Chemical Engineering Journal 368 (2019) 772–783

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Chemical Engineering Journal

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

Molybdenum selenide nanotubes decorated carbon net for a high T

performance supercapacitor
⁎
Manoranjan Ojha, Melepurath Deepa
Department of Chemistry, Indian Institute of Technology Hyderabad, Kandi, Sangareddy 502285, Telangana, India

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• tubes
Molybdenum selenide (MoSe ) nano-
are synthesized from SiO na-
2
2
nospheres scaffold.
• Carbon net (CN) with a holey nanos-
tructure is prepared from a templating
route.
• Encapsulated MoSe2@CN//CN super-
capacitor shows a capacitance of
101.3 mF cm−2.
• High energy density
12.22 µWh cm−2 is attained at a
of

power density of 0.5 mW cm−2.

• Toy fan is powered with this unique
supercapacitor; it outperforms many
MoS2 supercapacitors from literature.

A R T I C LE I N FO A B S T R A C T

Keywords: A unique encapsulated asymmetric supercapacitor is implemented with a yet unreported electrode architecture
Molybdenum selenide of molybdenum selenide nanotubes decorated carbon net (MoSe2@CN) hybrid. MoSe2 and CN are independently
Carbon synthesized hydrothermally by using SiO2 nanospheres as a scaffold and a template respectively. The synergistic
Capacitance effects of MoSe2, namely, a porous nanostructured morphology that enables easy electrolyte penetration, and
Supercapacitor
maximizes active MoSe2 sites’ utilization coupled with a high redox activity towards Li-ion insertion and ex-
Energy storage
traction via short ion-diffusion pathways and of CN, such as high electrical conductivity that ensures facile ion
and electron transport across the electrodes, and a distinctive holey nanostructure result in a superior areal
specific capacitance (SC) of 101.3 mF cm−2 (at 5 mV s−1)/88 mF cm−2 (at 0.5 mA cm−2) for the asymmetric
MoSe2@CN//CN cell contrasting strongly against the lower performances of the symmetric MoSe2, CN and
MoSe2@CN analogues. The MoSe2:CN proportion in the MoSe2@CN hybrid is found to be optimal at 3:1, for the
cell based on this hybrid delivers significantly enhanced SCs compared to its’ counterparts with lower (1:1 and
2:1) and higher (4:1) MoSe2 content. The MoSe2@CN//CN cell also outperforms many reported MoS2/carbon
nanomaterial composites in terms of the voltammetric and galvanostatic SCs. Further, an energy density of
12.22 µWh cm−2 at a power density of 0.25 mW cm−2 is achieved for the asymmetric MoSe2@CN//CN cell. The
demonstration of a mini toy fan using three such cells connected in series validate the practical usability of this
cell.

⁎
Corresponding author.
E-mail address: mdeepa@iith.ac.in (M. Deepa).

https://doi.org/10.1016/j.cej.2019.03.002
Received 31 December 2018; Received in revised form 21 February 2019; Accepted 1 March 2019
Available online 02 March 2019
1385-8947/ © 2019 Elsevier B.V. All rights reserved.
M. Ojha and M. Deepa
1. Introduction
Supercapacitors are at the forefront of energy storage research, for
they can offer a high burst of power for a short duration (required for
ignition start in vehicles), they can undergo a million charge-discharge
cycles without undergoing degradation, and they can be designed to be
composed of environmentally benign components, thereby enabling
their safe disposal. Carbon nanomaterials such as reduced graphene
oxide (RGO), activated carbon, carbon nanotubes (CNTs) etc have been
exhaustively used as active electrodes in supercapacitors, owing to the
following factors. (1) Their high electrical conductivities (in the range
of 10−2 to 104 S cm−1) [1] which allow fast charge transfer at the
electrode/electrolyte interface and rapid charge transport across the
cross-section of the active electrode, thus resulting in high power
densities (∼0.01 to 10 kW kg−1) [2]. (2) Ease of preparation and de-
position in the form of uniform thin coatings over current collectors,
render them to be scalable. (3) Chemical and electrochemical robust-
ness impart long term cyclability to the cell. Carbon nanomaterials rely
on the electrical double layer (EDL) mechanism for uptake and release
of charge. However, the voltage window over which they are generally
operated is rather narrow, typically less than or equal to 1 V. This limits
the energy density (E) of the supercapacitor, for E = ½ (SC)V2, where
SC is the specific capacitance. Energy density for carbon super-
capacitors, generally lies in the range of 2 to 5 Wh kg−1 [3]. Contrasting
with carbon supercapacitors that deliver low E and high P are the li-
thium ion batteries which provide high E but low P.
Considering the applications which are currently in vogue, namely,
consumer electronic devices, powered tools, voltage stabilizers, low
power equipment buffers, hybrid vehicles, medical and industrial
equipment, where supercapacitors can be either used alone or in
tandem with batteries, thus, improving the latter’s operational life, a
better balance between E and P is desirable. This can be achieved by
designing supercapacitors with components that can deliver this bal-
ance. Composites of metal chalcogenides or oxides with carbon na-
nostructures are capable of delivering this, for the chalcogenide/oxide
can sustain a wide voltage window (> 1 V), maximize E, while the
carbon ensures fast charge transfer and propagation, thus preserving a
high P. The drawback of low electrical conductivity of the chalcogenide
or oxide, can be addressed by preparing it in the form of a porous na-
nostructure that can impart short diffusion lengths, and enable fast
electrochemical reactions with ions in the electrolyte. For instance, a
porous alumina network interpenetrated into porous fibres of CNT
composites (21 wt% of ɤ-Al2O3/CNTf) delivered a SC of 16 mF cm−2
which was three times more than the bare CNTf at the same scan rate
(5 mV s−1) [4]. For a MWNTs-TiO2 nanotube hybrid electrode, SC of
4.4 mF cm−2 was obtained under a current density of 0.1 mA cm−2 [5].
In another study, a MnO2-CNT composite exhibited a SC of 1.0 F cm−2
at 1.28 mA cm−2 [6]. Cheng et al., reported a graphene-CNT-MnO2
composite with a SC of 22 mF cm−2 at a scan rate of 50 mV s−1 [7].
Similarly, metal di-sulfides have also been used alone or with
carbon nanomaterials with the objective of achieving high super-
capacitor performance. Amorphous MoSx thin-film-coated carbon fiber
paper based symmetric supercapacitor delivered a maximum SC of
83.9 mF cm−2 at a scan rate of 1 mV s−1 [8]. MoS2@carbon nanotube
(CNT)/RGO composite based flexible supercapacitor delivered a max-
imum SC of 29.5 mF cm−2 at a scan rate of 5 mV s−1 [9]. In an earlier
report, a composite of WS2 nanoparticles encapsulated amorphous
carbon tubes were coated over a Ni foam, and in a 3-electrode cell, it
gave a SC of 337 F g−1 at 10 A g−1. But the operational voltage window
was only limited to 0.55 V [10]. An asymmetric supercapacitor with a
NiSe@MoSe2 nanosheet array as a positive electrode and a nitrogen-
doped pomelo mesocarps-based carbon nanosheet as a negative elec-
trode produced a SC of 223 F g−1 at a current density of 1 A g−1 [11].
But the cell retained only 91.4% SC after 500 cycles, which is lower
than the cycle life attained in this work [11]. There are also reports on
CoS2 ellipsoids with anisotropic tube-like cavities [12], and sponge-like
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Chemical Engineering Journal 368 (2019) 772–783
NiS2 materials composed of loose thin wires [13]. Although CoS2 and
NiS2 delivered high SCs of 980 and 1685 F g−1 at 1 A g−1, but these
were achieved over narrow voltage windows of 0.5 and 0.4 V respec-
tively, and that too, in 3-electrode configurations [12,13]. A device
encompassing 2-dimensional (D) molybdenum diselenide (MoSe2) with
polyvinylidene fluoride-co-hexafluoropropylene/tetraethylammonium
tetrafluoroborate (PVdF-co-HFP/TEABF4) ion gelled PVdF/sodium
niobate (NaNbO3) delivered a SC of 18.93 mF cm−2 at a discharge
current of 0.5 mA [14]. In another study, MoS2 nanowall films were
deposited over a Ta electrode, and they showed a SC of 70 mF cm−2 at a
scan rate of 1 mV s−1 in an aqueous solution of 0.5 M H2SO4 in a 3-
electrode cell [15]. In yet another report on a WS2/RGO hybrid, the
highest SC was 350 F g−1 at 2 mV s−1 and also at 0.5 A g−1. Authors
observed that the hybrid delivered a substantially higher SC than the
individual components: WS2 and RGO [16].
By incorporating the best of the above-described design approaches,
here we describe the preparation of a molybdenum selenide@carbon
net (MoSe2@CN) hybrid and application to symmetric and asymmetric
supercapacitors supported over flexible Ni foam current collectors.
Encapsulated asymmetric supercapacitors with a MoSe2@CN//CN
configuration, not only outperformed other configurations, but they
also show outstanding performance metrics compared to literature va-
lues of metal chalcogenide based supercapacitors. This study furnishes a
detailed account of electrochemical and structural aspects, followed by
their use in a practical application.
2. Experimental
2.1. Chemicals
Tetraethyl orthosilicate (TEOS, 98%), ammonia solution (25%),
anhydrous ferric chloride, ethanol (98%) and hydrofluoric acid (HF)
were procured from Merck. Sodium molybdate dehydrate (99.5%),
hydrazine hydrate (50–60%), D-(+)- glucose, carbon black, ethanol
(98%), lithium perchlorate (LiClO4), sodium alginate, poly(vinylidene
fluoride) (PVdF, average MW: 534000), N-methyl pyrrolidone (NMP),
were procured from Sigma-Aldrich and used as such. Selenium power
(99%) was purchased from Alfa Aesar and used directly. Ultrapure
water (resistivity ∼18.2 MΩ cm) was obtained through a Millipore
Direct-Q3 UV system. Ni foam current collectors were procured from
Gelon and used after cleaning them with acetone.
2.2. Synthesis of SiO2 nanospheres
SiO2 nanospheres were prepared using a previously reported pro-
cedure [17]. 10 mL of ethanol, 15 mL of 25% ammonia solution and
8 mL of ultrapure water were taken in a 50 mL beaker and stirred for
5 min. To this solution, TEOS (0.8 mL) was added dropwise with stirring
over a duration of 45 min., and stirring was continued for 2 h at room
temperature. A white colored turbid solution was obtained which was
isolated by centrifugation and washed thoroughly with ultrapure water.
The solid was dried at 80 °C in air, and the resultant white solid was
labelled as SiO2 nanospheres and stored in a desiccator.
2.3. Synthesis of MoSe2 nanotubes
SiO2 nanospheres (12.5 mg) were taken in a 50 mL beaker and 5 mL
of ultrapure water and 7.5 mL of ethanol were added. The mixture was
stirred for 1 h. Sodium molybdate dihydrate (52.5 mg) was introduced
to the beaker and stirred for another 1 h. In a separate beaker, selenium
power (45 mg) was dissolved in 2.5 mL of hydrazine hydrate. The Se
solution was added to the sodium molybdate/SiO2 solution. The re-
sulting solution was stirred for 48 h at room temperature, after covering
with a petridish. The ensuing black mixture was transferred to a Teflon
lined autoclave and heated at 200 °C for 24 h and then cooled to room
temperature. The black precipitate obtained was isolated by
M. Ojha and M. Deepa
Scheme 1. Cartoons and photographs illustrate the preparation of (a) SiO2 template, (b) CN electrode, (c) MoSe2@CN electrode and MoSe2@CN//CN cell (shown in
(d)).
decantation and washed thoroughly with ultrapure water and ethanol
respectively. The black solid was dried and was labelled as MoSe2 na-
notubes and stored in a desiccator. Scheme 1 shows a cartoon illus-
trating the preparation of MoSe2 nanotubes.
2.4. Synthesis of carbon net (CN)
CN was synthesized by the mixing of SiO2 nanospheres and D-
(+)-glucose in a 1:1 w/w ratio. The 50 mg mixture was ground for 1 h,
and transferred to a 100 mL beaker. Ultrapure water (10 mL) was added
and after stirring for 24 h, anhydrous ferric chloride (5 mg) was in-
troduced and the formulation was heated to 80 °C and maintained at
this temperature for 20 min., till a thick mixture was obtained. The
thick mixture was transferred to a crucible and calcined in a box fur-
nace at 750 °C for 4 h in air where the final temperature was achieved in
approximately 1.5 h (rate of temperature increase: 8 °C per min). It was
allowed to cool to room temperature in the natural way. The obtained
carbon mixture was transferred to a 50 mL beaker and 5 mL of 2 M
hydrofluoric acid was added and stirred overnight, to extract the SiO2
nanospheres into the liquid phase. The black precipitate was thoroughly
washed with ultrapure water and collected by decantation method. It
was dried at 80 °C in air and labelled as carbon net or CN.
2.5. Cell fabrication
In a weight ratio of 3:1, MoSe2 powder (30 mg) and CN (10 mg)
were dry-grinded using a mortar-pestle assembly for 2 h to obtain a
MoSe2@CN hybrid. To this, 5 mg of each PVdF and carbon black (CB)
were added and grinded for 20 min. Thus, the weight ratio of MoSe2,
CN, PVdF and CB in the MoSe2@CN (3:1) hybrid was 60:20:10:10.
Then, requisite number of drops of NMP were added and grinded for
another 20 min. to obtain a good slurry. The slurry was coated over Ni
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Chemical Engineering Journal 368 (2019) 772–783
foam over a geometric area of 1.5 cm2. Finally, it was dried in a vacuum
oven at 70 °C for 12 h and the MoSe2@CN hybrid electrode was ob-
tained. The total loading of this material over Ni foam having a geo-
metric area of 1.5 cm2 is ∼1.2 mg, which implies that MoSe2 content is
0.72 mg, CN is 0.24 mg, PVdF and CB are 0.12 mg each. The weights
were measured on a high precision microbalance. Three more
MoSe2@CN (x:1) (x: 1, 2, 4) hybrids were prepared, by varying the
MoSe2 content in the hybrid. The proportions (by weight) of MoSe2, CN,
PVdF and carbon black in the corresponding three MoSe2@CN (x:1)//
CN cells labeled as 1:1, 2:1, and 4:1 are 40:40:10:10, 52:26:10:10 and
64:16:10:10 respectively. Their slurries were also coated over Ni foam
substrates and dried at 70 °C under vacuum. Similarly, two more slur-
ries were prepared with MoSe2:PVdF:CB and CN:PVdF:CB (by mixing
the components in weight ratios of 80:10:10), and these slurries were
applied over Ni foam substrates and subjected to the same thermal
treatment as described above for the hybrid to obtain the MoSe2 and CN
electrodes respectively. A 2 M aqueous electrolyte was prepared by
dissolving 2.12 g of LiClO4 in 10 mL of ultrapure water. An electrolyte
soaked Whatman filter paper separator was placed carefully between
two active electrodes. Symmetric cells with the following configura-
tions: MoSe2//MoSe2, CN//CN and MoSe2@CN//MoSe2@CN and an
asymmetric cell with MoSe2@CN (3:1)//CN architecture, were fabri-
cated, by first soldering Ni tabs on the free exposed (Ni-foam) edges of
the active electrodes and stapled as well to hold them in place. The cells
were heat sealed in polyethylene pouches, using a laminating machine.
Three more asymmetric cells were made in the MoSe2@CN (x:1)//CN
(x: 1, 2, 4) configuration only for the optimization of the MoSe2 content.
In this report, the term “MoSe2@CN” implies a 3:1 proportion for
MoSe2:CN by weight, unless specified otherwise.
M. Ojha and M. Deepa
2.6. Instrumentation techniques
X-ray diffraction patterns were recorded on a PANalytical,
X’PertPRO instrument with a Cu-Kα (λ = 1.5406 Å) radiation, as the X-
ray source. Surface morphology analysis was performed using a scan-
ning electron microscope (Carl Zeiss EV018). Transmission electron
microscopy (TEM) images were obtained on a JEOL 2100 microscope
operating at an accelerating voltage of 200 kV by using samples de-
posited over carbon coated copper grids by using the method of sus-
pension and evaporation. Optical absorption spectra of solutions were
measured in absorbance mode on a UV–vis spectrophotometer (T90+,
PG Instruments). Galvanostatic charge-discharge, cyclic voltammetry,
linear sweep voltammetry, self-discharge, on an Autolab PGSTAT 204
potentiostat-galvanostat and electrochemical impedance spectroscopic
(EIS) studies were performed on an Autolab PGSTAT 302 frequency
response analyzer.
3. Results and discussion
3.1. Structural aspects and electrical behavior of electrode components
SEM images of MoSe2, silica template, carbon net (CN) and
MoSe2@CN are displayed in Fig. 1. Fig. 1a and b show the SEM images
of MoSe2. As can be seen from the images, MoSe2, at the macroscopic
level, is composed of tubular shapes, and these elongated structures are
oriented randomly. The MoSe2 nanotubes also tend to aggregate, as
individual nanotubes are observed to be overlapping with each other,
and appear to be almost fused into one another. The morphology is also
porous; such a porous structure is conducive for facile percolation of
electrolyte during charge-discharge. This allows, apart from the surface,
Fig. 1. SEM images of (a, b) MoSe2, (c) SiO2 nanospheres template, (d, e) carbon net (CN) and (f) MoSe2@CN hybrid.
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the bulk of the material to also undergo redox reactions. The silica
template used for creating the carbon net, shows a uniform network of
well-connected spherical SiO2 particles, with a narrow distribution in
size, ranging from 0.2 to 0.4 µm (Fig. 1c). Such a microstructure enables
the formation of the mesoporous carbon net like structure, after silica is
selectively removed by an acid wash. The resulting material is aptly
labeled as CN, for it comprises of a net like, highly porous carbon
structure (Fig. 1d, e). Pore dimensions vary from 250 to 300 nm, and
they are distributed uniformly over several micron lengths. From a
macroscopic viewpoint, the carbon framework is composed of quasi-
spherical voids. It serves as the robust support for a holey structure,
which is again not only very useful for the percolation of electrolyte,
but since the carbon framework appears continuous, the high electrical
conductivity is preserved. This results in a high power density. Further,
due to the ample porosity, it is expected that a large number of ions can
anchor to the available active sites, thus resulting in a high SC. The
MoSe2@CN hybrid comprises of overlapping MoSe2 and CN structures
(Fig. 1f). They are practically indistinguishable from each other in the
image. Since MoSe2 and CN are enmeshed with each other, the strong
interfacial contact between the two components permits facile electron
transfer between MoSe2 and CN during charge-discharge. While MoSe2
switches between two redox states, concurrently, the CN captures the
Li+ or ClO4− ions from the electrolyte through electrostatic attraction.
The synergy between MoSe2 and CN is tapped in the MoSe2@CN//CN
based cell, which leads to a superior electrochemical response com-
pared to the CN//CN and MoSe2//MoSe2 cells.
The TEM image of MoSe2 reveals a uniform distribution of mingling
nanotubes separated by elongated pores (Fig. 2a, b). The tubes give the
appearance of being almost amalgamated into one another. Their
widths and lengths are in the ranges of 17 to 22 and 30 to 60 nm
M. Ojha and M. Deepa
Fig. 2. (a, b) TEM- and (c) lattice scale- images of MoSe2, (d, e) TEM- and (f) lattice scale- images of CN and (g) TEM- and (h, i) lattice scale- images of MoSe2@CN
hybrid.
respectively. They appear to be hollow (∼3.5 nm wide), with thick
shells, for white streaks are observed in the middle, along the length of
the nanotubes. The tubes also happen to be curled up in many regions.
Similar mesoporous microstructures have been observed for MoSe2
prepared using a KIT6 hard template [18]. The corresponding lattice
scale image also confirms this, as curved or bent fringes are visible
(Fig. 2c). The inter-fringe separation is ∼0.65 nm, which matches well
with an interplanar spacing of 0.6465 nm, corresponding to the (0 0 2)
plane of the hexagonal structure of MoSe2 (PDF: 872419). Carbon net
shows a sheet like structure with a holey shapes, roughly 7 nm in dia-
meter. The higher magnification image reveals swirled up fiber like
shapes (Fig. 2d, e). It is obvious from the image, that the carbon net has
a high effective surface area that can provide many electroactive sites
for ions to anchor to, during charge-discharge. The lattice fringes are
curled up in the high resolution image, and the inter-fringe distance is
0.34 nm, (Fig. 2f) which agrees with the (0 0 2) plane of graphitic
carbon (PDF#75-1621). The image of the MoSe2@CN hybrid shows
fiber and nanotube like shapes entangled together, indicating they are
mixed well (Fig. 2g). The lattice scale images show interplanar spacings
of 0.65 and 0.34 nm, (Fig. 2h and 2i) corresponding to orthorhombic
MoSe2 and graphitic carbon respectively.
XRD patterns of CN and MoSe2 are shown in Fig. 3a. The pattern for
CN shows three peaks at 2θ = 26.02°, 43.3° and 54.0° corresponding to
d = 3.40, 2.14, 1.70 Å, and they are assigned to the (0 0 2), (1 0 1) and
(0 0 4) planes of hexagonal graphite. MoSe2 is characterized by several
prominent peaks at 2θ = 13.68°, 31.39°, 37.84°, 47.45° and 56.93°
which match with d = 6.46, 2.85, 2.37, 1.91, and 1.62 Å. The d-values
are aligned to the (0 0 2), (1 0 0), (1 0 3), (1 0 5), and (0 0 8) planes of
MoSe2 with a hexagonal primitive lattice. Similar crystal structure for
MoSe2, synthesized by hydrothermal technique has been reported in the
past [19–21]. Raman spectra of MoSe2, MoSe2@CN and CN are shown
in Fig. 3b. Multiple lattice vibrational modes of MoSe2 are observed,
with the prominent ones positioned at 92 and 112 cm−1 which are
assigned to the E2g2 mode, or the in-plane bending of Se-Mo-Se bonds).
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The peak at 147 cm−1, is ascribed to the E1g mode, the in-plane bending
of the Se atoms. The peak at 237 cm−1, is due to the A1g mode corre-
sponding to the out of plane bending of Se atoms, where the Se atoms in
the successive layers oscillate in phase with respect to the central Mo
atom, that remains stationary [22]. Strong scattering peaks at
281 cm−1, and 335 cm−1 stem from the E2g1 mode (in plane bending of
Mo-Se-Mo) and due to a B2g mode respectively [23]. The latter mode is
Raman inactive in bulk MoSe2, but is known to appear at 314 [23] and
353 cm−1 [22], due to the breakdown of translation symmetry in nano-
layered MoSe2. CN shows two strong D and G bands at 1337 and
1555 cm−1. The former peak is due to the defects in CN caused by
oxygen functionalities that bind to the carbons in the graphitic network,
and the latter one is due to the in-plane stretching of the sp2 hybridized
carbons of the graphitic framework. A low intensity 2D band is also
observed at 2675 cm−1, which is an overtone of the fundamental D-
band. The D and G bands are blue- and red- shifted to 1347 and
1576 cm−1 in MoSe2@CN. This occurs possibly due to the electrostatic
and van der Waals’ interactions between the CN and MoSe2 nanotubes.
The attractive forces between the Mo4+ atoms and the polar C–O
groups on CN, strengthen the C–C bonds, thus causing the 1337 cm−1
band to shift to higher energies. Of all the MoSe2 peaks, only two dis-
tinctive peaks are observed at 240 and 283 cm−1 due to the A1g and the
E2g1 modes respectively. In several previous reports on MoSe2, only
these two peaks have been observed [24,25]. Raman spectral analysis
of MoSe2@CN shows the signature peaks of CN and MoSe2 with slightly
altered positions, indicating a uniform mixing of the two components.
CN, MoSe2, and MoSe2@CN are explored further by comparing their
conduction behavior estimated by I-V measurements (Fig. 3c). Samples
were manually compressed using a spatula into a rectangular cavity
created over a SS foil with an insulating sticky tape that served as a
spacer as well (Fig. 3d). By affixing another SS foil over this assembly,
the resulting SS/sample/SS configuration was subjected to dc mea-
surements. The plots for all the 3 samples: CN, MoSe2, and MoSe2@CN,
are almost linear, indicative of an Ohmic dependence of current on
M. Ojha and M. Deepa
Fig. 3. (a) XRD patterns of MoSe2 and CN. (b) Raman spectra of MoSe2, CN and MoSe2@CN. (c) I-V characteristics of MoSe2, CN and MoSe2@CN hybrid; inset shows
an enlarged view for MoSe2 and (d) schematic illustrating the cell configuration used for the I-V measurements in dc mode in (c).
applied bias. From the slopes, electrical conductivities (κ) were calcu-
lated by using the relation: κ (S cm−1) = ΔI/ΔV (l/a). The con-
ductivities are 2.6 mS cm−1, 1.1 μS cm−1 and 1 mS cm−1 for CN, MoSe2
and MoSe2@CN hybrid respectively. CN is characterized by the highest
electrical conductivity owing to the graphitic nature of the carbon
framework. The carbon atoms are predominantly sp2-hybridized, where
each carbon atom is covalently attached to 3 other carbon atoms in the
plane by σ-bonds. The fourth electron resides in an unhybridized π-
orbital oriented above and below the graphitic plane. This electron
moves freely between the layers, which is the reason for the high
conductivity of CN. MoSe2 is an indirect band gap semiconductor with a
layered structure where Mo and Se atoms form a 2D hexagonal lattice
with trigonal prismatic coordination. So the mechanism of electrical
conduction is different from that of CN. The valence band (VB) is made
up of filled d-orbitals of Mo, and the conduction band is composed of
the p-orbitals of Se, and since the absorption edge is at ∼900 nm, the
band gap is 1.38 eV (Fig. S1, supporting information). At room tem-
perature, transitions from the VB to the intra-gap defect states, result in
the observed conductivity of 1.1 μS cm−1. This is comparable to a
previously reported conductivity of MoSe2 (a × 10−4 S cm−1), where
the chalcogenide was prepared by an arrested precipitation technique
method [26]. By mixing CN with MoSe2, the conductivity of the ensuing
MoSe2@CN hybrid is enhanced by three orders of magnitude compared
to pristine MoSe2. This enhanced conductivity plays a pivotal role in
amplifying the charge storage attributes of the corresponding cell, for
supercapacitor electrodes are required to exhibit mixed conduction, and
allow fast transport and transfer of electrons and ions.
3.2. Optimization of MoSe2 in MoSe2@CN hybrid
To analyze the effect of MoSe2 content (in the MoSe2@CN hybrid)
on cell performance, the charge storage characteristics of four asym-
metric cells having different MoSe2 proportions re compared in Fig. 4.
The cells have the following configuration: MoSe2@CN (x:1)//CN,
where x = 1, 2, 3 and 4. The proportions (by weight) of MoSe2, CN,
PVdF and carbon black in the four cells labelled as 1:1, 2:1, 3:1, and 4:1
are 40:40:10:10, 52:26:10:10, 60:20:10:10, and 64:16:10:10 respec-
tively. A schematic illustrating the configuration of the four cells is
shown in Fig. 4a. Cyclic voltammograms and galvanostatic charge-
discharge characteristics for the 4 cells are compared in Fig. 4(b–h). It is
evident from the CV plots that the area enclosed in the voltammograms
at all scan rates (5, 20, 100 and 200 mV s−1) is significantly higher for
the MoSe2@CN (3:1) hybrid, relative to all other scan rates. The cor-
responding SCs also reflect this, for the 3:1 hybrid has a SC of
88 mF cm−2, in comparison to SCs of 44, 66 and 61 mF cm−2 obtained
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for 1:1, 2:1 and 4:1 hybrids, at the same current density of
0.5 mA cm−2. The MoSe2@CN (3:1) hybrid outperforms the remaining
3 hybrids with lower and higher MoSe2 contents, as can be seen from
the data in Table S1 (supporting information). These results clearly
show that MoSe2@CN (3:1) hybrid, which has been used in this study is
the optimal composition for maximizing the charge storage perfor-
mance.
3.3. Comparison of supercapacitor performances
Symmetric cells of CN//CN, MoSe2//MoSe2, MoSe2@CN//
MoSe2@CN and an asymmetric cell of MoSe2@CN//CN were con-
structed with an aqueous 1 M LiClO4 electrolyte sandwiched between
the electrodes. The device architectures are illustrated in Fig. 5. CV
scans, recorded at 5, 20 and 200 mV s−1 over a voltage window of 0 to
1 V for all the 4 cells, are shown in Fig. 5(a–c). An ideal supercapacitor
is expected to show a rectangular CV plot. Here, at a low scan rate of
5 mV s−1, the CV plot for the symmetric MoSe2 and MoSe2@CN cells
shows reversible broad oxidation/reduction peaks at +0.29/+0.20 V
respectively. The peaks are attributed to a Faradaic reaction of Li+ ions
with MoSe2.
MoSe2 + xLi+ + xe− ⇄ Lix MoSe2 (1)
The symmetric CN//CN and the asymmetric MoSe2@CN//CN cells
show flat cathodic and anodic profiles; CN possibly dominates the redox
response in these cells. At 200 mV s−1, all the four cells show leaf like
CV curves. The enclosed area in the voltammogram is the largest and
the least for the asymmetric MoSe2@CN//CN cell and the symmetric
MoSe2//MoSe2 cell respectively. The remaining two cells are char-
acterized by areas with intermediate magnitudes. The superior perfor-
mance of the asymmetric cell aligns with the synergistic effects of the
two components: MoSe2 and CN. MoSe2 undergoes fast oxidation/re-
duction reactions due to the nanostructured porous morphology that
allows rapid ingress and egress of ions (from and to the electrolyte).
This is simultaneously accompanied by efficient inflow and outflow of
electrons (from and to the current collector), afforded by the highly
conducting net like microstructure of CN. Since in MoSe2@CN, the two
constituents are mixed well, the ion and electron uptake, transfer and
transport are highly efficient processes, thus resulting in a high charge
storage capacity. Despite this synergy advantage, the asymmetric
MoSe2@CN//CN cell outperforms the symmetric MoSe2@CN//
MoSe2@CN cell, possibly due to the better reversibility of charge en-
abled by the asymmetric architecture of the former cell. In a symmetric
cell, the quantum of irreversible charge trapped by the electrodes is
hypothetically the same, given that the active material loadings at the
M. Ojha and M. Deepa Chemical Engineering Journal 368 (2019) 772–783

Fig. 4. (a) Schematic of a MoSe2@CN (x:1) cell, where x = 1, 2, 3 and 4. CV plots for the MoSe2@CN (x:1) cells compared at different scan rates of (b) 5, (c) 20, (d)
100 and (e) 200 mV s−1. Charge-discharge characteristics compared for the MoSe2@CN (x:1) cells at different current densities of (f) 0.5, (g) 1 and (h) 2.5 mA cm−2.

two electrodes are equal. In contrast, in an asymmetric cell, particu-
larly, where one of the two electrodes operates via the EDL charge
storage mechanism, the charge reversibility is enhanced due to reduced
charge trapping losses.
In the hybrid based cells, MoSe2@CN assists in sustaining the high
currents (Fig. 5e). Variation in specific capacitance (SC) as a function of
scan rate is exhibited in Fig. 5f. Areal SCs of the cells were calculated
using the following equation.
SC(mF cm−2) = ∫ [I (mA cm−2) × dV ]/[ν (Vs−1) × ΔV(V)]
In Eq. (1), the integral represents the area under the CV curve, re-
corded at a given scan rate (ν) and ΔV is 1 V. The areal SCs are larger for
the asymmetric MoSe2@CN//CN cell under all scan rates, in compar-
ison to the MoSe2@CN//MoSe2@CN, CN//CN and MoSe2//MoSe2
cells. The disparity in SCs is prominent over low scan rates of 5 to
200 mV s−1. At higher scan rates in the range of 400 to 1200 mV s−1,
the SCs are almost comparable for all the four cells. SC decreases from
101.3 to 5.7 mF cm−2 ongoing from 5 to 1200 mV s−1 for the asym-
metric MoSe2@CN//CN hybrid cell. SC declines from 44.8 to
5.2 mF cm−2, from 70.8 to 5.5 and from 70.2 to 5.6 mF cm−2 for the
symmetric cells of CN//CN, MoSe2//MoSe2, MoSe2@CN//MoSe2@CN
(2) respectively. On comparing the symmetric MoSe2@CN//MoSe2@CN
and asymmetric MoSe2@CN//CN cells, areal SC of the asymmetric cell
is 1.44 times greater than that of the symmetric cell at 5 mV s−1, and

Fig. 5. Cyclic voltammograms of symmetric cells of CN//CN, MoSe2//MoSe2, MoSe2@CN//MoSe2@CN and an asymmetric cell of MoSe2@CN//CN compared at scan
rates of (a) 5, (b) 20 and (c) 100 mV s−1. (d) Schematics of the four cells showcasing the cell architectures. (e) CV plots of MoSe2@CN//CN cell at different scan rates
(in mV s−1). (f) Rate capability as a function of scan rate for the four cells. Peak current versus (g) square root of scan rate and (h) scan rate for the four cells at low
and high scan rate ranges respectively. (i) CV plots of an asymmetric cell of MoSe2@CN//CN recorded at 100 mV s−1 over different voltage windows.

778
M. Ojha and M. Deepa
this difference is explained above. At a low scan rate (5 mV s−1) the
areal SC of symmetric CN//CN cell is nearly 1.5 times lower than that of
the symmetric MoSe2//MoSe2 cell. Current in the CV plots, follows the
equation: I = nFAD(dc/dx), where n is the electrons involved in the
reaction, F is Faraday’s constant, A is the active electrode area, D, is the
diffusion coefficient of ions, and dc/dx is the concentration gradient.
Current is largely controlled by the thickness of the diffusion layer (dx).
At low scan rate, there is possibly ion accumulation at the CN elec-
trode/electrolyte interface, which results in higher dx, and lower I. In
the case of MoSe2 based cell, diffusion of ions is slow due to the poor
electrical conductivity of pristine MoSe2, and therefore diffusion layer
thickness is lower, which results in higher I. At intermediate scan rates,
however, the CN//CN cell is characterized by larger SCs, for EDL for-
mation occurs rapidly, whereas in comparison, Faradaic reactions
particularly within the bulk of the electrode (MoSe2), require longer
time spans, and therefore SC is lower. The SCs are comparable at high
scan rates for all the cells, with a marginally increased SC registered for
the asymmetric MoSe2@CN//CN cell, compared to the rest of the cells.
This is due to the fact that the rate of supply of ions from the electrolyte
to the electrode equals the rate of their adsorption (if it is CN), or their
rate of mass transfer (if it is MoSe2). Thereafter, current saturates and
becomes independent of both, the material type and scan rate.
To further distinguish the charge stored via diffusion from the sur-
face confined capacitance in the four cells, the variation in peak or peak
(plateau) current densities is plotted as a function of the square root of
scan rate over 5 to 200 mV s−1 (Fig. 5g). At these lower scan rates, the
plots are almost linear, confirming diffusion to be the predominant
mechanism, and diffusion coefficients (D) are calculated using the
Randles-Sevcik equation and summarized in Table 1. In (3), n is the
number of electrons involved in oxidation/reduction (taken as 1 here),
C° is the bulk concentration of the electrolyte and A is the active
electrode area.
Ip,a or Ip,c = n3/2 × C° × A× D1/2 × ν1/2
−10 2 −1
Among the four cells, Da and Dc are equal (∼3 × 10 cm s )
and highest for the asymmetric MoSe2@CN//CN cell, and lowest for the
symmetric MoSe2//MoSe2 cell. It is the least for the pristine chalco-
genide based cell due to relatively poorer electrical conduction, which
hinders fast diffusion of ions. It must be recalled that every Li-ion im-
pregnated into the active electrode is balanced by an electron from the
external circuit. This mixed conduction is maximized when the active
material is a good electrical and ionic conductor. MoSe2 by its’ ability to
react with Li-ions and due to its’ layered crystal structure is a good ionic
conductor, but not an equally good electron conductor, which results in
lower Da and Dc. Over the higher scan rates of 400–1200 mV s−1, the
peak current densities are almost constant, as can be judged from
Fig. 5h. Diffusion coefficient is determined from the following equation.
D= (Ilimiting × l× n× F× C° × A)/2
At high scan rates, Da and Dc are enhanced by several orders of
magnitude, compared to their magnitudes at low scan rates. They are
∼10−6 cm2 s−1, for the asymmetric MoSe2@CN//CN cell. Surface
confined charge dominates at high scan rates.
The effect of cell voltage window for the asymmetric MoSe2@CN//
CN cell is displayed in Fig. 5i. Voltage windows (ΔV) of 0 to 0.2, 0.4,
Table 1
Diffusion coefficients determined from the CV plots for the four cells.
Cell Danodic (cm2 s−1)
Over 5 to 200 mV s−1 (Ip vs. ν1/2)
CN//CN 2.56 × 10−10
MoSe2//MoSe2 9.20 × 10−11
MoSe2@CN//MoSe2@CN 2.25 × 10−10
MoSe2@CN//CN 3.24 × 10−10
Chemical Engineering Journal 368 (2019) 772–783
0.6, 0.8 and 1 V were used at scan rate of 100 mV s−1. Leaf like profiles
are observed for the cell over the aforesaid voltage ranges. A broad
oxidation wave is clearly observed over the 0–1 V range, and this is not
visible in the other voltage windows. Areal SC decreases monotonically
from 48 to 40.1 mF cm−2 when the voltage window (ΔV) is reduced
from 1 V to 0.4 V and then drops steeply to 26.2 mF cm−2 when ΔV is
reduced further to 0.2 V. It is obvious that the cell can be used easily
over different voltage windows, depending upon the requirement.
SCs for the four cells were also determined from their galvanostatic
charge-discharge plots and these are compared in Fig. 6. Areal SCs were
calculated by using the following equation.
SC(mF cm−2) = 2[I(mA cm−2) × Δt(s)]/ΔV(V) (5)
Polarization plots for the 4 cells are compared at 3 current densities
of 10, 2.5 and 0.5 mA cm−2 in Fig. 6(a–c). At 2.5 mA cm−2, the profiles
of the 4 cells are almost triangular implying an ideal supercapacitor
behavior, akin to the leaf-like CV plots obtained at high scan rates of
200 or 1000 mV s−1. At 0.5 mA cm−2, only the CN//CN cell shows a
nearly isosceles triangular profile, whereas the remaining 3 cells, con-
taining MoSe2 show slow, a rather drawn out charging response, and a
non-linear discharge profile. This is possibly due to the redox behavior
of MoSe2 wherein charge ingress and egress are diffusion controlled
phenomena, unlike the CN//CN cell, where surface confined capacitive
charging/discharging processes occur. At 10 mA cm−2, the discharge
profiles of all the three cells (except the MoSe2//MoSe2 one, which
shows a linear drop), show two different slopes, indicating a depen-
dence of discharge characteristics on the voltage window. Variation of
SC as a function of current density (mA cm−2) is shown in Fig. 6d. In
the galvanostatic mode too, the asymmetric MoSe2@CN//CN cell per-
formance is enhanced compared to the remaining cells. The 4 cells obey
the following order: MoSe2@CN//CN > MoSe2@CN//Mo-
Se2@CN > CN//CN > MoSe2//MoSe2. MoSe2@CN//CN cell exhibits
(3) the highest areal SC of 88 mF cm−2 at a current density of 0.5 mA cm−2
and it is 1.44, 2.5, 1.8 times greater than that of the MoSe2@CN//
MoSe2@CN, MoSe2//MoSe2 and CN//CN cells respectively. The dif-
ferences in their performances are retained even at 10 mA cm−2, with
the MoSe2@CN//CN cell having an SC, approximately 1.16 and 1.75
times greater than that of MoSe2@CN//MoSe2@CN and CN//CN cells,
and a massive 7-fold increment is observed compared to the MoSe2//
MoSe2 cell.
There are not many reports that describe the areal SCs of MoSe2
based supercapacitors in literature [14]. Nonetheless, to make a rea-
sonably pertinent comparison, performance metrics of MoS2 based su-
percapacitors are used. In [14], for a MoSe2 electrode used with a PVdF-
co-HFP/TEABF4 ion gelled PVdF/NaNbO3 as the piezo-polymer elec-
trolyte, the SC was 18.93 mF cm−2 at 0.5 mA. Our value for the Mo-
Se2@CN//CN cell is higher (88 mF cm−2) at the same current density.
MoS2-graphene based coin cell gave a maximum SC of 12.8 mF cm−2 at
(4)
a scan rate of 5 mV s−1 and SC decreased to 3.1 mF cm−2 at a scan rate
of 1000 mV s−1 [27]. MoS2/RGO decorated with NiO nanoparticles
delivered a maximum SC of 15 mF cm−2 at a scan rate of 25 mV s−1.
When the same experiment was done with RGO decorated on NiO na-
noparticles, a maximum SC of 9.6 mF cm−2 was obtained, whereas with
MoS2, a SC of 2 mF cm−2 is obtained at the same scan rate [28].
MoS2@CNT/RGO composite based flexible supercapacitor delivered a
Dcathodic (cm2 s−1) Danodic (cm2 s−1) Dcathodic (cm2 s−1)
Over 400 to 1200 mV s−1 (Ip vs. ν)
2.72 × 10−10 9.80 × 10−7 9.81 × 10−7
1.36 × 10−10 8.80 × 10−7 7.70 × 10−7
2.80 × 10−10 9.84 × 10−7 9.84 × 10−7
3.06 × 10−10 1.00 × 10−6 1.00 × 10−6
779
M. Ojha and M. Deepa
Fig. 6. Galvanostatic charge-discharge plots of symmetric cells of CN//CN, MoSe2//MoSe2, MoSe2@CN//MoSe2@CN and an asymmetric cell of MoSe2@CN//CN
compared at current densities of (a) 0.5, (b) 2.5 and (c) 10 mA cm−2. (d) SC versus current density for the four cells. Comparison of (e) SC versus scan rate and (f) SC
versus current density of MoS2 based cells from literature with the asymmetric MoSe2@CN//CN cell (prepared herein); the literature values are presented against a
yellow background.
maximum SC of 29.5 mF cm−2 at a scan rate of 5 mV s−1 [9]. Amor-
phous MoSx thin-film-coated carbon fiber paper based symmetric su-
percapacitor delivers a maximum SC of 83.9 mF cm−2 at a scan rate of
1 mV s−1 and SC lowered to 18 mF cm−2 when scan rate was increased
to 100 mV s−1 [8]. The asymmetric cell fabricated herein shows a better
storage response, relative to the literature reports, and this is noticeably
evident from a plot shown in Fig. 6e. A valid comparison is also ac-
complished with SCs obtained through the constant current mode
(Fig. 6f). For a cell based on graphene-like MoS2/graphene composites,
a maximum SC of 27.6 mF cm−2 is achieved at a current density of
0.1 mA cm−2 which lowered to 19 mF cm−2 when the current density
was raised to 2 mA cm−2 [29]. Another experiment showed that a
MoS2@CNT/RGO assembly yielded an areal SC of 60 mF cm−2 at 0.1 A
cm−2 current density that decreased to 40 mF cm−2 upon increasing
the current density to 10 mA cm−2 [9].
3.4. Ragone plots, self-discharge and EIS studies
Ragone plots (energy density, E versus power density, P) of sym-
metric and asymmetric cells are presented in Fig. 7a. E and P were
estimated from the following equations.
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Chemical Engineering Journal 368 (2019) 772–783
ΔV 2 ⎤
E(mWh cm−2) = ⎡C(mF cm−2) ×
⎢
⎣ ⎥
2 × 3600 ⎦ (6)
P(mW cm−2) = 3600 × E/Δt (7)
−2
Highest energy density of 12.22 µWh cm is registered at a power
density of 0.5 mW cm−2 for the asymmetric MoSe2@CN//CN cell. It
decreases to 3.88 µWh cm−2, when the power density is raised to
10 mW cm−2. Compared to the best cell, energy density drastically
lowered by 45, 60, 30.6% for the symmetric- MoSe2@CN//MoSe2@CN,
CN//CN, MoSe2//MoSe2 cells respectively at the same power density
(0.5 mW cm−2). The advantage of having two different electrodes is
apparent from this study. We have compared our results with carbon
nanostructure based supercapacitors, for there is only one report on a
MoSe2 based cell in literature [14]. For a 2D-MoSe2 based cell [14], a
specific energy of 37.9 mJ cm−2 at a specific power of 0.27 mW cm−2
was obtained at a fixed discharge current of 0.5 mA. By converting our
values to the same units for the MoSe2@CN//CN cell, a specific energy
of 44 mJ cm−2 is attained at a specific power of 0.5 mW cm−2. This
shows that the MoSe2@CN//CN cell is able to retain a fairly high E at a
high P, for the specific power is almost double for our cell compared to
the 2D-MoSe2 cell [14]. Previously, a carbon-microelectromechanical-
M. Ojha and M. Deepa
system-based alternately stacked MoS2@RGO-CNT micro-super-
capacitor delivered a maximum E of 1.9 µWh cm−2 at a current density
of 2 mA cm−2 [29]. Flexible wet-spun CNT/graphene yarn super-
capacitor delivered a maximum E of 3.84 μWh cm−2 [30]. CNT-coated
carbon microfiber supercapacitor delivered an E of 9.8 µWh cm−2 at a P
of 0.189 mW cm−2 [31]. A graphene-cellulose paper based super-
capacitor gave an E of 1.5 µWh cm−2 at a P of 0.01 mW cm−2 [32].
Self-discharging of the 4 cells was compared by assessing the decline
in cell voltage as a function of time (Fig. 7b). The asymmetric Mo-
Se2@CN//CN cell discharges to about half of its initial voltage in
∼3 min. It decays to 0.2 V in 17 min., and assumes values below 0.1 V
after 32 min. The symmetric MoSe2@CN//MoSe2@CN cell shows a
slower decay in the initial part, for the cell voltage is 0.4 V after
5.7 min. But it declines rapidly, and becomes less than 0.1 V in
∼27 min. Cell voltages for CN//CN and MoSe2//MoSe2 drop to 0.4 V in
1.25 and 5.4 min. respectively, and then to less than 0.1 V in ∼5.4 and
∼18 min. The cell voltages are of appreciable magnitudes for roughly
35 min., for the symmetric cells, although for the asymmetric cell, cell
voltage takes almost 53 min. to reduce to 0 V.
Cycling stabilities of symmetric cells of CN//CN, MoSe2@CN//
MoSe2@CN and asymmetric cell of MoSe2@CN//CN are studied over
104 charge-discharge cycles operated at 5 mA cm−2 current density.
The SCs for these cells are plotted as a function of cycling number in
781
Chemical Engineering Journal 368 (2019) 772–783
Fig. 7. (a) Ragone plots and (b) self-discharge plots
for symmetric cells of CN//CN, MoSe2//MoSe2,
MoSe2@CN//MoSe2@CN and an asymmetric cell of
MoSe2@CN//CN. (c) Cycling stability of three cells.
(d) Ex-situ SEM image of the cycled MoSe2@CN
electrode extracted from the asymmetric
MoSe2@CN//CN cell after 10,000 cycles. Nyquist
plots recorded under an ac potential of 20 mV, over
a frequency range of 1 MHz to 0.1 Hz: (e) fresh cells
and (f) after 10,000 charge-discharge cycles. The
open symbols represent the experimental data, and
the solid lines represent the fits. The data were fitted
in the equivalent circuit shown as an inset of (e).
Fig. 7c. The symmetric CN//CN cell and asymmetric MoSe2@CN//CN
cell retain almost up to 98% of their initial capacitances whereas the
symmetric MoSe2@CN//MoSe2@CN cell retains up to 92%. The SEM
image of the cycled MoSe2@CN electrode extracted from the asym-
metric cell (Fig. 7d), shows the presence of both MoSe2 and CN struc-
tures, indicating that the electrode morphology is not affected much
with cycling.
Electrochemical impedance spectra of the fresh cells and post-cy-
cling are shown in Fig. 7e and f. The spectra were recorded under an ac
bias of 20 mV over a frequency range of 1 MHz to 0.1 Hz. All data were
fitted into an equivalent circuit shown as an inset of Fig. 7e and the
fitting parameters are provided in Table 2. All the plots comprise of an
arc and an inclined straight line. They were fitted into a parallel com-
bination of interfacial resistance to charge transfer (Rct) and a constant
phase element (CPE). The point of commencement of the arc represents
the bulk resistance of the electrolyte (Rb). Rb lies in the range of 0.75 to
1.14 Ω cm2. For the fresh cells, Rct is the lowest for the asymmetric
MoSe2@CN//CN cell, and highest for the symmetric CN//CN cell. The
interface at the MoSe2@CN/electrolyte is favorable for fast charge
transfer, for the Rct values do not differ much on going from the Mo-
Se2@CN//CN (5.4 Ω cm2) cell to the MoSe2@CN//MoSe2@CN
(7.8 Ω cm2) cell. However, it is thrice and twice of these values for the
CN//CN cell (18.2 Ω cm2). After 104 cycles, the Rct values are increased
M. Ojha and M. Deepa Chemical Engineering Journal 368 (2019) 772–783

Table 2 trend is preserved, but Yo is reduced compared to uncycled cells. Yo is

EIS parameters for the different cells. reduced by 20, 25 and 39.5% respectively, after 104 cycles for the
Cell State of Rb (Ω Rct (Ω CPE (Yo, S CPE (n) MoSe2@CN//CN, CN//CN and MoSe2@CN//MoSe2@CN cells respec-
the cell cm2) cm2) sn cm−2) tively. This implies that capacitance retention is the highest for the
asymmetric MoSe2@CN//CN cell and the lowest for the symmetric
CN//CN Fresh 0.75 18.2 0.16 0.76
MoSe2@CN//MoSe2@CN cell. This data evidences that the configura-
After 104 0.83 24.2 0.12 0.76
cycles
tion of the asymmetric cell is most conducive for a reversible response
and is least susceptible to degradation via pulverization during cycling.
MoSe2@CN// Fresh 0.89 7.84 0.38 0.66
MoSe2@CN After 104 0.95 15.43 0.23 0.70
The post-cycling n-values are slightly higher for the symmetric
cycles MoSe2@CN//MoSe2@CN and asymmetric MoSe2@CN//CN cells re-
lative to the corresponding n for the uncycled cells. This indicates that
MoSe2@CN//CN Fresh 1.06 5.44 1.70 0.69
After 104 1.14 8.42 1.36 0.77 cycling induces a passivating effect at the electrode surface, more so for
cycles the MoSe2@CN//CN cell than the remaining two cells. EIS parameters
complement the charge storage performance parameters of SC and
energy density.
compared to their initial magnitudes, but the same trend is maintained.
The straight line part in the plots is due to CPE, which is defined as the
measure of the digression from an ideal capacitive behavior. This non- 3.5. Usage of the MoSe2@CN//CN cell
ideality arises from the surface roughness and the non-uniform contours
of the MoSe2@CN and CN electrodes. CPE is given by 1/(jω)nYo, where Three asymmetric MoSe2@CN//CN cells were connected in series,
ω is the angular frequency. It is equal to 2π/t. Typically, n is less than 1 charged to 2.5 V, and then connected to a toy fan. The photographs of
for a non-ideal capacitor. When n = 1, Yo = C, as in an ideal capacitor. the toy fan prior to- and after- being connected to the 3 cells, are shown
Here, unlike an ideal capacitor, the EDL formation and the Faradaic in Fig. 8a–c. Photographs of 1 cell and 3 cells are displayed in Fig. 8d
reaction (in case of MoSe2) does not occur at a smooth planar elec- and e. The fan whirs for a few seconds, slows down (Fig. 8c′) then
trode/electrolyte interface. This is because at the macroscopic level, the comes to a halt, when the cells are discharged. The corresponding CV
current collector (Ni foam) is non-planar and has a mesh like surface plots and charge-discharge curves are shown in Fig. 8f and g. On
and at the nano- or micro- level, the active materials (MoSe2 and CN) comparing the CV plots of 1 cell versus 3-cells at 20 mV s−1, we find
also do not have flat levelled morphologies. that the cathodic and anodic peak/plateau current densities for the 3-
For the fresh cells of MoSe2@CN//CN, CN//CN and MoSe2@CN// cells shrink to one-third of the 1-cell magnitude, while the voltage
MoSe2@CN, Yo is 1.7, 0.16 and 0.38 S sn cm−2, and n = 0.69, 0.76 and window is expanded to ∼2.5 V from 1 V. The SC is observed to be
0.66 respectively. The magnitude of Yo is an indirect measure of the 25.2 mF cm−2 for 3-cells, which is close to one-third to that observed
capacitive response of the electrode. Yo is again highest for the asym- for 1-cell. Similarly, the galvanostatic responses monitored at
metric MoSe2@CN//CN cell, followed by the symmetric MoSe2@CN// 1 mA cm−2 (Fig. 8g), also reveal that while the time required for dis-
MoSe2@CN and CN//CN cells, in that order. Post-cycling, the same charging 1-cell is nearly 2.5 times than that of 3-cells, where the voltage
window of 3-cells is enhanced to 2.5 V. SC of 3-cells (21.5 mF cm−2) is

Fig. 8. (a-c, c′) Demonstration of a toy fan operated with 3 charged MoSe2@CN//CN cells connected in series. Photographs of (d) 1-cell and (e) 3- MoSe2@CN//CN
cells. Comparison of (f) CV plots and (g) charge-discharge plots of 1- and 3- MoSe2@CN//CN cells.

782
M. Ojha and M. Deepa
found to be approximately one-third of the SC of 1-cell (66 mF cm−2).
These experiments clearly bring out the promise that the MoSe2@CN
electrode has for practical applications.
4. Conclusions
MoSe2 nanotubes decorated over a carbon net based hybrid func-
tions as an efficient energy storage material, when employed in sym-
metric and asymmetric supercapacitors. Compared to the symmetric-
MoSe2//MoSe2, CN//CN, MoSe2@CN//MoSe2@CN cells, the asym-
metric MoSe2@CN//CN cell exhibits a superior SC under voltammetric
(101.3 mF cm−2) and galvanostatic (88 mF cm−2) modes not only due
to the combined beneficial effects of MoSe2, such as Faradaic charge
storage capability and short ion diffusion paths afforded by the nano-
porous morphology, and CN, like high electrical conductivity and a
unique morphology that maximizes ion uptake but also due to the en-
hanced charge reversibility which is an outcome of the asymmetric cell
configuration. The MoSe2 content in the MoSe2@CN hybrid is opti-
mized at 3:1, for this hybrid outperforms analogous MoSe2@CN hybrids
with lower (1:1 and 2:1) and higher (4:1) MoSe2 contents. Cycling
stability and energy density of the MoSe2@CN//CN cell are also sig-
nificantly improved relative to the symmetric cells. Practical demon-
stration of the MoSe2@CN//CN cell is accomplished by connecting 3
such cells in series, and using them to power a small toy fan. The
performance characteristics of the 3-cells also reveal that they can be
easily charged to 2.5 V, while delivering a SC of 21.5 mF cm−2 at
1 mA cm−2. The MoSe2@CN//CN cell also delivers an almost un-
paralleled performance in comparison to many MoS2 based super-
capacitors reported in literature.
Acknowledgements
Financial support from the Department of Science & Technology of
India (Project: India-UK Center for education and research in clean
energy (IUCERCE), Grant no. DST/RCUK/JVCCE/2015/04 (1) (G)) is
gratefully acknowledged by M. Deepa and M. Ojha. M.O. is thankful to
University Grants Commission (UGC) of India for the grant of junior
research fellowship. We thank the TEM facility of IITH for measure-
ments.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2019.03.002.
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