Nanomaterials 11 01248

Download as pdf or txt
Download as pdf or txt
You are on page 1of 28

nanomaterials

Review
Transition Metal Oxide Electrode Materials for Supercapacitors:
A Review of Recent Developments
Ruibin Liang 1 , Yongquan Du 1 , Peng Xiao 1,2, *, Junyang Cheng 1 , Shengjin Yuan 1 , Yonglong Chen 1 , Jian Yuan 1,2
and Jianwen Chen 3

1 School of Physics and Optoelectronic Engineering, Foshan University, Foshan 528000, China;
[email protected] (R.L.); [email protected] (Y.D.); [email protected] (J.C.);
[email protected] (S.Y.); [email protected] (Y.C.); [email protected] (J.Y.)
2 Guangdong-Hong Kong-Macao Joint Laboratory for Intelligent Micro-Nano Optoelectronic Technology,
Foshan University, Foshan 528225, China
3 School of Electronic and Information Engineering, Foshan University, Foshan 528000, China;
[email protected]
* Correspondence: [email protected]

Abstract: In the past decades, the energy consumption of nonrenewable fossil fuels has been in-
creasing, which severely threatens human life. Thus, it is very urgent to develop renewable and
reliable energy storage devices with features of environmental harmlessness and low cost. High
power density, excellent cycle stability, and a fast charge/discharge process make supercapacitors
a promising energy device. However, the energy density of supercapacitors is still less than that
of ordinary batteries. As is known to all, the electrochemical performance of supercapacitors is
largely dependent on electrode materials. In this review, we firstly introduced six typical transition

 metal oxides (TMOs) for supercapacitor electrodes, including RuO2 , Co3 O4 , MnO2 , ZnO, XCo2 O4
Citation: Liang, R.; Du, Y.; Xiao, P.;
(X = Mn, Cu, Ni), and AMoO4 (A = Co, Mn, Ni, Zn). Secondly, the problems of these TMOs in
Cheng, J.; Yuan, S.; Chen, Y.; Yuan, J.; practical application are presented and the corresponding feasible solutions are clarified. Then,
Chen, J. Transition Metal Oxide we summarize the latest developments of the six TMOs for supercapacitor electrodes. Finally, we
Electrode Materials for discuss the developing trend of supercapacitors and give some recommendations for the future
Supercapacitors: A Review of Recent of supercapacitors.
Developments. Nanomaterials 2021, 11,
1248. https://doi.org/10.3390/ Keywords: energy storage devices; supercapacitors; transition metal oxides; developing trend
nano11051248

Academic Editor: Jung-Sang Cho

1. Introduction
Received: 12 April 2021
Accepted: 4 May 2021
Owing to the rapid development of the global economy, accelerating the consumption
Published: 10 May 2021
of fossil fuels like coal, fuel, and natural gas, the problems of global climate change and
environmental pollution are increasing to significant levels. Developing solar, wind, tidal,
Publisher’s Note: MDPI stays neutral
and other renewable clean energy is a way to mitigate current energy and environmental
with regard to jurisdictional claims in
pollution problems [1–6]. However, those renewable clean forms of energy are severely
published maps and institutional affil- restricted by environmental factors and energy supply is intermittent [7]. Therefore, it is
iations. urgent to develop effective and reliable devices for energy storage [8,9]. As a new type
of storage device, supercapacitors have gained great attention in recent years thanks to
their advantages of fast charge/discharge rate, high power density, and very long cy-
cle life [10–14]. Supercapacitors have great potential in the area of portable electronic
Copyright: © 2021 by the authors.
equipment, renewable energy systems, and hybrid power cars [15–17]. There are two
Licensee MDPI, Basel, Switzerland.
categories of supercapacitors: electrical double-layer capacitors (EDLCs) and pseudocapac-
This article is an open access article
itors [18,19]. For EDLCs, energy is stored with the charge accumulating on the interface
distributed under the terms and between the electrode and electrolyte. For pseudocapacitors, the energy is stored through
conditions of the Creative Commons a fast and reversible faradaic redox reaction [20–22]. At present, the low energy density
Attribution (CC BY) license (https:// is still the bottleneck of supercapacitors [23,24]. According to the energy density formula,
creativecommons.org/licenses/by/ E = 12 × C × V 2 , where E represents the energy density, C represents the specific capaci-
4.0/). tance, and V represents the potential window, we can know that the energy density of a

Nanomaterials 2021, 11, 1248. https://doi.org/10.3390/nano11051248 https://www.mdpi.com/journal/nanomaterials


Nanomaterials 2021, 11, 1248 2 of 28

supercapacitor depends on both capacitance and operating voltage, and it can be enhanced
by increasing the potential window and using an electrode material with high capaci-
tance [25,26]. It is noteworthy that the design and preparation of electrode materials are the
key steps to determine the electrochemical performance of supercapacitors. In other words,
the performance of supercapacitors is highly dependent on electrode materials [27–30].
Electrode materials can be divided into three categories: carbon materials, conduc-
tive polymers, and transition metal oxides (TMOs). Carbon materials are usually used
as electrode materials for EDLCs. They have the characteristics of high specific surface
area, adjustable pore size distribution, and excellent electrical conductivity [31,32]. Owing
to the storage mechanism of EDLCs, carbon materials can provide high power density,
but low energy density, which limits the overall performance [33,34]. Carbon materials
such as graphene, carbon nanotubes, and carbon nanofibers have been widely studied
for electrode materials. However, low specific capacitance of carbon material limits the
capacity of the EDLCs [35], and the applications of those carbon materials are limited
by their high cost [36]. The conductive and pseudocapacitive properties of conductive
polymers are good, but the stability is poor, and conductive polymers can easily fall off the
substrate [37,38]. For example, the charge and discharge speed of polyaniline is low and
the stability of the charge/discharge process is poor [39,40]. TMOs have higher specific
capacitance (100–2000 F g−1 ), higher energy density than carbon materials, and better
chemical stability than conductive polymers [41–43]. Thanks to its high theoretical capaci-
tance and rapid faraday redox reaction, RuO2 is thought to be an optimal pseudocapacitive
electrode material [44–46]. However, its high price and toxicity to the environment seri-
ously hinder its application in supercapacitors [47–49]. Co3 O4 , MnO2 , and ZnO have the
advantages of being natural abundant and high specific capacitance, which makes them
substitutes for RuO2 [50,51]. The disadvantage of poor electrical conductivity is exhibited
by many metal oxide electrodes [52]. Because of the co-existence of two metal ions and
synergistic effects of elements, ternary metal oxides, AB2 O4 (A or B = Ni, Co, Mo, Mn, and
so on), have more active reaction sites and high electrical conductivity than binary metal
oxides [53]. In addition, spinel cobaltates (XCo2 O4 , X = Ni, Cu, Zn, Mn, and so on) and
metal molybdate (AMoO4 , A = Ni, Mn, Co, and so on) have received tremendous research
interest because of their low cost, enhanced electrochemical activity, and being a natural
abundant resource [54,55].
In this review, six transition metal oxide materials including RuO2 , Co3 O4 , MnO2 ,
ZnO, XCo2 O4 (X = Mn, Cu, Ni), and AMoO4 (A = Co, Mn, Ni, Zn) are firstly introduced.
Secondly, existing problems of those TMOs in practical application and the corresponding
methods are presented. The methods include synthesizing composites, preparing material
in nano scale, introducing battery-type material or oxygen vacancies, and modification
of quantum dots. Particularly, we introduce the latest developments of six TMOs for
supercapacitor electrode according to the strategies. Finally, the future development of
supercapacitors is discussed and recommendations on supercapacitors are exhibited.

2. TMOs-Based Electrode Materials


2.1. RuO2
RuO2 has high theoretical capacitance (2000 F g−1 ) and it can carry out rapid faraday
redox reaction. It has good electrical conductivity, high chemical and thermal stability,
as well as a big voltage window. Thus, RuO2 is called the most ideal pseudocapacitive
electrode material [40,56]. However, ruthenium is too expensive to be used for large-scale
synthesis of electrode materials.

2.1.1. RuO2 -Based Composite Electrodes


Synthesizing composites can improve the utilization of RuO2 and reduce the cost
of RuO2 electrode [57]. At the same time, the synergistic effect of the materials is ben-
eficial to improve the electrochemical performance of the electrode. Various forms of
RuO2 -based electrodes have been prepared such as metal sulfide-RuO2 electrode, metal
Nanomaterials 2021, 11, x FOR PEER REVIEW 3 of 29

Synthesizing composites can improve the utilization of RuO2 and reduce the cost of
Nanomaterials 2021, 11, 1248 3 of 28
RuO2 electrode [57]. At the same time, the synergistic effect of the materials is beneficial
to improve the electrochemical performance of the electrode. Various forms of RuO2‐
based electrodes have been prepared such as metal sulfide‐RuO2 electrode, metal oxide‐
oxide-RuO 2 electrode,
RuO2 electrode, carboncarbon material-RuO
material‐RuO 2 electrode,
2 electrode,
and multicomponent
and multicomponent RuOelec‐
RuO2‐based 2 -based
electrode [39,57–61].
trode [39,57–61]. AsimAsim et al. et al.decorated
[62] [62] decorated
carboncarbon nanotubes
nanotubes (CNTs) (CNTs) growncloth
grown carbon carbon
cloth (CNTS-CC) with RuO 2 nanorods (RuO 2 -NRs) via chemical vapor
(CNTS‐CC) with RuO2 nanorods (RuO2‐NRs) via chemical vapor deposition (CVD) and deposition (CVD)
and the annealing process. The prepared electrode has the characteristics of
the annealing process. The prepared electrode has the characteristics of both supercapac‐both superca-
pacitors
itors andand lithium
lithium batteries.
batteries. TheThe results
results show
show thatthat
thethe designed
designed material
material hashas
highhigh specific
specific
capacitance (176 F g − 1 ) and superior cycling stability (97% retention after 10,000 cycles at
capacitance (176 F g ) and superior cycling stability (97% retention after 10,000 cycles at
−1

40 −2 (Figure 1).
40mA
mAcm cm−2))(Figure 1).

Figure 1.
Figure 1. Electrochemical
Electrochemicalperformance
performance of different electrodes
of different in liquid
electrodes state supercapacitors
in liquid using us-
state supercapacitors
1 M H2SO4 electrolytes: (A) comparison of CV at 20 mV s−1; (B) GCD curves at 10 mA cm 2; (C) cal‐
ing 1 M H2 SO4 electrolytes: (A) comparison of CV at 20 mV s−1 ; (B) GCD curves at 10 mA cm2 ;
culated areal capacitance at a range of current densities; (D) calculated gravimetric capacitance at
(C) calculated areal capacitance at a range of current densities; (D) calculated gravimetric capaci-
tance at different current densities; (E) Nyquist plots of different samples, and the inset showing
the corresponding magnified high-frequency regions; and (F) cyclic stability over 10,000 cycles at
10 mA cm−2 . Reproduced with permission from [62]. Copyright 2019 Elsevier. CNTS-CC, carbon
nanotubes grown carbon cloth. CV, cyclic voltammetry. GCD, galvanostatic charge-discharge. ESR,
equivalent series resistance.
Nanomaterials 2021, 11, 1248 4 of 28

In addition, they demonstrate a reversible capacity of ~3.85 mAh cm−2 at the current
density of 100 mA cm−2 as a Li-ion batteries electrode. The excellent electrochemical
performance lies in the synergistic effect of metal oxide NRs and the unique structure
of CNTS-CC. Enlarged surface area and exposed active sites allow accessibility of the
ions/electrolytes to the electrodes. Ternary single-walled carbon nanotubes/RuO2 /polyindole
(SWCNT/RuO2 /PIn) nanocomposite fabricated by Zhu’s group [63] presents the specific
capacitance of 1283 F g−1 at 1.0 A g−1 . At 500 W kg−1 and 5000 W kg−1 , the energy densities
of the SWCNT/RuO2 /PIn electrode-based symmetric supercapacitor are 42 W h kg−1 and
33 W h kg−1 , respectively. It also shows good cycling stability and capacitive performance
of 1203 F g−1 at 1.0 A g−1 . Via the hydrothermal and annealing process, CuCo2 O4 /CuO
nanoneedles were synthesized directly on the conductive Ni foam (NF), on which RuO2
nanoparticles were deposited [64]. The CuCo2 O4 /CuO@RuO2 can work as water oxidation
catalysis and has low overpotential (279 mV at 10 mA cm−2 ), low Tafel slope, and stable
long-term performance. Besides, it achieves a high areal capacity up to 862.5 mAh cm−2
and a capacity retention of about 90.1% after 8000 cycles. The hybrid supercapacitor
fabricated by CuCo2 O4 /CuO@RuO2 and activated carbon achieves an energy density of
0.84 mW h cm−2 at 8 mW cm−2 .

2.1.2. Hydrographic RuO2


In the reports above, many electrode materials have the addition of carbon materials.
Theoretically, adding carbon materials can improve the surface area and conductivity of
electrodes [65]. However, some reports pointed out that the porous surface of carbon
materials was blocked by RuO2 particles, which results in reduced surface area, limited
electrochemical properties, and decreased double layer capacitance [66,67]. Hydrated RuO2
is a kind of nanocrystalline material with RuO2 as the core and a small amount of water
hydrogen bond on the surface. The form of porous structure provides conduction paths
for protons to enter the inner part of RuO2 [68,69]. The annealing treatment of activated
carbon-RuOx •nH2 O composites (annealing for 2 h in 200 ◦ C air) obviously improves the
discontinuity of the electron path in particles. Further, the obstacle of electron hopping
between particles is reduced because a large amount of active carbon (AC) powder is
introduced. The specific capacitance of the RuOx •nH2 O is 1340 F g−1 (at 25 mV s−1 ) [70].
Similarly, Yang’s group [71] synthesized RuO2 @SWCNTs/graphene (S/G) composites by
the sol–gel method. The hybrid electrode material, RuO2 @S/G-60, has a specific capaci-
tance up to 988 F g−1 and excellent rate capability at 1 A g−1 . Hexagon WO3 (h-WO3 ) and
hydrous RuO2 were respectively prepared on three-dimensional conducting carbon cloth
(CC) via the hydrothermal method [72], which meant fast electronic pathway, high conduc-
tivity substrate, high surface area, and enhanced electrochemical performance. Figure 2a–d
shows the field emission scanning electron microscopy (FE-SEM) images, transmission
electron microscope (TEM) image, and high resolution transmission electron microscope
(HRTEM) image of hydrous RuO2 at different magnifications. Figure 2e–h shows the
FE-SEM images, TEM image, and HRTEM image of h-WO3 at different magnifications.
The asymmetric supercapacitor was fabricated in H2 SO4 aqueous electrolyte with
h-WO3 /CC as negative electrode and hydrated RuO2 /CC as positive electrode. At an oper-
ating voltage of 1.6 V, the asymmetric supercapacitor device is optimized with volumetric
capacitance of 3.52 F cm−3 at 5 mA cm−2 . Moreover, at a power density of 40 W cm−3 , the
asymmetric supercapacitor device shows brilliant energy density of 1.25 W h cm−3 and it
also shows promising electrochemical stability. By comparison, an all-pseudocapacitive
asymmetric device [73] has an energy density of only 37 µW h cm−2 at 40 mW cm−2 , but a
remarkable 96% retention after 20,000 charge/discharge cycles.
Nanomaterials 2021, 11, x FOR PEER REVIEW
Nanomaterials 2021, 11, 1248 5 of 28 5 of

Figure 2. (a,b) Inset of (a) FE‐SEM images of hydrous RuO2 on carbon cloth at different magnifications; (c) TEM image of
Figure 2. (a,b) Inset of (a) FE-SEM images of hydrous RuO2 on carbon cloth at different magnifica-
the hydrous RuO2 and its EDS mapping; (d) HRTEM image of hydrous RuO2 and its SAED pattern in the inset of (d); (e,f)
FE‐SEMtions;
images(c)of
TEMh‐WOimage of the hydrous RuO2 and
3 on carbon cloth at different
its EDS mapping;
magnifications; (d) HRTEM
(g) TEM image of image of hydrous
the h‐WO RuO
3 nanorod and2 its EDS
and its SAED pattern in the inset of (d); (e,f) FE-SEM images
mapping; (h) HRTEM image of h‐WO3 nanorod. The inset shows the SAED pattern, of h-WO 3 on carbon cloth at different
reproduced with permission from
magnifications;
[72] Copyright (g) TEM
2019 Elsevier. image
FE‐SEM, of the
field h-WOscanning
emission 3 nanorod and itsmicroscopy.
electron EDS mapping;
TEM,(h) HRTEM image
transmission of micro‐
electron
scope. EDS,
h-WO energy dispersive X‐ray spectroscopy. HRTEM, high resolution transmission electron microscope. SAED, se‐
3 nanorod. The inset shows the SAED pattern, reproduced with permission from [72] Copyright
lected area electron diffraction.
2019 Elsevier. FE-SEM, field emission scanning electron microscopy. TEM, transmission electron
microscope. EDS, energy dispersive X-ray spectroscopy. HRTEM, high resolution transmission
The asymmetric supercapacitor was fabricated in H2SO4 aqueous electrolyte with
electron microscope. SAED, selected area electron diffraction.
WO3/CC as negative electrode and hydrated RuO2/CC as positive electrode. At an oper
2.2. Co3 O4 ing voltage of 1.6 V, the asymmetric supercapacitor device is optimized with volumet
capacitance of 3.52 F cm−3 at 5 mA cm−2. Moreover, at a power density of 40 W cm−3, t
Co3 O4 is a kind of transition metal oxide belonging to the spinel family, and the faradic
asymmetric supercapacitor device shows brilliant energy density of 1.25 W h cm−3 and
redox reaction of Co3 O4 can be described as follows [74]:
also shows promising electrochemical stability. By comparison, an all‐pseudocapaciti
asymmetric device [73] has an energy density of only 37 μW h cm−2 at 40 mW cm−2, bu
Co O4 + OH− ↔ 3CoOOH + e− (1)
remarkable 96%3 retention after 20,000 charge/discharge cycles.
CoOOH + OH− ↔ CoO2 + H2 O + e− (2)
2.2. Co3O4
Co3 O4 has the advantages of high
Co3O4 is a kind theoretical
of transition specific
metal oxidecapacitance
belonging to(3560 F g−family,
the spinel
1 ), low
and the
price, environmental
radicfriendliness, and
redox reaction of good
Co3O4chemical durability,
can be described so it is [74]:
as follows a promising active
material [75–77]. However, the capacitance in practical application differs a lot from the
Co O OH ↔ 3CoOOH e
theoretical value. A reason is that electron transfer is hindered owing to low conductivity,
slow kinetics, large volume expansion-contraction,
CoOOH and OHsevere
↔ CoO particle
H Oaggregation.
e Thus,
the capacitance and cycling performance of Co
Co3O4 has the advantages of
O are
3 high
4 limited [78,79].
theoretical specific capacitance (3560 F g−1), lo
price, environmental friendliness, and good chemical durability, so it is a promising acti
2.2.1. Co3 O4 Nanomaterials
material [75–77]. However, the capacitance in practical application differs a lot from t
Nanomaterials have a value.
theoretical large surface
A reasonwith numerous
is that active sites.
electron transfer The ultra-small
is hindered owing to low size
conductivi
of nanomaterialsslow
shortens thelarge
kinetics, electron/ion diffusion path, providing
volume expansion‐contraction, favorable
and severe particletransfer
aggregation. Thu
pathways [78]. Because the dimension
the capacitance and morphology
and cycling performance of Co the3Omaterials play[78,79].
4 are limited an important
role in improving the electrochemical performance, increasingly more attention has been
2.2.1.materials
paid to the synthetic Co3O4 Nanomaterials
in micro and nano scale [80]. A variety of Co3 O4 nanomate-
rials have been synthesized, such
Nanomaterials ashave
nanowires
a large [81], nanofibers
surface [82], nanoparticles
with numerous [83,84],
active sites. The ultra‐small si
and nanosheets [85]. Yue and co-workers [86] used a simple and environmentally friendly
of nanomaterials shortens the electron/ion diffusion path, providing favorable trans
one-step hydrothermal
pathways and[78].
calcination
Because method to prepare
the dimension Co3 O4 /reduced
and morphology of the graphene oxide
materials play an importa
(rGO) composites. roleTiny
in improving the electrochemical
Co3 O4 nanoparticles performance,
are dispersed increasingly
on rGO moreaattention
flakes and three- has be
paid to
dimensional structure is the synthetic
formed. materials in
The prepared micro and
electrode has nano
morescale
active[80]. A than
sites variety
Co3ofOCo
4 3O4 nan
nanowires [87] tomaterials
achieve have
betterbeen synthesized, such
electrochemical as nanowires
performance. The[81], nanofibers
optimized [82], nanopartic
electrode
Co3 O4 /rGO-120-12 [83,84],
shows and nanosheets
high specific [85]. Yue andof
capacitance 1152 F g−[86]
co‐workers 1 at 1 A ga−1simple
used and
. Indira environmenta
Priyad-
harsini [88] firstly prepared Co3 O4 nanoparticles by the sol–gel method. The obtained
Co3 O4 nanoparticles, carbon, and polyvinylidene fluoride (PVDF) were then mixed with a
mass ratio of 8:1:1. The electrode was prepared by coating the synthesized slurry uniformly
on the Ni foam substrate. The specific capacitance of the electrode at 11 mA cm−2 is
Nanomaterials 2021, 11, 1248 6 of 28

761.25 F g−1 . The reason for the low specific capacitance is that the addition of PVDF
increases the resistance between the collector and the redox active material, which results
in a decrease in the number of active sites and the electron/charge transport rate [89].
However, directly growing Co3 O4 active materials on conductive substrates such as carbon
fiber, carbon cloth, stainless steel sheet, and metal foam can avoid the addition of binder
and conductive additive [51]. Ag doped Co3 O4 nanosheets synthesized on Ni foam [90]
possess a specific surface area (176 m2 g−1 ) larger than the original Co3 O4 (108 m2 g−1 ).
There is still a superior specific capacitance of 1323 F g−1 at the current density of 10 A g−1
(92.84% of the initial specific capacitance), indicating outstanding rate capability of the
sample. Furthermore, it exhibits 104.7% of the initial capacitance at the first 2000 cycles.
The electrode materials prepared by Yang’s group [91] and Wang et al. [92] both show good
electrochemical properties (883 F g−1 and 1606.6 F g−1 at the current density of 1 A g−1 ,
respectively). Electrode prepared by Wei [93] has unique nanoarray structures. The SEM
images
Nanomaterials 2021, of Co
11, x FOR 3 O4REVIEW
PEER /NF with different heating times are shown in Figure 3a–i. Figure 3j–l 7 of
shows the element mapping images of Co3 O4 nanoflakes.

Figure 3. SEM images: (a–c) Co3O4/nickel foam (NF)—6 h; (d–f) Co3O4/NF—8 h; (g–i) Co3O4/NF—10 h; (j–l) element map‐
Figure 3. SEM images: (a–c) Co3 O4 /nickel foam (NF)—6 h; (d–f) Co3 O4 /NF—8 h; (g–i) Co3 O4 /NF—
ping images of Co3O4 nanoflakes, reproduced with permission from [93] Copyright 2021 Elsevier. NF, Ni foam.
10 h; (j–l) element mapping images of Co3 O4 nanoflakes, reproduced with permission from [93]
Copyright 2021 Elsevier.CoNF, Ni foam.
3O4 nanowires were anchored on the surface of the Co3O4 nanosheet, effective

expanding the surface area, providing rich active states for the faradaic redox reaction a
Co3 O4 nanowires were anchored on the surface of the Co O4 nanosheet,
promoting the diffusion rate of electrolyte ions. 3The
effectively
sample prepared at hydrotherm
expanding the surface
heating for 8 h (Co3O4/NF‐8 h) shows a high specific capacitance of 2053.1and
area, providing rich active states for the faradaic redox reaction F g−1 at 1 A g
promoting the diffusion rate of electrolyte ions. The sample prepared at hydrothermal
The working voltage of the hybrid supercapacitor device assembled by the hetero‐stru
heating for 8 h (Co 3 OCo
tured 4 /NF-8 h) shows a high specific capacitance of 2053.1 F g−1 at
3O4 array and graphene can reach 1.6 V. The maximum energy density of 22.2
− 1
1 A g . The workingh kg−1voltage of theand
is delivered hybrid supercapacitor
the excellent cycle isdevice
provedassembled by the
by the 93.3% hetero- retenti
capacitance
after 10,000 cycles.

2.2.2. A Strategy for Preparation of Co3O4 Nanomaterials


In recent years, metal organic frameworks (MOFs)‐based materials have attracted
tention in various fields of gas adsorption, energy device, pollutant degradation, electr
Nanomaterials 2021, 11, 1248 7 of 28

structured Co3 O4 array and graphene can reach 1.6 V. The maximum energy density of
22.2 W h kg−1 is delivered and the excellent cycle is proved by the 93.3% capacitance
retention after 10,000 cycles.

2.2.2. A Strategy for Preparation of Co3 O4 Nanomaterials


In recent years, metal organic frameworks (MOFs)-based materials have attracted
attention in various fields of gas adsorption, energy device, pollutant degradation, elec-
trocatalysis, and drug release [1]. Besides, with adjustable porous structure, controllable
pore size distribution, and high surface area, MOFs are thought to be an ideal template
for the preparation of Co3 O4 nanomaterials [94,95]. Commonly, Zeolitic Imidazolate
Frameworks-67 (ZIF-67) is used as precursor to synthesize Co3 O4 nanomaterials. With
ZIF-67 crystals as precursor, porous Co3 O4 nanoparticles [96] were transformed by simple
calcination treatment. The results show that ZIF-67-derived Co3 O4 nanoparticles exhibit
high specific capacitance (190 F g−1 at 5 A g−1 ) and capacitance retention (71.42% after 5000
cycles). Bao and co-workers [97] used ZIF-67 as a template and successfully constructed
a series of Co3 O4 embedded α-Co/Ni(OH)2 hollow nanocages. The prepared composite
(α-Co/Ni(OH)2 @Co3 O4 -70) has abundant electrolyte diffusion channels and reactive active
sites. At the same time, it possesses excellent conductivity and stability. Therefore, the high
capacitance of 1000 F g−1 is obtained at 1 A g−1 and the capacitance retention is 74% at
10 A g−1 . Meanwhile, the hybrid nanocages still maintain 72.34% of original capacitance
after 8000 charge/discharge cycles. In addition, α-Co/Ni(OH)2 @Co3 O4 -70//active carbon
(AC) device has an energy density of 23.88 W h kg−1 at a power density of 0.075 kW kg−1 .
Wei et al. [98] developed a novel method (bottom-up approach) to synthesize ZIF-67
nanosheets. The ZIF-67 is in situ converted into Co3 O4 ultrathin nanoparticles by thermal
treatment. The energy density at 790.7 W kg−1 of asymmetric supercapacitors prepared
with Co3 O4 //AC is 46.5 W h kg−1 . Moreover, the overpotential of 2D Co3 O4 ultrathin
nanoparticles at the onset potential is 230 mV and Tafel slope is 74.0 mV dec−1 . This shows
2D Co3 O4 ultrathin nanoparticles’ great performance in oxygen evolution reaction. Besides,
Co-based MOFs (Co-MOFs) have become fascinating templates for thermal transforma-
tion to generate porous Co3 O4 structures [99]. Li et al. [100] prepared 3D porous carbon
(3DPC)/Co3 O4 composites by pyrolysis of 3D graphene/Co-MOF precursor. The elec-
trochemical performance of the composites is not good (specific capacitance of 423 F g−1
at 1 A g−1 and capacitance attenuation of about 17% after 2000 cycles). This is because
MOFs-based electrodes are usually composed of insulation binder, conductivity additives,
and MOFs, which hinders the electrolyte penetration and reduces the electron transport
between electroactive sites of active material and electrolytes [101].

2.2.3. Electrode Materials on Conductive Substrates


Synthesizing electrode materials directly on conductive substrates can avoid the
addition of insulation binder so as to reduce interparticle resistance [51]. In order to
further obtain high performance electrode materials, Han et al. [102] synthesized petal-
like Co3 O4 @CoNi2 S4 nano-wall arrays on carbon cloth. The synergistic effect of Co-
MOF-derived Co3 O4 skeleton is utilized to improve the electrochemical activity of cobalt
nickel sulfide. The specific capacitance of the Co3 O4 @CoNi2 S4 electrode is 244.4 mAh g−1
at 1 A g−1 and a specific capacitance attenuation of 18.7% at 16 A g−1 . At a power
density of 884.4 W kg−1 , the energy density of the Co3 O4 @CoNi2 S4 //AC device reaches
55.6 W h kg−1 . After 10,000 cycles, the capacitance retention of Co3 O4 @CoNi2 S4 reaches
86%. Liao and co-workers [77] prepared Co3 O4 nanoparticles on graphene nanosheets
supported by carbon fabric. The electrode shows an unbelievable specific capacitance of
3480 F g−1 , which is close to the theoretical value (3560 F g−1 ). Besides, they fabricated
a flexible symmetric supercapacitor device with two pieces of prepared electrode. The
flexible supercapacitor has no sacrifices of electrochemical performance when it is bent
under bending angles from 0◦ to 150◦ . Furthermore, the supercapacitor delivers capacitance
Nanomaterials 2021, 11, 1248 8 of 28

of 580 F g−1 and 13.8% capacitance decline after 20,000 cycles.


Nanomaterials 2021, 11, x FOR PEER REVIEW
The maximum energy density 9 of
of the device is 80 W h kg−1 (Figure 4).

Figure 4. (a) CVs curve of the device at different bending angles; (b) GCD curves of the supercapacitor device at different
Figure 4. (a) CVs curve of the device at different bending angles; (b) GCD curves of the supercapacitor
current densities; (c) specific capacitance vs. current densities for the supercapacitor device; (d) cycling stability of the
device device
at 20 Aat
g−1different current
. The inset showsdensities;
the GCD (c) specific
curves capacitance
of the vs. current
last 10 cycles; densities
(e) Ragone forthe
plots of thesupercapacitor
supercapacitordevice in
device;
comparison (d)other
with cycling stability
reported of the device
supercapacitors; (f) Nyquist g−1of
at 20 Aplot . the
Thesupercapacitor
inset shows the GCD
device, thecurves
inset is of
thethe
equivalent
circuit,last
reproduced
10 cycles;with
(e)permission from of
Ragone plots [77].
theCopyright 2015 ACS.
supercapacitor device in comparison with other reported
supercapacitors; (f) Nyquist plot of the supercapacitor device, the inset is the equivalent circuit,
reproduced with permission from [77]. Copyright 2015 ACS.

2.3. MnO2
Owing to its rich natural content, no environmental pollution, and high theoretical
specific capacitance (1380 F g−1 ), MnO2 has been widely studied as the most competitive
transition metal oxide [103–105]. However, its application in supercapacitors is seriously
affected because of its poor conductivity and slow ion transport rate [106–108].

2.3.1. Carbon Materials@MnO2 Composite Electrode


Carbonaceous materials have excellent electrical conductivity and stability with large sur-
face area [31,32]. Carbon nanotubes [109,110], graphene [111,112], carbon nanowires [113,114],
carbon nanofibers [115], and other carbon materials can be used as scaffolds for depositing
MnO2 nanostructures. Large surface area with a great quantity of active sites is provided
specific capacitance (1380 F g−1), MnO2 has been widely studied as the most competitive
transition metal oxide [103–105]. However, its application in supercapacitors is seriously
affected because of its poor conductivity and slow ion transport rate [106–108].

2.3.1. Carbon Materials@MnO2 Composite Electrode


Nanomaterials 2021, 11, 1248 9 of 28
Carbonaceous materials have excellent electrical conductivity and stability with large
surface area [31,32]. Carbon nanotubes [109,110], graphene [111,112], carbon nanowires
[113,114], carbon nanofibers [115], and other carbon materials can be used as scaffolds for
and the contact path between electrode materials and electrolytes is shortened, which
depositing MnO2 nanostructures. Large surface area with a great quantity of active sites
enhances electrochemical properties [116]. The hollow N-doped carbon (HNC)@MnO2 3Dis short‐
is provided and the contact path between electrode materials and electrolytes
core–shell composites prepared
ened, which enhances by Caielectrochemical
et al. [117] exhibit a good [116].
properties electrochemical
The hollowcapacity
N‐doped of carbon
247.9 F g−1 at 0.5 A g −1 , as well as a retention capacity of 82.9% at 5 A g−1 after 2000 cycles.
(HNC)@MnO2 3D core–shell composites prepared by Cai et al. [117] exhibit a good elec‐
Via a simple one-step
trochemicalwatercapacity 40 ◦FC,g−1Long
bathofat247.9 at 0.5et
Ag al.
−1, [118]
as welldeveloped
as a retentioninterconnected
capacity of 82.9% at 5
δ-MnO2 nanosheets flexible
A g−1 after 2000electrode
cycles. Viaon activated
a simple carbon
one‐step cloth.
water bath The
at 40electrode
°C, Long etdisplays
al. [118] devel‐
brilliant chargeoped
storage performanceδ‐MnO
interconnected (a neglected degradation
2 nanosheets during on
flexible electrode theactivated
2000 times of cloth.
carbon
folding). WhenThe theelectrode
power displays
density brilliant charge storagesupercapacitor
of the asymmetric performance (a neglected W kg−1 , dur‐
is 1198.4degradation
ing the
the energy density can2000 times
reach of W
49.8 h kg−When
folding). 1 . After
the5000
power density
cycles, of capacitance
the the asymmetric supercapacitor
retention
is 1198.4 W kg −1, the energy density can reach 49.8 W h kg−1. After 5000 cycles, the capaci‐
of the asymmetric supercapacitor can reach 90.6%. Lei and co-workers [119] synthesized
tance retention of CNTs
MnO2 nanosheets@graphenated the asymmetric
network on supercapacitor cansteel
316 L stainless reachby90.6%. Lei and
the CVD methodco‐workers
[119] synthesized MnO2 nanosheets@graphenated CNTs network on 316 L stainless steel
followed by annealing treatment (Figure 5).
by the CVD method followed by annealing treatment (Figure 5).

Figure 5. Schematic fabrication of core–shell MnO2@CNTs composite electrodes on stainless steel. Reproduced with per‐
Figure 5. Schematic fabrication of core–shell MnO2 @CNTs composite electrodes on stainless steel.
mission from [119]. Copyright 2020 Elsevier.
Reproduced with permission from [119]. Copyright 2020 Elsevier.
Providing an effective electronic pathway, graphenated CNTs are interconnected to
Providing form
an effective electronicwith
porous structures, pathway,
MnO2 graphenated CNTs are distributed
nanoparticles uniformly interconnected
on thetosurface.
form porous structures,
Furthermore, with
theMnO
unique 2 nanoparticles
structure of MnO uniformly distributed on the
2 nanosheets@graphenated CNTssurface.
nanocompo‐
Furthermore, thesitesunique
shortensstructure of MnO
the ion transport 2 nanosheets@graphenated
distance, promotes charge transfer, CNTs nanocom-reversi‐
and accelerates
posites shortensblethe
redoxionreactions,
transport distance,
thereby promotes
improving charge transfer,
the capacitance and A
performance. accelerates
high energy den‐
reversible redox reactions,
sity of 51.2 W thereby improving
h kg−1 is obtained the capacitance
at 24.42 W h cm−2 and performance.
the maximum power A high en- is 0.4
density
ergy density ofkW51.2 kgW h kg−cm
−1 (200 W 1 is−2). 3D‐graphene/MnO
obtained at 24.42 W 2 foam −2 and the
h cmcomposite [120] was prepared
maximum by a com‐
power
density is 0.4 kW kg−1of(200
bination the CVD
W cm and−2hydrothermal method. The
). 3D-graphene/MnO 2
study
foam shows that
composite 3D‐graphene/MnO
[120] was 2

prepared by a composite
combination electrodes
of theinCVD the absence of carbon black
and hydrothermal have a high
method. Thespecific capacitance of
study shows
333.4 F g−1 at 0.2 A g−1 and excellent cycling stability.
that 3D-graphene/MnO 2 composite electrodes in the absence of carbon black have a high
specific capacitance of 333.4 F g−1 at 0.2 A g−1 and excellent cycling stability.
However, the high cost and complex preparation process of commercial carbon ma-
terials are not conducive to large-scale preparation. Therefore, it is very important to
develop low price and renewable materials to meet the increasing demand. Biomass re-
source is a renewable resource with high utilization value. Biomass resource utilization
has become a hot area and pillar of economic and social development in the future [121].
Biomass-derived carbon has the advantages of high natural abundance, environmental
friendliness, diverse structures, long cycle life, and low costs [36,122,123]. In addition,
the multistage pore structure and the inherent stability of carbon materials give biomass
carbon unique advantages and prospects in the application of electrochemical materials.
Hence, biomass-derived carbon has great potential in supercapacitors. Yang’s group [35]
used banana peel as a carbon source to synthesize MnO2 /biomass-based porous carbon
(BPC) composites by the hydrothermal method. The MnO2 /BPC composites electrode
has a great specific capacitance of 139.6 F g−1 at the current density of 300 mA g−1 and
70 F g−1 at 10 A g−1 . In addition, it loses 7.7% of the specific capacitance after 1000 cy-
Nanomaterials 2021, 11, 1248 10 of 28

cles. In Shen’s research [124], soybean pod was used as the precursor of carbon matrix to
prepare MnO2 /soybean pod carbon (SPC) composites by a one-step in situ hydrothermal
method. The prepared material retains the original tubular structure of the pods, with a
large number of δ-MnO2 nanorods covered on the surface. According to the research, the
MnO2 /SPC electrode has a better specific capacitance than the MnO2 electrode (530 F g− 1
and 362 F g− 1 , respectively). Besides, the symmetric MnO2 /SPC-based supercapacitor
displays high capacitance retention of 91% after 6000 cycles and maintains the energy
density of 35.1 W h kg− 1 at a high power density of 9000 W kg− 1 . The hollow structure
of MnO2 /carbon spheres (CSs) [125] was prepared by a simple one-step hydrothermal
method. First, 60 mg hollow carbon was dispersed in 30 mL 20 mM KMnO4 aqueous
solution by sonication. Then, this aqueous solution was heated at 160 ◦ C for 3 h in a
Teflon-lined stainless steel autoclave. After the reaction and cooling down, the product was
vacuum filtered, washed, thoroughly dried at 60 ◦ C, and then labeled as MnO2 /hollow CS-
20. An asymmetrical supercapacitor is assembled with the MnO2 /hollow CS-30 material
as the positive electrode and the hollow CS as the negative electrode. At the 2.0 V voltage
window, the maximum energy density (41.4 W h kg−1 ) is obtained at a power density of
500 W kg−1 . Moreover, the asymmetric supercapacitor shows a good cycling stability of
93.9% capacitance retention after 5000 cycles.

2.3.2. Introduction of Battery-Type Metal Oxides


According to Nie’s study [126], introducing battery-type metal oxides into MnO2 -
based electrodes has been thought to be an effective way to increase the capacity and energy
density of supercapacitors. Rapid redox reactions and synergistic effects of MnO2 and
battery metal oxides improve the overall performance of the electrode. The electrode [127]
obtained by depositing MnO2 on NiO nanosheets for 30 min has an ultra-high specific
capacitance of 1227.2 F g−1 (at 10 A g−1 ) and a capacitance retention rate of 76.7% after
10,000 cycles. Via a low temperature facile chemical bath deposition, Liu et al. [128] fabri-
cated leaf-like Co3 O4 @MnO2 nanosheets on the carbon cloth fibers (Co3 O4 @MnO2 CC) with
a hierarchical core–shell structure. The leaf-like Co3 O4 @MnO2 nanosheets exhibit brilliant
electrochemical performance, including super-high specific capacitance (616.7 F g−1 at
2 A g−1 ) and superior cyclic stability (83.1% retention after 10,000 cycles at 20 A g−1 ) as
well as high output potential of 1.2 V. The asymmetric supercapacitor (Co3 O4 @MnO2 CC-90
as the cathode and AC as the anode) has energy density of 54.71 W h kg− 1 at the power
density of 1.06 kW kg− 1 and 86.3% retention of specific capacitance after 10,000 cycles at
10 A g− 1 .

2.4. ZnO
Electrode materials largely determine the performance of supercapacitors [129]. There-
fore, people have been looking for electrode materials with good electrochemical perfor-
mance. TMOs have gotten extensive attention because of their high redox activity, good
theoretical capacitance, and low costs [130]. ZnO is a well-known active material that
has the characteristics of environmental protection, natural abundance, and ideal capaci-
tance [50,131,132]. Via the chemical coprecipitation method, Dhivya Angelin et al. [133]
modified the ZnO nanostructure with doping Zr. The experimental results indicate that
9 wt.% Zr-doped ZnO nanostructure has the best electrochemical performance of excellent
specific capacitance of 518 F g−1 (at 1 A g−1 ) and capacitance retention of 94% (5000 suc-
cessive galvanostatic charge-discharge cycles). ZnO nanomembranes (NMs) [134] were
prepared with 100 atomic layer deposition (ALD) cycles. Figure 6a shows the fabrication
procedure of ZnO NMs electrode and the corresponding supercapacitor. Figure 6b–d
display the SEM images of the ZnO NMs with 50, 100, and 200 ALD cycles.
In different electrolytes, the ZnO NMs have different specific capacitance, 846 F g−1
(6 M KOH at 1 A g−1 ), 465 F g−1 (1 M KCl at 1 A g−1 ), and 65 F g−1 (6 M Na2 SO4
at 1 A g−1 ), respectively. However, those materials mentioned all have the problem of
capacity attenuation during long-term cycling [135,136].
[133] modified the ZnO nanostructure with doping Zr. The experimental results indicat
that 9 wt.% Zr‐doped ZnO nanostructure has the best electrochemical performance of ex
cellent specific capacitance of 518 F g−1 (at 1 A g−1) and capacitance retention of 94% (500
successive galvanostatic charge‐discharge cycles). ZnO nanomembranes (NMs) [134
were prepared with 100 atomic layer deposition (ALD) cycles. Figure 6a shows the fabr
Nanomaterials 2021, 11, 1248 11 of 28
cation procedure of ZnO NMs electrode and the corresponding supercapacitor. Figure 6b
d display the SEM images of the ZnO NMs with 50, 100, and 200 ALD cycles.

Figure 6. Design and morphologies of ZnO nanomembranes (NMs) with various thicknesses: (a) schematic of the fabrica‐
Figure 6. Design and morphologies of ZnO nanomembranes (NMs) with various thicknesses:
tion procedure of ZnO NMs electrode and corresponding supercapacitor; (b–d) SEM images of ZnO NMs with (b) 50, (c)
(a) schematic
100, and (d) of layer
200 atomic the fabrication
deposition procedure of ZnO
(ALD) cycles. NMs
The red electrode
circles in (b) and corresponding
represent supercapacitor;
the existence of the holes in ZnO
(b–d) SEM with
NMs. Reproduced images of ZnO NMs
permission with (b)
from [134]. 50, (c) 100,
Copyright 2020and (d) 200 atomic layer deposition (ALD) cycles.
Elsevier.
The red circles in (b) represent the existence of the holes in ZnO NMs. Reproduced with permission
In different
from [134]. Copyright 2020 Elsevier.electrolytes, the ZnO NMs have different specific capacitance, 846 F g
(6 M KOH at 1 A g−1), 465 F g−1 (1 M KCl at 1 A g−1), and 65 F g−1 (6 M Na2SO4 at 1 A g−1
2.4.1. ZnO-Basedrespectively.
Composite However,
Electrodethose materials mentioned all have the problem of capacity atten
uation during
Numerous ZnO-based electrode long‐termmaterials
cycling [135,136].
are fabricated, such as carbon material-
ZnO electrode [137–139], medal oxides-ZnO electrode [140–142], and polymer-ZnO elec-
2.4.1.
trode [143,144], for theZnO‐Based
purpose Composite
of pursuing Electrode
good electrochemical performance. With
Numerous
asphalt as carbon source and ZnO ZnO‐based electrode
as template, materials
graphene are fabricated,
nanocapsules (GNCs)such as carbon
[145] were materia
ZnO electrode [137–139], medal oxides‐ZnO electrode [140–142],
synthesized by in situ KOH activation technology. High-speed channels for electron con- and polymer‐ZnO elec
trode [143,144], for the purpose of pursuing good electrochemical
duction, micropores for ion adsorption, and short pores for ion transport are provided byperformance. With as
phalt as carbon source and ZnO as template, graphene nanocapsules (GNCs) [145] wer
the 3D porous network. As supercapacitor electrodes, the GNCs exhibit great capacitance
of 194 F g−1 at 20 A g−1 (277 F g−1 at 0.05 A g−1 ) and capacitance loss of 2.6% after 15,000
cycles. Chebrolu et al. [146] fabricated a series of metal oxide composite nanostructures
using the chemical bath deposition method. Those metal oxide composite nanostructures
include ZnO nanowires, NiO nanosheets, ZnO/CuO nanowire arrays, ZnO/FeO nanocrys-
tals, ZnO/NiO nanosheets, and ZnO/PbO nanotubes, among which ZnO/NiO nanosheets
have the best electrochemical performance (at 8 mA cm−2 with a specific capacitance of
1248 F g−1 and long-term cycling stability). Because of ZnO/NiO nanosheets’ unique
surface morphology, increasing the electron transfer rate and electrical conductivity, the
energy storage properties are improved. Di’s group [147] reported that combing ZnO
with a small amount of Al2 O3 could prevent the ZnO nano-framework from collapsing.
Meanwhile, the specific surface area of the material could be increased to enlarge the
contact area between the composite and the electrolyte solution. The Al2 O3 -ZnO nanorod
displays a high specific capacity (463.7 F g−1 ) and favorable cyclic stability (96.9%), which
is higher than Al2 O3 and ZnO. In addition, the ion transferred number and the ion dif-
fusion coefficient of the Al2 O3 -ZnO nanorod are 6.3 and 7.6 × 10−13 cm2 s−1 . Studies
have shown that the electrochemical properties can be further improved by synthesizing
the ZnO-based multicomponent electrodes [65,148–150]. Obodo et al. [151] synthesized
Nanomaterials 2021, 11, 1248 12 of 28

Co3 O4 -CuO-ZnO@GO nanocomposite films by the hydrothermal method and then exam-
ined the effect of carbon ion irradiation on the properties of the prepared nanocomposite.
The results of X-ray diffraction (XRD) suggest that low doses of carbon ion irradiation
enhance the crystallinity of the materials, and high doses irradiation lead to deficien-
cies and disorder to the Co3 O4 -CuO-ZnO@GO, resulting in distortion and defects in the
structure of the material. According to the study of electrochemical performance, the
highest specific capacitance (1950 F g−1 at 10 mV s−1 ) is obtained at a radiation dose
of 5.0 × 1015 ions cm−2 , while the specific capacitance of 208 F g−1 and 1356 F g−1 are
obtained at 1.0 × 1015 ions cm−2 and 7.0 × 1015 ions cm−2 , respectively. Self-assembled
ZnO-CoO@nitrogen-doped carbon (NC) electrode [152] was prepared by the hydrothermal
method combined with annealing. Owing to high conductivity, rich oxygen vacancies, and
mesoporous structure, the electrode based on ZnO-CoO@NC shows a good cycle stability
of 92% specific capacitance retention at 2 A g−1 (40,000 cycles) without morphology change.
Besides, the graphene//ZnO-CoO@NC device also has 94% capacitance retention after
10,000 cycles at 2 A g−1 . At a potential window of 1.6 V, the device possesses an energy
density of 16.5 W h kg−1 at a power density of 396.51 W kg−1 and remains at 5.5 W h kg−1
at 5634.5 W kg−1 .

2.4.2. Problems of ZnO-Based Electrode


A study [153] pointed out that the surface morphology of the powder coating became
smoother and the exposed surface area lessened after a series of electrochemical reactions,
because of which specific capacitance decreased. To solve this problem, ZnO rods are pre-
pared by a hydrothermal method and then coated with a MoO4 2− modified carbon layer
(Mo-C) [154]. The carbon coating is composed of many tiny carbon spheres of 10–50 nm in
size. Owing to the mesoporous structure, ZnO@Mo-C possesses a larger specific surface
area (96.36 m2 g−1 ) than pure zinc oxide (0.835 m2 g−1 ). In addition, compared with
the electrode material prepared by Mohamed’s group [155], ZnO@Mo-C displays better
capacitance and rate capability (900 F g−1 at 1 A g−1 and 650 F g−1 at 10 A g−1 ). He and
co-workers [156] constructed ZnO flower nanostructures on nickel foam coated with hier-
archical α-Co(OH)2 . The unique structure increases the charge and ion transfer rates and
improves the contribution of pseudoactive substances in faradaic reactions. An asymmetric
supercapacitor is assembled in 3 M NaOH with NF@ZnO@Co(OH)2 as positive electrode
and NF@cellulose paper as the negative electrode. In cell voltage of 1.5 V, the asymmetric
supercapacitor exhibits maximum energy density of 62.57 W h kg−1 at a power density of
71 1.28 W kg−1 and, at 16,985.55 W kg−1 (maximum power density), it delivers an energy
density of 16.04 W h kg−1 . Ding et al. [157] anchored binder-free tin oxide nanosheets on
nickel foam by a one-step hydrothermal method, and then CoS was deposited on the ZnO
surface by electrodeposition. At a current density of 3 mA cm−2 , ZnO@CoS shows a high
specific capacity of 898.9 C g−1 , while specific capacity of pristine ZnO and ZnO precursor
are 614.4 C g−1 and 530.6 C g−1 , respectively. The assembled button-type asymmetric
supercapacitor displays an energy density of 45.2 W h kg−1 at 1039.1 W kg−1 with an areal
capacity of 2438 mC cm−2 . In addition, the capacity retention of 107% after 10,000 cycles
shows its remarkable cycling stability. Table 1 shows the electrochemical performance of
representative binary TMOs electrode materials.
Nanomaterials 2021, 11, 1248 13 of 28

Table 1. The electrochemical performance of representative binary transition metal oxides (TMOs) electrode materials.
SWCNT, single-walled carbon nanotube; CVD, chemical vapor deposition.

Material Preparation Method Electrolyte Specific Cycling Reference


Capacitance Stability
RuO2 hydrothermal method 1 M H2 SO4 400 F g− 1 84.7% (6000 cycles) [56]
MoS2 -RuO2 hydrothermal method 1 M KOH 972 F g− 1 / [59]
oxidation polymerization of
SWCNT/RuO2 /PIn
indole
1 M H2 SO4 1307 F g− 1 93% (3000 cycles) [63]
reduced graphene
oxide/Co3 O4
hydrothermal method 2 M KOH 472 F g− 1 95.6% (1000 cycles) [83]
Co3 O4 nanowires hydrothermal method 3 M KOH 310.4 C g− 1 80.3% (6000 cycles) [87]
CeO2 /Co3 O4 /rGO
nanoparticles hydrothermal method 6 M KOH 1606.6 F g− 1 / [92]
17% decay 2000
porous carbon/Co3 O4 pyrolysis of precursor 3 M KOH 423 F g− 1 cycles
[100]
MnO2 nanosheets/hollow
carbon nanofibers hydrothermal method 1 M Na2 SO4 293.6 F g− 1 / [104]
tannic acid-assisted etching
N-doped carbon@MnO2
process
1 M Na2 SO4 247.9 F g− 1 82.9% (2000 cycles) [117]
graphene/MnO2 foam CVD 1 M Na2 SO4 333.4 F g− 1 92.2% (2000 cycles) [123]
nitrogen-doped porous hydrothermal
hollow carbon pre-carbonization and 1 M Na2 SO4 255 F g− 1 89% (5000 cycles) [125]
spheres/MnO2 pyrolysis carbonization
Zr-doped ZnO physio-chemical 1 M KOH 518 F g− 1 94% (5000 cycles) [133]
ZnO nanomembranes atomic layer deposition 6 M KOH 846 F g− 1 89% (5000 cycles) [134]
ZnO@rGO direct microwave irradiation 0.1 M KOH 102.4 F g− 1 82.5% (3000 cycles) [137]
Co3 O4 -CuO-ZnO/GO hydrothermal method 0.5 M Na2 SO4 2045 F g− 1 83.02% (5000 cycles) [151]

2.5. XCo2 O4 (X = Mn, Cu, Ni)


Ternary transition metal oxide XCo2 O4 has a spinel structure. Generally, the two metal
ions exhibit high capacity and conductivity, so ternary transition metal oxide has more
abundant redox reactions and higher electrochemical activity than single metal oxides [158].
Thus, it has achieved great attention so far. When XCo2 O4 is used as electrode material, the
corresponding equations can be described as follows [52,159]:

MCo2 O4 + H2 O + OH− ↔ MOOH + 2CoOOH + e− (3)

2CoOOH + OH− ↔ 2CoO2 + H2 O + e− (4)


Shanmugavadivel and co-workers [160] prepared a MnCo2 O4 electrode by a simple
solution combustion method. At the scanning rate of 10 mV s−1 , the MnCo2 O4 electrode
shows the maximum specific capacitance of 270 F g−1 , and the capacitance attenuation after
1000 cycles is 7.6%. MnCo2 O4 nanosheets [161] prepared by galvanostatic electrodeposition
have the maximum specific capacitance of 585 F g−1 at 0.2 mA cm−2 . Furthermore, after
1500 cycles, the MnCo2 O4 electrode possesses a capacity retention rate of 51.8%. A battery-
type flexible electrode [162] was fabricated through coating mesoporous NiCo2 O4 on
an ultrafine nickel wire by electrodeposition, dealloying, and oxidation (Figure 7). The
electrode is flexible and displays a high specific capacity of 315.4 C g−1 at 1 A g−1 and 8.4%
area specific capacity loss after 50,000 cycles.
Via electrodeposition followed by air annealing, Pawar’s group [54] synthesized
ultrathin nanoporous CuCo2 O4 nanosheets on a nickel foam. After 5000 cycles, CuCo2 O4
nanosheets show the specific capacitance of 1473 F g−1 at 1 A g−1 with the capacity
retention rate of 93%.
Nanomaterials 2021, 11, 1248
Nanomaterials 2021, 11, x FOR PEER REVIEW 14 of 28 15 of

Figure 7. Schematic process showing the synthesis of porous polyvinylidene fluoride (PVDF)/NiCo2O4 coated on ultrafine
Figure 7. Schematic process showing the synthesis of porous polyvinylidene fluoride
nickel wire by electrodeposition and dealloying. Reproduced with permission from [162]. Copyright 2018 Elsevier.
(PVDF)/NiCo2 O4 coated on ultrafine nickel wire by electrodeposition and dealloying. Reproduced
with permission from [162]. Copyright 2018 Elsevier.
Via electrodeposition followed by air annealing, Pawar’s group [54] synthesized u
trathin nanoporous CuCo2O4 nanosheets on a nickel foam. After 5000 cycles, CuCo2O
2.5.1. Core–Shell Structure for MCo2 O4 -Based Electrode
nanosheets show the specific capacitance of 1473 F g−1 at 1 A g−1 with the capacity retentio
The electrochemical performance of the MCo2 O4 -based electrodes above is not ideal
rate of 93%.
and does not meet the requirements of high-performance supercapacitors. Because of
the lack of active2.5.1.
sites,Core–Shell Structure for MCoand
serious agglomeration, 2O4‐Based Electrode
destruction of electrode materials
during the long cycle,The the electrochemical
electrochemicalperformance
performance of the MCo2O4‐basediselectrodes
of the electrodes weakened [55].is not ide
above
The core–shell structure has a large number of electroactive sites and fast ion
and does not meet the requirements of high‐performance supercapacitors. Because of th diffusion.
Moreover, ions and electrons
lack of activeare accessible
sites, to the interior of
serious agglomeration, and the electroactive
destruction materials.
of electrode So,
materials durin
the long cycle, the electrochemical performance of the
the composites in the core–shell structure can possess a good cycle life and rate retention. electrodes is weakened [55]. Th
core–shell structure has a large number of electroactive
At the same time, compared with a single component, the heterostructure composites sites and fast ion diffusion. Mor
over,deliver
with two constituents ions andbetter
electrons are accessibleperformances
electrochemical to the interior owing
of the electroactive materials. So, th
to the synergistic
composites in the core–shell structure can possess a
effect [127,148]. Therefore, researchers speculate that the proper design of the core–shellgood cycle life and rate retention. A
the same time, compared with a single component,
structure can improve the cycle stability and prevent the collapse during the cycle [163]. the heterostructure composites wi
two constituents deliver better electrochemical performances owing to the synergistic e
Wang’s group [163] synthesized flower-like MnCo2 O4 micro-nanostructures via a
fect [127,148]. Therefore, researchers speculate that the proper design of the core–she
calcination process-assisted hydrothermal method. The prepared material possesses capaci-
structure can improve the cycle stability and prevent the collapse during the cycle [163]
tance of 1933.33 F g−1 at 1 A g−1 . The MnCo2 O4 @MnCo2 S4 //CNTs device delivers brilliant
Wang’s group [163] synthesized flower‐like MnCo2O4 micro‐nanostructures via a ca
cycle stability of 96% capacitance retentionhydrothermal
cination process‐assisted
after 5000 cycles. At the same time, it shows high
method. The prepared material possesses capac
energy density oftance
50.75ofWh kg −1 at 1260 W kg−1 . Xu and co-workers [164] designed and
1933.33 F g at 1 A g . The MnCo2O4@MnCo2S4//CNTs device delivers brillia
−1 −1
prepared hierarchical
cyclemesoporous
stability of 96% NiCo 2 O4 @MnO
capacitance 2 core–shell
retention nanowire
after 5000 cycles.arrays
At theon nickel
same time, it show
foam. After 8000 high
cyclesenergy
at 50 mA cm −2 , 113.6% original specific capacitance (1.23 F −2 )
cm[164]
density of 50.75 Wh kg at 1260 W kg . Xu and co‐workers
−1 −1 designe
was obtained. Anand asymmetric
preparedsupercapacitor was assembled
hierarchical mesoporous NiCo2O with
4@MnO the2prepared
core–shellsample
nanowire as arrays o
the positive electrode
nickelandfoam. ACAfter
as the8000negative
cycles atelectrode.
50 mA cm−2 The measurement
, 113.6% resultscapacitance
original specific show (1.23
that, with the potential
cm ) was
−2 window of 1.5An
obtained. V, the asymmetric
asymmetric supercapacitor
supercapacitor delivers a specific
was assembled with the prepare
F g−1 at
capacitance of 112sample as 1themA cm−2 electrode
positive and AC as
and a maximum the negative
energy densityelectrode.
of 35 W hThe kg−measurement
1 . In r
Zhu’s study [165], sults
theshowunique that,3Dwith the potential
hierarchical windowof
structure of CuCo
1.5 V, 2the
O4asymmetric
@Ni(OH)2 supercapacitor
provides deli
ers a area,
large specific surface specific capacitance
which enablesofrapid
112 F g −1 at 1 mA cm−2 and a maximum energy density of
response and enhances electrochemical
W h kg
properties (2160 F g at 1 A g and a good capacitance3D
−1. In Zhu’s study [165], the unique hierarchical structure
− 1 − 1 retention of 82.7% at 20ofACuCo
g−1 ).2O4@Ni(OH
provides large specific surface area, which enables rapid response and enhances electr
chemical properties
2.5.2. Introduction of Transition (2160
Metal F g−1 atMaterials
Sulfides 1 A g−1 and a good capacitance retention of 82.7% at
A g−1).
Transition metal sulfides have the characteristics of high faradic redox activities,
unique physical or chemical properties, and long cycle performance. The conductivity
2.5.2. Introduction of Transition Metal Sulfides Materials
of metal sulfides is higher than that of corresponding oxides, which is more convenient
Transition metal sulfides have the characteristics of high faradic redox activitie
for electron transfer. In addition, low electroconductivity restricts TMOs further appli-
unique physical or chemical properties, and long cycle performance. The conductivity
cation in supercapacitors. At the same time, transition metal sulfides can make up for
metal sulfides is higher than that of corresponding oxides, which is more convenient f
the shortcoming electron
of TMOs. Moreover,
transfer. because
In addition, lowofelectroconductivity
the synergistic effect between
restricts TMOsthe twoapplicatio
further
individual materials, the mixed structure electrode can also improve the whole active
in supercapacitors. At the same time, transition metal sulfides can make up for the shor
region and promote the of
coming transport of ions from
TMOs. Moreover, theofelectrolyte
because [19,166,167].
the synergistic Liu and
effect between co- individu
the two
workers [167] fabricated
materials,Co 9 S8mixed
the @NiCo 2 O4 nanobrushes
structure electrode canbyalso
NiCo 2 O4 nanosheets
improve the whole grown
active region an
on Co9 S8 hollowpromote
nanoneedles. Owing
the transport of to the
ions good
from theelectrical
electrolyteconductivity andand
[19,166,167]. Liu specific
co‐workers [16
capacitance of Co9 S8 and large specific surface area provided by the hollow nanoneedles
structure, remarkable electrochemical properties are displayed (a high specific capacitance
of 1966 F g−1 at 1 A g−1 and excellent capacitance retention of 92.9% after 5000 cycles).
Nanomaterials 2021, 11, x FOR PEER REVIEW 16

fabricated Co9S8@NiCo2O4 nanobrushes by NiCo2O4 nanosheets grown on Co9S8 ho


Nanomaterials 2021, 11, 1248 nanoneedles. Owing to the good electrical conductivity and specific capacitance 15 of 28 of C
and large specific surface area provided by the hollow nanoneedles structure, remark
electrochemical properties are displayed (a high specific capacitance of 1966 F g−1 a
Owing to its unique structure,
g−1 and excellentCuCo 2 S4 /CuCo
capacitance 2 O4 hasof
retention the advantages
92.9% after 5000of electrochemical
cycles). Owing to its un
surface area, excellent conductivity,
structure, CuCo2S4/CuCo short
2O4ion
hasdiffusion path, and
the advantages rapid electron surface
of electrochemical and ionarea, exce
transport rate [168]. Based onshort
conductivity, graphene aerogel and
ion diffusion path,CuCo S4 /CuCo
and 2rapid 2 O4 , the
electron andasymmetric
ion transport rate [
supercapacitorBased
is synthesized,
on graphene which delivers
aerogel energy
and CuCo density
2S4/CuCo 2O4of 33.2
, the W h kg−1supercapacitor
asymmetric , power is
density of 13.3 kW − 1
kg ,which
and outstanding long-term stability
thesized, delivers energy density of 33.2ofW73% capacitance
h kg retention
−1, power density of 13.3 kW
after 10,000 cycles.
and outstanding long‐term stability of 73% capacitance retention after 10,000 cycles.

2.5.3. Introduction
2.5.3.ofIntroduction
Oxygen Vacanciesof Oxygen Vacancies
There are three There
reasons that
are canreasons
three explainthat
whycan
theexplain
introduction
why the of oxygen vacancies
introduction is an vacanc
of oxygen
effective strategy to improve the electrochemical performance. (i) Introduction
an effective strategy to improve the electrochemical performance. (i) Introduction ofof oxygen
vacancies can adjust the surface
gen vacancies canchemical
adjust thestructure and enlarge
surface chemical the electroactive
structure and enlargesur-face
the electroactive
area exposed tofacetheareaelectrolyte.
exposed to the electrolyte. (ii) Oxygen vacancies can helpfor
(ii) Oxygen vacancies can help the diffusion thecharge
diffusion for ch
carriers. Therefore, the conductivity
carriers. Therefore, theofconductivity
TMOs is improved.
of TMOs(iii) Electrochemical
is improved. active sites active
(iii) Electrochemical
are created when areoxygen
createdvacancies
when oxygen are introduced because
vacancies are the oxygen
introduced because vacancies can vacancies
the oxygen serve can s
as active sites for redox reactions. The kinetics of surface reactions is accelerated
as active sites for redox reactions. The kinetics of surface reactions is accelerated and the an
capacitance is increased
capacitance [169–171].
is increased To improve
[169–171].slow reaction slow
To improve kinetics and poor
reaction conduc-
kinetics and poor con
tivity of CuCo2tivity
O4 electrode
of CuComaterial, Feng et al. [170] prepared oxygen-vacancy-enriched
2O4 electrode material, Feng et al. [170] prepared oxygen‐vacancy‐enri
CuCo2 O4 nanoflowers
CuCo2O4 nanoflowers in hypoxicvia
in hypoxic atmosphere a hydrothermal
atmosphere method followed
via a hydrothermal methodby followe
thermal treatment. The presence of oxygen defect sites and impurity bands
thermal treatment. The presence of oxygen defect sites and impurity bands provides provides
massive reaction sites
sive and fast
reaction sitesion
and intercalation, which improves
fast ion intercalation, electrical electrical
which improves conductivity
conductivity
and hydrophilichydrophilic
properties.properties.
The electrode material shows a brilliant specific capacitance
The electrode material shows a brilliant specific capacitance of o
1.2 F cm−2 at 1.2 mA cm −2 and rate capability of 69.4% capacitance retention at 20 A g−1 .
F cm−2 at 1.2 mA cm−2 and rate capability of 69.4% capacitance retention at 20 A g−1. Y
Yan et al. [171] soaked
al. [171]the prepared
soaked NiCo2 O4 nanostructures
the prepared in the different
NiCo2O4 nanostructures in theconcentration
different concentratio
of NaBH4 solutionNaBH (0.1 M, 0.3 M, 0.5 M, 0.7 M) to change the content of oxygen vacancies
4 solution (0.1 M, 0.3 M, 0.5 M, 0.7 M) to change the content of oxygen vaca
(Figure 8). (Figure 8).

Figure 8. (a) Schematic diagram of oxygen vacancies in NiCo2 O4 ; (b) the preparation scheme of the
electrodes. Reproduced with permission from [171]. Copyright 2018 Elsevier.
Nanomaterials 2021, 11, 1248 16 of 28

The results indicate that an appropriate oxygen vacancy content can increase the
diffusion rate of carriers. In addition, oxygen vacancies as active sites for redox reactions
can accelerate the surface kinetics reaction. The NiCo2 O4 nanosheets electrode treated
with 0.5 M NaBH4 has the best electrochemical performance (1590 F g−1 at 1 A g−1 and a
capacitance retention of 79.12% at 10 A g−1 after 10,000 cycles).

2.6. AMoO4 (A = Co, Mn, Ni, Zn)


Compared with carbon materials, pseudocapacitive materials like metal oxides and
organic conductive materials have higher specific capacitance owing to redox reaction on
the surface of the material. In addition, ternary metal oxides have more active sites and
faster redox reactions than single metal oxides, which become one of the materials to replace
RuO2 [53,172–174]. As the hotspots of mixed transition metal oxides, the transition metal
molybdates have attracted much attention because of their advantages including natural
abundance, high theoretical specific capacitance, and low costs [175]. The performance
of supercapacitors depends largely on the morphology and structure of their electrode
materials. Therefore, it is very important to design electrode materials with unique spatial
structure characteristics [176].

2.6.1. Core–Shell Structure for AMoO4 -Based Electrode


According to Yi’s study [127], the design of heterostructure composites has proved
to be a hopeful way to promote the electrochemical properties of TMOs. Core–shell
structure is a kind of heterostructure. The core–shell structure can supply large specific
surface area with rich porosity. Meanwhile, the electron transfer rate is accelerated by
core materials and electrochemical redox active sites are provided by shell materials. The
volume changes during the cycle process are adjusted by the structure. In addition, the
synergistic effect of each component is utilized to improve the electrochemical performance
of the electrode [177–180]. Xuan et al. [181] designed and prepared 3D self-supported
hierarchical CoMoO4 @CoS core–shell heterostructures on rGO/Ni foam. Figure 9 shows
the SEM images of CoMoO4 , CoS, and CoMoO4 @CoS with different magnification.
The unique material structure, the excellent conductivity of rGO, and the syner-
gistic effect between the two materials help to increase the electrochemical active sites
and enhance the capacitance. According to the electrochemical performance tests, the
core–shell CoMoO4 @CoS composite shows 81.1% retention of the initial capacitance
(3380.3 F g−1 at 1 A g−1 ) after 6000 cycles at 10 A g−1 . In order to further improve
the performance of MCo2 O4 materials, Hussain and co-workers [182] combined CoMoO4
with ternary metal sulfide NiCo2 S4 to synthesize three-dimensional walking palm-like
core–shell CoMoO4 @NiCo2 S4 @NF nanostructure by a two-step hydrothermal method. At
a current density of 5 mA cm−2 , the synthesized composite exhibits a high capacitance
of 17.0 F cm−2 . Besides, 114% capacitance retention after 10,000 charge/discharge cy-
cles reveals its remarkable cycling stability. The asymmetric supercapacitor fabricated
with CoMoO4 @NiCo2 S4 @NF and AC@NF as electrodes shows a high energy density of
60.2 W h kg−1 at a power density of 188 W kg−1 . Moreover, it lights 22 parallel-connected
red light emitting diodes for over 60 s.
Nanomaterials 2021, 11, x FOR PEER REVIEW
Nanomaterials 2021, 11, 1248 17 of 28 18 of

Figure 9. (a,b) SEM


Figure images
9. (a,b) SEMofimages
CoMoOof4 with different magnification; (c,d) SEM images of CoS with different magnification;
CoMoO4 with different magnification; (c,d) SEM images of CoS with
(e,f) SEM images of CoMoO4@CoS with different magnification. Reproduced with permission from [181]. Copyright 2020
different magnification; (e,f) SEM images of CoMoO4 @CoS with different magnification. Reproduced
Elsevier.
with permission from [181]. Copyright 2020 Elsevier.
The unique material structure, the excellent conductivity of rGO, and the synergis
2.6.2. Modification of Quantum Dots
effect between the two materials help to increase the electrochemical active sites and e
Quantum dots hance(QDs) are zero-dimensional
the capacitance. According to nanoparticles of metal
the electrochemical or semiconductor
performance tests, the core–sh
crystals with a diameter between 2 and 8 nanometers [183]. Quantum dots
CoMoO4@CoS composite shows 81.1% retention of the initial capacitance have attracted
(3380.3 F g−1
much attention for various
−1 applications owing to their
−1 characteristics such as quantum
1 A g ) after 6000 cycles at 10 A g . In order to further improve the performance
tunneling effect, surface
MCo2O4effect, and Hussain
materials, quantumand confinement
co‐workerseffect
[182][184]. It is noteworthy
combined CoMoO4 with that
ternary me
the size of the material
sulfide largely
NiCo2Sdecides the substantial
4 to synthesize variation of walking
three‐dimensional fundamental electrical
palm‐like core–shell C
MoO4@NiCo
and optical properties [185]. 2STherefore,
4@NF nanostructure by a two‐step
optical, electronic, andhydrothermal
mechanical method.
propertiesAt aofcurrent de
QDs are differentsity
fromof 5corresponding
mA cm−2, the synthesized
nanoparticles composite exhibits
[186]. For a highinfinite
example, capacitance of 17.0 F cm
exciton
Besides,
Bohr radius converts 114% capacitance
graphene to graphene retention
quantumafterdots
10,000 charge/discharge
(GQDs) and GQDscycles start reveals
to its r
fluoresce becausemarkable cycling stability.
electron distribution The asymmetric
is transparently modifiedsupercapacitor
by the crystal fabricated
boundary with C
with the dimensionMoOof 4@NiCo2S4@NF and AC@NF as electrodes shows a high energy density of 60.2 W
the crystal reducing to a nanometer scale [185]. Moreover, some
unique properties kgof
−1 at a power density of 188 W kg−1. Moreover, it lights 22 parallel‐connected red lig
zero-dimensional nanoparticles like distinct edge and quantum con-
finement effects emitting diodes forthe
help to improve overelectrochemical
60 s. performance [183]. Some studies
prove that quantum dot modification is an effective method for improving electrochemical
performance [187–189]. Hence, it can be speculated that quantum dot modification is a
promising strategy to improve the performance of AMoO4 -based electrode. To the best
of our knowledge, there are still relatively few reports in this regard. Zhu et al. [190]
ary with the dimension of the crystal reducing to a nanometer scale [185]. Moreover, some
unique properties of zero‐dimensional nanoparticles like distinct edge and quantum con‐
finement effects help to improve the electrochemical performance [183]. Some studies
prove that quantum dot modification is an effective method for improving electrochemi‐
Nanomaterials 2021, 11, 1248 cal performance [187–189]. Hence, it can be speculated that quantum dot modification is
18 of 28
a promising strategy to improve the performance of AMoO4‐based electrode. To the best
of our knowledge, there are still relatively few reports in this regard. Zhu et al. [190] syn‐
synthesized
thesized carboncarbon quantum
quantum dotsdots (CQDs)
(CQDs) modified
modified porous
porous NiCo NiCo 2 O4 sphere
2O4 sphere composites.
composites. The
The CQDs/NiCo −1 at
CQDs/NiCo 2 O4 composite
2O4 composite electrode
electrode possesses
possesses a specific
a specific capacitance
capacitance (856 F g(856
−1 atF1 gA g−1 )
−1 ) and excellent rate capability of 83.9%, 72.5%, and 60.8% capacity retention rate at
1 A gexcellent
and rate capability of 83.9%, 72.5%, and 60.8% capacity retention rate at 20, 50,
20, 50,
and 100andA g100 A g−1 , respectively.
−1, respectively. It also hasIt 1.25%
also has 1.25% capacitance
capacitance loss over
loss over 10,000 10,000
cycles at 5cycles
A g−1,
at 5 A g − 1 , which indicates its exceptional cycling stability. The maximum capacitance
which indicates its exceptional cycling stability. The maximum capacitance of graphene
of graphene −1 is four times
quantum dotquantum
modified dot modifiedelectrode
nano‐needle nano-needle[191]electrode
at 1 A g−1[191] attimes
is four 1 A ghigher than that
higher − 1 and 368 F g−In 1,
of purethanMnCo that of pure MnCo2 O4.5electrode
2O4.5 nano‐spherical
nano-spherical
(1625 Felectrode
g−1 and 368(1625
FF g−1g, respectively).
respectively).
Zhang’s research In Zhang’s research [192],
[192], mesoporous mesoporous
NiMoO NiMoO4 microspheres
4 microspheres were modified by were modified
silver quan‐
by silver quantum dots to fabricate the Ag QDs/NiMoO
tum dots to fabricate the Ag QDs/NiMoO4 microspheres (Figure 10). 4 microspheres (Figure 10).

Figure 10.
10. (a)
(a)Schematic
Schematicillustration ofof
illustration thethe
synthesis processes
synthesis for for
processes mesoporous NiMoO
mesoporous 4 microspheres; (b) schematic illus‐
NiMoO
Figure 4 microspheres; (b) schematic
tration of the synthesis processes for Ag quantum dots (QDs)/NiMoO4 microspheres. Reproduced with permission from
illustration of the synthesis processes for Ag quantum dots (QDs)/NiMoO4 microspheres. Reproduced with permission
[192]. Copyright 2020 Elsevier.
from [192]. Copyright 2020 Elsevier.

Owing to high specific surface area, plenty of active sites, enhanced interfacial conduc-
tivity, and porous structure, the Ag QDs/NiMoO4 microspheres exhibit specific capacitance
of 3342.7 F g−1 at 1 mV s−1 and 2074 F g−1 at 1 A g−1 (Figure 11).
Moreover, the asymmetric supercapacitor assembled with Ag QDs/NiMoO4 and
spore-derived activated carbon delivers high energy density of 48.5 W h kg−1 at a power
density of 212.5 kW h kg−1 and good cycling performance. Table 2 shows the perfor-
mance of representative electrodes based binary and ternary TMOs, and Table 3 shows the
performance of representative supercapacitors based on binary and ternary TMOs.
Nanomaterials 2021, 11, x FOR PEER REVIEW 20 of 29

Owing to high specific surface area, plenty of active sites, enhanced interfacial con‐
Nanomaterials 2021, 11, 1248 ductivity, and porous structure, the Ag QDs/NiMoO4 microspheres exhibit specific 19 of 28
capac‐
itance of 3342.7 F g−1 at 1 mV s−1 and 2074 F g−1 at 1 A g−1 (Figure 11).

Figure 11.
Figure 11. CV
CV and
and GCD
GCD measurements
measurements forfor the
theNiMoO
NiMoO44and
andAgAgQDs/NiMoO
QDs/NiMoO 4 electrodes in the three‐electrode system: (a)
4 electrodes in the three-electrode system:
contrastive CV curves at 20 mV s −1; (b) CV curves of Ag QDs/NiMoO4 electrode; (c) specific capacitances as a function of
− 1
(a) contrastive CV curves at 20 mV s ; (b) CV curves of Ag QDs/NiMoO4 electrode; (c) specific capacitances as a function
scan rates; (d) contrastive GCD curves at 2 A g−1; (e) rate performances of Ag QDs/NiMoO4 electrode; and (f) specific
of scan rates; (d) contrastive GCD curves at 2 A g−1 ; (e) rate performances of Ag QDs/NiMoO4 electrode; and (f) specific
capacitances as a function of current densities. Reproduced with permission from [192]. Copyright 2020 Elsevier.
capacitances as a function of current densities. Reproduced with permission from [192]. Copyright 2020 Elsevier.

Moreover, the asymmetric supercapacitor assembled with Ag QDs/NiMoO4 and


Tablespore‐derived activated
2. The performance carbonbased
of electrodes delivers high energy
on binary density
and ternary of 48.5 W h kg−1 at a power
TMOs.
density of 212.5 kW h kg−1 and good cycling performance. Table 2 shows the performance
Category of Material
Electrode representative electrodes based binarySpecific
Electrolyte and ternary TMOs, andStability
Cycling Table 3 shows the per‐
Reference
Capacitance
formance of representative supercapacitors based on binary and ternary TMOs.
CuCo2 O4 /CuO@RuO2 2 M KOH 862.5 mAh cm− 2 90.1% (8000 cycles) [64]
NiO/Co O4 performance of 3M KOH based on1242 −1
Table 2. 3The electrodes binaryC gand ternary95.5%
TMOs. (12,000 cycles) [75]
Co3 O4 micro-bundles 2 M KOH 282.3 C g− 1 74.6% (4000 cycles) [51]
binary
Category Electrode Material
Ag-doped Co3 O4 /NF Electrolyte 1425 F g− 1 Cycling Stability
3 M KOH Specific Capacitance 96.4 (5000 cycles) Reference[91]
transmission
CuCo
Co O
3 4 O 4/CuO@RuO
2@MnO
2 on carbon
2 2 M KOH 862.5 mAh cm −2
−1
90.1% (8000 cycles) [64]
metal oxides NiO/Co 3O4
1 M Na2 SO4
3 M KOH 1242 C616.7
g−1 F g 95.5% (12,000 83.1% (10,000 cycles) [75] [128]
cycles)
cloth
Co3O4NiO@MnO
micro‐bundles 2
2 M KOH / C g−1 F g− 1 74.6% (4000
282.31219.2 76.7%cycles)
(10,000 cycles) [51] [127]
Ag‐doped Co3O4/NF 30.2
M KOH
M K4(Fe[CN]6 ) 1425 F g−1 96.4 (5000 cycles) [91]
ZnO/CeO
binary transmission Co3O4@MnO 2
2 on carbon
495.4 F g− 1 95.6% (2000 cycles) [140]
in 3
1 M Na2SO4 M KOH 616.7 F g −1 83.1% (10,000 cycles) [128]
metal oxides cloth
ZnO@Mo–C 2 M KOH 900 F g − 1 / [154]
NiO@MnO
graphene 2
quantum / 1219.2 F g−1 76.7% (10,000 cycles) [127]
2M 6KOH 1625 F g − 1 80% (5000 cycles) [191]
dots/MnCo 0.2 M K4(Fe[CN] ) in 3
ZnO/CeO2 2 O4.5 495.4 F g−1 95.6% (2000 cycles) [140]
Ag QDs/NiMoO4 M KOH 3 M KOH − 1 81% (1000 cycles) [192]
ternary 2074 F g
ZnO@Mo–C 2 M KOH 900 F g−1 / [154]
transmission CoMoO 4 @NiCo2 S4 @Nickel
graphene quantum 3 M KOH 17.0 F cm− 2 114% 10,000 cycles. [182]
metal oxides Foam 2M KOH 1625 F g−1 80% (5000 cycles) [191]
dots/MnCo2O4.5
CuCo2 O4 @Ni(OH)2 2 M KOH 2160 F g− 1 92% (5000 cycles) [165]
Ag QDs/NiMoO4 3 M KOH 2074 F g−1 81% (1000 cycles) [192]
Co9 S8 @NiCo2 O4 3 M KOH 1966 F g− 1 92.9% (5000 cycles) [167]
Co‐
ternary transmission CoMoO4 @MoZn22 3 M KOH 923−2 C g− 1 92.3% (7000 cycles) [177]
MoO4@NiCo2S4@Nickel 3 M KOH 17.0 F cm 114% 10,000 cycles. [182]
metal oxides
Foam
CuCo2O4@Ni(OH)2 2 M KOH 2160 F g−1 92% (5000 cycles) [165]
Co9S8@NiCo2O4 3 M KOH 1966 F g−1 92.9% (5000 cycles) [167]
CoMoO4@MoZn22 3 M KOH 923 C g−1 92.3% (7000 cycles) [177]
Nanomaterials 2021, 11, 1248 20 of 28

Table 3. The performance of supercapacitors based on binary and ternary TMOs.

Operating Specific Energy Density


Electrode Material Voltage Capacitance Cycling Stability Reference

RuO2 //h-WO3 1.6 V 47.59 F g− 1 16.92 W h kg− 1 ~171.75% (6500 cycles) [72]
Co3 O4 //AC 1.6 V 310.4 C g− 1 0.4 mW h cm− 3 79.2% (10,000 cycles) [87]
Co3 O4 -NiO/GO//AC 1.65 V 133 F g− 1 50.2 W h kg− 1 82% (3000 cycles) [91]
Co3 O4 /NF—8 h//N-rGO/NF 1.6 V 62.5 F g− 1 22.2 W h kg− 1 93.3% (10,000 cycles) [93]
MnO2 /HCS-30//HCS 2.0 V 74.5 F g− 1 41.4 W h kg− 1 93.9% (5000 cycles) [125]
Co3 O4 @MnO2 @CC-90//AC 2.2 V 309.2 mF cm− 2 54.71 W h kg− 1 86.3% (10,000 cycles) [128]
graphene about 94% (10,000
electrode//ZnO-CoO@NC
1.6 V / 16.5 W h kg− 1 cycles) [152]
ZnO@CoS//AC 1.6 V 2438 mC cm− 2 45.2 W h kg− 1 107% (11,000 cycles) [157]
NiCo2 O4 @MnO2 //AC 1.5 V 112 F g− 1 35 W h kg− 1 ~71% (5000 cycles) [164]
CuCo2 S4 /CuCo2 O4 //graphene
aerogel
1.6 V 90.4 F g− 1 33.2 W h kg− 1 73% (10,000 cycles) [168]
CoMoO4 @CoS//AC 1.7 V 189.5 F g− 1 59.2 W h kg− 1 91.5% (6000 cycles) [181]
CoMoO4 @NiCo2 S4 @NF//
AC@NF
1.6 V 182 F g− 1 60.2 W h kg− 1 84% (5000 cycles) [182]
MnCo2 O4.5 -40 GQDs//rGO 1.3 V 200 F g− 1 46 W h kg− 1 77% (5000 cycles) [191]
Ag QDs/
NiMoO4 //spore-derived AC
1.7 V 120.5 F g− 1 48.5 W h kg− 1 84.4% (5000 cycles) [192]

3. Conclusions
The main purpose of developing supercapacitors is to meet the requirement of storing
renewable energy. Supercapacitors have the advantages of high-power density, excellent
cycle stability, and fast charge/discharge process. The performance of supercapacitors
largely depends on the electrode materials. TMOs are the most favored because of their
higher energy density and specific capacity than carbon materials, and better chemical
stability than conductive polymers.
In this review, we have summarized recent developments of TMOs-based electrode
materials for supercapacitors, including design, fabrication, and electrochemical perfor-
mances. RuO2 is the ideal TMOs electrode material, but high cost and toxicity are its
fatal shortcomings. Co3 O4 , MnO2 , and ZnO are supposed to substitute RuO2 . However,
existing problems like low conductivity hinder their practical application in electrode ma-
terials. Therefore, we have introduced some strategies to solve the problems. (i) Preparing
nano scale materials. The small size enlarges the contact surface and shortens the ion
diffusion distance between materials and electrolyte. The size of material largely decides
the substantial variation of fundamental electrical and optical properties. In addition,
optical, electronic, and mechanical properties of QDs are different from corresponding
nanoparticles. That is why QDs are very attractive in various fields. (ii) Utilizing the syner-
gistic effect. It is very important that, through different combinations of carbon materials,
transition metal oxides, transition metal sulfides, and other materials, the synergistic effect
between different components can be used to improve the electrochemical performance
effectively. In addition, some electrode materials containing metal sulfides exhibit good
electrochemical performance, which indicates that other binary metal materials such as
metal phosphides and metal nitrides also have potential for electrode materials. (iii) Syn-
thesizing composites with a special structure. Porous structure, core–shell structure, and
hollow structure can enlarge the surface area with generous electrochemical active sites and
reduce the resistance of ion and electron transfer, thus increasing the conductivity and the
rate of redox reaction. Further, the introduction of oxygen vacancies can not only increase
active sites, but also adjust the surface chemical structure, improving the conductivity. (iv)
Ternary transition oxides have higher conductivity, faster faradic reaction, and more active
sites than single metal oxides. At the same time, Tables 1–3 show that ternary transition
oxides have better performance than single transition oxides in the practical application
of both electrode and supercapacitor. We believe that ternary TMOs will be the focus of
future research on transition metal oxides.
Nanomaterials 2021, 11, 1248 21 of 28

Although much promising progress has been obtained in TMOs-based electrode


materials, low energy density is still an obstacle for the development of supercapacitors.
We have three recommendations on the development of supercapacitors. (i) Researchers
should aim efforts towards how to obtain raw material of electrode with low cost and no
pollution, and the use of biomass carbon materials is a good example. (ii) The development
of portable and wearable electronic devices drives the study of flexible supercapacitors.
That means, apart from increasing the energy density, it is necessary to achieve the stability
of the capacitance performance under different bending and deformation conditions. (iii)
At present, there are many reports on transparent and flexible electrodes for solar batteries.
Moreover, supercapacitors based on battery-type electrodes are also widely reported. At
the same time, hybrid supercapacitors can shorten the gap between conventional metal
ion batteries and supercapacitors [52]. We wonder whether supercapacitors could have
the possibility of solar charging in the future. If the wonder come true, that will represent
significant progress in the development of supercapacitors.

Author Contributions: Conceptualization, R.L., Y.D. and P.X.; investigation, J.C. (Junyang Cheng),
S.Y. and Y.C.; data curation, J.C.; writing—original draft preparation, R.L.; writing—review and
editing, R.L., Y.D. and P.X.; supervision, J.C. (Jianwen Chen) and J.Y. All authors have read and
agreed to the published version of the manuscript.
Funding: This work was supported by National Natural Science Foundation of China (Grant No.
61804029), Research Fund of Guangdong-Hong Kong-Macao Joint Laboratory for Intelligent Micro-
Nano Optoelectronic Technology (No. 2020B1212030010), Guangdong Provincial Key Laboratory of
Semiconductor Micro Display (2020B121202003), and the Project of Foshan Education Bureau (Grant
No. 2019XJZZ02).
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Liu, P.Y.; Zhao, J.J.; Dong, Z.P.; Liu, Z.L.; Wang, Y.Q. Interwoving Polyaniline and a Metal-organic Framework Grown in Situ for
Enhanced Supercapacitor Behavior. J. Alloys Compd. 2021, 854, 157181.
2. Prakash, D.; Manivannan, S. Unusual Battery Type Pseudocapacitive Behaviour of Graphene Oxynitride Electrode: High Energy
Solid-state Asymmetric Supercapacitor. J. Alloys Compd. 2021, 854, 156853. [CrossRef]
3. Sethi, M.; Shenoy, U.S.; Bhat, D.K. Simple Solvothermal Synthesis of Porous Graphene-NiO Nanocomposites with High Cyclic
Stability for Supercapacitor Application. J. Alloys Compd. 2021, 854, 157190. [CrossRef]
4. Sun, Z.Q.; Li, F.Z.; Ma, Z.Q.; Wang, Q.; Qu, F.Y. Battery-type Phosphorus Doped FeS2 Grown on Graphene as Anode for Hybrid
Supercapacitor with Enhanced Specific capacity. J. Alloys Compd. 2021, 854, 157114. [CrossRef]
5. Wang, Y.; Qiao, M.F.; Mamat, X. Nitrogen-doped Macro-meso-micro Hierarchical Ordered Porous Carbon Derived from ZIF-8 for
Boosting Supercapacitor Performance. Appl. Surf. Sci. 2021, 540, 148352.
6. Zan, G.T.; Wu, T.; Chen, H.X.; Dong, F.Q.; Wu, Q.S. BiVO4 Nanocoral Superstructures and Their Excellent Electrical/optical
Dual-functions. J. Alloys Compd. 2021, 852, 157035.
7. Wu, S.R.; Liu, J.B.; Wang, H.; Yan, H. A Review of Performance Optimization of MOF-derived Metal Oxide as Electrode Materials
for Supercapacitors. Int. J. Energy Res. 2019, 43, 697–716.
8. Anand, S.; Ahmad, M.W.; Al Saidi, A.K.A.; Yang, D.-J.; Choudhury, A. Polyaniline Nanofiber Decorated Carbon Nanofiber
Hybrid Mat for Flexible Electrochemical Supercapacitor. Mater. Chem. Phys. 2020, 254, 123480. [CrossRef]
9. Hu, Q.L.; Yue, B.; Shao, H.Y.; Yang, F.; Wang, J.H.; Wang, Y.; Liu, J.H. Facile Syntheses of Perovskite Type LaMO3 (M = Fe, Co, Ni)
Nanofibers for High Performance Supercapacitor Electrodes and Lithium-ion Battery Anodes. J. Alloys Compd. 2021, 852, 157002.
10. Kumar, K.S.; Choudhary, N.; Pandey, D.; Hurtado, L.; Chung, H.-S.; Tetard, L.; Jung, Y.W.; Tomas, J. High-performance Flexible
Asymmetric Supercapacitor Based on rGO Anode and WO3 /WS2 Core/shell Nanowire Cathode. Nanotechnology 2020, 31, 435405.
[CrossRef] [PubMed]
11. Yu, J.H.; Gao, X.L.; Cui, Z.X.; Jiao, Y.; Zhang, Q.; Yu, L.Y.; Dong, L.Y. Facile Synthesis of Binary Transition Metal Sulfide Tubes
Derived from NiCo-MOF-74 for High-performance Supercapacitors. Energy Technol. 2019, 7, 1900018.
12. Shin, S.Y.; Shin, M.W. Nickel Metal–organic Framework (Ni-MOF) Derived NiO/C@CNF Composite for the Application of High
Performance Self-standing Supercapacitor Electrode. Appl. Surf. Sci. 2021, 540, 148295.
13. Liu, Y.M.; Murtaza, I.; Shuja, A.; Meng, H. Interfacial Modification for Heightening the Interaction between PEDOT and Substrate
Towards Enhanced Flexible Solid Supercapacitor Performance. Chem. Eng. J. 2020, 379, 122326.
14. Gao, Y.-P.; Zhai, Z.-B.; Wang, Q.-Q.; Hou, Z.-Q.; Huang, K.-J. Cycling Profile of Layered MgAl2 O4 /reduced graphene oxide
Composite for Asymmetrical Supercapacitor. J. Colloid Interface Sci. 2019, 539, 38–44.
Nanomaterials 2021, 11, 1248 22 of 28

15. Meng, Z.H.; Yan, W.; Zou, M.Y.; Miao, H.; Ma, F.X.; Patil, A.B.; Yu, R.; Liu, X.Y.; Liu, N.B. Tailoring NiCoAl Layered Double
Hydroxide Nanosheets for Assembly of High-performance Asymmetric Supercapacitors. J. Colloid Interface Sci. 2021, 583, 722–733.
16. Gao, Y.-P.; Huang, K.-J. NiCo2 S4 Materials for Supercapacitor Applications. Chem. Asian J. 2017, 12, 1969–1984.
17. Du, Y.Q.; Xiao, P.; Yuan, J.; Chen, J.W. Research Progress of Graphene-Based Materials on Flexible Supercapacitors. Coatings 2020,
10, 892.
18. Chameh, B.; Moradi, M.; Hajati, S.; Hessari, F.A. Design and Construction of ZIF (8 and 67) Supported Fe3 O4 Composite as
Advanced Materials of High Performance Supercapacitor. Phys. E Syst. Nanostruct. 2021, 126, 114442. [CrossRef]
19. Niu, W.S.; Xiao, Z.Y.; Wang, S.F.; Zhai, S.R.; Qin, L.F.; Zhao, Z.Y.; An, Q.D. Synthesis of Nickel Sulfide-supported on Porous Carbon
from a Natural Seaweed-derived Polysaccharide for High-performance Supercapacitors. J. Alloys Compd. 2021, 853, 157123.
20. Pettong, T.; Iamprasertkun, P.; Krittayavathananon, A.; Sukha, P.; Sirisinudomkit, P.; Seubsai, A.; Chareonpanich, M.;
Kongkachuichay, P.; Limtrakul, J.; Sawangphruk, M. High-performance Asymmetric Supercapacitors of MnCo2 O4 Nanofibers
and N-doped Reduced Graphene Oxide Aerogel. ACS Appl. Mater. Inter. 2016, 8, 34045–34053. [CrossRef]
21. Zhou, W.; Han, G.Y.; Xiao, Y.M.; Chang, Y.Z.; Yuan, W.; Li, Y.P.; Liu, C.X.; Zhang, Y. Polypyrrole Doped with Dodecyl Benzene
Sulfonate Electrodeposited on Carbon Fibers for Flexible Capacitors with High-performance. Electrochim. Acta 2015, 176, 594–603.
22. Sun, L.; Fu, Q.; Pan, C.X. Mn3 O4 Embedded 3D Multi-heteroatom Codoped Carbon Sheets/carbon Foams Composites for
High-performance Flexible Supercapacitors. J. Alloys Compd. 2020, 849, 156666.
23. Liu, S.L.; Feng, Q.C.; Zhang, C.; Liu, T.X. Molten Salt-confined Pyrolysis towards Carbon Nanotube-backboned Microporous
Carbon for High-energy-density and Durable Supercapacitor Electrodes. Nanotechnology 2021, 32, 095605.
24. Zhang, M.M.; Song, Z.X.; Liu, H.; Wang, A.; Shao, S.Y. MoO2 Coated Few Layers of MoS2 and FeS2 Nanoflower Decorated
S-doped Graphene Interoverlapped Network for High-energy Asymmetric Supercapacitor. J. Colloid Interface Sci. 2021, 584,
418–428. [CrossRef]
25. Wu, P.; Cheng, S.; Yao, M.H.; Yang, L.F. A low-cost, Self-standing NiCo2 O4 @CNT/CNT Multilayer Electrode for Flexible
Asymmetric Solid-state Supercapacitors. Adv. Funct. Mater. 2017, 27, 1702160.
26. Liu, Y.B.; Huang, G.X.; Li, Y.Y.; Yao, Y.H.; Xing, B.L.; Liu, Q.R.; Jia, J.B.; Zhang, C.X. Structural Evolution of Porous Graphitic
Carbon Nanosheets Based on Quinonyl Decomposition for Supercapacitor Electrodes. Appl. Surf. Sci. 2021, 537, 147824.
27. Shi, Y.; Sun, L.; Zhang, Y.X.; Si, H.C.; Sun, C.; Gu, J.L.; Gong, Y.; Li, X.W.; Zhang, Y.H. SnS2 Nanodots Decorated on RGO Sheets
with Enhanced Pseudocapacitive Performance for Asymmetric Supercapacitors. J. Alloys Compd. 2021, 853, 156903.
28. Hao, J.Y.; Zou, X.F.; Feng, L.; Li, W.P.; Xiang, B.; Hu, Q.; Liang, X.Y.; Wu, Q.B. Facile Fabrication of Core-shell Structured
Ni(OH)2 /Ni(PO3 )2 Composite via One-step Electrodeposition for High Performance Asymmetric Supercapacitor. J. Colloid
Interface Sci. 2021, 583, 243–254.
29. Zhai, S.X.; Jin, K.; Zhou, M.; Fan, Z.Z.; Zhao, H.; Li, X.Y.; Zhao, Y.P.; Ge, F.Y.; Cai, Z.S. A Novel High Performance Flexible
Supercapacitor Based on Porous Carbonized cotton/ZnO Nanoparticle/CuS Micro-sphere. Colloids Surf. A 2020, 584, 124025.
30. He, W.D.; Wang, C.G.; Zhuge, F.W.; Deng, X.L.; Xu, X.J.; Zhai, T.Y. Flexible and High Energy Density Asymmetrical Supercapacitors
Based on Core/shell Conducting Polymer Nanowires/manganese Dioxide Nanoflakes. Nano Energy 2017, 35, 242–250.
31. Liu, B.G.; Shi, R.; Chen, R.F.; Wang, C.H.; Zhou, K.; Ren, Y.D.; Zeng, Z.; Liu, Y.Y.; Li, L.Q. Optimized Synthesis of Nitrogen-doped
Carbon with Extremely High Surface Area for Adsorption and Supercapacitor. Appl. Surf. Sci. 2021, 538, 147961.
32. Padya, B.; Kali, R.; Enaganti, P.K.; Narasaiah, N.; Jain, P.K. Facile Synthesis and Frequency-response Behavior of Supercapacitor
Electrode Based on Surface-etched Nanoscaled-graphene Platelets. Colloid. Surf. A 2021, 609, 125587. [CrossRef]
33. Avasthi, P.; Arya, N.; Singh, M.; Balakrishnan, V. Fabrication of iron Oxide-CNT Based Flexible Asymmetric Solid State
Supercapacitor Device with High Cyclic Stability. Nanotechnology 2020, 31, 435402. [CrossRef] [PubMed]
34. Zhang, Y.; Zhang, L.; Cheng, L.; Yang, D.D.; Wan, L.; Chen, J.; Xie, M.J. Synthesis of Faradaic-active N,O-doped Carbon
Nanosheets from M-trihydroxybenzene and Piperazine for High-performance Supercapacitor. Appl. Surf. Sci. 2021, 538, 148040.
[CrossRef]
35. Yang, G.J.; Park, S.J. MnO2 and Biomass-derived 3D Porous Carbon Composites Electrodes for High Performance Supercapacitor
Applications. J. Alloys Compd. 2018, 741, 360–367.
36. Li, C.J.; Dong, X.Q.; Zhang, Y.C.; Hu, J.; Liu, W.W.; Cui, X.; Hao, A.Y. MnOx Nanosheets Anchored on a Bio-derived Porous
Carbon Framework for High-performance Asymmetric Supercapacitors. Appl. Surf. Sci. 2020, 527, 146842.
37. Chen, H.; Li, W.L.; He, M.; Chang, X.W.; Zheng, X.L.; Ren, Z.Y. Vertically Oriented Carbon Nanotube as a Stable Frame to Support
the Co0.85 Se Nanoparticles for High Performance Supercapacitor Electrode. J. Alloys Compd. 2021, 855, 157506.
38. Wang, N.; Zhao, P.; Liang, K.; Yao, M.Q.; Yang, Y.; Hu, W.C. CVD-grown Polypyrrole Nanofilms on Highly Mesoporous Structure
MnO2 for High Performance Asymmetric Supercapacitors. Chem. Eng. J. 2017, 307, 105–112.
39. Kuo, C.-W.; Chang, J.-C.; Wu, B.-W.; Wu, T.-Y. Electrochemical Characterization of RuO2 -Ta2 O5 /polyaniline Composites as
Potential Redox Electrodes for Supercapacitors and Hydrogen Evolution Reaction. Int. J. Hydrogen Energy 2020, 45, 22223–22231.
40. Ates, M.; Yildirim, M. The Synthesis of rGO/RuO2 , rGO/PANI, RuO2 /PANI and rGO/RuO2 /PANI Nanocomposites and Their
Supercapacitors. Polym. Bull. 2020, 77, 2285–2307.
41. Wang, G.R.; Jin, Z.L.; Guo, Q.J. Ordered Self-supporting NiV LDHs@P-Nickel Foam Nano-array as High-Performance Superca-
pacitor Electrode. J. Colloid. Interface Sci. 2021, 583, 1–12.
Nanomaterials 2021, 11, 1248 23 of 28

42. Wu, D.J.; Han, H.C.; Hong, X.K.; Tao, S.; Xu, S.H.; Qian, B.; Wang, L.W.; Chen, X.F.; Chu, P.K. A Novel Self-branching
MnCo2 O4 /nanographene Hybrid Composites on Macroporous Electrically Conductive Network as Bifunctional Electrodes for
Boosting Miniature Supercapacitors and Sodium Ion Batteries. J. Alloys Compd. 2020, 846, 155720.
43. Saren, P.; Adhikari, A.D.; Khan, S.; Nayak, G.C. Self-Assembled GNS Wrapped Flower-like MnCo2 O4 Nanostructures for
Supercapacitor Application. J. Solid State Chem. 2019, 271, 282–291. [CrossRef]
44. Edison, T.N.J.I.; Atchudan, R.; Lee, Y.R. Facile Synthesis of Carbon Encapsulated RuO2 Nanorods for Supercapacitor and
Electrocatalytic Hydrogen Evolution Reaction. Int. J. Hydrogen Energy 2019, 44, 2323–2329. [CrossRef]
45. Ma, L.B.; Shen, X.P.; Zhou, H.; Ji, Z.Y.; Chen, K.M.; Zhu, G.X. High Performance Supercapacitor Electrode Materials Based on
Porous NiCo2 O4 Hexagonal Nanoplates/reduced Graphene Oxide Composites. Chem. Eng. J. 2015, 262, 980–988.
46. Lei, Y.; Li, J.; Wang, Y.Y.; Gu, L.; Chang, Y.F.; Yuan, H.Y.; Xiao, D. Rapid Microwave-assisted Green Synthesis of 3D Hierarchical
Flower-shaped NiCo2 O4 Microsphere for High-performance Supercapacitor. ACS Appl. Mater. Inter. 2014, 6, 1773–1780.
47. Liu, Y.J.; Zhang, X.; Matras-Postolek, K.; Yang, P. Ni2 P Nanosheets Modified N-doped Hollow Carbon Spheres towards Enhanced
Supercapacitor Performance. J. Alloys Compd. 2020, 854, 157111.
48. Samuel, E.; Aldalbahi, A.; El-Newehy, M.; El-Hamshary, H.; Yoon, S.S. Nickel Ferrite Beehive-like Nanosheets for Binder-free and
High-energy-storage Supercapacitor Electrodes. J. Alloys Compd. 2021, 852, 156929. [CrossRef]
49. Yi, M.J.; Lu, B.B.; Zhang, X.T.; Tan, Y.B.; Zhu, Z.Y.; Pan, Z.C.; Zhang, J.H. Ionic Liquid-assisted Synthesis of Nickel Cobalt
Phosphide Embedded in N,P Codoped-carbon with Hollow and Folded Structures for Efficient Hydrogen Evolution Reaction
and supercapacitor. Appl. Catal. B. 2021, 283, 119635.
50. Samuel, E.; Joshi, B.; Kim, Y.I.; Aldalbahi, A.; Rahaman, M.; Yoon, S.S. ZnO/MnO × Nanoflowers for High-Performance
Supercapacitor Electrodes. ACS Sustain. Chem. Eng. 2020, 8, 3697–3708. [CrossRef]
51. Chen, H.Y.; Du, X.M.; Sun, J.L.; Wu, R.Z.; Wang, Y.; Xu, C.J. Template-free Synthesis of Novel Co3 O4 Micro-bundles Assembled
with Flakes for High-performance Hybrid Supercapacitors. Ceram. Int. 2021, 47, 716–724.
52. Dai, M.Z.; Zhao, D.P.; Wu, X. Research Progress on Transition Metal Oxide Based Electrode Materials for Asymmetric Hybrid
Capacitors. Chin. Chem. Lett. 2020, 31, 2177–2188.
53. Hu, P.F.; Zhao, D.P.; Liu, H.Q.; Chen, K.F.; Xu, X. Engineering PPy decorated MnCo2 O4 Urchins for Quasi-solid-state Hybrid
Capacitors. CrystEngComm 2019, 21, 1600–1606.
54. Pawar, S.M.; Pawar, B.S.; Babar, P.T.; Ahmed, A.T.A.; Chavan, H.S.; Jo, Y.; Cho, S.; Kim, J.; Hou, B.; Inamdar, A.I.; et al. Nanoporous
CuCo2 O4 nanosheets as a Highly Efficient Bifunctional Electrode for Supercapacitors and Water Oxidation Catalysis. Appl. Surf.
Sci. 2019, 470, 360–367. [CrossRef]
55. Babulal, S.M.; Venkatesh, K.; Chen, T.W.; Chen, S.W.; Krishnapandi, A.; Rwei, S.P.; Ramaraj, S.K. Synthesis of MnMoO4 Nanorods
by a Simple Co-Precipitation Method in Presence of Polyethylene Glycol for Pseudocapacitor Application. Int. J. Electrochem. Sci.
2020, 15, 7053–7063. [CrossRef]
56. Yu, F.; Pang, L.; Wang, H.-X. Preparation of Mulberry-like RuO2 Electrode Material for Supercapacitors. Rare Met. 2021, 40,
440–447.
57. Xie, Y.B.; Yao, C. Electrochemical Performance of RuO2 -TiO2 Nanotube Hybrid Electrode Material. Mater. Res. Express 2019,
6, 125550.
58. Xu, J.; Wang, Q.F.; Wang, X.W.; Xiang, Q.Y.; Liang, B.; Shen, G.Z. Flexible Asymmetric Supercapacitors Based upon Co9 S8
Nanorod//CO3 O4 @RuO2 Nanosheet Arrays on Carbon Cloth. ACS Nano 2013, 7, 5453–5462.
59. Manuraj, M.; Chacko, J.; Unni, K.N.N.; Rakhi, R.B. Heterostructured MoS2 -RuO2 Nanocomposite: A Promising Electrode Material
for Supercapacitors. J. Alloys Compd. 2020, 836, 155420. [CrossRef]
60. Park, S.; Shin, D.; Yeo, T.; Seo, B.; Hwang, H.; Lee, J.; Choi, W. Combustion-driven Synthesis Route for Tunable TiO2 /RuO2
Hybrid Composites as High-performance Electrode Materials for Supercapacitors. Chem. Eng. J. 2020, 384, 123269.
61. Patil, A.M.; An, X.W.; Li, S.S.; Yue, X.Y.; Du, X.; Yoshida, A.; Hao, X.G.; Abudula, A.; Guan, G.Q. Fabrication of Three-dimensionally
Heterostructured rGO/WO3 ·0.5H2 O@Cu2 S Electrodes for High-energy Solid-state Pouch-type Asymmetric Supercapacitor.
Chem. Eng. J. 2021, 403, 126411. [CrossRef]
62. Asim, S.; Javed, M.S.; Hussain, S.; Ran, M.; Iram, F.; Lv, D.D.; Hashim, M.; Jawaria, R.; Saleem, M.; Gul, N.; et al. RuO2 Nanorods
Decorated CNTs Grown Carbon Cloth as a Free Standing Electrode for Supercapacitor and Lithium Ion Batteries. Electrochimica
Acta 2019, 326, 135009.
63. Zhu, D.H.; Zhou, Q.J.; Liang, A.Q.; Zhou, W.Q.; Chang, Y.N.; Li, D.Q.; Wu, J.; Ye, G.; Xu, J.K.; Ren, Y. Two-step Preparation of
Carbon Nanotubes/RuO2 /polyindole Ternary Nanocomposites and Their Application as High-performance Supercapacitors.
Front. Mater. Sci. 2020, 14, 109–119.
64. Zhang, P.; Liu, X.F.; He, H.W.; Peng, Y.J.; Wu, Y.H. Engineering RuO2 on CuCo2 O4 /CuO Nanoneedles as Multifunctional
Electrodes for the Hybrid Supercapacitors and Water Oxidation Catalysis. J. Alloys Compd. 2020, 832, 154962. [CrossRef]
65. Liu, S.Y.; Wang, R.C.; Ma, C.X.; Yang, D.H.; Li, D.X.; Lewandowski, Z. Improvement of Electrochemical Performance via Enhanced
Reactive Oxygen Species Adsorption at ZnO–NiO@rGO Carbon Felt Cathodes in Photosynthetic Algal Microbial Fuel Cells.
Chem. Eng. J. 2020, 391, 123627.
66. Wu, Z.S.; Wang, D.W.; Ren, W.; Zhao, J.; Zhou, G.; Li, F.; Cheng, H.M. Anchoring Hydrous RuO2 on Graphene Sheets for
High-performance Electrochemical Capacitors. Adv. Funct. Mater. 2010, 20, 3595–3602.
Nanomaterials 2021, 11, 1248 24 of 28

67. Jeon, S.; Jeong, J.H.; Yoo, H.; Yu, H.K.; Kim, B.H.; Kim, M.H. RuO2 Nanorods on Electrospun Carbon Nanofibers for Supercapaci-
tors. ACS Appl. Nano Mater. 2020, 3, 3847–3858.
68. Kim, Y.T.; Tadai, K.; Mitani, T. Highly Dispersed Ruthenium Oxide Nanoparticles on Carboxylated Carbon Nanotubes for
Supercapacitor Electrode Materials. J. Mater. Chem. 2005, 15, 4914–4921.
69. Parker, S.F.; Robertson, S.J.; Imberti, S. Structure and Spectroscopy of the Supercapacitor Material Hydrous Ruthenium Oxide,
RuO2 ·xH2o, by Neutron Scattering. Mol. Phys. 2019, 117, 3417–3423. [CrossRef]
70. Hu, C.C.; Chen, W.C.; Chang, K.H. How to Achieve Maximum Utilization of Hydrous Ruthenium Oxide for Supercapacitors. J.
Electrochem. Soc. 2004, 151, A281–A290.
71. Yang, L.; Zhang, J.M.; Zhang, Y.S.; Zhao, Y.L.; Yin, H.; Hua, Q.S.; Yuan, J.S.; Tang, J. A Ternary Composite RuO2 @SWCNT/graphene
for High Performance Electrochemical Capacitors. Mater. Lett. 2020, 259, 126860.
72. Ji, S.-H.; Chodankar, N.R.; Kim, D.-H. Aqueous Asymmetric Supercapacitor Based on RuO2 -WO3 Electrodes. Electrochim. Acta
2019, 325, 134879.
73. Jiang, Q.; Kurra, N.; Alhabeb, M.; Gogotsi, Y.; Alshareef, H.N. All Pseudocapacitive MXene-RuO2 Asymmetric Supercapacitors.
Adv. Energy Mater. 2018, 8, 1703043. [CrossRef]
74. Zhang, C.; Xiao, J.; Qian, L.H.; Lv, X.L.; Yuan, S.L.; Wang, S.; Lei, P.X. Hierarchically Porous Co3 O4 /C Nanowire Arrays Derived
from a Metal–organic Framework for High Performance Supercapacitors and the Oxygen Evolution Reaction. J. Mater. Chem. A
2016, 4, 16516–16523. [CrossRef]
75. Adhikari, S.; Selvaraj, S.; Ji, S.H.; Kim, D.H. Encapsulation of Co3 O4 Nanocone Arrays via Ultrathin NiO for Superior Performance
Asymmetric Supercapacitors. Small 2020, 16, 2005414. [CrossRef]
76. Wang, X.L.; Fu, J.W.; Wang, Q.F.; Dong, Z.J.; Wang, X.L.; Hu, A.Y.; Wang, W.; Yang, S.B. Preparation and Electrochemical Properties
of Co3 O4 Supercapacitor Electrode Materials. Crystals 2020, 10, 720.
77. Liao, Q.Y.; Li, N.; Jin, S.X.; Yang, G.W.; Wang, C.X. All-solid-state Symmetric Supercapacitor Based on Co3 O4 Nanoparticles on
Vertically Aligned Graphene. ACS Nano 2015, 9, 5310–5317.
78. Wang, X.M.; Yin, S.M.; Jiang, J.; Xiao, H.P.; Li, X.H. A Tightly Packed Co3 O4 /C&S Composite for High-performance Electrochemi-
cal Supercapacitors from a Cobalt (III) Cluster-based Coordination Precursor. J. Solid State Chem. 2020, 288, 121435.
79. Lu, J.L.; Li, J.E.; Wan, J.; Han, X.Y.; Ji, P.Y.; Luo, S.; Gu, M.X.; Wei, D.P.; Hu, C.G. A Facile Strategy of In-situ Anchoring of Co3 O4
on N Doped Carbon Cloth for an Ultrahigh Electrochemical Performance. Nano Res. 2020, 1–8. [CrossRef]
80. Chatterjee, M.; Sain, S.; Roy, A.; Das, S.; Pradhan, S.W. Enhanced Electrochemical Properties of Co3 O4 with Morphological
Hierarchy for Energy Storage Application: A Comparative Study with Different Electrolytes. J. Phys. Chem. Solids 2021, 148,
109733. [CrossRef]
81. Cao, J.M.; Li, J.Z.; Zhou, L.; Xi, Y.L.; Cao, X.; Zhang, Y.M.; Han, W. Tunable Agglomeration of Co3 O4 Nanowires as the Growing
Core for In-situ Formation of Co2 NiO4 Assembled with Polyaniline-derived Carbonaceous Fibers as the High-performance
Asymmetric Supercapacitors. J. Alloys Compd. 2021, 853, 157210.
82. Deng, J.C.; Kang, L.T.; Bai, G.L.; Li, Y.; Li, P.Y.; Liu, X.G.; Yang, Y.Z.; Gao, F.; Liang, W. Solution Combustion Synthesis of Cobalt
Oxides (Co3 O4 and Co3 O4 /CoO) Nanoparticles as Supercapacitor Electrode Materials. Electrochim. Acta 2014, 132, 127–135.
83. Xiang, C.C.; Li, M.; Zhi, M.J.; Manivannan, A.; Wu, N.Q. A reduced Graphene Oxide/Co3 O4 Composite for Supercapacitor
Electrode. J. Power Sources 2013, 226, 65–70. [CrossRef]
84. Kumar, R.; Youssry, S.M.; Soe, H.M.; Abdel-Galeil, M.M.; Kawamura, G.; Matsuda, A. Honeycomb-like Open-edged Reduced-
graphene-oxide-enclosed Transition Metal Oxides (NiO/Co3 O4 ) as Improved Electrode Materials for High-performance Superca-
pacitor. J. Energy Storage 2020, 30, 101539. [CrossRef]
85. Ji, Z.Y.; Liu, K.; Li, N.; Zhang, H.Y.; Dai, W.Y.; Shen, X.P.; Zhu, G.X.; Kong, L.R.; Yuan, A.H. Nitrogen-doped Carbon Dots
Anchored NiO/Co3 O4 Ultrathin Nanosheets as Advanced Cathodes for Hybrid Supercapacitors. J. Colloid Interface Sci. 2020, 579,
282–289.
86. Yue, X.-M.; Liu, Z.-J.; Xiao, C.-C.; Ye, M.; Peng, C.; Gu, Z.-Y.; Zhu, J.-S.; Zhang, S.-Q. Synthesis of Co3 O4 /reduced Graphene Oxide
by One Step-hydrothermal and Calcination Method for High-performance Supercapacitors. Ionics 2021, 27, 339–349.
87. Zhao, Y.; Liu, H.Q.; Hu, P.F.; Song, J.R.; Xiao, L. Asymmetric Hybrid Capacitor Based on Co3 O4 Nanowire Electrode. Ionics 2020,
26, 6289–6295.
88. Priyadharsini, C.I.; Marimuthu, G.; Pazhanivel, T.; Anbarasan, P.M.; Aroulmoji, V.; Mohana, L. Sol–Gel Synthesis of Co3 O4
Nanoparticles as an Electrode Material for Supercapacitor Applications. J. Sol. Gel Sci. Technol. 2020, 96, 416–422. [CrossRef]
89. Guan, C.; Liu, X.M.; Ren, W.N.; Li, X.; Cheng, C.W.; Wang, J. Rational Design of Metal-organic Framework Derived Hollow
NiCo2 O4 Arrays for Flexible Supercapacitor and Electrocatalysis. Adv. Energy Mater. 2017, 7, 1602391.
90. Aadil, M.; Zulfiqar, S.; Shahid, M.; Haider, S.; Shakir, I.; Warsi, M.F. Binder Free Mesoporous Ag-doped Co3 O4 Nanosheets with
Outstanding Cyclic Stability and Rate Capability for Advanced Supercapacitor Applications. J. Alloys Compd. 2020, 844, 156062.
[CrossRef]
91. Yang, X.Y.; Xiang, C.L.; Zou, Y.J.; Liang, J.; Zhang, H.Z.; Yan, E.H.; Xu, F.; Hu, X.B.; Cheng, Q.; Sun, L.X. Low-temperature
Synthesis of Sea Urchin-like Co-Ni Oxide on Graphene Oxide for Supercapacitor Electrodes. J. Mater. Sci. Technol. 2020, 55,
223–230.
92. Wang, Z.W.; Zhao, K.M.; Lu, S.X.; Xu, W.G. Application of Flammulina-velutipes-like CeO2 /Co3 O4 /rGO in High-performance
Asymmetric Supercapacitors. Electrochim. Acta 2020, 353, 136599.
Nanomaterials 2021, 11, 1248 25 of 28

93. Wei, G.; Yan, L.Q.; Huang, H.F.; Yan, F.X.; Liang, X.Q.; Xu, S.K.; Lan, Z.Q.; Zhou, W.Z.; Guo, J. The Hetero-structured Nanoarray
Construction of Co3 O4 Nanowires Anchored on Nanoflakes as a High-performance Electrode for Supercapacitors. Appl. Surf. Sci.
2021, 538, 147932.
94. Cheng, L.; Zhang, Q.S.; Xu, M.; Zhai, Q.C.; Zhang, C.L. Two-for-one Strategy: Three-dimensional Porous Fe-doped Co3 O4 Cathode
and N-doped Carbon Anode Derived from a Single Bimetallic Metal-organic Framework for Enhanced Hybrid Supercapacitor. J.
Colloid Interface Sci. 2021, 583, 299–309. [CrossRef] [PubMed]
95. Gong, Y.J.; An, J.N.; Dai, H.B.; Chen, R.Y.; Yu, C.Y.; Chen, Q.; Zhou, J.Y.; Sun, G.Z.; Huang, W. Hierarchically Tubular Architectures
Composed of Vertical Carbon Nanosheets Embedded with Oxygen-vacancy Enriched Hollow Co3 O4 Nanoparticles for Improved
Energy Storage. Electrochim. Acta 2020, 356, 136843.
96. Saraf, M.; Rajak, R.; Mobin, S.M. MOF Derived High Surface Area Enabled Porous Co3 O4 Nanoparticles for Supercapacitors.
ChemistrySelect 2019, 4, 8142–8149. [CrossRef]
97. Bao, Y.X.; Deng, Y.; Wang, M.Z.; Xiao, Z.Y.; Wang, M.H.; Fu, Y.L.; Guo, Z.Y.; Yang, Y.; Wang, L. A Controllable Top-down Etching
and In-situ Xxidizing Strategy: Metal-organic Frameworks Derived α-Co/Ni(OH)2 @Co3 O4 Hollow Nanocages for Enhanced
Supercapacitor Performance. Appl. Surf. Sci. 2020, 504, 144395.
98. Wei, G.J.; Zhou, Z.; Zhao, X.X.; Zhang, W.Q.; An, C.H. Ultrathin Metal–organic Framework Nanosheet-derived Ultrathin Co3 O4
Nanomeshes with Robust Oxygen-evolving Performance and Asymmetric Supercapacitors. ACS Appl. Mater. Interf. 2018, 10,
23721–23730.
99. Dai, S.M.; Han, F.F.; Tang, J.; Tang, W.H. MOF-derived Co3 O4 Nanosheets Rich in Oxygen Vacancies for Efficient All-solid-state
Symmetric Supercapacitors. Electrochim. Acta 2019, 328, 135103.
100. Li, S.M.; Yang, K.; Ya, P.; Ma, K.R.; Zhang, Z.; Huang, Q. Three-dimensional Porous Carbon/Co3 O4 Composites Derived from
Graphene/Co-MOF for High Performance Supercapacitor Electrodes. Appl. Surf. Sci. 2020, 503, 144090.
101. Zhang, L.J.; Zhang, Y.Y.; Huang, S.L.; Yuan, Y.L.; Li, H.; Jin, Z.Y.; Wu, J.H.; Liao, Q.F.; Hu, L.; Lu, J.G.; et al. Co3 O4 /Ni-based
MOFs on Carbon Cloth for Flexible Alkaline Battery-supercapacitor Hybrid Devices and Near-infrared Photocatalytic Hydrogen
Evolution. Electrochim. Acta 2018, 281, 189–197. [CrossRef]
102. Han, D.D.; Wei, J.H.; Zhao, Y.; Shen, Y.; Pan, Y.F.; Wei, F.; Mao, L.C. Metal–organic Framework Derived Petal-like Co3 O4 @CoNi2 S4
Hybrid on Carbon Cloth with Enhanced Performance for Supercapacitors. Inorg. Chem. Front. 2020, 7, 1428–1436.
103. Huang, Y.Y.; Bao, S.; Lu, J.L. Flower-like MnO2 /polyaniline/hollow Mesoporous Silica as Electrode for High-performance
All-solid-state Supercapacitors. J. Alloys Compd. 2020, 845, 156192. [CrossRef]
104. Noh, J.; Yoon, C.M.; Kim, Y.K.; Jang, J. High Performance Asymmetric Supercapacitor Twisted from Carbon Fiber/MnO2 and
Carbon Fiber/MoO3 . Carbon 2017, 116, 470–478.
105. Raut, S.D.; Mane, H.R.; Shinde, N.M.; Lee, D.; Shaikh, S.F.; Kim, K.H.; Kim, H.-J.; Al-Enizi, A.M.; Mane, R.S. Electrochemically
Grown MnO2 Nanowires for Supercapacitor and Electrocatalysis Applications. New J. Chem. 2020, 44, 17864–17870.
106. Lu, W.; Li, Y.; Yang, M.; Jiang, X.; Zhang, Y.X.; Xing, Y. Construction of Hierarchical Mn2 O3 @MnO2 Core–Shell Nanofibers for
Enhanced Performance Supercapacitor Electrodes. ACS Appl. Energy Mater. 2020, 3, 8190–8197.
107. Rani, J.R.; Thangavel, R.; Kim, M.; Lee, Y.S.; Jang, J.H. Ultra-High Energy Density Hybrid Supercapacitors Using MnO2 /Reduced
Graphene Oxide Hybrid Nanoscrolls. Nanomaterials 2020, 10, 2049.
108. Liu, P.B.; Zhu, Y.D.; Gao, X.G.; Huang, Y.; Wang, Y.; Qin, S.Y.; Zhang, Y.Q. Rational Construction of Bowl-like MnO2 Nanosheets
with Excellent Electrochemical Performance for Supercapacitor Electrodes. Chem. Eng. J. 2018, 350, 79–88.
109. Wang, Q.F.; Ma, Y.; Liang, X.; Zhang, D.H.; Miao, M.H. Flexible Supercapacitors Based on Carbon Nanotube-MnO2 Nanocompos-
ite Film Electrode. Chem. Eng. J. 2019, 371, 145–153.
110. Wu, K.Q.; Ye, Z.G.; Ding, Y.; Zhu, Z.X.; Peng, X.Y.; Li, D.S.; Ma, G. Facile Co-deposition of the Carbon@MnO2 Heterostructure for
High-performance Flexible Supercapacitors. J. Power Sources 2020, 477, 229031.
111. Zhao, Y.F.; Ran, W.; He, J.; Huang, Y.Z.; Liu, Z.F.; Liu, W.; Tang, Y.F.; Zhang, L.; Gao, D.W.; Gao, F.M. High-performance
Asymmetric Supercapacitors Based on Multilayer MnO2 /graphene Oxide Nanoflakes and Hierarchical Porous Carbon with
Enhanced Cycling Stability. Small 2015, 11, 1310–1319.
112. Wang, L.; Ouyang, Y.; Jiao, X.Y.; Xia, X.F.; Lei, W.; Hao, Q.L. Polyaniline-assisted Growth of MnO2 Ultrathin Nanosheets on
Graphene and Porous Graphene for Asymmetric Supercapacitor with Enhanced Energy Density. Chem. Eng. J. 2018, 334, 1–9.
113. Bose, N.; Sundararajan, V.; Prasankumar, T.; Jose, S.P. α–MnO2 Coated Anion Intercalated Carbon Nanowires: A High Rate
Capability Electrode Material for Supercapacitors. Mater. Lett. 2020, 278, 128457.
114. Sui, Z.Y.; Chang, Z.S.; Xu, X.F.; Li, Y.L.; Zhu, X.M.; Zhao, C.; Chen, Q. Direct Growth of MnO2 on Highly Porous Nitrogen-doped
Carbon Nanowires for Asymmetric Supercapacitors. Diam. Relat. Mater. 2020, 108, 107988.
115. Cakici, M.; Reddy, K.R.; Alonso-Marroquin, F. Advanced Electrochemical Energy Storage Supercapacitors Based on the Flexible
Carbon Fiber Fabric-coated with Uniform Coral-like MnO2 Structured Electrodes. Chem. Eng. J. 2017, 309, 151–158. [CrossRef]
116. Zhao, P.; Yao, M.Q.; Ren, H.B.; Wang, N.; Komarneni, S. Nanocomposites of Hierarchical Ultrathin MnO2 Nanosheets/hollow
Carbon Nanofibers for High-performance Asymmetric Supercapacitors. Appl. Surf. Sci. 2019, 463, 931–938.
117. Cai, W.R.; Kankala, R.K.; Xiao, M.T.; Zhang, N.; Zhang, X.Q. Three-dimensional Hollow N-doped ZIF-8-derived Carbon@MnO2
Composites for Supercapacitors. Appl. Surf. Sci. 2020, 528, 146921.
Nanomaterials 2021, 11, 1248 26 of 28

118. Long, X.; Tian, L.; Zhang, L.; Wang, J.; Chen, Y.; Emin, A.; Wang, X.; Xie, W.L.; Liu, D.Q.; Fu, Y.J.; et al. Interconnected
δ-MnO2 Nanosheets Anchored on Activated Carbon Cloth as Flexible Electrode for High-performance Aqueous Asymmetric
Supercapacitors. J. Electroanal. Chem. 2020, 877, 114656.
119. Lei, R.; Gao, J.H.; Qi, L.F.; Ye, L.L.; Wang, C.; Le, Y.; Huang, Y.; Shi, X.G.; Ni, H.W. Construction of MnO2 Nanosheets@graphenated
Carbon Nanotube Networks Core-shell Heterostructure on 316L Stainless Steel as Binder-free Supercapacitor Electrodes. Int. J.
Hydrogen Energy 2020, 45, 28930–28939.
120. Bai, X.L.; Gao, Y.L.; Gao, Z.Y.; Ma, J.Y.; Tong, X.L.; Sun, H.B.; Wang, J.A. Supercapacitor Performance of 3D-graphene/MnO2 Foam
Synthesized via the Combination of Chemical Vapor Deposition with Hydrothermal Method. Appl. Phys. Lett. 2020, 117, 183901.
121. Xiong, C.Y.; Yang, Q.; Dang, W.H.; Li, M.R.; Li, B.B.; Su, J.; Liu, Y.; Zhao, W.; Duan, C.; Dai, L.; et al. Fabrication of Eco-friendly
Carbon Microtubes@nitrogen-doped Reduced Graphene Oxide Hybrid as an Excellent Carbonaceous Scaffold to Load MnO2
Nanowall (PANI nanorod) as Bifunctional Material for High-performance Supercapacitor and Oxygen Reduction Reaction
Catalyst. J. Power Sources 2020, 447, 227387.
122. Li, M.L.; Yu, J.; Wang, X.D.; Yang, Z.L. 3D Porous MnO2 @carbon Nanosheet Synthesized from Rambutan Peel for High-performing
Supercapacitor Electrodes Materials. Appl. Surf. Sci. 2020, 530, 147230.
123. Huang, R.; Zhou, R.H.; Wang, L.; Zhu, Y.M. Dandelion-like CoO/Co3 O4 /Carbon Composites as Anode Materials for a High-
Performance Lithium Ion Battery. ChemistrySelect 2020, 5, 12932–12939. [CrossRef]
124. Shen, H.J.; Kong, X.D.; Zhang, P.; Song, X.L.; Wang, H.; Zhang, Y. In-situ Hydrothermal Synthesis of δ-MnO2 /soybean Pod
Carbon and Its High Performance Application on Supercapacitor. J. Alloys Compd. 2021, 853, 157357.
125. Du, W.; Wang, X.N.; Zhan, J.; Sun, X.Q.; Kang, L.T.; Jiang, F.Y.; Zhang, X.Y.; Shao, Q.; Dong, M.Y.; Liu, H.; et al. Biological Cell
Template Synthesis of Nitrogen-doped Porous Hollow Carbon Spheres/MnO2 Composites for High-performance Asymmetric
Supercapacitors. Electrochim. Acta 2019, 296, 907–915.
126. Nie, G.D.; Luan, Y.X.; Kou, Z.K.; Jiang, J.M.; Zhang, Z.Y.; Yang, N.; Wang, J.; Long, Y.-Z. Fiber-in-tube and Particle-in-tube
Hierarchical Nanostructures Enable High Energy Density of MnO2 -based Asymmetric Supercapacitors. J. Colloid Interface Sci.
2021, 582, 543–551.
127. Yi, T.F.; Mei, J.; Guan, B.L.; Cui, P.; Luo, S.H.; Xie, Y.; Liu, Y.G. Construction of Spherical NiO@MnO2 with Core-shell Structure
Obtained by Depositing MnO2 Nanoparticles on NiO Nanosheets for High-performance Supercapacitor. Ceram. Int. 2020, 46,
421–429.
128. Liu, G.; Ma, L.; Liu, Q.M. The Preparation of Co3 O4 @MnO2 Hierarchical Nano-sheets for High-output Potential Supercapacitors.
Electrochim. Acta 2020, 364, 137265.
129. Zhao, Y.; He, J.F.; Dai, M.Z.; Zhao, D.P.; Wu, X.; Liu, B.D. Emerging CoMn-LDH@MnO2 Electrode Materials Assembled Using
Nanosheets for Flexible and Foldable Energy Storage Devices. J. Energy Chem. 2020, 45, 67–73.
130. Chen, X.Y.; Wang, X.Z.; Liu, F.J.; Song, X.J.; Cui, H.Z. Fabrication of NiO–ZnO-modified g-C3N4 Hierarchical Composites for
High-performance Supercapacitors. Vacuum 2020, 178, 109453.
131. Murali, S.; Dammala, P.K.; Rani, B.; Santhosh, R.; Jadhao, C.; Sahu, N.K. Polyol Mediated Synthesis of Anisotropic ZnO
Nanomaterials and Composite with rGO: Application towards Hybrid Supercapacitor. J. Alloys Compd. 2020, 844, 156149.
[CrossRef]
132. Ouyang, Y.; Xia, X.F.; Ye, H.T.; Wang, L.; Jiao, X.Y.; Lei, W.; Hao, Q.L. Three-dimensional Hierarchical Structure ZnO@C@NiO on
Carbon Cloth for Asymmetric Supercapacitor with Enhanced Cycle Stability. ACS Appl. Mater. Interfaces 2018, 10, 3549–3561.
[CrossRef]
133. Angelin, M.D.; Rajkumar, S.; Merlin, J.P.; Xavier, A.R.; Franklin, M.; Ravichandran, A.T. Electrochemical Investigation of Zr-doped
ZnO Nanostructured Electrode Material for High-performance Supercapacitor. Ionics 2020, 26, 5757–5772. [CrossRef]
134. Naeem, F.; Naeem, S.; Zhao, Z.; Shu, G.Q.; Zhang, J.; Mei, Y.F.; Huang, G.S. Atomic Layer Deposition Synthesized ZnO
Nanomembranes: A Facile Route towards Stable Supercapacitor Electrode for High Capacitance. J. Power Sources 2020, 451,
227740. [CrossRef]
135. Miah, M.; Mondal, T.K.; Ghosh, A.; Saha, S.K. Study of Highly Porous ZnO Nanospheres Embedded Reduced Graphene Oxide
for High Performance Supercapacitor Application. Electrochim. Acta 2020, 354, 136675.
136. Liu, J.; Xu, T.; Sun, X.W.; Bai, J.; Li, C.P. Preparation of Stable Composite Porous Nanofibers Carried SnOx -ZnO as a Flexible
Supercapacitor Material with Excellent Electrochemical and Cycling Performance. J. Alloys Compd. 2019, 807, 151652.
137. Kumar, R.; Youssry, S.M.; Abdel-Galeil, M.M.; Matsuda, A. One-pot Synthesis of Reduced Graphene Oxide Nanosheets Anchored
ZnO Nanoparticles via Microwave Approach for Electrochemical Performance as Supercapacitor Electrode. J. Mater. Sci.-Mater.
Electron. 2020, 31, 15456–15465. [CrossRef]
138. Chaudhary, S.; James, L.S.; Kumar, A.B.V.K.; Ramana, C.V.V.; Mishra, D.K.; Thomas, S.; Kim, D. Reduced Graphene Oxide/ZnO
Nanorods Nanocomposite: Structural, Electrical and Electrochemical Properties. J. Inorg. Organomet. Polym. Mater. 2019, 29,
2282–2290. [CrossRef]
139. Wang, W.; Jiao, S.S.; Cao, J.Y.; Naguib, H.E. Zinc Oxide/carbon Nanotube Nanocomposite for High-performance Flexible
Supercapacitor with Sensing Ability. Electrochim. Acta 2020, 350, 136353.
140. Arunpandiyan, S.; Bharathi, S.; Pandikumar, A.; Arasi, S.E.; Arivarasan, A. Structural Analysis and Redox Additive Electrolyte
Based Supercapacitor Performance of ZnO/CeO2 Nanocomposite. Mat. Sci. Semicon. Proc. 2020, 106, 104765. [CrossRef]
Nanomaterials 2021, 11, 1248 27 of 28

141. Shaheen, I.; Ahmad, K.S.; Zequine, C.; Gupta, R.K.; Thomas, A.G.; Malik, M.A. Green Synthesis of ZnO-Co3 O4 Nanocomposite
Using Facile Foliar Fuel and Investigation of Its Electrochemical Behaviour for Supercapacitors. New J. Chem. 2020, 44, 18281–18292.
[CrossRef]
142. Zhou, H.Y.; Fu, W.B.; Muhammad, M.; Xie, M.Z.; Xie, E.Q.; Han, W.H. Self-assembled Microspheres Composed of Porous
ZnO/CoO Nanosheets for Aqueous Hybrid Supercapacitors. J. Phys. D Appl. Phys. 2019, 52, 505501.
143. Chakraborty, S.; Raj, M.A.; Mary, N.L. Biocompatible Supercapacitor Electrodes Using Green Synthesised ZnO/Polymer
Nanocomposites for Efficient Energy Storage Applications. J. Energy Storage 2020, 28, 101275. [CrossRef]
144. Simon, R.; Chakraborty, S.; Konikkara, N.; Mary, N.L. Functionalized Polystyrene Maleic Anhydride Copolymer/ZnO Nanocom-
posites for Enhanced Electrochemical Performance. J. Appl. Polym. Sci. 2020, 137, 48945. [CrossRef]
145. He, X.J.; Li, X.J.; Ma, H.; Han, J.F.; Zhang, H.; Yu, C.; Xiao, N.; Qiu, J.S. ZnO Template Strategy for the Synthesis of 3D
Interconnected Graphene Nanocapsules from Coal Tar Pitch as Supercapacitor Electrode Materials. J. Power Sources 2017, 340,
183–191.
146. Chebrolu, V.T.; Balakrishnan, B.; Cho, I.; Bak, J.S.; Kim, H.J. A Unique Core-shell Structured ZnO/NiO Heterojunction to Improve
the Performance of Supercapacitors Produced Using a Chemical Bath Deposition Approach. Dalton Trans. 2020, 49, 14432–14444.
[CrossRef]
147. Di, S.; Gong, L.G.; Zhou, B.B. Precipitated Synthesis of Al2 O3 -ZnO Nanorod for High-Performance Symmetrical Supercapacitors.
Mater. Chemi. Phys. 2020, 253, 123289.
148. Liu, X.J.; Liu, H.; Sun, X.Z. Aligned ZnO nanorod@Ni–Co Layered Double Hydroxide Composite Nanosheet Arrays with a
Core–shell Structure as High-performance Supercapacitor Electrode Materials. CrystEngComm 2020, 22, 1593–1601.
149. Obodo, R.M.; Nwanya, A.C.; Arshad, M.; Iroegbu, C.; Ahmad, I.; Osuji, R.U.; Maaza, M.; Ezema, F.I. Conjugated NiO-ZnO/GO
Nanocomposite Powder for Applications in Supercapacitor Electrodes Material. Int. J. Energy Res. 2020, 44, 3192–3202. [CrossRef]
150. Asgar, H.; Deen, K.M.; Haider, W. Estimation of Electrochemical Charge Storage Capability of ZnO/CuO/reduced Graphene
Oxide Nanocomposites. Int. J. Energy Res. 2020, 44, 1580–1593. [CrossRef]
151. Obodo, R.M.; Asjad, M.; Nwanya, A.C.; Ahmad, I.; Zhao, T.K.; Ekwealor, A.B.C.; Ejikeme, P.M.; Maaza, M.; Ezema, F.I. Evaluation
of 8.0 MeV Carbon (C2+ ) Irradiation Effects on Hydrothermally Synthesized Co3 O4 -CuO-ZnO@GO Electrodes for Supercapacitor
Applications. Electroanaly 2020, 32, 2958–2968. [CrossRef]
152. Yao, D.; Wang, F.L.; Lei, W.; Hua, Y.; Xia, X.F.; Liu, J.P.; Hao, Q.L. Oxygen Vacancies Boosting Ultra-stability of Mesoporous
ZnO-CoO@N-doped Carbon Microspheres for Asymmetric Supercapacitors. Sci. China Mater. 2020, 63, 2013–2027.
153. Chen, H.C.; Lyu, Y.R.; Fang, A.; Lee, G.J.; Karuppasamy, L.; Wu, J.J.; Lin, C.K.; Ananda, S.; Chen, C.Y. The Design of ZnO Nanorod
Arrays Coated with MnOx for High Electrochemical Stability of a Pseudocapacitor Electrode. Nanomaterials 2020, 10, 475.
154. Sun, L.; Zhang, Y.X.; Si, H.C.; Shi, Y.; Sun, C.; Zhang, Y.H. Porous Mo-C Coverage on ZnO Rods for Enhanced Supercapacitive
Performance. Dalton Trans. 2020, 49, 5134–5142.
155. Mohamed, I.M.A.; Yasin, A.S.; Liu, C.K. Synthesis, Surface Characterization and Electrochemical Performance of Zno@activated
Carbon as a Supercapacitor Electrode Material in Acidic and Alkaline Electrolytes. Ceram. Int. 2020, 46, 3912–3920. [CrossRef]
156. He, D.; Wan, J.N.; Liu, G.L.; Suo, H.; Zhao, C. Design and Construction of Hierarchical α-Co(OH)2 -coated Ultra-thin ZnO Flower
Nanostructures on Nickel Foam for High Performance Supercapacitors. J. Alloys Compd. 2020, 838, 155556.
157. Ding, S.X.; Li, X.Y.; Jiang, X.L.; Hu, Q.; Yan, Y.Q.; Zheng, Q.J. Core-shell Nanostructured ZnO@CoS Arrays as Advanced Electrode
Materials for High-performance Supercapacitors. Electrochim. Acta 2020, 354, 136711.
158. Li, Z.L.; Sui, Y.W.; Qi, J.Q.; Wei, F.X.; He, Y.Z.; Meng, Q.K.; Ren, Y.J.; Zhang, X.P.; Zhan, Z.Z.; Sun, Z. 3D Core-shell Pistil-like
MnCo2 O4.5 /polyaniline Nanocomposites as High Performance Supercapacitor Electrodes. Compos. Interface 2020, 27, 631–644.
159. Wang, H.Z.; Shen, C.; Liu, J.; Zhang, W.G.; Yao, S.W. Three-dimensional MnCo2 O4 /graphene Composites for Supercapacitor with
Promising Electrochemical Properties. J. Alloys Compd. 2019, 792, 122–129.
160. Shanmugavadivel, M.; Dhayabaran, V.V.; Subramanian, M. Fabrication of High Energy and High Power Density Supercapacitor
Based on MnCo2 O4 Nanomaterial. J. Phys. Chem. Solids 2019, 133, 15–20. [CrossRef]
161. Maile, N.C.; Shinde, S.K.; Patil, R.T.; Fulari, A.V.; Kolim, R.R.; Kim, D.-Y.; Lee, D.S.; Fulari, V.J. Structural and Morphological
Changes in Binder-free MnCo2 O4 Electrodes for Supercapacitor Applications: Effect of Deposition Parameters. J. Mater. Sci.
Mater. Electron. 2019, 30, 3729–3743. [CrossRef]
162. Wang, N.; Sun, B.L.; Zhao, P.; Yao, M.Q.; Hu, W.C.; Komarneni, S. Electrodeposition Preparation of NiCo2 O4 Mesoporous Film on
Ultrafine Nickel Wire for Flexible Asymmetric Supercapacitors. Chem. Eng. J. 2018, 345, 31–38.
163. Wang, X.; Xu, L.; Song, K.; Yane, R.; Jia, L.H.; Guo, X.F.; Jing, X.Y.; Wang, J. Synthesis of MnCo2 O4 @MnCo2 S4 Core/shell
Micro-nanostructures on Ni Foam for High Performance Asymmetric Supercapacitors. Colloid Surf. A 2019, 570, 73–80.
164. Xu, K.B.; Li, W.Y.; Liu, Q.; Li, B.; Liu, X.J.; An, L.; Chen, Z.G.; Zou, R.J.; Hu, J.Q. Hierarchical Mesoporous NiCo2 O4 @MnO2
Core–shell Nanowire Arrays on Nickel Foam for Aqueous Asymmetric Supercapacitors. J. Mater. Chem. A 2014, 2, 4795–4802.
165. Zhu, D.; Sun, X.; Yu, J.; Liu, Q.; Liu, J.Y.; Chen, R.R.; Zhang, H.S.; Li, R.M.; Yu, J.; Wang, J. Rationally Designed CuCo2 O4 @Ni(OH)2
with 3D Hierarchical Core-shell Structure for Flexible Energy Storage. J. Colloid Interface Sci. 2019, 557, 76–83.
166. Zhao, D.P.; Dai, M.Z.; Liu, H.Q.; Xiao, L.; Wu, X.; Xia, H. Constructing High Performance Hybrid Battery and Electrocatalyst by
Heterostructured NiCo2 O4 @NiWS Nanosheets. Cryst. Growth Des. 2019, 19, 1921–1929.
167. Liu, Q.; Hong, X.D.; Zhang, X.; Wang, W.; Guo, W.X.; Liu, X.Y.; Ye, M.D. Hierarchically Structured Co9 S8 @NiCo2 O4 Nanobrushes
for High-performance Flexible Asymmetric Supercapacitors. Chem. Eng. J. 2019, 356, 985–993.
Nanomaterials 2021, 11, 1248 28 of 28

168. Xu, X.W.; Liu, Y.; Dong, P.; Ajayan, P.M.; Shen, J.F.; Ye, M.X. Mesostructured CuCo2 S4 /CuCo2 O4 Nanoflowers as Advanced
Electrodes for Asymmetric Supercapacitors. J. Power Sources 2018, 400, 96–103.
169. Liu, H.Y.; Guo, Z.X.; Wang, S.B.; Xun, X.C.; Chen, D.; Lian, J.S. Reduced Core-shell Structured MnCo2 O4 @MnO2 Nanosheet
Arrays with Oxygen Vacancies Grown on Ni Foam for Enhanced-performance Supercapacitors. J. Alloys Compd. 2020, 846, 156504.
170. Feng, Y.M.; Liu, W.F.; Wang, Y.; Gao, W.N.; Li, J.T.; Liu, K.L.; Wang, X.P.; Jiang, J. Oxygen Vacancies Enhance Supercapacitive
Performance of CuCo2 O4 in High-energy-density Asymmetric Supercapacitors. J. Power Sources 2020, 458, 228005.
171. Yan, D.; Wang, W.; Luo, X.; Chen, C.; Zeng, Y.; Zhu, Z.H. NiCo2 O4 with Oxygen Vacancies as Better Performance Electrode
Material for Supercapacitor. Chem. Eng. J. 2018, 334, 864–872.
172. Chen, T.; Shi, R.; Zhang, Y.Y.; Wang, Z.H. A MnCo2 O4 @NiMoO4 Core-Shell Composite Supported on Nickel Foam as a
Supercapacitor Electrode for Energy Storage. ChemPlusChem 2019, 84, 69–77.
173. Gao, Y.F.; Xia, Y.C.; Wan, H.J.; Xu, X.; Jiang, S. Enhanced Cycle Performance of Hierarchical Porous Sphere MnCo2 O4 for
Asymmetric Supercapacitors. Electrochim. Acta 2019, 301, 294–303.
174. Zhao, Y.H.; Dong, H.X.; He, X.Y.; Yu, J.; Chen, R.R.; Liu, Q.; Liu, J.Y.; Zhang, H.S.; Yu, J.; Wang, J. Carbon Cloth Modified
with Metal-Organic Framework Derived CC@CoMoO4 -Co(OH)2 Nanosheets Array as a Flexible Energy-Storage Material.
ChemElectroChem 2019, 6, 3355–3366.
175. Daneshvar, S.; Arvand, M. In-situ Growth of Hierarchical Ni-Co LDH/CoMoO4 Nanosheets Arrays on Ni Foam for Pseudocapac-
itors with Robust Cycle Stability. J. Alloys Compd. 2020, 815, 152421. [CrossRef]
176. Liu, H.Q.; Zhao, D.P.; Liu, Y.; Hu, P.F.; Wu, X.; Xia, H. Boosting Energy Storage and Electrocatalytic Performances by Synergizing
CoMoO4 @MoZn22 Core-shell Structures. Chem. Eng. J. 2019, 373, 485–492.
177. Chen, H.; Hu, H.M.; Han, F.; Liu, J.D.; Zhang, Y.R.; Zheng, Y.H. CoMoO4 /bamboo Charcoal Hybrid Material for High-energy-
density and High Cycling Stability Supercapacitors. Dalton Trans. 2020, 49, 10799–10807.
178. Zhou, E.M.; Tian, L.L.; Cheng, Z.F.; Fu, C.P. Design of NiO Flakes@CoMoO4 Nanosheets Core-Shell Architecture on Ni Foam for
High-Performance Supercapacitors. Nanoscale Res. Lett. 2019, 14, 211.
179. Lv, Y.M.; Liu, A.F.; Che, H.W.; Mu, J.B.; Guo, Z.C.; Zhang, X.L.; Bai, Y.M.; Zhang, Z.X.; Wang, G.S.; Pei, Z.Z. Three-dimensional
Interconnected MnCo2 O4 nanosheets@MnMoO4 Nanosheets Core-shell Nanoarrays on Ni foam for High-performance Superca-
pacitors. Chem. Eng. J. 2018, 336, 64–73.
180. Wan, L.; Liu, J.X.; Li, X.; Zhang, Y.; Chen, J.; Du, C.; Xie, M.J. Fabrication of Core-shell NiMoO4 @MoS2 Nanorods for High-
performance Asymmetric Hybrid Supercapacitors. Int. J. Hydrogen Energy 2020, 45, 4521–4533.
181. Xuan, H.C.; Li, H.S.; Yang, J.; Liang, X.H.; Xie, Z.G.; Han, P.D.; Wu, Y.C. Rational Design of Hierarchical Core-shell Structured
CoMoO4 @CoS Composites on Reduced Graphene Oxide for Supercapacitors with Enhanced Electrochemical Performance. Int. J.
Hydrogen Energy 2020, 45, 6024–6035.
182. Hussain, I.; Ali, A.; Lamiel, C.; Mohamed, S.G.; Sahoo, S.; Shim, J.J. A 3D Walking Palm-like Core–shell CoMoO4 @NiCo2 S4 @Nickel
Foam Composite for High-performance Supercapacitors. Dalton Trans. 2019, 48, 3853–3861. [CrossRef] [PubMed]
183. Zhang, X.Y.; Fu, Q.G.; Huang, H.M.; Wei, L.; Guo, X. Silver-quantum-dot-modified MoO3 and MnO2 paper-like Freestanding
Films for Flexible solid-state Asymmetric Supercapacitors. Small 2019, 15, 1805235. [CrossRef]
184. Shen, T.; Yang, L.P.; Pam, M.E.; Shi, Y.M.; Yang, H.Y. Quantum Dot-carbonaceous Nanohybrid Composites: Preparation and
Application in Electrochemical Energy storage. J. Mater. Chem. A 2020, 8, 22488–22506. [CrossRef]
185. Manikandan, A.; Chen, Y.Z.; Shen, C.C.; Sher, C.W.; Kuo, H.C.; Chueh, Y.L. A Critical Review on Two-dimensional Quantum Dots
(2D QDs): From Synthesis toward Applications in Energy and Optoelectronics. Prog. Quant. Electron. 2019, 68, 100226. [CrossRef]
186. Xu, Q.; Cai, W.; Li, W.; Sreeprasad, T.S.; He, Z.Y.; Ong, W.-J.; Li, N. Two-dimensional Quantum Dots: Fundamentals, Photolumi-
nescence Mechanism and their Energy and Environmental Applications. Mater. Today Energy 2018, 10, 222–240. [CrossRef]
187. Ji, Z.Y.; Ma, D.W.; Dai, W.Y.; Liu, K.; Shen, X.P.; Zhu, G.X.; Nie, Y.J.; Pasang, D.; Yuan, A.H. Anchoring Nitrogen-doped Carbon
Quantum Dots on Nickel Carbonate Hydroxide Nanosheets for Hybrid Supercapacitor Applications. J. Colloid Interface Sci. 2021,
590, 614–621. [CrossRef]
188. Duan, H.Y.; Wang, T.; Wu, X.Y.; Su, Z.Y.; Zhuang, J.; Liu, S.L.; Zhu, R.M.; Chen, C.Y.; Pang, H. CeO2 Quantum Dots Doped
Ni-Co Hydroxide Nanosheets for Ultrahigh Energy Density Asymmetric Supercapacitors. Chin. Chem. Lett. 2020, 31, 2330–2332.
[CrossRef]
189. Samuei, S.; Rezvani, Z.; Shomali, A.; Ulker, E.; Karadas, F. Preparation and Capacitance Properties of Graphene Quantum
Dot/NiFe-Layered Double-Hydroxide Nanocomposite. Eur. J. Inorg. Chem. 2021, 2021, 258–266. [CrossRef]
190. Zhu, Y.R.; Wu, Z.B.; Jing, M.J.; Hou, H.S.; Yang, Y.C.; Zhang, Y.; Yang, X.M.; Song, W.X.; Jia, X.N.; Ji, X.B. Porous NiCo2 O4 Spheres
Tuned through Carbon Quantum Dots Utilised as Advanced Materials for an Asymmetric Supercapacitor. J. Mater. Chem. A 2015,
3, 866–877.
191. Zhang, M.W.; Liu, W.W.; Liang, R.L.; Tjandra, R.; Yu, A.P. Graphene Quantum Dot Induced Tunable Growth of Nanostructured
MnCo2 O4.5 Composites for High-performance Supercapacitors. Sustain. Energy Fuels 2019, 3, 2499–2508. [CrossRef]
192. Zhang, X.Y.; Li, Z.; Yu, Z.Y.; Wei, L.; Guo, X. Mesoporous NiMoO4 Microspheres Decorated by Ag Quantum Dots as Cathode
Material for Asymmetric Supercapacitors: Enhanced Interfacial Conductivity and Capacitive Storage. Appl. Surf. Sci. 2020, 505,
144513. [CrossRef]

You might also like