Electrochimica Acta 52 (2007) 28062814

Capacitive behavior of nanostructured MnO2 prepared by

sonochemistry method
Alireza Zolfaghari a, , Fatemeh Ataherian b , Mehdi Ghaemi b , Ameneh Gholami b
aChemistry and Chemical Engineering Research Center of Iran, Iran
b Department of Chemistry, Science Faculty, Tarbiat Modares University, Tehran, Iran
Received 20 May 2006; received in revised form 30 September 2006; accepted 3 October 2006
Available online 22 November 2006

Dedicated to the memory of Professor B.E. Conway

Abstract
Nanostructured manganese dioxide has been successfully prepared by a sonochemical method from an aqueous solution of potassium bromate
and manganese sulfate. Changing the proportions of reagents leads either to - or layered structures of MnO2 . The capacitive characteristics of
the samples were systematically investigated in aqueous electrolytes through means of cyclic voltammetry and chronopotentiometry methods.
The electrochemical properties of MnO2 were strongly affected by the pH of electrolyte employed and this material exhibited ideally capacitive
behavior in 0.5 M aqueous Na2 SO4 solution. A maximum specific capacitance of 344 F g1 was obtained for the layered structure determined via
cyclic voltammetry at a scan rate of 5 mV s1 in 0.5 M aqueous Na2 SO4 solution at pH 3.3. Excellent electrochemical reversibility of the materials
was also demonstrated.
Layered structure MnO2 showed higher energy density at high power density than the -structure material.
Impedance spectroscopy studies revealed that charge transfer resistance of the -structure oxide has higher value than that of the layered structure.
2006 Elsevier Ltd. All rights reserved.

Keywords: Manganese dioxide; Supercapacitor; Sonochemistry; Nanostructure; -Structure; Layered structure

1. Introduction The majority of pseudocapacitors fall into two main sub-

Supercapacitors are charge-storage devices that possess high
ideally power density, exhibit excellent reversibility, and have
very long cycle life. They are applicable in electronic devices,
such as power electronics, as well as in hybrid electric vehicles
and space flight technology [1,2].
Electrochemical supercapacitors can be classified based upon
the mechanism of charge storage: (i) electrical double layer
capacitor (EDLC) with capacitance mainly arising from the
charge separation at electrode/electrolyte interface and (ii) pseu-
docapacitors with capacitance arising from faradaic reactions
which, for a variety of different reasons, exhibit capacitative
behaviour [1].
a low cost technology employing non corrosive electrolytes
Corresponding author. Tel.: +98 21 44580720; fax: +98 21 44580762.
E-mail addresses: azhca@yahoo.com,
zolfaghari@ccerci.ac.ir (A. Zolfaghari).
classes: (i) metal oxides in aqueous electrolyte [3,4] and (ii)
conducting polymers that work both in aqueous and non-
aqueous electrolytes [5,6].
Most of work on supercapacitors utilizing pseudocapaci-
tance has focused on metal oxide materials. Amorphous hydrous
ruthenium oxide is the most promising material for super-
capacitors because of its high specific capacitance, excellent
reversibility and long cycle-life [3,7].
Ruthenium oxide is an expensive material; it is toxic and
requires the use of a strong acidic electrolyte such as sulfu-
ric acid. The acidic media can dissolve the metal oxide over
extended cycling leading to fade in the specific capacitance with
cycle-life [3]. Of course, the requirement of concentrated acid
does not render the RuO2 technology obsolete, as the success
and wide spread use of Pb-acid batteries illustrates, however,
would certainly find numerous applications. As a result, numer-
ous metal oxides have also been tested as possible candidates

0013-4686/$ see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2006.10.035
 A. Zolfaghari et al. / Electrochimica Acta 52 (2007) 28062814
for electrochemical supercapacitor devices. Candidate systems
include IrO2 [8] or CoOx , [9] but they suffer from limitations
similar to RuO2 , that is, they are expensive and require strong
acidic or alkaline electrolyte. In addition the potential window
over which they operate reversibly is significantly smaller than
that for RuO2 . On the other hand, MoO3 [10], NiO [3], V2 O5
[11] and MnO2 [1222] systems seem promising due primarily
to their lower cost. A significant body of work has already
been published studying the suitability of MnO2 compounds
for battery applications [23,24], but up to now only few papers
dealt with its use in electrochemical supercapacitors [1222].
It has already been shown that the nanostructure of the
electrode affects dischargecharge properties of the pseudoca-
pacitor, particularly at large current density [25]. Preparation
of the electrode from nanostructured MnO2 results in elec-
trodes having large specific surface area and enlarges the contact
area between active and conducting material [14,25,26]. Various
nanostructured composite electrodes of MnO2 were synthesized
via different methods [2022].
Needle-like manganese oxide was prepared by electrochem-
ical deposition on the surface of a graphite disc electrode in the
acidic solution of KMnO4 . The coating exhibited a capacitance
of 45 mF cm2 [20].
A manganese dioxide nanowire electrode was made by
immersing an anodic aluminum oxide template into a solgel
solution containing Mn(CH3 COO)2 and citric acid. The result-
ing electrode was found to have the specific capacity of
165 F g1 [21].
Electrochemical deposition of nano-sized manganese oxide
onto stainless-steel current collectors in an acidic solution of
MnSO4 was also reported. The specific capacitance value of the
electrode was 410 F g1 [22].
However, the use of templates and substrates is undesirable as
it introduces heterogeneous impurities and increases the produc-
tion cost. Thus research on easily controlled and template-free
methods to create nanostructured material is of great significance
and is the focus of the present work.
The preparation of -MnO2 3D urchin like nanostructures
by heating aqueous solution of KBrO3 and MnSO4 at 130 C
for 16 h in an autoclave has been reported [27]. The authors
suggest that the high specific area of the resulting material make
it of interest for Li battery applications but do not report any
electrochemical characterization.
We examine the possibility of shortening the reaction time,
as well as lowering the reaction temperature by application of
ultrasonic irradiation to the above process.
Sonochemistry methods have been successfully applied to the
preparation of various nanostructured materials including met-
als [2830], metal carbides [31], and metal oxides [3235] at
room temperature, ambient pressure, and short reaction time.
Sonochemistry derives its success in creating nanostructured
materials principally from acoustic cavitation; the formation,
growth, and implosive collapse of bubbles in a liquid. Bubble
collapse induced by cavitation produces intense local heating,
high pressures, and very short lifetimes. These hot spots have
temperature of roughly 5000 C, pressure of about 500 atm, and
heating and cooling rates greater than 109 K s1 . The chemical
2807
Table 1
The synthesis conditions of the various samples
Sample [KMnO4 ] (M) [KBrO3 ] (M) Duration time (min)
S1 0.125 0.250 566
S2 0.250 0.500 240
effects of cavitation produce both strong reductive and oxida-
tive radicals which are capable of causing secondary oxidation
or reduction reactions [3638].
We report here a sonochemical method for synthesis of
nanostructure manganese dioxide by oxidation of Mn2+ and the
characterization of the oxide as an active material for superca-
pacitor electrodes.
2. Experimental
2.1. Synthesis
Aqueous solutions of KBrO3 (Merck, research grade) and
MnSO4 (Merck, research grade) in various concentrations were
irradiated by ultrasound for different time intervals. A 24 kHz
ultrasound horn transducer system (UP 200 H, Dr. Hielscher
GmbH) with a 3 mm microtip (titanium alloy) and a sonic power
density of 390 W/cm2 was employed. The sonic horn was dipped
about 2 cm into the solution. Temperature was held constant
at 45 C during sonication. All the solutions were made from
doubly distilled water. Results are reported for two different
synthesis conditions, resulting in significantly different MnO2
morphologies, S1 and S2. The ratio of KMnO4 : KBrO3 was,
however, maintained constant. The synthesis conditions are pre-
sented in Table 1. After the reaction was complete, the resulting
black solid product was filtered, washed with distilled water to
remove by-products, and dried at room temperature in air and
subsequently characterized as described below.
2.2. Characterization methods
2.2.1. Chemical composition analysis
The value of n in Kz MnOn was determined using the poten-
tiometric titration approach of Vetter and Jaeger [39]. The total
amount of K in the powders was determined by flame photome-
tery (Schrown 410) and was found to be negligible.
The surface water content of each sample was determined by
weighing the sample before and after heating at 110 C for 2 h.
The structural water content was determined by measuring the
weight loss of the same samples after heating at 400 C for 2 h
[40].
2.2.2. Structural and morphological characterization
The crystallographic structure of the powder was investigated
using a diffractometer (Philips PC-APD with a Cu anode that
generated Cu K radiation, = 1.5406 A).
Surface morphology of the sample was examined with a scan-
ning electron microscope, SEM (Philips XL30) and an atomic
force microscope, AFM (DME DS 95) in AC mode. The synthe-
sized MnO2 powders were dispersed in doubly distilled water
2808 A. Zolfaghari et al. / Electrochimica Acta 52 (2007) 28062814
(0.25%). A few drops of the suspension were spread on glass
lamella, and dried at 70 C. The AFM images were obtained by
scanning an area of 1 m2 of the prepared sample with the scan
rate of 1.5 m s1 in ambient air at room temperature.
The specific surface area and pore size distribution were
determined by BrunauerEmmettTeller (BET) [41] analysis of
N2 adsorptiondesorption isotherms measured on sample using
a Quantasorb, Quantachrom apparatus.
2.3. Analysis of point of zero surface charge
The pHp.z.c. values of the samples were determined by poten-
tiometric titration using the following bath procedure: different
volumes of 0.1 M HCl or 0.1 M NaOH were added to a series
of NaCl solutions of different concentrations (1.0-103 M) such
that the total volume of each solution was 50 ml. After about
1 h the pH values were noted (blank solution) using a pH meter
(744 Metrohm). Fifty milligrams of solid sample were added
to each solution, immediately stopper, and shaken well. After
72 h of equilibration with intermittent shaking, the pH val-
ues of each of the supernatant liquids were noted. Then the
change of pH (pH) is plotted against initial pH (blank solu-
tion). The pHp.z.c. was estimated from where pH is equal to
zero [42].
2.4. Electrochemical measurement
Electrodes were prepared by mixing 60 wt% of MnO2
powder as active material with 10 wt% of acetylene black
(Alfa Aesar, >99.9%, S.A. 80 m2 /g), 25 wt% of graphite
(Alfa Aesar, conducting grade, 200 mesh), and 5 wt% of
poly(tetrafluoroethylene) dried powder (Merck). The three first
constituents were first mixed together to obtain a homogeneous
black powder. The poly(tetrafluoroethylene) powder was then
added with a few drops of ethanol. This resulted in a rubber-like
paste that was rolled into a film (100200 m thick) on a flat
glass surface. A piece of film (0.25 cm2 ) was cut and pressed
onto stainless steel grid current collector.
An Autolab, Eco Chemie. B.V. potentiostat/galvanostat was
used for all electrochemical measurements. A beaker type
electrochemical cell equipped with a MnO2 based working elec-
trode, an Ag/AgCl electrode (Metrohm AG 9101 Herisau, 3 M
KCl, 0.207 V versus SHE at 25 C) reference electrode and a
1 cm2 stainless steel grid counter electrode was used. A Lug-
gin capillary, whose tip was set at a distance of 12 mm from
the surface of the working electrode, was used to minimize
errors due to iR drop in the electrolyte. Aqueous solutions of
0.5 M Na2 SO4 with different pH values, achieved by addition of
HCl, employed as the electrolyte, were degassed with purified
argon before measurement. The solution temperature was main-
tained at 25 C by means of a water thermostat (RE 104 Ecoline,
LAUDA).
In order to determine the contribution of acetylene black
and graphite to the overall charge capacity of the electrode, a
cyclic voltammetry, CV, experiment was performed on a blank
electrode containing no MnO2 . The charge storage capacity
of this electrode was found to be negligible (104 C g1 )
compared to the charge of electrode with active material
(>101 C g1 ).
The average specific capacitance was calculated by integrat-
ing either the oxidative or the reductive CV half-cycle over the
potential window of the voltammogram. All the specific capac-
itances are reported per gram of active material.
3. Results and discussion
3.1. Theory and proposed mechanism
When synthesis of MnO2 was executed at room temperature
without sonication only a small amount of product was obtained,
even after 24 h. Fortunately this reaction was facilitated by ultra-
sonic radiation.
The redox synthesis of MnO2 in an aqueous media containing
Mn2+ ions has been proposed to occur following the reaction
[43]:
Mn2+ + 2H2 O MnO2 + 4H+ + 2e (1)
It is unlikely that reaction (1) occurs in a single step. The exis-
tence of a precursor, such as Mn3+ has been suggested [4446],
originating from the following reaction:
Mn2+ Mn3+ + e (2)
Mn3+ can disproportionate to Mn2+ and Mn4+ at acidic concen-
trations, according to reaction (3), or it may hydrolyze to form
an insulating intermediate MnOOH, according to reaction (4):
2Mn3+ + 2H2 O Mn2+ + MnO2 + 4H+ (3)
Mn3+ + 2H2 O MnOOH + 3H+ (4)
Subsequently, the product of reaction (4) is oxidized to MnO2 :
MnOOH MnO2 + H+ + e (5)
The final product contains Mn3+ as MnOOK or MnOOH and
Mn4+ as MnO2 .
3.2. Material characteristics
3.2.1. Chemical composition
The presently accepted formula for MnOn based on
the cation vacancy model, proposed by Ruetschi [47] is
Mn1xy 4+ Mny 3+ On4xy 2 OH4x+y , where x represents the
amount of cation vacancy. It has been proposed that manganese
dioxide contains considerable amounts of hydroxide and water
existed mainly in different forms. Hydroxide ions compensate
cation vacancies which may have arisen from Mn4+ ions miss-
ing during manufacturing of manganese dioxide. It could be
assumed that four ions of six oxygen ions in octahedron sur-
rounding the vacancy are hydroxide ions. Furthermore some
Mn4+ ions may reduce partially to Mn3+ , and hydroxide ions
are requisite to compensate the lacking of positive charge due
to Mn4+ ions replaced by Mn3+ ions. Finally water molecules
could be adsorbed mainly on the surface of the nano-sized pore
throughout the microporous material [48]. The amount of n
 A. Zolfaghari et al. / Electrochimica Acta 52 (2007) 28062814 2809

Fig. 1. XRD patterns of prepared samples: (a) S1 and (b) S2. The peaks are
noted with ().

could be evaluated through the potentiometric titration [39] and

in terms of n, there are (2n 3) Mn4+ ions and (4 2n) Mn3+
ions [40].
The water contents and chemical formula of prepared samples
are presented in Table 2. The amount of Mn3+ and water content
of S2 were found to be higher than those of S1.

3.2.2. Bulk and morphological properties

Fig. 1 shows X-ray diffraction (XRD) pattern of the prepared
samples. The diffraction peaks of S1 in Fig. 1a correspond to the
(1 2 0), (1 3 1), (2 3 0), (3 0 0), (0 0 2), (1 6 0), (2 4 2), (4 2 1) and
(0 0 3) planes, from left to right, respectively. All these peaks
can be indexed to pure orthorhombic -MnO2 (JCPDS card
14644, a = 6.36 A, b = 10.15 A, c = 4.09 A). No characteristic
peaks were observed for other impurities such as - or -MnO2 ,
Mn(OH)2 and Mn2 O3 . In Fig. 1b, the pattern is dominated by
two major peaks (e.g. at about 12 and 22 2) corresponding Fig. 2. AFM topography image: (a) S1 and (b) S2.
to (0 0 2) and (2 1 2) planes, respectively which are signature
features of synthetic birnessites material [49], and indicates that
there is layered structure in S2. It seems that the longer reac- than 90% of the population is within the 2050 and 8090 nm
tion time required producing S1-type MnO2 results in a more range for S1 and S2, respectively. These results are in agreement
crystallized structure. with the SEM images of S1 and S2 (Fig. 3).
AFM images show MnO2 powder samples to exhibit spher- The specific surface area and the pore size distribution of
ical nanostructure (Fig. 2). Analysis of the AFM images using S1 and S2 from the BET test are presented in Table 2. The
image processing software (DME, version 1.5.0.4) exhibit a volume of micropores compared to the volume of mesopores is
spherical structure with a narrow size distribution in which more negligible for both samples. The microporous volume of S1 is

Table 2
The water content, chemical formula, specific surface area and pore diameter of prepared samples

Sample Surface Structural Mn1xy 4+ Mny 3+ On4xy 2 OH4xy SBET Dav (A) Microporous Mesoporous
water (%) water (%) (m2 g1 ) volume (cm3 g1 ) volume (cm3 g1 )

S1 17.0 6.3 Mn0.838 4+ Mn0.017 3+ O1.403 2 OH0.597 301 46.0 0.02 0.33
S2 16.4 8.2 Mn0.762 4+ Mn0.066 3+ O1.246 2 OH0.754 161 69.1 <0.01 0.29
2810 A. Zolfaghari et al. / Electrochimica Acta 52 (2007) 28062814
Fig. 3. SEM image of (a) S1 and (b) S2 (the X sign shows a single particle with
diameter of 60 and 90 nm, respectively).
slightly higher than that of S2 (0.04 cm3 g1 ), but the average
pore diameter of S2 is bigger than that of S1. The lower pore
diameter of S1 leads to the augmentation of its BET surface
area.
3.3. Characteristics of point of zero surface charge
The effect of pH on the charge of manganese oxide surface
may be represented by [50]:
MnOH2(surf) + Mn(OH)(surf) + H+ MnO(surf) + 2Haq +
positive surface p.z.c. negative surface
(6)
The change in pH following addition of 50 mg of sample was
monitored as a function of pH for four different NaCl solutions.
pH control was achieved by the addition of either HCl or NaOH.
The point of zero charge, p.z.c., is expressed in terms of the
pH at which there is no net H+ or OH adsorption, i.e. where
pH following the addition of the sample is 0. Based on Fig. 4,
the pHp.z.c. s of S1 and S2 were found to be 2.21 and 1.89,
respectively. At pH close to the pHp.z.c. the net surface adsorption
or desorption decreases for both samples.
Fig. 4. Variation of pH as a function of initial pH for (a) S1 and (b) S2 in ()
0.05 M, (+) 0.1 M, () 0.2 M, and () 0.5 M aqueous NaCl solution.
3.4. Electrochemical properties
3.4.1. Cyclic voltammetry
Typical cyclic voltammograms, CVs, measured in aqueous
0.5 M Na2 SO4 solution for prepared samples are shown in Fig. 5.
The potential ranges were 0.00.8, 0.01.0, and 0.21.2 V ver-
sus Ag/AgCl and each measurement was taken at a sweep rate
of 5 mV s1 .
These CVs are relatively rectangular in shape and exhibit
near mirror-image current response on voltage reversal thus
indicating ideal capacitive behavior for both samples.
It may be concluded from a comparison of these curves that
the shape of CV is not significantly affected by changing the
chemical composition, structural phases, specific surface area
and pore diameter of prepared samples.
The specific capacitance (SC) of the electroactive material
can be estimated based on the following equation [51]:
voltammetric charge q
C= = (7)
potential window oxide loading V w
The specific capacitances of the layered structure manganese
dioxide, S2, and -MnO2 , S1, determined from calculation of
the charge from the CVs in Fig. 6 are ca. 344 and 275 F g1
in the potential window of 0.01.0 V at sweep rate 5 mV s1 ,
respectively.
The capacity measurements along with the BET results show
that the higher surface area of S1 is not the only factor that
determines the capacitance. The other important factor is pore
size of electrode material [1]. The average pore diameter of the
 A. Zolfaghari et al. / Electrochimica Acta 52 (2007) 28062814 2811

Fig. 6. Variation of the voltammetric charge density (q) with respect to sweep
rate (): (a) extrapolation of q to = from the q vs. 1/2 plot given the outer
Fig. 5. Cyclic voltammograms of (a) S1 and (b) S2 electrodes over different charge and (b) extrapolation of q to = 0 from the q1 vs. 1/2 plot given the
potential ranges. total charge at () pH 3.3 and () pH 6 for S1, () pH 3.3 and () pH 6 for
S2.
S2 material is 50% larger than that of S1. It is possible that the
larger specific capacitance of S2 is due to the fact that the larger
rate 5 mV s1 in 0.5 M aqueous Na2 SO4 solution with different
pores of this material are more readily accessible. In addition, it
pH is listed in Table 3. As shown, the highest specific capacitance
should be noted that the capacitance of this material is the result
belongs to layered structure MnO2 at pH 3.3.
of a redox process and not limited to electrostatic charging of
These results show that the increment of proton concentration
the double layer at the MnO2 electrode surface.
at constant concentration of Na+ cation results in an enhance-
Since, the electrochemical reversibility is one of the
ment of specific capacitance. This effect may originate from
predominant factors influencing the power capabilities of elec-
the penetration of cations into the sample pores that may be
trochemical supercapacitors the electrochemical reversibility of
attributed to high mobility and small size of proton compare to
the prepared samples was examined systematically by changing
Na+ cation. This conclusion has been presented in other pub-
the potential window of CV at 0.20.8, 0.01.0 and 0.21.2 V
lished work [52]. At pH 2.3, the capacitance suddenly decreases
versus Ag/AgCl that is shown in Fig. 5.
compare to higher pHs. This decrease could be resulted from
Rectangular and symmetric iE responses were observed at
the instability of the MnO2 electrode in the strong acidic solu-
S1 and S2 electrodes between 0.2 and 0.8 V indicating that
tion [52] or it could be arisen from approaching of electrolytes
both samples exhibited high electrochemical reversibility in
pH to pHp.z.c. resulting in reduction of surface adsorp-
this potential range and sweep-rate. As the potential range
tion. Therefore the capacitance measurement was limited to
over which the CV experiment was conducted was increased
pH > 3.
from (0.20.8 V) to (0.01.0 V), an irreversible anodic peak
developed between 0.8 and 1.0 V for both samples. No cor-
responding cathodic response is appeared. As the potential is Table 3
further expanded, a quasi-reversible faradaic process is observed The specific capacitance of the various samples in 0.5 M aqueous Na2 SO4
solution with different pH at scan rate 5 mV s1
just positive of 1.0 V. Charges and discharges of both electrodes
are not electrochemically reversible over the extended potential Sample Specific capacitance (F g1 )
range. pH = 2.3 pH = 3.3 pH = 3.7 pH = 4.5 pH = 6

S1 118 258 236 212 204

3.4.1.1. Effect of electrolytes pH. The specific capacitance of S2 171 344 316 262 229
the various samples in the potential window of 0.01.0 V at scan
2812 A. Zolfaghari et al. / Electrochimica Acta 52 (2007) 28062814

Table 4
The estimated charge density (C g1 ) at very low and very high sweep rate in
the various electrolytes pH for different samples
Sample pH = 3.3 pH = 6

q0 qT q0 qT

S1 122 213 102 179

S2 152 357 84 278

3.4.1.2. Effect of scan rate. Voltammetric charges were deter-

mined as a function of sweep-rate for electrodes of S1 and S2
materials, and the dependence of q on 1/2 for S1 and S2 are
shown in Fig. 6a. Voltammetric charge, q, increases with 1/2
(decreases with ). In Fig. 6b, the inverse of the voltammetric
charge, q1 , is plotted as a function of the square root of sweep
rate, 1/2 .
At high sweep rate, the diffusion of protons and sodium
cations is limited to the outer surface of electrode that is more
accessible. Therefore the extrapolation of q to = from the
q versus 1/2 plot (Fig. 6a) gives the outer charge q0 , which
is the charge on the active outer surface. The extrapolation of q
to = 0 from the q1 versus 1/2 plot (Fig. 6b) gives the total
charge qT , that is, the charge involved to the whole active inner
and outer surfaces [53].
The estimated charges at very low and very high sweep rates
at various pH for the different samples are presented in Table 4.
At pH 6, the higher value of q0 for S1 than that of S2 could
reveal the higher active outer surface of S1. At pH 3.3, q0 of S2
is more than that of S1, which is due to determining effect of
the high mobility of proton in the charge/discharge process. The
comparison of qT for both samples at particular pH indicates
that the accessible surface sites of S2 are much more than those
of S1. At lower pH, the higher values of qT for both samples
show that the access to surface sites is easier for proton than
sodium cations. Since, this augmentation for S2 is about twice
as high as that of S1, and S2 with larger pore diameter reveals
more specific capacitance, the charge storage could be a cation
diffusion driven process.
3.4.2. Charge and discharge properties of electrodes
To investigate the performance of the composite electrode,
both electrodes were charged and discharged at various current
densities. Fig. 7 shows the chronopotentiogram of S1 and S2
electrodes. The cutoff voltages for charging/discharging were
0.0 and 1.0 V at current density of 2.5 A g1 . A good linear varia-
tion of potential versus time was observed for both curves, which
is another typical characteristic of an ideal capacitor. A small iR
drop is observed, indicating a conductive characteristic of the
oxide material [22]. The specific capacitance was obtained from:
I t
C=
V
S2 electrodes show the largest specific capacitance, 295 F g1
when the current density is 1 A g1 . Also, there is a less of a
decrease in specific capacitance with increasing current density
for S2 electrodes than for S1 electrodes. This indicates the
higher accessible surface area in S2.
Fig. 7. Constant current charge/discharge curves for (a) S1 and (b) S2 electrodes
measured at 2.5 A g1 in 0.5 M aqueous Na2 SO4 solution at pH 3.3 between 0
and 1 V.
Ragone plots of different electrodes at various charge/
discharge current densities are shown in Fig. 8. The power den-
sity (p.d.) and the energy density (e.d.) of the electrodes can be
estimated from:
Q V E
P= = (9)
2tw tw
where P, Q, V, t, w and E are indicating of the average
power density, total charge delivered, the potential window of
discharge, discharge time, loading prepared sample and total
energy density, respectively. Although energy density decreases
as power density increases for both samples, it declines more
rapidly for S1 type electrodes than for S2 type. The fairly high
energy density of S2 at high power density provides one of
the basic requirements of a successful electrode material for
supercapacitors applications [2].
3.4.3. Impedance spectroscopy behaviors
Electrochemical impedance spectroscopy, a powerful tech-
nique for the investigation of the capacitive behavior of
electrochemical cells, has been also used to characterize our
materials. Fig. 9 presents Nyquist plots obtained at electrodes
made from S1 and S2 type MnO2 at 0 V versus Ag/AgCl over
the frequency range 0.01105 Hz. Both of the plots are similar
in form, composed of a semicircle at high and intermediated
(8)
Fig. 8. Ragone plots obtained for () S1 and () S2 electrodes.
 A. Zolfaghari et al. / Electrochimica Acta 52 (2007) 28062814
Fig. 9. Nyquist plots of the electrodes () S1 and () S2 in 0.5 M aqueous
Na2 SO4 solution at pH 3.3.
frequencies, followed by a relative linear response at the low-
frequencies. At very high frequencies, the measured resistance
is composed of the following terms: the ionic resistance of elec-
trolyte, the intrinsic resistance of the active material, and the
contact resistance at the active material/current collector inter-
face [54]. It can be seen that the above resistance measured at
S1 type electrodes is almost the same that at S2 type electrodes.
At high frequencies, Fig. 9 shows the presence of a semicir-
cle. Similar features at carbon double layer electrodes have been
described as a pseudo-charge transfer resistance associated with
the active carbon-current collector interface [54]. It seems that
the increasing of the contact surface area between the active car-
bon and the S2 as active material lead to a decrease in the contact
resistance and a minimization of the high frequency semicircle.
In our experiments, the amplitude of the semicircle changes
with the nature of the electrode active material, and it is smaller
for S2 than S1. The BET study showed that the pore size of S2
is bigger than that of S1 which improves the electrolyte accessi-
bility to S2. Therefore the pseudo-charge transfer resistance of
the S1 is more than that of S2.
At low frequencies, the imaginary part of the impedance,
for both samples, increases. As the redox process giving rise to
the pseudo-capacitative behavior is primarily a surface process,
the low frequency behavior results from penetration of the ac
signal inside the porous matrix increasing with the decrease of
frequency.
4. Conclusion
Nanostructured, -manganese dioxide, S1, and layered struc-
ture manganese dioxide, S2, were prepared using ultrasonic
radiation. Structural selectivity of the synthesis of manganese
dioxide could be controlled by dilution of reactants. AFM and
SEM studies demonstrate the nanostructured electrode material
was constructed from spherical particles.
Maximum specific capacitance values as high as 344 and
257 F g1 were obtained for the layered and -MnO2 , respec-
tively at scan rate 5 mV s1 in 0.5 M aqueous Na2 SO4 solution
at pH 3.3. These capacitance values compare favorable with that
reported in the literature for MnO2 electrodes deposited directly
on templates and substrates [2022].
2813
BET measurements have shown that the larger capacitance of
S2 than that of S1 could be explained by an increase in average
pore size of S2 compared to S1 that was thought to facilitate
electrolytes ion accessibility on the electrode surface. The elec-
trochemical impedance spectroscopy also tends to confirm the
above hypothesis.
In addition, the nanostructure samples demonstrate excellent
reversibility and high power density.
Acknowledgements
The financial support of National Committee of Nanotech-
nology in Ministry of Science, Research and Technology of Iran
is acknowledged. The authors would like to thank Dr. Wendy G.
Pell for her constructive comment.
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