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International Journal of Hydrogen Energy 29 (2004) 319 – 322

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Enhanced storage of hydrogen at the temperature

of liquid nitrogen
Li Zhoua;∗ , Yaping Zhoub , Yan Suna
a High Pressure Adsorption Laboratory, School of Chemical Engineering, Tianjin 300072, People’s Republic of China
b Group of Physical Chemistry, Department of Chemistry, Tianjin University, Tianjin 300072, People’s Republic of China
Accepted 3 June 2003

Abstract
Storage of hydrogen in activated carbon at liquid nitrogen temperature is considerably enhanced in terms of compression
and adsorption on activated carbon. To reach the capacity of 4:1 kg per 100 l of storage vessel, it needs to compress the gas
to as high a pressure as 75 MPa at 298 K, but only to 15 MPa if compressed at 77 K. The pressure is reduced to 6 MPa if the
container is 6lled with pellets of activated carbon AX-21. Liquid nitrogen is cheap in cost and widely available. Therefore,
storing hydrogen on activated carbon cooled by liquid nitrogen seems feasible for the hydrogen vehicle programs.
? 2003 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Enhanced storage; Hydrogen; Compression; Adsorption; Liquid nitrogen

1. Introduction
Fueling vehicles with hydrogen is the core of hydrogen
economy and has attracted research interest all round the
world. It is not only for protecting the atmosphere from
polluting by the emission of toxic gases from conventional
vehicles, but also for developing a renewable energy source.
Fueling cars with hydrogen is feasible either by using an
internal combustion engine or electric motor coupled with
fuel cells. The bottleneck is the onboard storage of hydro-
gen to satisfy the demand of energy density and cost compe-
tition. Several ways of storage, including liquid hydrogen,
compressed hydrogen, decomposed in situ from methanol
or from metal hydride, could not be proven as a practi-
cal method to compete with conventional cars. Therefore,
searching for a new way to store hydrogen is an urgent task
and, therefore, major research budget was put on hydro-
gen storage [1]. Storage of compressed hydrogen at ambi-
ent temperature and very high pressures was proposed again
recently, but the target pressure that satis6es practical con-
straints could not be reached at the present level of tech-
nology. Adsorptive storage of hydrogen on activated carbon
∗ Corresponding author. Tel.: +86-22-8789-1466.
E-mail address: zhouli@public.tpt.tj.cn (L. Zhou).
was proposed previously [2,3], yet it did not receive much
attention from the industry, especially when carbon nano-
tubes were claimed to possess abnormal performance as a
hydrogen carrier [4]. However, there is a big controversy on
this claim both experimentally and theoretically. The others
could not repeat the high-storage capacity claimed by some
authors. The enhanced storage of hydrogen, either by com-
pression or by adsorption on activated carbon, at the temper-
ature of liquid nitrogen is presented. It takes advantage of
the eCect of temperature on adsorption and hydrogen den-
sity as well as of the low cost and widespread availability
of liquid nitrogen to intensify the storage of hydrogen. The
storage capacity and the cost of hydrogen stored could meet
the criterion of commercialization.
2. A comparison of compression storage at 77 and 298 K
High-pressure compression has been considered again as
an option of storage method recently, and one expects to
gain about 20% savings in cost compared to liquid hydro-
gen. However, compression at ambient temperature is not
eCective compared to compression at the temperature of liq-
uid nitrogen (77 K). As shown in Fig. 1, which is drawn
based on the p–V –T data of hydrogen [5], the pressure of

0360-3199/03/$ 30.00 ? 2003 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/S0360-3199(03)00155-1
320 L. Zhou et al. / International Journal of Hydrogen Energy 29 (2004) 319 – 322
90
80
70
60
Capacity/g.L-1
50
40
30
20
10
0
0 10 20 30 40 50 60 70
p/MPa
Fig. 1. Storage of H2 by compression.
hydrogen must reach 75 MPa at 298 K to store 41 g H2 in a
1 l container, but only 15 MPa is required at 77 K. Storage
of hydrogen at as high a pressure as 75 MPa is presently
not technically feasible.
3. Storing H2 on activated carbon cooled by liquid
nitrogen
Adsorption increases the density of hydrogen near the
surface of carbon and, hence was applied to enhance the
storage of hydrogen or natural gas in the container. How-
ever, only physical adsorption is feasible for the use of hy-
drogen in motor vehicles. As a fundamental feature of phy-
sical adsorption, the amount adsorbed depends strongly on
temperature. An eCective way of enhancing the storage is
to reduce the temperature of storage if the amount stored at
ambient temperature could not meet the criterion of quali-
6cation. Liquid nitrogen is cheap in cost and widely avail-
able, and therefore, is a practical cooling media. Adsorption
isotherms of H2 at 77 K on powder and pellets of activated
carbon AX-21 were measured in our laboratory by an accu-
rate volumetric apparatus. Details of the measurement tech-
nique were given previously [6]. The isotherms obtained are
shown in Fig. 2, where symbols indicate the experimentally
measured amount adsorbed, but they are not the real quan-
tity of hydrogen 6xed on the carbon surface. Either volu-
metric or gravimetric method can only measure adsorption
through the diCerence or change in pressure or weight read-
ings, and give the quantity of excess adsorption. The total
quantity of hydrogen contained in the adsorbed phase is the
so-called absolute adsorption, which equals the sum of the
35
77 K
298 K 30
25
n/mmol.g-1
20
15
10
powder
pellets
5
80 90 100 0
0 1 2 3 4 5 6 7 8
p/MPa
Fig. 2. Adsorption isotherm on AC AX-21 at 77 K. Points: the
excess; Curves: the absolute.
excess adsorption plus the product of gas phase density and
the volume of the adsorbed phase. How to estimate the total
adsorption from the excess adsorption data was regarded as
a major challenge in high-pressure adsorption [7]. Based on
the principle that excess and absolute adsorption are equal
provided the surface concentration of adsorbate is dilute, the
authors proposed a method to calculate the absolute adsorp-
tion isotherm from the excess adsorption data [8,9]. Shown
as solid lines in Fig. 2 are the isotherms of absolute adsorp-
tion determined by the proposed method. The isotherms of
absolute adsorption always increase with pressure, although
the isotherms of the excess adsorption may decrease with
pressure or even show negative values [10].
The storage capacity in a given volume is the capacity
of adsorbed molecules on the carbon surface plus the volu-
metric capacity due to compression in the void space. The
volume of the void space before adsorption, Vtv , is the sum
of pore volume inside adsorbent particles and the volume
outside the particles. This volume is experimentally deter-
mined by the helium expansion method, provided helium
does not adsorb. Care must be exercised in terms of adsor-
bents containing extremely 6ne pores, where adsorption of
helium might be possible. However, the volume of the void
space is decreased to Vg after adsorption since a space of Va
was occupied by the adsorbed phase and
Vtv = Va + Vg : (1)
Multiplying both sides of Eq. (1) by the gas phase density,
g , we obtain
g Vtv = g Va + g Vg : (2)
 L. Zhou et al. / International Journal of Hydrogen Energy 29 (2004) 319 – 322
50
45
40
5
Gram of H2 stored in 1 L
35
30 4
25
3 1
20
2
15
10
5
0 0
0 1 2 3 4 5
p/MPa
Fig. 3. Storage capacity on AC AX-21 and by compression. (1)
Compressed; (2) Fixed on powder surface; (3) Total quantity stored
in unit volume of powder; (4) Fixed on pellets surface; (5) Total
quantity stored in unit volume of pellets.
Adding the excess adsorption, n, to both sides of Eq. (2),
we have
n + g Vtv = (n + g Va ) + g Vg
= n s +  g Vg
= Ctot ;
where Ctot is the total capacity of storage. Therefore, neither
Va nor Vg is needed for the evaluation of Ctot . Suppose the
bulk density and the skeleton density of adsorbent is, respec-
tively, b and s , then the volume occupied by “solid” or
“skeleton” part of adsorbent is Vs =b =s , and the void space
Vtv = 1 − b =s . Determination of b is a common practice
of the laboratory, but that of s requires a special technique.
The density of graphite was usually taken for the skeleton
density of activated carbon. But this may not be correct be-
cause the existence of closed pores or small pores that are
inaccessible to helium molecules makes the skeleton den-
sity of activated carbon smaller than that of graphite. The
volume of the skeleton part of activated carbon was deter-
mined as the diCerence between the volumes of adsorption
cell without and with loading adsorbent, and the density of
the skeleton carbon was calculated based on such a volume.
The “volumetric” storage capacity of activated carbon
AX-21 for hydrogen at 77 K is shown in Fig. 3 on the ba-
sis of a 1 l container. Curve 1 is the quantity of hydrogen
stored just by compression; curves 2 and 4 are the excess
321
12
77 K 11
10 77 K
9
der
8 pow
wt % stored
7
pellets
6
5
4
3
2
1
6 7 8 0 1 2 3 4 5 6 7 8
p/MPa
Fig. 4. Weight percentage of H2 stored on AC AX-21 powder and
pellets.
adsorption data on powder and pellets, respectively, based
on the mass of carbon contained in the 1 l container; curves
3 and 5 are the total storage capacity of a 1 l container
6lled with carbon powder and carbon pellets, respectively
(the bulk density of carbon powder is 0:3 kg=dm3 , and that
of carbon pellets is 0:72 kg=dm3 ). For example, 19:6 g hy-
drogen could be stored at 6 MPa in a vacant 1 l container,
(3) 32:5 g hydrogen stored in the same container 6lled with
0:3 kg of carbon powder, and 41 g hydrogen could be stored
if the container was 6lled with 0:72 kg of pellets. The De-
partment of Energy, USA set up a criterion of 6:5 wt% for
any potential hydrogen carrier. The value of such an index
is 10:8 wt% for carbon powder at 6 MPa, and even higher
at higher pressures as shown in Fig. 4. However, the stor-
age capacity expressed by weight percentage is not a proper
index since much more hydrogen can be stored per unit
volume of container 6lled with carbon pellets as shown in
Fig. 3, although the weight percentage of H2 is less than that
when the container was 6lled with carbon powder. This fact
may be explained by the changes of the bulk density and the
speci6c surface area in making pellets. The loss in surface
area leads to the decrease of gravimetric storage capacity,
but the increase in bulk density leads to more adsorbent
being 6lled in a given volume, which results in the increase
in the volumetric storage capacity.
Based on the above information, it is concluded that stor-
age of hydrogen at 77 K achieves considerable enhance-
ment due to both compression and adsorption. The pressure
needed for storing 4:1 kg hydrogen in a container of 100 l
322 L. Zhou et al. / International Journal of Hydrogen Energy 29 (2004) 319 – 322
by compression is decreased by a factor of 5 if the tempera-
ture is reduced from 298 to 77 K. The pressure is decreased
further by two and half times if the container is 6lled with
carbon pellets.
Such a method of storage provides important practical
implications. First, the storage capacity is acceptable for
driving practice and the reported data can be repeated in
any laboratory equipped with an accurate apparatus for ad-
sorption measurement and operated by quali6ed personnel.
Charging and discharging of hydrogen in activated carbon
is reversible, since no hysterisis was observed at any tem-
perature tested [6]. The adsorption of hydrogen on activated
carbon, as a typical physical adsorption, reaches equilibrium
fast. Second, activated carbon of a high speci6c surface area
can be produced at a large scale with reasonable cost. Third,
hydrogen is stored in gas state, therefore, is much cheaper
than liquid hydrogen, and cleaner and safer than methanol.
The storage facility is much simpler than that for on-board
producing hydrogen. Fourth, instead of hydrogen, nitrogen
is lost as evaporation loss; therefore, is safe and cheap. Fifth,
liquid nitrogen is widely available at low cost. It does not
need a nitrogen cylinder on board, but is required to add
some into the insulation jacket periodically, usually once a
week due to the large heat capacity of the fuel tank.
Acknowledgements
This work is subsidized by the Special Funds of Major
State Basic Research Projects (G2000026404) and sup-
ported by the National Natural Science Foundation of China
(#29936100).
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