Journal of Energy Storage 58 (2023) 106390

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Journal of Energy Storage

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Research papers

Outstanding energy storage performance in Co–Fe bimetallic

metal-organic framework spindles via decorating with reduced graphene
oxide nanosheets
Morteza Safari , Jamal Mazloom *
Department of Physics, Faculty of Science, University of Guilan, Namjoo Avenue, P.O. Box 413351914, Rasht, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: Reduced graphene oxides (rGOs; 3 and 5 wt%) decorated on Co–Fe bimetallic metal-organic framework (CoFe-
Co–Fe bimetallic MOF MOF) have been synthesized by the ultrasonic-assisted solvothermal method. XRD patterns did not show any
Reduced graphene oxide significant amendment in crystalline structure of MIL-88A and 3 % rGO@CoFe-MOF revealed better crystallinity
Electrochemical performance
than other samples. TEM and FESEM images clearly demonstrated that the rGO nanosheets are coated on the
Asymmetric supercapacitor
CoFe-MOF spindles. BET and BJH analyzes showed that the 3 % rGO@CoFe-MOF composite had the highest
specific surface area (149 m2 g− 1) and mean pore size (1.79 nm) compared to the other samples. The MOF and
rGO decorated on MOF samples were deposited on Ni foam (NF) and their electrochemical performance as
binder-free electrodes was evaluated in 3 M KOH electrolyte. The 3 % rGO@CoFe-MOF/NF electrode exhibits
outstanding specific capacitance of 2069.1 F g− 1 at a current density of 0.5 A g− 1 and good cycling stability with
91.3 % capacitance retention at a high current density of 10 A g− 1 after 5000 cycles. The assembled 3 %
rGO@CoFe-MOF//activated carbon asymmetric supercapacitor device delivers a maximum energy density of
75.8 Wh kg− 1 at a power density of 700 W kg− 1. The results exhibit that the 3 % rGO@CoFe-MOF can be a
propitious electrode material in energy storage devices.

1. Introduction hybrid supercapacitors. The accumulation of charges at the electrode-

electrolyte interface generates the energy in EDLCs, while rapid
Universal demands for sustainable energy storage and delivery reversible Faradaic reactions are devoted to the pseudocapacitors with
continue to push developing technology to its limits. Renewable energy Faradaic pseudocapacitance. In hybrid supercapacitors, both the electric
sources, such as wind, tidal and solar energies are all considered as double layers and Faradaic reactions are used to store energy [5,6].
viable solutions for the greenhouse effect and the fossil fuel crisis. Electrode materials with excellent capacitance, good stability and high
However, due to their intermittent nature, these renewable energies rate capability are crucial for powerful and efficient energy storage
require a dependable electrochemical energy storage device for practical devices. Rational design of electrode materials is a promising approach
application. Because of their compact size and portability for on-demand to optimize the performance of supercapacitors [7]. Metal-organic
usage, electrochemical supercapacitors and batteries are among the frameworks (MOFs), such as MILs [8,9], HKUST [10], ZIF [11], etc.,
most promising technologies for electrical energy storage [1,2]. Super­ are metal ion networks linked together by organic molecules. The
capacitors can maintain their power for extended periods than batteries tunable pore size and large surface area of MOFs make them suitable as
and deliver energy at higher rates [3]. Electrochemical supercapacitors electrode materials in energy storage devices [12,13]. Bimetallic MOFs
have lately attracted great research interest owing to the rapidly have a more complicated structure than monometallic MOFs and pro­
increasing demand for conversion and high-performing energy storage vide novel functionality via replacing the host metal ion with a second
devices with fast charge-discharge, excellent power density, and metal ion [14]. Also, bimetallic MOFs composed of transition metals
outstanding long-term cycling stability [4]. Supercapacitors are cate­ (nickel, cobalt, iron, etc.) with multiple valence states, improved elec­
gorized into three varieties based on their energy storage mechanism: tronic conductivity, and superior redox active sites are more attractive
pseudocapacitors, electrochemical double-layer capacitors (EDLCs), and as electrode materials for supercapacitors than monometallic MOFs

* Corresponding author.
E-mail address: j.mazloom@guilan.ac.ir (J. Mazloom).

https://doi.org/10.1016/j.est.2022.106390
Received 20 August 2022; Received in revised form 13 November 2022; Accepted 10 December 2022
Available online 22 December 2022
2352-152X/© 2022 Elsevier Ltd. All rights reserved.
M. Safari and J. Mazloom Journal of Energy Storage 58 (2023) 106390

[7,15,16]. The cobalt atom, as an element adjacent to iron in the peri­ 2. Experimental
odic table of elements, has a similar atomic radius compared with the
iron atom. Recently, few studies have shown that the cobalt‑iron 2.1. Materials
bimetallic MOFs have become the promising electrode materials in the
energy storage devices due to the synergistic effect between the iron and All the chemicals and reagents with analytical grade were used for
cobalt ions. Yu et al. [17] fabricated mesoporous bimetallic Co/Fe-MOF hybrid rGO@MOF preparation. Sodium nitrate (NaNO3), graphite
in the ionic liquid (IL)/supercritical CO2 (SC)/surfactant emulsion sys­ powder, hydrogen peroxide (H2O2, 30 %), potassium permanganate
tem. The bimetallic Co/Fe-MOF exhibited the highest specific capaci­ (KMnO4), hydrogen chloride (HCl, 37 %), sulfuric acid (H2SO4, 98 %),
tance of 319.5 F g− 1 at 1 A g− 1, which was 1.4 and 4 times higher than hydrazine monohydrate (N2H4⋅H2O), fumaric acid (C4H4O4, H2FUM), N,
single Co-MOF and Fe-MOF, respectively. The direct growth of MOFs on N-dimethylformamide (C3H7NO, DMF), iron (III) nitrate nonahydrate
current collectors without additives and binders can avoid the “dead (Fe(NO3)3⋅9H2O), activated carbon (AC), N-methyl-2-pyrrolidinone
volume” of electrode and enhance the electrolyte ion penetration effi­ (C5H9NO, NMP), and polyvinylidene difluoride ((C2H2F2)n, PVDF) were
ciency [18]. However, the straightforward use of pristine MOFs is obtained from Merck Company (Germany). Potassium hydroxide (KOH)
hampered by intrinsic limitations such as low electrical conductivity and and cobalt (II) nitrate hexahydrate (Co(NO3)2⋅6H2O, 98 %) were pur­
degradation in the electrolyte. To address this issue, it is logical to chased from Chem-Lab Company (Belgium).
combine MOFs with conductive materials such as carbon materials and
conductive polymers to build a desirable composite, where the syner­ 2.2. Graphene oxide synthesis
gistic effect achieves increased electrochemical performance [15].
Carbon-based materials, such as carbon quantum dots (CQDs), graphene Graphene oxide (GO) was prepared using a modified Hummer's
oxides (GOs) or reduced graphene oxides (rGOs), and carbon nanotubes process [14]. Firstly, equal weights of NaNO3 and graphite powder (2 g)
(CNTs) have been widely used in supercapacitor electrode active ma­ were dispersed into 100 mL H2SO4 and stirred in the ice bath for 1.5 h.
terials owing to their stable physical and chemical characteristics, large Then, the solution was treated with 12 g KMnO4 and stirred for 1.5 h.
specific surface area, good electrical conductivity, and compatibility After the solution color changed to dark brown, the ice bath was taken
with other composite materials [6,19]. away and the solution was stirred at 35 ◦ C for 3 h. 100 mL of deionized
Recently, the hybrids of MOFs with carbon nanomaterials were (DI) water was added to this mixture dropwise and stirred at a tem­
synthesized to enhance the specific capacitance of pristine MOFs owing perature of 90 ◦ C. After 1.5 h, the heating was stopped and adding 200
to their synergistic effects. Srimuk et al. [20] prepared the rGO/HKUST- mL DI water was started dropwise. Then, 30 mL H2O2 was added slowly
1 composite by solvothermal method and coated it on flexible carbon to stop the reaction of KMnO4 and stirred for 1 h. The obtained sample
fiber paper, which showed the maximum specific capacitance value of was washed three times with diluted HCl and DI water. The obtained
385 F g− 1 at 1 A g− 1. Krishnan et al. [21] synthesized the binder-free product was dried at room temperature and GO was obtained. Reduced
nitrogen-rich Cu-MOF/rGO electrode on glassy carbon using simple graphene oxide (rGO) was synthesized by dispersing 0.3 g GO in 100 mL
ultrasonication method. The electrode showed an excellent specific of DI water for 40 min. Then, the solution was treated with 3 mL of
capacitance of 867.09 F g− 1 at 1 A g− 1 and super-long cycling life. hydrazine monohydrate and refluxed in an oil bath at 100 ◦ C for 24 h.
Sundriyal et al. [22] studied the nickel intercalated ZIF-67/rGO com­ The black precipitate was collected after filtering and washing with
posite electrode coated over carbon paper and obtained a high specific ethanol and DI water three times. Further, the rGO powder was acquired
capacitance of 304 F g− 1 at 1 A g− 1. Ramasubramanian et al. [23] after drying at 60 ◦ C in vacuum oven.
investigated the performance of Fe-MOF combined with activated car­
bon (Fe-MOF@AC70 composite pressed onto nickel foam) for super­ 2.3. Preparation of CoFe-MOF electrodes
capacitor applications and reported the high specific capacitance of
596.5 F g− 1 at 1 A g− 1. Günduğar et al. [24] prepared rGO/MIL-101(Fe) The ultrasonic-assisted solvothermal approach was used to create the
by solvothermal technique and pasted on nickel foam, which presented CoFe-MOF [26]. Firstly, 16 mmol H2FUM as a linker was dissolved in 20
the specific capacitance of 250.6 F g− 1 at 0.5 A g− 1. Hong et al. [14] mL DMF and stirred vigorously. After 10 min, 0.145 g Co(NO3)2⋅6H2O
synthesized Ni-Co-MOF/GO through a one-pot solvothermal reaction and 0.403 g Fe(NO3)3⋅9H2O as metal precursors were added to this so­
and coated it onto nickel foam, which delivered a maximum capacitance lution. The crimson color sol was homogenized for 30 min using an ul­
of 447.2 F g− 1 at 1 A g− 1. Kumaraguru et al. [25] scrutinized the energy trasonic bath. The nickel foam substrates (NF, 2 × 1 cm2) were
storage performance of bimetallic Ni/Co-MOF/rGO composite casted on continually cleaned with 3 M HCl, DI water, acetone, and ethanol to
nickel foil and achieved the high capacitance of 1162 F g− 1 at 1 A g− 1. remove undesired chemicals such as NiO layers and, thereafter, dried in
To the best of our knowledge, there is no report on electrochemical the oven at 70 ◦ C for 30 min. For preparation of binder-free electrodes,
behavior of rGO@CoFe-MOF composites as supercapacitor electrodes. the bimetallic MOF solution was transferred to a 50 mL Teflon-lined
In the present work, the binder-free electrodes of the bimetallic CoFe- stainless autoclave and the cleaned NFs were dipped in the solution.
MOF with different concentrations (3 and 5 %) of reduced graphene The autoclave was heated at 120 ◦ C and maintained for 24 h. Then the
oxide grown on Ni foam (NF) have been synthesized using ultrasonic- autoclave was cooled and the as-synthesis material electrodes were
assisted solvothermal method for supercapacitor applications. We rinsed three times with pure ethanol and DMF. Finally, the CoFe-MOF/
studied the structural, morphological, compositional and electro­ NF electrodes were dried at 60 ◦ C for 12 h.
chemical properties of rGO@CoFe-MOF as novel electrode material,
which offers superior conductivity to improve the specific capacitance. 2.4. Preparation of rGO@CoFe-MOF electrodes
Finally, the asymmetric supercapacitor (ASC) device is assembled using
activated carbon (AC)/NF and 3 % rGO@CoFe-MOF/NF as negative and Firstly, in the separate beakers, certain amounts of rGO (3 and 5 wt
positive electrodes, respectively, in 3 mol L− 1 KOH electrolyte. The %) were dispersed in 10 mL DMF for 1 h using the ultrasonic device. The
robust and exceptional electrochemical performances of 3 % rGO colloidal suspensions were added to the crimson mixture containing
rGO@CoFe-MOF propose it to be a favorable electrode material for high- MOF precursors and sonicated for 2 h. The cleaned nickel foams were
performance supercapacitors. dipped in the black mixtures and transferred to a 50 mL autoclave at
120 ◦ C for 24 h. Afterward, the autoclave was cooled down to ambient
temperature, and the collected black powders and rGO@CoFe-MOF/NF
electrodes were washed several times with pure ethanol and DMF.
Finally, the products were dried at 60 ◦ C for 12 h. The loaded mass of the

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M. Safari and J. Mazloom Journal of Energy Storage 58 (2023) 106390

CoFe-MOF and rGO@CoFe-MOF composites as active materials on 1 × 1

cm2 area of Ni foams was about 2 mg.

2.5. Material characterization

The structure of the prepared samples was analyzed by X-ray

diffraction (X'Pert Pro, Panalytical) using Cu Kα (λ = 1.5406 Å) radia­
tion. The Perkin Elmer-Spectrum 65 recorded the Fourier-transform
infrared (FTIR) spectra of samples in the 400–4000 cm− 1. The Raman
spectra of the powder samples were collected in Teksan (Takram
P50C0R10, Nd:YAG laser) with an excitation wavelength of 532 nm.
Transmission electron microscopy (TEM, Zeiss EM900) and field emis­
sion scanning electron microscopy (FESEM, MIRA3, TESCAN-XMU)
were used to investigate the morphology of the mentioned samples.
The surface chemical compositions of 3 % rGO@CoFe-MOF composite
were probed by X-ray photoelectron spectroscopy (XPS, EA10, BESTEC
Co., Germany) with Al Kα (E = 1.487 keV) radiation. N2 adsorption/
desorption isotherms at 77 K were used to evaluate the textural prop­
erties of the samples using a BELSORP-mini II instrument. Barrett-
Joyner-Halanda (BJH) and Brunauer-Emmett-Teller (BET) techniques
were used to measure the pore size distribution and surface area of the Fig. 1. XRD patterns of GO, rGO, CoFe-MOF, and rGO@CoFe-MOF composites.
samples, respectively.
retained. Also, the XRD peaks of rGO@CoFe-MOF composites were
2.6. Electrochemical measurements intensified compared to pristine CoFe-MOF which revealed that the rGO
sheets act as a template to arrange the CoFe-MOF growth and cause
The electrochemical behavior of the materials in a standard three- better crystallinity of MOFs [31,32].
electrode configuration comprising platinum wire, Ag/AgCl electrode,
reduced graphene oxide@MOF hybrid electrodes, and 3 M KOH aqueous 3.2. Chemical properties: FTIR and Raman studies
solution was evaluated as counter electrode, reference electrode,
working electrodes, and electrolyte, respectively. The Metrohm Auto­ FTIR spectra of GO, rGO, CoFe-MOF, 3 and 5 wt% rGO@CoFe-MOF
lab/PGSTAT302N electrochemical workstation was utilized to perform are demonstrated in Fig. 2a. The characteristic peaks of GO are detected
electrochemical impedance spectroscopy (EIS), galvanostatic charge- as follows: a broad band at 3398 cm− 1 (O–H strong stretching mode)
discharge (GCD), and cyclic voltammetry (CV). By utilizing Zview and 1044 cm− 1 (C–O stretching mode) correspond to the vibration
software, the data obtained from EIS measurements were fitted with a bands of the epoxy, a peak at 1722 cm− 1 (C–– O stretching mode) related
suitable circuit. to the carboxylic groups, an absorption peak at 1613 cm− 1 (C– –C
stretching mode), and 1189 cm− 1 (C–OH stretch) [33,34]. The presence
2.7. Fabrication of asymmetric supercapacitor of C–– C band at 1635 cm− 1 in the rGO spectra revealed that the sp2
structure of carbon atoms was preserved [35]. For CoFe-MOF, as seen in
The asymmetric supercapacitor (ASC) device was assembled by Fig. 2a, the broad absorption at 3403 cm− 1 relevant to the stretching
integrating a binder-free 3 % rGO@MOF/NF positive electrode with vibration of the O–H bond confirms the presence of water in the
activated carbon (AC)/NF as a negative electrode in 3 M KOH aqueous product. The strong peaks located at 1619 and 1383 cm− 1 are associated
solution and a Whatman filter paper as a separator. The negative elec­ with asymmetric and symmetric vibration modes of the C–O bonds,
trode was made by mixing 90 wt% AC and 10 wt% polyvinylidene respectively, and assert the attendance of H2FUM as a linker of MOF. The
difluoride (PVDF, as a binder) in N-methyl-2-pyrrolidinone (NMP, as a existing peaks at 1661 and 1202 cm− 1 are relative to the C–
– O bond and
solvent). The cleaned Ni foam was covered with the obtained homoge­ stretch mode bond of carboxylic acids, respectively [36]. The C–H
nous slurry, and then dried at 100 ◦ C for 10 h. The electrochemical bonds corresponding to the aromatic rings are ascribed at the absorption
measurements (CV and GCD) were carried out in a two-electrode system peaks from 796 to 1099 cm− 1 [37]. The peak at 670 cm− 1 is related to
with 3 % rGO@CoFe-MOF/NF positive and AC/NF negative electrodes the carbonyl group [38]. The Co–O and Fe–O vibrations are placed at
using Zahner-Zennium instrument. 525 and 621 approving the existence of cobalt and iron metals in the
CoFe-MOF, respectively [39]. The rGO peaks cannot easily appear in the
3. Result and discussion (3 and 5 wt%) rGO@CoFe-MOF because of the high intensity of CoFe-
MOF peaks. However, the FTIR spectra of CoFe-MOF and rGO@CoFe-
3.1. Structural properties MOF were virtually identical, approving that the three samples have a
similar structure.
The crystalline structures of samples were assigned by X-ray Raman spectra of samples are exhibited in Fig. 2b. The double bond
diffraction (XRD) analysis and the related patterns are demonstrated in of the H2FUM molecule in CoFe-MOF was proved by the appearance of a
Fig. 1. The sharp peak at 2θ = 10.67◦ attributed to (002) plane in gra­ band at 3072 cm− 1 attributed to the stretching sp2 C–H vibration, and a
phene oxide XRD pattern and according to Bragg's relation the interlayer strong peak at 1654 cm− 1 corresponds to the symmetric vibration modes
distance was about 0.83 nm [27,28]. The characteristic peak of the – C bond. Furthermore, the bands placed at 1420 and 1288 cm− 1
of the C–
(002) plane for rGO at 2θ = 25.12◦ with d-spacing of 0.36 nm represents are ascribed to the symmetric vibration of the carboxylate groups and
a reduction in the interlayer distance of GO sheets owing to the removal the C–O bond, respectively. Despite the drying treatment, a peak
of oxygen functional groups [25]. The crystal structure of CoFe-MOF located at 2953 cm− 1 is related to sp3 C–H bond vibrations of DMF
was consistent with Fe-MIL-88A, and no traces of Fe2O3 and Co3O4 molecules, which remained after synthesis [40]. The present bands at
phases were found in the XRD patterns. The main peaks in XRD pattern 548, 1585 cm− 1 are related to Co–O species and 715 cm− 1 correspond
are indexed using the relevant reports [29,30]. When a small amount of to Fe–O bonds of CoFe(H2FUM) [41]. For the GO and rGO samples,
rGO (3 % and 5 wt%) is added to CoFe-MOF, the main MOF peaks are there are two main peaks located in 1360 and 1599 cm− 1, which are

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M. Safari and J. Mazloom Journal of Energy Storage 58 (2023) 106390

Fig. 2. (a) FTIR and (b) Raman spectra of GO, rGO, CoFe-MOF, and rGO@CoFe-MOF composites.

related to the D and G bands, respectively. The D band is caused by the GO, rGO, 3 and 5 % rGO@CoFe-MOF, respectively. The enhancement in
breathing modes of κ-point phonons with A1g symmetry, and the G band the ID/IG value of rGO compared to GO indicates the reduction in the
corresponds to a doubly degenerated phonon mode (E2g symmetry in the average size of graphene-like sp2 domains in the rGO sample, which
graphitic structure) and the in-plane bond-stretching motion of sp2 confirms the increase unrepaired defects in the rGO after the removal of
carbon atoms. The 2D band at 2684 cm− 1 is associated with the multi­ oxygen-containing functional groups [43,44]. Also, this ratio for the
layer structures of GO [42]. The Raman spectra of 3 and 5 % rGO@CoFe- composites was lower than the rGO, which could be due to the emerging
MOF demonstrated D and G bands, which are upshifted to higher fre­ of oxygen groups from MOF material [25]. Moreover, the in-plane
quencies than rGO. This confirms that the rGO has been successfully crystallite size of sp2 hybridization in the rGO@CoFe-MOF can be
placed on the CoFe-MOF. The ratio of D band to G band intensities (ID/ calculated using the following equation [45]:
IG) illustrates the extent of the defects in the graphene surface after
modifications, which was calculated to be 0.88, 1.01, 0.65, and 0.78 for

Fig. 3. FESEM images of (a) GO, (b, e) CoFe-MOF, (c, f) 3 % rGO@CoFe-MOF, and (d) 5 % rGO@CoFe-MOF.

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M. Safari and J. Mazloom Journal of Energy Storage 58 (2023) 106390

( )− 1
ID 3.4. Compositional analysis
La (nm) = 2.4 × λ4 × 10− 10
(1)
IG
The surface chemical compositions of the 3 % rGO@CoFe-MOF were
where λ is the laser excitation wavelength, which is equal to 532 nm. The scrutinized by XPS analysis (Fig. 5). The XPS survey spectrum (Fig. 5a)
La values are 29.5 and 24.6 nm for 3 and 5 % rGO@CoFe-MOF, revealed that the sample consists of Co, Fe, O, C with no other impu­
respectively. The values are increased in comparison to the La value of rities. The appearance of three peaks at 284.8, 286.3, and 288.7 eV in
rGO (19.0 nm), indicating the larger average sizes of crystalline graphite the high-resolution XPS spectrum of C 1 s (Fig. 5b) could be attributed to
domains in rGO@CoFe-MOF composites than rGO [37]. – O, and carboxylic bonds of rGO, respectively [47,48].
benzoic rings, C–
The peak with low intensity (in 288.7 eV) indicates that the composite
3.3. Morphological properties has less oxygen functionalities such as carbonyl, carboxyl and hydroxyl
groups. Similarly, the peak of 284.8 eV with the maximum intensity
The FESEM images of the synthesized GO, Co–Fe bimetallic-MOF, denotes the predominant nature of the aromatic part [25]. Fig. 5c ex­
and (3, 5 wt%) rGO@MOF hybrids at various magnifications are illus­ poses the deconvoluted XPS spectra of O 1s. The appearance of three
trated in Fig. 3. It can be understood from Fig. 3a GO has been mostly peaks at binding energies of 531.4, 532.1, and 533.0 eV are attributed to
single to few wrinkled sheets, which is confirmed by the Raman spectra. metal‑oxygen bonds, the oxygen components of the carboxylate groups
Fig. 3b,e demonstrate that the CoFe-MOF has a spindle-like morphology. in H2FUM, and C–O bonds of rGO@MOF, respectively [47]. The Fe 2p
The high magnification images of CoFe-MOF (Fig. 3e) and 3 % spectrum is portrayed in Fig. 5d. The peaks at 712.0, 716.8, and 725.8
rGO@CoFe-MOF (Fig. 3f) revealed that rGO is well decorated on the eV are associated with the Fe 2p3/2, the satellite peak, and Fe 2p1/2,
MOFs. As shown in Fig. 3b-d, increasing the amount of rGO from 3 to 5 respectively. The separation of the spin-orbit peaks was about 13.8 eV,
% reduces the size of spindles. corroborating the presence of Fe (III) in the composite [47,49,50]. The
The TEM images of the rGO@CoFe-MOF composites are shown in high-resolution XPS spectra of Co 2p (Fig. 5e) display spin-orbit doublet
Fig. 4. Fig. 4c demonstrates the low-magnification TEM image, which peaks, which are located at the binding energies of 781.5 (Co 2p3/2) and
confirms the spindle-like morphology of CoFe-MOF samples. The higher 797.7 eV (Co 2p1/2) with satellite peaks at 785.6 and 803.0 eV,
magnification TEM images (Fig. 4b and d) revealed that rGO sheets were respectively. The separation distance between the doublet peaks (Co
decorated on CoFe-MOF spindle. The rGO sheets were clearly observed 2p3/2 and Co 2p1/2) was 16.2 eV, confirming the existence of Co2+ in the
in Fig. 4a, which can act as a conducting interface to facilitate charge composite [25,51].
transfer [46]. The TEM results are completely consistent with FESEM
images. 3.5. Surface area and porosity measurement

The N2 adsorption/desorption isotherms and BJH curves are

demonstrated in Fig. 6. The samples exhibited type I/IV mixed isotherm

Fig. 4. TEM images of (a) rGO, (b) 3 % rGO@CoFe-MOF, (c, d) 5 % rGO@CoFe-MOF.

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M. Safari and J. Mazloom Journal of Energy Storage 58 (2023) 106390

Fig. 5. XPS spectra of 3 % rGO@CoFe-MOF: (a) Survey, (b) C 1 s, (c) O 1 s, (d) Fe 2p, and (e) Co 2p.

Fig. 6. N2 adsorption/desorption isotherms (the insets show pore size distribution) of (a) CoFe-MOF, (b) 3 % rGO@CoFe-MOF and (c) 5 % rGO@CoFe-MOF.

with H3 hysteresis loop at relative pressures above 0.3, which is indic­ The rGO@CoFe-MOF revealed the enhanced porosity and BET surface
ative of existing both microporous and mesoporous structures [40,52]. area compared to the pristine MOF. The enhancement in SBET of
The H3 type hysteresis loops for CoFe-MOF and (3, 5 wt%) rGO@CoFe- rGO@CoFe-MOF compared to pristine MOF can be related to the crea­
MOF revealed the presence of slit-like pores [53]. The pore size distri­ tion of extra porosity at the interface of rGO and MOF [54]. With
bution of the samples (the insets of Fig. 6) is centered below 2 nm, which increasing the rGO content from 3 to 5 %, SBET and rp are decreased
approves that micropores are the main component in the synthesized because of the stacking of rGO sheets around the porous CoFe-MOF
materials. Moreover, the calculation results for pore volume (Vp), spe­ spindles [52].
cific surface area (SBET), and average pore size (rp) are given in Table 1.
3.6. Electrochemical properties
Table 1
Textural parameters of samples evaluated from BET and equivalent series The electrochemical performance of CoFe-MOF/NF and rGO@CoFe-
resistance (Rs) and charge transfer resistance (Rct) estimated from EIS MOF/NF electrodes was appraised by CV and GCD curves. As depicted in
measurements. Fig. 7, CV curves were obtained at various sweep rates from 10 to 80 mV
Active material SBET (m2 Vp (cm3 rp Rs (Ω) Rct (Ω) s− 1 in a potential window of 0–0.5 V for all electrodes. As shown in
g− 1) g− 1) (nm) Fig. 7, the CV curves display a pair of redox peaks, manifesting the
CoFe-MOF 52.7 0.017 1.32 1.01 23.07 Faradaic behavior of charge storage [7]. For all of the electrodes, the two
3 % rGO@CoFe- 149.0 0.054 1.79 0.79 5.03 strong peaks detected in the potential range of 0 to 0.5 V can be related
MOF to the reversible redox reactions of Fe (III) ↔ Fe (II) and Co (II) ↔ Co (III)
5 % rGO@CoFe- 112.0 0.027 1.57 0.93 8.04 under OH‾ intercalation/deintercalation [55–57]. As clearly seen from
MOF
Fig. 7d, the substantial enhancement in the integrated area of the 3 %

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M. Safari and J. Mazloom Journal of Energy Storage 58 (2023) 106390

1
Fig. 7. CV curves for (a) CoFe-MOF/NF, (b) 3 % rGO@CoFe-MOF/NF, and (c) 5 % rGO@CoFe-MOF/NF electrodes, (d) Comparison of CV curves at 10 mV s− for
three electrodes.

rGO@CoFe-MOF cyclic voltammogram compared to the bimetallic rGO@CoFe-MOF were about 2.4 and 1.5 times higher than the CoFe-
CoFe-MOF proposes an outstanding improvement in specific capaci­ MOF, respectively. The 3 % rGO composite exhibited the highest
tance (Cs) of bimetallic MOF by rGO coating. Furthermore, the distance slope, indicating the superior diffusion kinetics of electrolyte ions. The
between the anodic and cathodic potential peaks (ΔVp) in the 3 % charge storage processes could be identified by the power-law rela­
rGO@MOF electrodes was reduced compared to the MOF electrode, tionship [60]:
indicating their high electrical conductivity of this electrode [58]. The
i = aνb (3)
peak currents gradually enhanced with increasing sweep rate. The pair
of redox peaks in the 3 % rGO@MOF/NF electrode is clearly observed
where i denotes a current density, ν stands for a sweep rate, a and b are
even at sweep rate of 80 mV s− 1, which indicates the excellent kinetic
adjustable variables. In general, the b-value is defined by the slope of log
reversibility and rate performance of this electrode compared to the
(i) against log (ν) plot at a fixed potential. If b ≈ 1, the charge storage
other electrodes. The slight shift in the position of the oxidation and
mechanism is considered the surface-controlled capacitive process,
reduction peaks to positive and negative potentials with increasing the
while b ≈ 0.5 represents the diffusion-controlled performance. As
sweep rate is mainly related to the polarization of the electrodes [2].
demonstrated in Fig. 8b, the b-values for 3 % rGO@CoFe-MOF are about
The charge storage mechanism of electrode materials is investigated
0.44 and 0.41, corresponding to the reduction and oxidation reaction
based on the functional reaction. From the linear relationship between
peaks, respectively, indicating that the charge storage mechanism is
the square root of sweep rate (ν1/2) and the peak current (Ip) in Fig. 8a, it
mainly dominated by the ion diffusion-controlled process. The contri­
is inferred that the electrochemical reaction processes were controlled
bution of the diffusion-controlled process and surface capacitive effect
by the ion diffusion [57]. The relationship is followed by Randless-
with the sweep rates were determined by Dunn's equation [60]:
Sevcik equation [59]:
i(V) = k1 ν + k2 ν1/2 (4)
Ip = 2.69 × 105 n3/2 SD1/2 Cν1/2 (2)
where k1 and k2 are constants, i(V) represents the current response at a
where Ip, ν, n, D, S, and C represent the redox peak current, the sweep
given potential, and ν is a sweep rate. The slope and intercept of the
rate, the electron transfer number, the diffusion coefficient, the surface
linear relationship between i(V)/ν1/2 and ν1/2 give the values of k1 and
area of the electrode, and the initial concentration of OH‾, respectively.
k2, respectively. The shaded regions in Fig. 8d-f indicate the surface-
Diffusion coefficient, D, is directly proportional to the slope of curves in
controlled contributions at a sweep rate of 10 mV s− 1, which occupy
Fig. 8a. The diffusion coefficients of the oxidation reactions in 3 and 5 %
17, 33, and 18 % of the total region for the CoFe-MOF, 3 % rGO@CoFe-

7
M. Safari and J. Mazloom Journal of Energy Storage 58 (2023) 106390

Fig. 8. (a) The curves of the peak current versus the square root of sweep rates (Randless-Sevcik's plot), (b) The plots of log i versus log ν, (c) Capacitance
contribution for three electrodes, the capacitive contribution of CV curves at 10 mV s− 1 for (d) CoFe-MOF, (e) 3 % rGO@CoFe-MOF, and (f) 5 % rGO@CoFe-MOF.

MOF, and 5 % rGO@CoFe-MOF, respectively (Fig. 8c). The high ranging from 0.5 to 5 A g− 1 (Fig. 9a-c). According to CV curve, the GCD
capacitive (surface) contribution of the rGO@CoFe-MOF composites test were recorded in the appropriate potential window of 0–0.45 V due
verified enhanced electrochemical kinetic performance of the electrodes to avoid the water electrolysis (oxygen evolution reaction) above 0.45 V
compared to pristine MOF electrode. [61]. The GCD curves have nonlinear shapes, which are attributed to the
GCD curves for all electrodes are presented at current densities Faradaic redox reactions on surface of electrode during OH‾ insertion/

1
Fig. 9. GCD curves for (a) CoFe-MOF/NF, (b) 3 % rGO@CoFe-MOF/NF, and (c) 5 % rGO@CoFe-MOF/NF electrodes, (d) Comparison of GCD curves at 0.5 A g− for
three electrodes, (e) The plot of specific capacitance at disparate current densities. (f) Cycling stability plot for the electrodes at 10 A g− 1.

8
M. Safari and J. Mazloom Journal of Energy Storage 58 (2023) 106390

extraction and confirm the pseudocapacitive characteristic. Moreover,

the iR drop before the plateau on discharge curve of MOF electrode
reveals the internal resistance of the electrode, which is reduced by rGO
decoration in rGO@MOF electrodes. The value of specific capacitance
(Cs) was calculated based on the GCD curves from the following equa­
tion [14]:
IΔt
Cs = (5)
mΔV

where Δt, m, ΔV, and I are the discharge time (s), the mass of active
material (g), the potential window (V), and discharge current (A),
respectively. The GCD curves of the three electrodes are given for
comparison in Fig. 9d. As exhibited in Fig. 9e, the Cs values of the 3 %
rGO@CoFe-MOF/NF electrode were 2069.1, 1941.8, 1776.5, and
1615.2 F g− 1 at current densities of 0.5, 1, 2.5, 5 A g− 1, respectively,
with high rate capability of 78.1 %. This value is much higher than CoFe-
MOF/NF (64.5 %) and 5 % rGO@CoFe-MOF/NF (71.2 %) electrodes.
The Cs values decline with an enhancement in the current density owing
to lacking time to accomplish the redox reactions by active materials and
augmentation in voltage drop [25]. The cycling stability of the three
electrodes was explored at 10 A g− 1 after 5000 cycles. As displayed in Fig. 10. The Nyquist plots of the electrodes (the inset shows an equiva­
Fig. 9f, the 3 % rGO@CoFe-MOF/NF electrode exhibits much higher lent circuit).
capacitance retention (91.3 %) than the other electrodes. The high Cs
and capacitance retention values for rGO@CoFe-MOF/NF electrodes can The decrease of the Rct values in rGO@MOF composites is owing to the
be ascribed to the synergistic effects between CoFe-MOF and rGO. The high electrical conductivity of rGO, which facilitates the charge transfer
hybridization of porous CoFe-MOF spindles with rGO sheets can be efficiency at the interface of electrode and electrolyte. Also, the Rs of
promoted the accessibility of electrolyte to active sites of electrode rGO@CoFe-MOF/NF electrodes is smaller than that of CoFe-MOF/NF
surface. Furthermore, the high electrical conductivity of rGO can facil­ electrode due to the existence of rGO, which has generated additional
itate the electron transport during charge-discharge cycles and the rGO defects to promote the electrical transport. Meanwhile, the 3 %
decorating on the MOF spindles can shorten the electrolyte ion diffusion rGO@CoFe-MOF/NF electrode has the smallest Rs (0.79 Ω) as a result of
distance, which accelerates the charge transport process [21,56]. The the highly oriented structure [56]. In Fig. 10, the steeper slope of the
drop in Cs and capacitance retention of 5 % rGO@CoFe-MOF/NF elec­ Nyquist plot at low-frequency region for the 3 % rGO@CoFe-MOF/NF
trode compared to 3 % can be related to restacking the rGO sheets and electrode disclosed faster ion diffusion and better capacitive perfor­
the reduction of available surface area active sites on the electrode [56]. mance than the other electrodes [55,56]. It can be owing to the
Table 2 compares the Cs value calculated in this work with other reports. improved diffusion rate of OH‾ species, which is attributed to the higher
The charge transfer kinetics of the electrode-electrolyte interface, specific surface area determined by BET analysis [62].
and conductivity were appraised using EIS analysis. The frequency To assess the potential application of the rGO@CoFe-MOF compos­
range for the EIS data acquisition was 0.01 Hz to 100 kHz, with AC ite, an asymmetric supercapacitor was made by utilizing the activated
voltage amplitude of 5 mV. The Nyquist plots of CoFe-MOF/NF and (3, 5 carbon pasted on nickel foam (AC/NF) as an anode, the 3 % rGO@CoFe-
wt%) rGO@CoFe-MOF/NF electrodes are shown in Fig. 10. The Nyquist MOF/NF electrode as a cathode electrode, and Whatman filter paper as a
plot was fitted with equivalent circuit model (see inset of Fig. 10) separator in the 3 M KOH electrolyte. Fig. 11a demonstrates the CV
comprised various elements such as equivalent series resistance (sum of curves of the single negative electrode (AC/NF) from − 1 to 0 V and the
electrolyte ionic resistance, electrode-to-current collector contact resis­ individual positive electrode (rGO@CoFe-MOF/NF) within a potential
tance, and electrode material intrinsic resistance; Rs), charge-transfer range from 0 to 0.5 V in a three-electrode system at a sweep rate of 10
resistance (the resistance to electron transfer at electrode and electro­ mV s− 1. The charge equilibrium (Q+ = Q− ) between the two electrodes is
lyte interfaces; Rct), constant phase element (double layer capacitance; essential to obtain the high electrochemical performance of an asym­
CPE) and Warburg impedance (OH‾ diffusion impedance at the surface metric supercapacitor in a two-electrode configuration. Therefore, the
of electrodes; Ws) [34]. The fitting of plots was performed using Zview mass loading of active materials on the positive and negative electrodes
software and the calculated parameters (Rct, Rs) were listed in Table 1.

Table 2
Comparison of the calculated specific capacitances in this work with other reported data for MOF/GO hybrids.
Active material Synthesis method Morphology Substrate Electrolyte Specific capacitance (F g− 1) at 1 A Reference
g− 1

Ni-Co-MOF/GO Solvothermal Chestnut Nickel foam 6 M KOH 447.2 [14]

rGO/Zn- Hydrothermal Laminate Titanium mesh 1 M H2SO4 237.70 [19]
MOF@PANI
rGO/HKUST-1 Solvothermal Irregular Carbon fiber 1 M NaNO3 385 [20]
paper
Cu-MOF/rGO Ultrasonication Irregular Glassy carbon 1 M Na2SO4 867.09 [21]
Ni/Co-MOF/rGO Co-precipitation Spherical particles @rectangular Nickel foil 1 M KOH 1162 [25]
rod
Ni-BPDC/GO Hydrothermal Micro-nanostrips Nickel foam 6M KOH 630 [31]
Ni/Co-MOF-rGO Reflux Spherical/rod Nickel foam 6M KOH 860 [55]
Ni-MOF/rGO-300 Hydrothermal Microsphere Nickel foam 6M KOH 954 [56]
3 % rGO@CoFe- Ultrasonic-assisted Spindle Nickel foam 3M KOH 1941.8 Present
MOF solvothermal work

9
M. Safari and J. Mazloom Journal of Energy Storage 58 (2023) 106390

Fig. 11. (a) CV curve of AC/NF and 3 % rGO@CoFe-MOF/NF of 10 mV s− 1 in the three-electrode configuration. (b) CV and (c) GCD curves of 3 % rGO@CoFe-MOF//
AC device in the two-electrode system. (d) Specific capacitance of the 3 % rGO@CoFe-MOF//AC at disparate current densities. (e) Cycling stability performance of
the 3 % rGO@CoFe-MOF//AC at 10 A g− 1. (f) Ragone plot.

can be calculated by the following equation [56]: at low current density may be ascribed to the higher ratio of the parasitic
side-chain reactions between the electrode and impurities present in the
m+ C− × ΔV−
= (6) electrolyte [65]. As illustrated in Fig. 11e, the cycling stability of the 3 %
m− C+ × ΔV+
rGO@CoFe-MOF//AC was recorded at 10 A g− 1 after 10,000 cycles. The
where ΔV+ (ΔV− ) and C+ (C− ) are the working potential window and ASC device demonstrates excellent capacitance retention of 83.8 %,
the specific capacitance of positive (negative) electrode, respectively. which promises a novel electrode material for supercapacitors. The
The specific capacitance of negative and positive electrodes may be energy density (Es) and power density (Ps) are the two major and
evaluated based on the CV curves using the following equation [63]: comparative parameters used to describe the supercapacitor perfor­
∫ mance. The Es (Wh kg− 1) and Ps (W kg− 1) of the 3 % rGO@CoFe-MOF//
I(V) dV AC asymmetric supercapacitor are evaluated by GCD curves using the
Cs = (7)
m νΔV following equations [66]:
∫
where I(V) dV is the integral area in the CV curve, m is the loading mass Cs (ΔV)2
Es = (9)
of the active material (g), ΔV is the working potential window (V), and ν 7.2
is the sweep rate. The mass ratio (m+/m− ) of 3 % rGO@CoFe-MOF and
AC electrode materials was obtained to be 1:4.5. Fig. 11b displays CV 3600 Es
Ps = (10)
curves of the 3 % rGO@CoFe-MOF//AC asymmetric supercapacitor Δt
device at disparate sweep rates. The asymmetric configuration operates The Ragone plot is depicted in Fig. 11f, which relates the power and
within a potential window ranging from 0 to 1.4 V. The redox peaks energy densities of the asymmetric supercapacitor device. A maximum
represent the pseudocapacitance contribution from the positive elec­ Es of 75.8 Wh kg− 1 is achieved at a Ps of 700 W kg− 1, and 41.7 Wh kg− 1 is
trode. This pseudocapacitance characteristic is demonstrated in GCD sustained at a higher Ps of 7000 W kg− 1. These values are superior than
curves at various current densities (Fig. 11c). According to Eq. (5), the Cs most of other reported ASC devices, such as rGO/HKUST-1 (42 Wh kg− 1
values of 3 % rGO@CoFe-MOF//AC were obtained 278.5, 257.6, 201.1, at 950 W kg− 1) [20], Cu-MOF@rGO (30.56 Wh kg− 1 at 600 W kg− 1)
and 153.1 F g− 1 at 1, 2, 5, and 10 A g− 1, respectively, with rate capa­ [21], Fe-MOF@AC70/carbon cloth (16.24 Wh kg− 1 at 897.5 W kg− 1)
bility of 54.9 %. The Coulombic efficiency (η) reflects the degree of [23], Ni-BPDC/GO (16.5 Wh kg− 1 at 250 W kg− 1) [31], 2D/2D NiCo-
reversibility of the charge-discharge process, which was calculated ac­ MOF/GO (36.83 Wh kg− 1 at 374.99 W kg− 1) [51], Ni/Co-MOF-rGO
cording to following equation [64]: (72.8 Wh kg− 1 at 850 W kg− 1) [55], and Ni-MOF/rGO-300 (17.13
τd Wh kg− 1 at 750 W kg− 1) [56].
η= × 100% (8) Finally, the best electrode was examined 3 % rGO@CoFe-MOF as a
τc
power source. As shown in Fig. 12, charging of two cells of the ASC
where τd and τc are discharge and charge times in the GCD curves, device connected in series by a power supply was able to light up the
respectively. As shown in Fig. 11c, the Coulombic efficiency at the blue light-emitting diode (LED, 20 mA, 3.6 V) and the red LED (10 mA,
current density of 1 A g− 1 for the ASC device was measured to be 86.4 %, 1.8 V) for about 10 and 45 min, consecutively. From the results, it was
which increased to 97.1 % at 10 A g− 1. The lower coulombic efficiency revealed that the 3 % rGO@CoFe-MOF//AC ASC device had an

10
M. Safari and J. Mazloom Journal of Energy Storage 58 (2023) 106390

Fig. 12. Photograph of rGO@CoFe-MOF//AC ASC devices connected in series, which turn on the blue and red LEDs. (For interpretation of the references to color in
this figure legend, the reader is referred to the web version of this article.)

outstanding performance in energy storage systems. Acknowledgements

4. Conclusion We appreciate Mr. Ali Monemdjou for his assistance in the con­
struction of the ASC device. Also, the authors would like to thank the
rGO@CoFe-MOF hybrids were manufactured on Ni foam using sol­ University of Guilan Research Council for its financial support.
vothermal method as binder-free electrodes for supercapacitor appli­
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