Solvothermal synthesis of shape-controlled manganese oxide

materials and their electrochemical capacitive performances

Wen-Yin Ko,
a)
Lung-Jing Chen, Yu-Hung Chen, and Kuan-Jiuh Lin
b)
Department of Chemistry, National Chung-Hsing University, 40227 Taichung, Taiwan
(Received 15 May 2013; accepted 9 August 2013)
We present a simple and quick procedure for the one-pot synthesis of manganese oxides under
a basic solvothermal condition in the presence of cationic surfactants acting as the template in
a 2-butanol/water solution. Three-dimensional spinel-type MnO
2
microspheres composed of small
nanoparticles have been fabricated for the rst time using our method. Their corresponding
electrochemical performances in the applications of supercapacitor electrodes exhibit a good
specic capacitance (SC) value of ;190 F/g at 0.5 A/g and excellent SC retention and Coulombic
efciency of ;100% and ;95% after 1000 charge/discharge cycles at 1 A/g, respectively.
This suggests its potential applications in energy storage devices. Further, we demonstrate that this
solvothermal technique enables the morphological tuning of manganese oxides in various forms
such as schists, rods, bers, and nanoparticles. This work describes a rapid and low-cost technique
to fabricate novel architectures of manganese oxides having the desired crystal phase, which will
highly benet various supercapacitor applications.
I. INTRODUCTION
Over the past few decades, the synthesis of inorganic
nanomaterials with desired sizes and shapes has been in-
tensively pursued due to their unique electronic, magnetic,
optical, and catalytic properties with respect to multiple
fundamental and practical technological applications.
17
By means of further investigations on crystal growth kinet-
ics and shape evolution, nanomaterials with different archi-
tectures have been successfully fabricated in the solution
phase.
8,9
By means of the cooperative self-assembly of in-
organic species and surfactants, where the surfactant surface
aggregates as templates, the surfactant-assisted strategy is
known to be a general and efcient method for the prep-
aration of uniform inorganic nanomaterials with controllable
sizes and shapes. Recently, various nano- and microstruc-
tures of metal oxides (particularly those of MnO
2
, SiO
2
, and
V
2
O
5
) in the form of spheres, porous shapes, layers, tubes,
wires, and rods have been successfully fabricated by using
this approach.
1014
Manganese oxide (MnO
2
)an important functional metal
oxideand its derivative compounds offer the following
advantages: possibility of numerous attainable oxidation
states of Mn, cost-effectiveness, variety of electrochemical
behaviors, and environmental compatibility; because of
these advantages, they have been the subject of intense
investigations for a wide range of applications such as
catalysts, water purication, water splitting, molecular
absorption, and battery materials.
1517
In addition, they
also provide reversible Faradaic (redox) reaction, appro-
priate electrode potential window, and high theoretical
capacitance; therefore, they have been considered for
use as a promising electrode material in electrochemical
supercapacitors for yielding high power density, excel-
lent reversibility, and long cycle.
18,19
More recently,
manganese oxides with various crystal types, morphol-
ogies, and sizes have been systematically investigated
with great enthusiasm for their unique properties that
promote their performances in applications involving
energy storage (e.g., supercapacitors).
16,20,21
Among them,
MnO
2
structures with a spinel-type crystal phase of
three-dimensional (3D) interconnected tunnels have
been recently fabricated to obtain better capacitance
performances in aqueous solutions as they can offer a
larger number of electrolyte transport paths for electron
transfer and proton/cation diffusion, thereby allowing
enhanced charge transport efciency through the electro-
des during the charge/discharge process and leading to
better supercapacitive performances.
22
In addition, as we
know, hierarchical microspheres assembled from small
nanostructured particles have been reported to exhibit
distinctive propertiesdifferent from those of the constit-
uent nanoparticleswith various potential applications
23
;
therefore, the creation of such a shape of MnO
2
is of
great signicance. Several types of morphologies of
MnO
2
materials have been previously reported includ-
ing nanotubes, nanorods, nanowires, nanosheets, and
nanoparticles
10,21,2426
; however, to the best of our
knowledge, spinel-type MnO
2
microspheres (MS-MnO
2
)
constructed from small nanoparticles have not been
Address all correspondence to these authors.
a)
e-mail: wyko@dragon.nchu.edu.tw
b)
e-mail: kjlin@dragon.nchu.edu.tw
DOI: 10.1557/jmr.2013.238
J. Mater. Res., Vol. 29, No. 1, Jan 14, 2014 Materials Research Society 2013 107
investigated. In this paper, we report a simple and quick
procedure for the one-pot synthesis of manganese oxides
under a basic solvothermal condition in the presence of a
cationic surfactant acting as a template in a 2-butanol/water
solution for the direct synthesis of spinel-type MS-MnO
2
comprising small MnO
2
nanoparticles. The galvanostatic
charge/discharge and cyclic voltammetry (CV) measure-
ments in 1-MNa
2
SO
4
aqueous electrolytes demonstrate that
the MS-MnO
2
display an improved specic capacitance
(SC) of ;190 F/g at 0.5 A/g. Interestingly, a superior SC
retention of ;100% and a stable Coulombic efciency of
;95% after 1000 cycles can be obtained, yielding excellent
long-termcharge/discharge cycling stability. In addition, by
means of the solvothermal method, various morphologies
of manganese oxides including schists, rods, bers, and
nanoparticles can be easily obtained by changing the ratio
of 2-butanol and water and the nature of the precursors as
well as cation surfactants. Therefore, the proposed method
can provide a simplistic technique to fabricate MnO
2
having novel architectures.
II. EXPERIMENTAL SECTION
A. Materials
Cetyltrimethyl ammonium bromide (CTAB), manganese
sulfate (MnSO
4
H
2
O), and (6)2-butanol used in the study
were purchased from Sigma-Aldrich. Tetraethyl ammonium
bromide (TEA; 98%) and potassium permanganate
(KMnO
4
) were obtained from Alfa Aesar (UK) and
SHOWA (Japan), respectively. All these reagents were
used in the experiments without any further purication.
B. Preparation of MS-MnO
2
In a typical experiment, the MnO
2
precursor of the
TEAMnO
4
powder, which was presynthesized by using a
modied Brock method by the cation-exchange process that
involved the replacement of a hard potassium cation of the
permanganate precursor with a soft organic TEA cation,
27
was dissolved in 2 mL of deionized water to yield a
homogeneous solution; then, the solution was added to
10 mL of 2-butanol under stirring, where 2-butanol acted
as a solvent as well as a reducing agent and TEA served as
a template. The mixed solution was subsequently sealed
in a Teon-lined autoclave and heated to 120 C at the
rate of 5 C/min and maintained at this temperature
for 3 h. This aging process accompanied an increase
in the pH, from the neutral pH of the initial sols up to pH
of 1112. After the solvothermal process, the precip-
itates (brownish-black color) were collected by centri-
fugation and washed in sequence with deionized water
to remove the possible unreacted material. The nal
products of the MnO
2
materials, denoted as MS-MnO
2
,
were dried in vacuum desiccators at the ambient
temperature.
C. Characterization
Powder x-ray diffraction patterns were recorded by an
analytical XPert Pro MRD equipped with Cu K
a
as the
x-ray source (k 5 0.15418 nm). An operational voltage
and current of 45 kV and 40 mA, respectively, were used
and the data were collected stepwise in the 2h range of
1080 with a scan step of 0.033/s. A Zeiss Ultra Plus
eld emission scanning electron microscope (FE-SEM;
Germany) was used to examine the morphology and size
of the as-prepared MS-MnO
2
. A JEM 2010 high-resolu-
tion transmission electron microscope (HRTEM; Japan)
operated at 200 kV was used to examine the morphology
and lattice structure of the MS-MnO
2
. The samples used
in the HRTEM analysis were prepared by placing a drop
of the MS-MnO
2
aqueous suspension onto a copper grid
covered with a carbon lm and evaporating the drop in air.
Thermal gravimetric analysis (TGA) curves were obtained
using a Perkin-Elmer TGA-7lab instrument. In a typical
analysis, approximately 10 mg of the as-synthesized
MS-MnO
2
sample was analyzed in a platinum pan at a
heating rate of 5 C/min under nitrogen atmosphere with a
ow rate of 150 mL/min.
D. Electrochemical measurements
All the electrochemical measurements were carried out
in a 1-M Na
2
SO
4
aqueous electrolyte solution at room
temperature by using the 672A electrochemical system
(CH Instruments, Austin, TX) with a three-electrode cell
that was composed of a MS-MnO
2
-based electrode as the
working electrode, a Pt lm as the counter electrode,
and an Ag/AgCl electrode as the reference electrode.
The working electrodes were fabricated using a mixture
of 70 wt% MS-MnO
2
powder with 25 wt% carbon black
and 5 wt% poly(tetrauoroethylene) (PTFE) binder; sub-
sequently, a small amount of alcohol was added into the
mixture to form a clay-like paste. The paste was then
incorporated in nickel foam (1 1 cm), dried in a vacuum
oven at room temperature, and followed by a compression
treatment under a pressure of 6000 kg/cm
2
for 5 min to
ensure that the active material completely adhered to the
nickel foam. The CV measurements were performed
between 0 and 0.9 V (versus Ag/AgCl) for scan rates in
the range of 2100 mV/s. The charge/discharge properties
were examined galvanostatically in the potential range of
00.9 V (versus Ag/AgCl) at current densities of 0.5 and
1 A/g. The SC of the fabricated electrodes was calculated
according to the relation C (F/g) 5 IDt/DVm, where I
denotes the constant discharge current, Dt is the discharge
time, mis the mass of the active materials (g), and DV is the
total potential difference (V).
III. RESULTS AND DISCUSSION
Figures 1(a)1(e) show the FE-SEM images of the
typical samples of the MnO
2
material prepared using our
W-Y. Ko et al.: Shape-controlled manganese oxide materials
J. Mater. Res., Vol. 29, No. 1, Jan 14, 2014 108
approach, revealing the morphological evolution with
the reaction time. A series of impressive microspheres
were observed at the reaction times in the range of 36 h
[Figs. 1(b)1(c)]; when the reaction time was above 12 h, a
needle-like morphology of manganese oxides was gener-
ated [Fig. 1(d)]. Notably, the population of such shapes
increased with an increase in the reaction time, whereas
the population of the microspheres decreased concomi-
tantly. After 48 h, nearly all the initial microspheres were
converted into such needle-like structures, as shown in
Fig. 1(e). These observations clearly show that the MnO
2
composites with a needle-like architecture evolve from the
initial microspheres. From the above observations, we can
show that the optimal condition for the production of attrac-
tive MS-MnO
2
can be obtained under a solvothermal condi-
tion at a heating temperature of 120 C and a gel time of 3 h.
A large number of microspheres can be clearly seen in
the FE-SEM image shown in Figs. 2(a) and 2(b), with the
size distribution ranging from 0.5 to 4.5 lm [Fig. 2(c)].
The corresponding TGA prole, shown in Fig. 3(a), in-
dicated that the thermal decomposition curve of MS-MnO
2
involved three weight-loss steps: the rst weight loss of
4.9% occurred below 145 C, which was due to the evap-
oration of physically adsorbed water molecules in
MS-MnO
2
, followed by a second weight loss of 34.4%
between 145 and 230 C, which was caused by the release
of the TEA
1
species according to the Hofmann degrada-
tion reaction; in the third step, a weight loss of 4.3% in the
temperature range of 230500 C was demonstrated,
which was associated with the combustion of remaining
TEA and the phase transformation of MnO
2
to Mn
2
O
3
and
Mn
3
O
4
.
22,28
Importantly, a weight loss of 43.6% after
calcination of MS-MnO
2
was observed, and the weight
loss of sample at temperatures 145230 C was signicantly
greater than that at any other heating temperature, which
suggests that the TEA-based template played a signicant
FIG. 1. FE-SEM images of the as-synthesized MnO
2
materials under solvothermal conditions and heating at 120 C for (a) 1 h, (b) 3 h, (c) 6 h,
(d) 12 h, and (e) 48 h.
W-Y. Ko et al.: Shape-controlled manganese oxide materials
J. Mater. Res., Vol. 29, No. 1, Jan 14, 2014 109
FIG. 2. (a, b) FE-SEM image and (b) size distribution of the as-synthesized MS-MnO
2
using the solvothermal method and heating at 120 C for 3 h.
FIG. 3. (a) TGA data and (b) XRD pattern of the as-synthesized MS-MnO
2
using the solvothermal method and heating at 120 C for 3 h.
FIG 4. (a) TEM image of the MS-MnO
2
fabricated using the solvothermal process and heated at 120 C for 3 h. (b) HRTEM image of the fringe
region of an individual MS-MnO
2
sample, indicating that MS-MnO
2
was constructed from sphere-like nanoparticles surrounded by surfactants.
(c) HRTEM image of an individual sphere-like nanoparticle of MS-MnO
2
taken along the [011] axis and its corresponding Fourier-transformed
diffraction pattern (inset), which can be indexed as the spinel-type structure of MnO
2
.
W-Y. Ko et al.: Shape-controlled manganese oxide materials
J. Mater. Res., Vol. 29, No. 1, Jan 14, 2014 110
role in the formation of the spinel MnO
2
microspheres.
To understand the crystalline structures of the as-prepared
MS-MnO
2
material, its corresponding XRD measurement
was carried out, as shown in Fig. 3(b). All the peaks can be
indexed as pure spinel-type MnO
2
(JCPDS no. 44-0992),
where it can be shown that the three main peaks at
2h 5 18.73, 36.14, and 65.09 can be correspondingly
indexed to the (111), (311), and (440) reections of the
spinel-type MnO
2
; this indicates that the as-prepared prod-
ucts are phase-pure spinel-type MnO
2
microspheres.
To further examine the conguration of these microstruc-
tures, the HRTEMimages were recorded. From Fig. 4(b), it
is revealed that the MS-MnO
2
material is composed of
numerous spherical nanoparticles with an average diameter
of 5 nm; interestingly, it is distinctly visible that these
nanoparticles are surrounded by a TEA-based template.
The corresponding clear lattice fringes and fast-Fourier-
transformed diffraction pattern data of the individual
small spherical nanoparticles of MS-MnO
2
, as shown in
Fig. 4(c), indicate their efcient crystallization; addition-
ally, two clear lattice fringes with basal distances of 2.02
and 1.86 can be observed, which are consistent with
the (400) and (331) planes of the spinel-phase MnO
2
,
respectively. These results indicate that the spinel-type
MS-MnO
2
microstructures are, in fact, built from these
small nanoparticles that are spontaneously assembled
through the assistance of the TEA-based template,
nally forming a 3D network of spherical microstruc-
tures (Fig. 5). This is the rst time that the spinel-type
MnO
2
with the shape of a microscopic sphere has been
fabricated; further, we believe that it can offer additional
electrolyte-transport paths for electron transfer and
proton/cation diffusion due to its 3D interconnected
FIG. 5. Schematic illustration of the solvothermal formation of the as-
prepared spinel-type MS-MnO
2
.
FIG. 6. FE-SEM images of the synthesized MnO
2
materials through the developed solvothermal method and heating at 120 C for 3 h under different
experimental conditions and changing the ratio of 2-butanol and water, nature of the precursors, and cation surfactants. See also SI, Table 1.
W-Y. Ko et al.: Shape-controlled manganese oxide materials
J. Mater. Res., Vol. 29, No. 1, Jan 14, 2014 111
tunnel crystal phase and unique microspherical archi-
tecture constructed from small nanoparticles. This architec-
ture permits enhanced charge-transport efciency through
the electrodes during the charge/discharge process and leads
to better supercapacitive performance. The considerable
impact of the morphology on the electrochemical properties
of MnO
2
materials has been pointed out
29
; therefore, much
effort has been expended in the controllable synthesis of
MnO
2
materials with desired and uniform structures for
energy storage applications. In this paper, we also employed
the proposed one-pot solvothermal method for the successful
synthesis of MnO
2
with different architectures, including
nanoparticles, bers, rods, and schists, by changing the ratio
of 2-butanol and water and the nature of the precursors as
well as the cation surfactants, as shown in Fig. 6.
For testing the electrochemical performances of
the spinel-type MS-MnO
2
materials, galvanostatic
charge/discharge measurements and CV measurements
were carried out in 1-M Na
2
SO
4
aqueous electrolytes by
means of a conventional three-electrode system (Fig. 7).
Broad redox peaks were obtained in the spinel-type
MS-MnO
2
which illustrated that the intercalation/
deintercalation of protons and electrolyte cations of Na
1
ions into the bulk material accompanied by a Faradaic
reaction occurred in the spinel-type MS-MnO
2
materials
[Fig. 7(a)]
30
; the Faradaic reaction can be a benecial
effect by the combination of surface-based double-layer
capacitance and volume-based pseudocapacitance, lead-
ing to boost the energy current density of the 3D transport-
pathway-based spinel-type MS-MnO
2
electrode and
resulting in improved capacitance performances. The SC
values of the spinel-type MS-MnO
2
were estimated through
galvanostatic charge/discharge cycling at 0.5 A/g in 1-M
Na
2
SO
4
aqueous solution, as shown in Fig. 7(b). It can be
clearly observed that the spinel-type MS-MnO
2
exhibits
a good SC value (190 F/g); signicantly, the obtained SC
values are competitive with those of other reported spinel-
type MnO
2
materials, including the slightly truncated
nanoparticles (21 F/g at 20 mV/s),
31
interconnected nano-
bers (241 F/g at 5 mV/s),
22
and particles with polyhedral
shapes (53 F/g at 10 mA/cm
2
).
32
The cycling stability
can be an area of concern for the practical applications
of supercapacitor electrodes; therefore, an endurance
test at a constant current density of 1 A/g for 1000 cycles
was conducted for the as-synthesized spinel-type MnO
2
electrode [Figs. 7(c) and 7(d)]. Almost 100% of the
initial capacitance was retained and the corresponding
Coulombic efciency remained signicantly high at ;95%
FIG. 7. (a) Representative CV curves (third curve) of the as-prepared spinel-type MS-MnO
2
material at a scan rate of 5 mV/s in 1-M Na
2
SO
4
aqueous solution using a three-electrode system with Ag/AgCl as the reference electrode and Pt wire as the counter electrode. (b) Galvanostatic
charge/discharge cycling tests recorded at a constant current density of 0.5 A/g for MS-MnO
2
in 1-MNa
2
SO
4
aqueous electrolyte. (c) Galvanostatic
charge/discharge curves and (d) relationship of the SC and Coulombic efciency with the number of cycles for the spinel-type MS-MnO
2
electrode
measured at a current density of 1 A/g in 1-M Na
2
SO
4
aqueous electrolyte.
W-Y. Ko et al.: Shape-controlled manganese oxide materials
J. Mater. Res., Vol. 29, No. 1, Jan 14, 2014 112
in the entire cycling process. Such results indicate that the
proposed spinel-type MS-MnO
2
material with 3D transport
tunnels has the potential application as a supercapacitor
electrode that can be used in long charge/discharge cycling
without any signicant microstructural modication or
phase changes in the crystals of the MS-MnO
2
material
and without any dissolution of the active material of the
electrode during the charge/discharge processes.
IV. CONCLUSION
In this paper, we have described the one-pot synthesis
of a 3D network of spinel-type MS-MnO
2
with the size
distributions in the range of 0.54.5 lm; these microspheres
are built from small MnO
2
nanoparticles with average sizes
of 5 nm assembled using the cationic surfactant as the
template. Such spinel-type MnO
2
microspheres have been
fabricated for the rst time by means of a solvothermal
method in a 2-butanol/water solution under a basic condi-
tion. CV and galvanostatic charge/discharge measurements
were carried out to characterize the fabricated MS-MnO
2
material in the form of a supercapacitor electrode; its SC
value was calculated to be ;190 F/g. Furthermore, ap-
proximately 100% of the SC retention and approximately
95%of the Coulombic efciency were obtained after 1000
charge/discharge cycles, exhibiting its excellent long-term
stability. Signicantly, the proposed solvothermal method
can enable the morphological tuning of MnO
2
, which has
been successfully used to obtain architectures of schists,
rods, bers, and nanoparticles. Therefore, this method can
possibly offer an attractive technique toward synthesizing
other metal oxides having the form of novel morphologies
that can widen the range of its applications in biosensors,
catalysis, fuel cells, and electronic nanodevices.
ACKNOWLEDGMENTS
We gratefully acknowledge the nancial support
from National Science Council of Taiwan (Grant Nos.
NSC-101-2113-M-005-014-MY3 and NSC 101-2628-
M-007-006). We also appreciate Dr. Lih J. Chen at
National Tsing Hua University, Taiwan, for providing
technical assistance in HRTEM measurements.
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Supplementary Material
Supplementary materials can be viewed in this issue of the Journal of Materials Research by
visiting http://journals.cambridge.org/jmr.
W-Y. Ko et al.: Shape-controlled manganese oxide materials
J. Mater. Res., Vol. 29, No. 1, Jan 14, 2014 114