Tuning the structural stability of LiBH4 through boron-based compounds towards superior dehydrogenation

Article abstract of DOI:10.1039/c7ta09376d

The remarkable destabilization effects of H₃BO₃, HBO₂, and B₂O₃ on dehydrogenation of LiBH₄ are revealed in this work. The effectiveness of destabilizing the structural stability is in the order of H₃BO₃ > HBO₂ > B₂O₃. Besides, through optimizing the molar ratio of LiBH₄ and H₃BO₃ and milling treatment, the destabilization effect, especially for dehydrogenation kinetics, is further enhanced. For example, at a temperature as low as 110 °C, 5.8 wt% hydrogen can be liberated in seconds from 2LiBH₄-H₃BO₃ prepared through pre-milling. The investigation reveals that each of the LiBH₄-H₃BO₃, LiBH₄-HBO₂ and LiBH₄-B₂O₃ systems undergo multiple dehydrogenation stages corresponding to different destabilization mechanisms. The reaction at lower temperature is ascribed to the H⁺?H^- coupling mechanism which should be enhanced by the [OH]^-?[BH₄]^- interaction mode. Pre-milling treatment of LiBH₄ and H₃BO₃ also promotes the H⁺?H^- interaction which may have originated from the increasing contact area as a result of the fine particles, and therefore probably reduced the reaction activation energy. Consequently, it gives rise to the superior dehydrogenation performance of lower temperature, rapid kinetics, pure hydrogen and high capacity, which are required for off-board hydrogen energy vehicle application.

Full text of DOI:10.1039/c7ta09376d

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Kun Chang, Zhaorong Chang et al.
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Tuning the structural stability of LiBH4 through boron-based
compounds towards superior dehydrogenation
Weitong Cai1,*, Juner Chen2, Liying Liu1, Yuanzheng Yang1, Hui Wang3,4,
*
1. School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, P.
R. China
2. Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China
3. School of Materials Science and Engineering, South China University of Technology,
Guangzhou 510640, P. R. China
4. Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, Guangzhou
510640, P. R. China
* Corresponding author:
Prof. W. T. Cai
Eꢀmail: mewtcai@gdut.edu.cn
Prof. H. Wang
Eꢀmail: mehwang@scut.edu.cn
Tel: +86ꢀ20ꢀ87113924
1

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Abstract
The remarkable destabilization effects of H3BO3, HBO2, and B2O3 on dehydrogenation of
LiBH4 are revealed in this work. The effectiveness for destabilizing the structural stability is in the
trend of H3BO3 > HBO2 > B2O3. Besides, through optimizing the molar ratio of LiBH4 and H3BO3
and the milling treatment, the destabilization effect, especially for dehydrogenation kinetics, is
further enhanced. In an instance, at temperature as low as 110 °C, 5.8 wt.% hydrogen can be
liberated in seconds from 2LiBH4ꢀH3BO3 prepared through preꢀmilling. The investigation reveals
that each LiBH4ꢀH3BO3, LiBH4ꢀHBO2 and LiBH4ꢀB2O3 systems undergo multiple
dehydrogenation stages corresponding to different destabilization mechanism. The reaction at
lower temperature is ascribed to the H+⋅⋅⋅H¯ coupling mechanism which should be enhanced by
the [OH]¯···[BH4]¯ interaction mode. Preꢀmilling treatment of LiBH4 and H3BO3 also promotes
the H+⋅⋅⋅H¯ interaction which may be originated from the increasing contact area as a result of the
fine particle, and therefore probably reduced the reaction activation energy. Consequently, it gives
rise to the superior dehydrogenation performance of lower temperature, rapid kinetics, pure
hydrogen and high capacity, which are required for the offꢀboard hydrogen energy vehicle
application.
Key words: hydrogen storage, destabilization, dehydrogenation, lithium borohydride, borate acid
2

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1. Introduction
Light weight element materials such as Mgꢀbased hydride, alanate, amide and borohydride
are regarded as important hydrogen storage materials especially in the hydrogen energy vehicle
application [1ꢀ4]. Recently, alkali metal borohydrides have received much attention as promising
candidates because of their high hydrogen capacity [5, 6]. Among them, LiBH4 has been studied
most comprehensively since 2003 due to the high hydrogen gravimetric density and volumetric
density of 18.4 wt.% and 121 kg/m3, respectively [7]. Thermogram shows that pristine LiBH4
undergoes three endothermic steps at 108ꢀ112, 258ꢀ286 and 483ꢀ600 °C [8]. The first stage
corresponds to the reversible polymorphic transformation without any hydrogen emission, and the
second stage is attributed to the fusion of LiBH4 accompanying with a minor dehydrogenation of
approximately 2 wt.%. The main dehydrogenation starts at 380 °C liberating 80% hydrogen in
LiBH4. This major dehydrogenation reaction is as following:
LiBH4 → LiH + B + 3/2H2 (1)
However, the extremely high thermodynamic stability and sluggish kinetic barrier originating
from the [BH4]¯ structural stability of LiBH4 hampers its application as hydrogen storage material
[9, 10]. Therefore, destabilization of the structural stability through altering the reaction path was
proposed to augment the hydrogen storage performance of LiBH4 by Vajo et al. in 2005 [11].
Since then, extensive efforts have been paid for establishing destabilized LiBH4 systems with
enhanced properties, such as LiBH4ꢀMgH2/CaH2/YH3/NdH2, LiBH4ꢀSiO2/TiO2/SnO2, and so on
[11ꢀ31]. The destabilization reaction normally is LiBH4 + MHx → LiH + MBx + H2 for the
LiBH4ꢀmetal hydride systems, while it is a redox reaction of LiBH4 + MOx → LiMOx + B + H2 for
the LiBH4ꢀmetal oxide systems. Besides, the dehydrogenation pathway also can be controlled by
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confining LiBH4 in highly ordered nanoporous carbon leading to lower dehydrogenation
temperature [32, 33]. Since the thermodynamic stability of metal borohydrides was reported to
correlate with Pauling electronegativity of cation [34], new perspective of elemental substitution
had been employed to LiBH4 leading different and sophisticated destabilization reactions [35]. A
variety of novel complexes were synthesized with tunable dehydrogenation temperature, such as
Limꢀ4Zr(BH4)m (m=4, 5, 6), LiK(BH4)2, Li4Al3(BH4)13, etc. [36ꢀ42] Besides, anion substitution
study of Li8B8H32ꢀxFx from theoretical calculation suggested a lower dehydrogenation temperature
of 100 °C for LiBH3.75F0.25 [43].
More recently, new complexes and/or systems were synthesized and investigated according
to H+⋅⋅⋅H¯ interaction mechanism which show enhanced dehydrogenation behavior, such as
LiBH4·NH3, LiBH4·NH3BH3, LiBH4ꢀLiNH2 [44ꢀ50]. Motivated by this mechanism and to reveal
the synergetic effect of coexistence of oxygen and hydrogen atoms on the dehydrogenation of
LiBH4, H3BO3 containing [OH]¯ unit were selected and introduced into LiBH4, including
HBO2/B2O3 for comparison. Besides, the preparation parameters of stoichiometric ratio and
preꢀmilling treatment were also investigated for further strengthening the destabilization effect.
Fascinating result was achieved in the case of 2LiBH4ꢀH3BO3 system prepared by preꢀmilled
LiBH4 and H3BO3, in which 5.8 wt.% hydrogen with high purity was liberated at temperature as
low as 110 °C in seconds. Table 1 shows the comparison of dehydrogenation performance of
typical LiBH4ꢀadditive systems. It clearly declares that high dehydrogenation temperature or
hydrogen purity is the main challenge for these investigated systems. Significantly, the
2LiBH4ꢀH3BO3 system may be used as offꢀboard hydrogen storage material requiring the
comprehensive performance of lower dehydrogenation temperature, rapid kinetics, high hydrogen
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purity and capacity.
Table 1 Comparison of dehydrogenation performance of typical LiBH4ꢀadditive systems.
Capacity Temperature
No.
System
Advantages
Disadvantages
Ref.
(wt.%)
(°C)
lower dehydrogenation
temperature; fast
This
1
2LiBH4ꢀH3BO3
5.8
110
limited reversibility
kinetics; high hydrogen
purity and capacity
work
high dehydrogenation
temperature; in some
cases, destabilization
effect is limited by back
pressure and/or
2
3
4
LiBH4ꢀMgH2
LiBH4ꢀYH3
LiBH4ꢀNdH2
8
440
350
370
[11]
[15]
[16]
fast kinetics; superior
reversibility; high
hydrogen purity and
capacity
7.2
6.0
5
LiBH4ꢀCaH2
7.7
427
[55]
nanosized effect
6
7
8
9
LiBH4ꢀSiO2
LiBH4ꢀTiO2
LiBH4ꢀSnO2
LiBH4ꢀFe2O3
7
3
3
6
350
250
400
200
[7]
fast kinetics; high
hydrogen purity; high
capacity in some cases
high dehydrogenation
temperature;
[12]
[17]
[12]
irreversibility
impure hydrogen
involving B2H6;
irreversibility;
thermodynamic
unstability of some
compounds at room
temperature
10
Li4Al3(BH4)13
21.6
40ꢀ80
[38]
lower dehydrogenation
temperature; fast
kinetics
11
12
LiZn2(BH4)5
LiSc(BH4)4
35.0
4.3
ꢀ35ꢀ150
177ꢀ400
[37]
[56]
impure hydrogen
involving
relative lower
dehydrogenation
temperature in some
cases; fast kinetics
13
LiBH4·NH3
36
34
280
[44]
[45]
NH3/cꢀ(NHBH)3 or
others; limited
reversibility
14 LiBH4·NH3BH3
2. Experimental
100ꢀ450
LiBH4 (95%, Sigma Aldrich) and H3BO3 (99.5%, Yongda chemical agent, China) were used as
starting materials. By heating H3BO3, HBO2 was obtained at temperature 150 °C for 20 h under
air atmosphere, and B2O3 was acquired at 250 °C for 6 h under vacuum condition. LiBH4ꢀ48.4 wt.%
H3BO3/HBO2/B2O3 composites were synthesized by hand milling for 10 minutes using a mortar
and pestle, both LiBH4 and H3BO3 were asꢀreceived. LiBH4ꢀH3BO3 with molar ratio of 1:2/2:1/3:1
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was prepared under the same conditions, in this occasion asꢀreceived LiBH4 and H3BO3 and
preꢀball milled LiBH4 and H3BO3 were used. The preꢀball milling was performed by a vibratory
ball mill (QMꢀ3C, Nanjing Nanda Instrument Plant) at rotation speed of 600 rpm for 1 h. The
samples were loaded into a stainless steel vessel together with hardened stainless steel balls and
the weight ratio of balls to powders was 120:1.
The gaseous species released from the composites were detected by a mass spectrometer (MS,
HidenꢀQic 20) under temperatureꢀprogrammed desorption mode (TPD). The composites were
heated from room temperature to 500 °C with a heating rate of 4 °C minꢀ1 and high purity argon
purge of 60 mL/min. Dehydrogenation kinetics measurement was performed on a Sievertꢀtype
apparatus (PCTꢀPro 2000, Setaram) under static vacuum. Due to the limited volume of the sample
container, 0.1 g sample was applied to the apparatus in each measurement. The dehydrogenation
content was calculated with respect to the total weight of the composites. Phase analysis was
executed on an Xꢀray diffractometer (XRD, Philips X’Pert, Cu Kα radiation). The composites
were wrapped with a 3M film to avoid the air and moisture contamination, which caused a
scattering peak at 2θ≈18º in XRD pattern. The background induced by this plastic film was
removed from the acquired XRD patterns for each sample. Fourier transform infrared spectra
(FTIR, Vector 33, Bruker) were recorded from 32 scans at 4000 cmꢀ1ꢀ400 cmꢀ1 using 4 cmꢀ1
resolution. The background was subtracted from the spectra. All the samples were handled in a
glove box under high purity argon atmosphere. The O2 and H2O levels were below 1 ppm.
3. Results and discussions
LiBH4-H3BO3 (1:2, 2:1, 3:1) composites
3.1 Microstructure of LiBH4ꢀH3BO3 (1:2, 2:1, 3:1) composites
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Figure 1 XRD patterns (1) and FTIR spectra (2) of LiBH4ꢀH3BO3 (1:2, 2:1, 3:1) composites using
asꢀreceived LiBH4 and H3BO3 (a), preꢀmilled LiBH4 and H3BO3 (b). LiBH4ꢀH3BO3 composites
were mixture of LiBH4 and H3BO3.
In this section, the effect of molar ratio of LiBH4 : H3BO3 (1:2, 2:1, 3:1) and preꢀmilling
treatment of LiBH4 and H3BO3 was systematically investigated to reveal the synergistic effect of
oxygen and hydrogen atoms on the destabilization performance. Figure 1 shows the XRD patterns
and FTIR spectra of the LiBH4ꢀH3BO3 (1:2, 2:1, 3:1) composites. The diffraction peaks from
LiBH4 and H3BO3 were clearly identified in all composites. With the increasing molar ratio of
H3BO3, the diffraction intensity of LiBH4 became weaker while that of H3BO3 became stronger.
Besides, small diffraction peaks of LiH were detectable in the composites using preꢀball milled
LiBH4 and H3BO3. This indicates the occurrence of selfꢀdecomposition of LiBH4 [51] or side
reaction between LiBH4 and H3BO3 during the milling process. As revealed by FTIR spectra, the
vibrations from H3BO3 of OꢀH bond at 3216 cmꢀ1 and BꢀO bond at 1354, 1019 and 587 cmꢀ1 were
visible. It is interesting that in the LiBH4ꢀ2H3BO3 composite new vibrations from BꢀO bond at
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1445, 812, 645 and 548 cmꢀ1 and BꢀH bond at 1194 cmꢀ1 were detected which were also originated
from H3BO3 [52]. The vibration shifting indicates that the interaction of [BH4]¯···[OH]¯ distorts
the characteristic vibrations of BꢀH bond and OꢀH bond in LiBH4 and H3BO3, and it also would be
beneficial to the dehydrogenation enhancement as revealed in the following measurements. The
characteristic vibrations of BꢀH bond at 2385, 2291, 2223 and 1125 cmꢀ1 from LiBH4 gradually
became weaker with its decreasing molar ratio. Therefore, the LiBH4ꢀH3BO3 (1:2, 2:1, 3:1)
composites were mainly a mixture of LiBH4 and H3BO3 using either asꢀreceived components or
preꢀmilled ones.
3.2 Dehydrogenation of LiBH4ꢀH3BO3 (1:2, 2:1, 3:1) composites
Figure 2 TPDꢀMS of H2 evolution of LiBH4ꢀH3BO3 (1:2, 2:1, 3:1) composites using asꢀreceived
LiBH4 and H3BO3 (a), preꢀmilled LiBH4 and H3BO3 (b), pristine LiBH4 and H3BO3 (c). The
composites exhibited similar dehydrogenation behavior with three stages.
Figure 2 shows the TPDꢀMS results of H2 evolution for LiBH4ꢀH3BO3 (1:2, 2:1, 3:1)
composites using asꢀreceived LiBH4 and H3BO3, preꢀmilled LiBH4 and H3BO3, without any
poisonous B2H6 emission (data not shown here). These composites exhibited similar
dehydrogenation behavior which can be divided into three dehydrogenation stages of <150 °C
(first stage), 270ꢀ325 °C (second stage) and >325 °C (third stage). This behavior is different from
that of pristine LiBH4 and H3BO3 that implies the interaction between these two compounds.
Pristine LiBH4 starts to liberate hydrogen at about 280 °C and reach its peak point at 440 °C, and
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pristine H3BO3 liberates hydrogen from 120 °C reaching the peak temperature at 198 °C. When
using asꢀreceived LiBH4 and H3BO3, the dehydrogenation peak temperatures were
108 °C/300 °C/351 °C for LiBH4ꢀ3H3BO3, 51ꢀ96 °C/298 °C/383 °C for LiBH4ꢀ2H3BO3, and
83 °C/301 °C/405 °C for LiBH4ꢀH3BO3. By changing into preꢀmilled LiBH4 and H3BO3, the peak
temperatures were relatively reduced to 85 °C/290 °C/340 °C for LiBH4ꢀ3H3BO3,
94 °C/296 °C/379 °C for LiBH4ꢀ2H3BO3, and 92 °C/285 °C/394 °C for LiBH4ꢀH3BO3.
Significantly, it is necessary to emphasize that the dehydrogenation peak temperatures are
significantly lower (<110 °C) for those composites at first stage. Therefore, we focus on the
improvement effectiveness at this stage for further kinetics measurement, and to reveal the
hydrogen emission whether comes from the H+⋅⋅⋅H¯ interaction mechanism or not.
Figure 3 Isothermal dehydrogenation at 110 °C of LiBH4ꢀH3BO3 (1:2, 2:1, 3:1) composites using
asꢀreceived LiBH4 and H3BO3 (a), preꢀmilled LiBH4 and H3BO3 (b). The composites prepared
from preꢀmilled LiBH4 and H3BO3 exhibited better dehydrogenation kinetics.
Figure 3 shows the isothermal dehydrogenation kinetics at 110 °C for LiBH4ꢀH3BO3 (1:2, 2:1,
3:1) composites using asꢀreceived LiBH4 and H3BO3, and preꢀmilled LiBH4 and H3BO3. Pristine
LiBH4 liberates none of any hydrogen at this extremely lower temperature as revealed in Figure 2c.
The extremely sharp dehydrogenation curves clearly indicate that hydrogen was rapidly released
within seconds from the composites. 3.2 wt.%, 4.8 wt.% and 3.9 wt.% hydrogen was liberated
from LiBH4ꢀ3H3BO3, LiBH4ꢀ2H3BO3 and LiBH4ꢀH3BO3 respectively by using asꢀreceived LiBH4
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and H3BO3. 3.3 wt.%, 5.8 wt.% and 5.2 wt.% hydrogen was acquired from LiBH4ꢀ3H3BO3,
LiBH4ꢀ2H3BO3 and LiBH4ꢀH3BO3 respectively by using preꢀmilled LiBH4 and H3BO3. These
results declare that the dehydrogenation effectiveness is in the order of
2LiBH4ꢀH3BO3>LiBH4ꢀ2H3BO3>3LiBH4ꢀH3BO3, and the preꢀmilled ones show much better
performance. This should be attributed to the reduced reaction activation energy originating from
the increasing contact area between refining particles of LiBH4 and H3BO3 (see ESI). Table 2
shows the theoretical dehydrogenation capacity and observed value from LiBH4ꢀH3BO3 composite
under different molar ratio. It is clear that the observed capacity is very closed to the theoretical
value of H+⋅⋅⋅H¯ interaction mechanism, which indicates the liberated hydrogen is produced from
hydrogen atoms combined from LiBH4 and H3BO3.
Table 2 Dehydrogenation capacity of LiBH4ꢀH3BO3 composites at 110 °C. (unit: wt.%)
Molar ratio of LiBH4:H3BO3
Theoretical capacity of composite
Theoretical capacity of H+ꢀH¯
Observed capacity
3:1
11.8
2:1
10.4
1:2
6.9
4.7(3H+ꢀ3H¯)
3.3
5.7 (3H+ꢀ3H¯)
5.8
5.5 (4H+ꢀ4H¯)
5.2
3.3 Microstructure of dehydrogenated LiBH4ꢀH3BO3 (1:2, 2:1, 3:1) composites
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Figure 4 XRD patterns (1) and FTIR spectra (2) of LiBH4ꢀH3BO3 (1:2, 2:1, 3:1) composites after
dehydrogenation at 110 °C, using asꢀreceived LiBH4 and H3BO3 (a), preꢀmilled LiBH4 and H3BO3
(b). Destabilization reaction between LiBH4 and H3BO3 occurred during dehydrogenation.
Figure 4 shows the XRD patterns and FTIR spectra of LiBH4ꢀH3BO3 (1:2, 2:1, 3:1)
composites after dehydrogenation at 110 °C using asꢀreceived LiBH4 and H3BO3, and preꢀmilled
LiBH4 and H3BO3. In the XRD patterns, only diffraction peaks from LiBH4 and HBO2 were
clearly identified. By increasing the molar ratio of H3BO3, the intensity of LiBH4 decreased
whereas that of HBO2 increased, especially for LiBH4ꢀ2H3BO3 composite using preꢀmilled
components. These results suggest that more LiBH4 had been consumed under higher molar ratio
of H3BO3 leading to increasing dehydrogenation capacity (see Figure 3). FTIR spectra reveal the
characteristic BꢀH vibrations at 2385, 2291, 2223 and 1125 cmꢀ1 indicating partial LiBH4 retained
in the dehydrogenated composites. Besides, the BꢀO vibration peaks appeared at range of
1500ꢀ1200 cmꢀ1, 1100ꢀ900 cmꢀ1, 760ꢀ500 cmꢀ1 should be originating from the reaction product
HBO2. Herein, it is worthwhile to note that the reaction products of LiꢀBꢀOꢀH and/or LiꢀBꢀO
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should exist in this lowerꢀtemperature dehydrogenated products, although their BꢀO and BꢀH bond
vibrations was hard to be distinguished from that of HBO2 and LiBH4 due to the overlapping
profiles. Therefore, the destabilization reaction between LiBH4 and H3BO3 with molar ratio of 1:2,
2:1, 3:1 at 110 °C was proposed as following:
LiBH4 + H3BO3 → (1ꢀx)LiBH4 + HBO2 + LiꢀBꢀOꢀH/LiꢀBꢀO + H2
(2)
In our work, pristine H3BO3 was found to selfꢀdecompose into HBO2 and B2O3 when heating
up. In particularly, HBO2 emerged in the dehydrogenated products (equation 2). Therefore, it is of
interest to further reveal the promotion effect of HBO2 and B2O3 on the dehydrogenation behavior
of LiBH4. And then HBO2 and B2O3 was prepared and introduced into LiBH4 and the results were
shown in the following section.
LiBH4-H3BO3/HBO2/B2O3 composites
3.4 Microstructures of LiBH4ꢀH3BO3/HBO2/B2O3 composites
Figure 5 XRD patterns (a) and FTIR spectra (b) of pristine LiBH4, LiBH4ꢀH3BO3, LiBH4ꢀHBO2
and LiBH4ꢀB2O3 composites. The composites were mixtures of LiBH4 and H3BO3/HBO2/B2O3.
Figure 5 shows the XRD patterns (a) and FTIR spectra (b) of pristine LiBH4, LiBH4ꢀH3BO3,
LiBH4ꢀHBO2, and LiBH4ꢀB2O3 composites. As shown in Figure 5a, diffraction peaks from H3BO3
were identified, whereas that of HBO2 and B2O3`were invisible possibly due to their amorphous
structures. The diffraction peaks of LiBH4 in the composites were also detectable. Some unknown
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peaks in the diffraction patterns were originated from the impurities in LiBH4. FTIR spectra in
Figure 5b shows the characteristic vibrations of BꢀH bond from LiBH4 at 2385, 2291, 2223 and
1125 cmꢀ1. However, the BꢀH, OꢀH, BꢀO bond vibrations from H3BO3, HBO2, B2O3 were hard to
distinguish due to the overlapping peak. Only broad peaks of BꢀO bond at 1354, 1019 and 587
cmꢀ1 were identified in LiBH4ꢀH3BO3 composite. These results indicate that those composites
were mixtures of LiBH4 and H3BO3, HBO2, or B2O3 without any newly formed compounds.
3.5 Dehydrogenation of LiBH4ꢀH3BO3/HBO2/B2O3 composites
Figure 6 TPDꢀMS of H2 (a) and B2H6 (b) evolution of pristine LiBH4, LiBH4ꢀH3BO3,
LiBH4ꢀHBO2 and LiBH4ꢀB2O3 composites. Dehydrogenation temperatures of LiBH4 were
dramatically reduced in the presence of H3BO3/HBO2/B2O3.
Figure 6 shows the H2 and B2H6 evolution from LiBH4ꢀH3BO3, LiBH4ꢀHBO2, LiBH4ꢀB2O3
composites, together with pristine LiBH4 for comparison. It is obvious that pure hydrogen was
released from those composites without any poisonous B2H6 emission. When introducing H3BO3,
HBO2, or B2O3 into LiBH4, the dehydrogenation behaviors were significantly enhanced. For
LiBH4ꢀH3BO3, the peak temperature was greatly lower to 108 °C followed with two small peaks
at 300 °C and 351 °C. For LiBH4ꢀHBO2, the composite exhibits multiple dehydrogenations around
74 °C and the temperature between 300 °C and 350 °C. Hydrogen releasing from LiBH4ꢀB2O3
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takes place at the temperatures between 300 °C and 400 °C with a predominant peak at 307 °C. It
is obvious that these composites show similar dehydrogenation behavior at lower temperature (<
150 °C) for LiBH4ꢀH3BO3 and LiBH4ꢀHBO2 composites and at higher temperature (300ꢀ400 °C)
for three composites which implies the similar destabilization reaction.
Figure 7 Isothermal dehydrogenation of LiBH4ꢀH3BO3 (a), LiBH4ꢀHBO2 (b), LiBH4ꢀB2O3 (c),
together with pristine LiBH4 for comparison. Dehydrogenation kinetics of LiBH4 was significantly
enhanced by doping with H3BO3/HBO2/B2O3.
Figure 7 shows the isothermal dehydrogenation kinetics of pristine LiBH4 at 350 °C,
LiBH4ꢀH3BO3 at 110 °C and 350 °C, LiBH4ꢀHBO2 at 75 °C and 340 °C, LiBH4ꢀB2O3 at 300 °C
and 360 °C. These dehydrogenation temperatures were reasonably selected according to the
TPDꢀMS results. As shown in Figure 7, pristine LiBH4 exhibited sluggish dehydrogenation
kinetics resulting in a lower dehydrogenation capacity of 2.0 wt.% at 350 °C. Fortunately, the
situation was greatly changed by introducing boronꢀbased compound such as H3BO3, HBO2, and
B2O3. LiBH4ꢀH3BO3 composite released 3.2 wt.% and 8.6 wt.% hydrogen at 110 °C and 350 °C
respectively indicating two evident dehydrogenation stages which is consistent well with the
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TPDꢀMS result (see Figure 6a). LiBH4ꢀHBO2 composite released only 0.5 wt.% hydrogen at
75 °C and 6.6 wt.% hydrogen at 340 °C. 5.2 wt.% and 5.8 wt.% hydrogen was released from the
LiBH4ꢀB2O3 composite at 300 °C and 360 °C respectively. Combined with TPDꢀMS results in
Figure 6, the results indicate that the effectiveness of boronꢀbased compounds on improving the
dehydrogenation of LiBH4 is in the order of H3BO3>HBO2>B2O3. It undoubtedly declares that the
higher [OH]¯ content is, the stronger destabilization effect will been obtained. Table 3 shows the
dehydrogenation capacity comparison between theoretical and observed values, and it implies that
some of the hydrogenꢀcontaining compounds exist in the dehydrogenated product which was
revealed in the following.
Table 3 Dehydrogenation capacity of LiBH4ꢀH3BO3/HBO2/B2O3 composites. (unit: wt.%)
Composite
LiBH4ꢀH3BO3
LiBH4ꢀHBO2
LiBH4-B2O3
Theoretical capacity
Observed capacity
11.8
10.6
9.5
3.2 (110 °C)
8.6 (350 °C)
6.6 (340 °C)
0.5 (75 °C)
/
5.2 (300 °C)/ 5.8 (360 °C)
3.6 Microstructure of dehydrogenated LiBH4ꢀH3BO3/HBO2/B2O3 composites
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Figure 8 XRD patterns (a) and FTIR spectra (b) of pristine LiBH4, LiBH4ꢀH3BO3, LiBH4ꢀHBO2,
and LiBH4ꢀB2O3 composites after dehydrogenation. Destabilization effect between LiBH4 and
H3BO3/HBO2/B2O3 occurred during dehydrogenation.
Figure 8 shows the XRD patterns and FTIR spectra of pristine LiBH4, LiBH4ꢀH3BO3,
LiBH4ꢀHBO2, and LiBH4ꢀB2O3 composites after dehydrogenation. As revealed in Figure 8a,
diffraction peaks of Li4B2O5, LiB5O10H13 and Li3BO3 were clearly identified in the
dehydrogenated composites of LiBH4ꢀH3BO3 at 350 °C, LiBH4ꢀHBO2 at 340 °C, LiBH4ꢀB2O3 at
300 °C and 360 °C. Whereas, a possible diffraction peak of HBO2 together with peaks of LiBH4
were detected in the LiBH4ꢀH3BO3 composite dehydrogenated at 110 °C. And only the diffraction
peaks of LiBH4 were detected in the LiBH4ꢀHBO2 dehydrogenated at 75 °C. Furthermore, as
revealed by FTIR spectra in Figure 8b, the characteristic vibrations of BꢀH bond at 2385, 2291,
2223 and 1125 cmꢀ1 indicated that partial LiBH4 was remained in all the dehydrogenated
composites. For dehydrogenation of LiBH4ꢀH3BO3 at 350 °C, LiBH4ꢀHBO2 at 340 °C and
LiBH4ꢀB2O3 at 300 °C/360 °C, the BꢀH bond vibration at 2474 cmꢀ1 was visible declaring the
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formation of Li2B12H12[53]. Besides, bond vibrations from BꢀO, possibly even the overlapping
BꢀHꢀO vibration, at range of 1500ꢀ1200 cmꢀ1, 1100ꢀ900 cmꢀ1, 760ꢀ500 cmꢀ1 should be from
Li4B2O5, Li3BO3 and LiB5O10H13 which were revealed in XRD patterns shown in Figure 8a.
Unlike these FTIR spectra at high temperatures, not any new vibrations were detected in the
spectra of LiBH4ꢀHBO2 dehydrogenated at 75 °C.
According to the results above, remarkable dehydrogenation performance of those
composites is originated from the destabilization effect between LiBH4 and H3BO3/HBO2/B2O3.
Due to the same reaction products from LiBH4ꢀH3BO3, LiBH4ꢀHBO2, and LiBH4ꢀB2O3
composites at higher temperatures (>300 °C), the destabilization reaction equation is proposed as
following:
LiBH4 + H3BO3/HBO2/B2O3 → Li4B2O5 + LiB5O10H13 + Li3BO3 + Li2B12H12 + H2
3.7 Discussion
(3)
As revealed in this work, the coexistence of oxygen and hydrogen atoms in the form of
[OH]¯ show better destabilization effect on reducing the dehydrogenation temperature than that of
the LiBH4ꢀoxide and LiBH4ꢀmetal hydride systems [11ꢀ24]. The effect of [OH]¯ is implemented
through the [BH4]¯···[OH]¯ interaction emerging after milling of LiBH4 and H3BO3 as revealed in
Figure 1. Subsequently, we found that the observed capacity of LiBH4ꢀH3BO3 composite is much
lower than that of the composite’s theoretical value respectively, but very closed to the theoretical
capacity calculated from the H+ꢀH¯ coupling mechanism as shown in Table 2 [54]. These indicate
that the [BH4]¯···[OH]¯ interaction contributes to the enhancement of H+ꢀH¯ coupling leading to
the significant dehydrogenation improvement with respect to lower temperature and fast kinetics
as shown in Figure 2 and 3. Herein, it is also worthwhile to point out the tuning method to achieve
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superior dehydrogenation performance. Altering the molar ratio of LiBH4:H3BO3 is one of the
effective way to control the theoretical molar ratio of H+/H¯ . When three H+ in H3BO3 combines
with three H¯ in LiBH4, the 3LiBH4ꢀH3BO3 has a observed capacity of 3.3 wt.%; and
2LiBH4ꢀH3BO3 exhibits the best performance of 5.8 wt.% observed capacity. When four H+ from
H3BO3 combines with four H¯ from LiBH4, the observed values is reduced to 5.2 wt.% for
LiBH4ꢀ2H3BO3. Besides, it also reveals that HBO2 with less H¯ or B2O3 without H¯ leads to
limiting effect on reducing the dehydrogenation temperature and/or kinetics. Another way is to
increase the surface energy of the particle of LiBH4 and H3BO3 which will reduce the reaction
activation energy. Therefore, the composite from preꢀmilling treatment of LiBH4 and H3BO3
shows better dehydrogenation performance than the one from asꢀreceived of LiBH4 and H3BO3. At
the higher dehydrogenation temperature over 300 °C, hydrogen was released from the
hydrogenꢀcontaining compound LiꢀBꢀOꢀH or probably the reaction between residual LiBH4 and
HBO2 showing a similar behavior like LiBH4ꢀB2O3 composite.
We also found that the LiBH4ꢀH3BO3 composite showed partial reversibility under
appropriate rehydrogenation conditions (see ESI). This arises from the stable chemical stability of
the reaction products, and the reversibility improvement was still under way.
4. Conclusion
Focusing on the comprehensive target of lower dehydrogenation temperature, rapid kinetics,
pure hydrogen and high capacity, H3BO3/HBO2/B2O3 were found to display fascinating
improvement effect on the dehydrogenation of LiBH4 according to destabilization reaction. The
destabilization effectiveness is in the trend of H3BO3>HBO2>B2O3 which indicates the higher
[OH]¯ content benefit for enhancing the destabilization effect. Further investigation on
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LiBH4ꢀH3BO3 was carried out by altering the molar ratio of LiBH4 : H3BO3 and preꢀmilling
treatment of LiBH4 and H3BO3. The destabilization effectiveness is in the trend of
2LiBH4ꢀH3BO3>LiBH4ꢀ2H3BO3>3LiBH4ꢀH3BO3 and the preꢀmilled composites exhibit better
performance. 5.8 wt.% hydrogen is liberated in seconds at temperature as low as 110 °C from
2LiBH4ꢀH3BO3 prepared by preꢀmilling treatment of LiBH4 and H3BO3. The remarkable
destabilization improvement of H3BO3 on LiBH4 is attributed to the H+ꢀH¯ coupling mechanism,
and the appropriate molar ratio of [OH]¯ : [BH4]¯ and composite preparation treatment is found to
enhance the interaction between H+ and H¯.
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Acknowledgment
This work is financially supported by the Natural Science Foundation of China (Grants No.
51431001 and 5157010144), the Guangdong Natural Science Foundation (Grant No.
2014A030313222), the International Science & Technology Cooperation Program of China (Grant
No. 2015DFA51750), and the China Postdoctoral Science Foundation (Grant No. 2016M591982).
Research Fund for the Doctoral Program of Higher Education of China (Grant No.
20124420110007), Joint Training Project for Graduates Demonstration Base of Guangdong (Grant
No. 2013JDXM27), and the Guangdong Province Science & Technology Bureau (Grant No.
2016A010104) are also gratefully acknowledged.
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Reference
[1] H. J. Lin; J. J. Tang; Q. Yu; H. Wang; L. Z. Ouyang; Y. J. Zhao; J. W. Liu; W. H. Wang; M. Zhu,
Symbiotic CeH2.73/CeO2 catalyst: A novel hydrogen pump. Nano Energy, 2014. 9: 80ꢀ87.
[2] V. Stavila; R. K. Bhakta; T. M. Alam; E. H. Majzoub; M. D. Allendorf, Reversible Hydrogen
Storage by NaAlH4 Confined within
a TitaniumꢀFunctionalized MOFꢀ74(Mg)
Nanoreactor. ACS Nano, 2012. 6(11): 9807ꢀ9817.
[3] H. G. Pan; S. B. Shi; Y. F. Liu; B. Li; Y. J. Yang; M. X. Gao, Improved hydrogen storage
kinetics of the LiꢀMgꢀNꢀH system by addition of Mg(BH4)(2). Dalton Transactions, 2013.
42(11): 3802ꢀ3811.
[4] W. T. Cai; H. Wang; J. W. Liu; L. F. Jiao; Y. J. Wang; L. Z. Ouyang; T. Sun; D. L. Sun; H. H.
Wang; X. D. Yao; et al., Towards easy reversible dehydrogenation of LiBH4 by catalyzing
hierarchic nanostructured CoB. Nano Energy, 2014. 10: 235ꢀ244.
[5] L. H. Rude; T. K. Nielsen; D. B. Ravnsbæk; U. Bösenberg; M. B. Ley; B. Richter; L. M.
Arnbjerg; M. Dornheim; Y. Filinchuk; F. Besenbacher; T. R. Jensen, Tailoring properties
of borohydrides for hydrogen storage: a review. Physica Status Solidi (a), 2011. 208(8):
1754ꢀ1773.
[6] T. He; P. Pachfule; H. Wu; Q. Xu; P. Chen, Hydrogen carriers. Nature Reviews Materials, 2016.
1: 16059ꢀ16075.
[7] A. Züttel; P. Wenger; S. Rentsch; P. Sudan; P. Mauron; C. Emmenegger, LiBH4 a new
hydrogen storage material. Journal of Power Sources, 2003. 118(1ꢀ2): 1ꢀ7.
[8] A. Züttel; S. Rentsch; P. Fischer; P. Wenger; P. Sudan; P. Mauron; C. Emmenegger, Hydrogen
storage properties of LiBH4. Journal of Alloys and Compounds, 2003. 356-357: 515ꢀ520.
[9] P. Jena, Materials for Hydrogen Storage: Past, Present, and Future. The Journal of Physical
Chemistry Letters, 2011. 2: 206ꢀ211.
[10] S. Nakano; H. Fujihisa; H. Yamawaki; T. Kikegawa, Structural Analysis of Some
HighꢀPressure Stable and Metastable Phases in Lithium Borohydride LiBH4. Journal of
Physical Chemistry C, 2015. 119(8): 3911ꢀ3917.
[11] J. J. Vajo; S. L. Skeith; F. Mertens, Reversible Storage of Hydrogen in Destabilized LiBH4.
The Journal of Physical Chemistry B, 2005. 109(9): 3719ꢀ3722.
[12] X. B. Yu; D. M. Grant; G. S. Walker, Dehydrogenation of LiBH4 Destabilized with Various
Oxides. The Journal of Physical Chemistry C, 2009. 113(41): 17945ꢀ17949.
[13] Y. F. Zhou; Y. F. Liu; Y. Zhang; M. X. Gao; H. G. Pan, Functions of MgH2 in hydrogen
storage reactions of the 6LiBH4ꢀCaH2 reactive hydride composite. Dalton Transactions,
2012. 41(36): 10980ꢀ10987.
[14] M. Au; R. T. Walters, Reversibility aspect of Lithium borohydrides. International Journal of
Hydrogen Energy, 2010. 35(19): 10311ꢀ10316.
[15] K. B. Kim; J. H. Shim; Y. W. Cho; K. H. Oh, Pressureꢀenhanced dehydrogenation reaction of
the LiBH4ꢀYH3 composite. Chemical Communications, 2011. 47(35): 9831ꢀ9833.
[16] W. T. Cai; H. Wang; D. L. Sun; M. Zhu, NanosizeꢀControlled Reversibility for a
Destabilizing Reaction in the LiBH4–NdH2+x System. The Journal of Physical Chemistry
C, 2013. 117(19): 9566ꢀ9572.
[17] M. Au; A. Jurgensen, Modified Lithium Borohydrides for Reversible Hydrogen Storage. The
Journal of Physical Chemistry B, 2006. 110(13): 7062ꢀ7067.
21

Journal of Materials Chemistry A
Page 22 of 25
View Article Online
DOI: 10.1039/C7TA09376D
[18] Y. Zhang; W. S. Zhang; M. Q. Fan; S. S. Liu; H. L. Chu; Y. H. Zhang; X. Y. Gao; L. X. Sun,
Enhanced Hydrogen Storage Performance of LiBH4ꢀSiO2ꢀTiF3 Composite. The Journal of
Physical Chemistry C, 2008. 112(10): 4005ꢀ4010.
[19] Y. Zhang; Y. F. Liu; X. Zhang; Y. Li; M. X. Gao; H. G. Pan, Mechanistic understanding of
CoOꢀcatalyzed hydrogendesorption from a LiBH4 center dot NH3ꢀ3LiH system. Dalton
Transaction, 2015. 44(32): 14514ꢀ14522.
[20] X. L. Zheng; Y. S. Chua; Z. T. Xiong; W. D. Chen; Z. J. Jiang; G. T. Wu; P. Chen, The effect
of NH3 content on hydrogen release from LiBH4ꢀNH3 system. International Journal of
Hydrogen Energy, 2015. 40(13): 4573ꢀ4578.
[21] Z. Ding; X. Z. Zhao; L. L. Shaw, Reaction between LiBH4 and MgH2 induced by highꢀenergy
ball milling. Journal of Power Sources, 2015. 293(20): 236ꢀ245.
[22] H. Z. Liu; X. H. Wang; H. Zhou; S. C. Gao; H. W. Ge; S. Q. Li; M. Yan, Improved hydrogen
desorption properties of LiBH4 by AlH3 addition. International Journal of Hydrogen
Energy, 2016. 41(47): 22118ꢀ22127.
[23] Y. Li; P. Li; X. H. Qu, Investigation on LiBH4ꢀCaH2 composite and its potential for thermal
energy storage. Scientific Reports, 2017. 7: 41754.
[24] V. Shukla; A. Bhatnagar; P. K. Soni; A. K. Vishwakama; M. A. Shaz; T. P. Yadav; O. N.
Srivastava, Enhanced hydrogen sorption in a LiꢀMgꢀNꢀH system by the synergistic role of
Liꢀ4(NH2)(3)BH4 and ZrFe2. Physical Chemistry Chemical Physics, 2017. 19(14):
9444ꢀ9456.
[25] X. H. Xu; L. Zang; Y. R. Zhao; Y. Zhao; Y. J. Wang; L. F. Jiao, Hydrogen storage behavior of
LiBH4 improved by the confinement of hierarchical porous ZnO/ZnCo2O4 nanoparticles.
Journal of Power Sources, 2017. 359: 134ꢀ141.
[26] J. A. Puszkiel; M. V. C. Riglos; F. Karimi; A. Santoru; C. Pistidda; T. Klassen; J. M. B. von
Colbe; M. Domheim, Changing the dehydrogenation pathway of LiBH4ꢀMgH2 via
nanosized lithiated TiO2. Physical Chemistry Chemical Physics, 2017. 19(11):7455ꢀ7460.
[27] H. Z. Liu; X. H. Wang; H. Zhou; S. C. Gao; H. W. Ge; S. Q. Li; M. Yan, Improved hydrogen
desorption properties of LiBH4 by AlH3 addition. International Journal of Hydrogen
Energy, 2016. 41(47): 22118ꢀ22127.
[28] C. Liu; S. P. Huang, A firstꢀpriciples study of the tuning effect of a Fe2O3 cluster on the
dehydrogenation properties of a LiBH4 (001) surface. Dalton Transactions, 2016. 45(27):
10954ꢀ10959.
[29] K. B. Kim; J. H. Shim; S. H. Park; I. S. Choi; K. H. Oh; Y. W. Cho, Dehydrogenation reaction
pathway of the LiBH4ꢀMgH2 composite under various pressure conditions. Journal of
Physical Chemistry C, 2015. 119(18): 9714ꢀ9720.
[30] J. Shao; X. Z. Xiao; X. L. Fan; X. Huang; B. Zhai; S. Q. Li; H. W. Ge, Enhanced hydrogen
storage capacity and reversibility of LiBH4 nanoconfined in the densified zeoliteꢀtemplated
carbon with high mechanical stability. Nano Energy, 2015. 15: 244ꢀ255.
[31] A. Gasnier; F. C. Gennari, Graphene entanglement in mesoporous resorcinolꢀformadehyde
matrix applied to the nanoconfinement of LiBH4 for hydrogen storage. RSC Advances,
2017. 7(45): 27905ꢀ27912.
[32] X. F. Liu; D. Peaslee; C. Z. Jost; E. H. Majzoub, Controlling the Decomposition Pathway of
LiBH4 via Confinement in Highly Ordered Nanoporou Carbon. The Journal of Physical
Chemistry C, 2010. 114(33): 14036ꢀ14041.
22

Page 23 of 25
Journal of Materials Chemistry A
View Article Online
DOI: 10.1039/C7TA09376D
[33] X. F. Liu; D. Peaslee; C. Z. Jost; T. F. Baumann; E. H. Majzoub, Systematic PoreꢀSize Effects
of Nanoconfinement of LiBH4: Elimination of Diborane Release and Tunable Behavior
for Hydrogen Storage Applications. Chemistry of Materials, 2011. 23(5): 1331ꢀ1336.
[34] Y. Nakamori; K. Miwa; A. Ninomiya; H. W. Li; N. Ohba; S. I. Towata; A. Züttel; S. I. Orimo,
Correlation between thermodynamical stabilities of metal borohydrides and cation
electronegativites: Firstꢀprinciples calculations and experiments. Physical Review B, 2006.
74(4).
[35] M. B. Ley; L. H. Jepsen; Y. S. Lee; Y. W. Cho; J. M. B. von Colbe; M. Dornheim; M. Rokni;
J. O. Jensen; M. Sloth; Y. Filinchuk; et al., Complex hydrides for hydrogen storage – new
perspectives. Materials Today, 2014. 17(3): 122ꢀ128.
[36] H. W. Li; S. Orimo; Y. Nakamori; K. Miwa; N. Ohba; S. Towata; A. Züttel, Materials
designing of metal borohydrides: Viewpoints from thermodynamical stabilities. Journal
of Alloys and Compounds, 2007. 446-447: 315ꢀ318.
[37] D. Ravnsbæk; Y. Filinchuk; Y. Cerenius; H. J. Jakobsen; F. Besenbacher; J. Skibsted; T. R.
Jensen, A Series of MixedꢀMetal Borohydrides. Angewandte Chemie International
Edition, 2009. 48(36): 6659ꢀ6663.
[38] I. Lindemann; R. D. Ferrer; L. Dunsch; Y, Filinchuk; R. Černý; H, Hagemann; V. D'Anna; L.
M. L. Daku; L. Schultz; O. Gutfleisch, Al3Li4(BH4)13: A Complex doubleꢀCation
Borohydride with a New Structure. Chemistry-A European Journal, 2010. 16(29):
8707ꢀ8712.
[39] D. B. Ravnsbæk; L. H. Sørensen; Y. Filinchuk; F. Besenbacher; T. R. Jensen, Screening of
Metal Borohydrides by Mechanochemistry and Diffraction. Angewandte Chemie
International Edition, 2012. 51(15): 3582ꢀ3586.
[40] D. B. Ravnsbæk; Y. Filinchuk; Y. Cerenius; H. J. Jakobsen; F. Besenbacher; J. Skibsted; T. R.
Jensen, A Series of MixedꢀMetal Borohydrides. Angewandte Chemie International
Edition, 2009. 121(36): 6787ꢀ6791.
[41] E. Roedern; Y. S. Lee; M. B. Ley; K. Park; Y. W. Cho; J. Skibsted; T. R. Jensen, Solid state
synthesis, structural characterization and ionic conductivity of bimetallic alkaliꢀmetal yttrium
borohydrides MY(BH4)4 (M = Li and Na). Journal of Materials Chemistry A, 2016. 22(4):
8793ꢀ8802.
[42] B. Richter; D. B. Ravnsbæk; M. Sharma; A. Spyratou; H. Hagemann; T. R. Jensen, Fluoride
substitution in LiBH4; destabilization and decomposition. Physical Chemistry Chemical
Physics, 2017. 44(19): 30157ꢀ30165.
[43] L. C. Yin; P. Wang; Z. Z. Fang; H. M. Cheng, Thermodynamically tuning LiBH4 by fluorine
anion doping for hydrogen storage: A density functional study. Chemical Physics Letters,
2008. 450(4–6): 318ꢀ321.
[44] Y. H. Guo; G. L. Xia; Y. H. Zhu; L. Gao; X. B. Yu, Hydrogen release from amminelithium
borohydride, LiBH4*NH3. Chemical Communications, 2010. 46(15): 2599ꢀ2601.
[45] J. H. Luo; H. Wu; W. Zhou; X. D. Kang; Z. Z. Fang; P. Wang, LiBH4•NH3BH3: A new
lithium borohydride ammonia borane compound with a novel structure and favorable
hydrogen storage properties. International Journal of Hydrogen Energy, 2012. 37(14):
10750ꢀ10757.
[46] T. He; H. Wu; G. T. Wu; J. H. Wang; W. Zhou; Z. T. Xiong; J. E. Chen; T. Zhang; P. Chen,
Borohydride hydrazinates: high hydrogen content materials for hydrogen storage. Energy
23

Journal of Materials Chemistry A
Page 24 of 25
View Article Online
DOI: 10.1039/C7TA09376D
& Environmental Science, 2012. 5(2): 5686ꢀ5689.
[47] X. L. Zheng; G. T. Wu; W. L; Z. T. Xiong; T. He; J. P. Guo; H. Chen; P. Chen, Releasing 17.8
wt.% H2 from lithium borohydride ammoniate. Energy & Environmental Science, 2011.
4(9): 3593ꢀ3600.
[48] S. F. Li; W. W. Sun; Z. W. Tang; Y. H. Guo; X. B. Yu, Nanoconfinement of LiBH4•NH3
towards enhanced hydrogen generation. International Journal of Hydrogen Energy, 2012.
37(4): 3328ꢀ3337.
[49] B. C. Weng; Z. Wu; Z. L. Li; H. Yang; H. Y. Leng, Hydrogen generation from noncatalytic
hydrolysis of LiBH4/NH3BH3 mixture for fuel cell applications, 2011. 36(17):
10870ꢀ10876.
[50] Y. Zhang; Y. F. Liu; X. Zhang; Y. Li; M. X. Gao; H. G. Pan, Synthesis of a nanosized
carbonꢀsupported Ni composite and its remarkable catalysis for hydrogen desorption from
the LiBH4ꢀ2LiNH2 system. Journal of Physical Chemistry C, 2015. 119(44):
24760ꢀ24768.
[51] Y. G. Yan; A. Remhof; S. J. Hwang; H. W. Li; P. Mauron; S. i. Orimo; A. Züttel, Pressure and
temperature dependence of the decomposition pathway of LiBH4. Physical Chemistry
Chemical Physics, 2012. 14(18): 6514ꢀ6519.
[52] B. M. Concha; M. Chatenet; F. Maillard; E. A. Ticianelli; F. H. B. Lima; R. B. de Lima, In
situ infrared (FTIR) study of the mechanism of the borohydride oxidation reaction.
Physical Chemistry Chemical Physics, 2010. 12(37): 11507ꢀ11516.
[53] M. P. Pitt; M. Paskevicius; D. H. Brown; D. A. Sheppard; C. E. Buckley, Thermal Stabi lity
of Li2B12H12 and its Role in the Decomposition of LiBH4. Journal of the American
Chemical Society, 2013. 135(18): 6930ꢀ6941.
[54] P. Chen; M. Zhu, Recent progress in hydrogen storage. Materials Today, 2008. 11(12): 36ꢀ43.
[55] S. A. Jin; Y. S. Lee; J. H. Shim; Y. W. Cho, Reversible hydrogen storage in LiBH4ꢀMH2
(M=Ce, Ca) compositions. The Journal of Physical Chemistry C, 2008. 112(25):
9520ꢀ9524.
[56] Y. Nakamori; H. W. Li; K. Kikuchi; M. Aoki; K. Miwa; S. Towata; S. Orimo,
Thermodynamical stabilities of metalꢀborohydrides. Journal of Alloys and Compounds,
2007. 446-447: 296ꢀ300.
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Table of contents
LiBH4ꢀH3BO3 destabilization system shows significantly lower temperature,
rapid kinetics, pure hydrogen and high capacity through [BH4]¯···[OH]¯ interaction.