Rev Inorg Chem 2021; aop

Review article

Sayed Y. Attia, Saad G. Mohamed*, Yosry F. Barakat, Hamdy H. Hassan and Wail Al Zoubi*

Supercapacitor electrode materials: addressing

challenges in mechanism and charge storage
https://doi.org/10.1515/revic-2020-0022 Introduction
Received October 6, 2020; accepted February 24, 2021;
published online March 10, 2021
It is worth emphasizing that the predictable exhaustion
of fossil fuel resources and its negative environmental
Abstract: In recent years, rapid technological advances
impacts have led to requests for evolving and improving
have required the development of energy-related devices.
renewable and eco-friendly energy resources to provide
In this regard, Supercapacitors (SCs) have been reported to
energy on demand to the world (Christopher and Dimitrios,
be one of the most potential candidates to meet the
2012; Chu and Majumdar, 2012; Cook et al., 2010; Dillon,
demands of human’s sustainable development owing to
2010; Hagfeldt et al., 2010; Kondratenko et al., 2013;
their unique properties such as outstanding cycling life,
Lashof and Ahuja, 1990; Nocera, 2009; Shao et al., 2018).
safe operation, low processing cost, and high power
density compared to the batteries. This review describes However, the intermittency of renewable energy sources
the concise aspects of SCs including charge-storage increasing the global demands for developing energy
mechanisms and scientific principles design of SCs as storage systems to efficiently store the electricity generated
well as energy-related performance. In addition, the most from hydro, wind, and solar energy sources and to secure
important performance parameters of SCs, such as the its sustainability by supply the world upon request (Bai
operating potential window, electrolyte, and full cell et al., 2015; Kim et al., 2015; Noori et al., 2019). Among the
voltage, are reviewed. Researches on electrode materials various energy-storage technologies, batteries and SCs
are crucial to SCs because they play a pivotal role in the depict the two leading electrochemical energy-storage
performance of SCs. This review outlines recent research devices as shown in Figure 1, which represented the rela-
progress of carbon-based materials, transition metal tionship between specific energy or energy density (Ed) in
oxides, sulfides, hydroxides, MXenes, and metal nitrides. (Wh kg−1) versus specific power or power density (Pd) in
Finally, we give a brief outline of SCs’ strategic direction for (W kg−1) (Arico et al., 2011; Armand and Tarascon, 2008;
future growth. Dunn et al., 2011; Goodenough, 2013; Liu et al., 2010a;
Miller and Simon, 2008; Rolison et al., 2009; Service, 2006;
Keywords: battery; electrode materials; storage mecha-
Singh et al., 2014; Tarascon and Armand, 2011; Winter and
nism; supercapacitors.
Brodd, 2004; Zhang et al., 2013; Zhang and Zhao, 2009).
Ed was referred to the amount of energy stored per unit
mass, area, or volume which means that how far keeping
the device working throughout the day, and the corre-
*Corresponding authors: Saad G. Mohamed, Mining and Metallurgy
Engineering Department, Tabbin Institute for Metallurgical Studies, sponding Pd referring to the amount of energy follows per
(TIMS), Tabbin, Helwan 109, Cairo 11421, Egypt; and Wail Al Zoubi, unit mass, area, or volume which means that the rate at
Materials Electrochemistry Laboratory, School of Materials Science which the device can deliver its charges. In batteries,
and Engineering, Yeungnam University, Gyeongsan 38541, Republic of energy is stored as chemical energy in chemical bonds
Korea, E-mail: [email protected] (S. G. Mohamed),
inside its electrodes active materials and converted this
[email protected] (W. A. Zoubi). https://orcid.org/0000-0001-
7465-4582 (S. G. Mohamed) chemical energy to electrical energy through redox re-
Sayed Y. Attia and Yosry F. Barakat, Mining and Metallurgy actions as in a lead-acid battery or through intercalation as
Engineering Department, Tabbin Institute for Metallurgical Studies, in lithium-ion battery (Liu et al., 2016; Noori et al., 2019).
(TIMS), Tabbin, Helwan 109, Cairo 11421, Egypt, Owing to their high energy density, batteries in the elec-
E-mail: [email protected] (S.Y. Attia), [email protected]
(Y.F. Barakat)
tronics market are currently widely used (Arico et al., 2011;
Hamdy H. Hassan, Chemistry Department, Faculty of Science, Ain Dunn et al., 2011). Conversely, owing to a great resistive
Shams University, Abbasiya, Cairo 11566, Egypt loss due to sluggish electron transport and ions transport,
2 S.Y. Attia et al.: Supercapacitor electrode materials

batteries generate thermal energy during their high power Ed, either specific capacitance or voltage window or both of
operation leading to a lot of safety problems (Choi et al., these quantities should be increased (Noori et al., 2019;
2012; Hu and Xu, 2014). In this regard, SCs have attracted Shao et al., 2018; Tong et al., 2016).
much attention as the next-generation energy storage In this review, we present an overview of scientific
technology, mostly due to their unique electrochemical basics of SCs including background, electrochemical
features such as long cycling life, excellent low- feature with focusing on the charge storage mechanisms,
temperature performance, and high power density than along with energy-related performance including
batteries (Attia et al., 2020; Béguin et al., 2014; Conway, the capacitance, energy, and power densities beside, the
2013; Jeong et al., 2011; Kötz and Carlen, 2000; Lei et al., most important performance factors of SCs, such as the
2012; Mohamed et al., 2018a; Shen et al., 2015b; Singh et al., operating potential window, electrolyte, and full cell
2014; Wang et al., 2012a; Xiao et al., 2014a; Zhai et al., 2011; voltage, are described. Moreover, we highlighted the recent
Zhang and Zhao, 2009). However, the SCs market can progress of some electrode materials for SCs such as
provide Ed up to 5 Wh kg−1 which higher than that of the carbon-based materials, transition metal oxides, sulfides,
conventional electrolytic solid-state capacitor, but it’s even hydroxides, MXenes, and metal nitrides.
less than batteries (up to 200 Wh kg−1) (Shao et al., 2018;
Wang et al., 2013a). Therefore, the large-scale production
of SCs has been restricted due to their comparatively low
energy density. In this regard, the energy storage field has
Historical overview and some
witnessed a dramatic growth in the research efforts that fundamental concepts of SCs
proceeding with the aim of achieving SCs with high Ed like
batteries without losing their high power density and long Electric capacitors are described as a sandwich construc-
cycle life (Jiang et al., 2012a; Naoi et al., 2013; Wang and tion including two parallel conductive plates usually made
Xia, 2013; Wang et al., 2013a; Yan et al., 2014). of metals separating by a dielectric or insulator substance,
Ed is the bottleneck to assess the electrochemical the dielectric such as air, oiled paper, mica, glass, porce-
behavior of SCs, on this base, and according to Equation (1) lain, or titanate as shown in Figure 2a (Halliday et al., 2013;
(Noori et al., 2019; Shao et al., 2018; Sharma et al., 2019; Hickey and Villines, 1970; Shen et al., 2015a). By applying
Simon and Gogotsi, 2010; Yu et al., 2015): outside voltage difference through the two parallel plates,
1 the charging process is generating and the positive and
Ed = Cs V 2 (1) negative charges are separated and accumulated on each
2
plate creating a positive electrode and the negative elec-
where Cs is the specific capacitance of the cell and V is the trode. Subsequently, when the external source is removed,
applied voltage window of the cell. Therefore, to increase the positive and negative charges remain at the corre-
sponding electrode producing the voltage difference which
is named the cell-voltage of the assembled capacitor.
Consequently, on connecting these two electrodes with a
load, the discharging process starts. With this idea, the
capacitor plays a role in storing and delivering charges
(Yu et al., 2015). The first discovered capacitor was the
“Leyden jar” in 1745, it is a glass vessel which covered from
inside and outside with metal foils, the foils acted as the
electrodes and the jar acted as the dielectric, and by
rotating the glass jar the static electricity could be gener-
ated (Halliday et al., 2013; Noori et al., 2019; Sharma et al.,
2019; Yu et al., 2015).
Electrolytic capacitors are the latest progress in the
technology of the capacitor, in which the dielectric is
replaced with an ionic electrolyte (Noori et al., 2019; Yan
et al., 2014; Yu et al., 2015). Within the electrolytic capac-
Figure 1: Ragone plot illustrated the specific power density versus
specific energy density for different electrochemical energy storage
itor, the ions can be transferred freely in the electrolyte,
systems (Noori et al., 2019). Copyright © 2019 The Royal Society of creating at the electrode/electrolyte interface a much larger
Chemistry. charge density than that created at the interface of
 S.Y. Attia et al.: Supercapacitor electrode materials 3

Co3O4, etc. (Seker et al., 2009), TMSs such as CoS, MnS, NiS,
etc., and conducting polymers (CPs) (Seker et al., 2009)
such as polyaniline, polythiophene, polypyrrole (PPy),
polyvinyl alcohol (PVA), etc (Dhibar and Das, 2015; Gao
et al., 2013; Sharma et al., 2019; Wu et al., 2010a). (iii) The
last type of materials used in SCs is known as battery-type
that involves a non-capacitive Faradic performance and
nature (Attia et al., 2020). These three types will be
described in detail later. The nature of electrode material
such as its affinity to adsorb ions on its surface in addition
to its texture nature controls the electrochemical behavior
of this material. Consequently, since 2000, the dramatic
growth of nanoscience and progressive characterization
Figure 2: The scheme represents (a) a traditional capacitor and (b) a
supercapacitor. methods has witnessed a significant increase in the
amount of research related to SCs following the emergent
increased request for high-energy, high-power, and benign
electrode/dielectric (Noori et al., 2019; Yu et al., 2015). energy-storage systems (Long et al., 2015).
Consequently, the capacitance (Cs) of electrolytic capaci-
tors is often measured by mF, whereas those of dielectric
capacitors in the µF range (Noori et al., 2019). SCs (so-called Charge storage mechanisms in SCs
ultracapacitors or electrochemical capacitors) in which
instead of using conventional dielectrics between the The electrode active material used in SCs are classified into
plates, use an electrolyte that ionically bridges between the three main types in accordance with their charge storage
two electrodes (Figure 2b) which are separated by an ion- mechanism: (I) Electric double layer, (II) Pseudocapaci-
permeable substance (Noori et al., 2019; Shao et al., 2018). tors, and (III) Battery-type material as demonstrated in
In SCs, the charge storage process is classified into (i) Figure 3 (Lu, 2013; Noori et al., 2019; Shao et al., 2018;
Electric-double-layer capacitors (EDLCs) that describe the Sharma et al., 2019).
materials in which the charge is separated forming Generally, electrical charges can be stored either on
“Helmholtz double-layer” and electrostatically adsorbed the surface of active electrode material forming double
at the electrode/electrolyte interface creating a potential layer charging proceeding a capacitive nature or within
difference between the two electrodes which means that no the bulk of active material proceeding a noncapacitive
electron shift between the electrolyte and the electrodes nature (Noori et al., 2019). These types are schematically
i.e., capacitive non-Faradic behavior which characterized summarized in Figure 4:
by long cycling stability but low Cs as in carbon materials
and its derivatives (Attia et al., 2020; Chen, 2017; Conway,
1991; Noori et al., 2019; Sharma et al., 2019; Simon and Electric-double-layer capacitance (EDLCs)
Gogotsi, 2010; Wang et al., 2016a; Yu et al., 2015; Zhao
et al., 2011). The first EDLC was manufactured in 1957 by EDLCs are described as electrochemical materials that
General Electric using its plates made of activated charcoal store the electric charge directly in the double-layer at the
(Seker et al., 2009; Sharma et al., 2019). (ii) The second type electrode/electrolyte interface [50]. The EDLC has a pair of
is known as Pseudocapacitors (PCs), which involved a polarizable electrodes with current collectors, a separator,
Capacitive-Faradaic process that describes the material in and an ionic electrolyte solution, respectively. The mech-
which the electrochemical behavior is capacitive in nature anism of charge storage in EDLCs depends on the electro-
but storing the charge happens by charge-shifting Faradaic static adsorption of the electrolytic ions on the electrode
reactions within the double layer especially when using surface. Therefore, the way to get high capacitance for
redox electrolyte supplying a high Cs compared to EDLCs EDLCs is by using an electrode material with a more effi-
(Brousse et al., 2015; Chen, 2017; Conway, 1991; Wang cient access surface area in addition to its good electronic
et al., 2016a; Yu et al., 2015; Zhao et al., 2011). The first conductivity i.e., selecting the electrode material is a
explored PCs material was RuO2 by B. E. Conway during critical step to improve the behavior of SCs. Therefore,
1975–1980. The materials that exhibit redox behavior and Nanostructured carbon-based materials with a great
utilized in PCs are TMOs RuO2, Fe3O4, MnO2, NiO, ZnO, specific surface area (SSA) and excellent electronic
4 S.Y. Attia et al.: Supercapacitor electrode materials

Figure 3: Different electrochemical energy

storage materials.
(a) EDLC, (b) PCs, and (c) battery type
materials, respectively (Shao et al., 2018).
Copyright © 2018 American Chemical
Society.

defined pathway for electrolyte access. Ji et al. (Ji et al.,

2014) investigated the relationship between the Cs and the
SSA for several carbon materials. The Cs (F g−1) increases as
the SSA of the carbon-based material increased. Figure 3a
illustrates the configuration state of a typical EDLC cell
(Wang et al., 2013a). The capacitor is charged and electrical
energy is stored when electric charges accumulate on the
electrode surfaces, and ions of opposite charges are ar-
ranged on the electrolyte side. The capacitor is discharged
at loads when the accumulated ions are released from the
electrode surfaces and moved back into the bulk of the
Figure 4: Schematic representation of the three types of electrode electrolyte (Noori et al., 2019; Shao et al., 2018; Zhai et al.,
materials used in SCs.
2011).
The capacitance of EDLCs is analogous to a conven-
conductivity are the materials of EDLC’ s choice. Carbon- tional capacitor and can be described as follows (Noori
based materials include graphene and its derivatives (Chen et al., 2019):
and Dai, 2014; Dong et al., 2017; El-Kady et al., 2016; Liu Cdl = ϵr ϵ0 A/d
and Peng, 2017; Shao et al., 2015; Wang et al., 2015a),
activated carbon (AC) (Davies and Yu, 2011), carbon where Ɛr is the relative dielectric constant in the double-
nanotubes (Wang et al., 2016b), carbon nanohorns (Izadi- layer, Ɛ0 is the permittivity of free space, and d represents
Najafabadi et al., 2011; Lin et al., 2017; Wang et al., 2017a; the effective thickness of a double-layer with a surface area
Zhang et al., 2015a), carbon fibers (Su et al., 2014; Wang A. As a result of the electrostatic charge storage mechanism
et al., 2017b; Zhu et al., 2017), carbon cloth (Jiang et al., including no faradaic reaction at the EDLC electrodes
2016; Wang et al., 2014a), and porous carbons (Luo et al., surface, EDLCs allow very rapid energy uptake and
2016; Wang et al., 2016c; Yun et al., 2015; Zhang et al., delivery, i.e., exhibit better power performance as
2014a) are characterized by electrochemical stability, high compared to batteries. Hence, highly reversible charging/
electrical conductivity, and the high accessible surface discharging and excellent cycling life (millions of cycles)
area besides its low cost and ease of processing. In addition are achievable for EDLCs, whereas batteries continue a few
to the highly accessible surface area, the porosity of the thousand cycles at best. Besides, the solvent of the elec-
active material governed the double-layer capacitance of trolyte is not involved in the charge storage mechanism,
the carbon-based materials. Chmiola et al. and Largeot et unlike in lithium-ion batteries where it contributes to the
al. (Chmiola et al., 2008; Largeot et al., 2008) reported the solid-electrolyte interphase. High-capacitance EDLCs are
relationship between pore size and ionic size, their study also achieved by increasing the electrode surface area,
illustrated that the highest Cs can be obtained when the which can be additionally increased by using a porous
size of the pore nearly matches the ionic size. Over the last structure. Nevertheless, because of the electrostatic surface
years, porous electrode structures have attracted consid- charging mechanism, EDLCs still suffer from a limited
erable attention, providing a very high SSA and well- energy density (Noori et al., 2019).
 S.Y. Attia et al.: Supercapacitor electrode materials 5

Pseudocapacitors and battery-type Although RuO2 and MnO2 are known as PC metal
materials oxides, redox peaks may appear in their cyclical voltam-
mogram (CV) curves if the experimental conditions are
Despite the outstanding enhancements in the structure of changed. For example, the CV of MnO2 noted in the po-
carbon-based materials, its low energy density usually tential range from −1.0 to 1.0 V (vs. Ag/AgCl) shows a clear
limits the EDLC-based SCs to just a few seconds of power set of redox couple (as in battery-type material), while the
delivery in applications. Accordingly, to overcome the CV in the potential range from 0 to 0.9 V is quite rectan-
challenge of low energy density in SCs, many research gular (i.e., capacitive nature) (Noori et al., 2019). This
efforts focus on developing other electrode active mate- finding suggests that PC possibly comes from a special
rials. SCs with greater energy densities can be attained by metal oxide state.
using PC materials which are considered as another PC materials typically show higher Cs and Ed compared
type of electrode active material for SCs, in which the to the EDLCs. Generally, the magnitude of Cs of PC material
storing of energy takes place by Faradaic charge-transfer is 1–2 orders greater than that of EDLC. PC systems, how-
reactions when the ions are adsorbed on or near the ever, frequently show low power and lack of a long life
surface of the electrode material electrochemically. An cycle and mechanical stability. The reason is that PC pro-
exchange of charges across the double-layer, instead of cesses generally include TMOs with poor conductivity and
a static separation of charges across a fixed distance, sluggish diffusion rate of ions (Kou et al., 2017).
results in oxidation-reduction reactions indicated as Figure 3b and c depicted the PCs materials and the
Oad + ne− → Red. battery type materials, respectively. Both are similar in the
The charge, ne−, exchanged in this reaction and the charge storage process that takes place via Faradic
energy storage are indirect and analogous to that of a reversible reactions but the main difference between them
battery. The most famous PCs materials are transition is in battery material the Faradaic reactions occur
metal oxides/sulfides/nitrides/phosphides and CPs (Wang throughout the bulk of the electrode involving the elec-
et al., 2012a). Monometal oxides such as RuO2 (Patake and trolyte contribution. Therefore, the material used for
Lokhande, 2008; Patil et al., 2011; Zheng et al., 1995), MnO2 battery-type must be fabricated in a way that permits the
(Dey et al., 2017; Huang et al., 2015; Rakhi et al., 2016), easy diffusion of the reacting ions throughout the material.
cobalt oxides (CoO, CoOOH, Co2O3, Co3O4) (Aloqayli et al., On the other hand, in PCs materials, there is no ion diffu-
2017; Cheng et al., 2017; Liu et al., 2013a; Zhu et al., 2015a), sion throughout the bulk of the material, but only all the
NiO (Liu et al., 2017; Meng et al., 2016; Sk et al., 2016), CuO Faradaic reactions take place on or near the surface of the
(Bhise et al., 2017; Chen and Xue, 2014; Wang et al., 2015b), active electrode materials. Therefore, the diffusion length
iron oxides (FeOOH, Fe2O3, and Fe3O4) (Liu et al., 2015a; (L) in PCs, should be much less than the diffusion layer
√̅̅
O’Neill et al., 2015; Zhao et al., 2016), and V2O5 (Lee and thickness, i.e., L < 2 Dt (Noori et al., 2019) where (D) rep-
Goodenough, 1999), and mixed metal oxides (ternary) resents the diffusion coefficient and (t) is the time of
(Zhang et al., 2015b) such as AB2O4 (A = Ni, Mn, Co, Zn diffusion.
or Cu, and B = Mn, Fe or Co) (Augustyn et al., 2014; However, not all Faradaic processes contribute to PC
Pendashteh et al., 2014) charge storage, since some of the Faradic reactions are
The pseudo-capacitive behavior of ruthenium oxide, noncapacitive in nature as in battery materials. Although
RuO2, is widely investigated. The electrochemical reaction Faradaic redox reactions are involved in both battery and
of RuO2 electrodes can be described as a fast, reversible, PC materials, both processes’ kinetics and electrochemical
and redox behavior as the following reaction profiles differ completely.
RuO2 + nH+ + ne− ↔ RuO2-n(OH)n (Noori et al., 2019). Generally, the relationship between current (i) and
However, high ruthenium costs limited their applica- potential scan rate (v) is expressed as (i = a vb) (Noori et al.,
tions to a number of high-value electronic equipment. 2019). In PC electrodes, the current changes linearly with
Academic institutions have focused on searching for other the sweep rate (i.e., b = 1).
materials cheaper than RuO2, such as other transition Therefore, PC kinetics resemble the electrochemical
metal oxides (iron, vanadium, nickel, and cobalt) and/or adsorption-controlled process (i.e., i α v), which is opposed
their corresponding sulfides. A suitable alternative to RuO2 to the redox diffusion-controlled process (i.e., i α v1/2)
appears to be manganese oxides with relatively low costs, governing the electrochemical performance of battery-type
low toxicity, environmental benignity, and potentially materials. Accordingly, the kinetic information from a CV
high theoretical capacitance up to 1300 F g−1. can, therefore, be used to distinguish between batteries
6 S.Y. Attia et al.: Supercapacitor electrode materials

and PCs. In this regard, it should be emphasized the main processes as illustrated in Figure 6. But the critical point
difference between capacitance and capacity. here is the confusion arises between PCs and batteries
materials since both are Faradic. There are two main
properties that enable to differentiate between PCs and
Capacitance versus capacity batteries (Arico et al., 2011; Simon and Gogotsi, 2010;
Zhang and Zhao, 2009), (i) phase change of the host active
Each storing process in EDLC and PC is known to be material in batteries which converts into obvious redox-
capacitive in nature and/or performance, with classic coupled CV peaks and GCD plateaus profiles (as seen in
rectangular CVs as presented in Figure 5a in which the Figures 5b and d), while the PCs material either exist CVs
current is almost constant with changing potential. And rectangular-shaped or CVs with significantly widened
their galvanostatic charge/discharge (GCD) profiles are peaks; (ii) the intrinsic kinetics of Faradaic processes
quasitriangular in shape as depicted in Figure 5c, in which since in batteries the Faradic redox reactions are
a linear time-dependent change in potential at constant controlled by diffusion processes of the ions from the
current is observed (Noori et al., 2019; Shao et al., 2018). electrolyte (i.e., I α v0.5) in which good linearity between
On the other hand, for batteries type materials, their CVs the square root of scan rate and peak current density of
are characterized by an obvious Faradic redox-couple as anodic or cathodic reactions (Attia et al., 2020), but in PCs
seen in Figure 5b and their corresponding GCD profile the current is directly proportional to the scan rate (I α v).
characterized by a relatively nonlinear time-dependent Some materials, for instance, the layered-structured
charge/discharge plateau at constant voltage stage as materials such as V2O5, TiO2, MoS2, and WS2 exhibit
exhibited in Figure 5d (Noori et al., 2019; Shao et al., 2018). diffusion-controlled (battery-like) behavior in their bulk
Now, it is important to distinguish between capacitance state, however, they behave like pseudocapacitive mate-
and capacity as following: capacitance is used to char- rials while turning to nanostructures and therefore called
acterize the capacitive charge storage process (EDLC or extrinsic pseudocapacitors (Choi et al., 2020). I.e., after
PC), and can be estimated by the following equation nanosizing, the traditional definition of “pseudocapacitive
C = ΔQ/ΔV (F), where, ΔQ is the amount of charge stored materials” cannot well differentiate it from that of “battery
along with a given voltage ΔV. On the other hand, the term materials”. Dunn and co-workers (Augustyn et al., 2014;
capacity is used to identify the non-capacitive Faradic Choi et al., 2020) provided that for extrinsic pseudocapa-
process (as in battery-type materials) and can be esti- citive materials, in the bulk phase, they behave as battery
mated by ΔQ/3.6 (mAh) (Noori et al., 2019). Now, it is clear materials, but after the size reduction, pseudocapacitive
to distinguish between the three types of charge storage behavior emerges.

Figure 5: Electrochemical behavior of typical

electrochemical supercapacitor and typical
battery.
(a and b) cyclic voltammogram curves, and
(c and d) galvanostatic charge-discharge
curves. ESR: represents equivalent series
resistance.
 S.Y. Attia et al.: Supercapacitor electrode materials 7

EDLCs PCs Battery

Capacitive – Capacitive Non-capacitive
non-Faradic Faradic
Faradic

Figure 6: Different charge storage mechanisms.

Supercapacitor versus battery

(charge/discharge performance)
The difference between the energy of a battery and SCs is Figure 7: Charge/discharge profiles of battery, EDLC, and hybrid
clearly shown in Figure 7. At the start of the discharge, the device (Noori et al., 2019). Copyright © 2019 The Royal Society of
voltage provided by the battery drops rapidly. After that, Chemistry.
the voltage will remain relatively constant until the battery
is nearly exhausted (referring to the discharge plateau), the
voltage will then drop sharply. Due to the relative long-
Scientific principles of SCs
term constant voltage of the battery, it is always hard to
Physical capacitors
determine exactly the state-of-charge of the battery, which
means that the batteries provide a steady voltage in the
A typical capacitor is that the parallel plates capacitor, in
vast majority of their discharge time (∼95%) (Noori et al.,
which when charging a capacitor, the plates will have
2019). On the other hand, as depicted in Figure 7, SCs
equal and opposite magnitudes of charge Q, producing a
output voltages almost linearly decrease as current flows,
voltage difference V between the terminals of the capacitor.
preventing its full spectrum of energy from being used.
The voltage difference between the two plates becomes
Practically, while there is still a lot of energy in the SC, after
zero when the capacitor is fully discharged. The charge Q
a certain voltage drop a connected device won’t work.
and the potential difference V are related to each other
Because the operating voltage of SCs changes linearly with
through the proportionality constant C, where C represents
time during the charge/discharge process, the state-of-
the capacitance of the capacitor.
charge of SCs can be measured accurately (Noori et al.,
The basic equation which defines the typical
2019). A fixed voltage line exhibits the discharge profile of
condenser process is (Shao et al., 2018), (Noori et al., 2019),
the battery, the area below the discharge line, qV, shows
(Halliday et al., 2013):
the battery energy. The voltage of a capacitor device that
charged up to a total charge q varies linearly with the Q = CV (2)
stored charge. The total energy a capacitor can store is
therefore equal to the area below the EDLC straight line, In a typical capacitor, the value of capacitance does not
i.e., ½ qV that can also be described as ½ CV2 (Noori et al., depend on the number of collected charges on the plates but
2019). depends on the voltage difference as well as the geometry of
The charge that is stored with SC is, therefore, half that the charged plates. The measuring unit of capacitance is in
of a battery when both are charged to a terminal charge of q farads (F) where 1 F = 1 coulomb/volt (C/V).
with the potential V. By differentiating Equation (2) with respect to time, we
In some cases, when the charge/discharge profile of obtain:
SC deviates noticeably from the typical capacitive
dQ C x dV
performance as exhibited in Figure 8, Therefore, the use of = (3)
dt Δt
E d = 21 Cs V 2 no longer holds, because the energy that
SC saves/delivers could either be overestimated or under- From a constant current definition: I = dQ/dt
scored (Noori et al., 2019). Therefore:
8 S.Y. Attia et al.: Supercapacitor electrode materials

Figure 8: The charge/discharge profiles of two

supercapacitors differ significantly from an
ideal capacitive performance.
(a) overestimated and (b) underestimated
(Noori et al., 2019). Copyright © 2019 The
Royal Society of Chemistry.

I x dt The energy stored (E) by the capacitor during the

dV = (4)
C charging process is the work done by the capacitor during
In a typical capacitor, however, the capacitance is charging:
constant, the capacitance of a capacitor depends on the Q 1 2 1 2 2 1
E = ∫V dQ = ∫ dQ = Q = C V = CV 2 (8)
voltage: C 2C 2C 2
Vf
I tf Another parameter used to identify the capacitor is its
∫ dV = ∫ dt (5)
Vi C ti power, which considered as the amount of stored or delivered
energy per unit time i.e., referring to the rate of energy transfer
I as written in the following equation (Shao et al., 2018):
ΔV = Δt (6)
C
E
P= (9)
From Equation (6), we can conclude the following: t
(1) In a typical capacitor, there is a linear relationship
Generally, The performance of SCs can be evaluated
between the applied voltage across the plates of
using several important parameters such as specific
capacitor ΔV, and time (t).
capacitance, energy, and power density:
(2) And the slope of changing voltage ΔV with time Δt is
I/C.
(3) The greater the capacitance, the more sluggish the
voltage throughout the capacitor changes (i.e., the Capacitance
greater the capacitance, the slower the voltage
throughout the capacitor that means taking more Capacitance for capacitive materials
time).
(4) The higher the current, the quicker the voltage across Since capacitance (C) is defined as the charge/storage
the capacitor, i.e., taking less time. capability (Q) of an SC across a specific voltage (V ),
(5) During charging (as the current moves across the
capacitor), the voltage will rise, and during discharg-
ing (when the current flows out of the capacitor), the
voltage will decline.

The energy stored during charging the capacitor or the

energy delivered during discharging the capacitor can be
obtained by integrating the area below the discharge curve
obtained from the GCD profile i.e., V–Q plot (as exhibited in
Figure 9).
The work (W) done by the capacitor when a certain
charge Q passes across it is (Noori et al., 2019):
Figure 9: (V–Q) a plot of a typical capacitor obtained at a constant
W = QV (7) current for a certain time.
 S.Y. Attia et al.: Supercapacitor electrode materials 9

ΔQ dQ/dt I For capacitive electrode materials

C= = =
ΔV dV/dt dV/dt
where (dQ/dt) represents the discharge current, (dV/dt) is As mentioned before (see Equation (8)), the energy stored
the slope of the discharge curve, and (dt) is the discharge during charging the capacitor or the energy delivered
time. during discharging the capacitor can be obtained by inte-
grating the area below the discharge curve obtained from
I I x dt
C= = the GCD profile i.e., V–Q plot
dV/dt dV
According to Equation (8), the measuring unit of en-
I x dt
Cs = ( F g−1 ) (10) ergy is Joule which must be converted into (Wh) as follow:
m dV
Q I xt Axs V
where (Cs) represents the specific capacitance. C= = ( ) by multiplying X
V V V V
I x dt 10
Cs = ( C oulombs g−1 ) (11) C=
I x V x t A x Vx s
( )
m V2 V2
where (Cs) represents the specific capacity and m is the
Since: power (W) = I (A) x V (volt)
mass of active material.
P xt W xs
∴C = ( 2 ) (14)
Capacitance for noncapacitive materials V2 V

ΔQ
By combination between units of Equations (8) and (14)
Since C = ΔV = IdV
dt I
= dV/dt
1 Wxs 2
I xV I x V x dt E= V
C= = 2 V2
V dV
dt )V
( dV E = 21 W x s since (E) represents the energy.
1 W x s 1000 h 1
By integration: Ed = x x = Wh/kg
2 g Kg 3600 7.2
I ∫ V dt I ∫ V dt
∴C = = 1
∫V dV V2 Hence, E d = CV 2 ( Wh/kg) (15)
2 7.2
2 I ∫ V dt
∴C = (12) where (Ed) represents the energy density for capacitive
V2
material.
2 I ∫ V dt Ed
∴C s (13) Pd = ( W/kg)
m V2 t
Where ∫V dt represents the area of the GCD-discharge curve 3600 x E d
Pd = ( W/kg) (16)
– I: is the applied current density. t( s)
– V: is the operating potential window. where (Pd) represents the power density for capacitive
– m: is the mass of active electrode material. material.

Energy and power densities For noncapacitive electrode materials

The specific energy or energy density of the electrode The energy stored during charging the capacitor or the
activated material or the device as a whole (Wh kg−1) is the energy delivered during discharging the capacitor can be
amount of the energy stored in storage devices by unit mass obtained by integrating the area below the discharge curve
or volume/area respectively. Specific power (W kg−1) or obtained from the GCD profile i.e., V–Q plot
power density is the quantity of power that an energy E = ∫Q dV
storage system can supply per unit mass or volume/area of
the active electrode or entire device. E = ∫C V dV
The connection between these two major parameters is
I x dt
reflected in the so-called Ragone plot, an important plot for E=∫ V dV
dV
comparing the performance of energy storage devices.
10 S.Y. Attia et al.: Supercapacitor electrode materials

E = I ∫ V dt

I ∫ V dt A.V.s W.s Wh 1000

Ed = ( = = × )
m g g kg 3600

where (I) is the applied current density, (V ) represents the

voltage window of the SC, (dt) represents the discharge
time obtained from GCD-discharge curve, and (∫Vdt)
represents the area under the GCD discharge curve, and (m)
mass of the active material.

I ∫ V dt
Ed = Wh/kg (17)
3.6 x m
3600 x E d
Pd = W/kg (18)
t ( s)
Figure 10: Schematic classification of the 2-electrode assembled
where (Ed) and (Pd) are the energy density and its corre-
device.
sponding power density for noncapacitive electrode
materials.
m+ Cs+ ΔV+ = m− Cs− ΔV−

m+ C xΔV−
Types of supercapacitor devices = (19)
m− C+ x ΔV+

Symmetric, asymmetric, and hybrid devices where m+ and m− are the mass loaded on each of positive and
negative electrodes (g), C− and C+ are the specific capacitance
The two-electrode cell setup is assembled from a pair of of each electrode (F g−1), and ΔV+ and ΔV− are the potential
electrodes (positive and negative electrodes) including the window of positive and negative electrodes (V).
active materials, isolated in a given electrolyte by an ion- Besides, there are excessive needs for the miniaturi-
permeable separator. SCs (Devices) are classified into two zation of power systems for environmental, medical, bio-
main groups; symmetric and asymmetric according to the logical, and other electronic applications. Consequently,
type of electrode active material used (as shown in the reduction in the size of the micro-power devices such
Figure 10). The symmetric device includes both positive as micro-supercapacitors (SCs) (Wang et al., 2011a) is
and negative electrodes of the same material, generally important for future improvement in portable electronic
made of EDLC based materials with the same mass load micro-devices. In recent years, great efforts have been
(i.e., m+ = m−). While for asymmetric SCs the two electrodes devoted to fabricating micro-SCs with different active
are made of two different active materials, i.e., one EDLC electrode materials, including carbon-based materials,
and one PC, gathering in the same electrolyte. Or using the CPs, and graphene/metal oxide composites. Moreover,
same electrode active material with different masses load various methods have been developed to prepare micro-
(m+ ≠ m−), also considered as asymmetric SCs. There is a SCs, such as photolithography, laser direct writing, print-
subtype of asymmetric SCs when one of the two different ing methods.
electrodes active materials is a noncapacitive faradic In 2013, El-Kady et al. (El-Kady and Kaner, 2013)
(i.e., battery type) and the other is a capacitive type, in this designed graphene micro-SCs through a scalable method,
case, the device is considered as hybrid SC [10]. they used a light scribe DVD burner to fabricate micro-SCs
on graphite oxide films by direct laser writing. And when
compared to previous energy-storage devices, this micro-
Mass balance equation supercapacitor displayed significantly higher power and
energy densities.
The mass load of the positive and negative electrodes should Wang et al. (Wang et al., 2011a) in-situ prepared a
be balanced to offset the Cs and Ed of the device. The charges flexible micro-supercapacitor using polyaniline nano-
stored on each of the positive and negative electrodes should wire arrays micro-electrodes, which attained high volu-
be balanced according to the following Q+ = Q− (Shao et al., metric capacitance (588 F cm−3), besides its high power
2018), (Noori et al., 2019), (Lee et al., 2011) density.
 S.Y. Attia et al.: Supercapacitor electrode materials 11

Performance parameters of operating voltage of SC. Cycling efficiency and rate capa-
bility can also be influenced by the ionic conductivity and
supercapacitors electrochemical stability of the electrolyte. It is possible to
classify aqueous electrolytes into acids (for instance,
The following three fundamental parameters “current, H2SO4), alkaline (for instance KOH), and neutral (for
voltage, and time” are essential to be measured to enable example, Na2SO4).
us to evaluate the electrochemical performance of SCs. Moreover, aqueous electrolytes show the following
And all the other parameters such as operating potential criteria: high ionic/electronic conductivity, low cost, sim-
window, energy density, power density, capacitance/ ple to handle, and non-flammable. Aqueous electrolyte
capacity, equivalent series resistance (ESR), retention SCs can reach higher capacitance than those with non-
capability, cycling stability, and coulombic efficiency can aqueous electrolyte.
be measured from them. The following electrochemical Nonetheless, because of the low thermodynamic water
techniques CV, GCD, and EIS are used to determine the stability window as well as the insufficient stability of
three important parameters. For example, EIS is suitable water throughout the long-life cycling test, the voltage
for measuring ESR, GCD profile is better to measure range is still being restricted. Therefore, its energy den-
the discharging time, capacitance/capacity, energy, and sities are limited. Recently, some researchers have
power, and CV is used to determine the suitable operating demonstrated that the aqueous neutral electrolytes may
potential window as well to differentiate between the show a large potential window of ∼1.6–1.9 V, which is
noncapacitive-type electrode and capacitive-type elec- higher than the theoretical voltage of water degradation,
trode. Also, it is important to highlight that the mea- 1.23 V (Abbas et al., 2015; Bichat et al., 2010; Demarconnay
surements of the 3-electrode (3-E) cell set-up differ from et al., 2010; Fic et al., 2012; Gao et al., 2012a; Lin et al., 2015).
that of device (2-electrode [2-E]) measurements. This large operating voltage window is owing to the high
overpotential of hydrogen (H2) evolving as well as the
generation potential [OH−] ion in the aqueous neutral
The operating potential window electrolyte. In accordance with the Nernst equation
(Ered = −0.059 pH), the potential would change to a lower
The operating potential window is the maximum possible value if the pH value increased. On the other hand, because
limit that ensures (i) the electrolyte’s chemical stability of its higher operating voltage windows of Organic elec-
against anodic and cathodic reactions, and (ii) the active trolyte and IL-based SCs usually varying between 2.5–2.8 V
electrode’s stability against decomposition. The term “po- and 3.5–4 V, respectively, both organic electrolyte-based
tential window” is typically applied to electrodes and the SCs and IL-based SCs dominate the markets at present
term “voltage window” for devices (Noori et al., 2019). A 2-E
cell setup only considers the device as a whole and does
not deliver any data about every single electrode that
formed the device. Therefore, while researchers’ ultimate
purpose is to produce an SC device (i.e., a 2-E system),
however, there is no alternative to use a 3-E to further
investigate in-depth active electrode materials and obtain
more information about individual electrodes.
Figure 11 summarizes the difference between the 3E –
and 2E – cell set up with respect to the CV profile of the
positive and negative electrodes individually or assembled.

Electrolyte

SCs commonly use electrolytes, typically divided into three

types (Zhong et al., 2015): (i) aqueous ionic electrolyte, (ii)
organic salt dissolved in an organic solvent, and (iii) ionic Figure 11: Schematic plots for CVs in a 3E cell setup, and of the
liquid (IL) which is pure liquid salt. The electrolyte is device (2E), respectively (Noori et al., 2019). Copyright © 2019 The
considered as one of the main factors determining the Royal Society of Chemistry.
12 S.Y. Attia et al.: Supercapacitor electrode materials

(Khomenko et al., 2008; Péan et al., 2015; Pohlmann et al., resistance between the active material and current collec-
2015; Sillars et al., 2012; Zhong et al., 2015). This increment tor, and (iii) concentration polarization results from mass
in the voltage window will boost the energy density transportation within the electrochemical reaction. Based
significantly. on this polarizing mechanism and/or the surface redox
The two most widely used solvents for organic elec- responses, at the interface of the electrode/electrolyte, a
trolytes are acetonitrile (ACN) and propylene carbonate passivation layer often forms. This passivation layer may
(PC). ACN is a very strong solvent for organic electrolytes influence the voltage window of the active materials and
since it can dissolve greater quantities of electrolyte salt their capacitance. Note, with different electrolytes
with stronger ion conductivity. However, during battery (different pH or different ion types), and with different
production and recycling ACN is still leading to environ- electrode material constructions (particle sizes or crystal
mental and toxic problems. PC solvent is considered safer phases), the voltage range can change.
and environmentally friendly than ACN. This may be In developing a high-performance flexible SC, gel
leading to a broader stable electrical window, a wider polymer electrolyte (solid-state) (Samui and Sivaraman,
temperature range of operation, and an appropriate con- 2010) has an important role to enhance ion mobility, thus
ductivity of the ion. There is also a very strict requirement the ionic conductivity and consequently, the electro-
for the organic electrolyte to hold moisture below 3–5 ppm chemical response of SC. Solid-gel polymer electrolyte has
(Zhong et al., 2015). If not, there will be significant perfor- many advantages over liquid electrolytes, for example,
mance loss, decreased voltage window, and even safety being environmentally safe since there is no risk of spillage
challenges. in electrical energy systems, also it can be used as a thin
The IL has a melting point below a certain temperature film, both as an electrolyte and a separator.
level, where the atmosphere can supply the necessary heat. A series of conducting thin-film solid electrolytes
The ILs have a variety of characteristics, including low based on a poly(vinyl alcohol)/poly(vinyl pyrrolidone)
flammability, low vapor pressure, chemically stable and (PVA/PVP) polymer blend was made by the solution-
thermal stability, and a wider electrical voltage window casting technique (Hatta et al., 2005). The conductivity of
from 2 to 6 V, usually 4.5 V, but it has lower ionic con- the PVA/PVP blend that had a composition of 80% PVA
ductivity than both organic and aqueous electrolytes and 20 wt% PVP was the highest at around 10−7 S cm−1. The
(Watanabe et al., 2017). PVA/PVP blend with the highest conductivity was then
Organic electrolytes and ILs are typically characterized studied further by adding different amounts of potassium
by (i) lower ion conductivity and greater viscosity hydroxide ionic dopant using water was as a solvent to
compared with aqueous electrolytes, thereby preventing prepare PVA/PVP–KOH-based alkaline solid polymer
the penetration of ions. (ii) Moreover, since the ionic con- blend electrolyte films, the conductivity increased to
ductivity is at least one order less than that of aqueous 10−4 S cm−1 by adding 40 wt% KOH.
electrolytes, the internal resistances of SCs are higher.
Therefore, the capacitance of organic or IL-based electro-
lyte SCs is relatively low and displays a low power density. Full cell voltage of the device
Such SCs also face high costs of ILs and safety issues of
organic electrolytes concerning their high toxicity, flam- As mentioned before, the electrolyte is considered as one of
mability, and ease of volatility (Shao et al., 2018). the main factors to determine the stable potential window
Furthermore, the electrolyte decaying and the electrode of SCs. Only within a stable potential range can every
material oxidation will happen when the used voltage electrolyte be operated. .The electrolytes’ stability depends
exceeds the stable voltage window. Thus, electrolytes and on many factors including salt type (cations and anions),
active materials are aging more rapidly and even the SC solvent, and purity levels. Three key factors decide the
may destroy. operating voltage of the SCs: (i) the stable electrolyte
Some kinetic effects must be considered to determine operating window, (ii) electrode’s standard potential limit,
the voltage window and electrochemical behavior. These and (iii) the passive layer at the interface between elec-
kinetic effects lead to polarization in the electrode active trode/electrolyte. The voltage window of the overall SC is
material; three types of polarization that take place are given as the following (Shao et al., 2018):
(Winter and Brodd, 2004): (i) activation polarization con-
E device = E positive − E negative
cerning with Faradaic charge-transfer system, (ii) ohmic
polarization which defined as the summation of ionic and For the SC system, separated electrodes’ potentials are
electronic resistance of cell parts besides the contact extended in the opposite direction during charging until
 S.Y. Attia et al.: Supercapacitor electrode materials 13

each electrode reaches approximately the same capaci- Equivalent series resistance (ESR)
tance. Therefore, the operating voltage window of the
device depends on the upper and lower potential limits of The ESR is well defined as the summation of bulk electro-
the positive and negative electrodes, respectively. lyte resistance, the contact resistance between the elec-
As demonstrated in Figure 12, for aqueous asymmetric trode and the current collector, and the electrode itself
structure. The overpotential for oxygen evolution at the resistance (Mei et al., 2018). ESR is a significant factor that
positive electrode (such as RuO2 or MnO2) and the over- restricts the speed at which an SC can start the charging or
potential for the evolution of hydrogen at the negative discharging process, therefore, the more the ESR value the
electrode (such as carbon or Fe3O4) extend beyond the low the power performance of the SCs.
thermodynamic stability of water, even up to 2 V (Shao
et al., 2018).
In Figure 12 some points must be considered: Rate capability
(i) The aqueous electrolyte’s thermodynamically stable
range is the energy difference (e.g.,) between the Rate capability is well-defined as the device’s ability to
lowest unoccupied molecular orbital (LUMO) and the maintain capacitance/capacity as current density rises
highest occupied molecular orbital (HOMO) (Good- (Zhou et al., 2010). A system with a high rate capability
enough and Kim, 2010). indicates the fast kinetics of electrochemical active elec-
(ii) When the applied potential (µp) of a positive electrode trode material i.e., the ease of ion diffusion, short diffusion
more than HOMO, the electrolyte will oxidize if it does pathways, and fast electrons/ions transportation.
not form a passive layer for the movement of the
electrons from the (HOMO) to the positive electrode
(Goodenough and Park, 2013). Cycling performance
(iii) When the negative electrode has lower applied a
potential (µn) than that of (LUMO), the electrolyte Cycle stability is described as the extent of how well the
reduction will be done unless the passive layer pre- device is charged/discharged repeatedly. Cycle stability is
vents the transfer of electrons from the negative generally defined as a percentage of the initial capacity/
electrode to the electrolyte (LUMO) (Goodenough and capacity the device maintains after a specific number of
Park, 2013). i.e., in the absence of the passivation cycles. Generally, the capacity/capacitance of the device
layer, the electrode electrochemical potentials (µp) sufferers as it stays charge/discharge (Xia et al., 2015).
and (µn) should be located within the theoretical
thermodynamic stability range of the electrolyte. In
Coulombic efficiency
other words, the voltage window of the complete cell
device may extend the thermodynamic stability win-
Coulombic efficiency (CE) is the ratio of the total charge
dow of the electrolyte when there is a passive layer.
takes out from the device/electrode to the total charge
put into the device/electrode over a full cycle. If the dis-
charging time equals the charging time, in this case, the
device delivered 100% coulombic efficiency (Noori et al.,
2019).
CE can be measured from the following relation:
– CE% = ttdc × 100. Where td and tc are the discharge and
charge time.

Electrode materials for

supercapacitors
Selecting electrode materials referring to its conductivity,
surface morphology, porosity, and effective surface area
Figure 12: Schematic diagram depicting an aqueous system’s cell can affect the nature of charge storage as well as the per-
operating potential window. formance of SCs. Therefore, further development of new
14 S.Y. Attia et al.: Supercapacitor electrode materials

materials with a unique structure will provide an abun- size for a given ionic electrolyte size can be established by
dance of active sites, and offering effective paths for the scientific research. Some studies indicate that for aqueous
diffusion of ions, besides the increased conductivity, electrolytes, the pore size of 0.4 or 0.7 nm can be helpful
which promotes electron transport during electrochemical while the pore size of 0.8 nm would match organic elec-
redox reactions. This will all show the high potential of this trolytes (Raymundo-Pinero et al., 2006; Salitra et al.,
material in practical applications of SCs. Now, the most 2000). Some reports have investigated the relationship
common active electrode materials used for SCs will be between the pores and the ion size to achieve maximum Cs
introduced. (Ania et al., 2007; Zhong et al., 2015). Functional groups
on the surface of carbon-based materials can also boost
Faradaic redox reactions, leading to an increase in the Cs
Carbon-based materials of approximately 5–10% (Kötz and Carlen, 2000). An
electrode made from AC with SSA of 1000 m2 g−1 roughly
Owing to its superb electronic conductivity, great SSA, delivered a Cs of 100 F g−1 in an aqueous electrolyte
abundance with low cost, safe processing, high thermal (Pandolfo and Hollenkamp, 2006; Shao et al., 2018).
and chemical stability, carbon-based materials attract Carbon Aerogel is an ultra-light, porous synthetic mate-
great interest as active electrode material for SCs (Jiang rial made from a cross-linkage network of carbon nano-
et al., 2013; Presser et al., 2011; Wang et al., 2016d; Zhang particles (Arico et al., 2011; Li et al., 2006). It can combine
and Zhao, 2009; Zhang et al., 2009). Carbon-based mate- with the current collectors without a binding agent
rials exhibit a strong rectangular type of CV curves and because combined with the current collector chemically.
symmetrical GCD profile indicating its typical capacitive Therefore, it attains less ESR which produces high Pd.
performance (Gao et al., 2014a). The electrochemical per- Electrodes made from carbon aerogel exhibited a Cs of
formance of carbon-based materials depends mainly on 104 F cm−3 and delivered an Ed of 90 Wh kg−1 and Pd of
their accessibility to the electrolyte ions. Consequently, the 20 W kg−1 (Chien et al., 2012).
Cs of carbon-based materials shall be controlled by the Roldan et al. (2011) improved the Cs of several
effectiveness of SSA, porosity, electrical conductivity, and carbon-based electrodes by the addition of hydroqui-
surface functionality (Arbizzani et al., 2001; Frackowiak none into the electrolyte however its lower cycling life
and Beguin, 2001; Raymundo-Pinero et al., 2006; Salitra performance still challenges (65% of Cs retained after
et al., 2000; Wang et al., 2012a). As suggested by Conway 4000 cycles). Wang et al. (2011b) utilized an electrode
(Conway, 2013) the double-layer carbon-type SCs must made from rGO treated with t-Bu-hydroquinone, the as-
have the following three characteristics: (1) high enough prepared electrode reached a strong Cs through the
SSA, reach to 1000 m2 g−1; (2) sufficient intra-/interparticle retention of 94% efficiency after 800 cycles. Chen et al.
conductivity in the porous matrices; and (3) sufficient ac- (Chen et al., 2014a) have reported an improvement in the
cess of electrolyte to the intrapore space of carbon-based Cs by adding porous CNT to anthraquinone. Campbell
materials. Therefore, the choice of electrode materials for et al. (2014) have described a process to increase the Ed of
use in SCs, measured by their high and accessible surface graphene macro-assembled using anthraquinone as a
area along with the strong electronic conductivity (Chen non-covalent functionalizing agent and the obtained
et al., 2015; Wang et al., 2012a). The most famous carbon- hybrid-electrode possesses an Ed of 23 Wh kg−1 which is
based materials are; AC (Fang and Binder, 2006; Lu et al., 2.9 times more than the pristine graphene macro-
2017a), carbon aerogels (Endo et al., 2001), carbon nano- assembled electrodes.
tubes (Shiraishi et al., 2002), porous carbons (Portet et al., A single layer Graphene, 2D carbon-based, has much
2009), and carbon nanofibers (Xu et al., 2008). attention because of its exciting achievements, which
AC is the first chosen material for the EDLC type of include high electronic conductivity, good mechanical
SCs (Yang et al., 2002). These materials are porous strength, and high SSA. Theoretically, graphene SSA of
with large SSA, even its conductivity is relatively low 2630 m2 g−1 can supply a Cs of 550 F g−1 1. Graphene sheets
(1250–2500 S m−1), it is still adequate for SCs applications. were used as electrodes for SCs by El-Kady et al. (2012) The
AC classified into micropores (<20 Å), mesopores (20–500 Å) used graphene sheets are not stacked yielding a mesopores
and macropores (>500 Å). The porous structure of AC structure that facilitates its wettability by ionic electrolytes
contributes to its high SSA (Arbizzani et al., 2001; Frack- reaching a voltage window up to 4 V. This SC can deliver an
owiak and Beguin, 2001). Sometimes, the whole SSA of AC Ed of 85.6 Wh kg−1 which is equal to the nickel-metal
is not helpful for the Cs if the electrolyte ions are large, in hydride battery and exhibit Pd greater than the battery (Liu
size, to enter the smaller micropores. The suitable pore et al., 2010b).
 S.Y. Attia et al.: Supercapacitor electrode materials 15

One-atomic thick carbon sheets, so-called, chemically Figures 14a and b exhibit the field emission scanning
modified graphene, manifest a Cs 135 F g−1 in an aqueous electron microscopy (FE-SEM) images of the as-synthesized
electrolyte and 97 F g−1 in an organic electrolyte (Stoller α-MnS and α-MnS/rGO, respectively. Figures 14c and d show
et al., 2008). Xu et al. (2013) demonstrated the ability to the transmitted electron microscopy (TEM) images of α-MnS
display a flexible SC with a 120 μm graphene thick-film, and α-MnS/rGO, respectively. Figure 14c shows the aggre-
showing a Cs 186 F g−1. gated- and folded-flakes of α-MnS, while Figure 14d displays
Reduced graphene oxide (rGO) manifests a Cs of about that the presence of rGO inhibits its aggregation.
100–150 F g−1 in organic electrolytes (Liu et al., 2010b; Wen
et al., 2012), and 150–230 F g−1 in aqueous ionic electrolytes
(Lei et al., 2012; Wang et al., 2012b) which is still lower than Transition metal oxides, sulfides, and
its theoretical Cs (550 F g−1). The lower value of Cs may be hydroxides
attributed to the restacking of the separate sheets of rGO
during the reduction or drying method (Wen et al., 2012), Choosing suitable electrode materials and designing are
which makes most of the surface of rGO not accessible for key issues for reaching high energy and power densities in
charge storing. the performance of asymmetric and/or hybrid SCs. Gener-
Owing to their relatively high SSA, good conductivity, ally, metal oxides can deliver much higher energy density
and good mechanical strength, 1D carbon nanotubes have for SCs than that of conventional carbon-based materials
extensively been studied as active electrode material for and better electrochemical stability than polymeric mate-
SCs or as conductive substrates for SCs (Hu et al., 2009; rials (Sharma et al., 2019). Their energy storage not only
Kaempgen et al., 2009; Lin et al., 2013). A lot of researchers like electrostatic carbon-based materials but also show
reported the use of a CNT-based electrode for hybrid SCs. electrochemical Faradaic reactions between electrode
Singh et al. (2014) hydrothermally synthesized nano- active materials and the electrolytic ions within suitable
particles of NiS on the surface of multiwalled CNTs using voltage windows (Zhao et al., 2007).
graphene as a negative electrode. The assembled hybrid The general metal oxide requirements in SC applica-
device showed a Cs of 250 C g−1 at 1 A g−1. Suggesting, one of tions are as follows (Conway, 2013): (1) the oxide should be
the most efficient strategies to enhance the electrochemical conductive electronically, (2) in multiple oxidation states,
performance of SCs is the deposition of Faradaic materials the metal can coexist over a continuous range without
on conductive carbon-based materials (Borenstein et al., changes to phase without any phase changes involving
2017). The compositions, characteristics, and efficiency of irreversible modifications of the 3-dimensional structure,
these composite electrodes are summarized in Table 1. and (3) the ease of moving of ions during the intercalation
Nagaraju et al. (2014) described the preparation of nano- into the oxide lattice within reduction (and out of the lattice
sheets of rGO/V2O5 electrodes, delivering almost double within oxidation), allowing easy interconversion of
the energy of the pristine electrode of 2D V2O5. Wang et al. O2− ↔ OH−.
(2014b) investigated the growth of nanoflakes structure of To date, explored metal oxides include ruthenium
NiO hydrothermally upon 3D graphene skeletons. The as- oxide, manganese oxide, cobalt oxide, nickel oxide, and
prepared composite material manifests a Cs of 1097 C g−1. vanadium oxide (Wang et al., 2012a). RuO2 is a well-studied
Mohamed et al. (2018a) have reported an achievable pro- material, and its charge storage is described as a rapid
cess to boost the electrochemical performance of nano- reversible redox reaction combined with the electro-
flakes α-MnS by combining α-MnS with an underlying adsorption of ions on the RuO2 surface. For the positive
conductivity-supporter rGO forming a composite of α-MnS/ part of an asymmetric SC, RuO2 is the most desirable
rGO. The mechanism of synthesis of α-MnS nanoflakes and pseudocapacitive active electrical material, but the high
α-MnS/rGO is illustrated and schematically proposed in ruthenium cost restricts its widespread use (Trasatti and
Figure 13. The existence of rGO acting as a matrix for the Kurzweil, 1994). Researchers have attempted to develop
nanoflakes of α-MnS, suggesting an effective way to RuO2 composites with different carbon materials to
improve the electronic conductivity as well as offering a decrease the RuO2 percentage without loss of its capaci-
large electrode/electrolyte accessible surface area for the tance. Hwang et al. (2015) recently, revealed an asymmetric
charge-transfer reaction, and effective pathways for ions SC using a composite of laser-scribed graphene (LSG)/hy-
transportation (Quan et al., 2016; Tang et al., 2015). The drous-RuO2 acting as a positive electrode and AC as a
obtained Cs of the α-MnS/rGO reached 700 F g−1 at a current negative electrode. Figures 15a and b, exhibited the TEM
density of 1 A g−1 which is a superior value compared to and SEM images, respectively of nanoparticles RuO2 that
α-MnS (240 F g−1). have been successively precipitated on the graphene flakes
16 S.Y. Attia et al.: Supercapacitor electrode materials

Table : Comparison of positive electrode, negative electrode, operating voltage, and retention (after cycling) for different supercapacitors
electrodes.

Positive electrode Negative electrode Operating voltage Retention Ref

(cycles)

FeCoS/reduced graphene AC . V polyvinyl alcohol/KOH .% () (Yan et al., )
oxide film
FeCoS Hollow nanoneedle AC . V ( M KOH) .% () (Huang et al., )
arrays HNNA @ carbon nanofibers.
NiCoS/N-doped carbon foams Mesoporous carbon/ . V ( M KOH) .% ( ) (Shen et al., b)
N-doped carbon foams
NiCoS/graphene aerogel. AC . V polyvinyl alcohol/KOH .% ( ) (Li et al., a)
CoNiO/D C AC . V ( M KOH) % () (Zhu et al., )
Co−Ni−S/carbon fiber Graphene/carbon fiber . V ( M KOH) .% (,) (Chen et al., b)
MoO−x/CNTs CNTs . V (LiCl/PVA) % (,) (Xiao et al., b)
NiS/CNTs AC . V ( M KOH) % () (Dai et al., )
Ni(OH)/CNTs/carbon fiber AC . V (KOH) % () (Tang et al., )
NiS/CNTs Graphene . V ( M KOH) % () (Singh et al., )
VO/reduced graphene oxide Reduced graphene oxide . V ( M KCl) (Nagaraju et al., )
NiO/D graphene AC . V ( M NaOH) % () (Wang et al., b)
Ni(OH)/graphene Graphene . V ( M KOH) .% () (Yan et al., )
NiCoO/graphene AC . V ( M KOH) (Wang et al., c)
NiCoO/graphene AC . V ( M KOH) % () (Li et al., )

Figure 13: Schematic illustration of the

synthesis of MnS and α-MnS/rGO (Mohamed
et al., 2018a). Copyright © 2018 Wiley‐VCH
Verlag GmbH & Co.

surface. In this case, the (LSG) wrapping construction RuOx(OH)y + zH+ + ze− ↔ RuOx
inhibits the aggregation of nanoparticles RuO2 as well as − z(OH)y + z(Max(z) = 2).
provides and facilitates effective paths for ionic/electronic
transportation. The (LSG) wrapping RuO2 electrode dis- According to the GCD curve, the graphene/RuO2 com-
played noticeable pseudocapacitive performance and its posite electrode has reached a Cs of 1139 F g−1. According to
reversible redox-reaction charge storage according to the Figure 15d, the asymmetric SC was assembled. The positive
following equation (Long et al., 1999): and negative electrode curves shown in Figure 15e are first
 S.Y. Attia et al.: Supercapacitor electrode materials 17

Qu et al. (2009) explored the MnO2-(δ-type) in various

neutral electrolytes including lithium sulfate, sodium sul-
fate, and potassium sulfate.
The hydrated ions of (K+) have the least ionic radius
(3.31 Å) and the maximum ionic conductivity of these
different neutral aqueous electrolytes. Therefore, its
accessibility to the inner surface of δ-MnO2 is faster and
easier than the other two ions.
Consequently, the nanorods MnO2 demonstrated the
highest capacitance in the K2SO4 aqueous electrolyte at a
high scan rate than the other electrolytes.
Moreover, MnO2 was used as a positive electrode in
connection with the AC as a negative electrode to assemble
an asymmetric SC in 0.5 mol/L aqueous electrolyte K2SO4.
In addition to the high surface absorption/desorption
redox reactions of MnO2 and the high reversibility of AC,
the assembled asymmetric SC showed excellent cycling
Figure 14: (a–b) The FE-SEM of the as-synthesized α-MnS and efficiency, with capacitance retention of 94% of its initial
α-MnS/rGO, and (c–d) exhibited the TEM image of α-MnS and
value even after 23,000 cycles. Due to its PC performance
α-MnS/rGO, respectively (Mohamed et al., 2018a). Copyright © 2018
Wiley‐VCH Verlag GmbH & Co.
that occurs on or near the surface, the efficiency of MnO2 is
significantly influenced by morphology, surface area, and
particle size (Wei et al., 2011).
examined to measure the respective capacity and stable Huang et al. (2014a) reported an effective hydrother-
potential windows. Figure 15f displays the CV curves of the mal approach to manufacture porous structured nano-
assembled asymmetric cell which provide a maximum tubes of MnO2. The as-prepared microstructure provides a
output voltage of 1.8 V, which are both rectangular and highly effective contact area of MnO2, shortens the ion
capacitive in nature. MnO2 was one of the most desirable diffusion pathways, and rapid kinetics between the active
positive electrode candidates to replace RuO2 among the material and the electrolytic ions.
various PC materials, because of its abundant, cheap, and Jiang et al. (2012b) demonstrated the preparation of
relatively high theoretical Cs (Dupont and Donne, 2015; Ou nanoflowers structured of MnO2, these nanoflowers
et al., 2015; Wei et al., 2011). Usually, neutral aqueous consisted of thin nanoflakes. The SSA of this material was
electrolytes are used for MnO2. Table 2 summarizes the examined and exhibited nearly 213 m2 g−1. The inter-
electrochemical outputs of asymmetrical SCs based on connected nanoflakes provide effective pathways and
MnO2. access for ions transportation. Though MnO2 is one of the

Figure 15: (a) The SEM image, (b) the TEM

image of the nanoparticles (LSG)-wrapped
RuO2, (c) The scheme illustrates the
structure of LSG/RuO2 demonstrating the
cause of rapid ion/electron
transportation, (d) The structure of
assembled asymmetric SC, (e) the CV
curves of the individual positive and
negative electrodes, and (f) the CV profiles
of the assembled asymmetric
supercapacitor of LSG/RuO2//AC within
different operating voltages windows
(Hwang et al., 2015). Copyright © 2015
Elsevier Ltd.
 18 S.Y. Attia et al.: Supercapacitor electrode materials

most attractive pseudocapacitive electrode materials, its

(Sumboja et al., )

(Huang et al., b)

(Zhang et al., b)

(El-Kady et al., )

(Su and Miao, )

(Cheng et al., )

(Chen et al., a)
(Wang et al., )
(Hong et al., )

(Hong et al., )

low conductivity remains the key limit for reaching high Cs,

(Chen et al., )

(Gao et al., c)

(Wu et al., b)
(Guo et al., )
(Xie et al., )
rate capability, and cycle performance.
Two main methods have been developed to further
increase the conductivity of MnO2. The first is the direct
growth of MnO2 on the surface of the current collector (Gao
Ref

et al., 2012b). The second is forming a composite with a

highly conductive carbon material (Yu et al., 2011).
Retention (cycles)

% ()
.% ()
.% ()

.% ()

.% ()
% ()
.% ( )
.% ( )
% ()

% ( )

% ( )
% ()
For example, Gao et al. (2012b) reported the electro-
deposition of vertically aligned nameplates MnO2 on the
surface of Ni foam. And an asymmetric device was fabri-
cated using MnO2 precipitated on the surface of Ni foam as
a positive electrode and graphene hydrogel as a negative
electrode. This assembled SC reached an Ed of 23.3 Wh kg−1
 kW/kg

. kW/kg
Power density

 W/kg
.W/kg
.W/kg

. Wh/kg

. mW cm−

within a voltage window of 2 V.

Other transition metal compounds, such as cobalt
oxides or nickel oxides, or their hydroxides are considered
typical battery-type Faradic materials that can be used as
positive electrode material in connection with capacitive
Energy density

. μWh cm−

. Wh/kg
. Wh/kg
. Wh/kg
. Wh/kg
. Wh/kg
. Wh/kg
. Wh/kg
 Wh/kg
. Wh/kg
. Wh/kg
. Wh/kg

. Wh/kg
 Wh/kg

carbon materials for assembling hybrid SCs. These battery-

type electrodes attract a lot of attention due to their high
theoretical capacity (C g−1) and their low cost.
Owing to its structure of spinel crystal, Co3O4 can
supply a 3D ions diffusion architecture. During charging of
Co3O4 in the aqueous ionic electrolyte, the Co3O4 phase is
. V ( mmol I/ M NaSO/. M KI)

changed into the oxyhydroxide phase throughout revers-

ible redox Faradic reactions indicating typical battery-type
phase transformation (Shao et al., 2018).
Table : The electrochemical performances of MnO-based asymmetric supercapacitor.

Vidyadharan et al. (2014) prepared ultrathin nano-

wires Co3O4 and utilized it in a hybrid SC as the positive
. V ( M NaSO)

 V (. M NaSO)

. V ( M NaSO)
. V ( M NaSO)

. V ( M NaSO)

electrode material. Showing a capacity of ∼555 C g−1 at

. V (KCl/PAAK)
 V ( M NaSO)
 V ( M NaSO)

 V ( M NaSO)

 V ( M NaSO)

 V ( M NaSO)
 V (HPO/PVA)
Voltage window

. V (LiCl gel)

1 A g−1 and ∼100% CE. Tunable mesoporous Co3O4 nano-

 V ( M KCl)

structure exhibited a Cs of 85 F g−1 at a high current density

of 20 mA cm−2 and maintained 93% cycling retention in 3 M
KOH (Xiong et al., 2009). Ultra layered structured of Co3O4
showed a good Cs (548 F g−1) at 8 A g−1(Meher and Rao,
Graphene hydrogel
Negative electrode

2011). A 3-D hollow structured Co3O4 exhibited a Cs of

Graphene/CNTs

548 F g−1 at 5 mV s−1 (Wang et al., 2014c). Nanoporous

Porous carbon

Porous carbon

CNT/graphene
Carbon fiber

structured Co3O4 exhibited a Cs of 476 F g−1 and delivered

Graphene

CNTs/AC

an Ed of 42.3 Wh kg−1 (Deori et al., 2013).

FeSe

CNTs
CNTs

LSG
rGO

Owing to its high theoretical capacity and natural

AC

AC

abundance, Co(OH)2 is also a promising candidate to be

used in hybrid SC as a positive electrode active material.
MWCNTs/MnO/PPy composite

Also, there are usually several angstroms spacing between

the layers of these hydroxides, which facilitate the inter-
δ-MnO/Porous carbon

MnO/CNTs/graphene
MnO/porous carbon

calation of the electrolytic ions (Augustyn et al., 2014).

MnO/carbon fiber
Positive electrode

MnO/graphene

Gao et al. (2014b) had constructed a hybrid SC with the

MnO/graphene
MnO/graphene

positive electrode made of single-layered β-Co(OH)2 and

MnO/CNTs

MnO/CNTs
MnO/CNTs

MnO/LSG
MnO/rGO

the negative electrode made of N-doped graphene. As

shown in Figure 16, the thin layered β-Co(OH)2 structure
MnO

MnO

facilitates the diffusion of electrolyte ions as well as

 S.Y. Attia et al.: Supercapacitor electrode materials 19

provides the electroactive sites. Consequently, the single- as electrochemical efficiency in comparison to their individ-
layered β-Co(OH)2-based electrode material delivered a ual or mono metal oxides (Jiang et al., 2012c; Pendashteh
remarkable capacity of 1420 C g−1. Similarly, nanolayered et al., 2014; Zhou et al., 2014). Spinel structure of Cobaltite
α-Co(OH)2 deposited upon a stainless steel substrate MCo2O4 (M = Mn) (Liu and Wang, 2013), Ni, Fe (Jiang et al.,
exhibited a Cs of 860 F g−1 for a 0.8 mg cm−2 in 1 M KOH 2012c; Xu et al., 2017), Cu (Gu et al., 2015; Naik et al., 2017), or
electrolyte (Gupta et al., 2007). Zn (Hu et al., 2013) have attracted much interest because of its
On the other hand, Luan et al. (2013) developed a ability to store and supply large amounts of charges owing to
hybrid device in which the positive electrode is made of a its multiple oxidation states beside its good electrical con-
nanoflakes array of NiO and the negative electrode is made ductivity compared to mono metal oxides (Lee et al., 2016;
of a film of reduced graphene hydrogel. The hybrid device Yang et al., 2013). For example, nickel cobaltite (NiCo2O4)
could reach a window of 1.7 V. Yu et al. have developed a showed much more electrical conductivity than those of
cost-effective approach utilizing a feasible method of mono metal oxides as nickel oxide or cobalt oxide (Wu et al.,
activation for the construction of porous Ni@NiO core– 2015, 2016). Hierarchical NiCo2O4 was successively synthe-
shell electrodes active material. The porous active Ni@NiO sized by the hydrothermal approach and investigated as an
electrode exhibited a capacity of 1.2 C cm−2 at 8 mA cm−2 (Yu active electrode material for SCs and exhibited a remarkable
et al., 2014). Senthilkumar and Selvan (2014) assembled a Cs of 1393 F g−1 at 0.5 Ag−1, with excellent stability (Wang
hybrid device using β-Ni(OH)2 as the positive electrode and et al., 2016e). Yuan et al. (2012) synthesized nanosheets
AC as the negative electrode. The fabricated device dis- structure of NiCo2O4 and utilized it as an active electrode for
played a stable voltage window up to 1.4 V. In the same SCs, exhibiting a great electrochemical behavior with a Cs of
manner, Huang et al. (2014c) fabricated a hybrid device 1450 F g−1 at 20 Ag−1. A core–shell nanotube array of
using β-Ni(OH)2 @ Ni acting as a positive electrode and the ZnCo2O4@MnO2 (Figure 17) was prepared and delivered a Cs
negative electrode is constructed from AC. This hybrid SC of 1981 F g−1 at 5 Ag−1 (Ma et al., 2015). As well as, asymmetric
was examined in an aqueous ionic electrolyte and showed SC was assembled in which ZnCo2O4@MnO2 nanotubes on Ni
790.3 C g−1 of specific capacity. foam as a positive electrode and Fe2O3 on the iron sheet as a
TMOs have been widely explored as active electrode negative electrode, showing Ed of 37.8 Whkg−1 with excellent
materials for SCs because of fast electrochemical response, capacitance retention 91% even after 5000 cycles within a
environmental cleanness, low manufacturing cost, and their voltage window of 1.3 V.
feasible processability (Wang et al., 2012a). However, the Iron oxide and cobalt oxide both exhibited a high
relatively low electronic conductivity of these oxides limits electrochemical behavior. Therefore, it is expected that the
their utilization due to a decline in their capacitive perfor- co-existence of both iron and cobalt in iron cobaltite
mance over long-life cycling (He et al., 2012a; Ji et al., 2013; (FeCo2O4) showed an excellent active electrode material
Pendashteh et al., 2013; Zhu et al., 2016a). Bimetallic transi- that offered more redox reactions than its corresponding
tion metal compounds showed better electrochemical per- single components, in much the same way as nickel
formance than monometallic. In this respect, SCs’ cobaltite (Jiang et al., 2012c). Iron attracts great interest as a
applications are especially sensitive to mixed transition metal substituent because of its environmental benignity,
oxides as they have improved electronic conductivity as well abundance, and low cost (Yang et al., 2011). So far,
research on iron cobaltite is not enough (Mohamed et al.,
2014), but the results on its electrochemical energy storage
performance suggested its potential as electrode active
material for SCs application (Mohamed et al., 2014; Yuan
et al., 2014). Porous architectures electrodes are a powerful
method to progress the electrochemical performance of the
electrode materials. Since the existence of porosity leading
to an increase in the electrode/electrolyte contact interface
area, shortening the paths of charge/ions transfer, as well
as motivating the electrolyte penetration (Salunkhe et al.,
2014; Torad et al., 2014; Yang et al., 2011; Zhu et al., 2016b).
Very recently, porous FeCo2O4 nanowires have been
Figure 16: Scheme diagram of the single-layered β-Co(OH)2
examined as an electrode active material for SCs which
showing the adsorption/desorption of electrolyte ions (Gao et al., showed a Cs of 407 F g−1 at a scan rate of 10 mV s−1 in initial
2014b). Copyright © 2014 WILEY‐VCH Verlag GmbH & Co. cycling (Pendashteh et al., 2015). The growth mechanism of
20 S.Y. Attia et al.: Supercapacitor electrode materials

explored and displayed a Cs of 1.88 F cm−2 at 100 mA cm−2

(Zhu et al., 2014).
Mohamed et al. (2017) have been reported a simple
preparation of FeCo2O4 nanosheets, a highly porous
structure. This high porous structure was electrochemi-
cally examined as an active electrode material for SCs in 6 M
KOH as an electrolyte solution. The results showed good Cs
and excellent cycling performance, suggesting their
potential as an active electrode for SCs. Figure 20a and b
exhibited the SEM-analysis of the nanosheets FeCo2O4.
Additionally, the porous structure of FeCo2O4 was depicted
using the TEM-analysis (Figures 20c and d).
Nanocomposite materials are another strategy to in-
Figure 17: The TEM analysis of ZnCo2O4@MnO2 nanotube arrays crease the performance of nanostructured transition metal
(Ma et al., 2015). Copyright © 2015 The Royal Society of Chemistry. compounds in which carbon materials were incorporated
into the TMOs. Such as Co3O4/graphene (He et al., 2012b;
Xiang et al., 2013), Co3O4/CNTs (Shan and Gao, 2007),
porous FeCo2O4 nanowires is schematically illustrated in which provided a better electronic conductivity and a
Figure 18 and its TEM-analysis that confirming that the sufficient and effectiveness of contact area.
wires are composed of very fine nanoparticles is depicted in Perera et al. (2011) have reported a fabrication of
Figures 19a and b, as well as the electrochemical perfor- asymmetric SC in which V2O5-CNT and carbon fibers were
mance of porous nanowires FeCo2O4 as a bimetallic oxide, utilized as the positive electrode as a negative electrode,
have been examined and compared with its corresponding respectively. The obtained results revealed an Ed of
mono metal oxide such as (Co3O4 and Fe3O4) and the 46.3 Wh kg−1 and its corresponding Pd of 5.26 kW kg−1.
results showed the superiority of FeCo2O4 as seen in However, the bad electronic conductivity of most of
Figure 19c and d. TMOs confines its electronic transportation, leading to a
Iron cobaltite nanosheets have been examined as gradual loss of its Cs (Chen et al., 2014c; Dam et al., 2013; Fu
an electrode material for SCs in 1 M LiClO4 and PC and et al., 2015; Yu et al., 2008; Zhou et al., 2008). Therefore,
delivered a Cs of 433 F g−1 at 1 mV s−1 (Mohamed et al., developing new electrode materials with high capacitance
2014). Also, submicron-tube arrays of FeCo2O4 have been performance and high electrical conductivity is another

Figure 18: Schematic diagram illustrated the

formation mechanism of nanoparticles of
FeCo2O4 and the growth of nanowire porous
structure of FeCo2O4 (Pendashteh et al.,
2015). Copyright © 2015 The Royal Society of
Chemistry.
 S.Y. Attia et al.: Supercapacitor electrode materials 21

Figure 19: (a) and (b) The TEM-images of

porous nanowires FeCo2O4, exhibiting that
the nanowires consist of nanoparticles,
(c) and (d) are the electrochemical perfor-
mance of porous nanowires FeCo2O4, Co3O4
nanoflakes, and Fe3O4 in 3 M KOH solution
(c) the CV curves of samples at 5 mV s−1, and
(d) the GCD curves of samples at 1 A g−1
(Pendashteh et al., 2015). Copyright © 2015
The Royal Society of Chemistry.

Figure 20: Microstructure analysis of

nanosheets FeCo2O4.
(a) and (b) the SEM images, and (c) and (d) the
TEM image declaring the high porosity
(Mohamed et al., 2017). Copyright © 2017
Elsevier Ltd.

strategy to develop the performance of SCs. TMSs are conductivity (Jiang et al., 2012d). The advantage that TMSs
considered a promising candidate as electrode materials have over TMOs is that the sulfur atom has less electro-
for SCs owing to their relatively high electronic negativity than the oxygen atom (Cho et al., 2013; Ellis
22 S.Y. Attia et al.: Supercapacitor electrode materials

et al., 2010; Xiao et al., 2013), thus, substituting oxygen shows better energy storage performance than those of
atom with the sulfur atom in the compound may yield a mono metal sulfides, owing to the richer oxidation states of
more flexible structure, in addition to the satisfactory the bimetal sulfides that provide multiple redox reactions
electrical conductivity of TMSs (Mohamed et al., 2018b). than those of the mono metal sulfides (Liu et al., 2013b; Luo
From the examples of TMS, cobalt sulfides (Li et al., 2015), et al., 2013). Yang et al. (Yang et al., 2015) examined the as-
nickel sulfides (Yang et al., 2014; Zhu et al., 2012), and prepared ZCS nano-artichokes, this structure showed a Cs
copper sulfides (Hsu et al., 2014). A hierarchical hollow of 486.2 F g−1 at 2 A g−1A g−1. Zhang et al. (Zhang et al., 2017)
structured nanotube CoS1.097 (Liu et al., 2015b), exhibited a suggested the preparation of ZCS- double-shelled, this
Cs of 764 F g−1 and acceptable capacity retention of 85% material reached a Cs of 1266 F g−1 at a current density of
even after 500 cycles. A nanotube cobalt sulfide was hy- 1 A g−1. Gao et al. (Gao et al., 2018) explored the synthesis of
drothermally prepared and delivered a Cs of 285 F g−1 at ZCS microspheres-like structure that delivered a high Cs of
0.5 A g−1 (Wan et al., 2013a). The 3-D hierarchical structure 1516 F g−1 at 1 A g−1. Li et al. (Li et al., 2019b) reported the
of cobalt sulfide showed a Cs of 555 F g−1 at a current of formation of nanoparticle structure of ZCS and examined
5 mA cm−2 and satisfactory cycle life (Wang et al., 2011c). its behavior for SCs applications, the prepared electrode
Du et al. (2014) developed CoNi2S4@graphene exhibited a Cs of 1269.1 F g−1 at 0.5 A g−1. Tong et al. (2016)
(CNS@GR) as a nanocomposite electrode for SCs, exhibit- reported the formation of ZCS nanosheets-like structure
ing a Cs of 2009.1 F g−1 at 1 Ag−1 and retained 755.4 F g−1 at grown on N2-doped graphene/carbon nanotubes, the as-
4 Ag−1 of initial capacitance even after 2000 cycles. prepared electrode revealed a Cs of 2484 F g−1 at 2 A g−1, and
Figure 21 demonstrated the electrochemical performance delivered Ed of 50.2 Wh kg−1 at a Pd of 387 W kg−1. Hussain
of the as-synthesized CoNi2S4@graphene at different ratios et al. (2019) have been studied the effect of morphology on
of reduced graphene (GR). A nanotube structured of the electrochemical performance of ZCS. Between four
NiCo2S4 has been synthesized as electrode active material electrodes prepared at different operation times, only
for SCs with Cs of 933 F g−1 at 1 Ag−1 (Wan et al., 2013b). the rods – like structured ZCS electrode that obtained at a
Urchin-like structure of NiCo2S4 was prepared by a pre- hydrothermal reaction time of 12 h reached the best Cs
cursor conversion process, delivering a Cs of 1050 F g−1 at (2418 F g−1) and delivered Ed of 51 Wh kg−1 at a Pd of
2 Ag−1 reported (Chen et al., 2013b). 400 W kg−1 with satisfactory cycling performance. Figure 22
Mono metal sulfides, like zinc sulfide and cobalt sul- showed the electrochemical performance (GCD and CV) of
fide, have low-cost advantages, electroactivity, high theo- the as-prepared sample at a different hydrothermal time.
retical Cs (Mohamed et al., 2018a). Therefore, it is Attia et al. (2020) have been reported a facile single
predictable that the bimetallic zinc cobalt sulfide (ZCS) approach hydrothermal method to prepare microspheres

Figure 21: The electrochemical performance

of nanocomposite of CNS@ GR.
(a) GCD curves, (b) Cs versus current density
for CNS@GR at different rations of GR, (c)
Cycling performance and coulombic
efficiency of CNS@ GR, and (d) the last 20
cycles of CD curves (Du et al., 2014).
Copyright © 2015 The Royal Society of
Chemistry.
 S.Y. Attia et al.: Supercapacitor electrode materials 23

containing the nanoflakes-like structure of ZCS and

explored its electrochemical performance as electrode
active material for SCs. exhibiting an excellent Cs of
2393 F g−1 (at 1 A g−1) and acceptable cycling performance of
88% after 5000 cycles at 10 A g−1. Furthermore, a hybrid SC
was gathering including ZCS and AC as the positive and the
negative electrodes, respectively. Supplying an Ed of
58.8 Wh kg−1 at Pd of 815 W kg−1 Figure 23 showed the
microstructure analysis of the as-prepared ZCS. The syn-
ergistic effect due to the coexistence of Zn and Co together
in the bimetallic sulfide (ZCS) was indicated in Figure 24
that illustrated the remarkable electrochemical perfor-
mance (CV and GCD) of ZCS in comparison with its corre-
sponding mono metal sulfide.
The flowing table (Table 3) summarizes the electro-
chemical performance of some recently reported ZCS
electrodes.
Even with the attractive properties of most of TMOs
and/or TMSs, such as their superior electrochemical
response, low processing cost, and ease of manufacturing,
there is no escape from developing new materials for SCs. Figure 23: (a–b) FE-SEM images, (c) the TEM image of the as-
Nowadays, MXenes and metal nitrides are exciting new prepared Zn0.76Co0.24S, (d) selected area electron diffraction spec-
materials with great potential for SC application trum of Zn0.76Co0.24S, and (e–g) energy dispersive X-rays mapping of
Zn, Co, and S on a selected area, respectively (Attia et al., 2020).
Copyright © 2020 Elsevier Ltd.

MXenes
Gogotsi (Naguib et al., 2011). The 2D MXenes can be derived
The 2D materials are a promising candidate for a lot of from the crystalline MAX Phases. The phases of MAX are
electronic and energy storage devices related to their crystalline solids with layered hexagon structure, whose
unique electronic structures and extremely high surface general chemical formula Mn+1AXn, where “M” is an early
areas. In this regard, MXenes have a great potential for transition metal (Sc, Ti, V, Zr, Hf, Cr, Nb, Mo, Ta), “A” is one
energy storage applications such as SCs and batteries due of the elements from groups III–VI (Al, Ga, Si, In, Tl, Bi, Sn,
to their superior electronic conductivity, great surface Ge, Pb, P, S, As, Te), and “X” is carbon and/or nitrogen, and
areas, adsorption ability, hydrophilicity, the effectiveness n = 1, 2, or 3 (Barsoum, 2000; Anasori et al., 2017).
of surface reactivity, and environmentally benignity As manifested in Figure 25a, every layer of X atoms is
(Naguib et al., 2013; VahidMohammadi et al., 2017; Xie inserted or sandwiched in-between two layers of transition
et al., 2014). The 2-D MXenes were first advanced by Yury metals forming the Mn+1Xn layer and every two Mn+1Xn

Figure 22: The electrochemical performance

ZCS at different preparation times.
(a) GCD curves and (b) CV curves (Hussain
et al., 2019). Copyright © 2019 Elsevier Ltd.
24 S.Y. Attia et al.: Supercapacitor electrode materials

Figure 24: The electrochemical performance.

(a) CV curves of ZCS, ZnS, and CoS at scan
rate 100 mV s−1, and (b) GCD plateaus of ZCS,
ZnS, and CoS at a current density 1 A g−1 (Attia
et al., 2020). Copyright © 2020 Elsevier Ltd.

Table : The energy density, power density, and retention of some ZCS electrodes.

Sample Ed Pd Retention (cycles) Ref

− − −
ZCS-Microspheres containing . Wh kg  W kg ZCS//AC % ( cycles @  A g ). (Attia et al., )
Nano-flakes
ZCS nanoparticles . Wh kg−  W kg− ZCS//AC .% ( cycles @ (Li et al., b)
 A g−)
ZnCoS nanomaterials . Wh kg−  W kg− ZCS//porous rGO % ( cycles @  A g−) (Zhang et al., )
(Zn-Co-S) porous-Nanosheets . Wh kg−  W kg− ZCS//AC % ( cycles @  A g−). (Tao et al., )
ZCOSH-NC . Wh kg− . W kg− ZCOSH//AC .% ( cycles @  A g−). (Li et al., )
Nano-cluster
ZCS-rod-like structured @ NF  Wh kg−  W kg− ZCS//AC % ( cycles @  A g−) (Hussain et al., )
ZnCoS nanospheres  Wh kg− . kW kg− Ni(OH)@ZCS-NSs//VN @ ZCS-NSs (Sun et al., )
% ( cycles @  mA cm−)

layers are interleaved and surrounding with a layer of the corresponding MXenes (Alhabeb et al., 2018; Ghidiu
atoms A. The 2D transition-metal carbide and/or nitride et al., 2014; Naguib et al., 2013; Soundiraraju and George,
layers Mn+1Xn, so-called MXenes (Naguib et al., 2011, 2012, 2017; Tran et al., 2018; Urbankowski et al., 2016; Zhou
2014) can be obtained by exfoliation of MAX phase (Bar-
soum, 2000). Using HF acid as an etchant agent followed
by the sonication step. During the HF treatment the atoms
of “A” are withdrawing from the structure of the MAX
phase, yielding multiple layers of Mn+1Xn, that can be
converted into monolayers or/and a few layers by disper-
sion during the sonication step. Figures 25a and 26b
demonstrate examples of the crystal structures of M3AX2
and M3X2, respectively.
Mixtures of “F, O, or OH” groups terminate the surface
of MXenes during the exfoliation process (Halim et al.,
2016; Hope et al., 2016).
In analog to graphene, the 2D-MXenes Mn+1Xn have
hexagonal symmetry and excellent conductivity, but the
point of distinction here is the hydrophilicity nature of
MXenes that comes from the groups terminate on its
surface (Anasori et al., 2015a). Experimentally, a lot of Figure 25: The crystalline structure of (a) M3AX2, (b) out-of-plane
ordered double transition metals M′2M″AX2, and (c) in-plane double
MAX phases were successfully obtained, among them,
transition metals (M′2/3M″1/3)2AX, the solid lines represent the
Ti2AlC, Ti2AlN, V2AlC, Zr3AlC2, Nb2AlC, Ti3AlC2, Ti3SiC2, border of the unit cells (Khazaei et al., 2019) Copyright © 2020
Ta4AlC3, Nb4AlC3, have been successfully exfoliated into Elsevier Ltd.
 S.Y. Attia et al.: Supercapacitor electrode materials 25

of Mo2TiAlC2 has successfully been prepared and exfoli-

ated into their corresponding 2D MXenes phase of Mo2TiC2
(Anasori et al., 2015a, 2015b; Meshkian et al., 2017).
On the other hand, the iMAX phases are considered as
MAX phases with in-plane ordered double transition metals,
in which each layer in iMAX phases includes both metals M′
and M″ as described in Figure 25c (Chen et al., 2018;
Figure 26: The crystal structure of 2D-MXenes. Dahlqvist et al., 2017; Halim et al., 2018; Lu et al., 2017b;
(a) M3X2, (b) out-of-plane ordered double transition metals M′2M″X2,
Meshkian et al., 2018; Tao et al., 2017). Accordingly, the
and (c) in-plane double transition metals (M′2/3M″1/3)2 X (Khazaei et
al., 2019), Copyright © 2020 Elsevier Ltd.
corresponding 2D-Mxenes phase so-called iMXenes ob-
tained from the exfoliation of the iMAX phase will include
two types of transition metals in each layer as manifested in
et al., 2016) Ti2C, Ti2N, V2C, Zr3C2, Nb2C, Ti3C2, Ti3C2, Ta4C3, Figure 26c. For example, the following iMAX phases are
Nb4C3. successfully fabricated and most of them have already been
Fu et al. (2017) successfully constructed a flexible exfoliated.
electrode of 2D-layered-structure Ti3C2 that delivered a
(M′2/3 Zr1/3 )2AlC where, M′ = V, Cr and
great volumetric capacitance (892 F cm−3) and superior
cycling stability without any capacitance loss after 10,000
(M′2/3 M″1/3 )2 AlC where, M′ = Cr, Mo, W, and M″ = Sc, Y .
cycles. Hu et al. (2018) investigated MXenes of Ti3C2 ob-
tained by etching MAX phase of Ti3AlC2 in HF aqueous Sometimes, during the exfoliation process, active
solution with different concentrations from 6 Rto 15 M. The metals such as Sc, Y, and Al are dissolved, resulting in the
highest Cs was achieved in 6 M HF-etched MXene. production of 2D M1.33C MXenes with ordered vacancies
The formation of nanocrystalline ε-MnO2 on MXene (Dahlqvist et al., 2018). In this regard, the iMAX phase of
nanosheets was described by Rakhi et al. (2016) The com- (Nb2/3Sc1/3)2AlC has successfully been fabricated and its
posite denoted as (ε-MnO2/Ti2C or ε-MnO2/Ti3C2) The exfoliation yielding a 2D Nb1.33C MXene with a number of
presence of nanocrystalline ε-MnO2 causing an improve- distributed vacancies (Halim et al., 2018).
ment in the SSA of the nanocomposite electrode, leading to
enhance the Cs of the nanocomposite electrode by about
three times more than that of pure MXene-based symmetric
SCs. The assembled symmetric (ε-MnO2/MXene) SC of Metal nitrides (MNs)
attained a satisfactory cycling performance of about 88%
Cs retention even after 10,000 cycles. Owing to their unique properties, such as satisfactory
Recently, when two different transition metals (M′, M″) electrochemical performance, superior chemical stability,
are mixed with element A and element X, this will result in MNs attract great interest as electrode material for SCs
the formation of an alloy of MAX phases and consequently, (Balogun et al., 2015). Zhu et al. (Zhu et al., 2015a) devel-
the formation of its corresponding alloy MXenes phases. In oped two different MNs: porous layered TiN, and nano-
this regard, the following alloys of MXenes have already particles Fe2N upon the surface of graphene sheets and
been experimentally prepared: (Ti0.5Nb0.5)2C, (V0.5Cr0.5)3C2, explored as electrode material for asymmetric SCs. Das
(Nb0.8Zr0.2)4C3, (Nb0.8Ti0.2)4C3, and Ti3CN (Yang et al., 2016). et al. (2015) have been fabricated nanoparticles MNs
The proper stoichiometry choice of M′ and M″, A, and (M = Co, Cr) with particle size about 20–30 nm, in the at-
X, results in the production of two different types of the mosphere of (NH3 + N2) at small operation temperature.
novel MAX phases including the binary transition metals, The asymmetric SC was assembled using MNs as positive
named oMAX and iMAX phases (Anasori et al., 2015a, electrodes and AC as negative electrodes showed high Cs of
2017). 37 and 75 F g−1 for M = Co, Cr, respectively at 30 mA g−1.
The oMAX phases are considered as a MAX phase with Choi et al. (Choi et al., 2006) reported that the surface
out-of-plane ordered double transition metals as shown in modification of nanocrystalline VN results in a new class of
Figure 25b (Anasori et al., 2015a, 2015b; Meshkian et al., SCs that show remarkable Cs, the formation of nanolayered
2017). And its corresponding MXene phases are shown in VOx (lower electronic conductivity) on the surface of the
Figure 26b, in which the inner layer of the MXene contains electronically-conductive nanocrystalline VN results in a
only one transition metal M″ and the outer layer contains sequence of reversible redox reactions which are known to
the other transition metal M′. For example, the MAX phase be attributable to high Cs.
26 S.Y. Attia et al.: Supercapacitor electrode materials

Conclusion and perspective adsorbed anions in the positive electrode are detected
whereas anions at the negative electrode still to be
Nowadays, portable electronics and transport technologies desorbed.
rely more on energy storage equipment than ever before. In In conclusion, to improve the performance of SCs, the
this respect, there is a strong demand to enhance energy following aspects should be focused on:
storage systems to be more efficient and compatible with (i) Detailed information about energy storage mecha-
the ongoing rapid technological progress that required nisms at the electrode/electrolyte interface should be
high energy and power densities. Therefore, considerable acquired.
research has long been devoted to the development of (ii) Developing electrodes to create hierarchical porous
advanced electrode active materials for energy-storage structures and prevent the formation of dead volume.
devices. Among these energy storage devices, SCs, that (iii) Obtaining structure with high electrochemical
considered one of the most efficient electrochemical response related to conductivity, the effectiveness of
energy storage systems that attract much attention for the surface area, providing and facilitating penetration of
latest generation energy storage systems. Since it fills the ions from the electrolyte to the electrode material.
gap between the traditional capacitors (having high power
Perspectives of this work are:
density) and the batteries (having high energy density).
(1) Electrolytes with wide and a stable voltage window,
The common challenge that faces the technology of SCs is
along with a satisfactory ionic conductivity, are also
to increase its relatively low energy density without
required to boost the energy density along with the
reducing its high power density, and can be achieved
electrode materials. Moreover, the relation between the
through the selection and development of appropriate
morphology of electrode material, electrolyte ions, and
electrode material concerning electrochemical activity,
charge storage should be compatible.
conductivity, effective contact area, morphology, and
(2) More interest should be on developing asymmetric and
porosity of the material is possible.
hybrid SCs as well as exploring new materials for these
In this review, we have introduced the fundamental
SCs that will provide higher energy and power density,
considerations and basic principles of SCs concerning the
simultaneously.
mechanisms of energy storage and the electrochemical
performance of electrode materials in accordance with We are looking forward to a valuable and effective contri-
some essential parameters, such as specific capacitance, bution from this review to the energy storage sector.
energy density, and power density. Besides, a concise
description of electrode materials based on carbon mate- Author contribution: All the authors have accepted
rials, transition metals oxides, sulfides, in addition to some responsibility for the entire content of this submitted
new materials such as MXenes and metal nitrides. Also, the manuscript and approved submission.
state-of-the-art developments in SCs’ electrode materials Research funding: None declared.
were incorporated. Conflict of interest statement: The authors declare no
Moreover, some promising experimental character- conflicts of interest regarding this article.
ization could be used for a more deep understanding of
the charge storage performance of SCs. For instance, the
use of nuclear magnetic resonance spectroscopy (NMR)
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