OPEN MnO2 Nanorods Intercalating

SUBJECT AREAS:
Graphene Oxide/Polyaniline Ternary
ELECTRONIC PROPERTIES
AND DEVICES Composites for Robust High-Performance
ELECTRONIC MATERIALS

Supercapacitors
Received
17 March 2014 Guangqiang Han1, Yun Liu1, Lingling Zhang1, Erjun Kan2, Shaopeng Zhang1, Jian Tang1 & Weihua Tang1

Accepted
1
4 April 2014 Key Laboratory of Soft Chemistry and Functional Materials (Ministry of Education of China), Nanjing University of Science and
Technology, Nanjing 210094, People’s Republic of China, 2Department of Applied Physics, Nanjing University of Science and
Published Technology, Nanjing 210094, P. R. China.
28 April 2014

New ternary composites of MnO2 nanorods, polyaniline (PANI) and graphene oxide (GO) have been
prepared by a two-step process. The 100 nm-long MnO2 nanorods with a diameter ,20 nm are
Correspondence and
conformably coated with PANI layers and fastened between GO layers. The MnO2 nanorods incorporated
requests for materials ternary composites electrode exhibits significantly increased specific capacitance than PANI/GO binary
should be addressed to composite in supercapacitors. The ternary composite with 70% MnO2 exhibits a highest specific capacitance
W.H.T. (whtang@mail. reaching 512 F/g and outstanding cycling performance, with ,97% capacitance retained over 5000 cycles.
njust.edu.cn) The ternary composite approach offers an effective solution to enhance the device performance of
metal-oxide based supercapacitors for long cycling applications.

S
upercapacitor or electrochemical capacitors, featuring high power density, long cycle life, fast charge and
discharge rates1–7, have attracted tremendous attention in energy storage. During the last decades, different
kinds of materials have been studied as possible supercapacitor electrodes, namely, carbonaceous materials,
conducting polymers and transition metal oxides8–11. Among them, transition-metal oxides such as RuO212–13,
NiO14,15 and MnO216–20, are the most widely used electrode materials thanks to their large capacitance, high
surface area and relatively good electrical conductivity. Compared to other transition-metal oxides, MnO2 is
generally regarded as the most promising one for the next generation of supercapacitors because of its ideal
capacitor performances, good cycle stability, low cost and environmental friendliness21,22. However, the poor
electrical conductivity and densely packed structure limit its application in the development of high-performance
supercapacitors23. For this purpose, some efforts have been made to develop nanostructured MnO2/carbonace-
nous materials (ca. graphene, carbon nanotube or carbon nanofibers) based binary composites24,25 or their ternary
composites with conducting polymers26–31. The carbonaneous materials or conductive polymers act as not only 3-
dimensional (3-D) scaffold but conductive wrappings to enhance the specific capacitance and cycle stability of the
electrodes fabricated with these composites. Our recent studies have shown that conductive polymer coatings
prepared via in-situ redox process can greatly improve the conductivity and specific area of the resulted
composites32,33.
As one of the most appealing carbon materials, graphene features superior electrical conductivity, excellent
mechanical flexibility, and high thermal and chemical stability34,35. Compared with pristine graphene, graphene
oxide (GO) has good dispersion in many solvents, particularly in water, and this is important for solution-
processing and further derivatization36,37. Though some losses in electrical conductivity when converting from
graphite, GO has demonstrated to be a potential substrate to improve the conductivity and stability of MnO238. To
enhance the performance of MnO2-graphene composite electrodes, conductive materials were further incorpo-
rated to form ternary composites composites to achieved significantly increased specific capacitance and cycling-
stability from the ternary composites based supercapacitors26–31. By depositing 5–10 nm MnO2/polyaniline
(PANI) nanoparticles onto sulfonated graphene nanosheets, the composite (sGMOPANI) based two-electrode
cell showed an electrochemical capacitance of 276 F/g at 1 A/g current density30. The ternary composites of
graphene/MnO2 nanostructures with carbon nanotube or poly(3,4-ethylenedioxythiophene):poly(styrenesulfo-
nate) showed ,20% or 45% increased capacitance than graphene/MnO2 composites, with the highest value as

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Figure 1 | Illustration for formation of GOPM nanocomposites: (a) in-situ polymerization of aniline, (b) dispersion of graphene oxide sheets and MnO2
nanorods in solution by ultrasonication and self-assembly during the second aniline polymerization.

high as ,380 F/g achieved28. The nanostructure of graphene/MnO2 synthesis of PANI. However, the sharp peak at 2h 5 11.0u, corres-
seems to be important for the performance and stability of the capa- ponding to its (002) plane for pure GO42, almost disappeared, which
citors. Moreover, the overall specific capacitance of MnO2/carbon is attributed to the increase in inter-space distance of graphene layer
composites is generally limited to 250 F/g due to the relatively low due to intercalation of PANI/MnO2 between GO sheets.
weight loading of MnO2 on carbon surface (usually less than 64 The Raman spectra of GOPM and pristine components are shown
wt.%)25. We were intrigued whether the high loading of MnO2 in Fig. 3b. It can be clearly seen that both GOPM-46 and MnO2
nanorods into binary composites of conductive polymers and solu- samples feature a sharp peak at 640 cm21, corresponding to the
tion-exfoliated GO nanosheets can improve the electron transport Mn-O vibration perpendicular to the direction of the MnO6 octa-
and contribute to the energy storage of the whole composite film to hedral double chains of MnO243. The Raman-active peaks at
achieve robust high-performance supercapacitors. 1350 cm21 and 1600 cm21, corresponding to the in-plane bond-
We report herein the successful fabrication of graphene oxide- stretching motion of C sp2 atoms (G band) and the breathing modes
polyaniline-MnO2 ternary composites, where MnO2 nanorods were of or of benzenoid rings of GO (D-band), were significantly sup-
incorporated to intercalate PANI/solution-exfoliated GO nano- pressed in intensity for GOPM-46 sample. The typical peaks for
sheets. MnO2 nanorods were thus fastened onto GO sheets via PANI also weakened in GOPM, mainly due to its low content in
PANI layer (Fig. 1). The PANI layer has several advantages: (1) to the hybrid composite.
anchor MnO2 nanorods onto the surface of GO, (2) to prevent GO To confirm the XRD and Raman results, the compositions and the
sheets and MnO2 nanorods from stacking/aggregating; (3) to valence states of GOPM were further characterized with XPS and the
improve the charge transfer between GO and MnO2 and (4) to results are shown in Fig. 3c–f. The peak ,284.6 eV (for C 1s) ori-
prevent MnO2 from falling off GO sheets during cycling electro- ginating from the graphitic sp2 carbon atoms and the peak at
chemistry. The composites exhibited greatly improved capacitive 531.9 eV corresponding to O1s in C–OH bond are observed for
performance than GO-MnO2 and GO-PANI composites. The tern- GO (Fig. 3c). The existence of C, N, O, Mn in GOPM can be con-
ary composites with 70 wt.% MnO2 delivered a highest specific firmed from Fig. 3d. For GOMP, the XPS peaks of N 1s (Fig. 3e) are
capacitance of 512 F/g at 0.25 A/g current density, with the capa- further decomposed into three Gaussian peaks with binding energies
citive retention of as high as 97% observed after 5100 cycles. of 398.6 (-N5), 399.7 (-NH-) and 400.1 (-N1-)37. The peak at
400.1 eV is assigned to the quinoid amine and nitrogen cationic
Results radical (N1), while the one at 398.6 eV (5N–) is due to benzenoid
Preparation and characterization of ternary composites. The amine. The Mn 2p spectrum is analyzed in Fig. 3f. Both Mn 2p3/2
ternary composites were prepared with a two-step protocol as peak at 643.0 eV and Mn 2p1/2 peak centering at 654.5 eV are clearly
shown in Fig. 1. After a first step of coating solution-exfoliated GO observed, which are in good agreement with the energy splitting of
nanosheets39 with polyaniline, MnO2 nanorods40 were allowed to the standard spectrum of MnO244. The peak-to-peak separation
self-assembly onto the GO sheets and then wrapped by in-situ between Mn 2p1/2 and Mn 2p3/2 level is 11.5 eV, which is approxi-
prepared polyaniline coatings in the second step. The MnO2 (in mately the same value as that literature for MnO245.
weight ratio) content in the ternary composites was determined The morphologies of dry MnO2, GO-PANI and GOPM-46 are
with thermogravimetric (TGA) analysis (Figure 2). Hence, the as- observed with FESEM and TEM (Fig. 4,5). Pristine MnO2 nanorods
prepared MnO2-PANI-GO composites (GOPM) are designated as
GOPM-20, GOPM-46 and GOPM-70, meaning that mass
percentage of MnO2 in the composites is about 20%, 46% and
70%, respectively.
Typical X-ray diffraction (XRD) pattern of as-prepared hierarch-
ical porous GOPM-46 and free MnO2, PANI and GO are shown in
Fig. 3a. It can be seen that the XRD pattern of GOPM is similar to
those of free MnO2 and PANI, indicating that the MnO2 particles
have been well immobilized by PANI onto GO substrate. All of the
major reflections [2h 5 21.2u (120), 28.0u (310), 37.5u (131), 42.5u
(300), 59.0u (160) and 69.7u (003)] in the XRD pattern can be indexed
to the orthorhombic phase of c-MnO2 with lattice constants a 5 6.36
Å, b 5 10.15 Å and c 5 4.09 Å (JCPDS 14-644), confirming that c-
MnO2 crystalline phase forms in the synthesis, which is in good
agreement with the reported patterns for c-MnO241. The broad peak
centered at about 25.3u, attributing to the diffraction of (110) plane of
the as-formed PANI crystalline phase, suggests the successful Figure 2 | TGA curves of GO, PANI, MnO2 and GOPM.

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Figure 3 | (a) X-ray diffraction patterns and (b) Raman spectra of GO, MnO2, PANI, GOPM-46; XPS spectra of (c) GO, (d) GOPM-46 and N 1s in (e)
GOPM-46 and (f) Mn 2p in GOPM-46.

with a length of 200 nm grow into nanospheres with diameters ran- by 30% (Fig. 5d). Nevertheless, the intimate contact between GO
ging from 300 to 600 nm (Fig. 4a). The in-situ prepared PANI self- sheets and PANI wrapped MnO2 nanorods with different lengths
assembled on GO sheets like a broccoli composed numerous of small can be clearly observed from both SEM and TEM images, which is
flower buds with a diameter of 50 nm (Fig. 4b). When MnO2 nanor- important for improving electrical conductivity. A close look at the
ods were introduced to GO-PANI system, GOPM hybrid composites SEM image of ternary composites, GOPM-70 boasts increased por-
feature a porous yet densely packed structure (Fig. 4c), with GO osity than GOPM-46, which can be confirmed by BET measurement.
layers intercalated by porous interpenetrating networks of PANI- The GOPM-70 and GOPM-46 exhibit a surface area of 91.37 and
wrapped MnO2 nanorods. PANI functions as both protecting coat- 73.65 m2/g, respectively, much higher than that for GO-PANI
ing for MnO2 nanorods to avoid aggregation and adhesive to fasten (,36.92 m2/g). The increased surface area can be explained with
GO sheets and MnO2 nanorods into densely packed structure. the constitution of the ternary composites. Since PANI has the equi-
Exfoliated GO sheets feature transparent wrinkled tulle in TEM valent mass with GO, more MnO2 nanorods were uncovered by
image (Fig. 4d), while PANI formed a compact layer on top of GO PANI with the increase of MnO2 content. More porous structure
sheets for GO-PANI composites. was therefore obtained to present higher surface area before heavy
A close look at the TEM images of GOPM (Fig. 4f and Fig. 5c,d), aggregation of MnO2 occurs.
one would clearly observed the existence of MnO2 nanorods, featur-
ing a length less than 100 nm and a diameter ,20 nm. With the Capacitive performance of ternary composite. The capacitive
content of MnO2 nanorods increasing from 46% to 70% in the com- performance of GO, MnO2, GO-PANI, GO-MnO2 and GOPM
posites, the dimensions of MnO2 nanorods was observed to increase were evaluated by cycle voltammetry (CV) and galvanostatic

Figure 4 | FE-SEM images of (a) dried pristine MnO2, (b) GO-PANI and (c) GOPM-46; TEM images of (d) GO sheets, (e) GO-PANI and (f) GOPM-46.

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Figure 5 | FE-SEM image of (a) GOPM-46 and (b) GOPM-70, TEM image of (c) GOPM-46 and (d) GOPM-70.

charge/discharge techniques in 1 M Na2SO4 solutions. Fig. 6a shows 1, 2 and 4 A/g. As illustrated in Fig. 7a, all the curves exhibit an
the CV curves of GOPM-46 at different scan rates. At low scan rates equilateral triangle shape, indicating high reversibility of the hybrid
(#50 mV/s), GOPM-46 exhibits slight redox peaks, suggesting the materials during charge/discharge process. The charging/dischar-
pseudocapacitance feature of GOPM. The asymmetrical CV curves ging process took longer time at lower current density, which is
can be attributed to the combined double-layer and pseudocapacitive attributed to the sufficient insertion or release of Na1 during the
contributions to the total capacitance. The high CV currents indicate charging/discharging process. The specific capacitance (C) of the
the high conductivity and low internal resistance for GOPM as the electrode can be calculated according to equation: C5 It/mV, where
electrode material. Fig. 6b shows CV curves of GO, MnO2, GO- C is the specific capacitance (F/g), I is the charge-discharge current
PANI, GO-MnO2 and GOPM at 50 mV s21, where GOPM-46 (A), t is the discharge time (s), V is the potential window (V), m is the
exhibits the highest capacitance than other electrodes. This can be mass of active material in the working electrode (g)46. The galvano-
attributed to the unique porous structure of hybrid GOPM, which static charge/discharge curves of MnO2, GO-MnO2, GO-PANI,
effectively prevent the self-aggregation of GO sheets and MnO2 GOPM at 0.25 A/g current density are compared in Fig. 7b. The
nanorods. More importantly, the hybrid GOPM with PANI-coated specific capacitance of GOPM (409 F/g) is much higher than that
MnO2 nanorods intercalated GO nanosheets affords higher sur- of MnO2 (150 F/g), GO-MnO2 (162 F/g) and GO-PANI (20 F/g) at
face area to provide better conductive paths for fast electron the same current density. Same trend is observed for GOPM when
transportation. further increasing current density in the range of 0.25,4 A/g
The galvanostatic charge/discharge curves of GOPM in 1 M (Fig. 7c), indicating the robustness of the as-prepared hybrid
Na2SO4 solution were carried out at a current density of 0.25, 0.5, GOPM as electrode materials.

Figure 6 | (a) CV curves of GOPM-46 at scan rate of 10, 20, 30, 40, 50 and 100 mVs-1; (b) CV curves of GO, MnO2, GO-PANI, GO-MnO2 and GOPM-46
at scan rate of 50 mV s-1.

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Figure 7 | Galvanostatic charge/discharge curves of (a) GOPM-46 at different current density; (b) MnO2, GO-MnO2, GO-PANI and GOPM-46 at
0.25 A/g current density; (c) specific capacitance curves of MnO2, GO-MnO2 and GOPM composites at different current densities; (d) capacitance
retention of GOPM-70 over cycling times.

The specific capacitance of GOPM is found to increase with the The electrochemical properties of GOPM were further evaluated
content of MnO2 in the composite, as shown in Fig. 7c. The specific with electrochemical impedance spectroscopy (EIS). The impedance
capacitance of GOPM-70 (412 F/g), GOPM-46 (306 F/g) and spectra of composite electrodes before and after 3000 cycles were
GOPM-20 (252 F/g) is about 1,2 times higher than that of MnO2 measured in the frequency range of 100 kHz–0.1 Hz at open circuit
(130 F/g) and GO-MnO2 (156 F/g) at the current density of 1 A/g. potential with an AC perturbation of 5 mV (Fig. 8). Theoretically, an
Further increase of MnO2 content over 90%, however, leads to ideal Nyquist impedance plot features a semicircle over the high
decreased capacitive performance, e.g., the GOPM with 92% MnO2 frequency region and a linear part in the low frequency range. The
delivered a specific capacitance of 382 F/g at 1 A/g current density. larger semicircle observed for the electrode corresponds to higher
The specific capacitance of 412 F/g at 1 A/g for GOPM-70 is much interfacial charge-transfer resistance (Rct) for the layer on the elec-
better than graphene/MnO2 (78 wt.% MnO2) binary composite trode, attributed to the poor electrical conductivity of the materials.
under similar testing conditions25. This improvement may be And the straight line of the Nyquist plot corresponds to the resistance
explained with the contribution of conductive PANI in facilitating (Rs) resulting from ion diffusion/transport, i.e., the more vertical line
charge transport and energy storage. Compared with the ternary is indicative of an electrode more close to an ideal capacitor47. The
composite sGMOPANI30, our composite with MnO2 nanorods equivalent series resistance (ESR) of pristine MnO2, GO-PANI,
exhibited 11% improved capacitance in supercapacitors at same cur- GOPM-46 and GOPM-70 obtained from the intersection of the
rent density of 1 A/g. The specific capacitance of GOPM decreases Nyquist plot at the x-axis is 2.6, 0.7, 1.8, and 1.6 V, respectively.
with current density, with ,62% capacitance retained for GOPM-70 Considering the similar morphology of GO-PANI and GOPM, the
when the current density increased from 0.25 A/g to 4 A/g. difference in ESR of electrodes can be attributed to the different
The electrochemical stability of GOPM-70 nanocomposites was conductivities of electrode materials. The smaller ESR of GOPM than
investigated at 4 A/g current density. As shown in Fig. 6d, the capa- GO-PANI suggests the decreased charge transfer resistance in the
citance of GOPM electrode retained about 97% of the highest capa- presence of MnO2 nanorods as core48. The high resistance of ion
citance even after continuous galvanostatic charge/discharge process transfer in GO-PANI would be attributed to high charge density,
for 5100 cycles, indicating a good cycling ability of the hybrid com- resulting in low capacitance. In contrast, GOPM-46 exhibited a short
posites. The support carbon matrix GO allowed the strong depos- diffusion path length of ions in the electrolyte, which could be seen
ition of PANI-protecting MnO2 nanorods on the surfaces of GO, from the low resistance of the capacitative part on the Nyquist plot.
which enhanced the mechanical strength of composite materials, This may be explained by the structure of the composite: the forma-
resulting in the long charge/discharge ability. Interestingly, the spe- tion of GOPM results in the surface charge of GO being compensated
cific capacitance showed slight increase in the first 150 cycles before by the negative charge from both Cl2 doped PANI and MnO2 nanor-
decreased slowly in the later cycles, which may be explained with the ods, leading to a lower resistance of ion transfer. Moreover, the
insufficient contact of nanocomposites with Na2SO4 aqueous solu- presence of GO-PANI with high electrical conductivity resulted in
tion at the beginning of electrochemical measurement39,47. a lower charge transfer37. After 3000 cycles, the calculated ESR for

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Figure 8 | Nyquist impedance plots of (a) MnO2, GO-PANI and GOPM composites before cycle and (b) GOPM after 3000 cycles.

GOPM-46 based electrode increased from 1.8 to 2.4 V, while the ESR America) under nitrogen atmosphere at 77 K. FE-SEM analyses were observed with a
Hitachi S4800 FESEM at an accelerating voltage of 15 kV. TEM analyses were taken
increased from 1.6 to 2.1 V for GOPM-70. The increased resistance
with a JEOL JEM-2100 microscope.
is probably attributed to the loss of adhesion of some active material The electrochemical properties of the composite were investigated on a CHI660D
with the current collector or the dissolution of some PANI/MnO2 electrochemical workstation (Shanghai, China) with conventional three-electrode
during the charge/discharge cycling. system at room temperature. To prepare the working electrodes, the polytetrafluor-
oethylene with acetylene black (15 wt%) in ethylene solution were added to as-pre-
pared composites to produce a homogeneous paste before pressed onto nickel foam
Discussion current collectors. The electrodes were then dried under vacuum at 60uC for 24 h.
By using a quick and facile two-step process, MnO2 nanorods were The electrochemical performance of composites was investigated with standard CV,
successfully coated by in-situ prepared PANI and intercalated into galvanostatic charge–discharge and EIS technique in 1 M Na2SO4 solution. CV
measurements were performed in voltage ranging from 0 V to 0.8 V at a scan rate of
GO sheets. The as-prepared ternary composites with different loading 10, 30, 50 and 100 mV/s, respectively. Charge-discharge processes were carried out
of MnO2 were evaluated as electrode materials for supercapacitors. galvanostatically at 0.25,4 A/g current density in 0,1 V voltage range.
The ternary composites presented highly porous nanostructure with
significantly increased surface area (91.37 and 73.65 m2/g, respect-
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performance. J. Power Sources 241, 231–238 (2013). of China (Grant No. 21074055), Program for New Century Excellent Talents in University
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