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INSTITUTE OF PHYSICS PUBLISHING MEASUREMENT SCIENCE AND TECHNOLOGY
Meas. Sci. Technol. 15 (2004) 127–130 PII: S0957-0233(04)65966-2

Sievert-type apparatus for the study of

hydrogen storage in solids
R Checchetto1 , G Trettel and A Miotello
Dipartimento di Fisica dell’Università di Trento and INFM, I-38050 Povo (TN), Italy

E-mail: checchet@science.unitn.it

Received 7 July 2003, in final form 22 September 2003, accepted for

publication 15 October 2003
Published 4 November 2003
Online at stacks.iop.org/MST/15/127 (DOI: 10.1088/0957-0233/15/1/017)

Abstract
We report on a Sievert-type experimental apparatus for the study of
hydrogen storage in metals forming the hydride phase. The apparatus is
realized by only using commercial components and allows the study of the
hydrogen absorption and desorption kinetics as well as the determination of
the pressure–composition (P–C) diagram of the material–hydrogen system.
The apparatus can operate over a wide range of temperature, 300–700 K,
and H2 pressures, 1–80 bar. The H2 storage efficiency can be measured with
a good accuracy ∼ 3%. The experimental errors in the hydrogen absorption
and desorption kinetics are ∼1% and 6%, respectively.

Keywords: hydrides, absorption kinetics, desorption kinetics,

hydrogen storage

1. Introduction (a) thermogravimetric techniques, that is by measuring the

One of the most important challenges for the development of
the ‘hydrogen energy economy’ is the availability of a safe and
efficient system for H2 storage. Compared to the commercial
systems such as gas pressurization (CGH2 ) or liquefaction
(LH2 ), H2 absorption in metals forming hydride phase presents
many advantages: a very high volumetric efficiency, a low cost
of the storing operations (no compression or liquefaction work
is required nor cryogenic temperatures) and a high intrinsic
safety [1]. Unfortunately, commercial hydrides such as FeTiH2
and LaNi5 H6 suffer from a low gravimetric efficiency, typically
lower than 2 wt%, while innovative hydrides such as MgH2 and
alanates present slow absorption and desorption kinetics also at
high temperatures. The need for a material able to overcome
these limits at practical operative conditions of pressure (1–
10 atm) and temperature (30–100 ◦ C) has stimulated the
interest of many research laboratories.
An important step in the experimental research is the
analysis of the H2 storage efficiency of the new materials and
the study of their absorption and desorption kinetics. There are
two kinds of experimental approach. At a fixed temperature,
the sample is contained in a chamber at a certain H2 pressure
and the quantity of absorbed hydrogen is evaluated by
1 Author to whom any correspondence should be addressed.
variation of the sample mass by a microbalance, or
(b) volumetric techniques, that is by measuring the H2
pressure variation in a reaction chamber [2].
The accuracy of volumetric techniques is potentially greater
compared to that of thermogravimetric techniques since large
changes in gas pressure are measured rather than small changes
in mass: this advantage is particularly marked when the gas
involved is hydrogen. In the simplest design the volumetric
apparatus records the change of the H2 pressure within a fixed
sample volume resulting from the reaction progress [3]. In
the more sophisticated volumetric devices the H2 gas pressure
in the reaction chamber is maintained constant during the
experiment by modifying, for example, the length of a bellow
that is part of the reaction chamber [4].
In this paper we present a simple and user-friendly
experimental apparatus for the study of the hydrogen storage
in metal compounds based on the volumetric technique
(Sievert-type apparatus): the apparatus allows the study of
the hydrogen absorption and desorption kinetics keeping the
pressure constant in the reaction chamber as well as the
determination of the pressure–composition (P–C) diagram
of the metal–hydrogen system in a wide temperature and H2
pressure range, 300–700 K and 1–100 bar respectively.

0957-0233/04/010127+04$30.00 © 2004 IOP Publishing Ltd Printed in the UK 127

R Checchetto et al
Figure 1. Schematic diagram of the sample apparatus. SC, sample
chamber; RC, reservoir chamber; AC, admission chamber; TC,
K-type thermocouple; VLV, variable leak valves; PV, pneumatic
on–off valve; MV, manually operated valve; PG, strain pressure
gauge; MP, mechanical pump.
2. Experimental apparatus and procedures
A schematic diagram of the apparatus is presented in figure 1.
It is made up of three stainless steel chambers of calibrated
volume, the sample chamber SC (VSC = 26.3 ± 0.4 cm3 ), the
reservoir chamber RC (VRC = 64.0 ± 0.7 cm3 ) and the gas
admission chamber AC (VAC = 52.6±0.9 cm3 ), on–off valves
(manual and pneumatic), variable leak valves, pressure gauges
and a tubular oven. SC is connected with RC by two variable
leak valves (VLV1 and VLV2) and an on–off pneumatic valve
(PV1): RC maintains the H2 pressure in SC constant during the
experimental run by providing or removing H2 gas. The sample
temperature is monitored by a K-type thermocouple positioned
in the tubular oven in contact with SC and controlled with
a proportional integrative and derivative (PID) system. The
pressures in SC and RC are monitored by two strain gauges
with 70 mbar to 100 bar measurement range and 0.1% F.S.
accuracy. The apparatus is evacuated up to 10−2 mbar pressure
by a mechanical pump provided with zeolite traps. During
the experimental run data acquisition and system operations
are automatically controlled by personal computer: the home-
made Labview® software acquires, as a function of time, the
sample temperature T and the pressures in SC and RC, PSC
and PRC respectively, and controls the opening and closing of
the PV1 and PV2 pneumatic valves.
A schematic diagram of SC is presented in figure 2: the all-
metal sealing is ensured by an Ni gasket. The sample, typically
in the form of powders produced by ball-milling, is contained
in an open metallic cylinder made of porous stainless steel
(nominal pore size 0.5 µm) to avoid particle dispersion during
the evacuation and the pressurization of SC. The large porosity
and the open end of the cylinder impede the formation of
hydrogen pressure gradients between RC and the internal part
of the cylinder which could influence the hydrogen absorption
and desorption kinetics.
The apparatus is also connected with an He cylinder which
is used to fill SC and RC before measurements and after the
periodic maintenance operations in order to check for the
presence of leaks.
128
Figure 2. Schematic diagram of SC: the arrow in the figure
indicates the Ni gasket.
2.1. Absorption kinetics
Having established the sample temperature T , the experimen-
tal procedure for the study of the absorption kinetics starts
with the filling of AC with H2 gas at a calibrated pressure. The
measurement is triggered by opening the on–off V1 valve that
directly connects AC and SC: this step allows the establish-
eq
ment of the required PSC pressure in a time interval shorter
than 1 s (the V1 valve is then immediately closed). Before
0
this step, RC was filled with H2 gas at pressure PRC higher
eq
than the pressure PSC . Upon H2 absorption by the sample in
SC, PSC decreases. Its value fluctuates between two extremes,
eq eq
PSC −
P and PSC +
P by H2 gas admission from RC to
eq
SC: when PSC < PSC −
P then the PV1 valve is opened
eq
and it is closed when PSC > PSC +
P. In order to maintain
eq
an effectively constant PSC value,
P is established so that
eq

P/PSC ∼ 0.05. The variable leak valves VLV1 and VLV2
are needed to control the gas flux between SC and RC and
are calibrated in order to avoid H2 overpressures in SC. The
PSC and PRC pressure transients are schematically reported
in figure 3: the time step tn corresponds to the nth refilling
of SC, while
PRC n
is the pressure decrease in RC. The ab-
sorption kinetics is obtained by plotting, at each time step tn ,
the total number of absorbed hydrogen moles (cH ) given by
tn

PRC n
VRC /RTRC , where
PRC n
= PRC
0
− PRC , R is the gas
constant and TRC the temperature of RC, ∼300 K. Note that
the time interval tn −tn−1 is not fixed by the experimental proce-
dure and only depends on the hydrogen absorption kinetics of
the material. The experimental run automatically stops when
the time interval tn − tn−1 is larger than a previously defined
value.
The relative uncertainty in the nth point of the absorption
kinetics (cH ), εnth , can be evaluated by the relation εnth =

Figure 3. Schematic diagram of the H2 pressure transients in SC
and RC during the absorption process. Kinetics of the H2 absorption
process.
εV + εPnth ,
where εV ∼ 1% is the relative uncertainty on the
RC chamber volume and εPnth is the relative uncertainty on
the
PRCn
term. εPnth is given by δ P ∗ /
PRC
n
where δ P ∗ is the
resolution of the pressure gauge in RC ∼ 0.01 atm. In a typical
experimental run
PRC n
−
PRCn−1
∼ 0.2 atm, and the relative
uncertainty on the first point of the absorption kinetics is thus
∼6% (0.01 + 0.01 atm/0.2 atm), decreasing to ∼3% on the
second point (0.01 + 0.01 atm/2 × 0.2 atm) and reaching a
lowest limit ∼1% due only to the uncertainty on the volume
of RC.
2.2. Desorption kinetics
The procedure for the analysis of the desorption kinetics starts
with the sample in SC at equilibrium with H2 gas at pressure
0 values of PSC .
PSC and temperature TSC and RC under vacuum conditions.
The experimental procedure is triggered by the opening of
V1: this operation produces the evacuation of SC up to the
required new equilibrium pressure PSC (the V1 valve is then
immediately closed). Upon hydrogen desorption from the
sample, the pressure PSC in the SC chamber increases. When
the pressure PSC reaches an edge value PSC +
P valve PV1 is
opened and hydrogen gas is removed from SC to RC. The PV1
valve is then closed when the pressure reaches a low limit value
PSC −
P, with PSC +
P < PSC 0
. Valve PV1 is then closed
and valve PV2 is opened for a short time interval to evacuate
RC. The experimental run automatically stops when the time
interval tn − tn−1 is larger than a previously defined value. The
PSC and PRC pressure transients are schematically reported in
figure 4: the time step tn corresponds to the nth evacuation of
SC, while δ PRC is the corresponding pressure increase in RC.
The desorption kinetics (cH ) is obtained by plotting, at each
time step tn , the total number of desorbed hydrogen moles
given by nδ PRC VRC /RTRC , where TRC is the temperature of
the RC chamber which is close to room temperature.
The relative uncertainty in the nth point of the
desorption kinetics (cH ), εnth , can be evaluated by the relation
εnth = εV + εPnth , where εV ∼ 1% is the relative uncertainty
Sievert-type apparatus for the study of hydrogen storage in solids
Figure 4. Schematic diagram of the H2 pressure transients in SC
and RC during the desorption process. Kinetics of the H2 desorption
process.
on the RC volume and εPnth is the relative uncertainty on the
pressure increase on the δ PRC term. As the RC chamber
is evacuated after each opening of the PV1 valve, the εPnth
uncertainty has the same value on each experimental point.
With pressure steps δ PRC in RC ∼ 0.2 atm, the relative
uncertainty on the nth point of the desorption kinetics is thus
∼6%.
2.3. Pressure–composition isotherm
The procedure starts with the sample in the SC chamber under
0
vacuum conditions at temperature TSC and RC at PRC pressure
and TRC temperature. The P–C isotherm is obtained by a
repeated sequence of absorption cycles at progressively higher
eq
When equilibrium is established in SC between the H2
eq
gas, at PSC pressure, and hydrogen absorbed in the solid, the H2
gas moles absorbed by the sample are evaluated by subtracting
from the total number of H2 moles transferred from RC to SC
the number of H2 moles remaining in the gas phase in the SC
chamber:
∗
eq
PRC VRC PSC VSC
n abs (PSC ) = −
RTRC RTSC
∗
where
PRC is the pressure decrease in RC and VSC the
effective value of the SC chamber at temperature TSC which
accounts for the presence of temperature gradients between
the central part and the edge of the oven. For hydride forming
metal, in plateau conditions (that is the two-phase region), the
dominating term in the relative uncertainty of the n abs value is
given by the error on the chamber volumes, εVSC∗ ∼ 2% and
εVRC ∼ 1%, because δ P ∗ = 0.01 atm and PSC and
PRC are
in the 1–10 atm order. When the sample absorbs only limited
hydrogen quantities, that is the sample is in the α phase or the
β phase is completely formed, the relative uncertainty is much
larger, in the 20–30% order.
129
R Checchetto et al

desorbed H2 moles ( x 10-3 )

5
10
4
0,45
pressure [atm]

SC
0,40 chamber
3

PRESSURE (atm)
0,35
0,30
MgH 2-graphite (10 wt%) 0,25
2 0,20
T = 350 ° C 0,15
0,10 RC
1 1 0,05 chamber
0,00
450 500 550 600 650 700
TIME (s)
0
0 500 1000 1500 2000 2500 3000
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7
time (s)
[H 2 ]/[Mg]
Figure 7. Hydrogen desorption kinetics at 350 ◦ C with the SC
Figure 5. P–C isotherm at 350 C of the MgH2 –graphite system ◦ chamber maintained under vacuum conditions: in the inset we
(90 wt% Mg–10 wt% g-C). report a detail of the pressure transient in SC and RC.

7 the pressure transient in SC and RC. Figure 7 shows the

hydrogen desorption kinetics at 350 ◦ C with SC maintained
6
absorbed H2 moles (x 10-3 )

under vacuum conditions: in the inset we report a detail of the

5
pressure transient in SC and RC.
16
PRESSURE (atm)

4 14 4. Conclusions
RC chamber

3 12
We have presented an easy to realize experimental apparatus
SC chamber
10 for the analysis of the hydrogen storage in solids. The H2
2
storage efficiency can be measured with a good accuracy
1
8
0 20 40 60 80 100
∼ 3%. The experimental errors in the hydrogen absorption
TIME (s) and desorption kinetics are ∼1% and 6%, respectively.
0
0 500 1000 1500 2000
Acknowledgments
TIME (s)

Figure 6. Hydrogen absorption kinetics at 350 ◦ C and 10 atm H2 This work was supported by the Ministero per l’Istruzione,
pressure: in the inset we report a detail of the pressure transient in Università e Ricerca (COFIN 2001). We thank L M Gratton
SC and RC. for useful discussion and C Cestari for the support to assemble
the apparatus.
3. Illustrative experiments
References
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absorption and desorption kinetics. The sample was prepared mobility and transport MRS Bull. 27 675
by ball-milling commercial Mg and graphite powders with [2] Gerard N and Ono S 1992 Hydrogen in Intermetallic
Compounds II, Surface and Dynamic Properties,
a final 90%–10% weight composition. Figure 5 shows the
Applications (Springer Topics in Applied Physics
P–C isotherm of the system: the measurement indicates that vol 64) ed L Schlapbach (Berlin: Springer)
Mg has not completely transformed to MgH2 (this result was [3] Ryan D H and Coey J M D 1986 Thermopiezic analysis: gas
confirmed by XRD analysis, not reported here), which suggests absorption and desorption studies on milligram samples
that the sample was not completely activated. The measure also J. Phys. E: Sci. Instrum. 19 693
[4] Gerard N, Belkbir L and Joly E 1979 High accuracy volumetric
shows a plateau at 5.5 atm H2 pressure at 350 ◦ C, in very good
device for hydrogen sorption kinetic studies J. Phys. E: Sci.
agreement with literature data [5]. Instrum. 12 476
Figure 6 shows the hydrogen absorption kinetics at 350 ◦ C [5] Sandrock D G and Huston E L 1981 How metals store hydrogen
and 10 atm H2 pressure: in the inset we report a detail of Chemtech 11 754

130