Nanomaterials 11 01248
Nanomaterials 11 01248
Nanomaterials 11 01248
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
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
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.
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 .
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.
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.
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].
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.
2.4. 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 .
Table 1. The electrochemical performance of representative binary transition metal oxides (TMOs) electrode materials.
SWCNT, single-walled carbon nanotube; CVD, chemical vapor deposition.
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
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).
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.
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
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.
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