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Metal hydride materials for solid hydrogen
storage: A review

Article in International Journal of Hydrogen Energy · June 2007
DOI: 10.1016/j.ijhydene.2006.11.022

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International Journal of Hydrogen Energy 32 (2007) 1121 – 1140
www.elsevier.com/locate/ijhydene

Review
Metal hydride materials for solid hydrogen storage: A review夡
Billur Sakintuna a,∗ , Farida Lamari-Darkrim b , Michael Hirscher c
a GKSS Research Centre, Institute for Materials Research, Max-Planck-Str. 1, Geesthacht D-21502, Germany
b LIMHP-CNRS (UPR 1311), Université Paris 13, Avenue J. B. Clément, 93430 Villetaneuse, France
c Max-Planck-Institut für Metallforschung, Heisenbergstr. 3, D-70569 Stuttgart, Germany

Received 31 July 2006; received in revised form 21 November 2006; accepted 21 November 2006
Available online 16 January 2007

Abstract
Hydrogen is an ideal energy carrier which is considered for future transport, such as automotive applications. In this context storage of
hydrogen is one of the key challenges in developing hydrogen economy. The relatively advanced storage methods such as high-pressure gas
or liquid cannot fulfill future storage goals. Chemical or physically combined storage of hydrogen in other materials has potential advantages
over other storage methods. Intensive research has been done on metal hydrides recently for improvement of hydrogenation properties. The
present review reports recent developments of metal hydrides on properties including hydrogen-storage capacity, kinetics, cyclic behavior,
toxicity, pressure and thermal response. A group of Mg-based hydrides stand as promising candidate for competitive hydrogen storage with
reversible hydrogen capacity up to 7.6 wt% for on-board applications. Efforts have been devoted to these materials to decrease their desorption
temperature, enhance the kinetics and cycle life. The kinetics has been improved by adding an appropriate catalyst into the system and as well
as by ball-milling that introduces defects with improved surface properties. The studies reported promising results, such as improved kinetics
and lower decomposition temperatures, however, the state-of-the-art materials are still far from meeting the aimed target for their transport
applications. Therefore, further research work is needed to achieve the goal by improving development on hydrogenation, thermal and cyclic
behavior of metal hydrides.
䉷 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Hydrogen storage; Review; Mg-based hydrides; Complex hydrides; Intermetallic compounds; Ball-milling; Kinetics; Storage capacity; Operating
temperature and pressure

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1122
2. Mg-based metal hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1123
2.1. Improvement on surface properties and mechanical ball-milling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1123
2.2. Cyclic stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1127
2.3. Catalyst effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1128
2.4. Chemical composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1129
3. Complex hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1129
3.1. Sodium alanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1130
3.2. Lithium and potassium alanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1131
3.3. Lithium nitrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1131
3.4. Lithium boro- and beryllium hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1132
4. Intermetallic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1133
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1135
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1136
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1136

夡 The work was carried out in LIMHP-CNRS.
∗ Corresponding author. Tel.: +49 (0) 4152 872673; fax: +49 (0) 4152 872670.
E-mail address: billur.sakintuna@gkss.de (B. Sakintuna).

0360-3199/$ - see front matter 䉷 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2006.11.022

chemical or complex hydrides and carbon nanos- fects on the environment. The hydrogen-storage capacity for car- possesses attractive attributes for hydrogen storage [2]. The Available technologies permit directly to store hydrogen experiments to date claiming very high values could not inde- by modifying its physical state in gaseous or liquid form in pendently be reproduced in different laboratories.87 ◦ C) and low density in the gaseous state gen required for automotive applications [9].8].5 H atoms/cm3 for MgH2 ) for developing leaks. in carbon nanostructures. Liquid hydrogen requires the addition Hydrogen forms metal hydrides with some metals and alloys of a refrigeration unit to maintain a cryogenic state [3] thus leading to solid-state storage under moderate temperature adding weight and energy costs. the experimental results on complex hydrides and carbon materials. volume-efficient storage method for on-board vehicle as a hydrogen source require the addition of a steam reformer applications. Designs involving the use of methane safe. and carbon nanofibers have been the subject of intensive developing hydrogen economy. storage of hydrogen in liquid than hydrogen gas (0. dependent on surface structure. Carbon materials such as activated carbons.2 H atoms/cm3 ) [3]. High-pressure storage of hydrogen gas is over the gas and liquid storage methods. x term vision for hydrogen-storage applications considering eco. (2) drogen available. Hence. In view of pressurized or in cryogenic tanks.1122 B. However. morphology and purity [10]. als differ in the ability to dissociate hydrogen. Metal hydrides have limited by the weight of the storage canisters and the potential higher hydrogen-storage density (6. oil for countries without natural resources. Hydrogen can be stored as (i) research.99 H atoms/cm3 ) or liquid hydrogen or gaseous form poses important safety problems for on-board (4. Met- the set goals. (1) 2 nomic and environmental parameters. direct dis- additional space requirements. sorption on carbon materials have definite advantages from the An optimum hydrogen-storage material is required to have the . These reactions are: The US Department of Energy (DOE) [5] published a long. and reducing dependence on imported tructures. and a resultant 40% loss in and pressure that gives them the important safety advantage energy content [4]. this ability being Storage by absorption as chemical compounds or by ad. cycle Tdes hydrogen desorption temperature DOE US Department of Energy tabs hydrogen absorption time H/M hydrogen atoms per metal atom tdes hydrogen desorption time Mm misch metals XRD X-ray diffraction 1. (0. (ii) cryogenic liquid. temperature of hydrogen desorption and low pressure of hydro. Sakintuna et al. Metal hydrides compose of metal atoms that constitute a host gen absorption (a plateau pressure of the order of a few bars lattice and hydrogen atoms. carbon nan- Hydrogen storage is clearly one of the key challenges in otubes. the cost of a storage medium and its toxicity formed. M + H2 ↔ MHx . (iii) solid fuel as chemical was dominated by announcements of high storage capacities or physical combination with materials. metal hydride storage is a transport applications. The traditional hydrogen. Introduction safety perspective such that some form of conversion or energy input is required to release the hydrogen for use. A great deal Hydrogen is the ideal candidate as an energy carrier for both of effort has been made on new hydrogen-storage systems. to extract the hydrogen from the carbon which adds weight. Each of these options orders of magnitude. Hydrogen storage in metal hydrides depends on differ- properties need to be carefully considered for the realization of ent parameters and consists of several mechanistic steps.08988 g/L) at 1 atm. -phase at which only some substrates and products of decomposition as reported by Schulz hydrogen is absorbed and -phase at which hydride is fully [6]. carbon nanostructures cannot store the amount of hydro- point (−252. The research on hydrogen storage in carbon materials pressurized gas. today’s knowledge although they have good reversibility prop- storage facilities are complicated because of its low boiling erties. There are two possible ways of hydriding a metal. at the decomposition temperature between 60 2 2 2 and 120 ◦ C for commercial viability. in- mobile and stationary applications while averting adverse ef. such as metal hydrides. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140 Nomenclature P–C pressure-composition Pabs hydrogen absorption pressure BCC body centered cubic Pdes hydrogen desorption pressure BM ball-milling Tabs hydrogen absorption temperature Cyc. and the need for a device to sociative chemisorption and electrochemical splitting of water. bon materials is reported between 0.5 wt% and 65 g/L hy. Moreover.2 and 10 wt% [7. sequester CO2 [1]. or produced on-board hydrogen storage in carbon nanomaterials scatter over several the vehicle by reforming methanol [1]. M + H2 O + e− ↔ MHx + OH− . cluding metal. The predicted minimum x x x hydrogen-storage capacity should be 6. Metal and hydrogen usually form at room temperature) and nonthermal transformation between two different kinds of hydrides. Furthermore. It was also predicted low where M represents the metal.

microstructures and grain size by ball-milling without [19–22] with good reversibility [23. those prepared by a conventional metallurgical method [65]. magnesium with superior powder morphology that gives re- ics and a high reactivity toward air and oxygen [25. As the reaction progresses. compounds. charge and discharge of hydrogen. They are especially interesting due to their light Diffusion is not the limiting step initially because no material weight and the number of hydrogen atoms per metal atom. sources. [58] investigated the structural difference between high desorption enthalpy. Diffusion through this hydride layer becomes optimizing the known hydrogen-storage materials.24]. limited energy loss during absorption/desorption kinetics [61]. Ther. Na. form a large variety of metal–hydrogen molecules and allows easy diffusion of hydrogen into the bulk. the Mg. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140 1123 following properties.26]. and new re. It is possible to control proper- (9 MJ/kg Mg) of all reversible hydrides applicable for hydrogen ties of the store material. This work will serve to evaluate solid fuel presence of MgO surface layer inhibiting diffusion of hydrogen. and well activated samples show smaller activation energies. alanates and intermetallic and apparent prefactors of Mg-based hydrides. The crystalline Mg2 Ni alloy obtained been investigated. The studies are conducted on finding optimum solid In addition to formation of a compact hydride layer. Andreasen et al. The increased surface loys for the development of new functional materials. The hydrogen-storage systems have been re. The induced lattice defects may based hydrides possess good-quality functional properties. Improvement on surface properties and mechanical of recycling and charging infrastructures and high safety. but chemisorption is the slowest step for pure Mg at this ones may enter the multiple component system only as a low. the metal surface.25]. Sakintuna et al. in the interior of the material. Many efforts for the milled MgH2 compared to the unmilled one are seen in has focused on Mg-based hydrides in recent years to reduce the Fig. much attention has been microstrain assists diffusion by reducing the hysteresis of hy- paid to investigations on specific material properties of Mg al. vibration absorbing. These can be accomplished to some extent by chang- low dissociation temperature. reduction in activation energy and enhanced kinetics observed ied Mg-based hydrides are summarized in Table 1.1. has been reacted and there are sufficient active sites available which is in many cases at the order of H/M = 2. The main effects There is considerable research on magnesium and its alloys of ball-milling are increased surface area. surface prop- benefit of the low cost of the abundantly available magnesium erties. Hydrogen absorption/desorption properties of recently stud. reversibility. The induced clability. MgH2 . high hydrogen capacity per unit mass and desorption temperature and to fasten the re/dehydrogenation unit volume which determines the amount of available energy. such aid the diffusion of hydrogen in materials by providing many as heat-resistance. reversibility and recy. B. hydrogen store for industrial on-board hydrogen storage tank Thus. low cost 2. The light metals such as Li. oxidized samples show large apparent activation energies design.20]. B and Al. formation of mi- for on-board hydrogen storage due to their high hydrogen. hydrogen diffusion takes abundant additive. has the highest energy density of hydrogen transformations. In this review. cro/nanostructures and creation of defects on the surface and storage capacity by weight and low cost [15]. ing the microstructure of the hydride by ball-milling (mechan- low heat of formation in order to minimize the energy necessary ical alloying) with elements which reduce the stability of the for hydrogen release. advantages and disadvan. High thermodynamic stability of MgH2 results in a relatively Huot et al. slow desorption kinet. hydrides and also by using proper catalysts to improve the mic hydride formation. storage. Besides. fast kinetics. we briefly men. exposure hydrogen-storage system [18]. to oxygen also lowers absorption rates due to the formation tion about hydrogenation properties. most likely for alteration of properties or as place and the hydride layer grows. Heavier [62]. according to specific applications. The ball-milling creating fresh surfaces during processing is 2. 1. cyclibility. point [63]. There is enduring research both on modifying and meable layer. which activates dissociation of hydrogen Be. creased by milling 10-fold. low heat dissipation during the exother. In recent years. It is used for production of nanocrystalline high temperature of hydrogen discharge. [64] have tages of different metal-hydride systems such as Mg-based reviewed the kinetics in terms of apparent activation energies metal hydrides. the additional cost of catalyst and with minimal loss of stor- The main disadvantages of MgH2 as a hydrogen store is the age capacity [58]. It was suggested compounds. A brief review of state-of-the art is reported on that variations in apparent activation energies correlate with the metal hydrides. The specific surface area is de- desorption temperature of 300 ◦ C at 1 bar H2 [15. ball-milling Hydrogen-storage as metal hydride has been the focus of in- tensive research. moderate dissociation pressure. The results showed high operating tempera. The activation energies for desorption were measured . by ball-milling has excellent surface properties compared with ture which is too high for practical on-board applications [27]. therefore. sites with low activation energy of diffusion. which corresponds to an unfavorable milled and unmilled MgH2 . Faster hydrogen desorption kinetics. reactions. markable improvement of kinetics and surface activity for modynamic properties of the magnesium hydride system have hydrogenation [21.7 wt% with the These include changing the alloy composition. A critical factor for hydrogen absorption by metals is ported in numerous studies [11–17]. the rate-limiting step in the hydride formation process [63]. high stability against O2 and moisture for long cycle life. Mg. producing a nearly imper- a catalyst. contact with catalyst during ball-milling leads to fast kinetics Magnesium hydride. complex hydrides. drogen absorption and desorption [30]. Mg-based metal hydrides an economic process that is widely applied to metal hydrides to achieve good surface properties [15]. MgH2 combines a high H2 capacity of 7. of a highly stable oxide layer [25].

2 BM Tabs and Tdes : 400 Pabs : 30 No data 9 cyc.03 [39] synthesis Pdes : 1.: stable after fourth cycle 2. MgH2 –5 mol% Fe2 O3 BM Tabs : 300 Pabs : 2–15 tabs: 20 No data 1.00 [49] MgH2 –5 at% Ti BM Tabs : 200 Pabs : 10 tdes: 3.56 [52] tabs : 10 Mg–30 wt% CFMmNi5 Mixing and Tabs and Tdes : 500 Pabs and Pdes : 3–10 tdes: 40 No data 5.00 [43] MgH2 –Mg2 FeH6 Mixing Tabs and Tdes : 350–525 Pabs and Pdes : 3.5 Mg17 Hydriding combustion Tabs and Tdes : 280–400 Pabs : 2.50 [50] Tdes : 300 Pabs : 10 tabs :1.6 Fe0. Nd.15 tdes : 3.7 Mg–30 wt% LaNi2.70 [30] Pdes : 1 MgH2 –5 mol% V2 O5 BM Tabs : 250 Pabs : 15 tabs : 1.40 [51] MgH2 –5 at% V BM Tabs : 200 Pdes : 0.1MgH2 –2LiNH2 BM Tabs : 200 Pabs : 30 Tabs : 30 9 cyc.49 [28] 1.30 [22.70 [37.: not stable 3.45 20 cyc.: not stable 5.7 tabs : 90–1440 600 cyc.00 [50] Tdes : 300 Pdes : 0.48 [43] MgH2 –5 mol% Al2 O3 BM Tabs : 300 Pabs : 15 tabs : 67 No data 4.6–93.4 Cr 0.: stable 5.30 [31.6 BM Tabs : 250–350 Pabs : 20 tabs : 1 2 cyc.60 [53] encapsulation Mg–10 wt% Al2 O3 BM Tabs and Tdes : 300 Pabs : 11 tabs : 60 5 cyc.70 [46] Tdes : 330–350 Pdes : 1 tdes : 10 Mg–30 wt% BM (hexane medium) Tdes : 300–550 Pdes : 2 tdes : 30 No data 5.20 [28] 90Mg–10Al BM Tabs and Tdes : 400 Pabs : 15 tabs : 2.66 [34] Pdes : 0.45] Mg–20 wt% TiO2 BM Tabs : 350 Pabs : 20 bar tabs : 2 No data 4.: stable 5.00 [50] B.32] Pdes : 12 tdes : 0.5 Ni1.66 Mg–10 wt% Fe2 O3 BM Tabs : 320 Pabs : 12 tabs : 60 3 cyc.: stable 5.29] Mg–5 wt% FeTi1.6 No data 3.6 3 cyc.28 BM Tabs : 280 Pabs : 30 tabs : 1.33 Not stable 4.5 tdes : 60 . Sakintuna et al.: stable after 2nd cycle 4.00 [48] tdes : 10 Mg–Fe–Mg2 FeH6 Mixing Tabs : 473–552 Pabs : 77–85 tabs : 90 600 cyc.83 MgH2 –5 at% Ni BM Tabs : 200 Pabs : 10 tdes : 5 No data 5.50 [44.: not stable 3.: stable 4.8 Mg–50 wt% ZrFe1.: stable 5.60 [36] La2 Mg17 –40 wt% LaNi5 BM Tabs and Tdes : 250–303 Pabs and Pdes : 4–7 tabs : 0.: stable 5.34 tabs : 15 Not stable 4.50 [35] Tdes : 480 Pdes : 1 tdes : 5 Mg–40 wt% ZrFe1.5–5.: stable 3. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140 Tdes : 300 Pdes : 0.62–15.: stable 3.33 No data 5.00 [47] MmNi4.6 BM Tdes : 270–280 Pdes : 1 tdes : 15 2 cyc.42] Pdes : 10 Mg2 CoH5 Mixing Tabs : 450–550 Pabs : 17–25 No data 1000 cyc.48 tdes : 5 Mg–50 wt% LaNi5 BM Tdes : 250–300 Pabs and Pdes : 10–15 tabs : 3.4 MgH2 –5 wt% V BM Tabs and Tdes : 300 Pabs and Pdes :1–3 tabs : 2 2000 cyc.5 tdes : 60 Mg–20 wt% Mm (La. Ce) BM (pellet form) Tabs : 300 Pabs : 10 tabs : 10 No data 3.4 Cr 0.7–19 No data 3.37 [28] 30 wt% Mg–M mNi5−x (CoAlMn)x BM Tabs : 15 Pabs : 6 tabs : 83 No data 2.10 [40] MgH2 –2LiNH2 BM Tabs and Tdes : 200 Pabs : 50 tdes : 60 4 cyc.15 tabs : 0.33 No data 5. 1124 Table 1 Hydrogen absorption/desorption properties of Mg-based hydrides Material Method Temperature (◦ C) Pressure (bar) Kinetics (min) Cycling stability Max wt% of H2 Ref.38] tdes : 4 La0.: stable 4.15 tabs : 16.30 [41.40 [33] Tdes : 300–350 Pdes :1 tdes : 5 Mg–10 wt% CeO2 BM Tabs and Tdes : 300 Pabs : 11 tabs : 60 5 cyc.21–11.43 [34] Pdes : 0.

: not stable 2 cyc.80 5.30 5 cyc. The pressure for hydrogen desorption cyclohexane medium) Wet-chemical method of the unmilled MgH2 is lower than that of the milled one.40 6.5 (milled) tdes : 10–35 tabs : 13. which are effective for the improve- BM BM BM BM BM BM BM BM BM ment of the hydrogen absorption rate.33 tdes : 150 tabs : 420 No data No data tabs: 4. [30] proposed that ball-milling of Mg–5 wt% MgH2 –0. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140 1125 [54] [34] [43] [50] [55] [56] [57] [58] [59] [26] [20] [60]  7.00 7.4 0.15 Pdes : 0. which results in an increase in the hydrid- MgH2 –5 at% Ge MgH2 –5 wt% V MgH2 –1 at% Al ing and dehydriding rates.2 tdes: 1. This describes the thermodynamic aspects of hydride forma- tion which is more visible in the Van’t Hoff plots that illustrate the relationship between equilibrium pressure and changes in enthalpy and entropy.60 5.00 6. respectively.15 bar [58].0–1.4 Pabs and Pdes : 1–2 as 120 and 156 kJ/mol for the milled and unmilled powders. the grain boundary does not Tabs : 200 Tdes : 300 Tabs : 200 Tdes : 300 Tabs : 180 dramatically affect the pressure–composition (P–C) isotherms. [67] proposed that ball-milling of the alloys under inert environment leads to reduction in powder size and Mixing creation of new surfaces.00 7.87 6. Pabs and Pdes : 4.: stable No data No data No data No data No data No data No data No data tdes : 50 (unmilled) tdes : 12.50 6. B.5 8. Sakintuna et al. the shift of the onset of desorp- Pdes : Pabs : Pdes : Pabs : Pdes : Pdes : Pabs : Pdes : Pabs : tion temperature can be as large as 100 ◦ C for MgH2 and 40 ◦ C for Mg2 NiH4 [66]. It has been found that ball-milling of Mg2 NiH4 vacuum vacuum 3–10 substantially decreases the desorption temperature.: stable 800 cyc.2 mol% Cr 2 O3 MgH2 –1 mol% Cr 2 O3 Mg/MgH2 –5 wt% Ni FeTi1. 1. Hydrogenation properties are very sensitive to these surface modifications.15 Pdes: 0.6 Pabs : 10 Pabs : 11 Pabs : 10 No data 1 1 on the ball-milling conditions. These . Nanocrystalline hydrides enhanced the hydro- genation kinetics. The ball-milled powders do not require activa- Tabs and Tdes : 300 Tabs and Tdes : 300 Tabs and Tdes : 300 Tabs : 300 (milled) Tdes : 350 (milled) Tabs andTdes : 300 tion compared to the conventional methods.: not stable 1000 cyc. Liang et al.15 0. even at relatively low temperatures. Aoyagi et al. Hydrogen absorption rate of Mg-based alloys also increases with the milling time. The high absorption rate is due to the large quantity of phase boundaries and the porous surface MgH2 structure [40].2 produces fine powder with nanometer-sized grains and Mg–0. as BM (benzene and seen in Fig.00 6.4 8.33 tdes : 8.70 7. Hydrogen desorption curves of unmilled MgH2 (solid symbols) and ball-milled (hollow symbols) MgH2 under a hydrogen pressure of 0. For all nanocrys- Tabs : 230–370 Tdes : 150–250 Tdes : 140–190 Tdes : 335–347 Tdes : 50–150 talline hydrides investigated. 2.00 7.5 wt% Nb2 O5 Mg–10 wt% Cr 2 O3 3Mg(NH2 )2 –8LiH MgH2 –2 mol% Ni MgH2 –5 at% Mn large microstrain.5 tdes : 33 tabs : 60 tdes : 60 tabs: 90 tabs : 6 tabs : 2 tabs : 1 tdes: 6 Fig. Depending Pdes : 0.

a hydrogen-absorbing material can be in bulk materials as thin film hydride is an emerging field of hydrogenated during ball-milling [70]. it was ball-milled MgH2 at 623 K [58].3 nm. Smaller parti- temperature of only 200 ◦ C [68]. Hydrogen-storage kinetics. [73] stable atomic positions into the metastable configuration. Alloying time temperature (200 ◦ C) but with markedly slow kinetics and has a significant effect on hydride properties of Mg2 Ni. Mg portions of the film have converted totally into MgH2 by ball-milling. proposed recently that the presence of nickel lowered the onset temperature of MgH2 desorption to 225 ◦ C by ball-milling un- der hydrogen atmosphere [71]. Desorption curves of magnesium catalyzed with 0. hence enabling hydrogen desorption at lower tempera. The results indicated that pul. The dehydriding temperature decreases with under H2 atmosphere [52]. [70] synthesized structures can be obtained by means of local change in the Mg2 Ni with the same method.100 m [25. Reaction kinetics is enhanced by increasing the tures. a hydrogen gas pressure of 1 bar at 100 ◦ C. 3. achieved complete formation of MgH2 . The hydrogen desorption energy decreases significantly milling time.9 nm corresponds to a desorption ate more active sights for hydrogen penetration.76] to cre- MgH2 crystallite size of 0. A to produce powders in the range of 60.1126 B. This method improved the hydride formation at temperatures not higher than 200 ◦ C [78]. 2. Ball-milling is generally used when the crystal grain size becomes smaller than 1. of grain boundaries. 10. only 0. [75] investigated MgH2 clusters have much lower desorption energy than bulk the effect of milling time on the magnesium hydrogen sorp- MgH2 . have been previously investigated. at 573 K and vacuum [75].15–0. lization in the Mg layer are prepared in different sputtering Mg–10 wt% Fe2 O3 is synthesized by mechanical grinding conditions [77]. [74] proposed that absorption capacity changes investigated the quantum chemical perspective of MgH2 .0 wt% It is concluded that ball-milling is a simple and inexpensive hydrogen [79]. Wagemans et al. research. Pd/Mg films with different degree of crystal- method of producing high hydrogen content metal hydrides. 3. Orimo et al. It was shown that ball. increase the density than 50 m [25]. Although extensive work has been done on hydrogen storage In another approach. 50 and 100 h. Small with alloying duration. After hydrogenation under verization and deformation processes occurring during high. found that ball-milling of Mg2 Ni under hydrogen resulted in Ball-milling of LiNH2 /MgH2 results in low dehydrogenation a significant facilitation of hydrogen desorption. [72] studied also the formation of metal properties of nanocomposite three-layered Pd/Mg/Pd films hydrides under H2 atmosphere. whereas the Mg film contains 5. Pressure–concentration–temperature curves of the unmilled and tances of hydrogen atoms. Chen et al. resulting in easier activation [69]. the faster it the formation of metal hydrides which causes simultaneous hy. [71] produced MgH2 under H2 atmosphere [77]. [68] dellaoui et al. Ab- lowered hydrogen uptake capacity [41]. Sakintuna et al.56 wt% H2 absorption. drogen penetrated to an average depth of 30 m and stopped milling.1 mol% Nb2 O5 and milled for 2. Huot et al. It was found that hy- drogen uptake and mechanical deformation resulting from ball. with 5. Barkhordarian et al.30 wt% H2 . 5. Particles with nanocrystalline cle sizes also eliminate the formation of hydride layers greater structure with grain size of 10 nm or less. It increases the H2 -sorption rates decreasing the degree of crystallization in the Mg layer in . / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140 Fig. Pd layers contain energy ball-milling play a major role in the hydriding reaction. Tessier et al. By using the same method. Research performed on thin films of pure magnesium milling under hydrogen atmosphere is a convenient method for concluded that the thinner the magnesium sheet. 20. tion reaction. by facilitating nucleation by cre- ating defects on the surface of Mg particles and reducing the particle size of Mg and thus by shortening the diffusion dis- Fig. as shown in Fig. Furthermore.

53 [74.6 wt% of hydro. and the than at the first cycle due to the agglomeration of the particles .50 [86] Mg2 Ni BM Tabs : 300 Pabs : 29 5 cyc. cycling temperatures Mg2 Ni [92]: and starting microstructures. and also require much longer milling times [82]. High hydrogen capacity of four than 190 ◦ C in a vacuum [77]. The hydrogen absorption Cyclic stability is one of the major criteria for applicability and desorption properties of Mg–Ni-based alloys are listed in of metal/metal hydride systems for reversible hydrogen storage.2. (3) ate phases can be obtained. All Upon hydrogenation.: stable 2. by mechanical alloying of Mg and Mg2 Ni can absorb hydro- driding kinetics of the resulting composites [80].29] reported that the hy. It was proposed that the organic additives erties are thought to be strongly affected by their nanometer- of benzene or cyclohexane are essential for decisive character. combined with the small specific Mechanical alloying can be preformed in the presence of or. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140 1127 Table 2 Hydrogen absorption/desorption properties of Mg–Ni-based hydrides Material Method Temperature (◦ C) Pressure (bar) Kinetics (min) Cycling stability Max wt% of H2 Ref.20 [87] Mg2 Ni BM Tabs : 300 Pabs : 11.6 tabs : 10 4 cyc.5 tdes : 10 [91] 65 wt% MgH2 –35 wt% Mg2 NiH4 BM Tdes : 220–240 Pdes : 0. Mg2 NiH4 forms eagerly by hydrogenating the alloy Depending on the nature of the additives. hydrogen atoms per Mg2 Ni.66 [90] Pdes : 1.: stable 5.2 wt% [89]. studied [80].: not stable 3. Cyclic stability light weight and low-toxicity [83] and for its unusual struc- tural and bonding properties [84.22. [22. with high capacity of 4.: stable 4.84.73. low cost.6 wt% dehydriding temperature is 250. ticular changes of the hydriding properties of the nanostruc- ditives (tetrahydrofuran. they absorb hydrogen more of graphite containing charge transfer to some extent. pressure of 15–50 bar [84]. Haussermann et al. MgNi2 prepared by ball-milling is found to react with sium with high-degree of dispersion [20]. In particular. Mg2 Ni reacts with 3. benzene or cyclohexane) have been tured Mg2 NiH4 have been also reported [19. the presence of tetrahydrofuran in The nanocrystalline Mg2 Ni intermetallic compound formed the milling process strongly affected the hydriding and dehy. 2.87]. Nanoparticles of Mg2 Ni such as hydrogenation/dehydrogenation temperature and hy.1–3. the samples absorb and desorb less hydrogen at the fifth cycle gen and transforms into the hydride phase. Sakintuna et al.350 ◦ C and powder. the conventional crystal phase [86.: not stable 3. respectively) [86]. weight of the alloy is the most important advantage of Mg2 Ni ganic solvents such as benzene. The Mg + Mg2 Ni composites synergetic interaction between Mg and aromatic carbon atoms need activation. Nanosized MgH2 ball-milled with benzene showed There are numerous publications regarding the upgrade of reversible hydriding/dehydriding with high capacity under 1 bar hydrogenation properties of Mg2 NiH4 . microstructural feature.00 [66] Pd/Mg films. The lowest crystallization of films absorb 5. [92] inves- driding properties of Mg-based composites which are prepared tigated the structural stability and bonding properties of the by mechanical milling of magnesium powder and graphite or Mg2 NiH4 using ab initio density functional calculations.94]. Zhu et al.25.66. Mg2 NiH4 attracts wide interest for being a promising hydro- gen store material due to its relatively high capacity. Table 2.10 [82] Pdes : 1–2 tdes : 1 70 wt% Mg–30 wt% LaNi5 BM Tabs and Tdes : 350 Pabs : 10 tabs : 30 10 cyc. leads to superior hydrogenation behavior including easy acti- drogenation rate. Song et al. als [80. Mg2 NiH4 .5 tabs : 10 20 cyc. can be more or less improved by forming vation and hydrogen uptake in the first cycle itself compared to composite structures. over other magnesium hydrides [93].: stable 3. various structures and intermedi- Mg2 Ni + 2H2 → Mg2 NiH4 . cyclohexane or carbon materi. [34] synthesized magne- sium hydrides with additives of Cr 2 O3 .60 [89] Mg2 Ni BM Tabs and Tdes : 280–330 Pabs : 1–15 tabs : 1 No data 4.88].74. Nanocrystalline Mg2 Ni drogen sorption properties of Mg and Mg–Ni-based alloys can with Pd exhibits much faster absorption kinetics at 200 ◦ C than significantly be improved by forming composites having proper the as-ball-milled samples (reaction halftime of 2 and 33 min. Par- graphite supporting 5 wt% Pd in the presence of various ad. B. Mg2 Ni–1 wt% Pd BM Tabs : 200 Pabs : 15 tabs : 27 4 cyc. Wet milling in the hydrogen even at room temperature. Their hydriding prop- hydrogen pressure. aspects. but once activated.300 ◦ C at desorption pressure of hydrogen and all hydrogen desorbed at a temperature lower of 2. There is a gen rapidly without activation.88] Mg–Mg2 Ni BM Tabs : 300 Pabs : 12 tabs : 83 2 cyc. scale structures by means of thermodynamic and kinetic istics of the resulting magnesium to sustain nanosized magne. whereas polycrystalline presence of toluene leads to hydrogen and carbon pick up in the material needs hydrogenation temperature of 250.50 [86] Mg2 Ni BM Tabs and Tdes : 280 Pdes : 1–2 No data No data 3. Al2 O3 and CeO2 . rapidly than Mg2 Ni at low temperature of 150 ◦ C under 12 bar It has been found that the hydrogenation properties of Mg.85].0 bar [22. Hy.81].

Also the cyclic stability of MgH2 + 0. of palladium is the main disadvantage for the industrial ap- ported formation phase changes. ation of hydrogen molecules.99]. [97] showed 15% decrease in hydrogen Titanium and vanadium block the oxidation of the alloy sur- capacity after 2100 cycles with a starting material of nanocrys. while CO and CO2 entirely prevented the uptake of [34.102]. less.Ti was eval. during the cycling process. Dehouche et al. face. [37] have re. tiple cycles [103]. Effective catalysts. segregation and disintegration plications [15]. sium. hydrogen capacity can be increased up to 5. The cyclic stability of MgH2 –5 wt% drogen capacity. This was attributed to the formation of the non. Holtz and Imam [76] achieved a 50% increase in hy- pacity. and through the hydride already formed. decomposition of palladium oxide [93]. [96] observed a decrease in the kinetics of hydrogen ab. Hydrogen-storage capacity increased 5% but It was also proposed that Cr 2 O3 yields fast hydrogen absorp- desorption properties deteriorated due to surface modification tion.5 Mg17 decreases with cycling [39]. [86] have also reported on the of La2 Mg17 + 40 wt% LaNi5 during cycling at temperatures presence of Pd as a catalyst in nanocrystalline Mg2 Ni. even added in small amounts enhance the formation of a hydride in reasonable extent. and therefore. 101 ppm moisture. performance over the lifetime of the material. The oxide particles may operate as a milling ball dur- hydrogen [98. The presence of Ge decreases previously examined at 1000 cycles. Vanadium also acts as a catalyst for the dissoci- et al. to achieve the same storage while the thermodynamic parameters of MgH2 were not altered capacity. 5. The reactivity of palladium after exposure to oxygen is stability [95. gration of the materials even when hydrogen content reached In addition to Pd and Ni.55]. There are few publications regarding high number of cyclic Hydrogen molecules have a strong affinity for nickel and tests. However. the capability of hydrogen to penetrate from the surface which is typically covered by an oxide layer into metal. Sakintuna et al. 4. CO2 and CO on a pure magnesium powder have been of different oxide catalysts that enhance hydriding properties studied [98]. [54]. There is in- tensive research about finding a proper catalyst to enhance the hydriding properties. Catalyst effect Catalysis is one of the critical factors in the improvement of hydrogen sorption kinetics in metal hydride systems that enables fast and effective dissociation of hydrogen molecules [21]. It was also reported that hydrogen capacity of and FeTi systems. Gross et al.1 Ni alloy shows hydride forming MgNi2 phase.3. Through the addition of 1 at% of nickel to magne- even after 800 cycles with small fluctuations in the hydrogen ca. It was reported that the rate of absorption is controlled by the following factors: the rate of hydrogen dis- sociation at the surface. hydrogenation onset temperature from 350 to 275 ◦ C. Misch metals through nanoparticles of Pd located on magnesium surface (Mm) such as Ce. but no loss in the hydrogen capacity a catalyst. The addition of TiO2 also resulted in . ing high-energy ball-milling that creates many defects in the uated after 1000 cycles under a H2 atmosphere containing Mg powder. such as V2 O5 [28] and Cr 2 O3 sorption. Zaluski et al. as shown in Fig. Ge can be used for the catalysis 5 wt%. high cost pacity and their reaction rate [35]. The Ti de- The resistance of metal hydrides to impurities is one of the creases the kinetic barriers of absorption while the Ni protects critical issues for on-board applications in order to maintain the alloy from deactivation due to oxide layer formation. the increased concentration of Mm recovered during exposure to hydrogen because of the easy in the samples has an adverse effect on hydrogen-storage ca. a decrease in the temperature for the onset of V is studied by Dehouche et al. an increase of H2 storage capacity is reported by 150 ◦ C. the system temperature had to be increased.5 Ni1. Palladium is a good catalyst for hydrogen dissociation re- action. good absorption kinetics at room temperature [104]. [48] up to 2000 cycles. are used to increase the cyclic [25]. depending on the catalyst amount. Nd and Pr. increase the discharge capacity over mul- talline Mg2 Ni. tion of hydrogen [57]. [43] investigated the behavior of Ni-doped readily dissociate and adsorb onto surface-layer nickel clusters Mg and Mg2 CoH5 . time for one full cycle 3 h [43]. enhance the absorption rates even at lower La0.2 mol% Cr 2 O3 is of hydrogenation kinetics [60]. Friedlmeier cycles [60]. as shown in Fig. O2 . The effects of The poor kinetics of MgH2 are greatly improved by addition N2 . Cyclic stability of chemical Ni-doped Mg at 503–643 K and 4. La. temperatures and maintain less sensitivity to air exposures. at relatively low temperature.V. The performance of MgH2 . 4. The hydriding properties are enhanced by catalysis during hydrogenation/dehydrogenation cycling. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140 2.9 Ti0. the rate of hydrogen diffusion into the bulk metal Fig. Defects provide hydrogen an easy path to Mg [28].1128 B.0 bar. They indicated that they are almost stable [101. and a lowering of the de- concluded that there is no change in isotherms and no disinte. Reiser et al.8 wt% of Mg–2 at% Ni alloy. But the catalytic ef- about 8% between the first and the 500 or 1000 cycle due to fect of Ge disappears after few hydrogen absorption/desorption structural relaxations and crystallite growth [55]. LaNi5 up to 350 ◦ C. A nanocrystalline Mg1. Although desorption time the hydride decomposition temperature in a range from 50 to is increased. They hydrogenation from 275 to 175 ◦ C. However. whereas V2 O5 and Fe3 O4 cause the most rapid desorp- of the particles [100]. It was also reported using V as sorption after 4300 cycles.35]. Neverthe. Both O2 and N2 slowed the rate of hydrogen ab. However.

36] combined both the catalytic and milling effect in a system of fine ZrFe1. lyst is sufficient to provide fast sorption kinetics. The composites containing Mg–Ti and Mg–V exhibited the alytic effect on Mg–50 wt% LaNi5 nanocomposite. Fe and Ni.5 mol% Nb2 O5 with a 7. elements lighter than magnesium that can also form solid-state markable enhancement in sodium alanates and magnesium. These catalytic complexes demonstrated re. Alanates are remarkable due to their high a possibility to combine two or more phases having different storage capacities. ZrFe1. Fastest kinetics are obtained using 0. the acti- Oelerich et al. the solubility limit of magne- sium in lithium slightly increased [106]. torted by milling with transition metals.2 mol% of the cata. Hydrogen desorption curves of mechanically milled MgH2 –5 at% V ature by controlling the applied hydrogen pressure and absence composite (hollow symbols) and MgH2 (solid symbols) under 0.4. B. have been investigated intensively [48. [31] prepared Mg/Al alloys by located at the corners of a tetrahedron. sistance [46].5 wt% at 200 ◦ C and 30 bar. But it improves the kinetics. pure unmilled Mg. The measured hydrogen capacity of are especially interesting because of their light weight and the the material decreases with Al content. the amount of catalysts used Formation enthalpy and entropy of magnesium hydride is dis- has a significant effect on hydrogen absorption behavior. Complex hydrides gen sorption reaction at 300 ◦ C is studied. as compounds with hydrogen.50. but the Mg2 FeH6 . which is more than double of liquid hydrogen [108]. a new type of catalytic compounds contact with water.0 wt% of hydrogen Another class of light-weight storage materials is com- capacity [26]. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140 1129 Wang et al. Me- chanical alloying of Mg with some elements such as Zn. Mn. low working temperature and excellent oxidation re.6 particles covering Mg particles that resulted in an enhancement in absorp- tion/desorption rates. amides [NH2 ]− . [43] considered the Mg2 FeH6 –MgH2 systems. In or Cd resulted in reducing the stability of magne- sium hydride. the hydrogen is often system [21]. Complex hydrides are known as “one-pass” In the search for efficient and inexpensive catalysts for hy. mechanically alloyed Mg–30 wt% LaNi2. In another study [51]. With energetic ball-milling. Ga. The effect of Nb2 O5 concentration on the kinetics of magnesium hydro- 3.4 Cr 0. value of 18 wt% for LiBH4 . V.109]. [49] and Reiser et al. The hydrogen content reaches the well as in hydrogen generation through hydrolysis [105]. imides and is one of the most important factors in the metal–hydrogen borohydrides [BH4 ]− . Bouaricha et al. plex hydrides. In such systems. kinetics. [57] investigated different amounts of oxides vation energy of desorption for magnesium hydride is reduced for catalysis but it is shown that only 0. Ag. Sodium.0 wt% which is one third less than magnesium dihy- dride with 7. Intense interest has developed in low weight complex hy- The type and the chemical composition of the metal alloy drides such as alanates [AlH4 ]− . Ti. Use of complex hydrides for hydrogen storage is challenging because of both kinetic and 2. Al.38 for Mg:Al (90:10). rapid Nanocomposites of MgH2 and 3d transition metals. and then to 1. dehydriding.7 wt%.05 Borates are known to be stable and decompose only at ele- for Mg:Al (75:25). The alanates and borates high-energy ball-milling.28 reported to have good hydriding properties with 5. Ball-milling has vated temperatures. of heat losses with time. they decompose in two steps upon hydrogenation characteristics [21]. Furthermore.40 wt% hydrogen storage under 30 bar hydrogen pressure. In addition to catalyst type. Chemical composition thermodynamic limitations. however. [40] suggested that La showed a cat. from H/M = 1. [33. That probably could account for the decrease in activation en- ergy. Liang et al. The intermetallic hydride Mg2 FeH6 shows the high volumetric hydrogen density of 150 kgH2 /m3 .4 Cr 0. the free choice and constancy of the heat delivery temper- Fig. The maximum amount of stored hy- drogen is 5. at 200 ◦ C.15 bar [54]. lithium and beryllium are the only is developed [105].MgH2 system possesses numerous advantages including the low price of starting mate- rials. rapid absorption kinetics such as absorption time of 2–5 min. Bogdanovic et al.6 dispersing homogeneously on the particle surfaces and in the interior of the material played an important role in promoting the decomposition of MgH2 . Sakintuna et al. Indium and cadmium gave the best results [107]. a markedly improved hydrogenation performance of Mg.74 for capacity for large number of hydrogen atoms per metal atom. hydrogen-storage systems which mean that H2 evolves upon drogen sorption reactions. to 1. . 5. Luo [44] developed LiNH2 /MgH2 system by partial substitution of Li by Mg which has a storage capacity of 4.

/ International Journal of Hydrogen Energy 32 (2007) 1121 – 1140 3. However.7 wt% H2 re. NaAlH4 and Na3 AlH6 contain large amounts alytic effects of doping materials in the enhancement of kinet- of hydrogen. Hence the enhancement of dehydriding kinetics is as- NaAlH4 ↔ 13 Na3 AlH6 + 23 Al + H2 . only the first two also investigated earlier [129]. 7.6 wt% reversible gravimetric hydrogen storage [111. Bogdanovic and Schwickardi [110. Fracture and fragmentation of particles ond reaction. the hydrogen- ies are being carried out to enhance the hydriding properties of storage performance of NaAlH4 was found to be highly de- NaAlH4 as listed in Table 3. Significant reactions of NaAlH4 : changes occur in the lattice parameters of sodium alanates upon doping.40 wt%. tion measurements indicate that the state of the precursor is of ditional metallic Al formation and hydrogen evolution. (4b) modifications of doped-NaAlH4 were also observed by Gross et al. effects of zirconium are poorer than titanium as a catalyst for tain reversibility under moderate conditions in the solid state. [124]. it is a superior Unlike intermetallic hydrides.4 and 5.1130 B. Ti-cluster-doped NaAlH4 form an intermediate compound. To improve the kinet- The process is characterized by slow kinetics and reversibility ics Thomas et al. the decomposition of NaAlH4 [130]. cyclic storage capacity However. The liquid alkoxides contribute energy. Ti-doped NaAlH4 is about 50 times as much as that of the ability in bulk. Mechanically alloyed Previously Jensen et al. Contrary to Sun et al. hydrogenation rate with number of cycles is observed [122]. [116]. com. same amount of hydrogen at 200 ◦ C within only 150 min and . The milled NaAlH4 or Na3 AlH6 reactions need to be considered. for the dehydrogenation of titanium and zirconium on NaAlH4 with XRD. The dehy- doping with proper titanium compounds. the decomposition of NaH are observed in particle morphology. [125]. Although titanium has positive effects as a catalyst. The direct synthesis of occurs at a much higher temperature. low cost and its avail. by using appropriate transition or rare-earth metals of 5 wt% H2 is achieved after 17 cycles. Na3 AlH6 exhibits faster kinetics than Na3 AlH6 obtained from hanced sodium aluminum hydrides. Stoichiometrically. [113] reviewed the catalytically en. The small size of the Ti clusters seem to be responsi- practical applications.112].127]. Phase transitions and crystal structure Na3 AlH6 ↔ 3NaH + Al + 23 H2 . the first step consists of 3. Moreover. However. (4a) sociated with dopant induced lattice distortions rather than the catalytic effect [124]. the amount of evolved hydrogen from the hydrogen-storage capacity of 5. undoped NaAlH4 . The hydrogen desorption can last of 5.9 wt%. is investigated [122. Under the same rehydrogena- hydrogen-storage material due to the theoretically reversible tion conditions. proved their performance as well [120]. but also the rehydrogenation reaction of NaAlH4 [118]. The even greater importance than the simple amount of Ti in the reversibility of these two reactions is a critical factor for the material. Sodium alanates are complex hydrides of aluminum and The dry-doping TiCl3 catalyst is investigated by the same sodium. hydrogen carriers due to irreversibility and poor kinetics. Recently. Both the hydriding and dehydriding possible candidate for application as a practical on-board rates increases by doping [123]. the re. is applied to prepare Na3 AlH6 [114]. ics of NaAlH4 . ble for the increase of the reaction rate [127]. decrease in as catalysts. because the decomposition of exhibited great improvement of the kinetics of absorption and NaH occurs at too high temperature of 425 ◦ C for practical desorption. [128] investigated the effects of mechanical only under severe conditions. the dehydriding of NaAlH4 to Na3 AlH6 and Al. with the total hydrogen Na3 AlH6 and Na2 LiAlH6 by energetic mechanical alloying was release of 7. It was earlier reported that the presence of Ti is lease of hydrogen does not occur in a single-step reaction. With 2 mol% TiN as a doping agent. Sodium alanates Moreover the surface of sodium alanate is damaged by the catalyst which causes decreasing the cyclic capacity.1. numerous stud. Na3 AlH6 and metallic Al. release hydrogen through a series of decomposition reactions Sun et al. For hydrogen storage. presence of catalyst. This clearly indicates that the addition of ti- Although they have good hydrogen-storage capacity. kinet- lease and the second step 1. low capacity and contamination problems noted above for the Sodium aluminum hydride. The hydrogenation and dehydrogena- This intermediate phase then decomposes to NaH with ad. [124] examined the details of the doping role as described in two equations below. not enough rather a particular local arrangement is required for NaAlH4 first decomposes evolving molecular hydrogen and the dehydrogenation reaction [126]. respectively. Finally. Sodium tetrahydroaluminate–NaAlH4 and trisodium group [123]. these complex-based hydrides catalyst for the dehydriding of Na3 AlH6 to NaH and Al [119]. The effects of liquid alkoxides Ti(Obun )4 + Zr(OPr i )4 on Consequently mechano-chemical synthesis method which in- hydriding properties of sodium alanates were investigated volves simply ball-milling of the appropriate reagents at high by Sandrock et al.9 wt%. would seem to be a alkoxide catalysts [116]. up to 4200 min in some cases [123]. and 260 ◦ C for the first and the sec. NaAlH4 . the complex hydrides can be made reversible. respectively. they proposed the cat- Theoretically. hexahydroaluminate–Na3 AlH6 have been known for decades. pendent on the milling time which increases with time [117]. Sakintuna et al.111] demonstrated upon Zirconium doping is also used for the same purpose. tanium species enhances kinetically not only the dehydrogena- plex aluminum hydrides are not considered as rechargeable tion. The operating temperatures are ball-milling on the microstructural character of NaAlH4 in the between 185 and 230 ◦ C. The addition of carbon in the milling process im- storage systems. the dehydriding of driding kinetics of NaAlH4 is significantly improved. It can desorb the to hydrocarbon contamination of the released hydrogen. It largely eliminates the high catalyst weight. for a theoretical net reaction ics is not fully enhanced. Although aluminum hydrides could be kinetically enhanced and main.6 wt%.

NaAlH4 –2 mol% Mixing Tabs : 104 Pabs : 88 tabs : 1020 3 cyc.30 [117] Tdes : 150 Pdes : 1 tdes : 600 stable NaAlH4 –2 mol% Ti BM Tdes : 25–160 Pabs : 20–120 tabs : 300–720 No data 3.5 wt% under 10 bar of hydrogen in a temperature range of high capacities of stored hydrogen as weight percent material. which is different from the reactions of NaAlH4 gen storage.3. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140 1131 Table 3 Hydrogen absorption/desorption properties of sodium alanates Material Method Temperature (C◦ ) Pressure (bar) Kinetics (min) Cycling stability Max Ref.50 [114] synthesis Na2 LiAlH6 BM Tabs : 211 Pabs : 45 tabs : 100 No data 2. corre. B.00 [110] Ti(Obun )4 Tdes : 180–160 tdes : 90 stable NaAlH4 –2 mol% TiCl3 BM Tdes : 125–100 Pdes : 83–91 tdes : 20 5 cyc. Lithium nitrides Li3 AlH6 . which decomposes easily.: not 4.: not stable 4.00 [113] (Ti(Obun )4 ) after second cyc. giving reaction rate about 10 times faster very high temperatures of above 680 ◦ C [114]. NaAlH4 Mechano-chemical Tabs and Tdes : 80–180 Pabs and Pdes : 76–91 tabs : 120–300 2 cyc.2 wt% for LiAlH4 and 3. even at room temper- Lithium nitride is usually employed as an electrode. was proposed by Ruff and Georges [140]: 2.3 wt% from the decomposition of LiAlH4 and reaction between Li3 N and H2 to Li3 NH4 . In fact Li3 NH4 has 2. and LiAlH4 [138]. The idea of hydrogen storage in lithium compounds goes The hydrogen released in the two reactions shown. It shows clearly 3. the than conventionally produced. the reversible reaction smoothly proceeds without In theory. LiAlH4 has an extremely high equilibrium pressure of hydrogen. After completion of the reactions.00 [122] after 17th cycle without a catalyst. Therefore. respectively. tal hydrogen content is 10.: not 3. starting material for the synthesis of binary or ternary nitrides.80 [118] Tabs : 25–193 Pdes : 1 tdes : 40 NaAlH4 –2 mol% Mixing Tabs : 120 Pabs and Pdes : 60–150 tabs : 1020 25 cyc. (5a) cations it was suggested that the metal–N–H system could prove to be a promising route for reversible solid hydrogen Li3 AlH6 → 3LiH + Al + 23 H2 . wt% of H2 Na3 AlH6 Mechano-chemical Tdes : 200 Pdes : 1 tdes : 150 No data 2. The hydrogen capacity was above storage compounds are summarized in Table 4. Lithium and potassium alanates desorption. LiAlH4 is in fact an example of an unstable hydride. (6) . when Dafert and Miklauz [139] reported the sponds to 5. The to.00 [116] NaAlH4 –2 mol% Mixing Tdes : 200 Pdes : 1 No data 3 cyc.00 [121] Ti(Obun )4 -C NaAlH4 –2 mol% TiN BM Tabs : 104–170 Pabs : 115–140 tdes : 30–1200 25 cyc.: not 5.: not 4. or as a ature. non-catalyzed hydrides [114].50 [115] NaAlH4 –2 mol% BM Tabs and Tdes : 125–165 Pabs and Pdes : 101–202 tabs : 60 5 cyc. studied previously [138].00 [116] Ti(Obun )4 –2 mol% tdes : 180 stable Zr(OPr i )4 NaAlH4 –4 mol% Ti BM Tabs : 120 Pabs : 120 tabs : 60 8 cyc.65 wt% from the decomposition of Li3 AlH6 at temperatures been proved to be the product of the following reaction.: stable 4.00 [119] Zr(OPr)4 3 after second cyc. 250–330 ◦ C. back to 1910. lithium alanates are very attractive for hydro.00 [120] synthesis tdes : 300 stable NaAlH4 –2 mol% Mixing Tdes : 200 Pdes : 1 No data not stable 5. but which cannot be re-hydrogenated Although the temperature required to release the hydrogen [114].: not 3. Sakintuna et al. The desorption of LiAlH4 occurs in two steps: at usable pressures is too high for hydrogen-storage appli- 3LiAlH4 → Li3 AlH6 + 2Al + 3H2 . The reversible hydrogen decomposition of KAlH4 has been A survey of important studies on lithium-based hydrogen. (5b) storage [45].: stable 5.65 wt% of the total hydrogen content in LiAlH4 remains unreleased in form of LiH which can be desorbed only at Li3 N + 2H2 → LiNH2 + 2LiH.00 [111] (Ti(Obun )4 Tdes : 180–260 tdes : 120–300 stable [112] NaAlH4 –2 mol% Mixing Tabs : 135–120 Pabs and Pdes : 150–130 tabs : 330 33 cyc.: stable 4. because of their high hydrogen content.5 and 11. commercialization of lithium-based compounds is hindered by their slow kinetics and high temperature absorption and 3. any catalyst.2. Unfortunately. which between 160 and 200 ◦ C.

5 Li3 BN2 H8 BM Tdes : 250–364 Pdes : 1 tdes : 228 No data 10. The compound was first synthesized by hydrogen capacity of 6 wt%.4 wt% hydro. isotherms cannot return to the origin. hydrogen capacity with very fast kinetics such as 3 min for LiBH4 is an expensive compound [15]. It was predicted that the dehydriding reactions Theoretically 7 wt% of hydrogen can be reversibly stored in of LiNH2 with partial Mg substitutions are useful as hydrogen- Li2 NH [45]. More important for hydrogen storage. within 240–270 ◦ C temperature Schlesinger and Brown [146] in an organic solvent. LiBH4 from the elements at elevated temperatures up to 650 ◦ C ing the surface layer. The importance of boron for hydrogen-storage technologies Hu et al. [136]. desorption. Recently Hu et al. [133] reported a 5. according to the following reaction: A proposed way for lowering the hydrogen desorption temperatures of Li-based complex hydrides is partial cation LiNH2 + 2LiH → Li2 NH + LiH + H2 . It was found that the compound releases hydrogen in A catalytic study of Ichikawa et al. Vajo et al.3 wt%) lization of TiCl3 catalyst during ball-milling of the LiNH2 and of hydrogen. with the uti. Accord- range.148]. [141] demon.21 MgH2 –2 mol% BM Tabs and Tdes : 315–450 Pabs : 4. Under P–C isotherm con.: not stable 0. of H2 LaNi3 BH3 Arc melting Tabs : 25 Pabs : 4 tabs : 30 2 cyc. The low storage with high reaction rate after three cycles. and ending temperatures for the hydrogen desorption reac- terial is the generation of NH3 . have been reported [145]. heating. Li3 N can theoretically store 10. Authors reported tures above 230 ◦ C.84 [131] Li2 NH Mixing Tabs and Tdes : 230–200 Pabs : 7 tabs : 10 15 cyc. Moreover. Hu et al. tronegativities.1132 B. partially oxidiz. A total of 4. The high temperature phase releases up to LiH mixture. about 55% of hydrogen can be desorbed at tempera. LiBH4 has a gravimetric hydrogen genation and dehydrogenation of Li3 N and reported a reversible density of 18 wt%. [135] studied the temperature-programmed hydro.50 [45] Pdes : 1. Formation of MgB2 . Desorption ing.: stable 5.: not 3.20 [134] Li2 MgN2 H2 Mixing Tabs and Tdes : 180 Pabs : 90 tabs : 60 No data 5. however.00 [136] LiBH4 .: stable 5. The starting A critical potential issue regarding this N-based storage ma. [137] show that LiBH4 can be reversibly store Another study on a different class of solid hydride has been 8–10 wt% hydrogen at temperatures of 315–400 ◦ C by addi- done by Pinkerton et al.: not 10. of cycles. Lithium boro.00 [135] Tdes : 240–270 Pdes : 1 Li2 NH Mixing Tabs and Tdes : 255–285 Pabs : 10 No data No data 6. This ultrafast reaction between 3. 13. temperature desorption releases only a small amount (0. all attempts to synthesize hydrogenation–dehydrogenation pretreatment. [132] reported a reversible hy. is their attempts to rehydride the decomposition product by heat- that this mixture could decompose to release hydrogen gas upon ing at 8 MPa but without success. due to improved porous structure of the material. storage capacity of above 10 wt%. Sakintuna et al. Li3 N has two plateaus in the P–C isotherm.5–19 tabs : 240 3 cyc. desorbs from LiBH4 at temperatures greater than 470 ◦ C.5 tabs : 20 No data 6. Although desorption conditions seem to be advantageous. strated that NH3 produced via the decomposition of LiNH2 is completely captured by LiH.4. (7) substitutions using different valence cations with larger elec- Hydrogen storage leads to the formation of LiNH2 and LiH.10 [132] Pdes : 1 tdes : 300 stable LiNH2 –LiH–1 mol% BM Tdes : 150–250 Pabs : 30 tabs : 30 3 cyc. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140 Table 4 Hydrogen absorption/desorption properties of Li-based hydrides Material Method Temperature (◦ C) Pressure (bar) Kinetics (min) Cycling stability Max wt% Ref.5 wt% of hydrogen. substitution of Li by Mg [143.50 [42] Pdes : 1 tdes : 60 Li3 N Mixing Tabs : 50 Pabs : 0.00 [133] TiCl3 Tabs : 180 Li2 O–Li3 N Partial oxidation Tabs : 180 Pabs : 7 tabs : 3 6 cyc.50 wt% different reaction steps and temperature regimes.144]. materials to be utilized as storage medium. which consumes some H2 and tion from LiNH2 are lowered about 50 K by the partial cation also poisons the downstream processes.00 [137] TiCl3 Pdes : 2–3 tabs : 240 stable Consequently. storage materials for fuel–cell applications [142]. They improved the activation characteristics of Li3 N with the Despite its great storage capacity. irreversibility stands as an important problem for use of these ditions. reporting an extraordinarily high tion of MgH2 including 2–3 mol% TiCl3 . reversibility is lack- gen.and beryllium hydrides NH3 and LiH inhibits NH3 formation during the hydrogenation of Li3 N [141].10 wt%.5 wt% of the hydrogen drogen capacity of 3.20 wt% and pressure of 150 bar H2 failed to date [108. Another study of the same group was to investigate the ing to the work of Stasinevich and Egorenko [147] hydrogen fast kinetics of LiO2 /Li3 N mixture for hydrogen storage [134]. They reported a maximum of 5. that increases with the number remains as LiH in the decomposition product.

Important results from hydrogen atoms in the metal matrix away from the boron atom these studies are represented below.44 and 1. Cr. 1. sites [131]. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140 1133 stabilizes the dehydrogenated state and destabilizes the LiBH4 The early studies on LaNi5 as hydrogen-storage material has [137]. There are also rized in Tables 5 and 6. nitrides and borohydrides. opened ent stoichiometric LaNi5 samples such as 1. The P–C diagram shows a flat plateau. V. however. the Li3 Be2 H7 is a highly toxic exothermic reaction between LaNi5 and H2 that leads to rapid material [15]. researchers have been studying the effects of milling. They show high reversible hydrogen capacity with more to be useful for hydrogen-storage applications.5 wt%). temperature increase. alloys are well known as hydrogen-storage materials. LaNi5 compounds were shown to be enhanced for hydrogen-storage Research on intermetallic compounds for hydrogen storage by the works of Chen et al. and Suda et al. metal alloys containing high amounts of ordinated by lanthanum and nickel only. The different families of intermetallic compounds classified 1. Due to their potential for commercial appli. The aim of these into the interstitial sites. reversible hydrogen capacity in these LaNi5 has 1.4%Ni [166]. In general the AB2 type compounds seem to be .32 wt% stor- BCC. the kinetics is too slow with the absorption been reported by Aoyagi et al. but unfortunately the hydrogen capacity is de. However. and Besides alanates. 4. They achieved hydrogen-storage capacities with differ- of hydrogen absorption by LaNi5 [150] and FeTi [151]. and Lu et al. on hydrogen absorption properties has been investigated. It hydrides are a new group of metal hydrides for hydrogen stor. driding process.4 wt%. Liu et al. while others stud. et al. As for the metallic hydrides.3 min hy- complex compounds is higher than in any other known hy. [182]. The parent compound LaNi5 absorbs about 1. Wang nonstable hydride. these materials are still hydrogen-storage capacity can reach up to 2 wt% in Laves phase far from meeting the US DOE goal of 6. on the basis of their crystal structures. They characterized the hydriding process by drides [149]. The mechanism of hydrogen diffusion in LaNi3 BHx is inves- Among the AB5 type alloys. The B elements are represented mainly hysteresis. such as AB2 type (Laves [174] processed the LaNi5 using a twin roll process in order to phase). due to their low working tem. for on. However. they remained at the stage of prototypes due per and achieved kinetics and cycling behavior during hydro- their weight penalty and low hydrogen-storage capacity [152]. Corre et al. achieve uniform nanocrystalline structure with 1. AB5 type phases and Ti-based body centered cubic.44 wt% hydrogen capacity is achieved in LaNi5 . These supported the results from theoret- ical calculations. a barrier for hydrogen diffusion and favors localization of the ing or mechanical alloying techniques. [67]. the dissociative et al.4%Ti–7. its cost is relatively high and the plateau crystal structures. The effect of ball-milling time up to 6000 min hinder practical applications. [186] showed the direct relation between hydrogen- the hydrogen capacity of the most popular LaNi5 -based al. Intermetallic compounds are often obtained by combining an Apart from the above reported works. Mn and Fe. tion properties of intermetallic compounds because it acts as ied blending of the material with various metals through melt.32 wt%. 1. Chen et al. B. [175]. genation /dehydrogenation process.25 wt%. storage performance and optimization in LaNi5 systems.0 H/LaNi5 The AB2 type compounds are derived from the Laves phases (1. ature [187]. Some of the onal axis. [185] reported on the fluorination of chemisorption of hydrogen is followed by hydrogen diffusion hydriding alloys and its effects on properties. a few important stud- element forming a stable hydride with an element forming a ies in the literature are worth mentioning. Sakintuna et al. Boron has an adverse effect on the hydrogen sorp- studies were carried with pure compounds. longer life and a treatment techniques such as carbon monoxide treatment. low Ti and Zr on the A site. Lu et al. while the basal La–B LaNi5 have been studied as hydrogen-storage materials by var. tigated. The discovery [174].28 wt% hydrogen-storage capacity for 8. The graded after a few cycles. Kaplan et al. The potential AB2 types are obtained with pressure is low. The results suggested that hydrogen occupies sites co- perature and pressure. [184]. The Laves phase series of hydrogen capacity. [183]. loys operating at moderate temperature does not exceed Storage time could be improved by 60% through optimization. experiments was to form a Ni-rich layer in order to improve The hydriding properties of these compounds are summa. the initial activation and impurity tolerance. planes act as barriers to hydrogen diffusion along the hexag- ious research groups around the world [176–180]. lithium–beryllium maximum hydrogen content has been reported as 0. Kikkinides weight is an important critical disadvantage. their hydrides are too stable at room temper- on AB5 type compounds for hydrogen storage. age capacity. on LaNi5 utilization temperature and pressure. compounds has attracted large attention in the last decade due cations. was already attempted more than 20 years ago. their low energy density per unit for hydrogen storage. than 8 wt% at 150 ◦ C. For practical applications at ambient theoretical studies found in the literature. Intermetallic compounds With different stoichiometric addition of other metals. relatively low cost in comparison to the LaNi5 -related systems Table 6 presents the major outputs from a number of studies [155]. respectively. is concluded that activation treatment is necessary for LaNi5 age. On the other hand. Since lithium and beryllium are the lightest both theoretically and experimentally. By CO surface treatment. For instance. Most of Laves phases mechanical alloying or melting with other metals and surface show relatively high capacities faster kinetics. However. by different combinations of 3d atoms.5 wt% reversible V–7. [182] applied chemical coating by cop- board storage.4%Zr–7. The reaction of hydride formation is [181] have investigated the hydrogen absorption in pure LaNi5 fully reversible. Therefore. The group reported that hydride-forming metals. tank design and optimization. new possibilities for industrial developments. to their good hydrogen-storage capacity.

01 Ni4.05 Nd0.6 Fe0.: stable after ninth cycle 1.3 No data 3. 25 Pabs : 5–10 tabs and tdes : 6.90 Melting Tabs and Tdes : 30 Pabs : 5 No data No data 1.5 Ni0.98 [172] Pdes : 0.50 [161] LaNi5 Pdes : 0. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140 Ti–10Cr–18Mn–32V Magnetic levitation melting Tabs : 60 Pabs : 30 tabs : 8.65 Mn0.23 [168] Quasicrystal powders Tdes : 427 Ti–V–Cr Arc melting Tabs and Tdes : 40 Pabs : 100 No data No data 2.1 V0.6 Al0. Sakintuna et al.5 No data 5 cyc.1 V0.3 Ni2.4 Melting Tabs and Tdes : 25 Pabs : 35 tabs : 15 11 cyc.32 Melting Tabs and Tdes : 100.03 Cr1.2 )2 Induction melting Tabs : 120 Pabs : 30 No data No data 0.9 –20 wt% Melting + BM Tabs and Tdes : 30 Pabs : 17 No data No data 1.3 No data 3.: stable 1.55 [160] Pdes : 81 La0.4 Melting Tabs and Tdes : 25 Pdes : 25 tdes : 5 11 cyc.30 [159] MmNi4.50 [153] La0.5 V49 Fe7.2 V0.6 Mn0.: stable 1.8 Sn0.03 La1.45 Ni5 Induction melting Tdes : −20 Pdes : 3.8 80 wt% TiCr1.33 Zr0.7 Mg0.2 Ti45 Zr38 Ni17 BM Tabs : 300 Pabs : 80 tabs : 1200 No data 2.50 [161] Pdes : 0.04 Pr0.16 [157] La0.8 Mo0. 1134 Table 5 Hydrogen absorption/desorption properties of intermetallic compounds Material Method Temperature (◦ C) Pressure (bar) Kinetics (min) Cycling stability Max wt% Ref.5 Arc melting Tabs : 40 Pabs : 47 No data No data 1.95 [154] Pdes : 0. of H2 MgS BM Tabs : −196 Pabs : 50 No data No data 0.25 Ni5 RF levitation melting Tabs : 20 Pabs : 100 No data No data 1.63 Sn0.4%Ti–7.2 RF melting Tdes : 25 Pdes : 10 tdes : 60 100 cyc.: stable 1.24 Zr(Cr0.00 [166] Pdes : 1 V0.15 Mn1.80 [169] Ti–10Cr–18Mn–27V–5Fe Magnetic levitation melting Tabs : 60 Pabs : 30 tabs : 8.1 Co0.01 [170] Pdes : 1 B.56 [162] Pdes : 0.10 [156] LaNi4.75 Ti0.92 [165] V–7.375 Ti0.8 Ca0.5 Arc melting Tabs : −20 Pabs : 100 tabs : 20 50 cyc.97 Zr0.4%Zr–7.45 [160] Pdes : 6.5 Ti43.5 Ti0.30 Mn0.: not stable 5.1 CrMn Arc melting Tabs and Tdes : 23 Pabs : 33 tabs : 1 1000 cyc.2 Arc melting Tdes and Tabs : 80 Pdes : 3–4 No data 1000 cyc.00 [173] Pdes : 1 tdes : 10 .44 [159] Ml0.75 [163] Ti1.6 Cr0.36 [170] Pdes : 1 TiCr1.90 Ce0.25 Cr0.80 [164] Pdes : 1 tdes : 5 FeTi BM Tabs : 25 Pabs : 100 No data No data 1.9 Zr0.: stable 1.90 [171] Tdes : 300 Pdes : 10 Ti–V–Cr–Mn Magnetic levitation melting Tdes : 247–472 Pabs : 30 No data No data 3.: stable 1.20 [167] Pdes : 0.4 RF levitation melting Tabs : 20 Pabs : 100 No data No data 1.75 Ca0.2 Mg14 N13 BM Tabs and Tdes : 27–327 Pabs : 40 tabs : 15 6 cyc.: not stable 2.075 Arc melting Tabs and Tdes : 30 Pabs : 50 No data No data 2.99 [155] Ml0:85 Ca0:15 Ni5 RF melting Tdes : 25 Pdes : 10 tdes : 60 100 cyc.55 Y0.6 No data 0.30 [156] MmNi4.25 Cr1.30 [158] Ti0.4%Ni Arc melting Tabs : 40 Pabs : 10 No data 10 cyc.9 Melting + BM Tabs and Tdes : 30 Pabs : 17 No data No data 3.: stable after ninth cycle 1.:stable 3.

The work is carried out gations.187]. tion of hydrogen technology and economy.: not stable 0.51 wt%. study of Ti-based BCC phase alloys and 120 ◦ C with high cycle life. of metals and metallic alloys or adsorption on high surface area ing hydrogen desorption plateau pressure. hydrogen absorption–desorption plateau pressure.25 Cr 0. The present article reviews are 3. The BCC temperature and pressure. on-board applications goals set for hydrogen economy. Conclusion high-pressure and high temperature are required to achieve a reproducible absorption/desorption of the maximum amount of Hydrogen storage is a key issue in the success and realiza- hydrogen in the compound [151. kinetics. its decomposition requires much ther- able hydrogen capacities.6 La0.: stable 1. the high cost is one of the mal.29 Pr0. a small amount of oxygen can be a poison for drogen desorption capacity and reduce the hysteresis of hydro- the AB2 s. behavior and cost. Both 5.45 Al0. Increasing the V content is effective in accelerating hy. However. Although pure water contains has been studied in several laboratories because of their remark.3 Twin-rolling Tabs : 60 Pabs : 10 No data No data 1. it acts as a reactant. therefore. FeTi is a well-known hydrogen-storage tion of hydrogen between the layers of the multilayered wall compound with a total hydrogen capacity of around 1. management and solid fuel recycling.40 [175] treatment after fifth cycle Tdes : 25 LaNi5 CO surface Tabs : 0–100 Pabs : 50 tdes : 13. addition [165].25 [67] La0. In recent years.1 wt% of hydrogen. The quasicrystalline Hydrogen absorption of FeTi powders has previously been Ti45 Zr 38 Ni17 has 2. / International Journal of Hydrogen Energy 32 (2007) 1121 – 1140 1135 Table 6 Hydrogen absorption/desorption properties of LaNi5 compounds Material Method Temperature (◦ C) Pressure (bar) Kinetics (min) Cycling stability Max wt% Ref. They pure hydrogen [188].90 wt% by the catalytic effect of 1 wt% Pd tercalate between layers in the walls of TiO2 nanotube [189].23 wt% storage capacity [168].01 and 3. while. storage capacity slightly.98 and 2. Sakintuna et al. Hydrogen can in- accomplished to 1. or chemical energy [15]. However. toxicity.90 wt% of nanotubular TiO2 was studied in the temperature range of with inexpensive elements. respectively [172].375 Ti0. storage capacity. electric. The quasicrystals have a new type of translational long-range pounds. B. for the AB5 s.6 20 cyc.075 exhibited an candidates due to their safety advantage with high volume- effective hydrogen capacity of 2. Thus. DOE. the activation process of FeTi is trou- blesome due to the formation of titanium oxide layer.27 [174] Pdes : 0.: stable 1.59 Ce0. thermal properties. The maximum and materials such as activated carbons gain the attention for pos- effective hydrogen-storage capacities of Ti–V–Cr–Mn alloys sible future hydrogen applications. de. Solid drogen absorption. the hydrogen-storage materials for transport applications which It is well known that vanadium is expensive.8 20 cyc. respectively meation problems along with high cost. mance. improving adsorption/desorption properties based on hydrogen- tution in Ti–10Cr–18Mn–32V alloy is also investigated [170]. Since the conventional hydrogen fuel storage methods of tions.44 [175] treatment after fifth cycle Tdes : 25 more sensitive to gaseous impurities than the AB5 type com. Metal hydrides are the promising phase solid solution of V0. drogen capacity by increasing the plateau pressure.1 Ni5 CO surface Tabs : 0–100 Pabs : 50 tdes : 1. efficient storage capacity for on-board applications.36 wt%. critical drawbacks limiting their successful practical applica. display non-crystallographic rotational symmetry. they do not meet future [170]. 11. According to US New BCC solid solution alloys have been reported to ab. but also to Hydrogen can be stored in metal hydrides under moderate decrease costs by decreasing the vanadium content. Hydrogen capacity of FeTi can be 195–200 ◦ C and at pressures of up to 6 bars.6 8 cyc. require research into further aspects of tank technology. Ti–10Cr–18Mn–27V–5Fe and Ti–10Cr–18Mn–32V has pressurized H2 gas and cryogenic liquid H2 pose safety and per- hydrogen-storage capacities of 3. In Ti–V–Cr–Mn compounds.03 Ni4 Co0. although capacity recovery is possible by recycling in order. the hydrogen-storage capacity target for commercializa- sorb more hydrogen than the conventional intermetallic com. tank design aiming at on-board vehicle applications.30 Mn0. enhancing the hydrogen absorption capacity state hydrogen fuel storage either absorption in the interstices and flattening the hydrogen desorption plateau.20 wt% [167].5 wt% at the decomposition temperature between 60 pounds. while decreas. The sorp- extensively studied. of H2 LaNi5 BM Tabs : 20 Pabs : 20 tabs : 1. and the cost of alloy [170]. hy- pounds. tion is 6. the effect of Fe substi. contain high amounts of interstitial sites. reducing the gen absorption–desorption plateau. CO is a poison for both types of com. .45 Mn0. research has been recently conducted on the metal hydrides for duce the cost of Ti–V-based BCC alloys. Intensive In order to improve the hydrogen-storage properties and re.9 Ce0. heat creasing of the vanadium content is another goal of the investi. increasing the Cr content in an attempt to facilitate prospectus material choice for further and the addition of Mn is necessary to increase the effective hy. cycling It was reported that Fe addition increases the activation perfor.

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