Received: 6 March 2018 Revised: 25 June 2018 Accepted: 28 June 2018

DOI: 10.1002/er.4170

REVIEW PAPER

Graphene a promising electrode material for

supercapacitors—A review

Aicha S. Lemine1 | Moustafa M. Zagho1 | T. M. Altahtamouni1 | Nasr Bensalah2

1
Materials Science and Technology
Program, College of Arts and Sciences,
Qatar University, Doha 2713, Qatar
2
Department of Chemistry and Earth
Sciences, College of Arts and Sciences,
Qatar University, Doha 2713, Qatar
Correspondence
Dr Talal M. Altahtamouni, Materials
Science and Technology Program, College
of Arts and Sciences, Qatar University,
Doha 2713, Qatar.
Email: taltahtamouni@qu.edu.qa
Funding information
GCC Co‐Fund, Grant/Award Number:
GCC‐2017‐007
Summary
The global demand for high performance and environmentally friendly energy
storage systems leads to intensive research on new and advanced electrode
materials that are able to satisfy the fast‐growing global market in various
applications. The 2D graphene material is one of the most promising
candidates for next‐generation energy storage applications, particularly
supercapacitor devices due to its exceptional intrinsic properties such as
highest theoretical specific surface area (2600 m2/g), high electrical charges
mobility (230 000 cm2/V·s), thermal conductivity (3000 W/mK), and highest
strength (130 GPa). This comprehensive review summarizes the most recent
progress made on the graphene material in its different structural forms of
foams (3D), thin films (2D), nano‐fibers (1D), and nano‐dotes (0D) for
supercapacitor electrodes. It initiates with a brief historical introduction on
graphene discovery and its current production techniques that retain its intrin-
sic properties ranging from mechanical exfoliation of graphene in high quality
to its epitaxial growth by chemical vapor deposition on metal substrates and its
derivation by chemical reduction of graphene oxide. In addition to highlighting
its main characterization techniques such as Raman spectroscopy, atomic force
microscopy, and transmission electron microscopy, as well as, its critical
properties including electrical, optical, mechanical, and thermal properties.
Its potential applications are also illustrated with emphasizing on its usage as
an electrode material in supercapacitors. Finally, its main challenges and
future prospects are considerably pointed out.

KEYWORDS
advanced materials, two‐dimensional materials, graphene, energy storage, supercapacitors,
nanoporous material

1 | INTRODUCTION carbon allotropes were reported, and the scientific com-

In 1789, the “Carbone” was listed in “Traite´ Elementary
de Chimie” by Antoine Lavoisier as a recently recognized
chemical element.1 He indicated that it is the elemental
component in forming both diamond and graphite mate-
rials which highlight on its versatility. Thereafter, several
munity is passionate to investigate the unique properties
of carbon that enable it to be formed in a range of various
structures starting from fullerenes in 0D, to nanotubes in
1D, to graphene in 2D, or to diamond and graphite in 3D.
The 3D carbon allotropes were well known and used
for centuries, while the 1D and 0D allotropes are studied

Int J Energy Res. 2018;1–17. wileyonlinelibrary.com/journal/er © 2018 John Wiley & Sons, Ltd. 1
2 LEMINE
at a later time and discovered in past decades.2 The
graphite, nanotubes, and fullerenes are formed from
graphene sheet either through stacking it, rolling it into
a cylindrical shape, or wrapping it into a spherical shape,
respectively, as illustrated in Figure 1.3
Accordingly, graphene is the backbone for the
majority of graphitic materials.3 It is well known as a
two‐dimensional, flat carbon sheet, and a single layer of
carbon atoms bonded in a form of hexagonal lattice struc-
ture. This sheet is the thinnest material in the universe
with a thickness of one carbon atom; hence, it has gained
a global attention in numerous fields including materials
science, chemistry, and physics.4 This attention is derived
from graphene exceptional properties including its
high specific surface area of ~2630 m2/g, the strong
mechanical strength of ~1 TPa, and excellent electrical
and thermal conductivities.5 These properties lead
graphene to be an outstanding candidate particularly in
applications of energy conversion and storage.
Nowadays, the supercapacitors or ultracapacitors are
the most high performance and environmentally friendly
electrochemical systems for energy storage applications
FIGURE 1 Schematic diagrams of graphene as the backbone for various graphitic materials3 [Colour figure can be viewed at
wileyonlinelibrary.com]
ET AL.
that are capable to satisfy the fast‐growing global market
in various applications such as memory backup systems,
energy capture sources, electric vehicles, hybrid electric
vehicles, portable electronic devices, industrial power
and energy management, and recently in Airbus A380
planes.6-9 These devices are favorable among other energy
storage systems due to their long cyclic life (>100 000
cycles), fast dynamics of charge propagation, safe and
reliable performance, high power capability, and low
maintenance.10,11 Besides their power density that is
thousands of times higher than the modern Li‐ion
batteries with an energy density that is much larger than
the conventional capacitors but lower than ordinary
batteries.12 Thus, there are great research efforts towards
enhancing the performance of supercapacitor devices to
have considerable energy densities exceed that of
ordinary batteries.
Moreover, this review paper will comprehensively
summarize the up‐to‐date research efforts on the utiliza-
tion of 2D graphene material in upgrading the
performance of energy storage systems, specifically
supercapacitor devices to overcome the conventional
LEMINE ET AL. 3

batteries and to fulfill global market demand. Accord-

ingly, it will illustrate on its effective preparation
techniques, latest discovered properties, and potential
applications. It will follow with a highlight of most recent
progress made in supercapacitor devices based on
graphene electrodes and explore its main challenges
besides pointing out on its future prospects.

2 | GR APHENE: P REPARATION
TECHNIQUES

The outstanding properties of graphene sheet are highly

dependent on its preparation techniques; hence, they
are the key challenge in synthesizing a high‐quality
graphene sheet. For instance, if graphene sheets are not
separated sufficiently from each other, the graphene will
undergo irreversible agglomerates to restock through
Van der Waals interactions which will result in the for-
mation of graphite.13 The prevention of this aggregation
is the key challenge in processing graphene, as its unique
properties are associated particularly with the individual
graphene sheets.14 Following are the most popular and
FIGURE 2 The application of simple scotch tape method on
effective preparation techniques for graphene:
HOPG for graphene mechanical exfoliation18 [Colour figure can
be viewed at wileyonlinelibrary.com]

2.1 | Mechanical exfoliation

This simple technique was developed by Geim and
Novoselov in which an adhesive scotch tape undergoes
stick and peel process dozen times on the highly oriented
pyrolytic graphite (HOPG) that is commercially available
in cheap cost as illustrated in Figure 2.15,16 The result of
this technique is monolayer thin graphene sample exfoli-
ated from 1‐μm‐thick graphite flakes. Then, the graphene
sample on the tape will be tested using an optical micros-
copy before transferring it onto a clean substrate (eg, pure
SiO2) through the gentle press of the tape.17
The main drawback of this technique is the contami-
nation of graphene sample by the glue residues from
scotch tape which limit the mobility of its electrical
charge carriers (electrons and holes). Thus, a post‐deposi-
tion heat treatment is required to remove these residues
by heating the deposited sample on the substrate up to
~500°C under vacuum pressure.18 Also, this method is
restricted in minor scale production due to the intensive
need of labors and its uneven graphene films; hence,
other approaches for graphene preparation are developed
and attracted more interest.
2.2 | Chemical vapor deposition (CVD)
It is the most favorable approach to produce graphene
films in mono‐layer or few layers on a large‐scale
production. In 2006, Somani and coworkers were able to
successfully synthesize graphene films in very few layers
via using camphor to be the precursor on underneath
Ni substrate before application of CVD technique.19 This
pioneer research work has established a novel synthesis
method of graphene films with a set of unresolved
concerns such as minimizing graphene folding and con-
trolling its layers number. Thereafter, much advancement
was achieved by controlling the thickness of deposited
graphene layers on various metal substrates. Conse-
quently, it is found that it is possible to transfer the
graphene layers from one metal substrate to another
through the chemical etching of coated metal substrate.20
This will upgrade the quality of obtained graphene layers
and lower the necessity to undergo any complicated
chemical or mechanical routs.
Moreover, the growth of graphene on metal sub-
strates (eg, Co, Cu, and Ni foils) via CVD mechanism
with high to mediate carbon solubility of >0.1%atomic
C is through the carbon diffusion into the thin film of
metal substrate at a certain growth temperature followed
by the carbon precipitation on metal surface from bulk
metal due to cooling.21 For instance, the graphene
growth onto underneath copper (Cu) foil is through
undergoing following four‐step processes as stated by Li
and coworkers22:
4 LEMINE ET AL.

1 The Cu substrate will be exposed to direct contact
with hydrogen (H2) and methane (CH4) flows simul-
taneously which will lead to the formation of CxHy
species under certain temperature due to methane
catalytic decomposition onto the Cu surface. Thus,
the saturation of Cu surface with CxHy species is
highly dependent on hydrogen partial pressure, meth-
ane flow and partial pressure, and temperature.
2 Then, the supersaturated Cu surface with CxHy spe-
cies will undergo nuclei formation upon its cooling.
3 These nuclei will grow further forming islands of
graphene onto the Cu surface which is still saturated
to supersaturate with CxHy species.
4 After a period of time, the Cu surface will be fully cov-
ered by graphene under a certain temperature (T),
methane partial pressure (PMe), and methane flow
rate (JMe).
2.3 | Chemically derived graphene
It is another viable route in which the graphite will be
chemically converted into graphene oxide that will
be reduced to afford considerable quantities of graphene
single sheets. The graphite oxide (GO) is usually pro-
duced based on Hummers method in which the graphite
will undergo oxidation using various oxidants such as
concentrated nitric acid, sulfuric acid, and potassium
permanganate.23 This GO has less hydrophobicity and
thus easier to be exfoliated using water to produce
highly stable single‐layered sheets with uniform
thickness which are the graphene oxide. Then, the
obtained graphene oxide sheets will be chemically
reduced into graphene using various reducing agents
like sodium borohydride and hydrazine as demonstrated
in Figure 3.25

FIGURE 3 (A) Is a schematic illustration of graphite oxidation into graphene oxide followed by its reduction by hydrazine to form reduced
graphene oxide, while (b) is the reaction mechanism of epoxy reduction in presence of hydrazine24
LEMINE ET AL. 5

Moreover, the comparison between each of the pre‐

mentioned techniques in terms of their main advantages
and disadvantages is clearly demonstrated in Table 1.

3 | GR APHENE: CHAR AC TER IZ A-

TION AND PROPERTIES

3.1 | Graphene characterization

techniques
3.1.1 | Raman spectroscopy:
Shows fingerprints for various carbon allotropes through
displaying clearly their 2D, G, and D peaks at Raman
shifts of ~2700, ~1580, and ~1350 cm−1, respectively,
which are resulted from the alteration of their electron
bands.29 The detection of these bands will allow the char-
acterization of graphene layers including the presence of FIGURE 4 The Raman spectra of single layer graphene and
defects, doping concentration, and number of available graphite at 514‐nm excitation30
layers. The G band arises near 1580 cm‐1 as a result of
sp2 carbon atoms undergoing in‐plane vibration. While Additionally, most of the researchers use Raman spectra
the 2D band appears at 2700 cm‐1 from the second‐order because it is one of the non‐destructive tools for charac-
Raman scattering process at double frequency of D band. terizing and controlling the quality of mono/few‐layer
For D band, it originates at 1350 cm‐1 as a consequence of graphene. This is due to the crucial dependence of
edge dislocation defect or presence of atomic disorder in graphene properties on its number of layers and impuri-
graphene. These bands are illustrated clearly on the ties presence. Also, following the trend of Raman spectra
Raman spectra for both single layer graphene and graph- for graphene will assist in determining its thickness,
ite at 514‐nm excitation as shown in Figure 4.30 strain in its layers, the effect of defects, and doping.31

TABLE 1 The main advantages and disadvantages of graphene

production techniques26-28 3.1.2 | Atomic force microscopy (AFM):
Graphene It is one of the common imaging techniques that success-
Production Advantages Disadvantages fully determine the thickness of graphene layers in nano-
Technique (Pros) (Cons) meter scale. It has an attractive feature for phase imaging
Mechanical ‐Easy and low ‐Labor intensive. which enables distinguishing pristine graphene free of
exfoliation in cost. defects from its functionalized version. This is due to
‐No need for ‐Uneven films. variation of interaction forces in between attached
certain functional groups to graphene and the AFM tip.32
equipment. However, the AFM is not only used for graphene imaging
‐Unsuitable for and thickness detection; instead, it is also used for its
large‐scale production. mechanical characterization due to its ability in deter-
Epitaxial ‐Utmost even ‐High operating mining minor forces arisen from a process of deforma-
growth by films. temperatures. tion. Thus, various AFM modes allow the investigation
CVD of electrical, magnetic, elastic, and mechanical properties
‐Large‐scale ‐Difficulties in controlling of graphene flake.33
production. adsorption energy and
morphology.
3.1.3 | Transmission electron microscopy
Graphene oxide ‐Versatile ‐Low stability of the (TEM):
reduction handling of colloidal dispersion.
suspension. Is the most used tool for imaging nano‐size material to
‐Rapid process. ‐Partial reduction about atomic scale resolution by transmitting a beam of
‐Straightforward to graphene. electrons to pass across the ultra‐thin sample towards
up‐scaling.
imaging lenses and finally detector.34 It is the proper tool
6 LEMINE
to resolve the atomic features of graphene as it is a one‐
atom‐thick layer. However, the traditional TEM cannot
be operated at high voltage as it will damage the
graphene monolayer; hence, its resolution is limited by
the low operating voltages.
3.2 | Graphene properties
Graphene has many attractive properties such as highest
specific surface area (2600 m2/g), high electrical charge
mobility (230 000 cm2/V·s), thermal conductivity
(3000 W/mK), and highest strength (130 GPa).35,36 This
section will briefly illustrate the main properties of
graphene that are highly utilized in various potential
applications.
3.2.1 | Electrical properties:
Graphene is a zero energy gap semiconductor due to its
2D honeycomb carbon lattice structure. It has a high den-
sity of charge carriers (electrons and holes) that behave in
unusual nature as massless relativistic particles (Dirac
fermions).37 These charge carriers are very fast and free
to move across the graphene. Thus, its electrical conduc-
tivity is high particularly in single layer due to low defect
density within its crystal lattice which refers to its high
quality. This is because defects are main scattering sites
that limit charge carriers mean‐free paths, hence
inhibiting charge mobility and lowering conductivity.
Beside intrinsic sources, there are other extrinsic sources
that affect graphene electrical conductivity including
substrate ripples, surface charge traps, interaction with
underneath substrate during measurement, and interfa-
cial phonons.38
3.2.2 | Optical properties:
The large area of mono/few‐layer graphene with zero
energy band gaps is commonly utilized as ultra‐fast
photo‐detector. This is because the light absorbed on
graphene surface will generate pairs of electron and hole
(charge carriers) that will recombine rapidly in Pico‐sec-
onds depending on the density of charge carriers as well
as the temperature.39 Thus, the application of an external
field on graphene will separate these pairs and generate
the photocurrent. Additionally, numerous research
papers have reported that monolayer graphene is capable
of absorbing around 2.3% of incident light in wide‐range
wavelength.40-42 It is also reported that linear increase
of graphene layers will increase the amount of absorbed
light as the absorption of every layer is A = 1 – T = πα = 2.3%,
where the α is fine structure constant and equals ≅ 1/
ET AL.
37.43 This fine structure constant could be used to well
describe transmittance property of graphene.43
3.2.3 | Mechanical properties:
It is well known that redistribution of electrical charges
within any crystalline material is due to alteration of its
inter‐atomic distances via application of external stress
on it,44 thus, modifying significantly its electron mobility
and introducing a band gap in its electronic structure. For
graphene material, it has been frequently observed with
an uppermost modulus of elasticity and strength after
carbon nanotubes.45-47 The summary of the recently
reported mechanical properties of mono/bi/tri‐layers
graphene investigated via AFM and Raman spectroscopy
is demonstrated in Table 2. It is noted that a monolayer
graphene (2D) has the utmost tensile strength of
~130 GPa and stiffness of 1.02 TPa close to graphite
(3D). It is also observed that graphene has a high
tensile strain of ~1.3% in tension compared with that
in compression.
3.2.4 | Thermal properties:
The presence of phonon scattering property and strong
C―C covalent bonds resulted in high thermal conductiv-
ity for graphene. This leads to its utilization in numerous
electronic devices for thermal management which nowa-
days is a crucial parameter for high efficiency and better
reliability in any electronic device. Additionally, single
layer graphene is repeatedly reported with a thermal
conductivity of ~5000 W/mK at 25°C (RT). Whereas,
supported graphene is reported with a thermal conductiv-
ity of ~600 W/mK.51 The value of graphene thermal
conductivity is measurable by a set of methods and sum-
marized in Table 3. It is proven that monolayer graphene
has a highest thermal conductivity of ~5300 W/mK as
TABLE 2 The intrinsic stiffness and tensile strength for different
graphene structures48-50
Mechanical
Method Material Properties
Raman Graphene Strain ~1.3%
spectroscopy in tension
Strain ~0.7%
in compression
AFM Mono‐layer E = 1.02 TPa;
σ = 130 GPa
Bi‐layer E = 1.04 TPa;
σ = 126 GPa
Tri‐layer E = 0.98 TPa;
Graphene σ = 101 GPa
LEMINE ET AL.
TABLE 3 The thermal conductivities of graphene and reduced graphene oxide51-53
Method Material
Confocal micro‐Raman spectroscopy Suspended graphene flake mono‐layer graphene
Thermal measurement method Mono‐layer (suspended)
Mono‐layer (on SiO2 support)
Electrical four‐point measurement Reduced graphene oxide flake
measured using confocal micro‐Raman spectroscopy
compared with suspended graphene flake with conduc-
tivity up to ~4800 W/mK. On the other hand, the thermal
measurement method indicates that suspended single
graphene layer is more thermally conductive than single
layer deposited on the SiO2 support.
4 | GR APHENE: P OTENTIAL
A PP L I C A T IO N S
The graphene unique properties have been utilized in a
range of potential applications including transparent
conductors, terahertz devices, touch screens, optical
limiters, photodetectors, upgrading ordinary batteries,
and light emitting devices.54,55 Following is a brief illus-
tration on some of the potential applications based on
graphene material:
4.1 | Transparent electrodes
Graphene thin film (<30nm) is reported as semi‐trans-
parent to the visible light compared with thick films
which are non‐transparent.56 Thus, conductivity and
transmittance of graphene film are adjustable via con-
trolling its film thickness and its reduction degree. It is
also proven that conductivity of graphene thin film
increases with decreasing its transmittance and increas-
ing its degree of reduction.57 Consequently, these param-
eters have to be optimized to achieve a high performance
conducting and transparent thin film of graphene. Addi-
tionally, the flexible, conducting, and transparent nature
of graphene thin film results in being a promising candi-
date for electrode material in both electronic and opto-
electronic applications.58
4.2 | Solar cell
The pre‐illustrated graphene transparent electrodes are
also used in solar cells.58 It is reported that most of the
vertical solar cells consist of ITO/P3HT:PCBM/Al config-
uration.59 In such cell, both electron acceptor (PCBM)
and donor (P3HT) phases are placed in direct electrical
contact with the anode (ITO) and cathode (Al) electrodes.
7
Thermal Conductivity
at RT (25°C)
4100‐4800 W/mK 4840‐5300 W/mK
3000‐5000 W/mK
600 W/mK
0.14‐0.87 W/mK
Thus, the polymeric acceptor and donor materials usually
result in current leakage due to recombination of charge
carriers.59 Therefore, to overcome this unfavorable effect,
graphene was introduced to obtain a new configuration
of ITO/GO/P3HT:PCBM/Al which shows high efficiency
in holes collection with band energies around 4.4‐4.5/
4.9/4.9:4.2/4.2 eV, respectively.59 It is also reported that
graphene film in 2‐nm thickness leads to optimum effi-
ciency in contrast to graphene films with >4‐nm thick-
ness.60 This is due to enlargement of serial resistance as
a consequence of the decrease in film transmittance with
its thickness.
4.3 | Electrochemical sensors and
biosensors
Graphene is also a promising candidate for numerous
biological and electrochemical sensors as a result of its
unique properties that enable it to be sensitive to the
changes in the chemical and biological environments.
The change in these environments is monitored by
recording the changes in the graphene conductivities as
displayed in Table 4. The reduced graphene oxide (rGO)
could be utilized alone as active material within electro-
chemical/bio‐sensors or in combination with other mate-
rials such as Gold (Au) in biosensors for DNA molecules
through monitoring the change in its electrical current (I)
versus applied electric potential (V), and such sensors
have a detection limit up to ~μM/L. Whereas, it could
be used unaccompanied to detect the presence of gases,
particularly nitrogen dioxide (NO2) and ammonia (NH3)
via measuring the change of electric current (I) over a
period of time (t) with a detection limit that reaches
~100 ppm which is significant in industrial applications
for monitoring such pollutant gaseous emissions.
4.4 | Next‐generation batteries
The unique properties of graphene specifically its high
surface area to volume ratio (SA/V), chemical stability,
ultrathin flexible nature, and superior electrical conduc-
tivity have been utilized in composing it with several
transition metal oxide nanoparticles such as: SnO2,
Fe3O4, Co3O4, and Mn3O4 which have very high
8 LEMINE ET AL.

TABLE 4 The biosensors and electrochemical sensors based on reduced graphene oxide (rGO)

Reduction
Active Material Method Sensor Type Analyte Measurement Detection Limits Reference

rGO Thermal Gas NO2, NH3 I vs t ~100 ppm 61

Molecular HCN, DDT G vs t ~ppb 61
Chemical Gas NO2, NH3 R vs t ~ppm 62
rGO+Au Electrochemical Bio DNA I vs V ~μM/L 63
rGO+DNA Chemical Bio DNA, Bacterium G ~Single stranded DNA 63
molecule
~Single bacterium

theoretical capacities.64 This composite will advance the adsorption on electrode interface resulting in the forma-
energy storage applications including the Li‐S, Li‐O2, tion of electric double layer (EDL‐capacitors) or via elec-
Na‐ion, and Li‐ion batteries. The Li‐ion batteries (LIBs) trons transfer between electrode material and electrolyte
are frequently reported with remarkable rechargeable as a result of Faradic redox reactions (pseudo‐capaci-
characteristics, longer life cycle, and high specific tors).70 It is frequently reported that pseudo‐capacitors
energy.64 Accordingly, numerous electrode materials are have higher energy densities than EDL capacitors.70
proposed for LIBs based on these nanoparticles for Whereas, their cyclic stability and rate capability are very
enhancing its specific capacities to overcome the cur- low with respect to EDL capacitors as their electrodes are
rently being used electrodes that are based on pure graph- based on the low conductivity materials and involve
ite material. However, the direct application of these the slow electrochemical reaction processes. However,
metal oxides in LIBs is restricted due to their low electri- the pseudo‐active species are often used to improve
cal conductivity.65 Thus, a new strategy of composing overall energy storage capacitance for supercapacitors.
them with graphene will overcome such issue as it will On the other hand, supercapacitor devices are in a
provide a mechanical support for these nanoparticles as similar structure to the batteries because they consist
well as prevent their volume from expansion‐contraction mainly of two‐current collector followed by two
during the charging‐discharging processes.65 In such
TABLE 5 The resultant properties of graphene‐based composite
composition, the nanoparticles of metal oxide will be
materials for lithium‐ion batteries
encapsulated by graphene sheets via assembly of oxide
nanoparticles in positive charge and graphene oxide Energy Current
sheets in negative charge by electrostatic attraction Density, Density,
between unlike charges.65 For instance, the resultant Material mA·h/g mA/g Cycles Reference
composite of graphene‐encapsulated Co3O4 has been Pure Co3O4 900 ‐ ‐ 66
reported with an ultra‐high reversible capacity around Graphene 1000‐ 74 ~130 66
1100 mA·h/g at its initial 10 cycles and 1000 mA·h/g after encapsulated‐Co3O4 1100
130 cycles as illustrated in Table 5.66 Free Mn3O4 115‐300 40 ~10 66
Graphene‐Mn3O4 730‐780 400 ~50 66
5 | GR APHENE: AS ELECTR ODE Pure SnO2 782 ‐ ‐ 66
M A T E R I A L I N SU P E R C A P A C I T O R Graphene‐SnO2 625 10 ~10 66
DEVICES
Graphene‐wrapped 1026 35 ~30 67
Fe3O4
5.1 | Supercapacitors: principle and
performance Graphene‐Si 2200 ‐ ~50 67
Graphene 290 50 ~50 68
The supercapacitor devices are used for short load cycle nanosheets
applications due to their static electrical energy storage.69
CNS+CNT 480 50 ~20 68
These devices are the best candidates for hybrid electric
Disordered 794‐1054 ‐ ‐ 68
automobiles and mobile electronic gadgets. This is a
graphene
consequence of their optimum power density and rapid
charging/discharging abilities in the absence of degrada- Pure 372 ‐ ‐ 68
graphite
tion. They store the electrical energy either via ion
LEMINE ET AL.
electrodes that are separated by an ion‐permeable separa-
tor in an electrolyte solution to avoid short‐circuit as
shown in Figure 5.71 These components must be taken
into high consideration for designing any supercapacitor
device as they build up such devices and thus certainly
will affect its overall performance. Therefore, the perfor-
mance evaluation of supercapacitor devices is typically
based on the following criteria72,73:
1 Power and energy densities (>conventional batteries)
2 Outstanding cycle stability (>100 times of conven-
tional batteries)
3 Rapid charging‐discharging processes (within
seconds)
4 Minimum self‐discharging rate (ie, high time constant
value (τ = R × C))
5 Safe in operation
6 Low in cost
Additionally, supercapacitors with optimum effi-
ciency have to fulfill necessities of minimum equivalent
series resistance (ESR), large cell operating voltage, and
high capacitance (C). In which the ESR comes from
intrinsic resistance associated with electronic properties
FIGURE 5 (A) Is a schematic illustration of the equivalent circuit model for a supercapacitor with two electrodes (B). (C) demonstrates the
typical structure and components of conventional supercapacitor, and (D) shows its flexible counterpart71 [Colour figure can be viewed at
wileyonlinelibrary.com]
9
of electrode matrix and electrolyte solution, contact resis-
tance from the electrode with the current collector, and
mass transfer resistance resulted from ions within
matrix.74 Whereas, thermodynamic stability of electrolyte
solution limits cell operating voltage and the electrode
material which impact significantly the cell capacitance.
Thus, the advancements of electrode material and
electrolyte solution will obviously optimize the overall
performance of supercapacitors.
Therefore, the effective electrode materials for
supercapacitors must have a high surface area with
suitable pore sizes, high electrical conductivity with good
stability, and high density to attain highest volumetric
energy densities for dense power and energy sources.75
Thus, numerous electrode materials including carbon
fibers, carbon nanotubes, mesoporous carbon, and
activated carbons were frequently studied and tested to
enlarge power density as well as the specific capacitance
of supercapacitors as displayed in Table 6. The carbon‐
based materials owe long cycle life, excellent mechanical
and chemical stability, good electrical conductivity, and
adjustable nano‐structures.80 On the other hand, the
electrolyte solution has to be chosen carefully, and
the non‐aqueous electrolytes are usually recommended
10 LEMINE ET AL.

TABLE 6 The summary for main carbon electrode materials used frequently in supercapacitor devices

Aqueous Organic
Electrolyte Electrolyte

Carbon Specific surface Density Electrical Cost F/g F/cm3 F/g F/cm3 Reference
material area (m2/g) (g/cm3) conductivity
(S/cm)
0D fullerene 1100‐1400 1.72 10−8‐10−1418 Medium ‐ ‐ ‐ ‐ 76
1D CNTs 120‐500 0.6 10 ‐10
4 519
High 50‐100 <60 <60 <30 76
6
2D graphene 2630 >1 10 High 100‐205 >100‐205 80‐110 >80‐110 76
3D graphite 10 2.26 10 423
Low ‐ ‐ ‐ ‐ 76
Carbon aerogels 400‐1000 0.5‐0.7 1‐10 Low 100‐125 <80 <80 <40 77
Activated carbon 1000‐3500 0.4‐0.7 0.1‐1.0 Low <200 <80 <100 <50 78
Activated 1000‐3000 0.3‐0.8 5‐10 Medium 120‐370 <150 80‐200 <120 78
carbon fibers
Templated 500‐3000 0.5‐1.0 0.3‐10 High 120‐350 <200 60‐140 <100 79
porous carbon
Functionalized 300‐2200 0.5‐0.9 >300 Medium 150‐300 <180 100‐150 <90 79
porous carbon

for designing supercapacitors with high power and
energy densities due to their low resistivity (hence mini-
mizing ESR) and operability at high cell voltages up to
3.5 to 4.0eV.81
Moreover, the supercapacitor devices store the electri-
cal charges electrostatically via electrolyte ions adsorption
onto electrodes with the ultimate reachable specific
surface area; hence, electrode materials with large spe-
cific capacitance considerably contribute in determining
the efficiency of energy storage in such devices. Graphene
has been also reported as a satisfactory candidate for
supercapacitor electrodes because of its chemical stabil-
ity, low cost, the uppermost specific surface area of
~2630 m2/g, outstanding electrical conductivity, good
mechanical flexibility, and an intrinsic capacitance of
~21 μF/cm2.76 Thus, the surface area of the graphene
sheet affects significantly the performance of
supercapacitor devices. However, the main drawback of
using graphene as an electrode material in supercapacitor
devices is its agglomeration and then restacking via Van
der Waals attraction forces in between adjacent sheets.76
This restocking will reduce its effective surface area and
thus dropping its capacitance.
Therefore, the addition of metal oxide nanoparticles
such as MnO2 and RuO2 to the graphene can overcome
this drawback and its superior capacitance.76 This
approach of utilizing nanoparticles to advance the elec-
trochemical performance of supercapacitors based on
graphene electrodes indicates the positive interaction
between the nanoparticles and graphene sheets. For
instance, the composition of graphene with MnO2 nano-
particles as electrode materials for supercapacitors has
resulted in overall capacitance of ~216 F/g which exceeds
bulk MnO2 (~6.8 F/g) and individual graphene (~10.9 F/
g).77 It is also reported that asymmetric supercapacitor
with MnO2/graphene composite as its positive electrode
and individual graphene as its negative electrode have
shown an ideal power density of ~30 kW/kg as well as
an energy density of ~42 Wh/kg.77
Furthermore, graphene‐based supercapacitors show
specific energy densities of ~85.6 Wh/kg at RT and
~136 Wh/kg at 80°C, at a high current density of ~1 A/
g as reported by Jang and coworkers.78 They have also
reported that face‐to‐face restacking is prevented between
graphene sheets due to their curved nature which
maintains large pores in 2 to 25‐nm sizes as shown in
Figure 6.78 Besides that, fast charging/discharging capa-
bilities within few seconds and negligible deficiency in
either energy density or capacitance have made it the
ideal candidate compared with present batteries.
5.2 | Graphene‐based supercapacitor
electrode materials
Graphene is frequently reported as a key electrode mate-
rial in supercapacitor devices as it can be assembled into
sets of various structures such as free‐standing graphene
in the form of dots or powders with zero‐dimensional
(0D) structure, graphene in the form of fibers or yarns
with one‐dimensional (1D) structure, graphene in the
form of thin films or sheets with two‐dimensional (2D)
structure, and graphene in the form of foams or compos-
ite network with metal oxides/hydroxides nanoparticles
or conductive polymers with three‐dimensional (3D)
LEMINE ET AL.
FIGURE 6 The curved graphene sheets image under scanning
electron microscopy (sem) in a scale bar of 10 μm79
structure.82 Following is an illustration of these various
graphene structures:
5.2.1 | 0D graphene dots and powders
Are usually obtained through the graphene oxidation‐
reduction technique, and they regularly have a fast
charge transfer and high power density as a result of their
high surface area and good electrical conductivity.83
However, supercapacitor electrodes based on such struc-
ture are reported with a modest capacitance value of
~200 F/g, hence, low energy density and unsatisfactory
overall performance of such device.83 Thus, it is usually
hybridized with conductive polymers (polythiophenes or
polypyrrolesor) and metal oxides (MnO2 or Fe3O4) /
hydroxides (Co (OH)2 or Ni (OH)2). This will result in
hybrid electrodes with integrating the pseudo‐capacitance
and EDL capacitance, hence maximizing its modest
capacitance value. For instance, the composite powders
of graphene‐MnO2 have been experimentally reported
with a specific capacitance of 211.5 F/g at a scan rate of
2 mV/s and ~75% retained capacitance even after 1000
charging‐discharging cycles in the presence of 1 M of
Na2SO4 as an electrolyte.84 However, superior electrical
conductivity and high surface area of graphene powders
can be fully utilized through properly loading the nano-
particles of metal oxides/hydroxides on its surface
which will provide additional pseudo‐capacitance and
act as spacers between the graphene nano‐dots, hence
11
preventing them from restocking. For instance, it is
reported that the synthesis of nanocomposite powders of
rGO‐Fe3O4 is accomplished through a facile method of
electrostatic interaction between GO and Fe3O4 nanopar-
ticles, followed by a hydrothermal method for rGO for-
mation via GO reduction.85 Such nanocomposite
electrode showed upgraded specific capacitance of
169 F/g which is larger compared with 68 F/g for Fe3O4
at a current density of 1 A/g and well‐retained capaci-
tance of ~88% after 1000 charging‐discharging cycles in
the presence of KOH as an electrolyte with 6 M.85
5.2.2 | 1D graphene‐based yarns and
fibers:
Are the most promising candidates for upcoming
supercapacitors generation for portable and wearable
electronics due to their combined advantages of high
flexibility, light‐weight, tiny volume, and high electrical
conductivity. For instance, a supercapacitor with elec-
trodes composed of rGO in fiber‐form deposited on Au
wires is proven to have large specific capacitance around
101.9 μF/cm and a small loss in capacitance <1% when it
is twisted into S‐shape or bent to 120°.86 However, it is
recently reported that hybrid electrode materials of 1D
carbon nanotubes (CNTs) grown by CVD technique on
2D graphene sheets (G) have significantly improved the
mechanical flexibility, thermal, and electrical conductiv-
ity compared with each of them before the hybridiza-
tion.86 This hybrid fiber of CNT‐G showed an overall
capacitance of 1.2 to 1.3 mF/cm2 and steady cyclic volt-
ammetry performance even at high bending cycles more
than 200 in fabric structure.86 It is also reported that its
capacitance was increased through the implementation
of the coaxial wet‐spinning assembly process in forming
polyelectrolyte wrapped into CNT‐G in the form of core‐
sheath fibers,86 in which the wrapped polyelectrolyte act
as a sheath layer to prevent the short circuit from occur-
rences as a result of CNT‐G contact with each other, thus,
attaining a high surface area and effective ion mobility
between electrodes resulting in a large capacitance of
177 mF/cm2.86
5.2.3 | 2D graphene‐based films and
sheets:
Particularly, the thin films are frequently used for the
formation of flexible supercapacitors due to their light-
weight, tunable thickness, and combined merits of: high
electrical conductivity that lowers the diffusion resistance
and leads to enhancement of the energy and power den-
sities, superior mechanical property which makes them
effortless gathered into freestanding films for strong
12
mechanical stability, and 2D structure that provides high
surface area to act as wide electrolytes transport
platform.87,88 The graphene‐based films are produced in
numerous processing methods such as Langmuir‐
Blodgett, interfacial self‐assembly, layer‐by‐layer
deposition, vacuum filtration, and spin‐coating.89 The
processing of graphene films is limited by its restocking
due to Van der Waals attractive forces and inter‐planar
π‐π interactions. This restocking will diminish the surface
area of graphene films and limit electrolyte ions diffusion
in between them. Thus, appropriate spacers are often
used to overcome the stacking of graphene films such as
conductive polymers, transition metal oxides/hydroxides,
metals (Au or Pt) /metal oxides (SnO2) materials, or
carbonaceous materials (CNT or carbon powders).90 For
instance, a supercapacitor based on flexible graphene
films has used carbon powders as spacers between its
films to avoid their restocking, hence form an open
structure for ion diffusion channels and charge storage.91
It is reported that this multilayered graphene structure
resulted in a large specific capacitance of 138 F/g at a
scan rate of 10 mV/s and a low capacitance loss of
3.85% even after 2000 cycles at a specific current of
10 A/g in aqueous electrolyte.91 It is also proven that
use of Pt metal in nanoparticles form as spacers between
the graphene sheets have enlarged its specific capacitance
to 269F/g compared with 14F/g for un‐spaced graphene
sheets.92 This specific capacitance can be further enlarged
through the hybridization of graphene sheets with
pseudo‐active species such as Co (OH)2 metal hydroxide
nanoparticles that will contribute in pseudo‐capacitance
and provide a desirable void spacing between graphene
sheets. Thus, such type of hybrid electrode materials
showed a remarkable specific capacitance of 1335 F/g at
a current density of 2.8 A/g.93
5.2.4 | 3D graphene‐based foams and
aerogels:
Are extremely appropriate for outstanding supercapacitor
performance, optimum power and energy densities due to
their consistency of macro/micro/meso‐interconnected
pores resulted in the large surface area for rapid
electron/ion transport channels.94 Thus, numerous
processing techniques are available to fabricate 3D
graphene‐based electrodes in supercapacitor devices such
as template‐directed assembly technique that is com-
monly used to form the 3D macro‐porous graphene
foam.95 For instance, it is reported that Co3O4 nanoparti-
cles were assembled into the 3D graphene foam through
the CVD technique on a Ni substrate. This flexible
nanocomposite electrode material resulted in a specific
capacitance of ~1100 F/g up to 500 cycles at a current
LEMINE ET AL.
density of 10 A/g; hence, the 3D graphene foam is
observed as a promising supporter for pseudo‐active
species.96 On the other hand, the unique class of porous
and ultralight carbon materials is well known as
graphene aerogels. This class of materials shows high
ratios of surface area‐to‐volume and strength‐to‐weight.97
This resulted in a reduction of the transport distances
between the electrolyte and bulk electrode material
through providing multi‐dimensional transport pathways
for ions/electrons. Thus, the graphene aerogels are poten-
tially used to form high‐performance and binder‐free
electrodes for numerous electrochemical applications.
For example, a high flexibility and all solid‐state
supercapacitor were developed based on attaching a
high‐density and free‐standing graphene hydrogel on its
flexible current collector with the use of polyvinyl alcohol
as its gel electrolyte.98 This type of 3D nano‐hybrid
electrode material resulted in a specific capacitance of
298 F/g and a well‐retained capacitance of ~87% after
10 000 charging‐discharging cycles.98
6 | G RAPHENE: C HALLENGES A ND
FUTURE PROSPECTS
The proven remarkable intrinsic properties of graphene
material involving its long electron mean free paths, opti-
cal, electrical, thermal, and mechanical had made it a
competitive candidate in range of potential applications.
Thus, most of the published researches in last 5 years
have extremely investigated graphene as it opens up a
promising future for nano and microscale electronics.99
On the other hand, graphene as a new 2D material is still
yet facing countless challenges starting from its prepara-
tion mechanisms, to its characterization techniques, and
final device fabrication. Thus, latest reports have exten-
sively illustrated on the scalability of graphene through
CVD synthesis technique to chip scale on various
substrates which will ease the transfer of graphene layer
for following device fabrication.100 Such discoveries
provide attractive prospects for further development of
semiconductor manufacturing.
Additionally, exfoliation of graphite into graphene
oxide (GO) chemically and then into graphene via chem-
ical and thermal reduction offers profitable production
approach on a large scale for reduced GO.100 The main
challenge of such approach is that its thermal and chem-
ical reduction drops significantly the mechanical and
electrical properties as well as the chemical stability of
produced graphene.101 Therefore, the control of graphite
oxidation and GO reduction is highly significant in
adjusting produced graphene properties as electrical con-
ductivity, mechanical properties, and energy band gap.102
LEMINE ET AL.
In other words, controlling the modifications on graphite,
GO, and reduced GO is critical in expanding its use in
various applications that are based on high‐quality
graphene materials.
Besides that, there are health risks associated with
the production of graphene and its derivatives due to
the possibilities of handling and inhaling toxic reducing
chemicals.103 These risks must be assessed via
examination of bio‐compatibility and toxicity for these
carbon‐based structures and derivatives.103 On the other
hand, the distinguishability of single‐layer graphene
using optical microscope needs an appropriate substrate
to generate contrast between dissimilar layers because
of their interference.104 This means that visibility of
graphene under the optical microscope is highly depen-
dent on incident light wavelength as well as substrate
thickness. Thus, further research is required for develop-
ing more advance characterization method of pristine
graphene without being affected by the underneath
substrate material.
Moreover, the main future prospects of graphene‐
based electrode material in energy storage systems, par-
ticularly supercapacitor devices, involve the consideration
of the following future aspects:
i. Efficient design architectures of graphene‐based
electrodes that will alter its chemical, physical, and
mechanical behaviors which will, in turn, reflect
on its energy storage performance and subsequently
the overall efficiency of supercapacitor device. Thus,
the future prospects should pay more attention to
the graphene in 3D structures compared with
other structures; due to its unique network which
is based on an interconnected porous structure
that is utilizable for more ion/charge pathways,
large surface area, and overcome the collapse of
graphene layers.105
ii. Nanocomposites electrodes comprising graphene
with either nano‐conductive polymers or nano‐metal
hydroxides/oxides are still the most favorable combi-
nation for high power and energy densities. Conse-
quently, the future prospects should explore more
such nanohybrid structure which is necessary to
control the graphene interfacial interaction with
pseudocapacitive nano‐materials towards advancing
the Faradic processes occurring across this interface.
iii. The current industry market requires more deform-
able and flexible energy storage devices for commer-
cialization purposes to broaden its usage.106
Accordingly, one of the most important future pros-
pects is the emphasis on upgrading the mechanical
flexibility of energy storage devices, particularly the
graphene‐based supercapacitors.
13
iv. The self‐powered hybrid systems with multifunc-
tional have attracted a considerable interest in future
development of supercapacitors in high flexibility to
be combined with other energy devices such as
nano‐generators, solar cells, and LIBs.107 Thus, the
main future challenge will be optimization of inte-
grated flexible graphene‐based supercapacitors with
other electronic devices to attain an efficient and
valuable multifunctional system.
7 | C ON C L U S I ON S
In summary, graphene is a new 2D material with out-
standing properties that have been utilized in numerous
potential applications such as supercapacitor devices
which have utilized it as its electrode material to improve
their capacitance, energy, and power densities towards
more efficient energy storage devices. These devices store
the electrical energy either through the ion adsorption to
form the EDL‐capacitance or via the reversible Faradic
reactions to form the pseudo‐capacitance. It is frequently
proven that a simultaneous function of these capacitances
will improve the overall performance of supercapacitors
which can be attained through compositing graphene
with either conductive polymers or metal hydroxides/
oxides. These outstanding electrode materials need more
research efforts to improve the interactions between their
composite materials in order to optimize the pseudo‐
capacitance as well as upgrading the performance of
supercapacitors. For instance, it is proven that the
Co3O4 metal oxide nanoparticles which were assembled
into the 3D graphene foam through the CVD technique
on a Ni substrate resulted in a flexible nanocomposite
electrode material with specific capacitance around
1100 F/g up to 500 cycles at constant current density of
10 A/g; hence, the 3D graphene foam is observed as the
most promising supporter for pseudo‐active species due
to its porous structure. Additionally, the graphene mate-
rial in its various forms ranging from 3D, 2D, 1D to 0D
is still facing a number of critical issues particularly in
developing a cost‐effective and environmentally process-
ing method that synthesize graphene on high quality
and large quantity. This requires more investigation of
its physics and chemistry in order to obtain its optimum
processing conditions. Accordingly, future research
prospects should focus on the development of flexible,
free‐standing, nano‐composite, and multifunctional
graphene‐based supercapacitors in order to attain a com-
bination of high‐performance pseudo‐capacitance and
EDL‐capacitance to effectively satisfy the global demand
of efficient energy storage systems.
14 LEMINE ET AL.

D E C LA R A T I O N S O F I N T E R E S T 7. Wei W, Cui X, Chen W, Ivey DG. Manganese oxide‐based

materials as electrochemical supercapacitor electrodes. Chem
None declared. Soc Rev. 2011;40(3):1697‐1721. https://doi.org/10.1039/
C0CS00127A

CO N SE NT F O R PU BL ICA TI O N 8. Xu B, Yue S, Sui Z, et al. What is the choice for

supercapacitors: graphene or graphene oxide? Energ Environ
Not applicable. Sci. 2011;4(8):2826. https://doi.org/10.1039/c1ee01198g
9. Lv W, Li Z, Deng Y, Yang Q‐H, Kang F. Graphene‐based mate-
rials for electrochemical energy storage devices: opportunities
E TH ICA L A PP R O V A L A N D CO N SE NT T O
and challenges. Energy Storage Mater. 2016;2:107‐138. https://
P A RT IC IP ATE doi.org/10.1016/j.ensm.2015.10.002
Not applicable. 10. He Y, Chen W, Li X, et al. Freestanding three‐dimensional
graphene/Mno2 composite networks as ultralight and flexible
supercapacitor electrodes. ACS Nano. 2013;7(1):174‐182.
FUNDING https://doi.org/10.1021/nn304833s
Not applicable. 11. Ke Q, Wang J. Graphene‐based materials for supercapacitor
electrodes—a review. J Mater. 2016;2(1):37‐54. https://doi.org/
10.1016/j.jmat.2016.01.001
AUTHORS' CONTRIBUTION 12. Wang Y, Shi Z, Huang Y, et al. Supercapacitor devices based on
graphene materials.pdf. J Phys Chem C. 2009;113(30):
Equivalently.
13103‐13107. https://doi.org/10.1021/jp902214f
13. Zhang LL, Zhou R, Zhao XS. Graphene‐based materials as
A C K N O WL E D G M E N T S supercapacitor electrodes. J Mater Chem. 2010;20(29):5983.
https://doi.org/10.1039/c000417k
Dr. Talal M. Altahtamouni gratefully acknowledges
Qatar University for funding the project: GCC Co‐Fund 14. Ojha GP, Pant B, Park SJ, Park M, Kim HY. Synthesis and
characterization of reduced graphene oxide decorated with
Program Grant GCC‐2017‐007.
CeO2‐doped MnO2 nanorods for supercapacitor applications.
J Colloid Interface Sci. 2017;494:338‐344. https://doi.org/
ORCID 10.1016/j.jcis.2017.01.100
15. Wu Z, Winter A, Chen L, et al. Three‐dimensional nitrogen
T. M. Altahtamouni http://orcid.org/0000-0002-9794-2234 and boron co‐doped graphene for high‐performance all‐solid‐
state supercapacitors. Adv Mater. 2012;24(37):1‐6. https://doi.
org/10.1002/adma.201201948
R EF E RE N C E S
16. Basu S, Bhattacharyya P. Recent developments on graphene
1. Bose S, Kuila T, Mishra AK, Rajasekar R, Kim NH, Lee JH. and graphene oxide based solid state gas sensors. Sens Actua-
Carbon‐based nanostructured materials and their composites tors B. 2012;173:1‐21. https://doi.org/10.1016/j.snb.2012.07.092
as supercapacitor electrodes. J Mater Chem.
2012;22(3):767‐784. https://doi.org/10.1039/C1JM14468E 17. Niu Z, Zhang L, Liu L, Zhu B, Dong H, Chen X. All‐solid‐state
flexible ultrathin micro‐supercapacitors based on graphene.
2. Kuila T, Bose S, Mishra AK, Khanra P, Kim NH, Lee JH. Adv Mater. 2013;25:4035‐4042. https://doi.org/10.1002/
Chemical functionalization of graphene and its applications. adma.201301332
Prog Mater Sci. 2012;57(7):1061‐1105. https://doi.org/10.1016/
18. Yoon SM, Choi WM, Baik H, et al. Synthesis of multilayer
j.pmatsci.2012.03.002
graphene balls by carbon segregation from nickel nanoparti-
3. Liu J, Cui L, Losic D. Graphene and graphene oxide as new cles. ACS Nano. 2012;6(8):6803‐6811. https://doi.org/10.1021/
nanocarriers for drug delivery applications. Acta Biomater. nn301546z
2013;9(12):9243‐9257. https://doi.org/10.1016/j.actbio.2013.08.016
19. Chang H, Wu H. Graphene‐based nanocomposites: prepara-
4. Yi M, Shen Z. A review on mechanical exfoliation for the tion, functionalization, and energy and environmental
scalable production of graphene. J Mater Chem A. applications. Energ Environ Sci. 2013;6(12):3483. https://doi.
2015;3(22):11700‐11715. https://doi.org/10.1039/C5TA00252D org/10.1039/c3ee42518e
5. Xu J, Zhang D. Multifunctional structural supercapacitor based 20. Byon HR, Lee SW, Chen S, Hammond PT, Shao‐Horn Y.
on graphene and geopolymer. Electrochim Acta. Thin films of carbon nanotubes and chemically reduced
2017;224:105‐112. https://doi.org/10.1016/j.electacta.2016.12.045 graphenes for electrochemical micro‐capacitors. Carbon N Y.
6. Su CY, Lu AY, Xu Y, Chen FR, Khlobystov AN, Li LJ. High‐ 2011;49(2):457‐467. https://doi.org/10.1016/j.carbon.2010.
quality thin graphene films from fast electrochemical exfolia- 09.042
tion. ACS Nano. 2011;5(3):2332‐2339. https://doi.org/10.1021/ 21. Fu C, Kuang Y, Huang Z, et al. Supercapacitor based on
nn200025p graphene and ionic liquid electrolyte. J Solid State Electrochem.
LEMINE ET AL.
2011;15(11‐12):2581‐2585. https://doi.org/10.1007/s10008‐010‐
1248‐9
22. Chee WK, Lim HN, Zainal Z, Huang NM, Harrison I, Andou Y.
Flexible graphene‐based supercapacitors: a review. J Phys
Chem C. 2016;120(8):4153‐4172. https://doi.org/10.1021/acs.
jpcc.5b10187
23. Wu X, Lian M. Highly flexible solid‐state supercapacitor based
on graphene/polypyrrole hydrogel. J Power Sources.
2017;362:184‐191. https://doi.org/10.1016/j.
jpowsour.2017.07.042
24. Singh V, Joung D, Zhai L, Das S, Khondaker SI, Seal S.
Graphene based materials: past, present and future. Prog Mater
Sci. 2011;56(8):1178‐1271. https://doi.org/10.1016/j.pmatsci.
2011.03.003
25. Stankovich S, Dikin DA, Piner RD, et al. Synthesis of
graphene‐based nanosheets via chemical reduction of exfoli-
ated graphite oxide. Carbon N Y. 2007;45(7):1558‐1565.
https://doi.org/10.1016/j.carbon.2007.02.034
26. Choi HJ, Jung SM, Seo JM, Chang DW, Dai L, Baek JB.
Graphene for energy conversion and storage in fuel cells and
supercapacitors. Nano Energy. 2012;1(4):534‐551. https://doi.
org/10.1016/j.nanoen.2012.05.001
27. Zhang X, Zhang H, Li C, Wang K, Sun X, Ma Y. Recent
advances in porous graphene materials for supercapacitor
applications. RSC Adv. 2014;4(86):45862‐45884. https://doi.
org/10.1039/c4ra07869a
28. Gómez‐Navarro C, Meyer JC, Sundaram RS, et al. Atomic
structure of reduced graphene oxide. Nano Lett.
2010;10(4):1144‐1148. https://doi.org/10.1021/nl9031617
29. Li M, Tang Z, Leng M, Xue J. Flexible solid‐state
supercapacitor based on graphene‐based hybrid films. Adv
Funct Mater. 2014;24(47):7495‐7502. https://doi.org/10.1002/
adfm.201402442
30. Ferrari AC, Meyer JC, Scardaci V, et al. Raman spectrum of
graphene and graphene layers. Phys Rev Lett. 2006;97(18):1‐4.
https://doi.org/10.1103/PhysRevLett.97.187401
31. Lu CH, Yang HH, Zhu CL, Chen X, Chen GN. A graphene
platform for sensing biomolecules. Angew Chem Int Ed.
2009;48(26):4785‐4787. https://doi.org/10.1002/anie.200901479
32. Ohzuku T, Brodd RJ. An overview of positive‐electrode mate-
rials for advanced lithium‐ion batteries. J Power Sources.
2007;174(2):449‐456. https://doi.org/10.1016/j.jpowsour.
2007.06.154
33. Chaikittisilp W, Hu M, Wang H, et al. Nanoporous carbons
through direct carbonization of a zeolitic imidazolate frame-
work for supercapacitor electrodes. Chem Commun.
2012;48(58):7259‐7261. https://doi.org/10.1039/c2cc33433j
34. Wu ZS, Ren W, Gao L, Liu B, Jiang C, Cheng HM. Synthesis of
high‐quality graphene with a pre‐determined number of layers.
Carbon N Y. 2009;47(2):493‐499. https://doi.org/10.1016/j.
carbon.2008.10.031
35. Ganesh V, Pitchumani S, Lakshminarayanan V. New symmet-
ric and asymmetric supercapacitors based on high surface area
porous nickel and activated carbon. J Power Sources.
2006;158(2):1523‐1532. https://doi.org/10.1016/j.jpowsour.
2005.10.090
15
36. Gilje S, Han S, Wang M, Wang KL, Kaner RB. A chemical
route to graphene for device applications. Nano Lett.
2007;7(11):3394‐3398. https://doi.org/10.1021/nl0717715
37. Meyer JC, Geim AK, Katsnelson MI, Novoselov KS, Booth TJ,
Roth S. The structure of suspended graphene sheets. Nature.
2007;446(7131):60‐63. https://doi.org/10.1038/nature05545
38. Largeot C, Portet C, Chmiola J, Taberna PL, Gogotsi Y, Simon
P. Relation between the ion size and pore size for an electric
double‐layer capacitor. J Am Chem Soc.
2008;130(9):2730‐2731. https://doi.org/10.1021/ja7106178
39. Pandolfo AG, Hollenkamp AF. Carbon properties and their
role in supercapacitors. J Power Sources. 2006;157(1):11‐27.
https://doi.org/10.1016/j.jpowsour.2006.02.065
40. Wehling TO, Novoselov KS, Morozov SV, et al. Molecular dop-
ing of graphene. Nano Lett. 2008;8(1):173‐177. https://doi.org/
10.1021/nl072364w
41. Davies A, Yu A. Material advancements in supercapacitors:
from activated carbon to carbon nanotube and graphene. Can
J Chem Eng. 2011;89(6):1342‐1357. https://doi.org/10.1002/
cjce.20586
42. Zhang J, Zhao XS. On the configuration of supercapacitors for
maximizing electrochemical performance. ChemSusChem.
2012;5(5):818‐841. https://doi.org/10.1002/cssc.201100571
43. Xiao X, Peng X, Jin H, et al. Freestanding mesoporous VN/
CNT hybrid electrodes for flexible all‐solid‐state
supercapacitors. Adv Mater. 2013;25(36):5091‐5097. https://
doi.org/10.1002/adma.201301465
44. Makarova TL, Sundqvist B, Scharff P, et al. Electrical proper-
ties of two‐dimensional fullerene matrices. Carbon N Y.
2001;39(14):2203‐2209. https://doi.org/10.1016/S0008‐
6223(01)00036‐7
45. Schniepp HC, Li JL, McAllister MJ, et al. Functionalized single
graphene sheets derived from splitting graphite oxide. J Phys
Chem B. 2006;110(17):8535‐8539. https://doi.org/10.1021/
jp060936f
46. Hass J, De Heer WA, Conrad EH. The growth and morphology
of epitaxial multilayer graphene. J Phys Condens Matter.
2008;20(32):323202. https://doi.org/10.1088/0953‐8984/20/32/
323202
47. Liu C, Li F, Ma L‐P, Cheng H‐M. Advanced materials for
energy storage. Adv Mater. 2010;22(8):E28‐E62. https://doi.
org/10.1002/adma.200903328
48. Kaempgen M, Chan CK, Ma J, Cui Y, Gruner G. Printable thin
film supercapacitors using single‐walled carbon nanotubes.
Nano Lett. 2009;9(5):1872‐1876. https://doi.org/10.1021/
nl8038579
49. Lee C, Wei X, Kysar JW, Hone J. Measurement of the elastic
properties and intrinsic strength of monolayer graphene. Sci-
ence. 2008;321(80):385‐388. https://doi.org/10.1126/science.
1157996
50. Wang JJ, Zhu MY, Outlaw RA, et al. Free‐standing
subnanometer qraphite sheets. Appl Phys Lett.
2004;85(7):1265‐1267. https://doi.org/10.1063/1.1782253
16
51. Balandin AA, Ghosh S, Bao W, et al. Superior thermal conduc-
tivity of single‐layer graphene. Nano Lett. 2008;8(3):902‐907.
https://doi.org/10.1021/nl0731872
52. Liang J, Huang Y, Zhang L, et al. Molecular‐level dispersion of
graphene into poly (vinyl alcohol) and effective reinforcement
of their nanocomposites. Adv Funct Mater.
2009;19(14):2297‐2302. https://doi.org/10.1002/adfm.200801776
53. Xie X, Qu L, Zhou C, et al. An asymmetrically surface‐modified
graphene film electrochemical actuator. ACS Nano.
2010;4(10):6050‐6054. https://doi.org/10.1021/nn101563x
54. Wang X, Zhi L, Müllen K. Transparent, conductive graphene
electrodes for dye‐sensitized solar cells. Nano Lett.
2008;8(1):323‐327. https://doi.org/10.1021/nl072838r
55. Lotya M, Hernandez Y, King PJ, et al. Liquid phase production
of graphene by exfoliation of graphite in surfactant/water solu-
tions liquid phase production of graphene by exfoliation of
graphite in surfactant/water solutions. Mater Sci Forum.
2009;131(10):3611‐3620. https://doi.org/10.1021/ja807449u
56. De S, King PJ, Lotya M, et al. Flexible, transparent, conducting
films of randomly stacked graphene from surfactant‐stabilized,
oxide‐free graphene dispersions. Small. 2010;6(3):458‐464.
https://doi.org/10.1002/smll.200901162
57. Yoo EJ, Kim J, Hosono E, Zhou HS, Kudo T, Honma I. Large
reversible Li storage of graphene nanosheet families for use
in rechargeable lithium ion batteries. Nano Lett.
2008;8(8):2277‐2282. https://doi.org/10.1021/nl800957b
58. Cai Y, Zhang A, Ping Feng Y, Zhang C. Switching and rectifi-
cation of a single light‐sensitive diarylethene molecule
sandwiched between graphene nanoribbons. J Chem Phys.
2011;135(18):135. https://doi.org/10.1063/1.3657435
59. Gao W, Alemany LB, Ci L, Ajayan PM. New insights into the
structure and reduction of graphite oxide. Nat Chem.
2009;1(5):403‐408. https://doi.org/10.1038/nchem.281
60. Zhang J, Yang H, Shen G, Cheng P, Zhang J, Guo S. Reduction
of graphene oxide via <scp>l</scp> ‐ascorbic acid. Chem
Commun. 2010;46(7):1112‐1114. https://doi.org/10.1039/
B917705A
61. Salas EC, Sun Z, Lu A, Tour JM. Reduction of graphene oxide
via. ACS Nano. 2010;4:4852‐4856.
62. Cote LJ, Cruz‐Silva R, Huang J. Flash reduction and patterning
of graphite oxide and its polymer composite P. Goins, L.J. Cote,
R. Cruz‐Silva, J. Huang *. J Am Chem Soc.
2009;131(31):11027‐11032.
63. Chen S, Zhu J, Wu X, Han Q, Wang X. Graphene oxide‐Mno2
nanocomposites for supercapacitors. ACS Nano.
2010;4(5):2822‐2830. https://doi.org/10.1021/nn901311t
64. Chou SL, Wang JZ, Chew SY, Liu HK, Dou SX. Electrodeposi-
tion of MnO2 nanowires on carbon nanotube paper as free‐
standing, flexible electrode for supercapacitors. Electrochem
Commun. 2008;10(11):1724‐1727. https://doi.org/10.1016/j.
elecom.2008.08.051
65. Akhavan O, Choobtashani M, Ghaderi E. Protein degradation
and RNA efflux of viruses photocatalyzed by graphene‐tung-
sten oxide composite under visible light irradiation. J Phys
Chem C. 2012;116(17):9653‐9659. https://doi.org/10.1021/
jp301707m
LEMINE ET AL.
66. Cai Y, Zhang G, Zhang YW. Polarity‐reversed robust carrier
mobility in monolayer MoS2 nanoribbons. J Am Chem Soc.
2014;136(17):6269‐6275. https://doi.org/10.1021/ja4109787
67. Wu ZS, Ren W, Wang DW, Li F, Liu B, Cheng HM. High‐
energy MnO2 nanowire/graphene and graphene asymmetric
electrochemical capacitors. ACS Nano. 2010;4(10):5835‐5842.
https://doi.org/10.1021/nn101754k
68. Chen S, Zhu J, Wang X. From graphene to metal oxide
nanolamellas: a phenomenon of morphology transmission.
ACS Nano. 2010;4(10):6212‐6218. https://doi.org/10.1021/
nn101857y
69. Yan J, Fan Z, Wei T, Qian W, Zhang M, Wei F. Fast and revers-
ible surface redox reaction of graphene‐MnO2 composites as
supercapacitor electrodes. Carbon N Y. 2010;48(13):3825‐3833.
https://doi.org/10.1016/j.carbon.2010.06.047
70. Lee JS, Kim SI, Yoon JC, Jang JH. Chemical vapor deposition
of mesoporous graphene nanoballs for supercapacitor. ACS
Nano. 2013;7(7):6047‐6055. https://doi.org/10.1021/nn401850z
71. Chen T, Dai L. Flexible supercapacitors based on carbon
nanomaterials. J Mater Chem A. 2014;2(28):10756. https://doi.
org/10.1039/c4ta00567h
72. Cheng H, Dong Z, Hu C, et al. Textile electrodes woven by car-
bon nanotube‐graphene hybrid fibers for flexible
electrochemical capacitors. Nanoscale. 2013;5(8):3428‐3434.
https://doi.org/10.1039/c3nr00320e
73. Güneş F, Shin HJ, Biswas C, et al. Layer‐by‐layer doping of
few‐layer graphene film. ACS Nano. 2010;4(8):4595‐4600.
https://doi.org/10.1021/nn1008808
74. Gan S, Zhong L, Wu T, et al. Spontaneous and fast growth of
large‐area graphene nanofilms facilitated by oil/water inter-
faces. Adv Mater. 2012;24(29):3958‐3964. https://doi.org/
10.1002/adma.201201098
75. Vickery JL, Patil AJ, Mann S. Fabrication of graphene‐polymer
nanocomposites with higher‐order three‐dimensional architec-
tures. Adv Mater. 2009;21(21):2180‐2184. https://doi.org/
10.1002/adma.200803606
76. Lehtimäki S, Suominen M, Damlin P, Tuukkanen S, Kvarnström
C, Lupo D. Preparation of supercapacitors on flexible substrates
with electrodeposited PEDOT/graphene compositeS. ACS Appl
Mater Interfaces. 2015;7(40):22137‐22147. https://doi.org/
10.1021/acsami.5b05937
77. Sun Y, Wu Q, Shi G. Graphene based new energy materials.
Energ Environ Sci. 2011;4(4):1113. https://doi.org/10.1039/
c0ee00683a
78. Kim J, Cote LJ, Kim F, Yuan W, Shull KR, Huang J. Graphene
oxide sheets at interfaces. J Am Chem Soc.
2010;132(23):8180‐8186. https://doi.org/10.1021/ja102777p
79. Liu C, Yu Z, Neff D, Zhamu A, Jang BZ. Graphene‐based
supercapacitor with an ultrahigh energy density. Nano Lett.
2010;10(12):4863‐4868. https://doi.org/10.1021/nl102661q
80. Worsley MA, Pauzauskie PJ, Olson TY, Biener J, Satcher JH Jr,
Baumann TF. Synthesis of graphene aerogel with high electri-
cal conductivity. J Am Chem Soc. 2010;132(40):14067‐14069.
https://doi.org/10.1021/ja1072299
LEMINE ET AL.
81. Soldano C, Mahmood A, Dujardin E. Production, properties
and potential of graphene. Carbon N Y. 2010;48(8):2127‐2150.
https://doi.org/10.1016/j.carbon.2010.01.058
82. Tung VC, Kim J, Cote LJ, Huang J. Sticky interconnect for
solution‐processed tandem solar cells. J Am Chem Soc.
2011;133(24):9262‐9265. https://doi.org/10.1021/ja203464n
83. Cao X, Shi Y, Shi W, et al. Preparation of novel 3D graphene
networks for supercapacitor applications. Small.
2011;7(22):3163‐3168. https://doi.org/10.1002/smll.201100990
84. Dong XC, Xu H, Wang XW, et al. 3D graphene‐cobalt oxide
electrode for high‐performance supercapacitor and enzymeless
glucose detection. ACS Nano. 2012;6(4):3206‐3213. https://doi.
org/10.1021/nn300097q
85. Wu Q, Sun Y, Bai H, Shi G. High‐performance supercapacitor
electrodes based on graphene hydrogels modified with 2‐
aminoanthraquinone moieties. Phys Chem Chem Phys.
2011;13(23):11193‐11198. https://doi.org/10.1039/c1cp20980a
86. G. Shi, L. Zhang, Preparation of highly conductive graphene
hydrogels for fabricating supercapacitors with high rate capa-
bility (2011) 17206–17212. doi:https://doi.org/10.1021/
jp204036a.
87. D. Jiang, V.R. Cooper, S. Dai, Porous graphene as the ultimate
membrane for gas separation, (2009).
88. Dimitrakakis GK, Tylianakis E, Froudakis GE. Pillared
graphene: a new 3‐D network nanostructure for enhanced
hydrogen storage. Nano Lett. 2008;8(10):3166‐3170. https://
doi.org/10.1021/nl801417w
89. Gómez‐Navarro C, Burghard M, Kern K. Elastic properties of
chemically derived single graphene sheets. Nano Lett.
2008;8(7):2045‐2049. https://doi.org/10.1021/nl801384y
90. Xia J, Chen F, Li J, Tao N. Measurement of the quantum
capacitance of graphene. Nat Nanotechnol. 2009;4(8):505‐509.
https://doi.org/10.1038/nnano.2009.177
91. Stoller MD, Ruoff RS. Best practice methods for determining
an electrode material's performance for ultracapacitors. Energ
Environ Sci. 2010;3(9):1294. https://doi.org/10.1039/
c0ee00074d
92. Emmenegger C, Mauron P, Sudan P, et al. Investigation of
electrochemical double‐layer (ECDL) capacitors electrodes
based on carbon nanotubes and activated carbon materials. J
Power Sources. 2003;124(1):321‐329. https://doi.org/10.1016/
S0378‐7753(03)00590‐1
93. Bao Q, Zhang H, Yang JX, et al. Graphene‐polymer nanofiber
membrane for ultrafast photonics. Adv Funct Mater.
2010;20(5):782‐791. https://doi.org/10.1002/adfm.200901658
94. Ritter KA, Lyding JW. Characterization of nanometer‐sized,
mechanically exfoliated graphene on the H‐passivated Si
(100) surface using scanning tunneling microscopy. Nanotech-
nology. 2008;19(1):015704. https://doi.org/10.1088/0957‐4484/
19/01/015704
17
95. Kötz R, Carlen M. Principles and applications of electrochemi-
cal capacitors. Electrochim Acta. 2000;45(15‐16):2483‐2498.
https://doi.org/10.1016/S0013‐4686(00)00354‐6
96. Conway BE, Birss V, Wojtowicz J. The role and utilization of
pseudocapacitance for energy storage by supercapacitors. J
Power Sources. 1997;66(1‐2):1‐14. https://doi.org/10.1016/
S0378‐7753(96)02474‐3
97. Emtsev KV, Bostwick A, Horn K, et al. Towards wafer‐size
graphene layers by atmospheric pressure graphitization of sili-
con carbide. Nat Mater. 2009;8(3):203‐207. https://doi.org/
10.1038/nmat2382
98. Fuertes AB, Alvarez S. Graphitic mesoporous carbons synthe-
sised through mesostructured silica templates. Carbon N Y.
2004;42(15):3049‐3055. https://doi.org/10.1016/j.carbon.2004.
06.020.
99. Martin P. Electrochemistry of gaphene: new horizons for sens-
ing and energy storage. Chem Rec. 2009;9(4):211‐223. https://
doi.org/10.1002/tcr.200900008
100. El‐Kady MF, Shao Y, Kaner RB. Graphene for batteries,
supercapacitors and beyond. Nat Rev Mater. 2016;1(7):16033.
https://doi.org/10.1038/natrevmats.2016.33
101. Chen L, Liu Y, Zhao Y, Chen N, Qu L. Graphene‐based fibers
for supercapacitor applications. Nanotechnology. 2016)
032001. doi:https://doi.org/10.1088/0957‐4484/27/3/032001;
27(3):032001.
102. K. Vuorilehto, M. Nuutinen, Supercapacitors—basics and
applications, (2014).
103. R. Agrawal, C. Chen, Y. Hao, Y. Song, C. Wang, Graphene for
supercapacitors, in: Graphene‐Based Energy Devices, 2015: pp.
171–214. doi:doi.org/10.1002/9783527690312.ch6.
104. Yang W, Ni M, Ren X, et al. Graphene in supercapacitor appli-
cations. Curr Opin Colloid Interface Sci. 2015;20(5‐6):416‐428.
https://doi.org/10.1016/j.cocis.2015.10.009
105. Guo CX, Li CM. A self‐assembled hierarchical nanostructure
comprising carbon spheres and graphene nanosheets for
enhanced supercapacitor performance. Energ Environ Sci.
2011;4(11):4504‐4507. https://doi.org/10.1039/c1ee01676h
106. Yang H, Kannappan S, Pandian AS, Jang J‐H, Lee YS, Lu W.
Graphene supercapacitor with both high power and energy
density. Nanotechnology. 2017) 445401. doi:https://doi.org/
10.1088/1361‐6528/aa8948;28(44):445401.
107. Strauss V, Marsh K, Kowal MD, El‐Kady M, Kaner RB. A sim-
ple route to porous graphene from carbon nanodots for
supercapacitor applications. Adv Mater. 2018;30(8):1‐10.
https://doi.org/10.1002/adma.201704449
How to cite this article: Lemine AS, Zagho MM,
Altahtamouni TM, Bensalah N. Graphene a
promising electrode material for supercapacitors—
A review. Int J Energy Res. 2018;1–17. https://doi.
org/10.1002/er.4170