i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 8 3 3 e1 6 8 4 0

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Thermodynamics analysis of hydrogen storage

based on compressed gaseous hydrogen, liquid
hydrogen and cryo-compressed hydrogen

Zhao Yanxing a, Gong Maoqiong a,b,*, Zhou Yuan a,**, Dong Xueqiang a,
Shen Jun a,b
a
Key Laboratory of Cryogenics, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing
100190, China
b
University of Chinese Academy of Sciences, Beijing 100039, China

article info abstract

Article history: Safe, reliable, and economic hydrogen storage is a bottleneck for large-scale hydrogen
Received 12 January 2019 utilization. In this paper, hydrogen storage methods based on the ambient temperature
Received in revised form compressed gaseous hydrogen (CGH2), liquid hydrogen (LH2) and cryo-compressed
16 April 2019 hydrogen (CcH2) are analyzed. There exists the optimal states, defined by temperature
Accepted 19 April 2019 and pressure, for hydrogen storage in CcH2 method. The ratio of the hydrogen density
Available online 15 May 2019 obtained to the electrical energy consumed exhibits a maximum value at the pressures
above 15 MPa. The electrical energy consumed consists of compression and cooling down
Keywords: processes from 0.1 MPa at 300 K to the optimal states. The recommended parameters for
Hydrogen storage hydrogen storage are at 35e110 K and 5e70 MPa regardless of ortho-to parahydrogen
Cryo-compressed hydrogen (CcH2) conversion. The corresponding hydrogen density at the optimal states range from 60.0 to
Liquid hydrogen (LH2) 71.5 kg m
3 and the ratio of the hydrogen density obtained to the electrical energy
Ambient temperature compressed consumed ranges from 1.50 to 2.30 kg m
3 kW
1. While the ortho-to para-hydrogen con-
gaseous hydrogen (CGH2) version is considered, the optimal states move to a slightly higher temperatures comparing
Power consumption to calculations without ortho-to para-hydrogen conversion.
© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

achieved thermally, electro- or photolytically [1e3] using va-

Introduction riety of raw materials such as coal, natural gas, biomass,
boron hydrides, hydrogen sulfide, water, etc. Hydrogen utili-
Hydrogen is considered the next generation energy carrier zation mainly includes hydrogen-based fuel cells and internal
with high calorific value (per kilo) and zero-pollution. Exploi- combustion engines. The latter is a very mature technology,
tation of hydrogen energy consists of production, storage and and its energy utilization efficiency is much higher than that
utilization. Production and utilization of hydrogen are mature for gasoline engines [4]. Usage of hydrogen-powered fuel cells
technologies. Large-scale production of hydrogen is currently is currently the best way to utilize hydrogen, and it is believed

* Corresponding author. Key Laboratory of Cryogenics, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences,
Beijing 100190, China.
** Corresponding author.
E-mail addresses: [email protected] (G. Maoqiong), [email protected] (Z. Yuan).
https://doi.org/10.1016/j.ijhydene.2019.04.207
0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
16834 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 8 3 3 e1 6 8 4 0

to be wildly applied in next-generation vehicles. Significant of LH2 are satisfactory. LH2 is an ideal method, however, it
progress in this area have been achieved in Japan [5,6]. consumes a lot of electricity during the liquefaction stage.
Unfortunately, hydrogen is the lightest substance in na- Theoretically, it requires about 4e10 kWh to produce 1 kg of
ture. Its density is only 0.081 kg/m3 at 300 K and 0.1 MPa, which liquid hydrogen [20]. This accounts for over 30% of the com-
is ten thousand times less than that of water. Moreover the bustion energy stored in hydrogen. This percentage will be
liquefaction of hydrogen with a normal boiling point of ~20 K even bigger during practical applications. The boil-off char-
has a Carnot efficiency of 0.073 and so the liquefaction re- acteristic is another unfavorable factor that will further
quires a lot of energy. Thus, highly reliable, economically reduce LH2 efficiency [21]. Due to the unavoidable heat influx
feasible and safe hydrogen storage technology prevents large- into the storage vessels, ~2e3% of evaporated hydrogen will be
scale hydrogen utilization. This problem needs a near-term lost per day [19]. Thus, LH2 is more preferred for the high-tech
solution. industries, which are concerned more with performance than
Various hydrogen storage technologies are at different cost (like aerospace industry).
stages of their development. However, none of commercial
products meet all the requirements set by the US Department
of Energy (DOE) in 2017 [7]. Five main factors (such as gravi- Compressed gaseous hydrogen storage
metric and volumetric capacities, operating temperature,
cycle life and system fill time) need to be taken into account to Ambient temperature compressed gaseous hydrogen storage
develop the most efficient hydrogen storage system [8]. (CGH2) is the most mature technology widely adopted in va-
Hydrogen storage materials are required to have at least 5.5 wt riety of practical application. In 2010, over 80% of the total 215
% of hydrogen. Currently, the compressed gaseous hydrogen operating hydrogen refueling stations worldwide adopted
(including ambient temperature compressed gaseous CGH2 method [22]. CGH2 is simple, provides fast filling/
hydrogen, CGH2 and cryo-compressed hydrogen, CcH2), liquid releasing rate and has low costs. However, the biggest weak-
hydrogen (LH2) and material-based hydrogen storage (MH2, ness of CGH2 is its low volumetric density, which makes CGH2
such as metal hydrides) are three primary storage methods [9]. less popular in practice. Current on-board hydrogen storage
The CGH2 and LH2 have been commercialized, while the CcH2 tanks have operational pressures up to 70 MPa but they pro-
developed by the automobile company BMW [10] is a prom- vide hydrogen density of only 39.1 kg/m3. Volumetric density
ising method and the MH2 attracts attention since it operates does not increase proportionally to the pressure increase,
at low pressure. which makes it extremely difficult to increase volumetric
density by pressurization only. Additionally, high pressures
present a serious safety problem [20]. Sun et al. [23] suggested
Material-based storage that 50e55 MPa storage pressures will provide the most opti-
mized trade-off with cost effectiveness. Recently, supercriti-
In material-based storage (MH2), hydrogen atoms or mole- cal cryo-compressed hydrogen storage (CcH2) has been
cules are tightly bound with other elements either by phys- proposed by BMW [10] company and developed by many
isorption and/or chemisorption. Physisorption involves others [24,25]. Their concept consists of storing hydrogen in a
adsorption of hydrogen atoms or molecules on to the surface pressure vessel that can operate at cryogenic temperatures (as
of, e.g., nanomaterials [11] such as carbon nanotubes and low as 20 K) and high pressures (e.g. ~35 MPa). CcH2 can store
metal organic framework. Less than 1 wt% of hydrogen high-density hydrogen, similar to LH2, without evaporative
adsorption capacities were reported for porous materials at losses in routine use. Since this method involves no lique-
ambient conditions [12]. Chemisorption involves absorption faction, power consumption is expected to be significantly
of hydrogen molecules and their disintegration into hydrogen reduced.
atoms followed by their incorporation into the material lat- In this paper, the thermodynamics analysis, including the
tice. Examples of such materials are metal hydrides, liquid storage density and power consumption, of hydrogen storage
organic hydrogen carriers [13,14], etc. When absorbed, methods based on CGH2, LH2, CcLH2 and CcH2 is performed.
hydrogen can potentially be stored at high density and low The optimal parameter for hydrogen storage is expected to be
pressure, which is safer comparing to CGH2 and LH2. However, put forward.
hydrogen must be released at high temperatures or low
external pressures [15]. These processes often have slow re-
action kinetics, low reversibility and high dehydrogenation Modeling
temperatures. Thus, these weaknesses yet remain to be
solved [16,17]. In fact, there are still no materials that can fulfil Schematics of the CcH2 system is shown in Fig. 1. Hydrogen
all of the target parameters for the hydrogen storage systems will undergo compression, refrigeration and storage pro-
set by the US DOE [18,19]. cesses. Compression process consists of several compressing
and cooling units, which produce high-pressure and near-
room temperature hydrogen. Then the hydrogen is cooled in
Liquid hydrogen storage a refrigerator or using, for example, liquid nitrogen, after
which it is stored in specially designed containers. The ther-
Liquid hydrogen storage (LH2) can achieve higher density than modynamic properties of hydrogen are calculated by Refprop
CGH2. Usually, hydrogen is liquefied at ~20 K at atmospheric 9.1 [26]. It is considered the most accurate computation tool to
pressure or higher. Both volumetric and gravimetric capacities obtain thermodynamic and transport properties of hydrogen
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 8 3 3 e1 6 8 4 0 16835

Fig. 1 e Schematics of the cryo-compressed hydrogen storage (CcH2).

[27]. Uncertainty associated with density determination is Analysis of hydrogen cooling

0.1% at temperatures from the triple point to 250 K and at
pressures up to 40 MPa. Between 250 and 450 K and at 300 MPa Cooling load of hydrogen above the critical temperature is
uncertainty in density determination is 0.04%. Estimated un- almost linear (see Fig. 3). To reduce energy consumption
certainty for heat capacity values is 1.0%. Estimated un- during cooling process, it is essential to match the cooling
certainties of vapor pressures and saturated liquid densities temperature and thermal load of hydrogen. Ideally, these two
calculated using the Maxwell criterion are 0.2% [28]. parameters must demonstrate constant temperature differ-
ence. Usually, the temperature difference should be neither
too big nor too small. At the same time, exergy efficient of the
Results and discussion cooling system and pressure loss of the heat transferring
media need to be considered as well. However, in practice, it is
Analysis of multistage hydrogen compression process hard to achieve small temperature difference just using one
single refrigerator. Thus, multi-temperature cooling process is
Isentropic exponent of hydrogen is 1.41, which will lead to a generally preferred for this purpose (such as cascade refrig-
high discharge temperature even at a moderate pressure ratio eration cycle used in natural gas liquefiers, which is achieved
of 4e8. Thus, multistage compression is preferred for practical by multi-stage pure refrigerant cycling [29]). Mixed refrigerant
applications. At the same time, the infinite multistage cycle [30], Reverse Brayton cycle [31] and Claude cycle [32]
compression approaches isothermal compression, thereby could maintain relatively small heat transfer temperature
decreases the energy consumption, but increases initial in- difference between the cold and warm media. Therefore, it is
vestment and system complexity. Therefore, it is essential to possible to achieve near constant and small temperature dif-
optimize the compression stage. Power is consumed by the ference between the cooling fluid and the hydrogen. Under
compression unit mainly during compressing and cooling
processes. In our calculation, adiabatic efficiency of the
compressor was set to 70%. The inlet and outlet air tempera-
tures of the air cooler were set to 298 and 310 K, respectively.
The temperature of the hydrogen at the outlet of the air cooler
was set to 300 K.
Fig. 2 shows power consumption of the compressors and
the fans during multistage hydrogen compression process.
The mass flow rate of hydrogen is set to 5 kg/h and the initial
and final pressures are set to 0.1 and 35 MPa, respectively.
Two or more additional stages compression processes
significantly decrease power consumption. However, power
consumption does not change significantly when more
stages exist in the process (for example six). The different in
power consumption is ~3% when five and six compression
stages are implemented. We selected a five stage compres-
sion process. Power consumption of such five-stage pro-
cesses occupies 47% of that of single stage compression. In
the calculation, the pressure ratio of each compression stage Fig. 2 e Power consumption of the compressors and the
is set to the same in a certain multistage compression fans during multistage hydrogen compression and air
processes. cooling processes. X-axis shows the number of stages.
16836 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 8 3 3 e1 6 8 4 0

ZQ    Q
1 Troom 1 Troom
P¼
1 dq ¼ lnðKq þ TR Þ
q
x TR þ Kq x K 0
0
   
1 Troom 1 Troom
¼ lnðKQ þ TR Þ
Q
lnðTR Þ
x K x K (3)
       
1 Troom KQ þ TR Q Troom TR
¼ ln
Q ¼ ln
1
x K TR x TR
Tobj Tobj
   
Q Troom Troom
DT
¼ ln
1
x Troom
TH2min TH2min
DT

where DT is the temperature difference between the cooling

medium and the hydrogen.

Analysis of density and power consumption of CcH2

In this work we analyzed densities of gaseous hydrogen at

Fig. 3 e Cool down of hydrogen (a) 0.4 MPa and (b) at
5e70 MPa and at 35e300 K and of liquid hydrogen at
70 MPa.
0.1e20 MPa and 20e26 K (see Fig. 5). Even at 70 MPa and 300 K,
the density of hydrogen is only 39.1 kg/m3. Apparently only by
pressurization, it is very hard to achieve high density of
hydrogen. Liquid hydrogen has a relatively high density:
71.0 kg/m3 at 20 K and 0.4 MPa. However, gaseous hydrogen
this assumption, the smallest power consumption is calcu- above 15 MPa can have higher density than liquid hydrogen.
lated by the following equation (using data from Fig. 4). However, simply pursuing high density can be uneco-
ZQ ZQ ZQ   nomic, especially for large-scale or long-term storage situa-
dq 1 1 Troom tions. Power consumption to achieve high density of hydrogen
P¼ ¼ dq ¼
1 dq (1)
hq x
Tevap
x Tevap must be considered. The ratio of the hydrogen density ob-
0 0 Troom
Tevap 0
tained to the electrical energy consumed consisting of
where hq is the refrigeration efficiency, dq is the thermal load compression and cooling down processes from 0.1 MPa at
under constant temperature, Q is the total thermal load, Tevap 300 K to the optimal states is defined, that is j ¼ hydrogen
is the cooling temperature, Troom is the room temperature, and density/power consumption, as shown in Fig. 6. In this sec-
x is the relative Carnot efficiency. Considering typical practical tion, the ortho-to para-hydrogen enthalpy of conversion is
refrigeration efficiency, x is set to 0.3 for the whole tempera- ignored but it will be calculated in the next section. At room
ture zone. temperature, j increases as hydrogen pressure increases at
Since the cooling load of hydrogen is almost linear as 5e70 MPa (see Fig. 6). Thus, it is a good choice to increase the
function of the increasing temperature, it can be represented pressure for storage of hydrogen at room temperature from
by: both density and power consumption points. Since the coef-
Tobj
TR ficient of performance (COP) of the refrigerator declines
Tevap ¼ TR þ q ¼ TR þ Kq (2) sharply at very low temperatures, it is ineffective to liquefy
Q
hydrogen at any pressure. Index j of liquid hydrogen is
where Tobj and TR represent the maximum and minimum
noticeable lower than that of most of CcH2 because of the
cooling temperature, respectively.
Combining Eqs. (1) and (2), power consumption of
hydrogen cooling is as follows:

Fig. 4 e Cool down of hydrogen: sensible heat þ latent Fig. 5 e Isobaric densities of hydrogen at various
heat. temperatures.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 8 3 3 e1 6 8 4 0 16837

Separation industries. Thus, mature, reliable and high-

efficient refrigeration technologies are already available,
such as mixed refrigerant cycle, cascade refrigeration cycle,
and nitrogen Reverse Brayton cycle, etc. Additionally, liquid
nitrogen cooling is also an efficient way, because of the small
temperature difference between nitrogen and hydrogen. In
the future, large-scale refrigeration based on pulse tube
refrigerator will be also available. Therefore, it is important to
optimize CcH2 at this temperature zone to obtain high
hydrogen density as it can be then easily transferred to these
mature existing technologies. Recommended CcH2 parame-
ters for this temperature range together with those for CGH2
and LH2 are shown in Table 1.
At 70 MPa, CGH2 has the best u and j values because power
Fig. 6 e Density of hydrogen per total power consumption consumption is the lowest. However, intensity is also low.
at different temperatures and pressures. Densities of the recommended parameters in cases 1e14 vary
from 60.0 to 71.5 kg/m3; j values vary from 1.50 to 2.30. Cases 4
to 14 achieve better densities and j values than CGH2 at
latent heat. Although the latent heat accounts for about 10% of
70 MPa. Although densities of hydrogen gas of these cases are
the total cooling heat, the isothermal condensation process
slightly lower than those for LH2, their j values are much
makes this part of refrigeration power noticeable (see Fig. 3).
better than LH2.
The latent heat consumes 41% of the total cooling power. That
In the case of fuel cell applications, hydrogen storage in
is also why CcH2 has much more efficient electricity con-
cars and in hydrogen refilling stations need to be seriously
sumption than LH2. A maximum value of j exists at each
considered as well. The biggest challenge in these applications
pressure except for 5 and 10 MPa. Thus, an optimal tempera-
may be the heat leakage problem. Heat leakage problem has a
ture for hydrogen storage is above 15 MPa, and the bigger the
more serious effect on CcH2 than on CGH2 and LH2. For
pressure, the bigger the optimal storage temperature is. CGH2
example, if the temperature is 80 K (such as in case 7), the
at 70 MPa has very efficient power consumption, which also
pressure will rise from 35 up to 42 MPa. Fortunately, in these
helps to achieve higher j value comparing to LH2. CcH2 is even
applications, the hydrogen will be consumed quickly. Conse-
more efficient at 20 MPa, and has higher j value than CGH2 at
quently, the temperature increase due to unexpected heat
70 MPa.
leakage should be easily offset. Additionally, thermal storage
The total power consumption per total combustion energy
devices could be added to CcH2 to decrease the heat leakage.
stored in the hydrogen at different temperatures and pres-
In some cases (such as cases 8e14), CcH2 can be put into a
sures is also interesting index (see Fig. 7). Index u represents
liquid nitrogen Dewar. The heat leakage will have no effect on
ratio between total power consumption and heat of combus-
the hydrogen because the heat from the hydrogen will be
tion of hydrogen. Power consumed during hydrogen storage
transferred to the liquid nitrogen.
during LH2 process corresponds to ~35% of the energy stored
in this hydrogen. CcH2 method shows good performance as it
Consideration of ortho-to parahydrogen conversion
consumes only 25% of the total energy, stored in the
hydrogen.
Parahydrogen (or orthohydrogen) content in gaseous
CcH2 at 80e160 K need to be analyzed in detail. This tem-
hydrogen is a function of an equilibrium temperature. Para-
perature zone is wildly used in Liquefied Natural Gas and Air
hydrogen concentration at equilibrium, xpH2, as function of
temperature, T (K), as well as normal-hydrogen to
equilibrium-hydrogen enthalpy of conversion in the hypo-
thetical state of ideal gas, DHN-E, are shown in Fig. 8 xpH2 values
at 300 and 20 K are ~25% and 99.8%, respectively, which im-
plies noticeable enthalpy of conversion especially at very low
temperatures. According to Valenti [33], enthalpy of conver-
sion in the hypothetical state of ideal gas can be well
approximated as conversion in the real state at any pressure.
DHN-E and the enthalpy of vaporization of parahydrogen at
20 K is ~532 and 447 kJ/kg, respectively. For a long-term stor-
age, the process from normal-hydrogen to equilibrium-
hydrogen should be completely finished, otherwise the tem-
perature will increase. Enthalpy of conversion will signifi-
cantly increases cooling efforts required for efficient hydrogen
storage.
Catalytic conversion of orthohydrogen to parahydrogen is
Fig. 7 e Total power consumption per heat of combustion needed for a quick conversion and can be executed in a batch
of hydrogen at different temperatures and pressures. mode or in a continuous mode. Continuous mode, in which
16838 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 8 3 3 e1 6 8 4 0

Table 1 e Parameters proposed for storage of hydrogen (case 1e14) without consideration of ortho-to parahydrogen
conversion.
case1 case2 case3 case4 case5 case6 case7 case8
T (K) 35 35 40 50 60 60 70 80
p (MPa) 5 10 15 20 25 30 35 40
r (kg$m
3) 60.0 68.2 69.3 66.8 65.0 68.9 67.3 66.1
j (kg$m
3$kW
1) 1.50 1.60 1.68 1.75 1.83 1.90 1.96 2.02
u (%) 20.3 21.6 20.9 19.3 18.1 18.4 17.4 16.6

case9 case10 case11 case12 case13 case14 case15 case16

T (K) 80 90 90 100 100 110 300 20

p (MPa) 45 50 55 60 65 70 70 0.4
r (kg$m
3) 69.0 67.9 70.4 69.3 71.5 70.5 39.3 71.7
j (kg$m
3$kW
1) 2.08 2.13 2.18 2.22 2.26 2.30 1.71 1.01
u (%) 16.8 16.2 16.4 15.8 16.0 15.5 11.7 36.0

Fig. 9 e Density of hydrogen per total power consumption

Fig. 8 e Parahydrogen concentration at equilibrium, xpH2, at different temperatures and pressures.
as a function of temperature, T (K), and normal-hydrogen
to equilibrium-hydrogen enthalpy of conversion in the
catalytic conversion is calculated through a continuous con-
hypothetical ideal gas state, DHN-E, as a function of
version according to the following equation:
temperature, T (K), defined with respect to the universal
gas constant R [33]. DHTa
DHTaþDT
PðTa KÞ ¼ þ PðTa þ DT KÞ; PðTa ¼ 250 KÞ ¼ 0 (4)
x  Troom
Ta

Ta

where DHTa is the DHN-E at equilibrium temperature Ta and x is

the catalyst is placed within the heat exchangers, is more the relative Carnot efficiency equal to 0.3.
efficient because the energy released by the conversion itself Consideration of ortho-to parahydrogen conversion with
is extracted at the highest possible temperature of the lique- Eq. (4), Fig. 6 is translated to Fig. 9. Since the power con-
faction. In this study, the liquefaction work caused by sumption increases at low temperature results in j decrease,

Table 2 e Proposed parameters for storage of hydrogen (cases 1e14) considering ortho-to para-hydrogen conversion. Case
15 and case 16 represent CGH2 and LH2, respectively.
case1 case2 case3 case4 case5 case6 case7 case8
T (K) 35 40 50 60 70 80 90 100
p (MPa) 5 10 15 20 25 30 35 40
r (kg$m
3) 60.0 63.4 61.3 60.1 59.3 58.8 58.5 58.4
j (kg$m
3$kW
1) 1.22 1.32 1.44 1.56 1.68 1.78 1.87 1.95
u (%) 25.0 24.3 21.6 19.5 17.9 16.8 15.9 15.2

case9 case10 case11 case12 case13 case14 case15 case16

T (K) 100 110 110 110 120 120 300 20

p (MPa) 45 50 55 60 65 70 70 0.4
r (kg$m
3) 61.2 61.2 63.8 66.3 65.7 67.8 39.3 71.7
j (kg$m
3$kW
1) 2.02 2.08 2.14 2.19 2.23 2.28 1.71 1.01
u (%) 15.5 15.0 15.2 15.4 14.9 15.1 11.7 36.0
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 8 3 3 e1 6 8 4 0 16839

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