Journal of Energy Storage 56 (2022) 105897

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Journal of Energy Storage

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Review Article

Current advances of nickel based metal organic framework and their

nanocomposites for high performance supercapacitor applications: A
critical review
Shiwani Khokhar a, Hardeep Anand a, *, Prakash Chand b, *
a
Department of Chemistry, Kurukshetra University, Kurukshetra 136119, India
b
Department of Physics, National Institute of Technology, Kurukshetra 136119, India

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

Keywords: The Current review is a comprehensive document in which we outline recent advances in the fabrication of metal
Nickel metal-organic frameworks organic framework based on nickel (Ni-MOF) and their high energy supercapacitor applications as electrode
Nanocomposites materials. Ni-MOFs have ignited a lot of interest in energy storage systems due to their extraordinary properties
Supercapacitor
among various transition metal-based metal organic frameworks such as superior electrochemical performance,
Electrode material
outstanding rate capability, highly porous structure, abundant active sites, high specific capacitance, strong
Specific capacitance
redox activity, and eco-friendly have sparked intense interest in the development of growing supercapacitors to
satisfy the soaring requirement for efficient electrochemical energy storage devices. However, reviews on Ni-
MOFs and its nanocomposites as electrode material for high energy supercapacitor applications are very rare.
The current review also presents the synthetic methods such as hydro/solvothermal approach, microwave-
assisted, slow evaporation, sonochemical, electrochemical, and mechanochemical in electrochemical energy
storage systems. Several nanocomposites of Ni-MOFs with carbon nanotubes, graphene, and polymers along with
characterization techniques have been briefly reviewed here. Furthermore, this study outlines the current issues
as well as some potential solutions that may embolden remarkable strategic design of agile Ni-MOFs nano­
materials for high performance supercapacitors in the upcoming period.

1. Introduction
Due to environmental difficulties such as global warming, pollution,
rise in carbon dioxide emissions and fuel shortages, it is now important
to develop clean, efficient, and long-term energy storage sources [1–4].
There has been a wide range of research into the evolution of energy
generating technology including fuel cells and solar cells, as well as
energy storage technologies such as water electrolysis, lithium batteries,
vanadium redox flow batteries, and capacitors. The two major cate­
gories of electrochemical devices (batteries and capacitors) have
received a significant amount of research attention. Since batteries have
a high energy density, they have a limited power density, whereas or­
dinary capacitors have a high-power density but a low energy density
[5]. Nippon Electric Company (NEC) developed a technology called a
supercapacitor in 1978. The supercapacitor, also known as an electro­
chemical capacitor (EC), has spanned the gap between the battery and
the traditional capacitor. Supercapacitors are gaining popularity
because of their high density of power, exquisite cycle lifetime (>106
cycles), high-rate capabilities, quick rate of charge/discharge, flexible
operating temperature, (− 40 ◦ C to 70 ◦ C) high specific capacitance and
cheap maintenance cost [6–8]. Although supercapacitors have a higher
energy density than capacitors and a higher power density than batteries
[9–11]. The Ragone plot, as depicted in Fig. 1, illustrates the balance
between energy and power density for energy stowing in several systems
(capacitor, supercapacitor and battery) [12]. Supercapacitors are split
into three groups based on the charge storage mechanism or cell
configuration: electric double layer capacitors (EDLCs) and pseudo-
capacitors and hybrid capacitors [13]. Fig. 2(a) depicts the various
types of supercapacitors and the materials used to make them. EDLCs are
based on non-faradic process in which the charge is physically held via
electrostatic charge adsorption at the electrode-electrolyte interface
[14,15]. Pseudo-capacitors store charge faradically through redox pro­
cesses. In pseudo-capacitor, fast and reversible faradic redox reaction
takes place at the electrode-electrolyte interface under the applied

* Corresponding authors.
E-mail addresses: hanand@kuk.ac.in (H. Anand), Prakash@nitkkr.ac.in (P. Chand).

https://doi.org/10.1016/j.est.2022.105897
Received 5 August 2022; Received in revised form 25 September 2022; Accepted 15 October 2022
Available online 26 October 2022
2352-152X/© 2022 Published by Elsevier Ltd.
S. Khokhar et al.
Fig. 1. Ragone plot of the power-energy density range for different electro­
chemical energy storage devices [Reprinted with permission from Ref. [12] ©
Publisher of Open Access Journal (2022)].
potential [16]. The pseudo-capacitors have larger specific capacity and
energy density than those of EDLCs, since faradaic reactions take place
nearer to the electrode surface as well as on the electrode surface
[17,18]. Low power density is the biggest drawback of pseudo-
capacitors, due to the fact that faradic processes are relatively slow as
compared non-faradic processes. Hybrid supercapacitors choose a bal­
ance of faradic and non-faradaic materials to hold charge. Although
pseudo-capacitors have large specific capacitances, they have moderate
power density and cyclic stability. EDLCs, on the other hand, have an
excellent cyclic durability and high density but poor specific capacity.
Hybrid supercapacitors are a mixture of EDLC and Pseudo-capacitors to
achieve high energy and power density and maintain cyclic stability
[19,20]. Based on the configuration of electrode material, super­
capacitors are divided into two varieties, symmetric supercapacitor (SC)
and asymmetric supercapacitor (ASC) [21]. The symmetric super­
capacitor is considered as a device with similar materials with the same
capacitances at both electrodes. The symmetric arrangements of EDLCs
are created by two identical carbon-based electrodes. Their application
is restricted due to their small potential window and low energy density.
Asymmetric supercapacitors (ASCs) are devices with two distinct elec­
trode materials and well-spaced potential windows. The asymmetric
devices have greater areal capacitance and energy density than the
symmetric device [6,22]. Supercapacitors have lower energy densities
than batteries, and improving energy density up to battery levels is
extremely challenging [23]. The capacitance and square of the voltage
have a direct correlation with the energy and power densities. To
enhance the energy density and power density of supercapacitor, effort
must be made to enhance both voltage and capacitance values. The
value of capacitance and voltage depends on the electrode material used
[24,25]. The electrode materials in supercapacitors have a significant
impact on capacitance performance [26]. A wide range of electrode
materials, including carbon-based stimulants (activated carbon, carbon
nanotubes, graphene etc.), conducting polymers (PANI, PPy, and PTh),
metal oxides (RuO2, MnO2, IrO2, NiO, Co3O4, SnO2, CuO, V2O5), and so
on, have been produced and have made considerable advancement in
the development of novel electrodes [27]. Carbon-based materials, on
the other hand, have low capacitance, metal oxides have weak con­
ductivity, and conducting polymers are unstable. Both faradaic and
EDLC contribute to the capacitance of pseudocapacitive nanostructures.
When the size of pseudocapacitive nanocrystals is minimized, i.e., the
specific surface area is increased, the EDLC contribution becomes more
prevalent [28]. Current research on electrode materials is mostly
focused on improving the porosity and effective surface area. Porous
materials such as metal-organic frameworks (MOFs) have lately aroused
interest and investigations have been carried out on potential use of
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Journal of Energy Storage 56 (2022) 105897
MOFs in the sector of electrochemical energy storage.
The energy storage industry has grown dramatically in terms of
supercapacitor fast charging, particularly in highly active electrode
material. More than 20,000 MOFs have been reported as of now, pro­
duced by numerous organic linkers and one or more metal centers.
MOFs are an inimitable family of materials generated when metal ions
engage with organic linkers. MOFs are being researched for a variety of
purposes, including catalysis, drug delivery, gas storage/separation, and
energy storage devices, owing to its unique characteristics, such as
adjustable pore diameter, organised crystalline structures, and
extremely specific surface area [29,30]. Alternatively, the employment
of MOFs in the realm of energy storage systems has been the focus of
numerous researches. Because of their highly organised structures and
abundance of redox metal centres, MOFs have lately been widely
exploited as electrode materials in supercapacitor [31,32]. Transition
metal-based MOF have bewitched a lot of attention in energy storage
systems owing to their outstanding properties among several other
metal organic frameworks [33]. Due to flexible topologies, huge surface
areas, and tunable pore widths transition metal-based MOF have
aroused the interest of academics for future deployment in descendants
electrochemical energy storage devices [34]. Transition metal MOFs
including Zn, Fe, Cd, and Co have been studied extensively for their
energy stowing efficiency [35,36]. From among numerous transition
metal MOFs, nickel-based MOFs (Ni-MOFs) are one of the potential
electrode materials for supercapacitor applications due to their ability to
produce extreme high theoretical specific capacitance because it has
organised porous structure, ample active sites which enhance the
transfer of ions, variable oxidation state (Ni2+, Ni3+), flexible topologies
[48]. According to our knowledge till now, there are many review pa­
pers on MOFs but there is no review paper till date which has focused
only electrochemical behaviour of Ni-MOFs and its nanocomposites.
Researcher who wants to work further in Ni-MOFs field, this review
paper will help them to a great extent. In the present review paper, we
have discussed the literature of Ni-MOFs as electrode material for
supercapacitor as well as different synthesis methods and characteriza­
tion techniques. Firstly, we have discussed different methods used for
Ni-MOFs synthesis such as slow evaporation method, sonochemical
method, microwave heat-assisted method, electrochemical method,
mechanochemical method, hydrothermal/solvothermal method. After
that, we have discussed the literature where Ni-MOF is used as electrode
material. We have divided Ni-MOFs into three parts such as pristine Ni-
MOFs, composites of Ni-MOFs and bimetallic Ni-MOFs. Then we dis­
cussed various characterization techniques to explore the structure,
crystallinity, pore size, surface area, and electrochemical properties of
synthesized Ni-MOFs.
2. Metal-organic frameworks (MOFs)
Metal-organic frameworks (MOFs) are a novel class of porous ma­
terials made up of metal ions and organic ligands that are linked
together by coordinate bonds to create one-, two-, or three-dimensional
structures [37]. Coordinate bonds are the most essential bonding in­
teractions in MOFs. On the other hands, lesser attractions include
hydrogen bonds, Vander Waals forces, metal-metal bonds. They are
responsible for the flexibility of their rigorous structure and broadening
the range of potential uses [38,39]. MOFs, also recognised as porous
coordination polymers (PCPs).The phrase coordination polymers first
emerged in 1960, but significant development in this subject began in
1995, when Yaghi and his colleagues created the term metal-organic
frameworks (MOFs) [40–42]. A lot of research have been conducted
on metal-organic frameworks (MOFs) for energy conversion and storing
because to their ordered porous structure, large pore volume, huge
surface area, adjustable geometrical morphology, versatile functionality
and abundant active sites, strong electrochemical responsiveness and
chemical tenability [43,44]. Different characteristic properties of MOFs
are shown in Fig. 2(b). MOFs still have a few shortcomings that impede
S. Khokhar et al.
them from achieving their full potential [45]. The majority of reported
MOFs as electrode materials have low electrical conductivity, instability
in structure and low utilisation of active sites which limit their use in
electrochemical domains. One approach to avoiding these difficulties is
to optimize MOFs by creating composites [46]. MOFs are attained by
utilizing inexpensive initial materials, such as metal salts of transition
metals like Fe, Co, Ni, Cu as they have many co-ordination numbers,
they can be used to design different kinds of MOFs [47]. Mostly nickel
metal has been utilized to construct MOFs as supercapacitor electrode
materials because they may provide active sites for redox behaviour,
which results in charge storage [48]. This review focuses on the use of
MOFs based on Ni for energy storage.
Fig. 2. (a) Classification of supercapacitor and their corresponding material (b) Characteristics properties of MOFs.
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Journal of Energy Storage 56 (2022) 105897
2.1. Methods of synthesis
Fabrication of metal-organic frameworks (MOFs) has risen in popu­
larity in the recent couple of decades since it allows for the availability of
a wide range of adorning nanostructures. The metal salt and ligand so­
lution are either prepared separately or then mingled together, or the
metal salt and ligand are added to the solvent. The primary goal of MOF
synthesis is to provide conditions that result in specified inorganic
building components without destruction of the organic ligand [49].
MOF synthesis involves reaction conditions and simple methods such as
hydro/solvothermal approach, microwave-assisted, slow evaporation,
sonochemical, electrochemical and mechanochemical methods
depending on the final structures and characteristics. MOF design is
often driven by intermolecular interactions that restrict their repetition,
S. Khokhar et al.
as well as synthetic parameters that necessitate optimization to allow for
a precise assembly of building units. Minor changes in pH, solvent po­
larity, concentration and temperature have been leading to creation of a
completely new phase [50,51]. Organic solvents with high solubility are
commonly used, such as dimethylformamide, acetonitrile, dieth­
ylformamide, ethanol and methanol. Because solvent affects the prop­
erties of MOFs, it must be chosen based on the desired idiosyncratic of
the final MOFs. The kinetics of reaction, morphology, physical and
chemical properties, stability, and practical need of MOFs can all be
dramatically ameliorate by combining MOFs and suitable materials
[52]. Fig. 3(a) provides a summary of the MOF synthesis techniques.
2.1.1. Slow evaporation method
The slow evaporation method is very simple and easiest of all the
accessible synthesis methods since no external energy source is required.
Slow evaporation technique delivers MOFs by slowly concentrating a
precursor dissolved in an organic solvent or amalgamation of solvents in
an anaerobic atmosphere and in another words, it can be said that, in
slow evaporation method, metal salts solution (Sol A) and ligand solu­
tion (Sol B) were combined with stirring and resulting solution (Sol C)
was kept at room temperature for slow evaporation for several days to
months and crystals form when a critical concentration is reached to
endorse nucleation and crystal growth [53]. Without any need for
external energy, the slow evaporation method normally requires 7 days
to 7 months of synthesis time [54]. This strategy is attractive because
MOFs can be created without the use of external energy; however, it is a
time-consuming process, and gave low yields which are the main
drawback of this method. Fig. 3(b) depicts the schematic diagram of
slow evaporation method.
2.1.2. Sonochemical method
Sonochemical/Ultrasonic method is a fast, energy-efficient and eco-
friendly technique that involves high-energy ultrasonic radiations to
obtain desired MOFs at ambient temperature. The frequency range of
ultrasound is 20 kHz to 10 MHz. Metal salt and ligand were separately
dissolved in a solvent and were labeled as Sol A and Sol B respectively.
Both solutions were mixed together via vigorously stirring. The reaction
mixture was then exposed to ultrasonic radiation, which provides
incredibly high pressures and temperatures. The application of ultra­
sound speeds up the nucleation and significantly shortens the crystal­
lisation time. Precipitates start to form in 8–30 min and after that they
were filtered and dried in oven to get the desired MOF. However, it can
also decrease the size of particles and the yield of synthesis [55]. One of
the main limitations in the scale up of sonochemical equipment is the
energy consumption. Fig. 3(c) depicts the schematic diagram of sono­
chemical method.
Israr et al. reported an efficient ultrasonic synthesis of a Ni-BTC
adopting (Ni(NO3)2.6H2O) as the metal source and 1,3,5-benzenetricar­
boxylic acid (H3BTC) as the organic ligand, both mixed in the polar
aprotic solvent N,N-Dimethylformamide (DMF). The two solutions were
stirred and irradiated for 2 h at varied power levels and temperatures
under 20 kHz ultrasound. The product samples were kept at room
temperature after sonication and the resultant light green solid crystals
(Ni-BTC) were filtered [56].
Qu et al. prepared hybrid Ni-MOF/Ti3C2Tx nanosheet through facile
ultrasonic method applied for 8 h under argon gas flow. It was concluded
that Ti3C2Tx is evenly deposited onto Ni-MOF nanosheets, boosting
electronic conductivity and avoiding Ni-MOF nanosheet agglomeration.
At a current density of 1 A/g, the Ni-MOF/Ti3C2Tx hybrid nanosheets
have a specific capacitance that can reach a maximum of 867.3 F/g [57].
2.1.3. Microwave heat assisted method
Microwave heating is another rapid synthesis technique which
started being employed in MOF materials recently. Many well-known
and novel MOF structures have been created using microwave tech­
niques that evenly heat the sample solution to mitigate temperature
4
Journal of Energy Storage 56 (2022) 105897
gradients in the reaction and synthesize the nanomaterials and nano­
composites. Microwave power is the driving force behind this synthesis.
Microwave energy is used in the microwave-assisted method to generate
nanosized crystals after microwave energy input. A reaction mixture in
an apt solvent is placed in a Teflon vessel, which is covered and
microwaved for the pertinent time and temperature. With the assistance
of microwave power, the solution temperature can be quickly raised and
the heat can be efficiently transferred into the micro/nano structures,
thus significantly shortening the reaction duration. The microwave unit
converts microwave energy into heat energy by conjugating microwave
energy with the dipole moment of the precursors, causing molecular
motion due to the expeditious heating of the solution mixture. It is very
efficient and can be used to significantly reduce reaction times [58,59].
Schematic diagram of microwave heat assisted method shown in Fig. 3
(d).
Chen et al. effectively synthesized a Zn-doped Ni-MOF with a porous
honeycomb-like microspherical structure utilizing a microwave-assisted
synthesis process by using NiCl2.6H2O, Zn(CH3COO)2.2H2O as metal
source and terephthalic acid as organic linker and HCl as the modulator.
Metal salts and organic ligand are dissolved in DMF and stir for half
hour, after that 0.5 ml HCl was added dropwise. HCl was employed as a
modulator to regulate MOF nucleation and development while also
reducing agglomeration. The mixture was then agitated for 180 min to
achieve homogeneity. The solution was then put through a process in a
microwave reactor. After that, the reactor was placed inside a micro­
wave oven. The solution product was spontaneously cooled to room
temperature after the microwave-assisted reactions continued 6 min on
a moderate heat. The material demonstrated improved electrochemical
performance, such as superior capacitance, high-rate capability, and
cycle stability. Ability at 1 A/g and 20 A/g is 237.4 mAh/g and 122.3
mAh/g, respectively [60].
But Microwave heating also poses some limitations such as possi­
bility of varying the reaction conditions by adjusting the irradiation
power, time of reaction and the temperature is also its limitation because
different instruments are unable to deliver the same conditions.
2.1.4. Electrochemical method
Electrochemical method is also a common synthesis strategy which is
often used in producing MOF materials at industrial scale. Metal salts are
altered by metal ions in the electrochemical method. The electro­
chemical synthesis of MOFs does not require metal salts, because metal
cations are produced on the anode and diffuse to electrolytes mixture.
Metal ions are constantly delivered through anodic dissolution which
reacts with organic ligand and electrolyte in the reaction mixture,
yielding an ample amount of MOF crystals. The most important
advantage of the electrochemical method is mild synthesis condition
and rapidity. Furthermore, that method allows for producing a large
quantity of MOFs in a continuous process which is incredibly significant
from the perspective of the industrial manufacturing of these materials
[61]. The main disadvantage of electrochemical methods is that it
changes the system-specific properties such as the surface structure and
roughness [62,63]. Fig. 3(e) depicts the schematic electrochemical
method.
2.1.5. Mechanochemical method
The mechanochemical method entails completing a chemical reac­
tion with the aid of mechanical force. The foremost advantage of
mechanochemical synthesis is that mechanical force is applied via a
mechanical ball mill and the reaction occurs without the use of organic
solvents, which are cancerous, noxious, and detrimental to the envi­
ronment. If mechanical force is exerted to an amalgamation of metal
salts and organic linkers, chemical change occurred at ambient tem­
perature, resulting in the mechanical rupture of intramolecular bonds
and the development of new bonds. The first MOF synthesis using this
method was proclaimed in 2006. This method is now widely used for
large-scale MOF synthesis [61]. This method, however, produces a small
S. Khokhar et al. Journal of Energy Storage 56 (2022) 105897

Fig. 3. (a) Description of various methods used for the synthesis of required material (b) Schematic diagram of Slow Evaporation method (c) Schematic diagram of
Sonochemical method (d) Schematic diagram of Microwave Heat-assisted method (e) Schematic diagram of Mechanochemical method (f) Schematic diagram of
Electrochemical method (g) Schematic diagram of Hydrothermal method (h) Depict the influence of hydrothermal temperature on specific capacitance.

5
S. Khokhar et al.
amount of product. Fig. 3(f) depicts the schematic mechanochemical
method.
2.1.6. Hydrothermal/solvothermal method
To generate novel metal organic frameworks, the hydro(solvo)ther­
mal approach has been frequently employed because of its relative
simplicity and scalability, the solvothermal process is most recom­
mended approach for large-scale manufacturing. The hydrothermal
methodology includes heating the reaction mixture with an aqueous
solution in a special sealed reaction vessel. Solvothermal synthesis in­
volves heating a solvent to a temperature above its boiling point, leading
to a high yield of MOF materials. Aside from being employed for zeolite
synthesis, the principle of solvothermal synthesis has also been used
successfully for MOF synthesis [64]. There are significant advantages of
hydrothermal synthesis method over other methods like it involves
simple and single step reaction, does not require utilisation of expensive
equipment, moderate temperature condition and produced organised
morphology of crystal. In the solvothermal process the reagents (pre­
cursor, usually a metal salt and organic connector) are dissolved in a
given solvent or an amalgamation of solvents. Then, the dissolutions of
both reagents are mixed together and placed in a sealed bottle or a
Teflon-lined reactor. The reaction mixture is next heated up to a certain
temperature and left for a certain time. Hydrothermal synthesis can
generate nanomaterials which are not stable at elevated temperature.
The morphological characteristics of crystals grown under hydrothermal
conditions are closely related to the growth conditions [65]. Under
distinct hydrothermal conditions, the same crystal may exhibit different
morphologies. Fig. 3(g) depicts the schematic hydrothermal method.
According to Deng et al., MOFs are generally prepared by employing
hydrothermal or solvothermal synthesis procedures on small scales,
with reaction times ranging from several hours to days and introduced
two new Ni-based MOFs, [Ni0.5(DTA)0.5(H2O)]H2On (1) and [Ni(DTA)]n
(2), which were produced by combining the metal salt Ni(NO3)26H2O
with the organic ligand 2,5-di(1H-imidazol-1-yl) terephthalic acid via
hydrothermal techniques at temperatures of 120 ◦ C and 180 ◦ C for 48 h,
respectively. It was observed that various reaction temperatures cause
varied assembly processes and different final structures. Both Ni-MOFs
may be utilized directly as electrode for supercapacitor in a three-
electrode arrangement. The results reveal that compound 1 (291.2 F/
g) outperforms compound 2 (85.6 F/g) in terms of electrochemical
performance [66].
Du et al. adopted hydrothermal method to synthesize porous Ni-MOF
by using Ni(NO3)2⋅6H2O and BTC (trimesic acid) as metal salt and
organic linker, respectively and DMF as solvent. The mole fraction of
Ni2+:BTC was adjusted to 6:1, 4:1, 2:1, and 1:1, and the materials were
heated to 150 ◦ C for 12 h, yielding Ni-MOF 1–6, Ni-MOF 1–4, Ni-MOF
1–2, and Ni-MOF 1–1, respectively. Ni-BTC 1–6 demonstrated a spe­
cific capacitance of 1057.2 F/g in a three-electrode setup when sub­
jected to a current density of 1 A/g [67].
Li et al. synthesized Ni-MOF by adopting facile hydrothermal method
at various time and temperature and discussed the impact of calcination
temperature, time, and optimal preparation conditions on the electro­
chemical characteristics of electrode materials. From the results it was
revealed that optimal hydrothermal time for the investigated electrode
materials was 48 h. The electrochemical reaction rate of Ni-MOFs syn­
thesized at 100 ◦ C is quicker, the storage charge is greater, and the
specific electrical capacity is greater. They concluded that the electro­
chemical properties of electrode materials can also be strengthened by
the appropriate reaction parameters [68].
The growth conditions have a significant influence on crystal
morphology and specific capacitance under hydrothermal treatment.
For example, in 2020 Nirmal Manyani and his group synthesized a Ni-
BTC by using Ni(NO3)2.6H2O and BTC as metal salt and organic linker
respectively in solvent DMF:ethanol:H2O (1:1:1) at 145 ◦ C for 10 h.
Electrochemical study revealed that prepared Ni-BTC provide maximum
specific capacitance of the order of 309.05 F/g at 5 mV/s. In 2021, they
6
Journal of Energy Storage 56 (2022) 105897
then synthesized the same Ni-MOF by taking same metal salt, organic
ligand, solvent and at same time but at different temperature (145 ◦ C).
At a current density of 0.43 A/g, it was discovered that Ni-BTC that was
synthesized at a temperature of 145 ◦ C gave a specific capacitance of
234 F/g. So, it was clear that, alike crystals exhibit different specific
capacitance at various hydrothermal reaction parameter as shown in
Fig. 3(h) [69,70].
Hydrothermal synthesis was used by Manikandan et al. to create Ni-
MOF. They used Ni(NO3)2.6H2O as the metal salt, terephthalic acid as
the organic ligand, and N,N-dimethylformamide as the solvent. The
synthesis was carried out at 180 ◦ C for different reaction time (12, 18,
24, 30 h). SEM image of Ni-based MOF materials generated at various
reaction durations clearly indicate that entirely all Ni-MOFs have a
microsphere composed of several linked nanoflakes, with an expanse of
ranging from 2 to 6 μm. The diameter of the microsphere reduces as the
hydrothermal reaction time increases, and Ni-MOF-30 has a smaller
microsphere, which allows for improved electrolyte ion transport and
discloses extra accessible active sites than other reaction periods. When
scanned at a rate of 2 mV/s, the capacitance values of Ni-MOFs (Ni-
MOF12, Ni-MOF18, Ni-MOF24, and Ni-MOF30) are as follows: 500.6,
594.7, 1513.9, and 1555.3 F/g, respectively. From the results, it was
concluded that Ni-BDC show different morphology and capacitance
[71].
Among the various synthesis approaches, hydrothermal method is
best because it generates nanomaterial with negligible product damage
and also there is less chance of impurities as the reaction take place in a
closed Teflon-autoclave.
3. Ni-MOFs as electrode material for supercapacitor
MOFs are gaining popularity among research groups in a variety of
territory. MOFs have more porosity, huge specific surface areas, and
more structural and function variety than conventional inorganic porous
materials. The structural characteristics of MOFs may be adjusted by
using various metal centres ligands. The generated MOF structures are
essentially based on metal cluster geometries and organic linker shapes.
The use of a wide range of organic linkers has resulted in a huge number
of MOFs with varying topologies and pore structures. The organic ligand
is critical in influencing the compound structure as well as the topology
of the resulting framework [72,73]. The majority of the organic linker
that holds MOF structures together is made up of N, O, or S donor atoms
that are summarized in Table 1. Polycarboxylic acids have been recog­
nised as enticing synthesis applicants for innovative MOFs due to the
carboxyl group ability to generate four-membered rings (C–O–M–O)
containing core metal ions. Additionally, polycarboxylic acids contain
two or more carboxyl groups that could be entirely or temporary
deprotonated, resulting in a variety of fascinating higher-dimensional
structures. Among the many transitions metal-based MOFs, Ni-MOFs
are one of the most enticing electrodes for supercapacitor applications
due to their organised porous structure containing abundant active sites.
Nickel, being a transition metal element and a major aspect of Ni-MOF,
delivered a favourable metal site due to the abundance of Ni ions
(specifically, Ni2+ or Ni3+). Ma et al. fabricated a Ni-BTC by using
NiSO4.6H2O and BTC as metal precursor and organic ligand, respec­
tively for the hydrogen sorption performance of MgH2. The interaction
of Ni2+ with trimesic acid may be expected to be electrostatic in nature.
It can be shown that under ideal conditions, every Ni2+ connecting with
two carboxylic functional groups and every two trimesic demands the
utilisation of three Ni ions as shown in Fig. 4(a) [74].
3.1. Pristine Ni-MOF as electrode materials for supercapacitors
Nickel sources are significant, with 0.018 % of the earth's crust
composition. MOFs have been used effectively as electrodes in batteries
and fuel cells. In recent years, there have been two types of uses of MOFs
in SCs. MOFs have the potential to be serve as templates for the
S. Khokhar et al. Journal of Energy Storage 56 (2022) 105897

Table 1
Depict the various type of organic ligand used for preparation of MOFs.
S. no. Ligand structure Chemical name

1. COOH Terephthalic acid (BDC)

COOH
2. 4,4′ -bipyridine
N N

3. N 2-methylimidazole

CH3
N
H
4. COOH 1,3,5-tricarboxylic acid (trimesic acid) (BTC)

HOOC COOH
5. O 2,2′ -biphenyldicarboxylic acid
OH

HO

O
6. O Methacrylic acid

H2C
OH

CH3
7. COOH Iso-phthalic acid

COOH
8. 2,5-thiophenedicarboxylic acid

HOOC S COOH
9. COOH N 2,5-di(1H-imidazole-1-yl) terephthalic acid

N
N
COOH
10. COOH 5-nitroisophthalic acid

COOH
O2N
11. 4,4′ -trimethylenedipyridine

N N
12. H2N N NH2 Melamine

N N

NH2
13. Triethylenediamine / 1,4-diazabicyclo [2.2.2]-octane /DABCO

N
N
(continued on next page)

7
S. Khokhar et al. Journal of Energy Storage 56 (2022) 105897

Table 1 (continued )
S. no. Ligand structure Chemical name

14. COOH 5-pridin-4-yl-1H-pyrazole-3-carboxylic acid

HN

N
15. COOH 2,3,5,6-tetramethyl-1,4-benzendicarboxylic acid /TMBDC/ TM

H 3C CH3

H 3C CH3

COOH
16. COOH Tetrafluoroterephthalic acid (TFBDC)

F F

F F

COOH
17. HN H H NH 2,3,6,7,10,11-hexaiminotriphenylene / HITP

HN NH

H H
H H

HN NH
18. COOH Salicylic acid

OH

19. COOH 1,4-naphthalenedicarboxylic acid

COOH
20. COOH 9,10-anthracenedicarboxylic acid/ ADC

COOH
21. COOH Isonicotinic acid / Pyridine-4-carboxylic acid

N
22. 2,2-dimethyl-1,3-propanediamine
H2N NH2
H 3C CH3
23. O Salicylaldehyde

OH
(continued on next page)

8
S. Khokhar et al.
Table 1 (continued )
S. no. Ligand structure
24. HO OH
HO OH
HO OH
25.
HOOC COOH
26. COOH
HOOC
27.
N N
OH HO
production of porous metal oxides or porous carbons throughout the
synthesis process. Secondly, MOFs are used directly as electrode mate­
rials, which is more infrequent and difficult due to the peculiar structure
of MOFs [48]. However, their limited electrical conductivity frequently
limits their usage even more [75,76]. Using adequate organic ligands
and metal ions to overcome this is desirable. The ligand structure inside
the framework might be changed to improve ion insertion/extraction,
and oxidation-reduction behaviour of metal ions could be changed to
improve the electron transport channel. Ni is frequently used as the
primary raw precursor for the synthesis of MOF with exceptional elec­
trochemical properties due to its vast reserves, inexpensive and high
coordination number. Nickel-based materials were chosen as the metal
centre because of their relatively high specific capacitance, high effi­
ciency, and renewability, they are thermally and chemically resistant
[77]. Furthermore, they are simple to produce and need readily avail­
able, low-cost precursors [78].
Sheberla et al. demonstrated that the conductive porous Ni3(HITP)2
where HITP is 2,3,6,7,10,11-hexaiminotriphenylene, is attractive as an
effective electrode material for EDLCs. Devices constructed from pristine
Ni3(HITP)2 have a very superb areal capacitance of 18 F/cm2 and
extreme equivalent series resistance reduction. Ni3(HITP)2 is mainly
comprised of 2D layered Π-conjugated layers which are pierced by 1.5
nm diameter each cylindrical channel shown in Fig. 4(b). The CV and
GCD traces of a symmetrical device are approximately rectangular &
triangular, suggesting pseudocapacitive behaviors [79].
In mixed solvents of DMF/water/alcohol, Wang et al. reported a
simplistic solvent-assisted solvothermal technique to synthesize hierar­
chical Ni-BDC microflowers. The as-prepared Ni-MOF electrode has a
specific capacitance that is optimized to be 1093 F/g when operating at
a current density of 1 A/g due to its huge surface area and multilayered
structure. Fig. 5 (a), (b) shows Ni-MOF micro-flowers morphology with
diameters of 3–6 mm as revealed by SEM and TEM pictures, separately.
The ultrathin nanoplates that make up these flower-like particles are
well-defined [80].
Manikandan et al. prepared a Ni-MOF by using simple hydrothermal
method at different reaction times (12, 18, 24, 30 h). They concluded
that hydrothermal reaction time influences the energy storage capability
of the synthesized material. When compared to various reaction times,
the energy stowing potential of the Ni-MOF synthesized at reaction time
30 h was found to be the highest with microsphere morphology. In a
solution containing 6 M KOH electrolyte, when subjected to a current
9
Journal of Energy Storage 56 (2022) 105897
Chemical name
2,3,6,7,10,11-hexahydroxytriphenylene
4,4′ -biphenyldicarboxylic acid
2,6-naphthlenedicarboxylic acid
N,N′ -ethylenebis-salicylaldiminato
density of 1 A/g, it exhibits superior specific capacitance 1498.6 F/g.
The preliminary loss of weight that takes place below 200 ◦ C is a sign
that DMF has been removed from the samples. The second weight loss
occurs between 200 ◦ C–300 ◦ C due to the loss of solvated water mole­
cules. Ni-MOF decomposes into NiO from 400 ◦ C to 600 ◦ C, causing
substantial weight loss describes by TGA and DTA depicted in Fig. 5(c)
and 5(d), respectively [71].
Pan et al. adopted hydrothermal method to developed 2D Ni-MOF
nanosheets and further they do partial substitutionof1,4-
benzenedicarboxylic acid (PTA) with Xmmol of monocarboxylic ligand
benzoic acid (BA) (X = 0, 0.0375, 0.075, 0.15, and 0.3) to change the
morphology and electronic composition and label them Ni-MOF, Ni-
MOF-5, Ni-MOF-10, Ni-MOF-20, and Ni-MOF-40, respectively. The BA-
modified Ni-MOF nanosheets display immense specific capacity of
2.38C/cm2 at 1 mA/cm2 and excellent capacitance preservation of 88%
after 10,000 cycles. SEM and TEM revealed that thin nanosheets with
wrinkled edges emerged in pristine Ni-MOF, while BA-modified Ni-MOF
nanosheets become slightly thicker and stiffer. Both Ni-MOF and Ni-
MOF-10 have interlayer spacings that measure 9.91 and 10.16, respec­
tively, according to the higher-resolution TEM pictures, which corre­
spond to 200 plane [81].
Kale et al. adopted a simple solvothermal approach to synthesize
nanoflower like nickel 2-methylimidazole framework (Ni-MOF) at room
temperature, the resulting MOF was treated with sulfuric acid at three
different pH levels (1.5, 2, and 2.5). The impact of acid treatment on the
electrochemical properties of Ni-MOFs was examined. The Ni-MOF-2
sample that was treated with a solution of H2SO4 at an optimal pH of
2 exhibited superior electrochemical characteristics as well as improved
surface texture. The Ni-MOF-2 sample showed a greater specific capacity
of 467C/g at 1 A/g than the other samples when they were tested in an
electrolyte consisting of 6 M KOH. Because acid treatment increases Ni-
MOF-2 proton exchange [82].
Wang et al. synthesized a novel double-ligand Ni-MOF material
through ultrasonication process and synthesized MOF was explored as a
supercapacitor electrode material. The two ligands 4,4′ -bipyridine and
H2L (formed by condensation reaction of terephthaloyl chloride and (R/
S)- phenylalanine methyl ester) in the framework work together to
effectively manage the framework structure and charge density distri­
bution. The electrochemical performance of the Ni-MOF that was pro­
duced was outstanding. At a current density of 1 A/g, the novel
synthesized material has a capacitance of 318 F/g, suggesting that it
S. Khokhar et al. Journal of Energy Storage 56 (2022) 105897

Fig. 4. (a) Molecular structure of Ni-BTC [Reprinted with permission from Ref. [74] © Elsevier (2019)]. (b) Molecular structure of Ni3(HITP)2 [Reprinted with
permission from Ref. [79] © Letters (2016)].

10
S. Khokhar et al.
Fig. 5. (a) SEM image of Ni-BDC(b) TEM images of Ni-BDC [Reprinted with permission from Ref. [80] © Royal Society of Chemistry (2021)]. (c) TG curve of Ni-MOF
(d) DTA curve of Ni-MOF[Reprinted with permission from Ref. [71] © Springer Nature (2021)].
may be successfully used as electrode for supercapacitor [83].
In another way, Manyani and his colleagues adopted a hydrothermal
process to synthesis Ni-BTC, and then they used it as active materials. In
1 M KOH, Cyclic voltammetry (CV) and galvanostatic charge-discharge
(GCD) techniques were used to investigate the electrochemical charac­
teristics of the recently produced Ni-BTC. The results of these tests
showed that Ni-BTC possessed a high specific capacitance of 234 F/g at
0.43 A/g current density [70].
Lin et al. developed a Ni-MOF based on 2,2’-Biphenyldicarboxylic
acid,4,4′ -bipyridine as an organic linker, which they labeled [Ni3(BI­
PY)3(BPDA)2(HCOO)2(H2O)2]n and employed it as electrode and sar­
cosine detection. A synthetic Ni-MOF has a specific capacitance of 667
F/g when operating at 1 A/g and retains 82% of its original capacitance.
The Ni-MOFs appear to be enticing materials for next-generation
supercapacitors, according to the results [84].
Ma and his colleagues effectively created nano-sized coordination
polymers based on Ni metal (Ni-nCPs) nanosheets with well-defined
morphology at room temperature and atmospheric pressure, using a
self-assembly methodology. Because of their higher specific capacitance,
Ni-nCPs play a significant role in the fabrication of efficient super­
capacitors. Ni-nCPs has a large number of channels for electron and ion
transport, as well as sites which are electrochemically redox active in a
faradaic reaction and capacitive performance value of 1066.9 F/g at 1
A/g [85].
The researchers Li et al. demonstrated a straightforward sol­
vothermal procedure that does not require the use of a surfactant in
11
Journal of Energy Storage 56 (2022) 105897
order to produce 2D Ni-based metal-organic framework microsheets (Ni-
MOFms). The derived Ni-MOFms exhibited remarkable reversibility and
rate performance when employed as energetic materials for a super­
capacitor electrode. Its specific capacities were 91.4 and 60.0C/g,
respectively, when it was run at 2 and 10 A/g [86].
Wu et al. reported that anionic surfactants can regulate the Ni-MOF
structure. This control approach is based on the one-step hydrothermal
coordination of Ni2+ and 1,3-phthalic acid with anionic surfactants SDS
(sodium dodecyl sulfate). The formation of crystals on the surface of a
crystal can be prevented by utilizing the static sealing effect that exists
between negatively charged anionic surfactant head groups and metal
ions. This results in Ni-MOF having the structure of a nanoscale lamellar
flower. At a current density of 1 A/g, the specific capacitance of Ni-MOF
(without surfactant) is only 808 F/g. However, under the same cir­
cumstances, the specific capacitance of Ni-MOF with surfactant ap­
proaches 1036 F/g [87].
Rod-like array Ni-MOFs grown on nickel foam (NF) has synthesized
using effective electrochemical synthesis procedure, according to Cao
and his coworkers. The Ni-MOF/NF obtained required no further pro­
cessing and may be utilized directly as a binder-free electrode material.
Furthermore, the as-assembled Ni-MOF/NF exhibits areal capacity 5.11
C/cm2 at 2 mA/cm2 [88].
Ni-TDA [(Ni3(OH)2(C2H6O4S)2] material was produced by Yang
et al. through the utilisation of 2,5-thiophenedicarboxylate acid as an
organic linker. This material was later used as an electrode for a
supercapacitor in 2 M KOH. The appearance of two redox spikes within
S. Khokhar et al.
the range of 0–0.5 V in the cyclic voltammetry at varied scan rates
demonstrates that the capacitive behaviour is caused by faradic redox
processes. The symmetrical charging/discharging patterns demonstrate
the outstanding electrochemical capacity and reversible redox mecha­
nism. A maximum specific capacitance of 1518.8 F/g was measured
after applying a current density of 1 A/g to the material as shown in
Fig. 6 [46].
Ni-MOF was hydrothermally synthesized for employment as elec­
trode in supercapacitors by Nirmal et al. At a scan rate of 5 mV/s, the
constructed Ni-MOF has a supreme specific capacitance of 309.05 F/g in
1 M LiOH [89].
He et al. does the comparison study of Zn-MOF and Ni-MOF by using
mixed ligands such as 5-nitroisophthalic acid and 1,3-di(4-pyridyl)pro­
pane tagging them [M(NIPA)(1,3-dpp)(H2O)2H2O](M = Zn for HU15,
M = Ni for HU16) via hydrothermal method. HU15 and HU16 have
distinct center metal ions but identical porous frameworks with massive
brick-like channels. Because of the differences in cations and topologies,
these two materials exhibit varied electrochemical characteristics. Ni-
MOF(HU16) outperforms Zn-MOF(HU15) with 307.4 F/g (specific
capacitance) at 1A/g current density [90].
Li et al. reported the synthesis of hexagonal [Ni(HBTC)(4,4′ -bipy)]
and utilized it as electrode material. Electrochemical study revealed that
hexagonal [Ni(HBTC)(4,4′ -bipy)]exhibited 977.04 F/g in 3 M KOH
aqueous electrolyte at 0.5 A/g [91].
Fig. 6. (a) CV curve of Ni-MOF electrode at different scan rate (b) GCD profile of the Ni-MOF electrode at different current densities(c) Specific capacitance of the Ni-
MOF electrode derived from the discharge profile at different current density (d) Long-term cyclic stability of Ni-MOF at 20 A/g [Reprinted with permission from
Ref. [46] © Royal Society of Chemistry (2020)].
12
Journal of Energy Storage 56 (2022) 105897
Feng et al. effectively produced a 2D layered [Ni(Hppza)2]n utilizing
5-(pyridin-4-yl)-1H-pyrazole-3-carboxylic acid (H2ppza) with
NiCl2.6H2O and employed it as a supercapacitor electrode with KOH
electrolyte. The results revealed that the material has a substantial
capacitance of the order of 184 F/g at 5 mV/s, high-rate capability, and
cycle life. Charge and discharge studies over 1000 cycles reveal that Ni-
MOF may retain around 65 % of its original capacitance [92].
To resolve the poor electrical conductivity drawback of MOFs,
creating nanoscale MOF materials is one alternative and to meet this
objective Shi et al. adopted hydrothermal method, using environmen­
tally acceptable ingredients such as nickel(II) acetate tetrahydrate, 4,4′ -
bpyridine, and H2tfbdc (2, 3, 5, 6-tetrafluoroterepthalic acid), a novel
Ni-MOF [Ni(4,4′ -bpy)(tfbdc)(H2O)2] were generated and nanoparticles
were obtained via grinding. Ni-MOF nanoparticles attained a particu­
larly 2548 F/g specific capacitance at 1 A/g. This was accomplished
when the electrode were immersed in 1 M KOH [93].
Jiao et al. adopted solvothermal approach to synthesized Ni-BDC and
utilized it as supercapacitor electrode material and reported the effect of
mixed electrolyte on the electrochemical performance of electrode. One
strategy to boost the efficiency of energy storage devices is to add
moderate amounts of redox additives to the electrolyte. The addition of
K4Fe(CN)6 can generate a convertible Fe(CN)4− 3−
6 /Fe(CN)6 redox couple
and extending the voltage up to up to 1.4 V. The synergistic interaction
of Ni-MOF and Fe(CN)4− 3−
6 /Fe(CN)6 solution causes an improvement in
S. Khokhar et al.
the energy density as well as the power density. It was concluded that,
the addition of 0.1 M K4Fe(CN)6 to 3 M KOH electrolyte enhances the
specific capacity to 175.3 mAh/g at 1 A/g [94].
Employing salicylic acid as a new organic linker, Xu et al. success­
fully utilized Ni-based MOF ([Ni(HOC6H4COO)1.48(OH)0.52H2O])
nanorods with uniform shape and employed them as supercapacitor
electrodes under mild conditions. They had a huge specific capacitance,
a very high-rate potential, and excellent cyclability. At 1, 2, 3, 5, 7, and
10 A/g current density, specific capacitances of 1698, 1385, 1278, 1068,
998, and 838 F/g can be attained in 6 M KOH [95].
Kang et al. developed Ni3(BTC)2.12H2O via hydrothermal approach
and tested as electrode material for supercapacitor. It was found that
Ni3(BTC)2.12H2O displayed capacitance of 726 F/g at a current density
of 1 A/g and 94.6 % cycle durability [96].
Liao et al. successfully developed a series of M-BTC (M = Co, Ni, Zn)
and named it M3(BTC)2.12H2O. It was concluded that Ni3(BTC)2.12H2O
possesses highest specific capacitance 429 F/g at 5 mV/s. And further,
they synthesized Ni-MOF based on isonicotinic acid via hydrothermal
approach and utilized it first time as working electrode for SCs. Elec­
trochemical properties of the material were investigated in 6 M KOH and
highest specific capacitance 634 F/g at 5 mV/s was achieved [97,98].
After reviewing the pristine Ni-MOFs literature, it was concluded
that, [Ni(4,4′ -bpy)(tfbdc)(H2O)2] shows highest specific capaci­
tance2548 F/g at 1 A/g in 1 M KOH electrolyte. According to our
knowledge so far, the reason for [Ni(4,4′ -bpy)(tfbdc)(H2O)2] best results
is the presence of Π-conjugated bonds which gives superior electro­
chemical performance because of their remarkable electrolyte penetra­
bility, lack of steric hindrance, and fast electron transfer and electrolyte
diffusion during the electrochemical reaction.
Table 2 shows the pristine Ni-MOFs with different morphology were
developed by using various synthesis methods in order to achieve high
specific capacitance for improved electrochemical energy storage
devices.
3.2. Ni-MOF based nanocomposites as electrode materials for
supercapacitor
Metal-organic frameworks, with their highly organised crystal
structures and evenly dispersed active sites, have been reported to be
efficient and promising electrode materials for energy storage devices.
However, the scope of use of pure MOFs is limited because of their poor
conductivity which restricts their employment in supercapacitor [99].As
a result, there are difficulties in making optimum implementation of
MOFs as electrode materials. To solve the aforementioned issues,
numerous innovative techniques have been implemented. More impor­
tantly, much work has been expended in designing composites with
multiple components that have high electrical conductivity and struc­
tural stability [100]. Developing MOF-based composites using auxiliary
material is a design technique in which the productivity of MOFs is
enhanced by the supplementary component to increase inclusive effec­
tiveness [101,102]. This inimitable multi-component structure not just
enhanced electrical conductance but also preserved the structure of
porous Ni-MOF. Composites combines the strengths of all components
while also overcoming the drawbacks of separate components and
provide special properties through mutual modification [103]. Howev­
er, if the composite material is not inadequately selected, it will influ­
ence the pore diameters of synthesized MOF, creating a barrier that
makes it difficult for the electrolyte to pass through all of the pores.
Zheng et al. reported Mxene@pillared-layer [Ni(thiophene-2,5-
dicarboxylate)(4,4′ -bipyridine)]n MOF composites (Mxene@Ni-MOF).
Mxenes, also known as Ti3C2Tx, are members of an intriguing family of
two-dimensional transition metal carbides and carbonitrides that have
remarkable conductivity, variable surface chemistry, and excellent sta­
bility. The sturdy contact between both the organic ligands of Ni-MOF
and the groups on the exterior of Mxene plays a major role: it mini­
mizes the contact of Mxene surface groups, restricts Mxene oxidation,
13
Journal of Energy Storage 56 (2022) 105897
and enhances its layer space, permitting quick ion carriage. It would
appear that the Mxene@Ni-MOF possesses a high capacitance,
measuring 979 F/g when subjected to 0.5 A/g and outstanding reli­
ability, with only 2% degradation over 5000 cycles [104].
Zhang et al. designed a composite based on Mxenes and Ni-MOFs
(Ti3C2Tx/Ni-MOFs) for ultra-efficient supercapacitors. Aside from
improving composite conductance, Mxenes provide additional faradic
and electric double layer capacitance. At 1A/g, Ni-MOFs have a specific
capacitance of 786 F/g, whereas Ti3C2Tx/Ni-MOFs have 1124 F/g. SEM
image show that both Ni-MOF and Ti3C2Tx/Ni-MOFs has microbelt
morphology. The undivided 2D nanosheets joined with each other to
create the bulk structure are visible in Ni-MOFs without Ti3C2Tx. When
the Ti3C2Tx is introduced into the Ni-MOF microbelts, they become more
scattered [105].
Zhang et al. reported Ni-MOF@NiS2 nanosheets electrodes on carbon
cloth generated from Ni-BTC and Na2S as a sulfur source through sol­
vothermal and at various sulfidation times. The greatest specific
capacitance is found in the Ni-MOF@NiS2 sample after 10 min sulfida­
tion. At 3 min, the Ni-MOF@NiS2 ratio is low, indicating poor super­
capacitor characteristics. The ratio of NiS2 increases as the sulfidation
period increases up to 3 h, however the porous Ni-MOF progressively
disappears, as a consequence, the surface area is reduced, leading to a
decrease in specific capacity. To investigate the energy storage capa­
bilities for high-performance supercapacitors, the Ni-MOF@NiS2 sam­
ples were constructed into active electrodes. At 2 A/g, the Ni-
MOF@NiS2 product has a considerable specific capacitance1128 F/g
[106].
Zhang et al. generated CoNi-ZIF@N-CNT heterostructure composites
of bimetallic CoNi-ZIF NSs wrapped around N-doped carbon nanotube
(N-CNTs) at different mass fraction of nickel nitrate hexahydrate and
cobalt nitrate hexahydrate. A comparison demonstrated that the hybrid
constructed with a 1:1 mass ratio had the capacitance of 1118 F/g at a
current density of 1 A/g [107].
Due to unique properties of polypyrrole (Ppy), Ppy is desirable
electrode material choice for supercapacitors, and combining Ppy with
MOFs is predicted to significantly improve electron transport. Yue et al.,
constructed a hybrid composite of Ppy HF and MOF (Ni-CAT nanowires)
by using Ni(CH3COO)2.4H2O and HHTP as metal ions and organic
linker, respectively via a simple two-step synthesis involving electro­
deposition and solvothermal method, label them Ni-CAT-NWs/Ppy HF
and used it as an electrode for a supercapacitor. The Ppy HF was formed
by electrodeposition of Ppy onto nickel foam. After that, Ni-CAT-NWs
were grown onto Ppy HF using a solvothermal process. At 0.5 mA/
cm2, the PPy HF/Ni-CAT-NW electrode has a good areal capacitance of
1050 mF/cm2.Ni-CAT-NWs are coated on the exterior and interior sur­
faces of Ppy foam scaffolds to attain greater MOF freight, which may
provide adequate conductivity and penetrability for increased ions
permeability. The SEM revealed that high-density and well-organised
Ni-CAT-NW arrays on the exterior surface of Ppy HF scaffolds [108].
Zhang et al. investigated the effect of Mn doping in Ni-MOF (NiMn-
MOF) and reported the construction of bimetallic NiMn-MOF nano­
sheets on the surface of NiCo2O4 nanowire arrays (NiCo2O4@NiMn-
MOF) by adjusting the number of moles of nickel nitrate to manganese
nitrate. The material was evaluated as a potential anode materials, and
the results showed that it has a specific capacity of 243 mAh/g at 2 mA/
cm2 [109].
To fabricate a Ni-MOF@Co(OH)2 array on nickel foam, Shi et al. used
a two-step procedure. By performing a solvothermal technique to
generate Ni-MOF flakes on nickel foam, Co(OH)2 is then electro­
deposited onto the Ni-MOF substrate. The electrochemical behaviour of
Ni-MOF@Co(OH)2 is particularly promising for high-performance
supercapacitors. Ni-MOF@Co(OH)2 offers a large specific capacitance
of 1448 F/g (2A/g). Fig. 7 (a,b,c) depicts three distinct Ni-MOF-24 layer
adsorption geometries on Ni foam, with planer, side, and vertical di­
rections [110].
Wang et al. proposed a simple method for obtaining a NiO/Ni-MOF
S. Khokhar et al. Journal of Energy Storage 56 (2022) 105897

Table 2
Data related to pristine Ni-MOFs utilized as supercapacitor electrode.
Comparative study of pristine Ni-MOFs used as electrode material for SCs

Electrode material Method Precursors Solvent Electrolyte Morphology Potential Specific Efficiency Ref.
window capacitance
(F/g)

Ni-BDC Hydrothermal Ni(NO3)2.6H2O DMF 6 M KOH Microsphere 0–0.6 for 1555.3 at 2 – [71]
BDC CV and mV/s
0–0.5 for
GCD
Ni-MOF Solvothermal Ni(NO3)2.6H2O Methanol 6 M KOH Nanoflower 0–0.55 467 C/g at 1 87 % after [82]
2-methyl-imidazole A/g 10,000 cycles
Ni-MOF Ultrasonication Ni(ClO4)2.6H2O DMF 3 M KOH Hollow 0–0.5 318 at 1 A/g Excellent [83]
Bpy DI Water cycle
H2L (2:1) stability after
4000 cycles
Ni-BTC Hydrothermal Ni(NO3)2.6H2O DMF 1 M KOH – − 0.55 − 234 at 0.43 A/ – [70]
BTC Ethanol 0.55 g
DI Water
(1:1:1)
BA-modified Ni-BDC Hydrothermal NiCl2.6H2O DMF 2 M KOH Nanosheets 0–0.6 2.38 C/cm2 at 88 % after [81]
BDC Ethanol 1 mA/cm2 10,000 cycles
BA Water
(30:4:4)
[Ni3(BIPY)3(BPDA)2 Hydrothermal Ni(NO3)2.6H2O DMA 6 M KOH – 0–0.6 667 at 1 A/g 82 % after [84]
(HCOO)2(H2O)2]2 BIPY/BPY Water 5000 cycles
BPDC
Ni-nCPs Room NiCO3 Water 6 M KOH Cuboid flaky 0–0.6 for 1066.9 at 1 A/ 58.6 % after [85]
temperature MAA Ethanol CV and g 3500 cycles
synthesis 0–0.5 for
GCD
Ni-BTC Solvothermal NiCl2.6H2O DMF 3 M KOH Microsheet 0–0.4 91.4 C/g at 70 % after [86]
BTC Ethanol 1A/g 5000 cycles
Water
[Ni3(OH)2(C8H4O4)2 Solvothermal Ni(CH3COO)2.4H2O DMF 3 M KOH Flower – 1036 at 1 A/g 50 % after [87]
(H2O)4] 1,3- Ethanol 3000 cycles
Benzenedicarboxylic (1:1)
acid
Ni-BTC Electrochemical Ni(NO3)2.6H2O DMF 1 M KOH Rod-like 0–0.6 for 5.11 C/cm2 at 69.3 % after [88]
method BTC Ethanol CV and 2 mA/cm2 2000 cycles
0–0.45 for
GCD
Ni-TDA – Ni(NO3)2.6H2O – 2 M KOH Gear-like 0–0.5 1518.8 at 1 A/ 95.5 % after [46]
TDA g 10,000 cycles
Ni-BTC Hydrothermal Ni(NO3)2.6H2O DMF 1 M LiOH – 0–0.9 309.05 at 5 – [90]
BTC Ethanol mV/s
Water
(1:1:1)
[M(NIPA)(1,3 − dpp) Hydrothermal Zn(CH3COO)2.4H2O Water 6 M KOH – 0.05–0.55 27.86 (HU15) 71.79 % [83]
(H2O)⋅2H2O] Ni(CH3COO)2.4H2O and 307.4 (HU15) and
M = Zn, Ni H2NIPA (HU16) at 1 51 % (HU16)
HU15 for Zn 1,3-dpp A/g at 8 A/g
HU16 for Ni
[Ni(Hppza)2]n – NiCl2.6H2O – KOH – 0–0.4 184 at 5 mV/s 65 % after [92]
H2ppza 1000 cycles
Ni3(HITP)2 Chemical process NiCl2.6H2O Water 1M – − 0.6 − 18 μF/cm2 90 % after [79]
HATP TEABF4/ 0.02 10,000 cycles
ACN
Ni-BDC Solvothermal NiCl2.6H2O DMF 3 M KOH + Nanosheets 0–0.4 175.3 mAh/g 90.6 % after [169]
BDC 0.1 M K4Fe at 1 A/g 3000 cycles
(CN)6
Ni-BDC Solvothermal NiCl2. 6H2O DMF 1 M KOH Micro-flower 0–0.6 for 1093 at 1 A/g 55 % at 5 A/g [80]
BDC Methanol CV and
water 0–0.4 for
GCD
[Ni(4,4′ -bpy)(tfbdc) Hydrothermal Ni(CH3COO)2.2H2O water 1 M KOH Nanoparticles 0–0.6 for 2548 at 1 A/g – [93]
(H2O)2] 4,4′ -bipyridine CV and
Tfbdc 0–0.45 for
GCD
[Ni(HOC6H4COO)1.48 Hydrothermal Ni(NO3)2.6H2O Water 6 M KOH Nanorods 0–0.6 1698 at 1 A/g 94.8 % after [95]
(OH)0.52 1.H2O] Salicylic acid 1000 cycles
Ni3(btc)2.12H2O Hydrothermal NiCl2.6H2O DMF 2 M KOH – 0–0.4 726 at 1 A/g 94.6 % after [96]
BTC water 1000 cycles
(1:1)
[Ni(HBTC)(4,4′ - Solvothermal Ni(NO3)2.6H2O DMF 3 M KOH Hexagonal 0–1.4 977.04 at 0.5 92.34 % after [91]
bipy)] BTC A/g 5000 cycles
4,4′ -bipyridine
(continued on next page)

14
S. Khokhar et al.
Table 2 (continued )
Comparative study of pristine Ni-MOFs used as electrode material for SCs
Electrode material Method Precursors
Ni-MOF Solvothermal Ni(NO3)2.6H2O
Isonicotinic acid
Ni3(BTC)2⋅12H2O – Ni(CH3COO)2.4H2O
BTC
with various Ni-MOF alteration ratios from NiO by changing the quan­
tity of terephthalic acid. NiO/Ni-MOF-25, which had an alteration ratio
of 25 % NiO to Ni-MOF, demonstrated improved electrochemical
behaviour, with a specific capacitance of 1176.6 F/g at1 A/g, which was
greater than Ni-MOF and NiO. The improved electrochemical behaviour
of NiO/Ni-MOF-25 was due to its core-shell design, huge specific surface
area, and improved electrical conductivity. The FTIR and Raman spectra
of the investigated sample NiO/ Ni-MOF-25 revealed characteristic
features of both Ni-MOF and NiO, and demonstrating the effective
coalescence of the NiO/ Ni-MOF composite. As-prepared samples
exhibited isotherms of type IV, and nitrogen sorption isotherms sug­
gested the presence of H3 hysteresis loops as shown in Fig. 7(c, d, e)
[111].
In another approach, Li et al. created a composite by combining Ni-
MOF with hexagonal morphology and NiO nanoparticles (Ni-MOF@­
NiO) using a one-pot solvothermal technique and successive calcination.
The specific capacitance of the synthesized composite can reach up to
1192.7 F/g when monitored at 0.5 A/g and a remarkable capacity
preservation of 93.23 % across 5000 cycles in 3 M KOH. From the result
they concluded that excellent diffusion of NiO nanoparticles over the Ni-
MOF not only facilitates electrolyte ion movement, but also boosts the
redox active spots, electrical conductivity and avoids NiO nanoparticle
agglomeration [112].
Zhang et al. created a new hybrid nanomaterial composed from
walnut shells (WS) and Ni-MOF and vulcanised polyaniline (SPANI) is
utilized as a fake plate to prevent MOF agglomeration and as a wire
linking WS and MOFs used as an electrode material for SCs. Low-cost
and widely accessible WS, as a carbon source, WS serves as the depos­
ited substrate of Ni-MOF and electron transmission scaffold to boost the
composite stability and conductivity. WS@Ni-MOF/SPANI exhibited
remarkable 1722 F/g capacitance at 1 A/g [113].
Lee et al. derived hetero-nanostructures, Ni-MOF@NiS2@C (NMSC),
U-Ni-MOF@NiS2@C (U-NMSC), and P-Ni-MOF@NiS2@C (P-NMSC)
from Ni-MOF. NMSC (without additive), U-Ni-MOF (with urea), and P-
Ni-MOF (with PVA), respectively, via simple solvothermal and subse­
quent sulfurization process. Electrochemical study revealed that P-
NMSC exhibit highest specific capacitance of 2780 F/g at 2 A/g and
retained 88 % of its original capacitance subsequently 10,000 cycles
compared to NMSC and U-NMSC. The inclusion of PVA caused gaps
between the P-NMSC nanosheets, which might be attributed to the
chelation of PVA and Ni2+ ions, which results in the creation of a PVA-
Ni2+ complex, which causes gaps between the nanosheets [114].
Wen et al. successfully generated Ni-MOF/CNTs composites, which
exhibit superior electrochemical performance due to cooperative actions
between Ni-MOF peculiar structure and more conductive CNTs,
achieving a maximum specific capacitance of 1765 F/g at 0.5 A/g cur­
rent density [99].
Bi et al. constructed Co3O4@Ni-MOF nanosheet hybrid array and
utilized it as electrode material. From the outcomes, it was concluded
that Co3O4@Ni-MOF exhibited good capacitance 1980.7 F/g at 1 A/g
with adequate capacitance reservation (82.2 % after 2000 cycles).The
permeable Co3O4“core” serves as a conductive framework for the
attachment of Ni-MOF, and the Ni-MOF “shell” can show vast active sites
[115].
Chen et al. fabricated the nickel-terephthalate-based MOF (Ni-Tp) on
Journal of Energy Storage 56 (2022) 105897
Solvent Electrolyte Morphology Potential Specific Efficiency Ref.
window capacitance
(F/g)
DMF 6 M KOH – 0–0.6 634 at 5 mV/s 84 % after [97]
2000 cycles
Water 6 M KOH – − 0.1 − 0.8 429 at 5 mV/s 91.1 % after [98]
1000 cycles
Ni foam, which can be used immediately as supercapacitor electrodes.
Polyaniline (PANI) nanofibers coated on the surface will drastically
enhance the electrochemical characteristics. The electrochemical ex­
periments show that produced Ni-Tp/PANI electrode exhibit a cycling
steadiness of 85.4 % capacitance retaining after 3000 cycles and a
specific capacitance of 938.845 F/g at 1.818 A/g [116].
To ameliorate the electrochemical characteristics of Ni-MOF nano­
sheets, Pan et al. used a conductive platform consisting of a fishbone-like
Ni3S2/Co3S4 extended over nickel foam (NCS/NF) to generate Ni-MOF
nanosheets. At 1 mA/cm2, the Ni-MOF@Ni3S2/Co3S4/NF (Ni-
MOF@NCS/NF) had a remarkable areal specific capacity of 8.7C/cm2,
and the capacity retentivity was 65 % at 50 mA/cm2.The porous NCS
hybrid composites not only serve as a conductive support to optimize the
electronic conductivity of Ni-MOF nanosheets and prevent their aggre­
gation, but they also have a high specific capacity [117].
Wang et al. created Co-Ni Coordination polymers (CPs) with
controllable morphology and variable Co-Ni composition. With the help
of melamine, the shape of Co-Ni CPs may be transformed from micro­
spheres to nanorods utilizing a simple solvothermal approach.
Furthermore, the nitrogen-rich melamine produces pseudocapacitance
and enhances electrical conductivity and wettability. The Co-Ni CPs
work well in 2 M KOH electrolyte and attained 677 F/g specific capac­
itance at 1 A/g [118].
Duan et al. designed a variety of MnO2@Ni-HHTPx (denoted as
NHMO-x, x = 16, HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene)
nanoarrays of various lengths and used it as electrode materials for
aqueous asymmetric supercapacitors and investigate how the lengths
affect electrochemical energy storage performance. High specific
capacitance of 368.1 F/g is displayed by the device, which operates at 1
A/g and amazing cycle steadiness by combining the high redox activity
of MnO2 with the good electron and ion conductivity of Ni-HHTP [119].
Jiang et al. effectively synthesized Cu2+ and Zn2+ bimetallic doped
metal-organic framework Ni2(bdc)2(dabco)(CuZnNiMOF), where bdc is
1,4-benzenedicarboxylic acid and dabco is 1,4-diazabicyclo[2.2.2]-oc­
tane) via a solvothermal process and used it in a supercapacitor as an
electrode component. In 3 M KOH and mixed 3 M KOH + 0.05 M K4Fe
(CN)6 electrolytes, the electrochemical behaviour of the CuZnNi-MOF as
the electrode for supercapacitors was studied. The outcomes indicated
that K4Fe(CN)6 has a positive impact on the electrochemical perfor­
mance. A relatively high capacity of 112.5 mA h/g at 1 A/g can be
attained in mixed electrolyte, which is significantly greater than the
value of 68.7 mAh/g evaluated in 3 M KOH electrolyte [120].
To optimize MOF conductivity, Deng et al. suggested an innovative
Ni-MOF/Cu-MOF strategy. When compared to pure Ni MOF, the syn­
thesized compound has a threefold high capacitance of 1424 F/g at 2 A/
g and excellent rate capacity in 1 M KOH [121].
Ran et al. developed ultrathin Ni-MOF/C-CNTs nanosheets with
interpenetrated carboxylated carbon nanotubes (C-CNTs) by in-situ
induced growth technique. The Ni-MOF/C-CNTs nanosheets developed
had good capacity retention and 680 C/g specific capacity at 1 A/g. 1D
C-CNTs, because of their anisotropic properties, can not only provide
rapid electron transport and minimal diffusion routes, but they can also
effectively adjust the layer thickness of Ni-MOFs [122].
Yue et al. proposed a concise hydrothermal method for developing
hierarchical MoS2@Ni-MOF composite structures as electrode for
15
S. Khokhar et al. Journal of Energy Storage 56 (2022) 105897

Fig. 7. (a) DFT analysis of adsorption mode of Ni-MOF-24 layer on Ni-foam with planar mode (b) DFT analysis of adsorption mode of Ni-MOF-24 layer on Ni-foam
with side mode (c) DFT analysis of adsorption mode of Ni-MOF-24 layer on Ni-foam with vertical mode [Reprinted with permission from Ref. [110] © Elsevier
(2021)]. (d) FTIR spectra of NiO, Ni-MOF, NiO/Ni-MOF(e) Raman spectra of NiO, Ni-MOF, NiO/Ni-MOF-25(f) Nitrogen sorption isothermal of NiO, Ni-MOF, NiO/Ni-
MOF [Reprinted with permission from Ref. [111] ©American Chemical Society (2021)].

16
S. Khokhar et al.
supercapacitors application, in which accordion-like nanosheets of Ni-
MOF integrated on the nanoflower MoS2. It was discovered that
doping non-metallic S elements improves charge transfer and allows
MoS2 to grow in accordion-type Ni-MOF layers. The MoS2@Ni-MOF
material has a remarkable specific capacitance1590.24 F/g at current
density 1 A/g and exceptional cycle stability [123].
MOF integrated with graphene can enhance the interfacial interac­
tion with the electrolyte and accelerate ion transfer kinetics. Based on
this concept, Xiao et al. combined the Ni-MOF with HQG (GM-LEG@Ni-
MOF). The GM-LEG@Ni-MOF exhibit remarkable capacitance of 987.6
F/g at 0.5 A/g current density and a large capacity retention of 85.6 %
after 3000 cycles [124].
In another approach, Ni-MOF nanosheet aggregates on polyaniline
(PANI) were used to adorn Ni foam (Ni-MOF/PANI/NF) and using it as
binder-free electrode for SC, were instantly developed by Cheng and his
colleagues. Although PANI is a prominent conducting polymer, its price
is very low, and it possesses an exceptionally high specific capacitance,
stimulates Ni-MOF development and assures strong mechanical adher­
ence. At 2 mA/cm2, the Ni-MOF/PANI/NF has a high areal capacitance
of 3626.4 mF/cm2 and an excellent rate capacity of 71.3 % at 50 mA/
cm2 [125].
Ni-MOF arrays were grown on the outside of NiCo2O4 nanowires by
Li et al. using the solvothermal approach. The NiCo2O4 nanowires,
which are deposited on the carbon fabric, perform admirably as a
conductive scaffold. The Ni-MOF layers, which have a larger surface
area and more pores, are closely attached to the NiCo2O4, which further
helps to ensure good kinetics of electron transport and ion dissemination
inside the hybrid electrode, but also strengthens the electrochemical
behaviour. NiCo2O4@Ni-MOF has a 208.8 mAh/g specific capacity and
cycle stability of 68.2 % following a 10-fold increase in current density
for the hybrid electrode, which was constructed [126].
Further, Zhang and its co-workers designed NiCo2O4@Ni-MOF by
using solvothermal approach. At 5 mA/cm2, the as-synthesized NiC­
o2O4@Ni-MOF electrode has a super areal capacitance of 7.23 F/cm2
(1390 F/g) [127].
Yang et al. worked on the synthesis of novel hybrid structure
CNT@Ni-MOF deposited on the graphene/Ni foam (GN). The GN sub­
strate has intense electric conductivity and load capacity, while the Ni-
MOF has a huge storage capacity and the CNT increases the surface area.
As a result, superior electrochemical characteristics may be predicted of
the materials as a whole. The greatest energy density value reported for
Ni-MOF@CNT/GN is 0.3396 mWh/cm2, which is the greatest value ever
reported [128].
Cheng et al. constructed a sphere-flake-sphere structure based on Ni-
MOF and RGO coated on metallic polyester fabric (RGO/Ni-MOF/
metallic fabric electrodes or RNMEs) and employed it as a working
electrode in 6 M KOH. At 4 mA/cm2, the RNMEs areal capacitance can
reach 260 mF/cm2. The sphere-flake-sphere structure generated by the
RGO and Ni-MOF increases the conductivity and electrochemical per­
formance of the constructed flexible RNMEs electrode [129].
Rawool et al. synthesized Ni MOFs with various surface morphol­
ogies utilizing three carboxylic acids with varied molecular lengths,
including BDC (1,4-Benzene dicarboxylic acid), NDC (2,6-Naph­
thalenedicarboxylic acid), and BPDC (4,4’-Biphenyl dicarboxylic acid).
Material characterization investigations demonstrated that Ni-MOFs
with longer organic linkers, such as 4,4’-Biphenyl dicarboxylic acid
(Ni-BPDC), had a high surface area and pore diameters. It was observed
that area under the CV curve is largest for Ni-BPDC and smallest for Ni-
BDC. Further, electrochemical performance of Ni-BPDC is enhanced by
making its composite with carbon nanofibre (CNF) integrating both a
double-layer electrochemical capacitor (EDLC) and a faradaic charge-
storage mechanism. The pattern of the CV curve seen in the case of
Ni-BPDC/CNF is akin to that of Ni-BPDC but with a comparatively large
area, which is owing to the combination of the EDLC character of CNF
and the faradaic nature of Ni-BPDC in the hybrid composite [47].
Zhu et al. were using the electrodeposition approach to make poly[N,
17
Journal of Energy Storage 56 (2022) 105897
N′ -ethylenebis-(salicylaldiminato) nickel(II)] (poly[Ni(salen)]) and its
composites with MWCNTs via linear sweep potential (LSP), potentio­
static (PS), and one-step potential pulse (SPP) modes, correspondingly.
Electrodepositing poly[Ni(salen)] on MWCNTs provides several advan­
tages, including high efficiency, ease of operation, and additional
operational parameters on growth. The electron conduction and specific
surface area of the produced composite are improved by integrating
MWCNTs and poly[Ni(salen)]. With the same deposition time, the poly
[Ni(salen)] produced using PS mode demonstrated superior capacity
performances as supercapacitor electrode materials. The specific ca­
pacitances of composite made by LSP, PS, and SPP modes were 72.8,
151.5 and 106.2 F/g at 0.02 mAcm2, respectively, owing to variation in
the width of poly[Ni(salen)] wrapped on MWCNTs and the length of
poly[Ni(salen)] nano-belt [130].
It was cleared from the above discussion that, PVA surfactant assisted
Ni-MOF@NiS2@C shows best electrode material performance (2780 F/g
at 2 A/g). Low-temperature sulfurization of Ni-MOF preserved the ma­
terial original porous structure in the core area and promoted its
encapsulation by a nickel sulphide and amorphous carbon shell, which
functioned as a barrier against the rapid volume change that occurs
during charging and discharging.
Table 3 presents the data related to Ni-MOFs based nanocomposites
utilized as supercapacitor electrode.
3.3. Bimetallic Ni-MOF as electrode material for supercapacitor
Metal nodes of various valences can be used in an electrochemical
process to oxidize and reduce materials. The variable pore size and huge
specific surface area are advantageous for improving electrochemical
recital, making MOFs intriguing applicant materials for supercapacitors.
Inertness and less stability of MOFs make it hard to use them directly as
electrode materials in supercapacitors. Researchers have looked into
different ways to make MOF electrode materials more useful, and doping
is one of them [75,76]. Compared to Ni-MOFs made of just one metal,
the inclusion of another metal ion in the structure can significantly
improve the electrical conductivity, structural stability, and capacitance
of the Ni-MOFs [131]. Bimetallic MOFs are metal-organic frameworks
that have two distinct metal ions as their skeleton terminals [132].
Co/Ni organic framework material (Co/Ni-MOF) was generated via a
solvothermal approach by Chen and his colleagues. The electrochemical
performance of bimetal MOF is regulated by varying the concentrations
of Ni and Co metals. Co/Ni-MOF-2 with a Co to Ni fraction of 1:2 had the
greatest conductivity, with ions transfer time of just 16.7 s and the
maximum capacitance at 1 A/g (2608 F/g) and also an excellent dura­
bility (88 %) throughout 5000 cycles. The EDX image displays a ho­
mogenous density of Co, Ni, C, and O on the surface of Co/Ni-MOF-2,
with Co content of 12.87 %, Ni of 19.81 %, C of 38.97 %, and O of 28.35
%, respectively. SEM and TEM demonstrate that bimetallic Co/Ni-MOF-
2 possesses smooth homogeneous surface sphere-like morphology as
shown in Fig. 8 [133].
Han et al. developed Mn/Ni-MOFs with diverse Ni and Mn mass
proportions (1:1, 2:1, and 3:1) via a one-step solvothermal technique,
which they designated as MNM-n (n = 1,2, and 3). To generate materials
with improved capacitance, a composite material (MNM@C-n, n = 1, 2,
and 3) consisting of MNM-n and MWCNTs was generated. The specific
capacitance of the as-prepared composites Mn/Ni-MOF@MWCNTs
(MNM@C-3) electrode at 1 A/g in 1 M LiOH aqueous solution is
793.6 F/g. Multi-walled carbon nanotubes (MWCNTs) provide active
anchoring sites in the architecture of the optimum Mn/Ni-MOF, boost­
ing electron transport and structural integrity with reduced contact
resistance and charge transfer resistance [134].
Ni-MOF was grown on carbon nanofibers (CNFs) modified with Co
nanoparticles (C-Co@MOF) by Tian et al. The incorporation of Co
nanoparticles in CNFs not only promotes CNF-MOF hybridization, but
also releases Co ions to partake in MOF growth which demonstrated a
satisfactory rate performance and excessive capacitance of 1201.6 F/g at
S. Khokhar et al. Journal of Energy Storage 56 (2022) 105897

Table 3
Data related to Ni-MOFs based composites utilized as supercapacitor electrode.
Comparative study of Ni-MOF based nanocomposites used as electrode material for Sc

Electrode material Method Precursors Solvent Electrolyte morphology Potential Specific Efficiency Ref.
window capacitance
(F/g)

Ti3C2Tx/Ni-MOF Ultrasonication Ni(NO3)2.6H2O DMF 6 M KOH Microbelts 0–1.6 1124 at 1 A/g 74.8 % after [105]
BDC Water 4000 cycles
Ti3C2Tx (6:1)
Ni-BTC/NiS2 Ultrasonication Ni(NO3)2.6H2O DMF 3 M KOH Thin nanosheets 0–0.6 1128 at 2 A/g 95.2 % after [106]
BTC DI Water 10,000
Na2S.9H2O cycles
PPY HF/Ni-CAT-NWs Solvothermal Ni – 3 M KCl Hexagonal column 0–0.5 1050 mF/cm2 80 % after [170]
(CH3COO)2.4H2O shape at 0.5 mA/cm2 6000 cycles
HHTP
Pyrrole
Ni-MOF/Co(OH)2 Electrodeposition Ni(NO3)2.6H2O DMF 1 M KOH Fluffier flakes − 0.2–0.5 1448 at 2 A/g 87.3 % after [110]
Co(NO3)2.6H2O 8000 cycles
BDC
NiO/Ni-MOF Hydrothermal NiO DMF 2 M KOH Nanoflakes on 0–0.7 1176.6 at 1A/g 88.7 % after [111]
BDC DI Water massive nanosheets 2000 cycles
(10:1)
P-Ni-MOF/NiS2/C Solvothermal Ni(NO3).6H2O DMF 6 M KOH Thin nanosheet 0–0.6 2780 at 88 % after [114]
Sulfurization BDC DI Water 2A/g 10,000
PVA (2:1) cycles
Ni-MOF/NiO Solvothermal Ni(NO3)2.6H2O DMF 3 M KOH Hexagonal 0–0.48 1192.7 at 0.5 93 % after [112]
Calcination BTC A/g 5000 cycles
Bpy
Ni-MOF@Ni3S2/Co3S4 Hydrothermal NiCl2.6H2O DMF 2 M KOH Nanosheets on 0–0.6 8.7C/cm2 at 1 96.2 % after [117]
BDC Ethanol fishbone like mA/cm2 1000 cycles
Ni3S2/Co3S4 Water skeleton
(15:1:1)
Co-Ni-MOF Solvothermal Ni(NO3)2.6H2O Ethylene 2 M KOH Nanorods 0–0.4 677 at 1 A/g 92.6 % after [118]
Co(NO3)2.6H2O glycol 10,000
BTC cycles
Melamine
MnO2/Ni-HHTP – Ni Ethyl 3 M KOH Nanorods 0.2–0.6 368.2 at 1A/g - [119]
(CH3COO)2.4H2O acetate
HHTP
MnO2nanosheet
Co3O4@Ni-MOF Solvothermal Ni(NO3)2.6H2O DMF 1 M KOH Nanoparticles − 0.2–0.6 1980.7 at 1A/g 82.2 % after [115]
BDC deposit on chiffon 2000 cycles
Co3O4
WS@Ni-MOF/SPANI Solvothermal Ni(NO3)2.6H2O DMF 6 M KOH 0–0.5 1722 at 1 A/g 90.4 % after [113]
BDC 20,000
Aniline cycles
Walnut shell
CoNi-ZIF@N-CNT Ultrasonication Ni(NO3)2.6H2O Methanol 6 M KOH Thin layer on 0–0.6 1118 at 1 A/g 85.9 % [107]
Co(NO3)2.6H2O smooth surface
2-
methylimidazole
Ti3C2 MXene@[Ni Ultrasonication NiCl2.6H2O DI Water 3 M KOH Pillared layer 979 at 0.5 A/g 98 % after [104]
(thiophene-2,5- TDC 5000 cycles
dicarboxylate)(4,4- 4,4′ -bipyridine
bipyridine)]n
(CuZn-Ni)2(bdc)2(dabco) Solvothermal Ni(NO3)2.6H2O DMF 3 M KOH + Cuboid 0–1.65 112.5 mAh/g 47.9 % after [120]
Cu(NO3)2.6H2O 0.05 M K4Fe microcrystal at 1 A/g 3000 cycles
Zn(NO3)2.6H2O (CN)6
BDC
DABCO
Ni-BDC/PPy Hydrothermal Ni(NO3)2.6H2O DMF 3 M KOH Flower like 0–1.5 715.6 at 0.3 A/ 88 % after [150]
BDC g 1000 cycles
pyrrole
Ni-MOF/C-CNTs Solvothermal Ni(NO3)2.6H2O DMF 3 M KOH Nanosheets 0–0.7 680C/g at 1 A/ 68 % at 10 [122]
BTC g A/g
C-CNT
MoS2@Ni-MOF Hydrothermal Ni(NO3)2.6H2O DI water 3 M KOH Sheet coated on 0–0.43 1590.24 at 1 87.97 % after [123]
Na2MoO4⋅2H2O nanosphere A/g 20,000
Thiourea cycles
BDC
GM-HQG/Ni-MOF Hydrothermal NiCl2.6H2O DMF 3 M KOH Lamellar 0–0.45 for CV 987.6 at 0.5 A/ 85.6 % after [124]
BDC nanosheets and g 3000 cycles
GM-LEG 0–0.4 for GCD
Ni-MOF/PANI Direct growth NiCl2.6H2O – 2 M KOH Nanosheets − 0.1–0.8 3626.4mF/ 81.6 % after [125]
method BDC cm2 at 2 mA/ 10,000
Aniline cm2 cycles
(continued on next page)

18
S. Khokhar et al. Journal of Energy Storage 56 (2022) 105897

Table 3 (continued )
Comparative study of Ni-MOF based nanocomposites used as electrode material for Sc

Electrode material Method Precursors Solvent Electrolyte morphology Potential Specific Efficiency Ref.
window capacitance
(F/g)

NiCo2O4@Ni-MOF Solvothermal Ni(NO3)2.6H2O DI water 2 M KOH Nanowires on − 0.1–0.6 208 mAh/g at 68.2 % at 20 [126]
BDC closely packed 2 mA/cm2 mA/cm2
NiCo2O4 nanoflakes
NiCo2O4@Ni-MOF Solvothermal Ni(NO3)2.6H2O DMF 3 M KOH Needle grow on − 0.2–0.8 1390 at 5 mA/ 90.5 % after [127]
BDC nanosheets cm2 3000 cycles
NiCo2O4
Ni-MOF/CNT/GN Direct growth Ni DMF PVA-KOH gel Flower composed 0–1.65 359 at 1 mA/ 93 % after [128]
method (CH3COO)2.4H2O of nanosheets Cm2 4000 cycles
BDC
CNT
Ni-MOF/rGO Hydrothermal NiCl2.6H2O DMF 6 M KOH Sphere-flake- − 0.2–0.5 260 mF/cm2 at 80 % after [129]
BTC sphere 4 mA/cm2 2000 cycles
rGO
Ni-BPDC/CNF Room temperature NiCl2.6H2O Distilled 6 M KOH Nanoplates − 0.1–0.6 for 250 mAh/g 92 % after [47]
synthesis BPDC water CV and 5000 cycles
CNF − 0.1–0.4 for
GCD
Ni-BDC/PANI Hydrothermal NiCl2.6H2O DI water 3 M KOH Rectangular 0–0.55 938.8 at 1.818 85.4 % after [116]
BDC cylinder like A/g 3000 cycles
Aniline
Poly[Ni(salen)]/MWCNTs Electrodeposition Ni(salen) Aceto- 1 M Et3MeNBF4 Nanobelts 0–1.2 106.2 at 0.02 – [130]
monomer nitrile in acetonitrile mA/cm2
MWCNT
Ni-BDC/CNT Hydrothermal NiCl2.6H2O DMF 6 M KOH Thin sheets with 0.8–1.6 1765 at 0.5 A/ 95 % after [99]
BDC ribbon shape g 5000 cycles
CNT
NiCo2O4@NiMn-MOF Solvothermal Ni(NO3)2.6H2O DMF 2 M KOH Nanosheets − 0.1 − 0.6 243 mAh/g at 65 % at 2 [109]
Mn(NO3)2.6H2O wrapped on 2 mA/cm2 mA/cm2
BDC nanowires
Urea
Ni-MOF/Mxene Ultrasonication NiCl2.6H2O DMF, – Sheet like 0–0.6 867.3 at 1 A/g 87.1 % after [57]
BDC ethanol, DI 5000 cycles
Mxene water

0.5 A/g [135].
Using the solvothermal approach, Jiang et al. created a variety of
bimetallic MOFs with terephthalic acid as the ligand and Ni2+, Co2+,
Mn2+, and Cu2+ as metal ion nodes. And it was successfully proven that
NiCo-MOFs and NiMn-MOFs had good electrochemical performance,
exhibiting specific capacities of 882, 747, and 345 F/g at 0.5 A/g,
respectively, for NiCo-MOFs, NiMn-MOFs, and NiCu-MOFs. Further­
more, NiCo-MOF electrode materials have a substantially longer cycle
life than NiMn-MOF and NiCu-MOF electrodes. The optimized conduc­
tivity and synergistic impact of Ni2+ and Co2+ are responsible for this
[136].
Li et al. worked on improvement in the electrical conductivity and
stability of Ni-MOF. For this purpose, they reported the preparation of
Mo-doped Ni-MOF nanosheets which they referred to as M-NMN, which
are made of Mo-based clusters that are trapped in the pores of the Ni-
MOF arrangement through hydrothermal treatment. The outcomes
reveal that the M-NMN-1 with a Ni/Mo molar proportion of 1:1 has
outstanding electrochemical characteristics.M-NMN-1 electrode mate­
rial produced has a high specific capacity of 802 C/g at 1 A/g, as well as
superior 92.8 %cycle stability after 20,000 cycles [137].
Zheng et al. demonstrated solvothermal method for the preparation
of Mn-doped ultrathin Ni-MOF nanosheet array on nickel foam Mn0.1-
Ni-MOF/NF (Ni/Mn atomic ratio is 0.9/0.1). It has an extreme high
specific capacity 1178 C/cm2 at 2 mA/cm2. Areal capacities of 6.48 and
4.72 C/cm2 at 2 and 20 mA/cm2, separately, with an excellent rate ef­
ficiency of 72.8 % in 6 M KOH [138].
Adopting carbon cloth (CC), CoNi-MOFs with nanosheet and nano­
tube arrays of ultrathin thickness are synthesized by Xu et al. using Co
(OH)2 as both a substrate and a reference of Co. Layered-structure MOFs
have short electron transport channels and a reduced electrolyte ion
diffusion pathway when they are utilized within the construction of
supercapacitors as electrode materials. The synthesized electrode ma­
terial has a high areal capacitance of 1.01 C/cm2 at 2 mA/cm2 and a
high-rate potential [140].
Xian et al. generated the imidazole framework (Zn-Ni(MeIm)2) using
a standard solvothermal technique, which was then calcined in a ni­
trogen atmosphere (Zn-Ni(MeIm)2(N2-723K), and activated with KOH
(Zn-Ni(MeIm)2(KOH)). At 5A/g, the Zn-Ni(MeIm)2, (Zn-Ni(MeIm)2(N2-
723K), and (Zn-Ni(MeIm)2(KOH) electrodes demonstrated specific ca­
pacitances of 378, 192, and 573 F/g, respectively. When Zn-Ni(MeIm)2
was utilized as a supercapacitor material in6 M KOH (aqueous electro­
lyte), the pseudocapacitive behaviour was observed. These results sug­
gested that Zn-Ni(MeIm)2 have the potential to be used as
supercapacitors electrode material [141].
Wang et al. fabricated hierarchical 3D Co-doped Ni-MOFs micro-
flowers (Cox-Ni-MOF x = (Co/Ni) = 0.5, 2 and 5) using a simple one-
step hydrothermal methodology. The incorporation of Co boosts the
electrochemical characteristics of Ni-MOFs and provides more open
hierarchical structure, huge surface area which facilitating interaction
between active sites and electrolyte ions, particularly in Co2-Ni-MOFs. It
was concluded that, Co2-Ni-MOFs displayed a high specific capacitance
of 1300 F/g at 1 A/g and an excellent retention of 71 % after 3000 cycles
[142].
Jiao et al. proposed an effective hydrothermal technique for
increasing the conductivity of MOFs by replacing Ni2+ with Zn2+ or
Co2+in the Ni-MOF. Due to the similar diameters of the Co and Ni ion
radii, the Co2+fractionally replaces the Ni2+, which may lead to an
escalation of free holes and, thus, an elevation in the MOF conductivity.
[Ni3-x-Cox(OH)2(TPA)2(H2O)4].2H2O(x = 0.69 for Co/Ni-MOF) and
[Ni3-x-Znx(OH)2(TPA)2(H2O)4].2H2O (x = 0.66 for Zn/Ni-MOF) pre­
serves the Ni-MOF unique crystalline morphology structure and pro­
vides marvelous electron and ion transport routes, as well as a greater

19
S. Khokhar et al.
Fig. 8. (a, b) SEM Image of the Co/Ni-MOF-1(c, d) SEM Image of the Co/Ni-MOF-2(e, f) SEM Image of the Co/Ni-MOF-3(g) TEM Image of the Co/Ni-MOF-2(h, i)
Elemental mapping of Co/Ni-MOF-2 [Reprinted with permission from Ref. [133] © Elsevier (2021)].
specific capacity. Ni-MOF, Co/Ni-MOF, and Zn/Ni-MOF had specific
capacities of 122, 236.1, and 161.5 mAh/g, respectfully, when subjected
to a current density of 1 A/g [143].
And further, Jiao et al. fabricated the Zn/Ni-MOF composite using
polypyrrole(PPY)as the matrix material for high performance super­
capacitor electrode. It was observed that by using the Lewis acid as the
catalyst and oxygen as the oxidant to create composites at room tem­
perature, the Zn/Ni-MOF could facilitate the polymerization of pyrrole.
Because of its high theoretical capacitance, good conductivity, and wide
potential window, polypyrrole (Ppy) is a promising electrode candidate.
The high electrical conductivity of Ppy (10–100 S/cm) compared to
MOFs (10− 2 S/cm) will almost definitely result in significantly improved
electron transport. The large capacity of MOFs and the quick electron
transport of Ppy are combined in such hybrid-structured electrodes
which show Zn/Ni-MOF@Ppy demonstrated remarkable electro­
chemical properties and 160.1 F/g specific capacitance at 1 A/g [144].
According to the above explanation, bimetallic MOFs had more
active sites for redox reaction than monometallic MOFs. Bimetallic Co/
Ni-MOF shows the highest 2608 F/g specific capacitance at 1 A/g
because metal nodes of various valences assist in the oxidation and
reduction of materials in an electrochemical reaction due to synergistic
effect between Cobalt and Nickel.
20
Journal of Energy Storage 56 (2022) 105897
Data related to bimetallic Ni-MOFs utilized for high performance
supercapacitor summarized in Table 4.
4. Characterization techniques
To explore the structure, crystallinity, pore size, surface area, and
electrochemical characteristics of synthesized and functionalized MOFs,
it should be evaluated. Powder X-ray diffraction (XRD) which provides
absolute information about the structure, scanning electron microscopy
(SEM), transmission electron microscopy (TEM) to evaluate crystal size
and morphology which can be coupled with energy dispersive X-ray
spectroscopy (EDS) to understand further about elemental composition
and distribution, X-ray photon spectroscopy (XPS), cyclic voltammetry
(CV), galvanostatic charge-discharge (GCD), and elemental impedance
spectroscopy (EIS)were all used to explore the properties of the MOFs.
Some of the characterization approaches that were extensively used to
explore the MOF characteristics are discussed below.
4.1. Powder X-ray diffraction (XRD)
XRD spectra are employed to detect the bulk crystallinity of MOF
samples. Once the crystalline nature of a sample has been confirmed,
S. Khokhar et al. Journal of Energy Storage 56 (2022) 105897

Table 4
Data related to bimetallic Ni-MOFs utilized as supercapacitor electrode.
Comparative study of bimetallic Ni-MOF used as electrode material for SCs

Electrode material Method Precursors Solvent Electrolyte morphology Potential Specific Efficiency Ref.
window capacitance
(F/g)

Co/Ni-MOF Solvothermal Co(NO3)2.6H2O DMF 1 M KOH Spherical 0–0.55 2608 F/g at 1 85 % after [133]
NiCl2.6H2O A/g 5000 cycles
BDC
Mn/Ni- Solvothermal Ni(NO3)2.6H2O DMF 1 M LiOH Petal 0–0.6 for CV 793.6 F/g at 1 74.92 % after [134]
MOF@MWCNTs MnCl2.4H2O Ethanol and A/g 1000 cycles
BDC Water 0–0.5 for
MWCNT (6:1:1) GCD
C-Co@Ni-MOF Solvothermal Co DMF PVA-KOH Flower like 0–0.75 1201.6 F/g at 45 % at 15 A/g [135]
(CH3COO)2.4H2O nanosheets 0.5 A/g
Ni(NO3)2.6H2O
BDC
NiCo-MOF Solvothermal Ni(NO3)2. 6H2O DMF 2 M KOH Flower like- 0–0.6 882 F/g 82.4 % after [136]
CoCl2.6H2O microsphere at 0.5 A/g 3000 cycles
BDC
Mo/Ni-MOF Solvothermal NiCl2.6H2O DI water 3 M KOH Hexagonal nanorod 0–1.6 802 C/g at 1 A/ 92.4 % after [137]
Na2MoO4.2H2O g 20,000 cycles
Bpy
Mn/Ni-MOF Solvothermal MnCl2.4H2O DMF 6 M KOH Nanosheets 0–0.8 1178 C/g at 2 80.6 % after [138]
Ni(NO3)2.6H2O Ethanol mA/cm2 5000 cycles
BDC DI Water
(14:1:1)
Co/Ni-MOF/CC Solvothermal Ni(NO3)2.6H2O DMF 1 M KOH Ultrathin sheet with 0–0.5 177.7 F/g at 96.5 % after [140]
BDC nanotube array 0.21 A/g 10,000 cycles
CC/ZnO/Co(OH)2
Zn-Ni(MeIm)2 Solvothermal Ni(NO3)2.6H2O DMF 6 M KOH Spherical like − 0.1–0.5 573 F/g at 5 A/ – [141]
(KOH) Zn(NO3)2.6H2O Ethylene nanoscale particle g
H-MeIm glycol
(40:15)
Co/Ni-MOF Solvothermal Ni(NO3)2.6H2O DMF 6 M KOH Flower like 0–0.6 1300 F/g at 1 71 % after [142]
Co(NO3)2.6H2O A/g 3000 cycles
BDC
Co/Ni-MOF Hydrothermal Co(NO3)2.6H2O DMF 3 M KOH Flower like − 0.2–0.45 236.1 mAh/g 82.8 % [143]
NiCl2.6H2O at 1 A/g
BDC
Zn/Ni-MOF@PPY Hydrothermal Zn(NO3)2.6H2O DMF 3 M KOH Flower like 160.1 F/g at 1 78.8 % after [144]
NiCl2.6H2O A/g 5000 cycles
BDC

additional data, such as the size of the unit cell, can be obtained from the
crystalline material. Since many crystalline solids can't be made into
single crystals of the sufficient size and/or quality to be studied with
single-crystal X-ray diffraction techniques, therefore powder diffraction
data is needed to determine structural properties of such materials
[145]. Powder XRD is an excellent technique for investigating frame­
work and crystalline features of synthesized material. The sample swings
at an angle θ in the stream of the collimated X-ray beam, while the X-ray
detector is situated on an arm that rotates at an angle of 2θ to receive the
diffracted X-rays. In powder X-ray diffraction, a powder of the material
is used instead of a single crystal to make the diffraction pattern. Powder
diffraction is frequently simpler and more convenient than single crystal
diffraction since it does not require individual crystals for analysis. The
intensity of a diffraction peaks is plotted across the detector angle, 2θ. By
comparing the observed powder pattern to simulated patterns obtained
from single crystal X-ray data, MOF phase purity can be confirmed.
According to CCDC No. 636901, the XRD spectra of Ni-BTC exhibits
diffraction spikes at11.8◦ , 18.01◦ , 20.83◦ , 22.28◦ , 23.83◦ , and 33.48◦ ,
corresponding to (11–1), (150), (151), (220), (02-4) and (025) planes of
Ni-MOF, correspondingly [146].
According to CCDC No. 638866, Ni-BDC show diffraction peaks of2θ
values of 9.3◦ , 11.8◦ , 15.6◦ , 18.3◦ , 23.9◦ , 28.1◦ corresponding to (h, k, l)
plane values (100), (010), (10-1), (2-10), (020), (2-21), respectively.
Spike location at 26.6◦ belonging to (002) plane describes the charac­
teristics peak of graphene [128]. Diffraction peak at 25.6◦ correspond­
ing to (002) reflection plane was the characteristic peak of CNT [147].
Spikes at 44.5◦ , 51.8◦ , and 76.4◦ indexed to the (111), (200), and (220)
planes belong to nickel (JCPDS no. 04-0850) from the NF substrate.
Fig. 9(a) illustrates the XRD spectrum of graphene (GN), Ni-MOF/GN
and Ni-MOF@CNT/GN. The Ni-MOF/GN reflection sketch was well
preserved after CNTs were incorporated [128].
4.2. X-ray Photoelectron Spectroscopy (XPS)
X-ray Photoelectron Spectroscopy (XPS), which is sometimes
referred to as Electron Spectroscopy for Chemical Analysis (ESCA), is a
type of spectroscopy that examines molecules through the exploitation
of X-rays. There will be more than one chemical phase in a sample that
needs to be measured using XPS Comparing two or more intensities in
XPS spectra to quantify the amount of material at the surface of a sample
is known as quantitative XPS. X-ray photoelectron spectroscopy (XPS) is
commonly used to detect electronic state and chemical species present at
the surface by observing peak locations and peak patterns [148].
The surface compositions as well as oxidation states of Ni-MOF, NiO,
and NiO/Ni-MOF-25 (25 % conversion ratio) were recognised using XPS
spectra depicted in Fig. 9(b). The existence of Ni, O, and C elements
illustrating the victorious synthesis of the NiO/Ni-MOF composite.
Spikes of Ni 2p separated at 856–856.3 and 873.6–874 eV were affiliated
with Ni 2p3/2 and Ni 2p1/2 spin orbits, respectively but two broad band
at 861.4 and 879.6 eV are satellite peaks of Ni 2p3/2 and Ni 2p1/2. XPS
spectra of O 1s show that peaks of NiO deconvoluted at 529.7 and 532.1
eV due to lattice oxygen and oxygen present at surface in the form of
hydroxyls. At 533.1, 532.1, and 531.6 eV, NiO/Ni-MOF and Ni-MOF
includes three analogous fitted peaks owing to oxygen in adsorbed

21
S. Khokhar et al. Journal of Energy Storage 56 (2022) 105897

Fig. 9. (a) XRD pattern of different sam­

ples (i) Graphene on nickel foam (GN)
substrate (ii) Ni-MOF/GN electrode (iii) Ni-
MOF@CNT/GN electrode [Reprinted with
permission from Ref. [128] © Elsevier
(2019)]. (b) XPS spectra of (i) NiO/Ni-
MOF-25 (ii) Ni 2p (iii) O 1s (iv) C 1s
[Reprinted with permission from
Ref. [111] ©American Chemical Society
(2021)]. (c) Nyquist plot of MWCNT, Ni-
MOF, Co3O4-Ni-MOF and Co3O4-Ni-MOF/
MWCNT [Reprinted with permission from
Ref. [168] © Springer Nature (2021)].

22
S. Khokhar et al.
water, surface hydroxyls/C–O, and metal oxygen (M–O), corre­
spondingly. According to C 1s XPS spectrum peaks of C–
– C (284.8 eV)
and O–C– – O (284.8 eV) in NiO/Ni-MOF and Ni-MOF were equivalent
(288.5 eV) [111].
4.3. Surface morphology analysis
The surface morphology of working electrode material merely plays
a subordinate role on the charge storage performance of supercapacitor.
Optimized morphology minimizes material degradation. Surface
morphology of the working electrode was analysed by scanning electron
microscope (SEM), transmission electron microscopy (TEM) and Energy
Dispersive X-Ray Analysis (EDX). Both quantitative and qualitative data
about MOFs can be obtained using SEM in conjunction with EDS.
4.3.1. Scanning electron microscope (SEM)
The scanning electron microscope (SEM) is an effective technique for
evaluating a huge variety of MOF parameters, including the crystal size,
morphology, and atomic composition of the materials being examined.
A focussed beam of high-energy electrons is applied in SEM to generate a
variety of signals at the sample surface. Accelerated electrons in a SEM
contain significant amounts of kinetic energy, which is dispersed as a
variety of signals caused by electron-sample interactions. Most SEM
systems capture data over a specific region of the sample surface and
create a two-dimensional (2D) picture [149]. Although most MOFs are
insulating, picture distortions such as charging effects can often distract
from, or entirely obstruct, the capture of quality SEM images. The most
prevalent way to solve these problems is to coat the sample with a
conductive substance to reduce charge build-up from the electron gun.
4.3.2. Transmission electron microscopy TEM)
Transmission electron microscopy (TEM) is another useful tool for
studying MOFs and obtaining detailed morphology and crystal aspects
that SEM cannot provide. In the case of nanocrystalline MOFs, TEM is
hugely advantageous. TEM may also be used to identify surface features
and imperfections in crystal structures. The primary distinction between
TEM and SEM is that the earlier permits the analysis of the sample in­
ternal structure, whereas the latter only provides for the evaluation of
the surface.
Wang et al. satisfactorily developed a Ppy-MOF composite by
merging Ni-MOF sheet with polypyrrole utilizing a simple wet-chemical
method. Sequence of Ppy-MOF composites with varying Ni-MOF masses
are synthesized, which are breviloquent as Ppy-MOF-x (x is the mass of
Ni-MOF, which can be 0.05, 0.1, 0.15, 0.2, or 0.3 g). Under the same
parameters, the Ppy-MOF-0.2 composite electrode has a significantly
larger discharge time and a greater specific capacitance (715.6 F/g at
0.3 A/g) than other composite materials. The surface morphology was
analysed by SEM, and the results showed that Ni-MOF has a coherent
framework that looks like flowers and has a diameter of 10 μm. High
magnified SEM image (220 nm) shows that Ni-MOF flowers are
composed of thin nanosheets. Ppy has an anomalous globular arrange­
ment with 0.5 μm average size. Thin strips of Ni-MOF are coated with
Ppy after the incorporation of Ppy into Ni-MOF [150].
Zhang et al. demonstrated a mixed methodology for preparing
redesigned Ni-MOFs by employing BTC as a modifier to partially ex­
change the terephthalic acid ligands (mole proportion of PTA: BTC was
set to 10:0, 9:1, 8:2, and 7:3), with the final Ni-MOFs designated as Ni-
MOF-0, Ni-MOF-1, Ni-MOF-2, Ni-MOF-3, respectively. It was found that
CV zones of Ni-MOF-2 electrodes are greater than those of other Ni-
MOFs, 920 F/g in 6 M KOH electrolyte at 1A/g, which is a higher spe­
cific capacitance. Morphology of Ni-MOFs was investigated by SEM and
TEM which revealed that without BTC (Ni-MOF-0) nanosheets
agglomerate. With the addition of BTC (Ni-MOF-1), spheres resembling
albizia flowers are created between the nanosheets. Once the BTC/PTA
mole ratio is adjusted to 2:8 (Ni-MOF-2) spheres resembling albizia
flowers with a rising diameter are detected. When the mole fraction of
23
Journal of Energy Storage 56 (2022) 105897
BTC:PTA is raised to 3:7 (Ni-MOF-3), the nanosheets vanish and nano­
wires are replacing the aggregate bulk spheres as the dominant form
[151].
Zhong et al. adopted hydrothermal and successive calcination pro­
cess to synthesize Ni-MOF/rGO-300 (calcined at 300 ◦ C) which show
Specific capacitance of 954 F/g at 1 A/g and reliability of 80.25 % at 5
A/g. Pristine Ni-MOF show uniform and monodispersed spheres
whereas Ni-MOF/rGO-300 had nanoflakes and porous morphology,
while rGO had layered structure that was thinner. TEM was used to
better comprehend the detailed structure which revealed that Ni-MOF/
rGO-300 nanoflake that is regular and unbroken, whose results were in
accordance to those of their respective SEM analyses [152].
Table 5 depicts the morphology of some Ni-MOFs and Ni-MOFs based
nanocomposite which was revealed by SEM and TEM.
4.3.3. Energy Dispersive X-Ray Analysis (EDX)
Energy Dispersive X-Ray Analysis, generally abbreviated as EDS or
EDX, is an x-ray method used to evaluate the elemental composition of
materials. Energy dispersive X-ray spectroscopy (EDX) is an analytical
way to analyse and characterising materials. Focused particles (protons
or electrons) are employed to study the material. An electron from a
higher binding energy electron level falls into the core hole and emits an
X-ray with the energy of the difference in electron level binding en­
ergies. EDX systems are attachments to Electron Microscopy (SEM) or
Transmission Electron Microscopy (TEM) equipment that use the mi­
croscope imaging ability to detect the material of relevance. In a multi-
technique strategy, EDX becomes incredibly effective, offering spatial
distribution of constituents via mapping. EDX analysis produces a
spectrum that illustrates the spikes that are proportional to the
elemental composition of the material under investigation. On the graph
of the EDS data, the unit of energy measured in keV is plotted along the
x-axis, and peak intensity is plotted along the y-axis. Computer software
converts the peak location on the x-axis into the atoms represented by
the energy changes [153]. Although EDS is an efficient and effective
approach, it has certain limitations that restrict its usefulness. First and
foremost, EDS is not an extremely sensitive approach. If the concen­
tration of an element in the sample is too low, the quantity of energy
emitted by X-rays after impacting the sample will be inadequate to
accurately estimate its percentage. Furthermore, EDS is ineffective for
elements with low atomic numbers.
4.4. Electrochemical techniques
Supercapacitor performance can be determined through parameters
like cell capacitance, series resistance, energy density, time, and oper­
ating voltage. The properties of the electrode materials that are
employed in the construction of SCs have a direct impact on the elec­
trochemical properties of SCs. Electrode were fabricating by dispersing
80 % active material, 10 % activated charcoal (AC) and 10 % binder
Nafion/polyvinylidene difluoride (PVDF) / polytetrafluoroethylene
(PTFE) in 4–5 drops of solvent ethylene glycol (EG) / N-methyl-2-pyr­
rolidone (NMP). The solution amalgamation was blend vigorously for
6–12 h at room temperature to impart homogeneity. After that, some
aliquot of the solution amalgamation was drop-casted on a foil electrode
in an area of 1 cm2. Then, the electrodes were dried in an oven for
approximately 12 h at 80 ◦ C. The function of the binder is to maintain
the adhesiveness of the active material to the electrode in the electrolyte
solution. The electrodes were dried and then examined electrochemi­
cally. Cyclic voltammetry (CV), galvanostatic charge/discharge (GCD)
and electrochemical impedance spectroscopy (EIS) are widely used
electrochemical techniques. All of these approaches need an electro­
chemical workstation to monitor key parameters including voltage,
current, time, equivalent series resistance, and capacitance in three- or
two systems. In cyclic voltammetry (CV), current is measured using a
fixed scan rate and potential, while galvanostatic charge/discharge
(GCD) uses current density and a fixed potential, and electrochemical
S. Khokhar et al. Journal of Energy Storage 56 (2022) 105897

Table 5
Depicts the morphology of Ni-MOFs and Ni-MOFs based nanocomposites.
Morphology based analysis of various Ni-MOF

S. no. MOF Morphology Specific capacitance SEM image TEM image Ref.
(F/g)

1. Ni-MOF-2 Albizia flower like-sphere nanosheets 920 at 1 A/g

[151]
(BDC:BTC = 8:2)

2. Ni-BTC Nanosize-sheets 1668.7 at 2 A/g

[163]

73. Ni-BDC/Ted Layer-Cuboid 804 at 1 A/g

[164]

4. Ni-BTC Nanosheets 1057 at 1 A/g

[67]
(BTC:Ni2+ = 1:6)

5. Ni-BDC Accordion like-nanosheets 988 at 1.4 A/g

[94]

6. Ni-MOF/rGO Nanoflakes 954 at 1 A/g

[152]

7. PPNF@Co-Ni MOF Flower like nanosheets 1096.2 at 1 A/g

[171]

8. Ni-MOF/Cu-MOF Layered 1424 at 2 A/g

[121]

9. Ni-MOF/graphene Aggregated 2D nanosheets 1017 at 10 mV/s

[172]

(continued on next page)

24
S. Khokhar et al.
Table 5 (continued )
Morphology based analysis of various Ni-MOF
S. no. MOF Morphology Specific capacitance
(F/g)
10. Zn/Ni-MOF Spherical 878 at 1 A/g
impedance spectroscopy (EIS) employs impedance or capacitance.
Mathematical equations can be used to quantify the power and energy
values of the tested device from the measured data. The primary goal of
these three methodologies is to evaluate the electrochemical properties
of energy storage devices from differing perspectives.
4.4.1. Cyclic voltammetry (CV)
Cyclic voltammetry (CV) is a potent and extensively used electro­
chemical technique for studying the reduction and oxidation mecha­
nisms of electrode material in supercapacitor. Randles briefly described
CV for the first time in 1938. It is a popular method for collecting
qualitative information on electrochemical processes. CV has become a
prominent and frequently used technique for studying the redox re­
actions between electrolyte ions and electrons from the electrode sur­
face, which plays a significant role in the charge storage mechanism in
the research of supercapacitors. It quantifies the current generated when
the input voltage exceeds the value predicted by the Nernst eq. CV
system is made up of several different parts, the most important of which
are an electrolysis cell, a potentiostat, a current-to-voltage converter,
and a data collecting system. A working electrode, a counter electrode, a
reference electrode, and electrolytic solution make up the electrolysis
cell. CV measurements are performed by applying an electric voltage to
the electrodes that vary frequently and predictably with time. Although
the potential of the working electrode changes in a linear fashion with
time, whereas the potential of the reference electrode does not change at
all. The working electrode receives electricity from the signal source
through the counter electrode and delivers it to the working electrode.
The role of electrolytic solution is to supply ions to the electrodes during
the oxidation and reduction processes. A potentiostat is an electrical
device that employs dc power supply to provide a stable and precise
potential while allowing tiny currents to flow without affecting the
voltage. The resultant current is measured by the current-to-voltage
converter, and the voltammogram is created by the data collecting
system [154]. The resultant electric current is measured and recorded.
The corresponding graph of current versus voltage is known as a vol­
tammogram, and the shapes of this graph can be used to interpret the
redox behaviour of an electrode material. The ideal EDLC characteristic
is illustrated by a voltammogram with a rectangular shape. CV curve
which shows redox peaks corresponding to reduction and oxidation of
metal centre confirm the pseudocapacitive behaviour. The quasi-
rectangular CV curve exhibits both EDLC and pseudocapacitive prop­
erties, indicating a hybrid supercapacitive behaviour [155]. To examine
the performance of energy storage devices, capacitance is often
measured at various scan rates. The specific capacitance of electrode is
related to the area of the CV curve, therefore the larger the integrated
CV, the greater the electrochemical capacitance shown in Eq. (1) [156].
Area under the curve
Cs = (1)
2 × m × v × ΔV
where Cs, m, v and ΔV corresponds to specific capacitance, active
mass of the material, scan rate, voltage window, respectively.
25
Journal of Energy Storage 56 (2022) 105897
SEM image TEM image Ref.
[173]
4.4.2. Galvanostatic Charge/Discharge (GCD)
Galvanostatic Charge and Discharge (GCD) is the industry standard
approach for testing the performance and cycle life of supercapacitors.
The most reliable parameter for assessing electrochemical performance
in SCs is GCD.A supercapacitor is charged and discharged at a steady
applied current between two predetermined voltage values. The GCD
technique monitors the relevant potential over time and reports the
existence of an electrochemical event in the supercapacitor (SC) elec­
trode material. The complete GCD technique consists of two major steps:
firstly, the supercapacitor is charged with a continuous current, and
secondly, the supercapacitor is discharged in a specific time. From GCD
curve specific capacitance can be calculated by using the Eq. (2)
I × Δt
Cs = (2)
ΔV × m
where I, Δt, ΔV and m corresponds to discharge current (A), time
taken by the device for discharging(s), voltage window (V) and the mass
of active materials (g), correspondingly.
Eqs. (3) and (4) are the expressions for calculating a supercapacitor
energy density (Wh/kg) and power densities (W/Kg), respectively:
1
E = C.ΔV 2 (3)
2
E
P= (4)
Δt
where C (F/g), ΔV (V), and Δt (s) are respectively, the specific
capacitance, working electrode potential, and discharge time.
The effectiveness of the supercapacitor is also evaluated through
volumetric specific capacitance and areal capacitance. The density of
active material is multiplied by the gravimetric specific capacitance in
the case of volumetric capacitance (F/cm3). Similarly, the areal capac­
itance (F/cm2) may be computed by dividing the electrode capacitance
by its area [157]. The region beneath the GCD potential curve is related
to the amount of energy consumed (or released) during the charging
process (or discharging) [158]. The symmetrical triangle pattern of the
GCD curves implies reversibility, stability, and illustrates the EDLC
behaviour of electrode material. Non-linear asymmetrical charge-
discharge shape, on the other extreme, suggest to a pseudocapacitive
charge storage mechanism [159].
Chu et al. created a number of different bimetallic CoNi-MOF
nanosheets by synthesising them on carbon fiber paper by altering the
molar ratio of Co/Ni via solvothermal method by adding 1,4-benzenedi­
carboxylic acid as organic ligand and NiCl2.6H2O as metal salt in the
presence of CFP. CoNi23/CFP (Ni:Co = 3:2) express the greatest specific
capacitance 2033 F/g at 1 A/gin 1 M KOH. Cyclic voltammetry displays
that addition of Co enhances the properties of Ni as we can see in CV
curve which show that peak current is considerably greater for CoNi23/
CFP than that of pure Ni-MOF. GCD curve also show that CoNi23/CFP
electrode exhibit the maximum discharge time [139].
In another approach, using a hydrothermal technique, Kim et al.
generated composites of reduced graphene oxide and a nickel metal
organic framework (Ni-MOF/rGO). The Ni-MOF/rGO composite was
S. Khokhar et al. Journal of Energy Storage 56 (2022) 105897

revealed to have a cubic structure, excellent crystallinity, and a high Table 6

specific surface area. The Ni-MOF/rGO composite utilized as the Data related to electrochemical performance of various Ni-MOFs and their
supercapacitor's electrode material had a high specific capacitance nanocomposites.
1154.4 F/g at 1 A/g in 6 M KOH. It was demonstrated that graphene Electrochemical based analysis of various Ni-MOF
could serve as a stable charge source for Ni-MOF, and that Ni-MOF could S. no. Electrode Electrolyte Potential Specific Ref.
be seen as a spacer inhibiting graphene restacking, resulting in an in­ material window (V) capacitance
crease in capacitance via synergetic interaction. Within the potential (F/g)
range of − 0.15 to 0.4 V, a couple of redox peaks are seen in CV curve. 1. Ni-DMOF- 2 M KOH 0–0.5 for CV 552 at 1 A/g [174]
The anodic peak is caused by the oxidation of Ni(II) to Ni(III), whereas ADC
the cathodic peak is caused by the reversal of the process. GCD curve 0–0.45 for
revealed that in the voltage range of − 0.15 to 0.4 V, at 1A/g computed GCD
2. Ni-BTC 3 M KOH 0–0.6 for CV 1668.7 at 2 A/ [163]
specific capacitances of the samples were rGO, Ni-MOF, and Ni-MOF/ g
rGO, which are 8, 847.3 and 987.3F/g, respectively [160]. 0–0.45 for
He et al. used a hydrothermal technique to create Ni-BPDC/GO GCD
composites from graphene oxide (GO) as a substrate and 4,4′ -biphe­ 3. Ni-BDC 2 M KOH 0–0.6 804 at 1 A/g [164]
4. Ni-BTC 3 M KOH − 0.1 − 0.6 1057 at 1 A/g [67]
nyldicarboxylic acid (BPDC) as an organic ligand. Within the compos­
5. Ni-BDC 6 M KOH 0–0.35 1127 at 0.5 A/ [30]
ites, highly dispersed Ni-BPDC macro-nanostrips are supported in a g
parallel fashion on the surface of the GO⋅As a consequence of reduced 6. Ni-MOF/rGO 6 M KOH − 0.15-0.4 1154.4 at 1A/g [160]
intrinsic resistance, charge-transfer resistance, and ion diffusion 7. Ni-BPDC/GO 6 M KOH 0–0.5 for CV 630 at 1A/g [161]
impedance, Ni-BPDC/GO composites offer greater specific capacitance,
0–0.4 for GCD
rate capability, and operating current density than Ni-BPDC.CV and 8. Coni-MOF/ 1 M KOH 0–1.45 2033 at 1A/g [139]
GCD results revealed that Ni-BPDC/GO composites have a significant CFP
specific capacitance of 630 F/g at 1A/g, as well as an excellent rate 9. S@Ni-MOF 3 M KOH 0–0.6 for CV 1453.5 at 1 A/ [162]
capability [161]. g
0–0.5 for GCD
Li et al. describe the simple solvothermal synthesis of hexagonal [Ni
10. Zn/Ni-MOF 6 M KOH 0–3.5 1620 at 0.25 [175]
(HBTC)(4,4′ -bipy)] (HBTC = 1,3,5-benzenetricarboxylic acid, 4,4′ -bipy A/g
= 4,4′ -bipyridine) materials with acceptable hexagonal shape at 80 ◦ C
and solvothermal times of 6, 12, 18, 24, and 30 h, and label them Y1,Y2,
Y3,Y4,Y5 respectively. When compared to the other four reaction time 4.4.3. Electrochemical impedance spectroscopy (EIS)
samples, the Ni-MOF morphology produced at 18 h (Y3) is complete and The recommended approach for monitoring Equivalent Series
more regular, yielding superior results. Simultaneously, this assembly Resistance (ESR) in supercapacitors is electrochemical impedance
creates a huge quantity of pores, resulting in a large ionic contact surface spectroscopy (EIS) [155]. The interaction between the electrolyte and
and a rise in the number of electroactive sites. A hexagonal Ni-MOF the materials is the primary factor of ESR. Equivalent series resistance
electrode demonstrated a specific capacitance of 977.04 F/g at 0.5 A/ (ESR) arises in all capacitors, irrespective of electrode materials or
g when it was immersed in a solution containing 3 M KOH.GCD dem­ capacitor construction [165]. ESR is an important factor for determining
onstrates that the shapes of curves exhibit pseudocapacitance features, the energy density and power density of a supercapacitor [166]. The EIS
which is congruent with CV [91]. data can be visualized in the complex plane using Nyquist plots. The real
Yue et al. investigated the use of metal-organic frameworks modified component Z' and the imaginary part Z" of the impedance are shown in
with non-metallic elements in supercapacitors. N@Ni-MOF, P@Ni-MOF, the complex plane, with Z' situated along the x-axis and Z" positioned
and S@Ni-MOF were synthesized utilizing urea, sodium dihydrogen along the y-axis, respectively [167]. At higher frequencies, super­
phosphate, and thioacetamide, respectively. Specific capacitance of capacitor becomes pure resistance, demonstrating that electrolyte ions
1453.5 F/g was exhibited by the S@Ni-MOF when measured at 1 A/g cannot penetrate the porous structures.
and the most stable cycle performance, with 89.23 % capacitance Zhang et al. effectively synthesized Co3O4-Ni-MOF by solvent-
retention after 5000 cycles. After sulfur modification, a more stable thermal approach, which was then coupled with acidulated multi-
framework structure and more active sites are formed, which could walled carbon nanotubes (MWCNTs); the resultant Co3O4-Ni-MOF/
contribute for the good electrochemical characteristics [162]. MWCNTs hybrid was used as an electrode in a supercapacitor. Co3O4-Ni-
Zhang et al. used a simple solvothermal method to create 2D Ni-MOF MOF/MWCNTs hybrid has less Rct value when the mass proportion of
without any extra treatment. According to electrochemical measure­ Co3O4-Ni-MOF and MWCNTs is 1:1.MWCNTs, Ni-MOF, Co3O4- Ni-MOF,
ments, the Ni-MOF has a negligible charge transfer resistance, a rela­ and Co3O4-Ni-MOF/MWCNTs had specific capacitances of 9.85, 14.76,
tively high capacitance of 1668.7 F/g at 2 A/g. After 5000 cycles, the 3.58, and 72.12 F/g, respectively, showing that the Co3O4-Ni-MOF/
specific capacitance is still 90.3 %, indicating strong cycle stability. SEM MWCNTs hybrid has a higher specific capacitance and superior elec­
and TEM revealed that Ni-MOF was layered with several 2D sheets, and trochemical performance. EIS data were taken to reveal much more
the nano-sized sheets were able to give a larger specific surface area, about electrochemical behaviour, and a Nyquist plot was drawn. In the
allowing for more charge storage and adequate space for active metal EIS curve, the majority of arc curvatures exist in the high frequency
centres [163]. zone, whereas straight lines emerge in the low frequency sector. The
Gao and his co-workers, prepared Ni-MOF using a one-step hydro­ charge transfer resistance value increases as the radius of the circular arc
thermal technique with a mixed solution of DMF and water rather than in the high frequency region increases. The higher the rectilinear slope
neat DMF. The Ni-MOF has a slackly stacked layer cuboid morphology of the low-frequency region is, the smaller the charge transfer resistance.
with ample mesopores, which is advantageous for supercapacitor charge The Nyquist plot of the Co3O4-Ni-MOF/MWCNTs hybrid shows a very
relocation. When examined in 2 M KOH electrolyte solution, this Ni- sharp line in the low-frequency section; this phenomenon can be seen
MOF functioning as working electrode showed exceptional 804 F/g more evidently in Fig. 9(c). The demonstrated arc is more likely to be
and 534 F/g specific capacitance at 1 A/g and 10 A/g current density, analogous to the Rct (charge transfer resistance) caused by the Faraday
respectively with good rate capacitance of 302 F/g retention after 5000 reaction on the exterior of the Co3O4-Ni-MOF/MWCNTs hybrid modi­
cycles [164]. fied electrode. MWCNTs, Ni-MOF, Co3O4-Ni-MOF, and Co3O4-Ni-MOF/
Electrochemical behaviour of various Ni-MOFs and its nano­ MWCNTs have Rct values of 4.005, 99.660, 7.703, and 0.867 Ω/cm2
composites are described in Table 6. respectively [168].

26
S. Khokhar et al.
5. Future perspectives and challenges
To meet the tremendous need for high-performance energy stowing
and conversion devices, the progress in electrode materials is critical.
Among many transitions metal-based MOFs, Ni-MOFs have received a
lot of attention in energy storage systems because of their outstanding
properties, such as organised porous structure, ample active sites which
enhance the transfer of ions, variable oxidation state (Ni2+, Ni3+),
flexible topologies, homogeneity and porosity. One more advantage is
that, Ni-MOFs are suitable templates for the synthesis of tailorable
nanostructured materials likes metal oxides/hydroxides, metal sulfides
etc. However, there are still substantial concerns and obstacles that
supercapacitor technologies on Ni-MOF based electrode materials face
in terms of economic feasibility. To ensure long-term operating stability
in practical applications of supercapacitors, it is important to consider­
ably enhance the endurance of electrode materials in charge/discharge
cycles. The preceding parts of this study highlight some of the research
and development activities in supercapacitor materials. These efforts are
important and need to be maintained in future to increase the power and
supercapacitor energy densities. Although much progress has been
achieved in this field, there are still significant difficulties ahead.
1. Major issues, such as their low intrinsic conductivity and poor me­
chanical/chemical stability throughout the charged-discharge pro­
cess, prevent the direct application of pristine Ni-MOFs as an
electrode material. Hence it is very important to create Ni-MOFs
composites with high electrical conductivity material such as Car­
bon nanotubes, graphene oxide, reduced graphene oxide etc.
2. A rapid and inexpensive approach of creating Ni-MOFs and their
derivatives is desperately needed to lower the cost of supercapacitors
and increase their reliability.
3. Ni-MOFs synthesis must be extended to create more nanocomposites
and bimetallic Ni-MOFs using various organic inorganic materials.
4. In order to develop optimized and cost-effective Ni-MOFs materials
for industrial purpose, low-cost organic ligands, mild temperature/
pressure conditions and industrial-grade solvents must be used.
6. Conclusions
The present review paper highlights the remarkable advances in
energy storage applications produced by Ni-MOF nanoparticles. A so­
phisticated analysis of the Ni-MOF electrochemical performances with
diverse carbon-based materials (carbon nanotubes, graphene, activated
carbon) and metals was carried out, with a particular emphasis on the
advantages and associated features performed by the individual com­
ponents in improving overall electrochemical performances. Experts in
the field are excited, and considering how quickly the scientists all over
the world are working to endorse agile and extremely assiduous nano­
composites based on Ni-MOF for supercapacitor electrode materials, the
subsequent energy storage/conversion devices will be economically
feasible early, helping to alleviate global energy concerns.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
27
Journal of Energy Storage 56 (2022) 105897
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