Materials Research Bulletin 50 (2014) 499–502

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Materials Research Bulletin

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Short communication

Supercapacitive properties of hydrothermally synthesized sphere like

MoS2 nanostructures
Karthikeyan Krishnamoorthy a, Ganesh Kumar Veerasubramani b,
Sivaprakasam Radhakrishnan a, Sang Jae Kim a,b,*
a
Nanomaterials and System Lab, Department of Mechanical Engineering, Jeju National University, Jeju 690-756, South Korea
b
Department of Mechatronics Engineering, Jeju National University, Jeju 690-756, South Korea

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

Article history: In this communication, we have investigated the supercapacitive behaviour of MoS2 nanostructures
Received 20 August 2013 prepared by a facile one-pot hydrothermal approach using ammonium heptamolybdate and thiourea as
Received in revised form 8 October 2013 starting materials. The X-ray diffraction study revealed the formation of randomly stacked layers of
Accepted 5 November 2013
MoS2. The field-emission scanning electron microscope studies suggested the formation of sphere like
Available online 12 November 2013
MoS2 nanostructures and a plausible mechanism for the formation of the obtained structure is discussed.
The cyclic voltammetry study shows the typical rectangular shaped curves with a specific capacitance of
Keywords:
106 F/g at a scan rate of 5 mV/s. Galvanostatic charge–discharge measurements suggested the maximum
A. Nanostructures
A. Chalcogenides
specific capacitance of about 92.85 F/g at discharge current density of 0.5 mA/cm2. Cyclic stability tests
C. Electron microscopy revealed the capacitance retention of about 93.8% after 1000 cycles suggesting a good cyclic capacity of
C. X-ray diffraction the prepared MoS2. The electrochemical impedance spectroscopic results such as Nyquist and Bode
D. Electrochemical properties phase angle plots suggested that the hydrothermally synthesized MoS2 nanostructures will be a suitable
candidate for electrochemical supercapacitor applications.
ß 2013 Elsevier Ltd. All rights reserved.

1. Introduction phosphite nanomaterials for energy storage devices [8,9]. Hence a

Nanostructured metal chalcogenides (NMCs) have attracted
great attention in a variety of energy devices including fuel cells,
solar cells, light-emitting diodes, Li-ion batteries, electrochemical
supercapacitors, and memory devices [1,2]. In recent years, the
research on the NMCs such as nickel sulphide, cobalt sulphide,
copper sulphide, vanadium sulphide materials becomes an area of
special interest in both preliminary research and also focuses
towards device fabrication [2–5]. The researchers believe that the
NMCs can be an ideal candidate for energy storage applications
such as an electrochemical supercapacitors and batteries technol-
ogy. Until now, carbon materials (such as activated carbon,
graphene, graphene oxide), transition metal oxides (such as NiO,
Co3O4, V2O5, Ni0.3Co2.7O4) are used as electrode materials for
supercapacitor applications [6,7]. Increasing demand in the energy
storage devices motivated the researchers to develop novel
materials for supercapacitor applications. Recently, Pang et al.
demonstrated the applications of cobalt phosphate and nickel
* Corresponding author at: Nanomaterials and System Lab, Department of
Mechanical Engineering, Jeju National University, Jeju 690-756, South Korea.
Tel.: +82 647543715; fax: +82 64 756 3886.
E-mail address: kimsangj@jejunu.ac.kr (S.J. Kim).
study of novel materials such as NMCs for supercapacitor
applications is an area of emerging interest. Among the various
NMCs, molybdenum disulphide becomes a material of significant
interest due to its unique atomic and electronic structure [10].
Moreover, nano MoS2 can be considered as an analogue of
graphene materials which is well known for its distinct electrical,
electrochemical properties and so on [10–12]. In recent years, the
research on MoS2 towards various applications has become much
popular due to its distinct physico-chemical properties which
make them versatile for a wide range of applications such as
hydrogen storage, as a catalyst, photo detectors and electrode
materials for lithium battery [12–16]. Due to its layered structure
consisting of covalently bound S–Mo–S trilayers separated by Van
der Waals forces [17], it is expected that this material can be a
suitable alternative to graphene nanosheets (a well known
material owing to its multiple applications in electronic industry
[18]). Unlike graphene, it can be easily synthesized at gram scale
with cost effective techniques such as hydrothermal, solvothermal
and sonochemical routes [19–21]. The study on the electrochemi-
cal properties of MoS2 shows that the capacitive performance of
MoS2 can be comparable to the carbon nanotubes (CNTs) and
graphene nanosheets [22,23].
Considering the works undertaken until now on the super-
capacitive behaviour of MoS2, only limited articles are available in

0025-5408/$ – see front matter ß 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.materresbull.2013.11.019
500 K. Krishnamoorthy et al. / Materials Research Bulletin 50 (2014) 499–502
the literature. Soon et al. reported that the presence of double layer
charge behaviour in MoS2 nanowall films [22]. Ma et al.
demonstrated the improved supercapacitance of polypyrrole
due to the intercalation of nano MoS2 [24]. More recently, Cao
et al. reported the fabrication of micro supercapacitors using
paintable MoS2 films and their results showed that MoS2 shows an
excellent electrochemical property in aqueous electrolyte [23].
Even though, these primary studies revealed the supercapacitive
applications of this material, there is much studies will be needed
to examine the potential applications of this material in this sector.
In this communication, we are reporting a one-pot hydrothermal
synthesis of MoS2 nanostructures and investigated its applications
as an electrode in supercapacitor with the use of cyclic
voltammetry, electrochemical impedance spectroscopy and gal-
vanostatic charge–discharge analysis.
2. Materials and methods
2.1. Materials
Ammonium molybdate, thiourea and sodium sulphate
(Na2SO4) were purchased from Dae Jung Chemicals, South Korea.
All the chemicals used in this work are of research grade and used
without further purification.
2.2. Synthesis of MoS2 nanostructures
The MoS2 nanostructures are synthesized by a hydrothermal
method using ammonium molybdate and thiourea as a starting
precursor. Briefly, 1 M solution of ammonium molybdate and 5 M
solution of thiourea are prepared separately and transferred into a
Teflon-lined stainless steel autoclave (100 mL capacity) and
hydrothermal reaction was carried out at 150 8C for 15 h. After
the completion of the reaction, the hot autoclave was cooled down
into room temperature naturally. Finally, the black precipitates of
MoS2 were collected and washed successively with deionized
water followed by absolute ethanol. The washing procedure is
repeated several times until the final product is free of any trace
amount of residual ions. After that the final product is dried at 80 8C
for overnight.
2.3. Characterization techniques
The phase purity and crystalline nature of the MoS2 nanos-
tructures were determined by Rigaku X-ray diffractometer (XRD)
operated at 40 KeV and 40 mA with CuKa radiation in the range of
10–608 with a step of 0.028. The size and morphology of the
synthesized MoS2 nanostructures were evaluated by field emission
scanning electron microscope (FE-SEM, JSM-6700F, JEOL Ltd).
2.4. Electrochemical measurements
The electrochemical properties were examined by using
AUTOLAB PGSTAT302N electrochemical workstation in 1 M
Na2SO4 solution as an electrolyte. The electrochemical analyses
were carried out in three-electrode configuration with MoS2
modified stainless steel substrates as working electrode, platinum
as counter electrode and Ag/AgCl as reference electrodes,
respectively. The working electrode was prepared by taking active
material MoS2, carbon black, and PVDF (in the weight ratio of
75:20:5) and mixed together with N-methylpyrrolidone (NMP) as
a solvent. The resulting mixture was coated onto the stainless steel
substrate (1 cm  1 cm) and allowed to dry at 60 8C in an oven for
overnight. The weight of the active material in the working
electrode is measured as 1 mg.
3. Results and discussion
In this study, a one-pot hydrothermal method is used to
synthesis the MoS2 nanostructures using ammonium molybdate
and thiourea as the starting materials. Fig. 1 shows the X-ray
diffraction pattern of the as prepared MoS2 nanostructures. It
shows the clear diffraction patterns at 2u = 13.128, 28.478, 32.358,
35.328, 44.118, and 57.478 arises from the (0 0 2), (0 0 4), (1 0 0),
(1 0 2), (0 0 6), and (1 1 0) planes of MoS2 [25]. The observed peaks
are broadened and show a little shift towards the lower diffraction
angle compared to the bulk 2H-MoS2 suggested the presence of
randomly stacked MoS2 layers. The disruption of stacking order in
the MoS2 is due to the intercalation of ammonia in between the
layers of MoS2 during the reaction process which leads to the
observed peak shift towards lower diffraction angle. This finding is
supported by the previous reports of XRD pattern of the randomly
stacked MoS2 [26,27]. Further, there is no characteristic peak of any
such impurities has been observed from the XRD pattern,
suggesting the synthesized MoS2 is of high purity. The surface
morphology of the synthesized MoS2 is examined by FE-SEM (as
shown in Fig. 2(a) and (b) which showed the formation of sphere
like morphology consisting of several individual MoS2 nanos-
tructures. The high magnification image shows the porous MoS2
nanostructures with thickness in several nanometers. It is well
known that porous nanostructures possess superior charge storage
behaviour, when compared to that of the bulk structures [28]. The
formation of the porous nanostructures of MoS2 combined into a
sphere is more likely due to the hydrothermal reaction condition
and the starting materials. The role of precursor materials in this
reaction (ammonium molybdate and thiourea) plays a vital role in
the achieved morphology of the MoS2. During the hydrothermal
reaction ammonium molybdate release the MoO4 and ammoni-
um ions, and thiourea acts as the sulphur source. Being a layered
structure, MoO4 ions react with the sulphur ions to form the MoS2
and the residual ammonia intercalation prevents the stacking of
MoS2 nanostructures and lead to self assembly into a sphere like
morphology.
Further, the prepared MoS2 is examined for their application as
an electrode material in supercapacitor. Fig. 3(a) shows the cyclic
voltammetry curves of MoS2 electrode with various scan rates. As
seen from the CV curves, the rectangular shaped curves with high
order of symmetry is found due to their double layer capacitance
behaviour and it also signifies the fast charge and discharge rates.
The presence of electrochemical double layer capacitance in MoS2
is in good agreement with the previous reports [22,24]. The current
density increases with increasing scan rates suggesting the
presence of ideal supercapacitive behaviour. The specific
Fig. 1. X-ray diffraction pattern of MoS2 nanostructures.
 K. Krishnamoorthy et al. / Materials Research Bulletin 50 (2014) 499–502 501

Fig. 2. Field emission scanning electron microscopic (FE-SEM) images of MoS2 nanostructures (a) low magnification and (b) high magnification images.

capacitance (Csp) of the MoS2 electrode is calculated from the CV
curves using the relation [29]:
R seen from Fig. 3(d), the charge discharge profiles clearly evidences
I dV
C sp ¼ ðF=gÞ
S  DV  m
where ‘‘I’’ is the current, ‘‘S’’ is the scan rate, ‘‘DV’’ is the potential
window and ‘‘m’’ is the mass of the active material. Fig. 3(b) shows
the variation of specific capacitance with respect to the scan rates. It
shows the specific capacitance of MoS2 increases with decreasing
scan rate which is presumably due to the fact that at lower scan rate
allows to diffuse the ions into the interlayer between the active
material, thereby providing more active sites for the charge-transfer
reactions [30]. The maximum specific capacitance obtained from the
CV curves is about 106 F/g at a scan rate of 5 mV/s. The observed
specific capacitance is high compared to the previous one reported
by Soon et al. [22]. Long term cyclic stability is one of the important
criterions for the practical applications of supercapacitor devices.
Fig. 3(c) shows the cyclic tests of the MoS2 electrodes for 1000 cycles
measured using cyclic voltammetry. It clearly shows that the MoS2
material possesses capacitance retention of about 93.8% even after
1000 cycles. This study suggested the long term cyclic stability of
MoS2 for supercapacitor applications.
Fig. 3(d) shows the galvanostatic charge discharge cycle of the
MoS2 nanostructures with various discharge current densities. As
that the discharge time is increased with a decrease in discharge
(1)
current. There is presence of potential drop or IR drop about 0.15 V in
the material at the beginning of the discharge cycle. The observed
potential drop is decreases when the discharge current density is
lowered. The major reason for the occurrence of potential drop is
more likely due to internal resistance of the active material used and
it also related to some other factors such as the solution resistance,
charge-transfer resistance of the material, contact resistance
between the electrode and electrolyte [30]. The specific capacitance
of MoS2 is also calculated from the galvanostatic charge discharge
cycle MoS2 electrodes using the relation [31]:
I Dt
C sp ¼ ðF=gÞ (2)
mDV
where I is the discharge current (mA), Dt is the discharge time (s),
m is the mass of the electro-active material (mg), DV is the
potential window. The maximum specific capacitance of MoS2 is
about 92.85 F/g at a constant discharge current density (0.5 mA/
cm2). The observed specific capacitance is agreed well with the CV

Fig. 3. Electrochemical studies of MoS2 nanostructures. (a) Cyclic voltammetric curves with different scan rates; (b) plot of scan rate vs specific capacitance; (c) capacitance
retention performance of MoS2 using cyclic voltammetry (scan rate 100 mV/s); and (d) galvanostatic charge–discharge profiles with different discharge currents.
502 K. Krishnamoorthy et al. / Materials Research Bulletin 50 (2014) 499–502
Fig. 4. Electrochemical impedance spectroscopic studies of MoS2 (a) Nyquist plot and (b) Bode phase angle plot (applied frequency vs phase).
curves. The energy density (ED) and power density (PD) are the
most important parameters of an electrochemical supercapacitor
device. The ED value of the MoS2 supercapacitors are calculated
from the CV measurements (at lower scan rate) using the given
equation [32]:
C sp V 2
ED ¼
2
where Csp is the specific capacitance (F/g) and V is the potential
window. The PD values are derived from the ED value divided by
the time taken (t) for the completion of one cyclic sweep values
using the equation [32]:
ED
PD ¼
t
The MoS2 supercapacitors exhibit a maximum ED value of
about 7.25 Wh/kg with a PD value of about 186.5 W/kg,
respectively. In order to understand the fundamental behaviour
of the supercapacitor electrode, EIS studies has been performed at a
frequency range of 0.01 Hz to 100 kHz in 1 M solution of Na2SO4.
The EIS data was analyzed using Nyquist plots, which show the
frequency response of the electrode/electrolyte system and are the
plots of the imaginary component (Z00 ) of the impedance against
the real component (Z0 ). Fig. 4 represents the EIS spectra of MoS2
electrodes which show the presence of small arc at higher
frequency region and straight lines at low frequency region [33].
The observation of arc in the high frequency range is likely
attributed to the charge transfer resistance and is about 15.7 V.
The presence of a straight line nearly parallel to the imaginary axis
revealed the ideal capacitive behaviour of the MoS2 electrode.
Fig. 4(b) shows the corresponding Bode phase plots with respect to
the applied frequency. It shows that the phase angle is about 678 at
0.01 Hz is close to that of ideal capacitor (phase angle is about 908
[34]) suggesting that the MoS2 electrodes possess good capacitive
behaviour.
4. Conclusion
In conclusion, the MoS2 nanostructures prepared by the
hydrothermal method have been examined for their electrochem-
ical supercapacitive properties. The CV studies showed the typical
rectangular shaped curves suggesting the double layer capacitance
behaviour. MoS2 nanostructures posses a maximum capacitance of
about 92.85 F/g as examined by the galvanostatic charge discharge
measurements at a discharge current density of 0.5 mA/cm2. The
cyclic stability tests revealed the capacitance retention of about
93.8% after 1000 cycles suggesting long term stability of the MoS2
electrodes. The Nyquist and Bode phase angle plots suggested that
the hydrothermally synthesized MoS2 nanostructures will be a
suitable candidate for electrochemical supercapacitor devices.
Acknowledgement
This research was supported by the 2013 Scientific Promotion
(3) Program funded by Jeju National University.
References
[1] C-H. Lai, M-Y. Lu, L-J. Chen, J. Mater. Chem. 22 (2012) 19.
[2] M-R. Gao, Y-F. Xu, J. Jiang, S.-H. Yu, Chem. Soc. Rev. 42 (2013) 2986.
[3] Q. Wang, L. Jiao, H. Du, J. Yang, Q. Huan, W. Peng, Y. Si, Y. Wang, H. Yuan,
CrystEngComm 13 (2011) 6960.
[4] J. Feng, X. Sun, C. Wu, L. Peng, C. Lin, S. Hu, J. Yang, Y. Xie, J. Am. Chem. Soc. 133
(4) (2011) 17832.
[5] T. Zhu, Z. Wang, S. Ding, J.S. Chen, X.W. Lou, RSC Adv. 1 (2011) 397.
[6] K. Krishnamoorthy, A. Ananth, Y.S. Mok, S.J. Kim, Sci. Adv. Mater. 6 (2014) 349.
[7] H.B. Wu, H. Pang, X.W. Lou, Energy Environ. Sci. (2013), http://dx.doi.org/10.1039/
C3EE42101E.
[8] H. Pang, S. Wang, W. Shao, S. Zhao, B. Yan, X. Li, S. Li, J. Chen, W. Du, Nanoscale 5
(2013) 5752.
[9] H. Pang, C. Wei, Y. Ma, S. Zhao, G. Li, J. Zhang, J. Chen, S. Li, ChemPlusChem 78
(2013) 546.
[10] Q.H. Wang, K.K. Zadeh, A. Kis, J.N. Coleman, M.S. Strano, Nat. Nanotechnol. 7
(2012) 699.
[11] H.S.S. Ramakrishna Matte, A. Gomathi, A.K. Manna, D.J. Late, R. Datta, S.K. Pati,
C.N.R. Rao, Angew. Chem. Int. Ed. 49 (2010) 4059.
[12] B. Visic, R. Dominko, M.K. Gunde, N. Hauptman, S.D. Skapin, M. Remskar, Nano-
scale Res. Lett. 6 (2011) 593.
[13] O.L. Sanchez, D. Lembke, M. Kayci, A. Radenovic, A. Kis, Nat. Nanotechnol. 8 (2013)
497.
[14] K. Bindumadhavan, S.K. Srivastava, S. Mahanty, Chem. Commun. 49 (2013) 1823.
[15] Y. Li, H. Wang, L. Xie, Y. Liang, G. Hong, H. Dai, J. Am. Chem. Soc. 133 (2011) 7296.
[16] J. Chen, N. Kuriyama, H. Yuan, H.T. Takeshita, T. Sakai, J. Am. Chem. Soc. 123 (2001)
11813.
[17] Y. Shi, W. Zhou, A.-Y. Lu, W. Fang, Y.-H. Lee, A.L. Hsu, S.M. Kim, K.K. Kim, H.Y. Yang,
L.-J. Li, J.-C. Idrobo, J. Kong, Nano Lett. 12 (2012) 2784.
[18] G. Venugopal, K. Krishnamoorthy, S.-J. Kim, J. Nanosci. Nanotechnol. 13 (2013)
3515.
[19] G. Tang, J. Sun, C. Wei, K. Wu, X. Ji, S. Liu, H. Tang, C. Li, Mater. Lett. 86 (2012) 9.
[20] M.M. Mdleleni, T. Hyeon, K.S. Suslick, J. Am. Chem. Soc. 120 (1998) 6189.
[21] X. Feng, Q. Tang, J. Zhou, J. Fang, P. Ding, L. Sun, L. Shi, Cryst. Res. Technol. 48 (2013)
363.
[22] J.M. Soon, K.P. Loh, Electrochem. Solid-State Lett. 10 (2007) A250.
[23] L. Cao, S. Yang, W. Gao, Z. Liu, Y. Gong, L. Ma, G. Shi, S. Lei, Y. Zhang, S. Zhang, R.
Vajtai, P.M. Ajayan, Small (2013), http://dx.doi.org/10.1002/smll.201203164.
[24] G. Ma, H. Peng, J. Mu, H. Huang, X. Zhou, Z. Lei, J. Power Sources 229 (2013) 72.
[25] N. Li, Y. Chai, Y. Li, Z. Tang, B. Dong, Y. Liu, C. Liu, Mater. Lett. 66 (2012) 236.
[26] Q. Li, M. Li, Z. Chen, C. Li, Mater. Res. Bull. 39 (2004) 981.
[27] Z. Wu, D. Wang, A. Sun, J. Mater. Sci. 45 (2010) 182.
[28] X. Chen, X. Li, Y. Jiang, C. Shi, X. Li, Solid State Commun. 136 (2005) 94.
[29] S.T. Senthilkumar, R. Kalaiselvan, N. Ponpandian, J.S. Melo, RSC Adv. 2 (2012)
8937.
[30] K. Krishnamoorthy, S.-J. Kim, Mater. Res. Bull. 48 (2013) 3136.
[31] K.V. Sankar, D. Kalpana, R. KalaiSelvan, J. Appl. Electrochem. 42 (2012) 463.
[32] D.P. Dubal, G.S. Gund, C.D. Lokhande, R. Holze, Mater. Res. Bull. 48 (2013) 923.
[33] K.K. Purushothaman, M. Cuba, G. Muralidharan, Mater. Res. Bull. 47 (2012) 3348.
[34] L. Yuan, X.-H. Lu, X. Xiao, T. Zhai, J. Dai, F. Zhang, B. Hu, X. Wang, L. Gong, J. Chen, C.
Hu, Y. Tong, J. Zhou, Z.L. Wang, ACS Nano 6 (2012) 656.