JMC Co3O4forsupercapa

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Shape-controlled synthesis of porous Co3O4 nanostructures for application in


supercapacitors

Article in Journal of Materials Chemistry · September 2010


DOI: 10.1039/C0JM00867B

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PAPER www.rsc.org/materials | Journal of Materials Chemistry

Shape-controlled synthesis of porous Co3O4 nanostructures for application in


supercapacitors
Ting Zhu, Jun Song Chen and Xiong Wen Lou*
Received 29th March 2010, Accepted 19th May 2010
DOI: 10.1039/c0jm00867b

In this work, we report a facile approach for the shape-controlled synthesis of cobalt carbonate/
hydroxide intermediates. Three different structures, viz., one-dimensional (1D) needle-like nanorods,
two-dimensional (2D) leaf-like nanosheets, and three-dimensional (3D) oval-shaped microparticles,
have been synthesized through varying experimental parameters such as precursor (cobalt acetate)
concentrations and volume ratio of polyethylene glycol to water. Phase-pure tricobalt tetroxide
(Co3O4) has been obtained by annealing these as-prepared intermediates without significant alterations
in morphology. With relatively high specific surface areas of 86.1–121.5 m2 g1, these products with
distinct nanostructures were tested for their potential application in supercapacitors. The results show
that these porous Co3O4 structures exhibit promising capacitive properties with high capacitance and
good retention. The needle-like nanorods show the highest capacitance of 111 F g1, and 88.2% of
which can still be maintained after 1000 charge–discharge cycles.

Introduction In view of their porous structure and relatively high specific


surface areas, the capacitive properties of derived porous Co3O4
In the past decades, transition metal oxides have been widely materials have also been evaluated and the needle-like Co3O4
used in gas sensors,1 optical and magnetic materials,2,3 hetero- nanorods exhibit the best performance among the three samples.
geneous catalysts,4 and electrochemical applications.5–7 As
a result, developing metal oxides with new morphologies and
structures for enhanced properties has attracted great research
Experiment section
interests. Cobalt oxide (Co3O4)-based porous structures have Materials preparation
been one of the subjects as they have been broadly employed in
the above-mentioned applications. Many efforts have been All chemicals were of analytical grade and used as received
devoted to develop effective approaches to synthesize Co3O4 without further purification. In a typical synthesis, cobalt acetate
mesostructures with different morphologies.8–17 At the same tetrahydrate (Co(Ac)2; Co(CH3COO)2$4H2O, Aldrich) and 0.5 g
time, cobalt based intermediate compounds, such as cobalt of polyvinyl-pyrrolidone (PVP; MW ¼ 58 000, Reagent Chem-
carbonates (CoCO3), beta-cobalt hydroxide (b–Co(OH)2), are icals) were first dissolved in a mixed solution of polyethylene
equally important, because inorganic salts such as metal nitrates glycol (PEG; MW ¼ 400, Aldrich) and de-ionized water at room
and carbonates have long been used as solid intermediates to temperature (the total volume is 20 ml), followed by the addition
obtain functional metal oxides and advanced ceramic materials of 0.25 g of urea (CO(NH2)2, Aldrich) under vigorous stirring.
by thermal decomposition.18,19 For example, we have previously After stirring for 15 min, the mixture was transferred into a 60 ml
demonstrated that Co3O4 nanotubes and mesoporous nano- Teflon-lined stainless steel autoclave and placed in an electric
needles can be obtained through appropriate thermal treatments oven at 220  C for 18 h. After that, the product was harvested,
of a b–Co(OH)2 precursor in nanoneedle shape.6,20 More and washed with de-ionized water and ethanol several times by
recently, Zeng and coworkers have obtained porous Co3O4 from a centrifugation–redispersion process. Then the final products
CoCO3 submicrometre particles, which demonstrates good were dried in an oven at 60  C for 24 h. The as-prepared powder
performance in gas-sensor application.21 was converted to Co3O4 via thermal decomposition at 300  C for
In this work, we report a study on the solvothermal synthesis
of Co-based intermediates in a mixed solution of polyethylene Table 1 Experimental conditions and morphologies of the products.
glycol (PEG) and water. Based on this technique, products with Samples I, II and III correspond to experiments 2, 4, and 6, respectively
a wide range of morphologies have been successfully synthesized,
Exp. No. [Co2+]/M PEG/ml Morphology
including 2D leaf-like nanosheets (designated as sample I), 3D
oval-shaped micro-particles (designated as sample II), and 1D 1 0.1 0 Overgrowth
needle-like nanorods (designated as sample III). By annealing at rhombus
300  C in air, these three products were converted into phase- 2 0.1 10 Leaf
3 0.01 20 Dumbbell
pure spinel Co3O4 with no substantial alterations in morphology. 4 0.02 20 Oval
5 0.05 20 Oval with
smooth facet
School of Chemical and Biomedical Engineering, Nanyang Technological 6 0.1 20 Rod
University, 70 Nanyang Drive, Singapore, 637457, Singapore. E-mail: 7 0.2 20 Thick rod
[email protected]

This journal is ª The Royal Society of Chemistry 2010 J. Mater. Chem., 2010, 20, 7015–7020 | 7015
2 h in air with a ramping rate of 1  C min1. In the experiments
(detailed conditions are given in Table 1), only the concentration
of Co(Ac)2 and volume ratio of PEG/water were adjusted while
keeping all other conditions unaltered.

Materials characterization
Crystallographic phases of all the products were investigated by
powder X-ray diffraction (XRD; Shimadzu XRD-6000, Cu Ka,
 Morphologies of samples were examined by field-
l ¼ 1.5406 A).
emission scanning electron microscopy (FESEM; JOEL, JSM-
6700F), transmission electron microscopy (TEM; JEM-2010,
200 kV) with selected area electron diffraction (SAED). Thermal
behavior of samples was characterized by thermogravimetric
analysis (TGA; Shimadzu TGA-60) at a heating rate of 5  C
min1 from room temperature to 600  C in a dynamic atmo-
sphere of air (200 mL min1) using a-alumina crucibles.
Measurement of specific surface area and analysis of porosity for
the Co3O4 products were performed through measuring N2
adsorption–desorption isotherms at 77 K with a Quantachrome
NOVA-3000 system.

Electrochemical measurements
The working electrode was prepared by mixing the 80 wt% of
electroactive material (Co3O4), 10 wt% of carbon black (super- Fig. 1 Field-emission scanning electron microscopy (FESEM) images of
P), and 10 wt% of polyvinylidene difluoride (PVDF, Aldrich). as-prepared sample I (A and B), sample II (C and D), and sample III (E
This mixture was then pressed onto the glassy carbon electrode and F).
(Aida Hengsheng Technology co. ltd, Tianjng, China) and dried
at 60  C. The electrolyte used was a 2 M KOH aqueous solution. needle-like nanorods in sample III, which are around 50 nm in
The capacitive performance of the samples was evaluated on diameter and 400 nm in length. The nanorods, prepared with an
a CHI 660C electrochemical workstation using cyclic voltam- increased [Co2+] of 0.1 M, demonstrate highly anisotropic 1D
metry and chronopotentiometry tests with a three-electrode cell growth along the long-axis.27 As indicated in Table 1, thicker rods
where Pt foil serves as the counter electrode and a standard (not shown) can be obtained when [Co2+] is doubled to 0.2 M.
calomel electrode (SCE) as the reference electrode. Co-based intermediates are formed via an aggregative attach-
ment process during the synthesis. Initially, small primary parti-
cles are formed in the solution when supersaturation is reached,
Results and discussion
followed by growth via a normal Ostwald ripening process. The
Table 1 shows the experimental conditions for materials resultant crystallites are aggregated and attached to one another
synthesis. Morphologies of all intermediate products were to form final crystals, as commonly described in a mineralization
examined with FESEM (images of sample 1, 3, 5 and 7 not shown process. It is also noteworthy that polymer (PVP) molecules and
here). Fig. 1 A and B show the morphology of sample I. It is urea have been introduced into the system, which may make the
observed that sample I consists of uniform leaf-like structures crystallization process extremely complicated. The morphologies
with about 1 mm in length and 300 nm in width. To the best of of resultant structures are determined by the concentration of
our knowledge, this type of Co-based nanostructure has not been Co2+, and more importantly the organic additives.
reported before, as the 2D architectures demonstrated previously The crystal phase of all samples was analyzed by powder X-ray
are generally hexagonal nanodiscs.22–26 It can be clearly identified diffraction (XRD), with the results shown in Fig. 2. It is clear
from the magnified image (Fig. 1B) that these ‘‘nano-leaves’’ have from pattern I that the leaf-like structure prepared in a PEG/
a relatively smooth surface, and a thickness of about tens of water mixed solvent system contains mixed phases of CoCO3
nanometres. Fig. 1C illustrates the oval-shaped CoCO3 micro- (space group R  3c, JCPDS file no. 11-0692; a0 ¼ 4.659 A  and
particles in sample II prepared in the absence of water with  
c0 ¼ 14.96 A) and b-Co(OH)2 (space group: R 3c, JCPDS file no.
a Co(Ac)2 concentration of 0.02 M. These oval-shaped particles 30-0443; a0 ¼ 3.183 A  and c0 ¼ 4.652 A).
 The formation of
are of relatively uniform size distribution, approximately 2 mm in b-Co(OH)2 can be attributed to the participation of the hydroxyl
length and 1 mm in width. Fig. 1D shows a FESEM image with groups from H2O or more likely the hydrolysis of urea.28 On the
a higher magnification, which shows that the surface of these oval- other hand, indicated by patterns II and III, the crystal phase of
shaped particles are quite rough composing of fine nanoparticles. samples II and III is mainly CoCO3 as the synthetic system does
Interestingly, dumbbell-shaped structures (not shown) are not contain added water (see Table 1). All the identified peaks
produced if the [Co2+] is decreased to 0.01 M, while oval-shaped can be indexed to the rhombohedral phase of CoCO3 (JCPDS file
particles with smooth surface are acquired when [Co2+] is no. 11-0692), and the absence of other diffraction peaks affirms
increased to 0.05 M. Fig. 1 E and F depict the morphology of the the phase-purity of these cobalt-based intermediates.

7016 | J. Mater. Chem., 2010, 20, 7015–7020 This journal is ª The Royal Society of Chemistry 2010
to Co3O4 is 13.6%. Based on the results, the actual weight losses
of samples I, II and III were determined to be 28.54%, 30.79%
and 36.14%, respectively. Therefore, it can be deduced that the
proportion of CoCO3 phase in sample I is approximately 79.1%,
implying that CoCO3 was the preferred phase to form than
b-Co(OH)2 in this synthetic system. Because of its relatively large
size (see Fig. 1 C and D), sample II is more robust to complete
thermal decomposition, leading to a weight loss that is slightly
lower than the theoretical value. On the other hand, needle-like
CoCO3 in sample III shows a slightly higher weight loss, which
may be due to the combustion of adsorbed organic species in
view of the considerable amount of PVP and PEG used in the
synthetic system (see Experimental section).
After being annealed at 300  C for 2 h in air, the as-synthesized
Co-based intermediates crystals were completely converted to
phase-pure spinel Co3O4. Fig. 4 shows the morphologies of the
Fig. 2 X-Ray diffraction (XRD) patterns of as-prepared samples I, II
products after heat treatment. It can be seen from Fig. 4A that
and III. The peaks marked by black dots and asterisks are attributed to
sample I shows good thermal stability as the overall structure is
CoCO3 and b-Co(OH)2, respectively.
largely intact, even though some broken or tips-cutoff ‘‘nano-
The thermal behavior of the as-prepared Co-based interme- leaves’’ can be observed. From the TEM image (Fig. 4B), it can
diates has been investigated by thermogravimetric analysis be observed that the surface of the leaves becomes much rougher,
(TGA), as presented in Fig. 3. These three samples demonstrate and the surface defects can be clearly revealed as a porous
similar TGA profiles. The initial weight loss of all three samples structure resulting from the thermal decomposition.20 The
up to 100  C can be mainly attributed to the evaporation of selected-area electron diffraction (SAED; Fig. 4B, inset) shows
absorbed/trapped water molecules. As the temperature rises, the a poorly defined hexagonal spot pattern, indicating the relatively
weight of samples II and III drops gradually until around 200  C poor single-crystallinity of these leaf-like structures, and the
where sharp weight loss is observed. Finally, it flattens out at topotactic transformation to (111) planes of Co3O4.6 The oval-
around 400  C. This is consistent with previously reported shaped microparticles in sample II are shown to be quite
thermal behavior of CoCO3.21 Compared to samples II and III,
the significant weight loss of sample I is only observed at around
240  C, which probably indicates its different chemical compo-
sition. The above decomposition process of the samples can be
described by the following two reactions:

6CoCO3 + O2 / 2Co3O4 + 6CO2

6Co(OH)2 + O2 / 2Co3O4 + 6H2O

From the above processes it can be calculated that the theo-


retical weight loss of CoCO3 to Co3O4 is 32.49%, while Co(OH)2

Fig. 4 FESEM (A) and transmission electron microscopy (TEM) (B)


images of sample I. FESEM images of sample II (C and D), and FESEM
(E) and TEM (F) images of sample III. The insets in B and F are
Fig. 3 Thermogravimetric analysis (TGA) curves of samples I, II and III a selected-area electron diffraction (SAED) pattern and a magnified
in air with a temperature ramp of 5  C min1. TEM image of the corresponding sample.

This journal is ª The Royal Society of Chemistry 2010 J. Mater. Chem., 2010, 20, 7015–7020 | 7017
Fig. 5 XRD partterns of samples I, II and III after annealing at 300  C
in air.

thermally stable (Fig. 4 C and D) with no collapse of structure.


Sample III also exhibits no substantial morphological alteration
after the annealing process (Fig. 4 E and F). From the TEM
image (Fig. 4F), it can be seen that these needle-like nanorods
self-organize to form compact bundles, which is in good agree-
ment with the FESEM analysis. The inset shows the tips of some
nanoneedles at a higher magnification. It is clear that these
needle-like nanorods appear thinner compared to the counter-
parts before annealing due to crystal shrinkage during thermal
decomposition. The crystallographic phase of all three samples is
again examined by XRD (Fig. 5). All diffraction peaks can be
assigned to the cubic phase of Co3O4 (space group Fd3m; lattice
 JCPDS file no. 42-1467).29,30
constant a0 ¼ 8.0837 A;
Brunauer–Emmett–Teller (BET) gas-sorption measurements
were performed at 77 K to investigate the textural characteristics
of the Co3O4 samples. Nitrogen adsorption–desorption
isotherms of these samples are shown in Fig. 6, and the insets
show the corresponding Barrett–Joyner–Halenda (BJH) pore
size distribution obtained from both branches of the isotherm.
These isotherm profiles can be categorized as type IV with small
hysteresis loops observed at a relative pressure of 0.2–0.9 for
sample I, and 0.5–1.0 for sample II, and no distinct hysteresis is
present for sample III. The BET specific surface areas of these
three samples are measured to be 86.16 m2 g1, 110.2 m2 g1, and
121.5 m2 g1 for samples I, II and III, respectively, which shows
that all of them possess relatively high specific surface areas. It
can be concluded from the BJH pore size distribution that both
samples I and II have pores with diameter less than 10 nm, while
Fig. 6 N2 adsorption–desorption isotherms of samples I (A), II (B), and
sample III has generally larger pores of about 20 nm. It can also
III (C). Inset in each isotherm is the corresponding pore size distributions.
be observed that sample II only shows a monomodal pore size
distribution in the range 4–10 nm, which together with the
isotherm indicates a well-defined mesoporous structure con- to be from 0 to 0.5 V with the same scanning rate. It can be
structed from crystal re-construction.20 clearly observed that there is a distinct pair of redox peaks during
Co3O4 has been widely studied as the electrode material for the anodic and cathodic sweeps, with the presence of a broad
supercapacitors and lithium-ion batteries.7,31–35 Here we analyze redox background. It is thus evident that our samples demon-
the electrochemical capacitance of the three samples. The strate pseudo-capacitive properties that originate from the
measurements are conducted using cyclic voltammetry (CV) in reversible and continuous electrochemical reactions of Co3O4
a 2 M KOH electrolyte, and the optimized CV curves are pre- involved in the charge–discharge processes.32,36,37
sented in Fig. 7. The voltage window of sample I (Fig. 7a) and Fig. 8 presents the dependence of the discharge specific
II (Fig. 7b) is from 0.15 V to 0.45 V with a scanning rate of capacitance of the electrodes on the charge–discharge cycle
0.015 V s1, while that used for sample III (Fig. 7c) is optimized number, and the insets are corresponding voltage profiles of the

7018 | J. Mater. Chem., 2010, 20, 7015–7020 This journal is ª The Royal Society of Chemistry 2010
Fig. 7 Cyclic voltammograms of samples I (A), II (B), and III (C) in
a 2 M KOH aqueous electrolyte at a scan rate of 0.015 V s1. The voltage
window used for samples I and II is from 0.15 V to 0.45 V, while that
used for sample III is from 0 to 0.5 V.

first 4 charge–discharge cycles. The measurements are performed


at a current density of 2.5 mA cm2 with the voltage windows the
same as that for the CV analysis. The specific capacitance can be
calculated according to the following equation:

Cm ¼ I  Dt/(DV  m),38,39 (1)


Fig. 8 Specific capacitance of samples I (A), II (B), and III (C) in an
where Cm (F g1) is the specific capacitance, I (mA) is the aqueous KOH (2 M) electrolyte as a function of cycle number. The insets
discharge current, Dt (s) is the discharge time, DV (V) is the show the voltage profiles of the first 4 charge–discharge cycles.
potential change during discharge, and m (mg) is the mass of
active material within the electrode. The specific capacitance
values of samples I, II, and III can thus be calculated from the a narrow voltage window. Lastly, to rule out the possibility of
discharge curves to be 44 F g1, 62 F g1, and 111 F g1, significant capacitive contribution of carbon back used in the
respectively, at the end of 1000 charge–discharge cycles. This preparation of electrodes, we have measured the capacitance of
indicates that as much as 86.9%, 80%, and 88.2% of their initial carbon black (super-P) to be only 0.38 F g1 after 1000 cycles
capacitance can be maintained for samples I, II, and III, under same testing conditions.
respectively. These results show that these active Co3O4 nano-
materials have relatively good supercapacitive properties with
Conclusions
excellent capacitance retention. Among them, sample III
possesses the highest capacitance and best retention capability, In summary, Co-based intermediates with different morphol-
largely due to its highest specific surface area and largest meso- ogies were synthesized in a solvothermal system with a mixed
pores granting good accessibility for the electrolyte. It should solvent of PEG400 and water. Three samples with distinct
also be noted that the voltage window used for sample III is morphologies, i.e., 1D needle-like nanorods, 2D leaf-like nano-
0–0.5 V, which is narrower than that of the other two samples, sheets, and 3D oval-shaped microparticles, were discussed in this
implying that the calculated capacitance based on eqn (1) can be report. It has been found that both the concentration of cobalt
further improved if the charge storage can be achieved within acetate precursor and the volume ratio of PEG400 and H2O play

This journal is ª The Royal Society of Chemistry 2010 J. Mater. Chem., 2010, 20, 7015–7020 | 7019
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