Coordination Chemistry Reviews 452 (2022) 214300

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Coordination Chemistry Reviews

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

Review

Metal-organic framework-based materials for flexible supercapacitor

application
Jing Yan a, Tong Liu b, Xudong Liu a, Yonghui Yan c, Ying Huang a,⇑
a
MOE Key Laboratory of Material Physics and Chemistry Under Extraodinary Conditions, Ministry of Education, School of Chemistry and Chemical Engineering,
Northwestern Polytechnical University, Xi’an 710072, PR China
b
School of Power and Energy, Northwestern Polytechnical University, Xi’an 710072, PR China
c
Institute of Flexible Electronics, Northwestern Polytechnical University, Xi’an 710072, PR China

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

Article history: The recent rapid growth in Metal-organic Frameworks (MOFs)-based supercapacitors (SCs) has reached
Received 30 August 2021 the level where there is a need for meet the demand of portable and wearable electronic equipment.
Accepted 22 October 2021 Herein, we focus on the recent progresses toward the MOFs-based flexible solid-state supercapacitors
Available online 11 November 2021
(FSSCs). Some pristine MOFs used for the FSSCs have been reported, but it is usually restricted by its
low conductivity. Now, there have the three strategies to improve the conductivity of MOFs material:
Keywords: exploiting new pristine conductive MOFs, developing the different multifunctional MOFs-based compos-
Pristine MOFs
ite materials and obtaining the MOFs-derived materials. In this review, the classification of MOFs-based
MOFs-based composite
MOFs-derived materials
material for FSSCs electrode materials, together with the typical fabrication techniques for MOFs-based
Flexible solid-state supercapacitors flexible devices, are totally discussed. A summary of the overall electrochemical performances and cur-
rent development of the reported MOFs-based material assembled devices are presented gradually to
predict the future tendency toward the actualization of an ultimate-performance MOFs-based FSSCs.
Ó 2021 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Brief overview of preparation techniques for MOFs-based flexible supercapacitor electrode. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. 3D printing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Electrospinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.3. Vacuum assisted filtration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.4. Substrate chemical/physical growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.4.1. Metal substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.4.2. Carbon-based substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.4.3. Textile substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.4.4. Polymer film . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3. MOFs-based material for flexible supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1. Pristine MOFs for flexible supercapacitors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2. MOFs composites for flexible supercapacitors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2.1. MOFs/Conductive polymers composites electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2.2. MOFs/Carbon-Based materials composites electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2.3. MOFs/Metal oxides composites electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.2.4. MOFs/other material composites electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.3. MOFs derived composites for flexible supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.3.1. MOFs derived porous carbon composites electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.3.2. MOFs derived metal oxides composites electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.3.3. MOFs derived metal sulfide composites electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

⇑ Corresponding author.
E-mail address: yingh@nwpu.edu.cn (Y. Huang).

https://doi.org/10.1016/j.ccr.2021.214300
0010-8545/Ó 2021 Elsevier B.V. All rights reserved.
J. Yan, T. Liu, X. Liu et al. Coordination Chemistry Reviews 452 (2022) 214300

3.3.4. MOFs derived transition metal hydroxide composites electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

3.3.5. MOFs derived metal selenide (phosphide) composites electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.3.6. MOFs derived Heteroatom doping composites electrode. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4. Conclusion and future challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

1. Introduction to unique and novel properties on the mesoscale and macroscales,

Energy is the fundamental need for the survival and develop-
ment of human civilization. The growing energy crisis and the seri-
ous environmental pollution caused by burning fossil fuels have
prompted global efforts to explore other renewable and clean
energy as the main resource in our daily lives. As an energy carrier,
electric energy can be generated through clean and renewable
resources, including solar energy, tidal or wind energy, it can pro-
vide great potential to meet our demands for sustainable energy. In
this aspect, fuel cells, rechargeable batteries and SCs are emerging
as effective energy storage devices. Among them, SCs as a kind of
reliable and efficient electrical energy storage (EES) devices, have
aroused extensive attention in the research areas, owing to their
considerable energy density, high power(>10,000 W kg 1), quick
charge–discharge capability, high safety and stable recyclability
[1–3]. In the recent years, with the emergence of utilizations in
various fields such as artificial electronic skins [4,5], implantable/
wearable medical devices (e.g. sphygmomanometers, wristbands
and spirometers) [6,7], wearable electronics [8] and active radio
frequency identification (RFID), flexible energy storage devices
such as flexible SCs [9], flexible zinc-carbon batteries, flexible alka-
line batteries, flexible lithium ion batteries [10], polymer lithium
metal batteries and all-polymer batteries have received wide
attention. Among them, FSSCs are regarded as the one of the most
promising flexible energy storage devices owing its long cycle life,
higher power density, environmentally-friendly and larger energy
density, etc [11]. Moreover, FSSCs do not require lithium or other
metal materials (less reserves in nature) as electrode materials,
and are simple to package, safe, low cost, reversible, lighter,
-have higher power density, and a wide operating temperature
range that can be used in the range of 25 to 70 °C. The FSSCs
device usually includes flexible electrodes, solid gel electrolyte,
the separator similar to traditional SCs, and flexible packaging
materials. The current research on FSSCs mainly focuses on the
mechanical flexibility of the devices, the purpose is maintain excel-
lent electrochemical properties under successive mechanical
deformation (such as twisting, folding, stretching and bending)
[12]. Based on this strategy, many materials have been demon-
strated with broad application prospects, such as carbon-based
materials like graphene, carbon nanotubes (CNTs) and activated
carbon (AC), metal oxides and metal hydroxides as well as conduc-
tive polymers (PANI, PPy and PEDOT), etc [13–15]. However, the
above materials have their own limitations. For instance, metal
oxides and metal hydroxides have high specific capacitance,
whereas display poor conductivity. In contrast, carbon-based
materials exhibit excellent electrical conductivity and stability,
but deliver low specific capacitance. Conductive polymers possess
the advantages of high specific capacitance, good machinability
and conductivity but poor stability. These factors limit the com-
mercialization of FSSCs, so scientists are urged to search for new
high-performance materials.
Hybrid framework materials are composed of organic and inor-
ganic units at the molecular/nano level. The extremely rich struc-
tural diversity and chemical versatility of this material can lead
2
thus exhibiting a wide spectrum of versatility that does not present
in traditional materials. Among them, MOF is a crystalline porous
material with a periodic network structure formed by self-
assembly of transition metal ions and organic ligands, has garnered
major developments because of its high specific surface area, high
porosity, controllable topology&morphology and chemical tunabil-
ity. These properties are of great importance in many applications,
for example, batteries [16–24], catalysts [25–27], gas storage and
separation [28,29], chemical sensors [30,31], and other applica-
tions [32]. Moreover, the open channels and nanoscale cavities
making it able to facilitate fast electron transportation for energy
storage and be one of the promising links between the field of
nano-materials and SCs. MOFs were first reported by Yaghi [33]
in the mid-1990s, usually synthesized by hydrothermal, micro-
wave assisted, solvothermal and surfactant-mediated synthesis
method. The downside is that majority of the pristine MOFs were
discovered to have low conductivity, thus blocking their applica-
tion in SCs. Therefore, there have the three strategies to enhance
the conductivity of MOFs material. The one is exploit new pristine
conductive MOFs by adjusting the types of organic ligands. The
second is exploring the different multifunctional MOFs-based com-
posite materials. Due to the synergy between the functional units,
the performances of the composite materials are usually better
than that of an individual component. Multiple conductive
matrixes have been integrated with MOFs, such as carbon-based
materials (AC, carbon onions, CNTs and graphene) or conductive
polymers (Polyaniline, polypyrrole, and Poly(3, 4-
ethylenedioxythiophene)). Such methods can provide structural
stability and high conductivity even during long-term cycling pro-
cess for MOFs composite electrodes. The third is obtaining the
MOFs-derived materials by pyrolysising MOFs as sacrificial tem-
plates (e.g., thermolysis under different atmosphere). This method
was certified as a new platform for developing electrode materials
because it not only maintains the porous structure of the MOFs
precursors, but also exhibits excellent electrical conductivity.
MOFs derived materials mainly include porous carbon materials
[34–37], metal compounds (such as sulfides [38–41], hydroxides
[42], oxides [43] as well as multifold composites).
As a promising SCs electrode material, MOFs-based materials
have also been tried to be applied to FSSCs by many researchers.
Herein, this review gives a summarisation of the latest progresses
on pristine MOF, MOFs-based composites and MOFs-derived mate-
rials as FSSCs electrodes as well as the crucial advantages that
MOFs-based materials offer in FSSCs electrodes, as shown in
Scheme 1. Our main objective is promoting knowledge transfer
from reported works to inspire new idea for the rapid development
of MOFs-based materials in FSSCs.
2. Brief overview of preparation techniques for MOFs-based
flexible supercapacitor electrode
To date, the fabrication of flexible electrode can be separated
into two main routes: (i) flexible freestanding films directly made
of active materials and (ii) flexible substrates type material that
J. Yan, T. Liu, X. Liu et al.
Scheme 1. Overview of MOFs-based material for FSSCs.
supporting/depositing active materials. Based on this, the success-
ful techniques that have been employed to prepare MOFs based
FSSCs electrode generally fall within four categories: 3D printing,
electrospinning, vacuum assisted filtration and substrate chemi-
cal/physical growth. We will introduce one by one as below.
2.1. 3D printing
3D printing is one of promising technology to manufacture elec-
trode due to its simplicity in system, low cost, scalability, and cus-
tomization. The developed 3D printing techniques include Fused
filament fabrication, Aerosol jet printing, Inkjet printing, Direct
ink writing (DIW) and Electrohydrodynamic printing. Among
them, DIW method possesses the big possibility to achieve
MOFs-based FSSCs electrode because its precise micropattern-
defining capability and efficient device processability.
Typically, a printable ink system for electrodes typically con-
sists of three components: active particles, inactive organic bin-
ders/additives, and solvents. The electrochemical performances of
the print electrode have a positive correlation with the dispersion
state, specific surface area and load density of active nanoparticles
or particles. However, the viscosity, rheological properties and
overall ‘‘printability” of inks are primarily controlled by inactive
organic binders/additives and solvents, which control the wettabil-
ity, dispersion stability and uniformity of the active particles.
Unfortunately, additives can affect the high electrical conductivity
and electrochemical properties of the material. Many efforts have
been devoted to develop the suitable ink and less binder even no
binder. As for MOFs-based FSSCs electrode, the binder is still nec-
essary because the MOFs particles difficult to form the high-
viscosity paste. Therefore, the development of binder-free, or a bin-
der that can contribute to electrochemical performance is the
future trend of 3D printing MOFs-based FSSCs.
Wu et al. [44] fabricated the hetero-nanostructured black
phosphorus/metal-organic framework hybrids all-integrated FSSCs
by using 3D printing method. Impressively, there are no obvious
decays of CV curves, when this all-integrated FSSCs were subjected
to different bending angles (0°, 45°, 90° and 180°), indicating the
3
Coordination Chemistry Reviews 452 (2022) 214300
outstanding flexibility and stability. Halder et al. [45] introduced
a free-standing FSSCs electrode of covalent organic frameworks
(COFs) thin sheets that prepared by 3D printing, which exhibited
an excellent flexibility and electrochemical properties. COFs, as
the analogue of MOFs, also successfully synthesized by Yaghi and
co-workers. COFs also have controllable pore sizes, high surface
areas and good flexibility in molecular designs, exhibiting great
potential in the energy storage and FSSCs electrode material. Thus
both MOFs and COFs are promising materials for printed FSSCs
application because of their organic and soluble property. There-
fore, in this review, we also add some relevant COF materials.
2.2. Electrospinning
The electrospinning has emerged as the one of reliable tech-
nique for preparing flexible fiber material. Electrospun carbon
nanofibers (CNFs) are kind of intrinsically flexible one-
dimensional carbon materials, its morphology are controllable,
environmentally friendly, easy to be combined with other materi-
als, simple preparation, low cost, and have the capacity of indus-
trial production [46–48]. In general, CNFs are produced by the
thermal treatment of electrospun polymer nanofibers, including
those made of polyacrylonitrile (PAN), polyvinylpyrrolidone
(PVP), cellulose acetate (CA), polyvinyl alcohol (PVA), polymethyl
methacrylate (PMMA), polyimide (PI), phenolic resin, pitch, lignin,
etc. Among them, PAN has been most widely employed as the car-
bon precursor for generating CNFs, owing to its high carbon yield
and predictable mechanical strength of the resulting products.
For the conversion of PAN nanofibers to CNFs, it is essential to
undergo a stabilization/pre-oxidation process in air, before the
high-temperature carbonization is conducted under an inert atmo-
sphere, in order to form non-plastic cyclic or ladder structures with
increased thermal stability. The PVP is a common alternative,
which can be readily dissolved in nontoxic solvents, such as water
and ethanol, rendering it a useful carbon precursor. The PAN, PI
and Pitch used for the preparation of CNFs usually have the high
mechanical strength.
J. Yan, T. Liu, X. Liu et al.
Carbon fiber materials are among the most employed materials
in various energy storage and conversion devices, where they offer
the inevitably-required electrical, chemical/electrochemical and
mechanical functions, acting as either active materials by them-
selves or substrate supports for other active materials or both.
However, pure electrospun CNFs have many shortcomings, such
as low specific surface area, high micropore content, poor conduc-
tivity and other defects, which severely restrict its application in
the direction of FSSCs. As for MOFs material, the further develop-
ment for FSSCs has encountered tremendous challenge owing to
the unitary porous structure (almost filled entirely with microp-
ores) and conventional morphology (e.g., sphere, polyhedron, and
rod shape). Therefore, the combination of MOFs material that pos-
sess high specific capacity, good stability, environment friendly,
safe, reliable, and low-cost with electrospun CNFs to assemble
FSSCs with excellent electrochemical performance is the important
subject. Based on many literatures, the general strategy for prepar-
ing MOFs/CNFs FSSCs by electrospinning can be divided into two
categories: 1. The MOFs material and polymer material are uni-
formly mixed in the spinning solution, and then the MOFs-
derived material/fiber composite is formed through pre-oxidation
and carbonization; 2. In situ growth method by preparing electro-
spun CNFs film that are incorporated with contain metal ions (or
ligands), followed by in situ growth of MOFs nanoparticles on elec-
trospun CNFs. The film made by electrospinning technology acted
as the substrate material. This strategy can be regarded as the com-
bination of electrospinning technology and substrate growth
method.
As for strategy 1, Wang et al. [49] have fabricated 1D nanopor-
ous carbon fibers (NPCFs) via electrospinning for FSSCs. The ZIF-8
nanoparticles were mixed with PAN solution and converted into
ZIF-8/PAN fibers by electrospinning, and then the NPCFs were
obtained by heating at 500 °C under an inert atmosphere. The
enhanced specific capacitance of NPCFs was contributed by their
enhanced electrical conductivity, which resulted from the
improved interconnectivity between the ZIF-8-derived NPCs. Such
improved interconnectivity was possible due to the linking of these
particles by the chains of PAN-derived carbon, which provided a
pathway to enable smooth charge transport and ionic diffusion
during charge/discharge. Lee et al. [50] fabricated ZnO quantum
dot (QDs)-decorated CNFs by carbonization of electrospun ZIF-8/
PVA nanofibers for high-performance FSSCs electrodes. During
the carbonization, the PVA nanofibers served as precursor for the
formation of a CNF structure and as an oxygen source to enable
the transformation of the ZIF-8 into finely dispersed ZnO QDs on
the CNFs surface. These ZnO QDs-decorated CNFs based electrodes
showed improved electrochemical performance compared with
other ZnO-based SCs. The CNFs supply an efficient conductive
pathway and the plum-branch-like ZnO QDs@carbons create an
ion-accessible area to enhance storage capacity and mass transfer
through the electrode. Li et al. [51] synthesized the FSSCs electrode
based on N and S co-doped hierarchically porous carbon polyhedra
embedded CNFs that prepared by carbonizating and electrospin-
ning ZIF-67/thiourea (TU) incorporated PAN precursor. This sample
showed great potential for high-performance FSSCs. Moreover, Yao
et al. [52] rationally designed N-doped graphite hierarchically por-
ous CNFs by electrospinning bimetallic Co/Zn MOFs, followed by
heat treatment and acid wash for FSSCs. The excellent electro-
chemical performance is attributed to the collective effect of hier-
archical porous, N-doping, conductivity and specific surface area.
The strategy 2 can be subdivided into the following three situ-
ations. i) secondary growth, MOFs crystallite seeds are incorpo-
rated into polymer nanofiber during the electrospinning process
and the MOFs growth is started by immersing the seeded nanofi-
bers in a MOF precursor solution. ii) the selected MOF precursors
(the metal ion or the organic linker) pre-added to the polymer
4
Coordination Chemistry Reviews 452 (2022) 214300
spinning solution via the electrospinning process and the MOFs
crystallization is initialized by immersion of the precursor-
polymer nanofiber in a solution of the other precursor. iii)
solvothermal or hydrothermal growth of MOF on the surface of
electrospun pure CNFs. The polymer nanofiber usually needs to
be activated for in situ growth by a nanofiber surface pretreatment
to achieve sufficient attachment. As a typical example, Wu et al.
[53] chose HKUST-1, ZIF-8, MIL-101(Fe), and Zn2(bpdc)2(bpee) to
demonstrate the effectiveness of MOF seeding in nanofibers to ini-
tiate subsequent intimate growth of MOF particles inside and on
the surface of a MOF-seeded polymer nanofiber structure by sec-
ondary growth to achieve a continuous, uniform, and defect-free
MOF membrane. This study successfully demonstrated that the
electrospinning of composite nanofibers combined with secondary
growth is a good approach to increase the loading fraction of MOF
in MOF-polymer nanofibers and to obtain continuous, freestanding
MOF layers on porous nanofiber support structures. Although this
example is not applied to FSSCs, it will give us more inspiration.
Han et al. [54] was prepared core–shell structure of CNF@Ni-
CAT self-supporting flexible membrane by skillfully combining
hydrothermal method and electrospinning. The synthesis strategy
of growing Ni-CAT nanorod arrays on the surface of electrospun
CNF membranes not only settles the agglomeration problem of
Ni-CAT nanorods, but also greatly increases the contact area
between the composite membranes and the electrolyte. Here, the
Ni-CAT is one kind of the 2D conductive MOFs, as the name sug-
gests, its conductivity is much better than many other ordinary
MOFs and also developed to applied for FSSCs. Tian et al. [55] pre-
pared a series of bimetallic MOFs with a flowerlike nanosheet
structure solvothermal grown on the electrospun nanofibers
(PPNF@M Ni MOF, M = Co, Zn, Cu, Fe) by controlling the incorpo-
ration of various types of metal ions for SCs electrodes, which pro-
vides a good idea for the design of MOF FSSCs electrodes.
The electrospun MOFs/CNFs with an appropriate design has
shown good mechanical stability in FSSCs under different types
of deformations. However, there remains a rather long way to go
before they are put into practical applications in large scales. Reg-
ulating the orientation of electrospun polymer nanofibers, pre-
oxidation and carbonization temperatures, the type of MOFs and
the amount of MOFs into CNFs are the possible strategy to signifi-
cantly boost the mechanical performance of CNFs/MOFs.
2.3. Vacuum assisted filtration
Vacuum filtration is a high scalable, low cost and easy process
that has been widely used for making the free-standing films.
Vacuum filtration setup usually consists of buchner funnel, filter
membrane and vacuum system. Different kinds of filter membrane
such as anodic aluminum oxide (AAO) filter membrane, Polyvinyli-
dene fluoride (PVDF) membrane, and cellulose membrane have
been used in making free-standing films. As for MOFs material, it
is difficult to filter into a soft and tight membrane due to the rigid-
ity of the MOFs material. Therefore, the MOFs material usually
need to be self-assembly combined with graphene, CNTs and 2D
metal carbides and nitrides (Mxene) etc. to form a film by filtering.
These contained MOFs-based film can be produced by peeling off
from the membrane after filtering and drying.
MOFs composite electrodes can be fabricated by filtering a
homogeneous solution suspension of MOFs and other easy-to-
film forming materials. This approaches tuning the film property
by controlling the ratio between MOFs and other material as well
as the total mass of active materials. For example, Zhao et al.
[56] constructed Mxene intercalated metal-porphyrin frameworks
(MPFs) conductive networks flexible film via a vacuum-assisted fil-
tration technology. The interlayer hydrogen bonds between MXene
nanosheets and MPFs nanosheets are expected to constraint the
J. Yan, T. Liu, X. Liu et al.
serious volume changes resulting from phase separation and struc-
tural collapse during the fast charge/discharge process, further
enhancing the durability. When it assembled as the FSSCs, the CV
curves under bending states of 0–180°show almost no change.
Similarly, Chen et al. [57] designed the flexible freestanding
GO/2D-MOF papers via vacuum-assisted filtration method. The
FSSCs exhibit high editability and bending-tolerance properties,
and perform very well under various severe service conditions,
such as being seriously cut, bent, and heavily loaded.
The big advantage of the vacuum filtration method to make
MOFs-based FSSCs is that it can be used as a membrane with high
active material loading, but the disadvantage is that MOFs materi-
als need to be combined with other materials that are easy to form
films, and the mass of MOFs materials in composite is small. Accu-
rately controlling the proportion of MOFs in composites film to bal-
ance flexibility and electrochemical performance is the focus of
research.
2.4. Substrate chemical/physical growth
The 3D printing, electrospinning technologies, vacuum assisted
filtration tend to prepare flexible freestanding films, but the use of
flexible substrates as support for active materials more widely be
used for FSSCs due to their cheap price, high flexibility, and large
availability. High-capacity flexible substrates electrodes are usu-
ally incorporate some active MOFs materials to increase their
capacitance [58]. There are two common ways to use substrates,
one is substrate chemical growth, that is grow MOF arrays on sub-
strate by solvothermal method, and the second is coating the ink
consist of MOFs-based active materials to the surface of substrate,
called physical growth. For the physical growth (also called physi-
cal coating), the MOFs-based active materials in powder form usu-
ally mixed with organic binders (e.g., PVDF) and further coated on
the flexible current collector. The low conductivity and relatively
poor stability of these organic binders not only add weight and
the difficulty of constructing FSSCs but also decrease the electro-
chemical performance. Therefore, the chemical growth method is
constantly being developed to construct FSSCs electrode due to
its binder-free and good stability.
The common flexible substrates for FSSCs are including the
metal substrates (stainless steel, nickel, copper, aluminum and
titanium), carbon-based substrates (carbon film, paper, foam, cloth
and graphene paper), textile substrates and polymer film according
to the type of substrate material. Here, we introduced the substrate
chemical/physical growth methods for MOF-based FSSCs from the
different types of substrates.
2.4.1. Metal substrates
As for MOFs based FSSCs electrode, the rigidity of the MOFs
powder makes it unsuitable for coating/growth on smooth metal
substrates. There are only a few reports on the use of metal as
the substrate of MOFs-based FSSCs. He et al. [59] grew the Cu3(-
BTC)2 on pretreated Cu foil and evaluated the CV at different bend-
ing angles. No obvious changes in CV curves were observed,
highlighting the great electrochemical stability and flexibility of
Cu-foil substrate. In addition, as one of the metal substrate, Nickel
foam (NF) is the most common SCs current collector. When testing
the electrochemical performance of powder samples, the powder
samples, acetylene black and PVDF are usually dissolved in N, N-
dimethylpyrrolidone (NMP) at a ratio of 8:1:1 and then coating
the paste to NF for testing. There are some reports regard it as
the flexible substrate, [60] but this is not strict because the flexibil-
ity of NF is very low.
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Coordination Chemistry Reviews 452 (2022) 214300
2.4.2. Carbon-based substrates
Compared with the metal substrates, the carbon-based sub-
strates exhibit high corrosive resistance, low weight, and good sur-
face modification capability, are usually be used for the MOFs
based FSSCs. The situations of directly using electrospun CNFs as
the substrate have been introduced in Section 2.2, and here we give
some examples of other carbon-based substrates. For instance,
Duan et al. [61] prepared the ZnO@ZIF-8 derived N-doped carbon
bubbles that grown on the flexible carbon cloth (CC) substrate,
and used it for high-rate FSSCs. Guan et al. has successfully grown
an Co-MOF array onto a CC to achieve the flexibility and then
transform it to hollow NiCo2O4 arrays [62] or secondary growth
of manganese oxide [63], etc. Carbon paper (CP) is a carbon fiber
composite paper with proven durability and very suitable for use
as a catalyst backing layer. It also used as FSSCs substrate because
of its corrosion resistance, high conductivity, excellent air perme-
ability, high strength and smooth surface. Xu et al. [64] was
dropped the mixture of ZIF-PPy onto flexible graphite paper to
make the FSSCs device, which exhibited the huge potential for
the use of flexible/wearable electronics.
2.4.3. Textile substrates
The textiles’ porous structure can provide ample space for sup-
porting active materials, and it is conducive to the quick absorption
of electroactive materials because of their hydrophilicity, which
leads to high surface mass loading of active materials and good
energy density. A case in point is a flexible reduced graphene
oxide/Ni-MOF/metallic fabric electrodes with a sphere-flake-
sphere structure constructed by using the fabric electrodes as the
substrate, which showed excellent electrochemical energy-
storage performance [65].
2.4.4. Polymer film
The polymer-based substrates (polyester film and polyimide
film) exhibit excellent bendability and low conductivity, it also
be used as electrode substrates for FSSCs. Pang et al. [66] was
coated the slurry of accordion-like Ni-MOF superstructure or AC
on the polyester (PET) film, and as-fabricated device exhibited
good flexibility functioning well under highly bent conditions.
Aniruddha Basu et al. [67] fabricated the SCs electrode by CO2 laser
treating MOF slurry coated polyimide (kapton) substrate. As we
know, when MOF material is grown or coated on a substrate, the
macroscopic morphology of the flexible material are largely depen-
dent on the surface and structure of the substrates, which is usu-
ally no morphology. With the development of micro-levels such
as interposing fingers, flexible materials also need specific macro
morphology. This work reported the micro-supercapacitor elec-
trode fabricated by CO2 laser treating MOF slurry, which is the first
flexible MOF-based interdigitated micro-supercapacitor. The
device showed near 100% retention after 200 000 cycles and good
stability under 150° bending.
In addition to the above two polymer films, the polypyrrole
(PPy) membrane was also prepared by peeling off the electrode-
posited pyrrole (Py) from the super 13Cr stainless steel plate by
Hou et al. [68] They were fabricated the flexible conductive Cu-
CAT MOF nanowire arrays by using the prepared PPy membrane
as substrate, and assembled it for FSSCs. Free-standing PPy mem-
branes with high surface/mass ratio, mechanical flexibility, high
electrical conductivity, and satisfactory capacitance have exhibited
a great advantage in FSSCs electrode active materials.
As for the method of substrate chemical/physical growth, the
interfacial interaction design between the MOFs active material
and substrate is the key issue of fabricate MOF-based FSSCs
electrode, which not only determines the loading of the active
material, but also affects the electrochemical stability of the elec-
trode. Therefore, the choice and surface modification of substrate
J. Yan, T. Liu, X. Liu et al.
material, growth methods of MOFs are all factors that need to be
considered to obtain the good MOF-based FSSCs electrode.
3. MOFs-based material for flexible supercapacitors
3.1. Pristine MOFs for flexible supercapacitors
The pristine MOFs firstly used for SCs electrode was Co8-MOF-5
(Zn3.68Co0.32O(BDC)(DEF)0.75) [69], which showed that MOFs elec-
trode behaves as an electric double layer capacitor and precise tun-
ing of MOFs structure may sharply improve capacitance values.
After that, some other MOFs were also be applied for the SCs elec-
trode, such as MIL-47, Co-MOF-71, MIL-100(Fe), Ni3(2, 3, 6, 7, 10,
11-hexaiminotriphenylene)2 (Ni3(HITP)2), mixed metallic MOFs,
etc [70–74]. The accordion-like pristine Ni based MOFs superstruc-
ture firstly reported for high-performance FSSCs by Pang Huan’s
group [66], which provided a facile and hydrothermal method to
prepare an accordion-like Ni-MOF superstructure and then used
the PET film as the flexible substrate to assemble the FSSCs device.
The flexible solid-state device had very little capacitance change
after 5000 charge and discharge cycles, and the attenuation was
only 7.2% at a current density of 5.0 mA cm 2. What’s more, the
flexible device also had outstanding mechanical flexibility after
bending in the range of 0–180°.
Inspired by the good electrochemical performance of
(Ni3(HITP)2) as SCs, Zhao et al. [75] prepared the conductive
Ni3(HITP)2 thin films as FSSCs through the modified air/liquid
interfacial method. By taking full advantages of the nanoscale film,
high porosity and excellent conductivity, the Ni3(HITP)2 based
FSSCs electrode exhibited high areal capacitance and rate capabil-
ity in comparison with most of reported other FSSCs.
As for single MOF material, Dai et al. [76] take a deep excavation
for the micro-electrochemical energy storage devices that focus on
the influence of MOF FSSCs from 3D MOF bulks (structure) to 2D
MOF nanosheets (morphology). The results showed that the FSSCs
based on 2D MOF nanosheets displayed remarkable electrochemi-
cal performance than that of FSSCs based on MOF bulks.
As we known, the pristine MOFs used for FSSCs usually
restricted by its conductivity. Therefore, improve the intrinsic
properties of pristine MOFs is also an alternative way to enhance
the energy storage ability. UIO66, one of Zr-MOF, has been proved
that environments (such pH value) for growing UIO66 can influ-
ence its intrinsic properties like electrical conductivity, surface
area and electrochemical performance [77]. In the Hung’s work
[78], UIO66 was synthesized by using precursor solutions with dif-
ferent pH values for hydrothermal process and deposited on CC
substrates with and without acid treatments. The FSSCs electrode
with UIO66 was prepared by using pH value of 6 on acidified CC
showed the highest areal capacitance.
Doping strategy using electron acceptor molecules is also been
demonstrated to tune the ohmic electrical conductivity of MOFs
thin-film electrodes. He et al. [59] enhanced the conductivity of
MOF Cu3(BTC)2 film over 40 times by doping with 7, 7, 8, 8-
tetracyanoquinododimethane (TCNQ). It exhibited the remarkable
areal capacitance of 95.1 mF cm 2 at a scan rate of 5 mV s 1 and
long-term stability with 94.1% capacitance retention up to 5000
charge–discharge cycles at 10 mA cm 2 when it as FSSCs. The
molecular doping engineering of MOF materials with excellent
electronic properties for energy storage and conversion applica-
tions are inspired.
Constructing bimetal MOFs (such as introduce Ni or Co) is
another way to increase the electrochemical properties of pristine
MOFs. Chen et al. [79] grew the porous honeycomb-like Ni/Co-MOF
on the substrate of CC (Ni/Co-MOF@CC) through a hydrothermal
process. This bimetal MOFs exhibited the excellent conductivity
6
Coordination Chemistry Reviews 452 (2022) 214300
as well as maximal specific capacity, good high-rate discharge abil-
ity, and long-term cycling life when it as FSSCs electrode. Similarly,
polycrystalline flower-like Ni-Co MOFs have been synthesised via
combining the facile hydrothermal method and further electro-
chemical activation [80]. In a large potential window of 1.8 V,
the FSSCs assembled by the AC, polybenzimidazole (PBI) and
Ni-Co MOF achieved the high specific capacitance of 172.7F g 1
at 0.5 A g 1, which corresponding to a high specific energy of
77.7 W h kg 1 and 0.45 kW kg 1. Yan et al. [81] also prepared
Ni-Co coordination hollow spheres for the application of FSSCs,
which delivered a good specific energy of 75.1 Wh kg 1.
Numerous efforts have been done to synthesis MOF materials
with high conductivity, but these strategies have rarely yielded
sample with the ideal result. In this situation, a new electrochem-
ical mechanism for the redox processes of MOFs has been devel-
oped by Zhang et al. [82] To be specific, the single crystals of
Mn-MOF and the secondary building unit MnII7(O2C)14(DMA)6 clus-
ter were constructed by the solvothermal reaction between MnCl2-

4H2O and a 6:1 mixture of 2, 7- and 2, 6-H2AQDC in DMA solvent.
Here, the Mn-MOF was regarded as a breathing MOF with a pliable,
yet robust, structure by regulating the addition of DMF. The flexibil-
ity of the secondary building unit conferred tolerance to perturba-
tions of the coordination environment of the manganese cations
during redox events, hence, a reversible electrochemical activity.
This work proposed a new ‘‘bipolar charging” mechanism that can
make flexible MOF materials have exceptional cyclic stability by
remarkably reducing the ionic traffic but don’t change the
conductivity.
3.2. MOFs composites for flexible supercapacitors
Nowadays, the requirement for mechanically flexible solid-
state devices is growing rapidly, so the main challenge we are fac-
ing is to make portable and wearable electronic products that more
flexible, ultra-thin, lightweight, and compact. The option of suit-
able materials to construct composite electrodes is a crucial factor
affecting the performance of FSSCs. In fact, numerous advanced
materials like carbon-based materials, metal oxide/nitride/
sulphide, conducting polymers (CPs), mxenes, polyoxometalates
(POM), black phosphorous and MOFs have been reported
[83–85]. Most of them show preferable electrochemical properties
in the aspect of energy density, cycle stability and specific capaci-
tance, so they have become the most attractive materials in the
field of FSSCs. However, although these advanced materials show
application potential, there are some limitations when used alone,
which is difficult to meet the needs of energy storage technology.
When pure MOFs are used as active ingredients of FSSCs, two
key issues are encountered: insufficient electrical conductivity
and structure stability. But when MOFs and conductive materials
are made into composite materials, synergistic effects can not only
amplify the advantages of individual materials, but also exhibit
new physicochemical properties to overcome their limitations.
Therefore, it is very important to develop MOFs-based composite
materials so as to increase the energy storage capacity [86–87].
In the following sections, we gave a summary of the synthesis
strategies and typical examples of MOFs composite materials for
FSSCs application.
3.2.1. MOFs/Conductive polymers composites electrode
CPs are a class of organic polymers that conduct through a
matrix of conjugated bonds. Its electrode function in SCs is based
on the faraday storage mechanism. CPs show a wide range of
potential applications in electrical energy storage equipment due
to low manufacturing cost, easy synthesis, good stability, reversi-
ble Faradaic redox capabilities and high pseudocapacitance. Many
studies are currently focus on the combination of CPs and MOFs to
J. Yan, T. Liu, X. Liu et al. Coordination Chemistry Reviews 452 (2022) 214300

Fig. 1. A) Schematic illustration of the two-step fabrication process of PANI-ZIF-67-CC electrode. After interweaving the MOF crystal with PANI, both electrons and electrolyte
can enter the MOF surface and EDLC is formed on the surface of the PANI-ZIF-67-CC electrode. B) Schematic illustration and optical photographs of PANI-ZIF-67-CC flexible
solid state SC device. Reproduced from Ref. [89] with permission from the American Chemical Society, copyright 2015. C) Schematic illustration of interaction and carrier
conduction between PANI and UiO-66. Reproduced from Ref. [90] with permission from the Elsevier, copyright 2018. D) SEM and TEM images of ZnO-CC (a and b), ZnO@ZIF-
8-CC (c and d) and PANI/ZnO@ZIF-8-CC, and (e and f). E) schematic illustration of the fabrication process of PANI/ZnO@ZIF-8-CC. Reproduced from Ref. [92] with permission
from the Royal Society of Chemistry, copyright 2019.

prepare composite materials with excellent electrochemical per-
formance that can be used in FSSCs. Among them, poly(3, 4-ethyle
nedioxythiophene)(PEDOT), PPy and polyaniline (PANI) have been
widely reported owing to their high conductivity.
3.2.1.1. MOFs@Polyaniline. PANI, as one of the CPs with good elec-
trical activity, simple synthesis route and excellent stability, has
been broadly applied in the preparation of composite materials
to overcome the defects of MOFs [88]. A preparation strategy for
a flexible hybrid conductive electrode (PANI-ZIF-67-CC) was pro-
posed by Wang’s group [89]. The hybrid electrode is made by
depositing PANI on CC with a cobalt-based MOF crystal (ZIF-67).
The PANI chains act as a medium for electronic transportation to
enhance the Faradaic process on the interface and thus greatly
improve the conductivity of the MOF. The superiority of the flexi-
ble electrode material comes from the synergistic effect of effec-
tively combining the electric double layer capacitor (EDLC)
capacitance generated by MOFs and the pseudocapacitance gener-
ated by PANI (Fig. 1A. At a scan rate of 10 mV s 1, the maximum
areal capacitance of the PANI-ZIF-67-CC composite electrode could
reach 2146 mF cm 2, which is about three times as much as the
ZIF-67-CC. Besides, PANI-ZIF-67-CC was used as the electrode
material and H2SO4/PVA served as the gel electrolyte to fabricate
a FSSCs (Fig. 1B). At a current density of 0.05 mA cm 2, the areal
capacitance of the device was as high as 35 mF cm 2, and the
capacitance retention rate can still reach 80% after 2000 cycles,
showing excellent cycle stability. In the following years, many sim-
ilar works were reported. Shao and colleagues [90] prepared the
composite electrode of UiO-66 and PANI for the first time via
in situ chemical polymerization, and then assembled a FSSCs with
H2SO4/PVA hydrogel as the electrolyte (Fig. 1C). Electrochemical
results indicated that the FSSCs can achieve a high specific capac-
itance of 647F g 1 at 1 A g 1, which is attributed to the non-
covalent p-p/NH-p interaction between two components that
leads to an increase of the conjugate delocalization length of PANI,
while effectively improving the carrier transfer ability. Moreover,
the UiO-66/PANI device also possessed high stability, it could keep
at 91% of capacitance retention even after 5000 cycles at 1 A g 1
and the bending tests showed that the UiO-66/PANI device still
maintained 90% of capacitive retention even after being bend at
180° for 800th. The MIL-series porous coordination polymers com-
posed of carboxylates and trivalent metal ions (Cr, Fe, Al) have the
advantages of large pores, good stability and large surface area.
Therefore, it also widely applied in the field of energy storage.
Wang et al. [91] obtained a PANI/MIL-101 composite electrode
through chemical synthesis, in which PANI grows in the pores of
MIL-101 to form an interpenetrating network. This well-designed
composite material exhibited high conductivity due to the forma-
tion of a strong bonding complex formed by the coordinated unsat-
urated metal sites in MIL-101 and the electron-rich imine groups
in PANI. The specific capacitance of PANI/MIL-101 electrode was
measured to be 1197 F g 1 at a current density of 1 A g 1. The test
results of the symmetric FSSCs assembled with the PANI/MIL-101
showed that it has good bending stability (90% of the initial capac-
itance can still maintained after of bending at 180° for 1000 cycles)
and cycle stability (capacitance retention rate after 10,000 cycles is
90%). At the same time, when four FSSCs were connected in series,
a red light-emitting diode (LED) with a rated voltage of 1.8 V can be
lit for 90 s.
In another case, Cao et al. [92] proposed a new method of ‘root-
etch-wrap’ to prepare hollow core–shell heterostructure electrodes
(Fig. 1D). Specifically, ZnO@ZIF-8-CC was prepared by etching pro-
cess, with ZnO hollow spheres (grown on CC) as the core and ZIF-8
as the shell. Subsequently, PANI was uniformly coated on the inner

7
J. Yan, T. Liu, X. Liu et al. Coordination Chemistry Reviews 452 (2022) 214300

Fig. 2. A) Schematic illustration of the fabrication of (a) ZIF-67 and (b) ZIF PPy. Reproduced from Ref. [64] with permission from the American Chemical Society, Copyright
2017. B) (a) Schematic illustration of the procedure for UiO-66/PPy-based flexible fiber supercapacitor device, SEM images of (b, c) carbon fibers, (d, e) UiO-66/PPy-coated
carbon fibers, and (f, g) surface and inside of gel electrolyte-coated fiber electrodes, (h) Digital photo and (i) SEM image of the UiO-66/PPy-based supercapacitor. Reproduced
from Ref. [99] with permission from the American Chemical Society, Copyright 2018. C) Schematic illustration of the procedure for PPy@UIO-66@cotton. Reproduced from
Ref. [100] with permission from Springer Nature, Copyright 2019. D) Schematic illustration of the procedure for PET/MOF/RGO/PPy composites. Reproduced from Ref. [101]
with permission from Elsevier, Copyright 2020. E) Schematic illustration of the procedure for Cu-CAT-NWAs/PPy. Reproduced from Ref. [68] with permission from Wiley-
VCH, copyright 2019.

and outer surfaces of ZnO@ZIF-8-CC to form a dense nano-coating
to prepare a PANI/ZnO@ZIF-8-CC composite electrode. The sche-
matic diagram of the entire production process of PANI/ZnO@ZIF-
8-CC is shown in Fig. 1E. Owing to the synergistic effect, the com-
posite electrode of core–shell structure had an ultra-high area
capacitance of 4839 mF cm 2 at a current density of 5 mA cm 2,
which is significantly higher than that of ZnO@ZIF-8-CC and
PANI-CC. When directly used it as symmetric FSSCs electrode, the
capacitance loss of this composite electrode was just 13% even
after 10,000 cycles. As mentioned earlier, textile electrode materi-
als have also received widespread attention with the fast growth of
electronic textiles and wearable electronic devices. However, the
electrochemical performance of textile-based materials is not sat-
isfactory. Therefore, it is always combined with some electroactive
materials (like CPs, metal oxides and carbon-based materials, etc.)
to prepare composite electrodes. Recently, Liu and colleagues fab-
ricated a textile electrode by coating ultrathin graphene nanosheet
layers on primary cotton fibers. The specific capacitance of the cot-
ton/graphene textile electrode could reach 40 F/g when the scan-
ning rate was 5 mV s 1. Subsequently, a three-dimensional
textile electrode material (PANI/ZnO/ZIF-8/G/PC) was prepared
with a strategy similar to which mentioned in the previous work.
This electrode exhibited more excellent electrochemical perfor-
mance than other textile electrodes and it remains stable under
different mechanical deformations. The acquired PANI/ZnO/ZIF-8/
G/PC electrode realized the high area capacitance of 1.378 F cm 2
when the current density was set at 1 mA cm 2. The reason for
excellent electrical performance of the hybrid electrode was that
the graphene layer, ZnO and PANI formed a three-dimensional por-
ous conductive network that promoted the faradaic process of the
interface. When the power density was 1542 lW cm 3, the energy
8
density of the FSSCs assembled by the PANI/ZnO/ZIF-8/G/PC elec-
trode had a high energy density of 235 lWh cm 3, [93–94].
3.2.1.2. MOFs@Polypyrrole. PPy, as a CP with nanotube form, simple
synthesis process, high conductivity, excellent ductility and good
flexibility, has been generally applied in energy storage devices,
drug delivery systems and biosensors [95]. The volume specific
capacitance of PPy can reach 400–500F cm 3, and it can easily
adapt to various forms while maintaining great electrochemical
performance due to its excellent flexibility. Recently, with the
development of flexible electronic devices (such as wearable sen-
sors, flexible watches, flexible smartphone), PPy has become one
of the most promising flexible electrode material additives due to
its rapid charging and discharging process, high energy density,
environmental stability and easy adaptation to different forms
[96–97]. Yamauchi and colleagues [64] proposed a new strategy
to enhance the electrochemical properties of MOF particles by uti-
lizing PPy tubes as the conductive interconnecting framework to
support zeolitic imidazolate framework ZIF-67 to in-situ grow
(Fig. 2A). This structure can maintain the porous structure of MOFs,
while the PPy tubes play the dual role of binder and dispersant,
which can connect or disperse MOFs particles to form a conductive
network. Driven by such well-designed MOF-PPy network, the
MOFs particles of ZIF-PPy network indicated the capacitance of
597.6 F g 1, higher than that (99.2 F g 1) of the pristine ZIF-67.
After assembled into FSSCs with the ZIF-PPy electrodes (flexible
graphene paper as current collector) and the PVA/Na2SO4 gel
served as electrolyte, the device delivered a maximum energy den-
sity of 0.0113 mW h cm 2 with a power density of 0.12 mW cm 2.
In addition, the PPy tubes also serve as an interconnection frame-
work to effectively improve the mechanical properties of MOF and
J. Yan, T. Liu, X. Liu et al.
maintain rapid electron/ion diffusion even under bending condi-
tions [98]. Therefore, the ZIF-PPy-based FSSCs device showed an
outstanding mechanical property, which CV curve just changes
slightly under different bending conditions.
Duan and co-workers [99] formed MOF/PPy hybrid electrodes at
the presence of dopamine in which UiO-66/PPy -was uniformly
deposited on the surface of CNFs using a facile one-pot electrode-
position process (Fig. 2B). The CNFs@UiO-66/PPy hybrid used as
electrodes to assemble FSSCs with PVA/LiCl as a gel electrolyte.
The device achieved an energy density and power density of
12.8 lWh cm 2 and 2102 lW cm 2 respectively, and also showed
excellent specific capacitance of 206 mF cm 2. Furthermore, the
FSSCs exhibited a good cycling stability (even after 10,000 charg-
ing/discharging cycles retained 89% of the initial capacitance)
and superb flexibility (96% of its initial capacitance was maintained
after 360° bending actions for 1000 times). It is worth noting that
the device showed a wide operating temperature range, and no sig-
nificant capacitance loss was observed during 100 repeated cool-
ing/ heating ( 15 °C to 100 °C) cycles. Recently, Zhang et al.
[100] constructed a PPy@UIO-66@cotton electrode for flexible
all-solid-state device, as shown in Fig. 2C. Much enhanced
conductivity of 14.29 S cm 1 for PPy@UIO-66@cotton electrode
in a two-electrode test system was obtained compared with the
binary PPy@cotton without UIO-66. As a result, the fabric electrode
displayed remarkable specific capacitance values 565F g 1 at a
current density of 0.8 mA cm 2 and showed stable cyclic behavior
as 90% capacitance retained over 500 galvanometric cycles.
Some researchers have also combined PPy&MOFs with carbon-
based materials to buffer their volume changes during the doping/
de-doping process and further improve the stability and cycle
ability of SCs devices. Barakzehi and co-workers [101] fabricated
a FSSCs by using binder-free and flexible electrodes which were
separated by a cellulosic membrane. This electrode was a ternary
composite coated fabric electrode formed by layer-by-layer assem-
bly method. First, Al-based MOF (MIL-53) was deposited layer by
layer on the modified PET surface, and then graphene oxide was
coated on PET/MOF-x to form a second layer, and it was further
reduced to graphene. Finally, the third layer is formed by in-situ
polymerization of PPy on PET/MOF-x/RGO (Fig. 2D). At a sweep
rate of 1 mV s 1, the composite electrode exhibited the areal
capacitance of 510 mF cm 2. The FSSCs device assembled by the
composite electrode yielded a remarkable volumetric capacitance
of 3.5F cm 3 and a power density of 0.6mW cm 3. The device (after
12 months of storage) also possessed high stability (85% of capac-
itance retention) even after 1000 continuous cycles. Besides,
supramolecular assemblies constructed through the encapsulation
of CPs by macrocyclic molecules have attracted increasing interest
in the fields of supramolecular chemistry and electrochemistry. Liu
et al. [102] firstly uploaded ZIF-8 onto carbon nanotube film (CNTF)
and further electrically deposited macrocycles and PPy to gain the
flexible conductive electrodes. They chose five different
supramolecular macrocycles to campare the electrochemical per-
formances of FSSCs. As a result, FSSCs device could realize an excel-
lent high areal capacitance of 1533 mF cm 2 at 5 mV s 1.
So as to farther increase the kinetics and energy storage perfor-
mance of MOF-based FSSCs, in recent years, many different types
of new MOFs with inherent conductivity have been developed.
However, since the conductive MOFs are usually in the form of pel-
lets or powders, a large amount of binders are required in the pro-
cess of electrode preparation, while inactive binders often damage
the electrochemical performance of devices. To solve this problem,
Xia and co-workers [68] proposed an effective strategy for the
preparation of MOFs hybrid nanostructured FSSCs electrodes (Cu-
CAT-NWAs/PPy) without substrates, additives and binders. The
integrated electrode is prepared by the controllable growth of
Cu-CAT-NWAs on the surface of PPy film which prepared by the
9
Coordination Chemistry Reviews 452 (2022) 214300
electro-polymerization process. The complete production process
was shown in Fig. 2E. The Cu-CAT-NWAs/PPy hybrid electrode
exhibited outstanding mechanical flexibility and superb electro-
chemical properties, in which the PPy substrate with good
mechanical flexibility could provide extra capacitance and an
effective charge transfer skeleton, while the conductive Cu-MOFs
nanowire array possessed high conductivity and sufficient active
surface area to make it fully contact with electrolyte. The hybrid
Cu-CAT-NWAs/PPy electrode exhibited areal capacitance of 463
mF cm 2 at a current density of 1.25 mA cm 2, which was approx-
imately fivefold higher than that of the pristine Cu-CAT MOF pow-
ders electrode. The optimized hybrid electrodes employed in FSSCs
with LiCl/PVA as a gel electrolyte and were demonstrated remark-
able electrochemical energy-storage performance, which can
achieve an areal capacitance of 252.1 mF cm 2 at the current den-
sity of 1.25 mA cm 2. It was significantly larger than some other
low conductive MOF-based SCs. The superb flexibility and stable
long-term electrochemical cycling life over a wide range of operat-
ing temperature of this FSSCs were also achieved, which main-
tained a capacitance retention of 91% after 1000 bending cycles
(180°), a capacitance decrease of only 10% over 8000 charging/dis-
charging cycles, and no obvious capacitance decay even under 100
repeated cooling ( 20 °C)/heating (100 °C) circulations. The excel-
lent electrochemical performances could be ascribed to the syner-
gistic effect of PPy substrate and Cu-CAT-NWAs.
Moreover, Zhao et al. [103] prepared wrinkled 2D ultrathin 5,
10, 15, 20-tetrakis (4-carboxylphenyl) porphyrin copper(II) (Cu-
TCPP) nanosheets and further composited with PPy via the
surfactant-assisted synthetic method, electrophoretic deposition
method and electrochemical polymerization technology. In the
energy storage process, the synergistic effect of Cu-TCPP and PPy
shortens the electrolyte ion transport path, provides a macrop-
orous channel and a 3D conductive network for fast ion/electron
transport. The FSSCs based on Cu-TCPP/PPy had a high surface
capacitance of 65.4 mF cm 2 at a current density of 0.2 mA cm 2,
and a maximum energy density of 2.27lWh cm 2 at a power den-
sity of 50lWcm 2.
3.2.1.3. MOFs@Poly(3, 4-ethylenedioxythiophene). PEDOT, as a kind
of pseudocapacitive CPs with high charge storage capacity, good
conjugated backbone and large electroactive potential window,
has become a hopeful electrode material in the field of energy stor-
age [104–106]. However, due to its low porosity and relatively
poor mechanical properties, PEDOT is hindered from being used
as an electrode material in FSSCs. To solve this problem, PEDOT
is usually used in combination with other SCs materials. Among
them, MOFs can effectively alleviate the electrochemical perfor-
mance deterioration caused by the volume expansion and contrac-
tion of PEDOT during the intercalation/delamination process.
Therefore, the composite material of MOFs and PEDOT is expected
to be the most promising flexible electrode material, due to the
multiple path they provided for the transmission of electrons and
ions. Fu and colleagues [107] proposed a new strategy for prepar-
ing flexible conductive porous electrodes with PEDOT as a coating.
Firstly, the mixture of HKUST-1 and GO (H-G) was coated on the
carbon nanotube film, and then PEDOT was deposited on it by elec-
trochemical deposition. The optimized electrode (PEDOT/HKUST-
1-CNTF) was employed in a FSSCs, which delivered an areal capac-
itance of 37.8 mF cm 2 (at a scanning rate of 5 mV s 1), volumetric
energy density of 0.051 mWh cm 3 and power density of 2.1 mW
cm 3. Moreover, the FSSCs also exhibited long-term electrochemi-
cal cycling stability and excellent mechanical flexibility. Subse-
quently, the research team adopted a similar strategy to
electrodeposit a mixture of PEDOT and GO on the UiO-66 to
prepare a flexible hybrid electrode (noted as PEDOT-GO/U-C)
[108]. After assembled into FSSCs with PVA/H3PO4 as the
J. Yan, T. Liu, X. Liu et al.
polymer-gelled electrolyte, the PEDOT-GO/U-C FSSCs also had high
stability (89% of its initial capacitance retention) even after 1000
continuous cycling at the scan rate of 80 mV s 1. Moreover, the
fatigue test revealed the excellent mechanical properties of the
PEDOT-GO/U-C device which can be twisted and folded arbitrarily
without destroying the electrochemical performance.
Some other material also been reported to combine with the
PEDOT&MOFs composites to enhance the flexible electrochemical
properties. Wang et al. [109] chose one kind of Zr-based MOF,
PCN-224, in situ grown on the CC and linked PEDOT/PMo12 by elec-
trodeposition method. The ‘‘conductive ink” PEDOT was used to
enhance the conductivity, and the [PMo12O40]3- with greater elec-
tron transfer ability was used to contribute capacitance. The PCN-
224@PEDOT/PMo12-CC-II exhibited the outstanding mechanical
flexibility, an excellent energy density, and good long-term cycle
ability when it as FSSCs electrodes.
3.2.2. MOFs/Carbon-Based materials composites electrode
Carbon-based electrode materials are attractive for energy stor-
age devices because of their remarkable chemical/thermal stabil-
ity, flexibility, high electrical conductivity, and light weight.
Generally, carbon-based materials are applied as EDLC electrodes
which can electrostatically reserve charge at the electrode–elec-
trolyte interface [110]. The advantages of EDLC include high rate
capability and superb cycle stability, which can still maintain
95%–100% of its premier capacitance even undergo 1000–10000
cycles. However, the energy density of the pure carbon-based
material electrode is relatively low due to the limitation of the
physical charge storage mechanism of the EDLC. In order to mind
the increasing requirement for energy storage devices with excel-
lent electrochemical performance, it is very urgent and necessary
to combine other pseudocapacitive materials with carbon-based
materials to improve the energy density of the device. At present,
the preparation of composite materials by MOFs and carbon-
based materials (such as AC, graphene, CNTs, etc.) exhibit better
charge transfer characteristics, so it have been proved to be a pos-
itive approach to enhance the electrochemical properties of FSSCs
electrodes.
3.2.2.1. MOFs@Carbon nanotubes. CNTs are a kind of typical carbon
materials with nano columnar structure. Due to its unique one-
dimensional (1D) nanostructure, CNTs exhibit excellent electrical
properties and good thermal/mechanical stability, such as low
internal resistance, high current load stability and high specific
volume. Therefore, CNTs have been widely concerned in energy
storage and other fields since they were reported in 1991 [111].
A flexible electrode (denoted as PANI-CNTs@ZIF-67-CC) with hier-
archical porous nanostructures was prepared by Song and co-
workers [112]. Electrochemical studies exhibited that the specific
capacitance of the PANI-CNTs@ZIF-67-CC hybrid electrode was
3511 mF cm 2 at a scanning rate of 10 mV s 1, which was much
larger than the electrodes without CNTs or PANI. The hybrid elec-
trode also had high stability (83% of initial capacitance retention)
undergo 1000 continuous charging/discharging cycles at
0.5 mA cm 2 of current density. The excellent electrochemical per-
formance could be ascribed to two aspects. On the one hand, por-
ous ZIF-67 was surrounded by plenty of CNTs, and some CNTs
passed through the ZIF-67, which greatly enhanced the electrical
conductivity of the nanocomposite. On the other hand, the syner-
gistic effect of CNT@ZIF 67-CC and PANI enhanced the electric dou-
ble layer capacitance and ascribed the Faraday pseudocapacitance.
The potential range of manganese-based materials is larger than
other metal-based materials, so it has been widely used as an elec-
trode material in the field of energy storage. Zhang and colleagues
[113] proposed a new strategy for preparing composite materials
by incorporating CNTs into Mn-based MOFs. CNTs can provide con-
10
Coordination Chemistry Reviews 452 (2022) 214300
tinuous conductive network and strong mechanical support for
composite materials, so the strategy can effectively improve the
structure flexibility, cycle stability and electrochemical perfor-
mance of Mn-based MOFs materials. When the CNTs@Mn-MOF
composite material was applied to the electrode material of the
Mn-based SCs, it showed excellent specific capacitance at
20 A g 1 (15 times higher than pure Mn-MOF). The assembled
FSSCs exhibited excellent performance, with maximum energy
density and power density of 6.9 W h kg 1 and 2240 W kg 1,
respectively. In addition, at the current density of 5 A g 1, the high-
est specific capacitance maintained 83% after 3000 charging/dis-
charging cycles.
So far, the composite materials of MOFs and CNTs have not been
fully explored as FSSCs materials. The results of several early stud-
ies in this review provide new ideas for researchers to improve
composite electrode materials for new FSSCs with higher energy
and power density.
3.2.2.2. MOFs@Graphene nanocomposites. The two-dimensional
structure of graphene makes it have excellent mechanical proper-
ties, carrier mobility, electrical conductivity, and Young’s modulus
value. In addition, its specific surface area (2630 m2 g 1) is larger
than CNTs and does not change with the pore size distribution,
which makes graphene more suitable for charge storage than other
carbon materials and shows the potential to change the current
energy storage pattern [114,115]. The pyridine and carboxylate
groups of graphene-based materials can enhance the coordination
bond to regulate the growth of MOFs, and they can participate in
the bonding because the presence of aromatic sp2 domains and
ionic groups, thereby further improving the comprehensive perfor-
mance of MOFs. Therefore, the introduction of graphene and its
derivatives (like graphene oxide (GO) and reduced graphene oxide
(RGO)) can combine the advantages of various components, allevi-
ate their shortcomings, and then obtain a composite electrode with
high selectivity, high conductivity and good stability [116,117]. It
should be noted GO is the product of graphene after oxidation. It
has rich surface functional groups and high catalytic activity.
RGO is reduced on the basis of GO, it is stable because of lost func-
tional groups. Here, we regard them as derivatives of graphene.
Zhou and co-workers [118] prepared Ni-MOFs@GO nanosheets
by in-situ hybrid method (Fig. 3A). Owing to the plentiful oxygen-
containing functional groups on the surface of GO nanosheets, the
continuous contact between Ni-MOFs and electrolyte was ensured,
which can store energy through Faraday reaction at high current
density. In addition, the unique flower like structure of Ni-
MOFs@GO and the synergistic effect between the components
made the composite material exhibit excellent electrochemical
performance. When the current density was 1 A g 1, the capaci-
tance of Ni-MOFs could be increased from 1457.7 F g 1 to
2192.4 F g 1 by adding 3 wt% GO. In addition, when the current
density was 10 A g 1, the capacitance retention of the composite
electrode could also be increased from 83.5% to 85.1% (after 3000
cycles). A different strategy for solving the lack of conductivity of
MOFs was proposed by Cheng and co-workers [65]. Based on the
metallic polyester fabric (MPF), they constructed a flexible fabric
electrode coated with sphere-flake-sphere structure formed by
RGO and Ni-MOFs, in which the spherical Ni-MOFs sphere and
RGO flakes were layered to form a sandwich structure (the fabrica-
tion process is shown in Fig. 3B. At 4 mA cm 2, the RGO/Ni-MOF/
metallic fabric electrode exhibited an areal capacitance of 260
mF cm 2. The FSSCs -were assembled with RGO/Ni-MOF/fabric
electrodes as flexible positive electrode and PPy fiber electrode as
flexible negative electrode (Fig. 3C), which delivered an areal
capacitance of 95 mF cm 2, an energy density of 7.72 mWh cm 2
and a power density of 3.07 mW cm 2. The FSSCs also showed a
J. Yan, T. Liu, X. Liu et al. Coordination Chemistry Reviews 452 (2022) 214300

Fig. 3. A) Schematic illustration of in-Situ Hybrid of Ni-MOFs with GO Nanosheets. Reproduced from Ref. [118] with permission from the American Chemical Society,
copyright 2016. B) Schematic illustration of fabrication process of RGO/Ni-MOF/metallic fabric electrodes. C) Schematic illustration of all-solid-state asymmetric fabric
supercapacitor. Reproduced from Ref. [65] with permission from Elsevier, copyright 2019. D) Schematic illustration of fabrication process of ZIF-67/RGO composite electrodes
and the electrochemical performance test of the symmetric supercapacitor. Reproduced from Ref. [124] with permission from the American Chemical Society, copyright 2018.

good cycling stability even after 1500 charging/discharging cycles
and retained 70% of the initial capacitance.
Composite materials prepared by RGO and different types of
MOFs really show significantly improved electrochemical perfor-
mance compared to a single component. Zhou and co-workers
adopted the method of adding RGO to HKUST-1 to prepare a
new composite material FSSCs with good electrochemical perfor-
mance and good mesoporous structure [119]. This method solved
the problem that the application of pure HKUST-1 was limited
due to its poor microporous structure and conductivity. The
hybrid electrode prepared by coating 10 wt% RGO/HKUST-1 on
flexible carbon fiber paper, the maximum specific capacitance of
this electrode at a current density of 1 A g 1 was 385 F g 1, which
was much higher than pure HKUST-1 (0.5 F g 1). This device
exhibited excellent electrochemical performance, its specific
power and specific energy were 3100 W kg 1 and 42 Wh kg 1,
separately. In addition, the FSSCs could power a rotating 3 V
motor for 9 min. Similarly, one-pot co-synthesis of a dual Ni/
Co-MOF-RGO nanocomposite coated on NF was reported by Mir
F. Mousavi et al, [120] which also showed the good electrochem-
ical performance. A high-performance RGO/Cu-MOF fiber elec-
trode with a hierarchically porous structure was prepared by
Wang et al. [121]. The assembled FSSCs delivered high energy
density. Later, Bian et al. [122] grew conductive Cu-MOF nanorod
arrays on the RGO-coated polyester (RGO/PET) yarn. This FSSCs
electrode also had excellent mechanical flexibility and electro-
chemical performance.
The properties of FSSCs -are not only decided by the electrode
material, the electrolyte is also critical to the overall performance
of the device such as the cycle stability and energy density. At pre-
sent, some redox active species (e.g. KI, K3[Fe(CN)6], hydroquinone)
can be selected as alternatives to aqueous and organic electrolytes
or mixed use with some aqueous electrolytes. Some studies have
shown that redox additive electrolytes (RAEs) can improve the
electrochemical performance of FSSCs effectively [123]. Sundriyal
and co-workers reported for the first time that in the presence of
optimized RAE solution (prepared by adding 0.2 M K3[Fe(CN)6] to
1 M Na2SO4), ZIF-67 and RGO were used to prepare large specific
surface area hybrid SCs electrode, which showed better electrolyte
ion diffusion and electron transport characteristics than pure ZIF-
67 [124]. The ZIF-67/RGO-redox system exhibited superb specific
capacitance (1453 F g 1) at a current density of 4.5 A g 1 and its
cyclic stability was outstanding, even after 1000 charge–discharge
cycles, the capacitance only decreases 9.5% of the initial value.
Moreover, the FSSCs device was also constructed based on the
obtained ZIF-67/RGO composite electrodes, which exhibited a high
energy density of 25.5 Wh kg 1 at 2.7 kW kg 1 and a capacity
retention of 88.8% after 1000 cycles, as shown in Fig. 3D. Two FSSCs
connected in series could power a white LED for up to three min-
utes. Composites of ZIF-67 with RGO showed highly improved
electrochemical properties than that of the earlier reported MOF-
based devices. The most important thing was that this proposed
design had a wide range of versatility, which can be extended to
prepare FSSCs devices with excellent performance.

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J. Yan, T. Liu, X. Liu et al. Coordination Chemistry Reviews 452 (2022) 214300

Fig. 4. A) Schematic illustration of the synthesis route of the 2D-MOF/GO paper. B) Schematic illustration of the electrochemical performance of an asymmetric all-solid
supercapacitor based on C-M/G-40//N-M/G-40 mixed paper under different severe conditions. C) Schematic illustration of the process of the preparation of C-M/G-40//N-M/
G-40 asymmetric micro-supercapacitor devices on a substrate. Reproduced from Ref. [57] with permission from Royal Society of Chemistry, copyright 2018.

2D-MOF nanosheets have more accessible active sites and
specific surface areas than 3D bulk MOF crystals, and the electrons
formed in the atomic thickness nanosheets made them become
very promising in the field of preparing binder-free electrodes.
However, the development of 2D-MOF as a flexible thin-film elec-
trode has been greatly restricted owing to the lack of solution pro-
cessing capabilities and the ability to integrate into devices from
rigid powder samples. A new type of 2D MOF, the
phthalocyanine-based (Ni2[CuPc(NH)8]) nanosheets, prepared by
ball milling mechanical exfoliation approach and introduced by
Feng et al. [125] The ultrathin nanosheets in this 2D MOF possess
facile solution-processability and high utilization of active sites.
Finally, the FSSCs were constructed by confusing Ni2[CuPc(NH)8]
nanosheets with exfoliated graphene. It not only displays out-
standing cycling stability, but also has high areal capacitance up
to 18.9 mF cm 2, which surpasses most of the reported CPs-
based and 2D materials-based FSSCs.
Moreover, the application of 2D-MOFs in electrode preparation
also encountered some obstacles, because the strong Vander Waals
interaction between the adjacent nanosheets makes the large-
sized 2D-MOF sheets prone to aggregation and face-to-face self-
restacking, which significantly deteriorates the approachability to
electrolyte ions as well as damages the electrochemical perfor-
mance of devices. Cheng and colleagues [57] proposed a way to
enhance the properties of 2D-MOF electrode materials by intro-
ducing highly conductive graphene sheets into 2D-MOF sheets in
a controlled manner to form an alternating graphene/MOF layers
structure. They prepared MOF/RGO hybrid papers by electrostatic
self-assembly method (Fig. 4A) showed the process of electrostatic
self-assembly. Specifically, the GO nanosheets can be attached to
the surface of the MOF nanosheets through strong electrostatic
attraction due to the GO nanosheets were electronegative and
the as-prepared MOFs were intrinsically electropositive. Subse-
quently, the independent 2D-MOF/RGO hybrid papers with excel-
lent flexibility, good mechanical properties and high conductivity
(0.32 X cm) were obtained through a vacuum assisted filtration.
In addition, they proposed a one-to-two strategy, that is, the prepa-
ration of two types of porous electrodes (RGO/Co-MOF and RGO/
Ni-MOF) for FSSCs through a MOF-derived synthesis method. This
method only need to change the metal ion precursors. The FSSCs
device displayed a high volumetric power density of 250 mW cm 3
and an ultrahigh volumetric energy density of 1.87 mWh cm 3.
Moreover, the device also proved outstanding mechanical flexibil-
ity and bending resistance performance, which can still maintain
remarkable properties under different harsh service conditions
(as shown in Fig. 4B). In particular, this work also demonstrated

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J. Yan, T. Liu, X. Liu et al. Coordination Chemistry Reviews 452 (2022) 214300

Fig. 5. A) An all-solid-state hybrid flexible supercapacitor based on the obtained MnOx-MHCF composite and AC. Reproduced from Ref. [128] with permission from Wiley-
VCH, copyright 2016. B) Schematic illustration of one-pot hydrothermal synthesis of Co3O4@Co-MOF composite. Reproduced from Ref. [129] with permission from Oxford
University Press, copyright 2019. C) Schematic illustration of the synthesis of Co3O4/Ni-based MOFs on a CC. Reproduced from Ref. [130] with permission from Elsevier,
copyright 2018. D) Schematic illustration of the synthetic approach for the NiCo2O4@Ni-MOF core/shell hybrid arrays on CC. Reproduced from Ref. [133] with permission from
the American Chemical Society, copyright 2019. E) Schematic illustration of the fabrication of Co3O4@Ni-MOF composites. Reproduced from Ref. [131] with permission from
Elsevier, copyright 2021.

that planar flexible micro-supercapacitors can be assembled by
sputtering and plasma etching MOF/RGO hybrid papers (Fig. 4C).
After charging the two micro-supercapacitors in series for a few
seconds, the light emitting diodes (LEDs) can be successfully lit.
3.2.3. MOFs/Metal oxides composites electrode
Metal oxides have been intensively reported as electrode mate-
rials for energy storage and conversion. As we all know, many oxi-
des from the transition metal family (such as RuO2, MnO2, Co3O4)
can serve as SCs electrode materials because of its high specific
surface areas and even pore size distributions [126]. In fact, MOFs
themselves exhibit some pseudocapacitance because of the
valence variability of the metallic ions that can serve as redox cen-
ters. But the potential application of combining MOFs with metal
oxides as SCs electrodes has not been thoroughly explored. By
compositing with metal oxides, the performance of MOF-based
electrodes can be significantly increased owing to the synergistic
effect between MOFs and metal oxides. Therefore, it is far more
effective to develop fabrication strategies of metal oxides/MOFs
nanocomposites by introducing metal oxides into the MOF sys-
tems. For instance, a combination of ZIF-8 and SnO2 quantum dots
was fabricated as an electrode, whereby the SnO2 quantum dots
were uniformly deposited to a zeolite-type MOF through a simple
in-situ epoxide precipitation route, giving rise to a composite SnO2
quantum dots@ZIF-8 possessing good mechanical stability, greatly
improved active surface areas, leading to a high specific capaci-
tance [127]. The SnO2 quantum dots@ZIF-8 hybrid electrode
yielded a maximum specific capacitance of 931F g 1, which was
far higher than that realized with the use of bare ZIF-8 (99F g 1)
and SnO2 quantum dots (241F g 1).
In another study, a MnOx with MOF-manganese hexacyanofer-
rate hydrate (MHCF) composite material was synthesized and
applied as the electrode material of a FSSCs [128] (Fig. 5A). The
hybrid material was produced by a facile one-step chemically
induced self-transformation method, which lead to a three-fold
increase in specific capacitance. The specific capacitance of the
hybrid electrode was 1200 F g 1 at 10 A g 1. The electrochemical
performance of the MnOx-MHCF composite material was compared
with that of the pristine MOFs, which only had a capacitance of
300 F g 1 at the same scan rate. After a much higher electrical con-
ductivity (compared with MnOx) was recorded, the MnOx-MHCF
composite material and AC were used as active materials for the
two electrodes of a FSSCs electrode. The electrodes were attached
and separated via PVA/KOH solid electrolytes. The areal capacitance
of the fabricated FSSCs was 175 mF cm 2 at 0.5 mA cm 2. Further-
more, the device exhibited good electrochemical stability under dif-
ferent bending angles, almost without changing the CV curves at
180° of bending, and a capacitance retention of 94.5% after 10,000
charge/discharge cycles at 5.0 mA cm 2. In addition, the electrode
formed by electrodeposition of MnO2 over Ni-MOF achieved a

13
J. Yan, T. Liu, X. Liu et al.
specific capacitance of 244 F g 1, which was far better than that the
bare Ni-MOF (177.5 F g 1).
Under alkaline conditions, the chemical stability and electrical
conductivity of the pure MOF materials always decays rapidly.
Thus Zheng and co-workers [129] have sought to improve the elec-
trochemical properties by combining Co-MOF with Co3O4 nano-
cube to prepare a highly alkaline-stable metal oxide@MOF
composite (Fig. 5B). The hybrid material with a unique characteris-
tic structure was prepared via a hydrothermal reaction. The as-
prepared composite exhibited high alkaline stability, which origi-
nal structure was retained even in 3.0 M KOH for 15 days. Further-
more, this Co3O4@Co-MOF composite electrode delivered a
maximum specific capacitance of 1020 F g 1 at 0.5 A g 1 in
3.0 M KOH. Only a minor drop in capacitance (3.3%) was detected
after 5000 charge/discharge cycles. The FSSCs -were fabricated by
using Co3O4@Co-MOF composite as positive electrode and AC as
negative electrode. Interestingly, the FSSCs were able to retain
99.72% of its initial capacitance even, after 400 times of bending
cycles at different bending degrees. Similarly, unique core–shell
Co3O4/Ni-based MOFs were successfully anchored on a CC sub-
strate by a facile two-step hydrothermal method, which exhibited
an excellent specific capacity (209 mAh g 1 at 1.0 A g 1) and a good
cycling stability (90% retention after 3000 cycles) [130] (Fig. 5C).
Zhang et al. [131] anchoring Ni-MOF nanosheet on CC and using
ZIF-derived ribbonlike Co3O4 as integrated composite cathodes
for advanced hybrid SCs (Fig. 5E). The FSSCs fabricated by the Co3-
O4@Ni-MOF electrode and AC showed prominent energy density of
68.6 Wh kg 1 at the power density of 510 W kg 1, and excellent
cycling stability (about 12% capacitance loss after 5000 charge–dis-
charge cycles). Later, Zhang et al. [132] gave an effective strategy to
increase the overall electrical conductivity and active surface area
of MOFs by implanting conductive NiCo2O4 nanowires on CC in
advance. The prepared NiCo2O4@Ni-MOF electrode possessed an
ultra-high areal capacitance and exceptional rate capability. In
addition, the FSSCs were successfully constructed by using the
NiCo2O4@Ni-MOF and NiCo2O4@PPy as electrodes, achieving both
high volumetric capacitance and energy density. Li et al. [133] con-
trolled the growth of Ni-MOF arrays on the surface of NiCo2O4
nanowires by modulating the formation reaction of MOFs
(Fig. 5D). By making full use of the attractive advantages of NiCo2-
O4 core and Ni-MOF shell and their synergistic effects, the opti-
mized NiCo2O4@Ni-MOF hybrid electrode exhibited enhanced
electrochemical properties.
3.2.4. MOFs/other material composites electrode
Researchers are aware of other materials that have a two-
dimensional structure similar to graphene, such as lamellar transi-
tion metal dichalcogenides (MoS2, WS2) and metal hydroxides
(cobalt hydroxide, layered metal carbides/nitrides) also have the
potential to become electrode materials for high energy density
FSSCs [134]. Moreover, cobalt/nickel sulfide materials, such as
Co3S4, CoS2, Co9S8, Co1-xS, CoxSy and NiS2 also have gained atten-
tion for their wide stoichiometric composition and good stability.
Therefore, combining these materials with MOFs to assemble the
FSSCs also the potential research areas.
Yang et al. [135] used the MoS2 expands in the accordion-type
Ni-MOF layers, and -S- joins the two materials to form a Ni-MOF
coating MoS2 composite structure. The prepared MoS2@Ni-MOF
combined the structural characteristics of the Ni-MOF and MoS2,
thus the improved electrochemical performance. The assembled
all-solid-state MoS2@Ni-MOF//AC can illuminate commercial red
LED lamps for up to 30 s.
NiS2 is quite suitable as SCs electrode materials due to the
variation in the chemical valence of Ni ions, high safety and out-
standing specific capacitance. Chen et al. [136] reported Ni-
MOF@NiS2 nanosheets electrode on CC by using Ni-BTC and Na2S,
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Coordination Chemistry Reviews 452 (2022) 214300
which showed the excellent cycling stability and rate performance
when it as all-solid-state asymmetric Ni-MOF@NiS2//AC device
(Fig. 6A).
Some of other material, such as cellulose nanofibers, zinc oxide
(ZnO), also be applied to MOFs-based FSSCs. ZnO is generally
applied in gas sensors, solar cells, and short-wavelength light-
emitting devices attributed to its fantastic optical and electrical
properties. Since ZnO holds a high energy density of 650 A g 1, it
is a good choice for FSSCs application. Zhu et al. [137] constructed
hierarchical ZnO@MOF@PANI on CC for SCs electrodes via elec-
trodeposition and hydrothermal methods. Among them, ZnO
nanorods not only served as a scaffold for supporting MOF@PANI
shell due to its effective channel for electron transport but also
as a self-sacrificial template that supply Zn2+ ions for MOF (ZIF-
Zn) formation, which demonstrated good rate capability and
cycling stability (Fig. 6D).
Zhou et al. [138] reported on the fabrication of c-MOF nanolay-
ers on cellulose nanofibers by vacuum filtration of the suspension
(Fig. 6B). The obtained freestanding cellulose nanofibers@c-MOF
nanopapers demonstrated high electrical conductivity, hierarchical
porosity, mechanical strength, and flexibility. Bending (90, 120°) or
even folding (180°) the device has no influence on the CV curves.
MXene is a general term for a new class of two-dimensional lay-
ered metal carbides, nitrides or carbonitrides. It has high conduc-
tivity, abundant surface functional groups, strong hydrophilicity,
high pseudocapacitance behavior, storage and release in ion inser-
tion and extraction as well as the negligible volume changes in the
process, which endow them promising candidates for FSSCs. Huang
et al. [56] reported a 3D interconnected ‘‘MPFs-to-MXene-to-MPF
s” conductive networks that formed by the alter insert of MXene
and 2D metal-porphyrin frameworks (Fig. 6C). This structure
affords to accelerate the ionic/electronic transport rates. The FSSCs
showed the areal energy density of 20.4 mW h cm 2, an areal capac-
itance of 408 mF cm 2, and capacitance retention of 95.9% after
7000 cycles.
3.3. MOFs derived composites for flexible supercapacitors
The two disadvantages of MOFs materials are: low conductivity
and poor stability. The poor chemical stability is owing to the nat-
ure of bonding in MOF structures where unlike covalent bonds of
many materials, MOFs are formed through reversible coordination
bonds between metal ions and organic linkers [139]. A good solu-
tion is construct the MOFs with good stability according to the
principle of soft, hard acid and alkali, such as high-valent metal
carboxylate skeleton, low-valent metal nitrogen-containing ligand
skeleton. Based on these stable MOFs materials as templates, dif-
ferent MOFs derivative materials can be obtained, such as porous
carbon, metals oxide, metal sulfide, metal hydroxide materials,
and metal selenide, phosphide. Moreover, the N, S, B and P-
doped MOF derivative can be obtained by adjusting the types of
ligands or additional adding N source, S source, B source, P source.
These above-mentioned materials can be used as excellent FSSCs
materials, the following will be introduced one by one.
3.3.1. MOFs derived porous carbon composites electrode
The MOFs have become the most attractive precursor template
for the preparation of porous carbon due to its self-installable
structural characteristics, high surface area and adjustability, high
porosity and high carbon content, especially the Zn-based MOFs or
Al-based MOFs. When calcined under inert gas above 900 °C, the
Zn element in Zn-MOFs will volatilize. Therefore, the Zn-MOFs usu-
ally selected as the precursor of porous carbon.
As one of example, Han et al. [140] synthesized one of the hier-
archical porous carbon materials by using a typical microporous
MOF (Zn(tbip)) that consisting of tbip linkers (tbip = 5-tert-butyl
J. Yan, T. Liu, X. Liu et al. Coordination Chemistry Reviews 452 (2022) 214300

Fig. 6. A) Schematic representation of the fabrication of Ni-MOF@NiS2 nanosheets arrays. Reproduced from Ref. [136] with permission from Elsevier, copyright 2020. B)
Schematic of synthesis procedure for cellulose nanofibers@c-MOF hybrid nanofibers. Reproduced from Ref. [138] with permission from the American Chemical Society,
copyright 2019. C) Schematic illustration of the synthesis and application of interlayer hydrogen-bonded MXene/MPFs films through a vacuum filtration method. Reproduced
from Ref. [56] with permission from Wiley-VCH, copyright 2019. D) Schematic illustration of the formation of ZnO@MOF@PANI nanoarrays on CC. Reproduced from Ref. [137]
with permission from Elsevier, copyright 2018.

isophthalate) and Zn metal ions as the precursor. Then, they used
these porous carbons to assemble FSSCs device, which exhibited
excellent mechanical and cycling stability, high energy density
and power density.
In addition to the direct pyrolysis of Zn-MOF, the combination
of Zn-MOF with other carbon materials (like CNTs or RGO) is also
a common strategy for preparing MOFs-derived carbon-based
composites. Wu et al. [141] prepared the hierarchical 3D all-
carbon electrode materials by assembling N-doped RGO quantum
dots (N-GQDs) on carbonized MOFs materials (cZIF-8) interweaved
with CNTs, which exhibited an energy density of 14 Wh kg 1 with
a power density of 89.3 W kg 1 and the 82% capacitance retention
after 5000 cycles attributed to the synergistic effect and hierarchi-
cal assembly of these components when it a assembled as FSSCs.
Among them, N-GQDs served as highly pseudocapactive materials,
CNTs acted as the electrical conductive network and cZIF-8 pro-
vided a large accessible surface area. Similarly, the MOFs@-
graphene derived hierarchical carbon electrode was synthesized
via a facile and environmental friendly process [141]. The FSSCs
electrode had been demonstrated the superior specific capacitance,
good cycle life and excellent mechanical bending performance.
Similarly, Chen et al. [98] prepared the CNTs wired ZIF-8 struc-
ture via an in-situ growth method and then pyrolysis of CNTs/ZIF-8
composites directly to obtain the highly nitrogen-doped continu-
ous graphitic carbon nitride polyhedron (GCNP). A FSSCs based
on GCNP electrode and PEO/NBR IPN electrolyte exhibited a high-
level specific energy density of 59.40 Wh kg 1 at a current density
of 1 A g 1, which is qualified for a promising candidate for FSSCs.
Wang et al. [142] grew the CNTs on CC firstly, and then N-doped
carbon coated CNT nanoarrays (CNT@N-C) and NiCoP nanoflake-
surrounded CNT nanoarrays (NiCoP/CNT) were synthesized based
on CNT/CC, as shown in Fig. 7A. The CNT@N-C was derived from
CNT@ZIF-8 and utilized as anode materials for constructing FSSCs.
The flexible devices showed the maximum energy density of 138.7
Wh kg 1 and a power density of 6.25 kW kg 1.
Due to the particularity of the MOFs material, its metal atoms
can be provided by using the corresponding oxide as sacrificial
template. Inspired by this, a new type of porous N-doped carbon
nanofiber network membrane was synthesized by Zhang et al,
[143] in which a continuous ZIF-8-derived carbon layer ‘‘welded”
adjacent carbon nanofibers through bifunctional ZnO nanoparticles
contained in the nanofibers (Fig. 7D). Here, ZnO nanoparticles were
not only used as a pore former to form multi-scale pores, but also
provided a zinc source for the in-situ growth of the ZIF-8 nanopar-
ticle layer. Due to the highly interconnected network, special spi-
der web-like surface nanostructure and layered pores, the
prepared carbon film showed outstanding conductivity, high speci-
fic surface area and excellent wettability. The robust electrochem-
ical stability in severely bending states shown by the FSSCs devices
demonstrates the potential application in flexible power supplies,
as shown in Fig. 7C.
Duan et al. [61] grew the ZnO nanorod arrays on CC by low-
temperature hydrothermal method firstly, then the core–shell
ZnO@ZIF-8 prepared by growing ZIF-8 on ZnO nanorod arrays.
Finally, CTAs@NCBs were obtained by catalytically depositing a
carbonaceous layer on the surface of ZnO and carrying out a reduc-
tion and evaporation process, the specific process is shown in
Fig. 7B. The assembled FSSCs device maintained a stable energy

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J. Yan, T. Liu, X. Liu et al. Coordination Chemistry Reviews 452 (2022) 214300

Fig. 7. A) Schematic illustration for the synthesis of NiCoP/CNT/CC and CNT@N-C/CC. Reproduced from Ref. [142] with permission from Elsevier, copyright 2020. B) Schematic
illustration of the fabrication processes of hierarchically porous CTAs@NCBs. Reproduced from Ref. [61] with permission from Elsevier, copyright 2017. C) Digital photographs
of HPNWC in different bending states. D) Schematic illustration of the fabrication procedure of HPNWC. Reproduced from Ref. [143] with permission from Elsevier, copyright
2019.

supply under various bending states, indicating a promising appli- [147] reported a simple way to grow MIL-88-Fe derived spindle-
cation in flexible and wearable devices. like a-Fe2O3@C on oxidized carbon nanotube fiber (S-a-Fe2O3@C/
OCNTF) directly. The FSSCs assembled by S-a-Fe2O3@C/OCNTF//
Na-MnO2 NSs/CNTF possessed an exceptional energy density of
3.3.2. MOFs derived metal oxides composites electrode
135.3 lWh cm 2 and a high specific capacitance of 201.3 mF
Generally speaking, compared with carbon materials and CPs,
cm 2 (Fig. 8C). Sam S.Yoon et al. [148] demonstrated CNFs deco-
transition metal oxides possess a higher specific capacitance value
rated with MOF-derived Mn-doped ZnO can be successfully pre-
and significant advantages in energy density. It is verified that
pared and used for FSSCs. The Mn-doped zeolitic imidazolate
MOFs can be used as precursor of uniformly carbon/ metal oxides
framework (ZIF-8) was grown directly on electrospun polyacry-
composites. The MOFs derived metal oxides composites can pro-
lonitrile nanofibers by a simple solution-phase synthesis
duce some synergistic effects that the individuals cannot provide,
(Fig. 8E). Then Mn@ZnO/CNFs prepared by carbonizating these
have gained the more and more attention for FSSCs.
composite fibers, which is a robust electrode material for long-
Shin et al. [144] present a new combination of nickel oxide–car-
life time high-rate energy storage/delivery devices.
bon composites fabricated by directly carbonizing a nickel metal–
Generally, the conversion of MOFs to metal oxide requires high-
organic framework (Ni-MOF)@ CNFs for a self-standing electrode
temperature calcination. Electrochemical oxidation treatment is
of the supercapacitor application (Fig. 8A). The FSSCs showed a
also another method to achieve it. Chen et al. [149] prepared
good cycle stability from the long-term cycling test. Han et al.
Co3O4 supported on CC by electrochemical oxidation the Co-
[145] synthesised the Bi2O3@C microrod by pyrolysising Bi-based
MOF/CC (Fig. 8D). The FSSCs based on this electrode showed great
MOF (CAU-17) and used it as negative electrode for FSSCs, which
rate capability and cycling performance.
showed high energy density of 49 W h kg 1 at a power density
In addition to the use of MOFs directly to prepare metal oxides,
of 807 W kg 1. The other free-standing nanocellulose/ZIF-67
the growth of metal oxides on MOFs-derived carbon materials has
derived porous Co3O4 polyhedron hybrid dual-layer films were
also been developed by researchers as FSSCs. Guan et al. [63] has
successfully layer-by-layer assembled by a water-based paper-
developed 2D MOF derived nanocarbon nanowall (MOFC) arrays
making process [146] (Fig. 8B). The flexible NPC-60 film electrode
on CC by a simple solution + carbonization process. The final hier-
(the ratio of porous Co3O4 polyhedron to NFC component was
archical electrode materials showed an abrupt improvement of
60:30) had a higher capacitance (594.8 mF cm 2 at 5 mV s 1 in
areal capacitances after decorating ultrathin flakes of MnO2 and
6 M KOH) than other samples, and a power density of
Bi2O3 on the flexible CC/MOFC substrate. After that, they also
799.97 W kg 1 at the energy density of 18.75 Wh kg 1. Yao et al.
16
J. Yan, T. Liu, X. Liu et al. Coordination Chemistry Reviews 452 (2022) 214300

Fig. 8. A) Schematic illustration for the synthesis of Ni-MOF derived NiO/C@CNF composite. Reproduced from Ref. [144] with permission from Elsevier, copyright 2020. B)
Schematic illustration for the synthesis of flexible nanocellulose/porous Co3O4 polyhedron hybrid film. Reproduced from Ref. [146] with permission from Springer Nature,
copyright 2021. C) Schematic of the synthesis process of the S-a-Fe2O3@C/OCTNF electrode. Reproduced from Ref. [147] with permission from the American Chemical Society,
copyright 2018. D) Scheme of the formation process of Co3O4 hierarchical structure on CC. Reproduced from Ref. [149] with permission from Elsevier, copyright 2020. E)
Schematic of the fabrication of freestanding and flexible Mn@ZnO/CNF. Reproduced from Ref. [148] with permission from Elsevier, copyright 2019.

reported a series of Co-based MOF derived N-doped carbon arrays
embedded with different metal compounds (including Co3O4) and
then assembled an asymmetric FSSCs, which had a power density
up to 23.5 kW kg 1 and good cycling stability after long-time rapid
charging and discharging [150 151] (Fig. 9B).
Bimetallic MOFs are -the very promising precursor and tem-
plate for the preparation of MOFs derivatives, including the prepa-
ration of carbides and metal compounds. Its advantages are: 1) The
distribution of metals and doping atoms is controlled by adjusting
the structure of MOFs; 2) The framework of MOFs derivatives have
a large number of micropores and mesopores, which can provide
channels for the transfer of product gas. Therefore, the construc-
tion of bimetal MOFs derivatives is often used in FSSCs. Mai et al.
[152] developed a unique strategy that pairing the binder-free
NiCo2O4 ultrathin nanosheets supported on carbon fiber paper
(Ni-Co-O@CFP) as cathode and mixed bi-MOFs ZIF-8/ZIF-67
derived nanoporous nitrogen-doped carbon nanosheets (NPC) as
an anode to fabricate the hybrid SCs(NCO||NPC-HSC). The FSSCs
be demonstrated the negligible change in performance while bent
at different states. Xu et al. [153] using the ZIF-8@ZIF-67 on a
waste biomass of cosmetic cotton to prepare flexible nitrogen-
doped carbon heteroarchitectures (hetero-fNCs), which showed a
high energy density of 30 Wh kg 1 at 1440 W kg 1 and good capac-
itance retention of 89.5% after 5000 cycles. The ultrathin zinc-
cobalt oxide nanoflakes@N-doped carbon hollow nanowall arrays
(ZnCo2O4@NC NWAs) -were synthesised by cation ion-
exchanging and post annealing vertically aligned 2D Co-MOF solid
nanowall arrays [154]. When it used for FSSCs, the ZnCo2O4@NC/
CTs electrode exhibited great electrochemical performance with a
wide work voltage up to 2.0 V, high areal energy density of
0.278 mWh cm 2 and long-term cycling stability (85.89% capaci-
tance retention over 6000 cycles).
It is also often used as FSSCs when MOFs derived metal oxide
combined with other materials that with good electrochemical
properties, such as carbon material, CPs, Mxene, etc. Here are a
few examples of bimetal MOFs derived oxides combined with
other materials. For example, a MOF-derived Co-Fe oxide porous
nanorod was introduced into the freestanding MXene film to pro-
duce a high-performance flexible electrode with excellent
deformability and editability [155] (Fig. 9A). In the system, MXene
layer acts as a binder and conductive additive to coat Co-Fe oxide,
which can effectively facilitate charge transfer and maintain the
excellent flexibility of the film electrode. In the meantime, Co-Fe
oxide can work as a spacer, thereby expanding the interlayer

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J. Yan, T. Liu, X. Liu et al. Coordination Chemistry Reviews 452 (2022) 214300

Fig. 9. A): a) Schematic illustration of the synthesis of Co-Fe oxide/MXene composite film, b) The optical images of Co-Fe oxide/Ti3C2TX composite film at different
deformation statues. Reproduced from Ref. [155] with permission from Elsevier, copyright 2020. B) Left: Schematic illustration of the ‘‘one for two” fabrication process: 2D
Co3O4 nanosheets cathode and N-doped carbon nanosheets anode are obtained from the same Co-MOF precursor and assembled into a flexible asymmetric supercapacitor;
Right: cycling test result of the asymmetric supercapacitor with PVA-KOH gel electrolyte. Reproduced from Ref. [151] with permission from Royal Society of Chemistry,
copyright 2016. C) Schematic diagram of the synthesis of ZnCo2O4@NiCo2S4@PPy core–shell nanosheets on NF. Reproduced from Ref. [157] with permission from IOP
Publishing, copyright 2021. D) Preparation Processes for GO/MOF and RGO/MOF-Derived Composite Aerogels. Reproduced from Ref. [161] with permission from the American
Chemical Society, copyright 2017. E) Schematic diagram of the formation of CC/SiCNWs@NiCo2O4 NAs. Reproduced from Ref. [159] with permission from Elsevier, copyright
2021. F) Schematic diagram of the formation of Co-MOF/Ti3C2Tx composite. Reproduced from Ref. [162] with permission from Elsevier, copyright 2018.

distance, improving the ion transmission path in the electrode. The
NiFe2O4/NiCo2O4/GO composites -have been successfully prepared
by FeNi-MIL-88/NiCo-MOF-74 as precursor [156]. The FSSCs
assembled by NiFe2O4/NiCo2O4/GO as positive electrodes and AC
as negative electrodes showed excellent cycle stability and an out-
standing energy density.
The core–shell ZnCo2O4@NiCo2S4@PPy nanosheets -were con-
structed via three-step methods. Firstly, growing the MOFs derived
leaf-like ZnCo2O4 nanosheets on NF through chemical bath deposi-
tion and annealing methods. The second and third step are com-
bining with NiCo2S4 and PPy by electrodeposition methods,
respectively. The ZnCo2O4@NiCo2S4@PPy/NiF electrode exhibited
the maximum areal capacitance (3.75 F cm 2) and specific capaci-
tance (2507.0 F g 1) at 1 mA cm 2 and 0.5 A g 1, respectively.
Moreover, its capacitance retention rate -was still 83.2% after
5000 cycles [157] (Fig. 9C). Lu et al. [158] prepared hollow NiCo2-
O4 nanocages (NCs) by growing on SiCNWs network/CC multiscale
substrate through a novel multi steps strategy containing of chem-
ical vapor deposition, MOFs-templating ion exchange and further
thermal treatment process, which were served as electrode mate-
rials for FSSCs. Later, Li et al. [159] also successfully fabricated the
hierarchical core–shell SiCNWs@NiCo2O4 NAs on CC substrate
(Fig. 9E). The CC/SiCNWs@NiCo2O4 showed a high specific capaci-
tance of 1604.7F g 1 (specific capacity of 222.9 mA h g 1) at 0.5
A g 1, good rate performance, and excellent cycling stability.
The following examples are the situation of monmetal MOFs
derived oxides combined with other materials. For instance,
MOF-derived copper oxide@mesoporous carbon (CuOx@mC)
embedded with PANI and RGO prepared by heat-treated Cu-MOF
firstly and then in-situ polymerization PANI [160]. The results
showed that a uniform and highly ordered interface layer of PANI
was formed on the surface of the Cu MOF-derived CuOx@mC
framework together with the RGO nanosheets. This highly efficient
conductive network can improve the ion diffusion process and
achieve a rapid redox reaction at the electrode/electrolyte inter-
face, thereby improving conductivity and enhancing capacitance
performance. By changing the pyrolysis temperature of Cu-MOF,
the ternary CuOx@mC@PANI@RGO obtained at 700 °C exhibited
the highest capacitance, up to 534.5 F g 1, and had good cycle sta-
bility as the FSSCs electrode.
A simple and universal method for large-scale preparation of
three-dimensional (3D) GO/MOF composite materials has been
introduced by using a simple hybrid process of MOF and GO
[161] (Fig. 9D). Through the freeze-drying and calcination process,
the obtained GO/MOF composite material used as the precursor for
the subsequent preparation of MOF-derived composite aerogels
(RGO/Fe2O3 and RGO/NiO/Ni). The RGO/Fe2O3 composite showed
good rate capability when it used as a SCs electrode, with high
specific capacitances of 869.2 and 289.6 F g 1 at current densities
of 1 and 20 A g 1, respectively. The capacitance -did not decrease
significantly after 5000 cycles. In addition, the FSSCs were fabri-
cated based on the obtained RGO/Fe2O3 composite aerogel. The
aerogel exhibited a high volume capacitance of 250 mF cm 3 at
6.4 mA cm 3, the 96.3% capacity retention rate and excellent
mechanical flexibility. In addition, Wang et al. [162] reported
Co-MOF/Ti3C2Tx composite grown on NF electrode via in-situ

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J. Yan, T. Liu, X. Liu et al. Coordination Chemistry Reviews 452 (2022) 214300

Fig. 10. A) Schematic illustration for the synthesis procedure of hl-MSC, u-hl-MSC, and u-hl-MSC/NRSs derived from the hl-MOF, u-hl-MOF, and u-hl-MOF/NRSs, respectively,
via hydrothermal and sulfurization procedures. Reproduced from Ref. [166] with permission from the American Chemical Society, copyright 2020. B) Schematic illustration of
the fabrication process of the Ni(OH)2@ZnCoS-NS positive electrode and VN@ZnCoS-NS negative electrode. Reproduced from Ref. [167] with permission from Royal Society of
Chemistry, copyright 2019. C) Schematic of the strategy for directly growing bimetallic MOF-derived nanosheets on CC substrate and their conversion to mesoporous zinc–
cobalt–sulfide nanoparticles embedded in N-doped carbon. Reproduced from Ref. [168] with permission from Royal Society of Chemistry, copyright 2019. D) Schematic
illustration of the formation of Mo-Co-S porous nanosheets on CC. Reproduced from Ref. [169] with permission from Wiley-VCH, copyright 2019. E) Synthetic scheme for the
growth of NiCoS/CC via a facile chemical bath deposition method followed with ion exchange and sulfidation treatment. Reproduced from Ref. [174] with permission from
Elsevier, copyright 2020.

hydrothermal synthesis, which was used as a binder-free electrode
for FSSCs applications, as shown in Fig. 9F. The result showed that
Co-MOF/Ti3C2Tx -had relative good electrochemical performance
with ultra-high specific capacitance and excellent cyclic stability.
3.3.3. MOFs derived metal sulfide composites electrode
Transition metal sulfides have relatively high electrical conduc-
tivity, richer redox reactions, high electrochemical activity, and
good stability, and will not cause structural collapse problem com-
pared with CPs, so it is a very promising electrode material for
FSSCs [163]. MOFs material is the good precursor to obtain metal
sulfides, it derived metal sulfides have been reported by some
work when it as FSSCs.
Chen et al. [60] prepared a MOF-reinforced Co9S8 self-supported
nanowire arrays for high-performance FSSCs by multi-step
method. Co-based nanowires with a composition of Co2(OH)2(-
CO3)2 on the NF substrate are first prepared by a simple hydrother-
mal method. Then the leaf-like Co-MOF deposited on the surface of
the oxide nanoarrays (NAs) after converting Co2(OH)2(CO3)2 into
Co3O4 nanowires by calcination process, forming Co3O4 NAs@Co-
MOF core–shell structure. The sulfurization was achieved via an
in-situ hydrothermal process to obtain Co9S8. This process not only
realized the chemical transformation, but also changed the mor-
phology of the Co-MOF from leaf-like microplatelets into
nanosheets wrapping around the 1D nanowires. Finally the FSSCs
were assembled, and 16 red LEDs were lighted up by this device
under bend and flat states, which demonstrated its potential for
practical applications. Wei et al. [164] reported the fabrication of
the NiCo2S4 nanorods grown on CC with hierarchical and porous
structure through a facile MOF-derived route for SCs. The FSSCs
19
was manufactured by using NiCo2S4@CC as the cathode and assem-
bled with N-doped porous carbon nanosheets grown on CC
(NC@CC) as the anode, which showed high energy density and
power density. Hu et al. [165] fabricated hierarchical CoS2
nanosheet arrays directly coated on the conductive CC by regulat-
ing the sulfuric agents with mutative activities, which can achieve
high energy density of 3.16 mWh cm 3 and power density up to
1.61 W cm 3.
The morphology of MOF-derived sulfide will affect its electro-
chemical performance. Kim et al. [166] prepared the urea-
assisted hierarchically layered cobalt-based MOF (u-hl-MOF) on
Ni foam firstly, and then -grew the nanorods and nanosheets on
its surface directly via the MOF-mediated method. This process
no need add additional cobalt precursor. This MOF realized its
own partial conversion by annealing with S powder under an
atmosphere of Ar gas. The results shown that the bulk internal u-
hl-MOF remains without any degradation but only the surface of
the u-hl-MOF was converted into cobalt sulfide@carbon (Co1–
xS@C) (Fig. 10A). A FSSCs was assembled by using u-hl-MSC, AC/
Super P, and PVA/KOH as the cathode, anode and electrolyte mate-
rials, respectively. This FSSCs exhibited an energy density of
270 mW h cm 2 with a high power density of 0.6 W cm 2 and high
areal capacitance of 1.35F cm 2.
Bimetal MOFs sulfides are also very common. Gao et al. [167]
converted the binary MOFs arrays to zinc-cobalt sulfide nanosheet
ZnCoS-NSs, and then -grew the Ni(OH)2 nanosheet by electrodepo-
sition method (Fig. 10B). The obtained Ni(OH)2@ZnCoS-NS was
confirmed to be a highly capacitive positive electrode (8.1F cm 2
at 3 mA cm 2, i.e., 2730F g 1), -had a good match with the similarly
constructed VN@ZnCoS-NS negative electrode (1.35F cm 2 at
J. Yan, T. Liu, X. Liu et al.
3 mA cm 2). Wang et al. [168] -grew the bimetallic sulfide
(ZnxCo1 xS) nanoparticle-embedded in nitrogen-doped carbon on
flexible CC (ZnxCo1 xS-NC) by MOFs-derived methods and use it
as the positive electrode to assemble the asymmetric FSSCs
(Fig. 10C). The bimetallic MOFs-derived nitrogen-doped meso-
porous carbon (MPC) used as the negative electrode. The FSSCs
exhibited great capacitance of 290 F g 1 at 1 A g 1 and high energy
density of 92.59 W h kg 1.
Mo-doped Co9S8 porous nanosheets on CC (Mo-Co-S/CC)
derived from Co-MOF for FSSCs also be reported, [169] as shown
in Fig. 10D. By using PVA/KOH gel as electrolyte, a Mo-Co-S/CC//
KOH//AC/CC FSSCs -were assembled, which can work under differ-
ent bending angles, showed a specific capacitance of 37.37 F g 1 at
1 A g 1 and delivered a maximum energy density of 14.68 Wh kg 1
at power density of 369 W kg 1, with the capacity retention of
80.07% over 30 000 cycles at a high rate of 20 A g 1. The MoO2@-
Cu@C composites in another work prepared successfully by using
polyoxometalates@Cu-BTC as template, and it showed good stable
performance retaining 91% of its highest charge capacity main-
tained after 5000 cycles [170]. Unique core–shell hollow iron-
cobalt sulfides nanoarrays/NF was fabricated through a novel
MOF template method [171]. The assembled FSSCs achieved a high
energy density of 43.6 W h kg 1 at a power density of 770 W kg 1
and retained 89.6% of its capacitance over 5000 cycles.
Jiang et al. [172] prepared one of new electrode materials for
FSSCs by the method of electrodeposition Ni-Co-S interconnected
nanosheet arrays on the surface of ZIF-8 derived N-doped hierar-
chical porous carbon nanofiber (Ni-Co-S@N-pCNF). A FSSCs -were
assembled by using Ni-Co-S@N-pCNF, active carbon loaded N-
doped hierarchical porous carbon nanofibers (AC@N-pCNF), and
KOH/MPF30AC-100 (Nippon ko-kan company, Japan) hybrids as
the positive electrode, negative electrode and electrolyte materi-
als/separator, respectively, which had the good mechanical flexi-
bility and electrochemical stability and almost no attenuation
during cycling under different bending states. The NiCo-LDH/
Co9S8 hybrids nanosheet arrays based on MOFs were synthesized
by Shi et al. [173] The FSSCs also can achieve an outstanding elec-
trochemical property. Similarly, the nickel–cobalt bisulfide (NiCoS)
nanosheets arrays on CC was also been reported as FSSCs elec-
trodes [174]. The specific processes were including the deposition
of 2D MOF precursors on CC skeletons, the conversion the MOF into
nickel–cobalt layered double-hydroxide by ion exchange process
and transformation the NiCoS by a sulfidation treatment
(Fig. 10E). The FSSCs exhibited a high specific capacitance, large
energy density and long cycle life.
We know that the solvent environment is very important for
MOF materials. When water is used as a solvent, zinc nitrate and
2-methylimidazole will form ZIF-L, and when methanol is used
as a solvent, zinc nitrate and 2-methylimidazole will form ZIF-8.
The two materials have different structures and morphologies.
ZIF-8 has been extensively studied by many researchers. Therefore,
the Zn0.76Co0.24S/NiCo2S4 nanosheets derived from Zn/Co-ZIF-L
were prepared successfully by Wang et al. [175] Beneficial from
the unique nanostructure design and the synergistic effects of
the electrode materials, the prepared samples possessed a maxi-
mum energy density at 48.1 Wh kg 1 and power density at
837 W kg 1.
The MOFs derived metal sulfide combined with other materi-
als also can enhance the electrochemical properties. Liu et al.
[176] first synthesized carbon-coated copper sulfide using the
widely used MOF HKUST-1 as a template, and then pre-
modified it on CC substrate. Then, the nanocomposite electrode
(PPy/Cu9S8@C-CC) was obtained by using the electrochemical
deposition PPy. The result demonstrated that the PPy/Cu9S8@C
is an ideal electrode material for energy storage and conversion
applications.
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Coordination Chemistry Reviews 452 (2022) 214300
3.3.4. MOFs derived transition metal hydroxide composites electrode
The metal ions contained in MOFs can be used as the precursor
ions of hydroxides because the binding force between metal ions
and organic ligands is relatively weak. MOFs can happen ion
exchange reactions with alkaline solutions such as NaOH and
KOH. The organic ligand will be substituted to obtain the corre-
sponding hydroxide. The porous hollow nickel–cobalt-manganese
hydroxide (NiCoMn-OH) polyhedra was reported by using ZIF-67
as the template [177] (Fig. 11A). The FSSCs of NiCoMn-OH//AC
device was also fabricated, exhibited good capacitance of
121.5 F g 1 at 1 A g 1, high energy density of 43.2 Wh kg 1 at a
power density of 0.79 kW kg 1, and excellent capacitance retention
(100% retention after 10,000 cycles). Similarly, hollow-structured
NiCo layered double hydroxide (H-NiCo LDH@ACC) was in-situ
grown on acidified carbon cloth (ACC) for FSSCs by ZIF-67-
derived methods [178] (Fig. 11C). The flexible H-NiCo LDH@ACC
electrode displayed a high specific capacity of 1377 mC cm 2
(3060 mF cm 2) at 1 mA cm 2, and a low charge transfer resistance
of 0.15 X, a capacity retention of 70% and a coulombic efficiency of
99% after 10,000 cycles at 80 mA cm 2.
Chen et al. [179] soaked Co-MOF@CC in a NiSO4 solution and in-
situ converted it to cobalt–nickel double hydroxide (CoNi-DH)
(Fig. 11B). The four kinds of CoNi-DH-S, CoNi-DH-N, CoNi-DH-Cl,
and CoNi-DH-C were obtained by changing the kind of soak solu-
tion. With this CoNi-DH-S electrode as the positive electrode, the
FSSCs delivered an impressive capacity of 204.8 C g 1, a superior
energy density of 42.5 Wh kg 1, and satisfactory cycle life (81.5%
reservation after 7500 cycles). Xu et al. [180] prepared the Ni-
MOF-derived 2D assembled Ni-Mn-C ternary composites that com-
posed of Ni(OH)2 and MnO2 nanosheets decorated on a carbon
matrix (Ni(OH)2-MnO2/C) for FSSCs (Fig. 11D). It delivered the high
power density, good cycling stability and excellent flexibility,
which maybe attributed to its high surface area, good electrical
conductivity and the synergistic effect among components.
A facile strategy has been developed to prepare the
ZnO@C@CoNi-LDH NRAs [181]. The ZnO nanorod arrays were
choosen to grow on the NF substrate by hydrothermal method
because it can used as self-sacrificial template to provide Zn ions
and a skeleton for the growth of ZIF-8. Subsequently, a shell of
CoNi-LDH was coated on the exterior surface of ZIF-8 pyrolysis
products to obtain ZnO@C@CoNi-LDH NRAs (Fig. 11E). The cathode
was prepared by the transformation of ZnO@ZIF-8 to Fe2O3@C
through a Fe-Zn cation exchange, followed by a further pyrolysis
process. An asymmetric FSSCs device was constructed by employ-
ing the well-defined ZnO@C@CoNi-LDH and Fe2O3@C, which
exhibited outstanding supercapacitive performances with a high
energy density (1.078 mW h cm 3), power density (0.4 W cm 3),
and outstanding cycling lifespans (retention 95.01% after 10,000
charge/discharge cycles).
3.3.5. MOFs derived metal selenide (phosphide) composites electrode
Research on transition metal sulfides has received widespread
attention, while research on transition metal compounds of sele-
nium, which is the same main group as sulfur, is relatively rare.
Transition metal selenides have properties similar to those of tran-
sition metal sulfides, and the density of selenium is higher than
that of sulfur, and its conductivity is also better than that of sulfur.
Therefore, in general, the specific capacitance and rate perfor-
mance of selenide should be better than that of sulfide.
The Sex@cobalt phosphide nanostructured array-activated car-
bon fiber textile (Sex@CPNA-ACFT) were successfully prepared
through phosphidization and selenium infiltration of the 2D Co-
MOF arrays grown on an ACFT under the optimized conditions
[182]. The FSSCs -were constructed by employing Se0.6@CPNA-
ACFT and FeS2 decorated RGO at etched CFT (FeS2@RGO-ECFT) as
positive electrode and negative electrode, respectively. It exhibited
J. Yan, T. Liu, X. Liu et al. Coordination Chemistry Reviews 452 (2022) 214300

Fig. 11. A) The as-synthesized NiCoMn-OH exhibits unique multi-order micro-architecture advantage employed in a quasi-solid-state supercapacitor for energy-storage
application. Reproduced from Ref. [177] with permission from Elsevier, copyright 2019. B) Formation process of wisteria flower-like CoNi-DH on carbon cloth fiber.
Reproduced from Ref. [179] with permission from Elsevier, copyright 2020. C) Schematic diagram for the synthesis of H–NiCo LDH@ACF and ACC. Reproduced from Ref. [178]
with permission from Elsevier, copyright 2019. D) Schematic illustration of the preparation of the hierarchical Ni(OH)2-MnO2/C composite. Reproduced from Ref. [180] with
permission from Royal Society of Chemistry, copyright 2018. E) Schematic illustration for the fabrication of ZnO@C@CoNi-LDH and Fe2O3@C core–shell NRAs for the
asymmetrical FSSC. Reproduced from Ref. [181] with permission from Elsevier, copyright 2017.

a maximum energy density of 70.6 Wh kg 1 (volumetric energy
density of 1.81 mWh cm 3) and a maximum power density of
8.163 kW kg 1 with no attenuation.
Jun et al. [183] reported a hybrid structure of P-doped Co3O4 (P-
Co3O4) ultrafine nanoparticles. The nanoparticles use the 1D MOF
derived from Co-layered double hydroxide as self-template and
reactant and happen the process of pyrolysis-oxidation-phosphori
zation. The assembled FSSCs devices possessed appreciable energy
and power density of 47.6 W h kg 1 and 750 W kg 1.
3.3.6. MOFs derived Heteroatom doping composites electrode
Heteroatom doping is a kind of carbon material with pseudoca-
pacitive properties formed by introducing heteroatoms with pseu-
docapacitance properties into MOFs-derived carbon materials. This
kind of carbon material not only cause the adsorption and desorp-
tion of the electric double layer of the charge during the charging
and discharging process, but also happen the redox reaction of het-
eroatoms. The MOFs-derived carbon material provides a good con-
ductive substrate for the heteroatoms, and the heteroatoms can
improve the conductivity and specific surface area, and bring fara-
day pseudocapacitance to carbon materials, thereby improving the
electrochemical performance of carbon materials. These heteroa-
toms generally include N, B, O, S, etc. N doping is the most com-
monly used method in the MOF derived material because the
organic ligands in MOFs often contain nitrogen, such as ZIF-8,
etc. After N with a five-electron structure is incorporated into the
carbon skeleton, it can form large p bond to provide more conduc-
tive electrons for the four-electron structure carbon, thereby
21
improving the conductivity of the carbon material. At the same
time, the N doped into the carbon skeleton often exists in the form
of pyridine nitrogen, pyrrole nitrogen, graphitic nitrogen and nitro-
gen oxide. During the electrochemical charge and discharge pro-
cess, these different forms of N will undergo different forms of
transformation.
To demonstrate the role of oxygen vacancies and N doping,
Tang et al. [184] introduced the abundant oxygen vacancies into
Co3O4 nanosheets by MOF-derived method (Fig. 12B). Firstly, the
surface of CC was treated with polydopamine to obtain N-doped
carbon cloth, and then Co-MOF was grown on the -CC. Finally,
the oxygen-deficient Co3O4/CC hybrid was achieved with one-
step reduction of sodium borohydride. The result showed that
the specific capacity was much higher than the counterpart elec-
trodes without oxygen vacancies or PDA treatment. The FSSCs with
Co-MOFs-derived carbon nanosheets as negative electrodes also
showed a high energy density.
Wu et al. [185] produced highly N and B co-doped porous car-
bon nanofiber network by using electrospinning PAN and ZIF-8
nanoparticles, sodium borohydride treatment and freeze-drying
(Fig. 12A). This novel electrode can maintain a high rate capability
and remarkable cyclic stability (94.5% capacitance retention) even
after 10 000 charge–discharge cycles. Jun et al. [186] synthesized
P-N co-doped Co3O4 carbon matrix through a carbonization + oxida
tion + phosphating pre-growed Co-MOF on the CC. The FSSCs
devices constructed with self-supported P-Co3O4@PNC and PNC
materials showed the high energy density of 69.6 W h kg 1 at a
power density of 750 W kg 1, and displayed good cycling stability
J. Yan, T. Liu, X. Liu et al. Coordination Chemistry Reviews 452 (2022) 214300

Fig. 12. A) Schematic illustration of the sustainable synthesis process of 3D-BN-CNF-ZF900. Reproduced from Ref. [185] with permission from Elsevier, copyright 2019.
B) Schematic preparation of nitrogen-doped Co3O4 nanosheets with oxygen vacancies on CC substrate. Reproduced from Ref. [184] with permission from Elsevier, copyright
2019. C) Schematic illustration of the synthesis of the P-Co3O4@PNC and PNC nanosheets on CF substrate. Reproduced from Ref. [186] with permission from Elsevier,
copyright 2020.

with a capacitance retention of 96.8% even after 10,000 cycles at
20 A g 1 (Fig. 12C).
Recently, the use of S doping to optimize the electrochemical
performance of carbon materials has also received widespread
attention. Tang et al. [187] reported the CC@CoO@S-Co3O4 for
FSSCs by using the Co-based MOFs as versatile scaffolds. The hol-
low S-doped Co3O4 sheath has been facilely prepared by the sur-
face etching of CoO nanowires for synchronous in situ growth of
well-aligned ZIF-67 and hydrothermal process. The FSSCs dis-
played a highest energy density of 0.71 mW h cm 3 at 21.3 mW
cm 3 power density, together with 87.9% capacitance retention
over 5000 continuous cycles. Pan et al. [51] prepared the N, S
dual-doped flexible hierarchically porous carbon polyhedra
embedded carbon nanofibers (NSCPCNFs) by electrospinning and
further pyrolysising the PAN precursor that consist of ZIF-67 and
thiourea (TU). Here, the N and S contents of NSCPCNFs enhanced
by decomposing TU at high temperature. The FSSCs assembled by
NSCPCNFs electrodes exhibited a specific capacitance of 103 F
g 1 at a current density of 0.5 A g 1, and energy density of
14.3 W h kg 1 at a power density of 250 W kg 1, as well as it also
exhibited a high capacitance retention and superior bending stabil-
ity. A summary of MOF classification, electrode nanostructure,
22
electrochemical performance and flexibility of MOF based flexible
electrodes and assembled devices is provided in Table 1.
4. Conclusion and future challenges
The research and developments of the MOFs-based FSSCs have
been progressed rapidly in recent years. Numerous efforts are
devoted to using MOFs-based SCs as a new platform for flexible
energy storage device. This review has briefly discussed the recent
development, covering some successful and promising research
works that can achieve high electrochemical performance based
on MOFs-based FSSCs. Some different structure of MOFs or MOFs
derivatives and their complexes (such as layer structure, sandwich
structure, core–shell structure, dendritic, etc.) also be developed
for use of FSSCs. These structures can provide more active reaction
sites, effectively shorten the ion/electricity load transmission path,
so as to achieve high-performance FSSCs. Except the extrode itself,
some researchers have begun to focus their research on other com-
ponents outside the electrodes, such as separators, electrolytes,
current collectors, and adhesives. Moreover, the research of elec-
trochromic, self-charging and self-repairing FSSCs has also
attracted extensive attention. In functional FSSCs such as elec-
 Table 1

J. Yan, T. Liu, X. Liu et al.

Comparison of electrochemical performances of MOF-based FSSCs.

Electrode material Structure Current Electrolyte Highest specific Current Types of Maximum Power density Flexibility Ref
collector capacitance density electrolyte energy density
2
Pristine MOF Cu3(BTC)2 film Cu foil Bu4NPF6 95.1mF cm PVA/LiCl gel 46mWh cm 3 33.3 W cm 3 Bendable (0–90°) [59]
Ni-MOF accordion NF 3MKOH 1021F g 1 1.4A g 1
PVA/KOH gel 4.18mWh cm 3
231.2mW cm 3 Bendable (0–180°) [66]
2 1
UIO66 octahedron CC H2SO4 3.87mF cm 2.5A g PVA/H2SO4 36mWh kg 1 157.44 W kg 1 Bendable [78]
gel
2 2
MOFs-based Cu-CAT-NWAs/PPy rod-like PPy 3MKCl 252.1mF cm 1.25 mA cm LiCl/PVA Bendable (0–180°) [68]
composites membrane Twistable (0–360°)
2 3
PANI-ZIF-67 Interweaved CC 3MKCl 2146mF cm PVA/H2SO4 0.0161mWh 0.833 W cm BendableTwistable [89]
MOF gel cm 3
crystals with
PANI chains
PEDOT/HKUST-1-CNTF cubic CNFs 3MKCl 128mF cm 2
0.4 mA cm 2
H3PO4/PVA 51lWh cm 3
2.1mW cm 3
Bendable (0–145°) [107]
rGO-HKUST-1 cubic CFP 1MNaNO3 365F g 1 4A g 1 polymer- 42Wh kg 1 3100 W kg 1
Bendable (0–180°) [119]
gelled
Ni-MOF@NiS2 nanosheets CC KOH 1128F g 1 2A g 1
PVA/KOH gel 23.5Wh kg 1 1.4 kW kg 1 Bendable [136]
3 1 3 3
CNF@c-MOF nanofiber CNFs 3MKCl 2800mF cm 1A g PVA/KCl 185.7mWh cm 0.37mW cm Bendable (0–120°) [138]
foldable (0–180°)
1 1 1 1
MOFs-derived Zn(tbip) derived porous sponge NF 6MKOH 369F g 0.5A g PVA/KOH gel 12.5Wh kg 7200 W kg Bendable (0–180°) [140]
material carbon
MIL-88-Fe derived S-a- spindle-like CNTFs Na2SO4 1232.4mF cm 2
2 mA cm 2
Na2SO4– 135.3lWh cm 2
2199.9 lW cm 2
Bendable (0–180°) [147]
Fe2O3@C/OCNTF CMC gel
1 1 2 2
Co-MOF derived Co3O4 sheet-like CC 1MKOH 226.1C g 1.3A g PVA/KOH gel 0.092mWh cm 1.34mW cm Bendable (0–180°) [149]
ZIF-67 derived N, S doped nanofibrous CNFs 1MH2SO4 396F g 1 1A g 1 PVA/H2SO4 14.3Wh kg 1 250 W kg 1 Bendable (0–180°) [51]
CNF gel
1 1 3 3
ZIF-67 derived v- Co3O4 nanosheets CC 2MLiOH 414C g 1A g PVA/LiOH 0.74mWh cm 14.70mW cm Bendable [184]
gel
23

Co-MOF derived Co9S8 leaf-like NF 10MKOH 4.48F cm 2 2 mA cm 2

PVA/KOH gel Bendable [60]
Zn/Co-MOF derived nanosheet CC 2MKOH 2730F g 1 3 mA cm 2
PVA/KOH gel 75Wh kg 1
0.4 kW kg 1
BendableTwistable [167]
ZnCoS-NS
1 1 1 1
ZIF-67 derived NiCoMn- nanosheet NF 3MKOH 1405F g 30A g PVA/KOH gel 43.2 W h kg 7.9 kW kg Bendable [177]
OH
1 2 1 1
Co-MOF derived nanostructured CFT 3MKOH 302mAh g 1 mA cm PVA/KOH gel 70.6Wh kg 8.163 kW kg Bendable [182]
Se0.6@CPNA-ACFT arrays

Coordination Chemistry Reviews 452 (2022) 214300

J. Yan, T. Liu, X. Liu et al.
trochromic, we also need to consider the influence of transparency
and response time on electrochemical performance. Therefore,
how to ensure that the electrode material has the best overall per-
formance is a priority. In summary, several challenges and bottle-
necks need be solved to realize the mass production and practical
application of MOFs in FSSCs.
(1) A standardized method for evaluating the mechanical flex-
ibility (including bending, twisting, washing) and electro-
chemical properties of FSSCs has yet to be developed. In
different literature reports, the electrochemical capaci-
tances calculated based on the mass of electrochemically
active materials and the whole mass of FSSCs take up half,
respectively; moreover, some use gravimetric capacitance
values, while others use areal capacitances. This makes it
impossible to compare the results accurately. Similarly, dif-
ferent methods used to analyze FSSCs mechanical integrity,
thus highlighting the need for standard comparison
methods. The ‘‘in situ” and/or ‘‘ex situ” characterization
techniques should be used to explore the impact of
mechanical deformation on the electrode material and
polymer gel electrolyte of the device electrolytes can be
further optimized in FSSCs.
(2) Need to develop new conductive MOFs materials. Existing
MOFs materials are still limited by their electrical conductiv-
ity. It has been reported that the solid–liquid interface and
capacitance characteristics of the electric double layer of
SCs with conductive MOFs as electrodes and ionic liquids
as electrolyte can increase the energy density of SCs [188].
Therefore, conductive MOFs are proved to be a promising
SCs electrode material and potential FSSCs electrode mate-
rial. Moreover, conductive MOFs have the characteristic that
their molecular scale model can reflect the actual structure
(periodic replication according to the unit cell), so that the
cross-scale simulation results based on this system can be
expected to be quantitatively compared with macro-scale
experimental measurements. At present, the theoretical
research on SCs is mainly aimed at a deep understanding
of its energy storage mechanism. If simulation technology
can be one step closer and accurately predict the energy
density and charge and discharge performance of actual
capacitors, this will greatly reduce the cost of experimental
research and improve the ability to design FSSCs.
(3) The polymer gel electrolyte of the device electrolytes can be
further optimized in FSSCs. Exploring new electrolytes is an
important link in the development of high-performance
FSSCs because the electrolyte not only provides support for
the ionic conductivity of the electrochemical process, but
also determines the electrochemical stability window of
the device. The liquid electrolyte in traditional SCs has been
difficult to adapt to new FSSCs application environments, so
some polymer hydrogel electrolytes have been developed.
Now, the PVA based gel electrolytes are usually used for
FSSCs but it also restricted by the low ion conductivity.
Therefore, the new electrolytes with higher ion conductivity
and larger operation voltage are worth developing.
(4) Detailed analyses are required to explore the energy storage
mechanism at the interface of MOFs based electrode/poly-
mer gel electrolyte. Many theoretical researchs are based
on the liquid electrolytes, but the theoretical basis of the
charge storage mechanism in gel electrolytes is complex
and difficult to understand because ions are trapped in the
polymer chain. In future research, the FSSCs charge storage
mechanism hopefully clarify by combining the advanced
in-situ characterization (micro and spectroscopy) and simu-
lation techniques.
24
Coordination Chemistry Reviews 452 (2022) 214300
(5) Explore new functions of FSSCs (shape-memory, or self-
healing) and integrate multifunctional MOFs-based FSSCs
(supercapacitor-sensor device, implantable healthcare/-
portable devices) become the future development direction.
For example, the self-charging electronic device can be pre-
pared by combining perovskite solar cells with FSSCs, which
can store solar energy converted by solar cells in SCs for use
by electronic devices. Researches on these integrated and
flexible devices are in the ascendant.
In summary, the MOFs-based material is a promising FSSCs
extrode material. Engineering the morphologies, structures and
properties of MOF material are helpful to improve their electro-
chemical performance. Continued research and development
should focus on development of multifunctional flexible material
that possess stretchable, foldable and bendable simultaneously
for practical FSSCs application. Moreover, indicating the underlying
mechanisms of MOFs-based FSSCs material is another significant
pointcuts need to be pursued.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
The authors thank to the supports by the National Natural
Science Foundation of China (No: 52072307) and Innovation Foun-
dation for Doctor Dissertation of Northwestern Polytechnical
University (grant no. CX202054).
References
[1] X. Xiao, L. Zou, H. Pang, Q. Xu, Synthesis of micro/nanoscaled metal-organic
frameworks and their direct electrochemical applications, Chem. Soc. Rev. 49
(1) (2020) 301–331, https://doi.org/10.1039/c7cs00614d.
[2] Y. Zhang, H.X. Mei, Y. Cao, X.H. Yan, J. Yan, H.L. Gao, H.W. Luo, S.W. Wang, X.D.
Jia, L. Kachalova, Recent advances and challenges of electrode materials for
flexible supercapacitors, Coordin. Chem. Rev. 438 (2021), https://doi.org/
10.1016/j.ccr.2021.213910 213910.
[3] K.B. Wang, Q. Xun, Q. Zhang, Recent progress in metal-organic frameworks as
active materials for supercapacitors, EnergyChem 2 (1) (2020), https://doi.
org/10.1016/j.enchem.2019.100025 100025.
[4] D.J. Lipomi, M. Vosgueritchian, B.C.K. Tee, S.L. Hellstrom, J.A. Lee, C.H. Fox, Z.N.
Bao, Skin-like pressure and strain sensors based on transparent elastic films
of carbon nanotubes, Nat. Nanotechnol. 6 (12) (2011) 788–792, https://doi.
org/10.1038/Nnano.2011.184.
[5] A.N. Sokolov, B.C.K. Tee, C.J. Bettinger, J.B.H. Tok, Z.N. Bao, Chemical and
engineering approaches to enable organic field-effect transistors for
electronic skin applications, Accounts Chem. Res. 45 (3) (2012) 361–371,
https://doi.org/10.1021/ar2001233.
[6] Q. Zheng, B.J. Shi, F.R. Fan, X.X. Wang, L. Yan, W.W. Yuan, S.H. Wang, H. Liu, Z.
Li, Z.L. Wang, In vivo powering of pacemaker by breathing-driven implanted
triboelectric nanogenerator, Adv. Mater. 26 (33) (2014) 5851–5856, https://
doi.org/10.1002/adma.201402064.
[7] S. Chatterjee, M. Saxena, D. Padmanabhan, M. Jayachandra, H.J. Pandya,
Futuristic medical implants using bioresorbable materials and devices,
Biosens Bioelectron 142 (2019) 111489. ARTN 11148910.1016/j.
bios.2019.111489.
[8] W. Gao, S. Emaminejad, H.Y.Y. Nyein, S. Challa, K.V. Chen, A. Peck, H.M. Fahad,
H. Ota, H. Shiraki, D. Kiriya, D.H. Lien, G.A. Brooks, R.W. Davis, A. Javey, Fully
integrated wearable sensor arrays for multiplexed in situ perspiration
analysis, Nature 529 (7587) (2016) 509–514, https://doi.org/
10.1038/nature16521.
[9] J. Yang, Q. Cao, X. Tang, J. Du, T. Yu, X.i. Xu, D. Cai, C. Guan, W. Huang, 3D-
Printed highly stretchable conducting polymer electrodes for flexible
supercapacitors, J. Mater. Chem. A 9 (35) (2021) 19649–19658, https://doi.
org/10.1039/D1TA02617H.
[10] C. Li, Y. Huang, X. Feng, Z. Zhang, H. Gao, J. Huang, Silica-assisted cross-linked
polymer electrolyte membrane with high electrochemical stability for
lithium-ion batteries, J. Colloid Interface Sci. 594 (2021) 1–8, https://doi.
org/10.1016/j.jcis.2021.02.128.
J. Yan, T. Liu, X. Liu et al.
[11] D.P. Dubal, N.R. Chodankar, D.-H. Kim, P. Gomez-Romero, Towards flexible
solid-state supercapacitors for smart and wearable electronics, Chem. Soc.
Rev. 47 (6) (2018) 2065–2129, https://doi.org/10.1039/C7CS00505A.
[12] X. Lu, M. Yu, G. Wang, Y. Tong, Y. Li, Flexible solid-state supercapacitors:
design, fabrication and applications, Energy Environ. Sci. 7 (7) (2014) 2160–
2181, https://doi.org/10.1039/C4EE00960F.
[13] X.M. Guo, N.N. Bai, Y. Tian, L.G. Gai, Free-standing reduced graphene oxide/
polypyrrole films with enhanced electrochemical performance for flexible
supercapacitors, J. Power Sour. 408 (2018) 51–57, https://doi.org/10.1016/j.
jpowsour.2018.10.083.
[14] S.J. Luo, J.L. Zhao, J.F. Zou, Z.L. He, C.W. Xu, F.W. Liu, Y. Huang, L. Dong, L.
Wang, H. Zhang, Self-standing polypyrrole/black phosphorus laminated film:
promising electrode for flexible supercapacitor with enhanced capacitance
and cycling stability, ACS Appl. Mater. Interfaces 10 (4) (2018) 3538–3548,
https://doi.org/10.1021/acsami.7b15458.
[15] R.R. Salunkhe, Y.V. Kaneti, Y. Yamauchi, Metal-organic framework-derived
nanoporous metal oxides toward supercapacitor applications: progress and
prospects, ACS Nano 11 (6) (2017) 5293–5308, https://doi.org/10.1021/
acsnano.7b02796.
[16] R. Zhao, Z. Liang, R. Zou, Q. Xu, Metal-organic frameworks for batteries, Joule
2 (11) (2018) 2235–2259, https://doi.org/10.1016/j.joule.2018.09.019.
[17] W.H. Li, W.H. Deng, G.E. Wang, G. Xu, Conductive MOFs, EnergyChem 2 (2)
(2020), https://doi.org/10.1016/j.enchem.2020.100029.
[18] X. Li, X. Yang, H. Xue, H. Pang, Q. Xu, Metal-organic frameworks as a platform
for clean energy applications, EnergyChem. 2 (2) (2020), https://doi.org/
10.1016/j.enchem.2020.100027 100027.
[19] H. Zhang, J. Nai, L. Yu, X.W.D. Lou, Metal-organic-framework-based materials
as platforms for renewable energy and environmental applications, Joule 1
(1) (2017) 77–107, https://doi.org/10.1016/j.joule.2017.08.008.
[20] Y. Bai, C. Liu, Y. Shan, T. Chen, Y. Zhao, C. Yu, H. Pang, Metal-organic
frameworks nanocomposites with different dimensionalities for energy
conversion and storage, Adv. Energy. Mater. (2021) 2100346, https://doi.
org/10.1002/aenm.202100346.
[21] S. Bai, X. Liu, K. Zhu, S. Wu, H. Zhou, Metal-organic framework-based
separator for lithium-sulfur batteries, Nat. Energy 1 (7) (2016) 1–6, https://
doi.org/10.1038/nenergy.2016.94.
[22] H. Wang, Q.L. Zhu, R. Zou, Q. Xu, Metal-organic frameworks for energy
applications, Chemistry 2 (1) (2017) 52–80, https://doi.org/10.1016/j.
chempr.2016.12.002.
[23] S. Zheng, H. Xue, H. Pang, Supercapacitors based on metal coordination
materials, Coordin Chem. Rev. 373 (2018) 2–21, https://doi.org/10.1016/j.
ccr.2017.07.002.
[24] S. Bai, B. Kim, C. Kim, O. Tamwattana, H. Park, J. Kim, D. Lee, K. Kang,
Permselective metal-organic framework gel membrane enables long-life
cycling of rechargeable organic batteries, Nat. Nanotechnol. 16 (1) (2021) 77–
84, https://doi.org/10.1038/s41565-020-00788-x.
[25] B. Zhu, R. Zou, Q. Xu, Metal-organic framework based catalysts for hydrogen
evolution, Adv. Energy. Mater. 8 (24) (2018) 1801193, https://doi.org/
10.1002/aenm.201801193.
[26] X. Li, Q.L. Zhu, MOF-based materials for photo-and electrocatalytic CO2
reduction, EnergyChem 2 (3) (2020), https://doi.org/10.1016/j.
enchem.2020.100033 100033.
[27] L. Hu, W. Li, L. Wang, B. Wang, Turning metal-organic frameworks into
efficient single-atom catalysts via pyrolysis with a focus on oxygen reduction
reaction catalysts, EnergyChem 3 (3) (2021), https://doi.org/10.1016/j.
enchem.2021.100056 100056.
[28] H. Li, L. Li, R.B. Lin, W. Zhou, Z. Zhang, S. Xiang, B. Chen, Porous metal-organic
frameworks for gas storage and separation: status and challenges,
EnergyChem 1 (1) (2019), https://doi.org/10.1016/j.enchem.2019.100006
100006.
[29] M. Bonneau, C. Lavenn, P. Ginet, K.I. Otake, S. Kitagawa, Upscale synthesis of a
binary pillared layered MOF for hydrocarbon gas storage and separation,
Green Chem. 22 (3) (2020) 718–724, https://doi.org/10.1039/C9GC03561C.
[30] L.E. Kreno, K. Leong, O.K. Farha, M. Allendorf, R.P. Van Duyne, J.T. Hupp, Metal-
organic framework materials as chemical sensors, Chem. Rev. 112 (2) (2012)
1105–1125, https://doi.org/10.1021/cr200324t.
[31] I. Stassen, N. Burtch, A. Talin, P. Falcaro, M. Allendorf, R. Ameloot, An updated
roadmap for the integration of metal-organic frameworks with electronic
devices and chemical sensors, Chem. Soc. Rev. 46 (11) (2017) 3185–3241,
https://doi.org/10.1039/C7CS00122C.
[32] D.D. Zhou, X.W. Zhang, Z.W. Mo, Y.Z. Xu, X.Y. Tian, Y. Li, X.M. Chen, J.P. Zhang,
Adsorptive separation of carbon dioxide: from conventional porous materials
to metal-organic frameworks, EnergyChem 1 (3) (2019), https://doi.org/
10.1016/j.enchem.2019.100016 100016.
[33] O.M. Yaghi, H.L. Li, Hydrothermal synthesis of a metal-organic framework
containing large rectangular channels, J. Am. Chem. Soc. 117 (41) (1995)
10401–10402, https://doi.org/10.1021/ja00146a033.
[34] H. Yi, H. Wang, Y. Jing, T. Peng, X. Wang, Asymmetric supercapacitors based
on carbon nanotubes@NiO ultrathin nanosheets core-shell composites
and MOF-derived porous carbon polyhedrons with super-long cycle life, J.
Power Sour. 285 (2015) 281–290, https://doi.org/10.1016/j.jpowsour.2015.
03.106.
[35] L.F. Chen, Y. Lu, L. Yu, X.W.D. Lou, Designed formation of hollow particle-
based nitrogen-doped carbon nanofibers for high-performance
supercapacitors, Energy Environ. Sci. 10 (8) (2017) 1777–1783, https://doi.
org/10.1039/C7EE00488E.
25
Coordination Chemistry Reviews 452 (2022) 214300
[36] P. Liu, S. Gao, G. Zhang, Y. Huang, W. You, R. Che, Hollow engineering to Co@
N-doped carbon nanocages via synergistic protecting-etching strategy for
ultrahigh microwave absorption, Adv. Funct. Mater. 31 (27) (2021) 2102812,
https://doi.org/10.1002/adfm.202102812.
[37] J. Yan, Y. Huang, Y. Yan, X. Zhao, P. Liu, The composition design of MOF-
derived Co-Fe bimetallic autocatalysis carbon nanotubes with controllable
electromagnetic properties, Compos. Part A Appl. Sci. Manuf. 139 (2020),
https://doi.org/10.1016/j.compositesa.2020.106107 106107.
[38] W. Zhao, Y. Zheng, L. Cui, D. Jia, D. Wei, R. Zheng, C. Barrow, W. Yang, J. Liu,
MOF derived Ni-Co-S nanosheets on electrochemically activated carbon cloth
via an etching/ion exchange method for wearable hybrid supercapacitors,
Chem. Eng. J. 371 (2019) 461–469, https://doi.org/10.1016/j.cej.2019.04.070.
[39] K. Zheng, G. Li, C. Xu, Advanced battery-supercapacitor hybrid device based
on Co/Ni-ZIFs-derived NiCo2S4 ultrathin nanosheets electrode with high
performance, Appl. Surf. Sci. 490 (2019) 137–144, https://doi.org/10.1016/j.
apsusc.2019.06.071.
[40] P. Zhang, B.Y. Guan, L. Yu, X.W. Lou, Formation of double-shelled zinc-cobalt
sulfide dodecahedral cages from bimetallic zeolitic imidazolate frameworks
for hybrid supercapacitors, Angew. Chem. 129 (25) (2017) 7247–7251,
https://doi.org/10.1002/ange.201702649.
[41] J. Yan, Y. Huang, X. Han, X. Gao, P. Liu, Metal organic framework (ZIF-67)-
derived hollow CoS2/N-doped carbon nanotube composites for extraordinary
electromagnetic wave absorption, Compos. B. Eng. 163 (2019) 67–76, https://
doi.org/10.1016/j.compositesb.2018.11.008.
[42] T. Deng, Y. Lu, W. Zhang, M. Sui, X. Shi, D. Wang, W. Zheng, Inverted design for
high-performance supercapacitor via Co(OH)2-derived highly oriented MOF
electrodes, Adv. Energy Mater. 8 (7) (2018) 1702294, https://doi.org/10.1002/
aenm.201702294.
[43] Y. Li, Y. Xu, W. Yang, W. Shen, H. Xue, H. Pang, MOF-derived metal oxide
composites for advanced electrochemical energy storage, Small 14 (25)
(2018) 1704435, https://doi.org/10.1002/smll.201704435.
[44] G. Wu, T. Wu, Z. Ma, Y. He, X. Wu, B. Tang, Z. Yu, S. Chen, N. Bao, Covalent
black phosphorus/metal-organic framework hetero-nanostructure for high-
performance flexible supercapacitors, Angew. Chem. Int. Edit. 60 (18) (2021)
10366–10374, https://doi.org/10.1002/anie.202101648.
[45] A. Halder, M. Ghosh, A. Khayum M, S. Bera, M. Addicoat, H.S. Sasmal, S. Karak,
S. Kurungot, R. Banerjee, Interlayer hydrogen-bonded covalent organic
frameworks as high-performance supercapacitors, J. Am. Chem. Soc. 140
(35) (2018) 10941-10945. 10.1021/jacs.8b06460.
[46] B. Zhao, J. Deng, R. Zhang, L. Liang, B. Fan, Z. Bai, G. Shao, C.B. Park, Recent
advances on the electromagnetic wave absorption properties of Ni based
materials, Engineered Science 3(23) (2018) 5-40. 10.30919/es8d735.
[47] G. Nie, X. Zhao, Y. Luan, J. Jiang, Z. Kou, J. Wang, Key issues facing electrospun
carbon nanofibers in energy applications: on-going approaches and
challenges, Nanoscale 12 (25) (2020) 13225–13248, https://doi.org/
10.1039/D0NR03425H.
[48] G. Nie, Z. Zhang, T. Wang, C. Wang, Z. Kou, Electrospun one-dimensional
electrocatalysts for oxygen reduction reaction: insights into structure-
activity relationship, ACS Appl. Mater. Interfaces 13 (32) (2021) 37961–
37978, https://doi.org/10.1021/acsami.1c08798.
[49] C. Wang, C. Liu, J. Li, X. Sun, J. Shen, W. Han, L. Wang, Electrospun metal-
organic framework derived hierarchical carbon nanofibers with high
performance for supercapacitors, Chem. Commun. 53 (10) (2017) 1751–
1754, https://doi.org/10.1039/C6CC09832K.
[50] G. Lee, Y.D. Seo, J. Jang, ZnO quantum dot-decorated carbon nanofibers
derived from electrospun ZIF-8/PVA nanofibers for high-performance energy
storage electrodes, Chem. Commun. 53 (83) (2017) 11441–11444, https://doi.
org/10.1039/C7CC05206E.
[51] Y. Li, G. Zhu, H. Huang, M. Xu, T. Lu, L. Pan, A N, S dual doping strategy via
electrospinning to prepare hierarchically porous carbon polyhedra embedded
carbon nanofibers for flexible supercapacitors, J. Mater. Chem. A 7 (15) (2019)
9040–9050, https://doi.org/10.1039/C8TA12246F.
[52] Y. Yao, P. Liu, X. Li, S. Zeng, T. Lan, H. Huang, X. Zeng, J. Zou, Nitrogen-doped
graphitic hierarchically porous carbon nanofibers obtained via bimetallic-
coordination organic framework modification and their application in
supercapacitors, Dalton Trans. 47 (21) (2018) 7316–7326, https://doi.org/
10.1039/C8DT00823J.
[53] Y.-N. Wu, F. Li, H. Liu, W. Zhu, M. Teng, Y. Jiang, W. Li, D. Xu, D. He, P. Hannam,
G. Li, Electrospun fibrous mats as skeletons to produce free-standing MOF
membranes, J. Mater. Chem. 22 (33) (2012) 16971, https://doi.org/10.1039/
c2jm32570e.
[54] S. Zhao, H. Wu, Y. Li, Q. Li, J. Zhou, X. Yu, H. Chen, K. Tao, L. Han, Core-shell
assembly of carbon nanofibers and a 2D conductive metal-organic framework
as a flexible free-standing membrane for high-performance supercapacitors,
Inorg. Chem. Front. 6 (7) (2019) 1824–1830, https://doi.org/10.1039/
C9QI00390H.
[55] D. Tian, N. Song, M. Zhong, X. Lu, C. Wang, Bimetallic MOF nanosheets
decorated on electrospun nanofibers for high-performance asymmetric
supercapacitors, ACS Appl. Mater. Interfaces 12 (1) (2019) 1280–1291,
https://doi.org/10.1021/acsami.9b16420.
[56] W. Zhao, J. Peng, W. Wang, B. Jin, T. Chen, S. Liu, Q. Zhao, W. Huang, Interlayer
hydrogen-bonded metal porphyrin frameworks/MXene hybrid film with high
capacitance for flexible all-solid-state supercapacitors, Small 15 (18) (2019)
1901351, https://doi.org/10.1002/smll.201901351.
[57] J. Cheng, S. Chen, D. Chen, L. Dong, J. Wang, T. Zhang, T. Jiao, B. Liu, H. Wang, J.
J. Kai, D. Zhang, G. Zheng, L. Zhi, F. Kang, W. Zhang, Editable asymmetric all-
J. Yan, T. Liu, X. Liu et al.
solid-state supercapacitors based on high-strength, flexible, and
programmable 2D-metal-organic framework/reduced graphene oxide self-
assembled papers, J Mater. Chem. A 6 (41) (2018) 20254–20266, https://doi.
org/10.1039/c8ta06785f.
[58] T. Qin, S. Peng, J. Hao, Y. Wen, Z. Wang, X. Wang, D. He, J. Zhang, J. Hou, G. Cao,
Flexible and wearable all-solid-state supercapacitors with ultrahigh energy
density based on a carbon fiber fabric electrode, Adv. Energy Mater. 7 (20)
(2017) 1700409, https://doi.org/10.1002/aenm.201700409.
[59] Y. He, S. Yang, Y. Fu, F. Wang, J. Ma, G. Wang, G. Chen, M. Wang, R. Dong, P.
Zhang, Electronic doping of metal-organic frameworks for high-performance
flexible micro-supercapacitors, Small Struct. 2 (3) (2021) 2000095, https://
doi.org/10.1002/sstr.202000095.
[60] X.X. Liu, Q. He, Y. Wang, J. Wang, Y. Xiang, D.J. Blackwood, R. Wu, J.S. Chen,
MOF-reinforced Co9S8 self-supported nanowire arrays for highly durable and
flexible supercapacitor, Electrochim. Acta 346 (2020), https://doi.org/
10.1016/j.electacta.2020.136201 136201.
[61] Z. Tang, G. Zhang, H. Zhang, L. Wang, H. Shi, D. Wei, H. Duan, MOF-derived N-
doped carbon bubbles on carbon tube arrays for flexible high-rate
supercapacitors, Energy Stor. Mater. 10 (2018) 75–84, https://doi.org/
10.1016/j.ensm.2017.08.009.
[62] C. Guan, X. Liu, W. Ren, X. Li, C. Cheng, J. Wang, Rational design of metal-
organic framework derived hollow NiCo2O4 arrays for flexible supercapacitor
and electrocatalysis, Adv. Energy Mater. 7 (12) (2017) 1602391, https://doi.
org/10.1002/aenm.201602391.
[63] X. Liu, C. Guan, Y. Hu, L. Zhang, A.M. Elshahawy, J. Wang, 2D metal-organic
frameworks derived nanocarbon arrays for substrate enhancement in flexible
supercapacitors, Small 14 (43) (2018) 1702641, https://doi.org/10.1002/
smll.201702641.
[64] X. Xu, J. Tang, H. Qian, S. Hou, Y. Bando, M.S.A. Hossain, L. Pan, Y. Yamauchi,
Three-dimensional networked metal-organic frameworks with conductive
polypyrrole tubes for flexible supercapacitors, ACS Appl. Mater. Interfaces 9
(44) (2017) 38737–38744, https://doi.org/10.1021/acsami.7b09944.
[65] C. Cheng, J. Xu, W. Gao, S. Jiang, R. Guo, Preparation of flexible supercapacitor
with RGO/Ni-MOF film on Ni-coated polyester fabric, Electrochim. Acta 318
(2019) 23–31, https://doi.org/10.1016/j.electacta.2019.06.055.
[66] Y. Yan, P. Gu, S. Zheng, M. Zheng, H. Pang, H. Xue, Facile synthesis of an
accordion-like Ni-MOF superstructure for high-performance flexible
supercapacitors, J. Mater. Chem. A 4 (48) (2016) 19078–19085, https://doi.
org/10.1039/C6TA08331E.
[67] A. Basu, K. Roy, N. Sharma, S. Nandi, R. Vaidhyanathan, S. Rane, C. Rode, S.
Ogale, CO2 laser direct written MOF-based metal-decorated and heteroatom-
doped porous graphene for flexible all-solid-state microsupercapacitor with
extremely high cycling stability, ACS Appl. Mater. Interfaces 8 (46) (2016)
31841–31848, https://doi.org/10.1021/acsami.6b10193.
[68] R. Hou, M. Miao, Q. Wang, T. Yue, H. Liu, H.S. Park, K. Qi, B.Y. Xia, Integrated
conductive hybrid architecture of metal-organic framework nanowire array
on polypyrrole membrane for all-solid-state flexible supercapacitors, Adv.
Energy Mater. 10 (1) (2019) 1901892, https://doi.org/10.1002/
aenm.201901892.
[69] R. Díaz, M.G. Orcajo, J.A. Botas, G. Calleja, J. Palma, Co8-MOF-5 as electrode for
supercapacitors, Mater. Lett. 68 (2012) 126–128, https://doi.org/10.1016/
j.matlet.2011.10.046.
[70] D.Y. Lee, S.J. Yoon, N.K. Shrestha, S.H. Lee, H. Ahn, S.H. Han, Unusual energy
storage and charge retention in Co-based metal-organic-frameworks,
Micropor. Mesopor. Mater 153 (2012) 163–165, https://doi.org/10.1016/j.
micromeso.2011.12.040.
[71] N. Campagnol, R. Romero-Vara, W. Deleu, L. Stappers, K. Binnemans, D. De
Vos, J. Fransaer, A hybrid supercapacitor based on porous carbon and the
metal-organic framework MIL-100 (Fe), ChemElectroChem 1 (7) (2014)
1182–1188, https://doi.org/10.1002/celc.201402022.
[72] Y. Yan, Y. Luo, J. Ma, B. Li, H. Xue, H. Pang, Facile synthesis of vanadium metal-
organic frameworks for high-performance supercapacitors, Small 14 (33)
(2018) 1801815, https://doi.org/10.1002/smll.201801815.
[73] D. Sheberla, J.C. Bachman, J.S. Elias, C.J. Sun, Y. Shao-Horn, M. Dincă,
Conductive MOF electrodes for stable supercapacitors with high areal
capacitance, Nat. Mater. 16 (2) (2017) 220–224, https://doi.org/10.1038/
nmat4766.
[74] Y. Jiao, J. Pei, D. Chen, C. Yan, Y. Hu, Q. Zhang, G. Chen, Mixed-metallic MOF
based electrode materials for high performance hybrid supercapacitors, J.
Mater. Chem. A 5 (3) (2017) 1094–1102, https://doi.org/10.1039/C6TA09805C.
[75] W. Zhao, T. Chen, W. Wang, B. Jin, J. Peng, S. Bi, M. Jiang, S. Liu, Q. Zhao, W.
Huang, Conductive Ni3(HITP)2 MOFs thin films for flexible transparent
supercapacitors with high rate capability, Sci. Bull. 65 (21) (2020) 1803–
1811, https://doi.org/10.1016/j.scib.2020.06.027.
[76] F. Dai, X. Wang, S. Zheng, J. Sun, Z. Huang, B. Xu, L. Fan, R. Wang, D. Sun, Z.S.
Wu, Toward high-performance and flexible all-solid-state micro-
supercapacitors: MOF bulk vs. MOF nanosheets, Chem. Eng. J. 413 (2021),
https://doi.org/10.1016/j.cej.2020.127520 127520.
[77] R. Sen, D. Saha, S. Koner, D. Mal, P. Brandão, Z. Lin, pH-tuned modulation of 1D
chain to 3D metal-organic framework: synthesis structure and their useful
application in the heterogeneous claisen-schmidt reaction, ChemPlusChem
80 (3) (2015) 591–598, https://doi.org/10.1002/cplu.201402340.
[78] Y.H. Hung, L.Y. Lin, H.Y. Lin, Y.S. Sung, Y.J. Hsiao, Y.C. Li, Enhanced energy
storage ability of UIO66 active material on acid-treated carbon cloth for
flexible supercapacitors, Electrochim. Acta 380 (2021), https://doi.org/
10.1016/j.electacta.2021.138241 138241.
26
Coordination Chemistry Reviews 452 (2022) 214300
[79] Y. Chen, N. Wang, W. Hu, S. Komarneni, In situ construction of porous Ni/Co-
MOF@Carbon cloth electrode with honeycomb-like structure for high-
performance energy storage, J. Porous. Mat. 26 (3) (2019) 921–929, https://
doi.org/10.1007/s10934-019-00735-9.
[80] C. Ye, Q. Qin, J. Liu, W. Mao, J. Yan, Y. Wang, J. Cui, Q. Zhang, L. Yang, Y. Wu,
Coordination derived stable Ni-Co MOFs for foldable all-solid-state
supercapacitors with high specific energy, J. Mater. Chem. A 7 (9) (2019)
4998–5008, https://doi.org/10.1039/C8TA11948A.
[81] L. Chen, D. Ou, G. Zhang, J. Yan, J. Liu, Z. Wang, Y. Wang, J. Cui, Q. Zhang, Y.
Zhang, Ni-Co coordination hollow spheres for high performance flexible all-
solid-state supercapacitor, Electrochim. Acta 337 (2020), https://doi.org/
10.1016/j.electacta.2020.135828 135828.
[82] Z. Zhang, H. Yoshikawa, K. Awaga, Discovery of a ‘‘bipolar charging”
mechanism in the solid-state electrochemical process of a flexible metal-
organic framework, Chem. Mater. 28 (5) (2016) 1298–1303, https://doi.org/
10.1021/acs.chemmater.5b04075.
[83] F. Miao, C. Shao, X. Li, K. Wang, Y. Liu, Flexible solid-state supercapacitors
based on freestanding nitrogen-doped porous carbon nanofibers derived
from electrospun polyacrylonitrile@polyaniline nanofibers, J. Mater. Chem. A
4 (11) (2016) 4180–4187, https://doi.org/10.1039/C6TA00015K.
[84] M. Zhu, Y. Huang, Q. Deng, J. Zhou, Z. Pei, Q. Xue, Y. Huang, Z. Wang, H. Li, Q. Huang,
Highly flexible, freestanding supercapacitor electrode with enhanced
performance obtained by hybridizing polypyrrole chains with MXene, Adv.
Energy Mater. 6 (21) (2016) 1600969, https://doi.org/10.1002/aenm.201600969.
[85] C. Hao, B. Yang, F. Wen, J. Xiang, L. Li, W. Wang, Z. Zeng, B. Xu, Z. Zhao, Z. Liu,
Flexible all-solid-state supercapacitors based on liquid-exfoliated black-
phosphorus nanoflakes, Adv. Mater. 28 (16) (2016) 3194–3201, https://doi.
org/10.1002/adma.201505730.
[86] Y. Xu, Q. Li, H. Xue, H. Pang, Metal-organic frameworks for direct
electrochemical applications, Coordin. Chem. Rev. 376 (2018) 292–318,
https://doi.org/10.1016/j.ccr.2018.08.010.
[87] S. Sundriyal, H. Kaur, S.K. Bhardwaj, S. Mishra, K.H. Kim, A. Deep, Metal-
organic frameworks and their composites as efficient electrodes for
supercapacitor applications, Coordin. Chem. Rev. 369 (2018) 15–38, https://
doi.org/10.1016/j.ccr.2018.04.018.
[88] P. Liu, J. Yan, Z. Guang, Y. Huang, X. Li, W. Huang, Recent advancements of
polyaniline-based nanocomposites for supercapacitors, J. Power Sour. 424
(2019) 108–130, https://doi.org/10.1016/j.jpowsour.2019.03.094.
[89] L. Wang, X. Feng, L. Ren, Q. Piao, J. Zhong, Y. Wang, H. Li, Y. Chen, B. Wang,
Flexible Solid-State Supercapacitor Based on a Metal-Organic Framework
Interwoven by Electrochemically-Deposited PANI, J. Am. Chem. Soc. 137(15)
(2015) 4920-3. 10.1021/jacs.5b01613
[90] L. Shao, Q. Wang, Z. Ma, Z. Ji, X. Wang, D. Song, Y. Liu, N. Wang, A high-
capacitance flexible solid-state supercapacitor based on polyaniline and
Metal-Organic Framework (UiO-66) composites, J. Power Sour. 379 (2018)
350–361, https://doi.org/10.1016/j.jpowsour.2018.01.028.
[91] H. Chen, R. Hong, Q. Liu, S. Li, F. Huang, Y. Lu, L. Wang, K. Li, H. Zhang,
CNFs@carbonaceous Co/CoO composite derived from CNFs penetrated through
ZIF-67 for high-efficient electromagnetic wave absorption material, J. Alloy.
Compd. 752 (2018) 115–122, https://doi.org/10.1016/j.jallcom.2018.04.142.
[92] X.M. Cao, Z.B. Han, Hollow core-shell ZnO@ZIF-8 on carbon cloth for flexible
supercapacitors with ultrahigh areal capacitance, Chem. Commun. 55 (12)
(2019) 1746–1749, https://doi.org/10.1039/c8cc09847f.
[93] Y.N. Liu, L.N. Jin, H.T. Wang, X.H. Kang, S.W. Bian, Fabrication of three-
dimensional composite textile electrodes by metal-organic framework, zinc
oxide, graphene and polyaniline for all-solid-state supercapacitors, J. Colloid
Interface Sci. 530 (2018) 29–36, https://doi.org/10.1016/j.jcis.2018.06.062.
[94] L.L. Xu, M.X. Guo, S. Liu, S.W. Bian, Graphene/cotton composite fabrics as
flexible electrode materials for electrochemical capacitors, RSC Adv. 5 (32)
(2015) 25244–25249, https://doi.org/10.1039/c4ra16063k.
[95] J. Yan, Y. Huang, X. Liu, X. Zhao, T. Li, Y. Zhao, P. Liu, Polypyrrole-based
composite materials for electromagnetic wave absorption, Polym. Rev. 61 (3)
(2021) 646–687, https://doi.org/10.1080/15583724.2020.1870490.
[96] W. Raza, F. Ali, N. Raza, Y. Luo, K.H. Kim, J. Yang, S. Kumar, A. Mehmood, E.E.
Kwon, Recent advancements in supercapacitor technology, Nano Energy 52
(2018) 441–473, https://doi.org/10.1016/j.nanoen.2018.08.013.
[97] Y. Huang, H. Li, Z. Wang, M. Zhu, Z. Pei, Q. Xue, Y. Huang, C. Zhi,
Nanostructured polypyrrole as a flexible electrode material of
supercapacitor, Nano Energy 22 (2016) 422–438, https://doi.org/10.1016/
j.nanoen.2016.02.047.
[98] C. Lu, D. Wang, J. Zhao, S. Han, W. Chen, A continuous carbon nitride
polyhedron assembly for high-performance flexible supercapacitors, Adv.
Funct. Mater. 27 (8) (2017) 1606219, https://doi.org/10.1002/
adfm.201606219.
[99] K. Qi, R. Hou, S. Zaman, Y. Qiu, B.Y. Xia, H. Duan, Construction of metal-
organic framework/conductive polymer hybrid for all-solid-state fabric
supercapacitor, ACS Appl. Mater. Interfaces 10 (21) (2018) 18021–18028,
https://doi.org/10.1021/acsami.8b05802.
[100] C. Zhang, J. Tian, W. Rao, B. Guo, L. Fan, W. Xu, J. Xu, Polypyrrole@metal-
organic framework (UIO-66)@cotton fabric electrodes for flexible
supercapacitors, Cellulose 26 (5) (2019) 3387–3399, https://doi.org/
10.1007/s10570-019-02321-3.
[101] M. Barakzehi, M. Montazer, F. Sharif, T. Norby, A. Chatzitakis, MOF-modified
polyester fabric coated with reduced graphene oxide/polypyrrole as
electrode for flexible supercapacitors, Electrochim. Acta 336 (2020), https://
doi.org/10.1016/j.electacta.2020.135743 135743.
J. Yan, T. Liu, X. Liu et al.
[102] S.S. Jia, W.S. Xu, Y. Chen, Y. Liu, Pyrrole/macrocycle/MOF supramolecular co-
assembly for flexible solid state supercapacitors, Chin. Chem. Lett. (2021),
https://doi.org/10.1016/j.cclet.2021.03.002.
[103] W. Zhao, W. Wang, J. Peng, T. Chen, B. Jin, S. Liu, W. Huang, Q. Zhao, Wrinkled
two-dimensional ultrathin Cu (II)-porphyrin framework nanosheets
hybridized with polypyrrole for flexible all-solid-state supercapacitors,
Dalton Trans. 48 (26) (2019) 9631–9638, https://doi.org/10.1039/
C8DT05069D.
[104] D. Zhao, Q. Zhang, W. Chen, X. Yi, S. Liu, Q. Wang, Y. Liu, J. Li, X. Li, H. Yu,
Highly flexible and conductive cellulose-mediated PEDOT:PSS/MWCNT
composite films for supercapacitor electrodes, ACS Appl. Mater. Interfaces 9
(15) (2017) 13213–13222, https://doi.org/10.1021/acsami.7b01852.
[105] G. Cai, P. Darmawan, M. Cui, J. Wang, J. Chen, S. Magdassi, P.S. Lee, Highly
Stable transparent conductive silver Grid/PEDOT:PSS electrodes for
integrated bifunctional flexible electrochromic supercapacitors, Adv. Energy
Mater. 6 (4) (2016), https://doi.org/10.1002/aenm.201501882.
[106] Y. Liu, I. Murtaza, A. Shuja, H. Meng, Interfacial modification for heightening
the interaction between PEDOT and substrate towards enhanced flexible
solid supercapacitor performance, Chem. Eng. J. 379 (2020), https://doi.org/
10.1016/j.cej.2019.122326 122326.
[107] D. Fu, H. Li, X.M. Zhang, G. Han, H. Zhou, Y. Chang, Flexible solid-state
supercapacitor fabricated by metal-organic framework/graphene oxide
hybrid interconnected with PEDOT, Mater. Chem. Phys. 179 (2016) 166–
173, https://doi.org/10.1016/j.matchemphys.2016.05.024.
[108] D. Fu, H. Zhou, X.M. Zhang, G. Han, Y. Chang, H. Li, Flexible solid-state
supercapacitor of metal-organic framework coated on carbon nanotube film
interconnected by electrochemically-codeposited PEDOT-GO,
ChemistrySelect 1 (2) (2016) 285–289, https://doi.org/10.1002/
slct.201600084.
[109] B. Wang, S. Liu, L. Liu, W.W. Song, Y. Zhang, S.M. Wang, Z.B. Han, MOF/PEDOT/
HPMo-based polycomponent hierarchical hollow micro-vesicles for high
performance flexible supercapacitors, J. Mater. Chem. A 9 (5) (2021) 2948–
2958, https://doi.org/10.1039/D0TA10603H.
[110] X. Chen, R. Paul, L. Dai, Carbon-based supercapacitors for efficient energy
storage, Natl. Sci. Rev. 4 (3) (2017) 453–489, https://doi.org/10.1093/nsr/
nwx009.
[111] S. Iijima, Helical microtubules of graphitic carbon, Nature 354 (6348) (1991)
56–58, https://doi.org/10.1038/354056a0.
[112] B. Zhang, J. Wang, X.G. Su, H.J. Duan, H.P. Cai, J.P. Wang, S. Yang, S.Q. Huo,
Enhanced microwave absorption properties of epoxy composites containing
graphene decorated with core-shell Fe3O4@polypyrrole nanoparticles, J.
Mater. Sci.-Mater. El. 28 (16) (2017) 12122–12131, https://doi.org/10.1007/
s10854-017-7026-z.
[113] Y. Zhang, B. Lin, Y. Sun, X. Zhang, H. Yang, J. Wang, Carbon nanotubes@metal-
organic frameworks as Mn-based symmetrical supercapacitor electrodes for
enhanced charge storage, RSC Adv. 5 (72) (2015) 58100–58106, https://doi.
org/10.1039/c5ra11597c.
[114] L. Huang, D. Santiago, P. Loyselle, L. Dai, Graphene-based nanomaterials for
flexible and wearable supercapacitors, Small 14 (43) (2018) 1800879, https://
doi.org/10.1002/smll.201800879.
[115] M.F. El-Kady, Y. Shao, R.B. Kaner, Graphene for batteries, supercapacitors and
beyond, Nat. Rev. Mater. 1 (7) (2016) 1–14, https://doi.org/
10.1038/natrevmats.2016.33.
[116] Y. Zheng, S. Zheng, H. Xue, H. Pang, Metal-organic frameworks/graphene-
based materials: preparations and applications, Adv. Funct. Mater. 28 (47)
(2018) 1804950, https://doi.org/10.1002/adfm.201804950.
[117] Z. Wang, J. Huang, J. Mao, Q. Guo, Z. Chen, Y. Lai, Metal-organic frameworks
and their derivatives with graphene composites: preparation and
applications in electrocatalysis and photocatalysis, J. Mater. Chem. A 8 (6)
(2020) 2934–2961, https://doi.org/10.1039/c9ta12776c.
[118] Y. Zhou, Z. Mao, W. Wang, Z. Yang, X. Liu, In-situ fabrication of graphene
oxide hybrid ni-based metal-organic framework (Ni-MOFs@GO) with
ultrahigh capacitance as electrochemical pseudocapacitor materials, ACS
Appl. Mater. Interfaces 8 (42) (2016) 28904–28916, https://doi.org/10.1021/
acsami.6b10640.
[119] P. Srimuk, S. Luanwuthi, A. Krittayavathananon, M. Sawangphruk, Solid-type
supercapacitor of reduced graphene oxide-metal organic framework
composite coated on carbon fiber paper, Electrochim. Acta 157 (2015) 69–
77, https://doi.org/10.1016/j.electacta.2015.01.082.
[120] M.S. Rahmanifar, H. Hesari, A. Noori, M.Y. Masoomi, A. Morsali, M.F. Mousavi,
A dual Ni/Co-MOF-reduced graphene oxide nanocomposite as a high
performance supercapacitor electrode material, Electrochim. Acta 275
(2018) 76–86, https://doi.org/10.1016/j.electacta.2018.04.130.
[121] Y.F. Wang, S.Y. Yang, Y. Yue, S.W. Bian, Conductive copper-based metal-
organic framework nanowire arrays grown on graphene fibers for flexible all-
solid-state supercapacitors, J. Alloy. Compd. 835 (2020), https://doi.org/
10.1016/j.jallcom.2020.155238 155238.
[122] Y. Yue, S.Y. Yang, Y.L. Huang, B. Sun, S.W. Bian, Reduced graphene oxide/
polyester yarns supported conductive metal-organic framework nanorods as
novel electrodes for all-solid-state supercapacitors, Energy & Fuels 34 (12)
(2020) 16879–16884, https://doi.org/10.1021/acs.energyfuels.0c03380.
[123] S. Senthilkumar, R. Selvan, J. Melo, Redox additive/active electrolytes: a novel
approach to enhance the performance of supercapacitors, J. Mater. Chem. A 1
(40) (2013) 12386–12394, https://doi.org/10.1039/C3TA11959A.
[124] S. Sundriyal, V. Shrivastav, H. Kaur, S. Mishra, A. Deep, High-performance
symmetrical supercapacitor with a combination of a ZIF-67/rGO composite
27
Coordination Chemistry Reviews 452 (2022) 214300
electrode and a redox additive electrolyte, ACS Omega 3 (12) (2018) 17348–
17358, https://doi.org/10.1021/acsomega.8b02065.
[125] M. Wang, H. Shi, P. Zhang, Z. Liao, M. Wang, H. Zhong, F. Schwotzer, A.S. Nia,
E. Zschech, S. Zhou, Phthalocyanine-based 2D conjugated metal-organic
framework nanosheets for high-performance micro-supercapacitors, Adv.
Funct. Mater. 30 (30) (2020) 2002664, https://doi.org/10.1002/
adfm.202002664.
[126] Z. Li, X. Ge, C. Li, S. Dong, R. Tang, C. Wang, Z. Zhang, L. Yin, Rational
microstructure design on metal-organic framework composites for better
electrochemical performances: design principle synthetic strategy, and
promotion mechanism, Small Methods 4 (3) (2020) 1–31, https://doi.org/
10.1002/smtd.201900756.
[127] Y. Gao, J. Wu, W. Zhang, Y. Tan, J. Zhao, B. Tang, The electrochemical
performance of SnO2 quantum dots@zeolitic imidazolate frameworks-8 (ZIF-
8) composite material for supercapacitors, Mater. Lett. 128 (2014) 208–211,
https://doi.org/10.1016/j.matlet.2014.04.175.
[128] Y.Z. Zhang, T. Cheng, Y. Wang, W.-Y. Lai, H. Pang, W. Huang, A simple
approach to boost capacitance: flexible supercapacitors based on manganese
Oxides@MOFs via chemically induced in situ self-transformation, Adv. Mater.
28 (26) (2016) 5242–5248, https://doi.org/10.1002/adma.201600319.
[129] Q. Xu, H. Pang, H. Xue, Q. Li, S. Zheng, A highly alkaline-stable metal
oxide@metal-organic framework composite for high-performance
electrochemical energy storage, Natl. Sci. Rev. 7 (2) (2020) 305–314,
https://doi.org/10.1093/nsr/nwz137.
[130] L. Zhang, Y. Zhang, S. Huang, Y. Yuan, H. Li, Z. Jin, J. Wu, Q. Liao, L. Hu, J. Lu, S.
Ruan, Y.-J. Zeng, Co3O4/Ni-based MOFs on carbon cloth for flexible alkaline
battery-supercapacitor hybrid devices and near-infrared photocatalytic
hydrogen evolution, Electrochim. Acta 281 (2018) 189–197, https://doi.org/
10.1016/j.electacta.2018.05.162.
[131] F. Zhang, J. Zhang, J. Song, Y. You, X. Jin, J. Ma, Anchoring Ni-MOF nanosheet
on carbon cloth by zeolite imidazole framework derived ribbonlike Co3O4 as
integrated composite cathodes for advanced hybrid supercapacitors, Ceram.
Int. 47 (10) (2021) 14001–14008, https://doi.org/10.1016/j.
ceramint.2021.01.269.
[132] F. Zhang, J. Ma, H. Yao, Ultrathin Ni-MOF nanosheet coated NiCo2O4 nanowire
arrays as a high-performance binder-free electrode for flexible hybrid
supercapacitors, Ceram. Int. 45 (18) (2019) 24279–24287, https://doi.org/
10.1016/j.ceramint.2019.08.140.
[133] G. Li, H. Cai, X. Li, J. Zhang, D. Zhang, Y. Yang, J. Xiong, Construction of
hierarchical NiCo2O4@ Ni-MOF hybrid arrays on carbon cloth as superior
battery-type electrodes for flexible solid-state hybrid supercapacitors, ACS
Appl. Mater. Interfaces 11 (41) (2019) 37675–37684, https://doi.org/10.1021/
acsami.9b11994.
[134] J. Yan, Y. Huang, X. Zhang, X. Gong, C. Chen, G. Nie, X. Liu, P. Liu, MoS2-
decorated/integrated carbon fiber: phase engineering well-regulated
microwave absorber, Nano-Micro Lett. 13 (1) (2021) 1–15, https://doi.org/
10.1007/s40820-021-00646-y.
[135] L. Yue, X. Wang, T. Sun, H. Liu, Q. Li, N. Wu, H. Guo, W. Yang, Ni-MOF coating
MoS2 structures by hydrothermal intercalation as high-performance
electrodes for asymmetric supercapacitors, Chem. Eng. J. 375 (2019),
https://doi.org/10.1016/j.cej.2019.121959 121959.
[136] J. Zhang, Y. Li, M. Han, Q. Xia, Q. Chen, M. Chen, Constructing ultra-thin Ni-
MOF@NiS2 nanosheets arrays derived from metal organic frameworks for
advanced all-solid-state asymmetric supercapacitor, Mater. Res. Bull. 137
(2021), https://doi.org/10.1016/j.materresbull.2020.111186 111186.
[137] C. Zhu, Y. He, Y. Liu, N. Kazantseva, P. Saha, Q. Cheng, ZnO@ MOF@ PANI core-
shell nanoarrays on carbon cloth for high-performance supercapacitor
electrodes, J. Energy Chem. 35 (2019) 124–131, https://doi.org/10.1016/
j.jechem.2018.11.006.
[138] S. Zhou, X. Kong, B. Zheng, F. Huo, M. Strømme, C. Xu, Cellulose nanofiber@
conductive metal-organic frameworks for high-performance flexible
supercapacitors, ACS nano 13 (8) (2019) 9578–9586, https://doi.org/
10.1021/acsnano.9b04670.
[139] F.B. Ajdari, E. Kowsari, M.N. Shahrak, A. Ehsani, Z. Kiaei, H. Torkzaban, M.
Ershadi, S.K. Eshkalak, V. Haddadi-Asl, A. Chinnappan, A review on the field
patents and recent developments over the application of metal organic
frameworks (MOFs) in supercapacitors, Coordin. Chem. Rev. 422 (2020),
https://doi.org/10.1016/j.ccr.2020.213441 213441.
[140] X.M. Cao, Z.J. Sun, S.Y. Zhao, B. Wang, Z.-B. Han, MOF-derived sponge-like
hierarchical porous carbon for flexible all-solid-state supercapacitors, Mater.
Chem. Front. 2 (9) (2018) 1692–1699, https://doi.org/10.1039/C8QM00284C.
[141] Z. Li, X. Liu, L. Wang, F. Bu, J. Wei, D. Pan, M. Wu, Hierarchical 3D all-carbon
composite structure modified with N-Doped graphene quantum dots for
high-performance flexible supercapacitors, Small 14 (39) (2018) 1801498,
https://doi.org/10.1002/smll.201801498.
[142] G. Zhao, Y. Tang, G. Wan, X. Xu, X. Zhou, M. Zhou, C. Hao, S. Deng, G. Wang,
High-performance and flexible all-solid-state hybrid supercapacitor
constructed by NiCoP/CNT and N-doped carbon coated CNT nanoarrays, J.
Colloid Interface Sci. 572 (2020) 151–159, https://doi.org/10.1016/j.
jcis.2020.03.084.
[143] L. Wang, H. Liu, J. Zhao, X. Zhang, C. Zhang, G. Zhang, Q. Liu, H. Duan,
Enhancement of charge transport in porous carbon nanofiber networks via
ZIF-8-enabled welding for flexible supercapacitors, Chem. Eng. J. 382 (2020),
https://doi.org/10.1016/j.cej.2019.122979 122979.
[144] S. Shin, M.W. Shin, Nickel metal-organic framework (Ni-MOF) derived NiO/
C@CNF composite for the application of high performance self-standing
J. Yan, T. Liu, X. Liu et al.
supercapacitor electrode, Appl. Surf. Sci. 540 (2021), https://doi.org/10.1016/
j.apsusc.2020.148295 148295.
[145] X. Yu, J. Sun, W. Zhao, S. Zhao, H. Chen, K. Tao, Y. Hu, L. Han, MOF-derived
Bi2O3@C microrods as negative electrodes for advanced asymmetric
supercapacitors, RSC. Adv. 10 (24) (2020) 14107–14112, https://doi.org/
10.1039/D0RA01470B.
[146] L. Xiao, H. Qi, K. Qu, C. Shi, Y. Cheng, Z. Sun, B. Yuan, Z. Huang, D. Pan, Z. Guo,
Layer-by-layer assembled free-standing and flexible nanocellulose/porous
Co3O4 polyhedron hybrid film as supercapacitor electrodes, Adv. Compos.
Hybrid Mater. (2021) 1–11, https://doi.org/10.1007/s42114-021-00223-2.
[147] Z. Zhou, Q. Zhang, J. Sun, B. He, J. Guo, Q. Li, C. Li, L. Xie, Y. Yao, Metal-organic
framework derived spindle-like carbon incorporated a-Fe2O3 grown on
carbon nanotube fiber as anodes for high-performance wearable asymmetric
supercapacitors, ACS Nano 12 (9) (2018) 9333–9341, https://doi.org/
10.1021/acsnano.8b04336.
[148] E. Samuel, B. Joshi, M.W. Kim, Y.I. Kim, M.T. Swihart, S.S. Yoon, Hierarchical
zeolitic imidazolate framework-derived manganese-doped zinc oxide
decorated carbon nanofiber electrodes for high performance flexible
supercapacitors, Chem. Eng. J. 371 (2019) 657–665, https://doi.org/10.1016/
j.cej.2019.04.065.
[149] Y. Tao, Y. Wu, H. Chen, W. Chen, J. Wang, Y. Tong, G.u. Pei, Z. Shen, C. Guan,
Synthesis of amorphous hydroxyl-rich Co3O4 for flexible high-rate
supercapacitor, Chem. Eng. J. 396 (2020) 125364, https://doi.org/10.1016/j.
cej.2020.125364.
[150] C. Zhu, C. Guan, D. Cai, T. Chen, Y. Wang, J. Du, J. Wu, X. Xu, H. Yu, W. Huang,
Carbon nanoarrays embedded with metal compounds for high-performance
flexible supercapacitors, Batter. Supercaps 3 (1) (2020) 93–100, https://doi.
org/10.1002/batt.201900174.
[151] C. Guan, W. Zhao, Y. Hu, Z. Lai, X. Li, S. Sun, H. Zhang, A.K. Cheetham, J. Wang,
Cobalt oxide and N-doped carbon nanosheets derived from a single two-
dimensional metal-organic framework precursor and their application in
flexible asymmetric supercapacitors, Nanoscale Horiz. 2 (2) (2017) 99–105,
https://doi.org/10.1039/C6NH00224B.
[152] M.S. Javed, M.K. Aslam, S. Asim, S. Batool, M. Idrees, S. Hussain, S.S.A. Shah, M.
Saleem, W. Mai, C. Hu, High-performance flexible hybrid-supercapacitor
enabled by pairing binder-free ultrathin Ni-Co-O nanosheets and metal-
organic framework derived N-doped carbon nanosheets, Electrochim. Acta
349 (2020), https://doi.org/10.1016/j.electacta.2020.136384 136384.
[153] G. Zhao, X. Xu, G. Zhu, J. Shi, Y. Li, S. Zhang, M.S.A. Hossain, K.C.W. Wu, J. Tang,
Y. Yamauchi, Flexible nitrogen-doped carbon heteroarchitecture derived
from ZIF-8/ZIF-67 hybrid coating on cotton biomass waste with high
supercapacitive properties, Micropor. Mesopor. Mat. 303 (2020), https://
doi.org/10.1016/j.micromeso.2020.110257 110257.
[154] D. Kong, Y. Wang, S. Huang, J. Hu, Y. Von Lim, B. Liu, S. Fan, Y. Shi, H.Y. Yang,
3D self-branched zinc-cobalt Oxide@N-doped carbon hollow nanowall arrays
for high-performance asymmetric supercapacitors and oxygen
electrocatalysis, Energy Stor. Mater. 23 (2019) 653–663, https://doi.org/
10.1016/j.ensm.2019.03.003.
[155] W. Xie, Y. Wang, J. Zhou, M. Zhang, J. Yu, C. Zhu, J. Xu, MOF-derived CoFe2O4
nanorods anchored in MXene nanosheets for all pseudocapacitive flexible
supercapacitors with superior energy storage, Appl. Surf. Sci. 534 (2020),
https://doi.org/10.1016/j.apsusc.2020.147584 147584.
[156] J. Pan, S. Li, F. Li, T. Yu, Y. Liu, L.i. Zhang, L. Ma, M. Sun, X. Tian, The NiFe2O4/
NiCo2O4/GO composites electrode material derived from dual-MOF for high
performance solid-state hybrid supercapacitors, Colloids Surf. A
Physicochem. Eng. Aspects 609 (2021) 125650, https://doi.org/10.1016/
j.colsurfa.2020.125650.
[157] J. Zhu, Y. Wang, X. Zhang, W. Cai, MOF-derived ZnCo2O4@NiCo2S4@PPy core-
shell nanosheets on Ni foam for high-performance supercapacitors,
Nanotechnology 32 (14) (2021) 145404, https://doi.org/10.1088/1361-
6528/abd20b.
[158] X. Yin, H. Li, R. Yuan, J. Lu, Hierarchical self-supporting sugar gourd-shape
MOF-derived NiCo2O4 hollow nanocages@SiC nanowires for high-
performance flexible hybrid supercapacitors, J. Colloid Interface Sci. 586
(2021) 219–232, https://doi.org/10.1016/j.jcis.2020.10.086.
[159] X. Yin, H. Li, R. Yuan, J. Lu, Metal-organic framework derived hierarchical
NiCo2O4 triangle nanosheet arrays@ SiC nanowires network/carbon cloth for
flexible hybrid supercapacitors, J. Mater. Sci. Technol. 81 (2021) 162–174,
https://doi.org/10.1016/j.jmst.2020.10.085.
[160] L. He, J. Liu, L. Yang, Y. Song, M. Wang, D. Peng, Z. Zhang, S. Fang, Copper
metal-organic framework-derived CuOx-coated three-dimensional reduced
graphene oxide and polyaniline composite: excellent candidate free-standing
electrodes for high-performance supercapacitors, Electrochim. Acta 275
(2018) 133–144, https://doi.org/10.1016/j.electacta.2018.04.089.
[161] X. Xu, W. Shi, P. Li, S. Ye, C. Ye, H. Ye, T. Lu, A. Zheng, J. Zhu, L. Xu, Facile
fabrication of three-dimensional graphene and metal-organic framework
composites and their derivatives for flexible all-solid-state supercapacitors,
Chem. Mater. 29 (14) (2017) 6058–6065, https://doi.org/10.1021/acs.
chemmater.7b01947.
[162] R. Ramachandran, K. Rajavel, W. Xuan, D. Lin, F. Wang, Influence of Ti3C2Tx
(MXene) intercalation pseudocapacitance on electrochemical performance of
Co-MOF binder-free electrode, Ceram. Int. 44 (12) (2018) 14425–14431,
https://doi.org/10.1016/j.ceramint.2018.05.055.
[163] J. Wang, Y. Huang, X. Han, S. Zhang, M. Wang, J. Yan, C. Chen, M. Zong,
Construction of hierarchical Co9S8@ NiO synergistic microstructure for high-
28
Coordination Chemistry Reviews 452 (2022) 214300
performance asymmetric supercapacitor, J. Colloid Interface Sci. 603 (2021)
440–449, https://doi.org/10.1016/j.jcis.2021.06.118.
[164] H. Huang, H. Shi, P. Das, J. Qin, Y. Li, X. Wang, F. Su, P. Wen, S. Li, P. Lu, The
chemistry and promising applications of graphene and porous graphene
materials, Adv. Funct. Mater. 30 (41) (2020) 1909035, https://doi.org/
10.1002/adfm.201909035.
[165] W. Chen, T. Wei, L.E. Mo, S. Wu, Z. Li, S. Chen, X. Zhang, L. Hu, CoS2 nanosheets
on carbon cloth for flexible all-solid-state supercapacitors, Chem. Eng. J. 400
(2020), https://doi.org/10.1016/j.cej.2020.125856 125856.
[166] C.S. Lee, J. Moon, J.T. Park, J.H. Kim, Highly interconnected nanorods and
nanosheets based on a hierarchically layered metal-organic framework for a
flexible, high-performance energy storage device, ACS Sustain. Chem. Eng. 8
(9) (2020) 3773–3785, https://doi.org/10.1021/
acssuschemeng.9b0699910.1021/acssuschemeng.9b06999.s001.
[167] W. Sun, Y. Du, G. Wu, G. Gao, H. Zhu, J. Shen, K. Zhang, G. Cao, Constructing
metallic zinc-cobalt sulfide hierarchical core-shell nanosheet arrays derived
from 2D metal-organic-frameworks for flexible asymmetric supercapacitors
with ultrahigh specific capacitance and performance, J. Mater. Chem. A 7 (12)
(2019) 7138–7150, https://doi.org/10.1039/C8TA12153B.
[168] M.S. Javed, H. Lei, J. Li, Z. Wang, W. Mai, Construction of highly dispersed
mesoporous bimetallic-sulfide nanoparticles locked in N-doped graphitic
carbon nanosheets for high energy density hybrid flexible pseudocapacitors,
J. Mater. Chem. A 7 (29) (2019) 17435–17445, https://doi.org/10.1039/
C9TA05180E.
[169] X. Zhou, Y. Ren, Y. Lu, Z. Cheng, W. Wang, Q. Wang, W. Huang, X. Dong, Porous
Mo-Co-S nanosheets on carbon cloth for all-solid-state flexible asymmetric
supercapacitors, Adv. Mater. Interface 6 (22) (2019) 1901138, https://doi.org/
10.1002/admi.v6.2210.1002/admi.201901138.
[170] Y. Zhang, B. Lin, Y. Sun, P. Han, J. Wang, X. Ding, X. Zhang, H. Yang, MoO2@
Cu@C composites prepared by using polyoxometalates@metal-organic
frameworks as template for all-solid-state flexible supercapacitor,
Electrochim. Acta 188 (2016) 490–498, https://doi.org/10.1016/
j.electacta.2015.12.037.
[171] K. Le, M. Gao, W. Liu, J. Liu, Z. Wang, F. Wang, V. Murugadoss, S. Wu, T. Ding, Z.
Guo, MOF-derived hierarchical core-shell hollow iron-cobalt sulfides
nanoarrays on Ni foam with enhanced electrochemical properties for high
energy density asymmetric supercapacitors, Electrochim. Acta 323 (2019),
https://doi.org/10.1016/j.electacta.2019.134826 134826.
[172] Y. Liu, Q. Lu, Z. Huang, S. Sun, B. Yu, U. Evariste, G. Jiang, J. Yao,
Electrodeposition of Ni-Co-S nanosheet arrays on N-doped porous carbon
nanofibers for flexible asymmetric supercapacitors, J. Alloy. Compd. 762
(2018) 301–311, https://doi.org/10.1016/j.jallcom.2018.05.239.
[173] Q. Yang, Y. Liu, L. Xiao, M. Yan, H. Bai, F. Zhu, Y. Lei, W. Shi, Self-templated
transformation of MOFs into layered double hydroxide nanoarrays with
selectively formed Co9S8 for high-performance asymmetric supercapacitors,
Chem. Eng. J. 354 (2018) 716–726, https://doi.org/10.1016/j.cej.2018.08.091.
[174] T. Liu, J. Liu, L. Zhang, B. Cheng, J. Yu, Construction of nickel cobalt sulfide
nanosheet arrays on carbon cloth for performance-enhanced supercapacitor,
J. Mater. Sci. Technol. 47 (2020) 113–121, https://doi.org/10.1016/j.
jmst.2019.12.027.
[175] Y. Zhao, H. Dong, X. He, J. Yu, R. Chen, Q. Liu, J. Liu, H. Zhang, R. Li, J. Wang,
Design of 2D mesoporous Zn/Co-based metal-organic frameworks as a
flexible electrode for energy storage and conversion, J. Power Sour. 438
(2019), https://doi.org/10.1016/j.jpowsour.2019.227057 227057.
[176] Y.P. Liu, X.H. Qi, L. Li, S.H. Zhang, T. Bi, MOF-derived PPy/carbon-coated
copper sulfide ceramic nanocomposite as high-performance electrode for
supercapacitor, Ceram. Int. 45 (14) (2019) 17216–17223, https://doi.org/
10.1016/j.ceramint.2019.05.277.
[177] Y. Du, G. Li, M. Chen, X. Yang, L. Ye, X. Liu, L. Zhao, Hollow nickel-cobalt-
manganese hydroxide polyhedra via MOF templates for high-performance
quasi-solid-state supercapacitor, Chem. Eng. J. 378 (2019), https://doi.org/
10.1016/j.cej.2019.122210 122210.
[178] X. Xuan, M. Qian, L. Han, L. Wan, Y. Li, T. Lu, L. Pan, Y. Niu, S. Gong, In-situ
growth of hollow NiCo layered double hydroxide on carbon substrate for
flexible supercapacitor, Electrochim. Acta 321 (2019), https://doi.org/
10.1016/j.electacta.2019.134710 134710.
[179] Y. Wu, H. Chen, Y. Lu, J. Yang, X. Zhu, Y.u. Zheng, G. Lou, Y. Wu, Q. Wu, Z. Shen,
Z. Pan, Rational design of cobalt-nickel double hydroxides for flexible
asymmetric supercapacitor with improved electrochemical performance, J.
Colloid Interface Sci. 581 (2021) 455–464, https://doi.org/10.1016/j.
jcis.2020.08.013.
[180] X. Xu, W. Shi, W. Liu, S. Ye, R. Yin, L. Zhang, L. Xu, M. Chen, M. Zhong, X. Cao,
Preparation of two-dimensional assembled Ni-Mn-C ternary composites for
high-performance all-solid-state flexible supercapacitors, J. Mater. Chem. A 6
(47) (2018) 24086–24091, https://doi.org/10.1039/C8TA06412A.
[181] Q. Yang, Z. Li, R. Zhang, L. Zhou, M. Shao, M. Wei, Carbon modified transition
metal oxides/hydroxides nanoarrays toward high-performance flexible all-
solid-state supercapacitors, Nano Energy 41 (2017) 408–416, https://doi.org/
10.1016/j.nanoen.2017.09.049.
[182] K. Chhetri, B. Dahal, A.P. Tiwari, T. Mukhiya, A. Muthurasu, G.P. Ojha, M. Lee,
T. Kim, S.H. Chae, H.Y. Kim, Controlled selenium infiltration of cobalt
phosphide nanostructure arrays from a two-dimensional cobalt metal-
organic framework: a self-supported electrode for flexible quasi-solid-state
asymmetric supercapacitors, ACS Appl. Energy Mater. 4 (1) (2020) 404–415,
https://doi.org/10.1021/acsaem.0c02340.
J. Yan, T. Liu, X. Liu et al. Coordination Chemistry Reviews 452 (2022) 214300

[183] S. Liu, Y. Yin, Y. Shen, K.S. Hui, Y.T. Chun, J.M. Kim, K.N. Hui, L. Zhang, S.C. Jun, [186] S. Liu, L. Kang, J. Zhang, E. Jung, S. Lee, S.C. Jun, Structural engineering and
Phosphorus regulated cobalt oxide@nitrogen-doped carbon nanowires for surface modification of MOF-derived cobalt-based hybrid nanosheets for
flexible quasi-solid-state supercapacitors, Small 16 (4) (2020) 1906458, flexible solid-state supercapacitors, Energy Stor. Mater. 32 (2020) 167–177,
https://doi.org/10.1002/smll.201906458. https://doi.org/10.1016/j.ensm.2020.07.017.
[184] S. Dai, F. Han, J. Tang, W. Tang, MOF-derived Co3O4 nanosheets rich in oxygen [187] S. Dai, Y. Yuan, J. Yu, J. Tang, J. Zhou, W. Tang, Metal-organic framework-
vacancies for efficient all-solid-state symmetric supercapacitors, templated synthesis of sulfur-doped core-sheath nanoarrays and nanoporous
Electrochim. Acta 328 (2019) 135103, https://doi.org/10.1016/ carbon for flexible all-solid-state asymmetric supercapacitors, Nanoscale 10
j.electacta.2019.135103. (33) (2018) 15454–15461, https://doi.org/10.1039/C8NR03743D.
[185] B. Dahal, T. Mukhiya, G.P. Ojha, A. Muthurasu, S.H. Chae, T. Kim, D. Kang, H.Y. [188] S. Bi, H. Banda, M. Chen, L. Niu, M. Chen, T. Wu, J. Wang, R. Wang, J. Feng, T.
Kim, In-built fabrication of MOF assimilated B/N co-doped 3D porous carbon Chen, M. Dincă, A.A. Kornyshev, G. Feng, Molecular understanding of charge
nanofiber network as a binder-free electrode for supercapacitors, storage and charging dynamics in supercapacitors with MOF electrodes and
Electrochim. Acta 301 (2019) 209–219, https://doi.org/10.1016/ ionic liquid electrolytes, Nat. Mater. 19 (5) (2020) 552–558, https://doi.org/
j.electacta.2019.01.171. 10.1038/s41563-019-0598-7.

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