Materials and Design 169 (2019) 107688

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Materials and Design

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

Biomass-derived ultrathin mesoporous graphitic carbon nanoflakes as

stable electrode material for high-performance supercapacitors
S. Sankar a, Abu Talha Aqueel Ahmed a, Akbar I. Inamdar a, Hyunsik Im a, Young Bin Im b, Youngmin Lee c,
Deuk Young Kim a,c, Sejoon Lee a,c,⁎
a
Department of Semiconductor Science, Dongguk University-Seoul, Seoul 04620, Republic of Korea
b
Dharma College, Dongguk University-Seoul, Seoul 04620, Republic of Korea
c
Quantum-functional Semiconductor Research Center, Dongguk University-Seoul, Seoul 04620, Republic of Korea

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

• Graphitic carbon was derived from

green tea wastes via KOH activation
in air.
• The hydrolysis treatment resulted in
the formation of graphitic-carbon
nanoflakes.
• Graphitic-carbon nanoflakes showed
an interconnected structure with
high porosity (i.e., pore volume ~
0.4713 cm 3/g).
• Graphitic-carbon nanoflakes played
an excellent role as a supercapacitor
electrode (i.e., specific capacitance ~
162 F/g).
• The results render a prospective way
to the recycling of biomass waste
resources.

a r t i c l e i n f o a b s t r a c t

Article history: With the motivation of materializing a high-performance electrode material for the high-energy supercapacitor,
Received 27 November 2018 ultrathin mesoporous graphitic‑carbon was synthesized from biomass green-tea wastes via the KOH activation
Received in revised form 4 March 2019 process combined with either of the water or the hydrochloric acid treatment. The water-treated graphitic‑carbon
Accepted 4 March 2019
showed an interconnected ultrathin-nanoflake structure with a high porosity, while the hydrochloric acid-treated
Available online 5 March 2019
graphitic carbon exhibited an aggregated structure of irregular nanoparticles. The supercapacitor with an elec-
Keywords:
trode of water-treated graphitic‑carbon nanoflakes displayed an enhanced specific capacitance of 162 F/g at 0.5
Biomass resource A/g. Furthermore, the device revealed an excellent cycle stability after multiple cyclic charge-discharge operations
Green tea waste (i.e., 121% cyclic capacitance retention over 5000 cycles). These may open up a new avenue toward the recycling
Graphitic carbon of biomass carbonaceous resources (e.g., green tea wastes) for inexpensive high-performance electrochemical
Nanoflakes energy-storage devices such as high-energy supercapacitors.
Electrode © 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
Supercapacitor (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
⁎ Corresponding author at: Department of Semiconductor Science, Dongguk University-
Seoul, Seoul 04620, Republic of Korea. The sustained depletion of non-renewable fossil fuels and the con-
E-mail address: sejoon@dongguk.edu (S. Lee). sistent increase of environmental problems have resulted in urgent

https://doi.org/10.1016/j.matdes.2019.107688
0264-1275/© 2019 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/).
2 S. Sankar et al. / Materials and Design 169 (2019) 107688
demands for sustainable, renewable, and clean energy sources. For the
realization of high-performance green energy-technology, recently,
many studies have been conducted in research fields of nanoscience
and nanotechnology [1–5]. The supercapacitor has attracted significant
attention as a next-generation energy-storage device due to its environ-
mental friendliness, long-term cycle stability, excellent charge-discharge
performance, high power, and enhanced efficiency [6–10]. Considering
the charge-storage mechanism, the supercapacitors can be classified
into two different device schemes. One is the pseudocapacitor that can
store the energy from the fast and reversible Faradaic reaction (e.g.,
electrosorption, intercalation process, and reduction-oxidation reaction)
[11,12]. And, the other is the electrical double-layer capacitor (EDLC), in
which the energy can be stored via the non-Faradaic reaction through
charge accumulation at the electrode-electrolyte interface [13,14]. In re-
cent years, EDLC has been of great interest because of its superior cyclic
stability and higher power density [15]. One of the most key elements
for high-performance EDLC is the electrode material because its electrical
conductivity, porosity, and surface area are closely related to the charge
storage at the interface between the electrode material and the electro-
lyte [16,17].
As an appropriate candidate of EDLC's electrode, various types of
carbon-based materials have been studied; for example, activated carbon
[18–21], carbon aerogels [22], onion-like carbons [23], carbon nanotubes
[24–26], carbon fibers [27], graphene [28], mesoporous carbons [29,30],
and graphitic carbon [31–39]. Among them, graphitic carbon has been
regarded as a prominent electrode material because of its low cost, excel-
lent electrochemical stability, high surface area (~1000–3000 m2/g),
good porosity, high specific capacitance, good electrical conductivity,
and environmental friendliness [40]. Recently, the synthesis of graphitic
carbon from the recyclable biomass resource has garnered particular at-
tention due to the global interest in eco-friendship [41,42]. Furthermore,
the interconnected pore networks in the biomass resources can deliver a
facile access of guest ions into the interior of EDLCs [43]. This provides an
increased specific surface area, and allows a prospective use of biomass-
derived graphitic carbon for the supercapacitor electrode. Among various
biomass resources, tea waste ashes could be effectively utilized as precur-
sor source materials for the preparation of eco-friendly carbonaceous-
electrode materials because they contain 3.5–7.0% of inorganic constitu-
ents as well as 93.0–96.5% of organic substances [44]. Previously, a few
of experimental studies have been reported as feasible ways for the prep-
aration of activated carbon electrodes by using tea wastes. For example,
Peng et al. [44] synthesized activated‑carbon from waste tea leaves
through the KOH activation in an argon atmosphere, and achieved the
specific capacitance of 330 F/g in 2 M KOH at 1 A/g. Inal et al. [45] also
synthesized mesoporous activated‑carbon from tea wastes through the
H3PO4 activation, and obtained the specific capacitance of 123 F/g at
1.5 mA/cm in 1 M H2SO4. To our best knowledge, however, the derivation
of the ‘ultrathin mesoporous graphitic-carbon nanoflakes’ from tea
wastes has not been reported so far even though graphitic carbon pos-
sesses substantial advantages such as high porosity and high conductivity
[31–39]. Therefore, an effective derivation of high-performance two-
dimensional graphitic carbon could be one of the greatest benefits for
the upcycling of the cheap and abundant biomass tea-waste resources.
All of the above prompt a study on the synthesis of the high-quality
ultrathin mesoporous graphitic carbon nanoflakes using the carbona-
ceous biomass resource of the tea waste. Therefore, the effective and fac-
ile methods were investigated in the present work so as to produce the
tea waste-derived mesoporous graphitic carbon for high-performance
supercapacitors electrode materials. The mesoporous graphitic carbon
was synthesized by using green-tea waste ashes through the KOH activa-
tion in air ambience combined with either of the water or the hydrochlo-
ric acid treatment. The methods enabled us to control the microstructure
of the graphitic carbon materials and to enhance their porosity, leading
to the excellent supercapacitor characteristics. In this article, the effects
of the water and the hydrochloric acid treatments on the morphological,
structural, and microstructural properties of the tea waste-derived
carbon products are systematically examined, and their electrochemical
performances as supercapacitor electrodes are assessed.
2. Experimental details
2.1. Synthesis of graphitic carbon
Fig. 1 illustrates the synthesis procedures for the graphitic carbon
nanoflakes and nanoparticles by using green-tea wastes. The green tea
waste was obtained from Dongsuh brown-rice green-tea bags (Dongsuh
Foods Co. Ltd., Republic of Korea), containing 30% of green tea and 70% of
brown rice harvested in Korea. All of the other chemical reagents within
the AR category were obtained from Sigma-Aldrich (St. Louis, Missouri,
USA). First, the raw material of the green tea waste was cleaned with de-
ionized (DI) water, and was dried at 100 °C for 12 h in an electric oven.
Then, the dried tea waste was carbonized at 500 °C for 1 h in air so as to
collect their ashes (i.e., tea waste ash (TWA)). After carbonization, the
mixture of TWA and KOH was prepared by mixing 12 g of KOH with
3 g of TWA. Next, the mixture of TWA-KOH was transferred into an alu-
mina crucible, and was activated at 700 °C (5 °C/min) for 2 h in air after
encapsulating the crucible. As soon as completing the activation process,
the KOH-activated TWA was stirred in either of DI water (100 ml) for 6 h
or 1 M HCl (100 ml) for 6 h so as to remove the captured potassium com-
pounds. Finally, the activated materials were filtered, rinsed, and dried
in an electric oven at 150 °C for 8 h. Through adopting the aforemen-
tioned DI water and HCl acid treatments, we obtained graphitic carbon
nanoflakes and nanoparticles, respectively. For convenience, the former
and the latter are denoted by ‘TWA-WC’ and ‘TWA-HC’, respectively.
2.2. Formation mechanism of graphitic carbon
The green tea waste contains both the inorganic (3.5–7.0%) and the
organic (93.0–96.5%) constituents. Through the carbonization process,
those components can be converted into carbonaceous precursors of
TWA with oxygen-containing groups. During the KOH activation, car-
bon and oxygen-containing groups would react with potassium hy-
droxide; therefore, carbonaceous chemicals (e.g., potassium carbonate
(K2CO3), carbon monoxide (CO) etc.) could be formed. The activation
at high temperature can be described by following chemical reactions
[46]:
2CðAshÞ þ 6KOH→2K2 CO3 þ 3H2 þ 2K ð1Þ
K2 CO3 →CO2 þ K2 O ð2Þ
CO2 þ C→2CO ð3Þ
2C þ K2 CO3 →3CO þ 2K ð4Þ
K2 O þ C→CO þ 2K ð5Þ
By washing the KOH-activated materials in DI water (or HCl acid),
the inorganic residues and contaminants could be removed from the
surface of the carbon product. This allows the formation of nanoporous
and/or mesoporous carbon nanostructures. The water and the acid
treatments play a vital role for not only controlling the structure of the
synthesized product but also improving its porosity [47–49]. In the
case of the hydrolysis treatment (i.e., DI water), the activated material
(i.e., irregular flakes) could lose their volatile matters; hence, the swell-
ing behavior becomes significant due to the increased elasticity inside
the interconnected flakes [49]. On the other hand, the acid treatment
(i.e., HCl) might decompose the base material of the KOH-activated
TWA mixture so that the particle structures are formed and intercon-
nected each other [50,51].
 S. Sankar et al. / Materials and Design 169 (2019) 107688
Fig. 1. Schematic illustration of the synthesis procedures for the TWA-derived graphitic carbon nanoparticles and nanoflakes via the KOH activation with the HCl and DI treatments,
respectively.
2.3. Material characterization
The morphological properties of TWA-WC and TWA-HC were exam-
ined by field-emission scanning-electron microscopy (FE-SEM) using an
Inspect-F50 chamber (FEI Company Inspect™, USA). The microstruc-
tural characteristics of the samples were monitored by transmission
electron microscopy (TEM) using a JEM 2100F instrument (JEOL Ltd.,
Japan). The crystallographic structures were also investigated by in-situ
selected-area electron-diffraction (SAED) measurements during the
TEM analysis. To characterize the structural properties, x-ray diffraction
(XRD) measurements were performed by using a D8-Advance Diffrac-
tometer (Bruker, USA). In addition, the Raman scattering characteristics
were analyzed under the backscattering geometry by using a LabRAM
HR-800 instrument (HORIBA Jobin Yvon Co., France). To examine the
textural characteristics, the nitrogen (N2) adsorption-desorption iso-
therm analyses were carried out at 77 K by using a BELSORP-mini II
equipment (MicrotracBEL, Japan). The pore surface area, the specific sur-
face area, the pore volume, and the average pore diameter were deter-
mined through Barrett-Joyner-Halenda (BJH) and Brunauer-Emmett-
Teller (BET) methods.
2.4. Electrochemical measurements
The electrochemical performances of TWA-HC and TWA-WC as
supercapacitor electrodes were evaluated through the cyclic voltamme-
try (CV), galvanostatic charge-discharge (GCD), and electrochemical
impedance spectroscopy (EIS) measurements by using a Versa STAT3
electrochemical workstation (Princeton Applied Research, USA). The
working electrode was prepared by mixing graphitic carbon (e.g.,
TWA-HC (80%) or TWA-WC (80%)) with polyvinylidene difluoride
(10%) and carbon black (10%) in N-methyl-2-pyrrolidinone solution.
Here, the masses of the active materials of TWA-HC and TWA-WC
were ~2.27 and ~1.98 mg, respectively. The mixture slurries were
painted on the stainless steel substrates (1 cm2), and were consequently
dried at 100 °C for 6 h. Then, the graphitic carbon electrodes were used
3
as a working electrode with the saturated-calomel reference-electrode
and the graphite counter-electrode. The electrochemical capacitive-
performances were measured in an aqueous solution of 1 M H2SO4 elec-
trolyte. CV measurements were conducted at various scan rates of
5–100 mV/s, and GCD properties were analyzed at different current
densities of 0.5–5 A/g in a potential window of 0–0.8 V. EIS measure-
ments were carried out in a frequency range of 0.01 Hz – 10 kHz. The
specific capacitance (Cs) of the prepared supercapacitor samples was
evaluated from the measured CV and GCD curves by using the following
equations [52,53]:
Z 
Cs ¼ I c  ds =ðs  m  ΔV Þ ð6Þ
¼ ðIa  Δt Þ=ðm  ΔV Þ ½ F=g ; ð7Þ
where Ia is the applied current [A], s is the scan rate [mV/s], Ic is the cur-
rent at the charged state [A], ΔV is the potential window [V], Δt is the
discharge time [s], and m is the mass [g] of the active material on the
working electrode.
3. Results and discussion
The morphological properties of the TWA-derived graphitic carbon
samples were monitored through the FE-SEM measurements. Prior to
discussing the morphologies of TWA-HC and TWA-WC, it should be
noted that TWA (i.e., raw source material) consists of the carbonaceous
fragments with the irregular sizes, ranging from several tens to
hundreds of micrometers (Fig. 2(a)). However, KOH-activated TWA
exhibited a structure of the aggregated porous-flakes (Fig. 2(b)),
resulting from the thermochemical decomposition of KOH. Fig. 2
(c) and (d) display the FE-SEM images of TWA-HC and TWA-WC that
had been prepared via the KOH activation of TWA and the subsequent
treatments using HCl and DI, respectively. The TWA-HC sample shows
an assembly of spherical nanoparticles (Fig. 2(c)), whereas the TWA-
WC sample displays an interconnected structure of the ultrathin
4 S. Sankar et al. / Materials and Design 169 (2019) 107688

Fig. 2. FE-SEM images of (a) TWA as a raw source material, (b) KOH-activated TWA, (c) TWA-HC nanoparticles, and (d) TWA-WC nanoflakes.

nanoflakes (Fig. 2(d)). Compared to the TWA-HC nanoparticles, the
TWA-WC nanoflakes possess a high specific surface area because of
their two-dimensional morphology (see also Fig. 3). Owing to the in-
creased swelling effect from the hydrolysis treatment, furthermore,
the shape and the size of the TWA-WC nanoflakes could become more
uniform than those of the TWA-HC nanoparticles.
The microstructural properties of the TWA-HC nanoparticles and the
TWA-WC nanoflakes were further elucidated through the TEM and
SAED measurements. As shown in bright-field TEM images, the spheri-
cal nanoparticles are densely assembled in TWA-HC (Fig. 3(a)), whereas
the ultrathin nanoflakes are interconnected and folded in TWA-WC
(Fig. 3(d)). From high-resolution TEM images, one can confirm that
the TWA-HC nanoparticles are amorphous (Fig. 3(b)) while the TWA-
WC nanoflakes are polycrystalline (Fig. 3(e)). The average sizes of the
amorphous nanoparticles are approximately 20–30 nm, and the
average widths of the polycrystalline nanoflakes are approximately
30–50 nm. The thicknesses of the stacked graphitic carbon nanoflakes
are 5–8 nm on average. The SAED patterns of TWA-HC (Fig. 3(c)) and
TWA-WC (Fig. 3(f)) further corroborate an amorphous nature of the
nanoparticles and a polycrystalline structure of the nanoflakes,
respectively.
Fig. 4(a) shows the XRD patterns of the TWA-HC nanoparticles and
the TWA-WC nanoflakes. Both samples reveal three diffraction peaks
at 2θ = 23, 43, and 60°, corresponding to (002), (100), and (004) planes

Fig. 3. (a) Bright-field TEM image of the TWA-HC nanoparticles, (b) high-resolution TEM image of the TWA-HC nanoparticles, (c) SAED pattern of the TWA-HC nanoparticles, (d) bright-
field TEM image of the TWA-WC nanoflakes, (e) high-resolution TEM image of the TWA-WC nanoflakes, and (f) SAED pattern of the TWA-WC nanoflakes.
 S. Sankar et al. / Materials and Design 169 (2019) 107688 5

After confirming the effective formation of TWA-derived graphitic

carbon nanostructures, the pore texture characteristics of TWA-HC
and TWA-WC were characterized by N2 adsorption-desorption iso-
therm measurements. As can be seen from Fig. 5(a), both samples
clearly reveal the type II/IV of the nitrogen physisorption isotherm re-
sponse with a typical H4 type hysteresis loop (categorized by IUPAC),
attributing to the meso- and micro-porous characteristics in graphitic
carbon nanostructures [63,64]. Through the BJH method, the specific
surface areas of TWA-HC and TWA-WC were determined to be ~966.4
and ~1057.8 m2/g, respectively. The pore size characteristics were also
evaluated by BET analyses using the pore diameter vs. the pore volume
curves (Fig. 5(b)). Compared to the TWA-HC nanoparticles (total pore
volume ~ 0.2438 cm3/g and average pore diameter ~ 2.35 nm), the
total pore volume and the average pore diameter of the TWA-WC
nanoflakes were increased up to 0.4713 cm3/g and decreased down to
1.66 nm, respectively. In addition, the pore surface area of TWA-WC
(~342.74 m2/g) was determined to be slightly greater than that of
TWA-HC (~329.87 m2/g). These imply that the TWA-WC nanoflakes
have a higher porosity (i.e., abundant mesopores) than the TWA-HC
nanoparticles. Therefore, the TWA-WC nanoflakes could be more bene-
ficial for improving the volumetric energy and the power characteristics
of the graphitic carbon-based supercapacitors, as discussed in detail
later.
Next, the electrochemical performances of both samples were exam-
ined after preparing the supercapacitors with the TWA-HC and TWA-WC
electrodes. Fig. 6(a) and (b) show the CV curves of the TWA-HC and the
TWA-WC electrodes at various scan rates (i.e., 5–100 mV/s), respectively.
Up to the scan rate of 25 mV/s, both the TWA-HC and the TWA-WC elec-
trodes exhibit a rectangular shape of CV curves, demonstrating an easy

Fig. 4. (a) XRD patterns and (b) Raman spectra of the TWA-HC nanoparticles and the
TWA-WC nanoflakes.

of graphitic carbon, respectively [33,54,55]. The broad (002) diffraction

pattern depicts a presence of parallelly-stacked graphene sheets inside
the solid solution of carbon materials [56]. In addition, the (100) plane
demonstrates the existence of highly-conductive sp2 hybridized carbon
with a honeycomb structure [57,58]. For the TWA-WC nanoflakes, the
(100) and (004) intensities are stronger than those of the TWA-HC
nanoparticles. This means that the TWA-WC nanoflakes involve a high
density of pores inside the solid-state graphitic carbon [44,59,60]. From
the above results, therefore, one can conjecture that the graphitic carbon
nanoflakes to have a good quality for the supercapacitor electrode mate-
rial (e.g., high crystallinity, high conductivity, high porosity etc.).
The graphitic natures of the TWA-HC and TWA-WC samples were
further examined through Raman scattering spectroscopy measure-
ments. As displayed in Fig. 4(b), Raman spectra of both TWA-HC and
TWA-WC clearly show three prominent bands at ~2840 cm−1 (2D
band), ~1570 cm−1 (G band), and ~1350 cm−1 (D band). The D band
corresponds to the defective and/or disordered features of the graphite
structure. The G band is associated with the E2g phonon vibration of the
graphitic sp2 hybridized carbon. The observed 2D band is a typical sig-
nature of the graphitic carbon [47,61]. In carbon materials, the intensity
ratio of the D band to the G band (= ID/IG) represents the degree of
graphitization [62]. The value of ID/IG is determined to be 0.95 and
0.92 for TWA-HC and TWA-WC, respectively. All of the above clarify
that, in comparison with the TWA-HC nanoparticles, the TWA-WC
nanoflakes have a less disordered lattice configuration and a relatively Fig. 5. (a) N2 adsorption-desorption isotherm and (b) pore size distribution of the TWA-
higher degree of graphitization. HC nanoparticles and the TWA-WC nanoflakes.
6 S. Sankar et al. / Materials and Design 169 (2019) 107688
transportation of the electrolyte ions into the carbon pores [65,66].
When the scan rate exceeds 50 mV/s, however, the CV curves are
distorted due to the Ohmic resistance from the electrolyte motion in
mesoporous graphitic carbon electrodes [52]. Although Cs decreases
with increasing scan rate because of the dispersion limit in the electrode
material, the TWA-WC electrode shows the higher Cs values than those
of the TWA-HC electrode (Fig. 6(c)). At the scan rate of 5 mV/s, further-
more, the TWA-WC electrode shows a greater magnitude of Cs
(~133 F/g) than that of the TWA-HC electrode (~122 F/g). This can be as-
cribed to the larger electrochemically-activated area (i.e., larger CV hys-
teresis loop) for the TWA-WC electrode (see also Fig. S1). The above
results elaborate that TWA-WC plays an excellent role as an electrode
material of the supercapacitor. The superior electrochemical perfor-
mances of TWA-WC can be interpreted by three following reasons.
Firstly, since the interconnected structure of the two-dimensional
TWA-WC nanoflakes has a large number of electrochemically active
sites (i.e., large specific surface area) [67], the diffusion of electrolyte
ions would be significantly enhanced at the electrode-electrolyte inter-
face. Secondly, a great deal of pores in mesoporous graphitic carbon
also provide the increased number of ionic diffusion channels [14]. Fi-
nally, the rapid ion transport can take place at the electrode-electrolyte
interface because the morphological nature of the graphitically-stacked
carbon nanosheets increases the electrical conductivity [68] (see also
the lower series and charge-transfer resistances of TWA-WC in Table S1).
Fig. 6(d) and (e) display the GCD curves at various current densities
for the TWA-HC and the TWA-WC electrodes, respectively. Both samples
show the Λ-shape of the symmetric GCD curves even at higher current
densities. This represents both samples to perform an ideal capacitive
behavior and to have a high electrochemical reversibility. To compare
the capacitive activities for TWA-HC and TWA-WC, the values of Cs are
plotted as a function of the current density (Fig. 6(f)). At a given range
of the current density (i.e., 0.5–5 A/g), the Cs values of TWA-WC
(80–162 F/g) are greater than those of TWA-HC (73–135 F/g). Further-
more, the maximum value of Cs(max) is higher for TWA-WC (~162 F/g
at 0.5 A/g), compared to TWA-HC (~135 F/g at 0.5 A/g). When consider-
ing that the applied current density is 0.5 A/g, the magnitude of Cs(max) of
TWA-WC (i.e., ~162 F/g at 0.5 A/g) is comparable or even higher than
that of other biomass-derived carbon materials used for supercapacitor
electrodes (Table 1). The enhanced specific capacity in TWA-WC can
be attributed to the higher conductivity and the higher electrolyte
Fig. 6. CV curves for the supercapacitors composed of the (a) TWA-HC and the (b) TWA-WC electrodes. (c) Cs as a function of the scan rate determined from the CV curves. GCD curves for
the supercapacitors composed of the (d) TWA-HC and the (e) TWA-WC electrodes. (f) Cs as a function of the current density determined from the GCD curves.
dispersion in the high-performance ultrathin mesoporous graphitic-
carbon nanoflakes, as described above.
The long-term cycle durability is a significant factor of the electrode
material for the practical application of the supercapacitor. The capacity
retention characteristics were assessed by repeating 5000 cycles of GCD
measurements at a consistent current density of 5 A/g (Fig. 7(a)). After
5000 charge-discharge cycles, the TWA-HC electrode exhibits a slightly
degraded capacity retention (~93%). However, the TWA-WC electrode
shows an excellent characteristic of the capacity retention up to ~121%
even after 5000 charge-discharge cycles. The increased capacity reten-
tion over 100% to 121% might be responsible for the increase in the spe-
cific surface area with increasing charge-discharge cycles. Namely, the
access of electrolyte ions into mesoporous graphitic-carbon nanoflakes
could be enhanced because of the gradual activation of mesopores due
to multiple charge-discharge cycles [27]. After performing 5000 charge-
discharge cycles, the structural integrity of TWA-HC is degraded,
resulting in a loss of the spherical-nanoparticle structure (see also
Fig. S2(a)). However, TWA-WC (Fig. S2(b)) still maintains a flake-like
structure because of the high surface area with a large porosity and a
low charge transfer resistance.
Finally, the electrochemical performances of TWA-HC and TWA-WC
were examined by EIS measurements. Fig. 7(b) and (c) show the
Nyquist plots of the supercapacitors that comprise the TWA-HC and
TWA-WC electrodes, respectively. Both TWA-HC and TWA-WC exhibit
the similar electrochemical transport characteristics (i.e., a straight line
at the lower frequency region and a semicircle at the higher frequency
region). The semicircle at the higher frequency region is associated
with a Faradaic process of the charge transfer at the electrolyte-
electrode interface, and is closely related to the charge transfer resis-
tance (Rct). The straight line at the lower frequency region is relevant
to the Warburg impedance (WZ) that represents the excellent elec-
tronic conductivity with an ideal capacitive behavior, arising from the
effective dispersion of electrolyte ions into the electrode material
[15,18]. Based on the equivalent circuit model [69] (inset of Fig. 7(c)),
the Rct values of the TWA-HC and TWA-WC electrodes were extracted
by using a Zview® software (see also Table S1). Before cycling, Rct of
TWA-WC (~6.4 Ω) was lower than that of TWA-HC (~9 Ω) because of
fewer electrolyte ions suffering from the charge-discharge process due
to the larger surface area and the higher porosity. In addition, the mea-
sured series resistance (Rs) of the TWA-WC electrode (0.26 Ω) is lower
 S. Sankar et al. / Materials and Design 169 (2019) 107688 7

Table 1
Comparison of the electrochemical performances for various biomass-derived carbons used as supercapacitor electrodes.

Biomass resource Activating agent Specific capacitance (F/g) Measurement condition Electrolyte Ref.

Cotton HCl 347 2 A/g 1 M H2SO4 [31]

Bamboo char K2FeO4 222 0.5 A/g 6 M KOH + PVA [32]
Cornstalk K4[Fe(CN)6] 213 1 A/g 6 M KOH [33]
Fibers of oil palm empty fruit bunches KOH + CO2 150 – 1 M H2SO4 [70]
Eggplant No activation 121 5 mV/s 6 M KOH [71]
Pine cone KOH 137 0.5 A/g 1 M Na2SO4 [72]
Oil palm kernel shell KOH 210 0.5 A/g 1 M KOH [73]
Fire wood Steam 142 25 mV/s 1 M H2SO4 [74]
Cow dung KOH 124 0.5 A/g 1 M Et4NBF4 [75]
Rice husk NaOH + CO2 120 0.1 mA/cm2 1 M EMIm.BF4 [76]
Coconut leaf CO2 133 200 mA/g 6 M KOH [77]
Banana fibers ZnCl2 74 500 mA/g 1 M Na2SO4 [78]
Coconut shell No Activation 154 10 mV/s 1 M Na2SO4 [79]
Coffee shell ZnCl2 156 1 mV/s 6 M KOH [80]
Cattail CO2 126 0.5 A/g 6 M KOH [81]
Waste tea K2CO3 203 1.5 mA/cm2 1 M H2SO4 [45]
Green tea waste from tea bag KOH 162 0.5 A/g 1 M H2SO4 This Work

than that of the TWA-HC electrode (0.32 Ω). This indicates that a negli-
gible iR drop occurs during the charge-discharge process. Since the con-
tinuous discharge-charge cycles might lead to the additional activation
of graphitic carbon, Rct is decreased for both cases (i.e., Rct = 7.9 Ω for
TWA-HC and Rct = 5.4 Ω for TWA-WC) after 5000 charge-discharge cy-
cles. The phase angles of TWA-HC and TWA-WC are observed at around
−80° and −84°, respectively (Fig. 7(d)), and these are comparable to
that of the ideal supercapacitor (i.e., −90°). From all the above results,
it can be concluded that the biomass TWA-derived graphitic carbon
products, particularly mesoporous TWA-WC nanoflakes, could be of
great benefit as a superb electrode material for the supercapacitors.
4. Conclusions
For the purpose of upcycling the biomass resource for the green
energy-technology, the mesoporous graphitic carbon structures of the
TWA-HC nanoparticles and the TWA-WC nanoflakes were successfully
synthesized from biomass TWA via the KOH activation process combined
with either of the water or the hydrochloric acid treatment, respectively.
Compared to the TWA-HC nanoparticles (pore volume ~ 0.2438 cm3/g,
surface area ~ 966.4 m2/g), the TWA-WC nanoflakes showed to have a
larger pore volume (~0.4713 cm3/g) and a higher surface area
(~1057.8 m2/g). Due to the higher porosity and the higher conductiv-
ity in TWA-WC, the supercapacitor devised with the TWA-WC elec-
trode clearly showed the excellent electrochemical performances
(i.e., high Cs ~ 162 F/g at 0.5 A/g and high cyclic capacitance reten-
tion ~ 121% after 5000 charge-discharge cycles). The results suggest
that the biomass TWA-derived ultrathin mesoporous graphitic car-
bon nanoflakes hold promise for high-performance electrode mate-
rials in next-generation high-energy supercapacitors.
CRediT authorship contribution statement
S. Sankar: Investigation, Writing - original draft. Abu Talha Aqueel
Ahmed: Methodology. Akbar I. Inamdar: Methodology. Hyunsik Im: Su-
pervision. Young Bin Im: Formal analysis. Youngmin Lee: Data curation.

Fig. 7. (a) Capacity retention as a function of the charge-discharge cycle number. Nyquist plots for the supercapacitors composed of the (b) TWA-HC and the (c) TWA-WC electrodes. The
solid and the open circles are the measurement data, and the solid lines are the best-fitted curves. The inset of (b) shows the Nyquist plot in a short impedance range, and the inset of
(c) illustrates the equivalent circuit of the fabricated supercapacitor. (d) Bode plots of the supercapacitors comprising the TWA-HC and the TWA-WC electrodes.
8 S. Sankar et al. / Materials and Design 169 (2019) 107688
Deuk Young Kim: Conceptualization. Sejoon Lee: Conceptualization,
Writing - review & editing.
Acknowledgements
This research was supported by the National Research Foun-
dation of Korea through the Basic Science Research Program
(2016R1A6A1A03012877 and 2017R1A2B4004281) funded by
the Korean government of the Ministry of Education.
Competing interests
The authors declare that they have no competing interests.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.matdes.2019.107688.
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