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IOP PUBLISHING NANOTECHNOLOGY
Nanotechnology 22 (2011) 125703 (9pp) doi:10.1088/0957-4484/22/12/125703

Synthesis, characterization and capacitive

performance of hydrous manganese
dioxide nanostructures
Jintao Zhang1 , Wei Chu2 , Jianwen Jiang1 and X S Zhao1,2
1
Department of Chemical and Biomolecular Engineering, National University of Singapore,
4 Engineering Drive 4, Singapore 117576, Singapore
2
College of Chemical Engineering, Sichuan University, Chengdu 610065,
People’s Republic of China

E-mail: chezxs@nus.edu.sg

Received 14 October 2010, in final form 27 December 2010

Published 14 February 2011
Online at stacks.iop.org/Nano/22/125703

Abstract
Hydrous manganese dioxide nanostructures were synthesized via a catalytic oxidation reaction
mechanism at mild temperatures. It was found that the morphology of the manganese dioxide
nanostructures was significantly influenced by the pH of the reaction system. With increasing
pH the morphology of manganese dioxide nanostructures changed from urchin-like structures
to nanobelts. The capacitive performance was investigated by using cycle voltammetry and
galvanostatic charge/discharge techniques. Hydrous manganese dioxide nanostructures obtained
from a basic solution exhibited a capacitance of 262 F g−1 at a current density of 250 mA g−1
and a capacitive retention of 75% after 1200 cycles, suggesting that this is a promising electrode
material for supercapacitors. The high specific capacitance is attributed to the hydrous nature
coupled with a high surface area (181 m2 g−1 ) of the manganese dioxide nanostructure.
S Online supplementary data available from stacks.iop.org/Nano/22/125703/mmedia
(Some figures in this article are in colour only in the electronic version)

1. Introduction used as supercapacitor electrodes [10]. Therefore, much

Supercapacitors, as energy storage devices, possess a higher
specific power density than batteries and a higher specific
energy density than conventional capacitors [1, 2]. Based
on the charge storage mechanism, there are two types of
supercapacitors, namely electrical double layer capacitors
(EDLCs) and pseudocapacitors. The pseudocapacitance comes
from the reversible redox reaction of electroactive materials,
such as conducting polymers and transition metal oxides [3].
However, the poor cycling stability of conducting polymers
during charge/discharge processes limits their applications [4].
Among transition metal oxides, hydrous ruthenium dioxide
(RuO2 ) offers a high pseudocapacitance [5, 6]. The high
cost of this noble metal is a big hurdle for practical uses [7].
Manganese oxides have attracted growing interest because of
their low cost, environmental friendliness, natural abundance,
and relatively high energy density [8, 9]. But bulk manganese
oxides display a poor rate capability and reversibility when
effort has been made to synthesize manganese oxides of
various nanostructures [9, 11–13]. Li and co-workers [14]
described a hydrothermal method for synthesizing manganese
dioxide nanostructures via a redox reaction mechanism with
manganese sulfate and ammonium persulfate as the precursor
at 140 ◦ C. It was found that the hydrothermal time and
temperature had a great influence on the capacitive properties
of the resultant manganese oxide along with the crystallinity,
structure, and morphology [11, 15]. It was also reported that
the redox reaction between manganese sulfate and ammonium
persulfate can be carried out at room temperature with
silver ions as a catalyst [16, 17]. Hollow structures of
manganese oxide were synthesized under acidic conditions by
using the catalytic method [18]. Electrochemical deposition
methods were also employed to prepare manganese oxide
nanostructures [12, 19]. The physicochemical properties of
the manganese oxide nanomaterials are significantly influenced
by the preparation method because different methods result in
different surface states and defects [20, 21].

0957-4484/11/125703+09$33.00 1 © 2011 IOP Publishing Ltd Printed in the UK & the USA
Nanotechnology 22 (2011) 125703
In this work, hydrous manganese dioxide nanostructures
with different morphologies were synthesized under different
pH conditions. The sample synthesized under basic conditions
was observed to exhibit a capacitance as high as 262 F g−1 at
a current density of 250 mA g−1 and a capacitive retention of
75% after 1200 cycles.
2. Experimental details
The hydrous manganese dioxide nanostructures were synthe-
sized using a low-temperature catalytic method [17]. In a
typical synthesis, 1.4 g of manganese acetate (Mn(CH3 COO)2 )
and 2.4 g of potassium persulfate (K2 S2 O8 ) were respectively
dissolved in 60 ml of deionized (DI) water. Then 150 μl of
silver nitrate (100 mM) was added into the K2 S2 O8 solution.
The two solutions were mixed under stirring at 60 ◦ C. After
12 h, the precipitates were filtrated off, washed with DI water
and ethanol, and dried at 60 ◦ C for 12 h. Another two
samples were also synthesized similarly except for adding 1 ml
NH3 ·H2 O and 1 ml H2 SO4 , respectively, to regulate the pH.
The solid samples thus obtained under basic (pH ∼ 11), neutral
(pH ∼ 8), and acidic (pH ∼ 1) conditions are designated as
MnO2 –B, MnO2 –N, and MnO2 –A, respectively.
Powder x-ray diffraction (XRD) measurements were
performed on a Shimadzu diffractometer operated using the
reflection mode with Cu Kα radiation at a step size of
0.06◦ s−1 . Fourier transform infrared (FT-IR) spectra were
recorded on a Perkin-Elmer 580B infrared spectrophotometer
using the KBr pellet technique. Thermogravimetric analysis
(TGA) data were collected on a thermal analysis instrument
(SDT 2960, TA Instruments, New Castle, DE) with a heating
rate of 10 ◦ C min−1 in an air flow of 100 ml min−1 . X-
ray photoelectron spectroscopy (XPS) measurements were
conducted on a PHI-5300 ESCA spectrometer (PerkinElmer)
with an energy analyzer working in the pass energy mode at
35.75 eV and the Al KR line was used as the excitation source.
Nitrogen adsorption–desorption isotherms were measured on a
Micromeritics ASAP 2020 system at −196 ◦ C. The specific
surface areas were calculated using the Brunauer–Emmett–
Teller (BET) method. The pore volumes were estimated
from the nitrogen volume adsorbed at a relative pressure
of 0.95. Pore size distribution curves were computed from
the desorption branches of the isotherms using the Barrett,
Joyner, and Halenda (BJH) method. The morphologies of
samples were characterized using a field-emission scanning
electron microscope (FESEM; JEOL, JSM-6700F) and a high-
resolution transmission electron microscopy (HRTEM; JEOL-
2100, 200 kV), respectively.
Electrochemical measurements were performed with
an Autolab PGSTAT302N at ambient temperature (about
22 ◦ C). The electrochemical cell (see figure S1 available at
stacks.iop.org/Nano/22/125703/mmedia) had a three-electrode
configuration with a bright Pt plate as the counter electrode and
an Ag/AgCl electrode as the reference electrode. A polished
glassy carbon working electrode (GCE) of diameter 5 mm was
used as a current collector. An electroactive sample was mixed
with acetylene black (mass ratio = 80:20) and ethanol to
achieve a slurry. A small amount of Nafion solution (0.5 wt%)
2
J Zhang et al
Figure 1. XRD patterns of MnO2 –A (a), MnO2 –N (b), and
MnO2 –B (c).
was added to paste the slurry on the GCE. A 0.5 M Na2 SO4
solution was employed as the electrolyte.
3. Results and discussion
3.1. Synthesis and characterization of hydrous manganese
dioxide nanostructures
In the hydrothermal system, Mn(CH3 COO)2 was oxidized
by K2 S2 O8 at 60 ◦ C in the presence of AgNO3 as a catalyst
according to the following reaction [16, 18]:
Ag+
Mn2+ + S2 O28− + 2H2 O −→ MnO2 + 2SO24− + 4H+ . (1)
Figure 1 shows the XRD patterns of samples MnO2 –
A, MnO2 –N, and MnO2 –B. The XRD pattern of MnO2 –A
(figure 1(a)) shows a series of diffraction peaks, which can
be indexed to the characteristic reflections of α -MnO2 (JCPDS
card no. 44-0141) [22, 23]. As for the XRD pattern of samples
MnO2 –N (figure 1(b)) and MnO2 –B (figure 1(c)), the main
peaks can also be indexed to the α -MnO2 phase. The broader
peaks indicate smaller crystalline particles or poor crystallinity
of MnO2 –N and MnO2 –B than that of MnO2 –A. The peak at
about 22.2◦ observed on sample MnO2 –N as indicated by a star
was attributed to the diffraction of an impurity. The present
results indicate that the acidic condition was favorable for the
formation of highly crystalline α -MnO2 .
Figure 2 shows the FESEM images of MnO2 –B, MnO2 –
N, and MnO2 –A. The low-magnification images of MnO2 –
B (figure 2(a)) and MnO2 –N (figure 2(c)) show the large
aggregated clusters. The enlarged image shown in figure 2(b)
reveals that MnO2 –B consists of nanowires, which are
entangled with one another to form big aggregates. In contrast,
MnO2 –N consists of nanoplates and nanowires. The sample
synthesized under acidic conditions, MnO2 –A, was composed
of intercrossed nanorods with sharp tips, exhibiting an urchin-
like morphology.
Figure 3 shows the HRTEM images of MnO2 –B, MnO2 –
N, and MnO2 –A. It can be seen that MnO2 –B is composed
Nanotechnology 22 (2011) 125703
Figure 2. FESEM images of MnO2 –B (a), (b), MnO2 –N (c), (d), and MnO2 –A (e), (f).
of nanowires. The enlarged image shown in figure 3(b)
reveals a belt shape of the nanowires. The HRTEM
image of the individual nanobelts shows the clear lattice
fringes. The lattice spacing between adjacent lattice planes
is ∼0.49 nm (figure 3(c)), corresponding to the distance of
two neighboring (200) crystal planes in α -MnO2 [24]. The
corresponding fast Fourier transform pattern (FFT) of the
individual nanobelts shown in figure 3(d) shows the diffraction
spots, indicating a single crystalline nature of the individual
nanobelts. Sample MnO2 –N (figure 3(e)) contained both
nanoplates and nanowires. The lattice-resolved HRTEM
image (figure 3(f)) reveals a lattice spacing of ∼0.24 nm,
indicating the presence of α -MnO2 phase. The TEM image
in figure 3(g) shows that MnO2 –A consists of intercrossed
nanorods. The enlarged image of typical nanorods shown in
figure 3(h) exhibits a pyramidal morphology of the nanorods.
The HRTEM image depicted in figure 3(i) reveals the lattice
spacing of the nanorods of ∼0.69 nm, the distance between
two (110) crystal planes, confirming the formation of α -
MnO2 [15]. On the basis of the FESEM and HRTEM results,
it can be concluded that the morphology and structure of the
manganese oxide materials are strongly dependent on the pH
of the synthesis system.
3
J Zhang et al
To investigate the formation mechanism of the manganese
dioxide nanostructures synthesized under different pH condi-
tions, intermediates were collected after different times and
characterized using the FESEM technique. Figure 4 shows the
FESEM images of the intermediates collected after different
reaction times. It is seen from figure 4(a1) that the intermediate
synthesized in an acidic medium after 1 h reaction displays
a three-dimensional (3D) spherical morphology resembling a
ball of nanosheets. Figure 4(a2) shows the morphology of
the intermediate collected after 4 h, exhibiting the spherical
structures with lots of sharp nanorods covering the surface.
Upon further increasing the reaction time to 8 h, the spheres
transformed to an urchin-like structure consisting of nanorods.
An enlarged FESEM image shown in figure S2 (available
at stacks.iop.org/Nano/22/125703/mmedia) reveals that the
nanorods were epitaxially grown from nanosheets on the
surface of the macrospheres. According to the FESEM
results, it is believed that the urchin-like structure formed
via a ripening process or dissolution–recrystallization process
because of the great difference between the morphologies of
the intermediates and the final product. Initially, the fast
formation of MnO2 resulted in the aggregation of nanosheets
to form spheres under acidic solutions. Then, the epitaxial
Nanotechnology 22 (2011) 125703
Figure 3. TEM and HRTEM images of MnO2 –B (a)–(c), MnO2 –N (e), (f), and MnO2 –A (g)–(i). The corresponding FFT pattern of HRTEM
image (c), (d).
growth of nanorods on the surface of macrosphere occurred
with the slower reaction rate due to the decrease in the
concentration of reactants. As the reaction proceeded, the
whole system was transferred to a thermodynamically stable
environment due to the exhaustion of reactants [18]. With
increasing reaction time the MnO2 nanosheets dissolved and
then recrystallized along the previously formed nanorods
because of the one-dimensional (1D) growth habit of the α -
MnO2 crystal [14, 25, 26], resulting in the formation of the
urchin-like structures [22].
Figures 4(b1)–(b3) show the morphology of the interme-
diates during the formation of MnO2 –N. The FESEM image
of the intermediate collected after 1 h reveals nanorod clusters
along with few having a lamellar structure. Further increasing
the reaction time led to the formation of clusters with larger
nanorods (figure 4(b2)), which may be due to growth of newly
formed MnO2 colloids on the early formed ones. As the
reaction proceeded, the intermediate gradually transformed to
4
J Zhang et al
nanowires and nanoplates (figure 4(b3)). The evolution of
MnO2 –B exhibits a similar process, with the initially formed
clusters with small nanosheets undergoing a transformation to
nanobelts with increasing reaction time (figures 4(c1)–(c3)).
On the basis of the above observations the formation
of MnO2 –A, MnO2 –N and MnO2 –B is believed to undergo
a similar ripening process, which is characteristic of
a dissolution–recrystallization process. However, great
difference between the morphologies of intermediates and the
final products were observed. The formation of MnO2 –A
agrees well with what has been observed previously [22, 27].
Our experimental results indicated that 1D structures
(e.g. nanowires and nanobelts) preferably formed at high pH,
although other factors might also influence the growth of MnO2
nanostructures.
Figure 5 shows the FT-IR spectra of the samples. The
strong peaks of MnO2 –B, MnO2 –N, and MnO2 –A appearing
at the wavenumbers lower than 800 cm−1 are due to
Nanotechnology 22 (2011) 125703 J Zhang et al

Figure 4. FESEM images of the intermediate samples during the formation of MnO2 –A (a1)–(a3), MnO2 –N (b1)–(b3), and
MnO2 –B (c1)–(c3). The intermediates were collected after 1 h (a1), (b1), (c1), 4 h (a2), (b2), (c2), and 8 h (a3), (b3), (c3). All scale bars are
400 nm.

the characteristic Mn–O stretching vibrations in manganese

oxides [28]. For MnO2 –B and MnO2 –N, the peaks centered
at about 3400 cm−1 and about 1633 cm−1 are attributed to
the O–H stretching vibration and O–H bending vibration of
adsorbed water molecules, respectively [21]. The FT-IR results
indicate the presence of absorbed water within the structures
of as-prepared samples. As for MnO2 –A only broad humps
related to adsorbed water are seen (figure 5(c)), indicating the
decrease in the water content in MnO2 –A.
Figure 6 shows the TGA and differentiated TGA (DrTGA)
curves of the samples. Three major weight loss events can
be seen from the DrTGA curves. The first weight loss event
below 250 ◦ C originated from the physically adsorbed water
while the subsequent weight loss below 500 ◦ C arose from the
removal of structural water [29], confirming that the samples
were hydrated. The last weight loss event at about 550 ◦ C Figure 5. FT-IR spectra of MnO2 –B (a), MnO2 –N (b), and
was due to the transformation of manganese dioxide (MnO2 ) MnO2 –A (c).
to manganese sesquioxide (Mn2 O3 ), releasing oxygen [30].
In addition, the weight loss below 500 ◦ C for sample MnO2 –
3.2. Capacitive performances of hydrous manganese dioxide
A (∼5 wt%) is lower than that of MnO2 –B and MnO2 –N
nanostructures
(∼8 wt%), indicating a decrease in the content of water in
MnO2 –A. The TGA results are in good agreement with the FT- The capacitive performances of MnO2 –B, MnO2 –N, and
IR data. MnO2 –A were characterized using cyclic voltammetry. Cyclic

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Nanotechnology 22 (2011) 125703
Figure 6. TGA (a) and DrTGA (b) curves of samples MnO2 –B,
MnO2 –N, and MnO2 –A.
voltammograms (CVs) of the MnO2 –B electrode (figure 7(a))
were measured in 0.5 M Na2 SO4 electrolyte at scan rates
of 100, 50, 25, 10, 5, and 2 mV s−1 , respectively. For
comparison, the CV curves of MnO2 –N and MnO2 –A are
shown in figure S3 (available at stacks.iop.org/Nano/22/
125703/mmedia). The CV curves show a nearly rectangular
shape, indicating good electrochemical capacitive behavior.
No redox peaks can be seen on the CV curves at different scan
rates, indicating that the charge–discharge process of the active
materials occurred at a pseudo-constant rate over the whole
potential window [15]. The current of MnO2 –B, MnO2 –N,
and MnO2 –A at 0.5 V in response to the scan rate is shown
in figure 7(b). The good linear relationship confirms the good
capacitive behavior, because the capacitive current is linear to
the scan rate under cycle voltammetry [31].
The CV curves of MnO2 –B, MnO2 –N, and MnO2 –A in
0.5 M Na2 SO4 electrolyte at scan rates of 10 and 100 mV s−1
are shown in figure 8. At a scan rate of 10 mV s−1 , the
CV profiles (figure 8(a)) of MnO2 –B, MnO2 –N, and MnO2 –
A are similar rectangular shapes, showing good capacitive
behavior at a low scan rate. At an increased scan rate of
100 mV s−1 , the rectangular shape of voltammograms of
all samples is maintained with only slight distortion at the
switching potential, which reveals that samples possess good
capacitive behavior at a higher scan rate. It can be noted that
the area under the CV curves represents the total amount of
stored charge, because the specific capacitance C (F g−1 ) can
be calculated using C = Q/(E × m) (where Q is the charge
in C , E is the potential window in V, and m is the mass of
active material in g) [8]. As a result, a large area of an electrode
generates a high Q , thus a large capacitance at a given
potential window and the same mass of electrode material. As
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J Zhang et al
Figure 7. (a) CVs of MnO2 –B in 0.5 M Na2 SO4 at different scan
rates. (b) Dependence of anodic and cathodic currents on scan rate
for MnO2 –B, MnO2 –N, and MnO2 –A, respectively.
MnO2 –B possesses the highest area under the CV curves, it
indicates the highest capacitance. The CVs indicated that
charge storage is strongly dependent on the morphology of
manganese oxide nanostructures.
The capacitive performance was also investigated using
the charge/discharge technique, and the results are shown in
figure 9. It is seen that the charge/discharge profiles of all
samples exhibit an isosceles triangle-like behavior at a current
density of 1000 mA g−1 , indicating a good reversibility. The
specific capacitance (C, F g−1 ) can be calculated from the
charge–discharge curves using the following equation [11]:
i t
C= (2)
mE
where i in A is the charge–discharge current, t in s is the
charge or discharge time, m in g is the mass of the active
electrode material, and E in V is the voltage range of charge
or discharge. The specific capacitances of MnO2 –B, MnO2 –
N, and MnO2 –A at the current density of 1000 mA g−1 were
199, 139, and 121 F g−1 , respectively. Table 1 summarizes
the specific capacitances at different current densities. It is
seen that the specific capacitance in 0.5 M Na2 SO4 electrolyte
follows MnO2 -B > MnO2 -N > MnO2 –A at a given current
density. MnO2 –B shows the highest specific capacitance
(262 F g−1 ) at a current density of 250 mA g−1 . The
specific capacitance is larger than that reported in the literature,
including flowerlike MnO2 (121.5 F g−1 at a current density of
1000 mA g−1 ) [21], α -MnO2 (the maximum capacitance with
a value of 152 F g−1 at a current density of 500 mA g−1 ) [23],
and MnO2 nanostructures (205 F g−1 at a current density of
200 mA g−1 ) [32].
Nanotechnology 22 (2011) 125703 J Zhang et al

Figure 8. CVs of MnO2 –B, MnO2 –N, and MnO2 –A in 0.5 M

Na2 SO4 at scan rates of 10 mV s−1 (a) and 100 mV s−1 (b).

Figure 10. N2 adsorption–desorption isotherms (a) and the

corresponding pore size distributions (b) of MnO2 –B, MnO2 –N, and
MnO2 –A. The inset of (a) shows the enlarged N2
adsorption–desorption isotherm of MnO2 –A.

Table 1. Specific capacitance of MnO2 –B, MnO2 –N, and MnO2 –A

in 0.5 M Na2 SO4 at different current densities.
Specific capacitance (F g−1 )
5000 2000 1000 500 250
Sample mA g−1 mA g−1 mA g−1 mA g−1 mA g−1
MnO2 –B 167 176 199 234 262
MnO2 –N 119 124 139 160 193
MnO2 –A 100 110 121 140 161
Figure 9. Charge–discharge curves of MnO2 –B, MnO2 –N, and
MnO2 –A in 0.5 M Na2 SO4 at a current density of 1000 mA g−1 .
MnO2 –A. Indeed, the BJH pore size distribution curves derived
from the desorption branches (figure 10(b)) reveal the presence
Figure 10 shows the N2 adsorption–desorption isotherms of bimodal mesopores for MnO2 –B. However, the bimodal
and BJH pore size distribution curves. MnO2 –B and MnO2 – distribution is not obvious for MnO2 –N. For sample MnO2 –A,
N (figure 10(a)) exhibit a similar isotherm with a hysteresis only pores with average diameter of about 3.8 nm can be seen.
loop in the relative pressure range of 0.7 < P/P0 < 1.0, Based on the FESEM and TEM observations, the small pores
indicating the existence of mesopores [15, 21]. In contrast, can be attributed to the interstitial space from the interleaving
the N2 adsorption–desorption isotherms of MnO2 –A (inset of nanowires or nanorods.
figure 10(a)) exhibit a hysteresis loop in a broader relative Table 2 reports the specific surface area, total pore volume,
pressure range of 0.45 < P/P0 < 1.0. The abrupt and average particle size of MnO2 –B, MnO2 –N, and MnO2 –
nitrogen uptake occurring at 0.9 < P/P0 suggests the A. The BET surface area (181 m2 g−1 ) and total pore volume
presence of an interstitial space between the nanostructures (0.86 cm3 g−1 ) of MnO2 –B are larger than that of both
(e.g. nanowires, nanorods) of MnO2 –B, MnO2 –N, and MnO2 –N and MnO2 –A. The high surface area and large

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Nanotechnology 22 (2011) 125703 J Zhang et al

Figure 11. Cycle life of MnO2 –B, MnO2 –N, and MnO2 –A in 0.5 M
Na2 SO4 at a current density of 5000 mA g−1 between 0 and 0.9 V.

Table 2. Specific surface area, total pore volume, and average

particle size of MnO2 –B, MnO2 –N, and MnO2 –A.
BET surface Pore volume Average particle
Sample area (m2 g−1 ) (cm3 g−1 ) size (nm)
Figure 12. Core-level XPS curves of O 1s (a) and Mn 2p (b) for
MnO2 –B 181 0.86 33 MnO2 –B and MnO2 –A before and after 1200 cycles.
MnO2 –N 99 0.52 61
MnO2 –A 31 0.08 192
also showed a decrease in the intensity. These observations
indicate the partial fracture of Mn–O–Mn band, suggesting an
pore volume of MnO2 –B are essential for providing a high
irreversible transformation from MnO2 to MnOOH.
capacitance. Besides, an appropriate content of adsorbed
The changes in the XPS signals of O 1s and Mn 2p can
water is favorable for enhancing the diffusion of ions within
be understood on the basis of the charge storage mechanism
the active material [5, 33]. The present results indicate
of MnO2 . Here, two mechanisms are outlined to help us
that hydrous MnO2 with a high surface area is favorable for
understand charge storage in MnO2 -based electrodes. For
achieving a good capacitive performance.
crystalline MnO2 , the dominant mechanism is redox reactions
To evaluate the long-time cycling stability of MnO2 –
between manganese (III) and manganese (IV) involving
B, MnO2 –N, and MnO2 –A, the specific capacitances were
insertion and extraction of protons or alkali cations in the bulk
measured by charge–discharge experiment at a current density
of the active material according to the following equations [35]:
of 5000 mA g−1 . The relationship of capacitance retention to
the cycle number is shown in figure 11. After 1200 cycles, MnO2 + H+ + e− ⇔ MnOOH (3)
the capacitance retention of MnO2 –B is about 75%, indicating
a good stability. MnO2 –N exhibits a comparable capacitance MnO2 + M+ + e− ⇔ MnOOM. (4)
retention of about 71%. As for MnO2 –A, the capacitance
As for amorphous MnO2 , the mechanism is mainly due
retention decreased to about 56% in the first 300 cycles. Then,
to a surface faradic reaction involving surface adsorp-
the capacitance is almost constant with a retention of about
tion/desorption of electrolyte cations on the MnO2 elec-
55% after 1200 cycles.
trode [29]:
XPS was employed to characterize MnO2 –B and MnO2 –
A before and after a stability test. The core-level XPS signals (MnO2 )surface + M+ + e− ⇔ (MnO− +
2 M )surface (5)
of O 1s and Mn 2p are shown in figure 12. The O 1s
spectra were deconvoluted into oxide (Mn–O–Mn), hydroxide where M+ = H+ , Na+ , K+ , Li+ .
(Mn–O–H), and water (H–O–H) [34]. Table 3 summarizes For MnO2 –A with a good crystallinity it is believed
the deconvoluted data. For MnO2 –B and MnO2 –A, the peak that the charge storage process was mainly governed by the
centered at about 529.6 eV (figure 11(a)) is ascribed to lattice insertion and extraction of Na+ ions from the electrolyte into
oxygen O2− from Mn–O–Mn. The peaks at about 532 eV the manganese oxide nanorods. Based on the XPS results the
are due to hydroxyl groups in Mn–O–H. Figure 12(b) exhibits content ratio of Mn–O–Mn decreased from 59.8% to 13.6%
Mn 2p1/2 and Mn 2p3/2 signals centered at about 642.0 and whereas that of Mn–OH increased from 27.9% to 52.5% after
653.5 eV [11]. After 1200 cycles, a higher content of 1200 cycles of charge–discharge. The observed changes on
hydroxide oxygen (Mn–OH) and water (H–O–H) and a lower the XPS signals of O 1s can be attributed to the irreversible
content of oxide (Mn–O–Mn) were observed on MnO2 –B and transformation from MnO2 to MnOOH, because the lattice
MnO2 –A. The core-level XPS signals of Mn 2p (figure 12(b)) strain caused by the insertion–extraction of Na+ during the

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Nanotechnology 22 (2011) 125703 J Zhang et al

Table 3. Core-level XPS analysis of samples MnO2 –B and MnO2 –A before and after the stability test.
O 1s (eV)
Sample Mn 2p3/2 Mn–O–Mn Mn–OH H–O–H
MnO2 –B As-prepared BD (eV)a 642.0 529.6 531.5 533.4
Area % 57.8 36.1 6.1
After 1200 cycles BD (eV)a 642.1 529.7 531.9 533.8
Area % 41.4 38.0 20.6
MnO2 –A As-prepared BD (eV)a 641.8 529.6 531.3 533.2
Area % 59.8 27.9 12.3
After 1200 cycles BD (eV)a 641.9 529.8 531.9 533.2
Area % 13.2 52.5 34.3
a
Binding energies of peak position.

charge–discharge process would result in the fracture of the
Mn–O–Mn band, eventually resulting in the poor cycling
stability of MnO2 –A [36]. In contrast, for MnO2 –B the XPS
data exhibited a small increase in the hydroxide (36.1–38.0%)
and a small decrease (57.8–41.4%) in oxide, suggesting a weak
influence from the strain effect. The poor crystallinity and the
small particle size of MnO2 –B favored release of the lattice
strain caused by the insertion–extraction of Na+ , leading to the
good capacitance retention.
4. Conclusions
Hydrous manganese dioxide nanostructures prepared under
different pH conditions exhibited different physical and
chemical properties. It was found that the specific capacitance
of the sample prepared under basic conditions exhibited the
best capacitive performance including the highest capacitance
of 262 F g−1 at a current density of 250 mA g−1 and the best
stability (a capacitance retention of 75% after 1200 cycles).
The high surface area and hydrous nature are attributed to
the highest specific capacitance of the sample. The long-time
cycling stability is dependent on the crystalline nature of MnO2
and the charge storage process.
Acknowledgment
Financial support from Ministry of Education with a project
number of MOE2008-T2-1-004 is greatly appreciated.
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