Chemical Engineering Journal 507 (2025) 160799

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Chemical Engineering Journal

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Enhancing hydrogen sorption kinetics of Ti-based hydrogen storage alloy

tanks through an optimized bulk-powder combination strategy
Liansen Bian a,b, Longfei Shao b, Bolun Wang b , Jiaqi Zhang b, Yinghui Li b , Zhigang Hu b ,
Jianxin Zou b,* , Kemin Zhang a,* , Xi Lin b,*
a
School of Materials Science and Engineering, Shanghai University of Engineering Science, Shanghai 201620, China
b
Shanghai Key Laboratory of Hydrogen Science & Center of Hydrogen Science, Shanghai Jiao Tong University, Shanghai 200240, China

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

Keywords: The kinetic performance of Ti-based hydrogen storage tanks (HSTs) is crucial for meeting the demands of on­
Hydrogen storage board hydrogen storage and energy storage applications. However, the hydrogen sorption kinetics of Ti-based
Ti-based hydrogen storage alloy pellets HSTs are limited by the heat transfer characteristic of Ti-based alloy beds. In this study, we incorporated pol­
Bulk-powder combination strategy
yvinylidene fluoride (PVDF) and expanded graphite (EG) with Ti-based alloy powders using a novel compaction
Thermal conductivity
and cladding process, producing bulks with a higher thermal conductivity 56.94 times of the powders. Such an
Hydrogen sorption rates
enhancement can be attributed to the reduced contact thermal resistance between the Ti-based alloy particles via
PVDF glues. The addition of EG slightly increases the thermal conductivity, which favors the compaction and
minimizes the kinetic degradation of the alloy caused by local damage of PVDF coatings during cycling. Through
the optimized combination of bulks and powders, the volumetric hydrogen storage density of the Ti-based HST
can reach as high as 66.51 g L-1, 4.05 % higher than that of the powders only. Consequently, 90 % of hydrogen in
the Ti-based HST can be absorbed in 0.70 h and desorbed in 0.91 h. The hydrogen absorption rate of the tank
filled mixtures is increased by 54.35 % compared to that of powders only. Our results have shown that hydrogen
sorption kinetics of solid-state hydrogen storage tanks can be significantly enhanced through a strategy of
combining high thermal conductivity bulks and powders together.

1. Introduction Solid-state hydrogen storage methods have the advantage in less

energy consumption and more safety compared with gaseous form of
Hydrogen is a promising energy carrier for sustainable development hydrogen storage [10–12]. Among manifold solid-state hydrogen ma­
with advantages of carbon-free, abundant sources, and high specific terials, Ti-based hydrogen storage alloys are regarded as one of the most
energy on a mass basis [1–3]. Hydrogen energy can be converted to promising solutions due to the fast hydrogen sorption at room temper­
electrical energy via fuel cells, which can serve as power sources for ature with high volumetric hydrogen storage density [13,14]. The Ti-
vehicles and energy storage systems [3–5]. Unfortunately, the light­ based hydrogen storage alloys must be filled in the HSTs for usage.
weight and highly flammable nature of hydrogen presents significant However, due to the low thermal conductivity of Ti-based hydrogen
challenges for its storage [6,7]. Typically, hydrogen is stored as com­ storage alloy powders bed [15–17], the hydrogen absorption and
pressed gas at 35 MPa in Type III or 70 MPa in Type IV hydrogen storage desorption rates of Ti-based HSTs are significantly lower than the
tanks (HSTs) for vehicles, or at 3–5 MPa in stainless steel spherical HSTs properties of the material itself, and hard to meet the demands of fuel
for energy storage systems [8,9]. However, compressed HSTs have low cells [18]. Thus, the heat transfer characteristic of Ti-based alloy beds
volumetric hydrogen storage density and present safety risks associated must be improved to enhance the hydrogen absorption and desorption
with hydrogen, making it challenging to promote their use in the rates of Ti-based HSTs.
automotive and energy storage fields. Therefore, identifying efficient Typically, heat transfer characteristics are enhanced through the
and safe hydrogen storage methods is crucial to advancing the hydrogen following approaches: (1) compacting alloy powders with lightweight,
energy industry chain. high-thermal-conductivity materials such as carbon or aluminum

* Corresponding authors.
E-mail addresses: [email protected] (J. Zou), [email protected] (K. Zhang), [email protected] (X. Lin).

https://doi.org/10.1016/j.cej.2025.160799
Received 14 December 2024; Received in revised form 23 January 2025; Accepted 17 February 2025
Available online 18 February 2025
1385-8947/© 2025 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
 L. Bian et al. Chemical Engineering Journal 507 (2025) 160799

[18–20]; and (2) incorporating additional heat transfer elements, disks or bulks, preserving their original properties throughout use.
including metal fins, tubes, and foams [21–23]. Generally, adding these In this work, we developed a novel compaction and cladding method
heat transfer elements significantly reduces hydrogen storage density, to prepare Ti-based hydrogen storage alloy bulks by combining the alloy
increases the structural complexity of HSTs, and raises costs. Therefore, powders with polyvinylidene fluoride (PVDF) and expanded graphite
compacting alloy powders is a key approach to enhancing hydrogen (EG). We investigated the effects of PVDF and EG on the hydrogen ab­
absorption and desorption rates with minimal or no reduction in sorption and desorption rates of the Ti-based alloy bulks, along with
hydrogen storage density. Manai et al. [17] compared hydrogen ab­ their thermal conductivity. Additionally, we measured the effective
sorption and desorption kinetics of loose Ti-Mn alloy powders bed and thermal conductivity of the bed at varying pressures. The hydrogen
compacted Ti-Mn alloy bed. The thermal conductivity of the compacted absorption/desorption performance of hydrogen storage tanks (HSTs)
Ti-Mn alloy bed was just increased from 1 to 1.22 W m− 1 K− 1 with with a volume of 1 L was compared for cases filled with powders, bulks,
limited kinetic improvement. Piao et al. [15] applied binder epoxy resin and a mixture of bulks and powders. This work presents a new strategy
and the thermal conductor flake graphite to Ti0.95Zr0.07Cr1.0Mn0.6 for advancing the applications of Ti-based HSTs.
Fe0.25Cu0.15 alloys, forming metal hydride compacts (MHCs). The ther­
mal conductivity of MHCs was increased from 1.31 to 5.21 W m− 1 K− 1, 2. Experimental details
which shortened the hydrogenation reaction time by 50 % and lowered
the abrupt temperature of the metal hydride bed by 20 K. However, the 2.1. Sample preparation
hydrogen storage capacity is reduced from 1.75 wt% to 1.50 wt% as
well. Therefore, the forming process must be optimized to further We propose a novel approach in which a high-strength binder layer is
enhance thermal conductivity without compromising hydrogen storage applied to the surface of the alloy particles. This coating bonds the
density and kinetics. In addition, another key requirement of the form­ particles together, reduces contact thermal resistance, enhances the
ing process is to ensure the anti-pulverization durability of compacted thermal conductivity of the bulk, and mitigates the tendency for

Fig. 1. (a) Traditional method and (b) novel proposed compaction and cladding method in this work for the preparation of bulks.

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chalking. We refer to this method as the compaction and cladding hydrogen desorption under vacuum conditions. A 50-cycle durability
method, as illustrated in Fig. 1. Compared to traditional methods, this test was performed at 298 K, with hydrogen absorption at 3 MPa and
approach is expected to significantly improve both the thermal con­ desorption at 0.15 MPa.
ductivity and formability of the material. In this work, Ti-based alloy The thermal conductivity of alloy powders was conducted at 298 K
powders were obtained from Baotou Zhongke Xuanda New Energy using the hot disk method in Setaram Superem-TPS and bulks was
Technology Co., Ltd., with an average particle size of approximately conducted at 298 K using the laser-flash method in Netzsch LFA467HT.
500 µm. As a typical binder, polyvinylidene fluoride (PVDF) powders are The effective thermal conductivity of alloy powders (or bulks) and
used as an additive material and mixed with Ti-based alloy powders to hydrogen was measured using the steady-state method. The schematic
prepare bulk samples. In this work, PVDF were obtained from Arkema S. and physical diagram of the hydrogen control is shown in Fig. 2(a). The
A, with a molecular weight of 1.8 million. Expanded graphite (EG) is self-constructed device is shown in Fig. 2(b). The device was filled with
used as a lubricant in the bulk processing. In this work, EG were ob­ the alloys, with insulating materials placed at the top and bottom to
tained from Qingdao Teng Sheng Da Tan Su Ji Xie Co., Ltd., with an ensure uniform radial heat transfer. The central heat source was set to
average particle size of approximately 198 µm, a purity of 99 %, and an 303 K, and the temperature difference between the two internal ther­
expansion ratio of 300 times. Each bulk weighed approximately 1.50 g mocouples was observed to assess effective thermal conductivity. The
with 10 mm diameter and was prepared for further testing. effective thermal conductivity λe can be calculated by Eq.(1):
qrh
T(r) − Th = − ln(r/rbed ) + A (1)
2.2. Characterization and measurements λe

The crystal structure and microstructure of the alloy bulks were here, Th is the surface temperature of the heating rod, rh is the radius of
examined using X-ray diffraction (XRD XPert Pro MPD) and scanning the heating rod, rbed is the inner radius of the test bed, and A is the
electron microscopy (SEM FEI QUANTA FEG250) across different sam­ coefficient. r and T(r) are the locations of the thermocouple and tem­
ple conditions: unannealed, post-annealed, after a single hydrogenation perature of thermocouples, respectively. q is the surface heat flow
cycle, and after the 50th hydrogenation cycle. Additionally, energy- density of the heating rod, which is calculated by the power meter.
dispersive X-ray spectroscopy (EDS FEI QUANTA FEG250) was The materials were uniformly loaded into the aluminum tank (Fig. 2
employed for detailed elemental analysis. (c)), which has a total volume of 1 L with a volume loading of 85 %. The
The pressure-composition-temperature (PCT), kinetic, and cycling Ti-based HSTs will be activated under the conditions same as the ma­
tests for both bulks and powders were conducted using an Automatic terials. The hydrogen absorption kinetics of the Ti-based HSTs were
High-Pressure Gas Adsorption Instrument (HPSA-auto 2023L003A). tested at 3 MPa and temperatures of 283 K, 298 K, and 323 K in the water
Activation of the bulks or powders involved evacuation at 353 K for 30 jacket (Fig. 2(c)). After completing hydrogen absorption at 283 K and 3
min, followed by hydrogen absorption at 3 MPa and subsequent MPa, the HSTs were used to measure hydrogen desorption kinetics at

Fig. 2. (a) Hydrogen control schematic and physical diagram; (b)The self-constructed device for the effective thermal conductivity of alloy powders (or bulks) and
hydrogen; (c) The photographs of the Ti-based HST and its testing device (water jacket).

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0.1 MPa and 323 K. During both the hydrogen absorption and desorp­ resulting in a similar particle size distribution. The carbon, PVDF, and
tion tests, temperature changes were monitored at three specific points Ti-based alloy particles are uniformly distributed.
(A, B, and C), as shown in Fig. 2(c). Fig. 5 shows photographs of the Ti-based alloy bulk with 1 wt% PVDF
and 3 wt% EG prepared by compaction and cladding method for the
3. Results and discussion inactivation state and the dehydrogenated state after the 10th cycle and
50th cycle. The bulk is compacted and densified, making it easier to
3.1. The characteristics of prepared Ti-based alloy bulks store and scale up for large-scale applications. After 10 cycles, the alloy
bulk remains largely intact. However, the edge of the bulk is slightly
Fig. 3 presents the XRD patterns of the Ti-based alloy bulk with 1 wt damaged, likely due to stress concentration at the edges. Unfortunately,
% PVDF and 3 wt% EG using the traditional method and the compaction after 50 cycles, the alloy bulk is completely crushed into powders. In the
and cladding method, as well as the dehydrogenated state after the first broken bulk shown in Fig. 5(c), white large particles of PVDF are visible,
and the 50th cycle. The carbon peaks corresponding to EG are visible for indicating that the PVDF was not fully mixed, resulting in local
the samples using the traditional method and the compaction and aggregation.
cladding method, which is reduced after hydrogen absorption and The thermal conductivity values of powders and alloy bulks with
desorption cycles. It may be due to the reduction of the degree of crys­ different compositions are shown in Fig. 6. The thermal conductivity of
tallinity of carbon under the effect of stress caused by the hydrogen the powders is relatively low, with a value of 0.18 W m− 1 K− 1. After
absorption and desorption cycles. The peaks for the Laves phase of compacting the powders without PVDF and EG, the thermal conduc­
TiMn2(Zr, Fe, Cr) are more prominent after the hydrogen absorption and tivity of the bulk increases to 1.50 W m− 1 K− 1, which falls within the
desorption cycle, which is the main hydrogen storage phase. range of pure alloy powders compaction [24]. Upon adding 1 wt%
Fig. 4 presents the SEM and EDS mapping images of a Ti-based alloy PVDF, the thermal conductivity of the bulk increases significantly to
bulk with 1 wt% PVDF and 3 wt% EG. The EDS elemental mapping re­ 10.25 W m− 1 K− 1. And when we add 1 wt% EG further, the thermal
veals the distribution of elements: C, F, and Ti, represented by red, conductivity of the bulk only increases to 11.70 W m− 1 K− 1. Further
green, and blue, respectively. Since the F element is exclusively derived increasing the additive amount of EG, the thermal conductivity is not
from PVDF (i.e., (C2H2F2)n), its presence confirms the incorporation of enhanced obviously, which is in the range of 11.40 ~ 11.70 W m− 1 K− 1.
PVDF in the sample. In Fig. 4(a), large PVDF particles are observed Indeed, if the amount of EG is significantly increased, the thermal con­
interspersed with the Ti-based alloy particles using traditional method. ductivity would increase further [25]. However, such a mass increase of
In Fig. 4(b), the distribution of PVDF becomes more uniform for the EG would significantly reduce the hydrogen storage capacity of the bulk,
samples prepared by compaction and cladding method, closely match­ making it an unsuitable option for practical applications. Considering
ing that of the Ti-based alloy particles. The PVDF successfully coats the the lubricating effect of EG during the compaction process, an addition
Ti-based alloy particles, while large carbon particles are also observed of 1~5 wt% EG is preferred.
interspersed among the Ti-based alloy particles. In Fig. 4(c), after the
first hydrogen absorption and desorption cycles, the Ti-based alloy 3.2. The hydrogen absorption and desorption performances of Ti-based
particles are crushed due to the stresses induced by the hydrogen ab­ alloy bulks
sorption and desorption reactions. If the PVDF fully coats the Ti-based
alloy particles and the stresses do not exceed the tensile strength of Firstly, the effect of PVDF on the hydrogen absorption rate of alloy
the PVDF, the particles will remain intact. However, this would pre­ bulks was evaluated, as shown in Fig. 7(a). The hydrogen absorption
dictably result in a dramatic decrease in the hydrogen absorption and pressure and temperature were 3 MPa and 298 K, respectively. It can be
desorption kinetics. In this work, since the PVDF content is only 1 wt%, observed that both the hydrogen absorption rate and the maximum
it partially coats the Ti-based alloy particles, causing the particles to hydrogen storage capacity decrease as the PVDF content increases. For
break along the uncoated areas after cycling. In Fig. 4(d), it is observed the bulk with 0 wt% PVDF and 3 wt% EG, 1.60 wt% of hydrogen is
that the Ti-based alloy particles are pulverized under the effect of stress, absorbed in 2.58 min. In comparison, the bulk with 1 wt% PVDF and 3
wt% EG also achieves about 1.60 wt% hydrogen absorption but requires
3.03 min. However, when the PVDF content is increased to 5 wt%, only
1.49 wt% of hydrogen is absorbed, and the absorption finishes in a
longer time of 3.65 min. It is thus evident that the coated PVDF
adversely affects the hydrogen absorption kinetics, due to the reduction
of hydrogen diffusion channels. Thus, a PVDF content of 1 wt% is rec­
ommended, as it offers an acceptable balance of hydrogen absorption
kinetics, storage capacity, and high thermal conductivity.
The effect of EG on the hydrogen absorption rate of alloy bulks is also
revealed and shown in Fig. 7(b). It is evident that the hydrogen ab­
sorption rate increases with the addition of EG. Approximately 1.60 wt%
of hydrogen is absorbed in 4.14, 3.18, and 3.00 min for EG contents of 0,
1, and 3 wt%, respectively. However, when the EG content increases to
5 wt%, the hydrogen absorption rate becomes similar to that of the 3 wt
% EG, with only a slight reduction in the maximum hydrogen storage
capacity. Thus, the recommended additive amounts of PVDF and EG are
1 wt% and 3 wt%, respectively.
Fig. 7(c) and (d) present the hydrogen absorption and desorption
PCT curves of powders and bulks, respectively. Comparing the PCT
curves of the powders and bulks at 298 K, it is observed that the
Fig. 3. XRD patterns of the Ti-based alloy bulk containing 1 wt% PVDF and 3 hydrogen absorption and desorption equilibrium pressures for the bulk
wt% EG, prepared using (a) the traditional method for inactivation state and are 1.425 MPa and 0.795 MPa, respectively, which are higher than the
the compaction and cladding method for (b) the inactivation state, (c) the corresponding values of 1.087 MPa and 0.546 MPa for the powders. The
dehydrogenated state after the first cycle, and (d) the dehydrogenated state van’t Hoff fitting curves are plotted in Fig. 7(e). According to the van’t
after the 50th cycle. Hoff equation, the calculated hydrogen absorption enthalpy change

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Fig. 4. The SEM and EDS mapping images of the Ti-based alloy bulk with 1 wt% PVDF and 3 wt% EG prepared using (a) the traditional method for inactivation state
and the compaction and cladding method for (b) the inactivation state, (c) the dehydrogenated state after the first cycle, and (d) the dehydrogenated state after the
50th cycle.

Fig. 5. Photographs of the Ti-based alloy bulk with 1 wt% PVDF and 3 wt% EG prepared by compaction and cladding method for (a) the inactivation state and the
dehydrogenated state after (b) the 10th cycle and (c) the 50th cycle.

values of powders and bulks are 19.36 kJ mol− 1 K− 1 and 20.70 kJ mol− 1 storage applications, key technical indicators for the hydrogen storage
K− 1, respectively. Correspondingly, the calculated hydrogen desorption tank include the volumetric hydrogen storage density, as well as the
enthalpy change values are 29.28 kJ mol− 1 K− 1 and 30.70 kJ mol− 1 K− 1. hydrogen absorption and desorption rates. Thus, we use a 1 L aluminum
tank as the hydrogen storage unit, filling it with hydrogen storage ma­
terials at a ratio fixed at 90 % of the tank’s total volume. The powders or
3.3. The hydrogen absorption and desorption behaviors of Ti-based HSTs bulks are firstly filled into the aluminum tank under vibration condi­
tions. The filled masses of the powders and bulks are 3.80 kg and 3.20
The hydrogen storage materials must be filled in a tank to absorb and kg, respectively. This results in an apparent density of 3555.6 kg m− 3 for
desorb hydrogen. For hydrogen fuel cell vehicles and distributed energy

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[29]. Fig. 9 presents the evolution of effective thermal conductivity for

hydrogen with powders, hydrogen with bulks, and hydrogen with both
bulks and powders. The effective thermal conductivity increases
significantly with hydrogen pressure below 1.5 MPa. When the
hydrogen pressure exceeds 1.5 MPa, the effective thermal conductivity
shows little change. The effective thermal conductivity for the bed of
powders is only 0.59 W m− 1 K− 1 at 3 MPa, which is enhanced to 9.56 W
m− 1 K− 1 for bulks. For the mixture of bulks and powders, the value is
10.32 W m− 1 K− 1. This explains why the HST filled with the mixture of
bulks and powders has the highest hydrogen absorption rate, as shown
in Fig. 8.
The Ti-based HSTs are applied to supply hydrogen to fuel cells, uti­
lizing the waste heat generated by the fuel cell at temperatures of
323–333 K for effective operation. In this study, we evaluated the
hydrogen desorption rate of Ti-based HSTs filled with a mixture of bulks
and powders at various temperatures, as shown in Fig. 10. The HST
desorbed approximately 65.02 g, 64.62 g, and 63.44 g of hydrogen at
283 K, 298 K, and 323 K, respectively. Consequently, 95.34~97.74 % of
the total absorbed hydrogen was desorbed. The value of t90% was
determined to be 5.96 h, 1.80 h, and 0.91 h at 283 K, 298 K, and 323 K,
respectively. Correspondingly, the average hydrogen desorption rates
are 0.16 g min− 1, 0.54 g min− 1 and 1.04 g min− 1, repectively.
Fig. 11 presents the cycle performance for the Ti-based HST filled
Fig. 6. The thermal conductivity values of powders and alloy bulks with with the mixture of bulks and powders with hydrogen absorption at 3
different compositions. MPa and temperatures of 298 K in the water jacket and hydrogen
desorption at 0.1 MPa and temperatures of 298 K in the water jacket.
the bulk bed, which is lower than that of the powders bed (4222.2 kg After every 10 cycles, the HSTs were evacuated and subsequently tested
m− 3). Thus, we mix the bulks and powders to enhance the filled mass in for hydrogen absorption completely. Remarkably, even after 50 cycles of
the tank. After thorough mixing, approximately 4.0 kg of bulks and hydrogen absorption and desorption, the hydrogen absorption capacity
powders were filled into the tank, resulting in an increased apparent showed no measurable decrease. Furthermore, the HSTs’ hydrogen ab­
density of 4444.4 kg m− 3 for the bed. The mass ratio of bulks to powders sorption and desorption kinetics remained stable, exhibiting a perfor­
is approximately 4:1. mance equivalent to their initial state.
The hydrogen absorption curves for the three HSTs filled with As is well known, heat transfer enhancement methods, such as fins,
powders, bulks, and a mixture of bulks and powders are presented in meshes, and tubes[26], can increase the hydrogen absorption rate, but
Fig. 8. The hydrogen absorption pressure for all HSTs is 3 MPa. To this often leads to a significant reduction in storage capacity. In our
compare the hydrogen absorption/desorption rates, we define t90% as work, the mixed filling of alloy bulks and powders significantly en­
the time required to reach 90 % of the maximum hydrogen absorption/ hances the thermal conductivity and apparent density of the bed,
desorption capacity. Approximately 66.51 g of hydrogen was absorbed thereby improving both hydrogen storage density and absorption rate of
by the HST filled with the mixture of bulks and powders, which is higher HSTs simultaneously. Fig. 12 presents a comparison of the hydrogen
than the 63.92 g absorbed by the powders-filled HST and the 51.03 g storage performance of HST filled with the mixture of bulks and powders
absorbed by the bulk-filled HST. The system hydrogen storage density of in this work and those reported in studies from the past few years
the HST filled with the mixture of bulks and powders is 66.51 g L-1, [30–35]. It can be seen that, for the same hydrogen storage capacity, the
which is close to the volume storage density of liquid hydrogen. The hydrogen absorption rate of the HST filled with the mixture of bulks and
values of t90% for the HSTs filled with powders, bulks, and the mixture of powders is significantly higher than that of the HSTs in the other cases.
bulks and powders are 1.04 h, 0.65h and 0.70h, respectively. Corre­ Thus, the method proposed in this work can be applied to design HSTs
spondingly, the average hydrogen absorption rates are 0.92 g min− 1, with high hydrogen absorption and desorption rates, as well as high
1.17 g min− 1 and 1.42 g min− 1. Compared to the HST filled with pow­ hydrogen storage density.
ders, the average hydrogen absorption rate of the HST filled with the
mixture of bulks and powders increased by 54.35 %, while the maximum 4. Conclusion
hydrogen storage capacity increased by 4.05 %.
Furthermore, as the temperature increases, the maximum hydrogen In the present work, we proposed a novel strategy for preparing Ti-
storage capacity of the HSTs decreases (Fig. 8(b) and (c)), which is due based hydrogen storage bulks incorporating polyvinylidene fluoride
to the reduced hydrogen storage capacity of the materials at a constant (PVDF) and expanded graphite (EG) using the compaction and cladding
hydrogen pressure of 3 MPa, as observed in the PCT curves shown in process. Under the influence of partial coatings with 1 wt% PVDF on the
Fig. 7. For example, in the HST filled with the mixture of bulks and Ti-based alloy particles, the particles adhered together, reducing contact
powders, the maximum hydrogen storage capacity decreases to 62.14 g thermal resistance and resulting in a high thermal conductivity of 10.25
at 298 K and 51.61 g at 323 K. The corresponding average hydrogen W m− 1 K− 1. This represents a 6.83-fold enhancement compared to the
absorption rate of the HST reduces to 1.07 g min− 1 and 0.39 g min− 1. original bulks and a remarkable 56.94-fold improvement compared to
This is because the hydrogen absorption rate depends on the pressure the powders. The addition of a small amount of EG enhances the
difference between the hydrogen pressure and the hydrogen absorption hydrogen absorption rate of the bulks, mitigating the negative impact of
equilibrium pressure, which decreases with temperature when the the partial PVDF coatings, and slightly increases the thermal conduc­
hydrogen pressure is held constant. tivity to 11.40–11.70 W m− 1 K− 1. Finally, the optimal additive amounts
As is well known, the effective thermal conductivity of the material of PVDF and EG are 1 wt% and 3 wt%, respectively, achieving a balance
bed is the key limiting factor for the hydrogen absorption/desorption between thermal conductivity, hydrogen absorption rate, and hydrogen
rate of HSTs [26–28], which is related to the hydrogen pressure directly storage capacity.
Furthermore, the bulk-powder combination strategy was employed

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L. Bian et al. Chemical Engineering Journal 507 (2025) 160799

Fig. 7. (a) Hydrogen absorption kinetics curves for alloy bulks with varying amounts of PVDF; (b) Hydrogen absorption kinetic curves for alloy bulks with varying
amounts of EG; (c) Hydrogen absorption and desorption PCT curves for powders; (d) Hydrogen absorption and desorption PCT curves for bulks with 1 wt% PVDF and
3 wt% EG; (e) The van’t Hoff plots for powders and bulks with 1 wt% PVDF and 3 wt% EG.

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L. Bian et al. Chemical Engineering Journal 507 (2025) 160799

Fig. 8. The hydrogen absorption curves for the three Ti-based HSTs at 3 MPa and different temperatures: (a) 283 K; (b) 298 K; (c) 323 K.

Fig. 9. The evolution of effective thermal conductivity versus hydrogen pres­ Fig. 10. The hydrogen desorption curves for the Ti-based HST filled with the
sure for storage beds of powders, bulks, and bulks and powders. mixture of bulks and powders at 0.1 MPa and different temperatures.

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Fig. 11. (a) The cycling performance prior to 50 cycles and (b) the hydrogen absorption and desorption mass changes for the Ti-based HST filled with the mixture of
bulks and powders.

Fig. 12. Comparison of hydrogen storage performance of HSTs in the present work with the reported results [30–35].

to increase the volumetric hydrogen storage density of Ti-based production, and also can be extended to all near room-temperature
hydrogen storage tanks (HSTs). At a 4:1 mass ratio of bulks to pow­ solid-state hydrogen storage materials, such as V-based materials and
ders, a volumetric hydrogen storage density of 66.51 g L-1 for 1 L Ti- rare-earth-based materials. This work thus provides a new strategy for
based HST was achieved, which is close to that of liquid hydrogen. 90 solving the problem of slow absorption and desorption rate of solid-state
% of total hydrogen storage capacity can be reached in 0.70 h at 283 K hydrogen storage systems and promoting their practical applications.
and 3 MPa, and desorbed in 0.91 h at 323 K and 0.1 MPa. Compared to
the HST filled with powders only, the average hydrogen absorption rate CRediT authorship contribution statement
of the HST filled with the mixture of bulks and powders increased by
54.35 %, while the volumetric hydrogen storage density increased by Liansen Bian: Writing – original draft. Longfei Shao: Investigation.
4.05 %. This is due to the significantly improved effective thermal Bolun Wang: Methodology, Conceptualization. Jiaqi Zhang: Data
conductivity of the alloy bed composed of bulks and powders in a curation. Yinghui Li: Software. Zhigang Hu: Formal analysis. Jianxin
hydrogen atmosphere. Zou: Writing – review & editing, Funding acquisition. Kemin Zhang:
This compaction and cladding process is easy to implement in mass Writing – review & editing, Conceptualization. Xi Lin: Writing – review

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L. Bian et al. Chemical Engineering Journal 507 (2025) 160799

& editing, Conceptualization. [14] W. Qiao, D. Yin, S. Zhao, et al., Effects of Cu doping on the hydrogen storage
performance of Ti-Mn-based, AB2-type alloys, Chem. Eng. J.. 465 (2023) 142837,
https://doi.org/10.1016/j.cej.2023.142837.
[15] M. Piao, X. Xiao, L. Zhan, et al., Laves phase double substitution alloy design and
Declaration of competing interest
device filling modification for Ti-based metal hydride hydrogen compressors, Int. J.
Hydrogen Energy. 50 (2024) 1358–1368, https://doi.org/10.1016/j.
The authors declare that they have no known competing financial ijhydene.2023.09.228.
interests or personal relationships that could have appeared to influence [16] K. Herbrig, C. Pohlmann, Ł. Gondek, et al., Investigations of the structural stability
of metal hydride composites by in-situ neutron imaging, J. Power Sources. 293
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