Progress in Natural Science: Materials International 32 (2022) 617–624

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Progress in Natural Science: Materials International

journal homepage: www.elsevier.com/locate/pnsmi

Influence of heat exchanger structure on hydrogen absorption-desorption

performance of hydrogen storage vessel
Jianguang Yuan b, c, Ming Yao a, Baozhou Zhao d, Yujie Lv a, Haixiang Huang a, Jinting Chen a,
Bogu Liu b, Bao Zhang b, c, Ying Wu b, c, *
a
School of Energy Power and Machinery Engineering, North China Electric Power University, No.2 Beinonglu, Changping District, Beijing, 102206, China
b
Institute of Energy Power Innovation, North China Electric Power University, No.2 Beinonglu, Changping District, Beijing, 102206, China
c
Jiangsu JITRI Advanced Energy & Materials Research Institute Co., Ltd. No.5 Chongyinanlu, Xingbei District, Changzhou, 213000, China
d
Institute of Biomedical Engineering and Health Sciences, School of Pharmacy & School of Medicine, Changzhou University, Changzhou, 213164, China

A R T I C L E I N F O A B S T R A C T

Keywords: The influence of heat exchanger structure on hydrogen absorption-desorption performance of hydrogen storage
Hydrogen storage materials vessel was studied, in which the AB5 (La0.25Ce0.75Ni4.4Al0.1Mn0.1Co0.4) hydrogen storage alloy was used as a
AB5 alloy typical representative. In order to obtain the data on reaction enthalpy, the PCT curve of the alloy was measured
Heat exchanger
with three different temperatures, and the linear fitting was carried out according to the Van't Hoff relation curve.
Hydrogen absorption-desorption performance
The SMCR (Spiral-mini-channel Reactor) reactor structure was adopted. The heat transfer method and its
Hydrogen storage vessel
simplified model were studied by finite element method to explore the effect of size of heat transfer structure,
particularly for heat pipe diameter, on the hydrogen absorption-desorption performance of hydrogen storage alloy
in the vessel.

1. Introduction of the cylindrical reactor to explore the influence of relevant parameters

such as porosity, intake pressure and heat transfer coefficient on the
Hydrogen energy is a kind of high-tech and pollution-free energy. hydrogen absorption process [3]. Zhang et al. proposed to apply Lab-
With the progress of science and technology, the urgency of environ- VIEW software to the activation device of multi-channel metal hydride
mental pollution control and the guidance of national policy support, hydrogen storage tank, and wrote four modules of cyclic activation test,
traditional high-pollution energy will be gradually replaced in the future, which could achieve the performance of cyclic activation and hydrogen
and clean energy will gradually occupy the world stage [1]. Hydrogen dehydrogenation test of 20-channel metal hydride hydrogen storage tank
storage alloy reaction vessel is a key reaction place for hydrogen storage [4]. Zhou et al. reported a solid magnesium-based hydrogen storage
and dehydrogenation of alloy materials, and is a key component for system heated by an external heating zone. The hydrogen storage tank
hydrogen storage and transportation in the process of hydrogen ab- was placed in the thermal zone formed by the external heating device,
sorption and desorption reaction. At present, hydrogen storage alloy and the tank and the thermal zone achieved thermal coupling [5]. Jiang
reaction vessel is mainly composed of metal tank, hydrogen storage alloy et al. studied a new type of hydrogen storage bed element for solid
material, guide pipe, heat exchange structure and other parts [2]. The hydrogen storage tank, which was made of hydrogen storage alloy, gel
solid state hydrogen storage device can be coupled with the corre- material and heat conduction material. This work could effectively
sponding fuel cell system, and the heat released in the process of improve the thermal conductivity of the bed, avoid the heat effect caused
hydrogen absorption can be used to drive the fuel cell to start, so as to by powder accumulation [6]. Wang et al. artificially enhanced the shell
meet the application requirements of the fuel cell. heat transfer of baffle rod heat exchanger (RBHEs). They suggested to use
At present, the work is focused on the structural design and heat spiral flat tube instead of traditional circular tube as heat exchange tube
transfer analysis of solid hydrogen storage devices in order to explore a in RBHEs. The flow, heat transfer and comprehensive performance of
more reasonable tank space layout and efficient heat transfer environ- spiral flat tube RBHEs and traditional circular tube RBHEs were
ment. Wang et al. established a two-dimensional axisy-symmetric model compared [7].

* Corresponding author. Institute of Energy Power Innovation, North China Electric Power University. No.2 Beinonglu, Changping District, Beijing, 102206, China.
E-mail address: [email protected] (Y. Wu).

https://doi.org/10.1016/j.pnsc.2022.09.014
Received 26 September 2022; Accepted 28 September 2022
Available online 18 October 2022
1002-0071/© 2022 Chinese Materials Research Society. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
J. Yuan et al. Progress in Natural Science: Materials International 32 (2022) 617–624

In this paper, the AB5 hydrogen storage alloy composition design was some problems in practical production, such as uneven local heat transfer
taken as the breakthrough point, identified for La0.25Ce0.75- and poor kinetic performance of hydrogen absorption/desorption [13].
Ni4.4Al0.1Mn0.1Co0.4 hydrogen storage alloy. According to the Van't Hoff Based on this, the SMCR structure was established in the simulation
relationship the thermodynamic properties of the alloy were analyzed process, and the spiral pipe inside the vessel. was designed. The structure
from the PCT curve to obtain the reaction enthalpy value of the can increase the contact area between the hydrogen storage bed elements
component of hydrogen storage alloys [8]. The SMCR (spiral mini and the heat exchange pipe, and effectively avoid the device safety
channel reactor) heat exchanger structure was designed to give the cor- problems caused by the uneven local force inside the pipe body [14].
responding governing equations, boundary conditions and initial con- In order to explore the influence of pipe diameter size of heat ex-
ditions, and put forward the idealized heat transfer hypothesis. change structure on the thermal effect of hydrogen absorption-
Numerical simulation was carried out by ANSYS Fluent 19.0 software to desorption inside the reaction vessel of spiral heat exchange structure,
explore the influence of the structure size of heat exchanger on the the two-dimensional simplified model diagram of SMCR structure is
thermodynamic and kinetic performance of hydrogen absorption [9]. developed, as shown in Fig. 2. Hydrogen flows from the upper boundary
of the reactor into the reaction bed at a certain pressure. The water flows
2. Experimental details

The composition design of hydrogen storage alloy plays an important

role in hydrogen storage performance. In the present investigation the
La0.25Ce0.75Ni4.4Al0.1Mn0.1Co0.4 [10] was selected as the experimental
material. The alloy was prepared by high vacuum induction melting
furnace on a water-cooled copper crucible under a high purity argon
atmosphere. The raw materials used in the alloy has commercially
available purity higher than 99.9%. Because of the low melting point of
rare earth and Mn, an excess amount of the materials of 3 wt% was
added. The prepared alloy was not subjected to heat treatment. The alloy
ingot was broken into powders with a particle size lower than 200 μm by
mechanical ball milling [11].
The phase structure of the alloy were characterized by X-ray
diffraction analysis (XRD) using a D8 Discover X-ray diffractometer with
Cu/Kα radiation (40 KV, 40 mA) at room temperature, and the scanning
parameters were 10–90
in 2θ, 0.2
in step size and 4s in count time [12].
The phase structure and composition of the alloy was analyzed by XRD
software. The particle morphology of the samples was analyzed by
scanning electron microscope (SEM, Nova nano-sem 450) equipped with
an energy-dispersive X-ray spectrometer (EDS).

3. Structural model

Fig. 1 is the schematic diagram of SMCR structure of the physical

model designed and established in the simulation. SMCR structure is the
heat exchange channel uniform along the axial arrangement of vessel,
and has many radial heat pipe arranged inside the hydrogen storage bed
body components. For hydrogen storage alloy with hydrogen absorption/
desorption process in thermal environment, the limitations of its struc-
Fig. 2. Simplified model diagram of spiral mini channel reactor.
ture determines that the model in actual production application may face

Fig. 1. The structural model of spiral mini channel reactor.

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along the spiral mini channel from the top to the bottom. The hydroge- Table 1
nation reaction takes place in the hydride bed in contact with a metal Initial conditions and related calculated parameters.
alloy La0.25Ce0.75Ni4.4Al0.1Mn0.1Co0.4. The formation of solid hydride The parameter name The parameter Unit
allows the hydrogen to be stored in solid form. The hydrogen absorption value
reaction gives off a large amount of heat. The hydrogen desorption re- The initial temperature 298 K
action absorbs a large amount of heat. Initial pressure 0.5 MPa
Base pressure 101 kPa
4. Numerical model Hydrogen storage alloy (filling) density 8445 Kg/m3
Hydrogen storage alloys porosity 0.6 –
Hydrogen storage alloy pecific heat capacity 419 J.(mol.K)1
4.1. Model idealization hypothesis Hydrogen storage alloys thermal conductivity 6 W.(m.K)1
Density(316) 7980 Kg/m3
The heat transfer process inside the hydrogen storage tube is a com- Specific heat capacity(316) 468 J.(mol.K)1
Thermal conductivity(316) 13 W.(m.K)1
plex and changeable process. In order to simplify the model and facilitate
Density of water 1 Kg/L
calculation, we put forward the following reasonable assumptions: Specific heat capacity of water 4.2 J.(mol.K)1
Thermal conductivity of water 0.6 W.(m.K)1
1. Consider hydrogen as an ideal gas, that is, ignore the volume occu- Convective heat transfer coefficient 1000 W.(m2.K)1
pied by hydrogen molecules; Change in enthalpy for hydrogen uptake 30.32 kJ/mol
Entropy change of hydrogen uptake 115.31 kJ/mol
2. Assume that the gas molecules and solid molecules in the vessel. are Change in enthalpy of hydrogen desorption 33.23 kJ/mol
in a state of thermal equilibrium; Change in entropy of hydrogen 125.55 kJ/mol
3. Viscous dissipation and compression work caused by hydrogen flow dehydrogenation
are ignored; Hydrogen uptake rate constant 75 s1
Metal particle size 32.5 μm
4. Ignore the radiative heat transfer inside the vessel [15]. 1
Activation energy 21890 J.mol

4.2. Boundary conditions and initial conditions



The boundary conditions of numerical simulation in this paper are as
ρCp eq
¼ θp ρp Cp þ 1  θp ρCp (6)
follows:

boundary conditions on the outer wall of heat exchange tube： keq ¼ θp kp þ 1  θp kv (7)

!
n ðkrTÞ ¼ hðText  TÞ (1) ΔH
Q¼ *Δρ (8)
Mn
!
n ðkrTÞ ¼ hðText  Tw Þ (2)
M n PA
ρ¼ (9)
rPg *!
n ¼0 (3) RT

kis the thermal conductivity, his the heat transfer coefficient, Tis the where ρis the density of the alloy; Cp is the isobaric specific heat capaci-
temperature at a certain moment, Text is the temperature outside the tube, ty;Cp、ρ is the isobaric specific heat capacity of the alloy; ug is the
Tw is the temperature of the heat transfer medium, and Tw is the gas hydrogen vector velocity;keq is the equilibrium reaction rate constant; Qis
pressure gradient. the heat; θp is the filling coefficient of the alloy; ρp is the filling density;
The hydrogen storage alloy filled in the reactor is AB5 rare earth alloy kv is the reaction rate constant; Δρis the increase of the alloy density in the
La0.25Ce0.75Ni4.4Al0.1Mn0.1Co0.4. The vessel material of the reactor is 316 saturated state [18].
stainless steel and the heat transfer structure material is 6063 aluminum The gas-solid mass conservation equation is:
alloy. The heat transfer medium is water, and the specific initial condi-
∂ðρεÞ
tions and thermodynamic material parameter characteristics is in Table 1 þ rðρ!
u Þ¼Q (10)
[16]. ∂t

where ε is porosity.
4.3. Mathematical model The airflow rate of the alloy reaction bed based on Darcy's theorem
can be calculated as follows;
According to the above model assumptions and the simplification of
the physical model, the relevant equations of the mathematical model are ! K
u ¼  rP (11)
as follows: μ
the thermal conductivity equation of the heat exchange tube wall is:
Kinetic equation of hydrogen absorption and desorption [19]：
∂T  
ρr Cpr r ¼ rðλr rTr Þ (4) dX P  Peq X  Xf Ea
∂t ¼  kv * * *exp  (12)
dt Peq X0  Xf RT
ρr is the density of heat exchange tube; Cpr is the specific constant pressure
heat capacity of the heat exchange tube; Tr is the temperature of heat whereXis the reaction fraction;X0 is the initial reaction fraction;Xf is the
exchange tube; λr is the thermal conductivity of the heat exchange tube final reaction fraction;kv is the reaction rate constant;Peq is the equilibrium
[17]. pressure;Ea is the activation energy of the hydrogen absorption reaction
The governing equation of hydrogen storage alloy material reaction [20]
bed is:   
X
7
ΔH 1 1
bed energy equation: Peq ¼ ai X i exp  (13)
i¼0
R Ts 303
∂T


ρCp eq þ ρCp、ρ ug *rT ¼ r keq rT þ Q (5)
∂t where ai is the reaction coefficient, and Ts is the alloy temperature.

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The energy balance equation of the heat exchange medium fluid is as 5. Results and discussion
follows [21]:

5.1. Microstructure of the hydrogen storage alloy

∂ ρCp w T

þ div ρCp、w u!
w T ¼ divðkw gradðTw ÞÞ (14) The XRD test result of the La0.25Ce0.75Ni4.4Al0.1Mn0.1Co0.4 alloy pre-
∂t
pared in the present paper is shown in Fig. 3. It can be seen that the
where ρis the density of heat exchange medium; Cp、w is the isobaric crystal structure of LaNi5 phase was CaCu5 hexagonal crystal structure,
specific heat capacity of heat exchange medium; u! w is the velocity vector
and the space group was P6/MMM, where multiple diffraction peaks
of heat exchange medium; T is the temperature of heat exchange me- could be observed between 30 and 50
and 55–80
[25]. The charac-
dium; kw is the thermal conductivity of heat exchange mechanism. teristic peaks were 2θ ¼ 31.2, 36.6, 42.1, 43.1, 45.8, 48.2, 59.8, 62, 63.8,
The continuity equation of the heat exchange medium is: 60.5, 70.1, 77, 82.6 and 85.1
, respectively. Corresponding to (101),
(110), (200), (111), (002), (201), (112), (211), (202), (300), (301),
divð u!
w Þ¼0 (15) (220), (113), (311), the diffraction peak shape can be seen from the
spectrum, indicating that the alloy sample has a good crystallinity [26].
The k-w complete turbulence model of kinetic energy and energy
From the SEM and EDS mapping of the La0.25Ce0.75-
dissipation represented by the flow of heat exchange medium in the pipe
Ni4.4Al0.1Mn0.1Co0.4 hydrogen storage alloy, it is clear to observe the
diameter of heat exchange structure is [22]:
structure morphology and the distribution of main elements, including
 observation of Mn element will be the condition of the local distribution.
ρð u! !
w  rÞ uw ¼ r The corresponding SEM images of the La0.25Ce0.75Ni4.4Al0.1Mn0.1Co0.4
 alloy are presented in Fig. 4 (a)-(b). It can be found that the particle size

T 2 2
 Pw I þ ðμ þ μT Þ u! !
w  r þ ð uw  rÞ  ðμ þ μT Þð u!
w  rÞI  ρkl of the alloy was about 50–100 μm. Meanwhile, the EDS mappings of the
3 3
alloy are shown. It can be seen that elements of La, Ce, Ni, Al, Mn and Co
þF distributed uniformly over the entire area of the alloy [27].
(16)
5.2. PCT curve and thermodynamic analysis of the hydrogen storage alloy
ρð u!
w  rÞk ¼ r½ðμ þ μT σ k Þrk þ Pk  ρβ0 k ω (17)
Fig. 5 shows the PCT curves of the La0.25Ce0.75Ni4.4Al0.1Mn0.1Co0.4
aω
ρð u!
w  rÞω ¼ r½ðμ þ μT σ w Þrω þ Pk  ρβ0 ω2 (18) alloy measured at 303, 318 and 333 K. The maximum hydrogen storage
k
capacity of La0.25Ce0.75Ni4.4Al0.1Mn0.1Co0.4 at 303 K was 1.50 wt%, and
Among them: the hydrogen absorption -desorption plateau pressure were 0.647 MPa
and 0.429 MPa, respectively. Increasing the temperature from 303 K to
ρk
μT ¼ (19) 333 K, the reversible hydrogen storage capacity decreased from 1.50 wt
ω
% to 1.46 wt%, and the hydrogen absorption-desorption plateau pressure
  increased to 1.727 MPa and 1.151 MPa, respectively.

! T   2 ρkr  u!
Pk ¼ μT r  u! !
w : r  uw þ ðr  uw Þ w (20) The platform slope factor can be obtained from the following formula
3
[28]:
where Pw is the fluid pressure of heat exchange medium; μis the dynamic  
Ps2
viscosity; μT is the comprehensive dynamic viscosity; lis pipe diameter Sf ¼ Ln
Ps1
length; F is the turbulent pressure; σ k is the wall stress coefficient; σ w is the
heat exchange medium stress coefficient; β0 is initial lag correction co- The lag factor can be obtained from the following equation:
efficient; k is heat exchange tube thermal conductivity; ω is heat transfer  
Ph1
medium thermal conductivity; Pk is pipe wall pressure [23]. Hf ¼ Ln (24)
The correlation formula of the fluid in the spiral coil heat exchange Ph2
tube is as follows: the Nusselt number is generally 2–3 times that of the
straight tube, and the Nusselt number of the spiral coil is selected as 2
times that of the straight tube in this paper [24]:
 0:85 
Re
Nu ¼ 0:0266 0:15 þ 0:225λ1:55 Pr0:4 (21)
λ

ρra vf
Re ¼ (22)
μf

μf Cp、w
Pr ¼ (23)
λ

where λf is comprehensive friction coefficient; ra is inner tube radius of

heat exchange tube;λis friction coefficient of heat exchange medium; Pris
Prandtl number; Re Reynolds number; ρis density of heat exchange me-
dium; vf is velocity of heat exchange medium; μf is dynamic viscosity of
heat exchange medium; Cp、w is isobaric specific heat capacity.

Fig. 3. XRD pattern of the La0.25Ce0.75Ni4.4Al0.1Mn0.1Co0.4 alloy.

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Fig. 4. SEM patterns of AB5 type La0.25 Ce0.75 Ni4.4 Al0.1Mn0.1Co0.4 with associated EDS maps for La, Ce, Ni, Al, Mn and Co.

Fig. 6. Van't Hoff linear fitting curve of the La0.25 Ce0.75 Ni4.4
Al0.1Mn0.1Co0.4 alloy.
Fig. 5. PCT curve of La0.25 Ce0.75 Ni4.4 Al0.1Mn0.1Co0.4 alloy at 303, 318
and 333K. relationship with 1/T, which conforms to the Van't Hoff relationship.
Table 3 shows that the reaction enthalpy and reaction entropy of LaNi5
Where, Sf is the slope factor; Ps2 is the pressure value at the end of the rare earth alloy are both larger, indicating that the reaction heat gener-
platform; Ps1 is the pressure value at the beginning of the platform; Hf is ated by LaNi5 alloy during hydrogen absorption is larger, while the
the lag factor; Ph1 is the hydrogen suction platform pressure; Ph2 is the decompression process is smaller, and the hydride generated is more
hydrogen desorption platform pressure [29]. stable [30,31].
According to Table 2, it can be found that AB5 rare earth alloy reached
the highest hydrogen absorption capacity at 318K, but the maximum 5.3. Validation of the model
hydrogen storage capacity varied slightly between 303 K and 333 K. With
the increase of temperature, the platform pressure and slope of the alloy In order to ensure that the following simulation results are
increased gradually. At 303, 318 and 333 K, the platform area of the alloy convincing, it is necessary to simulate and verify the hypothesis simu-
was wide and flat, and the change and value of the lag factor were small. lation established, and fit the relevant experimental data in the reference.
The alloy has good platform characteristics. Thus, between 303 and 333 In this paper, the average reaction fraction of hydrogen storage bed and
K, the temperature has little effect on the hysteresis and hydrogen storage the average temperature of the reaction bed for simulation verification
performance of the AB5 rare earth series alloy. were chosen. And some initial values and fixed conditions for the model
The Van't Hoff relation curve of the alloy is fitted linearly (see Fig. 6). validation process are required to be set. The volume of the hydrogen
It can be seen that LnP of AB5 hydrogen storage alloy has a certain linear storage vessel was set as 7 L, and the heat exchange medium was purified

Table 2
Hydrogen storage capacity, plateau slope and lag factor.
AB5 The Hydrogen storage (hydrogen absorption) (Hydrogen desorption) Slope of hydrogen Slope of hydrogen Lag
alloy temperature (K) amount (wt. %) Platform pressure (MPa) Platform pressure (MPa) absorption platform desorption plateau factor

1 303 1.5 0.647 0.429 0.452 0.2 0.412

2 318 1.51 1.239 0.682 0.748 0.311 0.598
3 333 1.46 1.727 1.151 1.122 0.476 0.406

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Table 3
Reaction enthalpy and entropy of hydrogen absorption-desorption in hydrogen storage alloy.
AB5 alloy Hydrogen absorption hydrogen desorption

Category Reaction enthalpy (kJ/mol.H) Reaction entropy (J/mol.H) Reaction enthalpy (kJ/mol.H) Reaction entropy (J/mol.H)
The numerical 30.32 115.31 33.23 125.55

water with an initial temperature of 293 K. The diameter of the heat diameter of 20 mm is reasonable by comprehensive analysis.
exchange pipeline was 15 mm. The inlet pressure of the hydrogen storage The average reaction fraction in the hydrogen storage bed is also an
vessel was 7 MPa, and the initial temperature of the elements of the important index to measure the hydrogen absorption reaction process.
hydrogen storage bed was 298 K. The equivalent heat transfer coefficient The curve of the average reaction fraction in the reaction bed with time
was 1000W/m2K. under different heat transfer structure sizes are shown in Fig. 9. It can be
This model was solved by ANSYS Fluent 19.0 simulation software, found that the four curves had basically the same trend with time, and the
using structured grid, and the governing equation was discretized and reaction fraction had a relatively large growth rate before 300 s. The
imported into the simulation software, where the time step was set to 0.1 hydrogen absorption process at this stage is mainly affected by the bed
s. temperature. After 300 s, the growth of reaction fraction is relatively
As seen from Fig. 7 (a), the experimental data and the numerical slow, which is mainly affected by the heat transfer environment in the
simulation results were compared for the variation of the average reac- vessel. The whole hydrogen absorption process reached hydrogen ab-
tion fraction with time. In the spiral coil heat exchanger hydrogen storage sorption saturation at about 900 s. With the decrease of the diameter of
vessel, the reaction rate was faster after the hydrogen absorption process the heat exchange tube, the change rate of the average reaction fraction
began, and the reaction fraction reached 0.5 at 40 s. The experimental in the reaction bed is smaller, and the time to reach the reaction equi-
data is consistent with the simulated data. After 460 s, the reaction librium is longer. The reason is that the smaller heat transfer pipe
fractions of experimental and simulated data tended to be stable, and the diameter corresponds to the lower heat transfer per unit time, and the
reaction rate decreased rapidly. The experimental data are in good heat transfer effect is worse than that of the large pipe diameter heat
agreement with the simulated data and the both show the same regu- transfer structure. When the diameter of the heat exchange tube was 20
larity. From Fig. 7 (b), the experimental temperature was slightly higher mm and 25 mm the average reaction fraction was very similar. It is still
than the simulated temperature, but it still kept a similar trend of change, necessary to comprehensively consider the influence of the heat ex-
and reached the highest temperature at about 180 s, at the temperature of change pipe size on the space occupation in the vessel, so the best pipe
343 K and 340 K, respectively. At about 480 s, the temperature dropped diameter is still 20 mm.
sharply and then increased to a certain extent. It is concluded that the The curve of the central temperature of the reaction bed with time
simulated data of the average reaction temperature of the reaction bed under four heat exchange pipe diameters is shown in Fig. 10, when the
are close to the experimental data. temperature of the heat transfer fluid was 343 K and the initial temper-
ature was 298 K. It can be seen that the change trend of the four curves
5.4. Thermal effect characteristics and hydrogen absorption-desorption was basically the same, which indicates that the size of the heat transfer
performance analysis of SMCR heat exchange structure pipe has less influence on the hydrogen desorption process than the
hydrogen absorption process. The time of the four dimensions reaching
The simplified SMCR heat exchange structure for experimental the lowest point was 75, 90, 150 and 190 s, respectively. This is attrib-
exploration and numerical simulation was selected, and the vessel was uted to that the metal hydride dehydrogenation process needs to absorb
filled with La0.25Ce0.75Ni4.4Al0.1Mn0.1Co0.4 alloy. According to the in- part of the heat to ensure the normal dehydrogenation. The heat ab-
structions for using SMCR hydrogen storage device, the designed volume sorption effect of dehydrogenation in this process was greater than that
of the device was 15.7 L, and the filling rate of the hydrogen storage bed of 343 K heat exchange fluid. Obviously, the heating effect of the heat
element was 0.6. Considering that the volume of hydrogen storage alloy exchange fluid was greater than the heat absorption effect of the dehy-
powder expands by about 25% after hydrogen absorption, some solid drogenation reaction, and the equilibrium state of heat exchange reached
structural components including heat exchange pipes account for about again at about 900 s.
15% of the interior space of the vessel. The hydrogen storage vessel was In order to facilitate the exploration of the reaction process of
filled with 50 kg of the hydrogen storage alloy powder through pre- hydrogen desorption, the curve of the average reaction fraction of the
liminary calculation. The structural dimension of spiral tube heat reaction bed with time under different heat exchange pipe diameters is
exchanger is shown in Table 4. In order to ensure more convincing shown in Fig. 11. The reaction fractions of heat transfer structures of all
simulation results, it is determined that the ratio of pipe diameter to wall sizes show the same change trend. At the beginning of the dehydroge-
thickness of heat exchange device was fixed, and four size structures were nation process the dehydrogenation rate was relatively slow: the rate of
set up. size 10 mm was the slowest, and the rate of size 20 mm was close to that
The temperature of hydrogen storage bed element is one of the of size 25 mm. With the continuous heat exchange between the heat
criteria to measure the excellent heat transfer effect of hydrogen storage exchange medium and the hydrogen storage alloy powder, the temper-
process, and also directly determines the whole process of hydrogen ature of the hydrogen storage alloy reaction bed gradually increased, and
absorption-desorption. Fig. 8 shows the curve of the central temperature the dehydrogenation rate gradually accelerated. When the dehydroge-
of the hydrogen storage bed with time under different heat transfer nation reaction was carried out for 900 s, the reaction fractions corre-
structure sizes, when the initial temperature of the heat transfer fluid was sponding to the four structural sizes were 0.15, 0.1, 0.09 and 0.07,
288 K and the inlet pressure was 0.5 MPa. Regardless of the size struc- respectively.
ture, the central temperature of the bed raised rapidly at the beginning of
hydrogen absorption reaction, reached a peak at about 300 s, and then 6. Conclusions
slowly decreased to a stable value. This is attributed to that at the
beginning of the hydrogen absorption reaction, the overall temperature The influence of SMCR heat exchanger structure on hydrogen
inside the vessel is relatively low, which is conducive to the hydrogen absorption-desorption performance of hydrogen storage vessel has been
absorption reaction. Although increasing the heat exchange pipe diam- studied, and the conclusions are summarized as follows:
eter can effectively reduce the bed temperature, it is at the cost of the
filling space inside the pipe body. Thus, it is believed that the pipe

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Fig. 7. (a) The average reaction fraction of spiral tube heat exchanger changes with time; (b) The average temperature of reaction bed of spiral tube heat exchanger
changes with time.

Table 4
Design dimensions of the structure.
Tank size

Inner diameter Length Thickness

100 mm 500 mm 8 mm
Dimensions of heat transfer structure
Size number Pipe diameter Wall thickness
Number 1 10 mm 0.8 mm
Number 2 15 mm 1.2 mm
Number 3 20 mm 1.5 mm
Number 4 25 mm 2 mm
Spiral pipe diameter radius of the circle
60 mm

Fig. 9. Average reaction fraction of different heat exchange pipe diameters with
the change of time.

Fig. 8. Center temperature curve of reaction bed with the change of time.

(1) La0.25Ce0.75Ni4.4Al0.1Mn0.1Co0.4 alloy is prepared to study

hydrogen storage thermodynamic property. According to the PCT
curve, the reaction enthalpy of hydrogen absorption-desorption is
30.32 and 33.2 kJ/mol H2, respectively.
(2) A simplified structure model of three dimensional SMCR heat
exchanger is established, and its effectiveness is verified. A nu- Fig. 10. The center temperature of the reaction bed varies with the change
merical simulation model is established to study the heat con- of time.
duction and dissipation performance of the vessel.
(3) Effect of different size of heat transfer structure on the average increasing heat transfer pipe diameter. Considering the utilization
reaction fraction and heat effect of hydrogen absorption- of space inside the vessel, the pipe diameter of 20 mm is selected
desorption has been studied. The heat transfer efficiency of as the best parameter, in which the excellent heat transfer
hydrogen absorption process is significantly improved by

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