REVIEW OF INTERSTITIAL METAL HYDRIDE ALLOYS USED IN

CONTEMPORARY HYDROGEN STROAGE APPLICATION

Gonzaga University
E. Petersen, C. Trebilcock, E. Dawson, P. Ferro
Alloy, Metal Hydride, Hydrogen Storage
Abstract
Hydrogen storage continues to be an area of research for contemporary problems. From large scale
hydrogen storage challenges (including storing energy from wind turbines in the Columbia River
gorge) to consumer hydrogen storage challenges (such as that associated with vehicular onboard
applications), there are a range of possible methods for storing hydrogen. Metal hydride (MH) alloys
are one possibility that continues to be studied. Characterization of candidate metal hydride alloys
involves development of equilibrium pressure-composition-temperature (PCT) plots through a range of
temperatures. The current work seeks to review currently published data and to infer long term trends
about MH alloys for future challenges. PCT data for commercially available MH hydrogen storage
canisters are compared with data measured in a lab investigation of MH canisters.
Background
Of the several successful methods for storing hydrogen, metal hydride alloys have proven to be a safe
and reliable way of storing hydrogen as an input for hydrogen fuel cells and for hydrogen internal
combustion engines [1]. The advantages of using metal hydride alloys as a means of hydrogen storage
are due to the high volumetric density that solid hydrogen storage methods avail. Other advantages
include the high purity of hydrogen that is delivered, a high number of reversible cycles, scalability
and the ability to tailor plateau pressure.
A review of recent hydrogen storage product releases was performed in searching for published metal
hydride data. It was apparent that one of the most anticipated additions to the consumer hydrogen
product market in 2015 will be the release of a commercial vehicle by Toyota. A four passenger
vehicle model, the Mirai is powered by fuel cell stacks and can reportedly deliver 114 kW of power
[2]. The hydrogen is stored on board as a pressurized gas in carbon-fiber composite tanks which have
a rated pressure of 70 MPa (10000 psi). [2]
Besides the automotive market, other companies appear to be involved in the development of a
manufacturing supply chain for future hydrogen products. American Elements [3], Pragma Industries
[4] and Vodik Labs [5] each respectively offer interstitial metal hydride alloys for hydrogen storage.
Additionally, Ergenics [6], H Banks [7], Hydrogen Components Inc. [8] have reported PCT curves for
their available alloys.
Recent publications by Klebanoff [9] and a PhD thesis by Jean Nei [10], published in 2012, include
explanations in the differences between candidate materials for storing hydrogen. They also include a
comprehensive review of the progress of hydrogen technology. A review of candidate interstitial metal
hydride materials is given by K. Young and Nei [11], published in 2013. In each of these texts, it is
explained that storing hydrogen is broadly categorized as either being physically stored or as being
chemically stored. One such chemical storage categorization discerns whether a candidate technology

is considered on-board reversible or off-board reversible. Of the latter, interstitial metal hydrides
are a reasonable candidate material as are complex hydrides and sorption materials.
On-board reversible candidate material categories include complex hydrides, interstitital metal
hydrides and sorption materials listed in order of decreasing hydrogen bond strength. Complex
hydrides are characterized by relatively strong, covalent bonding between the hydrogen and the lattice.
As a result, the heat of desorption of these materials are small negative values or positive values,
suggesting an exothermic desorption process. Interstitial metal hydrides, by contrast, involve only a
metallic bond between the dissolved hydrogen and the metallic lattice. The heat of desorption for these
types of materials ranges near -30 kJ/mol H2. This is, relatively speaking, a Goldilocks heat of
desorption in that it is not too high nor too low. Continuing in the spectrum of bond strength,
comparing sorption materials to metal hydrides and complex hydrides shows that it is easy to weakly
attach and detach hydrogen to and from the framework. Engineering predictability is reduced with
these conditions, and it is difficult to ascertain that a certain amount of hydrogen has been adsorbed or
desorbed for any given length of charging or discharging time.
Chao and Klebanoff provide an excellent review of interstitial metal hydrides for hydrogen storage
applications. [12]. The case is presented for arriving at interstitital metal hydrides as a candidate
material class for volumetrically efficient means of reversibly storing hydrogen. Further classification
of interstitial metal hydrides suggests at least three materials classes. These hydrides may be
categorized as belonging to one of the following categories: AB compounds, AB5 compounds, AB2
compounds, and V-Ti-Cr BCC alloys. [12]
The first of the aforementioned categories is AB compounds. An example of an AB compound used in
hydrogen storage is FeTi. Hydrogen Components, Inc (Bailey CO) offers portable hydrogen storage
containers with FeTi, and provides PCT data for each of the alloys used in its products. [8]
An example of a commercially-available AB5 alloy is that of Ergenics Hy-Stor 207. The literature
data reports the nominal chemistry of LaNi4.7Al0.3, and provides pressure-composition-temperature
(PCT) curve data at 25C. The data represented gives the pressure as a function of hydrogen:metal
atom ratio, indicating that the alloy is full or saturated with hydrogen when the hydrogen:metal atom
ratio is 1:1 [6]. Using molar masses, the estimated reversible capacity of this alloy on a weight
percentage basis is 1.4 weight percent at 25C.
Magnesium alloys have been studied for their relatively high storage capacity on a weight percentage
basis, due to magnesiums low atomic mass. The practical problems in producing magnesium-based
hydrogen storage alloys arise from magnesiums relatively high vapor pressure, which makes it
difficult to produce with standard foundry technologies. The work of Saita et al. [13] shows on
combustion synthesis production methods of Mg2NiH4 hydrides can give hydrogen storage capacities
in the 3.6% range.with desorption plateau pressures in the 0.5 MPa range at 25C. The work of Saita,
published in 2001, focused on advancements in processing technologies (e.g. combustion synthesis) to
produce an alloy with relatively high storage capacity on a mass basis, but the work cited no specific
products for which this alloy was designed. [13].

A review of battery materials from Chandra et al. [14] gives several example alloys and the expected
plateau pressure at or near room temperature. Table I is a summary of Chandras data.
Table I.
Type of
hydride
Elemental
AB5
AB2
A2B
AB
BCC

Summary of NiMH Battery Alloy Data [14]

Metal/alloy
Hydride
Wt. pct. hydrogen
Pd
LaNi5
ZrV2
Mg2Ni
FeTi
TiV2

PdH0.6
LaNi5H6
ZrV2H5.5
Mg2NiH4
FeTiH2
TiV2H4

0.56
1.37
3.01
3.59
1.89
2.6

Plateau pressure,
temperature
2 kPa, 298K
200 kPa, 298K
0.001 Pa, 323K
100 kPa, 555K
500 kPa, 303K
1 MPa, 313K

In the published work of Young and Nei [11], the comprehensive review shows how AB5 (misch metal
based) and AB2 (Laves phase based) continue to draw research interest in the realm of battery electrode
applications. The transition metal-based AB2 alloys are of interest due to their contribution in
reduction of rare earth metals. AB2 alloys used in batteries are composed of Laves phases. An impetus
for transitioning from AB5 to AB2 in batteries is due to the expected improvement in specific energy.
For example, Young [11] cites improvements including 310 to 340 mAh g-1 in AB5 vs. 384 to 450 mAh
g-1 in AB2.
Procedure
Two commercially-available portable hydrogen storage containers were repeatedly cycled through full
ranges of absorption and desorption cycles. Equilibrium pressure measurements were taken by
allowing the containers to settle overnight, and pressure readings were taken after at least 12 hours had
elapsed since the last absorption or desorption. A hand held dial pressure gage from Omega was used
to measure the settled pressure at room temperature. The canisters were weighed on a digital mass
balance, and the mass percentage of stored hydrogen was calculated based on knowing the mass of the
respective containers when they were completely depleted of reversible hydrogen and comparing to the
mass when it was completely filled (following room temperature charging at 250 psig). The estimated
reversible capacities of each of the canister types was known from Chao and Klebanoff et al.[12], as
summarized in Table II.
Table II.
Type

AB
AB2
AB5
V-Ti-Cr bcc

Summarized Properties of Interstitial Metal Hydrides [12]

Theoretical
Observed
Volume
capacity
reversible
expansion in
capacity
hydride
2.8
1.9
18 %
3.8
2.4
18 - 30 %
1.6
1.6
15 - 25 %
3.8
3.0
40 %

H (kJ mol-1)
28 - 35
22 - 35
24 - 35
28 - 35

To measure surface temperature changes during five minute desorptions, a Type K thermocouple was
mounted on the surface of a canister. The surface temperature was recorded at thirty second intervals
during the five minute desorption period.
Results
Figure 1 shows equilibrium desorption pressure measurements taken at 25C on a portable hydrogen
storage canister from Hydrogen Components, Inc. (HCI). The canister that the measurements were
taken from were the CL-370A, which is a canister that contains a metal hydride alloy of nominally
FeTi chemistry and a reversible capacity of 33g. The data shown in Figure 1 are from measurements
taken at equilibrium following desorption, as denoted by the circles, and is compared with data from an
HCI datasheet for a comparable alloy. The horizontal line is the reported plateau pressure for FeTi as
reported by Chandra [14]. Relatively good agreement between the measured data and the literature
values is shown.

Figure 1. Equilibrium pressure following desorption as a function of mass fraction of reversibly stored
hydrogen for a portable hydrogen storage container from Hydrogen Components Inc (HCI). The
nominal stoichiometry for the metal hydride alloy is FeTi. The dark circles represent equilibrium
pressure measurements taken following desorption and were taken at room temperature. Chandras
reported plateau pressure for FeTi (5 bar) is shown as a dark horizontal line. [14]

Figure 2 is the PCT data for an Ovonic canister containing an AB2 alloy. The reversible capacity of the
canister was 20g of hydrogen. Room temperature equilibrium data following desorption were taken.
A minimum time of 12 hours was the time that elapsed following a desorption before an equilibrium
pressure measurement was taken. The data shows an approximate plateau pressure of 100 psig at room
temperature. The plateau pressure for the alloy in the canister agrees reasonably with similar data
reported in [14].

Figure 2.
Log pressure as a function of mass fraction reversible hydrogen for a metal hydride
canister with a 20 g reversible storage capacity. The equilibrium data shown was taken at room
temperature. An apparent plateau pressure of approximately 100 psig is observed.
Figure 3 compares equilibrium plateau pressures for three proprietary AB2 alloys. [15] The three alloys
shown are considered candidates for vehicle on-board design as well as for stationary applications. The
plateau pressures represented in figure 3 compare well with the plateau pressure shown in figure 2.

Figure 3.
alloys [15].

Equilibrium plateau pressure as a function of temperature for three proprietary AB2

Figure 4 shows surface temperature as a function of desorption time in room temperature air for two
canisters. One canister (from HCI) contained an FeTi alloy, and the other canister (from Ovonic)
contained an AB2 alloy. During the desorption trials, each canister desorbed 1.0g. The Ovonic canister
demonstrated a greater desorption temperature change, possibly due to its smaller size. The data in
Table 2 provides example heats of desorption ranges for each of the two material classes represented in
Figure 3. However, this preliminarily would indicate an average higher heat of desorption for AB
compared with AB2 and thus a larger predicted temperature change. None withstanding, the difference
in canister size may explain the relative positions of the two curves shown in figure 3.

Figure 4.
Canister surface temperature as a function of desorption time in room temperature for
two canisters. One canister contained FeTi, and the other contained an alloy of AB2 type. The
temperature loss rates are different due to differences in alloy but also due to differences in canister
size and reversible capacity. The FeTi canister was approximately 20% larger by mass and had a
corresponding larger reversible capacity.
Figure 5 compares the surface temperature change for several five minute desorption trials for the
Ovonic canister (containing an AB2 alloy). The larger the change in canister mass, the larger the
observed change in surface temperature as was expected. The data shown is an example of the data
that may be collected during future heat transfer experiments in order to provide scale up data for
future hydrogen storage designs.

Figure 5.
Change in canister surface temperature as a function of desorbed hydrogen in air at
room temperature after five minutes desorption for an Ovonic canister with a reversible capacity of
20g of hydrogen. The canister contained an AB2 alloy.
Conclusion
Metal hydride alloys have proven to be a safe and reliable means by which to store hydrogen, and
recent publications continue to advance understanding of their increased applications. One of the most
prominent hydrogen storage product releases in the past year has been the Toyota Mirai, a fourpassenger vehicle powered and fuel cell stacks and capable of delivering 114kW of power. Recent
publications have sought to distinguish candidate materials for hydrogen storage and to provide a
general overview of hydrogen storage technology.
In testing done at Gonzaga Universitys Hydrogen Laboratory, relatively good agreement was found
with desorption measurement data pulled from published data sheets in which a metal hydride alloy of
nominally FeTi chemistry and 33g reversible capacity was used. Testing with an Ovonic canister
containing an AB2 alloy demonstrated appropriate coordination of the plateau pressure with data
published in [14] as well as published proprietary alloy data. In comparing surface temperature change
between a canister containing FeTI alloy and a canister containing an AB2 alloy, a difference in rate
was noted. Alloy type, canister size and reversible capacity were concluded as contributing factors.
Finally, a direct correlation was found experimentally between canister mass and change in surface
temperature. More research into the heat transfer of hydrogen storage designs will be needed in order
to further current understanding of effective metal hydride applications.

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