Mandal - H2 Storage Materials

Downloaded by University of Connecticut on 07 October 2011 Published on 13 May 2009 on http://pubs.rsc.org | doi:10.
1039/B818951J
Annual Reports on the Progress of Chemistry, Section A
Inorganic Chemistry
Vol 105
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REVIEW
www.rsc.org/annrepa | Annual Reports A
Hydrogen storage materials: present scenarios and future directions

Tapas K. Mandal and Duncan H. Gregory*
DOI: 10.1039/b818951j
Downloaded by University of Connecticut on 07 October 2011 Published on 13 May 2009 on http://pubs.rsc.org | doi:10.1039/B818951J
This review describes the present state of contemporary solid state hydrogen storage on the basis of research carried out during the last decade. The article focuses on the key aspects of materials based on the physical and chemical storage of hydrogen and emerging mechanisms for reversible storage. Among chemical storage materials, we consider metal hydrides (both light and complex), nitrides-imides-amides and other multicomponent systems and discuss the emergence of coordination polymers (metal organic frameworks; MOFs) among solids exhibiting physical storage. Signicant challenges remain if we are to meet the practical demands required of a solid state storage system, namely high storage density together with favourable sorption thermodynamics and kinetics and prolonged cycleability and lifetime. This review emphasises both how our understanding of the storage mechanism (as a process or phenomenon during hydrogen cycling) is evolving and how this understanding impacts on future materials design. The prospect of high capacity storage and fast kinetics in nanostructured materials is highlighted as is the role of complex, multi-component, composite systems in future hydrogen storage research.
1. Introduction
At the juncture of the 20th and 21st centuries it was realised that there was an urgent requirement for an alternative and sustainable energy vector as reserves of fossil fuels faded.1,2 Moreover, if the adverse eects of global warming and consequent climate change is to be arrested then the utilisation of green and renewable energy sources is imperative. As Grochala and Edwards and later van den Berg and Arean note in their articles,3 Jules Verne rst brought these issues to the attention of the public in a work of ction over 100 years ago: . . . water will one day be employed as a fuel, that hydrogen and oxygen will constitute it, used singly or together, will furnish an inexhaustible source of heat and light and water will be the coal of the future (The Mysterious Island, Jules Verne, 1874). Vernes work was to presage with uncanny pertinence the role of hydrogen as the fuel of the future and predict the coming of the so-called hydrogen economy. An uninterrupted and secure energy supply for the developed nations and meeting the increasing energy demands of the rapidly developing nations are essential. The burgeoning need for energy coupled with the rapid depletion of fossil fuels pose serious threats for sustainable development. Before the potential for hydrogen as a
West CHEM, Department of Chemistry, Joseph Black Building, University of Glasgow, Glasgow, UK. E-mail: d.gregory@chem.gla.ac.uk; Fax: +44 (0)141 330 8128; Tel: +44 (0)141 330 4888
Annu. Rep. Prog. Chem., Sect. A, 2009, 105, 2154 | 21

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The Royal Society of Chemistry 2009
future energy carrier can be realised, fundamental research including components of invention and discovery, subsequent implementation of new technology and socioeconomic acceptance must occur. These are the key steps to the hydrogen energy transition. The greater hydrogen energy picture centres around the production and storage of hydrogen, the two most important steps that currently represent a bottle neck to utilization of hydrogen more widely in fuel cell systems. It must be realized that unlike coal or oil, hydrogen is not naturally available. Thus, stable large-scale hydrogen production is necessary for the gradual switchover to the hydrogen economy. However a safe, ecient and economic storage medium is likely to be a crucial prerequisite before hydrogen would be globally acceptable as a fuel, particularly in mobile (automotive) applications. It should be emphasised here that while gaseous or liquid hydrogen is currently an option for prototype personal vehicles (cars) or larger commercial transport, solid state storage of hydrogen is potentially superior with regard to its storage capacity (both gravimetric and volumetric), energy eciency and safety.2 Nevertheless compact storage of hydrogen in a solid medium is the most demanding and challenging part of realising the hydrogen economy as far as mobile applications are concerned (Fig. 1).2b Hydrogen storage is thus a key research area where considerable international eort is concentrated. Since this review is written from a materials perspective, current chemical research in hydrogen storage materials will be highlighted capturing the discoveries and developments over the past decade (19982009), the many opportunities that could be seized and the future pathways that could be taken. Although many of the materials classes meet the majority of the US Department of Energy (US-DoE) criteria for vehicular applications (e.g. hydrogen storage capacity; the amount of hydrogen stored per unit mass and per unit volume),4 other factors such as non-reversibility, slow kinetics and sometimes thermodynamic barriers to hydrogen uptake-release limit or prevent their practical use. Holistic and systematic research towards understanding mechanism, structure and thermodynamics and
Fig. 1 Alternatives for storage of 4 kg hydrogen, with volume relative to the size of a car. (Reprinted from ref. 2b, with permission from Macmillan Publishers Ltd.)
22 | Annu. Rep. Prog. Chem., Sect. A, 2009, 105, 2154

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their inter-relationships are crucial to innovation and materials development. This review illustrates the extent of emerging materials discovery and design and demonstrates how an improved chemical understanding of storage processes informs an evolving materials design strategy.
2. Chemical storage
The chemical storage of hydrogen concerns materials where hydrogen is chemically bound in a compound. Therefore, the loading and unloading of hydrogen (hydrogenationdehydrogenation) in this class of compound requires a chemisorption step prior to the absorption of hydrogen in the bulk and the formation of chemical bonds to hydrogen. In contrast, physisorption (see section 3) is responsible in cases where molecular hydrogen is only physically adsorbed on the surface of a solid or in the internal volume of porous/framework structures. In the chemical storage scenario, hydrogen is strongly bound while in physisorption it is so weakly held that often very high pressures or low temperatures are required, making physisorbed materials much less attractive for practical uses at ambient or elevated temperatures. Among chemical storage materials, families of metal alloys and their hydrides constitute a core grouping that has been widely investigated for over a century.3,5 In general, the storage capacities of these materialswhich often contain f- and/or d-block elementsare too low to meet the DOE targets for vehicular applications but could nd utility in stationary applications due to sometimes excellent reversibility. For example, Mg2Ni (with a gravimetric capacity of 3.6 wt% hydrogen) and LaNi5 (1.28 wt%) are two classic alloy systems that are noteworthy due to their extraordinary cycleability.5 Light metal binary hydrides, however, are considered as an important class with respect to high hydrogen storage density but are plagued by high desorption temperatures, non-reversible thermodynamics and poor kinetics.6 MgH2 is one of the binary hydrides that still attracts huge attention owing to its light weight and high gravimetric density even given its kinetic and thermodynamic limitations for storage.7 On the contrary, complex chemical hydrides oer tremendous opportunities over the binaries in many respects.6,810 Among them, the borohydrides,810,11 aluminohydrides (alanates)6,810 and amides810,12,13 are close to meeting US-DoE targets in terms of storage capacity, reversibility, cost and toxicity. The complex hydrides divide rather neatly into 2 groups depending on their composition and bonding: borohydrides and alanates, (for example LiBH4 and LiAlH4) are hydridic in nature and contain hydrogen within complex anions ([BH4], [AlH4]) that can be represented as Hd. In contrast, the imides and amides, e.g. Li2NH, LiNH2 are protonic and contain hydrogen within complex anions ([NH]2, [NH2]) that can be represented as Hd+.These two distinct and discrete classes of complex hydride are covered separately in the sections below. 2.1 Light metal hydrides Among the light metal binary hydrides, magnesium hydride (MgH2) is the most attractive due to its low atomic weight, high hydrogen storage capacity and low cost.7 In Table 1, the gravimetric and volumetric density along with hydrogen desorption temperature and reversibility for selected light binary hydrides are compared with that of gaseous and liquid hydrogen.3a,7,14 Although, MgH2 has a high gravimetric capacity of 7.6 wt%, it suers from slow kinetics and a high decomposition temperature (B330 1C). A huge body of research has been devoted to improving its performance.7,1527

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Table 1 Hydrogen content of simple binary hydrides in comparison with gaseous and liquid hydrogen.3a,7,14 Tdec and kinetic reversibility of the hydrides are also given. Wt% H2 Volumetric density NH (atoms H/ml 1022) 4.2 0.49 5.3 2.3 5.1 6.7 8.84 9.1 Tdec (1C) 720 425 600 330 150 380 Kinetic reversibility Poor Good Good Very poor Irreversible a
Compound
100 H2, liquid 100 H2, gas (100 atm) LiH 12.6 NaH 4.2 CaH2 4.8 MgH2 7.6 AlH3 10.0 4.0 TiH2 a No literature data available.
Particle size reduction by ball milling, alloying or doping are among the most common approaches that are being pursued to speed up the kinetics in the Mg-H system.15,16 Catalytically enhanced systems show great promise for improved hydrogen storage characteristics and mechanical milling has been employed to prepare catalysed MgH2 composites.1719 Various additives include carbon,15f,21 transition metals,15d,22 oxides23,24 and halides.25 Milled Ni-doped19 MgH2 shows a 6.5 wt% storage capacity at 150250 1C and a remarkable improvement in sorption was reported for 1 mol% Nb2O5 doped milled MgH2 with high desorption kinetics at 160 1C under a helium ow.20 Further, a recent investigation of the eect of ZrNi activated alloys on milled MgH2 indicated signicant improvements in desorption kinetics.26 By comparing several compositions in this latter alloy system, it has been argued that the alloys are playing a crucial catalytic role distinct from grain size eects induced by milling.26 Although, the development of suitable catalysts has drastically reduced the charge-discharge times, the thermodynamics of the process remain almost unaltered. Chemical destabilisation27 of MgH2 and many other complex hydrides in a multicomponent mixture with designed reaction paths is a fairly new development that will be discussed separately below under multinary systems (section 2.4). However, it must be pointed out here that chemical destabilisation of MgH2 by alloying with Cu dates back to the work of Reilly and Wiswall in 1967.28 They reversibly hydrogenated Mg2Cu to MgH2 and MgCu2 at 240 1C (which is B40 1C lower than that of pure MgH2) with an equilibrium pressure of 1 bar.28 Similarly, in a recent study, alloying with Si was shown to destabilise MgH2 signicantly forming Mg2Si upon dehydrogenation.29 But the MgH2/Si system suers from slow kinetics at 150 1C, which is the required temperature for hydrogenation at 100 bar.29 Another very recent emerging trend in the MgH2 based materials is to chemically nanostructure hydride materials10,30 and this approach is highlighted in section 4 under New materials for hydrogen storage. These sections in particular emphasise the many opportunities that exist to improve reversibility and thermodynamics in light-weight metal hydrides. 2.2 Complex hydridic hydrides, borohydrides and alanates ([BH4] and [AlH4]) Hydrides containing complex anionic units with light elements like Al, B and achieving charge neutrality through ionic or partially covalent bonding with a more electropositive cation, such as, Li, Na, K, Mg and Ca, have been classied as

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so-called chemical hydrides. In these complex hydrides, the hydrogen within the anionic unit resides at the vertices of a tetrahedron with B or Al at the centre to form tetrahydroborates e.g. Li(BH4), Mg(BH4)2 or tetrahydroaluminates (also known as alanates), e.g. Li(AlH4), Na(AlH4). Although these tetrahydrometallates constitute an interesting storage class, the very large gravimetric and volumetric hydrogen densities (Table 2) that they exhibit is countered by their thermal stability and high desorption temperature which often makes them unsuitable for application. The desorption temperature and gravimetric hydrogen densities for some selected complex hydrides are shown in Table 2. Of these, the lightest borohydride LiBH4 has attracted enormous interest as a candidate hydrogen store due to its extremely high gravimetric hydrogen density (18.4 wt%),8,3234 although as yet it has not been possible to overcome the profound thermodynamic, kinetic and reversibility challenges that would enable it to be employed as a practical storage material. The rst thermal desorption of hydrogen from LiBH4 was reported in 1964 by Fedneva et al.35 and four years later Stasinevich and Egorenko36 showed that LiBH4 releases hydrogen at temperatures greater than 470 1C. According to Fedneva et al.35 the dierential thermal analysis prole of LiBH4 consists of three endothermic events. While the rst reversible endothermic eect at 108112 1C is attributed to a polymorphic transformation of LiBH4, the second peak at 268286 1C corresponds to melting with the onset of gradual decomposition of LiBH4.35 The main hydrogen release starts at 380 1C liberating 80% of the hydrogen in LiBH4. Moreover, another thermal event at around 490 1C was unexplained. However, in their study, Stasinevich and Egorenko conducted the thermal analysis under hydrogen pressures of 10 bar and according to them, the dehydrogenation reaction of LiBH4 releases only 3 of the 4 hydrogen atoms above 268 1C.36 This process can be represented as: LiBH4 - LiH + B + 3/2 H2 (1)
Analogous decomposition pathways are observed for other alkali metal borohydrides (NaBH4 and KBH4) but with an increase in the decomposition temperature with increasing atomic number of the alkali metal. In a later study, Zuttel et al. demonstrated that three distinctive desorption peaks exist during the dehydrogenation of LiBH4 when performed at a low heating rate.37 This suggests a more complicated mechanism and the presence of other intermediate phases during the
Table 2 Desorption temperature and gravimetric storage capacities of complex chemical hydrides3a,8 Storage capacity (wt%) 18.4 10.6 7.4 14.8 11.5 16.8 9.5 7.4 5.7 9.3 7.8
Compound
Tdes (1C)
380 LiBH4 NaBH4 400 500 KBH4 Mg(BH4)2 260280 Ca(BH4)2 320 Al(BH4)3 20 125 LiAlH4 NaAlH4 210 KAlH4 270 140200 Mg(AlH4)2 Ca(AlH4)2 250a a For complete desorption from neat Ca(AlH4)2.31

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decomposition. Only recently, has the involvement of a borohydride cluster, Li2B12H12, been elucidated as an intermediate in the thermal desorption of LiBH4.38,39 A series of systematic theoretical and experimental studies has been carried out to attempt to rationalise the thermodynamic stabilities of metal borohydrides, M(BH4)n (M = Li, Na, K, Mg, Cu, Zn, Sc, Zr and Hf).40 A good correlation has been observed between desorption temperature (Td), the enthalpy of desorption (DHdes) and the Pauling electronegativity (wP). Similar studies have been performed for Ca(BH4)2 and it was established that the ionic bonding exists between Ca and the covalent [BH4] unit and that there is a linear relationship between the heat of formation and wP of the cation.41 The same study also predicted a possible decomposition pathway as:
Ca(BH4)2 - 2/3 CaH2 + 1/3 CaB6 + 10/3 H2
(2)
with a calculated gravimetric capacity of 9.6 wt% of hydrogen. Thermogravimetric analysis leant support to the proposed reaction, yielding an experimental weight loss of 9.2 wt% and suggested that an intermediate species could be involved in the decomposition.41 Although the CaBH system has a high storage capacity, subsequent studies indicated that the dehydrogenation starts only at 640 K and the kinetics of dehydrogenation is very slow.42,43 Various approaches have been taken to address the thermodynamics and kinetics of hydrogenationdehydrogenation cycling in LiBH4 and the other complex borohydrides. These approaches were very much triggered by the chemical activation of NaAlH4 by Bogdanovic and Schwickardi in their seminal paper of 1997.44 In their pioneering study they showed that 2% Ti-catalyzed NaAlH4 (sodium alanate) undergoes reversible dehydriding-rehydriding reactions in the solid state under moderate conditions.44 The hydrogen desorption takes place in two steps. 3 NaAlH4 2 Na3AlH6 + 2 Al + 3 H2 Na3AlH6 2 3 NaH + Al + 3/2 H2 (3) (4)
While the rst step (3) amounts to 3.7 wt% hydrogen (with DH = 37 kJ mol1 H2), the second step (4) releases 1.8 wt% (with DH = 47 kJ mol1 H2) corresponding to a total of 5.5 wt% of hydrogen. The enthalpy values correspond to dehydrogenation temperatures of about 35 and 100 1C, respectively.45 The theoretical storage capacity of 7.4 wt% for the NaAlH4 system can be achieved if the remaining hydrogen stored in NaH is released. This, however, requires temperatures greater than 500 1C due to the very high stability of NaH. In fact, the two step decomposition mechanism of NaAlH4 to NaH, Al and H2 at 210220 and 250 1C respectively was rst demonstrated over 40 years ago.46 Subsequent studies revealed that similar two step decomposition reactions also take place for LiAlH4 and KAlH4.4752 Although, there have been reports of reversibility in these systems,51 the kinetics are extremely slow. Further, relatively harsh conditions are required (200400 1C and 1040 MPa) for cycling and the reversibility is essentially only partial. The rst examples of the use of titanium to catalyse dehydrogenation reactions took place in solution and include, for example, the Ti-catalysed dehydrogenation of LiAlH4 in ether by Wieberg et al. in 1951.53 However, the above discovery of Ti-catalysis for reversible hydrogen storage in the solid state under favorable thermodynamic conditions, as rst represented by the alanates,44 has created a vast amount of fresh research activity in main group complex hydrides. Many other catalytic dopants have since been studied, but no other metal-containing phases appear to outperform those containing Ti. Use of dierent additive compositions as a source for Ti impregnation/dispersion in NaAlH4 have produced results with some variance in

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Fig. 2 Temperature programmed desorption of hydrogen from NaAlH4 doped with 2 mol% of Ti(OBun)4. (Reprinted from ref. 54 with permission from Springer)
performance and catalytic enhancement and the doping methods themselves are also found to exert an inuence. For example, Jensen and Gross have shown that the onset of dehydriding reaction diers appreciably (Fig. 2) for solution doped and mechanically doped NaAlH4 materials.54 A nanocrystalline NaAlH4, synthesised directly by ball milling of NaH/Al with TiF3 catalyst under 1525 bar of hydrogen, demonstrated fast kinetics with a high reversible capacity of 4.7 wt%.55 Moreover, recently, Fang et al.56 reported a chemical activation of LiBH4 by mechanically milling 3 equivalents of LiBH4 with 1 equivalent of TiF3 that can rapidly release 5.7 wt% hydrogen at moderate temperatures (7090 1C) without any other gas impurities. However, the isothermal desorption proles indicated that it takes roughly an hour to fully release the hydrogen. Recently, theoretical57,58 and experimental5961 investigations have been performed on the Group-II metal (Mg and Ca), Group-III metal (Al) and mixed LiMgCa borohydrides owing to their potentially high storage capacity (Table 2). While the dehydriding reaction of pure Mg(BH4)2 starts at nearly 500 K, the addition of TiCl3 decreased the desorption temperature to 361 K,59 whereas the ball-milling had no eect on the dehydriding temperature.59a Also, reversible storage in TiCl3-catalysed Ca(BH4)2 has been demonstrated with a capacity of 3.8 wt%, when the Ca(BH4)2 was rehydrogenated at 623 K under 90 bar for 24 h.60 This improved rehydrogenation condition in Ca(BH4)2 suggested further study to exploit its full potential. New reversible hydrogen storage reactions have been predicted in the mixed LiMgCa borohydride systems.57b There remain ample opportunities for further performance optimisation and certainly there is a need to understand much more regarding the catalytic processes involved in Ti addition to alanates and borohydrides. 2.3 Complex protonic hydrides; nitrides, imides and amides Nitrides and their conjugate hydrogenated compounds imides and amides form the second class of complex hydrides although strictly these materials are not hydrides. The discovery of reversible hydrogen storage in Li3N by Chen et al.62 in 2002

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spurred intense activity in investigating the LiNH system and subsequently quaternary LiANH (where A = Group I and Group II metals) imide-amide-based systems.63101 The key chemical processes that occur during the hydrogenation and dehydrogenation of Li3N are represented by eqn (5). Li3N + 2 H2 2 Li2NH + LiH + H2 2 LiNH2 + 2 LiH (5)
Although the theoretical gravimetric hydrogen storage capacity of this system is 11.5 wt%, experimentally, the amount of stored hydrogen is less by B2 wt%, eectively storing between 9.310 wt% of hydrogen (Fig. 3). In spite of the fact that the above chemical process oers potentially very high storage capacity, the system suers from various drawbacks in terms of high operational temperature (especially in desorption), reversibility (only the imideamide step is reversible at practical working temperatures) and poor kinetics. Whereas the second step in eqn (5) involving the interconversion of imide and amide is readily reversible, the reverse dehydrogenation step to revert to the parent lithium nitride and hydrogen occurs at high temperature, under low pressure (4320 1C at 105 mbar). Immediately following the report of the (de)hydrogenation reactions in the LiNH system, a major research eort focused on reducing the desorption temperature for LiNH2/LiH, optimising performance and latterly attempting to understand the storage mechanism.6370 Pressure-composition (P-C) measurements performed on lithium imide show that B6.5 wt% of hydrogen can be reversibly stored at 255 1C according to the following reaction. Li2NH + H2 2 LiNH2 + LiH
1
(6)
The enthalpy change for this reaction is calculated to be 44.5 kJ mol H2 leading to favourable and reversible reaction thermodynamics.70 However, the temperature
Fig. 3 Gravimetric hydrogen absorption (Abs) and desorption (Des) curves in the lithium nitride-imide-amide system (Reprinted from ref. 62, with permission from Macmillan Publishers Ltd.).

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of hydrogen cycling remains high for practical on-board storage. Therefore, chemical destabilisation of LiNH2 itself was an early target in developing new materials with low desorption temperatures (Tdes). The substitution of more electronegative elements than Li in LiNH2 was suggested66,68 to weaken the bonding between Li+ and [NH2] thereby reducing Tdes. Synthesis of Mg-substituted LiNH2 from LiMg alloys and investigation of dehydrogenation reactions showed a drastic decrease of desorption temperature from B250 1C in pure LiNH2 to an onset temperature of B100 1C in (Li,Mg)NH2.71 However, a theoretical study of the modied amides, (Li,Mg)NH2, showed that the NH bonding is weakened in (Li,Mg)NH2 compared to LiNH2.72 In a later study, Zhang and Alavi pointed out that the relative strength of the metalN bonding was the key factor in explaining the experimental results of reduced desorption temperature in Mg-substituted LiNH2.73 In an eort to gain mechanistic understanding of the hydrogen storage process in the reaction between LiNH2 and LiH (eqn (6)), the work of Hu and Ruckenstein64,65 and Ichikawa et al.67 has led to the proposition of an ammonia mediated mechanism (eqn (7) and (8)). 2 LiNH2 - Li2NH + NH3 NH3 + LiH - LiNH2 + H2 (7) (8)
It is worth pointing out that the above elementary two step pathway was conrmed recently by in situ 1H NMR spectroscopy.70c However, others63,74,75 believed the dehydrogenation reaction to be redox or acidbase type where protonic hydrogen (Hd+) in LiNH2 and hydridic hydrogen (Hd) in LiH combine to give molecular hydrogen (H2). The exothermic combination of H and H+ probably drives the hydrogen desorption reaction,3a which also successfully explains the chemical destabilisation in amide-hydride systems. H+ + H - H2 (DH = 17.37 eV) (9)
This, in practice, was a major driving force in the future materials design of complex hydride systems, most notably in multi-component systems where chemical tuning of amides through doping and use of hydrides and borohydrides as secondary components in composite mixtures have met with some success. (These are discussed in section 2.4 in more detail). Among other approaches, the use of catalysts and modication of the microstructure via mechanical milling have been adopted to improve the performance of nitrogenous systems. While Ichikawa et al.70 studied the eect of ball milling and catalysts on the desorption of hydrogen, Hu and Ruckenstein76 investigated the storage performance of amides based on preparative routes. Ichikawa et al.67,70 have shown that upon ball milling the hydrogen desorption temperature range decreases to 180400 1C. Moreover, when catalysts were used during ball milling, the desorption temperature was reduced further and evidence of ammonia evolution could be almost negligible. The best performance was obtained when 1% of TiCl3 was added as catalyst resulting in 5.5 wt% of hydrogen being released between 150250 1C with no ammonia formation.67 Importantly, however, the process by which these catalyst additives work and the mechanism by which they inuence reaction pathways is not yet known. In fact, the connections between processes at the solid surface and those that occur in the bulk are vital ones to be made if these and

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other storage materials are to be understood and a step change in performance eected. Among several imide-amide systems, the role of structural modication on hydrogen storage kinetics in simple Li2NH itself is not well understood. Recently, Yang et al. have studied the crystal structure and phase transitions of a-, b- and g-Li2NH.90 It was mentioned that the phase transitions in Li2NH is dependent on the synthetic methods. Moreover, among all the modications, the a-phase showed higher reversible hydrogen storage capacity (6.8 wt%) and faster kinetics.76
Fig. 4 Hydrogen absorption at 230 1C and 7 atm initial hydrogen pressure (A) a-Li2NH, (B) b-Li2NH and (C) g-Li2NH. In (B): a, b and c corresponds to Li2NH synthesised by LiNH2 decomposition under vacuum at 230, 280 and 350 1C, respectively (Reprinted from ref. 76b with permission from American Chemical Society).

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Fig. 5 Structural transformation of lithium imide, Li2NH, to lithium amide, LiNH2, via non-stoichiometric intermediates (Reprinted from ref. 12b, with permission from The Japan Chemical Journal Forum and Wiley Periodicals).
Volumetric hydrogen desorption studies show that while a-Li2NH absorbs 5.4 wt% in 10 min, the b- and g-polymorphs display much slower kinetics with less than 2 wt% and 4 wt% reversible hydrogen capacity, respectively (Fig. 4).76 The higher storage capacity and faster kinetics have been attributed to the particle size that varies with thermal treatments under the synthesis condition.76 Nevertheless, it was also found that doping with Mg or Ca can reduce the dehydrogenation temperature of hydrogenated Li2NH.77,95,99 The structural and compositional changes in the LiNH system have been investigated by ex situ synchrotron X-ray diraction to elucidate the processes that occur during hydrogen uptake-release cycling in the solid state.93 The hydrogenation dehydrogenation of the imide-amide system occurs through non-stoichiometric intermediates, Li2xNH1+x (0 r x r 1), based on a cubic anti-uorite structure (Fig. 5). More importantly, the process seems to generate Frenkel-type defects, which in turn creates a mechanism for Li+ and H+ ion mobility. Subsequent structural studies by in situ neutron diraction during deuterationdedeuteration of Li3N indicated cell volume changes of Li2NH that was attributed to defect formation in cubic Li2NH, implying non-stoichiometric compounds.94 A recent study98 by synchrotron X-ray and neutron diraction of the LiMgNH system with the amide-hydride mixtures identied a mixed imide a-Li2Mg(NH)2 phase that has a superstructure based on the high temperature cubic anti-uorite Li2NH.102,103 The replacement of 2 Li atoms by one Mg atom creates ordered cation vacancies and results in a Li2NH supercell. The imide protons are also ordered, orienting the NH bonds between two vacant cation sites.98 At higher temperatures this a-Li2Mg(NH)2 phase undergoes a structural transition to b- and g-Li2Mg(NH)2 (similar to the high temperature Li2NH phase)104 where the Li, Mg and vacancies are randomly distributed over the tetrahedral sites. The structural transitions are believed to be driven by progressive disordering of the cations and vacancies as the temperature increases.98 A dramatic particle size-dependent catalytic enhancement of hydrogen absorption desorption has recently been reported in the LiMgNH system.101 A threedimensional diusion-controlled kinetic mechanism has been identied for the dehydrogenation process. The hydrogenation and isothermal dehydrogenation curves (Fig. 6) reveal that the onset of hydrogen absorption was, remarkably, lowered to 80 1C for a sample ball-milled for 36 h and consequently the dehydrogenation kinetics at 160 1C were notably improved compared to 3 h milled or hand milled samples.101

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Fig. 6 (A) Gravimetric hydrogen uptake versus temperature for Li2MgN2H2 as a function of milling time and (B) Isothermal dehydrogenation curves (at 160 1C) of hydrogenated Li2MgN2H2 samples (Reprinted from ref. 101, with permission from American Chemical Society).
From the close similarity of the mechanisms in the LiNH and LiMgNH systems, it is apparent that the vacancy distribution, defect concentration and the ionic mobility of Li+ and H+ play an important role in the storage processes. Recently, the crystal structure of a ternary imide, Li2Ca(ND)2, was determined by NPD.100a The structure of Li2Ca(ND)2 resembled a combined imide structure with an ordered arrangement of Ca[NH]6 octahedra and Li[NH]4 tetrahedra alternating along the c-axis, distinctly dierent from any of the polymorphs of Li2Mg(NH)2.100a The Li vacancy was attributed to defect reactions at elevated temperatures and the dehydrogenation mechanism was proposed to be mediated by small mobile ion migration in both amide and hydride.27b,100 Similar factors may well be fundamental to other complex hydride systems and could eventually lead to the improved understanding and better design of materials. Further work is required with respect to understanding and exploiting the defect chemistry, complex phase behaviour and the involvement of chemical intermediates in these and similar systems.

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2.4 Other multi-component systems: amide-hydride-borohydrides The underlying strategy behind employing more than one component is to alter the overall thermodynamics of hydrogen release, lowering Tdes, in addition to improving the kinetics of sorption. Indeed, it has been observed that in multinary systems the hydrogen uptake-release temperatures are lower and the kinetics often better than for the individual component systems. Performance is highly dependent on the reaction pathway of hydrogenation and dehydrogenation, together with the stability of the product formed in the dehydrogenated state. The report of reversible hydrogen storage by Chen et al.62,63 in a mixture of LiH and LiNH2 initiated a urry of research activity, which later opened up a number of diverse routes for complex hydride destabilization in the form of binary, ternary or multinary reactive mixtures involving amides, hydrides, borohydrides and alanates with substantial improvements in (de)hydrogenation thermodynamics.105137 The various multinary combinations studied can be classied mainly as binary (two component) and ternary (three component) systems. Moreover, the binary systems can be considered as simple when the combination involves a single metal hydride and an imide/amide, as compared to complex binaries where a hydride containing a complex anion, such as a borohydride or aluminohydride, is involved. As the number of components increases, the system becomes more and more complex often due to the increased number of intermediates (and/or reaction steps) involved in the hydrogenationdehydrogenation cycles and the non-trivial interplay between structures and reactivities. Simple binary component systems: Amides-hydrides. The lithium amidelithium hydride [LiNH2 + LiH] combination, containing both protonic and hydridic components was perhaps the rst step towards a reversible and light-weight multicomponent hydrogen store.62,63 The reactions with varying amide:hydride ratios and their mechanisms have been widely investigated. With the realisation that the LiNH2LiH system was restricted in its ability to release hydrogen under favourable and practical conditions, several alternative binary combinations of amides and hydrides have been investigated.74,105133 In addition to reacting Group-II hydrides such as MgH2 or CaH2 with LiNH2, another option was to react binary hydrides (such as LiH) with Mg(NH2)2 with the reasoning that the latter amide has a lower decomposition temperature than the lithium counterpart, LiNH2. The initial studies by Chen and co-workers reacted LiNH2 with MgH2 or CaH2 with the aim of destabilising the ternary imides.74 Their results showed a remarkable drop in the hydrogen uptake and release temperatures as revealed by temperature programmed absorption and desorption studies (Fig. 7). Based on the starting composition, the chemical formula of the compound produced in the LiNH2:MgH2 2:1 reaction was proposed to be Li2MgN2H2. Interestingly, after the rehydrogenation step, the initial components (LiNH2 and MgH2) were not regenerated and instead Mg(NH2)2 and LiH were the products.74 Subsequent studies of the LiMgNH system with varying ratios of Mg(NH2)2:LiH (or LiNH2:MgH2)105110 demonstrated that an onset of hydrogen desorption as low as 150 1C was achievable while maintaining up to B5 wt% of hydrogen in these systems.74,106108 Recently, Alapati et al.111 predicted a 1:1 LiNH2-MgH2 hydrogen storage system with 8.19 wt% capacity by density functional theory (DFT) calculations: LiNH2 + MgH2 2 LiMgN + 2 H2 (10)

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Fig. 7 Temperature-programmed absorption (a) and desorption (b) curves for (I) 2LiNH2 + CaH2, (II) 2LiNH2 + MgH2 and (III) Li2NH samples (Reprinted from ref. 74, with permission from Wiley-VCH).
First-principles calculations of total energies and vibrational free energies for the same binary composition have suggested the following sequential reactions:112 LiNH2 + MgH2 - 1/2 Mg(NH2)2 + LiH + 1/2 MgH2 - 1/4 Mg(NH2)2 + 1/4 Mg3N2 + LiH + H2 - 1/4 Li2MgN2H2 + 1/4 Mg3N2 + 1/2 LiH + 3/2 H2 - LiMgN + 2 H2 (11)
However, experimentally a new intermediate compound with composition Li2Mg2(NH)3 was identied113 on dehydrogenation of the initial mixture at 210 1C although this mixed imide phase was known long ago.114 LiNH2 + MgH2 - 1/3 Li2Mg2(NH)3 + 1/3 MgH2 + 1/3 LiH + H2 (12)
A recent XRD and IR investigation showed that the 1:1 LiNH2MgH2 system released 6.1 wt% H2 rst during ball milling and then by subsequent heating that followed a four step reaction.115 LiNH2 + MgH2 - 1/2 Mg(NH2)2 + LiH + 1/2 MgH2 (12 h ball milled) -1/2 MgNH + 1/4 Mg(NH2)2 + LiH + 1/4 MgH2 + 1/2 H2 (36 h ball milled) -1/2 Li2MgN2H2 + 1/2 MgNH + 1/2 LiH + 1/4 MgH2 + H2 (at 220 1C) -1/4 Mg3N2 + 1/4 Li2MgN2H2 + 1/2 LiH + 3/2 H2 (at 390 1C) (13)

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Nevertheless, the predicted product lithium magnesium nitride, LiMgN, was not realized in this study and only 1 equivalent of hydrogen was rechargeable under high hydrogen pressure.115 Given that in the initial studies of the reactions of LiNH2 with MgH2 an initial exchange reaction occurred to produce Mg(NH2)2 on dehydrogenation and subsequent rehydrogenation, further explorations employed various ratios of Mg(NH2)2 and LiH, as starting materials. According to Nakamori et al.,116 the following overall reaction occurs for a 1:4 Mg(NH2)2LiH ratio: Mg(NH2)2 + 4 LiH 2 1/3 Mg3N2 + 4/3 Li3N + 4 H2
(14)
Although a calculated value of 9.1 wt% of hydrogen was expected from the above reaction, the experimental weight loss at 527 1C was only B7 wt%. However, importantly, the major weight loss occurred below 230 1C which is lower than the equivalent desorption in the LiNH2 + 2 LiH system. Amide:hydride ratios of 1:2 and 3:8 for the Mg(NH2)2LiH system were also investigated, viz:74,107,109,117121 Mg(NH2)2 + 2 LiH 2 Li2Mg(NH)2 + 2 H2 3 Mg(NH2)2 + 8 LiH 2 4 Li2NH + Mg3N2 + 8H2 (15) (16)
Reactions (15) and (16) were expected to release 5.6 and 6.9 wt% of hydrogen. The above combinations were systematically investigated by thermogravimetry, PCT and XRD studies.120,121 While the pressure-composition isotherms were similar at 250 1C, the quantity of released hydrogen was more with higher LiH content. (5.4, 4.5 and 5.1 wt% for reaction 14, 15 and 16, respectively).120 Moreover, the mass spectrometry proles at B190 1C indicated an increase of ammonia production for compositions with smaller equivalents of LiH. According to the report of Aoki et al. all the reactions, Mg(NH2)2 + 2 LiH, 3 Mg(NH2)2 + 8 LiH and Mg(NH2)2 + 4 LiH, showed similar desorption PC isotherms with the formation of Li2Mg(NH)2 as the nal product at 250 1C and the equilibrium dehydriding reactions had no serious eect on the quantity of LiH.121 The structure of the intermediate imide Li2Mg(NH)2 was previously described in section 2.3. One fascinating outcome is the identication of a Li-rich and H-poor imide, Li2+xMgN2H2x, in the 3 Mg(NH2)2 + 8 LiH system studied by Nakamura and co-workers.119b The intermediate phase was synthesized and characterized as Li2.6MgN2D1.4 (using LiND2 and D2 gas)119b by combined synchrotron X-ray and neutron diraction experiments. The structure of Li2.6MgN2D1.4 has the same symmetry as the previously described Li2Mg(NH)2 but with a smaller cell dimension (Fig. 8). In addition, in the non-stoichiometric imide structure 30% of the D-sites are vacant [as compared to fully occupied sites in Li2Mg(NH)2] and the adjacent cation
Fig. 8 Structure of LiMgND intermediate (left) and formation scheme for Li2+xMgN2H2x (right) (Reprinted from ref. 119b, with permission from Elsevier B. V.).

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sites are 20% occupied (by contrast, vacant in Li2Mg(NH)2). Based on this, the following scheme has been proposed for the formation of the intermediate defect imide phase mediated by interfacial diusion of hydrogen (H from LiH and H+ from LiMgNH phase) (Fig. 8). More in situ studies by synchrotron and neutron diraction would enhance the understanding of the hydrogen uptake-release processes that occur in specic systems and the role of intermediates. A deeper understanding of intermediate structures and their formation mechanisms are key elements in the future design of materials.
Complex binary component systems: Amides-complex hydrides. Similar to the simple binary mixtures, complex binary composite systems are considered here as reactive mixtures of complex hydrides, such as borohydrides or aluminohydrides with amides or binary hydrides. Thermodynamic destabilisation with combined chemical systems occurs either through chemical destabilisation of the hydrogenated state or by formation of stable products on dehydrogenation.3b An illustration of the chemical destabilisation of LiBH4 was provided by Vajo and co-workers with a reduced decomposition temperature achieved in a 2:1 mixture of LiBH4 and MgH2 as compared to pure LiBH4.122 The formation of stable MgB2 (reaction (17)) in the dehydrogenated state seems to drive the reaction with an enthalpy gain of 25 kJ mol1 of H2.122 2 LiBH4 + MgH2 2 2 LiH + MgB2 + 4 H2 (17)
A reversible storage of more than 9 wt% hydrogen (theoretical capacity 11.9 wt%) has been demonstrated for reaction (17) when catalysed with 23 mole% of TiCl3.122 It is worth noting here that a very small amount of LiBH4 mixed with MgH2 also enhanced the dehydrogenation/hydrogenation kinetics of MgH2.123 The requirement of a reduced temperature (168 1C) for an equilibrium hydrogen pressure of 1 bar in the 2LiBH4MgH2 system indicates that both LiBH4 and MgH2 are destabilised.27 Subsequently, similar destabilisation strategies have been employed for many other complex hydride combinations.124 With the successful demonstration of the hydrogenation reactions (18) and (19), it has been suggested that MgB2 facilitates production of metal borohydrides by promoting the formation of the [BH4] complex anion.124b 2 NaH + MgB2 + 4 H2 - 2 NaBH4 + MgH2 CaH2 + MgB2 + 4 H2 - Ca(BH4)2 + MgH2 (18) (19)
Very recently, another new coupled complex hydride system, LiBH4/CaH2, was reported with a theoretical capacity of 11.7 wt% via the following reaction:124f 6 LiBH4 + CaH2 2 6 LiH + CaB6 + 10 H2 (20)
Interestingly, the above reaction, with TiCl3 added, reproducibly stores 9.1 wt% hydrogen (95% of the theoretical total accounting for the added wt. of catalyst in the calculation) and cycles between LiBH4CaH2 and LiHCaB6 in the hydrogenated and dehydrogenated state respectively.124f Despite many advantages, this system is highly unlikely to be suitable for onboard storage due to the high equilibrium temperature at 1 bar H2 (418 1C) predicted from thermodynamic calculations based on experimental data under diering conditions.124f

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Another destabilised complex binary mixture, which has been investigated simultaneously by Aoki et al. and Pinkerton et al., is that of LiBH4 and LiNH2.125,126 A dehydrogenation enthalpy of 23 kJ mol1 of H2 was predicted for a (2:1) LiNH2 + LiBH4 mixture, which is lower than either of the individual LiNH2 and LiBH4 components, according to the following dehydrogenation reaction (21) by rst-principle calculations.125a LiBH4 + 2 LiNH2 - Li3BN2 + 4 H2 (21)
Experimental investigations of this mixture were carried out by ball milling followed by XRD analysis and by p-c isothermal measurements. A new phase was identied upon ball milling and was indexed in a cubic cell (10.67 A).125a In a separate study Pinkerton et al. reported formation of a quaternary hydride, Li3BN2H8, that formed by either ball-milling or heating (above 95 1C) the same binary mixture.126a They also noticed melting of Li3BN2H8 at B190 1C followed by Z 10 wt% hydrogen release above B250 1C.126a Soon after, the compound was identied as a lithium borohydride amide, Li4(NH2)3BH4, with a bcc structure (lattice parameter 10.66 A).127 This phase, however, did not match with the starting stoichiometry indicating a non-stoichiometric reaction of LiBH4 with 2 LiNH2. The ideal reaction stoichiometry was determined to be a 3:1 ratio of LiNH2 and LiBH4 to produce the LiNBH quaternary phase. Although Li4(NH2)3BH4 had a high hydrogen content of 11.9 wt% and the major decomposition product of this phase above 260 1C was hydrogen, it is non-reversible.127 Recently, many new destabilised systems with enhanced hydrogen capacity and thermodynamics have been recognised by DFT based computational studies.111,128 However, it is often observed that the introduction of a non-hydride second species diminishes the overall gravimetric capacity of the mixed system. Chemical destabilization of LiAlH4 by LiNH2 was originally shown by Lu and Fang employing a thermogravimetric study of a 2LiAlH4 + LiNH2 mixture.129 The system released B8.1 wt% of hydrogen between 85 and 320 1C in three dehydrogenation steps without any catalysts.129 The reaction involved a two step decomposition of LiAlH4 similar to NaAlH4 (eqns (3) and (4)) followed by a third step as per the dehydrogenation in eqn (6). The resulting overall reaction can be represented as in eqn (22).129 2 LiAlH4 + LiNH2 - LiH + Li2NH + 2 Al + 4 H2 (22)
Ball-milling of other molar ratios, (1:1) and (1:2), of the LiAlH4LiNH2 system have also been investigated. The (1:1) LiAlH4LiNH2 system has emerged as an interesting case that releases 6.1 wt% hydrogen under ball-milling as reported by Xiong et al. and the enthalpy eect of the H2 release reaction was very low.130 Afterwards, reversible storage was reported by other groups in the LiAlNH system.131,132 For example, a Li3AlH63LiNH2 mixture with 4 wt% TiCl31/3AlCl3 releases 7.1 wt% of hydrogen in two dehydrogenation steps between 150 and 300 1C.132 It was demonstrated that in short-cycle experiments the system is 100% reversible with the following overall reaction (23):132 Li3AlH6 + 3 LiNH2 2 Al + 3 Li2NH + 9/2 H2 (23)
Recently, Liu et al. have reported a new chemical system LiAlH4Mg(NH2)2 (1:1) with a hydrogen content of 8.5 wt% and releasing 6.2 wt% under ball-milling near ambient temperature.133 The overall reaction was expressed as: Mg(NH2)2 + LiAlH4 - 1/3 Mg3N2 + 1/3 Li3AlN2 + 2/3 AlN + 4 H2 (24)
Further investigations are suggested to explore its potential for on-board storage concentrating on the capacity and reversibility issues.

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Ternary composite systems: Amides-hydrides-borohydrides. In addition to simple and complex binaries the strategy of hydride destabilisation was extended to ternary mixtures.134137 Recently Yang et al. have reported a self-catalysing ternary composite LiNH2/LiBH4/MgH2 (in a 2:1:1 molar ratio) that has resulted in enhanced low temperature desorption kinetics with reduction in ammonia liberation as compared to the state-of-the-art binary composites (Fig. 9).134 It is believed that the self-catalysing eect is due to a set of coupled reactions, LiNH2 + LiBH4 - Li4BN3H10 2 Li4BN3H10 + 3 MgH2 - 3 Mg(NH2)2 + 2 LiBH4 + 6 LiH
(25-1) (25-2) (25-3) (25-4)
2 Li4BN3H10 + 3 MgH2 - 3 Li2Mg(NH)2 + 2 LiBH4 + 6 H2 Mg(NH2)2 + 2 LiH 2 Li2Mg(NH)2 + 2 H2
where the rst step (251) occurs during the milling and the produced Li4BN3H10 melts and reacts with MgH2 when the mixture is heated to 100 1C (reaction (252)). The rst hydrogen desorption begins at 150 1C by reaction (253). The total capacity of 8.2 wt% can only be achieved at higher temperatures (up to 375 1C) with further reaction of Li2Mg(NH)2 and LiBH4 forming Mg3N2, Li3BN2, traces of LiH plus an unknown phase.134c It is thought that pre-formation of Li2Mg(NH)2 in step (25-3) provides nuclei for subsequent reaction (step (254)) in a Li4BN3H10 melt (acting as
Fig. 9 Hydrogen and ammonia desorption kinetics data as a function of temperature for 2:1:1 LiNH2/LiBH4/MgH2 ternary mixtures and comparison with other unary and binary systems (Reprinted from ref. 134c, with permission from Wiley-VCH).

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an eective mass transfer medium) and is self-catalysed.134c Another point to note is that step (254) is the only reversible one in the entire reaction sequence. A subsequent study systematically investigated the impact of MgH2 on the ternary system LiNH2LiBH4MgH2 with 2:1:x molar ratios and 0 r x r 1. This study suggested that the addition of MgH2 facilitates milling-induced reaction and reduces the ammonia release.135 Conversely, however, with the addition of MgH2 the total theoretical capacity of the system decreased. This work conrmed the direct involvement of MgH2 in the rst desorption event as x is varied in the LiNH2 LiBH4MgH2 ternary mixture. It corroborated the previous study for the (2:1:1) system (i.e., when x = 1) in demonstrating that this was the optimum composition for low temperature hydrogen release (B4 wt%) and indicated future opportunities for further kinetic enhancements.135 In a study of another ternary mixture, Mg(NH2)22LiHLiBH4, and with comparison with the LiNH2LiBH4MgH2 ternary system above, the former showed very similar hydrogen desorption, thermal eects and structural changes.136 However, Mg(NH2)22LiH0.67LiBH4 gave 9.1 wt% hydrogen at 300 1C, higher than the total theoretical capacity of the 2 LiNH2MgH2LiBH4 composite.136 The eects of varying the reaction stoichiometry in the (LiNH2)X(LiBH4)Y(MgH2)Z ternary system (ratio x:y:z) have been recently investigated by Sudik et al.137 Among the 2:1:2, 1:1:1, 2:0.5:1 and 2:1:1 ratios tested (in ref. 134), only 2:1:1 and 2:0.5:1 were reversible. The 2:0.5:1 stoichiometry had a maximum capacity of 8.6 wt% of which only 3.5 wt% was reversible at low temperature (180 1C). 2.5 Ammonia-borane and amido-boranes Ammonia-borane (NH3BH3) is considered to be an attractive candidate within the chemical storage category largely due to its safety features and a high hydrogen content of 19.6 wt% that exceeds that of gasoline.138141 NH3BH3 is a colourless solid that is stable at ambient temperature and was rst synthesised in 1955.142 Many other preparative methods, both in solution and in the solid state, have since been described.143146 In the context of amide-hydride destabilization combining the protonic and hydridic hydrogens, NH3BH3 is a remarkable compound in that both hydridic BH and protonic NH bonds exist within the same molecule.147 Moreover, the strong BN bond prevents ammonia and borane emission prior to hydrogen release under most thermolysis conditions. Although the detailed mechanism for the decomposition of NH3BH3 is not clear yet, signicant progress has been made towards understanding its hydrogen release reactions.141,148156 During thermal decomposition several intermediates have been reported and the desorption products vary depending on the thermolysis conditions (temperature range, ramping rate). Intermediate species such as polyaminoborane, [NH2BH2]n, polyiminoborane, [NHBH]n, and even a small fraction of borazine, [N3B3H6], have been identied as part of the dehydrogenation process. According to Wolf and co-workers149,150 the stepwise solid state decomposition of NH3BH3 to release 12 wt% H2 can be represented as: n NH3BH3 (s) - [NH2BH2]n (s) + n H2 (g) [NH2BH2]n (s) - [NHBH]n (s) + n H2 (g) [NH2BH2]n (s) - [N3B3H6]n/3 (l) + n H2 (g) (26-1) (26-2) (26-3)
NH3BH3 decomposition often requires a long induction period. Use of ionic solvents has been shown to reduce the induction period and speed up the kinetics of hydrogen

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release.152 Several approaches have been employed to reduce dehydrogenation temperatures,139 increase the kinetics of H2 release152,157168 and minimize borazine emission.152 Use of transition metals,157,158 base-metal catalysts,162 acid catalysis,163 nanoscaolds,139 ionic liquids152 and carbon cryogels164 are reported to improve dehydrogenation properties. Recently, a signicant development in the hydrogen release temperature has been reported by Xiong et al. in alkali-metal amidoboranes, LiNH2BH3 and NaNH2BH3, releasing 10.9 and 7.5 wt% of hydrogen (Fig. 10), respectively, at B90 1C via:169 n LiNH2BH3 (s) - (LiNBH)n (s) + 2n H2 (g) 10.9 wt%
(27)
or n NaNH2BH3 (s) - (NaNBH)n (s) + 2n H2 (g) 7.5 wt% (28)
In addition, the compounds do not release unwanted borazine by-product and the reactions are devoid of lengthy induction periods and foaming. Moreover, the dehydrogenation process is less exothermic than NH3BH3 (the enthalpies of dehydrogenation from Li- and Na-amidoborane are 3 and 5 kJ mol1 vs. 5 kJ mol1 for NH3BH3), which would facilitate its o-board materials regeneration.169,172 Another derivative of NH3BH3, solvent-containing calcium amidoborane, Ca(NH2BH3)2 2THF,170,171 has also been reported with enhanced dehydrogenation kinetics and suppressed borazine release. Contrary to previous reports, a recent study indicated a signicant amount of ammonia emission from the sodium amidoborane, thereby decreasing the practical hydrogen content and suitability for use in fuel cells.173 Despite the several advantages of ammonia-borane and amidoborane systems, the most serious drawback is the lack of facile reversibility which makes them unsuitable for on-board storage applications. The thermal decomposition of ammonia-borane and amidoboranes is less exothermic in comparison to their hydrolysis, making them nearly thermoneutral which would greatly facilitate their o-board regeneration
Fig. 10 Time evolution of hydrogen release from alkali amidoboranes and post milled ammonia-borane at about 91 1C (Reprinted from ref. 169, with permission from Macmillan Publishers Ltd.).

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from solid decomposition products (BNHx). In spite of major progress, signicant challenges remain for the development of ecient o-board regeneration of ammoniaborane. With an ecient regeneration procedure, these systems could possibly serve as an alternative to other complex chemical hydrides as a sustainable hydrogen storage medium.
3. Physical storage
Unlike chemical storage where the hydrogen is held chemically to component atoms within a solid (formation of chemical bonds), in physical storage systems the hydrogen is attached/included to/in a host-a surface or porous solid-by much weaker interactions/forces commonly dened as a process of physical adsorption or physisorption. Coordination polymers, metal organic frameworks (MOFs), polymers with intrinsic microporosity (PIMs), activated carbons and zeolites are among the widely investigated examples of materials for hydrogen storage that operate via physisorption.3b In physisorption the forces of attraction between the hydrogen and the host originate mainly from weak van der Waals interactions, thereby restricting any signicant hydrogen adsorption to that at very low temperatures and/or at very high pressures. Notable progress has been made during the past few years with gas storage in MOFs using innovative materials design to improve their performance in terms of increased storage capacity. Metal-organic frameworks (MOFs) MOFs (also known as coordination frameworks, coordination network materials or coordination polymers) can broadly be thought of as synthetic analogs of naturally occurring zeolitic materials, mostly with a three dimensional framework. These frameworks are interconnected in such a fashion that ordered networks of channels and pores are generated within the structure. Due to their porous structures, various small organic molecules, solvent molecules and gas molecules can diuse in and out of the channel structures, sometimes selectively. The primary building blocks that form the MOFs are multidentate organic ligands (linkers) coordinating to a metal ion or a cluster of metal atoms. MOF materials often form with solvent molecules trapped within the pores and following removal of these solvent guests, the host materials are typically high in surface area and of low density. The rst report of a MOF as a potential hydrogen storage medium was published by Yaghi and co-workers in 2003.174 They demonstrated an uptake of 4.5 wt% of hydrogen at 78 K and 1 wt% at ambient temperature and a pressure of 20 bar in a Zn-containing framework material (MOF-5) of composition Zn4O(BDC)3 (BDC = 1,4-benzenedicarboxylate).174 They also reported up to 2 wt% of hydrogen uptake in topologically similar (replacing BDC with naphthalene linkers) isoreticularMOF-8 (IRMOF-8) at room temperature and 10 bar.174 After these remarkable reports, the hydrogen uptake in MOF-5 was established independently at about 4.55.2 wt% at 77 K and B50 bar.175 Realising their high potential as new materials for hydrogen storage, Rowsell and Yaghi outlined several strategies to improve the storage capacity of MOFs under more favourable working conditions.176 A variety of parameters, such as pore size, adsorption energy, impregnation, catenation and incorporation of open metal sites and lighter metals in MOFs were proposed that can be tuned for performance optimisation.176 Many of these parameters are interrelated so, for example, pore size can be modied by changing organic linkers or by catenation that occurs with

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interpenetration or interweaving of networks. Moreover, impregnation of another adsorbent within large-pore MOFs can lead to reduced pores. Pore size, in turn, has a direct inuence on the hydrogen adsorption enthalpy. A pore size comparable to the diameter of molecular hydrogen should increase the van der Waals interaction thereby increasing the enthalpy.176 Similarly, higher enthalpy would also result from interaction of hydrogen with frameworks having coordinatively unsaturated metal centres or open metal sites. Subsequently, a variety of framework materials have been synthesized and investigated for hydrogen storage applications.175189 Hydrogen uptake studies on a series of MOFs (IRMOF-1, -6, -11, -20, -74, MOF-177 and HKUST-1) reveal that saturation uptake correlates with the surface area.175a,d At 77 K the saturation uptake and the saturation pressure varied widely in the series reaching a strikingly high capacity of 6.7 and 7.5 wt% in IRMOF-20 and MOF-177 at saturation pressures of 70 and 80 bar, respectively.175a Many of the initial studies aimed at highly porous frameworks with high surface areas. Another recent report by Lin et al. showed high hydrogen uptake of 6.07 wt% at 20 bar (at 77 K) and projected 7.01 wt% from Langmuir plots for MOFs with a BET surface area of 2932 m2 g1.181 It has been demonstrated in MOFs that high surface area and pore volume are approximately proportional to the amount of stored hydrogen.175a,181,190 Very high storage capacities have also been reported in a series of MIL (Materiaux de lInstitut Lavoisier) MOFs possessing extremely high surface areas and concentrations of unsaturated metal sites. It is noteworthy that MIL-101 (based on Cr-carboxylates) adsorbs large amounts of hydrogen reaching nearly 6.1 wt% at 77 K.188 Its high heat of adsorption (10 kJ mol1) at low pressures was believed to be related to small pore sizes.188 It must be pointed out that the maximum hydrogen uptake (up to the plateau of isotherm at 77 K) in the MOFs varies almost linearly with the specic surface area. However, a conicting scenario appears with large pores. While a large pore volume is required to enhance storage capacity, the interaction strength with hydrogen becomes weak with wider pores. In a Ni-based nanoporous framework with exible linkers, the hydrogen was shown to conne within the pores where the entry to the pores was controlled by dynamical opening of the pore windows.191 This implies that once hydrogen is adsorbed at high pressure it can be stored at low pressure. Moreover, the metal centre and the organic linker units were identied as the two major hydrogen binding sites in the MOFs by inelastic neutron scattering experiments and theoretical studies.192,193 MOFs with unsaturated coordination positions or open metal sites have been explored and shown to be attractive for hydrogen storage.177,178,184,192194 For example, HKUST-1 or Cu-BTC based on Cu(COO)4 unit and benzene-1,3,5tricarboxylate linkers possessing smaller pores (as compared to MOF-5) and Cu(II) open metal sites show enhanced hydrogenadsorbent interactions and consequently higher heats of adsorption.177,184,194196 Many possibilities for creating MOFs with exposed metal sites have been reviewed recently.197 It is proposed that increasing the hydrogen binding anity and accordingly imparting a high adsorption enthalpy can be achieved by systematic incorporation of unsaturated metal ions. Bhatia and Myers calculated the optimal enthalpy of adsorption to be 15.1 kJ mol1 for storage at 298 K with operating pressures between 1.5 and 30 bar.198 Limitations due to decreased H2 adsorption with increasing temperature have been improved in some MOFs by increasing H2-adsorbent surface interactions.184,199201 Recently, strong interaction between hydrogen and exposed metal sites within MOFs have been demonstrated with very high heat of adsorption values of 12.3 and

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13.5 kJ mol1.202,203 The total stored amount was dependent on surface area and pore volume which led to the conclusion that, a high surface density of strong adsorption sites is required for ecient storage under workable conditions.203 Recently, many so-called covalent organic frameworks (COFs) have been synthesised and structurally characterised.204208 By contrast to MOFs, within COFs the organic structural building units are held together by strong covalent bonds (for example, CC, CO, BO, SiC) as opposed to metals. The resulting solids possess a very low density and an ultrahigh porosity. These properties of COFs make them excellent candidates for hydrogen storage. Theoretical studies on prototypical COFs predict that storage of up to 10 wt% H2 in COF-5 (at 80 bar) and COF-8 (at 100 bar) is possible.204,207 In COF-8 an excess hydrogen uptake of 10 wt% has been found experimentally at 77 K and 100 bar (Fig. 11).208 These values are signicantly higher than the highest values reported in MOFs (7 wt% in MOF-177 and 7.1 wt% in MOF-5) although the pressure employed is quite high at 77 K.175a,209 Also, the 3-D COFs show 2.5 to 3 times higher storage capacity than the 2-D COFs. The associative hydrogen storage in COF-8 is the highest value reported for a framework material.208 Another new development for increasing the hydrogen uptake of MOFs is the hydrogen spillover technique.210 By employing this technique Li et al. reported an eightfold enhancement in hydrogen uptake in MOF-5 and IRMOF-8.210 The enhancement was attributed to the secondary spillover of hydrogen atoms from a Pt/activated carbon (AC) catalyst to the surface of MOFs in a composite system. Further, signicant improvement in H2 uptake capacity at near ambient temperature (30 1C) has been predicted in Li-doped MOF-C30 with a gravimetric uptake of 6 wt% at 100 bar and Fig. 12 shows how enhanced gravimetric capacity for an array
Fig. 11 Hydrogen adsorption isotherm of COF-108 in wt% at 77 K (Reprinted from ref. 208, with permission from American Chemical Society).

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Fig. 12 Gravimetric uptake of hydrogen as a function of BET surface area for MOF and Li-doped MOF at 300 K and 100 bar (Reprinted from ref. 211, with permission from American Chemical Society).
of Li-doped MOFs compares theoretically to the undoped materials.211 Hence despite a linear relationship with surface area in both doped and undoped materials, it is the lithium concentration that is believed to be the dominant factor for high uptake near room temperature.211 The introduction of Li-atoms within the framework has been proposed to functionalise the organic linkers211,212 and a gravimetric uptake of 4.5 wt% at room temperature and 10 wt% at 77 K at 100 bar has been predicted in MOFs by following this Li-doping strategy.213 Among the various MOFs reported, after independent authentication of 7.5 wt% hydrogen uptake at 77 K and 70 bar, MOF-177 is considered as an excellent material to serve as a benchmark adsorber.214 A very recent study by Schroder and co-workers showed promising uptake of 7.3 wt% in a Cu(II)-tetracarboxylate based framework (NOTT-103) at 77 K and 60 bar.215 This drop in pressure can be considered signicant in comparison to most of the previous studies conducted at pressures up to 100 bar. In summary, the small enthalpy change (heat of adsorption) in physically adsorbed MOFs oers a huge advantage for faster kinetics and reversibility over the chemisorbed materials. Heats of adsorption vary with the type of metal, framework topology, surface area and pore size and hence the extent of hydrogen adsorption in MOF materials can be inuenced by manipulating these parameters.216 Therefore, the exploration of new MOFs and developing an understanding of adsorption mechanisms are very important steps towards optimising the hydrogen storage properties of MOFs at near ambient conditions. Incorporation of moieties or functionalities that increase the interaction of the framework with hydrogen may increase the temperatures at which large quantities of hydrogen can be adsorbed. In addition, optimization of pore size without compromising the specic surface area and total pore volume will play a key role in developing viable materials.

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4. New materials for hydrogen storage

In this section, novel emerging materials for hydrogen storage will be considered. This will mainly encompass nanosized and nanostructured materials spanning the classes of solids described above. Both experimental studies and promising theoretical predictions of improved hydrogen storage will be highlighted. In parallel to common concepts in catalysis, it has been shown that decreasing the particle size to the nanoscale drastically improves the kinetics of hydrogenationdehydrogenation in metal hydrides and alloys. In this regard simple ball-milling can have a signicant eect in altering the grain size. Moreover, ball-milling can be also employed to disperse catalysts into chemical hydrides thus generating nanosized catalysts. As described in section 2.1, bulk MgH2 oers a high storage capacity of 7.6 wt% but its use is limited by the poor reversibility originating from the high thermal stability of the hydride and slow desorption kinetics.7 Although considerable eort has been devoted to modify the kinetics and lower Tdes of the bulk hydride, these approaches have aorded only relatively small improvements in the sorption kinetics and exerted little inuence over the desorption temperature (300 1C for bulk MgH2).7 However, in a combined quantum chemical (HartreeFock) and DFT study, Wagemans et al. have shown that both Mg and MgH2 become less stable with decreasing cluster size (below 20 Mg atoms), thereby decreasing the hydrogen desorption energy.217 The study showed signicant decreases in desorption energy below a crystal grain size of B1.3 nm. Moreover, another interesting outcome was the fact that the destabilization of MgH2 was stronger than Mg (Fig. 13).217 Similar destabilisation eects have been predicted in the case of Mg and MgH2 nanowires as well by DFT calculations.218 The calculations reveal the possibility of a room temperature hydrogen storage in MgH2 nanowires of 0.85 nm diameter.218 Recently, Li et al. have successfully synthesized nanowires of Mg and experimentally demonstrated the enhanced kinetics of hydrogen absorptiondesorption of nanowires as compared to bulk MgH2 and, moreover, the thinner the nanowire the lower the desorption energy (Fig. 14).219 Interestingly, despite the complete
Fig. 13 Calculated energies for Mg and MgH2 clusters as a function of cluster size (Reprinted from ref. 217, with permission from American Chemical Society).

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disappearance of nanowires (and their collapse to nanoparticles) after only 10 cycles, there was no change in capacity even after 50 hydridingdehydriding cycles.219 Also, Aguey-Zinsou and Ares-Fernandez have reported 7.6 wt% reversible storage near room temperature for Mg nanoparticles of 5 nm diameter.220 The size dependent performances even for a complex hydride, NaAlH4, have been reported recently by Balde et al.221 Hydrogen desorption temperatures of below 70 1C were achievable for 210 nm particles of NaAlH4 followed by reabsorption under low hydrogen pressures (beginning at 20 bar).221 Furthermore, recent reports describe the hydrogen desorption of hollow nanospheres of Mg(NH2)2 mixed with 2 moles of MgH2 nanoparticles starting at 375 K under hydrogen with enhanced desorption kinetics compared to bulk materials.222 Recently, the prospects of metal/metal hydride nanostructures were reviewed by Berube et al. considering both their advantages and disadvantages.223 Peng et al. have described some recent developments in Mg-nanostructures.30 There are advantages of low temperatue hydrogen cycling and fast kinetics but poor cycleability, degradation of sorption properties and a reduction in thermal conductivity would seem to suggest practical challenges that would need to be overcome.223 Therefore, the concept of hydride destabilization
Fig. 14 Hydrogen absorption (top) and desorption (bottom) curves of Mg nanowires at dierent temperatures; triangle, 3050 nm; circle, 80100 nm and square, 150170 nm diameters (Reprinted from ref. 219, with permission from American Chemical Society).

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via nanowire, nanotube or nanoparticle formation presents some immense opportunities for further development. More research is now required towards the development of synthesis methods for nanostructured materials together with much needed insight into every aspect of structure. Further, it is also worth noting that other structural factors may be utilised to modify and optimise sorption performance. For example, dierent polymorphs of MgH2 (a-, b- and g-phase) appear to have intrinsically dierent desorption temperatures.7c,224
5. Future directions and challenges for materials design

Despite signicant progress made in the development of solid state hydrogen storage materials, there remains immense challenges ahead before we enter into a genuine hydrogen energy era. Considering the two major storage types discussed, namely chemical and physical, there are advantages and disadvantages for mobile applications in both categories. For example, many of the complex chemical hydrides have high storage capacity with favourable kinetics or thermodynamics (to some extent), but mostly lack reversibility. Conversely, MOFs have very good reversibility, but the higher storage capacity is realized only at low temperatures (77 K) which is far beyond the operational temperature of PEM fuel cells. Apart from those discussed above, there are many other classes of materials that are also being investigated for potential hydrogen stores. These include PIMs,225227 carbon nanostructures,228,229 clathrates,230233 and zeolites.3b,234 Clathrates are compounds that are formed by association of two or more molecular entities and not by strong chemical bonds wherein one set of molecules encloses the other. Hydrogen is stored by a mode of encapsulation in a clathrate and can be released by changing the pressure or temperature.233 It is only recently that these materials have been suggested for hydrogen storage after the discovery of hydrogen clathrates.230233 More future work is necessary with clathrates before their potential can be judged. PIMs are formed either by polymerisation of monomers with rigid units (having restricted conformation or rotation) or by cross-linking of polymeric gels.225,226 They have been investigated for hydrogen storage due to their microporosity which gives rise to a large surface area and low density material. Storage capacities up to 2.17 wt% at 77 K and 10 bar have been reported in PIMs.227 However, due to the weak nature of interaction with hydrogen, similar to that of MOFs, their ambient temperature storage capacities are signicantly low. Strategies similar to those adopted for MOFs can be applied to PIMs towards improving their performance. Carbon materials including carbon nanotubes have been intensively invesitgated for hydrogen storage applications.228 Yang et al. have recently reported a reversible hydrogen uptake of 6.9 wt% at 77 K and 20 bar in an ordered porous carbon material.229 This is very a encouraging result and requires further attention. Besides carbon, hydrogen storage properties of inorganic nanowires and nanotubes of boron nitride (BN), titanium disulde (TiS2) and molybdenum disulde (MoS2) have been investigated.235 It seems apparent from the very limited studies of such systems that those involving light elements are more attractive than heavier ones to maximise the gravimetric capacity. For example, in collapsed BN nanotubes hydrogen uptake up to 4.2 wt% was reported at a pressure of 10 MPa.236 These diverse examples of very dierent materials show that there is still plenty of room for further invention and discovery in the bid to produce new solid state hydrogen storage solutions.

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Annual Reports on the Progress of Chemistry, Section A

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Hydrogen storage materials: present scenarios and future directions

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Ca(BH4)2 - 2/3 CaH2 + 1/3 CaB6 + 10/3 H2

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(25-1) (25-2) (25-3) (25-4)

2 Li4BN3H10 + 3 MgH2 - 3 Li2Mg(NH)2 + 2 LiBH4 + 6 H2 Mg(NH2)2 + 2 LiH 2 Li2Mg(NH)2 + 2 H2

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or n NaNH2BH3 (s) - (NaNBH)n (s) + 2n H2 (g) 7.5 wt% (28)

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4. New materials for hydrogen storage

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5. Future directions and challenges for materials design