J Nanopart Res (2020) 22:367

https://doi.org/10.1007/s11051-020-05103-2

REVIEW

Metal oxides nanostructure-based electrode materials

for supercapacitor application
Mahendra Singh Yadav

Received: 8 May 2020 / Accepted: 24 November 2020

# Springer Nature B.V. 2020

Abstract Recently, electrochemical supercapacitor has
drawn more attention because of its superior electro-
chemical properties including larger life cycle, higher
specific capacitance, and larger specific power. The
supercapacitor is also able to fill the energy and power
gap between battery and traditional capacitor. The
supercapacitor has been considered suitable as an ener-
gy storage device for next-generation higher power
applications. The ultracapacitor design using
nanostructure-based electrode materials has provided
better electrochemical properties. This review article
gives a brief overview about the latest research trends
on metal oxides nanostructure-based electrode materials
for ultracapacitors and, in addition, highlights the
nanomaterial effect on the electrode properties of
Highlights
• Development of alternative energy sources such as renewable
energy.
• Energy storage devices have received more attention and attained
a crucial role in storage of the maximum energy.
• Transition metal oxides are used as electrode materials for
pseudocapacitors.
• Nanomaterials are promising candidates for energy storage
device application due to their excellent physical and chemical
properties.
• Fabrication of supercapacitor electrodes.
M. S. Yadav (*)
Department of Electronics and Communication Engineering,
Jaypee University of Engineering and Technology, Guna, Madhya
Pradesh 473226, India
e-mail: mahsinyad18@gmail.com
ultracapacitors, which gives guidance in developing
high-performance next-generation ultracapacitors.
Keywords Nanoparticles . Nanocomposite . Metal
oxides . Nanostructure . Electrode materials .
Supercapacitor
Introduction
Historically, the first supercapacitor or ultracapacitor
was developed by General Electric in 1957. In this case,
energy has been stored by a double-layer mechanism in
the pores of carbon resulting in a very high specific
capacitance (US patent 2800616 n.d.). As another mile-
stone in its development, in 1966, a supercapacitor was
invented by the Standard Oil Company, Cleveland
(SOHIO), in which energy has been stored at a
double-layer interface (US patent 3288641 n.d.). In this
supercapacitor, a nonaqueous electrolyte has been used.
Followed by demonstration of pseudocapacitors and
development of materials for supercapacitor electrodes
and electrolyte during the last 3 decades, the perfor-
mance of supercapacitors has been improved to the
extent that it has been projected as an important element
in energy storage devices and energy delivery system
(US patent 2800616 n.d.; US patent 3288641 n.d.).
The present-day world is encountering crucial global
problems such as sharp increases in the price of oil,
natural gas, uranium, and coal, insufficient energy,
availability of potable water, declining hydrocarbons
and non-renewable sources, and global warming. To
 367 Page 2 of 18
meet the challenges, all countries have shifted focus on
the development of alternative energy sources such as
renewable energy, which are clean, green, safe, econom-
ical, and sustainable. Renewable energy sources are
continuously refilled naturally by the sun, wind, water,
heat emitted by earth, and plants (Simon and Gogotsi
2008).
Renewable energy technology converts these fuels
into a usable form of energy such as electricity, heat,
chemical, or mechanical power. Renewable and sustain-
able energy sources are also helpful in reducing serious
problems like global warming and prolonging the res-
ervoirs of non-renewable energy sources. Energy pro-
duction using solar, wind, tidal, and biomass has been
considered a good alternative with its few limitations
such as accuracy, less efficiency, and higher cost. In the
last decade, the generation of energy using renewable
energy sources has been increased. However, their con-
tribution to global energy production is very low, i.e.,
1%. The produced energy from the renewable energy
sources can be directly supplied to the grid for different
applications such as lighting, cooling to warming, and
transportation to communication.
In the vacations, unavailability of renewable sources
can lead to interruption of energy supply which can be
managed by stored electrical energy. In such circum-
stances, efficient energy storage devices are helpful to
meet the energy requirement. However, there are not
enough efficient storage devices that can store huge
amounts of energy and deliver when it is required. In
these conditions, energy storage devices like batteries
and supercapacitors have received more attention and
attained a critical role in storage of the maximum ener-
gy. The existing devices with new methods, designs,
and new materials do not fulfill the requirements of
energy storage up to the desirable level. Therefore, it is
necessary to think about improving the design and
methods and developing materials in order to up the
energy storage, which should be user friendly, less
hazardous, lightweight, economical, and highly effi-
cient. A supercapacitor electrochemical energy storage
device possesses many merits such as direct energy
conversion, nonexistence of moving parts, portability,
and suitable for mass production. However, the envi-
ronmental friendliness, portability, efficiency, econom-
ical, and lightweight are still serious problems in the
development of supercapacitors.
Electrical energy storage is used in several applica-
tions like electrical hybrid vehicles, standby power
J Nanopart Res (2020) 22:367
systems, and telecommunication devices such as mobile
phones, pagers, remote communication, and walkie-
talkies. It fulfills the requirement of the particular de-
vices that needs a higher amount of energy storage and
higher power. Basically, electrical energy is stored using
two different processes, namely, an electrostatic process
in which the negative and the positive electric charges
are separated on plates of capacitor and indirectly in
batteries in which chemical energy is stored in the form
of electrical energy.
Energy storage devices
Electrochemical energy storage devices are mainly clas-
sified into two major classes according to the basic
understanding of the fundamental properties, namely
batteries and capacitor or supercapacitor, which will be
separately discussed in the next section.
Batteries
A battery is an energy storage device that consists of one
or more electrochemical cells and which converts chem-
ical energy to electrical energy using chemical
reduction-oxidation reaction (Linden and Reddy
2001). Each cell has positive and negative electrode
materials and an electrolyte, which helps in the diffusion
of ions to move between the electrodes and the terminals
that permit the flow of energy in an external circuit
which performs the work. Additionally, batteries are
classified into two classes according to its chemical
properties, namely primary battery and secondary
battery.
Primary batteries
These are the basic class of batteries, used once and then
discarded. In these batteries, the electrode materials are
irreversibly charged in discharge process. Primary bat-
teries are not rechargeable. A few of such commercially
available primary batteries are Zn/Carbon, Mg/MnO2,
and Zn/MnO2.
Secondary batteries
This is the class of batteries which are rechargeable, and
they are used repetitively. The reversible change in the
composition of the electrode material has been utilized
J Nanopart Res (2020) 22:367
to develop the rechargeable battery. These active mate-
rials help out in restoring the charges via a reverse
current, which reverses the chemical reactions that take
place through the charging-discharging process. The
commercially available secondary batteries are lead ac-
id, Ni/MH, Ni/Cd, Li-ion, etc.
Capacitors
Traditional capacitors consist of two conducting plates
or electrodes separated with an insulating dielectric me-
dium. It is a device that stores electric energy and given
by the following mathematical relations:
A tive surface area electrode and thin electrolytic dielectric
C¼ε ð1Þ
d medium to obtain the capacitance with several orders of
where C is the capacitance, ε is the dielectric constant of
a medium, A is the area, and d is the distance between
the parallel electrodes.
When a voltage is applied to a capacitor, an opposite
charge develops on the surface of the electrodes. Capac-
itors store energy by charge separation. The charges are
retained with the help of dielectric. Capacitance (C) is
defined as the ratio of stored charge (Q) to the applied
voltage (V). It is given by the following mathematical
expression:
Q
C¼ ð2Þ
V er very high peak power. If compared with other energy
The conventional or traditional capacitor stores the
energy in a thin layer of dielectric medium supported
with metal plates that act as the electrode or terminal for
the device. The energy stored in a capacitor is expressed
by the following mathematical relations:
1
E¼ CV 2 ð3Þ
2 In EDLCs and pseudocapacitors, charge is stored
where C is the capacitance in farads and V is the applied
voltage between the terminal plates.
In capacitors, if the medium is a pure dielectric, then
it is known as the electrostatic capacitor, while if the
medium is an electrolytic (solid or liquid), then the
capacitor is referred to as the electrochemical capacitor.
Capacitor characteristics depend on the properties of
dielectric medium or materials. Traditional dielectric
capacitors can accumulate and deliver electric charges
rapidly and operate in pulse mode with pulse width scale
in nanoseconds. Although its charge storage ability is
poor in comparison to that of batteries, it offers various
Page 3 of 18 367
other advantages. Batteries have been studied widely in
the past couple of decades, due to its larger storage
capacity of energy in a small volume and weight. But
the shelf and the cycle life are serious issues with most
types of batteries. Degradation occurs if secondary re-
chargeable batteries are left unused, and they become
unusable because of self-discharge and corrosion ef-
fects. In the case of batteries, storage of electrochemical
energy involves irreversibility in chemical electrode
reagents. These issues are relatively manageable in
supercapacitors; hence, supercapacitors are of great in-
terest. This area matured extensively in the last decades.
Supercapacitors are also well known as electrochem-
ical capacitors or ultracapacitors, which used high effec-
magnitude greater than traditional capacitors (Conway
1999; Burke 2000; Kotz and Carlen 2000; Aricò and
Bruce 2005; Chu and Braatz 2002). Ultracapacitors or
electrochemical capacitors are also capable of achieving
higher energy density but yet maintain the higher power
density of traditional capacitors. These factors are ana-
lyzed using a Ragone plot which is used to compare the
energy density and power density of various energy
storage devices. The typical Ragone plot is shown in
Fig. 1. As far as applications are concerned, the larger
domain of consumer electronics is where these devices
are useful. Emphasizing the supercapacitor, it can deliv-
storage devices, a supercapacitor outperforms its
counterparts.
Based on the recent research and development trends,
electrochemical capacitors or supercapacitors are classi-
fied into three different classes, namely (i) electrochem-
ical double-layer capacitor (EDLC), (ii)
pseudocapacitor, and (iii) hybrid capacitor.
using non-faradaic and faradaic reactions and the com-
bination of both these processes for storing charges in
the case of hybrid supercapacitors. In the case of a non-
faradaic process, charge storage involves no chemical
mechanism, rather it is distributed on the surface. How-
ever, the faradaic process involves oxidation-reduction
reactions used for transferring charge between electro-
lyte and electrode. A graphical classification of the
different types and subtypes of supercapacitors is shown
in Fig. 2. This segment will give a brief overview of the
three different types of supercapacitors and subtypes,
via electrode material.
 367 Page 4 of 18
Fig. 1 Ragone plot showing the
power density against energy
density for various electrical
energy storage systems
Electrochemical double-layer capacitors
EDLCs are fabricated using two carbon-based elec-
trodes and separator. Figure 3 gives a schematic of
EDLCS. Similar to conventional capacitors, the electro-
chemical double-layer capacitor store charges non-
faradaically or electrostatically. In electrochemical
double-layer capacitor, there is no transport of charge
between electrolyte and electrode. It uses an electro-
chemical double layer of the charges for storing energy.
When potential is supplied, charges are accumulated on
the surface of electrodes. Following the usual attractive-
ness of unlike charges, the ions are diffused from the
liquid electrolyte solution into the pores of the active
electrode materials of opposite charge. But, the elec-
trodes are designed to stop the recombination of the
ions.
Therefore, a double layer of charges is built up at
each electrode. These double layers are associated with
an increase in surface area and decrease in the distance
between electrodes. It allows EDLCs to obtain higher
energy densities in comparison with conventional ca-
pacitors (Conway 1999; Burke 2000; Kotz and Carlen
2000). Due to the no transfer of charges between elec-
trode and electrolyte, there are no chemical changes
related with the non-faradaic process. Because of this,
charge storage in EDLCs is highly reversible. It allows
EDLCs to get very high cycling stability. Generally,
EDLCs operate with stable performance relating to the
electrochemical characteristics for a larger number of
charge-discharge cycles up to 10 6 cycles, while
J Nanopart Res (2020) 22:367
electrochemical batteries are generally limited to 103
cycles. Due to its cycling stability, EDLCs are suitable
for an application where user service is not possible, for
example mountain and deep sea environments (Conway
1999; Burke 2000; Kotz and Carlen 2000).
The electrochemical performance of EDLCs can be
altered by changing the nature of the electrolytes. Or-
ganic electrolyte or aqueous electrolyte can also be
employed in EDLCs. Generally, the aqueous electro-
lytes H2SO4, KOH, NaOH, Na2SO4, etc., have lower
ESR value and lower minimum pore size requirement in
comparison to organic electrolyte, for example acetoni-
trile based. In addition, aqueous electrolytes also have
low breakdown voltage.
Different types of carbon materials are used to store
charges in EDLCs. Some of the known electrode mate-
rials are activated carbons, carbon aerogels, and carbon
nanotubes (Simon and Burke 2008). Activated carbon is
also known as activated coal, activated charcoal, or
carbon activates. Activated carbon is economical, and
has a highly porous structure and a higher specific
surface area for the adsorption or chemical reactions
compared to other carbon-based materials. It is mostly
used as electrode materials in EDLCs. Activated char-
coal uses a complex porous structure composed of
different-sized micropores, mesopores, and macropores
resulting in a higher surface area. Carbon aerogels are
also used as electrode materials in EDLCs. The carbon
aerogels are made from a continuous network of
conducting carbon nanoparticles with distributed
mesopores, or it is also said that they consist of the
J Nanopart Res (2020) 22:367
Fig. 2 Taxonomy of
supercapacitors
nanoparticles. The covalent bonds are believed to form
between nanoparticles that provide very high porosity
(Maldonado-Hodar et al. 2000). Because of the contin-
uous structure and its chemical bonding to the current
collector, it does not require any additional adhesive
Fig. 3 Construction of electrochemical double-layer capacitor
Page 5 of 18 367
binding agents. Therefore, binder-less electrode carbon
aerogels lower the equivalent series resistance (ESR)
value than activated carbon (Aricò and Bruce 2005;
Frackowiak and Beguin 2001; Wang and Zhang
2001). The lower value of ESR gives higher power. It
 367 Page 6 of 18
is the main area of interest in carbon aerogel-based
electrodes for supercapacitor applications.
In recent times, carbon nanotubes (CNT) have
attracted more attention as electrode materials for
EDLCs (Frackowiak and Beguin 2001; An and Jeon
2002; Frackowiak and Beguin 2002; Pico and Rojo
2004; Du and Yeh 2005; Niu and Sichel 1997). In the
case of carbon nanotube-based electrode, the surface
area is used more efficiently to obtain a higher value
of capacitance compared to activated carbon electrode
for supercapacitors, though carbon nanotube-based
electrodes have a moderate surface area in comparison
to activated carbon-based electrodes (Frackowiak and
Beguin 2001; Frackowiak and Metenier 2000). The
carbon nanotube-based electrodes also have a lower
ESR value compared to activated carbon (Niu and
Sichel 1997; An and Kim 2001a, b). The double-layer
capacitance (Cdl) is determined with the help of the
following mathematical equation:
Q
C dl ¼ ð4Þ
V
where Q is the total charge on electrode surface and V
is the applied electrode potential. The amount of elec-
trical energy (E) is calculated by the following equation:
1
E¼ C dl V 2 ð5Þ
2
The amount of energy in EDLCs can be increased in
two different ways, namely increasing the applied po-
tential window (which depends on the electrolyte solu-
tion) and increasing the electrostatic charge related with
capacitance of the electroactive materials that are used
as electrode materials in the fabrication of EDLCs.
EDLCs are operated at different operating voltages of
about 1.0 V for aqueous and 3 to 3.5 V for non-aqueous
electrolyte solutions.
Pseudocapacitors
Pseudocapacitors store charge via the faradaic process
by the charge transfer between electrolyte and electrode
materials. Faradaic or pseudocapacitance occurs from
the reversible redox reactions on the surface or in the
near surface of active electrode materials. The interac-
tion between the electrode materials and the electrolyte
materials includes the faradaic reaction. It is also usually
described as charge transfer reactions (Conway 1999;
J Nanopart Res (2020) 22:367
Bard and Faulkner 2000; Zhang et al. 2012). The charge
transferred throughout faradaic reactions is voltage de-
pendent. The redox or pseudocapacitance is related
through the faradaic reaction which is also voltage de-
pendent. The diffusion of charges occurs in the faradaic
reaction resulting in a voltage-dependent capacitive be-
havior (Bard and Faulkner 2000; Zhang et al. 2012).
Pseudocapacitors or redox capacitors are achieved via
electrosorption, oxidation-reduction reactions, and in-
tercalation processes (Conway and Birss 1997). There
are three types of electrochemical processes that are
applied in the development of pseudocapacitors: these
are surface adsorption of ions from electrolytes, redox
reactions involving the ions from electrolytes, and dop-
ing and undoping of active ions (conducting polymer
materials) into electrode materials (Conway 1999). In
the case of layered structure materials, doping and
undoping mechanism is described as intercalation and
de-intercalation (Conway 1999). The first two processes
are primarily surface mechanism; they are mostly sur-
face area dependent. Intercalation and de-intercalation is
a bulk process which also takes place in conducting
polymer materials as well.
However, the electrode materials give a relatively
higher surface area, due to their micropores. It allows
distribution of the ions to and from the electrodes in a
cell; the specific capacitance of the materials is less
dependent on its surface area. The electrode must have
high electronic conductivity in all the cases in order to
distribute and collect the electron current. The faradaic
process can allow pseudocapacitors to obtain higher
capacitance and energy densities compared to EDLCs
(Park et al. 2010). Electrode materials are utilized to
store the charges in pseudocapacitors. In general, elec-
trode materials in the case of pseudocapacitors are
conducting polymers or transition metal oxides.
Conducting polymers or intrinsically conducting
polymers (ICPS) provide relatively high capacitance
and have high conductivity. Due to the high conductiv-
ity, they also show low ESR values. Moreover, they are
economical in comparison with carbon-based electrode
materials (Arbizzani and Mastragostino 2001). These
compounds can have metallic conductivity or conduc-
tivity like semiconductors. The main advantage of
conducting polymers is their processability.
Transition metal oxides are also used as electrode
materials for pseudocapacitors due to high conductivity
(Burke 2000; Kotz and Carlen 2000; Kim and Kim
2001a; Zheng and Jow 1995; Zheng and Cygan 1995).
J Nanopart Res (2020) 22:367
The pseudocapacitance may increase the capacitance of
electrochemical capacitors by several orders of magni-
tude over that of the double-layer capacitance. Metal
oxides consist of a class of materials which contain
oxygen and transition elements. It comprises an insula-
tor in addition to poor metals. Devices based on metal
oxides or conducting polymer electrode materials em-
ploy faradaic redox reactions, in addition to electrostatic
charge separation at the electrode-electrolyte interface
(Trasatti and Kurzweil 1994). The majority of related
research deals with ruthenium oxide because other tran-
sition metal oxides have still to acquire comparable
capacitance.
The capacitance of RuO2-based devices is obtained
via the insertion and removal or intercalation of protons
into their amorphous structure. In the case of their
hydrous form, the capacitance value is higher than that
of carbon and conducting polymer-based electrode ma-
terials (Zheng and Jow 1995; Zheng and Cygan 1995).
Moreover, the value of ESR is lower for hydrous RuO2
in comparison to that of other electrode materials.
Pseudocapacitors based on RuO2 also achieve higher
energy and power density, which is similar to EDLCs
and conducting polymer-based pseudocapacitors, but
the success of RuO2 is limited due to its expensiveness
and toxicity. However, in this research work, focus is
mainly on the metal oxide-based electrode materials for
energy storage devices such as supercapacitors.
Hybrid capacitors
Hybrid capacitors exploit both faradaic and non-faradaic
processes for storing charge. Hybrid capacitors are fab-
ricated by using one electrode of double-layer carbon
materials, and one other electrode of pseudocapacitance
materials. Hybrid capacitors have higher energy and
power density compared to EDLCs, without affecting
the cyclic stability and cost-effectiveness.
In the last decade, nickel oxide (NiO) is used as the
pseudocapacitance material in the positive electrode for
most hybrid supercapacitors. The energy density may be
relatively higher for hybrid capacitors compared to
EDLCs, but the limitation is its nonlinear charge-
discharge behavior. On the basis of recent research, the
efforts are focused on three different types of hybrid
supercapacitors, which are differentiated by electrode
configuration: composite, asymmetric, and battery
types. Composite electrodes combine carbon-based
Page 7 of 18 367
materials with metal oxide or conducting polymer ma-
terials. This includes both chemical and physical charge
storage processes simultaneously in a single electrode.
Asymmetric cells are a combination of both faradaic and
non-faradaic mechanisms via coupling an EDLC elec-
trode with a pseudocapacitor electrode (Jacob 2009). In
particular, the combination of an activated charcoal
negative electrode with a conducting polymer positive
electrode has attracted more attention (Kim and Kim
2001a; Mastragostino and Arbizzani 2002; Stoller and
Ruoff 2010). Asymmetric supercapacitors which con-
nect these two electrodes obtained larger energy and
power densities compared to EDLCs and have superior
cycling stability compared to pseudocapacitors
(Arbizzani and Mastragostino 2001; Laforgue and
Simon 2003; Mastragostino and Arbizzani 2002).
Similar to asymmetric hybrid supercapacitors,
battery-type hybrid supercapacitors couple two different
electrodes, although battery-type hybrid supercapacitors
are special in configuration in which a supercapacitor-
type electrode and a battery-type electrode are put to-
gether. This special type of configuration indicates the
requirement of higher energy supercapacitors and
higher power batteries.
The key performance parameters of supercapacitors
The essential performance parameters of electrochemi-
cal capacitors are specific capacitance, power density,
energy density, cycling stability, and rate capability
(Stoller and Ruoff 2010). To enhance power density
and energy density of ultracapacitors, it is necessary to
increase the value of specific capacitance and the oper-
ating potential window; the latter mainly depends on the
electrolyte that is used. Usually, the potential window is
0–1 V for the electrochemical capacitors based on the
aqueous electrolyte, while in the case of non-aqueous
electrolyte-based supercapacitors, a wider potential win-
dow can be achieved. Ionic liquid-based electrolytes are
capable of operating at a higher potential window of
3.5 V (Andrea et al. 2007). Ideal electrode materials for
supercapacitors necessarily have (i) a higher specific
surface area of electrode materials which control the
specific capacitance value of the device, (ii) control of
the porosity of electrode materials that influence the rate
capability and the specific capacitance of the device, (iii)
higher electronic conductivity of electrode materials that
is critical for the power density and rate capability, (iv)
 367 Page 8 of 18
the necessary electroactive sites in the electrode mate-
rials that allow pseudocapacitance, (v) higher chemical
and thermal stabilities that influence the cyclic stability
of device, and (vi) the raw materials and manufacturing
of electrode material and device are economical.
In recent times, the electrodes of the majority of
commercially available electrochemical capacitors are
prepared using carbon, which is economical and has
excellent resistance toward corrosion. Generally, the
energy density of recently available commercial
carbon-based EDLCs is typically 3–5 Wh/kg, much less
compared to electrochemical batteries. This lower ener-
gy density does not fulfill the requirement of energy
storage systems for solar power plants, vehicles, and
wind farms.
To enhance the energy density and specific capaci-
tance, metal oxides are examined as substitute electrode
materials for supercapacitors. The analyzed transition
metal oxides for supercapacitor electrodes are RuO2,
MnO2, NiO, Co3O4, SnO2, ZnO, TiO2, V2O5, CuO,
Fe2O3, WO3, etc. (Patake et al. 2009a; Yan et al.
2012). Specially, some transition metal oxides exhibit
very good pseudocapacitance. Pseudocapacitance is de-
veloped by the weakly attached and interstitial surface
ions, while in lithium-ion batteries the ions are deeply
inserted in the material lattice. The defects, surface
functional groups, and grain boundaries are treated as
very good redox centers for redox reaction or charge
storage reactions. Metal oxide-based electrodes for
supercapacitors provide an order of magnitude larger
capacitance compared to carbon-based electrodes. Var-
ious research reports show that pure metal oxide elec-
trodes may deliver higher energy density and specific
capacitance value at a lower current density or at a slow
scan rate. For instance, the supercapacitor is based on
the electrodeposited NiO thin-film electrode that pro-
vides capacitance of the order of 1776 F/g with 1 M
KOH as an electrolyte at a 1 mV/s scan rate, but just
23% of specific capacitance is retained at a 100 mV/s
scan rate (Liang et al. 2012). Hence, transition metal
oxides cannot be used alone as the electrode material for
supercapacitors for piratical purpose because of the
following demerits:
(i) Most of the metal oxides excluding for RuO2 ex-
hibit lower conductivity. The higher resistivity of
the transition metal oxides enhances the charge
transfer resistance and sheet resistance of the elec-
trode and particularly causes a higher IR drop at a
J Nanopart Res (2020) 22:367
higher current density. Therefore, the rate capability
and power density are poor, and that prevents its
practical applications.
(ii) The strains are initiated in the bare metal oxides
throughout the charge-discharge mechanism of
cells, which creates the cracking of the faradaic
electrode, gaining this poor long-term stability.
(iii) In the case of metal oxides, it is difficult to alter
the surface area, porosity, and pore distribution.
Therefore, it is the reason to make a composite elec-
trode for supercapacitors that contain transition metal
oxide as well as carbon, which includes the advantage
and reduces the drawbacks of both the components. In
the case of carbon and metal oxide-based composite
electrode, higher conductivity of the carbon materials
is good for the power density and the rate capability at a
higher current density. To store the charge and energy in
a carbon-metal oxide composite, the main sources are
metal oxides. The higher electroactive sites of transition
metal oxides provide higher capacitance and energy
density of the carbon-metal oxide composite electrode
for supercapacitors. The constituent, compositional, mi-
crostructural, and physical properties of the carbon-
metal oxide composite enhance the performance of the
prepared electrochemical capacitor electrodes. The elec-
trode specific surface area, porosity, pore size distribu-
tion, and electronic conductivity influence the
supercapacitor cell performance.
The aim of investigation is to develop a carbon-metal
oxide nanocomposite electrode for supercapacitors and
to provide higher power density, higher energy density,
good rate capability, and good cyclic stability.
Nanostructured materials for supercapacitors
The performance of energy storage systems is totally
dependent on the utilization of various types of electrode
materials, electrolytes, and the reversible electrochemi-
cal response between these two components (Luo et al.
2015). It is essential to think about how to explore the
development of new device structures, materials, and
novel hybrid interfaces on the surface of electrodes. In
the past decade, a huge amount of work has been carried
out in this direction, but still the need for abundance,
environmental friendliness, economical, stability, effi-
ciency, and capacity up to now remains to be obtained
J Nanopart Res (2020) 22:367
(Simon and Gogotsi 2008; Bard and Faulkner 2000;
Zhang et al. 2012; Hall et al. 2010).
Due to excellent physical and chemical properties of
nanomaterials, they are promising candidates for the
energy storage device application (Reddy et al. 2012).
The nanomaterials have a very small crystalline size, of
a few nanometers. Because of this, the nanomaterials
have at least one dimension with different morphol-
ogies, such as zero, one, and two dimensions (Sajanlal
et al. 2011). Generally, nanomaterials have two main
characteristics, namely, size-dependent optoelectronic
properties and larger surface to volume ratios, which
lead to higher density of surface dangling bonds (Reddy
et al. 2012; Sajanlal et al. 2011; Viswanathan et al.
2012; Zhang et al. 2013; Subbiah et al. 2005; Zhu and
Xu 2010; Jiang et al. 2014; Gogotsi et al. 2005; Simon
and Gogotsi 2010; Xia et al. 1935; Snook et al. 2011; Yu
et al. 2015). Nanomaterials join to form tubular, spher-
ical, and irregular shapes, which provide a higher spe-
cific surface area in a small specified volume (Sajanlal
et al. 2011). These structures are very important for the
development of catalysis, energy-converting devices,
nanodevices, and biological and chemical sensors
(Sajanlal et al. 2011; Viswanathan et al. 2012; Zhang
et al. 2013; Subbiah et al. 2005; Zhu and Xu 2010; Jiang
et al. 2014; Gogotsi et al. 2005; Simon and Gogotsi
2010; Xia et al. 1935). The very small size of
nanomaterials has two key effects, namely size effect
and surface- or interface-induced effect. In the case of
size effect, the continuous energy levels or density of
states of bulk material changes to set of discrete energy
levels and is also known as the quantum confinement
effect. It is shown in Fig. 1 that the surface or interface-
induced effect is due to the reduction in particle size,
which increases the surface to volume ratio. Therefore,
higher numbers of atoms are located on the surface
compared with bulk material. The size effect generally
changes the physical properties of the nanoparticles,
while the surface effect alters mechanical, chemical,
and optical properties. The existence of bigger grain
boundaries in the nanostructured materials acts as a fast
diffusion path for the active species or charges. It en-
hances the diffusion rate at an interface between elec-
trolyte and electrode. Therefore, the nanomaterials en-
hance the electrochemical performance of the energy
storage devices.
Different nanostructured materials have surface mor-
phology like nanohorns (Zhu and Xu 2010), nanofibers
(Subbiah et al. 2005), nanotubes (Zhang et al. 2013),
Page 9 of 18 367
microporous scaffolds (Viswanathan et al. 2012), and
hybrid nanostructures (Jiang et al. 2014), with a higher
specific surface area, and their composites are suggested
as promising candidates for supercapacitor electrode
materials. An abundance of carbon materials has in-
voked the huge interest in the carbon-based electrode
materials. Furthermore, it is economical with a tunable
pore structure (Gogotsi et al. 2005). The optimized pore
structure of carbon-based electrode materials improves
the surface area and capacitance of supercapacitors
(Simon and Gogotsi 2010). The key parameters of elec-
trode materials for electrochemical capacitors applica-
tions are surface area, density of surface active atoms,
pore size, electrical conductivity, and stability (Yu et al.
2015). In addition, the important parameters of electro-
lyte to be considered are environmental friendliness,
dielectric constant, electrical conductivity, and stability
(Roy and Srivastava 2015).
Currently, it has been observed that biomolecules or
organic molecules have been used to alter the surface
property of electrode material leading to the better per-
formance of electrochemical capacitors that utilize the
faradaic mechanism (Kearns and Roberts 2012). An
interface between the metal and biomolecules and the
formation of metal organic molecule framework are
predominately formed in composite electrode and that
enhances the supercapacitor performance (Bao et al.
2008). Electrode materials which are currently used in
the literature as promising electrode materials for
supercapacitors are discussed in the next section.
Metal oxide-based supercapacitors
Different transition metal oxides are synthesized and
investigated using various synthesis routes for electro-
chemical capacitor applications (Chmiola et al. 2006;
Balakrishnan and Subramanian 2014). In particular,
metal oxides due to their variable oxidation state and
existence of a double-layer charge hint at being chosen
as one of the alternative materials for several carbon-
based electrode materials in supercapacitors (Chmiola
et al. 2006; Balakrishnan and Subramanian 2014). How-
ever, some metal oxides are still expensive, and have a
lower specific surface area, less porosity, and the toxic-
ity of the initial precursor material, which limits their
possibility for large-scale production of supercapacitors
(Balakrishnan and Subramanian 2014). Hence, it is nec-
essary to develop an alternative transition metal oxide
 367 Page 10 of 18
electrode material, which is economical, non-toxic, en-
vironmental friendly, and naturally abundant.
In recent times, electrochemical capacitors based on
transition metal oxide films have attracted more interest
due to their possible applications in the energy storage
network of microelectronics devices. Several metal ox-
ides are used in the past decade to obtain higher capac-
itance like RuO2 (Bi et al. 2010), NiOx (Kim et al.
2013), Co3O4 (Wang et al. 2014), IrO2 (Chen et al.
2011), CoO (Zhang et al. 2014), Fe3O4 (Liu et al.
2013), MnO2 (Xie et al. 2013), SnO2 (Liu et al. 2014),
CdO (Chang et al. 2007), and MoO2 (Rajeshwari et al.
2009). Among these transition metal oxides, amorphous
hydrated RuO2 has been a potential candidate for
supercapacitor electrode materials. It also exhibits ex-
cellent reversibility, higher specific capacitance, and
longer life cycle (Soudan et al. 2001; Yoon et al.
2001). It has been reported that the RuO2-based elec-
trode prepared using the sol-gel method results in higher
energy density and power density (Zheng 1999). How-
ever, its toxic nature and its cost have hindered its use in
application. The solubility of RuO2 in the H2SO4 elec-
trolyte can reduce the specific capacitance over exten-
sive cycling. As an outcome, various transition metal
oxides are being investigated for potential application in
supercapacitor devices. The metal oxides such as IrO2
(Park et al. 2010) and CoOx (Lin et al. 1998) also suffer
similar limitations. In contrast, oxides, such as V2O5
(Lee and Goodenough 1999), MnO2 (Wang et al.
2005a), and MoO3 (Sugimoto et al. 2001), overcome
the limitation and hence can be utilized for application
in supercapacitors. The possibility of synthesizing
MnO2 using various chemical methods is very high;
therefore, other useful materials for electrochemical ca-
pacitor applications may be prepared. As the power
necessity in several applications increases remarkably,
the development of higher energy density
supercapacitors is undertaken by different groups across
the globe. Several such materials and their processing
route along with used electrolyte and obtained specific
capacitance are listed in Table 1.
NiO-AC nanocomposite
A FCC NiO nanoparticle with spherical shape, higher
purity, and well-dispersed and narrow size distribution
was successfully synthesized by a co-precipitation
method and is being characterized by different structural
characterization techniques such as XRD, SEM, and
J Nanopart Res (2020) 22:367
TEM. The synthesized NiO nanoparticles were used in
different ratios with activated charcoal (varying from
1:1 to 1:3) to prepare nanocomposite electrodes and
are being tested for its application in supercapacitor
devices. A symmetrical supercapacitor cell has been
fabricated by sandwiching 6 M KOH electrolyte in
between two identical AC-NiO nanocomposite elec-
trodes. The performance characteristics of fabricated
cells have been characterized using cyclic voltammetry,
a.c. impedance spectroscopy, and charge-discharge
methods. The obtained result shows that AC-NiO (1:1)
nanocomposite electrodes show excellent capacitive be-
havior which might be due to the proper compatibility of
activated charcoal and nanoparticles in 1:1 ratio
exhibiting higher surface area and electrical conductiv-
ity with proper ion-pore accessibility leading to the
e nh a nc em en t i n sp ec i f i c ca p ac i t a n ce u p to
233.3 mF cm−2 which is equivalent to single-electrode
specific capacitance of 84.8 F g−1. This corresponds to
the energy density of 5 Wh kg−1 and power density of
0.3 kW kg−1 with KOH as an electrolyte material. The
coulombic efficiency (η) for the fabricated cell has been
achieved to be 88% (Yadav and Tripathi 2017).
ZnO-AC nanocomposite
Hexagonal wurtzite ZnO nanoparticles with well-dis-
persed, higher purity, narrow size distribution, and
spherical shape have been synthesized successfully
using a co-precipitation method, and they are character-
ized using various structural characterization tech-
niques, such as SEM, ADXRD, and FTIR. The synthe-
sized uncapped ZnO NPs have been employed in two
different weight ratios (varying from 1:1 to 1:2) with
powder of activated charcoal to make nanocomposite
electrodes for supercapacitor device application. Sym-
metrical supercapacitor cells have been made by
sandwiching 1 M NaOH and 6 M KOH as electrolytes
between two identical electrodes (of ZnO-AC nanocom-
posite). The electrochemical performance of the fabri-
cated supercapacitor cells has been measured with the
help of cyclic voltammetry, a.c. impedance spectrosco-
py, and charge-discharge methods. The obtained results
show that ZnO-AC (1:1) nanocomposite electrodes give
the good capacitive behavior. It may be because of the
good compatibility of nanoparticles and activated char-
coal powder in 1:1 ratio. The specific capacitance has
been obtained in the case of supercapacitor cell A that is
in the order of 479.6 mF cm−2; it is equal to the specific
Table 1 Several materials and their processing route along with used electrolyte and obtained specific capacitance

Sr. no. Material Synthesis technique Electrolyte Specific capacitance (F/g) Reference
J Nanopart Res

1. RuO2 Sol-gel 0.5 M H2SO4 720 (Zheng et al. 1995)

2. RuO2 Templating method 1.0 M H2SO4 954 (Min et al. 2009)
3. RuO2 Electrodeposition 1.0 M H2SO4 788 (Park et al. 2004)
4. RuO2 Electrophoretic deposition 1.0 M H2SO4 734 (Jang et al. 2006a)
5. RuO2 Electrostatic spray deposition 0.5 M H2SO4 650 (Kim and Kim 2001b)
6. RuO2 Electrodeposition 0.5 M H2SO4 650 (Patake et al. 2009b)
(2020) 22:367

7. RuO2 Electrodeposition 0.5 M H2SO4 599 (Jang et al. 2006b)

8. RuO2 Thermal decomposition 0.5 M H2SO4 593 (Fang et al. 2001)
9. RuO2 Spray pyrolysis 0.5 M H2SO4 551 (Gujar et al. 2007)
10. RuO2 Electrodeposition 0.5 M H2SO4 534 (Ahn et al. 2006)
11. RuO2 Chemical oxidation 1.0 M H2SO4 500 (Chang and Hu 2004)
12. RuO2-TiO2 Chemical 1.0 M KOH 46 (Wang et al. 2005b)
13. RuO2-SnO2 Sol-gel 1.0 M H2SO4 690 (Hu et al. 2007)
14. RuO2-C Wet impregnation 1.0 M H2SO4 760 (Hu and Wang 2002)
15. RuO2-C Chemical method 1.0 M H2SO4 650 (Park and Park 2002)
16. RuO2-C Colloidal method 1.0 M H2SO4 407 (Kim and Popav 2002)
17. RuO2-C composite Colloidal solution method 1.0 M H2SO4 250 (Dandekar et al. 2005)
18. Ni(OH)2 CBD 2.0 M KOH 398 (Patil et al. 2009)
19. NiO CBD 2.0 M KOH 167 (Patil et al. 2008)
20. Ni(OH)2 SILAR 2.0 M KOH 350 (Kulkarni et al. 2009)
21. NiO Electrodeposition 1.0 M KOH 277 (Nam and Kim 2002)
22. NiO Electrochemical precipitation 1.0 M KOH 146 (Nam et al. 2002)
23. NiO Sol-gel 1.0 M KOH 125 (Wu et al. 2006)
24. NiO Calcination 2.0 M KOH 120 (Wang and Xia 2006)
25. Ni-Co CVD 1.0 M KOH 569 (Fan et al. 2007)
26. Ni(OH)2 Electrodeposition 3.0 M KOH 578 (Zhao et al. 2007a)
27. Mn-Ni-Co oxide Co-precipitation 6.0 M KOH 1260 (Luo et al. 2008)
28. NiO-RuO2 Co-precipitation 1.0 M KOH 210 (Liu and Zhang 2004)
29. NiFe2O4 CBD 1.0 M Na2SO3 223 (Gunjkar 2008)
30. NiFe2O4 SILAR 1.0 M Na2SO3 369 (Gunjkar 2008)
Page 11 of 18 367
Table 1 (continued)
367

Sr. no. Material Synthesis technique Electrolyte Specific capacitance (F/g) Reference

31. α-Co(OH)2 Electrodeposition 1.0 M KOH 860 (Gupta et al. 2007)

32. Co3O4 Template-free growth method 6.0 M KOH 746 (Gao et al. 2010a)
Page 12 of 18

33. Cobalt oxide SILAR 1.0 M KOH 165 (Kandalkar et al. 2008)
34. Co(OH)2 Electrodeposition 6.0 M KOH 280 (Wang et al. 2006)
35. Co-MnO2 Electrodeposition 0.5 M Na2SO4 396 (Zhao et al. 2007b)
36. Co-MnO2 Electrodeposition 1.0 M Na2SO4 498 (Kalakodimi and Miura 2004)
37. Co(OH)2/TiO2 Precipitation method 6.0 M KOH 229 (Tao et al. 2007)
38. Co3O4 Spray pyrolysis 2.0 M KOH 74 (Shinde et al. 2006)
39. V2O5 Chemical method 0.1 M K2SO4 170 (Cottineau et al. 2006)
40. V2O5-C Melt quenching 2.0 M NaNO3 32.5 (Chen et al. 2009)
2.0 M KNO3 31.5
2.0 M LiNO3 29.9
1.0 M Na2SO4 29.3
1.0 M K2SO4 28
1.0 M Li2SO4 25.1
41. Fe2O3 Electrosynthesis 0.25 M Na2SO3 210 (Nagrajan and Zhitomirsky 2006)
42. Fe3O4 Chemical method 1.0 M K2SO4 75 (Zhao et al. 2006)
43. Fe3O4-C Microwave method 6.0 M KOH 37.9 (Du et al. 2009)
44. MoO2-C Electrochemically induced deposition method 1.0 M Na2SO4 597 (Gao et al. 2010b)
45. MoO2 Thermal decomposition method 1.0 M H2SO4 140 (Rajeswari et al. 2009)
46. Bismuth oxide Electrodeposition 1.0 M NaOH 98 (Gujar et al. 2006)
47. Bismuth iron oxide Electrodeposition 1.0 M NaOH 81 (Lokhande et al. 2007)
48. SnO2 Electrodeposition 1.0 M Na2SO4 101 (Prasad and Miura 2004)
J Nanopart Res

49. SnO2 Electrodeposition 1.0 M NaOH 43 (Mane et al. 2009)

50. SnO2 Sol-gel 1.0 M KOH 16 (Wu 2002)
51. Copper oxide Electrodeposition 1.0 M Na2SO4 36 (Patake et al. 2009c)
52. Copper oxide CBD 1.0 M Na2SO4 43 (Dubal et al. 2010)
53. In2O3 Electrodeposition 1.0 M Na2SO3 190 (Kalakodimi et al. 2004)
(2020) 22:367

54. IrO2-MnO2 Thermal decomposition 0.5 M H2SO4 550 (Grupioni et al. 2002)
55. Nano MnO2 Soft chemical route 1.0 M Na2SO4 211 (Chen et al. 2010)
56. Birnessite-type MnO2 Microwave-hydrothermal (M-H) 1.0 M Na2SO4 210 (Ming et al. 2012)
J Nanopart Res (2020) 22:367 Page 13 of 18 367

capacitance of a single electrode, i.e., 342.6 F g−1. In the

same way, the improvement in the specific capacitance

(Yadav and Tripathi 2017)

of supercapacitor cell B has been obtained that is in the
order of 456.5 mF cm−2, which is equivalent to the

(Yadav et al. 2018b)

(Yadav et al. 2020b)

(Yadav et al. 2018a)

(Yadav et al. 2018c)

(Yadav et al. 2020a)

(Shao et al. 2009)
(Lu et al. 2011) specific capacitance of a single electrode, i.e.,

(Yadav 2020a)
326.1 F g−1. This is related to the power density of
1.72 kW kg−1 and energy density of 5.44 Wh kg−1 with
Reference

6 M KOH as the electrolyte for supercapacitor cell A.

Similarly, in the case of cell B, the power and energy
density values have been found as 1.40 kW kg−1 and
Specific capacitance (F/g)

3.28 Wh kg−1, respectively, with 1 M NaOH as the

electrolyte (Yadav et al. 2018b).

229.8
341.6
335.3
342.6
326.1

305.6
187.8
398.5
213.6
68.2
67.6
84.8
910
840

Mn2O3-Mn3O4-AC nanocomposite

Mn2O3 and Mn3O4 nanoparticles with narrow size dis-

tribution and spherical shape have been synthesized
M Na2SO4

using a co-precipitation method. The synthesized mate-

M H2SO4
M H2SO4

M H2SO4
M NaOH

M NaOH
1.0 M KOH

M KOH

M KOH

M KOH

M KOH
6.0 M KOH

M KOH
6.0 M KOH

rial has been characterized using various structural char-

Electrolyte

acterization tools, for example SEM, TEM, XRD, and

FTIR. Furthermore, the composite formation has also
6.0

6.0

6.0
1.0

1.0
6.0
1.0
6.0
1.0
1.0

1.0

been confirmed from the SXRD and SEM results. XPS

investigation has confirmed the existence of Mn, O, and
C. The application of nanocomposites using synthesized
uncapped Mn2O3-Mn3O4 and activated charcoal with
1:1 mass ratio as an electrode material for
supercapacitors has been established. The results show
encouraging performance of the synthesized nanocom-
Modified polyol process

posite. The performance of nanocomposite electrode

Synthesis technique

with H2SO4 electrolyte turns out to be better relative to

Electrodeposition

Co-precipitation
Co-precipitation

Co-precipitation

Co-precipitation
Co-precipitation

Co-precipitation
Co-precipitation

the other used electrolyte. The combination of Mn2O3-

Mn3O4 and activated charcoal having a concentration of
1:1 mass ratio resulted in an optimized composition
among the prepared nanocomposites. The specific ca-
pacitance has been obtained in the case of
supercapacitor cell A that is of the order of
Mn2O3-Mn3O4-AC nanocomposite

525.7 mF cm−2, which is equivalent to the specific

capacitance of a single electrode of 305.6 F g−1. In the
VxOy-AC nanocomposite

same way, the improvement in the specific capacitance

CuO-AC nanocomposite
ZnO-AC nanocomposite

ZnO-AC nanocomposite

ZnO-AC nanocomposite
NiO-AC nanocomposite
NiO/Ni nanocomposite

of supercapacitor cell B has been obtained that is of the

La-Doped Ni(OH)2

order of 322.9 mF cm−2, which is equivalent to the

specific capacitance of a single electrode that is
187.8 F g−1. The power density and energy density for
Table 1 (continued)

Material

supercapacitor cell A are respectively 0.98 kW kg−1 and

7.19 Wh kg−1, while for cell B, the power and energy
density values were found to be 0.94 kW kg−1 and
5.99 Wh kg−1 respectively. The values of coulombic
Sr. no.

65.
57.
58.
59.
60.

61.

62.

64.
63.

efficiency (ηt) have been achieved to be 80.22 and

 367 Page 14 of 18
79.02% of the fabricated cell A and cell B, respectively
(Yadav 2020a).
VxOy-AC nanocomposite
The synthesis of mixtures of orthorhombic and tetrago-
nal containing rod-shaped VxOy nanoparticles using a
co-precipitation method with narrow size distribution
has been established by structural and morphological
characterization methods. The oxidation states of vana-
dium cations have been confirmed to be the effect of
electronic property of material that has been used as one
of the components in nanocomposite (VxOy-AC). The
diffraction study and XPS investigation have confirmed
the various oxidation states and have also been related to
coordination number of cations in V3O7 and V4O9. Use
of the prepared oxide nanopowder and its composite
with AC has been evaluated as an electrode material.
Its performance in terms of observed capacitance, ener-
gy density, and power density suggests that nanocom-
posite (VxOy-AC) can be a promising candidate as
electrodes for supercapacitors. The maximum capaci-
tance equivalent to single-electrode capacitance is
398.5 F g−1, and power density and energy density for
a supercapacitor containing electrode composition of
1:1 ratio and 1 M H2SO4 respectively are
4.00 kW kg−1 and 8.89 Wh kg−1. The observation
suggests a better matrix for nanocomposite electrode
materials (Yadav et al. 2020a).
CuO-AC nanocomposite
CuO nanoparticles with narrow size distribution and
spherical shape were synthesized successfully using a
co-precipitation method. The synthesized material has
been characterized using various structural characteriza-
tion tools, for example SEM, TEM, SXRD, and FTIR.
Furthermore, the composite formation has also been
confirmed from the results. XPES investigation has
confirmed the reduction in particle size of CuO has not
changed the chemical environment of Cu. The applica-
tion of nanocomposite using synthesized uncapped CuO
and activated charcoal with 1:1 mass ratio as electrode
materials for supercapacitors has been established. The
results show encouraging performance of the synthe-
sized nanocomposite. The performance of nanocompos-
ite electrode with H2SO4 electrolyte turns out to be
better relative to the other used electrolyte. The combi-
nation of CuO and activated charcoal having
J Nanopart Res (2020) 22:367
concentration of 1:1 mass ratio resulted in an optimized
composition among the prepared nanocomposites. The
specific capacitance has been obtained in the case of
supercapacitor cell A that is of the order of
521.4 mF cm−2, which is equivalent to the specific
capacitance of a single electrode that is 260.7 F g−1. In
the same way, the improvement in the specific capaci-
tance of supercapacitor cell B has been obtained that is
of the order of 459.7 mF cm−2, which is equivalent to
the specific capacitance of a single electrode that is
229.8 F g−1. The power density and energy density for
supercapacitor cell A are respectively 0.84 kW kg−1 and
5.59 Wh kg−1, while, for cell B, the power and energy
density values were found to be 0.65 kW kg−1 and
4.15 Wh kg−1 respectively. The values of coulombic
efficiency (ηt) have been achieved to be 88.82% and
60.43% of the fabricated cell A and cell B, respectively
(Yadav 2020b; Yadav et al. 2020b).
Conclusions
Based on reviewed literature, it has been observed that
supercapacitors having electrode materials which are
cost-effective, environmentally friendly, and easy pro-
cessing are of greater interest. Furthermore, it was seen
that different morphology and particle size of the nano-
structured material provide higher kinetics for physical
and chemical reactions. Thus, the combination of both
the aspects can be used to enhance the supercapacitor
performance.
Funding Mr. Mahendra Singh Yadav received financial support
from the Jaypee University of Engineering and Technology, Guna,
Madhya Pradesh, India.
Compliance with ethical standards
Conflict of interest The author declares that he has no conflict
of interest.
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