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 7 ( 2 0 2 2 ) 4 9 0 e5 0 0

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The different effect of Co3O4 or/and carbon fiber

originated from biomass on the electrochemical
hydrogen storage performance of Co2B alloy

Jianxun Zhao a,b, Jian Lv a,*, Dayong Liu c, Wanqiang Liu a,**, Heng Liu d,
Peng Chen a, Xinwei Wang a, Yong Cheng e,***, Xin Guo a
a
School of Materials Science and Engineering, Changchun University of Science and Technology, Changchun, 130022,
China
b
Engineering Research Center of Optoelectronic Functional Materials, Ministry of Education, Changchun, 130022,
China
c
College of Electronic Science & Engineering, Jilin University, Changchun, 130022, China
d
Research Center for Nanotechnology, Changchun University of Science and Technology, Changchun, 130022, China
e
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, CAS,
Changchun, 130022, China

highlights graphical abstract

Co3O4 and Carbon Fiber have

different electrochemical effect on
Co2B alloy.

Co2Bþ2 wt.% Co3O4þ1 wt.%CF has
highest discharge capacity and
more excellent cycle life.

CF and Co3O4 could bring down the
capacity decay rate and charge
transfer resistance.

CF and Co3O4 have synergistic ef-
fect for Co2B alloy about hydrogen
diffusion.

article info abstract

Article history: Co2B alloy was synthesized via the method of high temperature solid phase. Carbon fiber
Received 1 August 2021 (CF) was prepared from cotton by calcination process. The addition of carbon fiber and
Received in revised form Co3O4 improves corrosion resistance and charge transfer speed of the composite material
14 September 2021 electrode. The Rct value of Co2B þ 1 wt.% CF was 360 mU, lower than the other composite
Accepted 1 October 2021 electrode could reduce charge transfer resistance. The overall electrochemical perfor-
Available online 19 October 2021 mance of Co2B þ 2 wt.% Co3O4 þ 1 wt.% CF was best among all the electrodes, and its Cmax
could reach 715.3 mAh/g. The high conductivity and multiple reaction sites provided by
carbon fiber and the catalytic effect of Co3O4 may be the main reasons for the improvement

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: lv154870211@163.com (J. Lv), wqliu1979@126.com (W. Liu), cyong@ciac.ac.cn (Y. Cheng).
https://doi.org/10.1016/j.ijhydene.2021.10.008
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 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 7 ( 2 0 2 2 ) 4 9 0 e5 0 0 491

of electrochemical performance, which enhance the kinetic performance of electro-

Keywords:
chemical reactions. The synergistic effect of carbon fiber and Co3O4 improves the elec-
Co2B
trochemical hydrogen storage properties of Co2B alloy. This work presents a simple and
Co3O4
effective method to improve the electrochemical hydrogen storage performance of cobalt-
Carbon fiber
boron alloys by adding transition metal oxides and carbon materials derived from biomass.
Composite material
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Hydrogen storage

cobalt and non-metallic materials such as boron, phosphorus,

Introduction
Hydrogen is widely deemed a pollution-free energy source
and can be produced continuously. Hydrogen is considered as
a kind of clean energy source which could replace oil and coal
in the future. However, there are some challenges in hydrogen
storage and transportation, so developing an effective and
economical hydrogen energy storage technology for the ap-
plications of hydrogen energy plays a vital role [1]. Many
methods have been discovered for hydrogen storage, such as
the common high-pressure and low-temperature compres-
sion of hydrogen, these methods still need low-temperature
conditions and high-pressure equipment, which are
restricted in practical application. In contrast, hydrogen
storage alloy can provide a stable, efficient, and convenient
hydrogen storage material through an electrochemical reac-
tion [4,5].
Solid phase hydrogen storage alloys such as AB5, AB2 Laves
and AB have been accepted for their excellent discharge per-
formance and low pollution [2,3]. In particular, the discharge
capacity of some magnesium-based alloy can reach more than
590 mAh/g [8]. The disadvantage in dynamic performance and
the cycle life limited their application in practice [9]. Among
many new type cathode materials of nickel-metal hydride (Ni-
MH) rechargeable batteries, cobalt-based alloy has attracted
more and more interest for its high discharge capacity and
excellent dynamic performance [7]. The alloy is made up of
sulfur and silicon [10e15]. Wang et al. [16] reported cobalt-
sulfur alloy was prepared by ball milling with the maximum
discharge capacity of more than 350 mAh/g and the capacity
decay of only 14.3% after 100 cycles. In the meantime, Cao
et al. [17] founded the CoeP nanoparticles with excellent
discharge performance and long cycle life. Moreover, He et al.
reported the synthesis of cobalt-silicon alloys by arc smelting
[6], which produced the superior discharge capability. The
CoeB alloys can easily undergo reversible reaction in the
process of charging and discharging [18]. However, cobalt is
toxic, environmentally unfriendly, and expensive, the corro-
sion resistance of the Co2B alloy is poor. All of these factors
limit the application of CoeB alloy in Ni-MH secondary bat-
teries. Therefore, improve the discharge capability and
corrosion resistance of the alloy is the main way to solve the
above problems. Some transition metal oxides have the ability
to improve the charging/dehydrogenation kinetics of the
alloy, such as ferric oxide, cobalt oxide, titanium dioxide, etc.,
which can be used as catalysts to improve the dynamic
properties of the alloy [28]. Among these metal oxides, Co3O4
has been widely used as a superior electrochemical material
in the field of catalysis, and mesoporous Co3O4 nanowires
have been used as materials for negative lithium-ion batteries
(LIB) with a theoretical capacity (890 mAh/g) [20].
Cobalt trioxide was added to the metal hydride electrodes,
the charge and discharge efficiency of the electrodes were

Fig. 1 e Schematic illustration of the synthesis process for Co2B, CF and Co3O4.
492 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 7 ( 2 0 2 2 ) 4 9 0 e5 0 0
significantly improved [30]. Co3O4 nanosheets was grown in
situ on the surface of hydrogen storage alloys [29]. The high-
rate dischargeability and the maximum discharge capacity
was enhanced. Both of their studies attribute the improve-
ment of discharge performance to the electrocatalysis of
Co3O4. However, the electrocatalytic performance of Co3O4
was astricted due to poor conductivity [32]. Carbon black,
conductive graphite and carbon fiber are common excellent
conductive materials. The poor physical stability of the elec-
trode in alkaline solution for Carbon black and graphite were
very brittle. Carbon nanotubes produce harmful products in
the preparation process, and its preparation cost is high,
which limits the practical application of carbon nanotubes in
battery electrode. Carbon fiber comes from a wide range of
sources, such as cotton fabric, paper, plant fiber and so on.
The preparation of carbon fiber was non-toxic for human body
and environment [33]. Zhang et al. reported that the carbon
fiber can provide more reactive sites for the alloy particles to
improve the discharging characteristics of the electrode and
enhance the electrochemical reaction kinetics of the electrode
by improving the electrical conductivity [29]. Wang et al. re-
ported that catkins were prepared as hollow carbon micro-
tubes by a high-temperature calcination method, which
increased the electrochemical properties of raw materials and
other electrochemical properties [21]. Therefore, adding car-
bon materials derived from biomass to Co2B alloy may
improve the electrical conductivity and increase the number
of active sites.
In this paper, Co3O4 or/and carbon fiber originated from
biomass was/were added to Co2B alloy, respectively. The
electrochemical hydrogen storage performance and kinetic
properties of the composite electrodes were investigated. The
mechanism of improving the electrochemical reaction of the
alloy was discussed. Carbon fiber is denoted as CF for the
convenience of the following text.
Experiment
Preparation
The fabricate process schematic diagram of Co2B, CF and
Co3O4 was shown in Fig. 1. All the reagents used in the
experiment were analytical grade and can be used directly.
Preparation of Co2B
Using a high-temperature solid-phase process, the original
Co2B alloy was synthesized [18]. The powder of cobalt and
boron was purchased from Aladdin Reagent Company, the
purity of cobalt powder was 99.5%，the purity of boron pow-
der was 99.9%. Cobalt powder (300 mesh) and boron powder
were evenly mixed in a stoichiometric ratio. The mixture was
placed in a quartz tube and sintered for 10 h in an atmosphere
of high purity argon at a temperature of 1073 K. At this point, a
cobalt-boron alloy is prepared. Next, to facilitate the
preparation of the electrodes, the alloy is ground into a pow-
der of about 200 mesh.
Preparation of carbon fiber and the composite material of Co2B
and CF
The carbon fiber was obtained by heating cotton at a high
temperature under argon atmosphere [21]. At first, an appro-
priate amount of cotton was washed frequently with distilled
water three times to move impurities remaining in the cotton.
Next, the remaining moisture was removed completely from
the washed cotton by drying in a vacuum drying oven at 60  C
for 12 h. In the end, the dried cotton was calcined at 600  C
under high-purity argon for 1 h in a tube furnace.
The composite material of Co2B and CF was synthesized by
the ball milling method. First of all, 1 wt.% and 2 wt.% of
carbon fiber were added to Co2B alloy powder, respectively.
Next, the composite and stainless balls were placed into a mill
container and milled for 5 min under the protection of argon
gas. The ball-to-material ratio was 5: 1. The electrode material
prepared by the above process is denoted as“Co2B þ xCF
(x ¼ 1 wt.%, 2 wt.%)”.
Preparation of Co3O4 and the composite material of Co2B and
Co3O4
The precursor of Co3O4 nanoparticles was cobalt (II) acetyla-
cetonate. Firstly, 5 g of cobalt (II) acetylacetonate was added
into 300 mL of absolute ethanol and mechanically stirred at
room temperature for 12 h to obtain a homogeneous gelati-
nous liquid. Then suction filtration was used to filter the
sediment on the filter paper. Secondly, the sediment was dried
in a vacuum drying oven at 60  C for 12 h after completing
suction filtration. And next, the sediment was calcined at
800  C for 1 h under the high purity Ar2. Finally, Co3O4 material
was obtained [22].
The composite material of Co2B and Co3O4 was synthesized
by the ball-milling method. Firstly, 1, 2, and 3 wt.% Co3O4 was
added into Co2B alloy powder, respectively, and then, the
composite and stainless balls were placed into a mill
container and milled for 5 min under the protection of argon
gas. The ball-to-material ratio was 5: 1. The electrode material
prepared by the above process is denoted as “Co2B þ y Co3O4
(y ¼ 1 wt.%, 2 wt.%, 3 wt.%)”.
Preparation of Co2B þ 1 wt.% CF þ 2 wt.% Co3O4
The composite material Co2B þ 1 wt.% CF þ 2 wt.% Co3O4 was
obtained by the ball milling method. At first, 1 wt.% CF and
2 wt.% Co3O4 were added in Co2B. And then, Ball-milling ex-
periments were carried out on in order to prepare the com-
posite material. The ball-to-material ratio was 5: 1, and the
running time was 5 min.
Characterization
Using a Rigaku Ultima IV with Cu Ka radiation, XRD tests were
performed for phase measurement in different samples. JEOL
 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 7 ( 2 0 2 2 ) 4 9 0 e5 0 0
JSM-5200 scanning electron microscope (SEM) was used to
observe the microcosmic appearance of different samples.
Electrochemical measurements
The electrochemical performance measurement of different
electrodes were carried out in a the tri-electrode system
included the working electrodes, reference electrode (Hg/HgO)
and counter electrode (Ni(OH)2/NiOOH), and 6 M KOH solution
was used as the cell electrolyte. The electrode plate was pre-
pared at a pressure of 10 MPa and the weight ratio of active
material to 1.0 g of nickel carbonyl powder was 1:5. During
each charging-discharging cycle, the charge current density
was set up at 100 mA/g for 10 h, and discharge to the cut-off
potential of 0.6 V at the current density of 20 mA/g (vs. Hg/
HgO) at 303 k.
Discharge stability retention rate Sx (%) of the active ma-
terial was expressed in the following equation:
Sx ð%Þ ¼ Cx =Cmax  100%
where Cx and Cmax represented the discharge capacity of the
x-th cycle and the maximum of discharge capacity, respec-
tively. The battery of high-rate dischargeablity (HRD) which
characterize battery discharge capability was calculated by
the equation (2):
HRDx (%) ¼ (Cx/C20)  100
The electrode was scanned in electrochemical workstation
with the frequency range 102 Hz to 105 Hz for the electro-
chemical impedance spectroscopy (EIS) was measured at half
discharge depth. The scan speed of 0.1 mV s1 was set up to
scan the working electrode potential from 4 to 4 mV at half
discharge depth to obtain linear polarization curves. The I0
was used to test the difficulty of the working electrode reac-
tion, the results can be calculated by putting the relevant data
into the equation (3).
Io ¼ IpRT/Fh
where Ip was the polarization current density (mA/g), R was
the gas constant; T was the representation of absolute tem-
perature(K); F represented the Faraday constant; h indicated the
over-potential of the electrode (mV). A potential kinetic polari-
zation test was performed at half discharge depth by scanning
the potential range from 1.4 V to 0.4 V at the scan speed of
5 mV/s to study the alloy electrodes' corrosion behavior. Ac-
cording to the Tafel fitting result, icorr was obtained.
Results and discussion
Material characterization
The XRD patterns of Co2B, Co3O4, Co2B þ x Co3O4 shown in
Fig. 2(a). The main phase structure of Co2B was quadrangular
(PDF 89-1994), with narrow and sharp peaks indicating the
alloy has good quality. Co3O4 material phase purity was
determined by X-ray diffraction. All the peaks correspond well
to the cubic spinel structure and correspond entirely to its
493
characteristic peaks (JCPDS card No. 42e1467). No character-
istic peaks from impurities and residues were seen. This
proved that the prepared cobalt oxide had high purity and
quality. It was evident that the prominent peaks of Co2B alloy
were weakened with the increased proportion of Co3O4 from
the XRD patterns of Co2B þ y Co3O4. However, no character-
istic peaks of Co3O4 were observed as the amount of Co3O4 was
too small. The XRD patterns of CF was performed in Fig. 2(b1).
There are two different broad peaks at 24.1 and 43.4 , which
correspond to the (002) and (110) surfaces of graphite carbon,
respectively. The diffraction peaks of the composite materials
Co2B þ x CF are shown in Fig. 2(b2). The characteristic peaks of
CF were not shown due to the small CF content in the sample.
The XRD pattern of the Co2B þ2 wt.% Co3O4þ1 wt.% CF was
performed in Fig. 2(c). Due to Co3O4 and CF's low content, their
characteristic peaks do not appear in the XRD patterns. The
diffraction peaks of Co3O4 and CF doped the composites ma-
terial closely match the characteristic peaks of Co2B, except
the height of the peaks were lower than Co2B. This change is
(1)
caused by the addition of Co3O4 and CF. There was no other
crystalline phase found in the XRD patterns, and this proved
that no new phase was produced during the doping process.
The SEM images of Co2B, Co2B þ Co3O4, Co2B þ CF, and
Co2B þ Co3O4þCF are shown in Fig. 3. From Fig. 3(aec), it can
be seen that the Co2B was composed of small particles of
about 2 microns in size. The size of Co2B particles was rela-
(2) tively uniform. Co3O4 particles show a hexagon's appearance.
Their size was about 300e400 nanometer, the particle size was
basically uniform, and there was no apparent agglomeration
phenomenon. The CF has a non-hollow cable-like structure
with a diameter of 5e10 microns and a cross-section of
approximately elliptical shape. As shown in Fig. 3(def), after
the addition of Co3O4, the surface of the alloy particles be-
comes rough, and Co3O4 particles can barely be observed. This
may be due to the small size of their particles and the small
amount of doping, so they were wrapped in Co2B alloy parti-
cles. When the CFs were added to Co2B alloy, the fibers winded
through the alloy particles, creating a wide gap between the
(3) fibers and the alloy particles, extending wherever the fibers
go. When both Co3O4 and CF were added to Co2B alloy, the
surface becomes smooth, CF passes through the alloy parti-
cles, and some of the alloy particles were attached to the
surface of CF. There were still some gaps between the CFs and
the alloy particles.
Discharge capacity
The discharge capacity of Co2B þ x CF and Co2B þ y Co3O4
composite material electrodes are shown in Fig. 4(a and b).
The initial cycle of all composite materials reached their
maximum discharge capacity. The discharge capacity of
composite materials Co2B þ x CF were higher than the raw
alloy Co2B for CF, which can increase the charge transfer rate
like cables inside the alloy electrode due to the high conduc-
tivity [19]. Meanwhile, the discharge capacity of composite
materials Co2B þ y Co3O4 also higher than the raw alloy Co2B
for the Co3O4 was a kind of efficient catalyst. When the elec-
trode surface is charged, the reaction is:
H2O þ e / Hads þ OH (4)
494 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 7 ( 2 0 2 2 ) 4 9 0 e5 0 0

Fig. 2 e The XRD patterns of Co2B, nano-Co3O4, Co2B þ x Co3O4 (a), CF(b1), Co2B, CF, Co2B þ x CF (b2), Co2B, Co3O4, CF,
Co2B þ 2 wt.% Co3O4 þ 1 wt.% CF (c).

The formula (4) was Walmer reaction, which can generate
hydrogen atoms on the electrode surface, but at the same
time, there are two other reactions as follow:
2 Hads / H2
Hads þ H2O þ e / H2 þ OH (6)
Reaction formula (5) was Walmer-Tafel reaction, and re-
action formula (6) was Helovsky reaction. Both of these re-
(5) actions were hydrogen absorption reactions, which will
 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 7 ( 2 0 2 2 ) 4 9 0 e5 0 0
Fig. 3 e The SEM images of Co2B (a), nano-Co3O4 (b), CF(c), Co2B þ Co3O4 (d), Co2B þ CF (e), Co2B þ Co3O4 þ CF (f).
reduce the hydrogen concentration. The hydrogen absorption
reactions were suppressed by Co3O4 nanometers particles.
Thereby Co3O4 particles enhanced the Walmer reaction and
enriched the alloy with hydrogen, allowing the electrode to
charge more efficiently [24].
According to the Fig. 4(c), the composite material showed
the highest discharge capacity when the amount of CF was
1 wt.%, the amount of Co3O4 was 2 wt.%. The discharge ca-
pacity of composite material Co2B þ 2 wt.% CF was lesser than
Co2B þ 1 wt.% CF. The discharge capacity of CF prepared in the
experiment is significantly lower than that of alloy [23]. The
excellent electrical conductivity of CF is beneficial to charge
transfer in electrochemical reaction, which improves the ki-
netic properties of the reaction and makes it difficult to greatly
increase the discharge capacity of the alloy [34]. Therefore, the
discharge capacity of the alloy decreases with increasing the
amount of CF. The electrochemical capacity of Co3O4 was
lower than that of Co2B alloy [25]. The discharge capacity of
Co2B þ y Co3O4 will decrease when more Co3O4 was added to
the electrode.
The maximum discharge capacity (Cmax) and capacity
retention of Co2B þ 1 wt.% CF, Co2B þ 2 wt.% Co3O4 and Co2-
B þ 1 wt.% þ 2 wt.% Co3O4 were listed in Table 1. The Cmax of
the composite material Co2B þ 1 wt.% CF and Co2B þ 2 wt.%
Co3O4 was 713.7 mAh/g and 695.4 mAh/g, respectively. The
Cmax value of the composite material Co2B þ 1 wt.% þ 2 wt.%
Co3O4 was 715.3 mAh/g. The capacity retention was calculated
by equation (1). The S50 of the composite material Co2-
B þ 1 wt.% CF, Co2B þ 2 wt.% Co3O4 and Co2B þ 1 wt.% þ 2 wt.%
Co3O4 was 70.16%, 71.96% and 71.66%, respectively. The
composite material Co2B þ 1 wt.% CF processed higher
discharge capacity than Co2B þ 2 wt.% Co3O4, however, the
capacity retention rate of Co2B þ 1 wt.% CF was lower than
Co2B þ 2 wt.% Co3O4. The composite material
495
Co2B þ 1 wt.% þ 2 wt.% showed the excellent discharge ca-
pacity and capacity retention rate due to the combination of
CF and Co3O4 play a synergistic role. The results of electro-
chemical hydrogen storage performance in cobalt-boron al-
loys in recent years has been investigated and are listed in
Table 2. Compared with the research results of others, the
results of this paper are better than those in Table 2.
Kinetic property
The electrochemical equation of Co2B alloy is shown below,
Co2B þ 10OH / 2Co(OH)2 þ BO3
3 þ 3H2O þ 7e
During the discharge of the alloy, boron is oxidized and
cannot be reduced. The cycle life of the electrode is reduced
due to oxidation or corrosion of the active material to form an
oxide layer. icorr can be obtained by fitting the Tafel curve. The
potentiodynamic polarization patterns of Co2B, Co2B þ 2 wt.%
Co3O4, Co2Bþ 1 wt.% CF and Co2B þ 2 wt.% Co3O4 þ 1 wt.% CF
electrodes were illustrated in Fig. 5. The data of icorr and Ecorr
were listed in Table 1. The icorr values of Co2B þ 2 wt.% Co3O4,
Co2Bþ 1 wt.% CF and Co2B þ 2 wt.% Co3O4 þ 1 wt.% CF were
simultaneously lower than those of Co2B. The Ecorr data of
three kinds of composite materials were higher than raw alloy
Co2B. Moreover, Co2B þ 2 wt.% Co3O4 þ 1 wt.% CF has shown
more excellent corrosion resistance than Co2B þ 2 wt.% Co3O4
and Co2Bþ 1 wt.% CF, the result was the same as the cyclic
stability of the composite electrode. For CoeB alloys, the
oxidation reaction of boron in high concentration alkaline
electrolyte was an irreversible reaction and this gradually
reduced the electrode's discharge [26]. The corrosion resis-
tance of Co2B alloy is improved after doping with Co3O4 and
CF, thereby enhancing the electrode's cycle stability.
496 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 7 ( 2 0 2 2 ) 4 9 0 e5 0 0

Table 2 e Results of electrochemical hydrogen storage in

CoeB alloy in recent years.
Year Discharge Discharge current Document
capacity(mAh/g) density(mA/g) number
2004 More than 300 100 [11]
2007 480.3 25 [26]
2008 330 100 [36]
2009 513.6 100 [37]
2010 ~570 25 [38]
2011 380 25 [39]
2017 530 300 [40]

Fig. 5 e Potentiodynamic polarization patterns of the

composite material electrodes.

Fig. 4 e Discharge capacities of Co2B þ x CF (a), Co2B þ x

Co3O4 (b), Co2B, Co2B þ Co3O4, Co2B þ CF, Co2B þ 2 wt.%
Co3O4 þ 1 wt.% CF (c).
Fig. 6 e HRD at different current densities of the composite
material electrodes.
Table 1 e Electrochemical characteristics of composites at
303 K.
Samples Cmax S50 Ecorr icorr Table 3 e Electrochemical kinetic parameters of
(mAh/ (%) (V) (mA) composites at 303 K.
g)
Sample Io (mA/g) Rct (mU) HRD120/%
Co2B 657.3 68.03 0.923 37.8
Co2B 38.09 426 65.3
Co2B þ 1 wt.%CF 713.7 70.16 0.892 29.4
Co2B þ 1 wt.%CF 81.82 360 71.4
Co2B þ 2 wt.%Co3O4 695.4 71.96 0.885 26.7
Co2B þ 2 wt.%Co3O4 58.98 393 69.6
Co2B þ 1 wt.%CF þ 2 wt.%Co3O4 715.3 71.66 0.871 25.4
Co2B þ 1 wt.%CF þ 2 wt.%Co3O4 114.21 379 74.5

It was very significant to possess excellent discharge per-

formance under high current density for practical applica-
tions of Ni-MH batteries. Fig. 6 demonstrated the HRD of Co2B,
Co2B þ 2 wt.% Co3O4, Co2Bþ 1 wt.% CF and Co2B þ 2 wt.%
Co3O4 þ 1 wt.% CF under different current densities. The
HRD120 of different composite material electrodes was showed
in Table 3. The HRD of the different material after doping CF or
Co3O4 was enhanced. The electrode of Co2B þ 2 wt.% Co3O4-
þ 1 wt.% CF (74.5%) showed a remarkably higher HRD120 than
that of Co2B(65.3%), Co2B þ 2 wt.% Co3O4(69.4%) and Co2Bþ
1 wt.% CF(71.4%). The HRD of the electrode was controlled by
 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 7 ( 2 0 2 2 ) 4 9 0 e5 0 0 497

the charge transfer on the electrode-electrolyte interface and

the hydrogen diffusion process in the electrode bulk. Ex-
change current density and charge transfer resistance was
used to indicate the electrochemical activity of electrodes.
The cycling performance of each electrode at different
current densities was investigated, and the results are shown
in Fig. 7. With the increase of discharge current density, the
maximum discharge capacity of the alloy and doped alloy de-
creases, the minimum discharge capacity and capacity reten-
tion rate also decreases. In each case of discharge current
density, the change of electrode discharge capacity follows the
following order: Co2B þ 2 wt.% Co3O4 þ 1 wt.% CF > Co2Bþ
1 wt.% CF > Co2B þ 2 wt.% Co3O4> Co2B. This shows that Co3O4
and carbon fiber can still play a role in improving the electro-
chemical hydrogen storage performance of the alloy at higher
discharge current density. The synergistic effect of Co3O4 and
carbon fiber on the electrochemical hydrogen storage perfor- Fig. 8 e Linear polarization curves of the composite
mance of the alloy is stronger than one of them. material electrodes.
The effects of CF and Co3O4 on the electrochemical activity
over the electrode/electrolyte interface was further investi- correlation between the charge transfer rate and the kinetic
gated. The electrode's surface charge transfer rate was properties of the electrodes. In fact, during charging and dis-
assessed by exchange current density I0. Fig. 8 demonstrates charging process of the electrode, the material with high
the linear polarization curves of Co2B and three composite impedance will form on the surface of the electrode, which
discharge materials. The data of I0 was listed in Table 3, which reduces the rate of charge transfer on the alloy surface. CF can
was calculated by equation (3). Obviously, I0 of Co2B þ 2 wt.% enhance the corrosion resistance and conductivity of the
Co3O4 þ 1 wt.% CF (114.12 mA/g) was higher than that of Co2B electrode. In addition, by doping Co3O4 with catalytic activity,
(38.09 mA/g), Co2Bþ 1 wt.% CF (71.4 mA/g) and Co2B þ 2 wt.% the kinetic performance of the electrode can be reinforced. As
Co3O4 (58.98 mA/g). The results were consistent with the a result, the charge transfer between the electrode surface and
HRD120 of the four composite materials. It illustrates a positive the electrolyte is accelerated [31].

Fig. 7 e The cycling performance of Co2B alloy and doped alloy under different discharge current densities (a) 60 mAh/g (b)
80 mAh/g (c) 100 mAh/g (d) 100 mAh/g.
498 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 7 ( 2 0 2 2 ) 4 9 0 e5 0 0

from cotton by calcination process, the different effect of

Co3O4 or/and CF on the electrochemical hydrogen storage
performance improvement of Co2B alloy was showed by ball-
milling to fabricate the different composite materials. Co2-
B þ 2 wt.% Co3O4 performed better capacity retention rate and
corrosion resistance than Co2B þ 1 wt.% CF, however, the Rct of
Co2B þ 1 wt.% CF was lowest than the other composite ma-
terials, which proves that charge transfer speed between the
electrode surface and the electrolyte were increased. Com-
posite material Co2B þ 2 wt.% Co3O4 þ 1 wt.% CF showed
higher discharge capacity and high-rate dischargeability than
Co2B þ 1 wt.% CF, Co2B þ 2 wt.% Co3O4 and raw alloy Co2B.
What's more, Co3O4 and carbon fiber in the alloy have the
effect of improving the charge transfer resistance and ex-
change current density due to the electrocatalysis of Co3O4
and the high conductivity of carbon fiber. Co3O4 and CF play a
synergistic effect on the electrochemical hydrogen storage
performance of the alloy. This paper presents a simple
method to improve the electrochemical hydrogen storage
performance of cobalt-boron alloys by adding transition metal
oxides and carbon material.

Fig. 9 e EIS curves and the equivalent circuit of the

Declaration of competing interest
composite material electrodes.

The authors declare that they have no known competing

The electrochemical impedance spectroscopy(EIS)analysis financial interests or personal relationships that could have
was performed to further study the kinetics of the alloy elec- appeared to influence the work reported in this paper.
trodes [27,35]. The EIS curves and the equivalent circuit of
Co2B, Co2B þ 2 wt.% Co3O4, Co2Bþ 1 wt.% CF and Co2B þ 2 wt.%
Co3O4 þ 1 wt.% CF was shown in Fig. 9. The contact resistance
Acknowledgements
was indicated R2, the capacitance between the alloy sheet and
the contact pole sheet was indicated C1. C2 meaned the con-
This work is financially supported by Jilin Province Develop-
tact capacitance between the sample particles, the double
ment Program of Science and Technology (no.
layer capacitance was denoted as C3, and R3 indicated the
20200401031GX), the Natural Science Foundation of Jilin
contact resistance between the alloy particles, the charge
Province (no. 20200201254JC), Science and Technology
transfer resistance is named Rct. The Warburg resistance was
Research Project of the Education Department of Jilin Province
defined as Wo. The charge-transfer resistance Rct was calcu-
(no. JJKH20200770KJ, no. JJKH20200763KJ), the “Program of
lated by the fitting program Z-View, which is based on the
Youth Talents” of Jilin Association of Science and Technology
circuit. The data of the EIS test were listed in Table 3. The Rct of
(no. 181906), and the Jilin Province Science and Technology
raw alloy Co2B electrode was 426 mU. The Rct values of com-
Development Project (no. 20190103023JH).
posite material electrodes of Co2Bþ 1 wt.% CF, Co2B þ 2 wt.%
Co3O4 and Co2B þ 2 wt.% Co3O4 þ 1 wt.% CF was 360 mU,
393 mU, and 379 mU, respectively. The influence of Co3O4 and references
carbon fiber on the dynamic properties of the electrode is
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