Progress in Natural Science: Materials International 27 (2017) 197–202

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Progress in Natural Science: Materials International

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Original Research

Synthesis and Electrochemical Properties of Porous α-Co(OH)2 and Co3O4 MARK

Microspheres
⁎
Yingying Xu1, Zhiyuan Liu1, Di Chen, Yuanjun Song, Rongming Wang
Beijing Key Laboratory for Magneto-Photoelectrical Composite and Interface Science, School of Mathematics and Physics, University of Science and
Technology Beijing, Beijing 100083, China

A R T I C L E I N F O A BS T RAC T

Keywords: Both α-Co(OH)2 and Co3O4 porous microspheres have been synthesized by the simple solvothermal process as
α-Co(OH)2 microspheres well as subsequent treatment. The morphologies and structures of the as-synthesized products were
Co3O4 porous microspheres characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron
Supercapacitor microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Both samples have spherical structures
Cycling stability
consisting of nanosheets, with similar crystallinity. The electrochemical properties of both samples were further
Rate capability
investigated. Both samples show excellent electrochemical performances including high specific capacity, good
cycling stability and rate capability. All results show that these microspheres exhibit potential applications in
energy storage field.

1. Introduction hydrothermal method [28] and radiation-induced pathways [29] have

been employed for the synthesis of Co(OH)2 nanostructures.
As ideal energy storage systems, supercapacitors have drawn much Hydrothermal/solvothermal has also been proved as an attractive
attention recently for their high power density, excellent reversibility, technique to produce anisotropic inorganic materials with highly
fast recharge ability and long cycle life [1–4]. They have energy uniform size and controllable 3D morphologies at the mesoscopic
densities higher than those of conventional capacitors, while posses- level. It has been applied in synthesizing various complex 3D archi-
sing power densities higher than those of batteries [5–9]. Therefore tectures of Co(OH)2 [30] or cobalt hydroxide carbonate [31], which can
they can be either directly used as power source or auxiliary power be used as precursor to produce Co3O4 superstructures with broom-
source along with batteries [10]. By the charge storage mechanism, like, dandelion-like and rose-like morphologies by thermal conversion
supercapacitors can be categorized as electrical double layer capacitors [31].
and electrochemical pseudocapacitors [11]. Through the Faradic redox In our work, α-Co(OH)2 microspheres were successfully synthe-
process, the pseudocapacitors can achieve much higher specific capa- sized by the solvothermal process in ethylene glycol. Then porous
citance than normal double layer capacitors [12,13]. To explore new Co3O4 microspheres were prepared by thermal treatment of the as-
economic supercapacitor with high performance, we have to develop prepared α-Co(OH)2 microspheres. Furthermore, the electrochemical
novel electrode materials derived from abundant natural sources with properties of the as-prepared α-Co(OH)2 and Co3O4 were investigated,
high surface areas and high electrical conductivity [7,14,15]. One of the which illustrated their performances and possible applications in
best candidates for anode materials is the nanomaterial based on cobalt supercapacitor as electrode materials.
hydroxide and oxide, which has been the subject of intense interests for
its wide-ranging applications such as toxic gas sensors [16], catalysts 2. Experimental
[17,18], magnetic semiconductors [19], lubricating materials [20],
rechargeable batteries [21,22] and supercapacitors [10,23–25]. 2.1. Materials preparation
For certain materials, special morphology and crystallographic form
are responsible for their application properties. In recent years, various The α-Co(OH)2 microspheres were synthesized by a facile sol-
routes including chemical precipitation [26], electrodeposition [27], vothermal method. All reagents were bought from Sinopharm

Peer review under responsibility of Chinese Materials Research Society.

⁎
Corresponding author.
E-mail address: rmwang@ustb.edu.cn (R. Wang).
1
The first two authors contributed equally to this work.

http://dx.doi.org/10.1016/j.pnsc.2017.03.001
Received 17 November 2016; Received in revised form 1 March 2017; Accepted 2 March 2017
Available online 27 March 2017
1002-0071/ © 2017 Chinese Materials Research Society. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
Y. Xu et al. Progress in Natural Science: Materials International 27 (2017) 197–202

Chemical Reagent Beijing Co., Ltd. They were analytically pure and
used without further purification. In a typical preparation process,
0.5 g Co(CH3COO)2·4H2O was dissolved in 30 ml ethylene glycol. After
stirring for 1 h, the solution was transferred into a 50 ml Teflon-lined
stainless steel autoclave and maintained at 200 °C for 6 h. After
naturally cooled to room temperature, the products were rinsed with
distilled water and anhydrous ethanol for several times to remove the
residual debris. Finally, the products were collected and dried in a
vacuum oven at 60 °C for 12 h. Moreover, Co3O4 microspheres were
obtained by further annealing the as-prepared α-Co(OH)2 micro-
spheres in air at 300 °C for 2 h.

2.2. Structure characterization

The microstructure of the samples was examined by a scanning

electron microscope (SEM, Zeiss Supra 55) and a transmission electron
microscope (TEM, JEM-2200FS) with field-emission guns. The crystal-
lographic structures of as-synthesized samples were identified by
powder X-ray diffraction (XRD, Shimadzu XRD-6000) with Cu Kα
radiation. X-ray photoelectron spectroscopy (XPS) measurements were
performed using a PHI 5700 ESCA spectroscopy with a monochro-
mated Al Kα radiation (hν=1486.6 eV). All XPS spectra were corrected
using the C 1 s line at 284.6 eV.

2.3. Electrochemical characterization

The supercapacitor properties of α-Co(OH)2 and Co3O4 micro-

spheres were characterized by three-electrode electrochemical methods
with a model CHI760E electrochemical workstation (Shanghai
Chenhua Equipments, China). Cyclic voltammetry (CV), galvanostatic
charge/discharge (GCD) and electrochemical impedance spectroscopy
(EIS) were carried out in a three-electrode cell with a Pt foil serving as
the counter electrode and a saturated calomel electrode (SCE) as the
reference electrode. A 2 M KOH aqueous solution was used as the
electrolyte.
The electrodes were prepared as follows: The as-prepared α- Fig. 1. SEM images of (a, b) α-Co(OH)2 and (c, d) Co3O4 microspheres. Scale bar: 1 µm
Co(OH)2 or Co3O4 materials were mixed with acetylene black and (e) X-ray diffraction patterns of α-Co(OH)2 and Co3O4 microspheres.
polyvinylidene fluoride (PVDF) binder at a weight ratio of 7:2:1. The
slurry was then coated on one side of Ni foil with a size of 1×1 cm and further characterized by TEM. Fig. 2a shows the bright field TEM
dried at 60 °C for 12 h. image of a α-Co(OH)2 hexagonal nanosheet. The width of the
nanosheet is measured to be approximately 300 nm. The selected area
3. Results and discussion electron diffraction (SAED) pattern of the nanosheet is shown in the
inset of Fig. 2a. The disperse ring of the SAED pattern reveal almost
3.1. Structure characterizations amorphous nature of the α-Co(OH)2 nanosheet. As shown in Fig. 2b,
High resolution TEM image of the nanosheet indicates that there exists
As shown in Fig. 1, the morphology and structure of the as- a great deal of nano-crystallines with size ~5 nm. Compared to that of
prepared microspheres were characterized by SEM and XRD. The α-Co(OH)2 nanostructure, the crystallinity of the Co3O4 microsphere is
microspheres samples collected directly after the solvothermal process much better. Fig. 2c displays bright field TEM image of one represen-
are shown in the SEM image in Fig. 1a and b with different tive Co3O4 microsphere with diameter of ~ 1 µm. The diffraction
magnifications. These microspheres with nearly spherical shape and contrast of the image is significantly enhanced. The improved crystal-
uniform diameters of about 3–4 µm, are consisted of abundant linity can also been observed from the diffraction rings of the
nanosheets with thickness of ~ 100 nm. As shown in Fig. 1e, all the corresponding SAED pattern shown in the inset of Fig. 2c. The high-
peaks of the XRD spectrum can be identified to the rhombohedral α- resolution TEM image of the Co3O4 nanosheet shown in Fig. 2d reveals
Co(OH)2 phase [32]. that the nanosheet consists of well crystallized nanoparticles. The
After the α-Co(OH)2 microspheres were annealed at 300 °C for 2 h lattice fringes with spacing of ~0.28 nm can be attributed to the (220)
in air, black powders were obtained. All peaks in XRD spectrum can be planes of cubic Co3O4.
assigned to spinal structure Co3O4 (JCPDS No. 43-1003) with good Further evidence for the chemical state of the as-synthesized α-
crystallinity and no other impurities were observed, which indicates Co(OH)2 and Co3O4 microspheres is obtained by X-ray photoelectron
that the α-Co(OH)2 microspheres annealed at high temperature have spectroscopy (XPS) analysis. Fig. 3a-c shows the electronic structure on
been oxidized completely into Co3O4, which is in agreement with the surface of the α-Co(OH)2 spheres. Besides the nominal chemical
previous reports [33–35]. As shown in SEM images in Fig. 1c and d, composition of Co and O, C element is also observed, which maybe
the obtained Co3O4 have similar spherical structures with diameter of originated from the the adsorption of carbon oxides on the surface of
about 1–2 µm. Detailed investigations also reveal that the Co3O4 the sample. Detailed information on the cobalt hydroxide state was
spheres are consisted of ultrathin nanosheets with nanopores on the obtained from the high resolution spectrum of Co 2p shown in Fig. 3b.
surface of the nanosheet. The two dominant peaks at 780.0 and 796.1 eV attributed to Co 2p3/2
The microstructure and crystallography of both samples were and Co 2p1/2 are characteristics of spinel phase of α-Co(OH)2 [15]. The

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Fig. 2. (a) TEM image of α-Co(OH)2 nanosheet and the corresponding selected area electron diffraction(SAED) pattern; (b) The high-resolution transmission electron microscopy
(HRTEM) image of the area indicated in (a); (c) A low magnification TEM image of Co3O4 microsphere and the SAED pattern inserted in the corner; (d) A HRTEM image of individual
Co3O4 nanosheet indicated in (c).

Fig. 3. (a-c) XPS spectra of α-Co(OH)2 microspheres: (a) survey; (b) Co 2p; and (c) O 1s. (d–f) XPS spectra of Co3O4 microspheres; (d) survey; (e) Co 2p; and (f) O 1s.

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additional two satellite peaks at around 786.0 and 801.9 eV were also porous α-Co(OH)2 microspheres electrode conducted at various
observed, which can be ascribed to the plasmon losses and final state charge-discharge current densities. The specific capacitance of the
effects, respectively [15,36]. Fig. 3c shows the XPS spectrum of O 1 s. electrode at different current densities can be calculated from the
The curve fitting of the spectrum indicates that the sample is composed equation,C = I⋅t / sΔV , where I is the discharge current, t is the total
of three main components. The strongest peak at 531.1 eV can be discharge time, s is the area of electrode and ΔV is the potential range
assigned to α-Co(OH)2, the dominating structure of the sample. The of charge/discharge. As shown in Fig. 4c, based on the above equation,
other two smaller shoulder peaks indicate the existence of small the specific capacitance of porous α-Co(OH)2 microspheres can be
amount of Co-O bonding (529.8 eV) for Co3O4 and H-O (532.8 eV) calculated to be 1327, 1228, 1033, 950 and 710 mF/cm2 at current
bonding for water [37,38]. density of 2, 5, 10, 20 and 50 mA/cm2, respectively. The specific
Fig. 3d-f shows the XPS spectra of Co3O4 microsphere. As shown in capacitances of α-Co(OH)2 microspheres is relatively high compared
Fig. 3e, the Co 2p spectrum shows two major peaks with binding with that in the literature show in Table 1. With the current density of
energies at 779.6 and 794.6 eV, corresponding to Co 2p3/2 and Co 2p1/ 2 A/g, the specific capacitances of α-Co(OH)2 microspheres are esti-
2, respectively, which are typically characterized as Co3O4 phase mated to be as high as 1327 F/g.
[39,40]. Furthermore, O1s peak was deconvoluted into two peaks (in The capacitance properties for Co3O4 microspheres consisted of
Fig. 3f), one at 529.8 eV for Co-O bonding corresponds to Co3O4, and thinner nanosheets were also studied carefully, as shown in Fig. 4d-f.
the other peak at 531.8 eV is typical of oxygen in an OH group and The presence of strong cathodic and anodic peaks also indicated good
strongly supports the presence of a hydroxyl species with bonding like pseudocapacitor behaviors. The redox reactions of these porous Co3O4
Co-OH and C-OH [7]. microspheres can be assigned as following:[15]

Co3O4 + OH− + H2 O ↔ 3CoOOH + e− (3)

3.2. Electrochemical properties
CoOOH + OH− ↔ CoO2 + H2 O + e− (4)
The electrochemical properties of both samples were investigated in
a three-electrode cell in 2 M KOH aqueous electrolyte. To study the Fig. 4d shows the CV curves of the as-prepared porous Co3O4
electrochemical performance, both samples were characterized by CV microspheres, which was conducted in a 2 M KOH aqueous electrolyte
and GCD tests as shown in Fig. 4. between 0 and 0.5 V (vs. SCE) at different scan rate of 5, 10, 20, 50 and
Fig. 4a shows the CV curves of porous α-Co(OH)2 microspheres at 100 mV/s−1. A distinct pair of current peaks can be clearly identified
various scan rates with stable potential window of −0.2–0.5 V (versus during the cathodic and anodic sweeps. At a low scan rate of 10 mV/
SCE). As expected, the cathodic peaks shifted towards negative s−1, one current peak can be clearly identified at 0.31 V during the
potential and the anodic peaks shifted towards positive potential with cathodic sweep, but one broad oxidation peak at 0.39 V is observed
the increasing scan rate, illustrating the typical pseudocapacitive during the anodic sweep. When increase of the scan rate, the oxidation
mechanism for porous α-Co(OH)2 microspheres electrode. Two possi- and reduction peaks in the CV curve become asymmetric, indicating
ble reactions are suggested for the electrochemical reactions [15]: significant reduce of the effective interaction between the ions and the
electrode.
Co(OH)2 + OH− = CoOOH + H2 O + e− (1) Fig. 4e presents the typical GCD curves of porous Co3O4 micro-
spheres at various current densities within a potential range of 0–0.4 V
CoOOH + OH− = CoO2 + H2 O + e− (2)
(versus SCE). The charging-discharging curves show well symmetry,
Fig. 4b further shows the galvanostatic charge-discharge curves of demonstrating the excellent electrochemical capacitance behavior and

Fig. 4. (a) CV curves at different scan rates, (b) GCD curves at different current densities and (c) specific capacitances in different current densities of α-Co(OH)2 microspheres; (d) CV
curves at different scan rates, (e) GCD curves at different current densities and (f) specific capacitances in different current densities of Co3O4 microspheres.

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Table 1
Results of the specific capacitance for α-Co(OH)2 and Co3O4 in the literature and our experiment.

Sample Specific capacitance condition Reference

Dodecyl sulfate -intercalated α-Co(OH)2 nanocones 1055, 848, 729, 632, 555, 420 and 300 F/g Current densities of 1, 2, 3, 4, 5, 10 and 15 A/g [41]
Co3O4 13.0 F/g Scan rate 1.0 mV/s [26]
Co3O4 aerogels 623 F/g Scan rate 25 mV/s [42]
Co3O4 nanowire array 922, 768 and 516 F/g Current densities of 2, 5 and 10 A/g [43]
Co3O4 3560 F/g Theoretical [43]
α-Co(OH)2 microspheres 1327, 1228, 1033, 950 and 710 F/ga Current densities of 2, 5, 10, 20 and 50 A/ga Our experiment
Co3O4 microspheres 1183, 1044, 821, 761 and 562 F/ga Current densities of 2, 5, 10, 20 and 50 A/ga Our experiment

a
Take the sample loading of 1 mg/cm2 used in our experiment.

good reversibility for redox process. The superior capacitances of the bounced back to the initial capacity, revealing the repeatability for
porous Co3O4 electrode is calculated to be 1183, 1044, 821, 761 and performances of porous α-Co(OH)2 microspheres and Co3O4 micro-
562 mF/cm2 at the current densities of 2, 5, 10, 20 and 50 mA/cm2 spheres.
(shown in Fig. 4f). The specific capacitances of Co3O4 microspheres are The electrochemical impedance spectroscopy (EIS) analysis was
estimated to be as high as 1183 F/g with the current density of 2 A/g. also employed as one of important methods for investigating the
Though lower than the theoretical value of 3560 F/g for Co3O4 [43]. fundamental behavior of electrodes. Fig. 5d shows the Nyquist plots
The specific capacitance is higher than that in the literature [42,43]. of both porous α-Co(OH)2 and Co3O4 microspheres in the frequency
The good electrochemical performance of microspheres can be ascribed region from 106 Hz to 0.01 Hz. The high-frequency intersection of the
to the distinct 3D network structure with high porosity. The presence of plots at the real axis represents the internal solution resistance (Rs)
pore channels is favorable for the accessibility of electrolyte OH﹣ to the including the electrolyte resistance, contact resistance between current
electrode active surface and a fast diffusion rate of electrons within the collector and electrode material and electrode material intrinsic
redox phase, which increase the specific capacitance [44]. resistance. Clearly, both porous α-Co(OH)2 and Co3O4 microspheres
The long-term cycling performances of both microspheres based with low internal solution resistances display superior electrical con-
electrodes at a current density of 5 mA/cm2 were conducted for 5000 ductivity.
cycles. As shown in Fig. 5a and b, both α-Co(OH)2 and Co3O4 porous
microspheres exhibit excellent stability with even 95.3% and 93.5% 4. Conclusion
retention of the initial capacitances, respectively. To further investigate
the electrochemical performance of both microspheres, rate capability In summary, we have synthesized porous α-Co(OH)2 and Co3O4
was also evaluated from a cyclic charge/discharge process. Fig. 5c microspheres consisting of abundant nanosheets by a simple solvother-
shows both microspheres possess good capacity retention at various mal and subsequently heat-treated process, respectively. The electro-
current densities ranging from 2 mA/cm2 to 50 mA/cm2. When the chemical properties of both microspheres based electrodes were
current density turns back to 2 mA/cm2, the specific capacity then investigated in a three-electrode system. Both samples show excellent

Fig. 5. Capacity retention of (a) the α-Co(OH)2 microspheres and (b) Co3O4 microspheres for 5000 cycles at a current density of 5 mA/cm2. (c) Rate capability at various current density
and (d) Nyquist plots of α-Co(OH)2 and Co3O4 microspheres.

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