Journal of Energy Storage 73 (2023) 109130

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Journal of Energy Storage

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Research papers

CTAB-assisted solvothermal growth of CuCo2S4 on nickel foam for

high-performance symmetric supercapacitor
S.A. Sanei, S.M. Masoudpanah *, M.Sh. Bafghi
School of Metallurgy and Materials Engineering, Iran University of Science and Technology (IUST), Tehran, Iran

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

Keywords: In this work, copper-cobalt sulfide (CuCo2S4) with spinel structure was directly grown on nickel foam by a two-
CuCo2S4 step solvothermal synthesis method using a mixture of water/ethanol as solvent and Na2S.9H2O solution as a
Solvothermal synthesis sulfur source. The effects of cetyltrimethylammonium bromide (CTAB) contents in the sulfurization step were
CTAB
analyzed by various structural, microstructural, and electrochemical characterization methods. The hierarchical
Symmetric capacitor
microstructure and high specific capacitance of 4230 F g− 1 at a current density of 1 A g− 1 were obtained by using
1.5 mmol CTAB during the sulfurization step. Furthermore, the free-binder CuCo2S4 electrode showed a high
specific capacitance of 429 F g− 1 in the negative potential window of − 1.0–0.0 V vs. Ag/AgCl at a current density
of 1 A g− 1. The symmetric CuCo2S4//CuCo2S4 capacitor stored a high energy density of 63 Wh kg− 1 at power
density of 2800 W kg− 1.

1. Introduction ions on the surface of electroactive materials. The pseudocapacitive

materials can attain the higher specific energy compared with EDLC
A lot of efforts are devoted to the wide applications of clean, materials due to the limited active surface sites for physically adsorption
renewable, and sustainable energy resources such as wind, wave, sun, of electrolyte ions [10]. The pseudocapacitive materials are typically
etc., owing to the challenges of fossil fuels such as changing climatic conducting polymers, transition metal hydroxides, layered double hy­
patterns, rising greenhouse gas emissions, air pollution, and global droxides (LDHs), metal nitrides, metal oxides, and metal sulfides
warming [1,2]. Energy storage and conversion technologies such as [11–14]. Among them, transition metal sulfides (TMSs) are promising
batteries, fuel cells, and supercapacitors (SCs) have to be developed for electroactive materials for their unique electrochemical properties, high
continuously exploiting the renewable energy resources [3–5]. The SCs abundance, low cost, and high theoretical capacitance [15–17]. The
and batteries are dependable contenders for low-cost and clean energy TMSs have higher electrochemical activity than their corresponding
storage systems. The SCs offer the suitable characteristics such as high oxides because of the higher ionic conductivity of sulfur ions than ox­
power density (several times more than batteries), quick charging ygen ions and higher electrical conductivity caused by their narrower
(within seconds), and outstanding cycling stability [6,7]. The charac­ band gap [18–20]. Bimetallic sulfides (BMSs) have higher active redox
teristics of SCs lead to their applications in the automotive industry, sites, higher conductivity, and higher storage performance than their
aerospace, medical, memory protection, battery improvement, energy corresponding single component counterparts, arising from the syner­
harvesting systems, power quality improvement, adjustable speed gistic effect of the multiple metal ions [21–24].
drives, high power actuators, hybrid electric vehicles, transportation, Among BMSs, CuCo2S4 is a new highlighted thiospinel for SC ap­
communication, and military [8,9]. plications due to the excellent chemical stability, rich redox reactions,
Based on the charge storage mechanism, the SCs are mainly classified relatively high electrical conductivity (~10− 4 Ω), and multiple oxida­
into electric double-layer capacitors (EDLCs) and pseudocapacitors. The tion states (Co2+, Co3+, and Cu2+) [20,25–28]. The various morphol­
charge storage mechanism in the EDLCs involves surface-controlled ion ogies of CuCo2S4 material such as nanorods [29,30], spheres [31,32],
adsorption without any electron sharing. The pseudocapacitive is a nanoneedles [33], flower-like [34,35], nanotubes [36], nanowire arrays
Faradic process by changing the valence state through reversible [37], nanosheets [38,39], and nanograss [40] demonstrate the high
exchanging electrons between electroactive materials and electrolyte electrochemical properties. The different chemical synthesis methods

* Corresponding author.
E-mail address: masoudpanah@iust.ac.ir (S.M. Masoudpanah).

https://doi.org/10.1016/j.est.2023.109130
Received 4 July 2023; Received in revised form 9 September 2023; Accepted 27 September 2023
Available online 4 October 2023
2352-152X/© 2023 Published by Elsevier Ltd.
S.A. Sanei et al. Journal of Energy Storage 73 (2023) 109130

including one-step hydrothermal reaction [41,42], and solvothermal 2.3. Electrochemical measurement
sulfurization [43–47], electrodeposition [48], and microwave-assisted
techniques [49,50] are applied for preparing the CuCo2S4 electrode. 2.3.1. Three-electrode system
The CuCo2S4 material can be directly grown on conductive substrates Electrochemical properties of the CuCo2S4/NF electrodes were
such as nickel foam (NF), carbon cloth, etc., by a two-step solvothermal measured in a three-electrode system on a Radstat10A (Kianshardanesh,
sulfurization method as an economical, environmentally, and scalable Iran) electrochemical workstation by cyclic voltammetry (CV), galva­
method [37,51,52]. nostatic charge-discharge (GCD), and electrochemical impedance spec­
One of the popular strategies for tuning the morphology is the troscopy (EIS) techniques. The mass loading of CuCo2S4 on nickel foam
application of surfactants. The surfactants as structure-directing re­ substrate was about 1 mg cm− 2. The mass loading was dependent on the
agents tend to reduce the surface tension of the solution, preventing the concentration of metal precursors. However, the higher added amounts
agglomeration of the particles. When the concentration of surfactant in of CTAB surfactant during sulfurization led to the higher mass loading
the solution reaches up to a critical micelle concentration (CMC), sur­ irrespective of the concentration of metal precursors. The higher mass
factant molecules aggregate and form self-assembly molecules, known loading detriment the electrochemical performance. The CuCo2S4/NF,
as micelles, with spherical, cylindrical, lamellar, and higher-order Ag/AgCl, and Pt wire were set up as working, reference, and counter
morphology [53–55]. Among the various surfactants, cetyl­ electrodes, respectively. The 3 M KOH aqueous solution was used as
trimethylammonium bromide (CTAB) as a typical cationic surfactant electrolyte. The values of specific capacitance were calculated from the
has a head group of trimethylammonium and a lengthy chain of alkyl GCD and CV curves as follows [57]:
groups [56]. The CTAB surfactant can promote ion exchange in sol­
IΔt
vothermal process and also plays an ion carrier and soft template role in CGCD = (1)
mΔV
the crystallization process, as well as changes the preferential crystalline
orientation [54]. ∫
idV
In this work, the CuCo2S4 material was grown on nickel foam using a CCV = (2)
2mϑΔV
two-step solvothermal technique. Furthermore, the effects of the appli­
cation of CTAB surfactant during the sulfurization step were evaluated which I is the applied current, i is the current response, ΔV is the po­
on the structural, microstructural, and electrochemical performance by tential window, v is the scan rate, m is the mass loading of electroactive
various techniques. material, and Δt is the discharge time. The electrochemical impedance
spectroscopy (EIS) was recorded in a frequency range of 0.01 Hz to 50
2. Experimental procedure kHz with a 10 mV amplitude of AC voltage.

Cu(NO3)2 3H2O, Co(NO3)2 6H2O, urea (CH4N2O), NH4F, Na2S 9H2O, 2.3.2. Two-electrode system
CTAB (C19H42BrN), and ethanol were purchased from Merck Co. The symmetric hybrid capacitor was constructed by using the C 1.5
sample as both positive and negative electrodes (The electrochemical
properties of the C 1.5 sample as negative electrode were presented in
2.1. Synthesis of CuCo2S4
Supplementary file). The charges of the positive and negative electrodes
must be balanced to fabricate a high-performance symmetric capacitor
The nickel foam (1 × 3 cm2) as current collector was chemically
as follows [57]:
cleaned by 37 wt% HCl solution, deionized water, and ethanol,
respectively, and then was dried at 80 ◦ C for overnight. m+ C− ΔV−
= (3)
Typically, 0.125 mmol Cu(NO3)2 3H2O, 0.25 mmol Co(NO3)2 6H2O, m− C+ ΔV+
1.5 mmol urea, and 0.5 mmol NH4F were dissolved in a mixture of 60 mL The energy density (ED) and power density (PD) were calculated as
water and 30 mL ethanol as solvent by magnetic stirring for 30 min. The follows [58]:
precursor solution and pretreated nickel foam (NF) were transferred into
a 100 mL Teflon-lined stainless-steel autoclave for heating up at 130 ◦ C 1
ED = CΔV 2 (4)
for 6 h to crystallize the CuCo layered double hydroxide (LDH) precursor 2
on nickel foam. The CuCo LDH precursor was then sulfurized in 0.2 M
ED
Na2S 9H2O aqueous solution (90 mL) at 160 ◦ C for 8 h. The CuCo2S4/ PD = (5)
Δt
nickel foam electrode was washed by distilled water and ethanol and
then was dried at 80 ◦ C for overnight. The various amounts of the CTAB
3. Results and discussion
surfactant (0.5, 1, and 1.5 mmol) were added during the sulfurization
step. The samples were symbolized on the base of CTAB contents. For
3.1. Structural and microstructural characterization
example, “C 0.5” symbol is related to the sample prepared by using 0.5
mmol CTAB surfactant.
XRD pattern of CuCo LDH precursor is presented in Fig. 1a. There are
reflections of Co(OH)2 phase with a hexagonal crystal structure and
2.2. Materials characterization Co2(OH)2(CO3) and Cu2(OH)2(CO3) phases with monoclinic crystal
structure. The crystallization of CuCo LDH precursor can be explained as
The CuCo2S4 powder was structurally characterized by an X-Ray follows [59]:
diffractometry on Bourevestnik instrument equipped by CuKα (λ =
xCo2+ + (1 − x)Cu2+ + vOH− + yCO3 − 2
1.514178 Å) lamp in the diffraction range of 2θ = 10–80◦ which each (6)
+HCO3 2− →(Cu, Co)(CO3 )y (HCO3 )z (OH)v
step of 0.04◦ was scanned for 0.5 s. The morphology of CuCo2S4/NF
sample was observed by scanning electron microscopy (SEM) (Vega II,
(Cu, Co)(CO3 )y (HCO3 )z (OH)v + (1 − v + z) OH−
TESCAN, Czech Republic). High-resolution transmission electron mi­ (7)
croscopy (HRTEM) (FEI Tecnai G2 F20 SuperTwin, USA) and selected +(0.5 − y − z)CO3 2− →(Cu, Co)(CO3 )0.5 OH + zH2 O
area electron diffraction (SAED) were performed for the structural and The OH− , CO2− 2−
3 , and HCO3 anions are released by chemically
microstructural analysis at 200 kV. N2 ad/desorption isotherms were decomposition of the urea (CO(NH2)2) and NH4F molecules [59,60]. The
measured on the Tristar 3000 instrument (Micromeritics, USA). The urea molecules are hydrolyzed to NH+
4 and OH species as follows [59]:
−
CuCo2S4/NF electrodes were degassed at 250 ◦ C for 5 h.

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S.A. Sanei et al. Journal of Energy Storage 73 (2023) 109130

Fig. 1. XRD patterns of (a) LDH precursor and (b) sulfurized LDH precursor obtained by the 1.5 mmol CTAB surfactant (C 1.5) and without CTAB surfactant (C 0).

CO(NH2 )2 + 3H2 O→2NH4 + + 2OH− + CO2 (8) phase can be described by dissolving the CuCo LDH precursor in the base
media developed during hydrolyzation the sodium sulfide (Na2S) as
CO2 + 2OH− →CO3 2− + H2 O (9) follows [63]:

The NH4F molecules are also decomposed to liberate the H species+ Na2 S + 2H2 O⇋2NaOH + H2 S (13)
which can react with CO2−
3 to form the HCO3 anions as follows [59]:
−

NaOH⇋Na+ + OH− (14)

NH4 F→NH4 + + F− (10)
H2 S⇋H+ + HS− (15)
NH4 + + H2 O→NH3 H2 O + H+ (11)
HS− ⇋H+ + S− 2
(16)
CO3 2− + H+ →HCO3 − (12)
− 2 2+
The released S anions can proceed the coprecipitation of Cu and
The liberation of OH− increases the pH value of the precursor solu­ Co3+ cations as follows [33]:
tion, leading to the precipitation of metal ions in the form of hydrox­
ycarbonate on the NF substrate. Furthermore, the CO2− 3 species Cu2+ + Co3+ + S− 2 →CuCo2 S4 (17)
improves the hydrophilicity and wettability of the electrode surface,
The molecules of the cationic CTAB surfactant are composed of a
facilitating heterogeneous nucleation and growth on the NF substrate.
long hydrocarbon chain and a trimethylammonium group as polar head
The released F− anions increase the mobility of ions by reducing the
[64]. The CTAB molecules are dissolved and ionized as CTA+ and Br− in
viscosity of the precursor solution. The NH4F agent activates the NF
the mixed water-ethanol solvent. When the CTAB surfactant was added
substrate by providing higher active sites for nucleation and growth of
to the sulfurization step, the liberation of S2− can be promoted by its
LDH [59,61]. Furthermore, the F− anions can coordinate the metal
absorption by CTA+ [54]. However, the long CTAB molecule slow down
cations and then slowly release metal cations during the solvothermal
the ion mobility, resulting in the lower crystallinity.
reaction [62]. The XRD patterns of the sulfurized LDH powders in the
The charge storage performance of the electroactive materials could
absence of CTAB surfactant (C 0) and in the presence of 1.5 mmol CTAB
be greatly impacted by tailoring the morphology. Fig. 2a1–a4 show the
surfactant (C 1.5) are presented in Fig. 1b. The XRD reflections of (111),
CuCo LDH precursor grown on the NF substrate. The CuCo LDH pre­
(022), (113), (004), (224), (115), (044), (335), (444) and (137) planes
cursor has the needle-like particles which are agglomerated as flower­
are related to the spinel cubic structure of CuCo2S4 phase with space
like morphology. The anisotropic growth of LDH can be attributed to the
group of Fd3m (PDF2# 42-14150). With adding the CTAB surfactant,
F− anions released from hydrolyzing the NH4F molecule. The F− anions
the diffraction peaks became weak and broad, indicating the lower
adsorb to the crystal facets, leading to 1D crystal growth [59]. Following
crystallinity and smaller particle size. The crystallization of CuCo2S4
the sulfurization step (Fig. 2b1–b4), the morphology is transferred from

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S.A. Sanei et al. Journal of Energy Storage 73 (2023) 109130

Fig. 2. SEM images of (a) CuCo LDH precursor, (b) sulfurized LDH without using the CTAB surfactant (C 0).

Fig. 3. SEM images of (a1–a4) C 0.5, (b1–b4) C 1, and (c1–c4) C 1.5 samples.

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S.A. Sanei et al. Journal of Energy Storage 73 (2023) 109130

needlelike LDH to sheet-like CuCo2S4 by dissolving the needle-like LDH type with H3 hysteresis loop related to the fragile agglomeration of
precursor and coprecipitating the copper and cobalt sulfides by the S2− nanoparticles [69]. The BET specific surface area is 2.9 m2/g which was
ions [65]. The sheet-like morphology of CuCo2S4 can also be attributed comparable with other previously reported work [51]. There is a
to the Na+ counter ions, inducing anisotropic 2D crystal growth [66,67]. mixture of mesopores (2–50 nm) and micropore (1–2 nm) between
Fig. 3 compares the SEM images of the C 0.5, C 1, and C 1.5 samples to CuCo2S4 nanoparticles.
indicate the role of CTAB surfactant on the morphology. With adding the
CTAB surfactant during sulfurization process, the large sheet-like 3.2. Electrochemical performance
CuCo2S4 particles evolved to the small particular morphology without
any clear pores, specially at the higher CTAB contents. Furthermore, the 3.2.1. Three-electrode system
uniform deposition of CuCo2S4 with particular morphology is appeared Fig. 7a shows the CV curves of the C 0, C 0.5, C 1, and C 1.5 elec­
with the increase of CTAB contents due to the enhancing the wettability trodes at a potential window of 0 to 0.5 V vs. Ag/AgCl at a scan rate of 1
of NF. The particular morphology can be attributed to the inactivating mV s− 1. There are two broad redox peaks related to the reversible
the effects of Na+ counter ions via their absorption by the released Br− Faradic reactions of Co2+/Co3+/Co4+ and Cu+/Cu2+ in the KOH elec­
anions [54,68]. The elemental distribution of Co, Cu, S, and C of the C trolyte as follows [38]:
1.5 sample (Fig. 4) confirms that there is a uniform distribution of
CuCo2 S4 + OH− + H2 O⇌CuSOH + 2CoSOH + e− (18)
CuCo2S4 material on the NF substrate. The thermal decomposition of
CTAB surfactant led to the deposition of carbon element on the CuCo2S4
CuSOH + OH− ⇌CuSO + H2 O + e− (19)
material.
Fig. 5 shows the TEM and HRTEM images and SAED patterns and CoSOH + OH− ⇌CoSO + H2 O + e− (20)
EDS spectrum of the C 1.5 sample. The CuCo2S4 nanoparticles are
entirely embedded within a carbon matrix as a composite structure. The The specific capacitance is proportional to the area enveloped by CV
carbon matrix can be attributed to the thermal decomposition of CTAB curve [70]. Therefore, the C 1.5 electrode has the higher specific
molecules during sulfurization process. The carbon matrix can facilitate capacitance than the other electrodes. The sheet-like morphology of C
the charge transfer and increases the electrical conductivity as a crucial 0 electrode shows a specific capacitance of 575 F g− 1 which increased up
factor for charge storage performance. As shown in Fig. 5b, the lattice to 305, 961, and 4019 F g− 1 for the C 0.5, C 1, and C 1.5 electrodes,
fringe of 2.85 Å is assigned to the (113) plane of CuCo2S4 nanoparticles. respectively. Fig. 7b shows the CV curves of the C 1.5 electrode at
The ring SAED patterns (shown as the inset in Fig. 5b and c) are also different scan rates ranging from 1, 3, and 5 mV s− 1. The oxidation peak
indexed as (113), (004), and (335) according to the spinel crystal shifts positively, while the reduction peak moves negatively with the
structure of carrollite CuCo2S4 phase. In addition to Co, Cu, and S ele­ increase of scan rate, due to the polarization phenomenon. However, the
ments of CuCo2S4 nanoparticles, the EDS spectrum shows the presence CV curves maintain their stable shape at the higher scan rates, indicating
of Br and Na elements originated from the CTAB molecules as surfactant the high reversibility of redox reactions [71]. The relationship between
and Na2S as sulfur source, respectively. specific capacitance vs. scan rate is shown in Fig. 7c. The C 1.5 electrode
The N2 adsorption/desorption isotherms and pore size distribution has the largest specific capacitance at all scan rates due to its small
plot of the C 1.5 electrode are presented in Fig. 6. The isotherms are IV particle size and the presence of carbon matrix, improving its electrical
conductivity. With the increase of scan rate from 1 to 5 mVs− 1, the

Fig. 4. Elemental distribution of the C 1.5 sample.

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S.A. Sanei et al. Journal of Energy Storage 73 (2023) 109130

Fig. 5. (a and b) HRTEM and (c, d, and e) TEM images (the insets are SAED patterns) of the C 1.5 samples and (f) color contrast to present the CuCo2S4 nanoparticles
and the carbon matrix (blue color) and (g) EDS spectrum of elements. (For interpretation of the references to color in this figure legend, the reader is referred to the
web version of this article.)

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S.A. Sanei et al. Journal of Energy Storage 73 (2023) 109130

Fig. 6. (a) N2 adsorption-desorption isotherms and (b) pore size distribution plot of the C 1.5 electrode.

Fig. 7. (a) CV curves of the various electrodes at a scan rate of 1 mV s− 1, (b) CV curves of C 1.5 electrode at different scan rates, (c) specific capacitance at different
scan rates, (d) Ln (ip) versus Ln (ν), (e) the current response caused by the diffusion- and capacitive-controlled mechanisms, and (f) contribution ratios of
various samples.

specific capacitance of the C 1.5 electrode decreases from 4019 to 2301 are shown in Fig. 7e. Fig. 7f compares the contribution of various storage
F g− 1. mechanisms for various samples. The diffusion-controlled process is
The charge storage mechanism influences the current response, prevalent in the C 0 and C 1.5 samples owing to their porous and hier­
which can be analyzed by the dependence of current response (i) on the archical microstructure and more redox reactions [75,76]. There is a
scan rate (ν) according to the power law [72]: i = aνb in which the b nearly equal proportion of the two mechanisms for the C 1 sample. For
value as the slope of Ln(ν)-Ln(ip) linear plot (Fig. 7d) shows the pre­ the C 0.5 sample, the capacitive-controlled process is predominant.
dominate storage mechanism. The b value of 0.5 is related to diffusion- Fig. 8a displays the galvanostatic charge/discharge (GCD) curves of
controlled process (battery-type behavior) and the b value of 1 shows a the C 0, C 0.5, C 1, and C 1.5 electrodes at a current density of 1 A g− 1.
capacitive-controlled process (capacitive-type behavior) [73]. The b The GCD curves are nonlinear with a pair of charge and discharge pla­
value of C 0 electrode is 0.52 which increases up to 0.62, 0.66, and 0.60 teaus related to the Faradaic reactions. The C 1.5 electrode has the
for the C 0.5, C 1, and C 1.5 electrodes, respectively. With adding the highest specific capacitance of 4230 F g− 1 in comparison to 714, 365,
CTAB surfactant during sulfurization process, the charge storage and 1146 F g− 1 for the C 0, C 0.5, and C 1 electrodes. The higher specific
mechanism changes from the capacitive-type to the battery-type capacitance of the C 1.5 electrode can be attributed to the smaller par­
behavior on account of its smaller particle size and higher electrical ticle size and higher electrical conductivity. The GCD curves of C 1.5
conductivity. To determine the contribution of various mechanisms, the electrode at various current densities are illustrated in Fig. 8b. The
CV curves were analyzed by calculating the k1 and k2 coefficients from dependence of specific capacitance on the current density is shown in
following equation [74]: Fig. 8c. The C 1.5 sample has the higher specific capacitance at all
current densities. With the increase of current density from 1 to 10 A
ip (v) = k1 ν + k2 ν0.5 (21)
g− 1, the specific capacitance of the C 1.5 electrode decreases from 4230
The contributions of current response caused by the capacitive and to 2275 F g− 1, corresponding to a capacity retention of 54 %. The rate
diffusion-controlled process are separated for the C 1.5 sample which capability of various electrodes is shown in Fig. 8d. However, the C 0, C

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S.A. Sanei et al. Journal of Energy Storage 73 (2023) 109130

Fig. 8. (a) GCD curves of the samples at a current density of 1 A g− 1, (b) GCD curves of the C 1.5 sample at various current densities, (c) specific capacitances at
various current densities, (d) rate capability of various samples, (e) comparison of specific capacitance and capability rate with the other previously published works,
and (f) cycling performance of the C 1.5 electrode at a current density of 10 A g− 1.

0.5, and C 1 electrodes shows the higher capacity retention than that of various potential windows at a scan rate of 20 mVs− 1. Fig. 10c shows the
C 1.5 electrode. At high current densities, only the exterior surfaces of GCD curves of the symmetric capacitor different working potential
the active material participate in Faradic redox reactions. As a conse­ windows of 0–1 to 0–1.4 V. The CV and GCD curves indicate that the
quence, the capacitive-type behavior controls the charge storage, CuCo2S4//CuCo2S4 capacitor can store the electrochemical energy in the
resulting in a significant reduction in the specific capacitance. At a low potential window of 0–1.4 V without any overpotential. As the potential
current density, the specific capacitance will be higher due to the window rises up to 1.5 V, the oxygen and hydrogen are evolved at the
participation both the outside and inside areas of the electroactive ma­ positive and negative electrodes, respectively. The CV and GCD curves of
terials in the electrochemical reactions and penetration the electrolyte the symmetric CuCo2S4//CuCo2S4 capacitor at various scan rates and
(OH− ) ions into more active sites [77,78]. Fig. 8e compares the specific current densities are shown in Fig. 10d and e, respectively. The CV and
capacitance and capability rate of the C 1.5 sample with various re­ GCD curves show the similar shape at all scan rates and current densities
ported CuCo2S4-based electrodes [31,37,38,40,41,44]. Although the C due to the strong reversibility of redox reactions caused by the small
1.5 sample has the low capability rate of 54 %, but its specific capaci­ particles and high electrical conductivity [79]. Furthermore, the specific
tance surpasses the other electrodes due to its hierarchical microstruc­ capacitance of the symmetric capacitor is 116 F g− 1 at 2 A g− 1 which
ture with small particle size and higher electrical conductivity caused by decreases up to 43 F g− 1 at 10 A g− 1. The energy density and power
the deposited carbon layer. The cycling performance of the C 1.5 elec­ density are 63 Wh kg− 1 and 2800 W kg− 1, respectively, by applying a
trode was evaluated at a current density of 10 A g− 1 (Fig. 8f). After 2500 current density of 2 A g− 1. Fig. 10f shows the cycling performance of
charge/discharge cycles, the specific capacitance decreases from 660 to symmetric supercapacitor at a current density of 2 A g− 1. The capacitor
548 F g− 1, indicating a capacity retention of 83 %. can sustain 81 % initial capacitance following 2000 charge/discharge
For studying the charge transfer resistance, the electrochemical cycles. The Ragone plot, energy density vs. power density, of the sym­
impedance spectroscopy (EIS) was performed. Fig. 9a shows the Nyquist metric CuCo2S4//CuCo2S4 capacitor is compared with other asymmetric
plots (− Z″ vs. Z′) of various electrodes. By fitting the EIS data according capacitors [29,37,38,40,50,80–82] in Table 1. At a power density of
to the equivalent circuit, the Rs, Rct, and Wo parameters were calculated 13,992 W kg− 1, the energy density drops to a minimum of 23.32 Wh
and summarized in Fig. 9b. The Rs value shows the total resistance of kg− 1 by applying the current density of 10 A g− 1. The higher energy
nickel foam, contact, and uncompensated solution resistance. The Rct density of the symmetric CuCo2S4//CuCo2S4 capacitor can be attributed
value as charge transfer resistance is related to the Faradic redox re­ to the higher specific capacitance of the CuCo2S4 electrode in the
actions between the electroactive materials and electrolyte (OH− ) ions. negative potential window.
The resistance caused by the ionic diffusion on the electrode surface
regarded as Warburg impedance (Wo). The C 1.5 sample has the lower 4. Conclusion
Wo and Rct values which is due to the smaller particle size and meso­
pores’ nature. In summary, a facile CTAB assisted two-step solvothermal method
has been used to prepare the free-binder CuCo2S4/nickel foam electrode.
3.2.2. Two-electrode system Adding the CTAB surfactant during the sulfurization led to the
An aqueous symmetric supercapacitor (ASC) device was designed by morphological evolution from large sheet-like to the particular one with
the CuCo2S4 electrodes as both positive and negative electrodes. Fig. 10a small nanoparticles. The CuCo2S4 nanoparticles were uniformly
shows the CV curves of the C 1.5 electrode in both positive (0–0.5 V vs. dispersed in the carbon matrix caused by thermally decomposition of the
Ag/AgCl) and negative (+0.2–(− 1.2) V vs. Ag/AgCl) range. Fig. 10b CTAB molecules. The specific capacitance increased from 714 to 4230 F
depicts the CV curves of the symmetric CuCo2S4//CuCo2S4 capacitor at g− 1 by adding further CTAB surfactant. Furthermore, the symmetric

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S.A. Sanei et al. Journal of Energy Storage 73 (2023) 109130

Fig. 9. (a) Nyquist plots and equivalent circuit, (b) the fitted values of resistance parameters.

Fig. 10. (a) CV curves of the C 1.5 electrode in both positive and negative potential windows at 1 mV s− 1, (b) CV and (c) GCD curves at various potential windows,
(d) CV curves at various scan rates, (e) GCD curves versus current density, and (f) cyclic performance at current density of 2 A g− 1, (g) Ragone plot.

CuCo2S4//CuCo2S4 capacitor showed high energy density of 63 Wh kg− 1

Table 1
at power density of 2.8 kW kg− 1 by applying a current density of 2 A g− 1.
Comparison of energy density (ED) and power density (PD) of CuCo2S4-based
capacitors (AC shows activated carbon).
CRediT authorship contribution statement
Positive electrode Morphology of ED (Wh PD (W Refs.
CuCo2S4 kg− 1) kg− 1)
S. A. Sanei: Data curation, Formal analysis. S.M. Masoudpanah:
CuCo2S4//CuCo2S4 Nanoparticles 63 2800 This Supervision, Conceptualization, Writing - review & editing. M. Sh.
work
Bafghi: Advisor, Conceptualization.
CuCo2S4//AC Nanowires 57 320 [29]
CuCo2S4//AC Nanosheets 46 992 [38]
CuCo2S4//Fe2O3/ Porous particles 90 662 [81] Declaration of competing interest
graphene
CuCo2S4//AC Nanowire 33 751 [37] The authors declare that they have no known competing financial
CuCo2S4//AC Sugar gourd-like 17 194 [82]
CuCo2S4//AC Mesoporous 15 400 [50]
interests or personal relationships that could have appeared to influence
CuCo2S4/CuCo2O4// Flower like 33 13,300 [80] the work reported in this paper.
graphene aerogel
CuCo2S4//CuCo2S4 Nanograss 32 3020 [40] Data availability

Data will be made available on request.

9
S.A. Sanei et al. Journal of Energy Storage 73 (2023) 109130

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