7062 J. Phys. Chem.

B 2006, 110, 7062-7067

Modified Lithium Borohydrides for Reversible Hydrogen Storage

Ming Au* and Arthur Jurgensen

SaVannah RiVer National Laboratory, Aiken, South Carolina 29808
ReceiVed: October 29, 2005; In Final Form: January 27, 2006

In an attempt to develop lithium borohydrides as reversible hydrogen storage materials with high hydrogen
storage capacities, the feasibility of reducing the dehydrogenation temperature of the lithium borohydride
and moderating rehydrogenation conditions was explored. The lithium borohydride was modified by ball
milling with metal oxides and metal chlorides as additives. The modified lithium borohydrides released 9 wt
% hydrogen starting from 473 K. The dehydrided modified lithium borohydrides absorbed 7-9 wt % hydrogen
at 873 K and 7 MPa. The modification with additives reduced the dehydriding starting temperature from 673
to 473 K and moderated the rehydrogenation conditions from 923 K/15 MPa to 873 K/7 MPa. XRD and
SEM analysis revealed the formation of an intermediate compound that might play a key role in changing the
reaction path, resulting in the lower dehydriding temperature and reversibility. The reversible hydrogen storage
capacity of the oxide-modified lithium borohydrides decreased gradually during hydriding/dehydriding cycling.
One of the possible reasons for this effect might be the loss of boron during dehydrogenation, but this can be
prevented by changing the dehydriding path using appropriate additives. The additives reduced the dehydriding
temperature and improved the reversibility, but they also reduced the hydrogen storage capacity. The best
compromise can be reached by selecting appropriate additives, optimizing the additive loading, and using
new synthesis processes other than ball milling.

1. Introduction In 1980, Alain Muller5 reported that 5 g of LiBH4 decom-

posed and released 13.8 wt % hydrogen at 723 K and 10-2
Alkali metal borohydrides such as LiBH4 and NaBH4 are
mmHg (1.3 Pa) pressure within 24 h by the reaction LiBH4 f
lightweight materials that contain large amounts of hydrogen.
LiH + B + 3/2H2 with a reaction enthalpy of -24.8 kcal/(mol
The theoretical gravimetric and volumetric hydrogen storage
of H2). After dehydrogenation, the sample was able to absorb
capacities (18.5 wt %, 121 kg/m3 and 10.6 wt %, 98.7 kg/m3,
11.8 wt % (6.65 L) of hydrogen at 923 K and 15 MPa within
respectively) are well above the U.S. Department of Energy
48 h. To improve the dehydrogenation and subsequent rehy-
(DOE) benchmark for transportation applications1 (7.5 wt %
drogenation processes, 10 wt % aluminum powder was mixed
and 65 kg/m3), even taking into account the weight and volume
mechanically with LiBH4. The mixed material then liberated
of the containment system. Lithium borohydride could be a
12.4 wt % hydrogen at 723 K and 1 Pa within 24 h.
superior hydrogen storage material if hydrogen absorption could
be reversed at moderate conditions. Borohydrides are also Subsequently, 15.2 wt % hydrogen was recharged onto the
relatively inexpensive and can be produced from abundant decomposed material at 923 K and 15 MPa within 12 h.
natural borax deposits.2,3 Unfortunately, these materials are very However, the extremely slow reversibility lasted for only two
stable. For example, heating above 673 K, that is, above its cycles. The dehydriding and rehydriding temperatures were too
melting point, is required to release the majority of the hydrogen high. Recently, Zuttle reported that 25% LiBH4 ball milled with
from LiBH4.4 Also, the rehydrogenation conditions are too harsh 75% SiO2 liberated 9 wt % (based on the weight of LiBH4 in
for practical application. However, the solid hydrogen storage the mixture) hydrogen starting from 523 K through the reaction
potential of these materials warrants investigation into possible LiBH4 f LiH + B + H2. He indicates that the reaction is
methods to resolve or alleviate these two major problems. partially reversible, but provided no detailed data in the report.6
Fedneva et al.4 investigated LiBH4 by DTA (differential Orimo studied the Raman spectra of NaBH4, KBH4, and LiBH4
thermal analysis). The thermogram of LiBH4 showed three and suggested that the stability of LiBH4 or LiNH2 can be
endothermic effects: at 381-385, 541-559, and 756-765 K. reduced by partial cation substitution using smaller-sized and/
The endothermic effect at 381-385 K is reversible and or higher-valence cations with higher electronegativities such
corresponds to LiBH4 polymorphic transformation. The second as Mg.7 By adding Mg into LiBH4 at a ratio of Li/Mg ) 9:1
peak at 541-559 K corresponds to LiBH4 fusion, accompanied through ball milling, the dehydriding temperature was reduced
by a slight decomposition, which liberates approximately 2% from 850 to 820 K.8 Vajo reported that the ball-milled mixture
of the hydrogen in the compound. The main evolution of gas LiH + 0.5MgB2 + 0.03TiCl3 absorbed 9 wt % at 350 °C and
starts at 653 K and liberates 80% of the hydrogen in LiBH4. 100 bar and desorbed 8 wt % hydrogen at 450 °C without
The cause of the small effect at 756-765 K is uncertain, but it counting the weight of the catalyst TiCl3. The true capacities
coincides with the liberation of 50% of the theoretical hydrogen based on the total weight of the mixed material were 7.84 and
content in LiBH4. 6.96 wt % for hydrogen absorption and desorption, respectively.
Using LiH + 0.5MgB2 + 0.03TiCl3 as the experimental sample
* Corresponding author. Tel.: 803-819-8442. Fax: 803-819-8432. E- for the measurement of P-C-T (pressure-composition-
mail: ming.au@srnl.doe.gov. temperature) isotherms, Vajo concluded that the rehydroge-
10.1021/jp056240o CCC: $33.50 © 2006 American Chemical Society
Published on Web 03/10/2006
Lithium Borohydrides for Reversible Hydrogen Storage J. Phys. Chem. B, Vol. 110, No. 13, 2006 7063

nation enthalpy of LiBH4 was reduced by 25 kJ/(mol of H2).

The kinetics was extremely slow: reaching equilibrium took
100 h.9
Most borohydride research has focused on “on-demand”
hydrogen sources, which rely on an irreversible catalyzed
hydrolysis reaction. The theoretical hydrogen yield by hydrolysis
is only 7.6 wt %, and a considerable amount of water must be
supplied. Ruthenium was used as the catalyst. Also, the issue
of the safe and cost-effective disposal or recycling of the
hydrolysis byproduct NaBO2 has not yet been resolved.10
A reversible borohydride material capable of releasing and
reabsorbing hydrogen at moderate conditions similar to those
employed for a standard metal hydride would represent a major
breakthrough in hydrogen storage technology. Motivated by the
high theoretical gravimetric and volumetric capacity, systematic
investigations were conducted to modify commercially available
LiBH4 for reversible hydrogen storage. A number of potential
additives were screened, and several of them were found to
Figure 1. Comparison of the modified LiBH4 materials with the
reduce the thermal decomposition temperature and improve the commercial LiBH4.
reversibility at relatively moderate conditions. Material char-
acterizations showed an interaction of the borohydride with the
additives, which helps in understanding the dehydriding/
rehydriding processes. The detailed results are reported herein.

2. Experimental Section
The LiBH4 powder (95% purity) and the additive powder
(99.9-99.99% purity) were purchased from Sigma-Aldrich and
used directly without any pretreatment.
For sample preparation, in an argon glovebox, 2 g of LiBH4
and the appropriate additive powder mixture was placed in a
25-mL hardened steel grinding bowl containing three 11-mm-
diameter tungsten carbide balls. (The weight ratio of the balls
to the powder was 32:2.) The sealed grinding bowls were
removed from the argon glovebox and put on a Frisch-7
planetary ball mill for 5-10 h of milling at 600 rpm. After
milling, the dehydriding temperatures of the modified borohy-
drides were first screened on a Perkin-Elmer TG/DTA thermal
analyzer. Then, 0.5 g of selected modified LiBH4 powders was
transferred to a Sieverts apparatus, a volumetric device with Figure 2. TPD of the TiO2-modified and commercial LiBH4 materials.
500 Pa (5 mbar) back-pressure, for temperature-programmed LiBH4 (see Figure 1). The materials 75% LiBH4 + 25% TiO2,
desorption (TPD) measurements. The temperature was ramped 75% LiBH4 + 25% V2O3, 75% LiBH4 + 25% ZrO2, 75%
from ambient to 973 K at a rate of 5 K/min. The rehydroge- LiBH4 + 25% SnO2, and 75% LiBH4 + 25% TiCl3 each
nations were conducted at 873 K and 7 MPa (99.9999% desorbed 8-9 wt % hydrogen from 448 to 473 K.
hydrogen) in the same Sieverts apparatus. The hydrogen To verify the influence of the ball milling on the lithium
absorption and desorption capacities were calculated according borohydride dehydrogenation, a sample of commercial LiBH4
to the total weight of the modified borohydrides including the was ball milled for 5 h without any additives. Figure 2shows
weight of the additives. Borohydrides that showed promising the TPD data for commercial LiBH4, ball-milled LiBH4, and
results were investigated by X-ray diffraction (XRD) in a Philips TiO2-modified LiBH4 samples. Commercial LiBH4 decomposes
X′Pert Pro X-ray diffractometer to determine their crystal starting from approximately 598 K at a very low rate. At about
structure and phase composition in different states: as milled, 723 K, the decomposition accelerates appreciably, resulting in
dehydrided, and rehydrided. The morphologies and additive a final release of 9 wt % hydrogen at about 873 K. A comparison
distributions of the new materials were analyzed with a Hitachi of the commercial LiBH4 with 5-h-milled LiBH4 shows that
S3600N scanning electron microscope (SEM) equipped with the ball milling alone does not reduce the dehydriding temper-
an energy dispersion spectrometer (EDS). The composition of ature or improve the dehydriding kinetics. The modified material
the dehydriding gas stream was analyzed with a Pfeiffer 75% LiBH4 + 25% TiO2 liberates the same amount of hydrogen
ThermoStar mass spectrometer in ambient environment. (9 wt %) as the commercial LiBH4, but does so starting at 473
K for the samples milled for 5-10 h and at 448 K for that
3. Results and Discussion
milled for 20 h. The effect of the TiO2 in reducing the
3.1. Dehydrogenation of the Modified LiBH4 Materials. dehydriding temperature is obvious. It is recognized that
In the initial TG/DTA screening, eight oxides and chlorides were extending the milling time does little to reduce the dehydriding
added to LiBH4 through ball milling. Five additives, namely, temperature, but does decrease the hydrogen capacity. For
TiO2, TiCl3, ZrO2, V2O3, and SnO2, were effective in reducing example, the 20-h-milled 75% LiBH4 + 25% TiO2 releases only
the temperature of rapid decomposition and increasing the 6.9 wt % hydrogen at 873 K. A possible reason for this behavior
desorption rate at low temperature compared to commercial will be discussed later in this article.
7064 J. Phys. Chem. B, Vol. 110, No. 13, 2006 Au and Jurgensen

Figure 5. Hydrogen absorption of the dehydrided materials 75% LiBH4

+ 25% TiO2 and 75% LiBH4 + 25% V2O3.

Figure 3. Effect of the additive TiCl3 on the dehydrogenation behavior

of LiBH4.

Figure 6. Isothermal hydrogen absorption of the material 75% LiBH4

+ 25% TiO2.
Figure 4. Dehydrogenation of 75% LiBH4 + 25% TiO2 at 473, 573,
and 673 K. conclusion was made on the basis of a comparison of the
materials 75% LiBH4 + 25% TiO2 and 90% LiBH4 + 10%
It is considered that the additives play a significant role both
TiO2 in our experiments. Obviously, there is a tradeoff issue,
in enabling lower-temperature hydrogen desorption and in
so the most reasonable compromise should be pursued.
releasing more hydrogen than commercial borohydride at the
same temperature. Zuttle6 reported that about 50% theoretical Although the TPD data provide an overall picture of the
hydrogen content (∼9 wt %) is liberated from LiBH4 catalyzed dehydrogenation process in a wide temperature range, isothermal
by SiO2 starting at 473 K. Given the mixture ratio of 25 wt % dehydrogenation studies are normally used to judge material
LiBH4 and 75 wt % SiO2, the actual hydrogen desorption of performance characteristics such as storage capacity and kinetics
the total amount of mixed material is far less than 9 wt %. In at the desired temperature. The isothermal dehydriding properties
the experiments reported here, about 9 wt % hydrogen was of the material 75% LiBH4 + 25% TiO2 are shown in Figure
released from the modified LiBH4-based materials (including 4. It appears that the dehydriding process follows first-order
the weight of the additive), and the dehydrogenation was kinetics. There are two stages in the dehydriding process: fast
initiated at 473 K. It is proposed that a possible overall LiBH4 dehydriding in the first short period and very slow dehydriding
dehydriding reaction is 2LiBH4 f2LiH + 2B + 3H2 because thereafter. The material desorbed about 8.0 wt % hydrogen
LiH is very stable up to 1173 K.6,7 This reaction liberates 13.79 within the first 100 min at 673 K. However, hydrogen desorption
wt % of the hydrogen from LiBH4. Upon addition of 25 wt % continued for about 10 h before the reaction was completed,
TiO2, the hydrogen released from our modified material 75% adding 0.5 wt % hydrogen for a total of 8.5 wt % desorption.
LiBH4 + 25% TiO2 is theoretically 10.34 wt %. Practically, The material desorbed about 4.5 and 1.5 wt % hydrogen at 573
the average dehydriding capacity of our modified LiBH4 and 473 K, respectively. This shows that the hydrogen desorp-
materials containing 25 wt % additives is about 9 wt %. This is tion is a temperature-dependent process.
understandable because of hydrogen evolution during ball 3.2. Rehydrogenation of the Modified LiBH4 Materials.
milling that is caused by the interaction of LiBH4 and TiO2. In Muller’s work,5 the modified material 90 wt % LiBH4 + 10
This issue is discussed further in the XRD analysis section. wt % Al desorbed 12.4 wt % hydrogen at 723 K within 12 h in
Reducing the additive loading increases the hydrogen de- the first dehydriding, but the dehydrided material could not be
sorption capacity, but it also raises the dehydriding temperature. recharged to its original capacity. The second dehydriding
Figure 3 shows a dehydriding comparison of the materials 75% yielded only 5 wt % hydrogen. The effect of the second
LiBH4 + 25% TiCl3 and 90% LiBH4 + 10% TiCl3. As expected, rehydrogenation was almost negligible, absorbing only 0.6 wt
the hydrogen desorption capacity increased from 8.2 to 9.2 wt % hydrogen. To study the dehydriding/rehydriding reversibility
% at 873 K as the TiCl3 loading was reduced from 25% to of the modified borohydrides, the material 75% LiBH4 + 25%
10%. However, the rapid dehydriding temperature increased TiO2 was selected for hydriding and dehydriding cycling tests.
from 373 to 523 K. The reaction kinetics also suffered. A similar After being dehydrided at 873 K for 1 h, the materials 75%
Lithium Borohydrides for Reversible Hydrogen Storage J. Phys. Chem. B, Vol. 110, No. 13, 2006 7065

Figure 7. XRD spectra of the material 75% LiBH4+ 25% TiO2 in different states.

LiBH4+ 25% TiO2 and 75% LiBH4 + 25%V2O3 were rehy- The XRD results for the dehydrided material 75% LiBH4 +
drided at 873 K and 10 MPa. As Figure 5 shows, the dehydrided 25% TiO2 are shown in Figure 7b. It appears that the LiBH4
materials LiBH4+ 25% TiO2 and 75% LiBH4 + 25% V2O3 decomposes into LiH, LiOH, TiB2, and trace amounts of Li7B6
absorb 7.8 and 7.9 wt % hydrogen, respectively, within 45 min. during hydrogen evolution. The additive TiO2 disappears. The
The rehydrogenation capacity increased to 8 wt % when the XRD spectrum does not indicate the visible presence of boron
absorption time was prolonged to 1 h. This shows that the new as the reaction 2LiBH4 f 2LiH + 2B + 3H2 would suggest.5
LiBH4 materials are reversible at the conditions tested. Obvi- More likely, LiBH4 might react with TiO2, resulting in the
ously, the rehydriding temperature and pressure are still too high. formation of LiH; LiOH; and, more meaningfully, intermediate
However, it is believed that the elevated conditions can be compounds such as TiB2. It is possible that some boron
moderated by adjusting the compositions and tuning the segregates from LiBH4 as amorphous clusters without reacting
thermodynamic stability of the modified LiBH4 materials. Figure with titanium. The intermediate phases might make the dehy-
6 shows the repeated isothermal rehydrogenation of the material drogenation reversible at relatively moderate conditions. The
75% LiBH4+ 25% TiO2 at 873 K and 7 MPa. The hydrogen hypothetical reversible reaction is given as 6LiBH4 + 2TiO2
absorption capacity decreases from 8.25 to 5.6 and 4.2 wt % in f 2LiH + 4LiOH + 2TiB2 + 2B +9H2. The contribution of
the second and third hydrogenations, respectively. To investigate the additive TiO2 might be to form intermediate boron com-
the possible causes, XRD and mass spectrum analyses were pounds that promote the decomposition of LiBH4, resulting in
conducted. low-temperature dehydriding and facilitating the recombination
leading to reversibility. It is not the intention of this work to
3.3. XRD Analysis of the Modified LiBH4 Materials. To prove the mechanism using the limited data presented here. The
identify the phase compositions during dehydrogenation and possible existence of the compound Ti7B6 has not been verified.
rehydrogenation, the material 75% LiBH4 + 25% TiO2 was More material characterizations and particularly designed
investigated by XRD in three different states: ball-milled, experiments have to be conducted to understand the actual
dehydrided, and rehydrided. The XRD spectrum of the 5-h- reactions.
ball-milled 75% LiBH4 + 25% TiO2 shows a structural change The XRD results for the rehydrided material 75% LiBH4 +
(see Figure 7a). The crystal structure of TiO2 has partially 25% TiO2 are shown in Figure 7c. The intensities of the
changed from anatase to rutile. In addition to the expected LiBH4 identifiable peaks are very low, which indicates that the materials
and TiO2, traces of TiB2 and LiB3O5 have formed through the are either in short-range disorder or in amorphous states. The
possible interaction between LiBH4 and TiO2 during ball milling. recombined LiBH4 is not detectable in our XRD experiments,
The XRD data confirmed partial LiBH4 decomposition and the although its existence is evidenced by our rehydriding and
combination of Ti with B. It is proposed that the intermediate subsequent dehydriding measurements (Figures 4-6). The
compound TiB2 dispersed within the matrix might provide a expected recombined LiBH4 could be in an amorphous state.
pathway for the reversible dehydriding/rehydriding reaction. Its Similar results have been reported by other laboratories.8 The
interesting role might be to facilitate the B-H bond dissociation visible peaks are identified as the TiB2, Li7B6, and possibly Li3-
and recombination process. The material 75% LiBH4 + 25% BO3. The additive TiO2 is not identifiable in the XRD spectrum
TiO2 can be expressed as LiBH4 + 0.09TiO2. According to this of the rehydrided material. However, the intermediate compound
molar ratio, most of the LiBH4 is not able to react with TiO2 TiB2 persists in both dehydrided and rehydrided states. It is
during ball milling. In most of our measurements, the oxide-/ interesting to note that TiO2 partially decomposes into TiB2
chloride-modified LiBH4 materials desorbed 8-9 wt % hydro- during the ball milling and dehydriding process. The intermedi-
gen, which is equal to one-half of the theoretical capacity of ate compounds derived from oxide additives, such as TiB2 in
LiBH4. 75% LiBH4 + 25% TiO2, might play a role in reducing the
7066 J. Phys. Chem. B, Vol. 110, No. 13, 2006 Au and Jurgensen

Figure 8. EDX element maps of the material 75% LiBH4 + 25% TiO2 (×4000).

Figure 9. SEM morphologies of the dehydrided and rehydrided material 75% LiBH4 + 25% TiO2 (×300).

decomposition temperature and providing reversibility for rehydrided samples of 75% LiBH4 + 25% TiO2 exhibited
lithium borohydride materials. There is also another possibility porous and layered features with the coarsen particles size shown
that rehydrogenation produces a new Li-B-H-Ti complex that in Figure 9.
has a lower stability and better reversibility than the original 3.5. Mass Spectral Analysis of the Gas Stream from
LiBH4. More experiments and characterization might provide Decomposition of the Commercial LiBH4. Mass spectral
clues to address this possibility. analysis indicates that the decomposition gas stream from
3.4. SEM Observation and EDX Mapping of the 75% commercially available LiBH4 consists mainly of hydrogen with
LiBH4 + 25% TiO2 Material. To verify the distribution and trace amounts of BH3 and H2O, see Figure 10. The H2O most
decomposition of the additive TiO2, SEM and EDX mapping likely comes from moisture absorbed during sample transfer.
were carried out. After a sample had been dehydrided at 873 However, BH3 formation, even in trace amounts, causes
K, the disassociation of titanium and oxygen through the permanent loss of the boron, resulting in a gradual decrease of
decomposition of TiO2 was observed in the element maps of the hydrogen storage capacity during dehydriding/rehydriding
the dehydrided material 75% LiBH4 + 25% TiO2 (see Figure cycling. We have not yet conducted mass spectral analysis on
8). Titanium can combine with boron to form TiB2 as suggested any modified LiBH4. However, it is possible that the formation
by the XRD data in Figure 7. A similar segregation of titanium of BH3 can be prevented by selecting appropriate additives and
and oxygen was also observed in the rehydrided materials 75% changing the reaction path in the modified LiBH4 materials.
LiBH4 + 25% TiO2 in our experiments. The dehydrided and The results of such investigations will be reported later.
Lithium Borohydrides for Reversible Hydrogen Storage J. Phys. Chem. B, Vol. 110, No. 13, 2006 7067

Figure 10. Mass spectra of the thermal decomposition of the material 75% LiBH4 + 25% TiO2.

Conclusions compounds other than oxides and chlorides might change the
B-H binding energy, resulting in the achievement of reversible
Modification of LiBH4 with additives such as metal oxides
dehydriding and rehydriding at reasonably moderate conditions.
and chlorides reduced the hydrogen desorption starting tem-
perature from 673 to 473 K. The modified lithium borohydrides Acknowledgment. The authors thank Drs. T. Motyka, J.
desorbed about 9 wt % hydrogen and could be recharged to Holder, T. Walters, K. Shanahan, and P. Cloessner for their
7-9 wt % hydrogen capacity at 873 K and 7 MPa. Five effective discussion, comments, and encouragement. This project was
additives were identified. Material characterization indicated that financially supported by the NNSA/PDRD program. Savannah
the additive reacts with lithium borohydride and produces an River National Laboratory is operated by Westinghouse Savan-
intermediate compound that can facilitate the reversible reaction nah River Company for the U.S. Department of Energy under
at relatively moderate conditions. The hydrogen storage capacity Contract DE-AC09-96SR18500.
of the oxide-modified lithium borohydrides decreased gradually
during hydriding/dehydriding cycling. One of the possible References and Notes
reasons for this result is the loss of boron through the formation (1) FY2002 Progress Report for Hydrogen, Fuel Cell and Infrastructure
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additives reduce the dehydriding temperature and improve the Chem. 1964, 9, 826.
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Patent 4,193,978, 1980.
The best compromise should be reached by optimization of the (6) Zuttel, A.; Rentsch, S.; Fesher, P.; Wenger, P.; Sudan, P.; Mauron,
additive loading. Extended ball milling does little to improve Ph.; Emmenegger, Ch. J. Alloys Compd. 2003, 356-357, 515.
dehydriding performance, but it reduces the hydrogen desorption (7) Nakamori, Y.; Orimo, S. J. Alloys Compd. 2004, 370, 271.
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S.; Zuttel, A. J. Alloys Compd. 2005, 404-406, 427.
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