Journal of Power Sources 243 (2013) 676e681

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Journal of Power Sources

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Direct growth of mesoporous MnO2 nanosheet arrays on nickel foam

current collectors for high-performance pseudocapacitors
Manab Kundu, Lifeng Liu*
International Iberian Nanotechnology Laboratory (INL), Av. Mestre Jose Veiga, 4715-330 Braga, Portugal

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Porous MnO2 nanosheets are directly

grown on Ni foam using one-step
electrodeposition.

The binder-free MnO2 nanosheets/Ni
foam electrode shows very low ESR
and Rct.

The electrode exhibits high capaci-
tance, good rate capability and long
cycle life.

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

Article history: Well-defined mesoporous MnO2 nanosheet arrays have been directly grown on Ni foam current col-
Received 5 February 2013 lectors using one-step electrodeposition, followed by a low-temperature thermal annealing process. The
Received in revised form as-deposited MnO2 nanosheets are 20e25 nm thick on average and are mesoporous with a pore size
18 May 2013
ranging from 2 to 8 nm. The potential for using these MnO2 nanosheet arrays as supercapacitor elec-
Accepted 11 June 2013
trodes has been explored by cyclic voltammetry and galvanostatic charge/discharge tests within a po-
Available online 18 June 2013
tential window of 0e1.0 V versus saturated calomel electrode. The cyclic voltammograms of the MnO2
nanosheet electrode show a typical pseudocapacitive behavior. The nanosheets exhibit specific capaci-
Keywords:
MnO2 nanosheet
tance of 201, 150, 122, 105 and 96 F g1 at current densities of 1, 5, 10, 15 and 20 A g1, respectively.
Electrodeposition Furthermore, it is found that upon cycling at 5 A g1, the specific capacitance loses 35% of its initial value
Binder-free electrode in the beginning 1800 cycles and then remains constant up to 3000 cycles, showing reasonably good
Supercapacitor cycling performance. The electrochemical impedance spectroscopy demonstrates that the equivalent
Energy storage series resistance and charge transfer resistance of the electrode are very low, suggesting that the nickel
foam supported MnO2 nanosheet array is a promising binder-free electrode for use in pseudocapacitors.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction reactions to realize energy storage [3]. To this end, two families of
materials are generally employed to fabricate pseudocapacitor
Pseudocapacitors, also known as redox capacitors, have attrac- electrodes, namely, electronically conducting polymers and tran-
ted tremendous research interest in recent years because they can sition metal oxides. Conducting polymers like polyaniline and
provide much higher specific capacitance and energy density than polypyrrole are able to provide reasonably high specific capacitance
electrochemical double-layer capacitors (EDLCs) [1,2]. Different and can operate over a broad potential window, but often suffer
from EDLCs which store energy based on electrostatic attraction from a lack of stability associated with swelling and shrinking
between ions in the electrolyte and the electrode surface, pseu- during cycling [4]. In contrast, transition metal oxides possess
docapacitors take advantage of fast and reversible surface redox higher specific capacitance and much better cycling stability as well
as variable valence states allowing for multiple redox reactions, and
* Corresponding author. Tel.: þ351 253140112; fax: þ351 253140119. are therefore more attractive for use as pseudocapacitor electrode
E-mail address: [email protected] (L. Liu). materials.

0378-7753/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jpowsour.2013.06.059
 M. Kundu, L. Liu / Journal of Power Sources 243 (2013) 676e681 677

To date, a variety of transition metal oxides have been investi- In this work, we report direct growth of mesoporous MnO2
gated for use in pseudocapacitors, including RuO2 [5,6], MnO2 [7e nanosheet arrays on a nickel foam current collector by using a one-
12], Fe3O4 [13], Co3O4 [14,15], NiO [16] and NiCo2O4 [17e19]. Among step and low-cost electrodeposition method. We then use the
them, MnO2 has been widely thought to be a promising candidate nickel foam supported mesoporous MnO2 nanosheet arrays as a
to replace the current state-of-the-art yet costly RuO2 because it is binder-free electrode and carefully investigate the electrode’s
more abundant, less expensive, environmentally benign and has a pseudocapacitive properties. We find that the as-deposited MnO2
relatively wide working potential window (e.g. 0e1 V) in aqueous nanosheet arrays exhibit specific capacitance as high as 201 F g1 at
electrolytes. a current density of 1 A g1, good rate capability over a wide range
In addition to electrode materials, the structure of electrodes of current densities from 1 to 20 A g1 and satisfactory cycling
is also a very important factor governing the performance of a performance with w65% capacity retention at 5 A g1 up to 3000
pseudocapacitor. In order to facilitate fast power delivery or up- cycles, which hold great potential for use as a high-performance
take, the contact impedance between the active material and the binder-free electrode in pseudocapacitors.
current collector should be kept low [3]. Conventionally, fabri-
cating a pseudocapacitor electrode involves multiple steps 2. Experimental
including preparing a mixed slurry of active materials, conduc-
tivity enhancer (usually activated carbon) and binder (e.g. PVDF), The Ni foam used in our experiments was purchased from
slurry coating on a current collector and subsequent curing, and Hezhe Jiaotong Group, China (110 PPI, 480 g m2, 0.3 mm thick).
final pressurization processing. The use of non-conductive binder Before electrodeposition, the Ni foam was carefully cleaned with a
not only blocks a portion of electrochemically active surface and 6 M hydrochloric acid solution in an ultrasonic bath for 10 min in
therefore reduces the specific capacitance of devices, but also order to remove the possibly existing nickel oxide layer on the
introduces extra contact resistance between the electrical con- outer surface, and then washed in sequence with de-ionized water
ductors (i.e. current collector and/or conductivity enhancer) and (18 MU cm) and absolute ethanol (99.5%, Labor Spirit Lda). Af-
the active materials, thus resulting in a reduced power density. terward, the Ni foam was dried at ambient temperature.
Therefore, many attempts have been made to develop binder-less The electrodeposition was performed in a two-electrode elec-
or binder-free electrodes in the past couple of years. For example, trochemical cell using a piece of freshly cleaned Ni foam as working
Yang et al. electrodeposited Ni(OH)2 nanostructures on conduc- electrode and a platinum wire as counter electrode. The electrolyte
tive nickel foam and obtained an unprecedentedly high specific was 0.02 M manganese acetate (SigmaeAldrich, analytical grade)
capacitance of 3152 F g1 [20]; Fan’s group fabricated metal oxide aqueous solution. A Keithley 2400 sourcemeter was used as a po-
coreeshell hybrid nanostructures by growing nickel hydrox- wer supply. The deposition was conducted at room temperature at
idenitrate flakes or MnO2 nanosheets onto metal oxide nanowire a current density of 10.5 mA cm2 for 3 min. After deposition, the Ni
arrays, which exhibited remarkably enhanced pseudocapacitance foam was thoroughly rinsed with de-ionized water and absolute
[21,22]. ethanol for several times, and then dried in air. Subsequently, the

Fig. 1. SEM micrographs of a nickel foam (a) before and (b) after electrodeposition. (c, d) Magnified top-view SEM micrographs of the deposited MnO2 nanosheet arrays. Inset of
Fig. (c): digital photographs showing the appearance of a Ni foam deposited with MnO2 nanosheets before and after mechanical bending.
678 M. Kundu, L. Liu / Journal of Power Sources 243 (2013) 676e681

sample was annealed in high-purity nitrogen at 150  C for 5 h. The In order to further study the microstructural feature of the
weight of the sample was measured before electrodeposition and electrodeposited manganese oxide nanosheets, extensive TEM
after thermal annealing using a high precision electronic balance investigation was carried out. As is seen in Fig. 2a, the nanosheets
(Sartorius CPA225D) in order to calculate the mass of the deposited exhibit foldaway silk-like morphology with a high degree of
active materials. transparency, indicating their ultrathin nature. Since the lateral size
The morphology of the as-prepared MnO2 nanosheets was of these nanosheets is much larger than their thickness, the
examined by scanning electron microscopy (SEM, FEI Quanta morphologies of twisting, waving and crumpling can be easily
FEG650), and their microstructure was investigated by trans- observed. The dark strips correspond to the folded edges or wrin-
mission electron microscopy (TEM, FEI TITAN ChemSTEM 80-200, kles of the nanosheets. Shown in the inset of Fig. 2a is a typical
probe-corrected). Selected-area electron diffraction (SAED) in
conjunction with energy dispersive X-ray spectroscopy was used to
identify the crystallographic phase of the deposited MnO2. To
prepare a TEM specimen, the deposited manganese oxide nano-
sheets were scratched from Ni foam using a doctor blade, and
subsequently dispersed into isopropanol by ultrasonication. A drop
of suspension was then casted on a carbon-coated copper grid and
dried in a vacuum oven at 110  C for 2 h for TEM examination. The
crystal phase of the sample was also investigated by X-ray
diffractometry (XRD, PanAnalytical X’pert Pro). The electrochemical
tests were carried out in a three-electrode electrochemical cell with
the Ni foam supported MnO2 nanosheet arrays as working elec-
trode, a platinum wire as counter electrode and a saturated calomel
electrode (SCE) as reference. The electrochemical performance of
the as-prepared MnO2 nanosheets was evaluated by cyclic vol-
tammetry (CV), galvanostatic charge/discharge technique and
electrochemical impedance spectroscopy (EIS) using a Biologic
VMP3 battery tester. All the tests were made at room temperature
in a 1 M Na2SO4 aqueous solution. The specific capacitance is
calculated based on the following equation:

I Dt
Cs ¼ (1)
mDV

where Cs is the specific capacitance of the active materials (F g1), I

stands for the discharging current (A), m is the mass of the loaded
active materials (g), DV represents the discharging potential range
(V), and Dt is the discharging time. In the following, all potentials
are referred with respect to the SCE reference, if not specified
otherwise.

3. Results and discussions

Fig.1a shows a representative SEM image of the Ni foam used. It is

seen that the foam consists of interconnected network of ribbon-like
ligaments with an average width of 80 mm. Since all the ligaments
are highly conductive and the macroscopic pores allow the elec-
trolyte to readily access the exposed surface, the manganese oxide
was found to deposit uniformly and conformally over the entire
skeleton of the Ni foam, as displayed in Fig. 1b. The direct growth of
manganese oxide on the current collector can help to eliminate the
fussy steps that are conventionally used to fabricate supercapacitor
electrodes, and also allows all electrochemically active sites to be
accessed by electrolyte more easily. Upon a closer look at the surface
of the Ni foam, it is observed that the deposited manganese oxide is
characterized by a high density array of vertically aligned nano-
sheets having a thickness of 20e25 nm, as shown in Fig. 1c and d.
These nanosheets are interconnected laterally, forming a highly
open and porous structure, and firmly adhere to the underlying Ni
foam. It is worth mentioning that even without using any binder, the
nanosheets still have a very tight connection with the underlying Ni
foam. This is evidenced by the fact that upon mechanical bending
of the Ni foam, the deposited nanosheets, both macroscopically and
microscopically, are not detached from the Ni foam surface, as seen Fig. 2. (a) Overview TEM image of the deposited MnO2 nanosheets. Inset: SAED
in Fig. 1c and its inset, which suggests that this MnO2 nanosheets/Ni pattern. (b) HRTEM image and (c) EDX spectrum of the fabricated mesoporous MnO2
foam electrode could be used to make flexible supercapacitors. nanosheets scratched from the nickel foam.
 M. Kundu, L. Liu / Journal of Power Sources 243 (2013) 676e681 679

SEAD pattern of the nanosheets, in which a set of diffraction rings is

clearly revealed. Extensive analysis confirmed that these nano-
sheets consist of orthorhombic MnO2 (COD database code 900-
3476), and the rings can be identified as the diffractions from (111),
(600), (112) and (610) planes, respectively. Fig. 2b shows a high
resolution TEM micrograph of the nanosheets, from which the
lattice fringes can be clearly seen. The interplanar spacing in a
representative crystallite is about 0.28 nm, which is close to that of
orthorhombic MnO2 (301) planes. Moreover, it is found that the
nanosheets have many mesoscopic pores with sizes ranging from 2
to 8 nm, which are not visible in the SEM micrographs. These
mesopores could result from the thermal decomposition of the
electrodeposited hydroxides upon annealing, as reported for other
nanostructures prepared in a similar way [21]. It is assumed that
the presence of these mesopores would benefit the improvement of
the electrochemical performance as they offer a remarkably
increased electrode/electrolyte contact area and facilitate mass
transport of the electrolyte within the electrode for fast redox re-
actions. Fig. 2c reveals a representative EDX spectrum of the
deposited MnO2 nanosheets, confirming that the nanosheets
consist of Mn and O. The C and Cu peaks are originated from the
carbon-coated copper grid.
To further examine the crystal phase of the nanosheets, XRD
measurement was carried out. Since the XRD signals of the sample
subjected to electrodeposition for 3 min were very weak, a sample
prepared with prolonged electrodeposition time (w20 min) was
used to identify the phase. Fig. 3 shows the XRD pattern of the
sample. The peaks located at 2q values of 37.1, 38.1 and 41.2 can Fig. 4. (a) Cyclic voltammograms of the nickel foam supported mesoporous MnO2
nanosheet electrode, which were recorded in 1 M Na2SO4 aqueous solution at scan
be indexed to the diffractions from (011), (002) and (211) crystal
rates of 5, 10, 30, 50, 80 and 100 mV s1. (b) Anodic current versus scan rate.
planes of orthorhombic MnO2 (COD database code 900-3476),
which is in good agreement with the above SAED result.
In order to explore the supercapacitive properties of the as- The anodic peak current versus the scan rate is plotted in Fig. 4b.
fabricated mesoporous MnO2 nanosheet arrays, cyclic voltamme- The quasi-linear relationship shown in this plot further corrobo-
try (CV) was carried out at different scan rates of 5, 20, 50, 80 and rates the occurrence of surface redox reactions and the pseudoca-
100 mV s1 in a fixed potential range of 0e1.0 V versus SCE, and the pacitive nature of the electrode [23]. Moreover, it indicates that the
corresponding CV curves are shown in Fig. 4a. It is seen that the CV surface redox reaction is a rate limiting step during charge/
profiles recorded at all scan rates are almost rectangular in shape discharge [24].
indicative of an ideal pseudocapacitive behavior due to the fast, The electrochemical performance of the as-fabricated MnO2
reversible and successive surface redox reactions which involve nanosheet electrode is further evaluated by galvanostatic charging/
both surface adsorption of electrolyte cations (i.e. Naþ) and proton discharging tests in the same potential range (i.e. 0e1.0 V versus
(Hþ) incorporation as described in equation (2) [3]: SCE) at various specific current densities. Fig. 5a and b shows the
charge/discharge profiles recorded at current densities of 1, 5, 10, 15
and 20 A g1. It reveals that at nearly all current densities the charge
MnO2 þ xNaþ þ yHþ þ ðx þ yÞe 4MnOONax Hy (2)
curves are symmetrical with their discharge counterparts. More-
over, the potentialetime profiles exhibit a good linearity, indicating
a well-defined capacitive behavior of these mesoporous MnO2
nanosheets. The specific capacitance of the nanosheet electrode is
calculated based on the discharge curves using equation (1) and is
plotted as a function of current densities in Fig. 5c. It is seen that the
MnO2 nanosheet electrode exhibits specific capacitance of 201, 150,
122, 105 and 96 F g1 at the current densities of 1, 5, 10, 15 and
20 A g1, respectively. This suggests that about 48% of the capaci-
tance is retained when the charge/discharge rate is increased from
1 to 20 A g1. The specific capacitance presented here is higher than
that of many carbon-based materials [25e27] as well as other
manganese oxide nanostructures reported recently [28e31].
In order to investigate the cycling performance of the electrode,
continuous galvanostatic charge/discharge tests were carried out at
a current density of 5 A g1. The variation of specific capacitance as
well as Coulombic efficiency versus cycle numbers are plotted in
Fig. 6. The Columbic efficiency is calculated by software according
to the following equation [32]:

td
h¼  100% (3)
Fig. 3. XRD pattern of the mesoporous MnO2 nanosheets supported on the Ni foam. tc
680 M. Kundu, L. Liu / Journal of Power Sources 243 (2013) 676e681

the capacitance value becomes quite stable till 3000 cycles. This
observed initial loss in specific capacitance might be due to the
material loss due to Mn dissolution into the electrolyte, which is
one of the major reasons for a limited cycling life of MnO2-based
electrodes [33,34]. Remarkably, it is found that the Columbic effi-
ciency remains >99% during the whole cycling test, suggesting that
the charge/discharge processes are highly reversible.
In order to study the kinetics and mechanism of charge transfer
at the electrode/electrolyte interface, electrochemical impedance
spectroscopy (EIS) measurements were conducted. Generally, by
analyzing the EIS spectrum in the high frequency region, one can
calculate the equivalent series resistance (ESR, Rs) of the electrode,
which includes the contribution from the inherent resistance of the
electrode materials, bulk resistance of the electrolyte and the
contact resistance at the electrode/electrolyte interface, according
to the intercept of the spectrum on the real axis. Moreover, the
charge transfer resistance (Rct) originating from diffusion of elec-
trons can be deduced from the diameter of the semicircle in the
high frequency region. By contrast, the EIS spectrum in the low
frequency region primarily reflects the magnitude of Warburg
resistance (Zw) which is associated with the diffusion of redox
species in the electrolyte. A sharp Warburg plot usually indicates
fast diffusion of ions toward the electrode. Fig. 7a shows an
experimental Nyquist plot (imaginary part Z00 versus real part Z0 )
of the as-fabricated mesoporous MnO2 nanosheet electrode,
measured at the open circuit potential in a range of 0.1 Hze1 MHz.
The data were fitted by Z-View software using equivalent circuit
model as shown in the inset of Fig. 7a. It was found that the fitted Rs
for the MnO2 nanosheets/nickel foam electrode is only 1.79 U. The
very low Rs value indicates that a tightly-coupled interfacial contact
exists between the electrodeposited MnO2 nanosheets and the
nickel foam current collector. Moreover, the Rct was found to be

Fig. 5. (a) Galvanostatic charge/discharge profiles measured at current densities of 1, 5,

10, 15 and 20 A g1. (b) Zoomed view of (a) for high rate charge/discharge profiles. (c)
The variation of specific capacitance as a function of current density.

where tc and td represent the time of charge and discharge,

respectively.
From Fig. 6, it is observed that about 35% of the specific capac-
itance value loses during the beginning 1800 cycles. After this stage,

Fig. 7. (a) Electrochemical impedance spectrum (EIS) obtained from the as-fabricated
mesoporous MnO2 nanosheet electrode. Inset: the enlarged EIS at high frequencies and
Fig. 6. The variation of specific capacitance and Columbic efficiency of the MnO2 the equivalent circuit diagram. The fitted curve is shown in solid line. (b) Frequency
nanosheet electrode versus cycle number upon cycling at a current density of 5 A g1. dependent specific capacitance of the electrode.
 M. Kundu, L. Liu / Journal of Power Sources 243 (2013) 676e681 681

merely 0.48 U, suggesting that the arrays of the deposited meso- MnO2 nanosheet arrays directly grown on nickel foam) allows
pores MnO2 nanosheets can provide an ideal pathway for ion and more active materials to be utilized as a capacitor at high fre-
electron transport without kinetic limitations. The low Rs and Rct quencies. All the above results suggest that the nickel foam sup-
values can be attributed, on the one hand, to the firm physical ported mesoporous MnO2 nanosheet arrays can serve as very
contact between the MnO2 nanosheets and nickel foam established promising binder-free electrodes for next generation high-
by electrodeposition; and on the other hand, to the binder-free performance pseudocapacitors.
nature of the electrode.
The frequency dependent specific capacitance is derived from References
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