Journal of Power Sources 450 (2020) 227678

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Journal of Power Sources

journal homepage: www.elsevier.com/locate/jpowsour

Boosting the supercapacitor performances of activated carbon with

carbon nanomaterials
Fang Cheng a, b, Xiaoping Yang a, b, Shuangpeng Zhang a, b, Wen Lu a, b, *
a
College of Chemical Science and Engineering, Yunnan University, Kunming, 650091, China
b
Institute of Energy Storage Technologies, Yunnan University, Kunming, 650091, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

� New nanocomposite electrodes are

developed from commercially available
materials.
� Increasing the compositing level en­
hances the performances of composite
electrodes.
� The composite electrodes outperform
conventional activated carbon
electrodes.
� The composite electrodes can be readily
scaled up for commercial
supercapacitors.
� The nanocompositing approach can be
extended for other energy-related
technologies.

A R T I C L E I N F O A B S T R A C T

Keywords: Improving the properties of conventional activated carbon electrodes for enhancing the performances of com­
Energy storage mercial supercapacitors has been an important research topic. Herein, we combine conventional activated car­
Supercapacitors bon and carbon black with carbon nanomaterials (i.e., carbon nanotubes and carbon nanofibers) to develop a
Activated carbon
new class of nanocomposite electrodes for high-performance supercapacitors. With the synergistic effects from
Carbon nanomaterials
Nanocomposites
these multiple components, the resultant nanocomposite electrodes exhibit superior performances over con­
Electrodes ventional activated carbon electrodes. The optimized quaternary nanocomposite electrode shows a high packing
density (0.63 g cm 3), a high rate capability (capacitance retains 77.5% at 80 A g 1 vs. 0.5 A g 1), a long cycle
life (capacitance retains 91.4% after charging/discharging at 10 A g 1 for 30000 cycles), and high volumetric
performances (capacitance: 66.1 F cm 3, energy density: 29.6 W h L 1, power density: 101.7 kW L 1), signifi­
cantly exceeding those of current supercapacitor technology. The nanocompositing approach developed in the
present work can be readily transferred into the industrial slurry process, utilizing commercially available ma­
terials, to produce highly capacitive nanocomposite electrodes for manufacturing high-performance super­
capacitor products at low costs. Broadly, this approach can be extended for mass-producing high-performance
nanocomposite electrodes for other energy-related technologies including, for example, batteries, fuel cells, and
solar cells.

* Corresponding author. College of Chemical Science and Engineering, Institute of Energy Storage Technologies, Yunnan University, Kunming, 650091, China.
E-mail address: wenlu@ynu.edu.cn (W. Lu).

https://doi.org/10.1016/j.jpowsour.2019.227678
Received 28 June 2019; Received in revised form 28 November 2019; Accepted 30 December 2019
Available online 29 January 2020
0378-7753/© 2020 Elsevier B.V. All rights reserved.
F. Cheng et al.
1. Introduction
Being able to combine the high energy storage capability of con­
ventional batteries with the high power delivery capability of conven­
tional capacitors [1,2], supercapacitors (also known as ultracapacitors
or electrochemical capacitors) have been developed for a wide range of
applications such as consumer electronics, medical electronics, elec­
trical vehicles, electrical utilities, and military defense systems [3,4].
However, the performances of state-of-the-art supercapacitors need to
be improved in order to satisfy the rapidly increasing performance de­
mands for these applications. Electrode materials play an important role
in determining the performances of supercapacitors and thus have
gained considerable research efforts in recent years [5].
Although a variety of materials including carbonaceous materials,
metal oxides, metal nitrides, and conjugated polymers have been
comprehensively researched as the electrode materials for super­
capacitors [6–8], activated carbon (AC) is still the predominant material
employed to fabricate electrodes for commercial supercapacitor prod­
ucts, which is largely due to the distinct advantages of AC including high
surface area, low cost, commercial availability, and well-established
production technologies [9,10]. Nevertheless, the performances of
currently available supercapacitor products are limited by the properties
of conventional AC electrodes that are fabricated in the industry, usually
by combining AC with a binder and a conductivity additive (i.e., carbon
black, CB) [11]. First, for example, the similarity in particle size distri­
butions between AC and CB implies the lack of a so-called“particle-­
mixing-interaction” [12], resulting in a low packing density for the
electrodes and thus a poor volumetric performance for the capacitors
[13,14]. In fact, it has been emphasized that enhancing the packing (and
mass loading) of electrodes is significantly important for electro­
chemical energy storage devices, including supercapacitors, to be useful
for commercial applications [15,16]. Second, the electrical conduction
network of a conventional AC electrode is actually formed based on the
aggregation of CB particles. Thus, in this system, the isolation of CB
aggregates, loose contact between CB aggregates and AC particles, and
direct point-to-point contact between AC particles usually indicate a
poor electrical conduction network for the electrode [11]. In addition,
AC has low electrical conductivity, low meso-/macroporosities, and low
electrolyte accessibility [17,18]. All of these factors result in a poor rate
capability for the electrodes and thus limited power characteristics for
the capacitors. Third, during the charge/discharge cycling of a con­
ventional AC- and CB-based supercapacitor, AC suffers from noticeable
expansion/contraction [19] and CB from severe agglomeration [11],
both inevitably causing an increased resistance for the electrodes and
thus a poor cycle life for the capacitors. It has been stressed, therefore,
that control of the dimensional change of AC and the agglomeration of
CB upon cycling is necessary to ensure a long cycle life for the capacitors
[20]. Consequently, it is very important to overcome the above­
mentioned shortcomings of conventional AC electrodes in order to boost
the performances of the state-of-the-art supercapacitors to meet the
performance demands for their applications.
On the other hand, owing to their unique properties of excellent
electrical conductivity, thermal conductivity/stability, and mechanical
strength, carbon nanomaterials, including carbon nanotubes (CNT)
[21], carbon nanofibers (CNF), and graphene [22], have been inten­
sively studied as electrode materials for supercapacitors [4,7,23]. Un­
fortunately, drawbacks associated with these nanomaterials, such as
high cost, low packing, difficulty in mass production, and in­
compatibility with the electrode manufacturing process presently used
in the industry, seriously hinder their practical utilizations for super­
capacitors [24]. Alternatively, attempts have been made to incorporate
carbon nanomaterials with AC to fabricate composite electrodes for
pursuing their practical applications for supercapacitors. In this regard,
CNT [25,26], CNF [27,28], and graphene [29,30] have been individu­
ally investigated for this purpose. However, performances of the resul­
tant composite electrodes are limited, which is largely attributed to the
2
Journal of Power Sources 450 (2020) 227678
inefficient effects of these carbon nanomaterials when separately
employed in the composites.
In this work, we incorporated conventional high-surface-area AC and
conductivity additive (i.e., CB) with carbon nanomaterials (i.e., CNT and
CNF), through a simple slurry process, to develop a new class of multi-
component nanocomposite electrodes for high-performance super­
capacitors. Owing to the synergistic effects from the filling of CB,
wrapping of CNT, bridging of CNF, and excellent conductivities of CNT
and CNF (forming an effective packing and electrical conduction
network) as well as the synergistic effects from the high microporosity of
AC and high meso-/macroporosities of CNT and CNF (forming a three-
dimensional (3D) hierarchical porous structure), the resultant nano­
composite electrodes exhibited superior performances over the con­
ventional AC electrodes. The final optimized AC/CB/CNT/CNF
quaternary nanocomposite electrode showed a high packing density
(0.63 g cm 3), a high capacitance (104.9 F g 1, 66.1 F cm 3), a high rate
capability (capacitance retained 77.5% at 80 A g 1 vs. 0.5 A g 1), a high
energy density (23.5 W h kg 1, 29.6 W h L 1), a high power density
(80.7 kW kg 1, 101.7 kW L 1), and a long cycle life (capacitance
retained 91.4% after charging/discharging at 10 A g 1 for 30000 cy­
cles), significantly outperforming current supercapacitor technology
[31]. In particular, the enhanced volumetric performances of our
nanocomposite electrodes indicate their significance in practical appli­
cations for commercial supercapacitors [15,16]. Thus, the nano­
compositing approach developed in the present work would
significantly benefit the supercapacitor industry, utilizing commercially
available materials, through a simple slurry process, to produce highly
capacitive nanocomposite electrodes on an industrial scale for
manufacturing high-performance supercapacitor products at low costs.
More importantly, this approach can also be extended to mass-produce
high-performance nanocomposite electrodes for other energy-related
devices including, for example, batteries, fuel cells, and solar cells.
2. Experimental
2.1. Synthesis of nanocomposite electrodes
Nanocomposite electrodes were prepared by following a slurry pro­
cedure similar to that currently used in the supercapacitor industry.
Briefly, the slurries were prepared by mixing predetermined amounts of
AC (YP–50F, Kuraray), CB (Super C45A, Timical), CNT aqueous
dispersion (5 wt%, diameter: 7–9 nm, length: 1–2 μm, Cnano), and CNF
aqueous dispersion with an aqueous binder solution. The CNF aqueous
dispersion was made by firstly treating a CNF powder (diameter:
50–100 nm, length: 5–50 μm, Aladdin) with an acid mixture of H2SO4/
HNO3 (3/1 by vol%), followed by dispersing the acid-treated CNF in
deionized water using ultrasonication. The aqueous binder solution was
obtained by dissolving a certain amount of carboxymethyl cellulose
sodium (CMC) (Shenzhen Kejin (MTI)) in a styrene butadiene rubber
(SBR) aqueous solution (50 wt%, Shenzhen Kejin (MTI)). The slurries
were cast onto a 21 μm-thick Al foil current collector, followed by drying
the obtained composite/Al foil panels at 60 � C for 12 h, resulting in sheet
electrodes with a uniform composite film (thickness: 100 μm) on the Al
foil. At the same weight percentage of the binder (CMC: 2%, SBR: 3%),
different types and amounts of conductive materials, CB, CNT, and CNF,
were introduced to synthesize the composites with varied compositing
levels as summarized in Table 1. Among them, the unitary system was
purposefully designed for evaluating the packing efficiency of compos­
ites and thus did not contain any conductive additives. Combining AC
with CB, in the manner of a typical AC/CB binary compositing system,
resulted in a so-called AC electrode (denoted as ACE), which has been
employed for manufacturing supercapacitor products in the industry for
years [11]. Moreover, CNT and CNF were introduced into the system to
improve the packing efficiency and capacitive performance for the
resultant nanocomposite electrodes (denoted as NCEs). From ACE,
partially replacing CB with CNT resulted in an AC/CB/CNT ternary
F. Cheng et al. Journal of Power Sources 450 (2020) 227678

Table 1
4IΔt
Compositions and properties of composite electrodes. C¼ (1)
mΔV
Compositing Electrode Composition (wt Packing Volumetric
system %)a density (g capacitance (F 1 1 1
cm 3) cm 3) E¼ � � CΔV2 (2)
2 4 3:6
Unitary – AC (95) 0.52 –
Binary ACE AC/CB (90/5) 0.56 59.0 3600E
Ternary NCE-1 AC/CB/CNT (90/ 0.59 62.3
p¼ (3)
Δt
1.25/3.75)
Quaternary NCE-2 AC/CB/CNT/CNF 0.62 65.4 where I (A) is discharge current; Δt (s) and ΔV (V) are discharge time and
(90/1.25/3.125/
voltage window, respectively, excluding the ohmic (IR) drop at the
0.625)
NCE-3 AC/CB/CNT/CNF 0.63 66.1 beginning of discharge; and m (g) is total mass of the electrode materials
(88.75/1.25/ of the capacitor.
3.75/1.25)
a
2% CMC and 3% SBR were used for all composite electrodes. 3. Results and discussion

nanocompositing system (i.e., NCE-1), and further introducing CNF
increased the compositing level to the quaternary of AC/CB/CNT/CNF,
leading to NCE-2 and NCE-3. Table 1 presents the compositions opti­
mized for all types of the compositing systems investigated in the present
work.
2.2. Characterization of physical properties
Morphologies of composite electrodes were studied by scanning
electron microscopy (SEM) with a Hitachi SU-8010 high-resolution
scanning electron microscope. Particle size distributions of composites
and the individual constituents composing the composites were ob­
tained by firstly ultrasonicating the corresponding samples in ethanol
and then measuring the resultant dispersions with a Micromeritics
Saturn DigiSizer II 5205 high definition digital particle size analyzer.
Packing efficiencies of composite electrodes were investigated by
pressing all electrodes at a same ratio under a certain rolling force and
subsequently measuring the packing densities of the resultant electrode
films. Porous structures of composites and the individual constituents
composing the composites were characterized by nitrogen adsorption
and desorption at 77 K with a Micromeritics ASAP-2460, where specific
surface area (SSA) of the samples was calculated using multi-point
Brunauer–Emmett–Teller (BET) method and pore size distribution
using density functional theory (DFT) method.
2.3. Characterization of electrochemical and capacitive properties
Prior to electrochemical investigations, all composite electrodes
were subjected to calendaring at a same ratio, followed by punching the
resultant pressed electrodes into circular discs with a diameter of 12
mm. Under the contents of O2 < 0.1 ppm and H2O < 0.1 ppm in a dry
glove box (VGB-10-1, Shenzhen Kejin (MTI)), two identical electrodes of
the same composite material were assembled with a 35 μm-thick cel­
lulose separator (TF4035, NKK) and a 1 mol L 1 tetraethylammonium
tetrafluoroborate (TEA-BF4)/acetonitrile (ACN) electrolyte (CF4101,
Jiangsu Guotai) into CR2025 coin-typed capacitors. All electrochemical
measurements were conducted at room temperature by using an elec­
trochemical workstation (VMP-300, Bio-Logic). Electrochemical
impedance spectroscopy (EIS) analysis was performed at open circuit
voltage over a frequency range from 100 kHz to 10 mHz and with an AC
voltage amplitude of 10 mV. Cyclic voltammetry (CV) measurements
were obtained within a voltage window between 0 V and 2.7 V and at
the scan rates varying from 5 to 500 mV s 1. Galvanostatic charge-
discharge (GCD) cycles were conducted using the constant current
densities between 0.5 and 80 A g 1 and with the cut-off voltages of 0 V
and 2.7 V. From the discharge process of a GCD cycle, gravimetric
capacitance (C, F g 1) of an electrode material and gravimetric energy
density (E, Wh kg 1) and power density (P, W g 1) of a capacitor were
calculated according to:
3.1. Morphologies and packing of nanocomposites
Morphologies of composite electrodes were characterized by SEM.
As shown in Fig. 1a, the AC/CB binary compositing system of a con­
ventional ACE was formed by the filling of CB particles into the voids
created between AC particles, where CB particles aggregated together to
form the electrical conduction network of the system. Essentially, this
system is characteristic of isolation of CB aggregates, loose contact be­
tween CB aggregates and AC particles, and direct point-to-point contact
between AC particles, altogether creating a poor electrical conduction
network for the system, which has been a problem for conventional
ACEs fabricated using CB as the sole conductive additive [11]. Upon the
introduction of CNT, the obtained AC/CB/CNT ternary nano­
compositing system (i.e., NCE-1) showed uniform and tight wrapping of
CNT around AC particles (Fig. 1b), which should be due to the
well-defined flexibility of CNT [32,33]. In addition, CNT appeared to be
able to reduce the aggregation of CB particles and make them disperse
more uniformly in the composite. As a result, CNT connected CB parti­
cles with CNT-wrapped AC particles to construct a uniform electrical
conduction network for the ternary system. Finally, addition of CNF in
the system resulted in AC/CB/CNT/CNF quaternary nanocomposites (i.
e., NCE-2 and NCE-3), where CNF further reduced the aggregation of CB
particles (Fig. 1c and d). It is interesting to note that, unlike the flexi­
bility and entanglement CNT, CNF is fairly rigid [34] and can serve as a
special bridge connecting CB particles and CNT-wrapped AC particles,
further reinforcing the structural stability for the composites. Therefore,
the synergistic effects from the filling of CB, wrapping of CNT, and
bridging of CNF provide AC with a 3D electrical conduction network
that would be able to enhance the packing and capacitive behavior for
the nanocomposite electrodes in the present work.
It has been pointed out previously that the main factors influencing
the packing efficiency of a multi-component composition are particle
size, particle size distribution, and particle shape of the constituents
composing the composite, where particle size distribution is considered
as more significant [35,36]. This principle was well demonstrated with
our nanocomposites. As shown in Fig. 2a, the components employed to
construct our nanocomposites, including AC, CB, CNT, and CNF,
distributed their sizes over a wide range.
AC particles distributed dominantly around 8 μm, rarely below 2 μm,
and absently above 18 μm. Similarly, CB particles were also not larger
than 18 μm, but slightly shifted their dominant distribution to a smaller
size region of 4 μm, and had an increased volume percentage in the size
region below 2 μm. CNT tubes had two sharp distribution peaks at
around 0.2 μm and 1.2 μm, respectively—all below 2 μm—a fairly small
size range compared to all other constituents employed in this work.
CNF fibers presented their sizes broadly over a wide range spanning
from 0.3 μm to 210 μm with a dominant distribution around 22 μm.
When these particles with varied sizes, distributions, and shapes were
integrated together, the resultant composites showed enhanced parking
efficiency.

3
F. Cheng et al. Journal of Power Sources 450 (2020) 227678

Fig. 1. SEM images of (a) ACE, (b) NCE-1, (c) NCE-2, and (d) NCE-3 composite electrodes. Scale bar: 1 μm.

Fig. 2. Particle size distributions of (a) individual constituents of composites and (b ~ d) composites showing different size regions.

Specifically, a low packing density of 0.52 g cm 3 was observed for
the simple unitary system consisting of AC particles only (Table 1). The
narrow particle size distribution, i.e., lacking of small and large particles
(Fig. 2a), and hence poor packing of AC should be responsible for this
result [37]. When CB particles were introduced into the composite，the
resultant AC/CB binary system showed a slightly increased packing
density of 0.56 g cm 3. Here, the improved packing can be attributed to
the contribution of CB particles filling the voids created between AC
particles (Fig. 1a). However, this improvement was fairly small, which
should be attributable to the similarity in particle size distributions
between AC and CB (Fig. 2a), being short of a so-called “particle-mix­
ing-interaction” effect resulting from the difference in particle sizes
between the two constituents of the composite [12]. In fact, the poor
packing of this AC/CB binary system (i.e., the conventional ACE) has
been an issue limiting the volumetric performances of current super­
capacitor products [13,14]. In this regard, CNT, with its smaller size

4
F. Cheng et al.
(Fig. 2a), contributed to the filling of the region below 2 μm (Fig. 2b and
c) and thus enhanced the packing for the resultant AC/CB/CNT ternary
nanocompositing system. Also, the uniform and tight wrapping of CNT
around AC particles (Fig. 1b) can reduce the free voids and further in­
crease the packing for this system (Table 1). Moreover, packing of the
composite was further improved when CNF was introduced to construct
the AC/CB/CNT/CNF quaternary nanocompositing system. Being able
to distribute broadly (Fig. 2a), CNF contributed to packing of the com­
posites over a wide size range and more significantly in both the small
(<2 μm) and large (>18 μm) size regions as illustrated in Fig. 2c and d,
respectively. In addition, the rigidity and bridging effect of CNF dis­
cussed earlier helped to connect different types of particles, further
reducing the free voids and thus enhancing the packing for the com­
posites (Table 1). Interestingly, with respect to NCE-2, NCE-3 showed a
further increased packing density (0.63 g cm 3), which should have
chiefly been a result of the increased packing contribution in the large
(>18 μm) size region (Fig. 2d). This improved packing efficiency can be
attributed to a larger amount of CNF being employed in NCE-3 than in
NCE-2, leading to a larger difference in sizes of components in the
composite [38]. Overall, along with the introduction of different-sized
constituents to increase the compositing level from unitary all the way
up to quaternary, particle size distributions of the resultant composites
become wider. Also, different shapes of these particles help fill the free
Fig. 3. Porous structures of individual constituents of composites and their resultant composites. (a) Nitrogen adsorption-desorption isotherms and (b ~ d) pore size
distributions of individual constituents of composites. (e) Nitrogen adsorption-desorption isotherms and (f) pore size distributions of composites.
5
Journal of Power Sources 450 (2020) 227678
voids created between particles in the composites. Both of these factors
can increase the packing efficiency for the composite as pointed out
previously [35,39,40]. Importantly, the enhanced packing of
multi-component compositing systems deduced from CNT and CNF
should be very useful in improving the volumetric capacitive perfor­
mances, while the high electrical conductivities of CNT and CNF in
facilitating the electron transport dynamics, for our nanocomposite
electrodes in the present work.
3.2. Porous structures of nanocomposites
Porous structures of the individual components composing the
composites and their resultant composites were investigated using ni­
trogen adsorption-desorption measurements at 77 K. Fig. 3a shows the
adsorption-desorption isotherm of AC, which was basically a combined
Type I and Type IV behavior as classified by IUPAC [41]. The dramatic
adsorption increase at a relatively low pressure (P/P0 < 0.1) in the
isotherm can be attributed to the presence of high-density micropores in
AC. The slight rise in the isotherm slope at P/P0 > 0.1 and the hysteresis
loop from a capillary condensation process in a medium pressure range
(P/P0 ¼ 0.4–0.8) demonstrated the presence of a small number of
mesopores in AC. Furthermore, an adsorption increase in the isotherm at
a high relative pressure (P/P0 ¼ 0.9–1.0) was hardly seen, indicating the
F. Cheng et al.
absence of macropores for AC. The inherently microporous architecture
of AC can be further confirmed by its pore size distribution, that is, most
of its pores resided in the micropore range (<2 nm) (Fig. 3b), small
amount in the mesopore region (2–50 nm) (Fig. 3c), and almost none in
the macropore region (>50 nm) (Fig. 3d). Indeed, although BET analysis
showed that AC had a specific surface area of up to 1898 m2 g 1，DFT
method further revealed that this high surface area was actually largely
contributed from micropores. As shown in Table S1 in Supporting in­
formation, the microporosity (91.67%)—defined by the ratio of the pore
volume of micropores to the total pore volume of all types of pores—of
AC was much larger than its mesoporosity (7.79%) and macroporosity
(0.54%), indicating that the pores of AC were composed of predomi­
nantly micropores, fewer mesopores, and hardly any macropores. As a
result, AC possessed a fairly small average pore diameter of 1.74 nm
(Table S1).
By contrast, CB displayed hardly measurable adsorption in the
micropore but slight adsorption in the mesopore regions (Fig. 3a),
meaning that it had almost unmeasurable micropores but a small
number of mesopores. Further, CB showed a distinct rise in the isotherm
at P/P0 ¼ 0.9–1.0 (inset of Fig. 3a), demonstrating its presence of a large
amount of macropores. Consequently, in comparison to AC, CB
possessed a much lower specific surface area and a lower microporosity
but a higher mesoporosity, a higher macroporosity, and a larger average
pore diameter (Table S1). Similarly, CNF also possessed no micropores,
but a small amount of mesopores and a large amount of macropores
(inset of Fig. 3a), and thus a specific surface area and porosities similar
to those of CB (Table S1). The meso-/macroporous characteristics of CB
and CNF can be further verified by their pore size distributions as shown
in the insert of Fig. 3d.
CNT possessed a moderate specific surface area of 323 m2 g 1 and a
very large pore volume of 1.45 cm3 g 1. Although distributing its pores
over the entire regions across micro-, meso-, and macropores, CNT
presented significantly larger meso-/macroporosities than micropo­
rosity (Table S1). CNT displayed a typical Type IV isotherm with an
abrupt adsorption rise at P/P0 > 0.9 (Fig. 3a), demonstrating its coex­
istence of significant amounts of meso-/macropores, which can be
further evidenced by its pore size distribution (Fig. 3c and d). Conse­
quently, CNT possessed the largest average pore diameter (6.87 nm)
among all constituents tested in this work (Table S1). In fact, CNT has
long been reported in literature as a typical meso-/macroporous carbon
material [23,26,42,43].
With the dominant constituent being AC, all composites studied in
this work showed nitrogen adsorption-desorption isotherms (Fig. 3e)
and pore size distributions (Fig. 3f) that resembled the Type I and Type
IV characteristics of AC (Fig. 3a and b), but with decreased micropo­
rosity and enhanced meso-/macroporosities (Table S1). Specifically,
compared to AC, ACE possessed a reduced surface area and a reduced
pore volume, which can be simply attributed to the lower amount of AC
in this composite than in pure AC. However, with its relatively higher
meso-/macroporous structures, the presence of CB resulted in high
meso-/macroporosities for the ACE composite in comparison with AC.
Moreover, upon the introduction of CNT and CNF, the resultant nano­
composites NCE-1 and NCE-2 were found to have further enhanced
meso-/macroporosities (Table S1). This phenomenon can be evidenced,
in comparison with ACE, by a steeper adsorption rise at P/P0 > 0.9 in the
isotherms (inset in Fig. 3e) and the presence of larger amounts of meso-/
macropores in the pore size distributions (inset in Fig. 3f) for NCE-1 and
NCE-2. The high meso-/macroporosities of CNT [23,26,42,43] and CNF
[27,28], as shown in Fig. 3c and d, should be responsible for this
observation. Finally, as shown in Table S1, the high packing design by
purposefully decreasing the amount of AC while increasing the amounts
of CNT and CNF was very useful for further enhancing the mesoporosity
for the resultant composite (NCE-3). Overall, through the synergistic
effects of combining the high microporosity of AC and the high mes­
o-/macroporosities of CNT and CNF, the resultant nanocomposites in the
present work possessed a hierarchical porous structure at the electrode
6
Journal of Power Sources 450 (2020) 227678
level.
It has been emphasized that, upon the charge of the material of an
electrical double layer capacitor (EDLC), its micropores are primarily
responsible for accumulating charge or electrolyte ions, while macro­
pores and mesopores (as ion-buffering reservoirs and ion-transporting
pathways) for transferring electrolytes to micropores and improving
the efficiency of the conduction process (i.e., reducing the ion diffusion
distances) [44,45]. Therefore, the hierarchical nanocomposites (along
with the high electrical conductivities of CNT and CNF) developed in
this work, possessing a good combination of enhanced ion diffusion and
facilitated electron transport dynamics, would be excellent electrode
materials for supercapacitor applications, which can be supported by the
similar hierarchical materials reported previously [46,47].
3.3. Electrochemical and capacitive performances of nanocomposites
For the purpose of practical applications, we evaluated the electro­
chemical and capacitive properties of our nanocomposite electrodes by
directly assembling them into supercapacitors using a symmetric two-
electrode configuration and with 1 mol L 1 TEA-BF4/ACN, the most
widely used electrolyte for commercial supercapacitor products. The
electrochemical and capacitive performances of the resultant capacitors
were comprehensively investigated by EIS, CV, and GCD.
In EIS analysis, the capacitors fabricated from all electrode materials
showed their EIS spectra (Fig. 4a) typical of an EDLC that can be
assigned into four components: an intersection between the EIS spec­
trum and the real impedance axis in the high frequency region repre­
senting the equivalent series resistance (Rs), a semi-circle in the high-
medium frequency region representing the charge transfer resistance
(Rct), a 45� Warburg impedance zone in the medium frequency region
representing the electrolyte ion diffusion resistance (Rd), and a vertical
straight line in the low frequency region representing the capacitive
characteristics (C) of the capacitor [48,49].
As can be seen in the inset of Fig. 4a, the ACE capacitor displayed
relatively higher impedances with a poorer capacitive behavior than
nanocomposite capacitors, which can be interpreted by the poor packing
and poor electrical conduction network formed in the conventional AC/
CB binary compositing system (Fig. 1a). Specifically, the isolation of CB
aggregates, loose contact between CB aggregates and AC particles, and
direct point-to-point contact between AC particles should be responsible
for the poor electrical conductivity of the AC/CB composite and hence a
high Rs and a high Rct for the resultant ACE capacitor. In addition, the
strong aggregation of CB aggregates in the AC/CB system [11] would
hinder the diffusion of electrolyte ions, resulting in a high Rd for the
capacitor. In terms of the porous structure, as discussed earlier, ACE was
characteristic of its high microporosity but low meso- and macro­
porosities (Table S1), implying the difficulty of electrolyte ions in
transporting within the electrode bulk material and hence a high Rd for
the capacitor [44,45]. Consequently, the ACE capacitor displayed a less
steep vertical straight line in the low frequency region (Fig. 4a), a phase
angle at 0.01 Hz far from 90� , a low frequency (f0) needed to reach the
phase angle of 45� (Fig. 4b), and a high time constant (τ0 ¼ 1/f0), all
together indicating its inferior capacitive behavior (Table 2).
By contrast, in the AC/CB/CNT ternary nanocompositing system
(Fig. 1b), CNT uniformly and tightly wrapped AC particles, significantly
reduced the aggregation of CB particles, and connected CB particles with
CNT-wrapped AC particles, altogether creating a more effective packing
and electrical conduction network. This structure, in conjunction with
the high electrical conductivity of CNT, increased the electrical con­
ductivity and improved the change transfer, i.e., lowering Rs and Rct, for
NCE-1 capacitor. Further, the reduced aggregation of CB particles by
CNT provided the composite with an easy-access-pathway for electrolyte
ions and thus lowered Rd for the capacitor. On the aspect of porous
structure, with its significant amounts of meso-/macropores, CNT
enhanced the meso-/macroporosities for NCE-1 (Table S1) so as to lower
the Rd for the capacitor. Together, these effects led to a significantly
F. Cheng et al. Journal of Power Sources 450 (2020) 227678

Fig. 4. Electrochemical and capacitive performances of supercapacitors fabricated from different composite electrodes. (a) Nyquist plots. (b) Bode plots. CV curves
obtained at (c) 10 mV S 1, (d) 100 mV S 1, and (e) 500 mV S 1. (f) Comparison of gravimetric capacitances versus different CV scan rates. GCD profiles obtained at
(g) 0.5 A g 1, (h) 10 A g 1, and (i) 30 A g 1. IR drops of supercapacitors are illustrated with dashed lines and arrows in (i). (j) Comparison of gravimetric capacitances
versus different GCD current densities.

improved capacitive behavior for the NCE-1 capacitor, in comparison
with the ACE capacitor, showing a steeper vertical straight line in the
low frequency region, a phase angle at 0.01 Hz closer to - 90� , a higher
frequency needed to reach the phase angle of 45� , and a lower time
constant (Fig. 4a and b, Table 2).
Moreover, upon the introduction of CNF in the AC/CB/CNT/CNF
quaternary nanocompositing system, the resultant NCE-2 and NCE-3
capacitors showed even lower impedances for all components and
steeper low-frequency vertical straight lines with the 0.01 Hz phase
angles further closer to 90� , the frequency needed to reach the phase
angle of 45� further increased, and the time constants further
decreased (Fig. 4a and b, Table 2). Indeed, the rigidity and bridging
effect of CNF as discussed earlier, linking all types of particles together
to make the quaternary nanocomposites electrically pack better (Fig. 1c
and d), along with the coexistence of CNT and CNF, enhancing the
meso-/macroporosities of the nanocomposites (Table S1), should be
responsible for this capacitive improvement. In this sense, with the
larger amounts of CNT and CNF employed, the NCE-3 capacitor
possessed further lower impedances and better capacitive behavior than
the NCE-2 capacitor. Consequently, as can be visually seen in Fig. S1,
along with the introduction of CNT and CNF to increase the compositing
level, the decrease in overall impedance (i.e., the sum of Rs, Rct, and Rd)
leads to increased frequencies at 45� phase angle and decreased time
constants for the resultant nanocomposites.
It is interesting to note that, the time constants observed for our
quaternary nanocomposites (NCE-2: 1.48 s, NCE-3: 1.39 s) are even
lower than those of the specifically designed mesoporous carbon nano­
materials of, for example, activated graphene (1.67 s) [50] and
few-layer carbon (2.1 s) [51], clearly demonstrating the superior
capacitive performance of our nanocomposite materials. It is the com­
bination of the synergistic effects from the filling of CB, wrapping of
CNT, and bridging of CNF (forming an effective packing and electrical
conduction network) with the synergistic effects from the high micro­
porosity of AC and the high meso-/macroporosities of CNT and CNF
(forming a hierarchical porous structure), resulting in facilitated ion
diffusion and electron transport for the materials [46,47], that is

7
F. Cheng et al. Journal of Power Sources 450 (2020) 227678

Fig. 4. (continued).

its rectangle shape (Fig. 4d and e) and capacitance (Fig. 4f). Galvanos­
Table 2
tatically, higher charging/discharging currents rendered a larger IR
EIS properties of supercapacitors fabricated from different composite electrodes.
drop for this capacitor (Fig. 4h and i) with a sharply decreased capaci­
Electrode Rs Rct Rd Phase angle Frequency at Time tance (Fig. 4j). These phenomena indicate the inferior rate capability of
(Ω) (Ω) (Ω) at 0.01 Hz 45� phase constant
the conventional ACE, which correlates well with its high impedances
frequency angle (Hz) (s)
(degree) (Table 2) that should result from the poor packing/conduction (Fig. 1a)
and the low meso-/macroporosities (Table S1) of the AC/CB binary
ACE 0.84 2.64 0.92 85.96 0.23 4.42
NCE-1 0.76 0.54 0.53 87.64 0.40 2.52
compositing system. In fact, poor rate capability of the conventional
NCE-2 0.74 0.10 0.49 88.08 0.68 1.48 ACE has been an issue limiting the power performance of super­
NCE-3 0.73 0.07 0.47 88.30 0.72 1.39 capacitors for years, which has drawn considerable attention in the
supercapacitor community [11,17,18].
In contrast, owing to the presence of carbon nanomaterials, nano­
responsible for this achievement. Moreover, the commercial availability
composites displayed significantly improved rate performance, which
of the materials we used indicates the great feasibility of our nano­
can be visually seen from their rectangular shape and high capacitances
compositing approach towards the practical applications for
during CV with high scan rates (Fig. 4d and e) as well as small IR drops
supercapacitors.
and long charge/discharge durations upon GCD with high currents
The superior capacitive behavior of our nanocomposites was subse­
(Fig. 4h and i). Highly packed and effective electrical conduction
quently demonstrated by CV and GCD measurements. At a low scan rate
network (Fig. 1b, c and d) as well as enhanced meso-/macroporosities
of 10 mV S 1, all capacitors showed their CV curves with a rectangle
(Table S1), and hence facilitated ion diffusion and electron transport
shape and sharp transient responses at both ends of the CV (Fig. 4c).
dynamics [46,47], of the nanocomposites should be responsible for this
Similarly, when galvanostatically charged and discharged with a small
improvement. To this end, when the compositing level increased from
current of 0.5 A g 1, these capacitors displayed a symmetric GCD profile
binary to ternary and finally to quaternary, the resultant nano­
with a negligible IR drop at the beginnings of the charge and discharge
composites presented gradually decreased impedances (Table 2,
processes (Fig. 4g). Although being characteristic of an EDLC [1,2],
Fig. S1), sharper transient responses at the ends of CV curves (Fig. 4d
these CV curves and GCD profiles were difficult to be used to differen­
and e), and smaller IR drops and longer charge/discharge durations in
tiate varying-rate materials, implying the unobstructed access of the
GCD profiles (Fig. 4h and i), leading to a rate capability ranking of
electrolyte ions to the bulk of all materials during a slow charging/di­
NCE-3 > NCE-2 > NCE-1 > ACE. As a result, a high-rate nanocomposite
scharging process. At this sluggish event, all materials displayed a
retained a high level of capacitance when the CV scan rate or the GCD
similar gravimetric capacitance of about 105 F g 1 (Fig. 4f and j).
current increased. For example, in CV measurements, upon the scan rate
Nevertheless, benefitting from their enhanced packing as discussed
increasing from 5 mV S 1 to 500 mV S 1, the capacitance retained
earlier, nanocomposites showed improved volumetric capacitances with
85.6% for NCE-3 versus that of 64.9% for ACE (Fig. 4f). In GCD mea­
respect to the conventional ACE (Table 1), for example, 66.1 F cm 3 for
surements, upon the current density increasing from 0.5 A g 1 to 80 A
NCE-3 versus 59.0 F cm 3 for ACE, clearly demonstrating the signifi­
g 1, the capacitance retained 77.5%, 72.1%, and 48.5% for NCE-3,
cance of our nanocompositing approach in promoting the commercial
NCE-2, and NCE-1, respectively versus that of 15.6% for ACE (Fig. 4j).
applications of AC for supercapacitors [15,16].
These demonstrate the rapid charge storage and delivery kinetics of the
Upon the increase in CV scan rate, the ACE capacitor gradually lost

8
F. Cheng et al.
nanocomposites in the present work [25–30].
From the discharge profiles obtained at a range of current densities,
energy and power densities of all capacitors were calculated and pre­
sented in Ragone plots (Fig. 5). The ACE capacitor presented a maximum
energy density of 23.7 W h kg 1 (26.6 W h L 1) and a maximum power
density of 30.4 kW kg 1 (34.0 kW L 1) (Table S2). Based on a simplified
estimation method [52], these performances can be translated to 5.9 W
h kg 1 (6.7 W h L 1) and 7.6 kW kg 1 (8.5 kW L 1) for a packaged
device, similar to those of current supercapacitor technology [31],
indicating the comparability of our ACEs with the commercial AC
electrodes employed in the industry. The increase in power density of
the ACE capacitor caused a sharp decrease in energy density, implying
that its stored energy could not be delivered in a fast manner, which
should be attributable to the inferior rate capability of the AC/CB binary
compositing system as discussed earlier.
In terms of energy storage ability, although having a similar gravi­
metric energy density to that of the ACE capacitor (Fig. 5a), nano­
composite capacitors displayed enhanced volumetric energy densities
(Fig. 5b). For example, the maximum volumetric energy density of 26.6
W h L 1 for the ACE capacitor increased to 29.6 W h L 1 for the NCE-3
capacitor. Moreover, the energy delivery capability of nanocomposite
capacitors was enhanced more significantly, and the power performance
of the capacitors was found to correlate well with the rate capability of
the materials, i.e., NCE-3 > NCE-2 > NCE-1 > ACE. As shown in
Table S2, upon the increase in composition level from the conventional
binary system (ACE) all the way to the quaternary system (NCE-3), the
maximum gravimetric power density was improved by 1.7 times (80.7
kW kg 1 vs. 30.4 kW kg 1) and the maximum volumetric power density
by 2 times (101.7 kW L 1 vs. 34.0 kW L 1). It should be emphasized that
the improved volumetric performances of nanocomposites result from
their enhanced packing (Table 1) and the improved power densities
from their enhanced rate capability (Fig. 4j), all due to the introduction
of CNT and CNF in the compositing systems. This clearly makes the
nanocompositing approach of the present work promising for
manufacturing commercial supercapacitor products with superior per­
formances (especially volumetric performances [15,16]) over current
supercapacitor technology [31].
Finally, in order to evaluate the long-term practical usability of our
nanocomposite electrodes, GCD cycling tests were performed for these
composites in comparison with the conventional ACE. Along with the
measurement of capacitance, the changes in columbic efficiency and
equivalent series resistance (ESR) of the devices were also investigated
to obtain an insight into the factors that may influence the cycling sta­
bility of the materials (Fig. 6).
At the beginning of GCD, all capacitors displayed a well-defined
symmetric charge/discharge profile (Fig. 6a). However, upon cycling,
the ACE capacitor showed gradually bent profiles with increased IR
drops and shortened charge/discharge durations (Fig. 6b, c and d),
presenting a continuous degradation in capacitance and columbic
Fig. 5. (a) Gravimetric Ragone plots and (b) volumetric Ragone plots of supercapacitors fabricated from different composite electrodes. GCD current density: 0.5–80
A g 1, cut-off voltage: 0–2.7 V. Performances are based on the total (a) mass and (b) volume of the coating films of the two electrodes of a supercapacitor.
9
Journal of Power Sources 450 (2020) 227678
efficiency and an increase in ESR. After 30000 cycles, the ACE capacitor
retained its capacitance at 69.5% only (Fig. 6e), along with a columbic
efficiency decreasing to 89.9% and an ESR increasing to 6.56 Ω (Fig. 6f).
The low meso-/macroporosities (Table S1) and high impedances
(Table 2) and hence a poor electrochemical reversibility of the AC/CB
binary compositing system should be responsible for its decay in
columbic efficiency, while the poor packing and poor particle-particle
contacts of this system (Fig. 1a) for its increase in ESR. Previously, the
electrochemical dilatometric study [19,20] and aging mechanism study
[11] have demonstrated that charging/discharging of an EDLC based on
AC electrodes and an aprotic organic electrolyte is connected with the
noticeable expansion/contraction of AC and the agglomeration of CB.
Thus, given its poor packing, the particle-particle contacts of ACE would
become looser upon the expansion/contraction of AC and the agglom­
eration of CB during charging/discharging, resulting in a gradually
increased ESR for the ACE capacitor. Under the worst circumstances,
these dimensional changes would break the electrode (shown with the
cracks in Fig. 6h) and cause sharp and sudden ESR increases for the
capacitor (Fig. 6f). Altogether, these factors led to a poor cycle life for
the conventional ACE capacitor (Fig. 6e).
By contrast, with the aid of CNT and CNF, nanocomposite capacitors
displayed significantly improved cycle lives, essentially maintaining
their well-defined charge/discharge profiles, low IR drops, and long
charge/discharge durations upon charging/discharging (Fig. 6a, b, c,
and d). They showed high capacitance retentions (Fig. 6e) accompa­
nying high columbic efficiencies and low ESRs (Fig. 6f). Further, their
capacitance retentions (NCE-3 > NCE-2 > NCE-1 > ACE) correlated well
with columbic efficiencies (NCE-3 > NCE-2 > NCE-1 > ACE) and ESRs
(NCE-3 < NCE-2 < NCE-1 < ACE), indicating that a high columbic ef­
ficiency and a low ESR were necessary to ensure a high cycling stability
for the capacitor. Electrochemically, the enhanced meso-/macro­
porosities (Table S1) and lowered impedances (Table 2) and hence a
high electrochemical reversibility of the nanocompositing systems
should be responsible for their high columbic efficiencies upon cycling.
Mechanically, the enhanced packing and the robust contacts between
particles of these systems (Fig. 1b, c and d) were responsible for their
low ESRs upon cycling. Specifically, the flexible and tight wrapping of
CNT around AC particles and the bridging of CNF between particles
provided the nanocomposites with a unique hierarchical 3D network
that could efficiently accommodate the expansion/contraction of AC
and prevent the agglomeration of CB during charging/discharging,
being able to maintain the integrity (shown with the absence of apparent
cracks in Fig. 6j) and thus a low ESR for the nanocomposite electrodes.
Indeed, after charging/discharging for 30000 cycles, ESR of the AC/CB/
CNT ternary system only raised slightly while that of the AC/CB/CNT/
CNF quaternary system remained almost unchanged (Fig. 6f).
It is known that, since dimensional changes of electrodes are always
related to the stability and lifetime issues of electrochemical devices
including supercapacitors, control of these changes is necessary for
F. Cheng et al. Journal of Power Sources 450 (2020) 227678

Fig. 6. GCD cycling performances of supercapacitors fabricated from different composite electrodes. GCD profiles obtained at the (a) 1st, (b) 10000th, (c) 20000th,
and (d) 30000th cycles. (e) Capacitance retentions and (f) columbic efficiencies and ESR changes upon GCD cycling. GCD current density: 10 A g 1, cut-off voltage:
0–2.7 V. SEM images of (g, i) fresh electrodes and (h, j) aged electrodes taken from the supercapacitors after GCD cycling for 30000 cycles. Scale bar: 50 μm.
Supercapacitors were fabricated from (g, h) ACE and (i, j) NCE-3 electrodes, respectively.

prolonging the cycle lives of electrochemical devices [19,20]. The
findings in the present work demonstrated that, with the introduction of
carbon nanomaterials (CNT and CNF) into the conventional ACE, the
enhanced packing of the resultant nanocompositing systems (Fig. 1 and
Table 1) provided the electrodes with a unique structure that is able to
accommodate the expansion/contraction of AC and minimize the
agglomeration of CB during charging/discharging so as to ensure an
excellent cycle life for the capacitor. To this end, for example, after
charged/discharged for 30000 cycles, the NCE-3 capacitor maintained
its ESR at as low as 2.23 Ω, columbic efficiency as high as 98.2%
(Fig. 6f), and capacitance retention up to 91.4% (Fig. 6e), significantly
outperforming its conventional counterpart (i.e., the ACE capacitor).
Moreover, along with the superior volumetric performances of NCE-3 in
comparison with AC, porous carbon, graphene, and CNT as well as their
composites reported previously [30,50,53–60] (Table S3), these results
clearly proved the effectiveness of our nanocompositing approach in
improving the electrochemical stability and volumetric performances,
and hence practical application significance [15,16], for conventional
AC electrodes.
4. Conclusion
In summary, using a simple slurry process to combine conventional
high-surface-area AC and conductivity additive (CB) with carbon
nanomaterials (CNT and CNF), we have developed a new class of
nanocomposite electrodes for high-performance supercapacitors.
Incorporating flexible CNT and rigid CNF into the composites was able
to significantly improve the properties of the resultant nanocomposite
electrodes. Specifically, packing densities and capacitive performances
of the composite electrodes were gradually enhanced along with the
increase in compositing level from binary (AC/CB) to ternary (AC/CB/
CNT) and finally to quaternary (AC/CB/CNT/CNF). This has been
demonstrated to be attributable to the introduction of CNT and CNF,
forming an effective packing and electrical conduction network as well

10
F. Cheng et al.
Fig. 6. (continued).
as a 3D hierarchical porous structure, in the composites. The final
optimized AC/CB/CNT/CNF quaternary nanocomposite electrode
showed a high packing density (0.63 g cm 3), a high capacitance (104.9
F g 1, 66.1 F cm 3), a high rate capability (capacitance retained 77.5%
at 80 A g 1 vs. 0.5 A g 1), a high energy density (23.5 W h kg 1, 29.6 W h
L 1), a high power density (80.7 kW kg 1, 101.7 kW L 1), and a long
cycle life (capacitance retained 91.4% after charging/discharging at 10
A g 1 for 30000 cycles), significantly outperforming current super­
capacitor technology [31]. Especially, the superior volumetric perfor­
mances of our nanocomposite electrodes indicate their significance in
practical applications for commercial supercapacitors [15,16]. There­
fore, the nanocompositing approach developed in the present work
stands for a facile path of utilizing commercially available materials to
develop highly capacitive nanocomposites that can be readily trans­
ferred into the industrial slurry process to fabricate large-scale elec­
trodes for manufacturing high-performance supercapacitor products at
low costs. Furthermore, this approach can be extended to mass-produce
high-performance nanocomposite electrodes for other energy-related
devices including, for example, batteries, fuel cells, and solar cells.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
CRediT authorship contribution statement
Fang Cheng: Investigation, Formal analysis, Writing - original draft.
Xiaoping Yang: Investigation, Methodology. Shuangpeng Zhang:
Investigation, Validation. Wen Lu: Conceptualization, Funding acqui­
sition, Project administration, Resources, Supervision, Writing - review
& editing.
Acknowledgements
This work was supported by The Special Significant Science and
Technology Program of Yunnan Province (grant number: 2016HE001-
2016HE002). Fang Cheng gratefully acknowledges support from
11
Journal of Power Sources 450 (2020) 227678
Yunnan University Innovative Research Fund for Graduate Students
(grant number: YDY17088).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jpowsour.2019.227678.
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