Journal of Alloys and Compounds 825 (2020) 154069

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Nickel/cobalt bimetallic metal-organic frameworks ultrathin

nanosheets with enhanced performance for supercapacitors
Xiaolong Zhang a, Jiemei Wang b, Xiang Ji b, Yanwei Sui a, Fuxiang Wei a, Jiqiu Qi a,
Qingkun Meng a, Yaojian Ren a, Yezeng He a, c, *
a
School of Materials Science and Engineering, China University of Mining and Technology, Xuzhou, 221116, PR China
b
China National Heavy Duty Truck Group Co., Ltd, No 777 huaao Road, Jinan, PR China
c
The Jiangsu Province Engineering Laboratory of High Efficient Energy Storage Technology and Equipment, Xuzhou, PR China

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

Article history: In this work, the lamellae-like Ni/Co metal-organic framework (Ni/Co-MOF) is synthesized via a facile
Received 23 October 2019 one-step hydrothermal process. By combining the advantages of mixed-metallic components and unique
Received in revised form structures, the fabricated Ni/Co-MOF electrode exhibits a superior specific capacity (568 C g
1 at 1 A g
1),
6 January 2020
good rate performance (80.1% retention at 10 A g
1) and high cycling stability (75.5% retention over 3000
Accepted 26 January 2020
Available online 27 January 2020
charge/discharge cycles). Besides, the assembling asymmetric supercapacitor based on the Ni/Co-MOF
and reduced graphene oxide (RGO) exhibits a high energy density of 42.24 Wh kg
1 at the power
density of 800 W kg
1, and excellent electrochemical cycling stability of 82.6% retention of original
Keywords:
Supercapacitor
capacitance over 6000 charge/discharge cycles.
Metal-organic frameworks © 2020 Elsevier B.V. All rights reserved.
Electronic materials
Ultrathin nanosheets

1. Introduction cobalt-based MOF has also been proved to shows a capacitance

value of 415.5 F g
1 in alkaline solution [18]. However, the low
Nowadays, the supercapacitor (SC), lithium ion battery, and electroconductibility and structural instability in most MOFs vastly
alkaline battery are extensively used as energy storage devices in hinder the further development in practical application.
the area of portable electronics, transportation industry and clean To solve this intrinsic restriction, different methods have been
energy [1e3]. The reason why the SC has a place in energy storage is developed in an attempt to enhance the electroconductibility and
that the SCs has some unique properties such as fast charge/ structural instability of the MOFs’ electrode materials. One of the
discharge, long cycling life, excellent power density and desirable common methods in enhancing the properties of MOFs-based
safety [4e7]. The performance of SCs largely depends on the elec- electrode materials is to incorporate another metallic element
trode active materials. Among all the electrode materials, the [19]. For example, Zhao and co-workers [20] have developed a Co-
transition metal derivatives such as oxides [8,9], sulfides [10e12] doped Ni-based MOF, which exhibits a high specific capacitance
and hydroxides [13e16] play an extremely important part. (~1067 F g
1 at 1 A g
1) and cycling stability (64.8% retention over
Thus far, the porous metal-organic framework (MOF) using as a 2500 cycles). Xiao et al. [21] recently reported that the layered
novel electrode active material for supercapacitor have attracted bimetallic Ni/Co-MOFs exhibits a high energy storage capacity of
tremendous attention. For instance, Gao et al. [17] have synthesized 1300 F g
1 at 1 A g
1 and retains 71% of the initial capacitance even
a stacked layer-cuboid structural Ni-MOF using facile hydrothermal after 3000 charge-discharge cycles. Gholipour-Ranjbar et al. [22]
method. The unique structural MOF exhibits a capacitance value of have also synthesized a Ni/Co-based bimetallic MOF for super-
708 F g
1 at 2 A g
1 current density and cycling stability of 56.6% capacitors with outstanding specific capacitance (~1049 F g
1 at
retention over 5000 charge/discharge cycles. Moreover, the porous 1 A g
1) and cycling stability (97.4% retention over 5000 cycles). In
addition, Rezaee et al. [23] recently reported that the petal-like
NiCo/NiOeCoO/Nanoporous carbon composite deriving from Ni/
Co-MOFs via a thermal treatment exhibits an excellent catalytic
* Corresponding author. School of Materials Science and Engineering, China
activity and durability.
University of Mining and Technology, Xuzhou, 221116, PR China.
E-mail address: hyz0217@hotmail.com (Y. He).
The introduction of Co2þ can effectively enhance the

https://doi.org/10.1016/j.jallcom.2020.154069
0925-8388/© 2020 Elsevier B.V. All rights reserved.
2 X. Zhang et al. / Journal of Alloys and Compounds 825 (2020) 154069

conductivity and cycling stability of the Ni-based MOFs. Another

way to improve the supercapacitive performance is to construct mþ  Cþ ¼ m
 C
(2)
special architecture to take full advantage of the nanoporous
structural characteristics. Nanoporous materials generally have in which m is the mass loading of the active material. According to
better electrochemical properties than bulk ones due to their the above formula, the masses of Ni/Co-MOF0.75 nanosheet and
unique pore size distribution and larger surface area, which facili- RGO are 1.6 and 4.7 mg, respectively.
tates electrolyte diffusion and ion transport. The power density (P, W kg
1) and energy density (E, Wh kg
1)
In this study, a facile one-step hydrothermal process is used for of the energy storage device were calculated according to Eq. (3)
the synthesis of the Ni-MOF and Ni/Co-MOF. By combining the and Eq. (4):
advantages of mixed-metallic components and unique lamellae- ð
like structures, the Ni/Co-MOF electrode perform a superior spe- I  DVdt
cific capacitance, outstanding rate capability and high cycling E¼ (3)
3:6  m
stability.
3600  E
p¼ (4)
2. Experimental Dt
in which I is the discharge current of Ni/Co-MOF0.75/NF//RGO. DV is
2.1. Synthesis of the MOFs the voltage window in three-electrode cell system.
The charge-storage behavior of the MOFs at peak potentials can
Ni/Co-MOF0.75 (the number represents the millimole mass of be obtained by analyzing the CV curves at different scanning rates
Co2þ) was first synthesized by a facile hydrothermal process. using Eq. (5):
Ni(NO3)2$6H2O (1.5 mmol), Co(NO3)2$6H2O (0.75 mmol) and tri-
mesic acid (H3BTC, 0.3 mmol) were dissolved in 30 mL N,N-dime- i ¼ a  vb (5)
thylformamide (DMF) under magnetic stirring for 20 min at room
temperature. The clarified mixture was transferred to a 50 ml The charge transfer mechanism from nondiffusive- and
Teflon-lined steel autoclave and maintained at 150  C for 12 h. diffusive-controlled processes is analyzed according to Dunn’s
Then, the resulting lavender precipitate was collected from the method [24]. The corresponding current response (i) in a fix voltage
mixed solution via centrifugation. Finally, the lavender precipitate are determined according to Eq. (6):
was rinsed by DMF and EtOH to remove excess metal ions and re-
sidual ligands, and dried for use. For comparison, the Ni/Co-MOF1.5 iðVÞ ¼ k1  v þ k2  v1=2 (6)
and Ni-MOF were synthesized in the similar process, except that
the amounts of Co(NO3)2$6H2O was changed to 1.5 and 0 mmol, where v is the scanning rate, k1v and k2v1/2 refer to nondiffusive-
respectively. and diffusion-controlled capacity, respectively.

3. Results and discussion

2.1.1. Material characterization
Crystallographic data of the MOFs were obtained through a The brief fabrication process of MOFs via a one-step hydro-
powder XRD. The morphology and structure of the synthetic ma- thermal process is summarized in Fig. 1a. XRD is performed to
terials were obtained by SEM (hitachchi S-4800), and HRTEM study the crystal structure of the as-prepared MOFs. From the XRD
(Tecnai G2F20). XPS (ESCALAB 250Xi) was performed to analyze the pattern shown in Fig. 1b, all the diffraction peaks of the Ni-MOF at
composition and chemical state of the samples. around 2q ¼ 11.6 , 33.7 and 59.6 can be well indexed to the (001),
(110), and (300) diffractions of the standard 3Ni(OH)2$2H2O phase
(JCPDS No. 22e0444), respectively. In addition, the primary
2.1.2. Electrochemical measurements diffraction peaks of the NiCo-MOFs are consistent with the Ni-MOF,
All electrochemical measurements were examined on a which indicates that the incorporation of cobalt into the Ni-MOF
CHI660E electrochemical analyzer using a typical three-electrode has not changed the topological structure of the crystal [25].
cell with a 2 M KOH electrolyte solution. A homogeneous slurry Moreover, the diffraction peaks of the Ni/Co-MOF0.75 and Ni/Co-
containing the fabricated MOFs, PVDF and acetylene black with a MOF1.5 are weaker than that of the pure Ni-MOF, due to the subtle
weight ratio of 8:1:1 in NMP was prepared, followed by supported damage of the topological structure caused by partially replacing
on Ni foam (NF) substrate and dried for used as the work electrode. Ni2þ with Co2þ [26].
The solidified mixture was about 1.5 mg. A platinum net To study the microstructure of the MOFs, SEM and TEM images
(10*10*0.1 mm) was severing as the counter electrode, and a SCE as are given in Fig. 2. As is shown in Fig. 2a, b, the Ni-MOF presents a
the reference electrode. The EIS data was measured within the heterogeneous morphology. Most of them are spherical structures
parameter of frequency (0.01e100 kHz). with smooth surfaces, while the rest are ultrathin nanosheets. The
The specific capacitance (C g
1) of the MOFs were evaluated by morphology of the MOF changes greatly with the addition of Co2þ.
Eq. (1): Obviously, the as-prepared Ni/Co-MOF samples present much
porose construction. As is shown in Fig. 2c, d, the SEM images of the
I  Dt
C¼ (1) Ni/Co-MOF0.75 presents spherical conformation composed of ultra-
m thin nanosheets. In Fig. 2e, f, the SEM images of the Ni/Co-MOF1.5
The asymmetric supercapacitor based on Ni/Co-MOF0.75/NF// shows that only a part of the MOFs nanosheets assemble into
RGO is assembled by using Ni/Co-MOF0.75/NF as the positive elec- regular spheres, while the other part of the MOFs transform into
trode and RGO as the negative electrode. To receive optimizing flower-like intermediates. TEM images (Fig. 2h) of the Ni/Co-
supercapacitors, the charges should be equilibrated by balancing MOF0.75 shows that the interior of the sphere is also consisted of
the mass of the negative and positive active material according to ultra-thin nanosheets with the thickness of about 10 nm. The
Eq. (2): magnified images in Fig. 2i shows the structural details of the ultra-
 X. Zhang et al. / Journal of Alloys and Compounds 825 (2020) 154069 3

Fig. 1. (a) Schematic illustration of the synthetic process of the MOF; (b) XRD pattern of the Ni-MOF and Ni/Co-MOFs.

Fig. 2. SEM images of (a, b) Ni-MOF, (c, d) Ni/Co-MOF0.75, (e, f) Ni/Co-MOF1.5 and TEM images of (g) Ni-MOF and (h, i) Ni/Co-MOF0.75; (j) STEM-HAADF of Ni/Co-MOF0.75.

thin nanosheets. Besides, the STEM-EDX elemental mapping of the using a three-electrode system. The CV curves of the active elec-
Ni/Co-MOF0.75 is performed in Fig. 2j. It can be found that the el- trodes at the same scanning rate are performed in Fig .4a. The
ements of Co, Ni, C and O are homogeneous and uniform distrib- charge storage capacity is connected with the mathematical area of
uted in the sample. a closed region of the CV curves. The closed area of Ni/Co-MOF0.75 is
XPS analyses (Fig. 3) indicate that Ni-MOF contain C, N, O and Ni the largest, indicating that it has the highest specific capacity. The
elements, while the Ni/Co-MOF0.75 sample has an additional Co anodic peaks of the MOFs were obtained at 0.415e0.518 V and the
element. In the high-resolution Ni 2p spectrum (Fig. 3c), in com- cathodic peaks acquired at 0.184e0.278 V, which were corre-
parison to the XPS data of Ni-MOF at 855.44 eV and 873.12 eV are sponding to the faradaic reactions below:
assigned to Ni 2p3/2 and Ni 2p1/2 of Ni2þ [27], the slight shift of the
corresponding peak of Ni/Co-MOF0.75e855.79 eV and 873.41 eV 3NiðOHÞ2 , 2H2 O þ 3 OH
43 NiOOH þ 5 H2 O þ 3 e
(7)
means the strong electronic interactions in the Ni/Co-MOF0.75 [28].
In addition, For Co 2p (Fig. 3d), the two main peaks at 781.3 eV (Co
2p3/2) and 796.5 eV (Co 2p1/2) present the spin-orbit characteristics 3CoðOHÞ2 , 2H2 O þ 3 OH
43 CoOOH þ 5 H2 O þ 3 e
(8)
of Co2þ [29], while the peaks at 785.1 eV and 802.3 eV are the The typical CV curve of Ni/Co-MOF0.75 within the scan rate rang
satellite peaks [30]. of 5e25 mV
1 is shown in Fig. 4b. A special pair of peaks can be
We evaluate the supercapacitive properties of the MOFs by acquired, which can be ascribed to the Faradaic redox reactions
4 X. Zhang et al. / Journal of Alloys and Compounds 825 (2020) 154069

Fig. 3. XPS spectra: (a) survey scan of Ni-MOF; (b) survey scan of Ni/Co-MOF0.75; (c) Ni 2p scan of Ni-MOF and Ni/Co-MOF0.75; and (d) Co 2p scan of Ni/Co-MOF0.75.

concerned to M-O-OH/M
O (M ¼ Co2þ or Ni2þ) [31]. As the scan parameter of frequency (0.01e100 kHz). The EIS (Fig. 4e) of all
rate increases, the corresponding current response is also observ- samples can be divided into two parts: one segment appears in the
ably increased, showing the charge storage characteristics of elec- high frequency region, in which the intercept of the X-axis is the
trode materials. The GCD curves are shown in Fig. 4c, the voltage of equivalent series resistance (ESR), while the charge transfer resis-
all samples can be charged to a high value, which is conducive to tance (Rct) between the interface of the electrodes and alkaline
improving the energy density of the energy storage device. The electrolyte is presented by the diameter of a semicircle. The other
capacitance of the electrode active materials can be calculated segment appears in the low-frequency region, in which the slope of
based on discharge time of the GCD curve. The Ni/Co-MOF0.75 the line stand for the diffusion resistance (Ws) of the electrolyte.
electrode deliver a superior capacitance of 568, 494, 474.6 and The ESR corresponding to the intercept of the X-axis and the Rct
455 C g
1 at the current density of 1, 5, 7 and 10 A g
1, respectively. correlating with the semicircle in the high-frequency area both
It can be found that the value of capacitance gradually decays with prove that the corresponding resistance of Ni/Co-MOF0.75 is smaller
the increase of scanning rate. The primary reason is that the po- than pure Ni-MOF. In addition, the ion diffusion resistance of the
tassium ions in the electrolyte cannot fully contact with the active samples presents similar trends. The above results manifest that
site of the electrode material under high current density. Ion the Ni/Co-MOF electrode exhibits more favorable charge transfer
adsorption mainly occurs on the surface of active substances, which kinetics than Ni-MOF. The cycling performance of the as-prepared
causes the attenuation of specific capacitance [32]. However, the electrodes are performed by charge/discharge test for 3000 cy-
Ni/Co-MOF0.75 still retains 80.1% at 10 A g
1, indicating outstanding cles. Compare to the Ni-MOF, the as-prepared Ni/Co-MOF0.75 elec-
rate capability. This is because the lamellae-liked MOF possess rich trode also performed better cycling stability with 75.5% retention
pores and high surface area, which can provide a buffer zone and over 3000 charge/discharge cycles (Fig. 4f). This shows that the
uniform reactive sites to further increase the supercapacitive per- introduction of Co2þ can also enhance the stability of the Ni-based
formance at the high current density. The charge storage capacity at active material. To better explain the enhancement of cycling life of
different current densities is performed in Fig. 4d, the specific the Ni/Co-MOF0.75, the EIS spectra before and after cycling test is
capacitance of the Ni-MOF and Ni/Co-MOF1.5 are only 407 and performed in Fig. 2f. We can found that the value of the ESR has
499 C g
1 at 1 A g
1. The corresponding capacitance retention rates slightly increased after cycling test, while the Rct and Ws remain
of the Ni-MOF and Ni/Co-MOF0.75 are 57.7% and 76.4%, respectively. almost constant after 3000 cycles. It is no obvious increase of
This further indicates that the supercapacitive performance of the impedance after cycles, which indicates that the bimetallic elec-
spherical conformation composed of nanosheets are more promi- trode material has excellent structural stability.
nent at high current density. The charge storage mechanism of Ni/Co-MOF0.75 is further
To explore the charge transfer mechanism and reaction kinetics, studied through to quantitatively calculations of its contribution
the electrochemical impedance spectroscopy (EIS) data of the MOF from nondiffusive- and diffusive-controlled processes. The calcu-
is determined with an AC voltage of 0.5 mV amplitude within the lated b values of the two marked peaks are 0.57 and 0.59, revealing
 X. Zhang et al. / Journal of Alloys and Compounds 825 (2020) 154069 5

Fig. 4. (a) CV curves of Ni-MOF and Ni/Co-MOF at a scan rate of 10 mV s
1; (b, c) CV and GCD curves of Ni/Co-MOF0.75; (d) Comparison of specific capacitances of MOFs; (e) EIS
spectra of MOFs; (f) EIS spectra of Ni/Co-MOF0.75 before and after charge/discharge cycles and cycling stability of MOFs; (g) CV curve of Ni/Co-MOF0.75; (h) Plots of I/v1/2 VS. v1/2 at
different potentials; and (i) Contributions at different scan rates for Ni/Co-MOF0.75.

that the as-prepared Ni/Co-MOF cathode exhibits more like NF//RGO, the mass loading ratio of the electrodes can be deter-
diffusive-controlled battery-like behavior. The CV curves of the mined according to charge balance theory [33]. The CV curves of
electrode is shown in Fig. 4g. The area of the closed shadow in- the Ni/Co-MOF0.75 and RGO at 10 mV s
1 in a three-electrode cell
dicates the nondiffusive-controlled processes. The shadow area is are performed in Fig .5a. It can be found that the maximum voltage
not completely inside the original CV curve, mainly because the can be charged to 1.6 V, which can be further corroborated by the
effect of polarization. From a linear plot of I/v1/2 VS. v1/2, the values CV and GCD curves. Fig. 5b exhibits the CV curves of the Ni/Co-
of k1 and k2 can be acquired (Fig. 4h) [32]. The nondiffusive- and MOF0.75/NF//RGO at various scan rates within the voltage win-
diffusive-controlled processes can be evaluated by these values. As dow rang of 0e1.6 V. The combination of pseudocapacitance and
is shown in Fig. 4i, the capacitive charge contribution increased electric double-layer capacitors (EDLCs) behavior can be found at
from 57.56% to 92.29% within the scan rate rang of 5e50 mV
1. It all scan rates. The GCD profiles is shown in Fig, 5c. It can be found
indicates that most surfaces of the Ni/Co-MOF are accessible to the that the charge/discharge curve is almost symmetrical, suggesting
electrolyte ions. In addition, the charge-storage behavior from the outstanding charge-storage reversible feature of the Ni/Co-
diffusion-controlled process gradually decays with the increase of MOF0.75/NF//RGO. In addition, ESR can also be measured based on
scan rate, resulting in a decrease of the total capacitance at a high voltage (IR) drops of GCD curve. For a particular SC, ESR is relatively
scan rate. stable at various current densities [34]. By combining the advan-
To measure the practical application of the Ni/Co-MOF0.75, an tages of mixed-metallic components and unique structures, the Ni/
asymmetric supercapacitor based on the Ni/Co-MOF0.75/NF//RGO is Co-MOF0.75/NF//RGO shows admirable performance. The specific
assembled by using Ni/Co-MOF0.75/NF as the positive electrode and capacitance of the Ni/Co-MOF0.75/NF//RGO can be calculated to be
RGO as the negative electrode. RGO is used as an excellent negative 190.1 C g
1 (based on the mass of the active material on both
material in energy storage, which shows a capacitance of 193 C g
1 electrodes) at 1 A g
1. Moreover, the device also possesses prefer-
at 1 A g
1 and has almost no capacitance attenuation after 10000 able cycling life with an ~82.6% retention of specific capacitance
charge/discharge cycles. Prior to assembling the Ni/Co-MOF0.75/ after 6000 cycles test at 10 A g
1 (Fig. 5d). The EIS spectra before
6 X. Zhang et al. / Journal of Alloys and Compounds 825 (2020) 154069

Fig. 5. (a) CV curves of the Ni/Co-MOF0.75 and RGO electrodes at 10 mV s
1; (b, c) CV and GCD curves of Ni/Co-MOF0.75/NF//RGO; (d) EIS spectra of Ni/Co-MOF0.75/NF//RGO before
and after charge/discharge cycles and cycling stability of the device; (f) Electrode design of the present asymmetric supercapacitor.

and after cycling test is performed in Fig. 5d. It can be found that the kg
1 at 852 W kg
1) [38]. Therefore, in view of the above results,
resistance of ions diffusing from electrolyte to electrode tends to the introduction of Co2þ in the Ni-based MOF has potential appli-
increase. The fabricated device delivers a high energy density of cability in the assembly of high-performance devices. The sche-
42.24 Wh kg
1 at the power density of 800 W kg
1 and the highest matic of the fabricated device is shown in Fig. 5e. When the
power density of 26.22 Wh kg
1 at an energy density of equipment starts to work, the rapid REDOX reaction takes place at
8000 W kg
1, which shows superior electrochemical performance the positive and negative electrodes.
than many previously reported supercapacitors, such as NS-BNs//
AC (41.04 Wh kg
1 at 750 W kg
1) [35], NiCo-MOF/NF//AC 4. Conclusions
(34.3 Wh kg
1 at 375 W kg
1) [36], NiO/C/RGO//AC (35.9 Wh
kg
1 at 749.1 W kg
1) [37], and Co3O4@NiCo2O4//AC (36 Wh In summary, we provide an efficient and simple method for
 X. Zhang et al. / Journal of Alloys and Compounds 825 (2020) 154069 7

enhancing the supercapacitive performance. The Ni/Co-MOF with carbon nanosheets microarray derived from MOFs for high performance
hybrid supercapacitors, J. Colloid Interface Sci. 539 (2019) 545e552.
ultrathin nanosheets structure shows a high specific capacitance of
[15] X. Xuan, M. Qian, L. Han, L. Wan, Y. Li, T. Lu, L. Pan, Y. Niu, S. Gong, In-situ
568 C g
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mental Research Funds for the Central Universities (No. for electrocatalytic oxidation of methanol, Appl. Catal. B Environ. 244 (2019)
2019XKQYMS01). 802e813.
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