Energy Reports 6 (2020) 2768–2784

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Energy Reports
journal homepage: www.elsevier.com/locate/egyr

Review article

Advances in graphene-based supercapacitor electrodes

Syeda Wishal Bokhari a , Ahmad Hassan Siddique b , Peter C. Sherrell c , Xiaoyu Yue a ,
∗
Kariappa Maletira Karumbaiah d , Shanghai Wei a , Amanda V. Ellis c , Wei Gao a ,
a
Department of Chemical and Materials Engineering, University of Auckland, Private Bag 92019 Auckland 1142, New Zealand
b
Ningbo Institute of Materials Technology and Engineering (NIMTE), Chinese Academy of Sciences, No. 1219 Zhongguan West Road, Zhenhai
district, Ningbo 315201, PR China
c
Department of Chemical Engineering, University of Melbourne, Parkville, Victoria 3010, Australia
d
Centre for Advanced Composite Materials, University of Auckland, Private Bag 92019, Auckland 1142, New Zealand

article info a b s t r a c t

Article history: Graphene-based materials are widely explored as the active electrode materials for energy storage
Received 2 May 2020 and conversion devices, especially supercapacitors (SCs). Their high electrochemically active surface
Received in revised form 31 August 2020 area, hierarchical porous structure, excellent compressibility, and high mechanical stability, as well as
Accepted 3 October 2020
excellent conductivity, are the critical merits for providing robust and facilitative channels for charge
Available online 16 October 2020
transport. Various studies have explored many possible ways to utilize the maximum potential of
Keywords: graphene-based SC electrodes, and graphene research is booming, given its exceptional charge storage
Graphene-based electrodes properties. This review focuses on the class-specific electrode materials for different types of SCs,
Supercapacitors followed by the classification and critical review of graphene-based electrodes reported in the past
Power density five years. The current challenges in the field have also been discussed with a focus on promising
Energy density
pathways for future research.
© 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Contents

1. Introduction..................................................................................................................................................................................................................... 2768
2. Types of supercapacitor electrodes .............................................................................................................................................................................. 2771
2.1. Electrochemical double layer (EDLC) electrodes .......................................................................................................................................... 2771
2.2. Pseudocapacitors .............................................................................................................................................................................................. 2773
2.3. Electrodes for asymmetric systems (ASCs) ..................................................................................................................................................... 2773
2.4. Electrodes for Hybrid Supercapacitors (HSCs) .............................................................................................................................................. 2775
3. Graphene-based electrodes for SCs .............................................................................................................................................................................. 2775
3.1. Key factors for designing graphene-based SC electrodes ............................................................................................................................ 2776
4. Classification of graphene-based electrodes systems ............................................................................................................................................... 2777
4.1. Functionalized/doped graphene ...................................................................................................................................................................... 2777
4.2. Graphene composites with transition metal oxides .................................................................................................................................... 2779
4.3. Graphene composite electrodes with carbon and conductive polymers ................................................................................................... 2781
5. The state-of-the-art graphene-based SC electrodes ................................................................................................................................................... 2783
6. Challenges, suggestions, and future outlooks ............................................................................................................................................................. 2783
Declaration of competing interest................................................................................................................................................................................ 2783
Acknowledgments .......................................................................................................................................................................................................... 2783
References ....................................................................................................................................................................................................................... 2783

1. Introduction the global economy and alarming level of fossil fuels diminution.
The ever-increasing reliance on electronic devices creates a global
Renewable and sustainable energy storage systems are being
intensively pursued, driven by the rapidly increasing demand of need for smart and efficient energy storage and conversion sys-
tems as a power source (Shepelin et al., 2019). The supercapacitor
∗ Corresponding author.
E-mail address: w.gao@auckland.ac.nz (W. Gao). (SC) has emerged as a pivotal player to address this global need,

https://doi.org/10.1016/j.egyr.2020.10.001
2352-4847/© 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
S.W. Bokhari, A.H. Siddique, P.C. Sherrell et al.
presenting the fastest charging and discharging of any electro-
chemical energy storage device, ideal for the rapid speed of the
modern world (Liu and Peng, 2017).
SCs are the high power density electrochemical energy storage
devices, occupying the top left quadrant in the Ragone plot of
energy density (amount of stored energy in a certain mass, W
h kg−1 ) and power density (time rate of energy transfer in a
certain mass, kW kg−1 ) (Gogotsi and Simon, 2011). They have a
very long-life cycle and a high degree of flexibility in electrolyte
choice, which makes them an ideal candidate for many high-
power electronics and automotive applications (Hossain et al.,
2017). SCs rely on highly conductive and high surface area elec-
trodes for maximum performance. The incorporation of nan-
otechnology since the early 2000s has made exponential growth
in performance of SCs. Graphene-based materials find essential
applications as efficient electrodes for SCs due to exceptional
chemical stability, electrical conductivity (200, 000 cm2 V−1 s−1 ),
mechanical properties (1 TPa Young’s modulus) and high theo-
retical surface area (3000 m2 g−1 ). They not only possess higher
power density but also offer excellent electrode structural stabil-
ity over millions of cycles with comparable energy densities in a
cost-effective package (Manjakkal et al., 2018; Gao et al., 2018).
Traditional supercapacitors, electrochemical double-layer ca-
pacitors (EDLCs), only rely on non-faradaic charge processes and
the assembly of a Helmholtz double layer at the surface of an
electrode. However, while this enhances stability dramatically, it
is fundamentally limited in terms of the total energy density of
the device. Different approaches have been introduced to design
high energy and power density SCs (Fig. 1).
(1) Electrochemical double-layer capacitors (EDLCs) store charges
electrostatically through the formation of an electric Helmholtz
double layer on the surface of the electrodes by the interac-
tion/physical adsorption/desorption of ions (Hossain et al., 2017).
(2) Pseudocapacitors (PCs) undergo a faradic mode of storing
charges by electron transfer between the electrode and elec-
trolytes, governed by electro-sorption/redox reaction or ions in-
tercalation processes to/from electrolytes (Cai et al., 2018).
(3) Asymmetric and hybrid supercapacitors (ASCs/HSCs) which
can further be divided into (i) ASCs, which combine two distinc-
tive electrodes (Faradic and double layer), has a wide working
potential and in turn, high energy and power (E-P) densities
(Rahmanifar et al., 2019; Sun et al., 2017), and (ii) Hybrid su-
percapacitors (HSCs) are a newly introduced class of SCs which
incorporate one battery type electrode (usually transition metal
oxides (TMOs)) and one capacitor type electrode (conductive
carbons), which undergo dual charge storage mechanism in a
single device, enabling them to attain so far the highest position
in the Ragone plot (Fig. 2) (Salanne et al., 2016).
The Ragone plot compares electrochemical devices based on
their power density, effectively characterizing the speed at which
a device can be charged or discharged, and their energy density,
the total amount of chargeable to be stored in the device (Allagui
et al., 2020; Christen, 2020). Therefore, the drive-in SC research
is to achieve a device that can be charged as fast as possible, but
capable of storing a much more significant amount of energy that
the current SC-based technologies.
For the electrostatic mode of storing charge, EDLCs require
the electrode materials to have a high electrochemically active
surface and a hierarchically porous structure so that ions can
diffuse to and accumulate on the surface of electrode materials
(Fig. 3a). The higher the electrochemically active surface area
(EASA) coupled with an appropriate pore structure enabling rapid
ion diffusion, the faster the charge–discharge process (Romano
et al., 2019). Here, porous carbons have several critical advantages
as they are lightweight, highly conductive, and, more importantly,
have an experimentally high specific surface area in the range of
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Energy Reports 6 (2020) 2768–2784
1500–3000 m2 g−1 providing more room for rapid charge storage
(Zheng et al., 2015). However, they still suffer from the limited
specific capacitance in the range of 120–200 F g−1 only (Forse
et al., 2016; Borenstein et al., 2017).
Conversely, for the faradic mode, pseudo-capacitance largely
depends on the electron affinity of the electrode material, so the
PCs require electrodes to undergo fast redox reactions required
in the electroactive materials (Song et al., 2019) (Fig. 3b). These
reactions do not involve any phase change that is commonly
observed in rechargeable batteries. An exception to this is in
case of the conducting polymers, they do undergo some sort
of analogous phase change as the counter ion diffuses into the
polymer structure to counter the backbone charge — similar to
how cations intercalate into an anode in an alkali ion battery
(Zhang et al., 2019a). Transition metal oxides (TMOs) coupled to
conductive carbons are generally used as PC electrodes due to
their excellent redox potential and inherent pseudocapacitance,
multiple stable oxidation states, and good reversibility (as the
electrons mostly come from the valence orbitals) (Lang et al.,
2011; Wei et al., 2018a). Ruthenium dioxide (RuO2 ) in sulphuric
acid (H2 SO4 ) electrolyte is one of the best examples of a high
pseudocapacitance evident from the very broad redox peaks in
a working potential of 1.2 V per electrode Conway (1991), Lu
et al. (2017a). TMOs do offer very high specific capacitance;
however, their poor cyclic stability and low conductivity limit
their widespread applications (Peng et al., 2018a).
ASC/HSCs are a hybrid design to overcome the shortcom-
ings of the parent systems by using one electrostatic and one
pseudocapacitive electrode (Fig. 3c), which enables the device
to acquire dual energy storage mechanism leading to improved
electrochemical performance (Liu et al., 2019a). For ASCs, both
electrodes are a capacitor type (one double layer and one pseudo).
For HSC, one electrode comes from the capacitor, and the other
is a battery electrode (typically an anode), thus bridging the
gap between batteries and supercapacitors (Bokhari et al., 2017;
Dubal et al., 2015). Such asymmetric and hybrid devices offer a
wide working potential, usually in the range of <2 V, an excellent
specific capacitance, remarkable cyclic stability for millions of
cycles, and an improved energy density without sacrificing power
density, which puts them on the top of Ragone plot (Fig. 2).
Therefore, the electrodes for ASC/HSC’s are usually carbonaceous
materials, TMOs, or their synergistic combinations in the form
of nanocomposites, all in asymmetric configuration (Dubal et al.,
2015, 2017). Besides, the properties of EDLCs, PCs, HSCs, and
ASCs, can all be further manipulated by using different electrolyte
types, aqueous or organic, liquid or solid, active, or passive;
however, this is beyond the scope of the current review.
This review studies (i) Electrodes based on different SC types,
(ii) the state-of-art of class-specific graphene-based electrodes
for SCs, importantly, the electrode work function/ surface po-
tential on graphene surfaces and (iii) the recent advances in
graphene-based nano-architectures, including reduced graphene
oxide (rGO), porous graphene (PGs), graphene fibres (GFRS),
graphene nanoribbons (GNRs), and 3D printed graphene. The fo-
cuses are on the significant performance parameters like working
potentials, energy-power profiles, rate performance, and cyclic
stability. After presenting a relative comparison of different
graphene-based electrode systems reported (3–5 years), the out-
look and challenges on the fields are briefly summarized.The
organization of main review sections is as follows.
Section 2 describes various type of electrodes based on the SC
types.
Section 3 describes key factors for designing graphene-based
electrodes.
Section 4 presents a classification of graphene-based elec-
trodes based on the hybridization type and presents some major
S.W. Bokhari, A.H. Siddique, P.C. Sherrell et al. Energy Reports 6 (2020) 2768–2784

Fig. 1. Classification of different types of supercapacitors and their representative electrode materials based on the charge storage mechanism that takes place in
each class of SC.

Fig. 2. Illustration of Ragone Plot for performance comparison of various energy storage and conversion systems displaying the progress of E-P density of the different
types of SCs and which position future devices are expected to obtain.

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S.W. Bokhari, A.H. Siddique, P.C. Sherrell et al.
Fig. 3. Schematics of working mechanisms for supercapacitors: (a) EDLC showing the formation of Helmholtz layer on the surface of the electrode, (b) Pseudocapacitors
displaying the redox reaction taking place on electroactive material, (c) Asymmetric/hybrid supercapacitors illustrating the dual charge storage mechanism that takes
place during electrochemical cycles.
examples of the best performance electrodes reports in the past
few years.
Section 5 gives an overview of the progress in the graphene
based SC field, compare various examples based on the classifi-
cation, and the progress so far made in improving the E-P density
of graphene based SCs.
Section 6 summarizes the whole conclusion from the review,
highlights the current challenges and present an insight to the
future prospective.
The review will form a base for understanding the work-
ing principles and the progress in graphene-based materials as
an electrode for supercapacitors, and an understanding of the
direction this field is moving into.
2. Types of supercapacitor electrodes
A plethora of materials has been studied as the electrodes for
SC, including traditional materials graphite and activated carbons,
and emerging nanomaterials like metal oxides, metal carbides,
quantum dots, graphene, CNTs, and composite materials (Hos-
sain et al., 2017). This section introduces the different types of
electrode materials according to their working mechanisms.
2.1. Electrochemical double layer (EDLC) electrodes
As explained above, charge storage in EDLCs is a res-lt of
the electrostatic interaction between the electrolyte ions and the
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Energy Reports 6 (2020) 2768–2784
surface of electrodes, thereby forming the oppositely charged
double layer at electrode–electrolyte interfaces (Borenstein et al.,
2017). Traditionally, porous (activated) carbon (AC) electrodes are
employed as EDLC electrodes owing to their natural abundance
and high specific surface area for the ion adsorption. Before
2005, enlargement of surface area was considered as the only
effective method to improve the charge storage in EDLC. After
2005, however, the importance of pore size and nanostructure of
carbon was considered as a very vital attire in the electrochemical
performance (Eliad et al., 2001, 2005; Misnon et al., 2014). Since
then, many efforts have been made to understand the charge
storage mechanism in the pores. Three types of pores are usually
present in ACs: micropores (< 2 nm), mesopores (2–50 nm),
and macropores (> 50 nm). The size of the pores and porosity
of the structure are controllable by the activation process using
oxidizing agents, which greatly enhance the EASA, and the pores
usually occupy 30%–80% of the total volume of the ACs (Zhang
et al., 2017a; Zuliani et al., 2017; Forse et al., 2017).
Yang et al. (2017a) investigated the relationship between
mesopores sizes and charge transfer resistance of carbon aerogels
prepared from polycondensation of resorcinol and formaldehyde
in the presence of catalyst by controlling the resorcinol and
catalyst ratio (R/C) as illustrated in Fig. 4. They reported that
the larger the pore size, the smaller is the ion diffusion resis-
tance. Moreover, in turn, a higher electrochemical performance
is achieved in a wide range of working potential (2.7 V), however
S.W. Bokhari, A.H. Siddique, P.C. Sherrell et al. Energy Reports 6 (2020) 2768–2784

Fig. 4. Schematics of synthesis of carbon aerogels with a variety of pore sizes.

Source: Reproduced with permission Yang et al. (2017a).

Fig. 5. (a) Flexible cellulose composite material for the EDLC and (b) Specific capacitance and capacitance retention of EDLC cells created from AC/NC composite
electrodes at different scan rates.
Source: Reproduced with permission Murashko et al. (2017).

this was negated by the recent studies that the larger pore size
than the size of solvated ions do not necessarily contribute to the
capacitance, and hence a hierarchical porous structure is desirable
(Vijayan et al., 2020). Lu et al. (2017b) studied the effect of surface
area on conductivity and resultant electrochemical performance
of the carbon materials. They presented biomass-derived KOH
activated porous carbons with an ultrahigh BET surface area of
3237 m2 g−1 and EASA of 1771 m2 g−1 . Furthermore, they obtained
a good conductivity of 33 Sm−1 by controlling the pore size
distribution of mesopores and consistent EDLC performance in
aqueous (222 F g−1 ), ionic (188 F g−1 ), and organic (202 F g−1 )
electrolytes.
Nevertheless, the low conductance of ACs has shifted the
research towards doping as a tool to induce more defects for
charge transport. Chen et al. (2018) activated 1.35 at. % nitrogen
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into porous carbon derived by pyrolysis of PVDF and obtained
a high SSA of 2289 m2 g−1 with excellent cyclic stability up
to 10,000 times. Another pathway is replacing ACs with other
carbon allotropes, including CNTs and graphene due to their ex-
cellent conductivity, high EASA, and mechanical strength (Pham
et al., 2015). The challenges with graphene and CNTs are the
difficulties in large scale production and processing, which limit
the reproducibility and raises the cost (Yang et al., 2016). One of
the possible solutions to this problem is to make composites with
other carbons as matrices or inducing spacers to avoid restacking
and to enhance the overall electrochemical performance (Li et al.,
2018a; Yan et al., 2017).
The complex electrode processing also greatly affects the con-
ductivity of the materials. Murashko et al. (2017) reported a
solution to this problem. They replaced the PVDF binder with
S.W. Bokhari, A.H. Siddique, P.C. Sherrell et al.
natural cellulose in the activated carbon (AC)-natural cellulose
composite (NC) via a phase inversion technique (Fig. 5a) and
optimized the ratio of AC into the composite. The increase in
the ratio of AC increased the specific capacitance and capacitance
retention by evenly distributed into the cellulose matrix and
forming a fine connected particle system until AC: NC 7:1. After
this, it does not affect the performance (Fig. 5b), which leads to
further research in designing of free-standing electrodes. Su et al.
(2018) studied the EDLC performance of a hydrothermally cross-
linked 3D hybrid of porous NiCO2 O4 and MnO2 on Ni substrate.
This binder-free electrode with a highly cross-linked structure
buffered the volume change effectively during the electrochemi-
cal cycling process. It resulted in a high areal capacitance of 616
mF cm−2 and a 90.1% capacitance retention after 5000 cycles.
2.2. Pseudocapacitors
Pseudocapacitors have a Faradic mode of storing charges
through reversible redox reactions in electroactive materials Zhai
et al. (2017), Owusu et al. (2017), Deng et al. (2017). Transi-
tion metal oxides (TMOs), transition metal nitrides (TMNs), and
conducting polymers are the widely explored candidates for PC
electrodes as they offer the highest working potential for redox
reactions (Zhang et al., 2017b). The reversible redox reactions tak-
ing place in the electroactive materials enable pseudocapacitors
to have higher specific capacitances than EDLC because not only
the surface but also the bulk of the electrode takes part in storing
charges (Zhou et al., 2017). However, the slower reaction kinetics
result in loss of power density (Lu et al., 2017a). One of the
recent examples of typical iron oxide based high performance PC
electrodes has been presented Sun et al. (2018). They designed a
unique crystalline-core/amorphous-shell of oxygen-deficient iron
oxide where the amorphous layer facilitates ion diffusion and
the oxygen defects in Fe2 O3 result in improved conductivity. This
unique structure enables the composite to achieve a high pseu-
docapacitance of 701 F g−1 and retaining up to 70% capacitance
during the cycling test and charged mobile phone in a series
configuration (Fig. 6).
Wang et al. (2017a) also presented a path to overcome the
cycling problem of TMOs by using poly-acrylonitrile (PAN) and
carbon nanotubes as a precursor to prepare high PC nitrogen-
doped carbon monoliths via a template-free method. The mono-
liths demonstrated an EASA of 13.8 m2 g−1 , a specific capacitance
of 380 F g−1 at 1 A g−1 current density with an 8% increase
in the capacitance after 3000 cycles. Li et al. reported an ul-
trahigh 151.2% capacitance retention over 20,000 cycles by in
situ growing nickel nanowires on nickel–cobalt double hydroxide
aligned carefully on nickel foam and the activation of nanowires
on the surface to high PC Ni(OH)2 and NiOOH during the cycling
performance (Li et al., 2018b).
Structural decomposition of the electrodes during the redox
cycling process results in low cyclic stability and subsequent
loss of capacitance (Kim et al., 2016). Nevertheless, given the
simultaneously high energy-power density requirements of su-
percapacitor research, pseudocapacitors offer great potential in
application due to their very high specific capacitances, which
are directly enhancing the energy density (E = 12 CV 2 ) and in
turn, substantially affects the power density (P = ∆Et ) (Yi et al.,
2018). The problems with their low conductivity and poor cycling
are addressed by making composites with conductive materials.
For example, by using carbonaceous materials as a conductive
backbone/matrix and lodge the electroactive materials on the
surface of the conductive backbone or to disperse them uniformly
among the sheets of 2D layered materials (Meng et al., 2016).
Another widely proposed method is to make the composites
of conducting polymers with TMOs or TMNs, giving a good rate
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Energy Reports 6 (2020) 2768–2784
performance and better cycling stability than the precursors (Na-
garaju et al., 2016; Lee et al., 2019). Zang et al. reported a 3 V de-
vice with stable cycling performance for up to 10,000 cycles. They
used a high PC TiS2 coated vertically aligned CNTs (VACNTS) and
reported an ultrahigh energy density of 60.9 W h kg−1 and 1250
W kg−1 (Fig. 7a) (Zang et al., 2018). Pan et al. reported the best
1 −1
solid-state PC performance (3946.5 F g− , 114.8 Wh kg at 643.8
−1
W kg ) by using bimetallic ZnCo-OH nanosheets (ZnCo1.5 (OH)
Cl0.5· 0.45H2 O @ PET substrate), showing the potential of free-
standing electrodes based on a conductive matrix (Fig. 7b) (Pan
et al., 2018).
2.3. Electrodes for asymmetric systems (ASCs)
Asymmetric supercapacitors (ASCs) are more advanced types
of SCs that can overcome the problems of energy-power densities,
cycling stability, and limited working potential of the symmetric
systems (Bokhari et al., 2017; Xiong et al., 2018). The definition
of an asymmetric system is quite broad, referring to any pos-
sible chemical, material, or physical (active mass or thickness)
difference of cathodes and anodes (Bokhari et al., 2019a). The
asymmetric systems have an expanded working potential, better
energy, and power densities because of the synergistic combi-
nation of working potentials and electrochemical properties of
the individual electrodes (Kouchachvili et al., 2018; Shao et al.,
2018). For example, Jiang et al. (2018), Zhao et al. (2018a), Liu
et al. (2018a), and Zhao et al. (2018b) used the typical PC repre-
sentative TMOs as anode for high energy-power ASCs benefitting
from the higher specific capacitances of TMO nanostructures and
the enlarged working potential of the devices. Fig. 8 shows the
full device performance of all-Mxene based ASC reported by Jiang
et al. (2018) By connecting the devices in series, they significantly
enhanced the working potential of ASC to 3 V, and obtained a
high capacitive performance and notable E-P profile, implying the
potential of ASC in enhancing the performance (see Fig. 8).
The main factors to consider for the asymmetric device design
m + ∆V +
are: (1) the electrode active mass balancing by using m+ = CC − ∆
− V−
and the total capacitance of the device equals C 1 = C1+ + C1− ,
total
where m is the mass of cathode and anode in grams, C is the
specific capacitance in farads and V is the working potential of
positive and negative electrodes; (2) The coulombic efficiency
based on charge storage on both electrodes is Q + = Q − =∼100%,
where Q + = C + V + and Q − = C − V − is the charge stored on
the cathode and anode, respectively; (3) the working potential of
ASC, which is V = V + + V − is greater or equals to the sum of
the individual working potential of both cathode and anode. V is
usually limited by the decomposition of electrolyte or over oxida-
tion/reduction of any one of the electrode materials (Feng et al.,
2018). Hence, by using these equations, the asymmetric device
configuration can be designed in a better way, nevertheless some
work also shows that equal mass-loading in both electrodes of a
full cell may also improve the symmetry of the cells depending
on the electrodes used (Krishnan et al., 2017a). Lukatskaya et al.
explained that there is a certain asymmetry in the electrochemi-
cal behaviour of EDLC materials, which arises from the difference
in the ion sizes based on the different pore diameters. Hence they
have different specific capacitances in a way that C+ ̸ = C− , so it
is of prime importance to balance the weight of active cathode
and anode materials to ensure a stable voltage window V+ =
V−and to enable anode and cathode to work in their appropriate
potential window respectively (Lukatskaya et al., 2016). The sim-
ilar mechanism goes for designing asymmetric systems of high
volumetric capacitance (F cm−3 ) and energy-power densities for
the portable electronics and vehicle applications.
S.W. Bokhari, A.H. Siddique, P.C. Sherrell et al. Energy Reports 6 (2020) 2768–2784

Fig. 6. (a) CV curves of CO and V-CO nanocomposite at 100 mV s−1 , (b) Specific capacitances of CO and V-CO at various scan rates, (c) Photographs of as-assembled
solid-state ASC device under different bending conditions, (d) GCD curves of ASC at different current densities, (e) Ragone plots of ASC with previous reports, and
(f) A mobile phone charged by one packed ASC system including three 5 × 5 cm2 single cells connected in series.
Source: Reproduced with permission Sun et al. (2018).

Fig. 7. (a) Fabrication process, Ragone plot comparison, and cyclic stability of TiS2 /VACNT hybrid PC electrodes. (b) SEM image of the bimetallic ZnCo–OH nanosheets
and the Ragone plot comparison of the symmetric PC with the previous metallic pseudo electrodes .
Source: Reproduced with permission Zang et al. (2018) and Pan et al. (2018).

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S.W. Bokhari, A.H. Siddique, P.C. Sherrell et al.
Fig. 8. (a) CVs of individual electrodes RuO2 , MXene, and of the full ASC device. (b) CVs of one ASC device and two devices connected in series, suggesting the
enlargement of potential window.
Source: Reproduced with permission (Jiang et al., 2018).
2.4. Electrodes for Hybrid Supercapacitors (HSCs)
HSCs are a particular type of asymmetric supercapacitors com-
bining two different charge storage mechanisms of two different
systems, i.e., batteries and capacitors (Zhang et al., 2019b). For
example, one electrode undergoes electrochemical double layer
mode of charge storage, while the other store charge by Faradic
mode (Ding et al., 2018). Current high-performance HSCs use
carbonaceous materials as the cathode and transition metal (ox-
ides/carbides) as the anode material in aqueous electrolytes. It
has been reported that the voltage window ranging up to 4 V and
∼70%–80% capacitance retention after 20,000 cycles (Wei et al.,
2018b; Nagaraju et al., 2018; Zuo et al., 2017). The high power
is mainly governed by the EDLC electrode, which is primarily
based on carbonaceous compounds, whereas the high capacitance
and cyclic stability is usually attributed to the faradic electrode.
Collectively, both electrodes enable the HSC devices to attain a
higher working potential in various electrolytes and a high E-
P density. First HSCs have been commercialized as generation-II
supercapacitors in the early 2000s, mainly by Japanese industries,
with much better performance than generation-I (EDLC/PC) su-
percapacitors (Yoshino et al., 2004). The only drawback is their
poor low temperature performance (Naoi et al., 2012). Now Tesla
and Lamborghini have also introduced HSCs in high performance
cars (Lamborghini, 2019).
Recently, Li et al. obtained a high energy density of 51 W h
kg−1 at a power density of 9.1 kW kg−1 by using an all TMO
system MnO2 //FeOOH in 1 M Na2 SO4 electrolyte (Li et al., 2019a).
Sankar et al. reported an HSC based on free-standing cobalt
phosphate cathode and activated carbon anode with an energy
density of 26.66 W h kg−1 at 750 W kg−1 power density as well
as excellent capacitance retention for up to 80% after 6000 cycles
(Sankar et al., 2018). Siavkumar et al. designed a nano-horn struc-
ture of CO3 O4 with an ultrahigh capacitance of 2751 F g−1 and
used it with an activated carbon cathode in an aqueous hybrid SC
with 100% coulombic efficiency and 91.37% capacitance retention
after 350,000 cycles (Sivakumar et al., 2018). Jiang et al. reported
a solid state flexible hybrid SC utilizing screen printable films of
graphene/CoS2 /Ni3 S4 . They achieved an energy density of 44.9 Wh
kg−1 at the power density of 224.8 W kg−1 , and 79.6% capacitance
retention after 10,000 cycles (Jiang et al., 2019). More recently,
Hoang et al. derived carbon dots by waste Zucchini and used
these carbon dots as a spacer to hinder the graphene restacking
(Microstructure in Fig. 9 a, b). The resultant composite was doped
with iodine in a one-step reduction and doping method using HI.
They achieved outstanding performance by incorporating EDLC
character from graphene and CDs, and pseudocapacitance via the
dopant in nanocomposite (Fig. 9 c, d) (Hoang et al., 2019).
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Energy Reports 6 (2020) 2768–2784
3. Graphene-based electrodes for SCs
Graphene has dominated the research in various fields of
science and technology due to its astonishing properties since
the time it was discovered by Geim and Novoselov (2010, 2007).
It has excellent thermal and chemical stability, which enables
the high life cycle of graphene based SCs in a vast range of
electrolytes (Balandin, 2011; Pop et al., 2012; Zhu et al., 2010;
Xu et al., 2014). A high mechanical strength (1 T Pa Young’s
modulus) (Papageorgiou et al., 2017; Akinwande et al., 2017;
Wang et al., 2015; Mortazavi et al., 2016; Lee et al., 2008), and
electrical conductivity (200,000 cm2 V−1 s−1 ), which facilitates the
electron movement (Deng and Berry, 2016; Naumis et al., 2017;
Melios et al., 2016; Zaminpayma et al., 2017), and a high optical
transparency (Ponraj et al., 2016; Bonaccorso et al., 2010; Loh
et al., 2010). Depending on its production method, graphene has
tunable structure–property relationships (Tang et al., 2013; Yu
et al., 2017). Taking into account the requirements of energy stor-
age and conversion, graphene offers a high tunable EASA (2630
m2 g−1 ), an exceptionally high electronic conductivity due to the
presence of free high mobility pi (π ) electrons (Fuhrer et al., 2010)
in its orbitals, above and below the individual graphene sheets
(Talirz and Pignedoli, 2018). The overlapping of pi-orbitals en-
hances the strength of C–C bonds so that the bonding/antibonding
(conductance and valence bands) states of these pi-orbitals con-
trol the electronic properties of individual graphene sheets (Neto
et al., 2009). Furthermore, the electronic conductivity of graphene
is temperature independent and 4.5×103 times higher than cop-
per (theoretical: 200,000 cm2 V−1 s−1 ) (Prasher, 2010), and so the
corresponding resistivity (10−6  cm) is much lower than silver
(Dixit et al., 2013). The electronic properties of graphene can
be further enhanced by structural tuning such as hetero-atomic
doping (Duan et al., 2015; Wang et al., 2018a), functionalization
(Radovic et al., 2018; Criado et al., 2015), and making composite
materials (Mao et al., 2015) based on the system requirements
(Wei et al., 2015).
Graphene in various forms, including reduced graphene oxide,
functionalized graphene, graphene doped with heteroatoms like
nitrogen or iodine, and composites of graphene with transition
metal oxides or polymers, have been widely designed and in-
vestigated as the supercapacitor electrodes (Ke and Wang, 2016).
Graphene offers versatile opportunities for structure tuning based
on the reaction protocols, which is an ideal approach to de-
sign application-specific materials. Many new graphene struc-
tures have also been reported including graphene nanoribbons
(GNRs) (Torabi et al., 2018; Lim et al., 2019), graphene quantum
dots (GQDs) (Zhang et al., 2018a,b; Li et al., 2018c), zig-zag
S.W. Bokhari, A.H. Siddique, P.C. Sherrell et al.
Fig. 9. (a) SEM and (b) TEM of Iodine doped CDT/graphene nanocomposite. (c) Cyclic stability after 10 000 cycles and (d) CV curves at 50 mV s−1 before and after
cyclic performance suggesting that the nanocomposite well retains its performance.
Source: Reproduced with permission Hoang et al. (2019).
graphene (Li et al., 2018c), graphene fibres (He et al., 2019),
graphene foams (Li and Zhi, 2018), 3D printed graphene struc-
tures (Wang et al., 2018b; Shen et al., 2018; Wang et al., 2019a),
and pillared graphene (Liu et al., 2018b; Peng et al., 2018b),
with essential applications in different types of energy storage
systems.
3.1. Key factors for designing graphene-based SC electrodes
Graphene does have an unmatched potential for energy stor-
age and conversion applications. However, some key factors need
to be considered while designing graphene-based electrode ma-
terials for utilizing its potential as SC electrodes. Until now, many
researchers reported interesting results in lab-scale, but to get
reliable performance in real-world applications, SCs need to be
optimized and monitored. Based on the present review and SC
system requirements, the following five factors can be crucial in
the designing and development of the electrodes.
a. Specific Surface Area (SSA) and Hierarchical Porosity
SCs store charges via an electrostatic mechanism, which puts
a specific surface area in direct relation with the charge storage.
On the other hand, a hierarchical porous structure is highly de-
sirable for SC electrode materials as they provide channels for
charge transport during electrochemical reactions. These pores
also facilitate the electrochemical reaction by shorter diffusion
pathways and guaranteed contacts between electrode–electrolyte
interfaces for high performance. The ‘‘wetting’’ phenomenon plays
an important role here as the inner walls of pores can also take
part in enhancing charge storage. The pores should be of the
optimal size to let the electrolyte ions gently pass through them
to obtain desirable electrochemical performance.
b. High Electrical Conductivity
Electrical conductivity is another crucial factor for electrodes
as it plays a pivotal role in facilitating charge transport. Graphene
has an intrinsically very high electronic conductivity due to the
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presence of a complete ring current in its structure lattices. Car-
bonization can further increase the conductivity of graphene by
increasing the degree of graphitization, thereby inducing defects
in the graphene sheets. On the other hand, carbonaceous mate-
rials, as the conductive backbone support, could be adapted to
increase the conductivity of the composite. If the conductivity is
low, the materials are not able to store a large number of charges;
hence, the E-P profile is not up to the mark.
c. Specific Capacitance and Rate Performance
The specific capacitance of a material is dependent on many
factors, including the structure of the material (e.g. surface area,
pore size), synthesis techniques, intrinsic conductivity, surface
functionality, as well as electrolyte used in the system. Rate
performance measures specific capacitance. The measurements
on a low and high current density/scan rate can also be used
to determine the efficiency of the device. For SC devices, the
specific capacitance of material should be high because it is
directly proportional to E-P density. Therefore, functionalization
or hybridization is a simple approach to improve the E-P profile
by enhancing the specific capacitance of the electrode and rate
performance of the device.
d. Structural and Cyclic Performance
Structural and cyclic stability of the material is also of prime
concern in high performance SCs. Structural deformation and
failure of electronic devices are one of the primary reasons for
performance deterioration. For example, it has been reported
that metal nanoparticles scratch off the carbon support surface,
causing the capacitance to fall quickly. Therefore, the electrode
material needs to maintain its structural stability for numerous
charging and discharging cycles.
e. Electrode Work Function and the role of electrolyte
SC electrodes work by electrostatically storing charges on
the surface, which indicates that the surface modification is an
essential and efficient method for improving SCs’ performance.
Therefore, electrode work function plays a critical role in sur-
face modifications of graphene for improving charge storage.
S.W. Bokhari, A.H. Siddique, P.C. Sherrell et al.
Fig. 10. (a) SEM and (b) TEM image of functionalized graphene nanocages. (c) CV curves (d) GCD curves of graphenenanocages demonstrating a perfectly rectangular
EDLC behaviour..
Source: Reproduced with permission Jiang et al. (2017).
For example, doping heteroatoms into graphene lattices, modi-
fies the electrode work function. On the other hand, electrolyte
plays a significant role in improving the E-P density of the SCs.
The rapid ion diffusion in the electrolyte to the electrode sur-
face is responsible for the high-power density. Hence, it is vital
to understand the chemistry and reaction mechanism of the
electrode–electrolyte interfaces and the electrode work function
to design devices with a better E-P density and cyclic stability.
f. Environmental and economic factors including cost-
efficiency
There are several electrodes with an excellent E-P profile and
outstanding cyclic performance. However, the cost-to-
performance issue of SCs devices is still lagging their large scale
and affordable applications. In the automotive industry, Tesla
and Lamborghini have introduced new cars that run on hybrid
supercapacitors to power the vehicle (∼2400 W kg−1 ) (Lam-
borghini, 2019; King, 2019). However, the price is too high (∼$3.8
million), which crucially depends on the powerhouse (energy
source) of the cars (King, 2019). The same issue also lies in
wearable electronics as they undergo a series of test requirements
(Tebyetekerwa et al., 2019). The graph of the price is in direct re-
lationship with the SCs performance. Therefore, one of the leading
research areas in SCs is to minimize the cost-to-performance ratio
to make the devices affordable yet useable.
4. Classification of graphene-based electrodes systems
In this section, we will review the recent development in
electrodes based on graphene and graphene-based composites
and their supercapacitive properties.
4.1. Functionalized/doped graphene
2D graphene sheets are ideal charge carriers; however, the
restacking of the sheets reduces the electrochemically available
surface area and is a big hurdle in accommodating their full
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electrochemical potential. To tackle this, graphene is chemically
functionalized, and the different architectures are created to
achieve the maximum electrochemical potential of graphene-
based nanocomposites (Singh et al., 2017; Teo et al., 2015).
Jiang et al. (2017) recently reported novel multilayered
graphene nano-cages (Fig. 10) using magnesium metal and car-
bon dioxide as precursors, and studied their EDLC performance in
6 M KOH electrolyte. Further, they post treated nano-cages with
nitric acid to induce oxygen functionalities. The functionalized
nano-cages showed a pseudocapacitive behaviour govern by the
highly reversible redox reaction of the oxygen functionalities
on the surface. This work proves that functionalization can be
a practical approach to inculcate a dual energy storage mech-
anism in carbon compounds. Bakandritsos et al. achieved an
ultra-high gravimetric capacitance by covalently functionalized
graphene with iron tetraaminophthalocyanine (FePc-NH2 ) and
exploiting the reactivity of fluorographene with diethyl bro-
momolonate, which resulted in highly conjugated π -π stacked
zwitterion surface (Bakandritsos et al., 2018).
Another effective way to overcome the restacking of 2D
graphene sheets is to induce ‘‘spacers’’ between the individ-
ual graphene sheets, which play a pivotal role in keeping the
graphene sheets apart. For electrochemical applications, conduc-
tive particles are added as spacers to the overall conductivity
of graphene electrodes as well as to enhance EASA of graphene.
CNTs, CNCs, metal nanoparticles have all been used and studied
as the spacer materials. For example, Alhabeb et al. (2017) in-
duced porous carbide derived carbons (CDCs) as spacers between
rGO, which effectively enhanced the wettability of the electrode
surfaces and delivered a high gravimetric capacitance even at the
electrode thickness of ∼50 µm, higher than that of rGO sheets
(Fig. 11). Bokhari et al. (2018) prepared a conductive matrix by
type-I hybridization of rGO sheets and CNTs and decorated the
matrix with bimorph akaganeite. The nanocomposite resulted in
a high specific capacitance of 533 F g−1 , an energy density of
36.6 W h kg−1 at a power density of 1.2 kW kg−1 .
S.W. Bokhari, A.H. Siddique, P.C. Sherrell et al.
Fig. 11. The rate performance comparison of rGO and CDC intercalated rGO. The
improved rate performance is attributed to the prevention of restacking by CDC
spacers and enhanced wettability of electrode inner surface.
Source: Reproduced with permission Alhabeb et al. (2017).
GFs with a 3D graphene scaffold have gained attention as
suitable candidates for SC electrodes. They offer a hierarchical
structure with a large number and distribution of pores (Sherrell
and Mattevi, 2016). GFs also buffer the solution very well owing
to their high compressibility and superior chemical and physical
stability. E.g., (Yang et al., 2017b) reported the best EDLC electrode
in the literature with an ultrahigh areal capacitance of 6.2 F
cm−2 at a high current density of 20 mA cm−2 . They prepared
an all-solid-state fibre electrode scaffold by direct deposition of
CNTs and rGO on Ni-coated carbon cotton using the alternative
fabrication method.
Graphene nanoribbons (GNRs), and graphene nanoplatelets
(GNPs) have a large surface area and a high specific capacitance.
On the other hand, they have an edge-functionalized graphene
architecture with unique porous morphology, low pore volume,
high EASA, as well as semi-conducting to metal electronic proper-
ties. They possess excellent charge storage properties. Sheng et al.
reported a high volumetric capacitance of 234.8 F cm−3 and 96%
Fig. 12. (a) Schematic illustration of conversion of MOFs nanorods to carbon nanorods and then to GNRs through a simple two-step method. (b) SEM image of MOFS
nanorods, (c) carbon nanorods, and (c) GNRs displaying the morphological difference .
Source: Reproduced with permission Pachfule et al. (2016).
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cycling stability after 10,000 cycles by using vertically oriented
GNRs and thus emphasized on free axial and radial ion diffusion
channels in graphene nanoribbons (Sheng et al., 2017).
Pradip et al. presented an interesting study for converting
MOFs nanorods to carbon rods and then to graphene nanorib-
bons via sonochemical treatment and thermal activation (Fig. 12).
These GNRs were tested in 1 M H2 SO4 and shown a specific
capacitance of 168 F g−1 at the current density of 1 A g−1 ,
and a typical rectangular CV curves characteristic to pure EDLC
behaviour. This method is unique but needs careful monitoring
for the conversion of MOFs to GNRs (Pachfule et al., 2016). Ping
et al. (2017), Xu et al. (2017), Xiang et al. (2016), and Pullini
et al. (2015) have also studied the supercapacitor performance
of GNRs and GNPs in both aqueous and non-aqueous electrolytes,
and emphasized on their potential for smart electronics. Recently,
De la Osa et al. designed highly conductive macrostructures of
GNPs via 3D printing graphene monoliths, and reported a specific
conductivity up to 385 Scm−1 along the longitudinal direction
of the monoliths, which is two times higher than the previous
reports (de la Osa et al., 2016).
The problem with GNRs, however, is the inert basal plans
that do not engage and remain intact during the electrochemical
process. This is where the hetero-atomic doping plays a crucial
role. Doping with nitrogen, sulphur, iodine, or boron modifies
the electronic structure by the difference in electronegativity of
carbon and dopants (Singh et al., 2017; Wang et al., 2019b).
Therefore, doped graphene has high electrocatalytically active
sites for charge storage with a minimum change of conjugation
length, which, due to superior charge polarization. The massive
shift in energy storage performance of the heteroatom doped
graphene drives interest for the dual doped graphene with two
different heteroatoms. A better charge storage mechanism be-
cause of the different bonding mechanism offering the synergistic
effects associated with carbon atoms and the doped species (Latiff
et al., 2017).
Gopalsamy et al. prepared highly porous GNRs co-doped with
nitrogen and sulphur to GNRs via the thermal annealing method.
They achieved a high specific capacitance of 442 F g−1 at 0.5
S.W. Bokhari, A.H. Siddique, P.C. Sherrell et al.
Fig. 13. Schematic illustration of the synthesis of Yb2 O3 /N-IC:GA and fabrication of a SSC (a) SEM image of Yb2 O3 /N-IC:GA nanocomposite (circles displaying the
Ytterbium oxide nanoparticles). (b) Rate performance of Yb2 O3 /N-IC:GA and Yb2 O3 /GA symmetric device. (c) 3D CV curve of Yb2 O3 /N-IC:GA at the scan rate of 200
mVs−1 (d) Cyclic performance of Yb2 O3 /N-IC:GA at the current density of 8 A g−1 .
Source: Reproduced with permission Farbod et al. (2019).
A g−1 , admirable rate capability, and ∼98.6% capacitance re-
tention after 10,000 cycles (Gopalsamy et al., 2017). Siddique
et al. reported an all graphene electrode system using iodine
doped graphene anode vs. chemically functionalized graphene as
cathode reporting a very high energy density of 91 Wh kg−1 at 0.4
k W kg−1 in aqueous electrolyte (Siddique et al., 2019). This all
graphene electrode system also maintained its high performance
and E-P (4.75 mWh cm−3 at 61.55 W cm−3 ) profile for a micro
supercapacitor in a polymer gel electrolyte after 2000 bend-
ing cycles to 180◦ angle (Siddique et al., 2020). They attributed
the performance to the same microstructure and similar surface
chemistry of both cathode and anode, which avoids electrode
imbalance, a typical performance deteriorating factor in graphene
devices. Recently, laser engraver assisted reduction of graphene
has been shown to give an energy density of as high as 17 Wh
kg−1 in an SC prototype device (Yar et al., 2020).
The above discussion emphasizes on the functionalization
methods to avail the full potential of graphene by avoiding the
restacking. The structure tuning does not only help in keeping
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the restacking at a minimum but also induces pseudocapacitive
character due to the presence of dopant. One of the current
challenges in this area is to optimize the dopant amount into
graphene sheets for a well conductive and high capacitance
electrode. Nevertheless, the literature cited above provides an
excellent insight into the role of functionalization in enhancing
the charge storage properties of graphene.
4.2. Graphene composites with transition metal oxides
Transition metal oxides (TMO) have attracted tremendous in-
terest as electrode materials for supercapacitors owing to their
superior redox activity, abundant reserves, high theoretical ca-
pacity, and low cost. However, they have poor conductivity and
low cycling stability, which restrict their widespread applica-
tions (Toth et al., 2017). Nevertheless, TMOs are most widely
used as electroactive components to enhance the capacitances
of graphene based nanocomposites (Bokhari et al., 2019b). The
S.W. Bokhari, A.H. Siddique, P.C. Sherrell et al.
Fig. 14. (a) CV curves at 100 mVs−1 and (b) GCD curves of the fabricated solid-state SC device based on epoxy linked graphene/PD4ET in series and parallel. (c)
Two devices and (d) three devices connected in series, which lit a red LED.
Source: Reproduced with permission Li et al. (2019b).
synergistic combination of graphene-TMOs results in a nanocom-
posite with high conductivity, specific capacitance, and excel-
lent cyclic stability (Patil et al., 2020). These hybrid nanocom-
posites find important applications in supercapacitor systems
(Mohapatra et al., 2017; Gajraj et al., 2020; Krishnan et al., 2017b).
Kaverlavani et al. reported a 3D composite of graphene
wrapped CuCo2 O4 hollow sphere electrodes with high surface
area and nano-pores, and obtained an ultrahigh capacitance of
1813 F g−1 at 2 A g−1 . They also achieved a superior energy
density of 45.2 W h kg−1 and a power density up to 15 kW
kg−1 in GW-CuCo2 O4 //rGO asymmetric configuration (Kaverlavani
et al., 2017). Jadhav et al. uniformly dispersed MnO2 nanorods
over graphene via the in-situ hydrothermal method and obtained
an energy density of 64.6 W h kg−1 and a high power density up
to 15 kW kg−1 in a 3 V symmetric gel SC (Jadhav et al., 2019).
Annamalai et al. (2019), Kumar et al. (2019), Beyazay et al. (2019),
Varghese et al. (2019), Liu et al. (2019b) have reported Mn-
oxides/graphene with reasonable SC performance demonstrating
the potential of MnOx-graphene as a desirable electrode system.
Iron oxides and their derivatives are also widely investigated as
SC electrodes. Zhu et al. (2019), Bhujel et al. (2019), Chodankar
et al. (2019), Polfus and Jayasayee (2019), and Ghaly et al. (2019)
et al. have studied different hybrids of FeOx with graphene and
reported a high E-P density.
Rare earth metal oxides and layered double hydroxides are
being explored as an electroactive component for SCs. Recently,
Zhang et al. deposited lanthanum oxide (La2 O3 ) on an rGO to
enhance the effective conductive area of rGO, and to facilitate
the contact between electrolyte and rGO with reasonable perfor-
mance in small current EDLC SC (Zhang et al., 2019c). Pourfarzad
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Energy Reports 6 (2020) 2768–2784
et al. reported ultrahigh energy and power density of 101 W h
kg−1 and 91 kW kg−1 , and high cyclic stability of 82.5% after
5000 cycles by an ASC configuration using NiCoFe-LDHS as anode
and Fe2 O3 /rGO as a cathode (Pourfarzad et al., 2019). Patil et al.
reported ZnO@NiCo LDH on a 3D graphene scaffold with superior
cyclic stability (Patil et al., 2019). Farbod et al. reported ytterbium
oxide deposited over a porous matrix of N-doped interconnected
graphene aerogels (Yb2 O3 /N-IC:GA) with 98.4% capacitance reten-
tion over 4000 cycles and good rate performance in symmetric
device configuration (Farbod et al., 2019). (Fig. 13) (Akinwande
et al., 2017; Alhabeb et al., 2017; Allagui et al., 2020).
These studies result in the potential of TMOs and
polymer/graphene nanocomposites for SC devices. TMOs used as
active material provide good capacitance in the composite by
utilizing their intrinsic pseudocapacitive nature and high redox
potentials. The key to obtaining a reasonable performance out of
the graphene/TMO system lies in combining them through strong
linkages so that during the electrochemical cycles, structure de-
terioration is at a minimum.
The above discussed literature provides an exciting insight
to understand the role of TMOs in capacitance enhancement of
the overall nanocomposite. One of the black boxes, however, is
to explain the chemistry of the system, which is responsible
for the improved performance. In other words, an explanation
of the complex structures and the role of each structural com-
ponent in the electrode performance would simplify the whole
electrochemical process of the graphene/TMO nanocomposites.
S.W. Bokhari, A.H. Siddique, P.C. Sherrell et al.
Fig. 15. (a) Ragone Plot to compare E-P density of different SC systems and (b) Trend in the number of publications on SC system (source:Scopus) and the improvement
in the E-P density over last 1o years.
4.3. Graphene composite electrodes with carbon and conductive
polymers
Conducting polymers have been widely explored as SC elec-
trodes for their high pseudo capacitances arising from the re-
versible redox reactions at the electrode–electrolyte interfaces.
Especially, Polyaniline (PANI), Polypyrrole (PPy), Polythiophene
(PTh) are the representatives offering high electrical conductiv-
ity and charge mobility, as well as chemical and environmental
stability (Mariappan et al., 2019). The key to making an effective
graphene-polymer nanocomposite lies in covalently drafting the
polymer chains on graphene to improve the dispersibility and
to reduce the interfacial charge transfer resistance so that the
ion transport can be facilitated. Previously, the non-covalent at-
tachment of polymers to graphene was by the grafting method.
However, non-covalent interactions suffer in weak interfacial in-
teractions, affecting cyclic stability. Hence, in recent years, many
efforts have been inducing a covalent linkage between graphene
and polymers to achieve a stabilized performance.
Li et al. induced epoxy linkage between graphene/PD4ET
nanocomposites, and reported cyclic stability of 98% after 10,000
cycles and a high E-P density of 66.11 W h kg−1 and 250 W kg−1
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(Li et al., 2019b) in an all solid-state configuration. A red LED was
lit by connecting the SC in series (Fig. 14). Wang et al. hydrother-
mally design ultra-thin sheet like graphene nanosheet/PANI com-
posite, which deliver a high specific capacitance of 532 F g−1 to
305 F g−1 at the scan rates of 2 mVs−1 to 50 mVs−1 (Wang
et al., 2017b). Zhang et al. reported a ternary nanocomposite
of cellulose nanofibers/rGO/PPy by controlled deposition of PPy
using oxidant precursor. The resultant 3D porous structure of the
aerogels gave a 95% cyclic stability and a constant capacitance
under different bending conditions (Zhang et al., 2019d). Farid
et al. simultaneously conducted thiol-treatment of GO and PANI,
showing a well-dispersive porous structure and high surface area.
The resultant nanocomposite significantly reduced the charge
transfer resistance, resulting in an excellent capacitance perfor-
mance (Farid et al., 2019). Tabrizi et al. reported an acid treated
GO/PANI nanocomposite with only 4.3% loss of the supercapacitor
performance after 5000 cycles. They referred this performance
to acid functionalization to act as a structure directing step for
GO-PANI linkage (Tabrizi et al., 2018).
Li et al. decorated carbon nanodots on graphene-PANI
(rGO@CN/PANI) via supra-molecular in-situ assembly method.
They obtained a much better electrochemical performance than
S.W. Bokhari, A.H. Siddique, P.C. Sherrell et al. Energy Reports 6 (2020) 2768–2784

Table 1
Comparative performance of graphene-based electrodes for supercapacitors.
Composite Method Electrolyte Voltage Current Specific Energy Power Cycling Ref.
window density capacitance density density stability
Zwitterion graphene Covalent 1 M Na2 SO4 0.7 V 1 A g −1 960 F g−1 59 W h 0.31 kW – Bakandritsos
network functionalization kg−1 kg−1 et al. (2018)
Free standing Ultra-sonication 3.5 M KCl 1.3 V 10 A g−1 200 F g−1 – – – Alhabeb
graphene-CDC film et al. (2017)
β -FeOOH/rGO/CNT Hydrothermal 1 M Na2 SO4 1.2 V 1 A g −1 533 F g−1 36 W h 1.2 kW kg−1 91% after Bokhari
self-assembly kg−1 2000 cycles et al. (2018)
MWCNTs/rGO fibres Polymer assisted meal 5 M PVA/LiCl 0.8 V 20 mA cm−2 250 F g−1 – – 118% after Yang et al.
deposition 10,000 cycles (2017b)
Vertically oriented Laser irradiation 1 M Na2 SO4 1 V 2 mV s−1 234.8 F 5.7 mWh – 96% after Sheng et al.
GNR fibres assisted hydrothermal cm−3 cm−3 10,000 cycles (2017)
synthesis
N/S co-doped GNRs In-situ thermal 1 M Na2 SO4 1.8 V 0.5 A g−1 442 F g−1 23.85 W h 0.448 kW 98% after Gopalsamy
annealing kg−1 kg−1 10,000 cycles et al. (2017)
All-graphene (IG/FG) Thermal annealing 1 M Na2 SO4 1.7 V 1 A g −1 434 F g−1 91 W h 0.42 kW 76% after Siddique
kg−1 kg−1 4000 cycles et al. (2019)
Graphene wrapped Solution phase 3 M KOH 1.5 V 2 A g −1 1813 F g−1 42.5 W h 15 kW kg−1 96% after Kaverlavani
CuCo2 O4 assembly followed by kg−1 6000 cycles et al. (2017)
thermal treatment
MnO2 /rGO Hydrothermal 1 M Na2 SO4 0.9 V 2 A g −1 759 F g−1 42.7 W h 22.5 kW 88% after Jadhav et al.
oxidation kg−1 kg−1 3500 cycles (2019)
Nanoporous Low-temperature 0.5 M KOH 1 V A g−1 641 F g−1 22.26 W h 0.166 kW 100% after Annamalai
Ru/MnOx /rGO treatment kg−1 kg−1 1000 cycles et al. (2019)
rGO supported Microwave irradiation 0.1 M KOH 0.9 V 20 mV s−1 596 F g−1 – – 83.2% after Kumar et al.
NiO/MnO2 2000 cycles (2019)
Self-standing Cathodic 0.5 M Na2 SO4 0.8 V 0.5 A g−1 546 F g−1 – – 100% after Beyazay
rGO/MnO2 electrodeposition 10,000 cycles et al. (2019)
δ -MnO2 /N-doped rGO Hydrothermal 1 M Na2 SO4 0.8 V 5 mVs−1 295.5 F g−1 24.2 W h 0.242 kW 97.8% after Liu et al.
kg−1 kg−1 8000 cycles (2019b)
α -Fe2 O3 /rGO Hydrothermal 2 M KOH 0.7 V 1 A g−1 533 F g−1 – – 77% after Zhu et al.
14,000 cycles (2019)
rGO/Fe2 O3 One step chemical 0.5 M H2 SO4 1.2 V 0.1 A g−1 86 F g−1 – – – Bhujel et al.
reduction (2019)
rGO/FeCo2 O4 thin films Hydrothermal 1 M Na2 SO4 1.3 V 3 A g −1 1710 F g−1 67.5 W h 1.25 kW 96% after Chodankar
kg−1 kg−1 5000 cycles et al. (2019)
V2 O5 /3D rGO Hydrothermal 1 M Na2 SO4 0.8–1 V 1 A g −1 612.5 F g−1 45.9 W h 0.9 kW kg−1 89.6% after Ghaly et al.
kg−1 10,000 cycles (2019)
Ni-Co-Fe Electrodeposition 3 M KOH 1.2 V 1 A g−1 3130 F g−1 101 W h 92 kW kg−1 82.5% after Pourfarzad
LDH/Fe2 O3 /rGO kg−1 5000 cycles et al. (2019)
ZnCo@NiCo/3D Hydrothermal 2 M KOH 0.8 V 5 mVs−1 7485 mF 171 mWh – 108% after Patil et al.
graphene scaffold cm−2 cm−2 5000 cycles (2019)

the bare graphene-PANI composites arising from the enhanced
electrostatic charge channels in the resultant electrodes (Li et al.,
2019c). Liu et al. synthesized paper-like flexible electrodes by
electrodeposition of PANI onto S-doped rGO/CNT, which gave
a specific capacitance of as high as 812 F g−1 in acidic elec-
trolyte medium (Liu et al., 2017). Zhou et al. prepared the 3D
nanocomposite of rGO/CNT/PANI with a hierarchical structure
achieving high electrochemical performance and cyclic stability
(Zhou et al., 2018). Xiong et al. (2017), Liu et al. (2018c), Jin
et al. (2017), Li et al. (2018d), and their co-workers have studied
rGO/CNT/PANI electrode systems with consistent performance
and cycling stability. Wang et al. reported a stretchable and self-
healing electrode by wrapping self-healing polymers around thick
rGO fibres (Wang et al., 2017c). These results are interesting
as the SC retained 82% capacitance with a 100% stretching ten-
sion and 54% after third self-healing, which opens a promising
direction for the self-healing wearable electronic devices.
More recently, Adusei et al. (2019) reported free-standing fibre
electrodes of CNT/rGO via CVD, and through strong interactions
between CNT-rGO, improving the mechanical strength of the
fibres. The fibres were further coated with PANI nanorods to
improve their strength and to avoid the use of additives. The
2782
SC based on CNT/rGO/PANI gave a high energy-power density
as well as excellent rate performance. Mangisetti et al. studied
an asymmetric SC by preparing nitrogen doped porous carbon-
graphene/PANI and N-doped porous carbon/gC3 N4 from bio-
waste seeds. The ASC gave a high electrochemical performance
and cyclic stability of up to 91% after 10,000 cycles in an aqueous
electrolyte system (Mangisetti et al., 2019). Islam et al. direct
grated graphene QDs on carbon fibre via in-situ ester linkages and
prepared conductive carbonaceous materials for SC electrodes
with a high cyclic stability (Islam et al., 2017). Ma et al. also fab-
ricated a carbonaceous electrode system with a large inter-layer
distance by depositing CNTs between open graphene papers. A 3D
conductive framework formed with achieving high cyclic stability
and superior rate performance (Ma et al., 2019).
Graphene composites with carbon and conducting polymers
are the preferred electrode for all EDLC supercapacitors. The
matching chemistry and similar structure backbone exhibit how
all carbonaceous electrode give a comparable EDLC performance
in line with the dual mechanism devices. Also, as explained in
the literature, all carbon composites provide a much better cyclic
stability and rate performance, which is proof of how well they
buffer the electrolyte during the electrochemical reaction. This
S.W. Bokhari, A.H. Siddique, P.C. Sherrell et al.
field is now moving into utilizing the bio-waste materials as a
carbon precursor with an increased focus on sustainability and
environmental protection.
5. The state-of-the-art graphene-based SC electrodes
There has been a lot of innovations going on in the design of
novel graphene-based electrodes. The comparative performance
of various types of graphene-based electrodes for SCs is also
presented in Table 1. Whereas Fig. 15(a) below presents a Ragone
plot comparison of the E-P density of various types of superca-
pacitors systems. It is worth noticing that the HSCs govern the
highest E-P density as a function of a highly stable and conductive
EDLC electrode and a high redox potential faradic electrode in
the system. Future developments in the SC field are expected to
output even better E-P densities and cyclic stabilities. Fig. 15(b)
presents a trend in the number of publications on various types
of SC systems published in the last ten years (source: Scopus)
as well as the improvements in the E-P density of SCs. Despite
a huge number of papers published on various types of SCs, the
E-P density is still not up to the mark. A breakthrough in the field
can be expected only if the current challenges are reported and
the black box between the electrodes class and final performance
is clearly explained to understand the underlying mechanism. It
does include not only the development of new types of electrode
materials but also optimizing other device components, including
the type of electrolytes, separators, etc.
6. Challenges, suggestions, and future outlooks
This review presents a state of the art of the research direction
in graphene-based supercapacitors. The utmost challenges for
using SCs in the industry are their low energy density and the
cost-to-performance issue. The problem of low energy density
may be effectively solved by hybridizing the electrode mate-
rials into various structural composition to attain the desired
performance.
The field of graphene based SCs is enriched with many exciting
conformations and functionalized structures. The prime proper-
ties of high SSA and intrinsic capacitance, excellent conductiv-
ity, very low resistivity, and good mechanical stability enable
graphene to be a potential candidate for flexible, smart, and even
wearable high-performance SC devices. However, some funda-
mental mechanisms still need to be explained clearly to refrain
from the inconsistencies, including unifying the protocols for
the lab to pilot scale synthesis of various structures. The ‘‘black-
box’’ region that lies unexplained between the structure and final
performance needs to be unveiled for a better understanding of
the electrochemical behaviour of designed electrodes. Some other
critical challenges that need urgent attention are as follows.
(I) Docile preparation and unification of synthesis protocols to
produce high quality graphene products in a controllable num-
ber of sheets, surface potential, lateral size, structure defects,
conductivity, and unstacking to provide a well-ordered electrode
structure for SCs.
(II) Cutting the cost for the large-scale synthesis of various high
surface area graphene-based SC materials with desired composi-
tion and surface properties.
(III) Design of a well conductive network of graphene materials
to use them as active electrode materials for different types of
SC devices, which will help to minimize the electrode imbalance,
which affects the performance.
(IV) Optimizing the packing density of graphene-based materi-
als while maintaining the intrinsic capacitive and flexible be-
haviour to obtain a high gravimetric and volumetric capacitance
for wearable devices.
2783
Energy Reports 6 (2020) 2768–2784
(V) Rationalizing the design of the SC device component in-
cluding electrolyte, electrodes, current collector, separators, sub-
strate, and the insulating packing because the performance of the
SC device is not only dependent on electrode but also on the
combination of other device parameters.
(VI) Clearly defining the electrochemical behaviour of graphene
electrodes in different electrolytes to provide a reliable basis for
reaction mechanism, so the ‘‘black box’’ may be unveiled for a
breakthrough in the ongoing research.
Regarding the long-term prospects, there is an infinite scope
of daunting challenges and opportunities for global researchers
to expand fundamental science at the forefront of this research
hotspot. Graphene based SCs undoubtedly have a profound ability
to make our lives better in every possible way. However, it may
take some time for them to go from the lab into commercial
products and onto affordable consumer products. We hope this
review article will provide a useful basis for the next research
focuses, not only in electrodes materials of supercapacitors but
also in the interdisciplinary fields of energy storage and con-
version. Overall, with ceaseless determination and tremendous
efforts from a diverse range of scientific communities and many
industrial sectors, the research questions in this review article
will unquestionably be surpassed.
Declaration of competing interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
Syeda Wishal Bokhari would like to acknowledge the Univer-
sity of Auckland for providing the doctoral scholarship. This work
is also partially supported by NATO SPS-MSYP G5647 project.
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