Composites Science and Technology 102 (2014) 82–86

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Composites Science and Technology

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

Solvothermal preparation of microspherical shaped cobalt–manganese

oxide as electrode materials for supercapacitors
Wen Lei a, Ping He a,⇑, Yuhao Wang a, Xingquan Zhang b, An Xia a, Faqin Dong a
a
State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, School of Materials Science and Engineering, Southwest University of Science
and Technology, Mianyang 621010, Sichuan, PR China
b
Analytical and Testing Center, Southwest University of Science and Technology, Mianyang 621010, Sichuan, PR China

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

Article history: Microspherical shaped cobalt–manganese oxide (CMO) as electrode materials for supercapacitor is syn-
Received 1 November 2013 thesized by solvothermal method. The microstructure and surface morphology of CMO are characterized
Received in revised form 13 July 2014 by X-ray diffraction and scanning electron microscopy, respectively. Cyclic voltammetry and chronopo-
Accepted 19 July 2014
tentiometry are employed for the characteristics of electrode process and the calculation of specific
Available online 26 July 2014
capacitance in KOH solution. It is shown that as prepared CMO with cobalt/manganese mole ratio of
1:2 has excellent specific capacitance of 348.0 F g1 at current density of 0.5 A g1. In addition, long-term
Keywords:
stability of the composites electrode is measured at current density of 1.0 A g1, and 58.6% of initial
A. Hybrid composites
A. Functional composites
capacitance is retained after 500 cycles.
A. Oxides Ó 2014 Elsevier Ltd. All rights reserved.
B. Electrical properties

1. Introduction manganese oxide as a candidate for pseudocapacitor due to the

Supercapacitors, also known as electrochemical capacitors,
have now been proved to be the most powerful candidates for
next-generation energy storage devices due to their high power
density, fast charge/discharge rate as well as better performance
of cycle stability compared with conventional battery and electro-
lytic capacitor [1]. Generally, on the basis of the energy storage
mechanism, supercapacitors can be classified into two categories,
i.e., electrical double layer capacitor and pseudocapacitor [2]. In
general, three kinds of electrode materials are used for the prepa-
ration of supercapacitors, including carbon materials, transition
metal oxides and conducting polymers [3].
Progress towards supercapacitors technologies can benefit from
the continuous development of a variety of different structure
materials [4]. Among those electrode materials above, hydrous
ruthenium dioxide stands out due to a number of desirable proper-
ties, such as high conductivity, high specific capacitance and good
environmental stability. However, the high cost, rareness and toxic
nature of RuO2 have limited its commercial attractiveness [5].
Therefore, cheaper metal oxides with various oxidation states
and excellent electrochemical behaviors are intensively studied
as alternative materials, including NiO [6], MnO2 [7], Fe3O4 [8]
and Co3O4 [9], etc. Most attentions have been focused on hydrous
⇑ Corresponding author. Tel.: +86 816 6089371.
E-mail address: heping@swust.edu.cn (P. He).
low cost of raw materials and the fact that manganese is more
environmentally friendly than any other transition metal oxide
systems, thus it has attained a large variety of applications.
To bridge the performances gap between these materials,
attempts at novel electrode design have been extensively made.
Despite the numerous of publications, nearly all of them can be
clarified into one general concept, that is, the use of pseudocapac-
itive materials conductive matrix hybrid nanostructures [10].
Recently, many two- or three-metal oxide composite materials,
such as CoMoO4 [11] and Co2SnO4 [12], have been synthesized
with excellent electrochemical properties. Prasad et al. [13] depos-
ited nanostructured and microporous nickel–manganese oxide
(NMO) and cobalt–manganese oxide (CMO) onto stainless steel
substrate by potentiodynamic method and found that the specific
capacitances of NMO and CMO were much higher than that of
any individual, indicating the possibility that electrochemical
performances of metal oxide composites were superior to that of
single metal–oxide materials.
In this paper, based on solvothermal preparation different from
the literatures above, precursor composed of Co and Mn was pre-
pared using urea as precipitator and hexadecyl trimethyl ammo-
nium bromide (CTAB) as template. Then the precursor was
calcined at temperature of 400 °C to obtain microspherical shaped
materials, exhibiting a higher specific capacitance (348 F g1 at
current density of 0.5 A g1) compared to the value reported by
Gobal and Chang (78 F g1 [14] and 180 F g1 [15], respectively).

http://dx.doi.org/10.1016/j.compscitech.2014.07.019
0266-3538/Ó 2014 Elsevier Ltd. All rights reserved.
 W. Lei et al. / Composites Science and Technology 102 (2014) 82–86
2. Experimental
2.1. Synthesis and characteristics of microstructured CMO
Cobalt acetate, manganous acetate, urea, CTAB and ethanol
were analytically pure and used without further purification. All
the chemicals were purchased from Chengdu Chemical Reagent
Factory (Chengdu, China). Distilled water was used throughout
the experiments.
In a typical procedure, 1.0 g CTAB and 2.0 g urea were dissolved
in solution containing 10 mL ethanol and 20 mL distilled water and
stirred with a magnetic stirrer for 10 min to form a homogeneous
solution at room temperature. Subsequently, different mole ratios
of cobalt acetate and manganous acetate with a total amount of
5 mmol were added to the above solutions, respectively. The solu-
tions were transferred into teflon-lined stainless steel autoclaves
with 50 mL capacity. The autoclaves were then loaded into an oven
preheated to 140 °C for 12 h. After the reaction system cooled
down to room temperature, the pink precipitate was collected
and washed with distilled water and absolute ethanol until no
Br- was detected, then it was dried at 60 °C for 12 h in air, followed
by calcination in a muffle furnace at a temperature of 400 °C.
As prepared samples with different mole ratios of cobalt acetate
and manganous acetate (1:2, 1:1, 2:1) were marked as CMO-1,
CMO-2 and CMO-3, respectively.
The morphologies of samples were investigated using a field
emission scanning electron microscope (Ultra 55, Zesis Corpora-
tion). The mole ratio of Co and Mn contained in CMO-1 was ana-
lyzed with energy dispersive X-ray (EDX) detector (HORIBA,
EMAX). The crystallographic structures were characterized by
XRD (X0 Pert PRO, Netherlands) with Cu Ka radiations
(k = 0.15406 nm) performed from 10° to 80° at a speed of 2° per
minute.
2.2. Electrode fabrication and electrochemical measurements
The fabrication of working electrodes was carried out as
follows: briefly, the electroactive materials, conductive carbon
black and polytetrafluoroethylene (PTFE) were mixed in a mass
ratio of 8:1:1 and dispersed in ethanol. The resulting composite
was ultrasound for 30 min to form a sticky slurry, which was even-
tually pasted onto a nickel foam sized 1 cm  2 cm, followed by
drying at 80 °C under vacuum for 24 h.
2.0 M KOH solution was used as electrolyte in all experiments at
room temperature. All electrochemical measurements were car-
ried out by introducing a three-electrode test system using plati-
num sheet as counter electrode, as prepared composite electrode
as working electrode and Hg/HgO electrode as reference electrode.
Cyclic voltammetry (CV) and galvanostatic charge–discharge tests
were performed between 0.5 and 0.5 V using PARSTAT 2273 elec-
trochemical workstation (Princeton Applied Research, USA).
3. Results and discussion
Shown in Fig. 1 are the selected XRD patterns of CMO with dif-
ferent ratios of cobalt acetate and manganous acetate. It is shown
that the samples presented similar XRD patterns with relatively
broad XRD peaks, indicating the amorphous nature of CMO. Due
to the poor crystallinity, the definite phase could hardly be ascer-
tained from Fig. 1. All the three samples could be a series of amor-
phous CMO containing various valences of Mn and Co and their
oxides [16].
It is found in the latter part of this work that the electrochem-
ical performances of CMO-1 based electrode were much better
than that of CMO-2 or CMO-3, so only the SEM images of CMO-1
83
CMO-1
CMO-2
CMO-3
Intensity / a.u.
10 20 30 40 50 60 70 80
2θ /
Fig. 1. XRD patterns of as-prepared CMO-1, CMO-2 and CMO-3.
are presented (Fig. 2). It is shown clearly in Fig. 2a and b that
microsphere shaped CMO-1 particles with various sizes were
asymmetrically ranged and there were many small particles uni-
formly scattering on the surface of microspheres like sea urchins.
In addition, it is shown that CMO-1 particles tended to exist in
the form of bigger particles with tiny trigonal planar structure cov-
ering on the surface. The mechanism for the formation of CMO-1
particle was probably as follows. CO2 3 and OH resulted from
the decomposition of urea at a high solvothermal temperature
[17]. Furthermore, Mn and Co possessed different binding ability
with CO2 
3 and OH , and emerged different nucleation and growth
mechanism under the action of CTAB during the whole solvother-
mal procedure, which could explain the observed microspherical
and sea urchins shapes.
Shown in Fig. 2c is a typical EDX wide-range spectrum of as pre-
pared CMO-1. It was indicated that CMO-1 was consisted of Mn, Co
and O without any other impurities in the composites, and the cal-
culated atomic ratio of Co and Mn was practically consistent with
the added amount of Co and Mn.
Shown in Fig. 3 are the typical CVs of different CMO electrodes
in 2.0 M KOH electrolyte at scan rate of 2 mV s1 (a) and CVs of
CMO-2 at different scan rates (b). It was obvious that the sur-
rounded CV area of CMO-1 was much larger than that of either
CMO-2 or CMO-3, suggesting a higher specific capacitance. Com-
pared to Mn oxides, the added Co oxides were less electroactive
when the pseudocapacitance was concerned. But the added Co
could suppress the anodic dissolution of the oxides and therefore
improve the electrochemical reversibility. In addition, since the
capacitance of Mn oxide was determined by a reversible, fast and
continuous redox reaction between its trivalent and tetravalent
states [18,19], reactions Mn2O3 + Co2O3 + 2H2O ? 2MnO2 +
2Co(OH)2 and Mn2O3 + 2CoOOH + H2O ? 2MnO2 + 2Co(OH)2
might probably happen and hinder the ideal pseudocapacitive
reaction and thereby decrease the overall specific capacitance [15].
The galvanostatic charge–discharge behaviors of CMO-1, CMO-2
and CMO-3 composite electrodes were investigated by chronopo-
tentiometry from 0.5 to 0.5 V at current density of 1.0 A g1 in
2.0 M KOH solution and the corresponding results were shown in
Fig. 4a. All the samples exhibited nonlinear charge/discharge
behaviors with time. The specific capacitance was evaluated from
the slope of the charge–discharge curves, according to the equation
C = IDt/(mDV), where I was the applied current, m was the mass of
each electrode, and Dt/DV was calculated from the discharge curve
after the IR drop. The inclined parts indicated superimposed redox
reactions, which was consistent with the cyclic voltammograms in
84 W. Lei et al. / Composites Science and Technology 102 (2014) 82–86

1.5
a CMO-1
2 mV s
-1
CMO-2
1.0 CMO-3

Current density / A g-1

0.5

0.0

-0.5

-1.0

-1.5
0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6
Potential / V (vs. Hg/HgO)

2
b 5 mV s
-1

-1
2 mV s
-1
1 mV s

Current density / A g-1

1

-1

-2

0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6

Potential / V (vs. Hg/HgO)

Fig. 3. CVs of as-prepared CMO-1, CMO-2 and CMO-3 nanocomposite electrodes in

2.0 M KOH solution at scan rate of 2 mV s1 (a) and CVs of CMO-2 at different scan
rates (b).

current densities, the current accumulating process was very slow,

Fig. 2. SEM images (a and b) and EDX (c) of as-prepared CMO-1.
Fig. 4a. Obtained specific capacitances of CMO-1, CMO-2 and
CMO-3 were 290 F g1, 172 F g1 and 127 F g1, respectively. As
well known, IR drop was associated with the equivalent series
resistance of the supercapacitor cell, suggesting that slower ionic
transport was occurring within the active materials or that protons
cannot diffuse freely across the thickness of CMO particles [20]. Low
internal resistance was of great importance in energy storing
devices, as less energy was wasted to produce unwanted heat dur-
ing charging/discharging processes [21].
In order to further characterize the capacitance behavior of
CMO-1, chronopotentiograms at current densities of 0.5 A g1
and 2.0 A g1 were also measured. It is shown in Fig. 4b that higher
specific capacitance could obtain at relative low current density.
This phenomenon had been attributed to the presence of inner
active sites which cannot proceed the redox transitions completely
at higher scan rates of CVs, probably due to the diffusion effect of
proton within all three samples [22]. The decay of specific capaci-
tance with increasing current density was due to that at low
which enabled full access of active pores/sites on the electrode,
thereby resulting in high specific capacitances [23]. By considering
spherical particles with a mean diameter of 8 lm, as depicted in
Fig. 2, the CMO particles tend to agglomerate rather than forming
a monolayer. The tiny trigonal deposited on the microspheres sub-
strate leaded to a larger number of clusters, which might increase
the area of material exposed to the electrolyte. If the electrochem-
ical process taken place only at the surface of the microspheres
substrate exposed to the electrolyte, the charge would decrease
as the sea urchins structure of microspheres were collapsed [24].
This might also explain why a low current density usually exhibit
higher capacitance values than bulk composite electrodes.
As shown in Fig. 5, the specific capacitance of CMO-1 decreased
slowly during whole cycles and it reached 170 F g1 after 500
cycles, 58.6% of initial capacitance was retained. It was the three-
dimensional intercalation and redox reactions occurring in the
solid activated materials of electrodes during the charge/discharge
process, which might result in the alteration of crystal structure or
crystallinity of electrode materials. There was a problem that the
cycle life was poor because of materials disintegration due to the
significant volume expansion during the charge and discharge
cycling [25]. Thus, the delamination of active materials owing to
ion insertion led to the loss of adhesion of some active material
with the current collector [26,27]. The collapse of crystal structures
or microspheres of electrode materials during the charge/discharge
process might result in the relative instability of specific capaci-
tance of CMO-1 [28].
 W. Lei et al. / Composites Science and Technology 102 (2014) 82–86 85

the microsphere shaped particles were asymmetrically ranged

-1
0.6 a CMO-(1) 290 F g
-1
and there were tiny trigonal planar molecules uniformed scattered
CMO-(2) 172 F g onto the surface of microspheres like sea urchins. The decrease in
-1
capacitance with increasing scan rate was attributed to the pres-
Potential / V (vs. Hg/HgO)

0.4 CMO-(3) 127 F g

ence of inner active sites which could not be accessed at higher
0.2 scan rates. 58.6% of initial capacitance of CMO-1 was maintained
at current density of 1.0 A g1 after 500 cycles.
0.0

Acknowledgements
-0.2

This work was supported by the Open Project of State Key Lab-
-0.4
oratory Cultivation Base for Nonmetal Composites and Functional
Materials (11zxfk26) and the Postgraduate Innovation Fund Project
-0.6 by Southwest University of Science and Technology (14ycx002).
0 100 200 300 400 500 600
Also we are grateful for the help of Analytical and Testing Center
Time / s
of Southwest University of Science and Technology.

0.6 b -1
0.5 A g 348 F g
-1

-1 -1
1.0 A g 290 F g References
-1 -1
2.0 A g 187 F g
Potential / V (vs. Hg/HgO)

0.4
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