Journal of Materials Science: Materials in Electronics

https://doi.org/10.1007/s10854-018-0277-5

A facile synthesis of self-assembling reduced graphene oxide/cobalt

carbonate hydroxide papers for high-performance supercapacitor
applications
Long Jiao1,2 · Xuexue Pan1,2 · Yunlong Xi3 · Junzhi Li1,2 · Junming Cao1,2 · Qing Guo1,2 · Wei Han1,2,3

Received: 11 April 2018 / Accepted: 23 October 2018

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract
Electrode materials as an important component for the supercapacitors (SC) mainly undertake energy storage. Hence, the
research hotspots in the SC fields are focused on the active materials of the electrode. In this study, we have provided a fac-
ile synthesis method to prepare reduced graphene oxide (RGO) and cobalt carbonate hydroxide (Co(CO3)0.5(OH)0.11·H2O)
nanorod composites. The RGO films were obtained by vacuum filtration of GO papers and hydrothermal method. And dur-
ing this hydrothermal, Co(CO3)0.5(OH)0.11·H2O nanorods also grow on the surface of RGO films. The as-fabricated RGO/
Co(CO3)0.5(OH)0.11·H2O composites are characterized by SEM, EDS, XRD measurement. According to the electrochemical
research results, the RGO/Co(CO3)0.5(OH)0.11·H2O electrodes own an ultrahigh volumetric capacitance of 1627 F cm−3 at a
current density of 0.5 A g−1. Besides, the energy density of the symmetrical supercapacitor (SSc) assembled with the RGO/
Co(CO3)0.5(OH)0.11·H2O electrode material is 9.22 mW h cm−3, and the capacity can be maintained 100.0% after 10,000
cycles when the composite material at the current density of 1 A g−1, these promote an efficient electrode material for elec-
trochemical supercapacitor applications.

1 Introduction supercapacitors (SCs) due to its higher power density (vs.

With the rapid economic development, fossil energy short-
ages and environmental pollution problem have become
particularly acute. Up to now, a large amount of sustain-
able and renewable energy resources (such as the hydro-
energy, solar energy and wind energy resources, etc.) have
been widely applied to our daily life with the help of vari-
ous energy conversion and storage devices [1–5]. Thereinto,
Electronic supplementary material  The online version of this
article (https​://doi.org/10.1007/s1085​4-018-0277-5) contains
supplementary material, which is available to authorized users.
* Qing Guo
qingguo@jlu.edu.cn
* Wei Han
whan@jlu.edu.cn
1
Jilin Supercapacitor Engineering Laboratory, College
of Physics, Jilin University, Changchun 130012, China
2
International Center of Future Science, Jilin University,
Changchun 130012, China
3
School of Physics and Electronic Engineering, Linyi
University, Linyi 276000, Shandong, China
battery), larger energy density (vs. traditional capacitor), fast
charge–discharge rate, long-cycling life (> 100,000 cycles)
and environment friendly, have been considered as a popu-
lar research hot spot [6–8]. Depending on the energy stor-
age mechanism, SCs can be classified into electrical double
layer capacitors (EDLCs) and pseudocapacitors. EDLCs are
based on electrostatic incorporation to form electrical dou-
ble-layer between the electrode and electrolyte interface [9,
10]. And the electrode materials for the EDLCs are usually
carbonaceous materials, such as active carbon [11], carbon
nanotube [12] and grapheme [13], etc. The pseudocapacitors
generally depend on the reversible faradaic redox reactions
of active materials with the electrolyte, such as transition-
metal oxides ­(MnO2 [14], ­CoOx [15], ­NiOx [16], ­SnO2 [17],
etc), hydroxides (such as Co(OH)2 [18], Ni(OH)2 [19]) and
conducting polymers (polyaniline [20], polypyrrole [21]).
The pseudocapacitors generally can afford higher theoretical
specific capacitance than that of EDLCs electrodes.
Among various transition-metal electrode materials,
cobalt-based materials with multiple oxidation states,
superior redox activity, controllable morphologies, eco-
friendliness, and low-cost fabrication have emerged as
potential SCs electrodes [22, 23]. Recently, the usual

13
Vol.:(0123456789)

Co-based active materials such as CoO, ­Co3O4, Co(OH)2,
­N iCo 2O 4 [24], ­C oMoO 4 [25] and C ­ oxSe [5], etc have
widely been studied by numerous researchers. These mate-
rials generally are based on Faradaic chemical reaction
­( Co 2+/Co 3+/Co 4+), hence, cobalt carbonate hydroxides
(Co(CO3)0.5(OH)0.11·H2O) as intermediate products also
present electrochemical storage energy behavior [26, 27].
And due to prominent environmental and resource issues,
low-cost and non-toxic cobalt carbonate hydroxides (Co(C
O3)0.5(OH)0.11·H2O) have drawn more attention in the use
of supercapacitors (SCs). Based on the fast and reversibe
reaction on the electrode surface, Co(CO3)0.5(OH)0.11·H2O
can reach the inside of the battery to achieve energy stor-
age in the three-dimensional space. However, low conduc-
tivity seriously limits its applications and developments.
It is well-known that reduced graphene oxide (RGO) has a
crystalline allotrope of sp2 bonded carbon with 2-D char-
acteristics, ultrathin nanosheets microstructure, excellent
electrical conductivity, wonderful mechanical strength and
high theoretical specific surface area (2675 m 2 g−1) [28,
29]. Therefore, RGO as conductive substrates are used for
the low conductivity of Co(CO3)0.5(OH)0.11·H2O to form
a 3D hybrid structure.
Here, we report a facile and efficient route to synthe-
size flexible stereometric composites structure with RGO
sheets and Co(CO3)0.5(OH)0.11·H2O nanorods for SCs, where
Co(CO3)0.5(OH)0.11·H2O nanorods are directly grown on the
RGO film via a simple hydrothermal deposition. In addi-
tion, RGO film were prepared by one-step simple vacuum
filtration method. The electrochemical performance of the
obtained RGO/Co(CO3)0.5(OH)0.11·H2O electrode is evalu-
ated in a three-electrode system at room temperature. Inter-
estingly, the as-prepared RGO/Co(CO3)0.5(OH)0.11·H2O film
exhibits high volumetric capacitance of 1627 F cm−3 a cur-
rent density of 0.5 A g−1 and good cycling stability in a 3 M
KOH electrolyte, making such a hybrid paper a promising
electrode for SCs applications.
2 Experimental section
2.1 Synthesis of GO thin films
All the chemicals are analytical grade and are used without
further purification. The experimental oxidation of graphene
(GO) is purchased from the six Element (changzhou) Mate-
rial Technology Co., Ltd.. The first step is to prepare the
GO film. In detail, 15 mg of GO powder was added to 30 ml
of deionized water to sonicate for another 30 min and then
filtered by a vacuum filter equipped with a 0.2 µm porous
polytetrafluoroethylene (PTFE) membrane to obtain a GO
film. The quality of GO films is about 2.1 mg (1 × 1 cm).
13
Journal of Materials Science: Materials in Electronics
2.2 Synthesis of preparation of RGO/
Co(CO3)0.5(OH)0.11H2O (RCCO)
The same mass of Co(NO 3) 2·6H 2O and urea were dis-
solved in 60 ml DI H ­ 2O at the same time and mixed by
magnetic stirrers for 30 min. The weight of cobalt salt used
for preparing the composite are 0.12, 0.24, 0.36, 0.48, 0.6,
0.75 g, respectively.Then, the above homogeneous solu-
tion and the pre-weighed GO films were also transferred
into a Teflon-lined stainless steel autoclave. The auto-
clave was sealed and maintained at 120 °C for 8 h. After
cooled to room temperature, the flexible hybrid RGO/
Co(CO3)0.5(OH)0.11H2O paper was rinsed under ultrasoni-
cation, and dried in a vacuum oven at 60 °C for 12 h.
2.3 Materials characterization
The scanning electron microscopy (SEM, Magellan 400)
equiped with an energy dispersive X-ray spectrometer
(SEM-EDX, Magellan 400) and transmission electron
microscopy (TEM, JEOL JSM-2010F) of as-fabricated
samples were used to characterize their morphology,
microstructure and element compositions. Crystal-
lite structures of the samples were identified by a Japan
Rigaku 2550 X-ray powder diffractometer (XRD) with
Cu Kα radiation (λ = 1.54056 Å) operating at 40 kV and
250 mA.
2.4 Electrochemical tests
The electrochemical performances of samples were
evaluated in a conventional three-electrode system with
a 3  M KOH aqueous solution as electrolyte. The com-
posite films directly attached on Ni foam collector by
roller were as the working electrode, the prepared RGO/
Co(CO3)0.5(OH)0.11·H2O film was aligned with the pre-
cleaned 1 × 2 cm Ni foam and placed on the roller press with
a thickness of 0.2 mm. Before rolling, the average weight
of RGO/Co(CO3)0.5(OH)0.11·H2O thin films was 2.36 mg, a
platinum electrode and a saturated calomel electrode (SCE)
were as the counter and reference electrodes, respectively.
The cyclic voltammetry (CV), galvanostatic charge–dis-
charge (GCD) and electrochemical impedance spectroscopy
(EIS) were carried out by an IVIUM (Netherlands) electro-
chemical working station. And the cycling stability of the
symmetric supercapacitors (SSCs) were tested by a LAND
CT21001A, respectively. EIS was measured at a frequency
ranging from 0.01 Hz to 100 kHz with amplitude voltage of
5 mV at open-circuit potential. The aqueous SSCs fabricated
by separating two electrodes with cellulose paper, consist-
ing of RGO/Co(CO3)0.5(OH)0.11·H2O papers on Ni foam as
Journal of Materials Science: Materials in Electronics

the negative and positive electrodes, were tested in a two
electrode system using 3 M KOH solution.
3 Results and discussion
3.1 Synthesis and structural analysis of the RGO/
Co(CO3)0.5(OH)0.11·H2O film
T h e fa b r i c a t i o n p ro c e s s e s o f f l ex i b l e RG O /
Co(CO3)0.5(OH)0.11·H2O papers are mainly divided into
two steps: the first is to prepare the GO films; the second
is to synthesize RGO/Co(CO 3) 0.5(OH) 0.11·H 2O papers,
as schematically illustrated in Fig. 1. Typically, via vac-
uum filtration process, various ultrathin GO nanosheets
formed a film with uniform thickness. Finally, RGO/
Co(CO3)0.5(OH)0.11·H2O papers were synthesized by one-
step facile hydrothermal method. Through this process GO
have been changed to RGO and Co(CO3)0.5(OH)0.11·H2O
nanorods successfully grow on the surface of the RGO films
(Fig. S1).
Figure  2a shows the XRD patterns of the GO pow-
der, GO film and Co(CO 3) 0.5(OH) 0.11·H 2O film. It can
be seen that GO powder and GO films have a diffrac-
tion peak corresponding to the (002) plane, but the 2θ of
diffraction peak increases due to the enlarged interlayer

Fig. 1  Schematic diagrams of
synthetic procedure of RGO/
Co(CO3)0.5(OH)0.11·H2O papers

Fig. 2  a XRD patterns of the

GO powder, GO film, RGO/
Co(CO3)0.5(OH)0.11H2O
composite film,
Co(CO3)0.5(OH)0.11H2O powder.
b SEM image of the GO film.
c SEM image of the GO/
Co(CO3)0.5(OH)0.11·H2O papers.
d SEM images of the RGO/
Co(CO3)0.5(OH)0.11·H2O papers
from cross-sectional view

13

spacing of sonication [30]. The diffraction peaks of RGO/
Co(CO3)0.5(OH)0.11·H2O papers are different from the dif-
fraction peaks of GO films and GO powders, where the
broad diffraction peaks at 21.6° can be found, correspond-
ing to the characteristic XRD patterns of the RGO (002)
[31], which is due to GO reduced with hydrothermal treat-
ment. The diffraction peaks of the powders collected after
hydrothermal reaction of RGO/Co(CO 3)0.5(OH)0.11·H2O
papers at 17.1°, 33.7°, 35.0°, 36.1°, 39.3°, 46.8°, 53.5°,
55.7°, 59.5°, 61.6°, 65.6°, correspond to (020), (221),
(040), (301), (231), (340), (060), (142), (412), (450) and
(023) reflections of Co(CO3)0.5(OH)0.11·H2O, respectively.
It was confirmed that these Co(CO3)0.5(OH)0.11·H2O mate-
rials grow on the RGO film surface. Figure  2b shows
the GO film, the surface of the film shows accumula-
tional lamina structure, which is composed of numerous
ultrathin GO nanosheets. This smooth structure is con-
ducive to the rapid transfer and storage of charge, which
can promote positive and negative electrolyte ions flow
and reaction. And RGO films owning oxygen containing
functional groups as the active substrate also is condu-
cive to adhesion of cobalt oxide. As shown in Fig.  2c,
it can be seen that Co(CO 3) 0.5(OH) 0.11·H 2O nanorods
are cross and evenly distributed on the surface of RGO
films, which facilitates the flow of ions and also increases
the specific surface area of the RGO films. The cross
sectional SEM image of the composite film in Fig. 2d,
appears obvious layer stacking which not only increases
the specific surface area, but also facilitates the flow of
positive and negative ions to enhance the redox reaction.
Besides, from cross-sectional view (Fig. 2d) of the RGO/
Co(CO3)0.5(OH)0.11·H2O composite films, their thickness
is mainly distributed at 1032 nm (Fig. S2) and the average
thickness of the film is about 1050 nm, which is used for
volume calculations of active materials. Figure S3a shows
the EDS diagram of RGO/Co(CO3)0.5(OH)0.11·H2O com-
posite. The composite film contains C, O and Co elements,
which evenly distribute in the composite film, as shown in
Fig. 3  The specific capacitances of RGO/Co(CO3)0.5(OH)0.11·H2O papers synthesized with a different mass of Co(NO3)2·6H2O and urea concen-
trations, b different hydrothermal temperature, c different hydrothermal time
13
Journal of Materials Science: Materials in Electronics
Figs. S3a, 2b, c. In addation, the TEM images of RGO and
Co(CO3)0.5(OH)0.11·H2O are shown in Fig. S4.
3.2 Electrochemical performance
of the as‑prepared RGO/Co(CO3)0.5(OH)0.11·H2O
film
Importantly, in order to investigate potential applications of
this composite films in the SC fields, their electrochemical
performance were measured by cyclic voltammetry (CV),
galvanostatic charge–discharge (GCD) and electrochemi-
cal impedance spectroscopy (EIS) methods in a traditional
three-electrode system. The specific capacitance are usu-
ally calculated by the CV and GCD curves. As shown in
Fig. 3a, when the mass of the cobalt nitrate hexahydrate and
the urea sample also are 0.60 g, the composite has larger spe-
cific capacitance of 140 F g−1. It is due to effective contact
area of RGO films for loading of Co(CO3)0.5(OH)0.11·H2O
nanorods. It can be seen in the Fig. 3b that the curve rises
and then falls, indicating that RGO/Co(CO3)0.5(OH)0.11·H2O
composite with the largest specific capacitance at 120 °C,
which is beneficial to the cobalt oxide attaching on the RGO
film. The curve in Fig. 3c rises first and then decreases,
reaching the maximum at 8 h, which presents that 8 h of
hydrothermal process make the material with great spe-
cific capacitance. The electrochemical properties of RGO/
Co(CO3)0.5(OH)0.11·H2O composite film were verified by the
method of 0.6 g of cobalt nitrate and urea, and the hydro-
thermal temperature was 120 °C and the hydrothermal time
was 8 h.
The CV and GCD measurements are performed in a three-
electrode cell using 3 M KOH electrolyte to evaluate the elec-
trochemical properties of the RGO/Co(CO3)0.5(OH)0.11·H2O
composites. Figure 4a shows that the CV curves of the film
at scan rates of 5, 10, 15, 20, 30, 50 mV s−1 present like-
rectangular shape with redox peaks in a potential range
from − 0.2 to 0.4 V, demonstrating that the energy storage
types of the composite films are based on double electrode
Journal of Materials Science: Materials in Electronics
Fig. 4  a CV curves of the RGO/
Co(CO3)0.5(OH)0.11·H2O papers
electrode in 3 M KOH. b Galva-
nostatic discharge curves and c
calculated specific capacitances
of RGO/MoS2 papers electrode
at a current density from 1 to
5 A g−1. d Nyquist plots of the
RGO/Co(CO3)0.5(OH)0.11·H2O
and RGO papers electrode
layer effect (RGO) and redox reaction (Co(CO3)0.5(OH)0.11·
H2O). Two pairs redox peaks observed in the potential
range correspond to the electrode reaction as follows:
2Co(CO3)0.5(OH) + OH ↔ CoOOH + CoCO3 + H2O + e−.
CoOOH + OH− ↔ ­CoO2 + H2O + e− [32]. Besides, with the
increasing of scan rates, the area of the CV curves increase
in grade increments, which indicates high rate performance
of the composites.
Galvanostatic discharge measurements are carried out in
3 M KOH solution between − 0.2 and 0.4 V at different cur-
rent densities range from 0.5 to 5 A g­ − 1, as shown in Fig. 4b.
The GCD curves exhibit slight hump, which be due to the
redox reaction, corresponding to the CV curves. According
to the following equation [13]:
I×t
Csp =
ΔV × m
where I is the charge–discharge current, Δt is the discharge
time, ΔV is the electrochemical potential window, and m
is the mass of active material within the electrode, Fig. 4c
shows the calculated specific capacitance ­(Csp) of the mate-
rial under different current densities. Evidently, the flex-
ible paper electrode exhibits excellent pseudocapacitances
of 275.8, 215.4, 201, 198.7, 197.5, and 194.5  F  g −1 at
0.5, 1, 2, 3, 4, and 5 A g−1, with corresponding volumet-
ric capacitances of 162.7, 126.9, 118.5, 117.2, 116.5 and
114.7 F cm−3, respectively. And the capacitance decreases
as the current density increases owing to that the electrolyte
ions can only reach the outer surface of the electrode at high
current density, and the internal active material does not
actively contribute to the pseudocapacitance. Even then,
the RGO/Co(CO3)0.5(OH)0.11·H2O composites also pre-
sent a high rate performance of 70.5% (the ratio of specific
capacitance at 5 A g−1 vs. 0.5 A g−1), attributed to the good
electrical conductivity of the RGO. Furthermore, at the
scan rate of 5 mV s−1, the RGO/Co(CO3)0.5(OH)0.11·H2O
can maintain 98.2% after 1000 cycles and the coulombic
efficiency is maintained at 100.0% (Fig. S5).
Figure  4d exhibits the Nyquist plots of the RGO/
Co(CO3)0.5(OH)0.11·H2O composites by the EIS measure-
ment. It is seen that the Nyquist plot consists of a semi-circle
measured and a vertical line at different frequency range.
The semi-circle is at the high frequency range, indicating the
total impedance of the supercapacitor devices, the intercept
on Z real is related to the internal resistance (solution or
ionic resistance, ­Rsol) while the diameter of the semicircle
arc is related to the charge transfer resistance ­(Rct) [31]. It
can be seen that the internal resistance (­ Rsol) of 0.6 Ω and
the charge transfer resistance (­ Rct) of 1.6 Ω, which is smaller
than the 3.1 Ω of the RGO.
To evaluate the practical application value of the RGO/
Co(CO3)0.5(OH)0.11·H2O electrode in the SC fields, we
have assembled the symmetrical coin type supercapacitor
(SSC) by using the RGO/Co(CO3)0.5(OH)0.11·H2O papers
on rolled Ni foam as the cathode and anode in 3 M KOH,
with one piece of cellulose paper as the separator. And the
13

SSC devices were tested by CV and GCD measurements in
a working potential windows of 0–0.6 V. The CV and GCD
curves of SSC reveal the rectangular and triangular shapes,
which conforms to the capacitive characteristics, as shown
in Fig. 5a, b, respectively. Besides, as shown in Fig. S6, the
SSC device also exhibits a high rate capability of 87.7%.
The volumetric power density (P) and energy density
(E) of various active materials were evaluated from the dis-
charge curves, according to the following equation [1]:
E = C ΔU2 ∕2V
E and transfer electrons, enhancing the materials capacitive
P=
Δt
where C is the total capacitance of SSC cell, ∆U is volt-
age difference, V is the total volum of the electrode mate-
rials, ∆t is the discharge time. By the above formula, the
calculated maximum energy density (E) is 9.22 mW h cm−3
(Fig. 5c) with the power density of 855 mW cm−3. This
E values of RGO/Co(CO3)0.5(OH)0.11·H2O papers outper-
form those of previously reported SCs devices, such as
N-doped porous carbon cloth device (2.03 mW h cm−3) [33],
­NiCo2Se4/NiCo2O4@PPy ASCs (5.18 mW h cm−3) [34],
­TiO2 nanowire arrays (6.27 mW h cm−3) [35], Hierarchi-
cal ­MnO2 nanowire/graphene hybrid fiber (5.8 mW h cm−3)
[36], etc. Furthermore, at the current density of 5 A g−1,
the SSC can maintain 100.0% after 10,000 cycles and
the coulombic efficiency of SSC is maintained at 100.0%
(Fig.  5d), indicating that this SSC device has excellent
cycle stability. In addation, the charge transfer resistance
Fig. 5  a CV curves of
the as-prepared RGO/
Co(CO3)0.5(OH)0.11·H2O
SSCs at different scan
rates in 3 M KOH. b GCD
curves, c ragone plots and d
cycling stability of the RGO/
Co(CO3)0.5(OH)0.11·H2O SSCs
devices
13
Journal of Materials Science: Materials in Electronics
(Rct) of the SSC is about 2.1 Ω, indicating lower diffusive
resistance (Fig. S7). Hence, based on the above research
results, RGO/Co(CO3)0.5(OH)0.11·H2O composites films can
continue to be studied as promising electrode materials in
the SC fields. The excellent electrochemical performance
is attributed to the synergistic effect between RGO and
Co(CO3)0.5(OH)0.11·H2O nanorods: (1) the RGO conduc-
tive network connects the separated Co(CO3)0.5(OH)0.11·H2O
nanorods, improving the electronic conductivity of the
electrodes; (2) the self-assembled cross-linked structure of
Co(CO3)0.5(OH)0.11·H2O nanorods can facilitate to collect
performance; (3) the absence of binder in the composites
increased the compactness of structure and decrease the
contact resistance.
4 Conclusions
In summary, by one-step facile hydrothermal reac-
tion, we have successfully synthesized flexible RGO/
Co(CO3)0.5(OH)0.11·H2O composites electrodes for electro-
chemical capacitors. RGO films consist of ultrathin graph-
eme nanosheets are obtained through vacuum filtration. The
Co(CO3)0.5(OH)0.11·H2O nanorods are grown on the RGO
film during the hydrothermal reaction. And, the synthesis
condition of the RGO/Co(CO3)0.5(OH)0.11·H2O composites
with the best properties contains 0.60 g cobalt nitrate hexa-
hydrate and 0.60 g urea, heating temperature of 120 °C and
8 h hydrothermal time of 8 h. The as-prepared composites
Journal of Materials Science: Materials in Electronics
exhibits an ultrahigh volumetric capacitance of 1627 F cm−3
at 0.5 A g−1. Most importantly, the assembled aqueous RGO/
Co(CO3)0.5(OH)0.11·H2O SSC devices possess high volu-
metric energy density of 9.22 mW h cm−3. Therefore, the
synthetic RGO/Co(CO3)0.5(OH)0.11·H2O composite films are
potential active materials for the future SC electrodes.
15. X. Zhang, X. Liu, S. Zeng, J. Fang, C. Men, X. Zhang, Q. Li,
Acknowledgements  The authors sincerely acknowledge financial
support from National Natural Science Foundation of China (NSFC
Grant Nos. 21571080), the Nature Science Foundation of Jilin Province
(20170101193JC).
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