Journal of Energy Storage 27 (2020) 101069

Contents lists available at ScienceDirect

Journal of Energy Storage

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

Synthesis, structural and electrochemical properties of Mn-MoO4/graphene T

nanocomposite electrode material with improved performance for
supercapacitor application
R. Thangappana, , R. Dhinesh Kumarb, R. Jayavelc
⁎

a
Department of Energy Science, Periyar University, Salem 636011, India
b
Department of Physics, Sri Vidya Mandir Arts and Science College, Uthangarai 636902, India
c
Crystal Growth Centre, Anna University, Chennai 600025, India

ARTICLE INFO ABSTRACT

Keywords: In this work a rapid and facile method has been adapted to synthesize Mn-MoO4/G nanocomposites through the
Supercapacitors self-limiting deposition of nanoscale Mn-MoO4 on the surface of graphene under hydrothermal conditions. The
Mn-MoO4 electrochemical performance of the nanostructured Mn-MoO4/G composite materials has been investigated. Mn-
graphene MoO4/G nanocomposite displays the specific capacitance as high as 302.08 Fg−1 at 0.1 Ag−1 which is sig-
Hydrothermal
nificantly higher than that of GO (121.39 Fg−1) and Mn-MoO4 (201.81 Fg−1) in aqueous electrolyte Na2SO4. It
has been observed that the capacitance retention ratio mainly depends on the current density with a maximum
retention of 93.8% at 0.7 Ag−1. The energy density of 41.9 Wh kg−1 at the power density of 208 W kg−1 which
is higher compared to pure Mn-MoO4. This is attributed to the higher operating voltage of the composite
electrode. The improved electrochemical performance may be due to the increase in the electrode conductivity
in the presence of graphene network, the increased effective interfacial area between Mn-MoO4 and the elec-
trolyte, as well as the contact area between Mn-MoO4 and graphene.

1. Introduction NiCo2O4 have been studied by researchers with various structures of

morphologies and desired micro/meso/nanoporous nanostructures as
Supercapacitors performing high power density, high specific en- electrode materials for supercapacitors [10–12]. In the different metal
ergy and long-term cyclability have attracted more interest for many oxides, RuO2 have shown high value of specific capacitance and high
reliable potential applications such as stand-by power systems, tele- cyclic stability, due to cost effective it is limited to large-scale appli-
communication devices and hybrid electrical vehicles [1,2]. In super- cations. Other reliable metal oxides like Ni, Mn and Co materials have a
capacitors, active materials are the most essential factor in leading the high value in supercapacitor devices. However, the semiconducting
electrochemical performance. In General, the electrode materials of property of these oxides is eradicating faster charge transfer at high
supercapacitors are of three types, conducting polymers [6–8], carbon current density and this attributes to reducing the rate capability [13].
materials [3–5] and transition metal oxides [9]. Each of them has its In order to solve this problem, many researchers investigated about the
own merits and limitations. Carbon materials perform outstanding hybrid nanostructures with the high conductive carbon based materials.
electrical properties, long life-cycles and high valued mechanical Hence, binary or ternary composites have been widely investigated to
properties, but very low double layer capacitance. Conducting polymers obtain materials with the combined nature of properties in a balanced
are low cost and highly flexible, but have poor cyclability. Transition merit of the three kinds of materials. In this aspect, the graphene(G) or
metal oxide materials have high specific capacitance but poor elec- graphene oxide(GO) based metal oxide composites are used as elec-
tronic conductivity, and in few materials they are high cost. trodes and it enables more interests from the researchers due their sy-
Generally for double layer capacitors carbon-based materials are nergistic performance between graphene or graphene oxide and metal
widely used as electrode material. However, they exhibit only low oxides [14–15].
specific capacitance and lower energy density than the redox based Transition metal molybdates have been considered to be a pro-
electrode materials. Metal oxides such as RuO2, NiO, Co3O4, MnO2 and mising, effective and scalable alternatives, because it offers many

⁎
Corresponding author.
E-mail address: [email protected] (R. Thangappan).

https://doi.org/10.1016/j.est.2019.101069
Received 23 July 2019; Received in revised form 19 September 2019; Accepted 7 November 2019
2352-152X/ © 2019 Elsevier Ltd. All rights reserved.
R. Thangappan, et al. Journal of Energy Storage 27 (2020) 101069

merits such as low cost, abundant resources and environmental 2.3. Synthesis of Graphene/Mn-MoO4 nanocomposites
friendliness. In particular, manganese molybdate (Mn-MoO4) has at-
tracted great research interest because of its excellent catalytic and In a typical synthesis process, 0.791 g of (NH4)6Mo7O24).4H2O,
electrochemical characteristics [16]. As one of the most important 0.027 g of Mn(CH3COO)2 and 0.19 g of critic acid were dissolved in
compounds, Mn-MoO4 exhibits considerable specific capacitance and 40 ml of deionised water (DI). The graphene oxide of about 0.1 g was
energy density. It is reported that the hierarchical Mn-MoO4/Co-MoO4 added to DI water of 40 ml and vigorously sonicated for 3 hrs con-
heterostructure nanowires contributes specific capacitance of tinously to get the uniform distribution. Then the above metal oxide
187.1 Fg−1 at a current density of 1 Ag−1 [17]. Because of the high precursor solution was added slowly to GO solution and stirred for 2 h
surface/volume ratio, the hierarchical nanowires exhibit better elec- to get a homogeneous solution. The solution was transferred into a
trochemical performance than Co-MoO4. Jayasubramaniyan et al. 100 ml Teflon lined autoclave and maintained at 180 °C for 24 h. The
achieved the highest specific capacitance of 143 Fg−1 and 551 Fg−1 at final product was centrifuged, washed with water, ethanol and dried
1 Ag−1 constant discharge density for the α-MnMoO4 nanorods pre- under vacuum at 60 °C. Pure Mn-MoO4 were synthesized through a
pared by co-precipitation and microwave hydrothermal methods [18]. similar procedure, in the absence of GO. Herein, GO was used as a metal
Xia et al. used graphene as the substrate to get the high surface/volume oxide support as they act as a metallic conductor. Pure graphene
ratio by hydrothermal method [19]. The Co-MoO4–graphene nano- without the presence of ammonium heptamolybdate tetrahydrate and
composites showed the highest specific capacitance of 394.5 Fg−1 at manganese acetate was also prepared under the same condition for
1 Mv s−1 scan rate. Recently, Debasis Ghosh et al. developed a hybrid comparison. The synthesized samples were subjected to further char-
composite of α-Mn-MoO4/graphene, which exhibited excellent cyclic acterization studies.
stability [16], could be attributed to the 3D graphene network and the
strong coupling between Mn-MoO4 and the 3D graphene. Thus, con- 2.4. Characterization
trolling the size and morphology of the nanomaterials through various
synthesis methods provided a platform to enhance the electrochemical XRD analysis of the prepared composite was carried out using
properties, conductivity, cyclability and energy and power densities. RIGAKU Ultima III X-ray diffractometer using Cu-Kα radiation
The synthesis of nanomaterials and nanocomposites by various (λ = 0.154056 nm) with a step of 0.01◦. SEM images were recorded
chemical processes is very tedious and takes long reaction time. using FEI Quanta FEG 200 microscope at an accelerating voltage of
However, the hydrothermal synthesis has been well recognized because 20 kV. TEM images were recorded using JEM 2100F microscope with
of its unique features of preparing nanomaterials. Compared to other an accelerating voltage of 200 kV. The samples were prepared by dis-
process hydrothermal process often occurs at a higher reaction rate persing in alcohol with the aid of 10 min ultrasonic vibrations. After
under the constant pressure and temperature with prescribed time. that a drop of the solution was transferred onto a standard holey
Therefore, the hydrothermal method adopted as a convenient method carbon-covered-copper grid and dried for TEM analysis. X-ray photo-
for preparing all types of composite materials. electron spectroscopy (XPS) analysis was performed using a Shimadzu
In this study, a new two-step strategy has been followed for the ESCA 3400 electron spectrophotometer. TG-DTA analyses were per-
synthesis of Mn-MoO4/G nanocomposites. The first step involves the formed using SII Nanotechnology EXSTAR 6300 at a heating rate of
synthesis of GO/(NH4)6Mo7O24).4H2O-Mn(CH3COO)2 composite under 10 °C/min under N2 atmosphere.
mild hydrothermal condition, followed by the synthesis of Mn-MoO4/G
nanocomposites by repeated washing and drying in vacuum atmo- 2.4.1. Electrochemical studies
sphere. The specific capacitance of the prepared nanocomposites is The electrochemical behavior of the Mn-MoO4/G nanocomposites
improved with an excellent cyclic stability at high rate operating con- was studied using a three-electrode cell set-up, which consists of a
ditions. working electrode, platinum wire as the counter electrode and Ag/AgCl
as the reference electrode. All electrochemical tests were performed
with aqueous electrolyte of 1 M Na2SO4. The working electrode was
2. Experimental prepared by the same procedure as our previous work [21] and elec-
trochemical measurements were analyzed using computer controlled
2.1. Materials potentiostat (VSP BioLogic (France)) in the potential range of −0.8 to
0.8 V.
Materials: The chemicals used in this work, were analytical grade
ammonium heptamolybdate tetrahydrate (AHM) (NH4)6Mo7O24). 3. Results and discussion
4H2O, manganese (II) acetate (Mn(CH3COO)2), citric acid (C6H8O7) and
graphite. 3.1. Formation mechanism

Fig. 1 shows the schematic illustration of the formation process of

2.2. Synthesis of graphene oxide (GO) Mn-MoO4/G nanocomposites. Hydrothermal method was favourable to
promote the stoichiometric chemical reactions between the Mn2+ and
Hummers and Offeman [20] method was adopted to prepare gra- MoO42− ions, and thus resulting in the formation of the crystalline Mn-
phene oxide (GO) from the graphite powder. About 1 g of graphite MoO4 nanoparticles. The GO sheets are transformed into graphene
powder was added to 24 ml of cooled (to 0 °C) concentrated H2SO4. through the chemical reduction by using citric acid as the reducing
About 6 g of KMnO4 was added gradually under simultaneous stirring agent by hydrothermal process. Meanwhile, Mn-MoO4 particles were
and cooling, so that the temperature of the mixture was maintained re-crystallized into nanoparticles, which were well-decorated on the
below 20 °C. The mixture was then stirred at 35 °C for 30 min. About graphene sheets.
46 ml of distilled water was slowly added by increasing the temperature
to 98 °C, and the mixture was maintained at the same temperature for 3.2. Structural analysis
15 min. The reaction was terminated by adding 140 ml of distilled
water, followed by the addition of 10 ml of 30% H2O2 solution. The The Fig. 2 displays the XRD patterns of GO, pristine graphene, pure
solid product was separated by centrifugation, washed repeatedly with Mn-MoO4, and Mn-MoO4/G nanocomposite. For the GO (Fig. 2a), a
5% HCl solution until the agglomeration was reduced, then washed 3–4 single diffraction peak observed at 11° corresponds to (001) plane
times with acetone, and dried in an air oven at 65 °C overnight. which confirms the formation of GO. For the graphene (Fig. 2b),

2
R. Thangappan, et al. Journal of Energy Storage 27 (2020) 101069

Fig. 1. Schematic illustration of the formation process of the Mn-MoO4/G nanocomposites.

Fig. 2. XRD patterns of (a) GO, (b) pristine graphene, (c) pure Mn-MoO4 and
(d) Mn-MoO4/G nanocomposite.

Fig. 3. SEM images of Mn-MoO4/G nanocomposites (a–c) with the different

diffractions occur at 26° (002) and 44° (100) confirming the presence of magnification and (d) pristine graphene.
carbon in the material and were indexed with the standard JCPDS
card.no 75-1621. The absence of secondary impurity in the material 3.3. Morphology studies
implies the high purity of the sample. The XRD pattern of the mono-
clinic Mn-MoO4 (Fig. 2c) strongly resembles the JCPDS file 78-0221 The morphology and structure of Mn-MoO4/G nanocomposites and
indicating the formation of manganese molybdenum oxide. The ab- graphene were studied by scanning electron microscopy (SEM).
sence of any other peaks confirms the phase purity of the as-prepared Fig. 3(a–c) show the SEM images of Mn-MoO4/G nanocomposites at
Mn-MoO4. In the composite the graphene peak is invisible, indicating various magnifications, revealing the formation of nanosized Mn-MoO4
that graphene sheets were well-decorated by numerous Mn-MoO4 na- particles on the graphene sheets. A close observation of the Mn-MoO4
noparticles. The other XRD peaks at 15.3, 18.4, 29.6, 36.5, 52.3, and reveals that particles were aggregated to form a cluster like structure. A
61.0° were attributed to the diffraction of (010), (100), (1̄11), (002), low-magnification SEM image of Mn-MoO4/G nanocomposites depicted
(2̄ 21), and (1̄13) planes of the monoclinic Mn-MoO4 (JCPDS NO: 78- in, Fig. 3a, shows that the Mn-MoO4 particles were decorated on the
0221). The diffraction peaks of the composite become broader compred graphene sheets. A low magnification SEM image shown in Fig. 3d,
to pure Mn-MoO4 due to presence of graphene and thus confirming the reveals that the graphene nanosheets were formed like a flexible thin
formation of Mn-MoO4/G nanocomposites. film with many wrinkles. Importantly, the Mn-MoO4 were tightly en-
capsulated by the flexible graphene sheets to form conductive networks

3
R. Thangappan, et al. Journal of Energy Storage 27 (2020) 101069

Fig. 4. TEM and HRTEM images of Mn-MoO4/G nanocomposites (a-d), its SAED pattern inset (a) and (e-f) pristine Graphene, its SAED pattern inset (f).

and thereby facilitating the fast electron transfer.

The TEM image of the Mn-MoO4/G (Fig. 4a) nanocomposite also
reveals the same morphology as observed in SEM and the corre-
sponding SAED pattern demonstrates the presence of both dot and ring
patterns due to the crystalline and amorphous nature of Mn-MoO4 and
graphene respectively. The observed pattern was due to the presence of
both graphene and Mn-MoO4 particles in the sample. Graphene was
prone to electrostatic stacking; however the TEM image of Mn-MoO4/G
nanocomposite shows a lower contrast between the graphene na-
nosheet and the coated carbon on copper grids, indicating the ultrathin
layers. The nanoparticles of Mn-MoO4 decorated on the graphene sur-
face act as a spacer and hinder the electrostatic restacking of graphene
thereby utilizing the maximum surface area of the composite. The in-
timate contact between the graphene sheets and Mn-MoO4 nano-
particles was strong enough that even under long time ultrasonication
during the TEM sample preparation. Fig. 4b shows the clearest view of
graphene sheet and Mn-MoO4 nanoparticles attachment at the edge of
graphene sheets. The size of Mn-MoO4 particles ranges from 6 to 15 nm.
The high-resolution TEM images (HRTEM) of the Mn-MoO4/G nano-
composites displayed in Fig. 4(c and d), shows the D-spacing values of
0.349, 0.251 and 0.151 nm which correspond to that of standard
JCPDS. No 78-0221. The pure graphene sheets (Fig. 4e) were trans-
parent with a few wrinkles and folds owing to the 2D nature. The Fig. 5. EDX analysis for Mn-MoO4/G nanocomposites and quantification of
HRTEM image at the higher magnification (Fig. 4f) shows the perfect elements present.
sheet morphology owing the flat surface and the corresponding SAED
pattern as an inset in the Fig. 4f. From the above observation, it be- fact that the particles are highly distributed on the graphene sheets. No
comes clear that the metal oxide particles and graphene were linked other impurities were observed in the material indicating the high
strongly together to form the composite. purity of the sample. This indicates that the proposed method (hydro-
Energy dispersive X-ray (EDX) analysis was performed and por- thermal process) was highly reliable and effective.
trayed in the Fig. 5. The presences of Mo, Mn, O and carbon elements in
the Mn-MoO4/G nanocomposite have been confirmed. The weight
percentage of Mo and Mn in Mn-MoO4/G was 24.34 wt% and 2.36%, as 3.4. Thermal analysis
determined by EDX analysis [inset of Fig. 5]. The molybdenum content
was higher compared to all other species in the compound, due to the The thermogravimetric analysis was carried out under an inert

4
R. Thangappan, et al. Journal of Energy Storage 27 (2020) 101069

Fig. 6. TGA curves of (a) Mn-MoO4/G nanocomposite, (b) pure Mn-MoO4 and
(c) GO. Fig. 7. Raman spectra of (a) pure Mn-MoO4, (b) Mn-MoO4/G nanocomposite
and (c) GO.

atmosphere at a ramp rate of 10 °C min−1. Fig. 6 shows the TGA curves

of GO, pure Mn-MoO4 and Mn-MoO4/G nanocomposites. For Mn- Mn–O–Mo bond. The band observed at 331 cm−1 can be assimilated to
MoO4/G nanocomposite (Fig. 6a) the weight loss was gradually de- MoO4 vibrations [22]. For the graphene based nanocomposite of Mn-
creased upto 500 °C due to the loss of physisorbed water molecules and MoO4 the Raman vibrational modes were shifted and appeared at
decomposition of the reactants with the weight loss of about 10.7%. 1350 cm−1, 1588 cm−1, respectively [23]. The D band at 1350 cm−1
After 500 °C, about 10.5% weight loss was observed up to 800 °C, due to represents the disorder induced in the graphitic structure, whereas the
the exothermic combustion reaction. The weight loss gradually de- G band at 1588 cm−1 appears from the vibration of sp2- bonded carbon
creased after 900 °C with low decomposition to form stable compound. atoms due to the E2g mode of graphite [24]. The ID/IG value (the peak
In pure Mn-MoO4 material similar weight loss was observed as that of intensity ratio between the 1350 and 1588 cm−1 peaks) generally
the composite (Fig. 6b). From 150 °C to 350 °C only 8.5% weight loss provides a useful index for comparing the degree of crystallinity of
was observed due to the decomposition of reactant present in material. various carbon materials, i.e., the smaller the ID/IG ratio, the higher the
There was a small weight increase observed around 500 to 700 °C. This degree of ordering in the carbon material. The ID/IG values of graphene
was mainly due to the oxidation of MoO2 to MoO3, which gains a oxide, Mn-MoO4/G composite, were 0.74 and 1.43 respectively. For
theoretical weight increase of 1.6 wt% (based on the mass of Mn- single layer graphene the D band should be sharp, however, the broad D
MoO4). After 700 °C there was a steady weight loss observed up to band in the Mn-MoO4/G nanocomposite indicates a few stacked layers
850 °C, due to combustion reaction of material to form a stable com- of graphene [25]. Therefore, the Raman results are consistent with the
pound. The TGA curves remains stable after 900 °C showing the stabi- formation of Mn-MoO4/G nanocomposite. Generally, the Raman spec-
lity of the material compare to pure. GO shows a relatively poor trum of graphene-based materials were characterized by two main
thermal stability with a rather low onset temperature for pyrolysis of features: the G band and the D band; the former arises from first-order
the labile oxygen-containing functional groups over 180–300 °C scattering of the E2g phonon of sp2-bonded carbon, while the latter was
(Fig. 6c). The minor weight loss observed below 100 °C in GO was due associated with vacancies, grain boundaries, and amorphous carbon
to the evaporation of absorbed water molecule intercalated in the as- species [26,27]. The Raman spectra of GO nanosheets represented in
synthesized GO sheet. There was a gradual weight loss after 300–800 °C Fig. 7(c) show the presence of G and D bands at 1566 and 1318 cm−1,
which corresponds to removal of steady oxygen functional groups ad- respectively. After hydrothermal reduction (i.e. composite) of the GO
hered to the 2D graphite structures. It can be observed that after into graphene, two significant changes in the Raman spectra were ob-
bonding Mn-MoO4 nanoparticles onto graphene, the weight loss was served: (i) the G band shifted toward a higher wave number, suggesting
decreased. From the TGA curves of Mn-MoO4/G nanocomposite, pure that re-graphitization had occurred, and (ii) the D band becomes more
Mn-MoO4 and GO, it is inferred that the weight loss percentage of prominent due to an increase in the defect level from the reduction
composite was less compared to pure material. This indicates that the reaction [26]. Thus the Raman study confirms that the GO was reduced
composite material has better stability and can effectively be anchored to graphene.
with the graphene without forming any allied compounds.

3.6. BET analysis

3.5. Raman spectroscopic analysis
N2 adsorption−desorption analysis was made to study the pore
The Raman spectra obtained for Mn-MoO4, Mn-MoO4/G and GO structure and the specific surface area of the sample. N2 ad-
were shown in Fig. 7(a–c) respectively. The Raman spectra of all sorption−desorption isotherms and pore size distribution curves are
samples were recorded over the wavenumber ranging from 200 cm−1 shown in Fig. 8(a and b). The isotherms can be classified as type IV,
to 1800 cm−1. Raman vibrational modes of Mn-MoO4 were positioned revealing the mesoporous structure of the Mn-MoO4/G nanocomposites
at 926, 873, 819, 369, 331 and 280 cm−1 (Fig. 7a), corresponding to (Fig. 8a). From the adsorption branch of the isotherm, the specific
the characteristic bands of Mn-MoO4. The band at 926 cm−1 was as- surface area of Mn-MoO4/G nanocomposite and pure Mn-MoO4 were
sociated with the symmetric stretching mode of the Mo–O bond, and calculated and found to be 69.69 and 17.84 m2 g−1 respectively, by the
the bands observed at 873 and 819 cm−1 correspond to the asymmetric Brunauer−Emmett−Teller (BET) method. The nanocomposite has a
stretching modes of oxygen in the O–Mo–O bond. The band located at stacked structure of curved graphene nanosheets, with numerous Mn-
662 cm−1 was attributed to the symmetric stretching mode of the MoO4 nanoparticles anchored on two sides of graphene sheets. The

5
R. Thangappan, et al. Journal of Energy Storage 27 (2020) 101069

Fig. 8. N2 sorption isotherms of (a) Mn-MoO4/G nanocomposite and (b) pure Mn-MoO4, pore size distributions of (a) inset MnMoO4/G nanocomposite and (b) inset
pure Mn-MoO4.

graphene sheets could not make two-directional bending [26,19], re- was confirmed at the binding energy of 643.8 eV as depicted in Fig. 9e,
sulting that the nanocomposite has abundant channels that are con- which was a signature of Mn2+ oxidation state [31].
ducive to the insertion/extraction of charged ions and the flow of
electrolyte. The pore size distributions (inset in Fig. 8(a and b) indicate
that the Mn-MoO4/G nanocomposites and pure Mn-MoO4 exhibit wide 3.8. Electrochemical studies
pore size distributions ranging from 6 to 90 nm, further confirming the
existence of mesopores and macropores. With a considerable surface The main improvement strategies for metal oxides as supercapacitor
area, conductive nature of graphene, and the small size of Mn-MoO4 electrodes are nanostructuring of metal oxides involves decreasing the
active nanoparticles, such a nanocomposite has potential for the elec- particle size and increasing its specific surface area to create a larger
trochemical capacitor applications that require a sufficient interface for interface between the electrode and electrolyte. Decreasing the particle
electrolyte access, low contact and charge-transfer impedance, and a size also reduces the path length for electronic transport, thus coun-
short transport length for both sodium ions and electrons. Therefore, teracting the poor electrical conductivity of their bulk metal oxides. The
enhanced electrochemical properties could be achieved for the Mn- Metal oxides supported carbon materials provide electrically con-
MoO4/G nanocomposites. ductive filler which facilitates the formation of a conductive network,
which is essential to the poorly conducting metal oxides. In addition,
the carbon materials also function directly as electrode materials based
3.7. XPS analysis on the electrochemical double layer charge storage mechanism. In the
obtained Mn-MoO4/G nanocomposite, both graphene sheets and Mn-
In order to estimate the elemental composition and oxidation states MoO4 nanoparticles play a major role as electrode materials to get a
of Mn-MoO4/G nanocomposite, XPS studies were performed. Fig. 9a synergistic effect. As seen in Fig. 10, the key strategy of electrochemical
shows the wide range survey spectrum of Mn-MoO4/G composite, with performance is nanostructured Mn-MoO4/G composite electrodes in
four peaks at 643.8 eV, 530.9 eV, 284.5 eV and 235.6 eV, indicating Mn which the dimensional confinement of Mn-MoO4 nanoparticles by the
2p, O 1s, C 1s, and Mo 3d levels, respectively. According to the semi- surrounding graphene sheets limits the volume expansion upon sodium
quantitative analysis of XPS, the C/O atomic ratio of GO was about 2.3 insertion, and the developed nanopores between Mn-MoO4 and gra-
[21,28]. In the synthesized Mn-MoO4/G nanocomposite, the C/O phene sheets could be used as buffered spaces during charge/discharge,
atomic ratio was found to be 2.1, including the oxygen content from resulting in the superior cyclic performances and eventually higher
Mn-MoO4. This observation further indicates that most of the oxygen- reversible capacities in comparison with the pure Mn-MoO4 electrode.
containing functional groups from GO were reduced during the hy- Fig. 11 illustrates the CV plots of Mn-MoO4/G nanocomposite, pure
drothermal process, whereas a few of the residual functional groups Mn-MoO4 and GO at different scan rates ranging from 1 to 100 mV s−1
provide a stable dispersion of the nanoparticles in the Mn-MoO4/G and the relation between the peak current with respect to the square
nanocomposites [29]. The Fig. 8b represents the C 1s core level spec- root of scan rates. Fig. 11a presents the CV plots of Mn-MoO4/G na-
trum of the Mn-MoO4/G nanocomposites, which can be deconvoluted nocomposite within the potential range of −0.8 V to 0.8 V at various
into three peaks with binding energies of 284.5, 286.8 and 288.6 eV, scan rates of 1–100 mV s−1 with 1 M of Na2SO4 as the aqueous elec-
corresponding to the sp2 hybridized carbon, CeOH, and O=]CeOH trolyte. The current in the CV curves of Fig. 10a was normalized with
functional group species, respectively. The Mo 3d core level spectrum in respect to the mass of the Mn-MoO4/G nanocomposite material and the
Fig. 9c shows two peaks with binding energies of 232.4 eV and same was followed for pure Mn-MoO4 and GO. The current density of
235.6 eV, corresponding to Mo 3d5/2 and Mo 3d3/2, respectively. The Mn-MoO4/G nanocomposite electrode was higher than the pure Mn-
Mo 3d5/2-Mo 3d3/2 energy separation was approximately 3.4 eV, which MoO4, revealing that the Mn-MoO4/G electrode has superior capaci-
was in good agreement with previously reported for Mo6+ oxidation tance and possesses the typical behavior due to graphene present in the
state [19]. Two different oxygen species could be distinguished on material. A couple of redox peaks can be observed in the CV plots of
deconvolution of core level spectrum of O1s electron lying between Mn-MoO4/G indicating the redox activity and pseudocapacitive beha-
530.2 and 533.4 eV as shown in the Fig. 9d. The binding energies of vior. The redox peak was associated with the reversible electron
530.2 and 533.4 eV have been assigned to the lattice oxygen and car- transfer between the Mn(II) and Mn(III) states. The redox peak poten-
boxyl groups, respectively [30]. The presence of Mn 2p in Mn-MoO4 tial shows a positive shift for the cathodic peaks and a negative shift for

6
R. Thangappan, et al. Journal of Energy Storage 27 (2020) 101069

Fig. 9. XPS survey spectrum (a), C 1s core level spectrum (b), Mo 3d core level spectrum (c), O 1s core level spectrum (d) and Co 2p core level spectrum (e) of Mn-
MoO4/G nanocomposite.

Fig. 10. Schematic diagram of charging and discharging mechanism using Mn-MoO4/G nanocomposite electrode in 1M Na2SO4 electrolyte in the electrochemical
cell, the structure of Mn-MoO4 and graphene sheets which enhances the cycle performance of electrodes.

7
R. Thangappan, et al. Journal of Energy Storage 27 (2020) 101069

Fig. 11. CV curves of (a) Mn-MoO4/G nanocomposite, (b) pure Mn-MoO4, (c) GO and (d) peak current with respective to square root of the different scan rates of
pure Mn-MoO4 and Mn-MoO4/G nanocomposite. .

the anodic peaks with the increasing scan rate, which may be due to nanocomposite and pure Mn-MoO4 electrodes was observed between
various resistive effects involved in the electrode. Again the increasing the both anodic and cathodic peak current with respect to square of
peak current with increasing scan rate was a consequence of the dif- applied scan rates. The electrode peak currents of nanocomposite also
fusion controlled process. Although aqueous electrolyte tends to de- increased to very high value in comparison to pure Mn-MoO4 electrode
compose beyond 1.23 V, the Mn-MoO4/G electrode shows a high op- at the applied scan rates. The observation indicates that the reactions in
erating voltage of 1.6 V. The probable reason was the other potential, the nanocomposite system were highly controlled by the diffusion
where oxygen evolution from water does not follow a measurable rate process and surface redox reactions taking place in the charge storage
until extra potentials were reached. There was an increase in the peak process than the pure electrode system [34,35]. This is attributed due to
current near (1 V), possibly due to the oxygen evolution at the elec- the presence of graphene and the high conductivity nature of the ma-
trode. In the case of the negative potential window, the current re- terial.
sponse slightly increased towards the negative cut off potential Fig. 12 illustrates the galvanostatic charge/discharge plots of Mn-
(−1.5 V) and the curve was possibly due to the over potential of hy- MoO4/G nanocomposite, pure Mn-MoO4, GO and comparison curve of
drogen evolution at the Mn-MoO4 electrode [32]. Therefore high utility charge-discharge at lowest current density of 0.1 Ag−1. As can be seen
of the pseudocapacitive Mn-MoO4 was achieved in the Mn-MoO4/G in the galvanostatic charge/discharge plots, the discharge time of Mn-
nanocomposite electrode, and the corresponding CV patterns at dif- MoO4/G was significantly longer in comparison to pure- Mn-MoO4 and
ferent scan rates are shown in Fig. 11(a). This can be attributed to the GO at both high and low current densities, indicating that Mn-MoO4/G
conductive graphene, which facilitated the charge transfer in the Mn- composites show a much higher capacitance. This was in coincidence
MoO4/G nanocomposite and ensure high electrochemical utilization of with the CV results. With an increasing current density, the specific
Mn-MoO4. The CV plots of pure Mn-MoO4 (Fig. 11b) and Mn-MoO4/G capacitance gradually decreases, due to the low diffusion of electrolyte
electrode were more or less similar to each other with a couple of broad ion at high currents and consequently access only to a few available
redox peaks during the positive and negative sweep indicating their reaction sites and thus resulting in an incomplete insertion reaction and
pseudocapacitive nature. Moreover the operating voltage for pure Mn- low specific capacitance [36]. The Mn-MoO4/G nanocomposite pos-
MoO4 was low compared to the composite. The CV curve for GO is sesses high specific capacitances up to 302.08 Fg−1 at 0.1 Ag−1 re-
shown in Fig. 11(c), the curve replicates the absence of redox peaks as spectively. While the pure Mn-MoO4 shows specific capacitances of
estimated within the scan range of −0.6 to 0.6 V and hence it possess 201.81–90.9 at 0.1–1 Ag−1 and for GO the specific capacitance was
the EDLC behavior. Therefore excellent current response from CV plots 121.39–25.641 Fg−1 at 0.1–1 Ag−1 respectively. For the better visua-
for the Mn-MoO4 and its graphene based composites indicates the rapid lisation of the specific capacitance with respective to different current
kinetics of the interfacial faradaic redox reactions as well as high rates densities a comparative plot is shown in Fig. 12(e) and Table 1. The
of electronic and ionic transport at the high scan rate of 100 mV s−1 figure clearly illustrates the linear decrease of specific capacitance with
[33]. The peak current (Ip) of a diffusion-controlled reversible reaction respect to increase in the current densities. Therefore, without con-
increases with an increase in scan rate (v), as shown in the Fig. 10d. An sidering the synergistic effect between Mn-MoO4 and graphene, the
almost linear/quasi-linear relationship for the Mn-MoO4/G capacitance value of Mn-MoO4/G nanocomposites was 302.08 Fg−1 at

8
R. Thangappan, et al. Journal of Energy Storage 27 (2020) 101069

Fig. 12. Galvanostatic charge-discharge curves of (a) Mn-MoO4/G nanocomposite, (b) pure Mn-MoO4, (c) GO at the different current densities, (d) comparison of all
at 0.1 Ag−1 and (e) comparison of specific capacitance of Mn-MoO4/G nanocomposite, pure Mn-MoO4 and GO with respect to different current densities.

Table 1 The enhanced electrochemical properties of Mn-MoO4/G were

Comparative specific capacitance of GO, pure Mn-MoO4 and Mn-MoO4/G na- probably attributed to the unique structure of the nanocomposite with
nocomposite with different current densities. ordered distribution of both components, as confirmed from TEM
Sample Current densities (Ag−1) analysis. Firstly, the loading of Mn-MoO4 nanoparticles on graphene
0.1 0.2 0.3 0.5 0.7 1.0 can exfoliate graphene sheets and inhibit the stacking/agglomerating of
Specific capacitance (Fg−1) graphene sheets, which leads to large regions in contact with negative
ions. And the well-exfoliated graphene sheets can also provide a highly
GO 121.7 115.3 98.0 76.9 49.3 15.7
Mn-MoO4 201.8 183.6 163.6 145.5 133.6 90.9 conductive network for charge transport during the charge/discharge
Mn-MoO4/G nanocomposite 302 268.3 203.7 179.1 151.6 129.1 processes. Secondly, the pure Mn-MoO4 particles have low surface/
volume ratios and contact with electrolyte only on the surface, which
lead to a large “dead” region inside the Mn-MoO4 particles. In com-
0.1 Ag−1 (201.81 Fg−1 to 121.39 Fg−1) (i.e. combination of pure and parison with pure Mn-MoO4, the nanoscale Mn-MoO4 particles were
GO capacitance). Thus, the enhanced capacitance in Mn-MoO4/G na- decorated on the graphene sheets with low crystallinity and have high
nocomposite further indicates a strong synergistic effect between Mn- surface/volume ratios. These nanoparticles can largely utilize the
MoO4 and graphene. The conductive graphene facilitates the charge electroactive component of Mn-MoO4 and possess sufficient order to
transport and thus improve the utilization rate of electrode materials, enable negative ion access. These results can be supported by nitrogen
even at high rates, which was confirmed by galvanostatic charge-dis- isothermal adsorption–desorption data. The Brunauer–Emmett–Teller
charge studies and the presence of graphene, would contribute to the surface area of the Mn-MoO4/G was 69.69 m2 g−1 which was nearly 4
double layer capacitance. times greater than the pure Mn-MoO4 (17.84 m2 g−1). Thirdly, the

9
R. Thangappan, et al. Journal of Energy Storage 27 (2020) 101069

excellent interfacial contact and the increased contact area between the The cycle performances of Mn-MoO4/G nanocomposite, pure Mn-
Mn-MoO4 nanoparticles and graphene can significantly provide the MoO4 and GO, electrodes during a charge discharge process over 1000
short diffusion and migration length for charge transport. cycles with a constant current density of 0.7 Ag−1 in a three-electrode
The relation between the energy density and the power density was cell are shown in Fig. 14b. It can be seen that Mn-MoO4/G nano-
studied by Ragone plots. The plot relating the energy density to the composite electrode maintains good charge-discharge performance, and
power density is an effective way to evaluate the supercapacitance the capacitance retention was 93% of the 1000th cycle, while poor
performance of the electrode material. The energy density (E, capacitance retention of about 10% and 25% after 1000 cycles can be
W h kg−1) power density (P, kW kg−1) and coulombic efficiency (ƞ) of observed for pure Mn-MoO4 and GO electrodes respectively. The
an electrode can be calculated using the following equations: [37-39] composite electrode shows better retention, which was ascribed to the
existence of graphene with good charge-discharge performance in the
E = 0.5CV 2/3.6 (2)
composite electrode. The good capacitance retention also supports the
P = E x 3600/t (3) existence of the synergistic effect between the graphene and Mn- MoO4
nanoparticles, indicates high dispersion and strong interaction between
= td / t c (4) the graphene and Mn-MoO4 nanoparticles which gives a high structural
−1
where C (F g ) is the specific capacitance of the electrode, V (V) is the stability of the composite electrode. The enhanced capacitive perfor-
voltage change during the discharge process after IR drop, t (s) is the mance is evolved due to the use of the aqueous electrolyte which results
discharge time, Δtc and Δtd are charging and discharging time respec- the high ionic conductivity and the strong interaction between the
tively. The specific energy and specific power density of the Mn-MoO4/ graphene and Mn-MoO4/G nanoparticles. The compoite material en-
G nanocomposite, pure Mn-MoO4 and GO electrodes were calculated ables the high charge transfer through the graphene material by the
and plotted in the Fig. 13. It was evident that the drop in energy density EDLC behavior and pure nanoparticles allows only short diffusion
of Mn-MoO4/G with increasing power density was smaller than pure length for access in the electrolyte. This attributes more electrochemical
Mn-MoO4. As shown in the Ragone plot (Fig. 13), at a power density of active region for increase in reversible Faradic reaction.
208 W kg−1, the Mn-MoO4/G composite electrode delivers an energy The electrochemical impedance spectroscopy can be used to study
density as high as 41.9 W h kg−1, which was larger than that of the pure the electron and ion transport phenomena in the graphene based
Mn-MoO4 electrode (28.02 W h kg−1). More importantly, the energy electrode. The Fig. 15 shows the typical Nyquist plots of Mn-MoO4/G
density of the Mn-MoO4/G nanocomposite electrode was still as high as nanocomposite, pure Mn-MoO4 and GO impedance spectra, which were
17.9 W h kg−1 even at a high power density of 2083 W kg−1. The in- recorded over the frequency range of 100 kHz to 1 Hz. The first inter-
crease in the energy density and power density was attributed to high section of the curves with the real axis with respective to high fre-
operating voltage (1.6 V) of composite electrode compared to the pure quency indicate the equivalent series resistance (ESR) of the material,
Mn-MoO4 electrode. These remarkable electrochemical properties make which includes; (a) the ionic resistance of the electrolyte within the
the present Mn-MoO4/G nanocomposite as the competitive electrode electrode, (b) the intrinsic resistance of the material, and (c) the contact
materials for advanced supercapacitors. For the real capacitors, the resistance at the working active material current collector interface
Ragone plots were tested in a two-electrode configuration. However, [40]. An ESR of 1.6 ohms was obtained for the Mn-MoO4/G nano-
these results obtained from the three-electrode cell is still valuable for composite electrode, whereas for graphene oxide, it was 0.84 ohms. A
materials investigation. slightly higher resistance in both the samples may be due to the ex-
From the galvanostatic charge/discharge plots, the Coulombic effi- istence of some oxygen functional groups, which may remain after the
ciency was calculated using the Eq. (4) and shown in Fig. 14a. The reduction of GO [41]. These functional groups take part in the devel-
highest Coulombic efficiencies of 93.7% and 89.8% were obtained at a opment of redox pseudo-capacitance which consequently produces re-
charge-discharge current density of 0.7 Ag−1 for Mn-MoO4/G and pure sistance due to the occurrence of redox reactions. However, the slight
Mn-MoO4 electrodes respectively. For an ideal capacitor, the galvano- decrease in the resistance of graphene oxide compared to Mn-MoO4/G
static charge/discharge plots should be triangular in nature. However, was due to the higher conductivity of the graphene oxide. Furthermore,
the galvanostatic charge/discharge plots of both the pure Mn-MoO4 and the presence of a semicircular shape in the intermediate frequency re-
Mn-MoO4/G nanocomposite deviate from linearity, indicating a pseu- gion in Fig. 15 is due to the interfacial charge transfer resistance (Rct) in
docapacitive nature of the electrode material, which also supports the the electrodes. The semicircle appears for graphene, composite and not
CV results. for the pure Mn-MoO4 electrode. Typically, semicircles with smaller
radii indicate lower resistance in charge transfer (Rct) and larger radii
indicate higher charge-transfer resistance in the electrode. The slope of
the tails extending beyond the semicircle in the low frequency region
(Fig. 15) provides a measure of the electrolyte diffusion resistance
which is also known as Warburg resistance (Rw). When there is no
diffusion resistance (Rw) [42,43], the tail at the low frequency region
should be vertical and normal to the real axis. In the composite elec-
trode, the slope of the Nyquist plot at the low frequency region was
slightly higher for nanocomposite revealing (indicating lower Rw re-
sistance) the facile ion diffusion within the electrode due to the mor-
phology.

4. Conclusion

A rapid and facile method has been reported to synthesize Mn-

MoO4/G nanocomposites through self-limiting deposition of nanoscale
Mn-MoO4 on the surface of graphene under the hydrothermal condi-
tions. The unique structure endows the composite with high-rate
transportation of both electrolyte ions and electrons (especially at high
rates) throughout the electrode matrix and superior electrochemical
Fig. 13. Ragone plot for Mn-MoO4/G nanocomposite, pure Mn-MoO4 and GO. . utilization of Mn-MoO4, resulting in the excellent electrochemical

10
R. Thangappan, et al. Journal of Energy Storage 27 (2020) 101069

Fig. 14. (a) Coulombic efficiency, cyclic performance (inset) and specific capacitance for 1000 cycles at 0.7 Ag−1 of Mn-MoO4/G nanocomposite, (b) capacitance
retention for Mn-MoO4/G nanocomposite, pure Mn-MoO4 and GO with respective to cycle number.

performance. The specific capacitance of Mn-MoO4/G nanocomposite

was 142.08 Fg−1 at 0.7 Ag−1, and the capacitance value was high over
a wide range of current density (the capacitance retention ratio is
93.7% for 0.7 Ag−1). After 1000 cycles, the capacitance of the electrode
decreases by only 6.3% of initial capacitance indicating the excellent
electrochemical stability. The energy density of composite electrode
was 41.9 W h kg−1 even at the low power density of 208 W kg−1 and
found to be higher than that of the pure Mn-MoO4 electrode. The en-
couraging results illustrate the exciting potential for high performance,
electrical energy storage devices based on the nanostructured Mn-
MoO4/G composite prepared by the fast, cost-efficient, and environ-
ment-friendly method. It is believed that the facile synthesis approach
presented in this study may provide the way for successful graphene-
based composites for microelectronics, photovoltaic, chemical sensors
and energy storage and conversion applications.

Declaration of Competing Interest

Fig. 15. Nyquist plot for Mn-MoO4/G nanocomposite, pure Mn-MoO4 and GO.
This statement is to certify that all Authors have seen and approved
the manuscript being submitted. We warrant that the article is the

11
R. Thangappan, et al. Journal of Energy Storage 27 (2020) 101069

Authors' original work. We warrant that the article has not received heterostructured nanowires with enhanced supercapacitor performance, Nat.
prior publication and is not under consideration for publication else- Commun. 2 (2011) 381–385.
[23] A.K. Gupta, C. Nisoli, P.E. Lammert, V.H. Crespi, P.C. Eklund, Curvature-induced D-
where. band Raman scattering in folded graphene, J. Phys.: Condens. Matter 22 (2010)
334205.
References [24] X. Fu, X. Song, Y. Zhang, Facile preparation of graphene sheets from synthetic
graphite, Mater. Lett. 70 (2012) 181.
[25] M.A. Pimenta, G. Dresselhaus, M.S. Dresselhaus, L.A. Cancado, A. Jorio, R. Sato,
[1] B.E. Conway, B.E. Electrochemical Supercapacitors: Scientific Fundamentals and Studying disorder in graphite-based systems by Raman spectroscopy, Phys. Chem.
Technological Applications, second ed., Kluwer Academic/Plenum Publishers, New Chem. Phys. 9 (2007) 1276.
York, 1999. [26] Y. Zhu, S. Murali, W. Cai, X. Li, J.W. Suk, J.R. Potts, R.S. Ruoff, Graphene and
[2] M. Winter, R.J. Brodd, What are batteries, fuel cells, and supercapacitors? graphene oxide: synthesis, properties, and applications, Adv. Mater. 22 (35) (2010)
Chem.Rev. 104 (2004) 4245. 3906–3924.
[3] E. Frackowiak, F. Beguin, Carbon materials for the electrochemical storage of en- [27] S. Stankovich, D.A. Dikin, R.D. Piner, K.A. Kohlhaas, A. Kleinhammes, Y. Jia, Y. Wu,
ergy in capacitors, Carbon N. Y. 39 (2001) 937. S.B.T. Nguyen, R.S. Ruoff, Synthesis of graphene-based nanosheets via chemical
[4] H. M.Inagaki, O.T. Konno, Carbon materials for electrochemical capacitors, J. reduction of exfoliated graphite oxide, Carbon N. Y. 45 (2007) 1558–1565.
Power Sources 195 (2010) 7880. [28] T. Kuila, S. Bose, K. P, A.K. Mishra, N.H. Kim, J.H. Lee, A green approach for the
[5] L. Wei, G. Yushin, Nanostructured activated carbons from natural precursors for reduction of graphene oxide by wild carrot root, Carbon N. Y. 50 (3) (2013)
electrical double layer capacitors, Nano Energy 1 (2012) 552. 914–921.
[6] G.A. Snook, P. Kao, A.S. Best, Conducting-polymer-based supercapacitor devices [29] B. Zhang, Q.B. Zheng, Z.D. Huang, S.W. Oh, J.K. Kim, SnO2-graphene-carbon na-
and electrodes, J. Power Sources 196 (2011) 1. notube mixture for anode material with improved rate capacities, Carbon N. Y. 49
[7] X. Lu, W. Zhang, C. Wang, T.C. Wen, Y. Wei, One-dimensional conducting polymer (13) (2011) 4524–4534.
nanocomposites: synthesis, properties and applications, Prog. Polym. Sci. 36 (2011) [30] X. Wang, X. Li, D. Liu, S. Song, H. Zhang, Green synthesis of PT/CeO2/Graphene
671. hybrid nanomaterials with remarkably enhanced electrocatalytic properties, Chem.
[8] Y.Z. Long, M.M. Li, C. Gu, M. Wan, J.L. Duvail, Z. Liu, Z. Fan, Recent advances in Commun. 48 (2012) 2885–2887.
synthesis, physical properties and applications of conducting polymer nano-tubes [31] G.C. Allen, S.J. Harris, J.A. Jutson, A study of a number of mixed transition metal
and nanofibers, Prog. Polym. Sci. 36 (2011) 1415. oxide spinels using X-ray photoelectron spectroscopy, Appl. Surf. Sci. 37 (1989)
[9] C.D. Lokhande, D.P. Dubal, O.S. Joo, Metal oxide thin film based supercapacitors, 111–134.
Curr. Appl. Phys. 11 (2011) 255. [32] H. Xia, Y.S. Meng, G. Yuan, C. Cui, L. Lu, A symmetric RuO2/RuO2 supercapacitor
[10] X. Wu, Y. Zeng, H. Gao, S. Jun, J. Liu, Z. Zhu, Template synthesis of hollow fusiform operating at 1.6 V by using a neutral aqueous electrolyte, Electrochem. Solid-State
RuO2•xH2O nanostructure and its supercapacitor performance, J. Mater. Chem. A 1 Lett. 15 (2012) A60.
(2013) 469–472. [33] M.C. Liu, L.B. Kong, X.J. Ma, C. Lu, X.M. Li, Y.C. Luo, L. Kang, Hydrothermal
[11] M.K. Wu, C. Chen, J. Zhou, F. Yi, K. Tao, L. Han, MOF-derived hollow double–- process for the fabrication of CoMoO4•0•9H2O nanorods with excellent electro-
shelled NiO nanospheres for high-performance supercapacitors, J. Alloy. Compd. chemical behaviour, New J. Chem. 36 (2012) 1713.
734 (2018) 1–8. [34] J. Yan, W. Sun, T. Wei, Q. Zhang, Z. Fan, F. Wei, Fabrication and electrochemical
[12] D. Yang, Pulsed laser deposition of manganese oxide thin films for supercapacitor performances of hierarchical porous Ni(Oh)2 nanoflakes anchored on graphene
applications, J. Power Sources 196 (2011) 8843–8849. sheets, J. Mater. Chem. 22 (2012) 11494.
[13] S. Nagamuthu, K.-S. Ryu, MOF-derived microstructural interconnected network [35] Y.H. Xiao, A.Q. Zhang, S.J. Liu, J.H. Zhao, S.M. Fang, D.Z. Jia, F. Li, Free-standing
porous Mn2O3/C as negative electrode material for asymmetric supercapacitor and porous hierarchical nanoarchitectures constructed with cobalt cobaltite nano-
device, Cryst. Eng. Commun. 21 (2019) 1442–1451. walls for supercapacitors with high specific capacitances, J. Power Sources 219
[14] J. Azadmanjiri, V.K. Srivastava, P. Kumar, M. Nikzad, J. Wang, A. Yu, Two- and (2012) 140–146.
three-dimensional graphene-based hybrid composites for advanced energy storage [36] D. Ghosh, S. Giri, C.K. Das, Synthesis, characterization and electrochemical per-
and conversion devices, J. Mater. Chem. A 6 (2018) 702–734. formance of graphene decorated with 1D NiMoO4•nH2O nanorods, Nanoscale 5 (21)
[15] H.J. Choi, S.M. Jung, J.M. Seo, D.W. Chang, L. Dai, J.B. Baek, Graphene for energy (2013) 10428–10437.
conversion and storage in fuel cells and supercapacitors, Nano Energy 1 (2012) 534. [37] V. Subramanian, H. Zhu, R. Vajtai, P.M. Ajayan, B. Wei, Hydrothermal synthesis
[16] .. Debasis Ghosh, S. Giri, M. Moniruzzaman, Tanya Basu, Manas Mandala, Chapal and pseudocapacitance properties of MnO2 nanostructures, J. Phys. Chem. B 109
Kumar Das, α-MnMoO4/graphene hybrid composite: high energy density super- (2005) 20207–20214.
capacitor electrode material, Dalton Trans. 43 (2014) 11067–11076. [38] J. Jiang, J. Liu, R. Ding, J. Zhu, Y. Li, A. Hu, X. Li, X. Huang, Large-scale uniform α-
[17] L.Q. Mai, F. Yang, Y.L. Zhao, X. Xu, L. Xu, Y.Z. Luo, Hierarchical MnMoO4/CoMoO4 Co(OH)2 long nanowire arrays grown on graphite as pseudocapacitor electrodes,
heterostructured nanowires with enhanced supercapacitor performance, Nat. ACS Appl. Mater. Interfaces 3 (2011) 99–103.
Commun. 2 (2011) 381. [39] A. Ghosh, E.J. Ra, M. Jin, H.K. Jeong, T.H. Kim, C. Biswas, Y.H. Lee, High pseu-
[18] S. Jayasubramaniyan, S. Balasundari, P.A. Rayjada, N. Satyanarayana, docapacitance from ultrathin V2O5 films electrodeposited on self-standing carbon-
P. Muralidharan, Microwave hydrothermal synthesis of α-MnMoO4 nanorods for nanofiber paper, Adv. Funct.Mater. 21 (2011) 2541–2547.
high electrochemical performance supercapacitors, RSC Adv. 8 (2018) 22559. [40] J. Gamby, P.L. Taberna, P. Simon, J.F. Fauvarque, M. Chesneau, Studies and
[19] X.F. Xia, W. Lei, Q.G. Hao, W. Wang, X. Wang, One-step synthesis of CoMoO4/ characterisations of various activated carbons used for carbon/carbon super-
graphene composites with enhanced electrochemical properties for supercapacitors, capacitors, J. Power Sources 101 (2001) 109–116.
Electrochem. Acta 99 (2013) 253–261. [41] P. Khanra, T. Kuila, S.H. Bae, N.H. Kim, J.H. Lee, Electrochemically exfoliated
[20] W.S. Hummers, R.E. Offeman, Preparation of graphitic oxide, J. Am. Chem. Soc. 80 graphene using 9-anthracene carboxylic acid for supercapacitor application, J.
(1958) 1339. Mater. Chem. 22 (2012) 24403–24410.
[21] R. Thangappan, S. Kalaiselvam, A. Elayaperumal, R. Jayavel, M. Arivanandhan, [42] M.D. Stoller, S. Park, Y. Zhu, J. An, R.S. Ruoff, Graphene-based ultracapacitors,
R. Karthikeyan, Y. Hayakawa, Graphene decorated with mos2 nanosheets: a sy- Nano Lett. 8 (2008) 3498–3502.
nergetic energy storage composite electrode for supercapacitor applications, Dalton [43] K. Zhang, L.L. Zhang, X.S. Zhao, J. Wu, Graphene/polyaniline nanofiber composites
Trans. 45 (2016) 2637–2646. as supercapacitor electrodes, Chem. Mater. 22 (2010) 1392–1401.
[22] L.Q. Mai, F. Yang, Y.L. Zhao, X. Xu, L. Xu, Y.Z. Luo, Hierarchical MnMoO4/CoMoO4

12