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Review

Research progress in LiBH4 for hydrogen storage: A review


C. Li a,b,*, P. Peng b, D.W. Zhou a, L. Wan b
a b

State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body, Hunan University, Changsha 410082, China School of Materials Science and Engineering, Hunan University, Changsha 410082, China

article info
Article history: Received 11 June 2011 Received in revised form 2 August 2011 Accepted 9 August 2011 Available online 3 September 2011 Keywords: Hydrogen storage materials LiBH4 Complex hydrides Review

abstract
Hydrogen is considered as the ideal candidate as an energy carrier for both mobile and stationary applications. However, the lack of efcient onboard hydrogen storage technology is becoming one of great obstacles impeding their industrial applications. Lithium borohydride (LiBH4) has been attracting a great deal of attention as a hydrogen storage material with high gravimetric hydrogen capacity. This manuscript about LiBH4 includes the synthesis, hydrolysis, structure, dynamics, intermediate compound, and the de/rehydrogenation properties improvement of LiBH4. LiBH4 can be synthesized by several methods, for example, direct synthesis from elements. In the hydrolysis of LiBH4 with the liberation of hydrogen gas, the byproduct will be different under different conditions. Structurally, LiBH4 has four different phases in experiment: Pnma, P63mc, Ama2 and Fm-3m. Dynamically, the high temperature (HT) phase of LiBH4 is a lithium fast-ion conductor. In the hydrogen desorption reaction of LiBH4, Li2B12H12 among the possible intermediate compounds is studied the most. Several methods have been proposed to improve the de/ rehydrogenation properties of LiBH4. The rst method is destabilization of the LiBH4. The second one is the use of catalyst. The third one is nanoscaffolding incorporation. The de/ rehydrogenation properties of LiBH4 have been changed considerably through the great efforts of researchers in recent years. Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

The inevitable exhaustion of petroleum reserves and other non-renewable energy necessitates the development of new energy sources. Hydrogen would be ideal as a synthetic fuel because it is lightweight, highly abundant and its oxidation product (water) is environmentally benign. A future hydrogen economy requires dense, safe, efcient and reversible hydrogen storage materials. Solid-state media are an advantageous alternatives for reversible and safe storage

compared with either liquid hydrogen tanks or compressed hydrogen gas, both of which require a large amount of energy and can pose serious safety risks [1]. In addition, a capacity of 5.5 wt.% is regarded as the target for onboard hydrogen storage by the U.S Department of Energy (DOE) for 2015 [2]. Various hydrogen storage materials, such as metal hydrides, nanocarbon materials, complex metal hydrides and metalorganic frame-works (MOFs), have been investigated. Among these materials, LiBH4 is one of the promising materials for hydrogen storage due to its high gravimetric and

* Corresponding author. School of Materials Science and Engineering, Hunan University, Changsha 410082, China. Tel.: 86 15873142062. E-mail address: lichuang4795@163.com (C. Li). 0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2011.08.030

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volumetric hydrogen densities of 18.5 wt.% and 121 kg H2/m3, respectively [3e7]. In this paper, we reviewed the recent progress in LiBH4, including the synthesis, hydrolysis, structure, dynamics, and intermediate compounds of LiBH4. The desorption of hydrogen of LiBH4 need harsh conditions. There are several methods to improve the de/rehydrogenation properties of LiBH4. The rst method is destabilization of the LiBH4. The systems of bimetallic borohydrides, LiBH4 and hydride, LiBH4LiNH2, LiNH2-MgH2-LiBH4, hydride and boride, and density functional theory (DFT) calculation results are reviewed. The second one is the use of catalyst. We reviewed the systems of LiBH4, LiBH4-MgH2, LiBH4 and other materials with the addition of catalysts. The third one is nanoengineering to conne LiBH4 in mesoporous scaffolds or mix LiBH4 with nanotubes and mesoporous gels. The recent research results are also reviewed.

2.

Synthesis

LiBH4 is salt-like and sensitive to moisture not to oxygen, which is a crystalline material with melting point at 275  C or 278  C and densities 0.681 or 0.66 g cm3 at 25  C [4,8,9]. In 1940, Schlesinger et al. [8] synthesized LiBH4 by the reaction of ethyl lithium with diborane (B2H6). The direct reaction (Eq. (1)) of LiH with diborane under suitable conditions can also synthesizes LiBH4 [10,11]. LiH 1=2B2 H6 /LiBH4 (1)

that LiBH4 have the potential to be a useful hydrogen storage compound. Hydrolysis of organics combined LiBH4 and NaBH4 was studied by Aiello et al. [21] in 1998. Results showed that with less violent reactions, these compounds were successful to produce hydrogen. Kong et al. [22] found that LiBH4 did not react with water vapor at room temperature. Hydrolysis of LiBH4 is high exothermic and can make the temperature of the reaction vessel rise to 202  C [23]. The hydrolysis reactions of LiBH4 are: LiBH4 4H2O / LiOH H3BO3 4H2 [24] and LiBH4 2H2O / LiBO2 4H2 [25]. It was indicated that the H2 yield by the hydrolysis reaction of LiBH4 was accelerated by adding a small amount of water (H2O/ LiBH4 0.3e2 mol/mol). The gravimetric and the volumetric hydrogen densities had maximum values at H2O/LiBH4 of 1:3 mol/mol (gravimetric and hydrogen density per unit weight of LiBH4 and H2O are 7.4 wt.% and 60 kgH2/m3, respectively). The structure of the byproduct below H2O/LiBH4 0.33 is LiBO2, while that at H2O/LiBH4 2 is LiBO2$2H2O. Then the byproduct between H2O/LiBH4 of 0.33 and 2 is a mixture of LiBO2 and LiBO2$2H2O [26]. Laversenne et al. [27] determined the stability of metaborate hydrates produced by the hydrolysis of LiBH4 and found that for lithium metaborate: LiBO2$2H2O is stable from ambient temperature up to 120  C, LiBO2$1/2H2O stable from 120 to 220  C, which breaks down above 220  C to form LiBO2$1/ 3H2O, which is stable up to 255  C. It is found that LiBH4 powder reacts spontaneously with steam including two major steps as following [28]: LiBH4 s 4H2 Og/LiBO2 $2H2 Os 4H2 g LiBO2 $2H2 Os/LiBO2 s 2H2 Og (5) (6)

The chemical industry synthesizes LiBH4 in a wet chemical reaction with solvents of ether or isopropyl amine, by a metathesis of NaBH4 with Li halides or chlorides [12,13]: NaBH4 LiBr/LiBH4 NaBr NaBH4 LiCl/LiBH4 NaCl (2) (3)

Direct synthesis from the metal, boron, and hydrogen (Eq. (4)) at 550e700  C and 3e15.5 MPa H2 has been reported to yield LiBH4, and this method is generally applicable to group IA and IIA metals [3,4,14,15]. The chemical inertness of boron prohibits its reaction with lithium and hydrogen to LiBH4 at lower temperatures. The reaction kinetics can be enhanced by forming a binary LiBx compound (e.g., Li7B6, LiB3, and LiB, etc.) [14,16,17]. Li B 2H2 /LiBH4 (4)

Wang et al. [18] investigated the adsorption of H2 molecules on LiB (0 1 0) surface by rst-principles calculations. It was found that H2 adsorbed on the LieB bridge site is more favorable than the other three sites (Li-top, B-top and hollow vertical). The adsorption belongs to a strong chemical adsorption.

3.

Hydrolysis

Hydrolysis is dened as the reaction of a hydride with water to liberate hydrogen gas [19]. Aiello et al. [20] studied LiBH4 for hydrogen production via hydrolysis with steam, and showed

Zhu et al. [29] found that the hydrolysis reaction of LiBH4 was fast, but never produced more than 50% of its theoretical yield because the products form a solid and impermeable mass clogging the reaction vessel, thus limit the full utilization of the hydride. In order to completely release the stoichiometric amount of H2 from LiBH4 hydrolysis, multiwalled carbon nanotubes (MWCNTs) were doped with LiBH4 by mechanical milling. The results show that MWCNTs carried LiBH4 can slowly react with water vapor at room temperature which is 25  C lower than the reaction temperature of neat LiBH4. Agglomeration can be avoided when the addition of MWCNTs exceeds 7wt.%, which results in a complete hydrolysis process [30]. Hydrolysis performance of LiBH4eNH3BH3 mixture was also investigated. The mixture can fully release its theoretical amount of hydrogen at room temperature without catalysts. In the presence of LiBH4, NH3BH3 can be fully hydrolyzed at room temperature. In return, in the presence of NH3BH3, the agglomeration can be avoided to result in a complete hydrolysis process [23]. A stoichiometric amount of hydrogen was generated by catalytic hydrolysis reaction of lithium borohydride solution over nano-sized platinum dispersed on LiCoO2 (Pt-LiCoO2) [31]. The corrosion characteristics of LiBH4 lms were measured by exposing them to a gas mixture of CO2/H2O/O2/N2 at ambient temperature for 1e24 h LiBH4 tends to react with H2O and CO2 to form Li2B4O7, Li2CO3 and LiOH during the corrosion process [32]. The surface oxidation induces the formation of a Li2O layer on LiBH4 [33].

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4.

Structure

In 1947, Harris et al. [34] reported that LiBH4 has an orthorhombic structure (space group Pcmn) with cell dimensions , b 4.43 A , and c 7.17 A . Soulie et al. [35] reported a 6.81 A that LiBH4 has orthorhombic symmetry (space group Pnma, , b 4.43686 A , c 6.80321 A ) by synchrotron a 7.17858 A X-ray powder diffraction at room temperature. In this structure each [BH4] anion is surrounded by four lithium Li cations and each Li by four [BH4], both in tetrahedral congurations. The [BH4] ions were strongly distorted from the ideal tetrahedral geometry. The same Pnma structure was also reported by Zu ttel et al. [9]. Nakamori et al. [36] found that the BH4 complexes has a nearly ideal tetrahedral shape by rst-principles calculations. At 408 K the Pnma structure transforms into a hexagonal phase (space group P63mc, , c 6.94844 A ) [35]. However, this P63mc structure a 4.27631 A was found to have imaginary normal modes of vibration in the theoretical calculations and a monoclinic structure with symmetry group Cc was proposed for the high-temperature phase of LiBH4 [37]. Using DFT calculations, Frankcombe et al. [38] found the Pnma structure to be the most stable of all considered phases for pressures below 1.0 GPa, above which the P2/c structure becomes more stable. Based on the closely related structure types, Vajeeston et al. [39] proposed that LiBH4 may have the structure of P42/nmc and P-421c. Hartman et al. [40] investigated the crystalline structure of LiBH4 using neutron powder diffraction. They found the Pnma structure with a nearly ideal tetrahedral [BH4] ions for the low temperature structure and the P63mc structure for the high-temperature phase. The phase transition occurs at 384 K. Filinchuk et al. [41] gained almost the same results as Hartman et al. [40] using a single crystal synchrotron diffraction, but the phase transition temperature is 381 K. Filinchuk et al. [42] found that at room temperature and a pressure of 1.2e10 GPa, LiBH4 forms a new phase with pseudotetragonal Ama2 structure. Where Li atoms are tetrahedrally coordinated by BH4 groups and the BH4 group has a totally new nearly square-planar coordination by four Li atoms. Above 10 GPa, LiBH4 forms a cubic phase with Fm-3m structure. Li atoms and BH4 groups are octahedrally coordinated. Recently, based on rst-principles density functional theory calculations, a new stable orthogonal structure with , Pnma symmetry was found (Lattice parameters, a 8.484 A , c 5.750 A ). For the high-temperature structure, b 4.348 A a new monoclinic P2/c structure was suggested [43].

Furthermore, in the low temperature orthorhombic phase, the charge transfer from the Li cation to the BD4 anion is 0.86(9) e, which is in good agreement with the ab initio calculated value of 0.895 e [44]. Theory and experiment agreed only on the symmetry of the room temperature, ambient-pressure polymorph of LiBH4. Experimental high temperature structure is indeed P63mc. Experimental investigations of LiBH4 are difcult owing to the weak diffracting power of the light elements for X-ray diffraction (XRD) and considerable incoherent scattering by H and high absorption by natural B and Li for neutron diffraction [42]. The DFT structure prediction has not been quite successful for LiBH4, due to the poor modeling of structure dynamics beyond the harmonic approach. The situation is particularly bad at high temperatures, where the entropy factors are very important. The crystal structure of various LiBH4 phases as shown in Fig.1. The experimental structure parameters of LiBH4 phases as shown in Table 1 [9,35,40e42,45]. The high temperature and high-pressure effects on LiBH4 have been investigated [42,46e50]. Based on the works of Pistorius [49] and Dmitiev et al. [50], the phase diagram of LiBH4 was given by Sundqvist et al. [47].

5.

Dynamics

To understand the mechanism of dehydrogenation better, intensive investigations on the dynamics have been performed, including the rotation and vibration motions of BH4 tetrahedra; the atomic motions of H, Li, and B; HeD exchange in BH4 units [35,40e42,51e79]. In the low temperature (LT) phase of LiBH4, reorientational motion of the BH4 groups is rapid and controls the spin lattice relaxation time [69]. Diffraction in the HT phase reports large thermal ellipsoids of the D atoms, suggesting orientational disorder in this phase [40,41]. In the HT phase of LiBH4, the  motion of the BH 4 ion is dominated by 90 reorientations while it displays a threefold jump behavior in the LT phase of LiBH4 [53]. In the solid state, rotational jump diffusion of the BH4 units is on the picosecond scale. The phase transition at 383 K is accompanied by a sudden increase of the rotational motion. In the liquid state, the translational diffusion of the BH4 ions was observed. The measured diffusion coefcients are in the 105 cm2 s1 range at temperature around 700 K [74]. Potential energy landscape for rotation of BH4 indicates that fairly localized minima and barriers higher than 0.6 eV exist in

Fig. 1 e Crystal structure of the LiBH4 phases: Pnma (a), P63mc (b), Ama2 (c) and Fm-3m (d).

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Table 1 e Experimental structural data of LiBH4 phases. Ref.


et al. [35] Soulie Zu ttel et al. [9] Hartman et al. [40] Hartman et al. [40] Filinchuk et al. [41] et al. [35] Soulie Hartman et al. [40] Filinchuk et al. [41] Filinchuk et al.[42] Filinchuk et al. [42]

Space group T(K)


Pnma 293 K Pnma 298 K Pnma 3.5 K Pnma 360 K Pnma 225 K P63mc 408 K P63mc 400 K P63mc 535 K Ama2 (2.4 GPa) Fm3m (18.1 GPa)

) a (A
7.17858 7.1730 7.1213 7.1914 7.141 4.27631 4.2667 4.3228 6.4494 5.109

) b (A
4.43686 4.4340 4.4060 4.4256 4.431 e e e 5.307 e

) c (A
6.80321 6.7976 6.6744 6.8641 6.748 6.94844 6.9223 7.0368 5.2919 e

) BeH (A
1.04e1.28 1.28e1.44 1.208e1.225 1.184e1.217 1.104e1.131 1.27e1.29 0.96e1.02 1.05e1.11 1.153e1.890 1.150

HeBeH( )
85.1e120.1 60e131 107.2e111.7 105.4e111.8 108.8e109.9 106.4e112.4 106e112 108e111 105.2e119.4 109.5

the LT phase, i.e., ordered BH4 ions. The HT structure shows shallow barriers of w0.2 eV without distinct energy minima, i.e., orientation of a single BH4 unit cannot be precisely dened [58]. The mechanism of hydrogen diffusion in LiBH4 is as follows: Hydrogen is directly exchanged between BH4 units at an extremely low rate and then transported through the ionic crystal by intact [BH4]units at diffusion rates similar to rates in isoelectronic ionic compounds. This results in an effectively fast diffusion of hydrogen, the self-diffusion constant of deuterium in LiBH4 is estimated to be D 7 1014 m2 s1 (473 K, 523 K) [57,77] and the value calculated by ab initio molecular dynamics is around 1.42 108 m2 s1 [55]. The hydrogens diffuse increasingly rapidly at 120e170  C and the boron atoms also diffuse rapidly at temperatures above 200  C. The HT phase has very rapid lithium ion diffusion [61]. The hydrogen atom is transported through the LiBH4 crystal even at temperatures below melting [56]. First principles calculations suggest that mobility of H in solid borohydrides is dominated by neutral interstitial H2, not charged defects [51]. In liquid LiBH4, exchange of hydrogen atoms between BH4 units is slow on the time scale of seconds [52]. In 2007, Matsuo et al. [70] rstly reported that the hexagonal phase exhibited a high electrical conductivity due to the Li superionic conduction. The ion conductivity in LiBH4 can be signicantly improved for the solid solutions LiBH4eLiX, X Cl, Br, I, and may be of importance for solid state lithium battery applications [70,75,80e85]. The complex hydrides consisting of combinations of the [BH4]1 and [NH2]1 anions, Li2BNH6 and Li4BN3H10, as lithium fast-ion conductors were also studied [86].

LiBH4 by Raman measurements [92] and NMR spectroscopy [93]. Friedrichs et al. [94,95] proposed an alternative hypothesis: Li2B12H12 is not a genuine decomposition product but a product of a side reaction, coming from interaction between the borane evolving from LiBH4 with the remaining LiBH4. 2LiBH4 5B2 H6 /Li2 B12 H12 13H2 (7)

The anhydrous Li2B12H12 exists as a white powder [96]. Theory calculations show that the structure of Li2B12H12 is C2/ m (No. 12) or P21/n (No. 14) [91,97]. But experimental results show that the real structure of Li2B12H12 is Pa-3 with cell [98,99]. As shown in Fig. 2(a), Li cation dimension a 9.5771 A lies on a near-trigonal-planar site formed by three [B12H12]2 anions, each of which resides in the octahedral cage dened by six Li cations. Each [B12H12]2 anion orients two H atoms to each of the Li cations, resulting in a strongly distorted octahedral coordination of the Li cation with six H atoms [99]. The structure of [B12H12]2 anion is a regular icosahedron of boron atoms with terminal B-H bonds as shown in Fig. 2(b) [93]. The following equation of LiBH4 dehydriding reaction via Li2B12H12 is proposed [91,92]: LiBH4 41=12Li2 B12 H12 5=6LiH 13=12H2 4LiH B 3=2H2 (8)

7. Dehydrogenation/rehydrogenation properties improvement of LiBH4


The main evolution of hydrogen starts above 380  C and only releases half of the hydrogen below 600  C [87]. The enthalpy DH and entropy DS of dehydrogenation were found to be 74 kJ mol1 H2 and 115 J K1 mol1 H2, respectively, based on

6.

Intermediate compound

At a low heating rate of 0.5 and 1 K min1, three distinct desorption peaks of LiBH4 were observed. This indicates that the hydrogen desorption reaction is divided into at least three steps with intermediate products [4,9,87,88]. The multistep reaction pathway together with the formation of an intermediate compound might account for the high reaction temperature and slow kinetics [89,90]. The rst-principles calculation suggested that monoclinic Li2B12H12 is the most stable among the candidate intermediate materials [91]. The formation of Li2B12H12 was observed during desorption of

Fig. 2 e Structure of Li2B12H12 (a) and B12 H12 2L anion (b).

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the pressure-concentration-temperature (PCT) isotherm measurement [15]. The hydrogen desorption reaction of LiBH4 is reversible, in which the end products LiH and boron absorb hydrogen at 600  C and 35 MPa to form LiBH4. The absorption reaction requires a long time (>12 h) and it is not necessarily completed [4100]. These conditions are too high to meet the requirement of the fuel cell operation. It has been proposed several methods to improve the de/rehydrogenation properties of LiBH4. The rst method deals with addition of metal, metal halides, oxides, amides, or metal hydrides to form composites or alloys after dehydrogenation. This approach is also referred to as destabilization of the LiBH4. The second approach is the use of catalysts. The third method is nanoengineering to conne LiBH4 in mesoporous scaffolds or mix LiBH4 with nanotubes and mesoporous gels [90,101,102].

higher pressures rst decomposition of MgH2 and subsequently simultaneous decomposition of LiBH4 and formation of MgB2 can be observed. The simultaneous decomposition of MgH2 and LiBH4 along with the formation of MgB2 and LiH could not be observed. Dehydrogenation of the LiBH4-MgH2 destabilized system process as follows: 2LiBH4 MgH2 /2LiH MgB2 4H2 11:6 wt% theoretical hydrogen capacity (11)

7.1. 7.1.1.

Reactant destabilization Bimetallic borohydrides

Orimo et al. [103,104] found that the thermodynamic stability of the ionic borohydrides can be correlated fairly well with the pauling electronegativity of the metal cations. According to this principle, an approach of producing multi-cation borohydrides MLi(BH4)m, in which M and M0 have different electronegativities, has been proposed to precisely tailor the thermodynamic stability. Several typical samples has been synthesized, including LiZr(BH4)5, Li2Zr(BH4)6, LiK(BH4)2, LiMn(BH4)3, LiSc(BH4)4, LiZn2(BH4)5 etc Al3Li4(BH4)13, [45,103,105e115].. Most of the MLi(BH4)m exhibit moderate thermodynamic stabilities between M(BH4)n and LiBH4. But borohydride structures containing complex anions, such as MSc(BH4)4 or MZn2(BH4)5, show only minor variations in the decomposition temperature with changes in alkali metal. The complex anions plays a key role in the structural stability of bimetallic borohydrides [116]. There are two ways to synthesize MLi(BH4)m. One is mechanical milling of the LiBH4/M(BH4)n mixture [105,113,114]. The other mechanochemical synthesis route was based on the following reaction [103]: MCln mLiBH4 /MLimn BH4 m nLiCl (9)

Walker et al. [128e131] found the formation of a Li-Mg alloy during desorption up to temperatures of 550  C and no formation of MgB2 under dynamic vacuum. Slow partial reabsorption from the Li-Mg alloy to LiBD4 and MgD2 without observing the formation of MgB2 in the desorbed state was observed. The effect of stoichiometry has only shown a change in the fraction of reaction products, not in the basic mechanism. LiBH4 can be modied by ball-milling with Al or Alcontaining compounds [119,120,122,135e140]. During cycling, AlB2 is formed in the dehydrogenated state and disappears in the hydrogenated state; its formation increases the stability of the products and thus results in a lower desorption temperature. Kang et al. [135] found that LiBH4-Al system possesses a theoretical capacity of 8.5 wt.% and could be reversibly operated at 400e450  C. The 6LiBH4-CaH2 composite has recently received much attention, as it can store a large amount of hydrogen through the following reaction [97,119,120,141e148]: 6LiBH4 CaH2 /6LiH CaB6 10H2 11:7 wt% (12)

The dehydrogenation reaction enthalpy of Eq. (12) is in the range of 40.7e60.2 (kJ/mol H2) [146,148,149]. Cho et al. [142e145] found that back pressure of hydrogen remarkably promotes the formation of metal boride during the dehydrogenation of 6LiBH4-CaH2 composite. The effect of CeH2, YH3 and ScH2 on the dehydrogenation of LiBH4 was also studied [142,143,150,151]. The reactions are: ScH2 2LiBH4 /ScB2 2LiH 4H2 8:91 wt% 6LiBH4 CeH2 /6LiH CeB6 10H2 7:4 wt% 4LiBH4 YH3 /4LiH YB4 7:5H2 8:5 wt% (13) (14) (15)

It worth noting that the starting materials of Eq. (9) can also synthesize the other tetrahydroborate such as Y(BH4)3, R(BH4)3, Zr(BH4)4 etc [117,118].. The reaction was expected to proceed as follows: MCln nLiBH4 /MBH4 n nLiCl (10)

7.1.2.

LiBH4 and hydride

A typical example for destabilization of the LiBH4 is the 2LiBH4-MgH2 system [119e133]. Mg were also used as a destablizing mixture [120,134]. Vajo et al. [123e125] obtained enhanced hydrogen sorption properties when MgH2 was added to LiBH4. Formation of MgB2 upon dehydrogenation reduces the de/rehydrogenation enthalpy by 25 kJ/(mol of H2) compared with pure LiBH4. The reversibility was also improved. Bo senberg et al. [126,127] found that at high temperatures and low pressures, independent decomposition of all hydrides and subsequent formation of MgB2 are observed, whereas at slightly lower temperatures and slightly

For the ScH2-2LiBH4 system, it was found that desorption of H2 is consistent with only thermal decomposition of LiBH4 and not the reaction of equation 13. The data provide no evidence that ScH2 has participated in the reaction and the expected ScB2 equilibrium product phase has not formed during desorption [150].

7.1.3.

LiBH4-LiNH2

It was revealed that LiBH4 is destabilized by mixing with LiNH2 and the mixture desorbs a large amount of hydrogen [121,152e160]. Pinkerton et al. [152e155,160] synthesized a new quaternary hydride with the approximate composition Li3BN2H8 by combining LiNH2 and LiBH4 powders in a 2:1 M ratio. This quaternary hydride with 11.9 wt.% theoretical hydrogen capacity melts at w190  C and releases !10 wt % hydrogen above w250  C. A small amount of ammonia

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(2e3 mol % of the generated gas) is released simultaneously. Tuning the particle size to the nanometer scale by inltration into nanoporous carbon scaffolds leads to dramatic improvements in the reversibility of Li3BN2H8 [155]. XRD results on single crystals of this Li3BN2H8 reveal that its true equilibrium composition is Li4BN3H10 [159,161,162]. The crystal structure of Li4BN3H10 in the cubic space group I213 with with an ordered arrangelattice parameters a 10.58e10.68 A 1 1 ment of [NH2] and [BH4] anions in a molar ratio of 3:1 [162e166]. The crystal structures of Li2BNH6 (LiBH4:LiNH2 1:1) is R-3 (No.148) [166]. Herbst et al. [163] suggested Li4BN3H10 / Li3BN2 1/2Li2NH 1/2NH3 4H2 as the likely dehydriding route, but Siegel et al. [165] found that the favored dehydrogenation reaction is Li4BN3H10 / Li3BN2 LiNH2 4H2. Li4BN3H10 has several disadvantages as a source of hydrogen: (1) the hydrogen release temperature 250  C is still rather high, (2) a small quantity of undesirable NH3 is produced simultaneously with H2 release, and (3) hydrogen release is exothermic and rehydrogenation is thus not thermodynamically favored. When Ni in the form of NiCl2 is added as a dehydrogenation catalyst, the H2 release temperature of Li4BN3H10 is less than 235  C [153,160].

by diffusion [132]. The long-time ball milling has led to the partial exchange of the Mg2 ions in the MgB2 crystal with the Li ions from the LiH crystal [179,180]. It is found that the solidstate hydriding proceeds in two elementary steps as shown below [101]: 2LiH MgB2 / Mg1x Li2x B2 xMgH2 2 2xLiH Mg1x Li2x B2 2 2xLiH 4H2 /2LiBH4 MgH2 (21)

(22)

7.1.4.

LiNH2-MgH2-LiBH4

The ternary LiNH2-MgH2-LiBH4 hydrogen storage system was investigated [167e173]. Yang et al. [167] reported the formation of a new self-catalyzed complex hydride by the mechanical milling of LiBH4-LiNH2-MgH2 in ratio of 1:2:1. This mixture was shown to release up to 4 wt.% hydrogen for temperatures starting at 423 K via multiple reactions. The onset of hydrogen release of the mixture could be reduced to 353 K via nanoscale engineering of the powders [172]. The reactions as follows [167]: 3LiNH2 LiBH4 /Li4 BN3 H10 2Li4 BN3 H10 3MgH2 /3MgNH2 2 2LiBH4 6LiH 2Li4 BN3 H10 3MgH2 /3Li2 MgNH2 2LiBH4 6H2 MgNH2 2 LiH/Li2 MgNH2 2H2 3Li2 MgNH2 2LiBH4 /2Li3 BN2 Mg3 N2 2LiH 6H2 (16) (17) (18) (19) (20)

Mn can enhance the hydriding kinetics of the 2LiH-MgB2 mixture, while V does not. The major factor in enhancing the hydriding kinetics is related to the dopants ability to induce the lattice distortion of MgB2 crystals [175]. Ti, TiH2, TiB2 improve both hydrogenation and dehydrogenation kinetics of MgB2-LiH system. TiF3 and TiCl3 additives can greatly enhance the dehydrogenation kinetics of the LiH/MgB2 mixture [177]. Remhof et al. [181] observed the synthesis of LiBD4 from AlB2, LiD and D2 and the cycling behavior of the reaction 2LiD AlB2 3D2 4 2LiBD4 Al by in situ neutron diffraction. LiBD4 forms at 450  C in an applied D2 atmosphere of 5 MPa within 2 h. The incomplete formation of AlB2 during adsorption was identied as the main reason for the hydrogen capacity loss and the decreasing kinetics upon subsequent cycling. A ternary magnesium nickel boride (MgNi2.5B2) together with MgH2 and LiH can be hydrogenated reversibly forming LiBH4 and Mg2NiH4 at temperatures below w300  C. The hydrogen capacity is low (w1wt.%) and the cycling temperature is much greater than 100  C [182].

7.1.6.

Results of DFT calculation

Sudik et al. [170] examined four (LiNH2)x-(LiBH4)Y-(MgH2)Z composites, where X:Y:Z 2:1:2, 1:1:1, 2:0.5:1 and 2:1:1 (original stoichiometry). All composites exhibit a hydrogen release event at rather low temperature, liberating between 2.3 (1:1:1) and 3.6 (2:0.5:1) wt.% by 200  C. At higher temperatures (200e370  C), the hydrogen release proles differ considerably between composites and release a total of 5.7 (1:1:1) to 8.6 (2:0.5:1) wt.%. Only the 2:1:1 and 2:0.5:1 are reversible (3.5 wt.% for 2:0.5:1 at 180  C).

7.1.5.

Hydride and boride

The hydrogenation and dehydrogenation of 2LiH-MgB2 mixtures has been investigated [101,123,132,174e180]. Through long-time ball milling of 2LiH-MgB2 mixtures, 8.3 wt.% hydrogen uptake at 265  C has been demonstrated. It is found that both solid-state hydriding and dehydriding are controlled

The calculated surface energy of low-index surfaces showed that the (010), (100) and (101) surfaces have similar surface energies of w0.12 J/m2 which means that the energy costs to create these surfaces by only breaking H-Li bonds in bulk LiBH4 are not high. The energy cost to create a single H vacancy in these surfaces is scattered in a narrow range between 180 and 200 kJ/mol. It is indicated that desorption of hydrogen from the crystalline surface needs to overcome high energy barriers [183]. Surface Li vacancies may potentially play an important mechanistic role in accelerating the kinetics of dehydrogenation from LiBH4 [184]. The energetics and structures of Ti-doped LiBH4 (001), (100), and (010) surfaces by DFT method have been studied. It is found that Ti prefers occupying the interstitial positions among three or four BH4 hydrides, forming local complex structures of TiB2H8-nBH4 (n 1, 2). The desorption energies from many positions of these stable complex structures are reduced signicantly with respect to those from the clean surface. The structural stability could be attributed to the symmetry-adapted orbital overlap between Ti and inside BH bonds [185]. Ti atoms introduced into the bulk of LiBH4 are thermodynamically unfavorable for all their oxidation states. Neutral hydrogen vacancies and interstitials or cation vacancies are less stable than their charged counterparts in LiBH4. BH4 groups change their mutual orientation, but BeH bonds remain intact [62]. A DFT study is performed for the hydrogen storage properties of the complex multinary storage Li-Mg-B-N-H (2LiNH2LiBH4-MgH2) system. It is found that reversibility occurs in the

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temperature range of 160e225  C with approximately 4.38 wt.% hydrogen storage capacity. The enthalpy of reversible de/rehydrogenation is found to be 55.17 kJ/mol H2. The total hydrogen storage capacity of this material is calculated to be 8.76 wt.% from the desorption behavior observed at different temperatures up to 350  C [186]. Anion substitution is one of the possible routes for the synthesis of new mixed material with tuneable thermodynamic properties [187,188]. DFT studies show that the reaction enthalpy decreased with the number of F substitution in LiBH4 (Li8B8H32xFx supercell). The Fsubstitution was not only viable in LiBH4 (Li8B8H32xFx) but also in LiH (Li8H8xFx) [188]. For a given H/F ratio, uorine ions are likely to belong to the same BH4 tetrahedron, rather than dispersed over the available tetrahedra [189]. The system of LiF-MgB2 was evaluated for reversible hydrogen storage. A signicant destabilization for both hydrogenation and dehydrogenation of this system as compared to highly stable LiBH4 was obtained. The reversible hydrogen storage capacity is up to 6.4 wt.%. The formation of LiBH4-yFy and LiH1xFx was observed during hydrogenation by in situ synchrotron XRD and attenuated total reection Fourier transform infrared spectroscopy (ATRFTIR) [190]. The experimental studies nd Cl, Br, I substitute for BH4 [82,85,191,192]. Our calculations for LT phase of LiBH4 give the same results as experiments and also nd that O, S prefer to occupy the interstitial site, and Se, Te are likely to replace BH4.

7.2.

Catalyst modication

The second approach to improve the kinetics of hydrogen absorption and desorption is the use of catalysts.

7.2.1.

LiBH4

The experimental results show that additives, such as Mg, Al, MgH2, CaH2, TiCl3, and MgCl2 are effective in reducing the dehydriding temperature, but some additives have a negative effect such as Ni, C (graphite), In, Ca, and NaH. The lowest dehydriding starting temperature was 60  C for the material LiBH4 0.2MgCl2 0.1TiCl3. It desorbed 5 wt.% of hydrogen at 400  C and absorbed 4.5 wt.% of hydrogen at 600  C and 7 MPa during dehydriding/re-hydriding cycles [193,194]. Boron addition reduces the dehydrogenation temperature from 500  C for pure LiBH4 to 350  C for LiBH4-B [195]. LiBH4-Ni systems exhibit improved hydrogen desorption performance, releasing the majority of hydrogen below 600  C. The dehydrogenated products could be rehydrogenated partly to LiBH4 at 600  C under 10 MPa hydrogen pressure [196]. Mg50Ni-LiBH4 showed a larger hydrogen storage capacity of 7 wt.% H at 573 K in just 300 s. Further analysis of this composite proved that a MgNi3B2 phase is formed under mild hydrogen cycle conditions, which is not reversible [197]. Mg50Ni-LiBH4-CeCl3 composite not only uptakes hydrogen faster than Mg50Ni-LiBH4, but also releases hydrogen at a lower temperature (225  C). The presence of CeCl3 has a catalytic role [198]. Zu ttel et al. [9,87] found that SiO2 plays a signicant role in destabilizing LiBH4 and helps to liberate large amount (9 wt.% for LiBH4) of hydrogen from the temperature of 200  C. The destabilization approach to SiO2-doped LiBH4

hydrogen storage composite is identied as 4LiBH4 2SiO2 / Li4SiO4 4B Si 8H2, and Li4SiO4 is the thermodynamic obstacle for its reverse action. For LiBH4-20 wt.%SiO2-30 wt.% TiF3 composite, the dehydrogenation temperature starts from 70  C and decreases by an average of 100  C from that of LiBH4 -20 wt.% SiO2. Its maximum amount attains 8.3 wt.% below 500  C [199]. In the case of the 4:1 LiBH4-TiO2, the onset temperature for dehydrogenation reduces to 150  C. Destabilization of the borohydride was achieved via a redox reaction with the TiO2 to form LiTiO2 and liberate all the available hydrogen from LiBH4. Furthermore, lithium titanate can also accelerate the decomposition of LiBH4, forming Li2O and TiB2 and resulting in a total hydrogen release of 9.0 wt.% [200]. The oxide-modied borohydride, LiBH4 75% TiO2 25%, desorbed 9 wt.% hydrogen from 100  C to 600  C and absorbed 8 wt.% hydrogen at 600  C and 7 MPa [194]. The order of destabilization of the LiBH4 for the oxides was Fe2O3 > V2O5 > Nb2 O5 > TiO2 > SiO2. The 2 h milled LiBH4-Fe2O3 sample (mass ratio of 1:2) releases 6 wt.% hydrogen below 200  C. XRD results revealed that the destabilization of LiBH4 by the oxides resulted from a redox reaction of LiBH4 MOx / LiMOx B 2H2 [201]. Modication of LiBH4 with additives such as metal oxides and chlorides (TiO2, TiCl3, ZrO2, V2O3, and SnO2) reduced the starting temperature of the hydrogen desorption from 400 to 200  C. The modied lithium borohydrides desorbed about 9 wt.% hydrogen and could be recharged to 7-9 wt.% hydrogen capacity at 600  C and 7 MPa. At the same temperature, the hydrogen pressure is much low than that of pure LiBH4, 35 MPa [100,202]. A solid-state reaction occurs between LiBH4 and TiCl3 to form LiCl at room temperature. Gold is found to react with molten LiBH4 to form a Li-Au alloy with CuAu3-type structure [203]. Several metal halides such as TiCl3, TiF3, and ZnF2 effectively reduced the dehydriding temperature through a cation exchange interaction. A number of other halides, MgF2, MgCl2, CaCl2, SrCl2, and FeCl3, did not reduce the dehydriding temperature of LiBH4 signicantly [204]. The LiBH4-TiF3 (mole ratio: 3:1) sample started to release hydrogen at around 100  C, and the hydrogen desorption capacity reached 5.0 wt.% at 250  C [205]. The mechanochemical process of 4LiBH4 VCln mixtures (with n 2 and 3) leads to no mixed metal borohydrides under the applied experimental conditions. The products are composed of crystalline LiCl and excess LiBH4. The reactions with VCl3 have stronger thermodynamical driving forces than with VCl2 [206]. LiBH4 was signicantly destabilized by the addition of FeCl2, CoCl2 and NiCl2, resulting in major hydrogen desorption at temperatures between 230  C and 300  C. FeCl2 and NiCl2 additions caused complete hydrogen desorption from LiBH4, but CoCl2 resulted in the formation of a small amount of diborane [207]. The ball milling of LiBH4 with chloride of Ce or La yielded Ce(BH4)3 and La(BH4)3, while uoride of Ce or La did not react with LiBH4 during ball milling at room temperature. The ball milled mixtures demonstrated dehydrogenation temperatures around 220e320  C, which were much lower than that of pure LiBH4 [208]. LiBH4 is heated by microwave irradiation at a temperature above 380 K, at which more than 13 wt.% of hydrogen is desorbed. This is due to a change in the conductivity accompanied by a structural transition [209].

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7.2.2.

LiBH4-MgH2

LiBH4-MgH2 composite exhibits excellent reversible hydrogen capacity, but it still presents high decomposition temperature over 350  C and sluggish kinetics [210]. For the purpose of optimizing its reaction performance, some additives were doped into this composite. The rst investigation of the dehydriding and re-hydriding properties of 2LiBH4-MgH2 mixtures in the solid state was reported. Such a study is made possible by high-energy ball milling of 2LiBH4-MgH2 mixtures at liquid nitrogen temperature with the addition of graphite. The 2LiBH4-MgH2 mixture ball milled under this condition exhibits a 5-fold increase in the released hydrogen at 265  C when compared with ineffectively ball milled counterparts. The re-hydriding is mainly due to MgH2 at this temperature because the amount of H2 released at this temperature is dominated by MgH2 [211]. The dehydrogenation onset temperature for LiBH4-MgH2Al (4:1:1 mol ratio) is 523 K. The major dehydrogenation pathway is 4LiBH4 MgH2 Al / 4LiH MgAlB4 7H2. As for the rehydrogenation of the LiH-MgAlB4 system, the two-step pathway of 4LiH MgAlB4 6H2 / Mg 4LiBH4 Al and Mg H2 / MgH2 is identied [212]. By introduction of Pd nanoparticles, the initial dehydrogenation temperature of the composite decreases from 340 to 260  C and the total weight loss reaches up to 8.0 wt.% below 400  C. Rehydrogenation results show 7.9 wt.% hydrogen can be rehydrogenated from the dehydrogenated product at 400  C under 35 atm of hydrogen for 6 h. The hydrogen desorption mainly includes two steps: rst, at temperature above 260  C, magnesium hydride reacts with Pd nanoparticles to generate Mg6Pd and the decomposition of MgH2; and then, above 350  C, magnesium reacts with LiBH4 to form MgB2 and LiH [213]. LiBH4-MgH2 composite with additive Nb2O5 yields a destabilized, reversible hydrogen storage material system with a capacity of approximately 6e8 wt.% hydrogen below 400  C and could be hydrogenated to 5e6 wt.% hydrogen capacity in 4 h at 400  C and 1.9 MPa. XRD and SEM analysis revealed that the intermediate compound NbH2 played a key role in changing the original path and resulted in the formation of MgB2 in the milling process [210]. The LiBH4-MgH2 composites with additive MoCl3 show a destabilized and reversible hydrogen storage property with a capacity of around 7 wt.% hydrogen at 300  C. The formation of Mo by the reaction of LiBH4 and MoCl3 during ball-milling process plays an important role in improving the dehydrogenation and hydrogenation properties of LiBH4-MgH2 system [214]. The LiBH4-MgH2 composites with the Ce-based additives CeH2, CeF3, and CeCl3 exhibited signicantly improved dehydrogenation kinetics and fairly good cycle stability compared with the uncatalyzed composite. The formation of CeB6 in these Ce-added composites may account for their improved hydrogen storage performance [215]. Various additives such as NbF5, TiF3, CeF3, LaF3 and FeF3 were used to dope 2LiBH4MgH2 system. Among the different additives, NbF5 exhibited the most prominent behavior. 2LiBH4-MgH2-0.05NbF5 dehydrided completely below 450  C with 8.1 wt.% hydrogen released. MgB2 was fully formed after dehydrogenation [216]. 3 mol% of TiCl3, HfCl4, ZrCl4, or VCl3 was added to the LiBH4MgH2 mixture. The lowest hydrogen desorption temperature

of 260  C was from the sample with TiCl3 addition. The amount of the catalyst also inuenced the kinetics of the hydride mixture and 5 mol% seems to be an optimum amount of TiCl3 that resulted in the lowest hydrogen desorption temperature, 240  C [217]. Compared to the neat LiBH4-MgH2 system, the samples containing Ru/C (ruthenium nanoparticles supported on MWCNTs) catalyst exhibit considerable enhancement on the de/rehydrogenation kinetics. Also, a reversible rehydrogenation capacity of w7.8 wt.% has been demonstrated under moderate conditions (500  C, 4 MPa) for 9 h, which is 2 wt.% higher than for the neat system. Moreover, the catalytically enhanced hydrogen absorption capacity persists well during three de/rehydrogenation cycles [218].

7.2.3.

LiBH4 and other materials

Several additives, TiCl3,V2O5, TiF3 and TiO2 were ball milled with the CaH2-LiBH4 mixture, TGA analysis showed that all of the mixtures released hydrogen in the range of 400e450 Cwith the desorption temperatures being in the order TiF3<TiO2 TiCl3<V2O5. Kinetic modeling measurements showed that the reaction is controlled by diffusion [140]. The addition of 5 wt.% of CoCl2 to the 2LiNH2-LiBH4 system greatly reduces the hydrogen desorption temperature. More that 8 wt.% of hydrogen can be desorbed from the Co-doped 2LiNH2-LiBH4 sample at temperature as low as 155  C. The active Co species catalyzing the process should be Co and/or Co2B [156]. It is found that ca. 10 wt.% hydrogen can be released from a 5 wt.% Co-doped LiBH4-2LiNH2 sample to form a plate-like Li3BN2 product with dramatically improved kinetics. Introduction of metallic Co into the LiBH4-2LiNH2 system decreased the melting temperature of the Li4BN3H10 phase, catalyzed the formation of B-N bonds and facilitated nucleation and growth of the dehydrogenated product [219]. Signicant improvements in the hydrogen absorption/ desorption properties of the 2LiNH2-1.1MgH2-0.1LiBH4 composite have been achieved by adding 3 wt.% ZrCo hydride. The composite can absorb 5.3 wt.% hydrogen under 7.0 MPa hydrogen pressure in 10 min and desorb 3.75 wt.% hydrogen under 0.1 MPa H2 pressure in 60 min at 150  C, compared with 2.75 wt.% and 1.67 wt.% hydrogen under the same hydrogenation/dehydrogenation conditions without the ZrCo hydride addition, respectively. The homogeneous distribution of ZrCo particles in the matrix and the destabilized N-H bonds are the main reasons for the improvement of H-cycling kinetics of the 2LiNH2-1.1MgH2-0.1LiBH4 system [220]. Doped with TiF3, LiAlH4-MgH2-LiBH4 (molar ratio 1:1:1) starts to release hydrogen at 60  C and completes dehydrogenation below 400  C. The system is partially reversible at moderate temperature and pressure (4 MPa, 400  C) with good cycling. The enhancement of the hydrogen sorption properties was attributed to the formation of intermediate compounds, including Li-Mg, Mg-Al, and MgeAleB alloys [221].

7.3.

Nanoporous scaffolds incorporation

The shorter diffusion distances for hydrogen and the other light elements within a nanoscale structure result in faster net rates for hydrogenation and dehydrogenation [222]. So the

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third method is nanoengineering to conne LiBH4 in mesoporous scaffolds or mix LiBH4 with nanotubes and mesoporous gels. Vajeeston et al. [223] predicted that the critical size of the nano-cluster and nano-whisker of LiBH4 is 1.75 nm and 1.5 nm, respectively. If one reduces the diameter below these critical sizes, the stability of the cluster/nano-whisker is drastically reduced. Under hydrogen pressure, LiBH4 can fully ll the mesopores of SBA-15 while the long-range order of the mesopores is maintained. The dehydriding starting temperature of conned LiBH4 was 150  C. However, SiO2 and decomposition products of LiBH4 react to form Li2SiO3 and Li4SiO4, leading to irreversible hydrogen loss [102]. The rate of hydrogen exchange is enhanced signicantly when LiBH4 is incorporated within a nanoporous carbon scaffold. The carbon scaffold serves not only as a nanoscale structure-directing agent but also as a host medium capable of constraining particle growth during cycling. The rate of dehydrogenation depends on pore size and can increase by as much as 50 times at 300  C for LiBH4 in a 13 nm carbon aerogel. In addition, the capacity loss over three cycles was reduced from 72% for bulk LiBH4 to w40% for LiBH4 conned in nanoporous hosts [124,222]. LiBH4 nanoparticles supported by disordered mesoporous carbon CMK-3, result in more favorable latent heat of dehydrogenation (40 kJ/mol H2), large amount of dehydrogenation capacity (14 wt.%) below 600  C and reversible capacity of 6.0 wt.% H2 at 350  C. It was revealed that such destabilization results from two kinds of mechanisms: nano-dispersion and reaction with mesoporous carbon [224]. The effects of nanoconnement on desorption of LiBH4 have been investigated in the presence of various porous hard carbon templates at a variety of pore sizes. Calorimetry signatures of both the structural phase transition and melting of nanoconned LiBH4 shifted to a lower temperature with respect to the bulk, nally vanishing below a pore size around 4 nm. The desorption of LiBH4 conned in these nanoporous carbons shows a systematic and monotonic decrease in the desorption temperature and concomitantly, mass spectroscopic analysis indicated a gradual reduction of the partial pressure of B2H6 with decreasing pore size, suggesting that formation of stable closoborane salts may be avoided by interrupting the reaction pathway [225]. The wetting and decomposition behavior of LiBH4 has been investigated in the presence of highly ordered nanoporous hard carbon (NPC) with hexagonally packed 2 nm diameter columnar pores. The onset desorption temperature of premelted LiBH4-NPC was reduced from 460 to 220  C. Mass spectra studies of the desorbed gases indicate B2H6 is produced in the decomposition of bulk LiBH4 and physical mixtures of LiBH4-NPC but not in premelted samples of LiBH4-NPC. These results indicate the nanoframework alters the decomposition pathway and eliminates the formation of B2H6 [226]. Compared to the bulk counterpart, the dehydrogenation temperature of LiBH4 incorporated into AC (activated carbon) was lowered by 150  C; the dehydrogenation rate was increased by over one order of magnitude; the temperature and hydrogen pressure required for hydride restoration were signicantly reduced; and the dissociation hydrogen pressure

was increased by around one order of magnitude in the LiBH4/ AC nanocomposite [227]. The LiBH4/Cnano (MWCNTs) mixtures (mass ratio, 1:2) showed superior dehydrogenation, hydrogen desorption starting at 250  C and the majority of hydrogen being released below 600  C. The mixtures could be reversed about 1/4 hydrogen at 10 MPa hydrogen pressure and 400  C based on a reaction of Li2C2 H2 / 2LiH 2C [228]. For the LiBH430 wt.% SWNTs composite milled for 1 h, 11.4 wt.% hydrogen can be discharged within 50 min at 450  C; over 6.0 wt.% hydrogen can be recharged at 400  C under an initial hydrogen pressure of 10 MPa [229]. The LiBH4-MgH2 composite with 10 wt.% puried SWNTs (single-walled carbon nanotubes) additive can release nearly 10 wt.% hydrogen within 20 min at 450  C. The observed property improvement was ascribed to the microconnement effect of the carbon nanotube network embodied in the hydride matrix [230,231]. LiBH4 and MgH2 nanoparticles are embedded in a nanoporous carbon aerogel scaffold with pore size Dmax w21 nm and react during release of hydrogen and form MgB2. The hydrogen desorption kinetics is signicantly improved compared to bulk conditions, and the nanoconned system has a high degree of reversibility and stability and possibly also improved thermodynamic properties [232].

8.

Conclusions

The present review provides the research progress in LiBH4 including the synthesis, hydrolysis, structure, dynamics, intermediate compound, and the de/rehydrogenation properties improvement of LiBH4. There are several ways to synthesize LiBH4. In the hydrolysis of LiBH4 with the liberation of hydrogen gas, the byproduct will be varied with the different proportions of LiBH4 and water as well as the temperature changes. Structurally, the low temperature structure of LiBH4 is Pnma, experimental high temperature structure is P63mc. At room temperature and under high pressure, LiBH4 forms Ama2 and Fm-3m structures. Dynamically, we reviewed the dynamics of LiBH4 including the rotation of BH4 groups, the atomic motions of H, Li, and B, and HeD exchange in BH4 units. It is found that LiBH4 exhibites a high electrical conductivity due to the Li superionic conduction and may be of importance for solid state lithium battery applications. It is difcult for full reversibility of LiBH4. The multistep reaction pathway together with the formation of an intermediate compound of LiBH4 in hydrogenation and dehydrogenation might account for the high reaction temperature and slow kinetics. One of the intermediate compounds studied the most is Li2B12H12 with a structure of Pa-3. The strong ionic and covalent bond in LiBH4 as well as bonding congurations also increase the activation energies for diffusion and results in slow hydrogen sorption kinetics. Another limitation for applications could be the release of diborane gas during decomposition which caused the loss of boron. Several methods have been proposed to improve the hydrogen storage properties of LiBH4 and there are considerable experiments. It has discovered numerous new less-stable

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bimetallic borohydrides, and numerous reactive mixtures showing high reversible hydrogen content and temperatures of de/rehydrogenation much superior to pure borohydrides. The thermodynamic and kinetic properties of LiBH4 has been improved by nanoscaffolding. Thus, the landscape of the eld has changed considerably over the past 5 years. However, many challenges are still wide open in this eld and much work has to be done, such as reducing the grain size, developing the new system, searching the suitable dopants and catalysts, nding the favorable nanoporous scaffolds, making more research about the mechanism and crystal structure involved in hydrogen storage and release, reducing the release of diborane gas and other by-products, which may contribute to the practical application of LiBH4 and other complex hydrides.

Acknowledgments
We acknowledge the fundings of this work by Hunan Provincial Natural Science Foundation of China No.09JJ6079 and PhD Programs Foundation of Ministry of Education of China No.200805321032.

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