www.nature.

com/scientificreports

OPEN Controllable synthesis

of sphere‑shaped interconnected
interlinked binder‑free
nickel sulfide@nickel foam
for high‑performance
supercapacitor applications
Batool Taher Al‑Abawi1*, Nazish Parveen1* & Sajid Ali Ansari2

The fabrication of energy storage electrode materials with high specific capacitance and rapid charge–
discharge capability has become an essential and major issue of concern in recent years. In the present
work, sphere-shaped interconnected interlinked binder-free nickel sulfide (NiS) grown on the surface
of a three-dimensional nickel foam (3DNF) was fabricated by a one-step solvothermal method under
optimized synthesis conditions, including different solvents, amounts of sulfur, and experimental
reaction times. The fabricated binder-free SS-NiS@3DNF-E electrodes were characterized by a
range of spectroscopic and microscopic techniques and further evaluated for their comparative
electrochemical supercapacitive performance in half-cell assembly cells. The optimized sphere-
shaped interconnected interlinked binder-free SS-NiS@3DNF-E-3 electrode showed an outstanding
specific capacitance of 694.0 F/g compared to SS-NiS@3DNF-E-1 (188.0 F/g), SS-NiS@3DNF-E-2
(470.0 F/g), and SS-NiS@3DNF-E-4 (230.0 F/g) as well as excellent cycling stability up to 88% after
6700 continuous charge–discharge cycles, with an energy density of 24.9 Wh/kg at a power density of
250.93 W/kg. The obtained results demonstrate that the interconnected interlinked binder-free NiS@
nickel electrode is a potential candidate for energy storage applications.

In recent years, due to the depletion of fossil fuels, increase in the energy demand for vehicle power applications,
and growing market of small electronic devices, environmental issues such as pollution and climate change have
become more p ­ rominent1,2. Therefore, society is turning to sustainable and renewable energy sources, includ-
ing solar energy, wind power, and geothermal e­ nergy1–4. These sources, however, are limited to specific times,
conditions, such as sunny or rainy, and locations. As a result, clean energy conversion and storage technologies,
including batteries, electrochemical supercapacitors (ESs), and fuel cells, have received much attention. These
technologies are used in tablets, smartphones, cameras, and hybrid vehicles, and they play an important role as
energy sources in daily l­ ife1–6.
Supercapacitors (SCs) have recently attracted much attention in the power field due to their high power
density, outstanding cycling stability, fast charge/discharge process, and low cost. In addition, the arrangement
of an SC between a battery with high energy storage capacity and a traditional capacitor with high energy density
results in better electrochemical performance in a variety of a­ pplications5,6. ESs are employed in devices that
can store a significant quantity of energy in a short period, such as hybrid platforms for trucks and buses, wind
turbine and solar renewable energy systems, pulsed laser technology, and mobile p ­ hones1,2,6. The first ESs were
reported in a patent filed by Beaker in 1957, which specified a capacitor based on large surface area c­ arbon7.
SCs are classified into three types based on the energy storage mechanism: electric double-layer capacitors
(EDLCs), pseudocapacitors, and hybrid SCs, which combine both types of capacitors. In EDLCs, energy is
stored through an adsorption/desorption process in which the ions of the electrode electrostatically interact

1
Department of Chemistry, College of Science, King Faisal University, P.O. Box 380, Hofuf 31982, Al‑Ahsa, Saudi
Arabia. 2Department of Physics, College of Science, King Faisal University, P.O. Box  400, Hofuf  31982, Al‑Ahsa,
Saudi Arabia. *email: [email protected]; [email protected]

Scientific Reports | (2022) 12:14413 | https://doi.org/10.1038/s41598-022-18728-1 1

Vol.:(0123456789)
 www.nature.com/scientificreports/

with the e­ lectrolyte6,8. In pseudocapacitors, the charge is stored through a redox reaction that occurs during
the charge/discharge ­process9–12. In addition, SCs are categorized as symmetric or asymmetric based on the
electrode configuration when identical or different electrode materials are u ­ sed8,9,13. The performance of SCs is
strongly influenced by the materials used in the electrodes. Carbon-based materials, such as activated carbon
(AC), graphene, and carbon nanotubes (CNTs), are utilized in EDLCs because they have a long cycle life and
strong electrical conductivity, although their capacitance is usually l­ ow1,5. In contrast, pseudocapacitors mostly
use metal oxides (MOs) and conducting ­polymers1,5. Ruthenium oxide ­(RuO2) is the most investigated elec-
trode material due to its high specific capacitance, long cycle life, and high ionic conductivity. Its usage in SCs is
restricted, however, due to its high cost and ­toxicity14. Therefore, transition MOs and their hydroxides are used
as alternative materials, such as manganese oxide (­ MnO2), nickel oxide (NiO), Ni(OH)2, cobalt oxide (­ Co3O4),
Co(OH)2, and vanadium oxide (­ V2O5)1–4,14. Because of their low cost, eco-friendliness, good theoretical specific
capacitance, and low resistance, these materials are useful for constructing high energy density devices. How-
ever, transition metal hydroxides/oxides suffer from poor cycling stability and low conductivity, which result
in decreased electron transport and relatively low theoretical c­ apacity2,3. Recently, there has been a significant
increase in research into transition metal sulfides (TMSs), such as ­CoS2, ­FeS2, MnS, CuS, and NiS, as promising
materials for SC e­ lectrodes8,11,15,16 because of their advantages over their oxides, such as cost effectiveness, low
environmental impact, excellent electrical conductivity, various valence states that provide sites for electro-
chemical activity, and higher ­capacitance16. Moreover, the shape, size, and morphology of metal sulfide-based
electrode materials can influence their electrochemical performance. The electrodes based on metal sulfides and
hydroxides operate on the faradic reaction mechanism as well as store energy over the electrode surface through
reversible redox reactions, which is the main reason why they provide better electrochemical performance than
the double-layer-based c­ apacitors16. For example, a MnS composite with reduced graphene oxide (rGO) has
been evaluated for use in SCs, and this electrode produces long cycling stability and high specific c­ apacitance17.
α-MnS/N-rGO was designed by Quan et al.18 as a cathode electrode material in asymmetric SC applications and
delivered an energy density of 27.7 Wh k­ g-1 at a power density of 800 W kg. Copper sulfide (CuS) has been used
as an electrode material, but its applications are limited by its low energy density and poor cycling stability, which
must be ­improved19. To solve these problems, introducing a carbon material, which has a high power density
and good cycling stability, into CuS preparation can enhance the performance of S­ Cs20. BoopathiRaja et al.21
stated that a CuS/rGO composite electrode results in excellent long-term cycling stability (97% retention) and
exhibits a 1604 ­Fg-1 capacitance at a current density of 2 ­Ag-1. Among all the above metal-based sulfides, NiS in
particular has attracted considerable attention in the fields of energy storage, including batteries and SCs, due to
its excellent physical and chemical properties and different phases, such as ­Ni7S6, ­Ni9S8, α-NiS, β-NiS, ­Ni3S4, and
­NiS2, most of which exist at room t­ emperature22–24. Among these phases, NiS (α-NiS, β-NiS) is the most stable
and sulfur-rich combination among the forms of nickel ­sulfides22,23. The phases are affected by temperature, and
α-NiS with a rhombohedral crystal structure appears at low ­temperatures22, while β-NiS in a hexagonal form
occurs at high t­ emperatures23,24. Therefore, NiS is chosen for electrode purposes based on its phase diagram,
which shows a rich sulfur structure and phase stability at normal temperature, which are the major points to
consider when using NiS as a next-generation energy storage-based electrode material. For these reasons, NiS
has been used as an effective electrode material due to its strong characteristics, including high conductivity,
thermal stability, and slower volumetric expansion during the charge–discharge p ­ rocess22,24. Few works have
25
been reported on NiS with different morphologies, such as that of Bhagwan et al. , who synthesized β-NiS (3D)
microflower electrodes with hierarchical geometries using a hydrothermal method, which exhibited high cycling
stability and a specific capacitance of 1529 F/g. Similarly, Naresh et al.22 prepared NiS on nickel foam by hydro-
thermal treatment and investigated NiS with different morphologies by varying the reaction time and studying
its role in the capacitive performance. Parveen et al.6 reported that hydrothermally synthesized shape-controlled
hierarchical flower-like nickel sulfide exhibited an excellent specific capacitance of 603.9 F/g with a high cycling
retention of 89% in aqueous electrolytes. Guan et al.16 and Balakrishnan et al.26 synthesized microflower-like
NiS via a solvothermal method using Ni(OH)2 as precursors. The fabricated electrode delivered a 1122.7 F ­ g-1
-1
specific capacitance at a 1 A ­ g current density and excellent cycling stability after 100 cycles. Due to the unsta-
ble structure and effective sulfur content in the NiSsystem, the electrochemical properties (capacitance, cycling
stability) of NiS in SCs are restricted. Subsequently, to address these issues, researchers attempted to synthesize
NiS with varying sulfur concentrations under different conditions and study the impacts on the morphology to
achieve excellent performance.
In the present work, a detailed study of the morphological changes of binder-free NiS@nickel foam and its
effects on the ES performance is presented. NiS is grown on a three-dimensional conducting substrate via a
simple and cost-effective solvothermal method and can act as a binder-free high-performance electrode mate-
rial for SC applications. Different morphologies can be obtained through different solvents and by varying the
amount of sulfur during the synthesis procedure. The fabricated sample with sphere-shaped interconnected
interlinked binder-free NiS grown at the surface of 3DNF using 0.15 mM thiourea as the sulfur precursor
is abbreviated as the SS-NiS@3DNF-E-1 electrode. The fabricated sample with sphere-shaped interconnected
interlinked binder-free NiS grown at the surface of 3DNF using 0.80 mM thiourea as the sulfur precursor is
abbreviated as the SS-NiS@3DNF-E-2 electrode. The fabricated sample with sphere-shaped interconnected inter-
linked binder-free NiS grown at the surface of 3DNF using 1.50 mM thiourea as the sulfur precursor is abbrevi-
ated as the SS-NiS@3DNF-E-3 electrode. The fabricated sample with sphere-shaped interconnected interlinked
binder-free NiS grown at the surface of 3DNF using 2.50 mM thiourea as the sulfur precursor is abbreviated as
the SS-NiS@3DNF-E-4 electrode. The electrochemical properties of the synthesized electrodes were evaluated
using a three-electrode system by cyclic voltammetry (CV) and the galvanostatic charge–discharge (GCD)
method in a 2 M KOH electrolyte solution. The optimized SS-NiS@nickel electrode showed an outstanding

Scientific Reports | (2022) 12:14413 | https://doi.org/10.1038/s41598-022-18728-1 2

Vol:.(1234567890)
www.nature.com/scientificreports/

Figure 1.  SEM images of the (a–c) SS-NiS@3DNF-M electrode, (d–f) SS-NiS@3DNF-E electrode, and (g–i)
SS-NiS@3DNF-P electrode.

specific capacitance of approximately 694.0 F/g with an excellent cycling stability (88%) after 6700 continuous
charge–discharge cycles.

Results and discussion
Effect of the solvent on morphological changes in SS‑NiS@3DNF electrodes.  To understand
the solvent effect on the morphology of SS-NiS@3DNF electrode nanostructures, we investigated this effect by
changing the solvent during synthesis at fixed ethylene glycol amount, reaction temperature, and reaction time.
When the synthesis proceeds in the presence of methanol, a few-layered sheet-like morphology of the NiS grown
on a conductive 3DNF (Supplementary Fig. S1 online) substrate (SS-NiS@3DNF-M, Fig. 1a) is observed. At high
magnification, the SEM image displayed in Fig. 1b shows that the SS-NiS@3DNF-M (area marked by the yellow
dotted line) is composed of few-layered nanosheets with a diameter of 2–3 µm and has macro- and microsized
pores inside the structure. In contrast, when the solvent is changed from methanol to ethanol during the solvo-
thermal experiment, the SEM image of the SS-NiS@3DNF-E electrode shows an irregular spherical morphology
(Fig. 1c) with a size of 10 µm to 15 µm (Fig. 1d). However, at higher magnification, the SEM image (Fig. 1d) of
SS-NiS@3DNF-E shows that each sphere is interconnected and interlinked to each other, which is beneficial for
contact of the electrolyte and active electrode material surface during the electrochemical process. In addition,
the SS-NiS@3DNF-P electrode displays an aggregated sphere-shaped morphology (Fig. 1e and f).
SEM images of the other electrode, i.e., SS-NiS@3DNF-E-1, SS-NiS@3DNF-E-2, SS-NiS@3DNF-E-3, and
SS-NiS@3DNF-E-4 prepared using different amounts of thiourea as the sulfur precursor, were also examined by
FESEM, and the results are displayed in Fig. 2. The SEM analysis results show that thiourea played an important

Scientific Reports | (2022) 12:14413 | https://doi.org/10.1038/s41598-022-18728-1 3

Vol.:(0123456789)
 www.nature.com/scientificreports/

Figure 2.  High- and low-magnification SEM images of (a) SS-NiS@3DNF-E-1, (b) SS-NiS@3DNF-E-2, (c)
SS-NiS@3DNF-E-3, and (d) SS-NiS@3DNF-E-4.

role in controlling the morphology and size of the nickel sulfide grown at the surface of 3DNF; thiourea is a very
inexpensive sulfur precursor and is easily available compared to other sulfur-based c­ ompounds27.
Figure 2a shows an SEM image of the SS-NiS@3DNF-E-1 electrode, which shows an aggregate intercon-
nected sheet-like structure deposited on 3DNF, whereas an irregular sphere-shaped morphology was observed
in the case of the SS-NiS@3DNF-E-2 electrode (Fig. 2b). With a further increment of the thiourea concentration
from 0.15 to 1.5 mM, the morphology of the SS-NiS@3DNF-E-3 electrode remains the same as that of the SS-
NiS@3DNF-E-2 electrode, but the size of the spherical particles entirely changes into a spherical morphology
with a uniform structure between 2 and 4 µm in size (Fig. 2c and Supplementary Fig. S2 online). The figure
shows that all sphere shapes were interconnected and interlinked to each other, which helped with contact of the
electrolyte and active electrode material surface during the electrochemical supercapacitive process. Figure 2d
shows an SEM image of the SS-NiS@3DNF-E-4 electrode, which displays irregular morphology and shape, and
the shape is not very clear compared to the other electrodes. These results show that the appropriate concentra-
tion of thiourea played an important role in the formation of well-defined SS-NiS@3DNF, which is discussed in
detail in the following synthesis mechanism section.
The above morphology was further examined by the TEM and HRTEM analysis which shows that the dark
colored spheres interlinked with the other spheres through the thin sheets (Supplementary Fig. S3 online). The
HRTEM images shows that the grown nickel sulfide at the surface of the three dimensional nickel foam has
well-ordered crystalline structure which well matched with previously reported work 22,25.

Proposed reaction mechanism of the SS‑NiS@3DNF electrode.  Morphological studies support

the role of the solvent and the effect of the sulfur precursor concentration as follows. The nickel salt and thio-
urea were dissolved in an ethylene glycol and ethanol solvent, which subsequently formed strong complexation
between nickel ions (­Ni2+) and thiourea, leading to the formation of a nickel-thiourea complex compound,
which subsequently decomposed during the thermal process. Additionally, thermal treatment prevents the pro-
duction of a large number of S­ 2− ions in the solution, which provides favorable conditions for the formation of
nickel sulfide products. The above statements can be expressed in terms of the following suggested r­ eaction27:
Ethylene glycol
Ni+2 + H2 NCSNH2 → [Ni(SCN2 H4 )2 ]+2 Reaction1
Ethanol

Decomposition
[Ni(SCN2 H4 )2 ]+2 → NiSReaction2
in thermal condition

Scientific Reports | (2022) 12:14413 | https://doi.org/10.1038/s41598-022-18728-1 4

Vol:.(1234567890)
www.nature.com/scientificreports/

Figure 3.  Schematic presentation of the SS-NiS@3DNF electrode fabrication.

The morphology of the SS-NiS@3DNF electrodes was significantly affected by various reaction parameters,
such as the thiourea concentration, reaction time, and solvent effect, which are systematically shown in Fig. 3.
The shape and size of the nanomaterial during synthesis have a significant effect on the reaction rate. In the
present case, ethylene glycol and ethanol play an important role in the fabrication of SS-NiS@3DNF electrodes.
Ethylene glycol and ethanol act as both reaction media and dispersion media and can efficiently absorb and
stabilize the surface of the particles, producing monodisperse metal sulfide crystals with good d ­ ispersity28.
However, ethylene glycol has a high permanent dipole moment and is an excellent susceptor of reactor heat
during hydrothermal treatment; it can take energy, which helps decompose the thiourea and nickel complex
compound ([Ni(SCN2H4)2]2+) and initiate the formation of the product on the provided s­ ubstrate29,30. During
the synthesis procedure, at the beginning of the reaction inside the Teflon reactor, frequent formation of nuclei
started, and after time, the nuclei tended to aggregate (3 h Supplementary Fig. S4a online) with nonbearing
nuclei, leading to the formation of a spherical shell (6 h, Supplementary Fig. S4b online) on 3DNF. After 12 h
(Supplementary Fig. S4c online), the sphere-shaped nickel sulfide started to interconnect and interlink with the
neighboring spheres.
After increasing the synthesis time (24 h, Supplementary Fig. S4d online), the spheres became larger in size,
and the interconnection between spheres decreased compared to the SS-NiS@3DNF after 12 h. The growth
procedure of the SS-NiS@3DNF electrode spheres was performed under controlled time and solution environ-
ment, resulting in interlinked-interconnected spheres of nickel sulfide grown on the nickel foam. When the
concentration of thiourea was low, the reaction rate was low due to the low ability of sulfur ions to react with
the crystal faces. Under low sulfur conditions, the nuclei tended to undergo isotropic growth and start form-
ing a thermodynamically favorable spherical morphology. In contrast, when the concentration of thiourea was
high, the nucleation rate was also high, and the consistent growth of nucleated particles was reduced; under this
condition, the synthesized nickel sulfide was large in size.
Supplementary Fig. S5 online shows the powder XRD pattern of the optimized SS-NiS@3DNF-E-3, which
showed smooth lines with sharp peaks at 30.09°, 34.58°, 45.80,° 53.5°, 60.7°, 62.64°, 65.3°, 70.61° and 73.2° 2θ
values corresponding to the (100), (101), (102), (110), (103), (200), (201), (004), and (202) planes, respectively. All
the peaks of the optimized and fabricated SS-NiS@3DNF-E-3 electrode were indexed and well matched JCPDF
No: 10–075-06136,22. XPS was also performed to determine the chemical composition and surface characteristics,
such as the surface percentage and nature of nickel and sulfur bonds, of the optimized SS-NiS@3DNF-E-3 mate-
rial (Supplementary Fig. S6)22,25. Figure 4a shows the XPS high-resolution Ni 2p core level spectrum, which is
divided into two broad peaks at binding energies of 871.80 and 853.3 eV assigned to ­Ni2+, while those observed
at 855.85 and 874.20 eV correspond to ­Ni3+ and two shakeup satellite bands, which further demonstrate the pres-
ence of Ni 2p in SS-NiS@3DNF-E-325. Figure 4b shows the high-resolution XPS S 2p spectrum, which contains
two main peaks at binding energies of 160.0 to 164.0 eV, which shows that sulfur is present in the sulfide phase
over the SS-NiS@3DNF-E-3 e­ lectrode25. The band observed at 168.2 eV was attributed to ­SO3. The presence of
other sulfur species was still obviously expected because the surface of sulfide easily oxidized in ambient air and
formed other forms of sulfur. However, the presence of high oxidation state sulfur does not appear to affect the
electrochemical performance.

Scientific Reports | (2022) 12:14413 | https://doi.org/10.1038/s41598-022-18728-1 5

Vol.:(0123456789)
 www.nature.com/scientificreports/

Ni 2p3/2
(a) S 2p1/2 (b)
Ni 2p1/2

Intensisty (a.u.)
Intensisty (a.u.)
S 2p3/2

850 860 870 880 174 171 168 165 162

Binding energy (eV) Binding energy (eV)

Figure 4.  High-resolution XPS spectra of (a) Ni 2p and (b) S 2p of the SS-NiS@3DNF-E-3 electrode.

60.0m (a) 0.4 (b)

40.0m 0.3
Current (mA)

SS-NiS@3DNF-E-1

Potential (V)
SS-NiS@3DNF-E-2 0.2
20.0m SS-NiS@3DNF-E-3
SS-NiS@3DNF-E-4 0.1
0.0
SS-NiS@3DNF-E-1
0.0 SS-NiS@3DNF-E-2
-20.0m SS-NiS@3DNF-E-3
-0.1 SS-NiS@3DNF-E-4
-40.0m
-0.2 -0.1 0.0 0.1 0.2 0.3 0.4 0 100 200 300 400 500 600 700
Potential (V) Time (s)

700 (c) 700 (d)

Specific capacitance (Fg )
Specific capacitance (Fg )

-1
-1

600 600
SS-NiS@3DNF-E-3
SS-NiS@3DNF-E-2

SS-NiS@3DNF-E-4
SS-NiS@3DNF-E-1

500 500 SS-NiS@3DNF-E-3

400 400

300 300 SS-NiS@3DNF-E-4

200 SS-NiS@3DNF-E-2
200

100 100
SS-NiS@3DNF-E-1
0 0
0 1 2 3 4 5 6 -1 7 8 9
Electrodes Current density (Ag )

Figure 5.  (a) Comparative CV graph of the SS-NiS@3DNF-E-1, SS-NiS@3DNF-E-2, SS-NiS@3DNF-E-3, and

SS-NiS@3DNF-E-4 electrodes., (b) comparative GCD graph of the SS-NiS@3DNF-E-1, SS-NiS@3DNF-E-2,
SS-NiS@3DNF-E-3, and SS-NiS@3DNF-E-4 electrodes., (c) comparative specific capacitance bar graph
of the SS-NiS@3DNF-E-1, SS-NiS@3DNF-E-2, SS-NiS@3DNF-E-3, and SS-NiS@3DNF-E-4 electrodes.,
and (d) specific capacitance at different current densities of the SS-NiS@3DNF-E-1, SS-NiS@3DNF-E-2,
SS-NiS@3DNF-E-3, and SS-NiS@3DNF-E-4 electrodes.

Electrochemical measurement.  The comparative electrochemical performances of all the fabricated

electrodes, i.e., SS-NiS@3DNF-E-1, SS-NiS@3DNF-E-2, SS-NiS@3DNF-E-3, and SS-NiS@3DNF-E-4, as pos-
sible binder-free electrodes for ES application were evaluated. The selection of the electrolyte is also an impor-
tant parameter in electrochemical supercapacitive applications because its characteristics should include a high
ionic concentration in a small amount of electrolyte and a low resistance. Therefore, KOH electrolyte is better
than the other electrolytes owing to its low resistance and high ionic concentration. The initial electrochemi-
cal supercapacitive behavior of all the electrodes (SS-NiS@3DNF-E-1, SS-NiS@3DNF-E-2, SS-NiS@3DNF-
E-3, and SS-NiS@3DNF-E-4) was analyzed by CV in a 2 M KOH electrolyte, and the results are displayed in
Fig. 5a and Supplementary Fig. S7 online. Figure 5a shows the comparative CV graph of the SS-NiS@3DNF-
E-1, SS-NiS@3DNF-E-2, SS-NiS@3DNF-E-3, and SS-NiS@3DNF-E-4 electrodes recorded at a fixed scan rate
of 10 mV/s within the potential range of −0.2 to 0.4 V. Figure S 7 shows the CV graph of the SS-NiS@3DNF-
E-1, SS-NiS@3DNF-E-2, SS-NiS@3DNF-E-3, and SS-NiS@3DNF-E-4 electrodes recorded at different scan rates
within the potential range of -0.2–0.4 V. The comparative CV curves of all the electrodes (Fig. 5a) revealed that
all the electrodes show the presence of the redox peak corresponding to the reversible faradic reaction over the

Scientific Reports | (2022) 12:14413 | https://doi.org/10.1038/s41598-022-18728-1 6

Vol:.(1234567890)
www.nature.com/scientificreports/

electrode due to the possible reversible reaction from Ni-S to Ni-S-OH in the charge storage mechanism, which
can be summarized as ­follows22,25:
NiS + OH− ⇆NiSOH + e−

The observed peak at approximately 0.34 V was assigned to oxidation of Ni-S to Ni-S-OH, and the cor-
responding reduction peak at 0.2 V was attributed to the reversible reaction process. In addition, among all
the electrodes, SS-NiS@3DNF-E-3 showed a high current response with a large integrated area compared to
SS-NiS@3DNF-E-1, SS-NiS@3DNF-E-2, and SS-NiS@3DNF-E-4 in the CV results, which indicates that the
electrochemical capacitive performance of the SS-NiS@3DNF-E-3 electrode may be higher than that of the rest
of the electrodes. From the CV curves, we can clearly see that when we increased the thiourea amount, the CV
integrated area became large for the SS-NiS@3DNF-E-1, SS-NiS@3DNF-E-2, and SS-NiS@3DNF-E-3 electrodes,
whereas in the case of SS-NiS@3DNF-E-3, the CV integrated area decreased, which may be due to a decrease in
the interconnectivity between neighboring spheres. The large CV integrated area might also be due to each sphere
being interconnected and interlinked to each other, which helps the flow of electrons during the electrochemi-
cal process over the electrode during the electrochemical measurements. The anodic and cathodic peaks of all
the electrodes were shifted to the right and left with increasing scan rate (Supplementary Fig. S7 online). The
small shift indicates that a more reversible and faster charge transfer phenomenon occurs during electrochemi-
cal analysis. For better recognition of the charge storage mechanism and potential specific capacitance of the
fabricated binder-free SS-NiS@3DNF electrodes, GCD analysis was performed in the potential range of −0.1 to
0.4 V, and the results are displayed in Fig. 5 and Supplementary Fig. S8 online. Figure 5b shows the compara-
tive GCD curves of the SS-NiS@3DNF-E-1, SS-NiS@3DNF-E-2, SS-NiS@3DNF-E-3, and SS-NiS@3DNF-E-4
electrodes recorded at a fixed current density of 1 A/g, whereas Supplementary Fig. S8 online shows the GCD
graph of the individual electrodes recorded at different current densities. The comparative GCD graph and
individual electrode GCD curves revealed that all the electrodes exhibited a pseudocapacitive nature, which is
also in accordance with the above CV results. The GCD graph also shows the presence of a voltage plateau from
0.31 to 0.40 V, again suggesting that the redox reaction plays an important role in the overall charge–discharge
process occurring over the electrode surface during the electrochemical process.
The comparative GCD graph and specific capacitance graph (Fig. 5c and d) clearly reveal that the SS-
NiS@3DNF-E-3 electrode shows a much better specific capacitance than the SS-NiS@3DNF-E-1, SS-NiS@3DNF-
E-2, and SS-NiS@3DNF-E-4 electrodes, which may be due to all the spheres being interconnected and interlinked
to each other, which provides a larger expose area and more electroactive sites for ions and electrons during
the redox reaction. Additionally, direct growth of NiS on the conductive 3DNF substrate facilitates ionic and
electronic transport, which enhances the overall performance of the SS-NiS@3DNF-E-3 electrode. Moreover, the
specific capacitance of all the fabricated electrodes was calculated from the discharge curves using the equation
mentioned in the electronic supplementary information, in which the highest specific capacitances of the SS-
NiS@3DNF-E-1, SS-NiS@3DNF-E-2, SS-NiS@3DNF-E-3, and SS-NiS@3DNF-E-4 electrodes were 188.0, 470.0,
694.0 and 230.0 F/g at a current density of 1 A/g. Additionally, the GCD profiles of each electrode were also
examined at different current densities. The specific capacitance of the SS-NiS@3DNF-E-1 electrode was 188.2,
180.4, 156.6, 140.0, 128.0, and 49.5 F ­ g−1 (Supplementary Fig. S8a online), whereas for the SS-NiS@3DNF-E-2
electrode, it was 470.0, 464.0, 432.0, 350.0, and 224.0 F/g (Supplementary Fig. S8b online). Similarly, for the SS-
NiS@3DNF-E-3 electrode, it was 694.0, 780.0, 688.0, 660.0, 504.0, and 288.0 F/g (Supplementary Fig. S8c online),
and for the SS-NiS@3DNF-E-4 electrode, the calculated specific capacitance was 230.0, 228.0, 210.0, 154.0,
112.0, and 48.0 F/g (Supplementary Fig. S8d online) at current densities of 1, 2, 3, 3.5, 4, and 6 A/g, respectively.
The GCD curves of all the individual electrodes and the corresponding specific capacitance performance at
different current densities clearly show that with increasing current density, the restriction of the electron and
electrolyte transport gradually decreases, which is responsible for the decrease in the capacitance of the elec-
trode. The relationship between the current density and specific capacitance is presented in Fig. 5d. The specific
capacitance of all the fabricated electrodes gradually decreased with increasing current density. This phenomenon
occurs due to the internal voltage drop and insufficient active material involved in the redox reaction at higher
currents. Furthermore, the specific capacitance of the optimized SS-NiS@3DNF-E-3 electrode is also compared
with those of previously reported nickel sulfide-based electrode materials in detail in Table 1. The optimized
SS-NiS@3DNF-E-3 electrode shows good specific capacitance even at high current density, which confirms the
good rate capability of the optimized electrode.
Long-term continuous charge–discharge cycling or the cycling stability of the electrode is a critical issue and
an important parameter for practical SC applications because MO-based electrodes usually suffer from a lack of
long-term stability due to electrode material degradation. The cycling stability of the optimized SS-NiS@3DNF-
E-3 electrode was evaluated by continuous GCD measurements for up to 6700 cycles at a fixed current density
of 3.0 A/g. According to the cycling stability curve (Fig. 6a), at the start of the cycling stability test, the specific
capacitance of the electrode increased due to the self-activation effect, and after that, it started slightly decreasing
and stabilized at more than 88% after 6700 cycles. The cycling stability results were also compared with previous
results, and the cycling stability in the present case was significantly higher than that of the other reported nickel
sulfide-based electrode materials in Table 1.
The energy density and power density are other major concerns for practical application of all electrodes
in SC applications. The energy and power densities of the optimized electrode were calculated from the GCD
curve using the equation mentioned in the electronic supplementary information at different current densities
and plotted on the Ragone diagram shown in Fig. 6b. The Ragone plot shows that the highest energy density
of the SS-NiS@3DNF-E-3 electrode was approximately 24.9 Wh/kg at a power density of 250.93 W/kg, and the

Scientific Reports | (2022) 12:14413 | https://doi.org/10.1038/s41598-022-18728-1 7

Vol.:(0123456789)
 www.nature.com/scientificreports/

Electrode Electrolyte Specific capacitance Retention Energy and power density Refs
NiS 2 M KOH 529 ­Fg–1 at 2 ­Ag–1 100% after 2000 cycles – 31

NiS@SS 2 M KOH 441 ­Fg–1 – 10.1 Wh/kg at 4.5 kW/kg 32

–1 –1 33
3D Ni3S2 1 M KOH 626.1 ­Fg at 5 ­Ag 2000 cycles 88.8 Wh/kg at 480 W/kg
–1 34
β-NiS 2 M KOH 415.8 ­Fg at 0.5 mAcm–2 91% after 2000 cycles –
–1 –1 35
NiS/rGO 2 M KOH 530.1 ­Fg at 4 ­Ag 90.90% after 2000 cycles –
1.96 mWhcm –3 at
Ni3S2 2 M KOH 694 ­Fg–1 at 3.45 A
­ g–1 89.3% after 5000 cycles 36
0.6 W cm–3
Ni3S2/CNT 2 M KOH 514 ­Fg–1 at 4 ­Ag–1 88% after 1500 cycles – 37

NiS-CFs 2 M KOH 635.1 ­Fg–1 at 1 ­Ag–1 96.4% after 5000 cycles – 38

NiS/RGO 6 M KOH 305 ­Fg–1 at 1.1 ­Ag–1 91% after 3000 cycles – 39

NiS@NF 6 M KOH 603.9 ­Fg–1 at 1 ­Ag–1 88.57% after 5000 cycles – 6

rGO-Ni3S2 6 M KOH 616 ­Cg–1 at 1 ­Ag–1 92.7% after 5000 cycles 38.2 Wh/kg at 0.224 kW/kg 40

–1 –1 41
NiS2 3 M KOH 695 ­Fg at 1.25 A
­ g 93.4% after 3000 cycles 15.7 Wh/kg at 254 W/kg
–1 42
NiO/NiS 3 M KOH 386.7 Fg − 1 at 1 ­Ag 97.6% after 3000 cycles –
–1 –1
SS-NiS@3DNF-E-3 2 M KOH 694 ­Fg at ­1Ag 88% after 6700 cycles 24.9 Wh/kg at 250.93 W/kg Present work

Table 1.  Comparison of the specific capacitance, energy density and power density of the SS-NiS@3DNF-E-3
electrode with those of other reported nickel sulfide-based electrode materials.

100 (a) (b)

Energy density (Wh/kg)

80
Retention (%)

60

40
10
20

0
0 2000 4000 6000 8000 200 400 600 800 1000
Number of cycles Power density (W/kg)

Figure 6.  (a) Cyclic retention up to 6700 cycles, and (b) energy and power density curve of the
SS-NiS@3DNF-E-3 electrode.

electrode maintained an energy density of 7.5 Wh/kg at a power density of 1500 W/kg at the current load. The
excellent electrochemical performance of the fabricated optimized binder-free SS-NiS@3DNF-E-3 electrode
is due first to its interconnected interlinked structure between spheres, which helps provide a large exposed
area and more electroactive sites during the redox reaction. Second, direct growth on Ni foam facilitates ionic
and electronic transport, which enhances the performance of the electrode. Third, direct growth on the 3DNF
substrate prevents binder and conductive additive adhesion, which decreases the resistance. These conditions
create an effective and stable pathway for charge transfer during the electrochemical supercapacitive process.

Conclusion
In the present work, a facile one-step solvothermal method was used to fabricate a binder-free sphere-shaped
interconnected interlinked SS-NiS@3DNF-E-3 electrode with appropriate solvent selection, optimized sulfur
precursor amount and satisfactory reaction time. The optimized SS-NiS@3DNF-E-3 showed excellent perfor-
mance in KOH electrolyte. The highest specific capacitance of the optimized electrode was 694.0 F/g at 1 A/g
with an excellent capacitance retention of 88% after 6700 cycles. The SS-NiS@3DNF-E-3 electrode delivered a
maximum energy density of 24.9 Wh/kg at a power density of 250.93 W/kg. In the current study, the superca-
pacitive performance of the SS-NiS@3DNF-E-3 electrode opens a new way to design cost-effective capacitors
with potential in various energy storage applications.

Methods
Materials.  Nickel chloride hexahydrate ­(NiCl2.6H2O) and ethylene glycol ­(CH2OH)2 were purchased from
Scharlau. Thiourea was obtained from BDH Chemicals Ltd., England. Other chemicals, such as ethanol metha-
nol and propanol, were purchased from Sigma–Aldrich. Nickel foam (99.99% purity) was obtained from MTI
Corporation, USA.

Scientific Reports | (2022) 12:14413 | https://doi.org/10.1038/s41598-022-18728-1 8

Vol:.(1234567890)
www.nature.com/scientificreports/

Characterization.  The morphological changes during the experiments were analyzed by field emission
scanning electron microscopy (FESEM). The phase and purity of the fabricated electrode material were tested
by X-ray diffraction (XRD, PAN analytical, X’pert-PRO MPD), and the chemical composition was examined by
X-ray photoelectron microscopy (XPS, ESCALAB 250 XPS system, UK). The electrochemical properties, such
as CV, charge–discharge (CD) and stability, were determined on a Metrohm Nova Auto lab electrochemical
workstation.

Electrochemical measurement.  The electrochemical performance of all fabricated nickel sulfide elec-
trodes was examined in a three-electrode system (half-cell system). Ag/AgCl, Pt, and a NiS@Ni foam sheet were
used as reference, counter, and working electrodes, respectively. All of the electrochemical measurements were
carried out on a Metrohm Nova Auto lab electrochemical workstation in 2 M KOH aqueous electrolyte solution.
The specific capacitance of the binder-free NiS@Ni electrodes was calculated based on the mass loading during
the solvothermal synthesis.

Calculation.  To estimate the specific capacitance of the fabricated NiS@Ni cathode electrodes inside the
half-cell assembly, the following equation was ­used6,16,26:
C = Idt/mdV (1)
−1
where C is the specific capacitance (­ Fg ), I is the applied current, t is the discharge time, m represents the mass
of active materials on the surface of the current collector, and dV is the applied potential window.
The power density and energy density were estimated from the following Eq.6,16,22,26:

E = 1/2 CV2 (2)

P = E/t (3)
where C is the specific capacitance, V is the applied potential window and t is the discharge time of the device.

Solvothermal synthesis of sphere‑shaped interconnected interlinked binder‑free NiS@3DNF

electrodes.  Synthesis of NiS@3DNF electrodes with different solvents.  The fabrication of binder-free SS-
NiS@3DNF using a simple solvothermal method was as follows. ­NiCl2.6H2O (0.63 mmol) and 1.97 mmol thio-
urea were added into an ethanol and ethylene glycol solvent (20 ml + 2 ml). The mixture was stirred for 15 min,
after which two Ni foam sheets (1 cm*1 cm, Supplementary Fig. S1 online) were added and sonicated for 5 min.
The above solution and Ni foam were transferred into a Teflon-linked autoclave and kept at 120 °C for 12 h. After
the reaction was completed, the autoclave was naturally cooled at room temperature. The synthesized electrodes
were washed with deionized water and ethanol several times to remove all ions and contaminants remaining
on the fabricated electrode. The washed samples were dried in an oven at 80 °C for 24 h. The fabricated sample
with sphere-shaped interconnected interlinked binder-free nickel sulfide (NiS) grown at the surface of three-di-
mensional nickel foam (3DNF) using ethanol as the solvent is abbreviated as the SS-NiS@3DNF-E electrode. To
better understand the solvent effect on the morphology of the NiS grown at the surface of nickel foam, methanol
and propanol were also used, and the other parameters were the same. The fabricated sample with sphere-shaped
interconnected interlinked binder-free NiS grown at the surface of 3DNF using methanol as the solvent is ab-
breviated as the SS-NiS@3DNF-M electrode. Similarly, the fabricated sample with sphere-shaped interconnected
interlinked binder-free NiS grown at the surface of 3DNF using propanol as the solvent is abbreviated as the SS-
NiS@3DNF-P electrode. After performing SEM analysis, SS-NiS@3DNF-E showed a better morphology, so in
this study, we chose ethanol as the solvent for further studies. Moreover, Supplementary Table S1 online shows
a comparison of the precursor material, synthesis method and morphology of NiS@Ni in the present case with
those in previously reported articles based on NiS synthesis.

Synthesis of SS‑NiS@3DNF with different sulfur precursor amounts.  The detailed synthesis procedure for direct
synthesis of SS-NiS@3DNF electrodes using the solvothermal method was the same as that discussed above.
However, in this experiment, different amount of thiourea (0.13, 0.65, 1.3, 1.97 mM) were used, and its effect on
the morphology was observed, whereas the amount of the nickel precursor and the reaction temperature and
time, i.e., 120 °C for 12 h, remained the same in all the synthesis processes. The fabricated sample with sphere-
shaped interconnected interlinked binder-free NiS grown at the surface of 3DNF using 0.13 mM thiourea as the
sulfur precursor is abbreviated as the SS-NiS@3DNF-E-1 electrode. The fabricated sample with sphere-shaped
interconnected interlinked binder-free NiS grown at the surface of 3DNF using 0.65 mM thiourea as the sulfur
precursor is abbreviated as the SS-NiS@3DNF-E-2 electrode. The fabricated sample with sphere-shaped inter-
connected interlinked binder-free NiS grown at the surface of 3DNF using 1.30 mM thiourea as the sulfur pre-
cursor is abbreviated as the SS-NiS@3DNF-E-3 electrode. The fabricated sample with sphere-shaped intercon-
nected interlinked binder-free NiS grown at the surface of 3DNF using 1.97 mM thiourea as the sulfur precursor
is abbreviated as the SS-NiS@3DNF-E-4 electrode.

Data availability
The dataset used and/and or analyzed during the current study available from the corresponding author on
reasonable request.

Scientific Reports | (2022) 12:14413 | https://doi.org/10.1038/s41598-022-18728-1 9

Vol.:(0123456789)
 www.nature.com/scientificreports/

Received: 4 May 2022; Accepted: 18 August 2022

References
1. Zhang, G. et al. High-performance and ultra-stable lithium-ion batteries based on MOF-derived ZnO@ZnO quantum Dots/C
core-shell nanorod arrays on a carbon cloth anode. Adv. Mater. 27, 2400–2405 (2015).
2. Guan, S., Fu, X., Zhang, B., Lei, M. & Peng, Z. Cation-exchange-assisted formation of NiS/SnS2 porous nanowalls with ultrahigh
energy density for battery–supercapacitor hybrid devices. J. Mater. Chem. A 8, 3300–3310 (2020).
3. Li, Z., Han, J., Fan, L. & Guo, R. Template-free synthesis of Ni7S6 hollow spheres with mesoporous shells for high performance
supercapacitors. CrystEngComm 17, 1952–1958 (2015).
4. Parveen, N. & Cho, M. H. Self-assembled 3D flower-like nickel hydroxide nanostructures and their supercapacitor applications.
Sci. Rep. 6, 27318 (2016).
5. Parveen, N. et al. Facile synthesis of SnS(2) nanostructures with different morphologies for high-performance supercapacitor
applications. ACS Omega 3, 1581–1588 (2018).
6. Parveen, N. et al. Solid-state symmetrical supercapacitor based on hierarchical flower-like nickel sulfide with shape-controlled
morphological evolution. Electrochim. Acta 268, 82–93 (2018).
7. Peng, H. et al. High-performance supercapacitor based on multi-structural CuS@polypyrrole composites prepared by in situ
oxidative polymerization. J. Mater. Chem. A 2, 3303–3307 (2014).
8. Wang, Y. & Xie, Y. Electroactive FeS2-modified MoS2 nanosheet for high-performance supercapacitor. J. Alloys Compd. 824,
153936 (2020).
9. Idris, N. H. et al. Rapid synthesis of binary α-NiS–β-NiS by microwave autoclave for rechargeable lithium batteries. Electrochim.
Acta 58, 456–462 (2011).
10. Kristl, M., Dojer, B., Gyergyek, S. & Kristl, J. Synthesis of nickel and cobalt sulfide nanoparticles using a low cost sonochemical
method. Heliyon 3, e00273 (2017).
11. Wu, D. et al. A novel self-branching MnCo2O4/ nanographene hybrid composites on macroporous electrically conductive network
as bifunctional electrodes for boosting miniature supercapacitors and sodium ion batteries. J. Alloys Compd. 846, 155720 (2020).
12. Li, J., Chen, D. & Wu, Q. Facile synthesis of CoS porous nanoflake for high performance supercapacitor electrode materials. J.
Energy Storage 23, 511–514 (2019).
13. Liu, Y., Zhou, Z., Zhang, S., Luo, W. & Zhang, G. Controllable synthesis of CuS hollow microflowers hierarchical structures for
asymmetric supercapacitors. Appl. Surf. Sci. 442, 711–719 (2018).
14. Gao, Y. P., Huang, K. J., Wu, X., Hou, Z. Q. & Liu, Y. Y. MoS2 nanosheets assembling three-dimensional nanospheres for enhanced-
performance supercapacitor. J. Alloys Compd. 741, 174–181 (2018).
15. Yang, J., Duan, X., Qin, Q. & Zheng, W. Solvothermal synthesis of hierarchical flower-like β-NiS with excellent electrochemical
performance for supercapacitors. J. Mater. Chem. A 1, 7880–7884 (2013).
16. Guan, B. et al. Synthesis of hierarchical NiS microflowers for high performance asymmetric supercapacitor. Chem. Eng. J. 308,
1165–1173 (2017).
17. Ranganatha, S. & Munichandraiah, N. γ-MnS nanoparticles anchored reduced graphene oxide: electrode materials for high per-
formance supercapacitors. J. Sci. Adv. Mater. Devices 3, 359–365 (2018).
18. Quan, H. et al. One-pot synthesis of α-MnS/nitrogen-doped reduced graphene oxide hybrid for high-performance asymmetric
supercapacitors. Electrochim. Acta 210, 557–566 (2016).
19. El-Hout, S. I. et al. High electrochemical performance of rGO anchored CuS nanospheres for supercapacitor applications. J. Energy
Storage 34, 102001 (2021).
20. Zhao, T. et al. Facile preparation of reduced graphene oxide/copper sulfide composite as electrode materials for supercapacitors
with high energy density. Compos. B Eng. 150, 60–67 (2018).
21. BoopathiRaja, R., Parthibavarman, M., Prabhu, S. & Ramesh, R. A facile one step hydrothermal induced hexagonal shaped CuS/
rGO nanocomposites for asymmetric supercapacitors. Mater. Today Proc. 26, 3507–3513 (2020).
22. Naresh, B. et al. Hydrothermal synthesis and pseudocapacitive properties of morphology-tuned nickel sulfide (NiS) nanostructures.
New J. Chem. 42, 2733–2742 (2018).
23. Bhardwaj, R., Jha, R., Bhushan, M. & Sharma, R. Comparative study of the electrochemical properties of mesoporous 1-D and 3-D
nano- structured rhombohedral nickel sulfide in alkaline electrolytes. J. Phys. Chem. Solids 144, 109503 (2020).
24. Qi, J. et al. Facile synthesis of Ag-decorated Ni3S2 nanosheets with 3D bush structure grown on rGO and its application as positive
electrode material in asymmetric supercapacitor. Adv. Mater. Interfaces 5, 1700985 (2018).
25. Bhagwan, J., Khaja Hussain, S., Krishna, B. N. V. & Yu, J. S. β-NiS 3D micro-flower-based electrode for aqueous asymmetric
supercapacitors. Sustain. Energy Fuels 4, 5550–5559 (2020).
26. Balakrishnan, A., Groeneveld, J. D., Pokhrel, S. & Mädler, L. Metal sulfide nanoparticles: Precursor chemistry. Chem. Eur. J. 27,
6390–6406 (2021).
27. Chen, D. et al. Microwave-assisted synthesis of metal sulfides in ethylene glycol. Mater. Chem. Phys. 82, 206–209 (2003).
28. Feldmann, C. & Metzmacher, C. Polyol mediated synthesis of nanoscale MS particles (M = Zn, Cd, Hg). J. Mater. Chem. 11,
2603–2606 (2001).
29. Tu, W. & Liu, H. Continuous synthesis of colloidal metal nanoclusters by microwave irradiation. Chem. Mater. 12, 564–567 (2000).
30. Rao, K. J., Vaidhyanathan, B., Ganguli, M. & Ramakrishnan, P. A. Synthesis of inorganic solids using microwaves. Chem. Mater.
11, 882–895 (1999).
31. Nandhini, S. & Muralidharan, G. Surfactant free nickel sulphide nanoparticles for high capacitance supercapacitors. AIP Conf.
Proc. 1942, 140060 (2018).
32. Sarma, M. P. & Wary, G. Synthesis and characterization of chemically deposited nanocrystalline PbS thin film. Adv. Sci. Lett. 22,
3755–3758 (2016).
33. Zhang, Z. et al. One-pot synthesis of hierarchically nanostructured Ni3S2 dendrites as active materials for supercapacitors. Elec‑
trochim. Acta 149, 316–323 (2014).
34. Patil, A. M., Lokhande, A. C., Chodankar, N. R., Kumbhar, V. S. & Lokhande, C. D. Engineered morphologies of β-NiS thin films
via anionic exchange process and their supercapacitive performance. Mater. Des. 97, 407–416 (2016).
35. Yang, J. et al. Electrochemical performances investigation of NiS/rGO composite as electrode material for supercapacitors. Nano
Energy 5, 74–81 (2014).
36. Xiong, X. et al. One-step synthesis of architectural Ni3S2 nanosheet-on-nanorods array for use as high-performance electrodes
for supercapacitors. NPG Asia Mater. 8, e300 (2016).
37. Zhu, T., Wu, H. B., Wang, Y., Xu, R. & Lou, X. W. D. Formation of 1D hierarchical structures composed of Ni3S2 nanosheets on
CNTs backbone for supercapacitors and photocatalytic H2 production. Adv. Energy Mater. 2, 1497–1502 (2012).
38. Tong, F. et al. NiS nanosheets with novel structure anchored on coal-based carbon fibers prepared by electrospinning for flexible
supercapacitors. CrystEngComm 22, 1625–1632 (2020).

Scientific Reports | (2022) 12:14413 | https://doi.org/10.1038/s41598-022-18728-1 10

Vol:.(1234567890)
www.nature.com/scientificreports/

39. Marand, N. A., Masoudpanah, S. M., Alamolhoda, S. & Bafghi, M. S. Solution combustion synthesis of nickel sulfide/reduced
graphene oxide composite powders as electrode materials for high-performance supercapacitors. J. Energy Storage 39, 102637
(2021).
40. Namdarian, A., Tabrizi, A. G., Maseleno, A., Mohammadi, A. & Moosavifard, S. E. One step synthesis of rGO-Ni3S2 nano-cubes
composite for high-performance supercapacitor electrodes. Int. J. Hydrog. Energy 43, 17780–17787 (2018).
41. Pang, H. et al. Microwave-assisted synthesis of NiS2 nanostructures for supercapacitors and cocatalytic enhancing photocatalytic
H2 production. Sci. Rep. 4, 3577 (2014).
42. Kim, S. Y., Gopi, C. V. V. M., Reddy, A. E. & Kim, H. J. Facile synthesis of a NiO/NiS hybrid and its use as an efficient electrode
material for supercapacitor applications. New J. Chem. 42, 5309–5313 (2018).

Acknowledgements
This work was supported through the Annual Funding track by the Deanship of Scientific Research, Vice
Presidency for Graduate Studies and Scientific Research, King Faisal University, Saudi Arabia [Project No.
GRANT387].

Author contributions
B.T.A.-A., N.P. and S.A.A. designed the study and performed the experiments; B.T.A.-A., N.P. and S.A.A. per-
formed the experiments, analyzed the data, and wrote the manuscript.

Competing interests 
The authors declare no competing interests.

Additional information
Supplementary Information The online version contains supplementary material available at https://​doi.​org/​
10.​1038/​s41598-​022-​18728-1.
Correspondence and requests for materials should be addressed to B.T.A.-A. or N.P.
Reprints and permissions information is available at www.nature.com/reprints.
Publisher’s note  Springer Nature remains neutral with regard to jurisdictional claims in published maps and
institutional affiliations.
Open Access  This article is licensed under a Creative Commons Attribution 4.0 International
License, which permits use, sharing, adaptation, distribution and reproduction in any medium or
format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the
Creative Commons licence, and indicate if changes were made. The images or other third party material in this
article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the
material. If material is not included in the article’s Creative Commons licence and your intended use is not
permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from
the copyright holder. To view a copy of this licence, visit http://​creat​iveco​mmons.​org/​licen​ses/​by/4.​0/.

© The Author(s) 2022

Scientific Reports | (2022) 12:14413 | https://doi.org/10.1038/s41598-022-18728-1 11

Vol.:(0123456789)