Journal of Alloys and Compounds 688 (2016) 184e197

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Synthesis and control of high-performance MnO2/carbon nanotubes

nanocomposites for supercapacitors
Jia-Wei Wang, Ya Chen*, Bai-Zhen Chen
School of Metallurgy and Environment, Central South University, Changsha 410083, China

a r t i c l e i n f o a b s t r a c t

Article history: The rational combination of transition-metal oxides and carbon materials has been regarded as an
Received 11 May 2016 efficient way of assembling the next-generation of electrode materials for supercapacitors. Here, a unique
Received in revised form nanomaterial consisting of carbon nanotubes (CNTs) grafted with MnO2 was synthesized for use in
30 June 2016
supercapacitors with high electrochemical performance. The synthesis was performed in three steps:
Accepted 1 July 2016
surface functionalization of the CNTs with carboxyl groups, grafting of Mn2þ with the carboxyl groups,
Available online 4 July 2016
and transformation of the Mn2þ into MnO2 nanoparticles by KMnO4 oxidation. The bonds between the
CNTs and the MnO2 particles are believed to form between the carbon of the carboxyl groups of the CNTs
Keywords:
Grafting oxidation
and the oxygen atoms of the MnO2 lattice. In addition, varying the acid-treatment time enabled control
Manganese dioxide of the growth density of MnO2 and affected the structural integrity of the CNTs, endowing the novel
Supercapacitor hybrid material with an adjustable electrochemical performance. As a consequence, the MnO2/CNTs
Carbon nanotubes composite with a 36 h acid treatment exhibited a maximum specific capacitance of up to 348 F g1 at a
Nanocomposites cyclic voltammetry scanning rate of 5 mV s1. A symmetric supercapacitor assembled with the electrodes
made from this MnO2/CNTs composite showed a capacitance decay rate of only 8.7% after 5000 cycles.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction capacitance. Among the previously investigated transition-metal

Supercapacitors, also known as electrochemical capacitors or
ultracapacitors, have been regarded as critical complementary
charge storage devices to conventional batteries in various appli-
cations because of their higher power density, fast charge/
discharge rate and long cycle life [1,2]. On the basis of the funda-
mental mechanism of charge storage, supercapacitors are divided
into two categories: electrochemical double-layer capacitors and
pseudocapacitors. The electrochemical double-layer capacitive
process is based on charge separation at the electrode/electrolyte
interface, whereas the pseudocapacitive process relies on redox
reactions that occur in the electrode materials [1,3].
The most critical factors governing the electrochemical perfor-
mance of supercapacitors are related to the electrode materials. The
electrode-active materials that are widely used for supercapacitors
include carbon, conducting polymers and transition-metal oxides.
Among the investigated electrode materials, transition-metal ox-
ides are considered good candidates because of their high
* Corresponding author.
E-mail addresses: wjwhappygirl@126.com (J.-W. Wang), chenya1973a@sina.com
(Y. Chen), yhscbz@yahoo.com.cn (B.-Z. Chen).
oxides, RuO2 exhibits excellent electrochemical properties [4];
however, its high cost and environmental toxicity have limited its
commercial application. Thus, other metal oxides, such as cobalt
oxide [5], titanium oxide [6], vanadium oxide [7], molybdenum
oxide [8] and manganese oxide [9] have been investigated as
possible substitutes for RuO2. In addition, two dimensional nano-
structure materials are increasingly used as electrode materials in
flexible supercapacitors recently, such as MoS2 [10], MXenes [11], g-
C3N4 [12], graphdiyne [13] and 2D transition metal oxides [14]. In
particular, manganese oxides, which are characterized by a high
specific capacitance, low cost, high abundance and environmen-
tally friendly nature, have attracted increasing interest as
electrode-active materials for supercapacitors [9]. Furthermore, a
MnO2 electrode operated in conjunction with a neutral aqueous
electrolyte is considerably safer than most other metal oxides (such
as RuO2 and NiO), which usually operate in conjunction with
strongly acidic or alkaline electrolytes. However, given the poor
electrical conductivity and low accessible active area of MnO2, the
achievement of MnO2 electrode materials with a satisfactory spe-
cific capacitance is difficult in practice, thus hampering the exten-
sive commercial application of MnO2 in energy storage devices [15].
To circumvent the aforementioned problems, one efficient

http://dx.doi.org/10.1016/j.jallcom.2016.07.005
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 J.-W. Wang et al. / Journal of Alloys and Compounds 688 (2016) 184e197
strategy is to choose an appropriate matrix with a high surface area
to support MnO2 nanostructures, which can not only accelerate
charge transport during the electrochemical redox process but also
prevent MnO2 agglomeration [16]. Thus, the incorporation of
nanostructured MnO2 into carbonaceous materials would be
effective and represent a significant advancement; specifically, it
would provide a large electroactive surface area and a reliable
electrical connection for the maximum utilization of MnO2. In this
respect, various carbonaceous materials, including activated carbon
[9,17], carbon nanotubes (CNTs) [18,19], carbon nanofibers (CNFs)
[20,21], graphene [22,23] and carbon aerogels [24], have been in-
tegrated with MnO2 for fabricating hybrid electrode materials. As
one of the most promising carbon nanomaterials, CNTs have one-
dimensional tubular structures and exhibit outstanding physico-
chemical properties, including high electrical conductivity, high
mechanical strength, high chemical stability and high activated
surface area. The combination of MnO2 and CNTs may integrate
both the excellent electrical conductivity and chemical stability of
CNTs and the high specific capacitance of MnO2. So far researchers
have reported several meaningful results concerned with MnO2/
CNTs composite. Li et al. [25] synthesized a MnO2/CNTs composite
with long cycle stability by a modified one-pot technique. The ob-
tained MnO2/CNTs composite showed a specific capacitance of
201 F g1 and exhibited an excellent cycle stability (no obvious
capacitance decay after 10 000 cycles at 1 A g1). Zhu et al. [26]
successfully prepared and used 3D CNT-graphene-Ni foam com-
posite as substrates to react with KMnO4, forming three-
dimensional (3D) MnO2eCNTegrapheneeNi hybrid foam. In
aqueous electrolytes, the 3D MnO2eCNTegrapheneeNi based
prototype supercapacitors shown specific capacitances of 251 F g1
at a current density of 1 A g1 with good cycling stability. Mai et al.
[27] first developed the flexible hybrid electrode based on MnO2
nanotubes (NTs) and CNTs composite. The as-synthesized free-
standing CNT/MnO2 NT hybrid electrodes were assembled in the
form of solid-state SC devices using polyvinyl alcohol (PVA)/LiCl as
gel electrolyte. The device exhibited a volumetric capacitance of
5.1 F cm3 and a high energy density of 0.45 mW h cm3 for the
entire supercapacitor volume.
Within this context, extensive efforts have been dedicated to
develop effective synthesis protocols, such as chemical co-
precipitation, thermal decomposition, and electrophoretic and
electrochemical deposition. Notably, the deposition of uniform
MnO2 onto hierarchical carbonaceous substrates, especially
monolithic substrates, is challenging. Therefore, the development
of a synthetic technique to prepare a MnO2ecarbonaceous material
composite with high electrochemical performance would represent
an important achievement. Recently, a grafting oxidation method
was demonstrated to be an efficient technique for the preparation
of MnO2-transition metal oxide and MnO2-organic composites.
Muralidharan et al. [28] investigated a material consisting of MnO2
grafted with V2O5 nanostructures that exhibited a specific capaci-
tance, rate capacity and stability considerably better than those of
pristine V2O5; however, the low electronic and ionic conductivity of
MnO2 were not improved. Downard et al. [29] modified the surface
of MnO2 nanorods with aryl groups using a grafting method. The
stable attachment of aryl groups opened many opportunities for
enhancing the performance of MnO2 materials through tuning their
surface properties. However, the organic-based systems suffered
drawbacks associated with high fabrications costs and the use of
highly toxic solvents. Ramirez-Castro et al. [30] recently prepared a
carbon/MnO2 nanocomposite via molecular bridging. The capaci-
tance of the obtained carbon/MnO2 nanocomposite electrode was
double that of a simple mixture of the two components, high-
lighting the intimate coupling of carbon and MnO2.
In our previous study, we successfully grafted uniform MnO2
185
particles onto the surface of activated carbon (AC) through a
grafting oxidation method [17]. The results preliminarily showed
that the obtained MnO2/AC composite exhibited excellent electro-
chemical properties. However, whether the grafting oxidation
method could be applied to a carbonaceous material of better
conductivity to prepare a MnO2/carbon composite with a higher
capacitance and better electrochemical performance was un-
known. In this paper, we adopted a MnO2/CNTs composite syn-
thesized through the grafting oxidation method as an electrode
material for electrochemical supercapacitors. The MnO2 uniformly
covered the CNTs, which provided a highly effective electron
pathway. In addition, the effect of the CNTs acid-treatment time on
the Mn2þ grafting and MnO2 synthesis was studied. The formation
mechanism and the effect of microstructure on the electrochemical
capacitive behavior of the binary composites were discussed.
2. Experimental
2.1. Materials
Mn(Ac)2$4H2O, KMnO4, and HNO3 (70%) (Sinopharm Chemical
Reagent Co., China) were analytical grade and used without further
purification. The multi-walled carbon nanotubes (MWCNTs, >97%
purity) used in this work were purchased from Shenzhen Nanotech
Port Co. Ltd. (Shenzhen, China), where the materials were prepared
through chemical vapor deposition (CVD). All of the aqueous so-
lutions were prepared using double-distilled water. The KMnO4/
Mn(Ac)2 molar ratio was maintained at 2:3 for all of the syntheses.
2.2. Synthesis of MnO2eCNTs composites
2.2.1. Acid treatment of CNTs
Multi-walled carbon nanotubes (MWCNTs) (5 g) and 50 mL
HNO3 were blended and subjected to ultrasonication for 1 h. After
the resulting mixture was enclosed in a PTFE-lined autoclave, the
autoclave was placed in an oven that was heated to 120  C at a rate
of 2  C min1 and maintained at 120  C for X h (where X was 12 h,
24 h, 36 h, or 48 h); it was then naturally cooled to room temper-
ature. The obtained acid and MWCNTs dispersion was slowly
poured into 10 L deionized water for dilution. The diluted solution
was then filtered and washed with deionized water until the filtrate
was neutral. The filtered MWCNTs powder was dried in an oven at
80  C for 12 h and then ground and labeled as CeX (where X was
12 h, 24 h, 36 h, or 48 h).
2.2.2. Grafting process
The acid-treated carbon nanotubes (CNTs) (1 g) were placed into
a 100 mL 0.3 mol L1 Mn(Ac)2 solution and ultrasonicated for
30 min. The obtained mixture was then placed in a water bath and
maintained at 60  C. Meanwhile, to prevent the agglomeration of
the CNTs, the mixture was continuously stirred for 24 h and then
naturally cooled to room temperature. Afterwards, it was filtered
and washed with deionized water until the filtrate was neutral. The
filter cake was dried in an oven at 100  C for 12 h, then ground and
labeled as CeX þ Mn(Ac)2 (where X was the duration of acid-
treatment, 12 h, 24 h, 36 h, or 48 h).
2.2.3. Oxidation process
The CeX þ Mn(Ac)2 (1 g) was placed in a 100 mL of a pre-
prepared 0.2 mol L1 KMnO4 solution and ultrasonicated for
30 min. The resulting mixture was maintained at 60  C for 24 h in a
water bath under continuous stirring and then naturally cooled to
room temperature. Afterwards, the mixture was filtered and
washed with deionized water until the filtrate was neutral. The
filtered powders were dried in an oven at 100  C for 12 h and then
186 J.-W. Wang et al. / Journal of Alloys and Compounds 688 (2016) 184e197
ground and labeled as MnO2/CeX (where X was the acid-treatment
time, 12 h, 24 h, 36 h, and 48 h).
2.3. Synthesis of pure MnO2
MnO2 powder was synthesized through a facile direct redox
reaction between KMnO4 and Mn(AC)2$4H2O. Firstly, 0.02 mol
KMnO4 and 0.03 mol Mn(AC)2$4H2O were separately dissolved in
two beakers that contained 100 mL distilled water. Then the
Mn(AC)2$4H2O solution was moved into water-bath and main-
tained at 60  C under continuously stirring. Kept the solution stir-
ring and dropped the prepared KMnO4 solution. After the mixture
solution maintained at 60  C under continuously stirring for 24 h,
the pH of solution was adjusted to 7 and naturally cooled to room
temperature. Afterwards the solution was filtered and washed with
deionized water until the filtrate was colorless. The filtered brown
powder was dried in an oven at 100  C for 12 h, then grinded and
marked as pure MnO2.
2.4. Materials characterization
X-ray diffraction (XRD) analysis was performed using a Rigaku-
TTRIII X-ray diffractometer (Japan) equipped with a graphite-
monochromated high-intensity Cu Ka radiation source. Fourier
transmission infrared (FTIR) spectra were recorded on a Nicolet
6700 spectrometer over the scanning range from 400 to 4000 cm1
at a resolution 4 cm1; the samples were compressed into KBr
discs. The morphologies of the products were investigated by field-
emission scanning electron microscopy (FESEM, FEI Nova NanoSEM
450) and high-resolution transmission electron microscopy
(HRTEM, JEOL JEM-2100F). Energy-dispersive X-ray (EDX) spec-
troscopy was performed on a JEOL JEM-2100 microscope operated
at 200 kV. X-ray photoelectron spectroscopy (XPS) was performed
on a RBD-upgraded PHI-5000C ESCA system (Perkin-Elmer)
equipped with an Al-Ka radiation source (hn ¼ 1486.6 eV). The
Brunauer-Emmett-Teller (BET) surface areas were tested by nitro-
gen sorption experiments conducted at 77 K with a Micromeritics
TriStar II 3020 automated gas adsorption analyzer.
2.5. Electrochemical measurements
The electrochemical properties of the as-synthesized samples
were measured in both three- and two-electrode cell systems with
a 0.5 mol L1 Na2SO4 aqueous solution as the electrolyte. To fabri-
cate the working electrodes, the prepared materials (70 wt%) were
mixed with acetylene black (20 wt%) and binder (polyvinylidene
fluoride, PVDF, 10 wt%) in an agate mortar. A slurry of the afore-
mentioned mixture was produced using N-methyl-2-pyrrolidone
(NMP) as a solvent.
In the three-electrode system, the slurry was brushed onto Ni
foam with an effective area of ~1 cm2. The foam was then dried in
air at 100  C for 60 min to remove the solvent and uniaxially
pressed into a thin electrode approximately 0.5 mm thick under
10 MPa. After the prepared electrode was completely dried, the
active material mass of each electrode was typically 5 ± 0.5 mg.
For the two electrode system of a symmetric capacitor, the
slurry, which was the same as that previously described, was
brushed onto a large piece of Ni foam current collector, then dried
for 1 h, and roll-pressed to a thickness of approximately 0.5 mm.
After the Ni foam was completely dried, the brushed Ni foam cur-
rent collector was cut into small, round pieces with a diameter of
8 mm and used as the electrodes. The mass of the active material of
each electrode was typically 2.5 ± 0.5 mg.
Before the electrochemical tests, the prepared electrodes were
soaked overnight in a 0.5 mol L1 Na2SO4 solution. The
electrochemical properties of the obtained materials were recorded
at room temperature using an electrochemical workstation (CHI
660B, Shanghai CH Instrument Company, China) using a three-
electrode electrochemical system with a 0.5 mol L1 Na2SO4
aqueous solution as the electrolyte. The fabricated MnO2 electrode
was used as the working electrode. A platinum foil (2  2 cm2) and
a saturated calomel electrode (SCE) were used as the counter and
reference electrodes, respectively. The ac-impedance spectra were
measured with a 5 mV ac signal superimposed on the open-circuit
potential (approximately 0.4 V vs. SCE) over the frequency range
from 102e105 Hz.
Cyclic voltammetry (CV) measurements were performed over
the potential range from 0 to 0.8 V (vs. SCE) at a scan rate ranging
from 2 to 200 mV s1 in a three-electrode system. The specific
capacitance was calculated from the CV curves according to eq. (1):
Z
1
C¼ IðVÞ dV (1)
m$v$DV
where m (g) is the mass of the active materials, v (mV s1) is the
potential scan rate, DV (V) is the sweep potential window, and I(V)
(A) is the voltammetric current of the curves.
The galvanostatic charge/discharge tests were performed using
a NEWARE auto-cycler (Shenzhen Neware Electronics Co. Ltd.,
China) in a two-electrode configuration of symmetric capacitors.
The cell was constructed using a filter-paper separator and two
prepared electrodes; it was constructed as a sandwich-type cell
(electrode/separator/electrode) in a 0.5 mol L1 Na2SO4 solution as
the electrolyte. The specific capacitance for the cell could be
calculated from the discharge curves on the basis of eq. (2):
I$Dt
C¼ (2)
m$DV
where I (A) is the applied current, Dt (s) is the discharge time, m (g)
is the mass of the total active material of the two electrodes, and DV
(V) is the discharging potential window.
The power density (P, kW kg1) and energy density (E, Wh kg1)
of the symmetric capacitors in the two-electrode configuration are
calculated from the galvanostatic chargeedischarge curves by us-
ing the eqs. (3) and (4):
0:5CðDVÞ2
E¼ (3)
3:6
E
P¼ (4)
t
where DV (V) is the applied potential window, t (s) is the discharge
time.
3. Results and discussion
The crystal structure of the carbon nanotubes (CNTs) and the as-
prepared MnO2/CNTs composites (MnO2/C-12, MnO2/C-24, MnO2/
C-36 and MnO2/C-48) were analyzed via XRD. As displayed in Fig. 1,
for the CNTs, the prominent diffraction peak at approximately 25.0
is assigned to the (002) plane reflection of the conjugated graphitic
system, indicating that the hexagonal graphite structure of the
CNTs is approximately intact. This diffraction peak is clearly
detected in the composite patterns as well. However, with
increasing acid-treatment times of the CNTs, the intensity of the
(002) diffraction peak decreases, revealing a sustained etching of
the CNT framework. In the patterns of the as-prepared MnO2/CNTs
composites, the broadened characteristic peaks appear at
 J.-W. Wang et al. / Journal of Alloys and Compounds 688 (2016) 184e197 187

Fig. 1. XRD patterns of the CNTs and the as-prepared MnO2/CNTs composites (MnO2/
C-12, MnO2/C-24, MnO2/C-36 and MnO2/C-48).

2q ¼ 12.8 , 28.8 , 36.7, 37.5 and 65.1. On the basis of a compar-

ison with the crystal data of different MnO2 polymorphs reported in
the literature [31], the MnO2/CNTs composites are a poorly crys-
tallized a-MnO2 material. This poor crystallinity originates mainly
from the smaller particle size of the MnO2 in the composite.
To further elucidate the structure and formation mechanism of
the MnO2/CNTs, FTIR spectroscopy was performed on the CNTs and
composites, as shown in Fig. 2. The FTIR spectra of pure CNTs
without any treatment and the CNTs acid-treated at 120  C for
different times (C-12, C-24, C-36 and C-48) are shown in Fig. 2a. The
absorption peak at approximately 3400 cm1 is observed n in all of
the spectra and is assigned to the stretching vibration of physically
adsorbed water molecules. As evident in Fig. 2a, the amount of
structural water in the acid-treated CNTs decreases with increasing
treatment time, reaching a minimum in the case of a treatment
time of 48 h. In the wavenumber region from 400 to 2000 cm1,
three distinct absorption peaks are observed at 1627, 1561 and
1086 cm1; these peaks are attributed to the carbonyl (C]O)
stretching, the carboxyl group (COO) anti-symmetric stretching,
and the CeOH stretching [32], respectively, which indicates that
carboxyl groups exist on the CNTs’ surface after the acid treatment.
Compared with the intensities of these three absorption peaks in
the spectrum of the CNTs without any treatment, those in the
spectra of the acid-treated CNTs are more intense, indicating that
the content of the carboxyl groups on the CNTs’ surface increases
dramatically after the hydrothermal acid treatment. Furthermore,
the amount of carboxyl groups on the CNTs’ surface increases when Fig. 2. Fourier transmission infrared (FTIR) spectra of the as-prepared materials. (a)
the acid-treatment time increases from 12 h to 36 h. However, the Pure CNTs and CNTs powders after different acid-treatment times; (b) the grafted CNTs
intensities of the two peaks related to C]O and COO decrease after materials after different acid-treatment times; and (c) the MnO2/CNTs after different
36 h of acid treatment, which we attributed to the fact that the acid-treatment times and Mn2þ grafting oxidation processes.
carboxyl groups on the CNTs’ surface are oxidized to CO2. We
confirmed this interpretation by monitoring the variation of the
treatment time exceeded 36 h, where the carbon layer under-
intensity of the absorption peak at 1086 cm1. The peak intensity
neath the carboxyl groups was re-exposed to the acid and formed
increases with increasing acid-treatment time and reaches a
newly oxidized CeOH. Furthermore, the absorption peaks in the
maximum when the time is 48 h. This result is explained by the
range from 500 to 800 cm1 are assigned to CeS stretching
carboxyl groups being further oxidized to CO2 when the acid-
188 J.-W. Wang et al. / Journal of Alloys and Compounds 688 (2016) 184e197
vibrations, which may be caused by a small amount of S impurities
in the CNTs.
The CNTs acid treated for different durations were used for
grafting; the FTIR spectra of the resulting grafted CNTs are shown in
Fig. 2b. The intensities of absorption peaks associated with the
carbonyl (C]O) stretching at 1629 cm1 and the carboxyl group
(COO) anti-symmetric stretching at 1569 cm1 significantly in-
crease when going from the C-12 þ Mn(Ac)2 to the C-36 þ Mn(Ac)2
material; however, the peaks related to C]O and COO are less
intense in the case of the C-48 þ Mn(Ac)2 material. Meanwhile, the
peak intensity related to CeOH stretching at 1086 cm1 increases
from the C-12 þ Mn(Ac)2 to the C-48 þ Mn(Ac)2 material. These
trends are consistent with the variation in the acid-treatment
process. After grafting, two bands at 501 cm1 and 598 cm1 are
evident in all of the cases and are assigned to the MneO stretching
vibrations [33,34]. These results indicate that Mn2þ is successfully
grafted onto the CNTs surface. Compared with the other grafted
CNTs samples, C-36 þ Mn(Ac)2 shows two high-intensity MneO
peaks, indicating that the COO group plays an important role in
Mn2þ grafting onto the CNTs surface. In addition, the absorption
peak at 1147 cm1 is associated with CeOeC stretching. According
to our previous discussion, the grafting process is mainly related to
the COO groups of the acid-treated CNTs surface. The grafting
process was maximized when the CNTs acid-treatment time
reached 36 h; subsequent extension of the acid-treatment time did
not enhance the grafting process.
Fig. 2c shows the FTIR spectra of the MnO2/CNTs (MnO2/C-12,
MnO2/C-24, MnO2/C-36 and MnO2/C-48) prepared through oxida-
tion of the grafted materials. After oxidation, the absorption peaks
associated with the carbonyl (C]O) stretching at 1629 cm1 and
the carboxyl group (COO) anti-symmetric stretching at 1569 cm1
decrease substantially, which contrasts the evident increase in the
absorption peak at 519 cm1, which is attributed to the MneO
stretching vibration of octahedral [MnO6]. Compared with the
spectra of the other composite samples, the spectrum of MnO2/C-
36 exhibits a high absorption intensity, indicating a high MnO2
content in this sample. Clearly, this results is attributable to the
high content of Mn2þ in C-36 þ Mn(Ac)2 obtained through the
grafting process. The inset in Fig. 2c contrasts the bands from 400 to
800 cm1 for the CNTs without any treatment with the bands of the
acid-treated CNTs, the Mn2þ grafted CNTs and the MnO2/CNTs. The
spectra clearly reveal the intensity changes in the MneO absorption
peaks throughout the whole grafting-oxidation process. When
Mn2þ is grafted onto the CNTs and then oxidized to MnO2, the in-
tensity of the MneO absorption peak gradually increases.
Furthermore, bonding between the CNTs and MnO2 particles are
believed to occur between the carbon in the carboxyl groups of the
CNTs and the oxygen atoms from the MnO2 lattice. Hence, we
inferred that the bonds between MnO2 and CNTs exist in the form
of CeOeMn [28]. And he bonds between the CNTs and the MnO2
particles are believed to form between the carbon of the carboxyl
groups of the CNTs and the oxygen atoms of the MnO2 lattice.
In summary, the amount of grafted Mn2þ is associated with
amount of COO on the surface of the CNTs, whereas the growth
density of MnO2 is closely related to the content of Mn2þ. Therefore,
we conclude that the amount and distribution of carboxyl groups
determine the growth state of the MnO2 coating.
The XPS spectra obtained from the as-prepared MnO2/CNTs
composites (MnO2/C-12, MnO2/C-24, MnO2/C-36 and MnO2/C-48)
are shown in Fig. 3. The XPS spectra were analyzed and fitted using
the Avantage XPS software. The C 1s region was adopted as a
reference for surface charging and was set as 284.9 eV. The man-
ganese oxidation state was determined from the Mn 3s and O 1s
core level spectra. The procedure for analyzing the Mn 3s spectrum
has been described previously [34-36]. From the O 1s data, the
average manganese oxidation state of the four composite samples
can be computed from the intensities of the MneOeMn and
MneOH components according to eq. (5):
ðIV  ðSMnOMn  SMnOH ÞÞ þ ðIII  SMnOH Þ
Ox $State ¼
SMnOMn
(5)
where S represents the signal of the different components of the O
1s spectrum.
Fig. 3a shows the XPS survey spectra of the MnO2/CNTs com-
posites in which the Mn 2p (~642 eV), Mn 3s (~84 eV), and O 1s
(~530 eV) peaks are attributed to MnO2. No Mn 2p3/2 signal asso-
ciated with KMnO4 (~647 eV) is observed [37], implying the
absence of KMnO4 in these composites. The Mn 2p, Mn 3s, and O 1s
core-level spectra were used to assess the oxidation state of man-
ganese in the MnO2/CNTs composites. Fig. 3b shows the Mn 2p
core-level spectra of the as-prepared MnO2/CNTs composites
(MnO2/C-12, MnO2/C-24, MnO2/C-36 and MnO2/C-48). Such Mn 2p
core-level spectra have been utilized to determine the various Mn
species present in a sample [37]. The binding energies of Mn 2p3/2
and Mn 2p1/2 are centered at 642.49 eV and 654.29 eV, respectively,
in good agreement with the binding energies of Mn 2p3/2 and Mn
2p1/2, as well as the spin-orbit splitting energy value (~11.8 eV) in
MnO2 [40].
Fig. 3c depicts the Mn 3s core-level spectra for the as-prepared
MnO2/CNTs composites (MnO2/C-12, MnO2/C-24, MnO2/C-36 and
MnO2/C-48). Because of the parallel spin coupling of the 3s electron
with the 3d electron during the photoelectron ejection, the Mn 3s
core-level spectra generally show peak splitting as a doublet
[34,38]; thus, the energy separation between the two peaks is
related to the mean manganese oxidation state. Because a lower
valence implies more electrons in the 3d orbital, additional inter-
action can occur upon photoelectron ejection. Consequently, the
energy separation of the Mn 3s spectrum will enlarge as the Mn
valence is reduced, and the inverse trend will be observed when the
manganese valence increases. As listed in Table 1, the relevant data
of the Mn 3s spectra for the MnO2/CNTs reveal that the peak
splitting of the doublet of the Mn 3s core-level spectra differs
slightly among all of the composites. The separation of peak en-
ergies (DEb) of the Mn 3s components for MnO2/C-12, MnO2/C-24,
MnO2/C-36 and MnO2/C-48 are 4.75, 4.73, 4.69 and 4.71 eV,
respectively. The values of the energy separation between the two
peaks have been reported to be 5.79, 5.50, 5.41, and 4.78 eV for the
reference samples of MnO, Mn3O4, Mn2O3, and MnO2, respectively
[34]. Therefore, we conclude that the Mn in MnO2/C-36 has the
oxidation state of manganese proposed in the literature [34e36],
the mean oxidation state of manganese in the composites is esti-
mated to be approximately 4.0.
The O 1s core-level spectrum was also used to confirm the
oxidation state of manganese in the composites. Fig. 3d shows the
slight difference in the O 1s envelope among MnO2/C-12, MnO2/C-
24, MnO2/C-36 and MnO2/C-48. To obtain the chemical composi-
tion, we analyzed the O 1s spectra through curve fitting, as shown
in Fig. 3d (relevant data in Table 1). The spectra were fitted with
three components related to the MneOeMn bond for the tetrava-
lent oxide, the MneOH bond for a hydrated trivalent oxide and the
HeOeH bond for residual structure water [37,39,40]. Table 1 pre-
sents the mean manganese oxidation states calculated according to
eq. (5). With respect to all of the as-prepared composites, the in-
termediate oxidation states of 3.56, 3.52, 3.66 and 3.56 are deter-
mined for MnO2/C-12, MnO2/C-24, MnO2/C-36 and MnO2/C-48,
respectively; furthermore, MnO2/C-36 again shows the highest
oxidation state. These values are roughly in agreement with those
oxidation states computed from the Mn 3s data. This result
 J.-W. Wang et al. / Journal of Alloys and Compounds 688 (2016) 184e197 189

Fig. 3. (a) XPS survey spectra of the as-prepared MnO2/CNTs composites (MnO2/C-12, MnO2/C-24, MnO2/C-36 and MnO2/C-48), (b) Mn 2p core level spectra of the as-prepared
MnO2/CNTs composites, (c) Mn 3s core level spectra of the as-prepared MnO2/CNTs composites, and (d) O 1s core level spectra of the as-prepared MnO2/CNTs composites. The
raw data are represented by dots, and the fitted data are represented by lines.

indicates an intermediate oxidation state between Mn4þ and Mn3þ, MnO2/CNTs composites (MnO2/C-12, MnO2/C-24, MnO2/C-36 and
which may be helpful for charge storage in the Faradaic reactions of MnO2/C-48). As presented in Fig. 4a, the CNTs have an average
MnO2 [41]. diameter of 50 nm and lengths that reach hundreds of microns. The
Fig. 4 shows FESEM images of the CNTs and the as-prepared CNTs exhibit a curled morphology with rough and uneven surfaces.
190 J.-W. Wang et al. / Journal of Alloys and Compounds 688 (2016) 184e197

Fig. 3. (continued).
 J.-W. Wang et al. / Journal of Alloys and Compounds 688 (2016) 184e197 191

Table 1
The data obtained from the XPS spectra.

Composite material Mn 2p (eV) Mn 3s (eV) O 1s (eV) Oxidation state

Mn 2p3/2 Mn 2p1/2 DeV Peak 1 Peak 2 DeV BE (eV) Area % Mn 3s/O 1s

MnO2/C-12 642.59 654.39 11.8 89.43 84.68 4.75 MneOeMn 530.16 53.21 4/3.56
MneOH 531.57 23.20
HeOeH 532.59 23.59
MnO2/C-24 642.49 654.29 11.8 89.39 84.66 4.73 MneOeMn 530.06 51.81 4/3.52
MneOH 531.54 24.64
HeOeH 532.47 23.55
MnO2/C-36 642.49 654.29 11.8 89.32 84.63 4.69 MneOeMn 530.11 59.65 4/3.66
MneOH 531.68 20.50
HeOeH 532.65 19.85
MnO2/C-48 642.49 654.29 11.8 89.38 84.67 4.71 MneOeMn 530.10 53.86 4/3.56
MneOH 531.58 23.38
HeOeH 532.54 22.76

Fig. 4. FESEM images of the as-prepared powdered samples (160 000): (a) CNTs, (b) MnO2/C-12, (c) MnO2/C-24, (d) MnO2/C-36, and (e) MnO2/C-48.
192 J.-W. Wang et al. / Journal of Alloys and Compounds 688 (2016) 184e197
The FESEM images of the MnO2/CNTs in Fig. 4bee reveal that the
surfaces of the CNTs are coated with MnO2 in all of the cases and
that the tubular morphology of the CNTs is essentially maintained.
As evident in the case of MnO2/C-12 in Fig. 4b, a thin layer of MnO2
was grown on the CNTs’ surface; however, the MnO2 layer is loose,
and its thickness is unevenly distributed. Fig. 4c shows that in
MnO2/C-24 the layer of MnO2 becomes fine and tightly concen-
trated on the long nanotubes; however, the MnO2 on the short
nanotubes remain loose. Comparatively speaking, the MnO2 layer
of MnO2/C-36 in Fig. 4d appears to be more homogenous. As
evident from MnO2/C-48, a piece of the loose MnO2 layer whose
thickness is approximately 25 nm fell off, and the bare CNTs are
observable. Carbonaceous materials are usually added to MnO2 to
improve its electrical conductivity [42]. Therefore, the contact de-
gree between the MnO2 and the added CNTs determines the elec-
trochemical performance of the composites. Among all of the
samples, the MnO2/C-36 composite is expected to exhibit the
greatest improvement in electrochemical performance.
Fig. 5 shows the HRTEM images of the as-prepared MnO2/CNTs
composites (MnO2/C-12, MnO2/C-24, MnO2/C-36 and MnO2/C-48).
The CNTs are coated with a MnO2 nanoparticle layer in all cases. In
the case of MnO2/C-12 in Fig. 5a, a layer of relatively loose and
uneven MnO2 agglomerations wrap around the CNTs surface, and a
clear dividing line between the coating layer and the CNTs is
observed. In the case of the MnO2/C-24 (Fig. 5b) and MnO2/C-36
(Fig. 5c) samples, the MnO2 layers interact more closely with the
CNTs. The MnO2 layer of MnO2/C-36 is the most uniform and fine
among the four composites. The insets of the HRTEM images show
Fig. 5. TEM images of the as-prepared materials: (a) MnO2/C-12, (b) MnO2/C-24, (c) MnO2/C-36, and (d) MnO2/C-48.
that the interplanar distance is approximately 0.25 nm, which
agrees well with the separation between the [211] planes of a-
MnO2.
From previous studies, KMnO4 is known to react with exposed
carbon and grafted Mn2þ simultaneously. Compared with the par-
ticle size of MnO2 prepared through the reaction between KMnO4
and carbon, the MnO2 synthesized through the reaction between
KMnO4 and the grafted Mn2þ is much finer. Moreover, the tightly
combined CNTs and MnO2 nanoparticle layer contribute to the
improvement in electrochemical performance. The difference in
the morphologies of the composites can be explained by the
mechanism of the acid-treatment and grafting process. The FTIR
results indicate that the amount of grafted Mn2þ reaches a
maximum when the acid-treatment time is 36 h and that the
grafting degree of Mn2þ is closely related to the carboxyl-group
content on the CNTs’ surface. However, in the acid-treatment pro-
cess, the carboxyl groups may mainly grow at highly active sites
(e.g., the edges of holes and the tips of the CNTs) during the initial
stage. As the acid-treatment time increases, the carboxyl groups
gradually and uniformly grow on the surface of the CNTs. However,
when the acid-treatment time exceeds 36 h, some of the carboxyl
groups are further oxidized to CO or CO2, resulting in the CNTs
surface being re-exposed and the uniform coverage of the carboxyl
groups being destroyed. The distribution of the carboxyl groups
must influence the distribution of Mn2þ on the surface of the CNTs
during the grafting process, as well as the reactions with KMnO4,
the exposed carbon and the grafted Mn2þ. This distribution leads to
different morphologies and thicknesses of the MnO2 coating on the
 J.-W. Wang et al. / Journal of Alloys and Compounds 688 (2016) 184e197 193

surface of the CNTs in the four composites. Accordingly, the closely

packed MnO2 layers of MnO2/C-36 are the most uniform and fine,
which is mainly due to the uniform distribution of carboxyl groups
and the major reaction between KMnO4 and the grafted Mn2þ.
The four samples (MnO2/C-12, MnO2/C-24, MnO2/C-36 and
MnO2/C-48) were analyzed by EDX to determine their Mn and C
contents; the results are shown in Fig. 6. Clearly resolved peaks
associated with Mn, C, O and K are observed in the spectra of the
prepared materials. The elemental analysis results (wt.%) for the
ratio of Mn and C are presented to the right of each spectrum. As
evident in Fig. 6, the content of Mn generally increases when going
from MnO2/C-12 to MnO2/C-36 but decreases in the case of the
MnO2/C-48 composite. These observations are consistent with the
variations in the MneO content observed from the FTIR spectra.
The weight percentage ratio of MnO2 in the MnO2/C-12, MnO2/C-
24, MnO2/C-36 and MnO2/C-48 composites are 64.85 wt%, 69.79 wt
%, 73.56 wt% and 67.76 wt%, respectively. And the weight per-
centage ratio of CNTs in the four composites are 35.15 wt%, 30.21 wt
%, 26.44 wt% and 32.24 wt%, respectively. Fig. 7. Nitrogen adsorptionedesorption isotherms of CNTs, MnO2/C-12, MnO2/C-24,
Fig. 7 shows the nitrogen adsorption isotherms for the CNTs and MnO2/C-36 and MnO2/C-48.
the as-prepared MnO2/CNTs composites (MnO2/C-12, MnO2/C-24,
MnO2/C-36 and MnO2/C-48). The BrunauereEmmetteTeller (BET)
surface areas of the CNTs, MnO2/C-12, MnO2/C-24, MnO2/C-36 and
MnO2/C-48 are 145, 119, 114, 107 and 117 m2 g1, respectively. The
BET surface areas of the MnO2/CNTs composites are substantially
smaller than that of the CNTs. The BET surface area decreases going
from MnO2/C-12 to MnO2/C-36 but increases for the MnO2/C-48
composite, which are contrary to the trend of the Mn content
determined by EDX. This difference is explained by the fact that the
grafting occurs primarily at the entrance of ultramicropores and
micropores [30]. Consequently, access to these pores is substan-
tially reduced for nitrogen and carbon dioxide molecules during the
gas adsorption measurements. Therefore, a further increase in the
concentration of grafted Mn2þ leads to a monotonic decrease of the
BET surface area, which is contrary to the variation in the FTIR re-
sults of the Mn2þ grafting. In addition, we note that the surface area
of the MnO2 obtained by the traditional co-precipitation method
and the hydrothermal method are 17 m2 g1 [31] and 45 m2 g1
[43], respectively. Thus, the surface areas of the MnO2/CNTs com-
posites via the grafting method are substantially higher.
Fig. 8 shows representative CV curves of the CNTs, the pure Fig. 8. CV curves of the CNTs, the pure MnO2 and the as-prepared MnO2/CNTs com-
MnO2 and the as-prepared MnO2/CNTs composites (MnO2/C-12, posites (MnO2/C-12, MnO2/C-24, MnO2/C-36 and MnO2/C-48) (scan rate: 5 mV s1,
potential window: 0e0.8 V, and electrolyte: 0.5 mol L1 Na2SO4; three-electrode
system).

MnO2/C-24, MnO2/C-36 and MnO2/C-48) at a scan rate of 5 mV s1

Fig. 6. EDX spectra of the as-prepared MnO2/CNTs composites (MnO2/C-12, MnO2/C-
24, MnO2/C-36 and MnO2/C-48).
in the potential window of 0e0.8 V, using a three-electrode elec-
trochemical system and a 0.5 mol L1 Na2SO4 solution as the
electrolyte. The CV curves are quasi-rectangular and symmetric in
shape, indicating a rapidly reversible Faradaic reaction and ideal
capacitive behavior of the composite electrodes. At a scan rate of
5 mV s1, the current densities of the as-prepared MnO2/CNTs
composite electrodes are substantially larger than that of the CNTs
and pure MnO2 electrode. The electrode specific capacitance was
calculated from the area enclosed by the CV curves through eq. (1).
On the basis of the CV curves, the calculated specific capacitance of
the CNTs is no greater than 3 F g1. And the specific capacitance of
the CNTs is 166 F g1. Furthermore, the CNTs surface of the MnO2/
CNTs composites is uniformly coated with a MnO2 layer; thus, it
rarely participated in the charge-storage process. As a result, we
concluded that the capacitance of the CNTs is negligible for all of
the composite electrodes. The calculated results show that the
specific capacitances of MnO2/C-12, MnO2/C-24, MnO2/C-36 and
MnO2/C-48 are 195, 292, 348 and 324 F g1, respectively. The higher
194 J.-W. Wang et al. / Journal of Alloys and Compounds 688 (2016) 184e197
capacitance of MnO2/C-36 can be attributed to the fact that the
particle size of the MnO2 active materials in the MnO2/C-36 com-
posites is uniform and fine, which could increase the probability of
conducting pathways being formed between the electrode and the
electrolyte at their interface. These pathways facilitate the elec-
trochemical reaction and enhance the capacitance. Compared with
the composites reported in the previous studies [25e27], the ob-
tained MnO2/C-36 also exhibits a much higher capacitance, which
may be ascribed to the tightly contact between the CNTs and MnO2
in the composite.
Fig. 9 shows the specific capacitances of the CNTs, the pure
MnO2 and the as-prepared MnO2/CNTs composites (MnO2/C-12,
MnO2/C-24, MnO2/C-36 and MnO2/C-48) at different CV scan rates
(2, 5, 10, 25, 50, 100, 150, and 200 mV s1) in the potential window
of 0e0.8 V, using a three-electrode electrochemical system and a
0.5 mol L1 Na2SO4 solution as the electrolyte. The specific capac-
itances of the pure MnO2 and the four composites decrease with
increasing scan rate. And there is no change in the specific capac-
itances of the CNTs when the scan rate increases from 2 to
200 mV s1. Notably, the MnO2/C-36 composite electrode exhibits
both the best rate performance and a specific capacitance signifi-
cantly greater than the other materials for the same scan rate. In
contrast to the MnO2/C-24 electrode, the MnO2/C-48 electrode
presents a better rate capability at scan rates of 2 mV s1 and
5 mV s1. However, the MnO2/C-24 electrode presents a better rate
capability when the scan rate is increased from 10 mV s1 to
200 mV s1. And the rate performance and specific capacitance of
the MnO2/CNTs composites are obviously better than those of the
pure MnO2.
The charge-storage mechanism of MnO2 is known to be mainly
based on a surface process that includes the adsorption/desorption
and insertion/extraction of proton and alkali cations [3,44,45].
Clearly, the diffusion of the cations (e.g., Naþ) on the MnO2 surface
and in its bulk and the transfer of electrons strongly influence the
rate capability. A higher scan rate results in a smaller available
capacitance because of the reduced diffusion time and the low
conductivity of MnO2 [44]. Therefore, the contact between MnO2
and the CNTs dramatically influences the electrochemical proper-
ties of the composites. The fine MnO2 particles synthesized by the
grafting oxidation method encase the CNTs closely, which enhances
Fig. 9. The specific capacitances of the CNTs, the pure MnO2 and the as-prepared
MnO2/CNTs composite (MnO2/C-12, MnO2/C-24, MnO2/C-36 and MnO2/C-48) elec-
trodes as a function of scan rate (scan rate: 2, 5, 10, 25, 50, 100, 150, and 200 mV s1,
potential window: 0e0.8 V, and electrolyte: 0.5 mol L1 Na2SO4; three-electrode
system).
the electrical conductivity of the MnO2/CNTs composites and en-
hances the charge-transfer rate. Remarkably, the MnO2/C-36
composite exhibits the best rate performance and the highest
capacitance, which is attributed to the most uniform distribution
and tight coating of the nanostructured MnO2.
The electrochemical performance of the as-prepared MnO2/
CNTs composites (MnO2/C-12, MnO2/C-24, MnO2/C-36 and MnO2/
C-48) was further evaluated by electrochemical impedance spec-
troscopy (EIS). The impedance spectra were measured using a
three-electrode electrochemical system with a 0.5 mol L1 Na2SO4
aqueous solution as the electrolyte. The amplitude of the ac signal
superimposed on the open-circuit potential (approximately 0.4 V
vs. SCE) was 5 mV and the frequency range was from 102e105 Hz,
the Nyquist plots are shown in Fig. 10. It can be seen that all of the
collected impedance spectra consist of depressed arcs at high fre-
quencies, straight lines inclined at a constant phase angle to the real
axis (Warburg region) at intermediate frequencies, and approxi-
mately vertical capacitive lines at low frequencies. The arc is mainly
caused by the charge-transfer reaction at the electrode/electrolyte
interface [46]. During the charging/discharging process, the cations
including Naþ and Hþ participate in the redox reaction [47]. In
addition, the Warburg impedance is associated with the semi-
infinite diffusion of cations in the electrode, and the capacitive
line is related to the accumulation of cations at the impermeable
interface under the finite diffusion condition.
To determine the values of the resistance and capacitance of the
oxide electrodes, the measured impedance spectra were fitted by
the complex nonlinear least square (CNLS) method [48] on the basis
of the equivalent circuit shown in Fig. 10. Here, Rs is the solution
resistance, Rct corresponds to the charge-transfer resistance in the
pseudocapacitive process, and CPE1 arises from the interfacial
double-layer charging. The Warburg impedance, Zw, is associated
with the cation diffusion in the electrode, and CPE2 represents the
non-ideal capacitive behavior at the impermeable interface. The
fitting results for the as-prepared MnO2/CNTs composites (MnO2/C-
12, MnO2/C-24, MnO2/C-36 and MnO2/C-48), including the solution
resistance (Rs), the charge-transfer resistance (Rct), the diffusion
resistance (WeR), the diffusion time constant (WeT), the double-
layer capacitance (Cdl) and the pseudocapacitance (Cps), are listed
in Table 2.
Fig. 10. Nyquist plots of the impedance spectra of the electrodes prepared with the
MnO2/CNTs composites (MnO2/C-12, MnO2/C-24, MnO2/C-36 and MnO2/C-48) (fre-
quency range: 102-105 Hz and electrolyte: 0.5 mol L1 Na2SO4; three-electrode
system).
 J.-W. Wang et al. / Journal of Alloys and Compounds 688 (2016) 184e197 195

Table 2
The impedance spectra fitting results for the electrodes prepared with the MnO2/CNTs composites (MnO2/C-12, MnO2/C-24, MnO2/C-36 and MnO2/C-48). (Frequency range:
105e102 Hz, electrolyte: 0.5 mol L1 Na2SO4, three-electrode system.)

Sample Rs (U cm2) Cdl (F cm2) Rct (U cm2) WeR (U cm2) WeT (U cm2) Cps (F cm2)

MnO2/C-12 0.6649 1.1157  105 1.8160 1.2670 1.5480 0.8828

MnO2/C-24 0.6450 3.6992  104 0.7261 0.6751 0.5497 1.0590
MnO2/C-36 0.6333 3.3555  103 0.5935 0.5284 0.4399 2.5699
MnO2/C-48 0.6999 1.4713  105 1.3333 0.9987 1.0601 1.0113

Remarkably, the charge-transfer resistances of the MnO2/C-12,

MnO2/C-24, MnO2/C-36 and MnO2/C-48 electrodes are only 1.82,
0.73, 0.59 and 1.33 U, respectively, which are much lower than that
of the MnO2 (4.5 U) synthesized by the traditional liquid-phase
method. Apparently, the rapid charge-transfer rate of the MnO2/
CNTs electrode is ascribed to the CNTs electronic structure, which
plays a critical role in promoting the energy storage capacity. MnO2/
C-36 exhibits a much lower reaction resistance (Rct), which is
attributed to the intimate coating of the CNTs surface by MnO2 to
improve the electrical conductivity. By contrast, the WeR and WeT
of MnO2/C-36 are the lowest. The WeT for finite diffusion is
described as WeT ¼ L2/D [49] (where L is the diffusion depth of
cations in the electrode and D corresponds to the chemical diffu-
sivity). The MnO2 layer of the MnO2/C-36 composite is thinner than
the others; therefore, the cations take less time to diffuse through
the oxide layer. According to the Cps values, MnO2/C-36 exhibits a
much higher specific capacitance, which is consistent with the re-
sults of the CV tests as well.
To evaluate the cyclic stability of the as-prepared materials,
galvanostatic chargeedischarge tests were performed on a two-
electrode symmetric supercapacitor system, which were assem-
bled using the as-prepared MnO2/CNTs composites as the electrode
material and a 0.5 mol L1 Na2SO4 solution as the electrolyte. The
chargeedischarge current density was 1 A g1 with the potential
window range from 0 to 0.8 V. As presented in Fig. 11a, the MnO2/
CNTs electrodes show well-shaped triangular charge/discharge
curves with a slight curvature, which originates from the co-
contribution of the pseudocapacitance and double-layer capaci-
tance of MnO2 material. From the discharge curves, the specific
capacitances of MnO2/C-12, MnO2/C-24, MnO2/C-36 and MnO2/C-
48 are calculated using eq. (2) as 192, 283, 331 and 305 F g1,
respectively. MnO2/C-36, with the highest specific capacitance, is
considered an effective material for high-performance electro-
chemical capacitors. Fig. 11b shows the galvanostatic char-
geedischarge curves of the MnO2/C-36 at different current density
(1, 2, 5, 10, and 20 A g1). According to the discharging time, the
specific capacitances are calculated to be 331, 309, 279, 247, and
Fig. 11. (a) Galvanostatic charge/discharge curves of the as-prepared MnO2/CNTs
216 F g1 at the current density of 1, 2, 5, 10, and 20 A g1, composites (MnO2/C-12, MnO2/C-24, MnO2/C-36 and MnO2/C-48) at the current
respectively. The specific capacitance at 20 A g1 is about 65% of density of 1 A g1; (b) galvanostatic charge/discharge curves of the MnO2/C-36 com-
that at 1 A g1, which demonstrates a very high rate capability of posites at different current density (1, 2, 5, 10, and 20 A g1) (electrolyte: 0.5 mol L1
the MnO2/C-36 composite. Na2SO4; two-electrode system).

We also performed long-term charge/discharge cycling tests

over 5000 cycles at a current density of 1 A g1 (Fig. 12) for these
20.9%, 13.4%, and 29.6%, respectively. In conclusion, the excellent
two-electrodes symmetric supercapacitors. In the first 500 cycles,
cyclic performance of MnO2/C-36 suggests that the compact layer
the capacitances of the four electrodes decrease quickly; however,
of MnO2 in this composite material could effectively prevent the
after 500 cycles, the capacitances tend to be stable, without any
degradation of active MnO2 nanoparticles.
obvious decay. The MnO2/C-36 electrode exhibits only an 8.7%
Impedance measurements were also performed on the two-
decay after 5000 cycles, evidently surpassing the performances of
electrode symmetric supercapacitor system assembled with the
electrodes based on MnO2 nanowires (49.0% decay after 5000 cy-
MnO2/C-36 composite electrodes before and after 5000 char-
cles), MnO2eactive carbon (8.7% decay after 1000 cycles) [35],
geedischarge cycles. As the Nyquist plots displayed in Fig. 13a, only
MnO2epolyaniline (8.6% decay after 1000 cycles) [50], MnO2eCNTs
a marginal increase in the Rct value (0.76 U) of the electrode after
textile (20% decay after 200 cycles) [51], MnO2egraphene oxide
cycling demonstrates a very high electrochemical stability of the
(15.9% decay after 1000 cycles) [52] and MnO2egraphene (17.6%
MnO2/C-36 composite. The Ragone plot of the MnO2/C-36 com-
decay after 1000 cycles) [47]. Over 5000 chargeedischarge cycles,
posite material is shown in Fig. 13b. According, the energy density
the decay rates of MnO2/C-12, MnO2/C-24 and MnO2/C-48 were
196 J.-W. Wang et al. / Journal of Alloys and Compounds 688 (2016) 184e197
Fig. 12. Discharge capacitance as a function of cycle number for the as-prepared
MnO2/CNTs composites (MnO2/C-12, MnO2/C-24, MnO2/C-36 and MnO2/C-48) (cur-
rent density: 1 A g1 and electrolyte: 0.5 mol L1 Na2SO4; two-electrode system).
Fig. 13. (a) Nyquist plots of the impedance spectra of the electrodes prepared with the
MnO2/C-36 composites (frequency range: 102e105 Hz and electrolyte: 0.5 mol L1
Na2SO4; two-electrode system); (b) Ragone plot of the MnO2/C-36 composite material
representing energy density versus power density.
of 19.2 Wh kg1 with the max power density of 6.4 kW kg1 are
achieved using the two-electrode symmetric systems at operating
voltages of 0.8 V, which are calculated by eqs (2)e(4). As compared
with the reported previously using the two-electrode symmetric
systems of AC//AC [53,54], CNTs//CNTs [55] and MnO2//MnO2 [53],
this symmetric systems exhibits high energy density. These results
indicate that the MnO2/C-36 composite is a very promising elec-
trode material with both high energy and good electrochemical
stability.
4. Conclusion
A unique nanomaterial composed of CNTs grafted with amor-
phous MnO2 was synthesized for use in supercapacitors. The bond
between the CNTs and MnO2 particles is believed to occur between
the carbon of the carboxyl groups of CNTs and the oxygen atoms of
the MnO2 lattice. The high capacitance of MnO2 as well as the
excellent cycling stability and superior electrical conductivity of the
CNTs were exploited in the composite. In addition, MnO2 layers
with different thicknesses coating the surface of the CNTs were
prepared through controlling the hydrothermal acid-treatment
time (12, 24, 36 or 48 h). We observed that the MnO2 layer thick-
ness substantially affected the capacitance, cycling performance
and conductivity of the obtained composites. As a consequence, the
MnO2/CNTs composite subjected to acid treatment for 36 h (MnO2/
C-36) exhibited a maximum specific capacitance of 348 F g1 at a
scanning rate of 5 mV s1. Additionally, the quasi-rectangular and
symmetric CV curves of MnO2/C-36 reflected its ability to undergo a
rapidly reversible Faraday reaction and its good electrochemical
behavior. A two-electrode symmetric laboratory supercapacitor,
which was assembled with the MnO2/C-36 composite electrodes
and tested through galvanostatic chargeedischarge cycling,
showed a specific capacitance of 331 F g1 at a current density of
1 A g1, with an attenuation rate of just 8.7% after 5000 char-
geedischarge cycles. Furthermore, the impedance test results
revealed that the charge-transfer resistance of MnO2/C-36 com-
posite is only 0.59 U. The as-assembled symmetric MnO2/C-36//
MnO2/C-36 electrodes exhibit a high energy densities of
29.4 Wh kg1 with the max power densities of 6.4 kW kg1, indi-
cating that such a material has great potential for use in high-
performance energy-storage systems. These results are encour-
aging for furthering the application of MnO2-based electrodes in
high-power-capability devices.
Acknowledgements
The authors acknowledge financial support from the National
Natural Science Foundation of China (Grant No. 51374252) and the
Natural Science Foundation of Hunan Province, China (Grant No.
12jj3014).
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