Electrochimica Acta 267 (2018) 170e180

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Morphology-dependent electrochemical properties of cobalt-based

metal organic frameworks for supercapacitor electrode materials
Rajendran Ramachandran a, b, Changhui Zhao a, b, Dan Luo a, Kai Wang a, b, Fei Wang a, b, c, *
a
Department of Electrical and Electronic Engineering, Southern University of Science and Technology, Shenzhen 518055, China
b
Shenzhen Key Laboratory of 3rd, Generation Semiconductor Devices, Shenzhen, 518055, China
c
State Key Lab of Transducer Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050,
China

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

Article history: The formation of cobalt metal organic frameworks (Co-MOFs) in different solvents and mixture is studied
Received 17 September 2017 systematically through solvothermal method. The synthesized Co-MOFs are characterized with X-ray
Received in revised form diffraction, Field emission scanning electron microscope and Brunauer-Emmett-Teller surface analyzer to
28 November 2017
know about its crystal nature, morphology and porosity, respectively. Based on the obtained results, a
Accepted 13 February 2018
Available online 14 February 2018
possible formation mechanism of Co-MOFs has been described with respect to nucleation rate and pH.
The electrochemical properties of as prepared Co-MOFs are studied in 3 M KOH for electrode material of
supercapacitors. A maximum specific capacitance of 958.1 F g
1 is achieved for Co-MOF/D-E (Co-MOF
Keywords:
Co-MOF
synthesized in DMF/Ethanol) at a current density of 2 A g
1. Simultaneously, the capacitance retention is
Specific capacitance maintained as high as 92.3%, even after 3000 cycles. The present study demonstrates that synthesis of
BET surface area Co-MOF with large surface area and micropore volume could be possible using DMF/EtOH mixture
Micropores solvent. The hybrid structure of nanoneedles with sharp edge nanorods offer more active sites for
Nucleation rate electrochemical reaction and ensure a higher charge storage capacity than other synthesized Co-MOFs in
this work.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction
In recent years, Supercapacitors or Electrochemical capacitors
have received much consideration among different energy storage
devices such as batteries, fuel cell and conventional capacitors due
to their high power density, fast charging-discharging rate, and
exceptionally long cycle life (up to 104 cycles) [1e4]. Super-
capacitors have made a bridge between the conventional capacitors
and batteries [5]. Based on the charge storage mechanism, super-
capacitors are divided into electric double capacitors and pseudo
capacitors [6]. The energy is stored by charge accumulation process
in EDLC's and by faradic reactions in pseudo capacitors [7]. There
are various kinds of materials have been studied for supercapacitor
electrodes like metal oxides, polymers and carbon based materials
[8]. One of the main challenges for available supercapacitors is the
* Corresponding author. Department of Electrical and Electronic Engineering,
Southern University of Science and Technology (SUSTech), No. 1088, XueyuanRoad,
Xili, Nanshan District, Shenzhen 518055, China.
E-mail address: wangf@sustc.edu.cn (F. Wang).
low energy density, which is still lower than that of rechargeable
batteries [9]. For achieving a high energy density of supercapacitor,
the ongoing researches have focused on two aspects: 1. Synthe-
sizing electrode materials with large surface area and 2. Searching a
new electrode material which has both higher capacitance and
larger potential window [10e12].
Metal-organic frameworks (MOFs), also known as coordination
polymers have received more attention in the field of electro-
chemical energy storage systems, including fuel cells, lithium ion
batteries, supercapacitors, solar cells; because of their large acces-
sible surface area, tunable size and pore volume, and incorporated
metal centers [13e15]. Recently, MOF has been used directly as
electrode materials [16,17]. MOF electrode material for super-
capacitors can be classified into two categories: 1. Since MOF can
serve as a precursor to synthesis, metal oxides, metal sulfides and
carbon materials, MOF derived materials have been used as elec-
trode material of supercapacitors [18,19]; 2. MOF themselves can be
used directly as electrode material of supercapacitors. MOFs can
give more accommodation space of electrolyte and active sites for
the redox reaction than MOFs derived materials due to their large
porosity and surface area. Several groups have reported that the

https://doi.org/10.1016/j.electacta.2018.02.074
0013-4686/© 2018 Elsevier Ltd. All rights reserved.
 R. Ramachandran et al. / Electrochimica Acta 267 (2018) 170e180
electrochemical properties of MOFs in supercapacitors including Ni
[20], Zn [21], Cu [22], Mn [23], Fe [24], Ce [25] and recently Co based
MOFs. Among various MOFs, Co-MOFs have received more atten-
tion, due to theirs better redox reaction ability than others. For
example, Diaz et al. first reported the supercapacitor behavior of a
Co-MOF and achieved a maximum capacitance of 0.47 F g
1 at
25 mV s
1 scan rate [26]. Later, the three dimensional structure of
Co-MOF was investigated by Lee et al. with capacitance of 206 F g
1
[27]. Very recently, a layered structure of Co-MOF has been evalu-
ated as supercapacitor electrode by Liu et al. [28]. These MOF ma-
terials have good electrochemical performances due to their redox-
active species; however, the number of the related reports is still
limited until now. Due to the poor electrical conductivity of MOF,
the specific capacitance is usually lower than that of pseudo
capacitive metal oxides [29]. It has been noticed that researchers
are attempting to achieve high energy density supercapacitors by
changing different types of MOFs electrodes. However, the energy
density not only depends on the type of materials, but also its
morphology, size and microstructure [30]. Therefore, the control
over the morphology of MOF with well-defined shapes and uniform
size remains an important goal of modern synthetic chemistry to
improve the electrochemical performance of supercapacitor elec-
trodes. Up to now, several kinds of methods have been proposed for
modulating morphology and size of MOFs, such as template
method [31], different solvents [32], sonochemical process [33],
and acid-based adjustment routes [34]. Among them, using
different solvent is the most convenient way to synthesis MOFs
with desirable structure and properties. Several solvents such as N,
N-dimethylformamide (DMF), Ethanol, 1-methyl-2-pyrrolidone
(NMP), N, N-diethylformamide (DEF) and water have been used
for MOFs synthesis under high temperatures. It is known that the
majority of MOFs are unstable in water, suffering from phase
changes, loss of crystallinity [35]. Cheng et al. [36], have studied the
aluminum based MOF preparation in DMF/water mixed solvent
with various volume ratios and found that increasing the volume
ratio of water in mixed solvent, which led to the different sizes and
morphologies of MOF. The optimization study of ethanol content in
water/ethanol mixed solvent system for Cu-MOF synthesis has
been studied by Zhang et al. [37]. Both reports have proved that the
surface area and porosity of the MOF could be increased with the
optimized volume ratio of mixed solvents rather than the use of a
single solvent system. Very recently, Israr et al. have studied the
surface area of Ni-BTC's which are synthesized by different mixed
solvents [38]. This report clearly demonstrated that the mixed
solvents could improve the porosity nature of the MOF. Since the
surface area and the porosity of MOF are the important factors for
energy storage applications, thus, efforts turned towards to find the
suitable solvent and volume ratios for MOF preparations. To best of
our knowledge, there is no report on the modulation of Co-MOFs
morphology and size with different mixed solvent systems and
its electrochemical properties towards supercapacitor.
Considering all these factors, we have carried out a systematic
investigation of Co-MOF formation in different mixture solvents
and studied the electrochemical properties for supercapacitor ap-
plications. We have built a solvent system alone and related
mixture, just by varying the composition of solvents while keeping
the other conditions unchanged, series of Co-MOF crystals with
different shape and sizes have been obtained. It should be noted
that the chemical structure and the geometries of organic linkers,
and the coordination modes of the metal ions are the most
important parameters for MOF synthesis [39]. Terephthalic acid
(H3BTC) was used as the organic linker in this work since the
binding ability of H3BTC with the common metal ions such as Co,
Cu, and Ni is higher than other organic linkers [40]. As synthesized
Co-MOFs were well characterized and tested for supercapacitive
171
behavior in 3 M KOH electrolyte. A maximum specific capacitance
of 958.1 F g
1 with energy density of 24.4 W h kg
1 was achieved
for MOF which was prepared in DMF/Ethanol mixture solvent (Co-
MOF/D-E). This research is meaningful in view of the following two
reasons: 1. The development of Co based MOF with different
structures for supercapacitors and 2. It provides a better under-
standing of the solvent mechanism for Co-MOF formation by using
H3BTC as an organic linker.
2. Experimental method
2.1. Materials
Cobalt (II) nitrate hexahydrate (Co(NO3)2.6H2O), 1,3,5-
tricarboxylic acid (H3BTC), N,N-diethylformamide ((CH3)2NCH),
Ethyl alcohol, Potassium Hydroxide (KOH) were purchased from
Sigma-Aldrich. All the solutions were prepared using Milli-Q water
(pH 7.2).
2.2. Preparation of Co-MOFs
Typically, 2 mM of H3BTC was added into 48 ml of DMF/Ethanol
mixed solution (1:1 ratio) and stirred for 10 min. After that, 3.6 mM
of Co(NO3)2$6H2O was added into the above solution and
continued stirring for another 10 min. Then the mixture was
transferred into a Telflon-lined stainless steel autoclave (70 ml ca-
pacity). After sealing, the autoclave was heated to 120  C for 12 h
and cooled naturally to room temperature. Finally the resulting
precipitate was washed several times with water and ethanol, and
dried at 70  C for 12 h in a vacuum oven. The prepared sample was
named as Co-MOF/D-E. Similarly, the other Co-MOFs, Co-MOF/D-W,
Co-MOF/D-W-E, Co-MOF/D and Co-MOF/E were prepared in DMF/
Water (1:1), DMF/Water/Ethanol (1:1:1), DMF and ethanol sol-
vents, respectively. The total volume of solvent in all the case was
kept to 48 ml.
2.3. Material characterization
X-ray diffraction system (Rigaku Smartlab) was used with Cu-Ka
radiation (l ¼ 1.540 Å). Step scanning was done with 2q intervals
from 6 to 55 . The surface morphologies of the samples were
characterized by using scanning electron microscope (Zeiss Merlin)
and transmission electron microscope (Tecnai F30). The N2
isotherm of the samples was measured using by BET ASAP 2020.
2.4. Electrochemical measurements
All the electrochemical measurements were carried out in an
electrochemical analyzer (CHI 660 E work station). The potentials
were measured with respect to Ag/AgCl (sat.KCl) as the reference.
Ni foam (purchased from Cabot, USA) and Pt wire were used as the
working and counter electrode, respectively. The cyclic voltam-
metry was performed at various scan rates in the potential range
from 0 to 0.5 V. The working electrode was prepared as follows: In
brief, a known amount of active material was dispersed in 5 wt % of
nafion and ethanol mixture, and the mixture was coated with Ni
foam (2 cm  1 cm  0.1 cm). The total surface area coated with
active material was 0.5  0.5 cm2. The mass of the active material of
electrode was 4 mg/cm2. Then, the electrode was dried for 3 h at
room temperature. Cyclic voltammetry (CV), Galvanostatic charge-
discharge (GCD) and Electrochemical impedance spectroscopy (EIS)
studies were carried out in 3 M KOH electrolyte solution under
ambient conditions. ECLab software was used for fitting the EIS
spectrum.
172 R. Ramachandran et al. / Electrochimica Acta 267 (2018) 170e180
3. Results and discussion
In order to check the purity of the Co-MOFs synthesized by
different solvents, X-ray powder diffraction (XRD) was recorded
and shown in Fig. 1. The sharp and clear observed diffraction peaks
indicating that the prepared Co-MOF samples have good crystal-
linity. All the diffraction peak positions were in good agreement
with the simulation based on Co-MOF single-crystal XRD data
(Cambridge Crystallographic Data Centre - 153067) [41,42]. There
are no other peaks in the powder diffraction pattern, indicating the
high-level purity of Co-MOF samples. The diffraction peaks of all
the samples (exclude at 10.3 for Co-MOF/D-W-E) are identical to
each other except for minor differences in their intensities. This is
probably due to the fact that some of the initial samples may
contain water or used solvent molecules in their pores, which lead
to minor alterations in their XRD pattern [36]. The disappeared
peak at 10.3 for Co-MOF/D-W-E sample indicates that the slightly
collapsed MOF network. Since the presence of water molecules in
the DMF/Ethanol effectively prevents the co-ordination between
the carboxyl groups and Co atoms, the peak disappears [37].
The morphology of synthesized Co-MOFs in different mixture
solvents was investigated by SEM analysis. SEM images of the
samples clearly show the difference in crystal size, morphology,
and dimensionalities. Uneven size of rod-like structure was
observed for the MOF synthesized in DMF solvent alone (Fig. 2
a&b). The width of the nanorods is in the range of a few hundred
nanometers to ~3 mm and the length up to several micrometers. It
can be seen that the obtained nanorods surface is completely
smooth and most of the nanorods are broken. When ethanol was
introduced to DMF (MOF-D/E), nano needles and rod kind hybrid
structure was formed with the size of needles from a few nm to
~2 mm. As evidenced from Fig. 2 c and d, the obtained nanorods in
the hybrid structure exhibit almost uniform size with sharp edges
of nanorods and nanoneedles with less than 2 mm width, which
suggests that the ethanol molecules could increase the hydrogen
bond strength of mixture solvent and ligands [37], and favorable for
small needle crystal size MOF formation. It could be seen appar-
ently that there were fissures on the surface of nanorods (Fig. 2 d),
which indicates that the ethanol molecules in DMF solvent might
create the rough surface of the MOF. Recently, some of the literature
Fig. 1. XRD pattern of (a) Co-MOF/D-E (b) Co-MOF/E (c) Co-MOF/D-W-E (d) Co-MOF/D-
W and (e) Co-MOF/D.
have reported the rough morphology of MOF structure obtained by
DMF/ethanol mixed solvent [43,44] though the mechanism is still
unclear. It is believed that the rough surface can increase the
porosity and hence, better electrochemical behavior would be
achieved. In addition, most of the nanoneedles were isolated and
attached on the rough surface rods (Inset picture of Fig. 2 (d)),
which also enhances the charge propagation during the electro-
chemical performance. As shown in Fig. 2 e and f, bulk rods with
crystal structures length up to ~15 mm are formed in water based
mixed solvents which might due to the slow nucleation process.
Cheng et al. have reported that one specific direction crystal growth
of MOF with longer size was obtained by water molecules [36].
Similar kind of bulk crystal growth has been found when water
molecules were introduced into mixture solvents (DMF/water and
DMF/water/ethanol). Pawar et al. have reported that the 1D
microrods with porous structure enhanced the electron transport
for photo degradations [45]. Similarly, the bulk crystal rods in Co-
MOF/D-W and Co-MOF/D-W-E could improve the electrochemical
properties than nanorod structures obtained in pure DMF. From
Fig. 2 g and h, it can be seen that needles in the range of a few nm to
~2 mm were obtained, suggesting that ethanol molecules are
favorable for a smaller size of MOF nanocrystal synthesis without
any capping agent. Since most of the needles were less than 100 nm
size, the aggregation of these needles may be responsible for
dropping surface area and porosity. Thus, the MOF synthesized in
pure ethanol (MOF-E) delivered lower electrochemical activities
than MOF-D/E. Fig. 2 i and j shows the nano and bulk crystal rods
with some of the hexagonal layer structure of Co-MOF. The size of
the hexagonal layer is around ~10 mm with a thickness of several
nanometers. The microstructure of Co-MOF/D-E was further
investigated by HRTEM analysis. From Fig. 3, the MOF synthesized
by DMF/ethanol solvent has demonstrated hybrid structure with a
large number of nanoneedles and rods. Needles with uniform size
can be observed from the images, which is consistent with SEM
studies.
The N2 adsorptionedesorption isotherms at 77 K and Bar-
retteJoynereHalenda (BJH) pore size distribution measurements
were further performed to evaluate the surface area and the
porosity of Co-MOFs. From Fig. 4, the isotherm of all Co-MOF
samples can be attributed as a typical type IV hysteresis and the
loop at a relative pressure between 0.7 and 1.0, indicating the
presence of mesoporous in MOF samples [18]. As shown in Fig. 4 a,
BET surface area of 31.98 m2 g
1 is observed for Co-MOF/D-E, which
is higher than that of the other Co-MOFs. The isolated small needle-
kind of structure on the one dimensional nanorod improves the
surface area of Co-MOF/D-E. Various surface areas of 5.73, 1.81, 2.27
and 3.84 m2 g
1 were achieved for Co-MOF/E, Co-MOF/D-W-E, Co-
MOF/D-W and Co-MOF/D, respectively. The result was further
validated by the Barrett-Joyner-Halenda (BJH) pore size distribu-
tion curve as shown in Fig. 4b which also shows the presence of
micro and mesoporous. The higher differential pore volume of Co-
MOF/D-E suggested the increased total pore volume. The total pore
volume of other MOFs roughly decreases (Table S1), which in-
dicates smaller BET surface area. Though Co-MOF/E has smaller
crystal sizes than Co-MOF/D-E, the more aggregation of nano-
needles reduced the surface area. It is known that the specific
capacitance of electrode materials depends on the specific surface
area, total pore volume and micro porosity; therefore, high surface
area and larger micro porous structures would directly facilitate
fast ion transport at the electrode/electrolyte interfaces, which in-
creases utilization of the electroactive materials and leads to higher
specific capacitance [46]. Therefore, the larger surface area and high
micropore volume of Co-MOF/D-E are likely to enhance its elec-
trochemical performance for supercapacitors.
Based on the results and discussion above, the formation
 R. Ramachandran et al. / Electrochimica Acta 267 (2018) 170e180 173

Fig. 2. SEM images of (a, b) Co-MOF/D (c, d) Co-MOF/D-E (e, f) Co-MOF/D-W (g, h) Co-MOF/E and (i, j) Co-MOF/D-W-E.

Fig. 3. HRTEM images of Co-MOF/D-E at various magnifications.

Fig. 4. (a) Nitrogen adsorption-desorption isotherms and (b) Pore size distribution curve of Co-MOFs.

mechanism can be described as follows (Scheme 1). Generally, fast
nucleation rate will lead to small crystal size of MOF formation and
vice versa [47]. The rate of nucleation and crystal growth can be
controlled by the deprotonation rate of organic linkers in solvents.
The solvents can decide the coordination interaction between the
metal ions and the organic linkers, resulting in MOF with tunable
size and morphology. H3BTC has higher coordination chemistry
(binding ability) of the Co(II) ions than other organic linker;
therefore, remarkably good yield of MOF can be easily obtained.
When DMF is used as a solvent alone, H3BTC is more favorable for
174 R. Ramachandran et al. / Electrochimica Acta 267 (2018) 170e180
Scheme. 1. Formation mechanism of Co-MOFs in different solvents.
the coordination of organic ligand with metal ions (Co(II)) due to
the higher deprotonation rate of H3BTC. Since DMF has better
ability to improve the deprotonation of H3BTC than water and
ethanol [38], weak coordination with hydrogen protons was
formed by the DMF molecules and produced one dimensional
nanorod crystals. When water is introduced into DMF, the depro-
tonation rate of H3BTC becomes slow, because water reduces the
solubility of H3BTC in the reaction mixtures and slows down the
nucleation rate. So the crystal size of Co-MOF in water based mixed
solvents is increased. The water molecules in mixed solvents (DMF/
water and DMF/water/Ethanol) can build up the growth of crystals/
particles in one specific direction; therefore, the nanorod structure
turns out to be longer with increased size for Co-MOF/D-W and Co-
MOF/D-W-E. When ethanol was introduced into DMF, the solubility
of H3BTC has grown and the coordination between H3BTC and
Co(II) is greatly improved. Hence, the nucleation rate becomes
much higher in DMF/EtOH solvent which results in the smaller size
of needle crystal structure with nanorod formation. In other words,
the lower pH value leads to a slower nucleation process. The pH of
DMF/EtOH solvent is higher than that of water mixed solvents
(Table S2), resulting in accelerated nucleation rate and the crystal
size is decreased. The coordination of H3BTC and Co(II) is much
higher in ethanol solvent alone than DMF/EtOH system, promoting
the crystal growth formation. In contrast, pH value of both DMF and
ethanol alone is lower than that of other solvent systems, while
faster crystal growth and smaller size of the Co-MOFs have still
been obtained. It is also notable that the obtained final product
yield in the single solvent systems (pure DMF and pure ethanol) is
relatively low compared with mixed solvent systems (Table S2).
This result indicates that the mixed solvent systems might be
beneficial for high yield MOF synthesis with large surface area,
especially DMF/ethanol mixed solvent. A comparison between our
work and previously reported morphologies obtained by other Co-
MOF synthesis conditions are listed in Table S3.
To investigate the potential application of the Co-MOF's as
working electrode of supercapacitors, the electrochemical perfor-
mances such as cyclic voltammetry, Galvano static charge-
discharge and electrochemical impedance have been tested. Fig. 5
shows the cyclic voltammetry (CV) curves of prepared Co-MOF
electrodes at second cycle. All the CV curves show one couple of
redox peaks, which indicate the pseudo capacitive behavior of the
electrodes from the surface redox reactions. The anodic and
cathodic peaks at about 0.35 V and 0.2 V might be due to the con-
version of different cobalt oxidation states like CoII to CoIII and then
CoIV [48].
CoðIIÞs þ OH
4CoðIIÞs ðOHÞad þ e
1 (1)
CoðIIÞs ðOHÞad 4CoðIIIÞs ðOHÞad þ e
1 (2)
The oxidation and reduction peaks of all the electrodes move to
the positive and negative directions at higher scan rates, which is
attributed to the internal resistance of the electrodes [49]. On the
other hand, the positive ions in electrolyte (Kþ) can easily diffuse
into all the available spaces of electrodes at lower scan rates,
leading to sufficient redox reactions [50]. In Fig. 5c, it was notable
that the redox peak position of Co-MOF/D-W-E sample occurs at
more positive potential might be due to higher internal or charge
 R. Ramachandran et al. / Electrochimica Acta 267 (2018) 170e180
Fig. 5. Cyclic voltammetry response of (a) Co-MOF/D-E (b) Co-MOF/E (c) Co-MOF/D-W-E (d) Co-MOF/D-W (e) Co-MOF/D and (f) Comparison of CV with bare electrode at 5 mV s-1
scan rate (second cycle).
transfer resistance. The redox peaks of all Co-MOF electrodes can be
observed significantly even at high scanning rates, which suggests
good rate capability. The area of CV curves reflects the capacitance
and real active surface area of the materials [51]. The area and
current level of CV curve for Co-MOF/D-E are larger than other
MOF's, which reflects more capacitive nature due to better ion
transport within the hybrid structure of nanoneedles and sharp
edge nanorods.
The galvanostatic charge-discharge (GCD) at different current
densities of Co-MOFs are shown in Fig. S1. The plateaus in the
charge and discharge curves of all electrodes are consistent with
the CV results, indicating the existence of pseudo capacitance
behavior due to the Faradic processes. The nonlinear shape of GCD
curves, attributed to the faradic reactions of Co2þ/Co3þ associated
with OH
, validates the CV results [52]. Fig. 6a shows the charge-
discharge curves of Co-MOF electrodes at a current density of
2 A g
1. The charge-discharge curves can be explained via two
ways: (i) small voltage drop (IR drop), (ii) charge transfer reaction of
the working electrode (redox reaction). A sudden drop of in current
at the start of discharge curve indicates the IR drop of electrode
which is attributed to the internal resistance. As seen in Fig. 6a, the
IR drop of Co-MOF/D-E electrode is lower than other electrodes,
which indicates the enhanced charge storage capacity and less
energy dissipated during charge-discharge process. The isolated
and less aggregated nanoneedles in Co-MOF-D/E makes most of the
surface of nanoneedles easily accessible by the electrolyte ions. This
will promote the charge transport and thus reduce the internal
resistance of the electrode. A similar reason has been reported by
Zhang et al. for NiCo2O4 nanoneedles [53]. The slope variation of
175
time dependence of the potential provides an evidence for pseudo
capacitive behavior, which results from redox reactions at the
interface between the electrode and the electrolyte or the elec-
trochemical adsorption-desorption. From Fig. 6a, the increase in
the charging/discharging time represents the higher specific
capacitance of Co-MOF/D-E electrode [54].
The specific capacitance of electrode materials is calculated from
galvanostatic discharge curves according to the following equation
[55],
i  Dt
Cs ¼ (3)
DV  m
where i is the constant current (A) of the charge-discharge process;
Dt is the discharge time (s), DV is the potential window (V) and m is
the mass of active material on the electrode (g).
A calculated maximum specific capacitance of 958.1 F g
1 was
achieved for Co-MOF/D-E at a current density of 2 A g
1. At the
same current density, the other electrodes, Co-MOF/E, Co-MOF/D-
W, Co-MOF/D-W-E and Co-MOF/D have exhibited the maximum
specific capacitance of 654.4, 626.9, 428.3 and 393.4 F g
1, respec-
tively. The specific capacitance of the electrode decreases in the
order of Co-MOF/D-E > Co-MOF/E > Co-MOF/D-W > Co-MOF-D-W-
E > Co-MOF/D. The specific capacitance depends not only on the
surface area but the micropores of the materials. Since the micro-
pores are leading contributor to the charge storage in electro-
chemical performance [56,57], the larger micropore volume of Co-
MOF/D-E sample implies the better ions transport within the
micropore network. The order of the specific capacitance
176 R. Ramachandran et al. / Electrochimica Acta 267 (2018) 170e180
Fig. 6. (a). Galvanostatic charge-discharge curve at 2 A g
1 current density (b) Specific capacitance as a function of current density (c) Capacitance retention behavior at 10 A g
1
current density (d) Ragone plot relating power density to achievable energy density.
enhancement is consistent with the micropore volume. The specific
capacitance is shown as a function of the current density in Fig. 6b,
when the discharge current density increases from 2 to 30 A g
1.
Even with the largest current density, 65.5% of capacitance can still
be maintained for Co-MOF/D-E electrode, demonstrating the good
rate of capability. When the current density increases from 2 to
30 A g
1, the electrode specific capacitance decreases due to the
decrease of effective interaction between electrode and electrolyte
ions at the high current densities [58]. A comparison is made with
the MOF materials and those reported in previous literature, as
shown in Table 1.
To investigate the cyclic stability of supercapacitor electrodes, an
endurance test was conducted using galvanostatic charging/dis-
charging cycles at 10 A g
1. From Fig. 6c, it can be seen that the
specific capacitance retains about 92.3% from the original capaci-
tance even after 3000 cycles for Co-MOF/D-E electrode, which in-
dicates the good rate capability and excellent electrochemical cyclic
stability among all the Co-MOF electrodes. This remarkable per-
formance can be ascribed to the efficient transportation of the
electrolyte ions within the microporous structures of rods and
needles during the fast charge/discharge process. The energy
density (E) and power density (P) of electrodes can be calculated as
follows [50],
1 CV 2
E¼2 (4)
3600
E
P¼  3600 (5)
t
Ragone plot of the energy density versus power density of Co-
MOF electrodes is shown in Fig. 6d. It is obvious that the energy
density decreases with increasing power density. As shown in the
figure, Co-MOF/D-E electrode delivered a maximum energy density
of 24.4 W h kg
1 at a power density of 0.429 kW kg
1. Even at
higher current density, energy density remaining at 16.11 at a po-
wer density of 6.444 kW kg
1, thanks to the high specific capaci-
tance of Co-MOF/D-E electrode. Whereas other electrodes have
delivered a maximum energy densities of 10.1, 16.09,10.99 and
16.8 W h kg
1 for Co-MOF/D, Co-MOF/D-W, Co-MOF/D-W-E and
Co-MOF/E, respectively. The high energy and power density of Co-
MOF/D-E suggests that the electrode could be used in high per-
formance supercapacitor applications.
Electrochemical Impedance Spectroscopy (EIS) measurement is
a well-known technique to study the frequency-dependent
behavior of the supercapacitive properties of electrodes [63,64]
and was investigated in order to have a better understanding of
 R. Ramachandran et al. / Electrochimica Acta 267 (2018) 170e180 177

Table 1
Comparison of specific capacitance of various MOF electrodes material towards supercapacitor applications.

Material Electrolyte Specific capacitance/F g
1 Current density or scan rate Reference

Ni-MOF 2 M KOH 726 1 A g
1 [59]

Cu-MOF/rGO 0.5 M Na2SO4 385 1 A g
1 [60]
Cu-MOF 1 M Na2SO4 85 1.6 A g
1 [22]
Zn-MOF 1 M Li2SO4 23 25 mA g
1 [61]
Zn-MOF/PANi 1 M H2SO4 477 1 A g
1 [62]
Co-MOF 0.5 M LiOH 179.2 10 mV s
1 [16]
Co-MOF 1 M LiOH 206.79 0.6 Ag-1 [27]
Co-MOF/D 3 M KOH 393.4 2 A g
1 This work
Co-MOF/E 3 M KOH 654.4 2 A g
1 This work
Co-MOF/D-W-E 3 M KOH 428.3 2 A g
1 This work
Co-MOF/D-W 3 M KOH 626.9 2 A g
1 This work
Co-MOF/D-E 3 M KOH 958.1 2 A g
1 This work

electrical resistance and ionic conductivity of Co-MOF electrodes.
Fig. 7 shows the Nyquist plot of Co-MOF electrodes measured with
an AC perturbation of 0.1 V in the frequency range from 1 Hz to
105 Hz. The plots are composed of a semicircle in the high frequency
region and a straight line in the region of low frequency. The ver-
tical line at low frequency region indicates the ideal capacitive
behavior of all Co-MOF electrodes [65]. The ionic conductivity of
the electrolyte system can be found from the intersection of the
curve at real axis at high frequency region and called as solution
resistance (Rs) of electrolyte [66]. It is noted that the ionic re-
sistances of all Co-MOF electrodes are approximately between 0.5
and 0.6 U and this small value of the solution resistance could be
negligible. The interfacial charge transfer resistance (Rct) reflects
the electron conductivity of electrode, which can be measured from
the diameter of semicircle in mid frequency range. It is well known
that the large semicircle diameter indicates high interfacial charge
transfer resistance, which is due to the poor conductivity of elec-
trode [67,68]. As seen from Fig. 7, the small interfacial charge
transfer resistance suggests excellent electrochemical performance
of Co-MOF- D/E electrode with high specific capacitance and good
rate capability comparing to other Co-MOF's electrodes. These re-
sults are consistent with CV and glavanostatic discharge curves.
Low time constant is another important characteristic for fast
charging function for supercapacitor electrodes. The time constant
of the electrode is calculated from the frequency (f *) corresponding
Fig. 7. Nyquist plot of Co-MOFs from the frequency range of 1 Hze105 Hz and its
equivalent fitting circuit model (Inset picture).
to the maximum imaginary component (Z00 ) of the semicircle using
formula below,
1
t¼ (6)
2pf *
The time constant of Co-MOF/D-E is calculated to be 0.0061s,
which is lower than that of other electrodes (Table 2) suggesting
the fast charging behavior due to the large pore size and fast ion
transport between electrode and electrolyte. The power capability
of prepared Co-MOF electrodes was measured by the “knee” or
“onset” frequency (fknee). The transition point between high fre-
quency and low frequency component is called “knee frequency”
and higher power density or faster charging of supercapacitors can
be achieved with a higher knee frequency [69]. In supercapacitors,
the stored charge is not fully accessible at the frequency above the
knee frequency [70]. Therefore, a high knee frequency is preferred
during charging/discharging cycle. A knee frequency of 14.68 Hz
has been obtained for Co-MOF/D-E, which is higher than other
electrodes suggesting the fast ion transport with good power
capability. Hence, Co-MOF/D-E electrode could be used for high
performance supercapacitor application.
Bode phase angle plots and the amplitude of the total imped-
ance versus frequency plots of all Co-MOF electrodes are shown in
Fig. 8. The phase angle of Co-MOF/D-E, Co-MOF/E and Co-MOF/D is
observed about 60 at low frequency, which indicates that the
pseudo capacitance of these electrodes is close to ideal capacitors.
The phase angle is slightly low for Co-MOF/D-W-E and Co-MOF/D-
W electrodes which might be due to the high internal resistance at
low frequency. Also, this may be due to the surface roughness of the
electrode-electrolyte interfaces [71]. Since the size of the rod and
layered structure of these samples is larger, it might introduce more
surface roughness at the electrode/electrolyte interface at lower
frequency region. It is noted that the phase angle has a maximum
value of
55 at characteristic frequency fc ¼ 1.5 Hz, which suggests
the more capacitance behavior at mid frequency range for Co-MOF/
D-W-E and Co-MOF/D-W. The phase angle of all Co-MOF tends
nearly zero at high frequency, which indicates that resistive
component is dominant due to the non-homogenous diffusion in
the less accessible site or some leakage of current in electrode may
govern the impedance. The plot of impedance versus frequency
exhibits three slopes at different frequency regions. At high fre-
quency, all the Co-MOF electrodes have a slope of almost zero,
which is due to resistive component at high frequency range (105-
103 Hz). A high value of slope has been observed for Co-MOF/D-E,
Co-MOF/E and Co-MOF/D electrode at low frequency range (100-
1 Hz) where the electrodes behave pure capacitive nature without
any resistance feature; and for the mid frequency region (103-
100 Hz) these electrodes exhibit both capacitive and resistive
feature. Whereas ideal capacitor behavior has been noticed for Co-
178 R. Ramachandran et al. / Electrochimica Acta 267 (2018) 170e180

Table 2
Various observed analysis parameters of Co-MOF samples.

MOF BET surface area/ Solution resistance Rs/ Charge transfer resistance Rct/ Time constant t/ Knee frequency- fknee/ Specific capacitance C/F
m2g
1 Ohm Ohm s Hz g
1

Co-MOF/D-E 31.98 0.57 1.7 0.00610 14.68 958.1

Co-MOF/E 5.73 0.62 2.6 0.0132 12.12 654.4
Co-MOF/D-W- 1.81 0.51 10.3 0.1091 1.468 428.3
E
Co-MOF/D-W 2.27 0.59 7.5 0.6100 1.778 626.9
Co-MOF/D 3.84 0.65 4.7 0.0233 3.831 393.4

Fig. 8. Bode plots of phase angle and bode plots of total impedance versus frequency (a) Co-MOF/D-E (b) Co-MOF/E (c) Co-MOF/D-W-E (d) Co-MOF/D-W and (e) Co-MOF/D.

MOF/D-W-E and Co-MOF/D-W electrodes at mid frequency region

due to the only capacitive component of the interface. Bode phase
angle plots also display similar behavior.
The electrochemical measurements indicate that the Co-MOF/
D-E electrode delivers high specific capacitance with good cycling
stability. This should be ascribed to the following factors. First, the
nanosized needles and sharp edge nanorods in Co-MOF/D-E pro-
vided abundant channels for ion exchange and therefore facilitated
easy electrolyte ions into electrode (Scheme 2). Secondly, the large
surface area and micropore volume leads to sufficient contact be-
tween the active material and the electrolyte, and shorten the
diffusion distance of OH
. Therefore, Co-MOF/D-E electrode can
enhance the electrochemical supercapacitive performance.

4. Conclusion

In summary, we have demonstrated a systematic investigation

on the synthesis of different structure and size of Co-MOFs in
various solvents. The crystal nature and porosity behavior of as-
prepared samples were studied by XRD and BET analysis. The Scheme. 2. Charge transport mechanism of Co-MOF/D-E electrode.

morphology of Co-MOFs synthesized in different solvents were

studied by SEM analysis and based on the obtained results, for-
EtOH mixture and EtOH alone. Electrochemical properties of Co-
mation mechanism has been described. These results have proved
MOF electrodes were tested in 3 M KOH electrolyte towards
that the synthesis of small crystal size of MOF is possible in DMF/
 R. Ramachandran et al. / Electrochimica Acta 267 (2018) 170e180
supercapacitor application and the results suggested that the Co-
MOF/D-E electrode could be used for high-performance super-
capacitor application. Maximum specific capacitance and energy
density of 958.1 F g
1 and 24.4 W h kg
1 have been achieved for Co-
MOF/D-E electrode at a current density of 2 A g
1. High capacitance
retention of 92.3% over 3000 cycles has been achieved, indicating
better stability of Co-MOF/D-E electrode than other electrodes.
These excellent electrochemical properties might be attributed to
the large surface area with high micropore volume of Co-MOF/D-E,
and fast ions transport into electrode/electrolyte interfaces.
Acknowledgement
This work was supported by National Natural Science Founda-
tion of China (Project No. 51505209) and Shenzhen Science and
Technology Innovation Committee (Projects No. JCYJ2017041
2154426330 and KQTD2015071710313656). Fei Wang is also sup-
ported by Guangdong Natural Science Funds for Distinguished
Young Scholar (Project No.: 2016A030306042) and the Guangdong
Special Support Program (Project No.: 2015TQ01X555).
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.electacta.2018.02.074.
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