Accepted Manuscript

Title: Designing two dimensional nanoarchitectured MoS2

sheets grown on Mo foil as a binder free electrode for
supercapacitors

Author: Karthikeyan Krishnamoorthy Ganeshkumar

Veerasubramani Parthiban Pazhamalai Sang Jae Kim

PII: S0013-4686(15)31073-2
DOI: http://dx.doi.org/doi:10.1016/j.electacta.2015.12.148
Reference: EA 26297

To appear in: Electrochimica Acta

Received date: 1-10-2015

Revised date: 21-12-2015
Accepted date: 23-12-2015

Please cite this article as: Karthikeyan Krishnamoorthy, Ganeshkumar Veerasubramani,

Parthiban Pazhamalai, Sang Jae Kim, Designing two dimensional nanoarchitectured
MoS2 sheets grown on Mo foil as a binder free electrode for supercapacitors,
Electrochimica Acta http://dx.doi.org/10.1016/j.electacta.2015.12.148

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 Designing two dimensional nanoarchitectured MoS2 sheets grown on Mo foil as a binder

free electrode for supercapacitors

Karthikeyan Krishnamoorthya, Ganeshkumar Veerasubramania, Parthiban Pazhamalaia,

Sang Jae Kima,b,*

a
Nanomaterials Laboratory, Department of Mechatronics Engineering, Jeju National University,

Jeju 690-756, South Korea.

b
Department of Advanced Convergence Technology & Science, Jeju National University, Jeju

690-756, South Korea.

*Corresponding author: Tel: +82-64-754-3715, E-mail: kimsangj@jejunu.ac.kr

Highlights ►

► Two dimensional MoS2/Mo binder free electrodes for supercapacitors are developed. ► MoS2 nanosheets are
grown on Mo surface via Kirkendall effect. ► Raman mapping was used to identify the number of layers in MoS2
sheets. ► The MoS2/Mo electrodes delivered a specific capacitance of about 192 F/g. ► The binder free electrodes
possess capacitance retention of 98% over 1000 cycles. ► ►

Graphical abstract

Abstract

In this study, we demonstrated the preparation of nanoarchitectured MoS2 sheets on Mo

foil via hydrothermal method and examined its use as a binder free electrode for supercapacitors.

The formation of well crystalline MoS2 sheets on Mo foil was confirmed by laser Raman
spectroscopy, Raman mapping, X-ray photoelectron spectroscopy, and field emission scanning

electron microscopic analyses. The cyclic voltammetric studies suggested that the charge-storage

mechanism in the MoS2/Mo electrodes is due to the contribution of combined pseudocapacitance

with electrochemical double layer capacitance. The MoS2/Mo electrodes delivered a specific

capacitance of about 192.7 F/g from the galvanostatic charge-discharge analysis at a current

density of 1 mA/cm2. The experimental results suggested that the prepared MoS2/Mo binder free

electrode will be a suitable candidate for electrochemical energy storage devices.

KEYWORDS: MoS2 nanosheets; Raman mapping; binder free electrode; Nyquist plot;

supercapacitors.

1. Introduction:

Supercapacitors or electrochemical capacitors have become an ideal energy storage

device due to their high power and energy density with long cycle life comparably better than Li-

ion batteries[1]. Supercapacitors can be widely classified as electrochemical double layer

capacitors and pseudocapacitors based on their charge-storage mechanism. Various electrode

materials have been examined for supercapacitors including carbon materials which can store

energy in the form of electrochemical double layer capacitance (EDLC), and metal oxides or

polymers which can provide pseudocapacitance via fast Faradaic reactions[2,3]. In order to

increase the device performance and efficiency, researchers involved in developing novel

electrode materials with various size and morphology. In this scenario, transition metal
chalcogenides (TMCs) has received considerable attention in the electrochemical energy storage

devices[4]. TMCs such as cobalt sulfide (CoS, CoS2) nickel sulfide (NiS, NiS2, Ni3S2),

molybdenum sulfide (MoS2), copper sulfide (CuS, Cu2S), and vanadium sulfide (VS, VS2) have

been studied as electrode materials for supercapacitors[5–7]. In particular, MoS2 gained special

interest among the TMCs and expected as suitable alternative for graphene and CNT in energy

harvesting and storage applications, due to its layered structure and intrinsic electrical

conductivity [8,9]. Moreover, molybdenum based materials (such as MoO3, MoO2, MoS2, etc)

exhibits multiple valence states and rich chemistry which makes them a viable candidate for

electrochemical applications[10,11]. MoS2 belongs to two dimensional TMC families in which

S-Mo-S layers are separated by van der Walls forces as similar to graphene[12]. This layered

structure of MoS2 results in pronounced anisotropic electrical conduction in parallel to the plane

and predominant hopping mechanism in perpendicular to plane[10,13]. MoS2 can exist in

different forms such as hexagonal 2H-MoS2, rhombohedral 3R-MoS2, and tetragonal 1T-MoS2

phases[14]. Recent studies on MoS2 suggested its use as an ideal candidate for applications

including photodetectors, piezoelectric, electrocatalysts, transistors, sensors, hydrogen storage,

and electrode materials for Li-ion batteries and electrochemical supercapacitors[6,8,12,15–19].

The advantage of MoS2 as an electrode material for electrochemical energy storage devices is

due to their high ionic conductivity over conventional metal oxides and graphite[20,21].

During this decade, studies have been undertaken and ongoing on investigating the

electrochemical capacitive properties of nanostructured MoS2. Considering the efforts taken until

now, Soon et al. reported the presence of electrochemical double layer capacitance in MoS2 films

obtained via thermal evaporation[22]. Our recent study demonstrated the supercapacitive

properties of sphere-like MoS2 nanostructures with a specific capacitance of 92.85 F/g [6]. Later
on, Huang et al. reported a specific capacitance of about 129 F/g for MoS2 nanosheets prepared

using L-cystine as a sulfur source[23]. Ma et al. reported a specific capacitance of 145 F/g for

MoS2 microspheres coated on nickel foam with pseudocapacitive nature[24]. More recently,

Ilanchezhiyan et al. reported a specific capacitance of 122 F/g for spherically cluster MoS2

nanostructures[21]. Further, evidential reports are available on the electrochemical properties

MoS2 based nanohybrids or nanocomposites for supercapacitor applications[8,25]. These studies

on the supercapacitive properties of MoS2 showed only medium performance as an electrode

material due to the semiconducting nature of 2H-phase MoS2 [6,21,23–25]. Another reason

might be due to the poor crystallinity of MoS2 prepared via chemical methods and aggregation of

layers (similar to that seen in reduced graphene oxide). Therefore, it is essential to take necessary

steps for improving the supercapacitive properties of MoS2.

The electrochemical properties of an electrode material can be improved via various

strategies such as doping, making composites or hybrids with other electroactive materials,

designing hierarchical structures, and creating porous nanostructures, etc[26–30]. Among these,

the design of nanoarchitectured electrodes via the integration of electroactive materials with the

current collectors is more promising strategy which can results in high specific capacitance,

energy and power density [5,31]. Recent studies suggested that the binder free electrodes based

on metal oxides, binary metal oxides, and metal chalcogenides delivered higher specific

capacitance than that of their conventional materials[28,32,33]. For instance, CoNi2S4 arrays

based binder free electrode for high energy application has been examined by Mei et al[31]. Our

recent study demonstrated the high performance supercapacitive properties of Ni3S2-Ni binder

free electrodes[5]. The improved electrochemical properties of the binder free electrodes can be

attributed to the high conductivity of metallic core with large electroactive area, which results in
short electron diffusion pathways and high electron transfer rates[28,34]. In this study, we aimed

to develop nanoarchitectured MoS2 electrode and investigate its application as an electrode for

supercapacitors.

2. Materials and methods

2.1 Materials used

Molybdenum (Mo) foil was obtained from Nilaco Corporation, Japan. Thiourea,

hydrochloric acid, sodium sulfate, and ethanol are purchased from Daejung Chemicals Limited,

South Korea. All the chemicals used in this research are of research purity and used without

further purification.

2.2. Growth of MoS2 nanosheets on Mo foil

A one-pot hydrothermal method was used for the preparation of MoS2 nanostructures on

Mo foil (act as substrate as well as Mo source) and thiourea as a sulfur source. Breifly, a piece of

Mo foil (3×4 cm) was cleaned by rinsing with dilute HCl, acetone, ethanol and dried at 60 °C.

An aqueous solution containing thiourea (0.5 M) was prepared using ultrasonication process and

transferred into a 100 mL Teflon lined autoclave in which the pre-cleaned Mo foil was already

placed (at an angle of 45°). Then, the hydrothermal sulfidation reaction was conducted at 180 °C

for a time period of 24 h. After completion of the reaction, the autoclave was cooled naturally to

room temperature and the obtained product was rinsed with water and ethanol and finally dried

in an oven at 80 °C for 4 h.

2.3 Instrumentation

The surface morphology of the prepared MoS2 grown on Mo foil was analyzed using

field emission scanning electron microscope (FE-SEM), ZEISS Instruments. The X-ray

diffraction analysis was performed on a Rigaku X-ray diffractometer operated at 40 keV and 40
mA with Cu Kα radiation in the range of 10-80°. The Raman spectrum and mapping of the MoS2

samples was obtained using LabRam HR Evolution Raman spectrometer (Horiba Jobin-Yvon,

France). The Raman system was operated at 10 mW laser power and an excitation wavelength of

514 nm with an Ar+ ion laser. The data were collected using a 10-s data point acquisition time.

The Raman mapping of MoS2 samples were analyzed using LabSpec (Ver. 6.2) software. The

chemical composition and state of elements present in the outermost part of the final products

was obtained by X-ray photoelectron spectroscopy (XPS) techniques using ESCA-2000, VG

Microtech Ltd. Here a monochromatic X-ray beam source at 1486.6 eV (aluminum anode) and

14 kV was used to scan the sample surface. A high-flux X-ray source with an aluminum anode

was used for X-ray generation, and a quartz crystal monochromator was used to focus and scan

the X-ray beam on the sample.

2.4 Electrochemical measurements

The electrochemical measurements such as cyclic voltammetry (CV), galvanostatic

charge-discharge analysis (CD), and electrochemical impedance spectroscopy (EIS) were carried

out in a three electrode system on AUTOLAB PGSTAT302N workstation using the MoS2/Mo

electrodes (with dimension 1×1 cm2) as working electrode, silver/silver chloride as reference

electrode, and platinum as counter electrode. A 1 M solution of Na2SO4 was used as an

electrolyte. The mass loading of the active material in the working electrode is calculated as 0.8

mg/cm2 from the method reported in literature[27].

3. Results and discussion

This study employed a hydrothermal route for the growth of MoS2 on Mo foil using

thiourea as sulfur source. After completion of the reaction, the color of the bare Mo foil changes

into dark black as shown in Fig. S1 (see supplementary material) suggesting the formation of
MoS2 on either side of the Mo foil due to the hydrothermal sulfidation process. The mechanism

of MoS2 growth on the Mo foil is due to the reaction between the sulfur ions released from

thiourea on the surface of the Mo foil under hydrothermal conditions via Kirkendall effect, a

mechanism similar to that of the previous studies on the growth of TMCs on metal

surfaces[5,35]. Breifly, the reaction pathways in the growth process can be divided into two

stages: At first, the released sulfur ions diffuse onto the inner surface of the molybdenum surface

to form layer of MoS2 during the initial phase of the reaction. After that with increasing reaction

time, the diffusion of sulfur ions onto the inner surface of the molybdenum was hindered by the

MoS2 layer whereas Mo atoms from the inner surface of the Mo foil can diffuse in the outward

direction through vacancy exchange and react with sulfur ions which finally result in the

formation of MoS2 nanostructures on the Mo foil. This is in close agreement with the previous

studies on the formation of CuS on Cu wires and Ni3S2 on Ni foam [5,36]. The possible chemical

reactions occurred at the interfacial (solid/liquid) sites during the hydrothermal reaction

conditions are more likely as follows:

NH2CSNH2 + 2H2O → 2NH3 + H2S + CO2 ----------------------------- (1)

H2S + H2O → 2H3O+ + S2- ----------------------------- (2)

Mo + S2- + O2 + 2H2O → MoS2 + OH- ----------------------------- (3)

The surface morphology, size, shape, and structure of the nanomaterials can effectively

influence their electronic, optical and electrochemical properties. The surface morphology of the

as grown MoS2 was examined by FE-SEM analysis and the low magnification micrograph (Fig.

1(a)) revealed the formation of uniform sheets of MoS2 on the Mo surface. The high

magnification micrograph (Fig. 1(b)) suggested that few layered 2D MoS2 hierarchical

nanosheets emerged on the surface Mo foil in vertical orientation. The FE-SEM micrograph
revealed the presence of almost vertically aligned MoS2 nanosheets with gaps between the

individual sheets firmly attached on the surface of Mo foil which can provide sufficient active

sites for the electrolyte ions and therefore, a better electrochemical properties are expected from

the prepared material. The X-ray diffraction pattern of the bare Mo foil and the MoS2 grown on

Mo foil are shown in Fig. S2 (see supplementary material). There is no peaks corresponding to

the MoS2 are observed in the XRD pattern of the MoS2 grown on Mo foil and only the peaks

corresponding the bare Mo foil was observed. The diffraction pattern raised from the Mo foil

overwhelms the diffraction from MoS2 which is due to the presence of thin MoS2 nanosheets (as

observed from FE-SEM micrographs) on the surface of Mo foil compared to the relatively thick

molybdenum foil. This finding is consistent with the recent study on the growth of MoS2 porous

thin films grown on Mo substrates [37]. Hence, we used spectroscopic studies such as Raman

and X-ray photoelectron spectroscopy for characterizing the MoS2 on Mo foil.

Raman spectroscopy is one of the prominent tools for characterizing the structural

bonding nature, crystallinity and associated defect levels in two-dimensional nanostructures such

as graphene, layered TMCs, and nanocomposites [38]. The Raman spectrum of the prepared

MoS2/Mo nanoarchitectures was examined in this study and is shown in Fig. 2 (a). It is well

known that pure Mo does not possess any active Raman modes, whereas MoS2 possess two

major Raman active modes represented as E12g and A1g modes. The Raman spectrum of the MoS2

grown on Mo foil exhibited the presence of two major vibrations bands at 381 and 405 cm-1

which can be assigned to the E12g and A1g modes of MoS2 respectively[19,39]. The band at 381

cm-1 corresponding to the E12g mode arises due to the vibration of S-Mo-S trilayers against the

adjacent ones whereas the band observed at 405 cm-1 (A1g mode) directly related to the out of

plane vibrations of the sulfur atoms in opposite direction. The band position of A1g mode directly
related to the thickness of MoS2 nanosheets and the observed A1g mode at 405 cm-1 was red

shifted compared to that of the bulk MoS2 (usually observed at 408 cm-1), suggesting the

presence of few-layered MoS2 originated from the Mo foil[40]. These findings confirmed the

presence of well crystalline MoS2 on the Mo foil via the hydrothermal method. Further, we

performed Raman mapping analysis in order to gain new insights about the number of layers

present in the prepared MoS2/Mo electrodes. Raman mapping analysis is one of the non-

destructive and reliable techniques for understanding the spatial distribution, number of layers,

and chemical bonding nature of layered two-dimensional nanostructures [41–43]. The observed

two Raman active modes (E12g and A1g) of MoS2 is highly sensitive to the thickness or number of

layers present in the MoS2 [44]. In case of MoS2 sheets, two types of analysis viz (i) integral

intensity ratio maps of E12g/A1g modes, and (ii) peak position mapping analysis of E12g and A1g

modes are used for identifying the number of layers using Raman mapping analysis [45,46]. The

integral intensity ratio map of E12g/A1g modes is provided in Fig. 2(b) which indicated the

presence of intensity ratios ranging from 0.1 to 0.7 for the prepared MoS2 samples. In general,

the integral intensity ratio of E12g/A1g modes is about 0.7 for bulk and varies upto 0.6, 0.3 and 0.1

for trilayers, bilayers, and monolayer of MoS2 respectively[45]. The E12g/A1g intensity ratio map

shown in Fig. 2(b) clearly revealed the presence of minor fractions of monolayer MoS2 (blue

region), and major fractions of bilayered MoS2 (green region), respectively. In addition to this, it

also indicated the presence of few layered (n<6) MoS2 (red region) with some bulk counterparts

(yellow regions) in the prepared MoS2. The peak position maps of A1g and E12g modes are

provided in Fig. 2(c) and (d) respectively. In general, the peak position of A1g and E12g modes

varies from 410 to 403 cm-1 (bulk to monolayer) and 380 to 386 cm-1 (bulk to monolayer),

respectively [46]. The spatial distribution maps shown in Fig. 2(c) and (d) clearly evidenced the
presence of monolayers, bilayers, few layers (n<5) and some bulk counterparts based on the

obtained color spots. The presence of bulk counterparts can be ascribed to the formation of MoS2

thin film on the Mo foils during the initial phase of the hydrothermal reaction as described

above. The presence of few layered MoS2 is due to the secondary phase of the reaction kinetics

in which Mo atoms migrates in outward direction which results in the formation of hierarchical

sheets. Collectively, the Raman mapping analysis (Fig. 2(b,c, and d)) revealed the presence of

few layered sheets (n<5) and some bulk counterparts.

The chemical and surface states of the Mo and S elements in the prepared MoS2/Mo

electrodes have been investigated using X-ray photoelectron spectroscopy. The XPS survey

spectrum of the MoS2/Mo electrodes is shown in Fig. 3(a) which revealed the presence of states

corresponding to Mo 3d, Mo 3p, S 2p, C 1s and O 1s states, respectively[47]. The C and O

signals were originated from the CO2 and H2O impurities as seen in many XPS analysis. In

general, MoS2 can occur in two major phases such as 2H-MoS2 and 1T-MoS2 in which the

former possess semiconducting nature whereas the later behaves like metallic nature[8,48,49]. In

order to confirm the nature of the phase in the prepared MoS2/Mo electrode, the deconvolution of

the Mo 3d and S 2s polymorphs has been performed. The deconvoluted spectra of Mo 3d is

shown in Fig. 3 (b) which revealed the presence of two major peaks around 228 and 231 eV

corresponding to the Mo4+ 3d5/2 and Mo4+ 3d3/2 states, respectively and a minor peak around 226

eV has been observed which corresponds to the presence of S 2s state[39]. The deconvoluted

spectrum of each component depicts the presence of major 1T phase and smaller 2H phase of

MoS2 has been observed. It has been reported that the 1T phase components of MoS2 appear at

lower binding energy compared to the 2-H counterparts[8,49]. The deconvoluted spectrum of S

2p (Fig. 3 (c)) indicated the presence of two major peaks around 161.7 and 162.7 eV which
corresponds to the S 2p3/2 and S 2p1/2 states respectively[37]. These studies confirmed the

formation of MoS2 on the Mo foil via the hydrothermal method.

Further, the prepared nanoarchitectured MoS2/Mo electrode are investigated for their

potential applications as an electrode material for supercapacitors. At first, the CV profiles of the

MoS2/Mo electrodes have been examined to understand their electrochemical charge-storage

mechanism. CV analysis is one of the fundamental techniques which can provide qualitative

information about the electrochemical process involved the electrochemical energy storage

reactions. The CV profiles of the MoS2/Mo electrodes measured at different current densities (as

shown in Fig. 4(a)) revealed the presence of quasi rectangular behavior, thus confirming the

mechanism of charge storage is due to the presence of electrochemical double layers [6,8]. In

addition to this, a small hump observed in the CV curves which is an indication of the ion

intercalation and redox reactions occurred due to the Mo(+4 to +3) transition state during the

electrochemical reaction[50]. Moreover, there was no such peak observed in the CV of bare Mo

foil (See Fig. S3. in supplementary material) suggested that these peaks are occurred due to the

MoS2 on the Mo surface. This finding suggested that the pseudocapacitance via intercalation

reactions and double layer capacitance contributed to the overall capacitance of the MoS2/Mo

electrode[50]. Moreover, the shape of the CV curves is quasi rectangular at all the tested scan

rates (5 to 100 mV/s) and the current density is increasing with an increase in scan rate, thus

suggesting an ideal capacitive behavior[26,51]. It is well proven that the merits of binder free

electrodes for supercapacitor applications is the utilization of both the conductivity of the inner

metal core and large electrochemically active area at the outer surfaces[5,31,47]. In order to

understand the role of inner Mo on the capacitive property of the MoS2/Mo electrode, we

examined the CV profile of bare Mo electrode. The comparative CV profiles of the bare Mo and
the as grown MoS2/Mo electrodes measured at scan rate of 25 mV/s are presented in the Fig. S3

(supporting document) which suggest that the contribution of the Mo is negligible (about 5.14

%) of the overall capacitance of the MoS2/Mo electrodes. The specific capacitance of the

MoS2/Mo nanoarchitectured electrode has been obtained from the CV curves using the

relation[6]:

Csp = [(∫IdV) / (S×∆V×m)] F/g ……………………….. (4)

where, “Csp” is specific capacitance (F/g), “∆V” is the potential window (V), “m” is the

mass of the active material (mg), and “S” is the scan rate (mV/s). Figure 4(b) shows the effect of

scan rate on the specific capacitance. At low scan rates, the specific capacitance is higher

whereas high scan rates leads to decrease in specific capacitance. This is due to the variation in

time constraints of the electrolyte ions to access the electroactive material at different scan

rates[6]. A specific capacitance of the MoS2/Mo electrode was about 180 F/g was obtained at a

lower scan rate of 5 mV/s.

In order to study the fundamental charge transfer and capacitive behavior of the

MoS2/Mo electrodes, the EIS analysis has been carried out at a frequency range of 0.01 Hz to

100 kHz in 1 M Na2SO4 electrolyte and the data was analyzed using Nyquist and Bode plots.

Figure 5 (a) represents the Nyquist plot of MoS2/Mo electrode with the presence of quasi semi-

circle in the low frequency region corresponding to the charge transfer resistance (Rct) followed

by a straight line at the high frequency region which is due to the Warburg impedance[52]. The

inset of Fig. 5(a) represents an equivalent circuit in accordance with the observed Nyquist plot

which showed the presence of solution resistance (Rs), constant phase element (CPE1 and CPE2)

involving the double layer and pseudocapacitance, charge-transfer resistance (Rct) and Warburg

impedance (Zw). The MoS2/Mo electrodes exhibited a low solution resistance (Rs) of about 4.4 Ω
with a presence of small semicircle region (magnified graph shown in inset of Fig. 5a) with a

charge transfer resistance (Rct) of about 1.4 Ω between the electrode and electrolyte has been

observed highlighting the good conductivity of MoS2/Mo electrode. The presence of straight line

(Warburg line) nearly parallel to the imaginary axis of impedance corresponds to the frequency

dependent ion diffusion kinetics of the electrolyte at the surface of the nanosheets[53]. Further,

the impedance begins at a low 45° portion suggesting the porous nature of the MoS2/Mo

electrodes[54]. Further, the Bode plot (Fig. 5(b)) represents the plot of phase angle against

applied frequency. It is known that the phase angle of an ideal capacitor is closer to -90° whereas

for pseudocapacitor, it is about -45° [6,55]. The Bode plot revealed that the phase angle is about -

70° at 0.01Hz, suggesting the combination of double layer and pseudocapacitive nature of the

MoS2/Mo electrodes.

The CD profiles of MoS2/Mo electrodes were investigated to understand their charge

storage behavior. A quasi triangular shaped symmetric charge-discharge curve has been obtained

for the MoS2/Mo electrodes at a constant current density of 2 mA/cm2 (as shown in Fig. 6(a))

suggested the combined EDLC-pseudocapacitance behavior. The discharge profiles of MoS2/Mo

electrodes at different current densities (from 1 to 5 mA/cm2) are given in Fig. 6(b). It shows that

the discharge time is low at high current density whereas lower current density resulted in a

higher discharge time. At lower current density, the electrolyte ions possess enough time for

accessing the electroactive sites which is not available at higher current densities due to the time

constraints of the electrolyte ions[23,56]. The specific capacitance of the MoS2/Mo electrodes

can be obtained from the charge-discharge analysis using the relation[57].

Csp = [(I∆t)/m∆V] F/g ……………………….. (5)

 where “I” is the discharge current (mA), “∆t” is the discharge time (s), “m” is the mass

of the active material (mg), and “∆V” is the potential window. A plot of specific capacitance

against the discharge current density is given in Fig. 6(c) which indicates the specific capacitance

of MoS2/Mo electrodes is high at low current density and vice versa. A specific capacitance of

about 192.7 F/g has been obtained for the MoS2/Mo electrodes at a current density of 1 mA/cm2.

The obtained specific capacitance of MoS2/Mo binder free electrodes is significantly higher

compared to that of MoS2 nanoflowers (168 F/g), L-cysteine derived MoS2 (129 F/g), MoS2

spheres (122 F/g), MoS2 nanospheres (92.85 F/g), and flower like MoS2 (19.1

F/g)[6,21,23,25,58]. This improved electrochemical performance of MoS2/Mo electrodes is due

to the nanoarchitectured design which shortens the electron diffusion pathways and increase

electron transfer rates. It is also attributed to the hierarchical structure with individual nanosheets

provide more electroactive sites for the electrolyte ions during the charging and discharging

process. The important parameters which are essential for the practical applications of the

supercapacitor devices are energy density (E), power density (P), columbic efficiency (η%) and

cyclic stability[59]. The energy density, power density and columbic efficiency of the MoS2/Mo

electrodes are calculated from the discharge cycles as follows[5]:

E = [(I*t*V)/ (7.2*M)] Wh/kg …………………………….. (6)

P = 3.6E/t W/kg ………………………….. (7)

η% = [(∆td) / (∆tc) ] × 100 ………………………………….. (8)

where, “I” is the current applied (mA), “t” is the discharge time (s), “V” is the potential

window (V), “M” is the mass of the active material (mg). Figure 6(d) depicts the Ragone plot of

the MoS2/Mo electrode which highlights that the energy density ranges from 38.54 to 17.70

Wh/kg with a corresponding power density ranging from 750 to 3750 W/kg. Moreover, the
obtained energy density (38.54 Wh/kg) of the MoS2/Mo electrode is significantly higher than

that of the reported values of MoS2 prepared by other methods[6,23]. The columbic efficiency of

about 98.5 % is obtained for the MoS2/Mo electrodes at current density of 2 mA/cm2 which

demonstrated their good capacitive properties. Further, the cyclic stability of the MoS2/Mo

electrodes has been examined using CV analysis at a low scan rate of 50 mV/s over 1000 cycles

(as shown in inset of Fig. 6(d)). It represents the MoS2/Mo electrode possess an excellent

capacitance retention of about 98 % over 1000 cycles indicating the good stability of the

electrode over long cycle life.

4. Conclusions

The key findings of the work demonstrated a facile route for the preparation of MoS2/Mo

binder free electrodes for supercapacitor applications. Raman, XPS, and FE-SEM analysis

revealed the formation of well crystalline MoS2 sheets on the Mo foil. The CV and EIS analyses

confirmed the contribution of both electrochemical double layer capacitance and

pseudocapacitance in the overall capacitance of MoS2/Mo electrodes. The nanoarchitectured

MoS2/Mo electrodes delivered a specific capacitance of about 192.7 F/g (from CD profiles) with

capacitance retention of about 98 %, suggesting their potential applications in the

electrochemical energy storage devices.

Acknowledgements

This work was supported by the National Research Foundation of Korea (NRF) funded

by the Korea Government GRANTs (2013R1A2A2A01068926, 2013R1A1A2064471) and by

the Jeju Sea Grant College Program 2016 Jeju funded by the Ministry of Oceans and Fisheries

(MOF), Korea.

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Figure captions:

Figure 1. Field emission scanning electron micrographs of MoS2 grown on Mo foil obtained at

(a) low and (b) high magnification.

Figure 2. (a) Laser Raman spectrum of MoS2 grown on Mo foil, (b) Raman mapping of integral

intensity ratio E12g/A1g modes, (c) peak position mapping of A1g mode, and (d) peak position

mapping of E12g mode.

Figure 3. X-ray photoelectron spectrum of MoS2 grown on Mo foil (a) survey spectrum, (b)

deconvoluted Mo 3d spectrum, and (c) deconvoluted S 2s spectrum.

Figure 4. Electrochemical properties of MoS2/Mo electrodes (a) CV curves measured at different

scan rates (5 to 100 mV/s), (b) Effect of scan rate against specific capacitance.

Figure 5. Electrochemical impedance spectrum of MoS2/Mo electrode (a) Nyquist plot and (b)

Bode phase angle plots.

Figure 6. Electrochemical properties of MoS2/Mo electrodes (a) Charge-discharge profile

measured at constant current density of 2 mA/cm2, (b) Discharge profiles measured at different

current densities, (c) Effect of discharge current density on specific capacitance, and (d) Ragone

plot. The inset of Figure 6(d) shows the capacitance retention analysis over 1000 cycles.

Figure 1.
Figure 2.
Figure 3.
Figure 4.

Figure 5.
Figure 6.