcu-
lated the enthalpy of reaction of the corresponding Figure 1. A view of the unit cell of Li4B4H10 with the atomic
decomposition reactions: charges (in red) obtained from the Mulliken population
analysis. Colours represent: Li, violet; B, pink; H, white.
4LiBH4 ðsÞ ! Li4 B4 H10 ðsÞ þ 3H2 ðgÞ
Downloaded by [ETH Zurich] at 07:18 17 November 2011

Dr Hð0Þ ¼ þ86:20 kJ mol1 , ð3Þ

4LiBH4 ðsÞ ! Li4 B4 H8 ðsÞ þ 4H2 ðgÞ

Dr Hð0Þ ¼ þ167:38 kJ mol1 , ð4Þ

Li4 B4 H10 Ð Li4 B4 H8 þ H2

Dr Hð0Þ ¼ þ81:18 kJ mol1 , ð5Þ
where in the first two equations the enthalpy is
expressed per mole of the reagent (LiBH4) decom-
posed. The last of the three equations can be expressed
in terms of the reduced formula units LiBH2.5, and
LiBH2. Doing that, we rewrote the last equilibrium
reaction as:
LiBH2:5 Ð LiBH2 þ 14H2 : ð6Þ
The geometry optimisation of the compound with the
analytical formula LiBH2.5, resulted in a quasi-ionic
crystal made by Li4B4H10, where B4 H 10 formed an
anion immersed in the Liþ cation sub-lattice. In fact,
the optimisation of the corresponding lithium sub-
lattice, obtained by removing the borate anions gave a
metallic crystal lattice with similar lattice parameters as
we obtained by lattice and geometry optimisation of
the pure lithium phase. The Mulliken populations
analysis together with the isodensity surface of the
electron density difference, reported in Figures 1 and 2,
showed that actually the tetraborate chains resembled
the hydrocarbon chain CnH2nþ2, with the relevant
difference that the borate chain was not neutral but
needed four lithium cations for ensuring charge neu-
trality. Similarly, Li4B4H8 showed a linear chain of
tetraborate immersed in a sublattice formed by cations
of lithium atoms. A view of the optimised unit cell
Figure 2. A view of the total electron density of Li4B4H10
projected on the crystallographic (ab) plane, which showed a
delocalised charge distribution along the tetraborate chain.
Colours represent: Li, violet; B, pink; H, white.
structure with the atomic charges, as calculated
from the Mulliken population analysis, is reported in
Figure 3, while the isodensity map of the electron
density is reported in Figure 4. Why did the tetraborate
show a linear structure? According to the known
borohydrides classification, we should expect a delta-
hedral structure with the formula unit B4H10, specif-
ically arachno-type structure where the hydrogen
atoms bridge between two boron atoms in a
3-centre-2-electrons (3c-2e) B–H–B bond scheme.
Contrarily, we found a linear chain formation. We
explain this by the concomitant presence of the metal
atoms: the lithium atoms were positively charged and
the borate chain as a whole carried a negative charge,
 1268 R. Caputo and A. Züttel
Figure 3. A view of the unit cell of Li4B4H8 with the atomic
charges (in red) obtained from the Mulliken population
Downloaded by [ETH Zurich] at 07:18 17 November 2011
analysis. Colours represent: Li, violet; B, pink; H, white.
Figure 4. A view of the total electron density Li4B4H8
projected on the crystallographic (ac) plane. The two
hydrogen atoms missing per formula unit, in comparison to
Li4B4H10, favoured a broader electron density distribution
along the tetraborate chain, in which the two terminal (BH2)
groups adopted the trans-configuration. Consequently, more
electron density states are spread over the whole chain and
more overlapping orbitals are allowed, as reflected in the
corresponding DOS reported in Figure 5. Colours represent:
Li, violet; B, pink; H, white.
as clearly shown by plotting the isodensity surface of
the electron density, as reported in Figures 2 and 4.
Closing the chain in one of the deltahedral proposed
structures for the borohydrides, could be favoured in
terms of orbital overlapping, unless electro-donor
species can supply electrons and hence induce an
open chain formation, due to a better spatial deloca-
lisation of the acquired charge over the whole borate
chain (which accordingly becomes borate anions). In
that case, the chains remained linear and there was no
necessity for the 3c-2e bond formation. Consequently,
the hydrogen atoms moved to form a 2c-2e bond with
boron atoms instead of bridging between them, as
would be expected in the case of anionic closed borate
cluster formation. Most interesting is the comparison
of the total electron density of states of Li4B4H8 and
Li4B4H10, reported in Figures 5 and 6. While Li4B4H10
showed a band gap of 4.69 eV, in Li4B4H8 the s-type
orbitals were shifted down at lower energies and the
p-type orbitals were shifted up and empty states were
made available. According to the formula unit, the
hydrogen content in Li4B4H10 is quite high, 6.22%wt.
molecular hydrogen, but if Equation (5) really
represented an equilibrium, the amount of hydrogen
released would be only 2.49%wt. at the expense of
81.18 kJ mol1. That could represent the limiting step
of the whole cycle de-hydrogenation and hydrogena-
tion of LiBH4. Clearly, neither the reactions reported
in the present work or all other similar studies recently
published [29–34] can univocally and unambiguously
assign the intermediate products and the possible
mechanism of the thermal decomposition of LiBH4.
The decomposition, in fact, can follow so many
different paths, which are driven by the manifold
chemistry of the binary and ternary phases made by
Li–B–H. Only an accurate description of the ternary
phase formation (Li–B–H) should shed light on the
mechanism of hydrogen release. On the other hand, the
diversity of possible ternary compounds made by
Li–B–H can represent the source of selectively driving
the processes of hydrogenation and de-hydrogenation.
In other words, only by the exact and unambiguous
identification of the chemical composition of the solid
and gas phases, resulting from thermal decomposition,
in terms of quantitative and qualitative chemical
analyses, can help to understand the mechanism of
hydrogen desorption and provide a hint on how to
make the process reversible.
3.3. Decomposition with the formation of Li2B12H12
Deserving its own consideration is the formation of
dilithium dodecahydrododecaborane, Li2B12H12, as a
possible intermediate for the thermal decomposition
of LiBH4, as recently reported [33,34]. First, in order
to ascertain the stability of the reported structure,
we optimised the geometry and relaxed the lattice
starting from the reference structure [34]. The optimi-
sation resulted with a very similar structure, lattice
 Molecular Physics 1269

Total electron density of states

5 30
Li4B4H8

Li2B12H12(ref)

Density of states (electrons/eV f.u.)

4

20
3

2
10

0 0
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–15 –10 –5 0 5 10
E–E F(eV)

Figure 5. Total electronic density of states of Li4B4H8 (left y-scale, red filled curve) and superimposed the DOS (right y-scale)
of the reference Li2B12H12 after full geometry optimisation. The reduced bad gap clearly confirmed the broader orbital
overlapping present in Li4B4H8, for which the p-region also extended to lower energies and pushed down the s-region.

Total electron density of states

7 30
Li4B4H10

6 Li2B12H12(ref)
Density of states (electrons/eV f.u.)

5
20

10
2

0 0
–15 –10 –5 0 5 10 15
E–EF (eV)

Figure 6. Total electronic density of states of Li4B4H10 (left y-scale, red filled curve) and superimposed the DOS (right y-scale)
of the reference Li2B12H12 after full geometry optimisation. The p-region showed the same band width, while the band gap
clearly was reduced in Li4B4H10, for which a broader spread of the s–p orbital was revealed. In Li2B12H12 the s and p state were
clearly more localised.

parameters a ¼ 9.579 Å and symmetry group Pa3,  IT of formation, calculated as the difference between the
number 205, as also confirmed by the comparison of total energy of Li2B12H12, and the corresponding total
our simulated XR-diffraction pattern, reported in energy of the elements, Li(bcc), -B and H2, was very
Figure 7 with the reported data [33,34]. The enthalpy low, 945.95 kJ mol1, without including, for the
 1270 R. Caputo and A. Züttel

Simulated XRD pattern

100
Li2B12H12
90
Li2B12H12(ref)

80

70

60
Intensity

50

40

30

20

10
Downloaded by [ETH Zurich] at 07:18 17 November 2011

0
10 15 20 25 30 35 40 45 50
2θ

Figure 7. Simulated XR diffraction patterns of Li2B12H12 (red line), as obtained after full geometry optimisation of the structure
modelled starting from LiBH4(hexag) and (blue line) Li2B12H12, as obtained after full geometry optimisation of the structure
reported in the literature [34]. The two diffraction patterns clearly differed: whereas the closo-dodecaborane of lithium, highly
symmetric, showed two markedly distinguished peaks at 16 and 18.25, our model clearly revealed a lower degree
of crystallinity.

moment, the zero-point energy and any thermal effects.
Actually, the relatively high stability of salts of
closo-dodecaborate, was already known, as reported
in recent review papers [35,36]. On the other hand, any
attempt to calculate the phonon dispersion and the IR
spectra, either using the linear response or the finite
difference methods, failed because of a strong lattice
instability due to one of the 130 irreducible representa-
tions of the normal modes of vibration of Li2B12H12.
Additional calculations are still under study. Further
analysis, using PWSCF code, after geometry optimisa-
tion, resulted in 13 imaginary normal modes among
the 312 ones. Clearly, the first modes provided
information on the translation- and rotation-induced
lattice instability, but the other seven negative fre-
quencies, 371.61 (g ¼ 2), 297.77 (g ¼ 3), 283.05
(g ¼ 2) cm1, (where g stands for the mode multiplic-
ity), indicated that the monoclinic structure suggested
up to now with symmetry P23,  was not the ground
state. Further analysis is still in progress, especially to
search for the ground-state structures of the general
compounds M2B12H12, where M ¼ Li, Na, K. For the
mass balance, the presence of Li2B12H12 in the residue
has to be accompanied by either the formation
of lithium hydride, metallic lithium, or any possible
lithium boride phase. For the sake of simplicity, and if
we assumed that only hydrogen formed in the gas
phase, the two possible paths of decomposition
involving the formation of Li2B12H12 led to the
formation of metallic lithium and lithium hydride
respectively, as follows:
12LiBH4 ! Li2 B12 H12 þ 10LiH þ 13H2 , ð7Þ
12LiBH4 ! Li2 B12 H12 þ 10Li þ 18H2 : ð8Þ
The corresponding enthalpies of reaction referring
to orthorhombic LiBH4 [24] were þ84.754 kJ mol1
and þ161.159 kJ mol1 respectively, while referring to
hexagonal-LiBH4 they become þ56.139 kJ mol1 and
þ122.50 kJ mol1. The hydrogen yield was respectively
1.08 and 1.5 mol H2 per mol of LiBH4. The enthalpies
fell in the range of the values calculated for the other
possible reaction paths, as reported in Table 2, and
basically many other possible paths can be hypothe-
sised on the mere stoichiometric considerations, simply
considering the possibility to form, for example
dilithium-dodecahydrododecaborane and lithium,
lithium hydride, elemental boron, any binary lithium
boride, in the solid phase and hydrogen, diborane
in the gas phase. For example, the reactions involving
the formation of diborane in the gas phase were worth
 Molecular Physics
consideration because they showed the complexity
of discriminating between possible energetically
allowed paths of reaction. In principle, in a very
combinatorial approach, we can have as many possible
reaction paths as the number of combinations of
possible candidate products under the stoichiometric
constraint. For example, the following two reaction
paths:
14LiBH4 ! Li2 B12 H12 þ 12Li þ B2 H6 þ 19H2 , ð9Þ
15LiBH4 ! Li2 B12 H12 þ 12Li þ LiB þ B2 H6 þ 21H2 ,
ð10Þ
resulted with enthalpy of reaction at T ¼ 0 K
of þ167.643 kJ mol1 and þ170.869 kJ mol1 of
decomposed LiBH4. In those two cases, the amount
of hydrogen released was 1.36 and 1.40 mol H2 per mol
Downloaded by [ETH Zurich] at 07:18 17 November 2011
LiBH4: all the paths considered showed a range of
hydrogen yield (1, 1.5), and few possible paths showed
a higher yield of hydrogen, as reported in Table 2.
In addition, we also supposed a reaction path in which
no hydrogen at all was released, but the thermal
decomposition proceeded via phase separation
between lithium hydride in the solid and diborane in
the gas phase. Only, bringing the system to higher
temperature, at least higher than the melting point of
lithium hydride, it would be possible to get started the
subsequent reaction path, which involved the reaction
between LiH and diborane. Nevertheless, a simple
consideration of forming dilithium dodecahydrodode-
caborane, as intermediate of the decomposition reac-
tion, raised obvious questions: given its high stability,
first, it cannot represent an intermediate, but a product
of the decomposition, second, if formed, it does not
react with hydrogen to reverse the reaction back to
LiBH4. To answer those questions we approached the
problem from the standpoint of molecular dynamics.
We attempted to elucidate the possible driving steps of
the mechanism by which hydrogen can be released in
the gas phase using Car–Parrinello molecular dynamics
at the constant temperature, 573.15 K, and at two
different constant pressure values, 1 and 100 bar.
A comprehensive study is still running, however our
preliminary simulations showed the formation of a
lithium borate chain and not as reported [33,34]
the formation of closo-dodecaborate(12) of lithium.
In addition, and in order to go deeply into the
mechanism, the full geometry optimisation of orthor-
hombic LiBH4 under an applied stress, equivalent to
hydrostatic pressure of 100 bar did not result in
dramatic distortion of the lattice parameters. Even
more interesting, we simulated the formation reaction
of Li2B12H12 starting from either the orthorhombic
1271
or the hexagonal phase of LiBH4. The hexagonal
phase, which is experimentally reported to be the high
temperature phase (see [32,37] and references therein),
was fully optimised. The resultant lattice parameters
were a ¼ 4.276 Å, c ¼ 6.948 Å, symmetry group P63mc,
IT number 186, and the heat of formation was
211.373 kJ mol1, which became 177.344 kJ mol1
when we included the zero point energies of all the
species involved, -B, Li(bcc), H2 and LiBH4 (hexag),
as reported in Table 1. A quantitative comparison with
the reported enthalpy of formation cannot easily be
done, because no distinction is made between different
phases in the literature [38,39]. Obviously, the number
of possible reaction paths, formulated simply on the
stoichiometric arguments, increased with the number
of possible intermediates can be formed, but for each
of them, the hydrogen yield in terms of mol of H2
released per mole of LiBH4 decomposed was always
lower than 2.0 and the corresponding enthalpies of
reaction fell in the same range of values. We had a
further confirmation of the variety and complexity of
the decomposition processes, when we modelled a
structure with the analytical formula Li2B12H12,
starting from the hexagonal phase of LiBH4. After
full geometry optimisation under hydrostatic pressure
of 100 bar, a network of boron–boron formed with
hydrogen–boron bond lengths in the range (1.186,
1.389) Å, boron–boron bond lengths in the range
(1.542, 1.793) Å. The enthalpy of formation was
þ170.902 kJ mol1, without including the zero-point
energy and any thermal effects. Clearly, it is not a
stable compound, but it is worthy of being considered
because it could elucidate one important aspect, in our
opinion, of the whole mechanism of the thermal
decomposition of LiBH4. To induce the clustering
and eventually the formation of dodecaborate(12)
structures the application of an external pressure is a
discriminating factor. In fact, a clear incipient boron
network formation was observed when optimising
the structure with the analytical formula Li2B12H12
under an applied external stress, as shown in the
electron density map reported in Figure 8. The
comparison with the closo-dodecaborate structure
(see Figure 9) highlighted an important difference,
which explained not only the high stability of the
closo-based compounds, but also pointed out one of
the major reasons for the poor reversibility of LiBH4.
The latter compound showed the typical charge
distribution of the icosahedral-based boron structure
[11] while the former exhibited an intriguing boron
network typical of amorphous phases, as also con-
firmed by plotting the electronic density of states in
Figure 10. Once the clustering process has been
initiated the reaction proceeded leading to
 1272 R. Caputo and A. Züttel
Downloaded by [ETH Zurich] at 07:18 17 November 2011

Figure 8. Li2B12H12 modelled starting from LiBH4(hexag): (up left) a top view of the 2  2  2 unit cell. (Up right)
A tridimensional view. (Down) A view of the total electron density projected on the a crystallographic plane that best fitted
the electron distribution along the boron network. A clear boron network was present on which the charge was delocalised.
The isodensity surface at 0.20 electrons Å3 is reported. Colours represent: Li, violet; B, pink; H, white.

the formation of a very stable compound, lithium
dodecaborate(12). In that case, the maximum yield in
terms of mol of H2 released per mol of LiBH4 was 1.5
and 1.08, depending whether in the residue metallic
lithium or lithium hydride was formed, respectively.
The structure of Li2B12H12, which we modelled and
optimised starting from hexagonal-LiBH4, strongly
resembled the amorphous structure obtained by hydro-
gen absorption in some of the lithium borides, formed
by dissolution of atomic lithium into -B, in particular
that with the analytic formula Li4B12. The comparison
of the simulated XRD pattern of Li4B4H10 and
Li4B4H8 with the reported XRD pattern of anhydrous
crystalline Li2B12H12 [34], which we calculated after
full geometry optimisation of the corresponding struc-
ture reported in the literature, showed that the peaks at
2 ¼ 21 and 22 actually indicated that the
closo-dodecahedron based intermediate cannot explain
all the features of the diffraction pattern therein
reported. Instead the two proposed linear chains of
tetraborate(8) and tetraborate(10) exhibited the two
mentioned peaks, as reported in Figure 11. Most
probably, none of the proposed structures can be
exactly compared with the experiments, because,
experimentally the final intermediates strongly
depend on the purity of the initial LiBH4, the specific
( p, T ) operative conditions and the chemical treatment
the residue underwent before being analysed.
Therefore, the comparison between theoretically mod-
elled structures and experimentally resolved ones could
mismatch. Nevertheless, we think that it is worth
putting effort in that direction. Furthermore, we con-
sidered the possibility to release the whole amount of
hydrogen in a one-step decomposition process, which
 Molecular Physics 1273

means by direct decomposition of LiBH4 in LiB and
H2, as reported in Table 2. We will extensively report
elsewhere the absorption of hydrogen in LiB and Li2B6
[40,41]. For the moment, it is worth noting that the
Downloaded by [ETH Zurich] at 07:18 17 November 2011
hydrogenation of LiB at low loading factor is an
exothermic process with hydrogen atoms bound to
both lithium and boron atoms with different partial
charge [40]. In addition, the relevance of lithium boride
(LiB) formation upon thermal decomposition was
revealed in another important result. The complete
desorption of hydrogen from the orthorhombic struc-
ture of LiBH4, resulted in lithium boride, LiB, of which
the optimised structure showed strong similarities, in
terms of enthalpy of formation and molecular rear-
rangement, with that calculated by absorption of
lithium in the -boron at a composition ratio 1 : 1. In
Figure 12 we have reported a view of the LiB structure
obtained after full geometry optimisation of Li
dissolved in boron with atomic ratio 1 : 1 per unit
cell. It was clear, on the basis of a generalised
mechanism of decomposition, that the possibility to
first have the decomposition in LiB and H2 and then

the re-hydrogenation of the residue LiB, represented

Figure 9. A view of the total electron density Li2B12H12,
projected on the crystallographic (ac) plane, as obtained after
full geometry optimisation of the structure reported in
the literature [34]. The closo-dodecaborate network
of boron atoms determined the typical charge distribution
entirely localised on the icosahedral net. Colours represent:
Li, violet; B, pink; H, white.
an alternative way to rationalise the whole process of
the thermal decomposition. In fact, the absorption of
hydrogen in LiB at loading factor x ¼ 2 and 2.5,
resulted in the formation of linear borate anions in an
incommensurate lattice of lithium cations, with ana-
lytical formula LiBHx, as we will report elsewhere [42].

Total electron density of states

9 30
Li2B12H12
8 Li2B12H12(ref)
Density of states (electrons/eV f.u.)

6 20

3 10

0 0
–15 –10 –5 0 5 10
E–EF (eV)

Figure 10. Total electronic density of states of Li2B12H12, as modelled starting from LiBH4(hexag) (left y-scale, red filled curve)
and superimposed is reported the DOS (right y-scale) of the reference Li2B12H12 after full geometry optimisation. The two
structures with the same analytical formula spanned the same energy interval, but while our model showed a small band gap and
a mixing and overlap between the s and p orbitals, the closo-dodecahedron based structure clearly showed more localised
orbitals. In fact, the s-region representing the H–B bond showed a single energy distribution at 12.4 eV lower than the Fermi
energy, whereas our model showed a doublet electron density distribution with a minimum at that value. In fact, the H atoms
in the reference model were equivalent per symmetry, while in our model they had two distinct chemical environments.
The electron density distribution is reported in Figures 8 and 9.
 1274 R. Caputo and A. Züttel

Simulated XRD pattern

100
Li4B4H10
90
Li4B4H8

80

70

60
Intensity

50

40

30

20

10
Downloaded by [ETH Zurich] at 07:18 17 November 2011

0
10 15 20 25 30 35 40 45 50
2θ

Figure 11. Simulated XR diffraction patterns of Li4B4H10 (red line) and Li4B4H8 (blue line). The two structures showed
a super imposable diffraction peak at 18.5, but the peaks in the range (21, 24) degrees clearly discriminated between the
two compounds.

4. Conclusions
The analysis of the possible decomposition paths
of reaction clearly highlighted the important role
played by lithium borides and boranes in the overall
energy balance and mechanism of decomposition.
Clearly, the kinetics of each reaction was not consid-
ered, but only the thermodynamics and in particular
the enthalpy and the Gibbs free energy of reactions, as
reported in Table 2, were derived from the total energy
and phonon calculations. One concern was about the
possibility to form boranes, and in particular diborane
in the gas phase. Generally, it is thought that B2H6,
even if it formed would decompose to H2 and
elemental boron, therefore boranes should not be
expected in the gas phase of the decomposition
products of LiBH4. Furthermore, a straightforward
comparison with the thermal desorption profiles
experimentally reported, is made quite difficult,
because they referred somehow to a mixture of metal
borohydrides and metal chloride [43] with and without Figure 12. A view of the total electron density of LiB,
adding silica [5] or TiO2 (see [44] and reference therein) projected on the crystallographic (ab) plane. The structure
with the aim to improve the kinetics of the hydrogen was obtained after full geometry optimisation of lithium
desorption process. Several attempts have been done absorbed in -B at atomic ration 1 : 1. Colours represent: Li,
in the direction to search for an appropriate co-reagent violet; B, pink; H, white.
to destabilise lithium borohydride and hence make
faster the gas desorption. Different intermediates, as Furthermore, the decomposition could proceed via for-
Li2B12H12, were also experimentally reported [33,34], mation of elemental boron, but it is not yet known
which in turn confirmed the high probability to form how to reverse the reaction, since boron can be formed
borate of lithium as products of decomposition. in any of its different allotropic structures, or even
 Molecular Physics
in a polymorphic phase, of which the hydrogenation
process could present a variety of different energeti-
cally accessible phases. In addition, it is well known
that B2H6 is a relatively stable, commercially available
compound, and it undergoes thermal decomposition
with and without catalytic activation forming tribor-
ane, pentaborane, and hexaborane [45]. In general,
oligomerisation is observed and decomposition is
to higher boron-number boranes.4 In fact, borohy-
drides containing more than ten boron atoms are
formed during thermal decomposition of diborane
at T ¼ 523 K and most likely also solid state boranes
can be formed [45]. Therefore, the formation of
boranes either in the gas or solid phase cannot be
excluded, unless reliable and quantitative chemical
analyses clearly show the exact gas phase composition
at different ( p, T ) conditions, at which the thermal
decomposition of LiBH4 is experimentally reported.
Downloaded by [ETH Zurich] at 07:18 17 November 2011
The heats of reaction of some possible reaction paths,
reported in the present work, clearly underlined the
important role played by the metal boride formation in
those particular (p, T) conditions at which the pyrolysis
occurs. In particular, the formation of LiB and Li2B6
and their subsequent hydrogenation represented an
important step worth further investigation in order
to make effectively reversible the de-hydrogenaiton
and re-hydrogenation processes of LiBH4. In fact, at
low loading factor, the hydrogenation of LiB was
exothermic, while that of Li2B6 was endothermic
[40,42], and their subsequent hydrogenation led
to the formation of linear chains of borane in the
lithium cation sublattice. We suggested that the
exact chemical identification of the intermediates of
reaction represents a key factor in driving the whole
process of de-hydrogenation and re-hydrogenation
of LiBH4, and accordingly improving its reversibility.
The lithium borides, in particular LiB, could play
that role.
Acknowledgements
The authors would like to thank Dr Adem Tekin for valuable
discussions and gratefully acknowledge the financial support
from the European Commission DG Research RTN Marie
Curie Actions-Hydrogen (contract MRTN-CT-2006-032474,
until February 2009) and the 7.Serie Interner FþE-Projekte,
EMPA funding. The computer facilities IPAZIA at
EMPA in Dübendorf, Switzerland are highly appreciated
(http://ipazia.empa.ch).
Notes
1. Early in 1941 H.I. Schlesinger and co-workers, among
them H.C. Brown, worked on the synthesis of metal
borohydrides, to obtain, at that time, new volatile
1275
compounds even of heavy metals in particular, uranium.
Most of the work was carried out under contracts with
the National Defense Research Committee. Recently,
interest has been revived for their potential use as
hydrogen reservoir materials, as shown by the increasing
amount of work published in the last decades
worldwide.
2. The solid state synthesis of some of the lithium borides
has been reported by R. Nesper and co-workers.
3. The heat of formation of LiBH4 was already determined
by Davis in the 1949 via the Hesse cycle in solution.
Recently, it was reported by Chase in 1998, as cited on
the NIST reference page. In all those works, nothing
is reported regarding the relationship between structure
and heat of formation. Our calculations, reported in the
present work, refer to the lowest orthorhombic energy
structure found by our modelling approach. Our
calculated entropy value is þ86.583 J mol1 comparable,
anyway with the reported value in the NIST web book,
which is equal to þ75.88 J mol1.
4. Regarding the formation of boranes, even at the solid
state, a systematic research has been done since the first
study by Alfred Stock in 1912, and since then there
has been a steady stream of other boron hydride
formations also at the solid state [46].
All figures can be viewed in colour online.
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