Activated carbon/manganese dioxide hybrid electrodes for high performance thin film

supercapacitors
Yunseok Jang, Jeongdai Jo, Hyunjung Jang, Inyoung Kim, Dongwoo Kang, and Kwang-Young Kim

Citation: Applied Physics Letters 104, 243901 (2014); doi: 10.1063/1.4884391

View online: http://dx.doi.org/10.1063/1.4884391
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 APPLIED PHYSICS LETTERS 104, 243901 (2014)

Activated carbon/manganese dioxide hybrid electrodes for high performance

thin film supercapacitors
Yunseok Jang,a) Jeongdai Jo, Hyunjung Jang, Inyoung Kim, Dongwoo Kang,
and Kwang-Young Kim
Department of Printed Electronics, Korea Institute of Machinery & Materials, Daejeon 305-343, South Korea
(Received 17 April 2014; accepted 9 June 2014; published online 17 June 2014)
We combine the activated carbon (AC) and the manganese dioxide (MnO2) in a AC/MnO2 hybrid
electrode to overcome the low capacitance of activated carbon and MnO2 by exploiting the large
surface area of AC and the fast reversible redox reaction of MnO2. An aqueous permanganate
(MnO4) is converted to MnO2 on the surface of the AC electrode by dipping the AC electrode into
an aqueous permanganate solution. The AC/MnO2 hybrid electrode is found to display superior
specific capacitance of 290 F/g. This shows that supercapacitors classified as electric double layer
C 2014 AIP Publishing LLC.
capacitors and pseudocapacitors can be combined together. V
[http://dx.doi.org/10.1063/1.4884391]

In recent years, supercapacitors have attracted consider-
able attention for their higher power density compared to
batteries and their higher energy density compared to com-
mon capacitors.1 These particular properties make them suit-
able for numerous applications in such diverse fields as
power electronics, military equipment, and hybrid electric
vehicles (HEVs).2,3 Supercapacitors can be classified into
two types depending on the charge storage mechanism.
Electric double layer capacitors (EDLCs) store the charge in
an electric field at the interface of electrodes and electrolytes.
Pseudocapacitors store the charge via the fast reversible re-
dox reaction at the interface of electrodes and electrolytes.
These two mechanisms depend on the nature of the electrode
material.3 Activated carbons (ACs) are the most widely used
electrode materials for EDLCs because of their large surface
area, low cost, nontoxicity, and easy processability.
However, their low energy storage capacity of about 100 F/g
is a disincentive for use as an electrode material for superca-
pacitors.4 Metal oxides such as RuO2, MnO2, CoOx, NiOx,
ZnO, SnO2, and Fe2O3 are the most widely used electrode
materials for pseudocapacitors because of their fast reversi-
ble redox reaction.5 Among these metal oxide materials,
RuO2 shows the best performance with a high specific capac-
itance (720 F/g),6 but it is expensive and toxic, which greatly
limits its commercialization. Of those materials, MnO2
appears to be the most promising materials for use in electro-
chemical capacitors due to its low cost and environmentally
friendly nature. However, MnO2 delivers a specific capaci-
tance of about 150 F/g, excluding the ultrathin MnO2 elec-
trode.6,7 Low capacitance of MnO2 results from poor
electronic conductivity (i.e., about 105 S/cm).8 Several
research groups such as Holze et al.,9 Wang et al.,10 Chen
et al.,11 Zhou et al.,12 and Long et al.7 have already con-
ducted preliminary studies on the carbon/MnO2 hybrid sys-
tem to overcome low conductivity of MnO2 by combining
the carbon with high electronic conductivity. As shown in
the supplementary material Table S1,13 they combined vari-
ous carbons (i.e., AC,9,14 activated carbon bead (ACB),10,15
a)
Author to whom correspondence should be addressed. Electronic mail:
yjang@kimm.re.kr.
graphite,11 carbon nanotube (CNT),12 and carbon aerogel
(CAG)7) with various MnO2 (i.e., nanorod,9 nanowire,10,12
powder,14 and film7,11). Their carbon/MnO2 hybrid systems
show a specific capacitance of about 110–375 F/g. We also
make the activated carbon/MnO2 hybrid system in this study.
In contrast to previous approaches, we used a functionalized
activated carbon (FAC) used in our previous work.16 Because
MnO2 film was made from aqueous solution containing so-
dium permanganate, functional groups such as hydroxyl and
carboxylic group on the FAC16 enhance the compatibility
between FAC and an aqueous permanganate solution and
make homogenous MnO2 layer on the FAC. And a relatively
high surface area of FAC maximizes the contact of FAC/
MnO2 hybrid electrode and the electrolyte solution, which
maximizes the redox reaction of MnO2 on FAC/MnO2 hybrid
electrode. As a result, it may help to maximize the capaci-
tance of the FAC/MnO2 hybrid electrode.
In this Letter, we propose a simple method for convert-
ing aqueous permanganate (MnO4) to MnO2 on the surface
of commercially available activated carbon by dipping the
activated carbon into an aqueous permanganate solution.
We used the FAC (specific surface area ¼ 1300 m2/g,
US Research Nanomaterials, Inc., coconut shell as raw mate-
rials) to offer a large surface area for the MnO2. As shown in
our previous work,16 polyvinyl phenol (PVP, Aldrich, Inc.)
and poly(melamine-co-formaldehyde) (PMF, Aldrich, Inc.)
were dissolved in propylene glycol methyl ether acetate
(PGMEA, Aldrich, Inc.) as the binder materials of the FAC
electrode. FAC electrodes with rectangular patterns covering
an area of 2  2 cm2 were deposited by spray-coating the
FAC solution on the SUS304 sheet. The coated FAC electro-
des were cross-linked for 30 min at 210  C on a hot plate.16
After the cross-linking of the FAC electrodes, a layer of
MnO2 was synthesized on the surface of the FAC electrode
using the simple method of dipping (i.e., soaking) it in an
aqueous solution containing sodium permaganate (NaMnO4).
After 0.1M NaMnO4 750 ll was put on the FAC electrode, it
was heated to 50  C in a jacked glass beaker and maintained
at that temperature with a water circulator (Jeio Tech, Inc.).
After the synthesis, the FAC/MnO2 hybrid electrode was
washed several times using distilled water, then blown with

0003-6951/2014/104(24)/243901/4/$30.00 104, 243901-1 C 2014 AIP Publishing LLC

V

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 243901-2 Jang et al.
FIG. 1. Specific weight plotted as a function of reaction time. Inset: digital
camera images (a) before and (b) after the MnO2 deposition of the FAC
electrode, (c) the homemade teflon reactor.
nitrogen gas, and dried at 200  C for 30 min to remove any
residual water.
Figure 1 shows specific weight (i.e.,
mass of FAC=MnO2 -mass of FAC
mass of FAC ) as a function of the reaction time
in the aqueous permanganate solution. As reaction time
increases, the specific weight increases. However, increasing
the reaction time to values above 180 min does not lead to a
further increase in the specific weight. There is no visible
discoloration of the permanganate solution during the depo-
sition. This shows the self-limiting deposition of MnO2 by
controlling the amount of FAC on the SUS304 substrate.7
From this result, MnO2 was synthesized on the FAC elec-
trode for 180 min using the homemade teflon reactor as
shown in Figure 1 inset. The color of the FAC electrode
turns from black to dark violet after the synthesis of MnO2
on the FAC electrode.
To confirm the deposition of MnO2 on the FAC elec-
trode, the morphology and distribution of MnO2 on the FAC
electrode were observed using scanning electron microscopy
(SEM), energy dispersive spectroscopy (EDS), and X-ray
diffraction (XRD). As shown in Figure 2, the SEM image of
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Appl. Phys. Lett. 104, 243901 (2014)
FIG. 3. X-ray diffraction patterns of the SUS304 substrate, the FAC elec-
trode on the SUS304 substrate and the FAC/MnO2 hybrid electrode on the
SUS304 substrate.
the FAC/MnO2 hybrid electrode is almost indistinguishable
from the SEM image of the FAC electrode. However, the
FAC/MnO2 hybrid electrode is clearly distinguishable from
the FAC electrode when viewed by EDS elemental mapping
and high resolution SEM, as shown in Figure 2. Mn elemen-
tal mapping clearly shows the deposition of MnO2. As can
be seen in Figure 2 inset, the FAC/MnO2 hybrid electrode
retains a porous texture after depositing the Mn oxide.
Figure 3 shows the XRD patterns of SUS304 substrate, FAC
electrode and FAC/MnO2 hybrid electrode on the SUS304
substrate. Though the peak position of SUS304 and FAC/
MnO2 hybrid electrode overlap at 66 , the three characteris-
tic peaks at 25 , 37 , and 66 (marked by arrow) confirm the
layered birnessite MnO2.17 These SEM, EDS, and XRD
results clearly show the deposition of MnO2 on the FAC’s
surface.
The electrochemical measurements of the FAC/MnO2
hybrid electrode and the FAC electrode were taken in a sin-
gle compartment at room temperature, using a three-
electrode quartz cell with an Ag/AgCl (3M KCl) reference
electrode and a Pt mesh counter electrode.18 A 1M Na2SO4
aqueous solution was used as the electrolyte. To characterize
the electrical performances of the FAC/MnO2 hybrid elec-
trode and the FAC electrode, a cyclic voltammogram (CV)
FIG. 2. Scanning electron microscopy
and energy dispersive spectroscopy
images: (a) the FAC electrode and (b)
the FAC/MnO2 hybrid electrode.
 243901-3 Jang et al.
and electrochemical impedance spectroscopy (EIS) were
studied using a Solartron 1470E system within the potential
voltage widow of 0.15–0.75 V for the FAC/MnO2 hybrid
electrode and 0.05–0.6 V for the FAC electrode at different
scanning rates (i.e., 5, 7.5, 10, 25, 50, 75, and 100 mV/s).
The cyclic voltammogram curves of FAC electrode are
indicative of an ideal double-layer capacitance, that of the
FAC/MnO2 hybrid electrode are not. (See supplementary
material Figure S1)13 It shows that the FAC/MnO2 hybrid
electrode has the Faradaic redox reaction, which comes from
the MnO2. As shown in Figure 4(a), the specific capacitance
of the FAC/MnO2 hybrid electrode19 was obtained by C
(F/g) ¼ (I dv)/(v V), where I is the response current density
(A/g) of the applied voltage (v), v is the scanning rate, and V
is the potential window of the FAC/MnO2 hybrid electrode.
The calculated specific capacitance of the FAC/MnO2 hybrid
electrode (i.e., mass loading: 0.54 mg/cm2) was about
290 F/g (or 157 mF/cm2 by C (F/g) ¼ (I dv)/(v V), where I is
the response current density (A/cm2) of the applied voltage
(v)) at a scanning rate of 5 mV/s in a 1M Na2SO4 electrolyte.
When it was calculated only by MnO2 mass from the FAC/
MnO2 hybrid electrode (i.e., mass loading: 0.27 mg/cm2), the
calculated specific capacitance was about 560 F/g. After
MnO2 was deposited on the FAC’s surface, the calculated
specific capacitance was about 2.7 times (or about 5.3 times
when calculated only by MnO2 mass) that of the FAC elec-
trode (i.e., 106 F/g). This high specific capacitance of the
FAC/MnO2 hybrid electrode results from the combination of
large surface area of the FAC (i.e., 1300 m2/g) and fast re-
versible redox reaction of MnO2.
To find the equivalent series resistance (ESR) of the
FAC/MnO2 hybrid electrode, the EIS was analyzed using
Nyquist plots. EIS were collected within a frequency range of
0.1 Hz–100 kHz for the FAC electrode and 0.01 Hz–100 kHz
for the FAC/MnO2 hybrid electrode, at a FAC voltage ampli-
tude of 10 mV. The Nyquist plots show the frequency
response of the electrode/electrolyte system and are a plot of
the imaginary component (Z00 ) of the impedance against the
real component (Z0 ).20 As shown in Figure 4(b) inset, the
ESR of the FAC electrode and the FAC/MnO2 hybrid elec-
trode can be obtained from the Z0 intercept of the Nyquist
plot and are similar (i.e., 0.58 and 0.48 X, respectively). The
ESR is extremely small compared to the previously reported
value (i.e., 2–3 X) in the MnO2.9 This low ESR results from
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Appl. Phys. Lett. 104, 243901 (2014)
high conductivity of FAC in the FAC/MnO2 hybrid. MnO2
has poor electronic conductivity about 105 S/cm, but FAC
has relatively high conductivity comparing MnO2.8 As shown
in Figure 4(b) inset, the diameter of the semicircle presents
the charge transfer resistance (Rct) in the FAC electrode and
the FAC/MnO2 hybrid electrode as 0.12 and 2.38 X, respec-
tively. The Rct of the FAC/MnO2 hybrid electrode is much
higher than that of the FAC electrode, which results from the
intercalation of alkali metal cation such as Naþ in the FAC/
MnO2 hybrid electrode for redox reactions. These intercala-
tion and redox reactions cause high Rct in the FAC/MnO2
hybrid electrode.
The supercapacitor was assembled in a 2032 coin cell by
placing a clean wipe (Bemcot wipers, Asahi Kasei Fibers
Corp.) as the separator and 1M Na2SO4 aqueous solution as
the electrolyte between two circular electrodes (i.e., two FAC
electrodes and two FAC/MnO2 hybrid electrodes, respec-
tively). As shown in the supplementary material Figure S2,13
the charge/discharge curves of FAC supercapacitor are almost
linear, which indicates that it has good electrical double-layer
properties. However, the charge/discharge curves of FAC/
MnO2 hybrid supercapacitor deviate slightly from ideal lin-
ear, and it can be attributed to different capacitive behavior of
FAC/MnO2 hybrid electrodes. Furthermore, the charge/dis-
charge curves of FAC/MnO2 hybrid supercapacitor exhibit
longer charge/discharge duration than one of the FAC super-
capacitor, indicating an enhancing charge storage capacity,
which is mainly ascribed to faradic capacitance of MnO2.10
The specific energy and power densities of the FAC superca-
pacitor and the FAC/MnO2 hybrid supercapacitor are exhib-
ited in the supplementary material S1.13
We demonstrated a method of overcoming the low
energy storage capacity of activated carbon and MnO2, by
combining the large surface area and relatively high conduc-
tivity of activated carbon with the fast redox reaction of
MnO2. Although various papers have reported that activated
carbon and MnO2 have a similar specific capacitance (i.e.,
about 100–150 F/g),6,7,16 the FAC/MnO2 hybrid electrode
exhibited superior specific capacitance of 290 F/g (or about
560 F/g when considering the MnO2 mass only) at a scanning
rate of 5 mV/s in a 1M Na2SO4 electrolyte. The large surface
area of the FAC provides a large redox reaction site for the
MnO2 on the FAC/MnO2 hybrid electrode, thus maximizing
its capacitance. This shows that supercapacitors classified
FIG. 4. (a) Specific capacitance of the
FAC electrode and the FAC/MnO2
hybrid electrode plotted at various
scanning rates. (b) Nyquist plots of the
FAC electrode and the FAC/MnO2
hybrid electrode. Inset: high frequency
region of Nyquist plots.
 243901-4 Jang et al. Appl. Phys. Lett. 104, 243901 (2014)

10
into EDLCs and pseudocapacitors are combined together
and this hybrid system constitutes a very useful method for
11
making high performance supercapacitors.
12
This study was supported by a grant (B55119-10-01-00/
13
KM3480/NK179D) from the cooperative R&D Program
funded by the Korea Research Council Industrial Science
and Technology, Republic of Korea.
14
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