Journal of Alloys and Compounds 914 (2022) 165354

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Journal of Alloys and Compounds

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

Optimization of VOSO4@C cathode materials with CNT and GO for

lithium-ion batteries ]]
]]]]]]
]]

⁎
Xumei Cui a,b, , Liu Zhang a,b, Yun Hu a, Dingyu Yang a, Jianxin Zou c
a
School of Optoelectronic Technology, Chengdu University of Information Technology, Chengdu 610225, China
b
Vanadium and Titanium Resource Comprehensive Utilization Key Laboratory of Sichuan Province, Panzhihua University, Panzhihua 617000, China
c
School of materials and environmental engineering, Chengdu Technological University, Chengdu 610031, China

a r t i cl e i nfo a bstr ac t

Article history: VOSO4 is a promising cathode material for lithium-ion batteries owing to its polyanionic structure and the
Received 23 December 2021 polyvalency of vanadium. In this study, carbon nanotubes (CNTs) and graphene oxide (GO) were adopted for
Received in revised form 30 April 2022 modifying the microstructure and improving the overall performance of VOSO4. Before the chemical
Accepted 6 May 2022
synthesis of VOSO4, the CNTs were firstly combined with precursor and CNT-VOSO4@C was formed via a
Available online 10 May 2022
one-step chemical synthesis. The results showed that CNTs could improve the charge–discharge perfor­
mance of the VOSO4@C. The initial discharge specific capacity of CNT-VOSO4@C was up to 151.6 mAh·g−1 at
Keywords:
VOSO4 0.05 C, and even at 1 C the capacity could reach 66.06 mAh·g−1. The discharge–capacity retention rate is
Carbon nanotube 100% after a long circulation. Secondly, CNTs and GO were composited with the synthesized VOSO4@C and
Graphene oxide the obtained composites VOSO4@C-CNT and VOSO4@C-GO exhibited good electrochemical properties with
Lithium-ion battery initial discharge specific capacities of 135.7 and 141.8 mAh·g−1 at 0.05 C, respectively. This may be attributed
Cathode material to the high specific surface areas and conductivities of CNTs and GO. When grinding the composites, CNTs
and GO are uniformly distributed among the particles, forming bridges between the particles, that can
increase the electrical conductivity between the particles and reduce the volume expansion of electrode
materials. CNT-VOSO4@C exhibits the best modification effect. This study proposes a feasible approach for
applying VOSO4 in lithium-ion batteries, particularly under weak currents.
© 2022 Elsevier B.V. All rights reserved.

1. Introduction rate performance of LFP which exhibited an important reference

Energy is crucial for realizing the sustainable development of the
national economy and security [1]. Electrochemical energy is a key
area related to social development [2]. Lithium-ion batteries are the
most commonly used high-energy electrochemical energy storage
batteries in mobile power supply, electric vehicles, and power grid
energy storage [3–5]. The cathode material is a key material that
determines the performance of lithium-ion batteries. Its perfor­
mance and price substantially affect the application of lithium-ion
batteries. Furthermore, they restrict the development of lithium-ion
batteries [6–9]. LiFePO4 (LFP) is one of the most popular cathode
materials used in new energy electric and hybrid vehicles owing to
its high energy density, safety, and stability, endowed by its poly­
anionic structure and economical as well as environment-friendly
nature [6]. Furthermore, Bo Wang et al. [10,11] investigated the high
⁎
Corresponding author at: School of Optoelectronic Technology, Chengdu
University of Information Technology, Chengdu 610225, China.
E-mail address: cuixumei@163.com (X. Cui).
value for fast-charging batteries. For satisfying the requirements of
energy utilization, we cannot neglect the exploration as well as re­
search of other cathode materials. For example, VOSO4 lithium-free
cathode material has been inadequately reported thus far; however,
its strong inductive effect affords its high voltage potential [12–14].
Furthermore, compared with other cathode materials, its relatively
low preparation temperatures and short preparation times are
considerably advantageous in large-scale applications. Therefore,
performance regulation of its application in lithium-ion batteries
should be investigated. If 1-mol Li+ can be inserted and extracted,
the theoretical discharge specific capacity of VOSO4 is approximately
164.5 mAh·g−1, and it has values of high energy and power den­
sities [15].
However, the challenging issue is that VOSO4 has a large particle
size and there apppear large gaps between the particles owing to its
high humidity sensitivity and strong acidic preparation environ­
ment, which hinders the conduction of the electrode material [16].
The intercalation and extraction of Li+ or Na+ induce a substantial
volume expansion of electrode material, resulting in poor battery

https://doi.org/10.1016/j.jallcom.2022.165354
0925-8388/© 2022 Elsevier B.V. All rights reserved.
X. Cui, L. Zhang, Y. Hu et al.
performance in long cycles [17–19]. To solve these problems, surface
modification methods are useful as they can effectively promote the
conduction of electrons and facilitate the transfer of Li+ [20]. The
conductive carbon black added during the electrode preparation
enhances the conductivity and improves the electronic conduction
between the active material and conductive current collector [21].
Furthermore, surface coating with an amorphous carbon layer is a
fairly effective method [22]. For example, Chen et al. [23] used
sol–gel for preparing carbon coated LFP composites. Furthermore,
Gaberscek et al. [24] used citric acid as the carbon source via the
sol–gel method and Chi et al. [25] performed in situ polymerizations
of dopamine. Both prepared LFP particles coated with a thin-film
carbon layer on the surface, which enhanced the conduction of
electrons. Therefore, the material exhibited excellent charge–­
discharge performance. Furthermore, carbon nanotubes (CNTs) and
graphene are investigated by several researchers because of their
high electronic conductivity and the research on lithium-ion bat­
teries is very prominent [26–30]. For example, Bo Wang et al. [31,32]
prepared in situ CNT and amorphous carbon embedded-LFP micro­
spheres with excellent electrochemical properties. This can be at­
tributed to excellent kinetics because CNTs facilitated good
electronic contact with active materials and produced an efficient
conductive network for fast electron transport. The pore structure of
the CNT increased the wettability of the active site with the elec­
trolyte and facilitated rapid Li+ supplies. Tan et al. [33] used the
hydrothermal approach for successfully preparing LFP microspheres
with a three-dimensional (3D) CNT conductive network, which ex­
hibited a high Coulombic efficiency at 5 C. Wang et al. [34] used
reduced graphene oxide (GO) as the framework for preparing a 3D
network structure of LFP composite materials, in which composite
samples with 5 wt% GO exhibited a high discharge rate performance
at 20 C. Furthermore, Lain-Jong Li and Tsung-Wu Lin [35–37] sys­
tematically studied the electronic properties of inorganic materials
and CNT. They rationally explained the energy utilization based on
the energy band structure. To achieve a good electrochemical per­
formance of VOSO4 in lithium-ion cathode materials, preparing
micro–nanostructured composites using CNTs and GO is an effective
method. They developed the 3D network structure for preventing
the growth of crystal grains and anchoring VOSO4 to further alleviate
the volume expansion of the crystal lattice, thereby improving its
cycle stability [38–41]. The one-pot synthesis method was applied
for synthesizing and preparing VOSO4 with good performance in the
early stage [42]. However, its micron grain size and large inter­
granular space hinder the conduction of electrons and lithium ions,
resulting in poor performance of long circulation.
In this study, VOSO4 was modified using the composite method
with CNTs and GO owing to their advantageous 3D structure and
strong acid resistance characteristics. VOSO4@C with fine particles
was prepared by comprehensively investigating the influence of the
adding time of CNTs and GO during the chemical synthesis of
VOSO4@C. Subsequently, high reversible capacity, good rate perfor­
mance and electrochemical stability were obtained.
2. Experimental Part
Multifunctional oxalic acid was used in the one-step chemical
synthesis of the VOSO4@C composite material, which was developed
by considering the CNTs or GO as a 3D skeleton structure [42]. The
mechanism diagram of the corresponding preparation process is
depicted in Fig. 1. At first, 1.000-g vanadium peroxide was added to a
100-mL beaker. Then, 20-mL deionized water was added into the
beaker, which was heated and stirred at a constant temperature of
90 ℃ for ~20 min to allow uniform dissolution. Furthermore, the
CNTs or GO with a 5% mass of VOSO4 was added and stirred evenly.
Then, an appropriate amount of concentrated sulfuric acid was
added into the beaker drop by drop to acidify V2O5. VO2+ could be
2
Journal of Alloys and Compounds 914 (2022) 165354
obtained by stirring for ~20 min. Next, 10-mL deionized water was
added to dilute the aforementioned solution with no heating. Sub­
sequently, 1.3-g oxalic acid was added as a reducing agent and coated
carbon source. The obtained solution was heated and evaporated at
90 ℃ until it became a colloid. Dark gray VOSO4@C composite ma­
terial was obtained after calcining the colloid at 280 ℃ for 2 h under
an N2 atmosphere. The composite materials with the CNT and GO
were named CNT-VOSO4@C and GO-VOSO4@C, respectively. The
composite material without the CNT or GO was named VOSO4@C.
Furthermore, the aforementioned prepared VOSO4@C were
physically compounded with 5 wt% CNT as well as GO and the
composite materials were named VOSO4@C-CNT and VOSO4@C-GO,
respectively.
The aforementioned compounded materials were tested using a
X-ray diffraction (XRD, Bruker, D8 advance) with Cu Kα radiation for
acquiring crystal structure information at a scan rate of 0.06º min–1
within a 10º–90º 2θ range. X-ray photoelectron spectroscopy (XPS,
Thermo Escalab 250Xi) test was performed. The morphology and
elemental distribution of the composite samples were obtained via
scanning electron microscopy (SEM, JEOL FESEM 6700 F). A Tecnai
G2 F20 S-TWIN electron microscope was used to examine high-
microimages and selected area electronic diffraction (SAED) images.
The surface areas of the samples were evaluated using JW-BK100A
Brunauer–Emmett–Teller.
CR2016 half-cells were used for evaluating the electrochemical
performance of the composite materials with Li as the anode. The
electrode sheets with the Al foil as the substrate comprised
VOSO4@C compounded materials, super P carbon black and PVDF
with a mass ratio of 8:1:1 and N-methyl-2-pyrrolidone (NMP) as the
solvent. After the coating of the electrode sheet, it was dried under
vacuum for 10 h at 107 °C. The cathode sheets were rolled six times
and were cut into disks with a diameter of 14 mm and were dried
under vacuum again at 107 °C for 2 h. The electrolyte was 1-M LiPF6
solution with EC:DMC:EMC (volume ratio of 1:1:1) as solvent.
CR2016 half-cells were assembled in an argon-protected glove box
(H2O, O2 < 0.01 ppm). After 24 h, charge–discharge tests were per­
formed in the assembled cells using a LAND battery test system
(Wuhan, China) at voltages of 2.0–4.3 V and 0.05, 0.1, 0.2, 0.5, and 1 C
rates. The electrochemical impedance spectroscopy (EIS) and cyclic
voltammetry (CV) were tested using an electrochemical workstation
(a Bio-Logic SP-150) at a signal amplitude of 5-mV as well as a fre­
quency range of 0.01–100 kHz for EIS and at a scanning rate of
0.1 mV/s for CV.
3. Results and discussion
The X-ray diffraction (XRD) patterns of the prepared composite
samples are depicted in Fig. 2. All the samples indicate sharp XRD
peaks corresponding to the VOSO4 standard card (PDF#86–0125) of
the orthogonal Pnma space group, indicating that the prepared
composites have an excellent crystalline structure with no impurity
phases [18]. The XRD peaks corresponding to carbon layer are not
detected in all the samples, indicating the amorphous nature of the
coated carbon layer decomposed by oxalic acid. Additionally, in the
XRD patterns of the CNT-VOSO4@C, GO-VOSO4@C, VOSO4@C-CNT,
and VOSO4@C-GO samples with 5 wt% CNT or GO, the XRD peaks
corresponding to GO or CNTs are also not detected. There is no dif­
ference between the four samples, which may be caused by the low
intensity of GO or CNTs. Moreover, this indicates that the adding
time of CNTs and GO during the compounding process of VOSO4@C
does not affect the crystallization of VOSO4.
XPS was used to determine the surface chemical composition and
chemical state of the CNT-VOSO4@C composite material. The test
results are depicted in Fig. 3. In Fig. 3(a), the spectrum peaks of O 1 s,
V 2p, N 1 s, C 1 s, S 2 s, and S 2p corresponding to CNT-VOSO4@C
composites can be clearly observed. The high-resolution spectra and
X. Cui, L. Zhang, Y. Hu et al.
Fig. 1. The mechanism diagram of the preparation process of the composite material samples.
Fig. 2. X-ray diffraction patterns of the composite samples.
Gaussian peaks of C 1 s, S 2p, and V 2p are depicted in Fig. 3(b-d).
According to Fig. 3(b), the positions of the binding energy peaks
appearing at 284.7, 285.7, and 289.2 eV represent the C–C, C–O, and
C]O peaks, respectively and their contents: 62.2%, 31.3%, and 6.5%
are determined using normalization analysis [43,44]. Fig. 3(c) de­
picted the characteristic peaks of S 2p. The two spin-orbit double
peaks of S 2p3/2 and S 2p1/2 are at 169.34 and 170.5 eV, respectively,
confirming the existence of the S–O bond [45]. In Fig. 3(d), the high-
resolution XPS spectrum of V 2p comprises two components located
at 517.8 and 525.2 eV, because of the spin-orbit splitting of V 2p3/2
and V 2p1/2, indicating the characteristic peak of V in the + 4 oxi­
dation state and the formation of the V–O bond [46].
SEM was performed on the prepared composite samples to ob­
serve the morphology and structure of the samples (Fig. 4). Based on
the comprehensive analysis of the figures, the particle size dis­
tribution of sample VOSO4@C is very even; however, the particle size
is ~3 µm (Fig. 4(a)). Fig. 4(b–e) depict the SEM images of the CNT-
VOSO4@C, GO-VOSO4@C, VOSO4@C-CNT and VOSO4@C-GO compo­
sites, respectively. Moreover, the CNT-VOSO4@C, and GO-VOSO4@C
composite particles are smaller than VOSO4@C and the CNTs pene­
trate or entangl between the particles, indicating that the particle
size ranges from 100 to 500 nm [47]. Furthermore, the particle size
of GO-VOSO4@C is very small (Fig. 4(c)), indicating that the GO ef­
fectively blocks the continuous growth of particles during the crys­
tallization process (the schematic diagram of GO-VOSO4@C
composite formation is presented in Fig. 4(f)) [29]. The reduction of
grain size can increase the specific surface area of the samples. To
verify this result, the specific surface areas of the samples were
3
Journal of Alloys and Compounds 914 (2022) 165354
determined. The results showed that the specific surface areas of
CNT-VOSO4@C, GO-VOSO4@C, and VOSO4@C were 18.957, 56.895,
and 2.931 m2/g, respectively. Fig. 4(d) shows that the CNTs are uni­
formly adsorbed on the surface of VOSO4@C particles, which is
beneficial to allow electron transport between particles. GO na­
nosheets in VOSO4@C-GO composite material are not clearly ob­
served (Fig. 4(e)) probably because its content is too small or too thin
to be easily identified. However, the particles are very evenly dis­
tributed [48]. To verify the element distribution in the sample, en­
ergy-dispersive X-ray spectroscopy (EDS) elemental distribution
scanning was performed on the CNT-VOSO4@C composite material
(Fig. 5). Fig. 5 shows that O, C, S and V elements are evenly dis­
tributed in the sample, and the distribution density of S and V ele­
ments is nearly the same, implying that the molar ratio of the S and
V elements is 1:1. Furthermore, the distribution of the C element is
consistent with that demonstrated via the SEM image, indicating
that the coated carbon layer is evenly distributed on the surface of
the sample.
Subsequently, the microscopic morphology of the particles
should be observed. Fig. 6(a) shows the action mechanism and
structure diagram of the CNTs 3D network structure in CNT-
VOSO4@C composites. Using the high-resolution transmission elec­
tron microscopy (HR-TEM) technique, high-resolution images of
CNT-VOSO4@C material were obtained effectively. Fig. 6(b) shows
that the particle size is not uniform; however, there is obvious CNTs
winding. In Fig. 6(c), the lattice fringes presented inside the particle
corresponding to the (020) crystal plane of the pure VOSO4 crystal
phase with the 0.3124-nm lattice spacing. The surface of the parti­
cles is coated with an amorphous carbon layer with a 5.6-nm
thickness. Furthermore, the amorphous carbon layer, with an ap­
proximate thickness of 4.2 nm, is coated on the surface of poly­
crystalline or amorphous CNTs (Fig. 6(d)). To confirm the crystal
forms, selected area electron diffraction (SAED) characterizations are
conducted (Fig. 6(f)). The presented circular diffraction rings corre­
spond to the polycrystalline characteristic of the CNTs (Fig. 6(e)).
Furthermore, the SAED pattern in Fig. 6(g) shows that the particle of
VOSO4 is a single crystal.
The lithium storage performance of the composites was in­
vestigated using RC2016 batteries. The initial discharge curves at
0.05-C current density are depicted in Fig. 7(a). The figure shows that
the discharge platform is consistent around 2.7 V; moreover, the
discharge specific capacity values of VOSO4@C, CNT-VOSO4@C, GO-
VOSO4@C, VOSO4@C-CNT, and VOSO4@C-GO are 128.7, 151.6, 109.8,
135.7, and 141.8 mAh·g−1 respectively. These values show that the
CNTs addition before synthesizing VOSO4 most prominently im­
proves the discharge capacity. The addition of CNTs before synthe­
sizing VOSO4 reduces the particle size, thereby increasing the
specific surface area and electron conductivity of the material [49].
However, GO-VOSO4@C exhibits the worst discharge performance,
X. Cui, L. Zhang, Y. Hu et al. Journal of Alloys and Compounds 914 (2022) 165354

Fig. 3. XPS spectrums of CNT-VOSO4@C composite material: (a) XPS full spectrum, (b) C 1 s, (c) S 2p, and (d) V 2p.

Fig. 4. SEM images: (a) VOSO4@C, (b) CNT-VOSO4@C, (c) GO-VOSO4@C, (d) VOSO4@C-CNT, (e) VOSO4@C-GO and (f) schematic of GO-VOSO4@C composite formation.

4
X. Cui, L. Zhang, Y. Hu et al.
Fig. 5. EDS mapping images of CNT-VOSO4@C composite material: (a) SEM image, (b) O element, (c) C element, (d) S element, and (e) V element.
which may be because of the small particle size and insufficient
packing density of the active material. Furthermore, the carbon layer
covered with the active material is not sufficiently thick to ensure
good electrical conductivity/contact between particles. Fig. 7(a)
shows that a high discharge specific capacity yields a high platform
voltage. The discharge specific capacities of VOSO4@C-CNT and
VOSO4@C-GO samples are considerably higher than that of the ori­
ginal VOSO4@C, which can be attributed to the addition of CNTs and
GO, respectively. These additions increase the contact between the
particles and facilitate the conduction of electrons by effectively
reducing volume expansion [20,31,33].
Fig. 7(b) shows the discharge specific capacity of each sample at
the current densities of 0.05, 0.1, 0.2, 0.5, 1, and 0.05 C, respectively.
Based on these results, the compounding of GO and CNTs improves
the discharge specific capacity of CNT-VOSO4@C, VOSO4@C-CNT, and
VOSO4@C-GO samples to a certain extent, of which the discharge
capacity of CNT-VOSO4@C is better than that of other samples. At the
current densities of 0.05, 0.1, 0.2, 0.5, 1, and 0.05 C, its average dis­
charge specific capacities are 108.8, 97.36, 89.34, 77.26, 66.06, and
110.54 mAh·g−1, respectively. However, the discharge specific capa­
cities of the original VOSO4@C are 69.8, 58.78, 48.66, 34.4, 19.16, and
63.62 mAh·g−1 respectively, which are attributed to the enhance­
ment of electron conduction and lithium-ion migration velocity
caused by CNT compounding and the corresponding interlaced pore
networks. Furthermore, adding CNTs before synthesizing VOSO4
reduces the particle size and boosts the electron conduction be­
tween VOSO4 particles, forming a 3D conductive network structure.
The charge and discharge performance of the sample GO-VOSO4@C
is not improved；however, it exhibits worse electrochemical per­
formance than VOSO4@C, which may be because the particles size
are too small. The carbon coating thickness is insufficient, affording
low conductivity and poor electrochemical performance [50]. To
characterize the influence of compound modification on circulation
life, the cyclic performance of the samples were tested at 0.2 C with
30 cycles (Fig. 7(c)). Fig. 7(c) shows that the initial discharge specific
capacities of VOSO4@C, CNT-VOSO4@C, GO-VOSO4@C, VOSO4@C-CNT
and VOSO4@C-GO composite samples within the 30 cycles are 53.2,
84.7, 43.9, 69.9 and 71.2 mAh·g−1, respectively. Furthermore, after 30
cycles of charge and discharge, the discharge specific capacity of
CNT-VOSO4@C remains ~85.2 mAh·g−1, with a capacity retention rate
of 100%. Its Coulombic efficiency is maintained at ~100% during the
entire circulation cycle, indicating that CNTs have a very prominent
modification effect on the VOSO4, and CNT-VOSO4@C composite
material exhibits good reversibility and stable crystal structure [51].
Other composite materials have different degrees of capacity
5
Journal of Alloys and Compounds 914 (2022) 165354
attenuation. After circulation, the capacity retention ratios of
VOSO4@C, GO-VOSO4@C, VOSO4@C-CNT, and VOSO4@C-GO are
90.22%, 92.7%, 89.0%, and 95.8%, respectively, which may be because
the particles are too large, thus causing particle damage during Li+
extraction or the particles are too small [50], causing severe ag­
glomeration and reduction of electronic conductance, further
proving that compound modification can effectively improve the
electrochemical properties of VOSO4@C. Furthermore, the structure
and performance of the recently reported VOSO4 cathode materials
are compared and the differences are presented in Table 1. VOSO4@C
electrode materials with excellent performance can be obtained
using carbon composites, particularly in terms of rate capability and
cycling stability.
To analyze the influence of compound modification on the
electrochemical properties of VOSO4@C, CV and EIS tests were used
to characterize the electrochemical reactivity of the five samples.
The test results are depicted in Fig. 7(d). The five samples show good
CV curves at a scanning rate of 0.1 mV·s−1. All samples have a pair of
redox peaks at around 2.87 (marked A) and 2.62 V (marked B), which
corresponds to the V3+/V4+ redox. The oxidation peak in the charging
process has peak-splitting phenomenon, indicating that the oxida­
tion is conducted in steps. However, the phenomenon in CNT-
VOSO4@C is not prominent, which indicates that CNT-VOSO4@C
exhibits fast kinetics. The peak-splitting phenomenon in the reduc­
tion process is not prominent, allowing the electrode have a better
discharge platform. Compared with the other four samples, CNT-
VOSO4@C shows the best electrochemical performance; the poten­
tial difference between the oxidation peak and reduction peak is
~0.3 V, and the redox peak is the sharpest with the highest peak
value, indicating that the CNT-VOSO4@C has excellent electro­
chemical reversibility and small polarization [52]. The CV curve of
GO-VOSO4@C shows a steamed bread peak with a potential differ­
ence of ~0.38 V, showing poor electrochemical activity. This finding
is consistent with the results obtained from the aforementioned
charge–discharge curve. The results show that the addition of GO
before synthesizing VOSO4 reduces the particle size. However, the
poor electrochemical performance may be because of the agglom­
eration of the particles or the thin carbon coating.
Fig. 7(e, f) depict the EIS curves of different composite materials
and the corresponding equivalent circuit diagram. The Nyquist
curves in Fig. 7(e) comprise a semicircular arc in the high-frequency
region, a quasisemicircular arc in the middle- frequency region and a
straight line in the low-frequency region. Fig. 7(f) depicts the
equivalent circuit diagram, in which RS, i.e., ohm resistances, corre­
spond to the part where the impedance curve intersects with the
X. Cui, L. Zhang, Y. Hu et al.
Fig. 6. (a) The action mechanism and structure diagram of the CNT 3D network structure in CNT-VOSO4@C composites, (b, f) TEM of CNT-VOSO4@C, (c, d) HRTEM of CNT-
VOSO4@C, (e, g) SAED of CNT-VOSO4@C.
horizontal axis in the high-frequency region. RSEI, i.e., the resistance
of the solid electrolyte interface (SEI) film corresponds to the
semicircle in the high-frequency region; Rct, i.e., the charge transfer
resistance corresponds to the semicircle in the intermediate fre­
quency region; ZW, i.e., Warburg impedance represents the diffusion
of Li+; and Constant-Phase Element (CPE) represents a double layer
capacitor and SEI capacitor [53,54].
Impedance parameters can be obtained using the Bio-Logic
software fitting (Table 2). The ohm resistances (RS) of the composite
materials VOSO4@C, CNT-VOSO4@C, GO-VOSO4@C, VOSO4@C-CNT,
and VOSO4@C-GO are very close, because the same electrolyte,
aluminum foil, and lithium metal sheets are used to assemble the
batteries. The solid electrolyte impedances (RSEI) of the composite
materials are 200.3, 82.89, 260.4, 120.4, and 117.6 Ω, respectively,
and charge transfer resistances (Rct) are 72.07, 19.21, 534.9, 59.57,
and 12.48 Ω respectively. RSEI and Rct of the CNT composite material
6
Journal of Alloys and Compounds 914 (2022) 165354
and VOSO4@C-GO sample are both reduced, showing that in the
electrochemical reaction process of these samples, Li+ passing
through the SEI film, mass transfer, and charge transfer between the
electrode interfaces are much easier [28,55]. Among them, the RSEI of
CNT-VOSO4@C is minimal, which is only 82.89 Ω. Furthermore,
VOSO4@C-GO has the smallest Rct value of 12.48 Ω. All these show
the improvement of the electrochemical properties. The total im­
pedance of the GO-VOSO4@C sample is relatively high, which may be
because that GO is added before synthesizing VOSO4@C and it sub­
stantially reduces the particle size of VOSO4. The limited carbon
source of coating causes the uneven distribution of carbon layers on
the surface of the GO-VOSO4@C particles and the severe agglom­
eration of nanoparticles, thereby increasing the impedance.
In conclusion, the CNT-VOSO4@C composite material exhibits the
best electrochemical performance. The addition of CNTs before
synthesizing VOSO4 effectively reduces the particle size of VOSO4,
X. Cui, L. Zhang, Y. Hu et al. Journal of Alloys and Compounds 914 (2022) 165354

Fig. 7. Electrochemical performance of composite materials: (a) initial discharge curves, (b) rate performance, (c) long cycle performance and Coulombic efficiency, (d) CV curves,
(e) EIS impedance curves, and (f) impedance spectrum equivalent circuit.

Table 1
Comparison of the structure and performance of VOSO4 electrode with those in literature.

Electrode Capacity (mAh g−1) Current density Potential window (V) Synthetic route Ref.

1st cycle 5th cycle

β-VOSO4 148 (~0.9 Li+) 90(~0.55Li+) C/20 2.4–3.1 n-butyllithium route [56]
α-, 128 (~0.8 Na+) 96 (~0.6 Na+) C/20 1.0–3.0 a simple dehydration [57]
β-VOSO4 144 (~0.9 Na+) 64 (~0.4 Na+) C/20
A2VO(SO4)2 110 (~1.1 Li+) Charge, C/20 2.0–4.9 (Li, Na)2SO4 + VOSO4·xH2O, ball-milling and annealing [19]
(A = Li, Na) 50 (~0.5 Li+) Discharge.
95 (~1.1 Na+) Charge, C/30 2.0–4.8
60 (~0.7 Na+) Discharge.
125.7 (~1.1 Li+/Na+) Charge, C/30 2.0–5.0
80 (~0.7 Li+/Na+) Discharge.
β-VOSO4 163.7 120 C/20 2.0–4.3 One-pot synthesis of VOSO4@C [42]
(~0.99 Li+) (~0.73 Li+)
CNT/GO β-VOSO4 151.6 66.06 – 2.0–4.3 CNT or GO modified VOSO4@C Our work
(~0.92 Li+) C/20 (~0.40 Li+) 1 C

7
X. Cui, L. Zhang, Y. Hu et al. Journal of Alloys and Compounds 914 (2022) 165354

Table 2
Fitting results for the EIS data presented in Fig. 7(f).
Sample Rs (Ω) RSEI (Ω) Rct (Ω)
VOSO4@C 4.744 200.3
CNT-VOSO4@C 5.546 82.89
GO-VOSO4@C 4.819 260.4 534.90
VOSO4@C-CNT 9.461 120.4
VOSO4@C-GO 8.015 117.6
thereby increasing the electron conduction and lithium-ion migra­
tion velocity between particles or within particles, and greatly slows
down the volume expansion of the composite material, which is
conducive to realizing the optimum performance of the VOSO4 li­
thium-ion battery.
4. Conclusion
CNTs and GO with high activity and conductivity were used as
composite additives for improving the overall performance of the
VOSO4@C. When CNTs and GO are added before the chemical
synthesis of the VOSO4@C materials, both could effectively reduce
the particle size of the composites. CNTs improve the charge–­
discharge performance of the VOSO4@C, with the initial discharge
capacity reaching 151.6 mAh·g−1 at 0.05 C. Moreover, CNTs can
maintain a discharge capacity of 66.06 mAh·g−1 at a high current
density of 1 C with a discharge capacity retention of 100% during
long circulation. This fully indicates that the addition of CNTs yield a
3D conductive network structure and improves the electronic con­
ductivity as well as lithium-ion transport, which is confirmed via CV
and EIS tests. CNTs and GO could be compounded after the chemical
synthesis of the VOSO4@C materials. And the composite materials
exhibit very good electrochemical performance with an initial dis­
charge specific capacity of 135.7 and 141.8 mAh·g−1, respectively, at
0.05 C. Furthermore, the GO compounded sample has the smallest
Rct value of 12.48 Ω.
Therefore, CNTs and GO can be directly used as conductive
composite additives of the VOSO4@C under certain conditions for
maximizing the electrochemical performance. As a lithium-free
cathode material, VOSO4 has important application prospects in the
field of weak current.
CRediT authorship contribution statement
Xumei Cui: Conceptualization, Supervision, Writing – review &
editing. Liu Zhang: Conceptualization, Methodology, Data curation,
Software, Writing – original draft, Visualization. Yun Hu:
Methodology, Formal analysis. Dingyu Yang: Methodology,
Investigation. Jianxin Zou: Methodology, Investigation.
Declaration of Competing Interest
The authors declare that they have no known competing fi­
nancial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
The authors thank the Key Project of Science and
Technology Department of Sichuan Province, China,
(no. 2017JY0038), Key Project of Vanadium and Titanium Resource
Comprehensive Utilization Key Laboratory of Sichuan Province,
China, (no. 2020FTSZ02), and the Scientific Research Fund of
Chengdu University of Information Technology, China,
(no. KYTZ202170) for their financial support.
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