10.1515 - Ntrev 2022 0042

Nanotechnology Reviews 2022; 11: 1005–1046
Review Article
Yunyi Dai, Chunli Liu, Yang Bai, Qingquan Kong, and Huan Pang*
Framework materials for supercapacitors

https://doi.org/10.1515/ntrev-2022-0042
received October 6, 2021; accepted January 4, 2022
Abstract: Framework materials, including metal–organic

framework materials (MOFs), Prussian blue/Prussian blue
analogs (PB/PBAs), and covalent framework materials
(COFs), are promising candidates for fabricating electrodes
for use in electrochemical devices, especially supercapaci-
tors. Supercapacitors have been widely investigated over
the past decade. Active materials as electrode materials are
vital to the development of the next generation of super-
capacitors. Therefore, designing and fabricating novel elec-
trode materials endowed with superior specific capacitance,
perfect cycling stabilities, and distinguished power/energy
density are crucial. In this review, we focus on framework
materials – MOFs, PB/PBAs, and COFs – and report elec-
trode materials based on their pristine forms, derivatives,
and composites for supercapacitors. Recent advances and
potential applications of framework materials in supercapa-
citors are also discussed. Furthermore, we discuss the Graphical abstract: Framework materials for supercapacitors:
opportunities and challenges for the future direction of Supercapacitors are perfect energy storage devices with superior
supercapacitors based on framework materials. cycling life, remarkable power/energy density, fast charge–
discharge rates, and environmental friendliness. Frameworks mate-
Keywords: supercapacitors, frameworks materials, metal–
rials, including metal organic frameworks (MOFs), Prussian blue/
organic framework materials
Prussian blue analogs (PB/PBAs), and covalent organic frameworks
(COFs), are outstanding candidates in supercapacitors. In this
review, we mainly report typical research progress on framework
materials, their derivatives, and composites in a supercapacitor.
1 Introduction
the development of effective energy storage and conver-
Severe environmental pollution, increasing fossil fuel
sion technologies, is also required [4,5]. Among these,
consumption, and global warming have become critical
chargeable batteries and supercapacitors are recognized
societal issues [1,2]. To overcome these issues, the explora-
as some of the most efficient and reliable technologies.
tion and development of renewable and environmentally
Chargeable batteries such as Li-ion, Li-sulfur, Na-ion, etc.
friendly energy sources, including wind, solar, biomass,
are popular owing to their excellent energy density and
hydraulic, ocean energy, are necessary [3]. Effectively uti-
promising cycling life [6–8]. However, their high internal
lizing these new sustainable energy sources, thus driving
resistance considerably curtails their power delivery cap-
ability and cyclic life [9]. Moreover, the battery could not

* Corresponding author: Huan Pang, School of Chemistry and be discharged fast enough in the sudden power consump-
Chemical Engineering, Yangzhou University, Yangzhou, China, tion in the application of electrical vehicles [10].
e-mail: huanpangchem@hotmail.com Supercapacitors are electrochemical energy storage
Yunyi Dai, Chunli Liu, Yang Bai: School of Chemistry and Chemical devices that connect batteries and capacitors to produce
Engineering, Yangzhou University, Yangzhou, China
a rapid charging energy storage device for intermediate
Qingquan Kong: Institute for Advanced Study, Chengdu University,
Chengdu, 610106, SiChuan, China specific energy [11,12]. Supercapacitors deliver superior power
Open Access. © 2022 Yunyi Dai et al., published by De Gruyter. This work is licensed under the Creative Commons Attribution 4.0
International License.
1006  Yunyi Dai et al.
density, remarkable cycling life, fast charge/discharge rate, COFs are typical crystalline porous polymers that allow for
and environmental friendliness, making them attractive for the precise integration of redox-active organic building
various applications. [13–15]. Nowadays, supercapacitors are blocks into an ordered nanostructure atomically, thus
widely applied in the regenerative braking system in elec- creating predesigned skeletons and nanopores [23]. Owing
tronic vehicles. Due to their fast energy recovery, they can to their promising structural characteristics, COFs have been
compensate the charge at the time when battery power is burgeoned as new candidates for developing promising elec-
not sufficient, which improved the lifetime of the braking trochemical devices, such as gas storage, catalysis, and
system and overall efficiency [16,17]. electrochemical devices, especially for supercapacitors
The energy storage mechanisms of supercapacitors [24]. PB and PBAs are also crystalline porous materials;
can be divided into electric double-layer capacitance their typical formula is MII3[MIII(CN)6]2·nH2O (M = Fe, Co,
(EDLC) and pseudocapacitance [18–20]. EDLC is based Ni, Mn, Cu, Zn, among others). They have received consid-
on charge storage between the electrolyte and electrode erable attention in electrochemical devices owing to their
interface without any electron transfer, and it mainly occurs diverse morphologies and easily controllable size [25].
in carbon-based materials. Pseudocapacitance involves the MOFs are well-known crystalline porous materials that
storage of charges via reversible redox reactions between the have been extensively investigated owing to their excellent
electrode and the electrolyte [21,22]. Several studies have structural characteristics [26,27]. MOFs are nanoporous
shown that supercapacitor electrode materials with pseudo- materials comprising metal ions and organic ligands, which
capacitance mechanisms are usually composed of metal have been explored widely in a broad range of fields, such as
oxides, metal sulfides, and conductive polymers, delivering water desalination, imaging, gas storage and separation,
an ultrahigh specific capacitance. catalysis, drug delivery, capacitive sensor, and so on [28–32].
To develop high-performance supercapacitors, fabri- Their high porosity and a large surface area provide
cating and developing active electrode materials is important. numerous Faradaic redox centers [33]. They are also per-
In particular, framework materials play a vital role in this fect precursors and sacrificial templates for fabricating var-
field. Framework materials including covalent framework ious derivatives such as nanoporous carbon, metal oxides,
materials (COFs), Prussian blue and its analogs (PB and metal hydroxides, and mixed metal oxides [34,35]. With the
PBAs), and metal–organic frameworks (MOFs), all exhibit addition of specific materials to MOFs, MOF composites
promising characteristics in supercapacitor applications. have been developed for application in supercapacitors.
Scheme 1: The timeline of key research about MOFs in supercapacitors.

Framework materials for supercapacitors  1007
Scheme 2: The timeline of key research about PB/PBA in supercapacitors.
In this review, we mainly report typical research pro- that are usually connected through coordination bonds,
gress on framework materials in supercapacitor applica- metallic bonding, auxiliary hydrogen bonds, or van der
tions. The timeline of breakthrough for framework materials Waals force interaction [13,34,63]. This perfect framework
in supercapacitors is illustrated in Schemes 1–3 [36–61]. The was first observed and constructed by Yaghi et al. in 1995
current issues of frameworks materials, their derivatives, and [36,64]. Based on their previous work, more functional and
their composites in the field of supercapacitors, as well as porous MOFs were synthesized. Owing to their control-
possible future development directions, are also summarized. lable pore sizes, tunable chemical compositions, lower
steric hindrance, remarkable electrolyte penetrability,
and metal ions with redox activities, MOFs have become
promising electrode materials for supercapacitors [3,65].
2 MOFs Compared with traditional porous materials, MOFs pos-
sess the advantages of a large specific surface area (SSA),
Metal–organic frameworks (MOFs) are important crystal- various scaffold structures, and abundant active sites
line and porous, organic–inorganic hybridized materials [13,66]. However, the electrical conductivity of MOFs is
with a periodic network structure [62]. Most of them com- inferior to that of carbonaceous materials owing to their
prise metal ions or metal ion clusters and organic ligands ordered network constructed via coordination bonds, which
Scheme 3: The timeline of key research about COFs in supercapacitors.

hinders their application in supercapacitors. Therefore, the material was fabricated by Li et al. through a one-pot hydro-
application of MOFs in supercapacitors can be classified thermal method [78]. They observed that the (001) crystal
into three categories. (i) pristine MOFs can be utilized as plane displays an outstanding structure for electron transport
new electrode materials by adjusting their morphologies, and electrolyte ion diffusion. In addition, the cross-inked
nanometer sizes, and areas of the active material [67,68]. mesh and porous nanostructure coating on the crystal plane
(ii) MOFs can be utilized as templates to prepare nano- (001) also facilitated the diffusion and storage of electrolyte
porous carbons, metal oxides, metal hydroxides, metal sul- ions compared with the crystal plane (100), indicating
fides, among others [69,70]. (iii) Some functional materials, ideal electrochemical performance for supercapacitors
carbon materials, metal or metal compounds, conductive poly- (Figure 1a). From the scanning electron microscope
mers, and other unique metal compounds are widely used to (SEM) images, the Y3 sample displayed a clear mesh struc-
compound with MOF to prepare composites with excellent ture (Figure 1b). Hence, the electrode fabricated with Ni-
electrochemical performance and cycling stability [71]. MOF in the Y3 sample exhibited 977.04 F g−1 at a current
density of 0.5 A g−1 as well as 92.34% capacitance reten-
tion over 5,000 cycles (Figure 1c). Galvanostatic charge/
discharge (GCD) curves of Y1-5 samples at 0.5 A g−1 indi-
2.1 Pristine MOFs cated that the Y3 sample was superior to the other four,
demonstrating perfect cycling stability. Moreover, the con-
2.1.1 Monometallic MOF structed asymmetric supercapacitor (ASC) manifested an
outstanding energy density value of 55.26 W h kg−1 with
The limited electrical conductivity of pristine MOFs con- 362.50 W kg−1 power density, while maintaining 33.98 W h kg−1
siderably hinders their application in supercapacitors with 3624.87 W kg−1. Its excellent performances were ascribed
[72,73]. High-performance electrode materials, especially to its layered framework structure, the (001) crystal plane, and
conductive nickel-based MOFs, are outstanding candi- cross-linked nanoporous nanostructure coating on the (001)
dates for design and synthesis to obtain unique pristine crystal plane.
MOFs that can deliver great conductivity and cycling sta- Apart from Ni-MOF, Co-MOF is also of great interest
bility [74,75]. Sheberla et al. prepared conductive Ni-MOF owing to its conjugate π bonds, excellent electrolyte
Ni3(HITP)2 (HITP = 2,3,6,7,10,11-hexaiminotriphenylene) penetrability, controllable functionality, and lower steric
as electrode materials through the coordination inter- hindrance, which makes it a good solution to conduc-
action between Ni ions and HITP ligands without any tivity and stability problems [79]. Sanati et al. fabricated
conductive additives or other binders. This research demon- a new Co-MOF (Co (II)-TMU-63, {[Co3(μ4-tpa)3 (μdapz)
strated the special performance of conductive Ni-MOF (DMF)2]·2DMF}n, H2tpa = terephthalic acid, dapz = pyra-
with a favorable areal capacitance value of 18 µF cm−2 zine-2,5-diamine), and an assembled Co(II)-TMU-63//AC
at 0.05 A g−1 and outstanding electrochemical stability, device was successfully built. It was tested in a 2 M KOH
retaining 90% of the initial values after 10,000 cycles electrolyte; the specific capacitance of this electrode mate-
[61]. Novel one-dimensional (1D) Ni-MOF nanorods ([Ni rial was up to 384 F g−1 at 6 A g−1, while maintaining
(HOC6H4COO)1.48(OH)0.52·1.1H2O]) with uniform morphology approximately 90% of the original values over 6,000
were successfully fabricated by Xu et al. under mild condi- charge–discharge cycles [80]. Liu et al. obtained a
tions [76]. In 6 M KOH, the Ni-MOF presented 1,698 F g−1 at layered Co-LMOF that exhibited a specific capacitance of
1 A g−1. Meanwhile, a promising cyclic retention of 94.8% was 2,474 F g−1 at 1 A g−1 and 94.3% retention over 2,000 cycles
achieved over 1,000 cycles. Furthermore, in an assembled [81]. These reports demonstrate that a high-performance
hybrid supercapacitor (HSC)—Ni-MOF//graphene, the HSC specific capacitance may have a trade-off with high stabi-
showed 166 F g−1 at 1 A g−1, exhibiting a promising capacitive lity and vice versa. Typically, EDLC materials have long
property. Jiao et al. designed a special HSC that assembles Ni- cyclic lives, high power, and low capacitance perfor-
MOF with CNTs-COOH in a solution with 3 M KOH and 0.1 M mances. Some frameworks with pseudocapacitive proper-
K4[Fe(CN)6], delivering 55.8 W h kg−1 and a power density of ties usually deliver higher capacitance values but a slightly
7,000 W kg−1 [77]. These favorable performances can be shorter cycling life than their EDLC counterparts [82]. To
ascribed to Ni-MOF that utilizes the redox reaction to store obtain MOFs with both high-performance capacitance and
energy, exhibiting a large surface area, high porosity, and high cycling stability, Zheng et al. prepared an ultrathin
owe a unique 1D chain structure. two-dimensional (2D) Co-MOF nanosheet (Co2(OH)2BDC,
A hexagonal Ni-MOF (denoted as [Ni(HBTC)(4,4′-bipy)]) BDC = 1,4-benzenedicarboxylate) by controllable one-pot
(HBTC = 1,3,5-benzenetricarboxylic acid, 4,4′-bipy = 4,4′-bipyridine) facile hydrothermal preparation methods (Figure 1d) [83].
Figure 1: (a) Schematic illustration of charge transfer process on (001) and rectangular crystal planes, respectively. (b) SEM image of
hexagonal Ni-MOF Y3 sample. (c) Cyclic performance of hexagonal Ni-MOF Y1-5 samples at 0.5 A g−1. Reproduced with permission from [78];
Copyright 2019, Wiley. (d) The preparation of ultrathin 2D Co-MOF nanosheets. (e) Schematic illustration of the length of electron trans-
portation in nanoparticle-based electrode. (f) SEM image of ultrathin 2D Co-MOF nanosheets. (g) Cycling performance of ultrathin 2D Co-
MOF nanosheets at a current density of 2.0 A g−1. Reproduced with permission from [83]; Copyright 2019, Elsevier. (h) Crystal structure of
Cu–CAT viewed along the c-axis. (i) TEM image of Cu–CAT nanowire (insets: SAED pattern). (j) Comparison of the specific capacitances of the
electrodes. (k) Cycling performance of Cu–CAT NWA-based supercapacitor. Reproduced with permission from [85]; Copyright 2017, Wiley.
(l) Schematic illustration of the synthesis process of Cu-DBC. (m) HRTEM image taken along c-axis. (n) Energy density and power density of
comparison with other reported materials. Reproduced with permission from [86]; Copyright 2019, Wiley.
The SEM image showed that the ultrathin Co-MOF had a Furthermore, an aqueous device with three different morphol-
more regular and larger layered structure than the bulk ogies (ultrathin, micro–nano, and bulk) of Co-MOFs (positive)
and micro–nano samples (Figure 1f), which could offer and active carbon (AC) (negative) was constructed. The ultra-
numerous redox-active sites for the rapid surface redox thin morphology delivered the best electrical performance in
reaction and display desirable pseudocapacitive beha- the ultrathin sample compared with the other two samples.
viors. Owing to the ultrathin structure of the 2D Co-MOF, Their research also proved that ultrathin 2D nanomaterials
its conductivity could be enhanced when mixed with are promising novel nanomaterials owing to their excellent
carbon additives (Figure 1e). When fabricated with ultra- electrochemical properties [84]. The research in MOFs with
thin 2D Co-MOF and tested in 3 M KOH, this electrode unique ultrathin morphologies is reasonable.
showed 1,159 F g−1 at 0.5 A g−1 and maintained at 96.7% Designing and synthesizing unique MOFs with other
during 6,000 cycles, where the electrode capacity changed metal ions may also improve the conductivity of pristine
from 1,106 to 1,070 F g−1 at 2.0 A g−1 (Figure 1g). These MOFs. Conductive MOF Cu-CAT nanowire arrays (NWAs)
behaviors could be ascribed to the ion-exchange mechanism. were fabricated by Li et al. for the first time [85]. These
NWAs were constructed via the coordination between Cu 0.2 A g−1. The electrode materials also maintained 72% of
ions and ligands HHTP (HHTP = 2, 3, 6, 7, 10, 11-hexahy- their initial capacity during 2,000 cycles, even at 5 A g−1.
droxytriphenylene), forming honeycomb-like porous struc- Moreover, the assembled symmetric solid-state supercapa-
tures (Figure 1h). Numerous oriented and high-density citor based on Cu-DBC electrodes exhibited 13.8 W h kg−1
nanowires homogeneously wholly covered the fibers and energy density with 0.1 kW kg−1 power density and main-
formed a uniform hexagonal top facet and hexagonal-prism tained 7.6 W h kg−1 under 5.0 kW kg−1 (Figure 1n). This
shape. This could facilitate the transportation of electrolyte indicated that supercapacitors based on Cu-DBC frame-
solutions to realize high-rate behaviors. HRTEM image and works possess promising energy density and power den-
SAED revealed the single-crystal features of NWAs (Figure 1i). sity as well as better electrochemical performance than
In the 3 M KCl solution, the electrode fabricated using Cu- other reported conductive MOFs.
CAT NWAs could exhibit 202 F g−1 at 0.5 A g−1 compared with
other well-known low-conductivity MOF materials (Figure 1j).
It also maintained 80% of the initial values after 5,000 cycles. 2.1.2 Multimetallic MOF
Moreover, a solid-state supercapacitor based on Cu-CAT
NWAs shows perfect stability, retaining more than 85% of The design and construction of monometallic MOFs with
its initial value after 5,000 cycles (Figure 1k). Liu et al. unique structures have received significant attention [87].
prepared a new conductive Cu-MOF (Cu-DBC) based However, monometallic MOFs still have shortcomings,
on linker 8OH-DBC (8OH-DBC = dibenzo[g,p]chrysene- such as low specific capacitance values and unsatisfactory
2,3,6,7,10,11,14,15-octaol) (Figure 1l) [86]. High-resolu- stability. Hence, the design and fabrication of multime-
tion transmission electron microscopy (HRTEM) image dis- tallic MOFs as electrode materials is an effective and
played a uniform microcrystalline structure, indicating its outstanding strategy for addressing these problems [88].
high crystallinity and perfect orbital interaction (Figure 1m). Multimetallic MOFs, also denoted as mixed metal–organic
Owing to the perfect orbital interaction between Cu ions and frameworks, embedded various central metal ions into the
8OH-DBC, these Cu-MOFs could possess excellent chemical same framework structure. This not only enhances the sta-
stability. Hence, Cu-DBC could be used in nonflammable bility of the pristine MOF structure but also improves the
and low-cost aqueous electrolytes compared with other tra- framework stability and the tuning of breathing behavior,
ditional MOFs. In 1 M NaCl solution, its gravimetric capaci- thereby delivering better performance compared to that
tance calculated from the discharge curve was 479 F g−1 at of monometallic MOFs [89,90]. To develop multimetallic
Figure 2: (a) Schematic illustration of the synthetic process of the Ni/Co-MOFs. (b) SEM image of Ni/Co-MOF0.75 sample. (c) Comparison of
specific capacitances of MOFs. (d) Electrode design of the present ASC. Reproduced with permission from [91]; Copyright 2020, Elsevier.
(e) Schematic illustration of the formation of 3-2 NiCo-MOF nanosheets arrays on nickel foam. (f) SEM image of 3-2 NiCo-MOF/NF.
(g) Ragone graphs of the 3-2 NiCo-MOF/NF//AC device. Reproduced with permission from [92]; Copyright 2019, Elsevier.
MOFs, two or more different metal ions can be incorporated morphology and completely covered the nickel foam sur-
into the same frame structure. This would provide MOFs face (Figure 2f). This could produce a three-dimensional
with additional degrees of structural stability and endow (3D) shape network with numerous open spaces, making
them with new behaviors [60]. However, research on multi- more efficient and faster ion charge transfer and electron
metallic MOFs in the field of supercapacitors remains lar- transport possible. When tested in 6 M KOH solution, the 3-2
gely unexplored, which may become one of the break- NiCo-MOF sample preserves 1003.5 C g−1 (2,230 F g−1) at
throughs in improving the electrochemical performance of 1 A g−1. In a hybrid supercapacitor (assembling Ni/Co MOF
supercapacitors. with AC), this device exhibited 34.3 W h kg−1 energy density
In the recent research, Ni/Co-MOFs have exhibited under 375 W kg−1 power density and 20.83 W h kg−1 energy
uniform size, oriented morphology, and ordered distribu- density with 7.50 kW kg−1 power density values (Figure 2g).
tion, which could enhance their electrochemical perfor- Remarkably, this HSC maintained approximately 75.2% of
mance [93]. To explore their applications, Zhang et al. the initial capacitance values during 6,000 cycles.
synthesized a lamellae-like Ni/Co-MOF through a facile Remarkable works on pristine MOF as electrode mate-
hydrothermal route (Figure 2a) [91]. With the combination rials for supercapacitors are listed in Table 1.
of multimetallic components and special lamellae-like
nanostructures, the fabricated Ni/Co-MOF0.75 displayed a
significant improvement in capacitance values and cycling
stability. The morphology analysis indicates the ultrathin 2.2 MOF derivatives
nanosheets, which are conducive to its electrochemical
properties (Figure 2b). The specific capacitance of this The relatively poor conductivity and chemical stability of
electrode was 568.0 C g−1 at 1.0 A g−1 (Figure 2c), along pristine MOFs still hinder the further application of MOFs
with the 75.5% initial values remaining after 3,000 cycles. in supercapacitors. To address these issues, using MOFs
In an assembled ASC based on this electrode material with as precursors to derive carbon materials or metal com-
the reduced graphene oxide (rGO) (Figure 2d), this device pounds, such as metal oxides, hydroxides, sulfides, among
delivered excellent cycling performance, with 82.6% capa- others, is a favorable strategy. These MOF derivatives dis-
citance retained during the 10,000 cycling tests. It also play satisfactory porous properties, unique morphologies,
delivered 42.24 W h kg−1 along with a power density of and tunable and controllable chemical compositions [17,59].
800 W kg−1. Bu and coworkers also prepared Ni/Co-MOF These outstanding behaviors could further enhance the
(Ni/Co-terephthalic acid/NF) nanosheet arrays on conduc- capacitance values, couductivity, and stability of MOF deri-
tive substrates via a facile one-step synthesis method vatives. For example, the MOF-derived metal oxides,
(Figure 2e) [92]. According to the SEM image, the 3-2 hydroxides, or sulfides exhibited superior capacitance
NiCo-MOF (Ni:Co = 3:2) displayed a triangle-like nanosheet values, along with promising capacitance retentions.
Table 1: Selected pristine MOFs for supercapacitors
Samples Electrolyte SC CR (%/cycles) ED/PD Ref.
Ni3(HITP)2 1 M TEABF4/ACN 18 µF cm−2 90/10,000 (2 A g−1) — [61]

(0.05 A g−1)
[Ni(HOC6H4COO)1.48(OH)0.52·1.1H2O] 6 M KOH 1,698 F g−1 (1 A g−1) 94.8/1,000 (1 A g−1) — [76]
[Ni3(OH)2(C8H4O4)2·(H2O)4]·2H2O 3 M KOH/0.1 M 175.3 mA h 93/3,000 (10 A g−1) 55.8/7,000 [77]
K4[Fe(CN)6] g−1 (1 A g−1)
Ni(HBTC)(4,4′-bipy) 3 M KOH 977.04 F g−1 92.34/5,000 33.98/ [78]
(0.5 A g−1) (0.5 A g−1) 3264.87
{[Co3(µ4-tpa)3(µdapz)(DMF)2]·2DMF}n 2 M KOH 384 F g−1 (6 A g−1) 90/6,000 (12 A g−1) 24.13/4,420 [80]
({[Co(Hmt)(tfbdc)(H2O)2]·(H2O)2}n 1 M KOH 2,474 F g−1 (1 A g−1) 94.3/2,000 (2 A g−1) — [81]
[Co2(OH)2BDC] 3 M KOH 1,159 F g−1 (0.5 A g−1) 96.7/6,000 (2 A g−1) — [83]
Cu-CAT 3 M KCl 202 F g−1 (0.5 A g−1) 85/5,000 (50 mV s−1) ≈2.6/≈200 [85]
Cu-DBC 1 M NaCl 479 F g−1 (0.2 A g−1) 80/2,000 (5 A g−1) 7.6/5,000 [86]
NiCo-MOF0.75 2 M KOH 568 C g−1 (2 A g−1) 82.6/6,000 (10 A g−1) 42.24/800 [91]
3-2 NiCo-MOF/NF 1 M KOH 2,230 F g−1 (1 A g−1) 75.2/6,000 (1 A g−1) 20.83/7,500 [92]
Abbreviations: SC, specific capacitance; CR, capacitance retention; ED, energy density; PD, power density.
Moreover, the addition of some functional materials could Although porous carbon derived from MOFs has attracted
compensate their disadvantages and enhance electroche- increasing attention, partial breakdown in the initial MOF
mical performances. structure during the carbonization and annealing processes
cannot be completely avoided. This results in a decrease in
the surface area and redox-active sites, limiting the conduc-
2.2.1 Porous carbon tivity of the as-prepared nanoporous carbonaceous materials
and their rate performance [108]. To solve the problems,
Nanoporous carbon is an excellent supercapacitor candi- Wang et al. fabricated a unique porous carbon possessing a
date owing to its optimized pore size distributions, per- “brick-and-mortar” sandwiched structure by using MOF-5-
fect thermal and physiochemical stability, high surface derived nanoporous carbon film as “mortar” and the gra-
area, and low cost for regeneration [94,95]. These advan- phene nanosheets as “brick” (Figure 3a) [107]. This porous
tages offer a shorter pathway for the diffusion of electro- carbon material (denoted as C-GMOF) remained a layered
lyte solutions, buffering the volume charge during the structure, and TEM analysis confirmed the formation of this
cycling process and obtaining more electrochemically active morphology (Figure 3b). A sandwich-shaped structure with a
sites for the adsorption and desorption of electrolyte ions superior surface area was conducive for convenient electron
[96]. Hence, designing and synthesizing nanoporous carbon transportation with less transport length and charge sto-
materials as electrode materials for supercapacitors is rage. In an electrochemical test, the GCD curve was almost
necessary. In the previous research, MOFs possessing high linear and symmetrical, indicating its excellent reversi-
SSAs and highly customizable pore structures have been bility (Figure 3c). This C-GMOF-based electrode material
explored as perfect templates for preparing carbon materials exhibited 345 F g−1 at 2 mV s−1, along with 201 F g−1 at
to support capacitive active materials [97,98]. MOF-derived 2 V s−1, which was relatively higher than other materials
carbon materials have attracted significant attention (Figure 3d). Furthermore, the specific capacitance remained
owing to their controllable morphologies and pore at 99% of its initial values after 10,000 cycles (Figure 3e),
structures [99]. The porous carbon derived from MOFs suggesting its outstanding cycling stability.
can possess abundant nanoscale cavities and provide
larger surfaces for electron desorption–adsorption as elec-
trode materials for supercapacitors [100]. 2.2.2 Metal oxides
To further study MOF-derived porous carbon mate-
rials, Qian et al. chose a zinc-organic framework as a Metal oxides, especially transition metal oxides (TMOs),
precursor to prepare robust cage-based mesoporous carbon have attracted considerable attention in the scientific com-
materials (BMM-9) through carbonization at high tempera- munity as electrode materials in supercapacitors owing to
tures [101]. BMM-9-900 (calcinated at 900°C) exhibited their high electrochemical response, perfect electrical con-
182.8 F g−1 at 1.0 A g−1, and the stability texts showed that ductivity, low manufacturing costs, large SSA, and easy
BMM-9-900 retained 98.5% initial values at 10 A g−1 during processability [109,110]. TMOs such as Co3O4, NiO, RuO2,
1,000 cycles. Khan et al. utilized MOF-5/AC as a soft tem- Mn2O3, Fe2O3, and some binary transition metal oxides
plate to derive carbon nanospheres via carbonization at have already been extensively researched for applica-
850°C, exhibiting 300 F g−1 at 1.5 A g−1 along with 91.5% tion in supercapacitors [111]. Among these TMOs, Co3O4,
capacitance values retained during 3,000 charge–discharge whose theoretical specific capacitance can reach up to
cycles [102]. Recently, some researchers observed that 3,560 F g−1, is one of the most widely utilized oxides in
nitrogen doping in carbon materials can improve the sur- electrode materials for supercapacitors [112,113]. Previous
face polarity and humidity, ultimately optimizing the elec- research has demonstrated that Co3O4 can be obtained
trical conductivity, which could also improve specific capa- via the calcination of ZIF-67 precursors [114]. However,
citance [103–105]. Tang et al. prepared flexible 3D N-doped approaching the theoretical capacitance of Co3O4 is still
porous carbon bubbles (CTAs@NCBs) connected via carbon difficult, which limits its application in supercapacitors
tube arrays derived from a ZnO@ZIF-8 nanoarray template considerably [115]. To improve their capacity and cycling
[106]. This material-assembled supercapacitor yielded an performance, Li et al. prepared nanoporous Co3O4 nano-
areal capacitance of 580 mF cm−2 in 1 mA cm−2, and 98.5% tubes by calcining nanoscale Co-MOF-74 crystals at 350°C
of its initial capacitance remained over 10,000 cycles. This [116]. A hexagonal cuboid morphology was achieved
could be ascribed to its structural characteristics because it during the annealing process. In the electrochemical
possessed excellent ionic conductivity and a high sur- tests with 2 M KOH electrolyte, Co3O4-350 presented
face area. 647 F g−1 at 1 A g−1, and there was no obvious decrease
Figure 3: (a) Schematic illustration of the fabrication process for porous carbon building using MOFs and GO as precursors. (b) TEM image of
the C-GMOF. (c) GCD curves of the C-GMOF, C-MOF, YP-50, and RGO at 50 A g−1. (d) Specific capacitances of the C-GMOF, C-MOF, YP-50, and
RGO at various scan rates. (e) Cycling performance of the C-GMOF at 200 mV s−1, and the inset shows CV curves before and after 10,000
cycles. Reproduced with permission from [107]; Copyright 2016, Elsevier.
during the 1,500 cycles tests in 2 A g−1. Liu et al. fabri- nanosheets on a carbon cloth [120]. They first annealed
cated dodecahedral NaBH4-reduced Co3O4 (R-Co3O4) through Co-MOF on a carbon cloth to fabricate derived cobalt
a conformal transformation route [117]. In their work, NaBH4 oxides and then combined them with NiCo-LDHs to con-
was used to modify the surface state of Co3O4 that dis- struct hybrid Co3O4@NiCoLDH. As calculated from the
played a dodecahedral morphology, uniform dimensions, electrochemical tests, this hybrid showed 1,708 F g−1 at
and rhombic dodecahedron morphology. This resulted in a 1.0 A g−1, representing 89% of the original capacitance
capacitance of 329 F g−1 at 1 A g−1, and 92% of the original values retained during 4,000 cycles at 10 A g−1. Further-
values were retained during 1,000 cycles. more, the constructed ASC (assembled with AC) delivered
Although Co3O4 has emerged as an excellent elec- 44.44 W h kg−1 energy density under 0.80 kW kg−1 power
trode material, researchers still observed that it has lim- density.
itations such as low ionic diffusivity, lack of outstanding Apart from Co3O4, NiO is also a competitive candidate
electron conductive routes, and drastic volume expan- for electrode materials in supercapacitors owing to its
sion [75]. The incorporation of conductive substrates rich oxidation states, abundant SSA, low cost, thermal
such as graphene or carbon cloth is a promising solution stability, and pronounced electrical properties [121]. NiO deli-
to these problems [118]. Vilian et al. incorporated rGO vers perfect capacitive properties, expressing 2,584 F g−1 the-
onto MOF-derived Co3O4 via a hydrothermal route [119]. oretical specific capacitance values [122,123]. Wu et al. fab-
In this work, Co3O4 has a hexagonal sheet-like structure, ricated Ni-MOF-derived NiO nanospheres via a simple
which assists in the electron accessibility of the electrode solvothermal method [124]. After calcination at 400°C,
materials. The rGO-Co3O4 delivered 1,300 F g−1 and 80.5% NiO hollow nanospheres with highly uniform shapes were
of its original capacitance over 5,000 cycles in 4 M KOH successfully obtained (denoted as N400) with a core-in-
at 4 A g−1. Furthermore, the assembled ASC exhibited double-shell structure. This N400 sample exhibited pro-
65.8 W h kg−1 energy density values under a 2.05 kW kg−1 mising electrochemical performance with 473 F g−1 at
power density. Yin et al. prepared Co-MOF-derived Co3O4 0.5 A g−1, and 94% original values were retained during
coated with the NiCo layer double hydroxide (NiCo-LDH) 3,000 cycles. In an asymmetric supercapacitor based on
N400 and AC (N400//AC), this device exhibited 12.5 excellent volumetric capacity of 2467.6 F cm−3. Moreover, a
W h kg−1 energy density along with a power density of flexible symmetrical supercapacitor retained 88.2% original
7.5 kW kg−1. Fabricating a hybrid nanocomposite is an values over 10,000 cycles. This indicated its promising
effective strategy to further improve their electrical con- application potential in supercapacitors. Yin et al. synthe-
ductivity and obtain the theoretical specific capacitance. sized hollow NiCo2O4 nanocages grown on a SiC nanowire
Li et al. prepared nanorod-composed yolk-shell microspheres network/carbon cloth [133]. With unique structural advan-
derived from Ni/Zn-MOF via a simple solvothermal method tages such as a hierarchical porous structure and inter-
[125]. In this study, the specific capacitances of the material woven conductive networks, this material exhibited a
calculated were 497 F g−1 at 1.3 A g−1, along with almost 100% specific capacitance of 1,377 F g−1 at 1 A g−1 and 88.3%
of the original values retained during 2,000 cycles, indicating capacitance retention over 6,000 cycles. When assembled
its excellent cycling performance. with AC as a supercapacitor, this supercapacitor delivered
Other monometallic oxides have also been developed 46.58 W h kg−1 energy density with 0.80 kW kg−1 power
for use in electrode materials. Yuan et al. fabricated layered density.
δ-MnO2 nanostructure materials using [Mn(C8H4O4)·(H2O)2]n Among the diverse binary metal oxides derived from
as a precursor to react with KMnO4 via a hydrothermal bimetallic MOFs, nickel–cobalt binary oxides have attracted
method [126]. Its specific capacitance can deliver 416 F g−1 considerable interest from the scientific community because
at 0.5 A g−1. The assembled ASC (MnO2//AC) exhibited of their high-power supercapacitor applications. Yu et al.
23.2 W h kg−1 with a power density of 425 W kg−1. Owing prepared a NiO/NiCo2O4 (1:1) derived from MOF-74-Ni/Co
to its layered nanostructure, access to cations from the MOF (1:1) (Figure 4a) [134]. The morphology analysis
electrolyte could be accelerated, thus facilitating pro- showed that the mixed metal oxide samples all inherited
mising electrochemical performance. Wang et al. synthe- the morphology of their precursors with nanowire shapes
sized ZnO/C materials by directly transforming MOFs into (Figure 4b). At different Ni/Co ratios, they observed that
hollow carbonaceous materials and then reacting them the NiO/NiCo2O4 (1:1) sample displayed a hollow nanowire
with glucose-derived polymers to form hollow Zn-coated structure, indicating its porous nature. In this study, the
carbonaceous composites [127]. ZnO/C-based electrode mate- calculated 732.0 C g−1 derived from NiO/NiCo2O4 (1:1) was
rials can deliver 394 F g−1 at 1 A g−1, indicating its promising much higher than of the other samples and monometallic
electrochemical performance. oxides at 1 A g−1 (Figure 4c). It also retained 92.5% initial
Recently, some binary or mixed metal oxides derived capacitance values at 10 A g−1 over 3,000 cycles, proving
from multimetallic MOFs have been widely investigated its excellent stability (Figure 4c). In an asymmetric super-
owing to their high SSA, unique nanostructure, and capacitor (NiO/NiCo2O4 (1:1)//AC), the specific energy den-
richer active sites [128]. In addition, their uniform metal sity reached 36.6 W h kg−1 along with a 6791.8 W kg−1
distribution is beneficial for reducing lattice distortion power density, which was much better than the reported
and further enhancing the capacity and cycling stability values (Figure 6c). Jayakumar et al. fabricated NixCo3−xO4
[129]. MOF-derived mixed metal oxides display notice- derived from ZIF-67 and then synthesized graphene/NiCo
able strengths compared with their single pure metal oxide hybrids (GNi:Co) [135]. During the hydrothermal
oxide counterparts [130]. Zhang et al. utilized an Fe- treatment, the GNi:Co (Ni:Co = 1:1) composite hydrogel
MOF gel (MIL-100-Fe) as a template to fabricate meso- displayed a highly microporous network with interlinked
porous LaFeO3 perovskite nanoparticles [131]. Owing to its graphene layers on nanosized Ni/Co particles (Ni:Co ratio
mesoporous structure and 2 nm concentrated pore size, of 1:1). The morphology analysis showed that these sam-
this synthesized LaFeO3 showed 241.3 F g−1 at 1 A g−1. ples possessed a hollow structure, thus helping to connect
Furthermore, the all-solid-state symmetric supercapa- the graphene layers (Figure 4d). Owing to the conducive
citor based on LaFeO3 delivered 34 W h kg−1 energy den- porous network from the surrounding graphene, this mate-
sity values with 900 W kg−1 power density, along with rial showed better electrochemical performance than other
the 92.2% initial values remaining after 5,000 cycles. compared counterparts. This GNi:Co 1:1 hydrogel displayed
Functional additives can be incorporated into these the highest specific capacitances of 2,870 F g−1 at 1 A g−1
binary or mixed metal oxides to further improve their compared with other samples (Figure 4e). Moreover, this
electrochemical performance. Xie et al. introduced MXene material presented a significant enhancement in cycle life,
nanosheets into derived CoFe2O4 nanorods [132]. This maintaining 81% capacitance retention after 5,000 long
could facilitate charge transfer, maintain its excellent flex- cycles (Figure 4f). In an ASC assembled with pure graphene
ibility, and enhance its ion transmission path. In the 1 M hydrogel, the ASC could provide a higher specific energy
LiCl electrolyte, the CoFe2O4/MXene composite exhibited an density of 50.2 W h kg−1 along with 750 kW kg−1 power
Figure 4: (a) The synthesis process of metal oxides with hollow nanowires. (b) TEM image of an individual NiO/NiCo2O4(1:1) hollow
nanowire. (c) Cycling stability at 10 A g−1 for 3,000 cycles. Reproduced with permission [134]; Copyright 2018, The Royal Society of
Chemistry. (d) SEM image of GNi:Co 1:1. (e) Specific capacitances of samples. (f) Cyclic performances of samples. (g) Ragone Plot of GNi:Co
1:1//Pure graphene with other reported works. Reproduced with permission from [135]; Copyright 2017, Wiley.
density (Figure 4g). These comparisons could be useful in the electrochemical test, this electrode material displayed
identifying this material for appropriate real-life applications. 875 C g−1 at 1 A g−1, which was better than that of other
samples (Figure 5c). The assembled HSC using 65Ni-MDH
and N-C as electrodes could retain 91.3% after 10,000 cycles
2.2.3 Metal hydroxides at 13.5 A g−1, and the Faradaic efficiency was close to 100%
during the cycling process (Figure 5d). It also showed
In recent years, transition metal hydroxides have been 81 W h kg−1 energy density along with 1.9 kW kg−1 power
considered as perfect electrode materials owing to their density and maintained 42 W h kg−1 under 11.5 kW kg−1.
high surface area and ultrahigh theoretical capacitance Many researchers have recently explored MOF-derived
(3,500–4,600 F g−1) [136]. MOF-derived metal hydroxides LDH. These derivatives exhibit multimetallic hollow struc-
are pseudocapacitive materials that can store numerous tures, enhancing the flow efficiency of ions and reducing
energies depending on the fast redox reactions that dras- the resistance of ion diffusion [142]. Among various LDH
tically improve energy storage and exhibit much higher materials, Ni/Co LDH exhibits attractive performance,
discharge capacities than EDLC materials [137,138]. Wu including high theoretical capacitance, rich redox reac-
et al. synthesized Co/Ni-double hydroxides with a novel tion sites, and excellent electronic conductivity [143,144].
wisteria flower-like microstructure on carbon cloth in the However, its easily agglomerated structure greatly hinders
NiSO4 solution [139]. This hybrid delivers 929.4 C g−1 at 2 mA its further applications [145,146]. A promising strategy
cm−2. The assembled ASC exhibits 42.5 W h kg−1 with 81.5% for overcoming this problem involves adjusting the mor-
capacity remaining after 7,500 cycles. Qu et al. utilized a phology by fabricating a hierarchical structure for instance
classic nickel–cobalt MOF-74 as a precursor to fabricate [147]. Xiao et al. utilized a Ni/Co-MOF (with Ni:Co = 7:3) to
highly porous double hydroxide (MOF-74-derived double synthesize LDH with hierarchical microspheres (Figure 5e)
hydroxide, denoted as MDH) via a facile alkaline treatment [141]. In their work, they constructed hierarchical LDH
(Figure 5a) [140]. The SEM image showed the formation of microsphere structures via a controllable alkaline hydro-
nanoscale 65Ni-MDH after KOH treatment of the as-synthe- lysis strategy. Owing to the high tunability of MOFs, Ni/Co
sized MOF-74 templates under controlled hydrothermal con- LDH can have a desirable composition and morphology.
ditions (Figure 5b). The SSA of MDH reached 299 m2 g−1. Hence, the surface area of the Ni/Co LDH was measured to
Its superior surface area could be ascribed to its inheri- be 201 m2 g−1, making it applicable for supercapacitors. In
tance from the porous nature of pristine MOFs, and the 1 M KOH solution, the Ni/Co LDH-based electrode
the 65Ni-MDH displays promising porous properties. In material showed 1,652 F g−1 at 1 A g−1, presenting almost
100% value after 2,000 cycles. Both these properties are 2.2.4 Metal sulfides
much better than those of other samples (Figure 5f and g).
Moreover, an ASC composed of this LDH and AC delivered Transition metal sulfides have also become one of the
32.9 W h kg−1/74.3 W kg−1 energy density/power density and most promising candidates for electrode materials in
maintained 26.0 W h kg−1 under 1817.3 W kg−1. supercapacitors owing to their higher specific
Figure 5: (a) Schematic illustration of MOF-74 converting to Ni–Co MDH. (b) SEM image of 65Ni-MDH. (c) Specific capacity of MDH electrodes
with different initial Ni(II)-to-Co(II) ratios. (d) Cycling stability and faradaic efficiency of the 65Ni- MDH//N–C device at 13.5 A g−1 for 10,000
cycles. Reproduced with permission from [140]; Copyright 2017, American Chemical Society. (e) Schematic illustration of the synthetic
strategy of the Ni/Co-LDH. (f) Specific capacitance of Ni/Co-LDH electrodes at current densities from 1 to 25 A g−1. (g) Cycling performance of
the Ni/Co-LDH electrodes at a current density of 5 A g−1. Reproduced with permission from [141]; Copyright 2019, American Chemical
Society.
capacitances, higher electrical conductivity, and richer in this nanohybrid are very active for rapid redox reac-
redox reactions than their oxide or hydroxide counter- tions, indicating their promising pseudocapacitive prop-
parts [39,148]. Some metal sulfides such as nickel sulfides erties. Moreover, the presence of rGO greatly enhanced its
and cobalt sulfides have attracted considerable attraction electronic conductivity, providing more efficient current
as promising candidates of high-performance supercapa- collection for rapid energy storage. In the electrochemical
citors [149]. However, it is difficult to deliver ideal capa- test with 2 M KOH electrolyte, it demonstrated 744 C g−1 in
city and cycling stability via using single-component 1 A g−1 and an impressive capacity retention of 89% over
forms of those sulfides [150]. To deal with these pro- 20,000 cycles (Figure 6b and c). In HSC assembled with
blems, strategies such as combining carbon-based mate- R-NiS/rGO and ZIF-8-modified nitrogen-doped graphene
rials (graphene, carbon nanotubes (CNTs), etc.) and other aerogel, 54 W h kg−1/46,034 W kg−1 energy density/power
pseudocapacitive materials can improve their conduc- density was achieved.
tivity and enhance their cycling stabilities [151,152]. Apart from monometallic sulfides, some bimetallic
Qu et al. reported NiS nanorods combined with rGO transition metal sulfides also possess better electroche-
derived from a Ni-MOF-74/rGO hybrid (Figure 6a) [38]. In mical activity, more varied stoichiometric chemistry, and
this study, R-NiS/rGO exhibited a remarkable integral richer redox reactions than single-component metal sul-
area and enriched active sites, implying a significantly fides [154,155]. It was observed that bimetallic metal sul-
improved specific capacitance. The NiS nanorod surfaces fides express lower kinetic energy barriers, which makes
Figure 6: (a) Schematic illustration of the synthesis procedure of the R-NiS/rGO from MOF precursors. (b) Specific capacities of R-NiS/rGO
based on different current densities. (c) Cycling performances of R-NiS/rGO and N-NiS. Reproduced with permission from [38]; Copyright
2018, The Royal Society of Chemistry. (d) SEM image of NiCo-S-1 samples. (e) Cycling performance of the NiCo-S-1//AC at 2 A g−1. (f) Ragone
plots of the current work and the other related devices. Reproduced with permission from [153]; Copyright 2020, The Royal Society of
Chemistry.
their charge transportation more effective than that in Sun et al. fabricated bimetallic copper cobalt selenide
monometallic metal sulfides [156]. Zhao et al. fabricated nanoparticles embedded in N-doped carbon layers (denoted
porous NiCo2S4 nanosheet arrays with enriched edge sites as (CuCo)Se/NC) via using CuCo-ZIF as a precursor [161].
on electrochemically activated flexible carbon cloth derived Their route involved the fabrication of CuCo-ZIF and the
from Co-MOF for the first time [157]. The morphology ana- selenization of the as-prepared bimetallic MOF. In the
lysis showed a dense and uniform coverage of the Ni–Co–S electrochemical tests with 2 M KOH, this hybrid exhibited
nanosheets on the carbon fiber surface. This leads to the 121.4 C g−1 at 1 A g−1. This is ascribed to the incorporation
formation of the desired hollow and porous structure, thus of Cu elements in CoSe matrix and the combination of
facilitating the diffusion of electrolyte ions and the inser- N-doped carbon layer. Furthermore, the constructed HSC
tion and disembedding process in the cycling stability test. device based on this hybrid delivered an energy density of
This material-based electrode delivered 2,392 F g−1 at 1 A g−1 16.3 W h kg−1 along with a power density of 155.3 W kg−1. It
and a desirable stability routine with 85.1% capacity reten- also possessed an excellent cyclic stability, retaining 96%
tion over 10,000 cycles at 30 A g−1. Furthermore, in an initial capacity over 5,000 cycles.
assembled ASC, it exhibited 30.1 W h kg−1/800.2 W kg−1 Transition metal phosphides have also attracted
energy density/power density. Zheng et al. developed increasing attention owing to their metalloid nature and
ultrathin NiCo sulfide nanosheet arrays on Ni foam with perfect electrical conductivity [162,163]. Chu et al. fabri-
robust adhesion [153]. Owing to the presence of Ni3S2 and cated ZnCo phosphide (Zn0.33Co0.67P) on Ni foam with a
Co(OH)2 in the synthesis process, these materials could special structure of ZnCo phosphide array [164]. This phos-
deliver ultrahigh capacity. The morphology analysis of phide electrode delivered 2,115 F g−1 at 1.0 A g−1 with 83.0%
NiCo-S-1 indicated that its unique structure offers abun- initial values over 7,000 cycles, which is caused by the
dant SSA and open channels for electrolyte transportation lower electronegativity of phosphorus. Furthermore, they
and penetration (Figure 6d). These properties can reduce assembled Zn0.33Co0.67P (positive) with Bi2O3 (negative) to
the diffusion distance and enhance the electrochemical form an alkaline supercapacitor. This device delivered
performance. With its superior structure, this material 83.05 W h kg−1 with a power density of 775.02 W kg−1 and
demonstrated the highest electrochemical performance, a superior power density value of 15642.58 W kg−1 along
delivering an ultrahigh value of 3,724 F g−1 at 1 A g−1 (Figure 6e). with a 26.94 W h kg−1 energy density.
In an assembled NiCo–S//AC supercapacitor, the capaci- Kshetri et al. fabricated MOF-derived cobalt telluride-
tance retention was stable with 90% retention after 3,000 carbon nanoporous structure composite on nickel foam
cycles. The ASC device also showed 44.76 W h kg−1/ [165]. The morphology analysis indicated a highly porous
0.80 kW kg−1 energy density/power density and main- nature and a uniform distribution of the constituent ele-
tained 24.99 W h kg−1 at 12.00 kW kg−1 (Figure 6f). These ments. This could lead to the unique charge storage
results indicate that NiCo–S has excellent potential for process and better electrochemical performances. In this
application in high-performance supercapacitors. work, the hybrid electrodes delivered an areal capacitance
of 307.5 mF cm−2 at 20 mA cm−2. Moreover, the assembled
symmetric supercapacitor delivered an energy density of
2.2.5 Other metal compounds 43.84 W h kg−1 and a power density 738.88 W kg−1. It also
retains 21.95 W h kg−1 energy density at a high power den-
Some metal compounds such as metal selenides, metal sity of 6173.44 W kg−1.
phosphides, and nitrile have attracted considerable atten- Liu et al. prepared Ni-doped Co–Co2N with a hetero-
tion. Transition metal selenides with promising electroche- structure via facial thermal annealing of MOF-derived
mical activity, promising electronic conductivity, and stabi- NiCo2O4 under an ammonia atmosphere [166]. At dif-
lity have been investigated for supercapacitor applications ferent nitridation temperatures, they observed that the
[158,159]. Chen et al. synthesized porous CoSe2 nanosheets sample nitridized in ammonia at 350°C exhibited the
derived from MOFs [160]. Owing to the porous nanostruc- best morphology. This made its nanoflakes uniform in
ture of CoSe2, it could express abundant contact interfaces morphology, and they grew vertically on the carbon fiber
between the electrode and electrolyte, reducing the diffusion surface, which offered large surface areas for electrolyte
path of ions for this fast electrochemical kinetic process. This ion access. Moreover, its thickness (less than 10 nm) also
device showed 713.9 F g−1 in 1 mA cm−2 accompanying the allows for faster electron transport, enhancing its elec-
impressive cycling property that maintained 92.4% initial trical conductivity. In 1 M KOH, the Ni-doped Co–Co2N
values in 5 mA cm−2 after 5,000 cycles. (also denoted as Ni/Co–N-350) delivered 361.93 C g−1 at
Table 2: Selected MOF derivatives for supercapacitors
MOFs (precursors) Samples Electrolyte SC CR (%/cycles) ED/PD Ref.

−1 −1 −1
Zn-MOF BMM-9 3 M KOH 182.8 F g (1 A g ) 98.5/1,000 (10 A g ) — [101]
MOF-5 MOF-5/AC-C NSP 850 6 M KOH 300 F g−1 (1.5 A g−1) 91.5/3,000 (5 A g−1) — [102]
ZnO@ZIF-8 CTAs@NCBs 1 M H2SO4 580 mF cm−2 (1 mA cm−2) 98.5/10,000 (20 mA cm−2) — [106]
MOF-5 C-GMOF 6 M KOH 345 F g−1 (2 mV s−1) 99/10,000 (200 mV s−1) 10.6/11,900 [107]
Co-MOF-74 Co3O4 2 M KOH 647 F g−1 (1 A g−1) 100/1,500 (2 A g−1) — [116]
ZIF-67 R-Co3O4 1 M KOH 329 F g−1 (1 A g−1) 92/1,000 (1 A g−1) — [117]
ZIF-67 RGO-Co3O4 0.1 M KOH 1,300 F g−1 (4 A g−1) 80.5/5,000 (4 A g−1) 65.8/2,048 [119]
Ni-MOF NiO 3 M KOH 473 F g−1 (0.5 A g−1) 94/3,000(5 A g−1) 12.5/7,500 [124]
NiZn-MOF NiO/ZnO 3 M KOH 497 F g−1 (1.3 A g−1) 100/2,000(5.2 A g−1) — [125]
Mn-MOF δ-MnO2 1 M NaOH 416 F g−1 (0.5 A g−1) 60.5/5,000 (5 A g−1) 23.2/425 [126]
ZIF-8 ZnO/C 1 M Na2SO4 394 F g−1 (1 A g−1) — — [127]
MIL-100-Fe LaFeO3 1 M Na2SO4 241.3 F g−1 (1 A g−1) 92.2/5,000 (10 A g−1) 34/900 [131]
CoFe-MOF CoFe2O4/Mxene 1 M LiCl 2467.6 F cm−3 88.2/10,000 (1.5 mA cm−2) — [132]
(0.2 mA cm−2)
ZIF-67 NiCo2O4/SiC/CC 1 M KOH 1377.6 F g−1 (1 A g−1) 88.3/6,000 (10 A g−1) 46.58/800 [133]
NiCo-MOF-74 NiO/NiCo2O4 6 M KOH 732 C g−1 (1 A g−1) 92.5/3,000 (10 A g−1) 36.6/6791.8 [134]
ZIF-67 NixCo3−xO4 2 M KOH 2,870 F g−1 (1 A g−1) 81/5,000 (10 A g−1) 50.2/750 [135]
Co-MOF CoNi-DH@CC 1 M KOH 929.4 C g−1 (2 mA cm−2) 81.5/7,500 (15 mA cm−2) 42.5/70.2 [139]
NiCo-MOF-74 Ni-MDH 2 M KOH 875 C g−1 (1 A g−1) 91.3/10,000(13.5 A g−1) 81/1,900 [140]
NiCo-MOF Ni/Co-LDH 1 M KOH 1,652 F g−1 (1 A g−1) 100/2,000 (5 A g−1) 26/1817.3 [141]
Ni-MOF-74/rGO R-NiS/rGO 2 M KOH 744 C g−1 (1 A g−1) 89/20,000 (20 A g−1) 54/46,034 [38]
Co-MOF NiCo2S4/ACC 6 M KOH 2,392 F g−1 (1 A g−1) 85.1/10,000 (30 A g−1) 30.1/800.2 [157]
NiCo-MOF NiCo-S 3 M KOH 3,724 F g−1 (1 A g−1) 90/3,000 (2 A g−1) 44.76/800 [153]
Co-MOF CoSe2 3 M KOH 713 F g−1 (1 mA cm−2) 92.4/5,000 (5 mA cm−2) — [160]
CuCo-ZIF (CuCo)Se/NC 2 M KOH 121.4 C g−1 (1 A g−1) 96/5,000 (0.8 A g−1) 16.3/155.3 [161]
ZnCo-MOF Zn0.33Co0.67P/Ni 6 M KOH 2,115 F g−1 (1 A g−1) 83/7,000 (10 A g−1) 83.05/ [164]
775.02
Co-MOF CoTe@C 2 M KOH 307.5 mF cm−2 83.33/10,000 (1 A g−1) 43.84/ [165]
(20 mA cm−2) 738.88
ZIF-L Co-Co2N 1 M KOH 361.93 C g−1 (2 mA cm−2) 82.4/5,000 (2 mA cm−2) 20.4/9,850 [166]
2 mA cm−2, which is much higher than that of other oxide materials (graphene), metals or their compounds, conduc-
counterparts. Remarkably, an ASC with Ni-doped Co–Co2N// tive polymers, and other compounds [17,167], which has
porous carbon was constructed, which maintained 82.4% of greatly broadened the research field of MOFs. Moreover,
its capacity after 5,000 cycles and achieved 20.40 W h kg−1 some metal derivatives also combine with other materials
energy density with 9.85 kW kg−1 power density. All of its such as carbonaceous materials, metal compounds to con-
properties indicate that Ni-doped Co–Co2N is an advanced struct composites. This helps in considerably enhancing
electrode material. their properties compared to their initial derived forms.
Remarkable works on MOF derivatives as electrode The construction of MOF composites could integrate their
materials for supercapacitors are listed in Table 2. advantages and mitigate the drawbacks of individual com-
ponents. For example, the additional nanoporous carbon
with MOF could facilitate fast ion diffusion and increase
2.3 MOF composites with functional charge storage performances [168].
materials
To develop high-performance electrode materials for super- 2.3.1 Carbonaceous material

capacitors, many researchers have explored additional
materials to further enhance the conductivity and the struc- Carbonaceous materials, including graphene and its deri-
tural stability of MOFs and their derivatives. One promis- vatives, CNTs, AC, and mesoporous carbon, possess a
ing approach involves the functionalization of MOFs and high surface area and provide EDLC [169,170]. An effec-
their derivatives with conductive materials, such as carbon tive strategy to address the poor conductivity of MOFs is
to combine them with these carbon materials [171]. The approach. Owing to the synergism between Cu-MOF and rGO,
as-prepared hybrids with carbon-based materials can this composite delivered high mechanical strength and con-
also facilitate rapid ion diffusion as well as the increased ductivity (Figure 7b). The morphology analysis showed that
charge storage properties via Faradaic reactions, thereby its crease-type structures reduce its ion-diffusion path, accel-
combining physical and chemical charge storage mechan- erating the transport and diffusion of ions on the electrode
isms in single-electrode materials [168]. surface (Figure 7c). The wavy nature of the rGO sheets also
Graphene oxide and reduced graphene oxide (GO improved their cycling efficiency. Combining the porous
and rGO) are considered as outstanding electrode mate- nature of Cu-MOF and conducting nature of rGO, GCD ana-
rials for supercapacitors [172–174]. Owing to their unique lysis indicated that this composite (1-GCE) delivered a pro-
layered structure, their ion diffusion and transportation mising discharge time at 0.8 A g−1. In the electrochemical
can be further enhanced. This could ensure excellent test, the specific capacitance was calculated to be 462 F g−1
performances in charge storage and delivery [175]. Liu at 0.8 A g−1, with 93.75% of the original capacitance retained
et al. prepared an Fe-MOF/graphene aerogel composite. after 1,000 cycles (Figure 7d and e). This highlights that
It possessed a high charge–discharge rate, promising the Cu-MOF/rGO composite is a promising candidate for
capacitive volume, and reliable cycling stability, exhibiting supercapacitors.
353 F g−1 at 20 A g−1 while maintaining 74.4% of the original Apart from graphene, other carbon materials such as
values retained after 10,000 charge–discharge cycles [176]. CNTs, mesoporous carbon, and carbon nanofibers also
RGO has emerged as a unique additive that is incorporated possess good availability, low weight, high conductivity,
into MOFs as electrode materials for SCs [177]. Gupta et al. and high chemical stability and are used as conductive
fabricated a Cu-MOF/rGO composite via two steps [178]. They materials for combining with MOFs. Rui et al. fabricated a
first synthesized Cu-MOF {[Cu2(L)(H2O)2]·(5DMF)·(4H2O)}n multiwall CNT and ZIF-67-Co hybrid fiber via a wearable
(Figure 7a) through a solvothermal method. The Cu-MOF/rGO and flexible fibrous device [179]. In the electrochemical test,
composites were then constructed via a facile ultrasonication the ZIF-67-Co/CNTs-derived Co3O4/CNTs were 110 F cm−3.
Figure 7: (a) Crystal structure of CuMOF framework. (b) The proposed approach for the construction of composite 1. (c) SEM image of
CuMOF/rGO composites. (d) Specific capacitance as a function of current densities for CuMOF–GCE, rGO–GCE, and 1–GCE. (e) Cycling
stability of rGO–GCE and 1–GCE over 1,000 cycles. Reproduced with permission from [178]; Copyright 2019, American Chemical Society.
Kim et al. synthesized a composite denoted as Ni-MOF@mC 375 W kg−1, which was superior to that of the previously
(mC: mesoporous carbon) [180]. This composite exhibited reported supercapacitors.
109 F g−1 and 91% initial capacitance retention over 5,000 Other transitional metal compounds, including nickel-
cycles. In a symmetric supercapacitor, the device pre- based compounds and manganese compounds, possess the
sented 38.8 W h kg−1 energy density and 21,005 W kg−1 high electrochemical activity and good electrical conductivity,
power density. which are effective in improving supercapacitors [189,190].
Zhu et al. prepared a Co-MOF with a hierarchical structure
on nickel foam (Co-MOF/NF) [191]. This composite presented
2.3.2 Metal and metal compounds 13.6 F cm−2 at 2 mA cm−2. The assembled ASC could achieve
1.7 mW h cm−2 energy density with a 4.0 mW cm−2 power den-
Although some carbonaceous composites can enhance the sity. It also maintained 69.7% of the initial values after 2,000
conductivity and overall electrochemical performance of cycles in the cycling stability tests. Li et al. combined NiO
MOF-based materials to a certain extent, they are usually nanoparticles on a hexagonal Ni-MOF through a simple
affected by hidden flaws: (1) the limited contact areas self-template method [192]. The maximum specific capaci-
between pristine MOF microparticles and conductive addi- tance was calculated to be 1192.7 F g−1 at 0.5 A g−1 with
tives, (2) MOFs in impeding their aggregation, (3) blocking 93.32% original values retained after 5,000 cycles. In the
of diffusion pores due to the conductive additives on pris- assembled Ni-MOF@NiO//AC device, a maximum energy
tine MOF surfaces. This has a negative effect on the diffu- density of 62.2 W h kg−1 was achieved. Xu et al. successfully
sion of ions and their accommodation in pristine MOFs, fabricated ultrathin Cu-MOF@δ-MnO2 nanosheets in neu-
leading to undesirable electrochemical performance [181]. tral environments via a simple reaction (Figure 8d) [188].
To realize higher specific capacitance values and excellent Morphology analysis showed a porous and hierarchical
energy density and power density in supercapacitors, selecting structure with micropores and mesopores. Compared with
proper electrode materials is essential [182]. Some metal the other samples, this composite delivered 667 F g−1 at
compounds can serve as pseudocapacitive positive elec- 1 A g−1 (Figure 8e). When assembled with AC to fabricate
trodes for storing charges through Faradaic redox reactions Cu-MOF@δ-MnO2//AC ASC, the specific capacitance was
[183,184]. Designing and fabricating well-aligned transi- 340 F g−1 at 1 A g−1. This ASC also exhibited only a 5%
tional metal oxides@MOF composites is a good strategy drop compared with the initial values after 6,000 cycles
for dealing with these problems [185]. (Figure 8f), indicating its excellent cycling performance.
Accordingly, Zhang et al. combined Ni-MOF with NiS2 These results proved that metal oxides@MOF is a promising
to fabricate a Ni-MOF@ NiS2 nanocomposite [186]. According material for supercapacitors.
to the morphology analysis, this composite exhibited
nanosheet arrays and possessed a unique heterostruc-
ture, which enhanced its conductivity and ability to 2.3.3 Conductive polymers
hold the porous MOF pristine structures. Electroche-
mical tests revealed 1,128 F g−1 at 2 A g−1 for this compo- Another effective strategy to enhance the conductivity
site-based electrode. Moreover, the assembled ASC deliv- of MOFs is to incorporate pseudocapacitive materials.
ered 23.5 W h kg−1 energy density under 1.4 kW kg−1 power Conductive polymers (CPs), such as polyaniline (PANI)
density. This ASC also maintained 95.2% of its original and polypyrrole (PPy), can serve as a circuit of electron
capacity retained over 10,000 cycles at 5 A g−1, proving its transport in contact with isolated MOF crystals, thus
excellent application in supercapacitors. Yue et al. synthe- offering extra pseudocapacitance [193,194]. The addition
sized a hierarchical MoS2@Ni-MOF composite structure of these polymers helps reduce the number of electroac-
[187]. The morphology of MoS2@Ni-MOF in the SEM image tive sites and increase internal resistance [195]. PANI is
indicated its perfect crystallinity and noticeable topographic an ideal candidate owing to its low cost, simple manufac-
contrast (Figure 8a). In 3 M KOH, the composite delivered turing process, superior capacitance performance, excellent
1590.24 F g−1 at 1 A g−1, which was much better than that of conductivity, promising chemical stability, and unique pro-
pristine MOFs and common MoS2 (Figure 8b). Moreover, the tonic acid doping mechanism [196–199]. Liu et al. prepared
cycling test also demonstrated the excellent stability of the ZIF-67@PANI composites by coating PANI into the ZIF-67
composites, maintaining a retention of 87.97% after 20,000 precursor [200]. From the SEM image, the morphology indi-
cycles (Figure 8c). In an ASC assembled with AC, this super- cated that ZIF-67 grew in situ under the PANI coating
capacitor displayed 72.93 W h kg−1 and a power density of (Figure 9a). They also observed that the ZIF-67@PANI-2
sample obtained the best combination of size and disper- introducing PPy into bimetallic MOFs [205]. In this
sion compared with the others. The GCD experiments exhib- study, the optimized composite with 0.15 mL PPy added
ited the longest discharge times and increased specific delivered 202 mA h g−1 at 1 A g−1. Furthermore, an ASC
capacitance of 224% (Figure 9b), which was 2,497 F g−1 at assembled with carbon nanotubes-COOH was constructed and
1 A g−1 (Figure 9c). Furthermore, the assembled symmetric exhibited 50.9 W h kg−1 with a power density of 1,338 W kg−1,
supercapacitor constructed by ZIF-67@PANI-2 maintained retaining 78.8% of its initial value at 10 A g−1 over 5,000 cycles.
92.3% capacitance after 9,000 cycles. The supercapacitor Liu et al. prepared NiCo-MOF nanosheet coating on nanotubes
achieved 71.1 W h kg−1 energy density with a power density PPy via a facile ultrasonic method (Figure 9d) [201]. The
of 504.72 W kg−1. addition of polypyrrole nanotubes effectively improved
In addition to PANI, PPy is also an excellent conjugated the conductivity and prevented aggregation of the NiCo-
conductive polymer that acts as a perfect pseudocapacitive MOF nanosheets. According to the morphology analysis,
additive for electrode materials in supercapacitors owing to NiCo-MOF nanosheets were coated around the polypyrrole
its high electrical conductivity, low cost, high biocompat- nanotubes (PNTs) (Figure 9e). Owing to its unique structure,
ibility, and excellent adhesion to the substrate [202–204]. this composite delivered 1,109 F g−1 at 0.5 A g−1 (Figure 9f).
Jiao et al. fabricated a Zn/Ni-MOF/PPy composite by Furthermore, the fabricated ASC (NiCo-MOF@PNTs//AC)
Figure 8: (a) SEM image of MoS2@Ni-MOF. (b) Specific capacity at various current densities. (c) Cycling stability at a current density of
20 A g−1. Reproduced with permission from [187]; Copyright 2019, Elsevier. (d) The preparation of ultrathin Cu-MOF@δ-MnO2 nanosheets.
(e) The specific capacitance of ultrathin Cu-MOF@δ-MnO2 nanosheets, ultrathin δ-MnO2 nanosheets, and Cu-MOF nanoparticles electrodes
at different current densities. (f) Cycling stability of ultrathin Cu-MOF@δ-MnO2 nanosheets, ultrathin δ-MnO2 nanosheets, and Cu-MOF
nanoparticles electrodes at 4 A g−1. Reproduced with permission from [188]; Copyright 2018, The Royal Society of Chemistry.
Figure 9: (a) SEM image of ZIF-67@PANI-2 samples. (b) GCD curves of four materials at the scan rate of 1 A g−1. (c) Specific capacity of ZIF-
67@PANI-1 and ZIF-67@PANI-2. Reproduced with permission from [200]; Copyright 2020, Elsevier. (d) The synthesis process of NiCo-
MOF@PNTs. (e) TEM image of NiCo-MOF@PNTs. (f) The specific capacitances at different current densities. (g) The cycling stability of NiCo-
MOF@PNTs (inset: the last ten cycles). Reproduced with permission from [201]; Copyright 2019, Elsevier.
presented 41.2 W h kg−1 and a power density of 375 W kg−1. [207–209]. Yu et al. prepared hierarchical Ni/P/N/C com-
This device also retained 79.1% capacitance after 10,000 posites using MOF as a template [210]. In the electroche-
cycles (Figure 9g). These results indicated that this nano- mical tests, Ni/P/N/C-500 (annealing at 500°C) could
composite is a promising choice for supercapacitors. reach 2887.87 F g−1 at 1 A g−1 with a 6 M KOH solution,
and the cycling test presented 90% initial values retained
after 1,000 cycles at 10 A g−1. Li et al. fabricated the N, S co-
2.3.4 Other compounds doped bimetal nanocomposite using a Ni/Co-MOF as the
precursor [211]. In this study, the specific capacitance
Yue et al. explore nonmetallic element (N, S, P, Se, etc.) reached 1,529 F g-1 at 1 A g−1, while maintaining 89.29%
modified MOFs in supercapacitors for the first time [206]. of the original rate after 10,000 cycles. In an ASC assembled
There is an increasing amount of research on nonmetallic with AC, 41.04 W h kg−1 with a power density of 750 W kg−1
materials applied to supercapacitors. Transition metal phos- was achieved.
phides and other chalcogenides have received significant He et al. prepared a functional heterostructure NiCoP-
research interest and are utilized in pseudocapacitor electrodes MOF nanosheet-stacked lamellar bricks via hydrothermal-
owing to their superior physical and chemical properties localized phosphorization method [212]. The composites
combine the intrinsic merits of MOFs and phosphides, 85.25% of the original values after 5,000 cycles, proving its
enabling higher activity and fast reaction kinetics. There- outstanding cycling stability.
fore, a high Faradaic capacitance and rate capability Remarkable works on MOF composites as electrode
could be enhanced. In three-electrode setup with 2 M materials for supercapacitors are listed in Table 3.
KOH, this composite exhibited an outstanding capacitance
of 728 C g−1 at 1 A g−1. Furthermore, the device (AC//NiCoP-
MOF) achieved a maximum energy density of 50.3 W kg−1 3 PB/PBAs
with a power density of 1011.2 W kg−1. It also maintained
almost no capacitance loss during 10,000 cycles, proving Prussian blue/Prussian blue analogs (PB/PBAs) are func-
its excellent cycling stability. Apart from nonmetallic element- tional coordination polymers with tunable chemical com-
related composites, there are other special hybrids that deliver position, large surface area, fast charge–discharge rate,
excellent electrochemical performance. Qu et al. prepared etc. They are the oldest and most invaluable MOFs branches
Ni-MOF/MXene hybrid nanosheets via the ultrasonic method owing to their excellent electrochemical performance
[213]. In this study, MXene nanosheets are dispersed on the [216,217]. The discovery of the first PB can be traced to
surface of Ni-MOF uniformly, which is a benefit for enhancing the 18th century. However, research on their electroche-
its electronic conductivity and preventing the aggregation of mical properties and applications has been studied until
Ni-MOF nanosheets. This hybrid showed 867.3 F g−1 specific 1978. The typical formula of PB/PBA is AxMy[M′(CN)6]z,
capacitance at 1 A g−1 and 87.1% capacitance retention after where A denotes the alkaline metal ion and M and M′ are
5,000 cycles at 5 A g−1. Ramachandran et al. synthesized a Co- transition metal ions such as Mn2+, Fe2+, Co2+, Ni2+,
MOF/MXene hybrid directly on Ni foam [214]. The mor- Cu2+, and Zn2+ [21,218,219]. [FeIII
4 [Fe (CN)6]3] is a typical
II
phology analysis indicated that the unique interlayer voids PB structure [220,221]. In this cubic molecule, the FeIII
space of MXene and Co-MOF on Ni foam could shorten the and FeII are located on the alternating corners of the
diffusion path and promote ion intercalation. In 6 M KOH, this cube, and the corner-shared octahedral in the PB is
composite could achieve an ultrahigh specific capacitance bridged by the linear CN anions [222]. The redox process
value of 3,741 F g−1 at 3 mA cm−2, and 92.1% capacitance of Fe ions in PB could also facilitate the electron transfer
remained after 3,000 cycles. Liu et al. reported a facile route pathway. Moreover, owing to the crystal structure of PB,
for preparing NiCo-MOF/acetylene black composites [215]. In the reversible intercalation and extraction of ions in
the electrochemical measurements, NiCo-MOF/AB-5 achieved electrolytes are well promoted, demonstrating its excel-
916.1 F g−1 at 1 A g−1. In an assembled ASC, it achieved 33.84 W lent electrochemical performances. Some metal hexa-
h kg−1 with a power density of 750 W kg−1. It also maintained cyanoferrates (MCHFs, M = Co, Mn, Cu. etc.) also have
Table 3: Selected MOF composites for supercapacitors
Sample Electrolyte SC CR (%/cycles) ED/PD Ref.
MIL-88-Fe/GA 1 M H2SO4 353 F g−1 (20 A g−1) 74.4/10,000 (1 A g−1) 27/4,300 [176]
CuMOF/rGO 1 M Na2SO4 462 F g−1 (0.8 A g−1) 93.75/1,000 (12 A g−1) — [178]
Co3O4/CNTs — 110 F cm−3 — — [179]
Ni-MOF@mC TEABF4 109 F g−1 (0.3 A g−1) 91/5,000 (5 A g−1) 38.8/21,005 [180]
Ni-MOF@NiS2 3 M H2SO4 1,128 F g−1 (2 A g−1) 95.2/10,000 (5 A g−1) 23.5/1,400 [186]
MoS2@Ni-MOF 3 M KOH 1590.24 F g−1 (1 A g−1) 87.97/20,000 (5 A g−1) 72.93/375 [187]
Co-MOF/NF 2 M KOH 13.6 F cm−2 (2 mA cm−2) 79.93/1,000 (50 mA cm−2) 1.7 mW h cm−2/4.0 mW cm−2 [191]
NiO@Ni-MOF 3 M KOH 1192.7 F g−1 (0.5 A g−1) 93.32/5,000 (0.5 A g−1) 62.2/352.5 [192]
Cu-MOF@MnO2 1 M Na2SO4 667 F g−1 (1 A g−1) 95/6,000 (4 A g−1) — [188]
ZIF-67@PANI 1 M KOH 2,497 F g−1 (1 A g−1) 92.3/9,000 (5 A g−1) 71.1/504.72 [200]
Zn/Ni-MOF/PPy 3 M KOH 202 mA h g−1 (1 A g−1) 78.8/5,000 (10 A g−1) 50.9/1,338 [205]
NiCo-MOF/PPy 2 M KOH 1,109 F g−1 (0.5 A g−1) 79.1/10,000 (5 A g−1) 41.2/375 [201]
Ni/P/N/C 6 M KOH 2887.87 F g−1 (1 A g−1) 90/1,000 (10 A g−1) — [210]
NS-BNs 6 M KOH 1,529 F g−1 (1 A g−1) 89.29/10,000 (1 A g−1) 41.04/750 [211]
NiCoP/NiCo-MOF 2 M KOH 728 C g−1 (1 A g−1) 100/10,000 (2 A g−1) 50.3/1011.2 [212]
Ni-MOF/MXene 2 M KOH 867.3 (1 A g−1) 87.1/5,000 (5 A g−1) — [213]
Co-MOF/MXene@Ni 3 M KOH 3,741 F g−1 (3 mA cm−2) 92.1/3,000 (6 mA cm−2) — [214]
Ni/Co-MOF/AB-5 2 M KOH 972.2 F g−1 (0.5 A g−1) 94.1/3,000 (5 A g−1) 33.84/750 [215]
typical PBA structures. Metal hexacyanoferrates are of of pristine PB/PBAs [225]. Hence, considering the advan-
low cost, show fine reversible redox performance, and tages of PB/PBA morphology with hollow nanostructures,
have unique structure, high capacity, and excellent developing a simple, cost-effective, and self-templating
cyclic stability [223,224]. PBAs are usually utilized as method is desirable. To further explore the ideal synthesis
precursors for the fabrication of functional transition method for hollow structures, some effective modifications
metal compounds or other nanoparticles [221]. Owing were made in the preparation of hollow structures.
to its structural advantages, the application of PB/PBA Yin et al. developed an effective self-templating
in supercapacitors has attracted considerable attention. method for the rational fabrication of cobalt hexacyano-
To better utilize PB/PBAs in supercapacitors, their applica- ferrate (CoHCF) with hollow structures using water-soluble
tions can be also divided into three categories: (1) Design precursors at room temperature [226]. In the electroche-
and synthesize Pristine PB/PBAs with unique morphology mical tests with 0.5 M Na2SO4 solution, the CoHCF-based
and hollow nanostructures; (2) the outstanding precursors electrode delivered 284 F g−1 at 1 A g−1, along with 92%
of PB/PBAs to fabricate derivatives, including metal oxides, initial values retained for 5,000 cycles. When assembled
phosphides, and selenides; and (3) functional materials, with AC, this asymmetric hybrid supercapacitor delivered
such as graphene and metal compounds, to further enhance an energy density of 47 W h kg−1 with a power density of
the performances of PB/PBAs. 1,000 W kg−1. Yin et al. fabricated hollow CoHCF micro-
tubes using polyacrylonitrile-Co(Ac)2 composite nanofibers
as templates [227]. In the Na2SO4 aqueous electrolyte, the
3.1 Pristine PB/PBAs capacitance of this hollow CoHCF microtube was 281.8 F g−1
at 1 A g−1. Meanwhile, 93% of the initial values remained
PB/PBAs are promising materials for energy storage devices, over 5,000 charge–discharge cycles. When assembling with
especially supercapacitors. However, their performances were AC, the supercapacitor exhibited 43.89 W h kg−1 energy den-
unsatisfactory. In the previous research, hollow nanostructures sity and 27.78 kW kg−1 power density.
with low density, tunable composition and morphology, and Wang et al. fabricated hollow structure cobalt hexa-
large surface areas have garnered considerable research cyanoferrate submicroboxes through a cation exchange
interest, which enhances the electrochemical performance method (Figure 10a) [228]. They selected manganese
Figure 10: (a) Schematic illustration of the formation mechanism of CoHCF submicrobox. (b) TEM image of CoHCF submicroboxes. (c) GCD
curves of the CoHCF at different current densities. (d) Specific capacitance of COHCF. (e) Ragone plots of the CoHCF//AC hybrid cells.
Reproduced with permission from [228]; Copyright 2017, Elsevier. (f) Schematic illustration of synthesizing hollow Co2HCFe nanocubes.
(g) SEM image of Co2HCFe nanocubes. (h) TEM image of Co2HCFe nanocubes. (i) The cycling stability of Co2HCFe at current densities of
5 A g−1. (j) The specific energy of Co2HCFe. Reproduced with permission from [229]; Copyright 2018, Elsevier.
hexacyanoferrate (MnHCF) as a sacrificial template and primitive uniform hexagonal bipyramidal nanostructure
Co2+ was added to the system, making soluble [Fe(CN)6]2− during this process. This helped to maintain the initial
coordinate with Co2+ to easily construct CoHCF. Then, the properties of PBA and further enhances its electrochemical
CoHCF layer was crystallized and deposited onto the performance. In 1 M KOH electrolyte, this binary oxide,
MnHCF surface, and a distinct hollow and robust nano- annealed at 500°C, exhibited 148 C g−1 at 0.5 A g−1 and
shell was obtained. The TEM image exhibited distinct maintained 74.5% of the original values retained during
hollow interiors in the CoHCF structure (Figure 10b). 5,000 cycles. Furthermore, the constructed ASC (assembled
The electrochemical tests indicated that the electrode with AC) achieved 22.7 W h kg−1 energy density under
material delivered 288 F g−1 at 0.5 A g−1 (Figure 10d), which 640 W kg−1, and the power density could reach 6,400 W kg−1
was better than that of its nanoparticle counterparts. More- with a remaining energy density of 11.1 W h kg−1. Zhang
over, the CoHCF submicrobox preserved 93.1% capaci- et al. fabricated a flexible hybrid film composed of MXene
tance after 8,000 cycles, indicating outstanding cycling and PBA-derived Ni–Fe oxides [233]. They utilized MXene
performance. After CoHCF assembly with AC, the ASC layers to wrap the cubic Ni–Fe oxide, forming a macro-
delivered 42.5 W h kg−1 energy density under 990 W kg−1 scopic flexible film. The areal capacitance was calculated
power density, sustaining 21.1 kW kg−1 power density along to be 1,038 mF cm−2 at 0.2 mA cm−2, and the capacity
with 13.5 W h kg−1 energy density (Figure 10e). remained at 90.88% of the primitive values over 10,000
Zhu et al. fabricated hollow cobalt hexacyanoferrate charge–discharge cycles. Recently, transition metal phos-
(Co2HCFe) nanocubes with uniform and dense hollow phides have also been chosen as promising electrode
structures (Figure 10f) [229]. The SEM image showed a materials. Wei et al. first prepared Co3[Co(CN)6]2 nano-
uniform size of 50 nm (Figure 10g). The HRTEM image cubes as templates and then annealed and phosphorized
showed the hollow structure of the Co2HCFe nanocubes them to fabricate CoP nanocubes [234]. This material deliv-
(Figure 10h). The GCD analysis at different current den- ered 600 F g−1 at 1 A g−1. They also fabricated FeP4 via a
sities indicated its excellent redox-activated properties. similar access. In an assembled ASC, CoP is positive
This also led to a specific capacitance of 2,526 F g−1 at and FeP4 is negative; CoP//FeP4 maintained a capacitance
0.5 A g−1, and the value also reached 378 F g−1 even of 89% after 10,000 cycles. It also exhibited 46.38 W h kg−1
at 20 A g−1 (Figure 10i). Moreover, Co2HCFe maintained with a power density of 695 W kg−1. This study demon-
90.25% retention after 2,000 cycles (Figure 10i). All of its strates an effective phosphorization engineering stra-
prominent electrochemical performances are attributed tegy for PB/PBAs to construct functional electrode
to its unique hollow structure. In an assembled ASC materials.
(Co2HCFe//AC), the maximum value of energy density Some transition metal compounds such as selenides
could reach 53.8 W h kg−1 with 1,242 W kg−1 power density. and phosphides have been recently studied with perfect
The maximum power density was 49,680 W kg−1, whereas electrochemical performance, for the application in super-
the energy density was 41.4 W h kg−1 (Figure 10j). These tests capacitor electrodes. To further enhance the electroche-
indicated that Co2HCFe nanocubes can become superior mical performance of supercapacitors, it is desirable to
electrode materials for future supercapacitors. introduce phosphorus and transition metal selenides into
transition metal. Accordingly, Zong et al. designed P-(Ni,
Co)Se2 selenides with nanotubes anchored on nanoflakes
and nanowires grown on activated carbon cloth (Figure 11a)
3.2 PB/PBA derivatives [235]. The SEM image of this derivative revealed uniform
and continuous nanocubes with a hierarchical network on
Compared to the pristine form of PB/PBAs with porous the selenide surface (Figure 11b). In the 3 M KOH electrolyte,
and hollow morphology, the PB/PBA derivatives possess the CV test possessed different potential windows for dif-
higher surface areas, conductivity, and more open diffu- ferent samples at 10 mV s−1, and the P-(Ni, Co) Se2 NA
sion channels. These lead to an obvious improvement in sample displayed the largest integral area (Figure 11c).
electrochemical performances. Hence, PB/PBAs have been From the GCD analysis at 2 mA cm−2, the selenide-based
widely used as precursors or sacrificial templates to fabri- electrode displayed 755 C g−1 (Figure 11d). In addition, the
cate derivatives, including TMOs or other metal compounds selenides could also retain 80.1% of their original values
with micro/nanostructured materials [218,230,231]. Xie et al. over 3,000 cycles, which was ascribed to the enhancement
utilized Ce–Fe PBAs as precursors to synthesize Fe–Ce in conductivity after phosphorus incorporation (Figure 11e).
oxides [232]. They first prepared pristine Ce[Fe(CN)6] and The assembled HSC delivered an energy density of 45 W h
then annealed it at different temperatures, retaining the kg−1 with a power density of 990 W kg−1 (Figure 11f). This
Figure 11: (a) Schematic illustration of the fabrication procedure of P-(Ni, Co) Se2 NAs on activated carbon cloth. (b) SEM image of P-(Ni, Co)
Se2 NAs. (c) HRTEM image of P-(Ni, Co) Se2 NAs. (d) GCD curves of P-(Ni, Co) Se2 electrode at various current densities. (e) Areal capacity of
NiCoP, (Ni, Co) Se2, P-(Ni, Co) Se2, and Se-NiCoP electrodes at different current densities. (f) Ragone plots of P-(Ni, Co) Se2//ZIF-8-derived
carbon HSC and the previously reported devices. Reproduced with permission from [235]; Copyright 2019, Elsevier.
work provided a new strategy for the composition and the remarkable cycling stability but a relatively narrow operation
nanostructure design of high-performance supercapacitor voltage window. Hence, Song et al. combined the merits of
electrode materials. CoHCF and MnO2 nanosheets to fabricate the nanostructured
hybrid composites [237]. This composite exhibits outstanding
electrochemical performances.
3.3 PB/PBA composites with functional
materials
3.3.1 Graphene
Although PB and its analogs exhibit outstanding proper-
ties, such as high stability/redox activity and open frame- Owing to the excellent performance of graphene and its
works, the relatively poor conductivity of these materials derivatives, including promising conductivity, high sur-
has presented a major obstacle for their applications face area, and chemical stability, they are perfect candi-
[236]. Conductive fillers such as carbon materials and other dates for combination with PB/PBAs [238]. To enhance
metal compounds must be added to enhance the conductivity their electrochemical activity and conductivity, graphene
of PB and PBA materials. The incorporation of functional has been frequently used for fabricating nanocomposites.
materials could also improve their electrochemical perfor- A ternary nanocomposite PPy-PB-GO (GO: graphene
mance compared with their pristine forms. For example, oxides) was synthesized via spontaneous polymerization
MnO2 nanosheets are an excellent electrode material in super- among pyrrole, PB, and GO [239]. The scheme could be
capacitors but suffer from lower conductivity. CoHCF delivers divided into two stages: (i) absorbing pyrrole onto the GO
surface and (ii) using pyrrole to reduce Fe3+ to Fe2+ and carbon materials. The cycling stability tests showed that
form insoluble PB nanocubes (Figure 12a). The SEM the PPy-PB-GO electrode could retain 96% of its initial
image showed that PB was anchored on the GO matrix capacitance after 2,000 cycles (Figure 12c), indicating its
(Figure 12b), and the PB nanocubes were protected by perfect cycling stability and a high degree of reversibility.
PPy. In the electrochemical analysis, the PPy-PB-GO elec- Goda et al. synthesized Cu-PBA/GO composites via depos-
trodes exhibited 525.4 F g−1, which was considerably better iting Cu-PBA nanocubes on GO surfaces [238]. This nano-
than those of most PBA-based materials and porous composite delivered 611.6 F g−1 at 0.5 A g−1 and maintained
Figure 12: (a) Schematic illustration of the fabrication procedure of PPy–PB–GO composites. (b) SEM image of PPy–PB–GO. (c) The cycling
stability of PPy–PB–GO electrode over 2,000 cycles. Reproduced with permission from [239]; Copyright 2015, Elsevier. (d) Schematic
illustration of the fabrication of Graphene@PB nanocomposites. (e) SEM image of Graphene@PB-5 nanocomposites. (f) Specific capaci-
tance of samples at 1 A g−1 (graphene denoted as G). (g) Ragone plots of Graphene@PB-5//AC ASC compared to the references. (h) Cycling
performance of Graphene@PB-5//AC at a current density of 5 A g−1. Reproduced with permission from [240]; Copyright 2018, The Royal
Society of Chemistry.
86% primitive values during 2,000 cycles at 4 A g−1. In one-step co-precipitation synthesis route [242]. In electro-
addition, the assembled supercapacitors could achieve chemical tests, cobalt–nickel hexacyanoferrate hybrids
54.37 W h kg−1 at a power density of 200 W kg−1, proving displayed 600 F g−1 at 0.2 A g−1 and maintained 94% of
its outstanding electrochemical performance. its original value during 2,000 cycles. When assembling
Wang et al. fabricated interlocked Graphene@PB nanosheets this cobalt–nickel hexacyanoferrate with CNT to test its
via a one-step facile hydrothermal technique [240]. They applications, the hybrid electrode achieved 30 W h kg−1
used [Fe(CN)6]4− to release Fe2+ and oxidize partial Fe2+ to energy density and 60 W kg−1 power density at 0.2 A g−1.
Fe3+ in acidic media. Subsequently, the graphene nanosheets
could constantly absorb Fe3+ ions to react with [Fe(CN)6]4−,
thus forming PB nanotubes on the graphene nanosheets 3.3.2 Metal compounds
(Figure 12d). A typical SEM image showed that the PB
nanocubes covered both sides of the graphene nanosheet Transition metal compounds (oxides, hydroxides, etc.)
surfaces, forming thicker graphene@PB-5 nanocomposites have also been investigated as perfect functional mate-
(Figure 12e). In the electrochemical test, this nanocompo- rials for supercapacitors. The hybridization between PB/
site exhibited 445 F g−1 at 0.5 A g−1, displaying better per- PBAs and 2D metal oxides leads to the formation of bidir-
formance than that of other samples at various current ectional coordinative interactions between them, thus
densities (Figure 12f). The assembled supercapacitors deliv- enhancing their electrochemical performance [243]. Pre-
ered 74.8 W h kg −1 and 5.5 kW kg−1 energy density/power vious research has shown that PB/PBAs fabricated with
density, respectively (Figure 12g). The nanocomposite also MnO2 can enhance electrochemical performance [237].
maintained a 97.2% initial value over 5,000 cycles (Figure 12h). MnO2-based materials are one of the most promising
This can be ascribed to the synergistic effect of the hybrid reversible, environmentally benign, and low-cost elec-
nanostructure that prevents the aggregation of PB nanoparti- trode materials for supercapacitors. They also deliver
cles and restacking of graphene nanosheets. higher capacitance performances compared with those
Sookhakian et al. prepared PB-nitrogen-doped gra- carbonaceous counterparts [46]. Zhang et al. combined
phene nanocomposites using the Fe(NO3)3 solution and PB with a unique coordination superamolecular net-
K4Fe(CN)6 via a simple process [222]. In a 1 M H2SO4 solu- work (CSN) with MnO2 to fabricate CSN-PB/MnO2 hybrids
tion, this composite-based electrode delivered 660 C g−1 (Figure 13a) [244]. The SEM image showed that the typical
at 1 A g−1. In addition, the stability tests showed that the PB was uniformly inserted into MnO2, and some adhered
nanocomposite retained 84.7% of its primitive values to the surface of MnO2, which is favorable for promising
during 1,500 cycles, which is also ascribed to the syner- electrochemical performance (Figure 13b). In electroche-
getic effects of N-graphene and PB nanoparticles that mical tests, this composite electrode exhibited a character-
prevent mechanical deformation. Zhang et al. fabricated istic pseudocapacitive feature at different scan rates from
PB/rGO hydrogels via a facile one-pot hydrothermal route 10 to 50 mV s−1 (Figure 13c). In further studies, the GCD
(denoted as PB-Co/rGOH) [241]. In their study, the CV tests of this composite displayed highly symmetrical prop-
tests of this hybrid and other compared samples were erties and relatively linear slopes (Figure 13d). Further-
analyzed, showing that the capacitance of PB-Co/rGOH more, in 1 M Na2SO4 solution, this composite electrode
was mainly attributable to the EDLC and pseudo-capaci- could deliver 315.3 F g−1 at 1 A g−1, which was higher than
tance region. Moreover, this composite-made electrode that of pristine MnO2 and the CSN-PB electrode. In parti-
exhibited the longest discharge time and showed 225.2 F g−1 cular, this composite retained 32.4% of the highest capa-
at 1 A g−1 with 82.4% original values maintained over 10,000 citance values at 30 A g−1, indicating good rate capability
cycles. Azhar et al. fabricated iron oxide/carbon composites (Figure 13e). Furthermore, the fabricated ASC, CSN-PB/
with nanoporous structures [236]. The morphology clearly MnO2//AC retained 85.5% of the original values over
showed that the iron oxide nanoparticles are firmly aggre- 20,000 cycles at 20 A g−1 (Figure 13f). Moreover, this device
gated to each other on the GO nanosheet surface. The specific achieved a maximum energy density of 46.13 W h kg−1 and
capacitance value of the iron oxide/carbon composite was a power density of 1.20 kW kg−1. Its power density could be
415.0 F g−1 at 2 A g−1, and the capacity retention reached up as high 18.00 kW kg−1, while retaining an energy density
to 120% over 8,000 cycles. This could be ascribed to the of 19.95 W h kg−1. These performances demonstrated their
activation of the hybrid that improve the surface wetting of potential applications in supercapacitors.
the electrode and led to the fast diffusion of ions in the Das et al. [46] fabricated a PB@MnO2 hybrid elec-
electrolyte. Xu et al. designed cobalt–nickel hexacyanofer- trode material, and this is the first report of a PB compos-
rate hybrids with CNT (K2.25Ni0.55Co0.37Fe(CN)6/CNT) via a ite with metal oxides (Figure 13g). In the morphological
analysis, the FE-SEM image showed that MnO2 is prefer- PB@MnO2 hybrid were preserved even at 10 A g−1, indi-
entially deposited on the surface of PB nanocubes, offering cating promising rate capability compared to pure PB
a porous surface morphology (Figure 13h). To evaluate its (Figure 13j). Moreover, they assembled a PB@MnO2 hybrid
electrochemical properties, GCD experiments were con- and polyaniline/graphene nanoplatelet (PG) as ASC. The
ducted at different current densities (Figure 13i). The spe- ASC exhibited great capacitive retention after 4,000 cycles
cific capacitance of PB@MnO2 was 608 F g−1 at 1 A g−1. (Figure 13k). Furthermore, it exhibited a 16.5 W h kg−1
Moreover, approximately 68% of the initial values of the energy density along with a 550 W kg−1 power density
Figure 13: (a) Schematic illustration of the fabrication of CSN-PB/MnO2 composite. (b) SEM image of CSN-PB/MnO2 composite. (c) CV curves
of CSN-PB/MnO2 composite at various scan rates. (d) GCD curves of CSN PB/MnO2 composite electrode at various current densities from 1 to
30 A g−1. (e) The specific capacitance of CSN-PB/MnO2 composite electrode. (f) Cycling performance of the Fe-PBA/MnO2//AC device at a
current density of 20 A g−1 for 20,000 cycles. Reproduced with permission from [244]; Copyright 2019, Springer. (g) Schematic illustration
of the synthesis of PB@MnO2. (h) SEM image of PB@MnO2 hybrid. (i) GCD curves of PB@MnO2 at several current densities. (j) The specific
capacitance of PB and PB@MnO2. (k) Cycling performance of the device at the current density of 1 A g−1. Reproduced with permission from
[46]; Copyright 2017, The Royal Society of Chemistry.
while retaining 11.3 W h kg−1 energy density under 5,497 W kg−1 Remarkable works on PB/PBAs as electrode materials
power density. These remarkable behaviors demonstrated for supercapacitors are listed in Table 4.
that the PB@MnO2 composite is a potential candidate for
electrode materials in supercapacitors. Sun et al. designed
and synthesized ZnCo-PBA@α-Co(OH)2 composites by
loading α-Co(OH)2 nanosheets onto Zn3[Co(CN)6]2 nano- 4 COFs
spheres [245]. In the electrochemical analysis, this compo-
site exhibited 423.92 F g−1 at 1 A g−1. In addition, they con- Covalent organic frameworks (COFs) are novel crystalline
structed a ZnCo-PBA@α-Co(OH)2//AC ASC, which displayed nanoporous materials possessing unique design features,
a 73.53% original value maintained after 5,000 cycles at perfect channel structures, tunable porosity, and ordered
5 A g−1, demonstrating its promising cycling stability. The 2D and 3D networks [24,246,247]. In 2005, the first COF
energy density of the ASC was calculated to be 49.13 W h was discovered by Liu et al. and denoted as COF-1 [47].
kg−1 with 1734.0 W kg−1 power density, indicating that the Subsequently, more porous COFs were discovered, denoted
device is an excellent electrochemical material. as COF-5, COF-102, COF-105, and so on. Owing to their
Figure 14: (a): 3D diagrams of interlayer C—H···N H-bonding in TpOMe-DAQ. (b) SEM image of TpOMe-DAQ thin sheet. (c) Cycling stability of
TpOMe-DAQ at 10 mA cm−2. Reproduced with permission [52]; Copyright 2018, American Chemical Society. (d) Synthetic scheme of Ni-COF.
(e) SEM image of Ni-COF. (f) TEM image of Ni-COF. (g) GCD curves at different current densities (1–10 A g−1). (h) The specific capacitance of
Ni-COF and Ni0-COF. (i) Cycling stability at a current density of 1 A g−1. Reproduced with permission from [53]; Copyright 2019, The Royal
Society of Chemistry.
[240]
intriguing esthetic structures and unique properties such as
[228]
[244]
[226]
[229]
[236]
[242]
[234]
[234]
[239]
[222]
[233]
[227]
[245]
[235]
[241]
[46]
Ref. large surface area, outstanding hydrothermal stability,
structural adaptivity, and low density, COFs have become
popular candidates for electrode materials in supercapaci-
76.8 mWh cm−3/0.4 W cm−3

tors [248]. However, their electrical conductivity and insu-
lating behavior considerably limit their further utilization
[249]. To overcome the shortcoming of COFs, designing
43.89/27,780
and fabricating COFs with unique building units, COF deri-

41.4/49,680
37.9/10,000
10.65/2,700
46.13/1,200
49.13/1,734
70.2/1,100
46.38/695
46.38/695
11.3/5,497
vatives, or constructing COFs with other functional mate-
42.5/990
45/446.3
28/1,400
47/1,000
ED/PD
rials are utilized. In the application of supercapacitors,

some 2D COFs have been received more research in recent
—
—
years. Researchers found that their stacked 2D structure
with small mesopores greatly impede the mass transfer
90.88/10,000 (1 mA cm−2)
80.1/3,000 (20 mA cm−2)
100/8,000 (200 mV s−1) and the full utilization. Moreover, the conductive COF
85.5/20,000 (20 A g−1)
90.25/2,000 (5 A g−1)
82.4/10,000 (5 A g−1)
93.1/8,000 (10 A g−1)
97.2/5,000 (10 A g−1)
73.53/5,000 (5 A g−1)
could also enhance its electrochemical performance and
89/10,000 (10 A g−1)
89/10,000 (10 A g−1)
84.7/1,500 (6 A g−1)
96/2,000 (5 A g−1)
94/2,000 (1 A g−1)
92/5,000 (5 A g )
93/4,000 (1 A g−1)
93/5,000 (5 A g−1)
−1
received extensive attention.

CR (%/cycles)
4.1 Pristine COFs
COFs have demonstrated remarkable performance as elec-

1,038 mF cm−2 (0.2 mA cm−2)
trode materials for supercapacitors. However, similar to

other framework materials (MOFs, PB/PBAs), their pristine
2,526 F g−1 (0.5 A g−1)
755 C g−1 (2 mA cm−2)
423.92 F g−1 (1 A g−1)

600 F g−1 (0.2 A g−1)
288 F g−1 (0.5 A g−1)
445 F g−1 (0.5 A g−1)

525.4 F g−1 (5 A g−1)
281.8 F g−1 (1 A g−1)
225.2 F g−1 (1 A g−1)
315.3 F g−1 (1 A g−1)
forms possess poor electrochemical conductivity and other

660 C g−1 (1 A g−1)
600 F g−1 (1 A g−1)
608 F g−1 (1 A g−1)

284 F g (1 A g )
415 F g−1 (2 A g−1)

345 F g−1 (1 A g−1)
−1
properties. Introducing functional units such as some

redox-active building units into COFs is a simple method
−1
of improving their conductivity and stability [250]. Feng

et al. synthesized a tetragonal 2D porphyrin COF with a
SC
high large crystallinity and surface area [251]. The intro-

duction of a porphyrin unit helps form conduction path-
0.5 M Na2SO4
0.5 M Na2SO4
0.5 M Na2SO4
0.5 M Na2SO4
ways, leading to high-rate charge carrier conduction. Ding

1 M Na2SO4
Electrolyte
1 M H2SO4
et al. constructed n-channel 2D COFs [252]. The adoption

1 M KNO3
1 M KNO3
1 M KNO3
6 M KOH
3 M KOH
3 M KOH
3 M KOH
3 M KOH
3 M KOH
4 M KCl
of benzothiadiazole (BTDA) units forms an electron-con-

—
ducting framework. Recently, some studies have explored

this method via condensation reactions and developed a
series of special pristine COFs applied in supercapacitors,
K2.25Ni0.55Co0.37Fe(CN)6/CNTs
considerably improving their electrochemical performance.

Halder et al. prepared interlayer hydrogen-bonded
Table 4: Selected PB/PBAs for supercapacitors
ZnCo-PBA@αCo(OH)2
COF TpOMe-DAQ using TpOMe (2,4,6-trimethoxy-1,3,5-

benzenetricarbaldehyde) and DAQ (2,6-diaminoanthra-
NiFe-O/Mxene
CSN-PB/MnO2
P-(Ni, Co)Se2
PB-Co/rGOH
quinone) as reactants, which had both superior chemical

PPy-PB-GO
PB@MnO2
Samples
Co2HCFe
stability under drastic conditions and reversible redox

PB/N/G
PB/GO
CoHCF
CoHCF
CoHCF
G@PB
response (Figure 14a) [52]. These COFs could be con-

FeP4
CoP
structed as continuous and uniform thin nanosheets, even

at the centimeter scale (Figure 14b). Moreover, quasi-rever-
sible redox peaks were observed at 1 mV s−1, indicating
PBAs composites
PBs composites
PBA derivatives
PBA derivatives
PB composites
PB composites
PB composites
PB composites
PB composites
PB composites
PB composites
PB derivatives
PB derivatives
pseudocapacitive properties. Furthermore, GCD analysis

Pristine PBs
Pristine PBs
Pristine PBs
Pristine PBs
was performed, and the areal capacitance was improved

PB/PBAs
from 135 to 169 F g−1. This COF also exhibited a remarkable

cycling performance, with almost no initial capacitance
values compromised over 100,000 cycles (Figure 14c). It electrochemical performance of functional COFs in
is postulated that the hydrophobic and steric protection supercapacitors.
from imine (C]N) bonds, methoxy nearby, and its inter-
layer hydrogen bonding all result in superior cycling
performances.
Some condensation reactions, such as Schiff-base 4.2 COFs derivatives
condensation and Knoevenagel condensation, are widely
used to introduce functional units to improve their prop- Considering their similarity in structures with MOFs,
erties. Li et al. utilized the Schiff-base condensation reac- except for the absence of metal ions, COFs can also serve
tion to construct an ultrastable triazine-based COF, which as a source of microporous carbon particles [256,257].
is denoted as PDC-MA-COF [253]. In the electrochemical Zhuang et al. used Knoevenagel condensation to synthe-
tests, the PDC-MA-COF exhibited 248.0 F g−1 along with size 2D olefin-linked COFs based on olefin (C]C) lin-
74% of the original values retained at higher current den- kages for the first time (denoted as 2DPPV) [49]. Owing
sities. The GCD experiments further showed its perfect to its highly periodic porous structure and crystalline fea-
symmetry and maximum specific capacitance: 335.0 F g−1 tures, 2DPPV possesses promising electrochemical perfor-
was achieved at 1.0 A g−1, along with outstanding cyclic mance. When fabricated at 800°C, 2DPPV-800 delivered
stability over 9,000 cycles at 5.0 A g−1. This can be ascribed 334.0 F g−1 at 0.5 A g−1 with almost no noticeable change in
to the interlayer H-bonding maintaining an ordered nano- the original values over 10,000 cycles. Zhou et al. synthe-
structure, enhancing the cycling stability of COF, and pro- sized B–N–C-n materials with MA and 4-FPBA, catalyzed
viding perfect capacitance retention. by Cu(NO3)2 (Figure 15a) [255]. The SEM and TEM image
The Knoevenagel condensation reaction is also an demonstrated capsules with hollow morphology (cavities
important method for fabricating high-molecular-weight of 0.02–10 µm) (Figure 15b and c). The CV analysis sug-
organic structures, including COFs. Recently, an increasing gested that the EDLC played a dominant role in the
number of studies have focused on this condensation reac- charge–discharge system of B–N–C, which was annealed
tion to construct high-performance COFs. Zhang et al. also at 1,000°C, along with 399.4 cm2 g−1 and 230 F g−1 at 5 A g−1
synthesized two 2D olefin-linked COFs (g-C48N6-COF and (Figure 15d). Under various current densities, this value
g-C30N6-COF) via the Knoevenagel condensation reaction was maintained over 150.0 F g−1 (Figure 15e). The cycling
[254]. Their COFs possessed highly crystalline honeycomb- text also showed that after 1,400 cycles, B–N–C main-
like structures and display well-defined nanofibrillar tained a capacitance of 192 F g−1 (Figure 15f), demon-
morphologies. In a micro-supercapacitor, the g-C30N6-COF- strating its promising electrochemical properties.
MSC exhibited 44.3 mF cm−2, and the g-C48N6-COF-MSC
exhibited 41.1 mF cm−2. Moreover, both the COF-MSC
delivered perfect cycling stability with almost 95% initial
values retained after 5,000 cycles. 4.3 COF composites with functional
Metal elements are also incorporated in unique COFs materials
to enhance their performance. Li et al. synthesized a Ni-
COF (with Ni2+) for high-performance supercapacitors via To improve the structural stability and electrical conduc-
a facile synthesis route (Figure 14d) [53]. This COF pos- tivity of COF electrodes during cycling, many materials
sessed a unique morphology with spherical flower-like such as metal and nanoporous carbon have been employed
shapes and abundant sheets (Figure 14e). It also dis- to form COF composites. Xu et al. fabricated COF composites
played a unique layered structure and optically translu- (denoted as CHCM) for the first time [246]. They combined
cent features (Figure 14f). The GCD experiments indicated COF with hydroxyl-terminated hyperbranched polyesters
the rapid charge transfer kinetics of Ni-COF (Figure 14g). (OHPs) first and then impregnated this hybrid on micro-
Owing to its enhanced electrical conductivity, highly porous electrically conducting carbon nanotube films
dense redox-active centers, and conjugated planar struc- (CNTFs) to construct COF@OHP@CNTF (CHCM). Due to
ture, the electrode based on this composite exhibited the incorporation of OHP, the capacitance of this hybrid
1257.0 F g−1 at 1.0 A g−1, which was better than Ni0-COF was greatly increased. When the heating time continued
(without Ni2+) at different current densities (Figure 14h). over 10 h, the performance of capacitance could also
This electrode delivered approximately 100% of the ori- enhance. In 2 M H2SO4 solution, this hybrid delivered
ginal values retained over 10,000 cycles (Figure 14i). 425 F g−1 at 0.2 mA cm−2. It also retained 80% initial capa-
This research also paved the way for enhancing the citance over 10,000 cycles at 0.8 mA cm−2. Carbon
Figure 15: (a) Schematic illustration of the synthesis procedures of the B-N-C capsules. (b) SEM image. (c) TEM image. (d) GCD curves of
B-N-C-1,000 at different current densities. (e) The specific capacitance of B-C-N-1,000. (f) Cycling stability of B-C-N-1,000 at a constant
current density of 20 A g−1. Reproduced with permission from [255]; Copyright 2018, Elsevier.
materials are promising additives for COFs. Han et al. poly- sheets and good flexibility. In a symmetrical supercapa-
merized redox-active TpPa-COFs with single-walled CNT citor device, COF/rGO electrode could yield 269 F g−1 at
under solvothermal conditions to construct SWCNT-COF 0.5 A g−1. It also retained 83% of the highest capacitance
nanocomposites [50]. In the GCD experiments, this nano- (222.0 F g−1) at 10.0 A g−1. Compared with pristine COFs
hybrid delivered 153.0 F g−1 at 0.5 A g−1, indicating a great and rGO, this composite delivered excellent performance
potential in the energy storage field. (Figure 16c). The cycling tests of the COF/rGO materials
RGO possesses many merits, including low weight, showed that 96% primitive values retained over 5,000
high flexibility, low volume, and perfect conductivity, cycles, proving its promising chemical stability (Figure 16d).
thereby making them outstanding carbonaceous addi- An et al. fabricated a hierarchical porous anthraquinone-
tives for electrode materials [259]. Li et al. prepared based COFs/graphene aerogel (DAAQ-COFs/GA) compos-
COF/rGO hydrogel composites via the in situ reaction of ite via electrostatic self-assembly and hydrothermal
their organic linkers in the presence of GO (Figure 16a) routes (Figure 16e) [54]. The SEM image showed that
[258]. This method included adding GO into the reaction each nanoflower-shaped DAAQ-COF was closely covered
solution under hydrothermal treatment and obtaining the by ultrathin graphene nanosheets and embedded in the
targeted composites. The SEM image of COF/rGO is shown 3D graphene networks (Figure 16f), which was ascribed
in Figure 16b. This composite possessed a hollow tubular to the powerful electrostatic attraction and π–π interac-
and 3D sponge-like structure, indicating its very thin tions. In the electrochemical tests, the electrode exhibited
Figure 16: (a) The preparation of COF/rGO aerogel. (b) SEM image. (c) The specific capacitances and capacities under different current
density. (d) The cycling stability of COF/rGO at a current density of 8 A g−1. Reproduced with permission from [258]; Copyright 2020, Nature
publishing group. (e) The synthesis procedure of DAAQ-COFs/GA composite. (f) SEM image of DAAQ-COFs/GA composites. (g) Cycling
stability at 5 A g −1 for 20,000 cycles (the inset shows the digital photograph of LEDs powered by DAAQ-COFs/GA//GA ASC). (h) Ragone plot
of the assembled ASC. Reproduced with permission from [54]; Copyright 2021, The Royal Society of Chemistry.
a capacitance of 378 F g−1 at 1 A g−1. This could contribute ASC (DAAQ-COFs/GA//GA), this device presented 88.9%
to the hierarchical porous properties and rapid Faradaic primitive capacitance retained over 20,000 cycles (Figure 16g).
reactions of the redox sites. Furthermore, in a constructed This supercapacitor also exhibited 30.5 W h kg−1 at a power
density of 700 W kg−1 (Figure 16h). The research presented
[246]
[258]
[254]
[254]
[253]
[255]
[49]
[50]
[54]
[52]
[53]
Ref. insights into the processing and practical application of
COF-based materials in supercapacitors.
Remarkable works on all COFs as electrode materials
−2
38.5 mWh cm−3/0.3 W cm−3

35.7 mWh cm−3/0.3 W cm−3
2.9 µW h cm /61.8 µW cm
for supercapacitors are listed in Table 5.

−2
5 Summary and outlook

13.5/7,500
30/6,654
30.5/700
130/839
ED/PD
Supercapacitors have a potential for a wide range of

—
—
—
—
practical applications, which may become an excellent
replacement for traditional Li-ion batteries and other
chargeable batteries. In recent years, research on frame-
100/100,000 (10 mA cm )
−2
80/10,000 (0.8 mA cm−2)

99.99/10,000 (0.5 A g−1)
95/5,000 (1.2 mA cm−2)
95/5,000 (1.2 mA cm−2)
work materials, their derivatives, and composites has

88.9/20,000 (15 A g−1)
99.99/2,000 (2 A g−1)
83.5/1,400 (20 A g−1)
demonstrated the superior capabilities of these materials

94/10,000 (1 A g−1)
96/5,000 (8 A g−1)
78/9,000 (5 A g−1)
and their unique structures. This explains their wide use

CR (%/cycles)
in supercapacitors, which has attracted considerable

attention. We conclude that there are significant advances
in the application of supercapacitors. The creative and
logical synthesis of excellent nanostructures considerably
improves the conductivity, cycling life, capacity, and
energy/power density of the assembled supercapacitors.
44.3 mF cm−2 (0.5 mA cm−2)
41.1 mF cm−2 (0.5 mA cm−2)
These advances demonstrate the promising performance

425 F g−1 (0.2 mA cm−2)
169 F g (3.3 mA cm )
−2
of framework materials in supercapacitors and provide

269 F g−1 (0.5 A g−1)
334 F g−1 (0.5 A g−1)
153 F g−1 (0.5 A g−1)

1,257 F g−1 (1 A g−1)
335 F g−1 (1 A g −1)
230 F g−1 (5 A g−1)
useful information for the development of higher-perfor-

378 F g−1 (1 A g−1)
mance supercapacitors.
All framework materials (MOFs, PB/PBAs, and COFs)
−1
exhibit promising nanostructures, promoting their further

SC
application in supercapacitors. The unique design and

synthesis facilitate the construction of frameworks with
superior structures, enhancing their electrochemical per-
EMIMBF4/PVDF-HFP
EMIMBF4/PVDF-HFP
formances. Through special conversions such as derivati-

zation and compositing with some functional materials,
they can overcome their shortcomings better than their
Electrolyte
2 M H2SO4
3 M H2SO4
0.1 M KOH
1 M H2SO4
1 M H2SO4
0.5 H2SO4
6 M KOH
6 M KOH
3 M KOH
initial counterparts. It has also attracted considerable

attention for the development of new framework materials
with outstanding electrochemical properties.
(1) Some pristine MOFs with functional structures, such
SWCNTs-TpPa-COFs
Table 5: Selected COFs for supercapacitors
as promising metal elements, superior ligands, and

special morphologies, can deliver excellent electro-
PDC-MA-COF
g-C48N6-COF
g-C30N6-COF
TpOMe-DAQ
chemical performance. Especially in ultrathin 2D MOF

B–N–C-n
COF/rGO
Samples
sheets, the specific capacitances, cycling stabilities,

COF/GO
Ni-COF
2DPPV
CHCM
and energy/power densities are all enhanced com-

pared to their counterparts.
(2) With controlled synthesis and special conversions,
MOF-derived materials often achieve better proper-
COF composites
COF composites
COF composites
COF composites
COF derivatives
COF derivatives
Pristine COFs
Pristine COFs
Pristine COFs
Pristine COFs
Pristine COFs
ties. Some MOFs were converted into carbonaceous

materials, while others were converted into metal
compounds with pseudocapacitive properties. Using
COFs
carbonaceous materials, especially porous carbon

and graphene materials, can significantly improve the Moreover, the relationships between the synthetic routes
cycling stability. Metal compounds, especially metal and MOF morphologies should also be paid more atten-
chalcogenides, exhibit superior capacity performance. tion. Monometallic MOFs with other transitional metal
Combining derivatives with functional materials, such elements can also investigate their performances in
as carbonaceous materials with metal compounds, supercapacitors.
can integrate the advantages of two components. (2) MOF derivatives deliver better performance in enhan-
(3) Some pristine MOFs have been combined with other cing capacitance. However, the conversion of pristine
functional materials. This could both remain the MOFs to their derivatives is complex and may not be
initial properties of the MOF and overcome the dis- well controlled. This could lead to the precise synth-
advantages with the help of functional materials. The esis of MOF derivatives with very hard-targeted mor-
combination of MOFs with carbonaceous materials phological features. Further research will contribute
can enhance their cycling stability and conductivity. toward building comprehensive synthesis routes
When combined with pseudocapacitive materials (metal and optimizing the design and fabrication of these
compounds and CPs), their capacities are significantly functional derivatives. Moreover, the doping in the
improved compared with their primitive counterparts. derivation is a better strategy for obtaining better
Moreover, MOF composites may deliver better electro- physicochemical properties compared to their undoped
chemical performance than most MOF derivatives. counterparts. However, few studies have been reported
(4) Compared with MOFs, PB/PBAs possess hollow core- on MOFs-based derivatives with metallic heteroatom
shell nanostructures that promote the diffusion of the doped, which will remain a challenge in the future.
electrolyte and enhance their electrochemical perfor- (3) With the combination of some carbon materials or
mance. Similar to MOFs, PB/PBAs can also serve as pseudocapacitive additives, the electrical conduc-
sacrificial precursors or templates for fabricating var- tivity of MOFs and their capacities are enhanced.
ious derivatives such as transitional metal selenides, Coating functional materials onto MOF derivatives,
oxides, and phosphides. such as adding carbonaceous materials onto metal
(5) In contrast to MOFs and PB/PBAs, pristine COFs with compounds derived from MOFs, may have a chance
superior building units attract more attention than to yield the advantages of both materials. Therefore,
their derivatives and composites. Owing to their spe- electrode materials with outstanding capacitance per-
cial condensation in the synthesis process, COFs with formance and excellent cyclic life can be obtained,
redox-active units, perfect channel structures, and making them promising for practical applications.
tunable porosities can be successfully constructed. Hence, the preparation and effective synthesis route
Some COFs with special molecule interactions enhance of functional derivatives and nanocomposites should
their charge–discharge cycles. be further studied. Moreover, the elements doping in
composites should also be investigated. Few studies
Numerous framework materials with unique morpholo- have been reported in MOF composites with het-
gies, nanostructures, and functionalities have been synthe- eroatom doped, which will remain the same challenge
sized and widely utilized in supercapacitors. Moreover, fra- in the future compared with MOF derivatives.
mework materials combined with other functional materials (4) PB/PBA nanocomposites are still under investigation,
have demonstrated potential in enhancing the electroche- and other PB/PBAs with hollow and unique morpholo-
mical performance, including capacity, cycling stability, and gies should also be investigated. Many pristine PB with
energy/power densities. Over the past several years, rapid a hollow structure can deliver promising performance.
developments have been witnessed in the fabrication and Hence, more research should focus on the influence of
application of framework materials, their derivatives, and these unique hollow structures on their properties. PB/
composites. More efforts are required to realize the practical PBA can also be treated like MOFs to fabricate deriva-
use of these materials. There are several main challenges to tives and special composites. Some studies have shown
be addressed as follows: that functional pseudocapacitive materials such as metal
(1) Despite the excellent advances in the study of MOFs sulfides, metal hydroxides, and MXene can combine with
for use in supercapacitors, the precise and systematic PB/PBAs to enhance their performance. More research
investigation of the relation between the properties should be conducted on the relations between the trans-
and structures of pristine MOFs is still wanting. Hence, ferring charge and these functional materials.
more attention should be focused on innovative syn- (5) Great progress has been made in the development of
thetic routes for MOFs, especially multimetallic MOFs. pristine COFs with unique building units. Hence, the
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Funding information: This work was supported by the [13] Zhao Y, Liu J, Horn M, Motta N, Hu M, Li Y. Recent advance-
National Natural Science Foundation of China (U1904215), ments in metal organic framework based electrodes for
Natural Science Foundation of Jiangsu Province (BK20200044), supercapacitors. Sci China Mater. 2018;61:159–84.
Changjiang scholars program of the Ministry of Educa- [14] Yao H, Zhang F, Zhang G, Luo H, Liu L, Shen M, et al.
A novel two-dimensional coordination polymer-
tion (Q2018270), and Jiangsu Students’ Innovation and
polypyrrole hybrid material as a high-performance
Entrepreneurship Training Program (202111117079Y). The electrode for flexible supercapacitor. Chem Eng J.
authors also acknowledge the Priority Academic Program 2018;334:2547–57.
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Author contributions: All authors have accepted respon-
application of high-performance hybrid supercapacitor.
sibility for the entire content of this manuscript and Small. 2018;14:1800285.
approved its submission. [16] Gogotsi Y, Simon P. Materials for electrochemical capacitors.
Nat Mater. 2008;7:845–54.
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Nanotechnology Reviews 2022; 11: 1005–1046

Framework materials for supercapacitors

Abstract: Framework materials, including metal–organic

Scheme 1: The timeline of key research about MOFs in supercapacitors.

Scheme 2: The timeline of key research about PB/PBA in supercapacitors.

Scheme 3: The timeline of key research about COFs in supercapacitors.

Table 1: Selected pristine MOFs for supercapacitors

Samples Electrolyte SC CR (%/cycles) ED/PD Ref.

Ni3(HITP)2 1 M TEABF4/ACN 18 µF cm−2 90/10,000 (2 A g−1) — [61]

Table 2: Selected MOF derivatives for supercapacitors

MOFs (precursors) Samples Electrolyte SC CR (%/cycles) ED/PD Ref.

To develop high-performance electrode materials for super- 2.3.1 Carbonaceous material

Table 3: Selected MOF composites for supercapacitors

Sample Electrolyte SC CR (%/cycles) ED/PD Ref.

76.8 mWh cm−3/0.4 W cm−3

and fabricating COFs with unique building units, COF deri-

rials are utilized. In the application of supercapacitors,

80.1/3,000 (20 mA cm−2)

97.2/5,000 (10 A g−1)

received extensive attention.

4.1 Pristine COFs

COFs have demonstrated remarkable performance as elec-

trode materials for supercapacitors. However, similar to

755 C g−1 (2 mA cm−2)

423.92 F g−1 (1 A g−1)

445 F g−1 (0.5 A g−1)

225.2 F g−1 (1 A g−1)

315.3 F g−1 (1 A g−1)

forms possess poor electrochemical conductivity and other

608 F g−1 (1 A g−1)

415 F g−1 (2 A g−1)

properties. Introducing functional units such as some

of improving their conductivity and stability [250]. Feng

high large crystallinity and surface area [251]. The intro-

ways, leading to high-rate charge carrier conduction. Ding

et al. constructed n-channel 2D COFs [252]. The adoption

of benzothiadiazole (BTDA) units forms an electron-con-

ducting framework. Recently, some studies have explored

considerably improving their electrochemical performance.

COF TpOMe-DAQ using TpOMe (2,4,6-trimethoxy-1,3,5-

quinone) as reactants, which had both superior chemical

stability under drastic conditions and reversible redox

response (Figure 14a) [52]. These COFs could be con-

structed as continuous and uniform thin nanosheets, even

pseudocapacitive properties. Furthermore, GCD analysis

was performed, and the areal capacitance was improved

from 135 to 169 F g−1. This COF also exhibited a remarkable

density of 700 W kg−1 (Figure 16h). The research presented

38.5 mWh cm−3/0.3 W cm−3

for supercapacitors are listed in Table 5.

5 Summary and outlook

Supercapacitors have a potential for a wide range of

80/10,000 (0.8 mA cm−2)

work materials, their derivatives, and composites has

demonstrated the superior capabilities of these materials

and their unique structures. This explains their wide use

in supercapacitors, which has attracted considerable

These advances demonstrate the promising performance

of framework materials in supercapacitors and provide