Electrochimica Acta 169 (2015) 317–325

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Design and influence of mass ratio on supercapacitive properties

of ternary electrode material reduced graphene oxide@MnO2@
poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate)
De Yan a, * , Yanhong Li a , Ying Liu a,1, Renfu Zhuo a , Baisong Geng a , Zhiguo Wu a ,
Jun Wang a , Pingyuan Ren a , Pengxun Yan a,b
a
School of Physical Science and Technology, Lanzhou University, 730000, China
b
State Key Laboratory of Solid Lubrication, Institute of Chemistry and Physics, Chinese Academy of Science, Lanzhou 730000, China

A R T I C L E I N F O A B S T R A C T

Article history: Design and fabrication of ternary hybrid material is an effective method to promote the performance of
Received 21 March 2015 supercapacitor electrode materials, because hybrid material does not only benefit from the advantages of
Received in revised form 11 April 2015 each component but also utilizes the synergetic effect between them. Reduced graphene oxide (rGO)
Accepted 13 April 2015
@MnO2@PEDOT-PSS (poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate)) ternary material is
Available online 15 April 2015
designed and fabricated. Electrochemical tests reveal that sample GMP20 (rGO 8 wt%, MnO2 72 wt% and
PEDOT-PSS 20 wt%) exhibits the highest high specific capacitance of 217.8 F g
1, excellent rate capability
Keyword:
and the best cycle stability with 93.7% capacitance retention after 1500 cycles at 2 A g
1. To investigate the
ternary hybrid material
MnO2
synergetic effect, electrochemical impedance spectroscopy (EIS), complex capacitance analysis and
synergetic effect complex power analysis are employed. The mass ratio of components has a great influence on
complex capacitance analysis supercapacitve performance of the hybrid electrode by affecting the synergetic effect. Results show that
complex power analysis GMP20 has well matched relaxation time, smallest impedance modulus and time constant, thus it fully
utilizes the synergetic effect and exhibits excellent supercapactive performance.
ã 2015 Elsevier Ltd. All rights reserved.

1. Introduction capacitance by forming electric double layer (EDL) at the

As the depletion of fossil fuel and deterioration of climate are
attracting great attention, the developments of alternative
sustainable and renewable green energy sources and energy
storage/conversion devices are urgently required [1,2]. Super-
capacitors, also known as electrochemical capacitors, have great
potential applications in portable electronics, memory backup
systems, hybrid electric vehicles, and industrial scale power and
energy management [3], due to their high power density and
excellent cycle stability. Two energy storage mechanisms and three
kinds of electrode materials are involved in supercapacitor
electrode materials: carboneous materials [4–6], such as activated
carbon, carbon nanotubes (CNTs) and graphene, can deliver
* Corresponding author at: School of Physical Science and Technology, Lanzhou
University, South Tianshui Road 222#, Lanzhou 730000, People’s Republic of China.
Tel.: +86 931 8912719; fax: +86 931 8913554.
E-mail address: yand@lzu.edu.cn (D. Yan).
1
Present address: College of Materials Science and Engineering, Taiyuan
University of Technology, 030024, China.
electrode/electrolyte interface; transitional metal oxides [7–9],
such as MnO2, RuO2 and Co3O4, and conductive polymers (CPs)
[10–12], such as PEDOT-PSS, polyaniline (PANI) and polypyrrole
(PPy), can deliver capacitance by pseudocapacitive contribution
and fast and reversible Faradaic contribution.
MnO2 is generally considered as one of the most promising
materials for high performance supercapacitors, not only for its
high theoretical specific capacitance but also for its low cost,
environmental benignity, and natural abundance [13,14]. If one Mn
atom in MnO2 is assumed to store one electron, the specific
capacitance of MnO2 can reach as high as 1370 F g
1 [13]. However,
the poor conductivity of MnO2 (10
5 ~ 10
6 S cm
1) [14,15] and
conglomeration occurring at high mass loading [16] often results in
limited performance, and thus hindered its wide applications. To
overcome its disadvantages, hybrid electrode materials of MnO2
nanostructures incorporated with carboneous materials or
conductive polymers are intensively studied, such as CNTs@MnO2
[17–19], graphene@MnO2 [20,21], MnO2@PPy [22], MnO2@PEDOT
[23]. The performances of these hybrid electrodes are improved
because the hybrid material does not only benefit from the high

http://dx.doi.org/10.1016/j.electacta.2015.04.078
0013-4686/ ã 2015 Elsevier Ltd. All rights reserved.
318 D. Yan et al. / Electrochimica Acta 169 (2015) 317–325
conductivity of the carboneous materials or conducting polymers
and the high specific capacitance of MnO2, but also benefit from
the synergistic effect between them.
The synergetic effect is of significant importance to hybrid
materials, because it is closely related to their rate capability and
maybe further affects their specific capacitance and cycle life. To
effectively utilize the synergetic effect, the structure of hybrid
material should be rationally designed and the mass ratio of its
components should be elaborately chosen. Design and fabrication
of ternary hybrid electrode materials is an exciting strategy and
effective method to further promote the performance of MnO2
based electrode. Recently, Li et al. [24] demonstrate an electro-
polymerization of pyrrole on CNT sponge and then hydrothermally
treated with KMnO4 to obtain CNT@PPy@MnO2 ternary material.
The specific capacitance of this material is 325 F g
1 at 2 mV s
1
and 90.2% capacitance is retained after 1000 cycles at 100 mV s
1.
They also obtained a specific capacitance of 241 F g
1 from
CNT@MnO2@PPy. A MnO2/CNT/CP ternary film electrode was also
designed and fabricated by Hou et al. [25], and a highest specific
capacitance of 425 F g
1 was obtained at low MnO2 loading. A
commercial supercapacitor separator supported graphite/PEDOT/
MnO2 material was obtained through two steps of electrodeposi-
tion by Tang et al. [26], and a specific capacitance of 195.7 F g
1 is
obtained at a 0.5 A g
1. Liu et al. [27] prepared PEDOT-PSS-PANI-
MnO2 ternary electrode materials by interfacial polymerization of
aniline (ANI) into PEDOT-PSS and subsequent electrodeposition of
MnO2 on PEDOT-PSS-PANI matrix. A highest specific capacitance of
61.5 F g
1 was obtained and capacitance retention of 68% at
100 mV s
1 for 500 cycles. As we can see, on one hand, high mass
loading and mass ratio of MnO2, which is of great importance for
practical applications, often result in capacitance fading. On the
other hand, the performance of some ternary materials is not as
good as some binary materials, which might be caused by their
irrational structure and poor utilization of synergetic effect.
Here, we report the design and fabrication of a ternary
supercapacitor electrode material based on our previous work
[20]. The schematic illustration of the ternary material rGO@M-
nO2@PEDOT-PSS (GMP) and its fabrication procedure are shown in
Fig. 1. This design has several advantages. On one hand, the porous
nanosheet arrays with interconnected MnO2 nanosheets greatly
shorten the diffusion path of ions and electrons in MnO2 and thus
contribute to the rate capability of the electrode. On the other
hand, the interconnected nanosheets form a self-supporting
structure to inhibit the conglomeration of MnO2. RGO mainly
serves as the conductive component to promote the conductivity
of the electrode. The excellent interfacial contact between MnO2
and rGO can significantly reduce the interfacial contact resistance
Fig. 1. Schematic illustration of fabrication procedure and structure of the rGO@MnO2@PEDOT-PSS (GMP) ternary hybrid material. GM was firstly prepared by hydrothermal
process with rGO and KMnO4 solution as reactants. Then it was added to PEDOT-PSS solution with calculated mass ratio and subjected to sonication to obtain GMP ternary
hybrid material.
and thus improves the conductivity of electrode. PEDOT-PSS,
possessing high conductivity, great ductility and processing
simplicity, is a polymer mixture of two ionomers. PEDOT is a
p-type doped conjugated polymer, while the sulfonyl groups in PSS
serve as “counter-ions” of PEDOT [12]. Wrapped by PEDOT-PSS, the
conductivity deep inside the pores of the MnO2 nanosheet arrays
and the connection resistance between adjacent units in electrode
is greatly improved. Therefore, the advantages of rGO (high
conductivity and specific area, excellent electrochemical and
mechanical stability), MnO2 (high specific capacitance) and
PEDOP-PSS (high conductivity, great ductility and processing
simplicity) are fully utilized in this rationally designed ternary
material.
The synthesis, characterization and supercapacitive proper-
ties of rGO@MnO2 (GM) were reported by our group previously
[20]. Here, we mainly focus on the influence of components'
mass ratio on supercapacitive property of the ternary material.
More importantly, since the synergetic effect was often
mentioned but rarely given any substantial proof in literature,
we demonstrated the analysis of synergetic effect based on EIS
analysis, complex capacitance analysis and complex power
analysis.
2. Experimental
2.1. Materials and methods
All the reagents are analytical grade and used without further
purification. Graphene oxide (GO) was prepared from powdered
flake graphite (400 mesh) by a modified Hummers method as
described previously [28]. For chemical conversion of GO to rGO,
50 mg GO powder was mixed with 200 mL of water, 2 mL of
hydrazine solution (20 wt% in water, BASF) in a 250 mL round-
bottom flask and the pH of the suspension was adjusted to 10 using
sodium hydroxide solution (Tianjin Chemical Company), and then
refluxed at 90  C for 24 h. Finally, the solid was washed with
distilled water and dried at 80  C for 12 h in a vacuum oven.
RGO powder (10 mg) was dispersed in deionized (DI) water
(30 mL) by ultrasonic vibration for 2 h, then KMnO4 powder
(30 mg) was added into above rGO suspension and stirred by
magnetic bar for 15 min. Subsequently, the total solution was
transferred into a stainless-steel autoclave with a capacity of
40 mL, sealed and heated at 100  C for 12 h. Finally, the autoclave
was cooled to room temperature naturally. The resultant product
was collected by centrifugation and repeatedly washed with
deionized water. The final product was dried in a vacuum at 60  C
overnight. The mass ratio of MnO2: rGO was about 9:1 according to
 D. Yan et al. / Electrochimica Acta 169 (2015) 317–325
thermogravimetric analysis (TGA, see Supporting Information of
our previous reports reference 20).
Calculated amount of PEDOT-PSS (Aldrich) and rGO@MnO2
were mixed in DI water. After sonicated for 30 min, the
homogeneous colloidal solution was dried at 60  C for 24 h in a
vacuum oven to obtain powder GMP ternary material.
Four samples with PEDOT-PSS/GMP mass ratios of 10 wt%,
20 wt%, 30 wt% and 40 wt% were fabricated and named GMP10,
GMP20, GMP30 and GMP40, respectively, according to PEDOT-
PSS percentage. The MnO2 mass ratios are about 81 wt%, 72 wt%,
63 wt% and 54 wt% in GMP10, GMP20, GMP30 and GMP40,
respectively.
2.2. Characterization
The crystallographic information of the products was investi-
gated by X-ray diffraction (XRD, Shimadzu X-ray diffractometer
6000, Cu Ka radiation) with a scan rate of 10 min
1. Raman
spectra were measured on a Laser Raman spectroscopy (HORIBA
Jobin Yvon LabRAM HR800) with 532 nm line of an Ar ion laser as
an excitation source. Morphologies of the samples were charac-
terized by field emission scanning electron microscopy (FESEM,
Hitachi S4800) and transmission electron microscopy (TEM,
Tecnai-G2-F30). Thermogravimetric analysis (TGA) data were
collected on a thermal analysis instrument (Setarm TGDTA92A)
with a heating rate of 5  C min
1 in an air flow.
2.3. Preparation of electrodes
The fabrication of working electrode was carried out as follows.
The as-prepared composite, carbon black and poly tetrafluoro
ethylene (PTFE) were mixed in a mass ratio of 85:10:5 and
dispersed in ethanol. Then the resulting mixture was coated onto
the nickel foam substrate (1 cm  1 cm) with a spatula, which was
followed by drying at 90  C for 12 h in a vacuum oven. The mass
loadings are 4.6, 6.3, 8.1 and 6.9 mg for GMP10, GMP20, GMP30 and
GMP40, respectively.
2.4. Electrochemical Tests
All of the electrochemical tests were carried on an electro-
chemical workstation (CHI 660E) in a three-electrode mode using
the as-prepared samples, a Pt foil and a saturated calomel
electrode (SCE) as the working electrode, counter electrode and
reference electrode, respectively, with 1 M Na2SO4 solution as the
electrolyte at room temperature. Cyclic voltammetry (CV) tests
were done between 0 and 1.0 V (vs. SCE) at different scan rates of 5,
Fig. 2. (a)XRD patterns and (b) Raman spectrum of rGO, MnO2, rGO@MnO2 (GM) and four ternary hybrid material GMP10, GMP20, GMP30 and GMP40.
319
10, 20, 50, and 100 mV s
1. Galvanostatic charge/discharge (GCD)
curves were measured in the potential range of 0-1.0 V (vs. SCE) at
different current densities of 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7 A g
1.
Specific capacitances of the electrode were calculated according to
the discharge curve using the equation C ¼ IDt=ðmDVÞ, where
C (F g
1) is the specific capacitance, I (A) is charge-discharge
current, Dt (s) is the discharge time, m (g) is the mass based on
MnO2, and DV (V) is the potential drop in the galvanostatic
discharge process. Electrochemical impedance spectroscopy (EIS)
measurements were carried out in the frequency range from
0.01 Hz to 1 MHz at open circuit potential with an AC perturbation
of 5 mV.
3. Results and discussion
As shown in Fig. 1, to fabricate the as-designed GMP material,
rGO [28] prepared from graphite oxide are added to KMnO4
solution, after hydrothermal reaction, porous nanosheet arrays of
birnessite type MnO2 (bir-MnO2) are uniformly grown on rGO.
The rGO@MnO2 (GM) binary material was then wrapped by
conductive polymer PEDOT-PSS to form ternary GMP material. In
this work, four samples with PEDOT-PSS:GMP ratios of 10 wt%,
20 wt%, 30 wt% and 40 wt% are fabricated and named GMP10,
GMP20, GMP30 and GMP40 according to PEDOT-PSS percentage,
and MnO2 ratios of them are about 81 wt%, 72 wt%, 63 wt% and
54 wt%, respectively.
3.1. Structure and morphology characterization
XRD patterns of rGO, MnO2, GM and four GMP samples are
shown in Fig. 2a. The four peaks at 12.3 , 24.8 , 36.6 and 65.5  can
be ascribed to the (0 0 3), (0 0 6), (1 0 1) and (11 0) plane of
bir-MnO2 (JCPDS NO.86-0666) which has a layered structure
consisting of edge-shared [MnO6] octahedral layers with a
diagnose interlayer spacing of about 0.72 nm. With increasing
PEDOT-PSS ratio, the relative intensity of MnO2 peaks is gradually
reduced. For GMP40, a wide peak shows up between 15 –30 ,
which is caused by amorphous PEDOT-PSS [29]. However, no peaks
from rGO are shown, which may because of its low mass ratio.
To confirm the existence of rGO in GMP, Raman spectrum is
employed and results are shown in Fig. 2b. RGO shows two peaks,
D band at 1360 cm
1 corresponds to breathing modes of rings or
K-point phonons of A1g symmetry, and G band at 1601 cm
1
represents the in-plane bond-stretching motion of the pairs of
C sp2 atoms (the E2g phonons) [30,31]. Three Raman bands located
at 490, 576 and 636 cm
1 are in good accordance with the
previously reported three major vibration features of bir-MnO2 at
320 D. Yan et al. / Electrochimica Acta 169 (2015) 317–325
500 ~ 510, 575 ~ 585, and 625 ~ 650 cm
1 [32,33]. The peak at 576
and 636 cm
1 correspond to the E2g (n3) stretching vibration mode
of Mn

O

Mn in the basal plane of [MnO6] sheets and the A1g (n2)
symmetric stretching vibration of Mn

O bond of [MnO6]
octahedron groups, respectively [34,35]. The two rGO bands and
three MnO2 bands are all clearly identified in the GM binary hybrid
material and thus further proving the existence of rGO in GMP.
When GM is wrapped by PEDOT-PSS, the two bir-MnO2 bands of
at 495.7, 575.9 cm
1 might be supressed, and only one Raman band
of MnO2 at 636 cm
1 shows up in the four GMP spectrums. The four
peaks at 1354, 1423, 1497 and 1571 cm
1 come from PEDOT-PSS
and correspond to the Cb-Cb stretching mode of the cyclic bond,
Ca = Cb symmetric stretching mode and Ca0 = Cb0 asymmetric
stretching mode of the PEDOT chains, and the vibration of the
quinoid structure [36–40], respectively. The two peaks at 1354 and
1571 cm
1 from PEDOT-PSS are very close to the D band
(1360 cm
1) and G band (1601 cm
1) of rGO, but they are definitely
not from rGO, because the two bands from rGO already cannot be
identified at 10 wt% of PEDOT-PSS, and the relative intensity of the
four peaks increase with increasing PEDOT-PSS ratio. Meanwhile,
the peak from MnO2 at 636 cm
1 slowly decreases with increasing
PEDOP-PSS ratio, indicating the binary GM is gradually wrapped by
PEDOT-PSS.
Fig. 3a shows the smooth surface of rGO after chemical
reduction. Hydrothermally treated with KMnO4 solution at 100  C
for 12 h, both sides of rGO are uniformly covered by MnO2 as shown
in Fig. 3b. Closer observation (Fig. 3c, d) reveals that the MnO2
coating is actually porous nanosheet arrays with interconnected
bir-MnO2 sheets of about 3-5 nm (Fig. 3e), and the sheets grew
perpendicular to the rGO surface. The interplanar space of a bir-
MnO2 sheet shown in Fig. 3e is about 0.7 nm, which agrees to the
diagnostic interplanar space of bir-MnO2. After wrapped by
different amount of PEDOT-PSS, four GMP samples are obtained.
For GMP10, the sheet array morphology of MnO2 can be clearly
seen from Fig. 3f, which indicate GM is not fully covered by PEDOT-
PSS. With increasing ratio of PEDOT-PSS from 10 wt% to 40 wt%
(Fig. 3f-i), the MnO2 nanosheet array morphology gradually
disappears and only PEDOT-PSS can be seen in FESEM images of
GMP40.
3.2. Supercapacitive performance
To investigate the reversibility of the electrochemical process
involved in GMP, cyclic voltammetry (CV) of the four GMP samples
is performed in 0-1.0 V in 1 M Na2SO4 solution in a three electrode
Fig. 3. FESEM images of (a) rGO, (b) and (c) GM, (f) GMP10, (g) GMP20, (h) GMP30, (i) GMP40. TEM (d) and HRTEM (e) image of GM.
system. Fig. 4a shows the representative CV curves (GMP20 is
presented in Fig. 4a, the other electrodes can be seen in Supporting
Information Fig. S1) of the GMP samples at various sweep rates and
Fig. 4b-f show the CV curves comparison of the four samples at a
certain scan rate. In the as-designed GMP material, PEDOT-PSS is a
p-type doped conducting polymer with capacitance reduction
under negative polarization at about
0.3 V due to the loss of hole
concentration, but exhibits no redox peak under positive
polarization in 0-1.0 V [12]. Bir-MnO2 can offer capacitance
through the intercalation/deintercalation of protons and alkali
cations in the bulk and the absorption/desorption of alkali cations
at the surface [41]. However, the CV curves of all samples exhibit no
redox peaks, and the quasi rectangular and symmetric shape
indicates the fast and reversible Faradaic reactions and ideal
capacitive behavior of them. At higher scan rates, the protons and
alkali cations may not have enough time to enter the deep body of
the material and the accumulation of charge at the interface may
result in the deviation of CV curve from rectangular [41]. Since the
CV curve area is proportional to the specific capacitance of the
electrode, it is worth noticing that the CV curve areas of GMP10 and
GMP20 are almost the same and both of them are the largest at
various scan rates (Fig. 4b-f), indicating large specific capacitance
of them. For PEDOT-PSS ratio larger than 20 wt%, the CV curve area
gradually decreases, reflecting relatively small specific
capacitance.
To investigate the energy storage capability of the GMP
samples, galvanostatic charge/discharge (GCD) tests are carried
out in 0-1.0 V, and the typical GCD curve (GMP20 is presented in
Fig. 5a, the other electrodes can be seen in Supporting Information
Fig. S2) and comparison of GCD curve are shown in Fig. 5a-d at 0.1,
1 and 3 A g
1 (comparison at other current densities can be seen in
Supporting Information Fig. S3). Although EDL capacitance and
electrochemical capacitance from MnO2 and PEDOT-PSS both
contribute to the energy storage of the GMP samples, their GCD
curves still show linear potential-time variation and highly
symmetric characteristics (Fig. 5b), indicating fast and reversible
Faradaic reactions, which agrees well with CV results. The IR drop
increases with increasing current density (Fig. 5c, d). It can be
ascribed to the internal resistance of the system related to the
contact resistance between current collector and electrode
material, solution resistance and charge transfer resistance [41].
At a current density of 0.1 A g
1 (Fig. 5b), GMP10 and GMP20 have
almost the same longest charge/discharge time, and that of
GMP20 becomes far longer than GMP10 with increasing current
density (Fig. 5c, d). Meanwhile, the charge/discharge time for
 D. Yan et al. / Electrochimica Acta 169 (2015) 317–325 321

Fig. 4. CV curves of (a) GMP20 at various voltage sweep rates, and CV curve comparation of GMP10, GMP20, GMP30 and GMP40 at (b) 5 mV s
1, (c) 10 mV s
1, (d) 20 mV s
1, (e)
50 mV s
1 and (f) 100 mV s
1, respectively.

GMP30 and GMP40 with higher PEDOT-PSS ratio is shorter than
that of GMP20 at a certain current density. As the discharge time is
proportional to specific capacitance, this reveals that GMP20 has
larger specific capacitance than other GMP samples.
To investigate the rate capability of the four GMP samples,
specific capacitances of them calculated from discharge curves are
shown in Fig. 5e. The specific capacitance of GMP20 decreases very
slowly with increasing current density while that of GMP10,
GMP30 and GMP40 decreases sharply, which implies that
GMP20 has the best rate capability of them. Since the rate
capability is closely related to the utilization of synergetic effect,
this implies that GMP20 has the best utilization of the synergetic
effect. The specific capacitances are 210.0, 217.5, 200.9 and
140.0 F g
1 for GMP10, GMP20, GMP30 and GMP40, respectively,
at a current density of 0.1 A g
1. Here, a highest specific capacitance
of 217.8 F g
1 is obtained from GMP20 with a very high MnO2 ratio
of about 72 wt% which is higher than most of the previous reports.
For comparison, specific capacitance of PEDOT-PSS-PANI-MnO2
prepared by Liu [27] is 61.5 F g
1, and that of MnO2/CNT-rGO
synthesized by Lei et al. [42] reaches 193 F g
1 at 0.2 A
1 with
MnO2 ratio not exceeding 41 wt%. Specific capacitance of
CNTs@MnO2@PEDOT-PSS prepared by Hou et al. [25] reaches

Fig. 5. GCD curves of (a) GMP20 at various current densities, and GCD curve comparasion of GMP10, GMP20, GMP30 and GMP40 at (b) 0.1 A g
1, (c) 1 A g
1 and (d) 3 A g
1. (e)
Specific capacitances at different current densities calculated by discharge plot, and (f) cycling stability of the four GMP samples tested by 2000 GCD cycles at 2 A g
1.
322 D. Yan et al. / Electrochimica Acta 169 (2015) 317–325

Table 1
Comparison of our results to some previous reports.

Sample MnO2 ratio 1

Specific capacitance (F g
1) Reference

PEDOT-PSS-PANI-MnO2 – 61.5 [27]

graphene@MnO2@PEDOT-PSS – 380 [14]
graphite/PEDOT/MnO2 11.1 wt% 195.9 [26]
MnO2/PPy/TSA 2 21.4 wt% 376 [43]
CNT@PPy@MnO2 39.1 wt% 325 [24]
MnO2/CNT-rGO 41 wt% 193 [42]
PPy/MnO2/CNTs 45.6 wt% 402.7 [44]
MnO2/GNS/CNTs 3 48 wt% 132 [45]
CNTs@MnO2@PEDOT-PSS 60 wt% 200 [25]
Si@C/MnO2 60 wt% 117.2 [46]
GMP20 72 wt% 217.8 This work

“–”means the authors did not mention it. Some of the results are directly obtained from literature, and others are calculated according to the authors’ description.
TSA: short for P-toluenesulfonic acid.
GNS: short for graphene nanosheets.

200 F g
1 at 5 mA cm
2 with 60 wt % MnO2 and 10 wt% PEDOT-PSS.
In literature, reports of ternary hybrid material with very high
specific capacitance usually has low MnO2 ratio. For comparison,
Table 1 shows the performances of some previously reported
MnO2 based ternary electrodes. For example, carbon nano-
tube@polypyrrole@MnO2 with 39.1 wt% MnO2 prepared by Li
et al. [24] shows a specific capacitance of 325 F g
1 at a scan rate of
2 mV s
1. Yu et al. [14] prepared graphene@MnO2 flowerlike
spheres@PEDOT-PSS ternary electrode by electrodepositon and
subsequent “dip and dry” process, and a highest specific
capacitance of 380 F g
1 was obtained, however, they did not
mention the mass ratio of its components. Commercial super-
capacitor separator supported graphite/PEDOT/MnO2 with 11.1 wt
% MnO2 prepared by Tang et al. [26] shows a specific capacitance of
195.9 F g
1 at 0.5 A g
1. However, high MnO2 mass ratio and mass
loading is of great importance for practical application. In this
work, GMP20 exhibits high specific capacitance of 217.8 F g
1 with
high mass loading of 6.3 mg and high MnO2 ratio of 72 wt%, which
can be ascribed to the rationally designed microstructure and
excellent conductivity between MnO2 nanosheets and different
units offered by PEDOT-PSS wrapping.
Cycling performance is crucial to evaluate electrode materials
and excellent cycling stability is required for practical
supercapacitor applications. The cycling stability of the four
GMP samples is tested by GCD cycles at a current density of
2.0 A g
1 in a potential window of 0-1.0 V. Fig. 5f compares the
cycling stability of them and shows that 66.2%, 85.0%, 71.4%, and
63.7% capacitance is retained after 2000 GCD cycles for GMP10,
GMP20, GMP30 and GMP40, respectively. The capacitance
retention of GMP20 still reaches 93.7% after 1500 cycles. Thus, it
is revealed that GMP20 exhibits excellent cycling stability
compared with other samples.
3.3. Synergetic effect analysis
To understand the electrochemical behavior of the four GMP
samples and investigate the synergetic effect, EIS of them are
collected at open circuit potential with an AC perturbation of
5 mV in the frequency range of 0.01Hz-1 MHz, and the results
are shown in Fig. 6a. Those Nyquist plots can be divided into
three parts: (1) a high-frequency intercept, which gives the
combinational resistance of ionic resistance of electrolyte,
intrinsic resistance of substrate, and contact resistance at the
active material/current collector interface; (2) A straight line
inclining about 45 to the real axis for GMP40, indicating the
diffusion controlled process in the low frequency region. While

Fig. 6. (a) Nyquist plots, (b) real part and (c) imaginary part of the complex capacitance versus frequency. (d) and (e) Bode plots, (f) normalized reactive power and active
power of the complex power versus frequency of the four electrodes GMP10, GMP20, GMP30 and GMP40.
 D. Yan et al. / Electrochimica Acta 169 (2015) 317–325
GMP10, GMP20 and GMP30 behave more closely to an ideal
capacitor with the inclination angle slightly lower than 90 ; (3) a
high to medium frequency region with one or two depressed
semicircles. Generally speaking, a standard semicircle described by
Debye equation [47,48] implies one relaxation time corresponding
to one relaxation process, and the diameter of the semicircle gives
the charge transfer resistance of this relaxation process. However, a
depressed semicircle which implies a group of relaxation times is
usually seen in most cases, because many relaxation processes take
place at the same time in an electrode and the corresponding
relaxation times of them are close to each other. Here, from the
insert of Fig. 6a, we can recognize two depressed semicircles for
GPM30 and GMP40, two including one incomplete for GMP10, and
one for GMP20, which is further proved by equivalent circuit
fitting. The Nyquist plots of GMP10, GMP30 and GMP40 can be well
fitted by the a two time constants circuit R(RC)(RC)QW written in
circuit description code (CDC), but this is a bad fitting for GMP20
(see Supporting Information, Table S1). The two depressed
semicircle reveal two groups of relaxation times corresponding
to two groups of relaxation processes take place in bir-MnO2 and
PEDOT-PSS. As we know, one of the most important reasons for the
design and fabrication of hybrid material is to utilize the
synergistic effect between its components. However, for GMP10,
GMP30 and GMP40, the two depressed semicircles implying the
two groups of relaxation times of the relaxation processes
happened in bir-MnO2 and PEDOT-PSS are of relatively big
difference, in other words they do not well match, and so their
utilization of synergistic effect are not obvious. While for GMP20,
only one depressed semicircle is shown, which exhibits that the
two groups of relaxation times of the processes happened in
bir-MnO2 and PEDOT-PSS are sufficiently close to each other, so
they are well matched and the synergetic effect is obvious.
Moreover, it is also obvious that GMP20 has the smallest
impedance modulus seen from Fig. 6a, which may also relate to
its synergetic effect.
Only well matched relaxation time is not enough for a
supercapacitor electrode, it is also strongly required that the time
constant of the electrode should not be too long, which means the
electrode should response quickly to external signals. To
investigate this point, complex capacitance analysis of the four
electrodes is employed based on EIS. Considering the electrode as
a whole system, the complex capacitance C ðvÞ can be written as
[49,50]:
C ðvÞ ¼ C 0 ðvÞ
jC 00 ðvÞ

Z 00 ðvÞ
C 0 ðvÞ ¼
vjZðvÞj2
Z 0 ðvÞ
C 00 ðvÞ ¼
vjZðvÞj2
where C 0 ðvÞ and C 00 ðvÞ are the real and imaginary part of the
complex capacitance C ðvÞ,v ¼ 2pf is the angular frequency, Z 0 ðvÞ
and Z 00 ðvÞ are the real and imaginary part of the complex
impedance Z ðvÞ, and jZðvÞj is the impedance modulus. The results
of the real and imaginary part of the complex capacitance versus
frequency are shown in Fig. 6b and c. Real part capacitance C 0 ðvÞ
corresponds to the capacitance of the electrode and decreases
sharply with increasing frequency which is often seen in literature
[51–53]. Imaginary part capacitance C 00 ðvÞ, corresponds to
irreversible energy dissipation and represents a relaxation
process during ion transport [54–56], reaches its maximum value
323
at the so-called relaxation frequency f 0 [52], defining a time
constant t 0 ¼ 1=ð2pf 0 Þ. t 0 is deemed as a dielectric relaxation time
characteristic of the whole system, and the rate capability of the
electrode can be quantitatively related to the time constant [50].
Smaller time constant implies better rate capability and quicker
response to external signals. The time constant obtained from
Fig. 6c is 10.8, 7.4 and 9.0 s for GMP10, GMP20 and GMP30,
respectively, and that of GMP40 is the largest of them and beyond
the frequency range of measurement. To give more details and for
the convenience of comparison, the relaxation frequency data
points are also marked with arrows in Nyquist plot (Fig. 6a) and
Bode plots (Fig. 6d and e). Obviously, the time constant of GMP20 is
the smallest of them, which together with Nyquist plots analysis
well explain why GMP20 has the best rate capability, which agrees
well with the results of Fig. 5f.
Complex power analysis is also employed from the electrical
point of view. Under AC perturbation, the power can be expressed
in its complex form as [49,50,57]:
SðvÞ ¼ PðvÞ þ jQ ðvÞ
PðvÞ ¼ vC 00 ðvÞjDV rms j2
Q ðvÞ ¼
vC 0 ðvÞjDV rms j2
where PðvÞ and Q ðvÞ are the real part (active power) and the
imaginary part (reactive power) of the complex power SðvÞ,
pffiffiffi
DV rms ¼ DV max = 2 and DV max is the maximum amplitude of the
AC signal. The normalized active power ðjPðvÞj=jSðvÞjÞ and reactive
power ðjQ ðvÞj=jSðvÞjÞ of the four ternary electrodes versus
frequency are shown in Fig. 6f. As we know, a resistor only has
the active power and an ideal capacitor only has the reactive
power, and an electrode of a supercapacitor behaves like a resistor
at high frequency and a capacitor at low frequency. Thus, Q ðvÞ
decreases and PðvÞ increases with increasing frequency, and the
intersection occurs when jPðvÞj=jSðvÞj ¼ jQ ðvÞj=jSðvÞj at the
frequency f 0 [58], corresponding to a phase angle of 45 . The
intersection frequency defines the frontier between the resistive
and the capacitive behavior. Time constants t 0 determined from
the intersection frequency by t 0 ¼ 1=ð2pf 0 Þ are 6.1, 5.4, 5.5 and
8.2 s for GMP10, GMP20, GMP30 and GMP40, respectively. These
time constants are slightly different from that obtained from
Fig. 6c, which may be caused by the distribution of relaxation time
of these electrodes. The two time constants of GMP20 determined
by the two methods are the closest of them. This also reflects
GMP20 has two groups of well-matched relaxation times and best
utilization of synergetic effect, which agrees well with the previous
analysis of Nyquist plots. Despite the small value difference of time
constants, their variation trend is the same, still the smallest time
constant is obtained from GMP20, and that of GMP30, GMP10,
GMP40 increasing in sequence. Thus, the complex power analysis
further explains the excellent rate capability and reveals the best
utilization of the synergistic effect for GMP20 from the electrical
point of view.
Therefore, EIS, complex capacitance analysis and complex
power analysis are employed to investigate the synergetic
effect of the as-designed GMP material. We can see that the
synergetic effect is strongly affected by the mass ratio of its
components for the as-designed structure and it may be often
the case for other hybrid structures. It is also revealed that
GMP20 with the optimal mass ratio has well matched
relaxation time, smallest impedance modulus and time
constant, thus it fully utilizes the synergetic effect and exhibits
excellent supercapactive performance.
324 D. Yan et al. / Electrochimica Acta 169 (2015) 317–325
4. Conclusion
A design of rGO@MnO2 nanosheet array@PEDOT-PSS ternary
supercapacitor electrode material is proposed and fabricated. This
design does not only utilizes the advantages of rGO (high
conductivity and specific area, excellent electrochemical and
mechanical stability), MnO2 (high specific capacitance) and
PEDOT-PSS (high conductivity, great ductility and processing
simplicity), but also utilizes the synergetic effect between them.
Electrochemical tests show that the sample GMP20 possesses the
highest specific capacitance of 217.8 F g
1 with a high MnO2 ratio of
72 wt%, excellent rate capability and the best cycle stability with
93.7% and 85.0% capacitance retention after 1500 and 2000 GCD
cycles at a current density of 2 A g
1. EIS, complex capacitance
analysis and complex power analysis are employed to investigate
the synergetic effect, and result reveals that the synergetic effect is
strongly affected by the mass ratio of its components. The
relaxation times of relaxation process in bir-MnO2 and PEDOT-
PSS are well matched in GMP20, and GMP20 also has the smallest
impedance modulus and time constant. These imply that GMP20
fully utilizes the synergetic effect compared with other samples.
Furthermore, this design is universal, for rGO, MnO2 and PEDOT-
PSS can be replaced by other carboneous materials, transitional
metal oxides and conducting polymers.
Acknowledgements
This work is financially supported by the National Natural
Science Foundation of China (Grant No. 11204114 and No.
11004098), the basic scientific research business expenses of the
central university and Open Project of Key Laboratory for
Magnetism and Magnetic Materials of the Ministry of Education,
Lanzhou University (LZUMMM2014013).
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.
electacta.2015.04.078.
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