Applied Surface Science 483 (2019) 1158–1165

Contents lists available at ScienceDirect

Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Full length article

Fabrication of 3D Co-doped Ni-based MOF hierarchical micro-flowers as a T

high-performance electrode material for supercapacitors
⁎ ⁎
Juan Wanga, Qin Zhonga, , Yongheng Xionga, Danyu Chenga, Yiqing Zenga, Yunfei Bub,
a
School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, PR China
b
Jiangsu Collaborative Innovation Center of Atmospheric Environment and Equipment Technology (CICAEET), School of Environmental Science and Engineering, Nanjing
University of Information Science & Technology, Nanjing 210044, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: Ni-based metal organic frameworks have attracted great interests as novel electrode materials for applications in
Ni-MOF supercapacitors, in virtue of their large specific surface area, high porosity and diverse coordination structure.
Co-doped Unfortunately, their specific capacitance and rate property are usually unsatisfying because of the poor con-
3D flower-like structure ductivity of MOF materials. Herein, 3D Co-doped Ni-based MOF (Cox-Ni-MOF, x = 100n (Co/Ni) = 0.5, 2 and 5)
Hierarchical microspheres
flower-like hierarchical microspheres are prepared via a facile hydrothermal process. The introduction of Co
Supercapacitors
promotes the electrochemical behaviors of Ni-MOF, especially Co2-Ni-MOF. It exhibits a prominent specific
capacitance of 1300 F/g at 1 A/g along with a superb rate performance (1021 F/g at 10 A/g). Meanwhile, ca-
pacitance for Co2-Ni-MOF retains 71% of the original capacitance even after 3000 cycles. The improvement of
electrochemical performance could be due to their unique structural and morphological characteristics including
the 3D flower-like hierarchical microspheres structure, higher specific surface area and enhanced electrical
conductivity. Moreover, a hybrid supercapacitor based on the Co2-Ni-MOF achieves an excellent energy density
of 25.92 Wh/kg at a power density of 375 W/kg.

1. Introduction
Severe environmental pollution urgently demands developing clean
energy and efficient energy storage devices. In this regard, metal-air
batteries, fuel cells and electrochemical capacitors have attracted tre-
mendous attentions [1–3]. Supercapacitors (SCs) are deemed to be the
most prospective electrochemical energy storage system thanks to their
high power density, long lifespan and fast charging capability [4–8].
However, the relatively poor energy output hinders their further ap-
plication of supercapacitors (SCs) [9]. For the purpose of improving the
energy density supercapacitors (SCs) without giving up their high
power density, extensive efforts have been concentrated on developing
electrode materials that are considered to be key factors determining
the electrochemical storage ability [10,11]. Nowadays, sundry super-
capacitor electrode materials like carbon materials, conducting poly-
mers and transition metal oxides have been developed vigorously
[12,13]. Yet, they cannot meet an increasing demand for super-
capacitors (SCs) with higher capacitance, electrochemical stability and
rate capability. Therefore, it is crucial to develop advanced materials
that can improve the electrochemical performance of supercapacitors.
Metal-organic frameworks (MOFs), constructed by coordination of
metal ions and organic brigands, are the goal that we have devoted
much efforts in the past 20 years [13,14]. They have been applied to a
variety of aspects containing gas separation and storage, catalysis,
sensing and so on [15–18]. As a matter of fact, MOFs can be applied to
be electrode materials for SCs. On one hand, high porosity MOFs owe a
large specific surface area that can store quantities of charge and fa-
cilitate diffusion of electrolyte ions. On the other hand, they can pro-
vide plentiful faradaic redox centers [19–21]. Since Co8-MOF-5 as an
electrode material was firstly reported for supercapacitors, the direct
use of MOF as an electrode material has been rapidly developed [22].
Two kinds of Zn-based MOF and Cd-based MOFs reported by Lin et al.
exhibit limited capacitances of 23 and 22 F/g, respectively [23]. No-
tably, Wei et al. fabricates a layered Ni-MOF, showing a remarkable
capacitance (1127 F/g at 0.5 A/g) [19]. However, from an overall
perspective, it is still challenging to use MOFs directly as SCs electrode
materials, because of the relatively poor conductivity of MOFs [24,25].
Different methods have been investigated to promote capacities of MOF
electrode materials. Yang et al. investigates the influence of Zn doping
on the capacitive performance of Ni-MOF, demonstrating that Zn
doping can alter the morphology as well as the structure of Ni-MOF
[26]. Meanwhile, a layered structure Zn-doped Ni-MOF exhibits a

⁎
Corresponding authors.
E-mail addresses: zq304@njust.edu.cn (Q. Zhong), jpu441@yahoo.com (Y. Bu).

https://doi.org/10.1016/j.apsusc.2019.03.340
Received 9 January 2019; Received in revised form 21 March 2019; Accepted 30 March 2019
Available online 31 March 2019
0169-4332/ © 2019 Elsevier B.V. All rights reserved.
J. Wang, et al.
higher capacitance (854 F/g at10 A/g) than the pure Ni-MOF (668 F/g
at 10 A/g) composed of nanosheets. Furthermore, a bimetallic Ni/Co-
MOF fabricated by Zhao. et al. performs a splendid specific capacitance
of 1049 F/g at 1 A/g, owing to the enhanced conductivity contributed
from the synergy between the Ni2+ and Co2+ ions. To date, most of the
reported Ni/Co-MOF has focused on a large amount of Co doping.
Hesari et al. fabricates a Ni/Co-based MOF, the molar ratio of
Ni2+:Co2+ is 1:1 [27]. However, Nesaraj et al. points out that low
doping amount of Co can enhance the electrochemical performances of
NiO electrode materials [28]. Inspired by the above results, we intend
to investigate whether low amount of Co doping will improve the
electrochemical behaviors of Ni-MOF.
In this work, we synthesized 3D Co-doped Ni-based MOFs hier-
archical micro-flowers (Cox-Ni-MOF) by a facile one-step hydrothermal
process. Co doping leads to 3D flower-like microspheres with a more
open hierarchical structure, which facilitates contact between active
sites and the electrolyte ions. In addition, part of Ni2+ is replaced by
Co2+ in Cox-Ni-MOF, thus generating more “free holes”, which in turn
improves the electrical conductivity of the MOF materials [29].
Meantime, the improved oxidation state and the synergy of bimetal in
MOFs are beneficial to heighten the electrochemical performances.
Moreover, a hybrid supercapacitor device was assembled and exhibited
outstanding energy density and power density.
2. Experimental part
2.1. Synthesis of MOFs
2.1.1. Synthesis of Ni-MOFs
The synthesis of the Ni-MOF refers to the experimental methods of
Zhou et al. with a slightly adjustment [12]. In a typical procedure,
solution A and B were prepared by dissolving Ni(NO3)2·6H2O (8 mmol)
and 1,4-benzenedicarboxylic acid (4 mmol) in 30 ml of DMF, respec-
tively. The solution B was poured into solution A after stirring for
30 min, then the dropwise addition of HCl (0.5 ml) to the mixture.
Subsequently, the green solution was poured into a 100 ml Teflon-lined
stainless autoclave for 24 h at the required temperature (180 °C). The
resulting samples were recovered by centralization, rinsed three times
with DMF and ethanol, respectively. In the end, drying the precipitate
in a vacuum oven for 12 h at 60 °C.
2.1.2. Synthesis of Co-doped Ni-MOFs
The synthesis of Co-doped Ni-MOFs refers to the preparation of Ni-
MOF except that different amount of Co(NO3)2·6H2O was dissolved in
solution A together with Ni(NO3)2·6H2O. The obtained Co-doped Ni-
MOFs with different amount of Co(NO3)2·6H2O (the molar ratio of Co/
Ni is 0.5%, 2% and 5%) were denoted as Cox-Ni-MOF, where x = 100n
(Co/Ni) = 0.5, 2 and 5.
2.2. Characterization
X-ray diffraction (XRD) patterns of the synthesized MOF materials
were collected on an X-ray diffraction analyzer. Fourier transform in-
frared (FTIR) spectra were measured on a Nicolet iS-10 infrared spec-
trometer. The morphology of the products was observed on the field
emission scanning electron microscopy (FE-CHEM, Quaint 250FEG)
and transmission electron microscopy (TEM, JEOLJEM 2100, 100 kV),
respectively. X-ray photo electron spectroscopy (XPS) was conducted on
a Thermo-VG Scientific Escalab 250 spectrometer. Under liquid ni-
trogen temperature (77 k), a Micromeritics ASAP 2460 instrument was
utilized to analyze the Brunauer-Emmett-Teller (BET) surface areas of
the samples through N2 adsorption-desorption isotherms. The pore size
and pore volume were determined by the Barrett-Joyner Halend (BJH)
analysis. Before the BET test, the samples were treated under vacuum
degassed at 150 °C for 4 h.
1159
Applied Surface Science 483 (2019) 1158–1165
2.3. Electrochemical measurements
2.3.1. Electrochemical measurements in a three-electrode configuration
Preparations and tests of all the electrodes according to previous
reports in our group, details are as follows [30]. An electrochemical
workstation (IVIUMnSTAT) was used to test the electrochemical prop-
erties of MOF electrode materials. The cyclic voltammetry (CV), gal-
vanostatic charge/discharge (GCD) and electrochemical impedance
spectroscopy (EIS) were investigated in a three electrodes setup. In
addition, cycle stability was executed on a CT2001A LAND Cell test
system. The three electrodes system adopts saturated Hg/HgO, Pt foil
and as-prepared active materials as the reference electrode, counter
electrode and working electrode, respectively. And the electrolyte was
made up of 6 M KOH alkaline solution. The working electrode was
manufactured through mixing active material (80 wt%), acetylene
black (10 wt%), and poly tetra fluoroethylene (10 wt%) well, and sub-
sequently the slurry was coat on a slice of nickel foam
(2.0 cm × 1.0 cm). Finally, drying the working electrode in a vacuum
oven at 80 °C. The mass loading of Ni-MOF, Co0.5-Ni-MOF, Co2-Ni-MOF,
Co5-Ni-MOF on nickel foam was 2.08 mg/cm2, 2.08 mg/cm2, 2.16 mg/
cm2, 2.00 mg/cm2, respectively. The specific capacitance (C (F/g)) was
calculated on the basis of the following Eq. (1):
I × Δt
C=
mΔV (1)
In this equation, I (A), Δt (s), m (g) and ΔV (V) stands for the dis-
charge current, discharge time, loading mass of active material and
discharge potential window, respectively.
2.3.2. Electrochemical measurements in a two-electrode configuration
A hybrid supercapacitor (HSC) was fabricated by using Co2-Ni-MOF
and active carbon (AC) as the positive electrode and negative electrode,
respectively. In order to realize the best electrochemical behaviors,
positive and negative electrodes should maintain charge equilibrium
and meet the relationship of q+ = q−(q = C × m × ΔV) [31]. There-
fore, the optimum mass ratio the two electrodes should satisfy the
following Eq. (2):
m+ C × ΔV−
= −
m− C+ × ΔV+ (2)
In this equation, m (g), C (F/g) and ΔV (V) stands for the mass of
active material, specific capacitance and discharge potential window,
respectively.
The energy density (E (Wh/kg)) and power density (P (W/kg)) of
the energy storage device were obtained according to the following Eqs.
(3) and (4):
C × (ΔV )2
E=
2 × 3.6 (3)
3600E
P=
Δt (4)
In these equations, C (F/g) stands for the specific capacitance, ΔV
(V) represents potential scope and Δt (s) refers to total discharge time,
respectively.
3. Results and discussion
3.1. Structure and morphology characterization
Fig. 1 displays powder XRD patterns of as-prepared samples. With
the increased Co amount, the four samples show similar patterns. The
peaks at around 2θ = 8.3° and 17° are the characteristic peaks of Ni-
based MOF, corresponding to (200) and (201) planes of
Ni2(OH)2(C8H4O4) reported in the literature (CCDC no. 985792)
[32,33]. However, compare with the simulated Ni-MOF, a minor shift
of some peaks to the left is observed for the as-prepared Ni-MOF
J. Wang, et al. Applied Surface Science 483 (2019) 1158–1165

Fig. 1. XRD patterns of obtained MOF materials.

Fig. 2. SEM and TEM images of (a–d) Ni-MOF, (e–h) Co2-Ni-MOF; (i) schematic illustration of the preparation for Ni-MOF and Cox-Ni-MOF.

samples, which may be due to the difference in solvent used. The sol-
vent plays a critical role in the formation of MOFs, dominating the self-
assembly process of metal ions and organic ligand. Besides, it can be
used as a structure-directing agent or a crystal media to influence the
growth process for crystal [34–36]. Therefore, there may be some dis-
crepancies in the XRD patterns between the as-prepared Ni-MOF ma-
terials and the simulated Ni-MOF. Moreover, it can be observed from
the partial magnification patterns of 2θ between 5° and 20°, compare
with the synthesized Ni-MOF, the peaks of Co-doped Ni-MOFs (Cox-Ni-
MOF) have a slightly shift towards higher angle side. This indicates that
Co has been doped into Ni-MOF successfully, the relatively larger Ni2+
ions (0.069 nm) was partially substituted by the relatively smaller Co2+
ions (0.065 nm), corresponding to the previous literature on MOFs'
substitution [37,38]. FTIR results are shown in Fig. S1. The peak at

1160
J. Wang, et al.
Fig. 3. XPS spectra taken from Ni-MOF and Co2-Ni-MOF: (a) survey spectra; (b) Ni 2p; (c) Co 2p.
Table 1
Specific surface area and pore volume of the synthesized Ni-MOF and Cox-Ni-
MOF samples.
Samples Ni-MOF Co0.5-Ni- Co2-Ni- Co5-Ni-
MOF MOF MOF
SBET (m2/g) 112.6 121.0 144.4 123.6
Total pore volume (cm3/g) 0.189 0.246 0.254 0.192
3590 cm−1 stands for the OeH stretching vibration. Other three ab-
sorption peaks at around 1150 cm−1, 1090 cm−1 and 831 cm−1 reflect
para-aromatic CH stretching modes. Besides, two intense bands at
1580 cm−1 and 1380 cm−1 represent antisymmetric as well as sym-
metric vibration of the eCOO− modes, respectively [39]. These ana-
lytical results are consistent with the reported literature [40].
SEM as well as TEM measurements were conducted to investigate
the microstructures and surface morphologies of the synthesized MOFs.
As depicted in Fig. 2, all the samples composed of microspheres but
differ in particulars. The microspheres (2.8 μm) consisting of sheet-like
nanoribbons are observed for Ni-MOF in Fig. 2a–d, which is a layered
structure and consistent with previous reports [12]. For Co2-Ni-MOF,
the sheet-like nanoribbons became wider and the diameter of micro-
spheres decreases slightly. Each microsphere is made up of numerous
interconnected nanoribbons to form a 3D flower-like ball (Fig. 2e–h).
Compare with Ni-MOF microspheres, the 3D flower-like microspheres
for Co2-Ni-MOF shows a more open hierarchical structure, which is
beneficial to fast diffusions of electrolyte ions and easier accesses of
more active sites to their interface in the redox process [41]. It is ob-
viously worth noting that the 3D flower-like hierarchical microspheres
are destroyed and more fragments appear with the increased amount of
cobalt (Co5-Ni-MOF in Fig. S2b). In addition, the selected area electron
1161
Applied Surface Science 483 (2019) 1158–1165
diffraction (SAED) patterns of Ni-MOF and Co2-Ni-MOF (Fig. S3) were
collected to better analyze their crystal structure. It can be seen that the
SAED patterns are composed of a set of clear concentric rings assigned
to the (200), (001) and (201) planes of Ni-MOF and Co2-Ni-MOF, de-
monstrating their crystal structure and polycrystalline nature [42]. In
addition, the dspacing of the (200) plane of Ni-MOF (0.53 nm) is slightly
larger than that of Co2-Ni-MOF (0.52 nm), corresponding to the phe-
nomenon that Co2-Ni-MOF shifts to a slightly higher angle than Ni-MOF
in the XRD patterns. Energy dispersive spectrometer (EDS) was carried
out for Co2-Ni-MOF and the results are shown in Fig. S4, demonstrating
the existence of both Ni and Co elements. On the basis of the above
experiments, we propose the following explanations (Fig. 2i) for the
formation of Ni-MOF and Cox-Ni-MOF. First of all, the aggregation and
nucleation of some metal ions (Ni2+ and Co2+) together with organic
ligands. Then they grow directionally to sheet-like nanoribbons. Fi-
nally, the sheet-like nanoribbons are interlaced to form hierarchical
microspheres. Interestingly, after the addition of Co, the sheet-like na-
noribbons become wider, which is beneficial to the formation of 3D
flower-like hierarchical ball.
The surface elements valence and constitution of the as-prepared
MOFs were studied on XPS. C, N, O and Ni elements are both observed
on the surface of Ni-MOF and Cox-Ni-MOF from the survey spectra
(Fig. 3a). Meantime, only weak peaks of Co 2p are observed for Co2-Ni-
MOF, because of the relatively low Co doping amount. In Ni 2p XPS
spectrum of Ni-MOF and Co2-Ni-MOF (Fig. 3b), two major peaks center
at around 856.3 eV and 873.9 eV are identified as Ni 2p3/2 and Ni 2p1/2,
respectively, matching well with the peaks of Ni2+ [43,44]. The other
two peaks at around 862.0 eV and 880.1 eV are satellite bands (marked
as “sat.”) of Ni 2p3/2 and Ni 2p1/2, respectively [45]. Only minor
amount of Ni3+ state was existed in Ni-MOF and Co2-Ni-MOF. There-
fore, we conclude that the main oxidation state of Ni in MOFs is Ni2+
J. Wang, et al. Applied Surface Science 483 (2019) 1158–1165

Fig. 4. Electrochemical properties of MOF electrodes: (a) CV plots of Co2-Ni-MOF; (b) GCD graphs of Co2-Ni-MOF; (c) CV profiles of MOF electrodes scanned at
20 mV/s (d) GCD profiles of MOF electrodes at 1 A/g; (e) calculated specific capacitances versus current densities of MOF electrodes; (f) EIS plot of MOFs (inset:
equivalent circuit of obtained the four electrodes).

with minor Ni3+. Moreover, the intensity ratio of Ni2+ peak/Ni3+ peak
in Ni 2p3/2 decreases after the addition of Co, which indicates that part
of Ni2+ is replaced by Co2+ in Co2-Ni-MOF, resulting in an increase of
“free hole”. This action may enhance the conductivity of the MOF,
thereby making a significant effect on reducing the charge transfer
resistance [46]. For Co 2p spectrum in Fig. 3c, the peak at binding
energy of 781.73 eV and 796.93 eV are assigned to Co 2p3/2 and Co 2p1/
2, which are contributed to cobalt coordinated with oxygen of the
linker. Co 2p electrons energy loss during the excitation valence elec-
trons results in several satellites [36]. The percentages of carbon,
oxygen, nickel and cobalt elements for Co2-Ni-MOF are determined to
be 47.39, 37.04, 13.38 and 0.53% under the consideration of the re-
lative surface sensitivities of the detected elements. In general, the
conclusion is that Co2-Ni-MOF has been synthesized successfully.
At the same time, the morphology of the synthesized materials has a
great effect on their specific surface area (SBET) and pore volume. BET-
BJH data of the samples are presented in Table 1 and Fig. S5. Co2-Ni-
MOF has the highest specific surface area of 144 (m2/g) and total pore
volume of 0.254 (cm3/g). The highest specific surface should be due to
the more open porous structure formed by 3D flower-like hierarchical
microspheres of Co2-Ni-MOF, which is consistent with SEM and TEM
images. Meanwhile, the synergistic effect of two metal ions can effec-
tively increase the specific surface area of MOFs [47]. As reported in the
literature, the large specific surface area and pore volume are usually
associated with better electrochemical behaviors. On one hand, it
provides an increased contact area between electrodes and electrolyte,
on the other hand, it offers more free buffer strain spaces during the
charge and discharge cycles [48,49]. However, as the amount of Co

1162
J. Wang, et al.
Fig. 5. Cyclic performances of MOF electrodes at 6 A/g.
reaches to 5% (Co5-Ni-MOF), the structure of the flower-like hier-
archical microspheres is destroyed, which in turn causes a decrease in
the specific surface areas, corresponding to a decline in electrochemical
performance. In addition, the pore size distribution is another im-
portant factor affecting the electrochemical performance. The pore size
of the synthesized MOFs (Fig. S5b) is concentrated around 2 nm, which
is close to the ideal ion transport channel of the supercapacitors [50].
The pores of the material can act as a reservoir of electrolyte ions,
significantly shortening the length of the diffusing ions and conquering
most of the kinetic problems involved during the Faraday redox reac-
tion.
Fig. 6. Electrochemical properties of Co2-Ni-MOF//AC HSC device. (a) CV plots; (b) GCD graphs; (c) cycling performance at 1 A/g; (d) Ragone plots.
1163
Applied Surface Science 483 (2019) 1158–1165
3.2. Electrochemical measurements of MOF materials
Electrochemical testing of as-prepared MOF electrode materials was
performed in 6 M KOH electrolyte system. As shown in Fig. 4a, CV
curves present two oxidation peaks at low scan rates and one reduction
peak, indicating their faradaic features. These peaks may be largely
because of the ion exchange and surface redox reactions, consistent
with the OH− intercalation and deintercalation in the MOFs [51,52]. As
the scanning speed increases, CV curves exhibit an integrated oxidation
peak. Meanwhile, the redox peak current density increases, but the
shapes of CV curves maintain unchanged. In addition, the oxidation
peak shifts to a higher voltage and the reduction peak shifts to a lower
voltage. But this does not imply a higher specific capacitance at higher
scan rates. During the redox process in the MOFs, the protons are ex-
changed with electrolyte and electrode surface. Because of the slow
proton transfer process, a high scan rate may result in proton depletion
or saturation in the electrolyte inside the electrode. This mainly leads to
an increase in the ionic resistivity, thus a decrease in the capacitance of
the electrode. Therefore, the relatively slow scan rate may be more
beneficial to the full utilization of the electrode materials [53]. A gal-
vanostatic charge-discharge test was carried on to further research the
electrochemical properties of the Co2-Ni-MOF electrode, as depicted in
Fig. 4b. At current densities from 1 A/g to 10 A/g, the electrode ma-
terials were charged to 0.45 V and then discharged. The nonlinear
shape of the GCD curve represents the faradaic performance of MOF
electrodes, the voltage platform observed during charge-discharge
process coincides with the redox peaks appearing in the CV curves. The
other three electrodes exhibit analogous CV curves and charge-dis-
charge curves, indicating that the as-prepared MOF electrodes could
accommodate OH− through the faradaic redox reaction processes.
CV plots at 20 mV/s and galvanostatic charge-discharge plots at a
J. Wang, et al.
1 A/g of as-prepared MOFs are observed in Fig. 4c and d. Obviously,
Co2-Ni-MOF has the largest integral area and longest discharge time,
implying that Co2-Ni-MOF may have the largest charge storage. Fig. 4e
presents the comparison of electrochemical behaviors among different
MOF electrodes. Apparently, Co-doped Ni-MOF electrodes (Cox-Ni-
MOF) exhibit higher capacitances than the pure Ni-MOF. Furthermore,
the Co2-Ni-MOF exhibits the highest capacitance of 1300 F/g at 1 A/g
while retaining 1021 F/g at 10 A/g, demonstrating its good rate per-
formance. The excellent electrochemical characteristics for Co2-Ni-MOF
could be as a result of the 3D flower-like morphology with a more open
hierarchical structure and highest specific area, which facilitate the
transportation of electron and the diffusion of electrolyte ions in the
redox reaction process.
Electrochemical impedance spectroscopy (EIS) is a significant
method to study the conductivity properties for electrode materials.
Fig. 4f shows the Nyquist diagrams of the electrodes within a frequency
scope of 10 kHz to 0.01 Hz, consisting of a semi-circular at high fre-
quency and a linear component at low frequency (inset is an equivalent
circuit) [54]. Here, Rs is composed of the contact resistance of the
material and the nickel foam substrate, the electrolyte resistance, and
the electrode resistance. The value of Rs can be represented by the value
of the intersection of the Z′ axis and the semicircular arc [55]. Rct re-
presents the charge transfer resistance aroused from the faradaic reac-
tions on the surface of the electrode materials. The value of Rct can be
determined by the semicircle diameter at high frequency. Combined
with equivalent circuit, we are able to obtain the values of Rs and Rct
(Table S1). It can be noticed that the Co2-Ni-MOF has relatively smaller
Rs. Furthermore, the charge transfer resistance (Rct) after Co doping is
significantly reduced. The values of Rct for Ni-MOF, Co0.5-Ni-MOF, Co2-
Ni-MOF, Co5-Ni-MOF are 16.59 Ω, 16.49 Ω, 10.38 Ω and 11.45 Ω, re-
spectively. All results indicates that Co2-Ni-MOF has better electrical
conductivity, which is in accordance with XPS results [56].
In order to study the cycle performance of Ni-MOF and Co2-Ni-MOF,
a continuous charge-discharge tests for 3000 cycles was carried out at
6 A/g. As presented in Fig. 5, the capacitance retentions for Ni-MOF and
Co2-Ni-MOF are 59% and 71%, respectively.
In view of above discussions, we can conclude that the Co-doped Ni-
MOF materials (Cox-Ni-MOF) perform better electrochemical proper-
ties. Co2-Ni-MOF electrode materials can achieve a high specific capa-
citance of 1300 F/g at 1 A/g and exhibit an outstanding rate perfor-
mance, which is close to or higher than the electrochemical
performances of MOF electrode materials reported recently (Table S2).
Although the electrochemical performances of Ni-MOF prepared by us
are lower than that of Zhou et al. (1457 F/g at 1 A/g), due to limitations
of the test conditions. The addition of low amount of Co does improve
the performances of the pure Ni-MOF. The improved electrochemical
behaviors of Cox-Ni-MOF may be attributed to the inherent merits:
First, the Cox-Ni-MOF materials with low amount of Co have a 3D
flower-like morphology with a more open hierarchical structure, higher
specific surface area and pore volume, which are in favor of sufficient
contact with the electrolyte and full utilization of the active materials.
Second, Cox-Ni-MOF materials have the relatively smaller charge
transfer resistance that benefits to faster electron transfer rate [57].
Third, synergy effect for Cox-Ni-MOF electrodes between Ni2+ and
Co2+ contributes to enhanced conductivity. It has been reported that
the concentration of “free hole” plays a significant part in the con-
ductivity for nickel-based materials. Due to the similar size of Co2+
radius (0.065 nm) and Ni2 + radius (0.069 nm), the relatively smaller
Co2 + ions could be able to diffuse into the Ni-MOF while partially
substituting Ni2+ ions, which forms more Ni2+ vacancies. This action
may lead to more “free hole” in the Co-doped Ni-MOFs, thereby en-
hancing the conductivity of MOFs [29,47,58].
3.3. Electrochemical measurements of Co2-Ni-MOF//AC HSC device
A simultaneous improvement of storage device in energy density
1164
Applied Surface Science 483 (2019) 1158–1165
and power density is meaningful. Hence, an HSC employing Co2-Ni-
MOF (1.76 mg) as the positive electrode and active carbon (6.31 mg) as
the negative electrode was fabricated to further estimate the electro-
chemical behaviors of Co2-Ni-MOF. Before fabrication, the electro-
chemical properties of active carbon were tested in three-electrode
system as well. The rectangle-like CV curves and the linear GCD graphs
(Fig. S6) of AC indicates that the device stores charge based on an
electrical double-layer capacitive mechanism. The capacitance of AC is
decided to be 160 F/g at a 1 A/g according to Eq. (1). As depicted in
Fig. 6a, a broad redox peak was observed in the CV diagrams of Co2-Ni-
MOF//AC HSC device, manifesting its faradaic behaviors caused by
Co2-Ni-MOF electrode. The shapes of CV graphs maintain nearly un-
changed with the increased current density, which implies that the
device has an excellent electrochemical reversibility. In addition, GCD
graphs (Fig. 6b) of Co2-Ni-MOF//AC HSC at various current densities
are almost symmetrical, implying the excellent electrochemical stability
of this device. In order to investigate the cycling stability of the Co2-Ni-
MOF//AC HSC, a constant charge-discharge measurement was con-
ducted at a 1 A/g (Fig. 6c). Even after 6000 cycles the capacitance re-
tention of Co2-Ni-MOF/AC HSC is still 78.1%. Fig. 6d presents the
Ragone plot of Co2-Ni-MOF//AC HSC correlating energy density and
power energy. A maximum energy density power density of 25.92 Wh/
kg is obtained at a power density of 375 W/kg, which is comparable or
even better than other nickeliferous HSC devices.
4. Conclusions
In conclusion, 3D Co-doped Ni-based MOF (Cox-Ni-MOF) flower-
like hierarchical microspheres were successfully synthesized. Co2-Ni-
MOF exhibits the highest specific capacitance of 1300 F/g at 1 A/g and
maintain 1021 F/g even at 10 A/g. The improved electrochemical per-
formance can be attributed to 3D flower-like microspheres with a more
open hierarchical structure and larger surface area, which will enlarge
contact area between the electrode and electrolyte while shortening the
path length for ion transport. In addition, the enhanced conductivity
due to the synergistic effect of Ni2+ and Co2+ ions. Moreover, the Co2-
Ni-MOF//AC HSC performed excellent energy density of 25.92 Wh/kg
at the power density of 375 W/kg. All these results demonstrate such a
type of Co-doped Ni-MOFs is promising as electrodes in super-
capacitors.
Acknowledgement
This work was financially supported by the National Key Research
and Development Program of China (2016YFC0203800), the National
Natural Science Foundation of China (51578288), Industry-Academia
Cooperation Innovation Fund Projects of Jiangsu Province
(BY2016004-09), National Natural Science Foundation of China
(21706132), Natural Science Foundation of Jiangsu Province
(BK20160834), Jiangsu Province Scientific and Technological
Achievements into a Special Fund Project (BA2015062, BA2016055
and BA2017095), Top-notch Academic Programs Project of Jiangsu
Higher Education Institutions.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.apsusc.2019.03.340.
References
[1] A.J. Amali, J.K. Sun, Q. Xu, From assembled metal-organic framework nano-
particles to hierarchically porous carbon for electrochemical energy storage, Chem
Commun (Camb) 50 (2014) 1519–1522.
[2] Y. Bu, G. Nam, S. Kim, K. Choi, Q. Zhong, J. Lee, Y. Qin, J. Cho, G. Kim, A tailored
bifunctional electrocatalyst: boosting oxygen reduction/evolution catalysis via
electron transfer between N-doped graphene and perovskite oxides, Small 14
J. Wang, et al.
(2018) e1802767.
[3] Y. Bu, O. Gwon, G. Nam, H. Jang, S. Kim, Q. Zhong, J. Cho, G. Kim, A highly
efficient and robust cation ordered perovskite oxide as a bifunctional catalyst for
rechargeable zinc-air batteries, ACS Nano 11 (2017) 11594–11601.
[4] D.I. Shin, Y.J. Oh, Tumor necrosis factor-associated protein 1 (TRAP1) is released
from the mitochondria following 6-hydroxydopamine treatment, Exp. Neurobiol.
23 (2014) 65–76.
[5] S. Wang, N. Liu, J. Su, L. Li, F. Long, Z. Zou, X. Jiang, Y. Gao, Highly stretchable and
self-healable supercapacitor with reduced graphene oxide based fiber springs, ACS
Nano 11 (2017) 2066.
[6] X. Han, K. Tao, D. Wang, L. Han, Design of a porous cobalt sulfide nanosheet array
on Ni foam from zeolitic imidazolate frameworks as an advanced electrode for
supercapacitors, Nanoscale 10 (2018) 2735–2741.
[7] D. Xiong, X. Li, Z. Bai, S. Lu, Recent advances in layered Ti3C2Tx MXene for elec-
trochemical energy storage, Small 14 (2018) e1703419.
[8] B. Li, M. Zheng, H. Xue, H. Pang, High performance electrochemical capacitor
materials focusing on nickel based materials, Inorg. Chem. Front. 3 (2016)
175–202.
[9] X. Liu, C. Shi, C. Zhai, M. Cheng, Q. Liu, G. Wang, Cobalt-based layered metal-
organic framework as an ultrahigh capacity supercapacitor electrode material, ACS
Appl. Mater. Interfaces 8 (2016) 4585.
[10] K. Xu, W. Li, Q. Liu, B. Li, X. Liu, L. An, Z. Chen, R. Zou, J. Hu, Hierarchical me-
soporous NiCo2O4@MnO2 core–shell nanowire arrays on nickel foam for aqueous
asymmetric supercapacitors, J. Mater. Chem. A 2 (2014) 4795–4802.
[11] K. Tao, X. Han, Q. Cheng, Y. Yang, Z. Yang, Q. Ma, L. Han, A zinc cobalt sulfide
nanosheet array derived from a 2D bimetallic metal-organic frameworks for high-
performance supercapacitors, Chemistry 24 (2018) 12584–12591.
[12] Y. Zhou, Z. Mao, W. Wang, Z. Yang, X. Liu, In-situ fabrication of graphene oxide
hybrid Ni-based metal-organic framework (Ni-MOFs@GO) with ultrahigh capaci-
tance as electrochemical pseudocapacitor materials, ACS Appl. Mater. Interfaces 8
(2016) 28904–28916.
[13] K. Tao, X. Han, Q. Ma, L. Han, A metal-organic framework derived hierarchical
nickel-cobalt sulfide nanosheet array on Ni foam with enhanced electrochemical
performance for supercapacitors, Dalton Trans. 47 (2018) 3496–3502.
[14] R. Bendi, V. Kumar, V. Bhavanasi, K. Parida, P.S. Lee, Metal organic framework-
derived metal phosphates as electrode materials for supercapacitors, Adv. Energy
Mater. 6 (2016) 1501833.
[15] M. Kurmoo, Magnetic metal-organic frameworks, Chem. Soc. Rev. 38 (2009)
1353–1379.
[16] J. Lee, O.K. Farha, J. Roberts, K.A. Scheidt, S.T. Nguyen, J.T. Hupp, Metal-organic
framework materials as catalysts, Chem. Soc. Rev. 38 (2009) 1450–1459.
[17] K.J. Erickson, F. Léonard, V. Stavila, M.E. Foster, C.D. Spataru, R.E. Jones,
B.M. Foley, P.E. Hopkins, M.D. Allendorf, A.A. Talin, Thin film thermoelectric
metal-organic framework with high Seebeck coefficient and low thermal con-
ductivity, Adv. Mater. 27 (2015) 3453–3459.
[18] X. Zhang, A. Chen, M. Zhong, Z. Zhang, X. Zhang, Z. Zhou, X.-H. Bu, Metal–organic
frameworks (MOFs) and MOF-derived materials for energy storage and conversion,
Electrochemical Energy Reviews (2018).
[19] J. Yang, P. Xiong, C. Zheng, H. Qiu, M. Wei, Metal–organic frameworks: a new
promising class of materials for a high performance supercapacitor electrode, J.
Mater. Chem. A 2 (2014) 16640–16644.
[20] A. Morozan, F. Jaouen, Metal organic frameworks for electrochemical applications,
Energy Environ. Sci. 5 (2012).
[21] Y. Wang, G. Ye, H. Chen, X. Hu, N. Zheng, S. Ma, Functionalized metal-organic
framework as a new platform for efficient and selective removal of cadmium (II)
from aqueous solution, J. Mater. Chem. A 3 (2015) 15292–15298.
[22] R. Díaz, M.G. Orcajo, J.A. Botas, G. Calleja, J. Palma, Co8-MOF-5 as electrode for
supercapacitors, Mater. Lett. 68 (2012) 126–128.
[23] Y. Gong, J. Li, P.G. Jiang, Q.F. Li, J.H. Lin, Novel metal(II) coordination polymers
based on N,N′-bis-(4-pyridyl)phthalamide as supercapacitor electrode materials in
an aqueous electrolyte, Dalton Trans. 42 (2013) 1603–1611.
[24] A. Fateeva, P. Horcajada, T. Devic, C. Serre, J. Marrot, J.M. Grenèche, M. Morcrette,
J.M. Tarascon, G. Maurin, G. Férey, Synthesis, structure, characterization, and
redox properties of the porous MIL-68(Fe) solid, Eur. J. Inorg. Chem. 2010 (2010)
3789–3794.
[25] G.D. Combarieu, M. Morcrette, F. Millange, N. Guillou, J. Cabana, C.P. Grey,
I. Margiolaki, G. FéRey, J.M. Tarascon, Influence of the benzoquinone sorption on
the structure and electrochemical performance of the MIL-53(Fe) hybrid porous
material in a lithium-ion battery, Chem. Mater. 21 (2009) 1602–1611.
[26] J. Yang, C. Zheng, P. Xiong, Y. Li, M. Wei, Zn-doped Ni-MOF material with a high
supercapacitive performance, J. Mater. Chem. A 2 (2014) 19005–19010.
[27] M.S. Rahmanifar, H. Hesari, A. Noori, M.Y. Masoomi, A. Morsali, M.F. Mousavi, A
dual Ni/Co-MOF-reduced graphene oxide nanocomposite as a high performance
supercapacitor electrode material, Electrochim. Acta 275 (2018) 76–86.
[28] G. Srikesh, A.S. Nesaraj, Chemical synthesis of Co and Mn co-doped NiO nano-
crystalline materials as high-performance electrode materials for potential appli-
cation in supercapacitors, Ceram. Int. 42 (2016) 5001–5010.
[29] J. Zhang, G. Cai, Z. Ding, T. Hong, X. Wang, C. Gu, J. Tu, Co-doped NiO nanoflake
array films with enhanced electrochromic properties, J. Mater. Chem. C 2 (2014)
7013–7021.
[30] Z. Lv, Q. Zhong, Y. Bu, In-situ conversion of rGO/Ni2P composite from GO/Ni-MOF
precursor with enhanced electrochemical property, Appl. Surf. Sci. 439 (2018)
413–419.
[31] B. Li, Y. Shi, K. Huang, M. Zhao, J. Qiu, H. Xue, H. Pang, Cobalt-doped nickel
1165
Applied Surface Science 483 (2019) 1158–1165
phosphite for high performance of electrochemical energy storage, Small 14 (2018)
e1703811.
[32] M. Adel, R. Pierre, S. Romain, L. Sébastien, M. Thomas, M. Bernard, F.O. Michel,
From hydrated Ni3(OH)2(C8H4O4)2(H2O)4 to anhydrous Ni2(OH)2(C8H4O4): impact
of structural transformations on magnetic properties, Inorg. Chem. 53 (2014)
872–881.
[33] S. Zhao, Y. Wang, J. Dong, C.-T. He, H. Yin, P. An, K. Zhao, X. Zhang, C. Gao,
L. Zhang, J. Lv, J. Wang, J. Zhang, A.M. Khattak, N.A. Khan, Z. Wei, J. Zhang, S. Liu,
H. Zhao, Z. Tang, Ultrathin metal–organic framework nanosheets for electro-
catalytic oxygen evolution, Nat. Energy 1 (2016).
[34] S. Gao, Y. Sui, F. Wei, J. Qi, Q. Meng, Y. He, Facile synthesis of cuboid Ni-MOF for
high-performance supercapacitors, J. Mater. Sci. 53 (2018) 6807–6818.
[35] M.L. Yue, Y.F. Jiang, L. Zhang, C.Y. Yu, K.Y. Zou, Z.X. Li, Solvent-induced cadmium
(II) metal-organic frameworks with adjustable guest-evacuated porosity: applica-
tion in the controllable assembly of MOF-derived porous carbon materials for su-
percapacitors, Chemistry 23 (2017) 15680–15693.
[36] S.H. Kazemi, B. Hosseinzadeh, H. Kazemi, M.A. Kiani, S. Hajati, Facile synthesis of
mixed metal-organic frameworks: electrode materials for supercapacitors with ex-
cellent areal capacitance and operational stability, ACS Appl. Mater. Interfaces 10
(2018) 23063–23073.
[37] I. Levin, M.C. Stennett, G.C. Miles, D.I. Woodward, A.R. West, I.M. Reaney,
Coupling between octahedral tilting and ferroelectric order in tetragonal tungsten
bronze-structured dielectrics, Appl. Phys. Lett. 89 (2006) 1664.
[38] C.F. Linares, S. Sánchez, C.U.D. Navarro, K. Rodríguez, M.R. Goldwasser, Study of
cancrinite-type zeolites as possible antacid agents, Microporous Mesoporous Mater.
77 (2015) 215–221.
[39] A.D. Su, X. Zhang, A. Rinaldi, S.T. Nguyen, H. Liu, Z. Lei, L. Lu, H.M. Duong,
Hierarchical porous nickel oxide–carbon nanotubes as advanced pseudocapacitor
materials for supercapacitors, Chem. Phys. Lett. 561-562 (2013) 68–73.
[40] S. Zhao, L. Zeng, G. Cheng, L. Yu, H. Zeng, Ni/Co-based metal-organic frameworks
as electrode material for high performance supercapacitors, Chin. Chem. Lett. 30
(2019) 605–609.
[41] Z. Lv, Q. Zhong, Y. Bu, J. Wu, 3D flower-like hierarchical Ag@nickel-cobalt hy-
droxide microsphere with enhanced electrochemical properties, Electron. Mater.
Lett. 12 (2016) 824–829.
[42] B. Wang, J. Shang, C. Guo, J. Zhang, F. Zhu, A. Han, J. Liu, A general method to
ultrathin bimetal-MOF nanosheets arrays via in situ transformation of layered
double hydroxides arrays, Small 15 (2019) e1804761.
[43] C.Z. Yuan, B. Gao, L.F. Shen, S.D. Yang, L. Hao, X.J. Lu, F. Zhang, L.J. Zhang,
X.G. Zhang, Hierarchically structured carbon-based composites: design, synthesis
and their application in electrochemical capacitors, Nanoscale 3 (2011) 529–545.
[44] B. Li, P. Gu, Y. Feng, G. Zhang, K. Huang, H. Xue, H. Pang, Ultrathin nickel-cobalt
phosphate 2D nanosheets for electrochemical energy storage under aqueous/solid-
state electrolyte, Adv. Funct. Mater. (2017) 27.
[45] J. Xu, C. Yang, Y. Xue, C. Wang, J. Cao, Z. Chen, Facile synthesis of novel metal-
organic nickel hydroxide nanorods for high performance supercapacitor,
Electrochim. Acta 211 (2016) 595–602.
[46] H. Xu, M. Zeng, J. Li, X. Tong, Facile hydrothermal synthesis of flower-like Co-
doped NiO hierarchical nanosheets as anode materials for lithium-ion batteries, RSC
Adv. 5 (2015) 91493–91499.
[47] Y. Jiao, J. Pei, D. Chen, C. Yan, Y. Hu, Q. Zhang, G. Chen, Mixed-metallic MOF
based electrode materials for high performance hybrid supercapacitors, J. Mater.
Chem. A 5 (2017) 1094–1102.
[48] C. Yan, G. Chen, X. Zhou, J. Sun, C. Lv, Template-based engineering of carbon-
doped Co3O4 hollow nanofibers as anode materials for lithium-ion batteries, Adv.
Funct. Mater. 26 (2016) 1428–1436.
[49] H. Kim, M.Y. Cho, M.H. Kim, K.Y. Park, H. Gwon, Y. Lee, K.C. Roh, K. Kang, A novel
high-energy hybrid supercapacitor with an anatase TiO2-reduced graphene oxide
anode and an activated carbon cathode, Adv. Energy Mater. 3 (2013) 1500–1506.
[50] G. Zhang, X.W. Lou, General solution growth of mesoporous NiCo2O4 nanosheets on
various conductive substrates as high-performance electrodes for supercapacitors,
Adv. Mater. 25 (2013) 976–979.
[51] N.A. Alhebshi, R.B. Rakhi, H.N. Alshareef, Conformal coating of Ni(OH)2 nanoflakes
on carbon fibers by chemical bath deposition for efficient supercapacitor electrodes,
J. Mater. Chem. A 1 (2013).
[52] H. Wang, Y. Liang, T. Mirfakhrai, Z. Chen, H.S. Casalongue, H. Dai, Advanced
asymmetrical supercapacitors based on graphene hybrid materials, Nano Res. 4
(2011) 729–736.
[53] U.M. Patil, R.R. Salunkhe, K.V. Gurav, C.D. Lokhande, Chemically deposited na-
nocrystalline NiO thin films for supercapacitor application, Appl. Surf. Sci. 255
(2008) 2603–2607.
[54] X. Li, R. Ding, W. Shi, Q. Xu, E. Liu, Ternary Ni-Co-F nanocrystal-based super-
capacitors, Chemistry 23 (2017) 6896–6904.
[55] X. Sun, NiCoP nanoarray: a superior pseudocapacitor electrode with high area ca-
pacitance, Chem. Eur. J. 23 (2017).
[56] J. Li, D. Xiong, L. Wang, M.K.S. Hirbod, X. Li, High-performance self-assembly
MnCo2O4 nanosheets for asymmetric supercapacitors, J. Energy Chem. 37 (2019)
66–72.
[57] H. Cheng, R. Xiao, H. Bian, Z. Li, Y. Zhan, C.K. Tsang, C.Y. Chung, Z. Lu, Y.Y. Li,
Periodic porous silicon thin films with interconnected channels as durable anode
materials for lithium ion batteries, Mater. Chem. Phys. 144 (2014) 25–30.
[58] M. Kohei, H. Siya, I. Mitsumasa, P. Wei, Enhanced conductivity and gating effect of
p-type Li-doped NiO nanowires, Nanoscale 6 (2013) 688–692.